POLYCHAR 23...Welcome to PolyChar 23 University of Nebraska-Licoln, Lincoln, Nebraska May 11-15, 2015 It is a pleasure to welcome you to PolyChar 23, the 23rd World Forum on Advanced

23rd World Forum on Advanced MaterialsUniversity of Nebraska-Lincoln

Lincoln , Nebraska U.S.A.May 11-15 , 2015

POLYCHAR 23

PROGRAM & ABSTRACTS

Welcome to PolyChar 23University of Nebraska-Licoln, Lincoln, Nebraska

May 11-15, 2015

It is a pleasure to welcome you to PolyChar 23, the 23rd World Forum on Advanced Materials. The localorganizing committee with the help and support of members of the PolyChar executive committee, interna-tional partners, and local supporters has arranged a program of activities that we hope you enjoy. I wouldlike to thank all the presenters for their contribution, without which there could not be a scientific program.Particular thanks goes to the plenary speakers, the keynote speakers, and the invited speakers that haveagreed to give direction to the program.

I would like to take this opportunity to thank our sponsors:

• The National Science Foundation,

• The International Union of Pure and Applied Chemistry (IUPAC),

• The IUPAC/Samsung fund,

• The John A. Woollam Company,

• The University of Nebraska-Lincoln (UNL),

• The UNL Office for Research and Economic Development,

• The UNL College of Engineering,

• The UNL Department of Mechanical & Materials Engineering,

• The City of Lincoln Convention and Visitors Bureau

Dr. Jeff Shield, Chair of the Department of Mechanical & Materials Engineering, and Dr. Tim Wei, Deanof the College of Engineering, have been kind enough to provided the needed staff, support and expertise tohost this conference. Without their help it would not be possible to arrange the conference.

Special thanks goes to Dr. Prem Paul, Vice Chancellor for Research & Economic Development at UNL,that has been a strong supporter of the activities of the Advanced Mechanics and Materials EngineeringInternational Laboratory (AMME-International) and the effort to bring PolyChar to UNL. He also providedsubstantial financial support for the conference.

Finally, special thanks goes to Mrs. Cherie Crist and Mrs. Mary Ramsier, that have worked tirelesslyto arrange all the activities, and to all the students that have been helping with the conference.

I hope you enjoy the program and your visit.

Sincerely,Mehrdad Negahban, Local Organizations ChairPolyChar 23

Local Organizing Committee

• Dr. Mehrdad Negahban, Local Chair, Mechanical & Materials Engineering

• Dr. Christopher Cornelius, Chemical & Biomolecular Engineering

• Dr. Stephen Ducharme, Physics And Astronomy

• Dr. Yuris Dzenis, Mechanical & Materials Engineering

• Dr. Lucia Fernandez-Ballester, Mechanical & Materials Engineering

• Dr. Jinsong Huang, Mechanical & Materials Engineering

• Dr. Carl Nelson, Mechanical & Materials Engineering

• Dr. Jeff Shield, Mechanical & Materials Engineering

• Dr. Li Tan, Mechanical & Materials Engineering

• Dr. Joseph Turner, Mechanical & Materials Engineering

• Mrs. Cherie Crist, Conference Secretary, Mechanical & Materials Engineering

• Mrs. Mary Ramsier, Mechanical & Materials Engineering

International Organizers

• Dr. Jean-Marc Saiter,AMME-LECAP, University of Rouen, France

• Dr. Michael Hess, Chosun University, Korea

• Dr. Jean-Jacques Pireaux, University of Namur, Belgium

• Dr. Rameshwar Adhikari, Tribhuvan University, Nepal

• Dr. Witold Brostow, University of North Texas, USA

• Dr. Eric Dargent, AMME-LECAP, University of Rouen, France

• Dr. Allisson Saiter, AMME-LECAP, University of Rouen, France

• Dr. Laurent Delbrelh, AMME-LECAP, University of Rouen, France

• Dr. Antonella Esposito, AMME-LECAP, University of Rouen, France

• Dr. Nicolas Delpouve, AMME-LECAP, University of Rouen, France

PolyChar 23 Symposia

• GP- General Papers, Organizers: Jean-Marc Saiter, Carl A Nelson, Mehrdad Negahban.

• CMSP- Characterization Methods and Structure-Properties Relations, Organizers: MehrdadNegahban, Christopher Cornelius, Jean-Marc Saiter.

• PMMS- Predictive Methods, Modelling, and Simulation, Organizers: Mehrdad Negahban.

• GEEN- Green Polymers, Green Engineering and Recycling, Organizers: Jean-Marc Saiter,Joseph Turner.

• BIOT- Biomaterials, Drug Delivery and Tissue Engineering, Organizers: Yuris Dzenis, JosephTurner, Carl A Nelson.

• FIC- Fibers, Interfaces and Composite Materials, Organizers: Yuris Dzenis, Antonella Esposito.

• NANO- Nanomaterials and Smart Materials, Organizers: Li Tan.

• DEMO- Dielectric, Electrical, Magnetic, Optical and Optoelectronic Properties, Organiz-ers: Stephen Ducharme, Laurent Delbreilh.

• PEOD- Polymers in Electronics and Optoelectronics Devices, Organizers: Jinsong Huang.

• PS- Progress in Polymer Synthesis, Organizers: Nicolas Delpouve, Rameshwar Adhikari.

• MPP- Mechanical Properties and Performance, Organizers: Mehrdad Negahban, Joseph Turner.

• CSPM- Characterization with Scanning Probe Microscopes, Organizers: Joseph Turner,Rameshwar Adhikari.

• RSP- Rheology, Solutions and Processing, Organizers: Mehrdad Negahban, Lucia Fernandez-Ballester, Antonella Esposito.

• PPSC- Processing and Properties of Semicrystalline Polymers, Organizers: Lucia Fernandez-Ballester, Eric Dargent.

8:00 AM Registration8:30 AM M1: Short Course (Auditorium, NU)12:00 PM Lunch (Ballroom, NU)1:00 PM M2: Short Course (Auditorium, NU)6:00 PM Reception (Sheldon Art Gallery)

8:00 AM Registration8:20 AM Opening/Plenary (Auditorium, NU)9:40 AM Coffee Break10:00 AM T2_1: CMSP (Heritage Room, NU) T2_2: PEOD (Auditorium, NU)12:00 PM Lunch (Ballroom, NU)12:50 PM T_3: Young Plenary (Auditorium, NU)1:40 PM T4_1: CMSP (Heritage Room, NU) T4_2: DEMO (Auditorium, NU)2:40 PM Coffee Break3:05 PM T5_1 CMSP (Heritage Room, NU) T5_2: DEMO (Auditorium, NU)

8:00 AM Registration8:30 AM Plenary (Auditorium, NU)9:25 AM Coffee Break9:45 AM W2_1: NANO (Auditorium, NU) W2_2: BIOT (Heritage Room, NU)12:00 PM Lunch (Ballroom, NU)1:00 PM W_3: Young Plenary (Auditorium, NU)1:50 PM W4: Posters (Ballroom, NU)

8:30 AM Plenary (Henzlik 124)9:25 AM Coffee Break9:45 AM TH2_1: FIC (Henzlik 124) TH2_2: PPSC (Henzlik 53)12:00 PM Lunch (Ballroom, NU)1:00 PM TH_3: Flory Medal Talk (Henzlik 124)2:00 PM TH4_1: CSPM (Henzlik 124) TH4_2: NANO (Henzlik 53)3:40 PM Coffee Break4:00 PM TH5_1: BIOT (Henzlik 124) TH5_2: PMMS (Henzlik 53)6:00 PM Social Hour & Banquet (Ballroom, NU)

8:30 AM Plenary (Auditorium, NU) 9:25 AM Coffee Break9:40 AM F2_1: PS (Auditorium, NU) F2_2: RSP/MPP (Heritage Room, NU)12:00 PM Lunch (Ballroom, NU)1:00 PM F_3: Awards and Closing (Auditorium, NU)

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POLYCHAR 23 Technical ProgramUniversity of Nebraska-Licoln, Lincoln, Nebraska

May 11-15, 2015

Monday, May 11, 2015 Starting: 8:30 AMM1: Short Course (Auditorium)Session Chairs: Michael Hess, Brett Fors (Assistants: Wenlong Li, Jase Kaser)

1. (8:30 AM, Short Course) Menard: DYNAMIC MECHANICAL ANALYSIS

2. (9:25 AM, Short Course) Schubert: RHEOLOGY AND PROCESSING

3. (10:20 AM, Short Course) Schönherr: CHARACTERIZATION OF POLYMERIC NANOSTRUC-TURES WITH COMBINED SCANNING PROBE AND FLUORESCENCE MICROSCOPIES

4. (11:15 AM, Short Course) Henning: MICROMECHANICS OF POLYMERS: MICRO- ANDNANOSCOPIC PROCESSES OF DEFORMATION AND FRACTURE

Monday, May 11, 2015 Starting: 1:00 PMM2: Short Course (Auditorium)Session Chairs: Kevin P. Menard, Sven Henning (Assistants: Marzieh Bakhtiary Noodeh, MitchellSchmidt)

1. (1:00 PM, Short Course) Saiter: GLASS TRANSITION AND GLASS TRANSITION TEMPERA-TURE

2. (1:55 PM, Short Course) Blümich: SOLID-STATE NMR

3. (2:50 PM, Short Course)Guenet: BASICS OF SCATTERING TECHNIQUES: X-RAY, NEUTRONS,LIGHT

4. (3:45 PM, Short Course) Fors: PHOTOCHEMISTRY IN POLYMER SCIENCE

5. (4:40 PM, Short Course)Hnatchuk: FRICTION, WEAR AND SCRATCH RESISTANCE OF POLY-MERS

Tuesday, May 12, 2015 Starting: 8:20 AMT0: Opening (Auditorium)Session Chair: Mehrdad Negahban (Assistants: Wenlong Li, John J. Bowen)Tuesday, May 12, 2015 Starting: 8:45 AMT1: Plenary (Auditorium)Session Chair: Jinsong Huang (Assistants: Wenlong Li, John J. Bowen)

1. (8:45 AM, Plenary) Ade: SOFT X-RAY CHARACTERIZATION METHODS: UTILITY AND OP-PORTUNITY

Tuesday, May 12, 2015 Starting: 10:00 AMT2_1: CMSP (Heritage Room)Session Chair: Bernhard Blümich (Assistant: John J. Bowen)

1. (10:00 AM, Keynote) Guenet: CHARACTERIZATION AND PROPERTIES OF HYBRID MATE-RIALS FROM POLYMERS AND SELF-ASSEMBLED SYSTEMS

2. (10:40 AM, Oral) Dargent: RELAXATION PROCESSES AND COOPERATIVITY IN COPOLY-MERS WITH A SIMILAR BACKBONE FLEXIBILITY

3. (11:00 AM, Oral) Pireaux: UNDERSTANDING (INDUCING, REPAIRING) ION BEAM DAMAGESIN POLYMERS - A POLYCHAR CONCERN

4. (11:20 AM, Oral) Delpouve: COUPLING APPROACHES FOR THE INVESTIGATION OF THEALPHA RELAXATION DYNAMICS IN INTERACTING NETWORKS

5. (11:40 AM, Oral) Adhikari: MORPHOLOGICAL, THERMAL AND ELECTRICAL PROPERTIESOF STYRENIC BLOCK COPOLYMER COMPOSITES WITH NANOCARBONS

Tuesday, May 12, 2015 Starting: 10:00 AMT2_2: PEOD (Auditorium)Session Chair: Jinsong Huang (Assistant: Wenlong Li)

1. (10:00 AM, Invited) Ouyang: PEDOT:PSS FOR PEROVSKITE SOLAR CELLS

2. (10:20 AM, Invited) Xiao: UNDERSTANDING THE EFFECT OF DEUTERATED CONDUCT-ING POLYMER AND SOLVENT ADDITIVE ON THE PERFORMANCE OF ORGANIC PHOTO-VOLTAICS

3. (10:40 AM, Oral) Ulanski: OTFTS WITH ULTRATHIN LAYERS OF POLY(3-HEXYLTIOPHENE)

4. (11:00 AM, Oral) Xiao: UNIVERSAL FORMATION OF COMPOSITIONALLY GRADED BULKHETEROJUNCTION FOR EFFICIENCY ENHANCEMENT IN ORGANIC PHOTOVOLTAICS

5. (11:20 AM, Oral) Jo: CONDUCTING POLYMER/GRAPHENE COMPOSITE FOR SUPERCAPAC-ITOR

Tuesday, May 12, 2015 Starting: 12:50 PMT3: Young Pleanary (Auditorium)Session Chair: Lucia Fernandez-Ballester (Assistants: Ramin Hosseinabad, Mitchell Schmidt)

1. (12:50 PM, Young Plenary) Stein: GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING:PRINCIPLES, MODELS, AND APPLICATIONS FOR NANOSTRUCTURED THIN FILMS

Tuesday, May 12, 2015 Starting: 1:40 PMT4_1: CMSP (Heritage Room)Session Chair: Christopher Cornelius (Assistant: Ramin Hosseinabad)

1. (1:40 PM, Invited) Blümich: NMR-SPECTROSCOPY AND NONDESTRUCTIVE TESTING BYCOMPACT NMR

2. (2:00 PM, Oral) Tashiro: STRUCTURE FORMATION PROCESS OF POLY(VINYL ALCOHOL)-IODINE COMPLEX REVEALED BY IN-SITU TIME-DEPENDENT X-RAY DIFFRACTION MEA-SUREMENT

3. (2:20 PM, Oral) Salim: THERMAL DEGRADATION IN THE MELT REACTION BETWEENPOLY(3-HYDROXYBUTYATE-CO-3-HYDROXYHEXANOATE) AND EPOXIDIZED NATURALRUBBER

Tuesday, May 12, 2015 Starting: 1:40 PMT4_2: DEMO (Auditorium)Session Chair: Stephen Ducharme (Assistant: Mitchell Schmidt)

1. (1:40 PM, Invited) Xu: ENHANCED SENSITIVITY OF PRESSURE SENSOR USING ELEC-TROACTIVE POLYMERS

2. (2:00 PM, Oral) Poddar: FLEXOELECTRIC EFFECT IN FERROELECTRIC AND RELAXORPOLYMERS OF VDF

3. (2:20 PM, Oral) Chan: RESPONSE OF SOLID POLYMER ELECTROLYTES TO ELECTRICFIELDS

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Tuesday, May 12, 2015 Starting: 3:05 PMT5_1: CMSP (Heritage Room)Session Chair: Yong-Rak Kim (Assistant: Ramin Hosseinabad)

1. (3:05 PM, Oral) Sun: INVESTIGATING ORGANIC MATERIALS USING SPECTROSCOPIC EL-LIPSOMETRY

2. (3:25 PM, Oral) Manhart: DESIGN OF ELASTOMER SURFACES WITH SPATIALLY CON-TROLLED TRIBOLOGICAL PROPERTIES APPLYING PHOTOLITHOGRAPHIC TECHNIQUES

3. (3:45 PM, Oral) Desai: ROLE OF EXTERNAL DONOR AND CO-CATALYST - ZIEGLER NATTACATALYST USING SPECTROSCOPY TECHNIQUE

4. (4:05 PM, Oral) Schamme: ROLE OF MOLECULAR MOBILITY AND FRAGILITY ON PHYSI-CAL STABILITY OF TWO AMORPHOUS PHARMACEUTICALS IN THE SUPERCOOLED ANDGLASSY STATES

5. (4:25 PM, Oral) Viel: MOLECULAR MOBILITY VS POLYMORPHISM OF CHIRAL PHARMA-CEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE

6. (4:45 PM, Oral) Denchev: STRUCTURE GRADIENTS BY MICROFOCUS SYNCHROTRON X-RAY DIFFRACTION IN SHELL-CORE POLYAMIDE MICROCAPSULES AND MOLDED COM-POSITES THEREOF

7. (5:05 PM, Oral) You: CHARACTERIZATION OF VISCOELASTIC-VISCOPLASTIC BEHAVIOROF POLYMERIC MATERIALS CONTAINING ALIPHATIC AND AROMATIC HYDROCARBONSDERIVATIVES

Tuesday, May 12, 2015 Starting: 3:05 PMT5_2: DEMO (Auditorium)Session Chair: Chinhan Chan (Assistant: Mitchell Schmidt)

1. (3:05 PM, Invited) Jonas: NANOIMPRINTED FERROELECTRIC/SEMICONDUCTING POLY-MER DEVICES

2. (3:25 PM, Oral) Sangoro: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS IN POLY-MERIZED IONIC LIQUIDS

3. (3:45 PM, Oral) Dencheva: FROM LOADED SHELL-CORE MICROCAPSULES TO THERMO-PLASTIC HYBRID COMPOSITES: A NEW PATHWAY FOR THE PREPARATION OF CONDUC-TIVE AND MAGNETIC POLYAMIDE COMPOSITES

4. (4:05 PM, Oral) Anada: DIVERSITY OF MICROSTRUCTURE OF POLYMER SOLID INVESTI-GATED BY MOTION OF IMPURITY IONS

5. (4:25 PM, Oral)Hagg Lobland: THERMOELECTRIC GENERATORS (TEGS) WITH LONG SER-VICE LIVES

Wednesday, May 13, 2015 Starting: 8:30 AMW1: Plenary (Auditorium)Session Chair: Li Tan (Assistants: Marzieh Bakhtiary Noodeh, Yan Zou)

1. (8:30 AM, Plenary) Laine: SYNTHESIS, PROCESSING AND PROPERTIES OF SILSESQUIOX-ANE MACROMONOMERS AND POLYMERS

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Wednesday, May 13, 2015 Starting: 9:45 AMW2_1: NANO (Auditorium)Session Chair: Li Tan (Assistant: Marzieh Bakhtiary Noodeh)

1. (9:45 AM, Keynote) Dzenis: SIMULTANEOUSLY STRONG AND TOUGH CONTINUOUS POLY-MER NANOFIBERS AND NANOCOMPOSITES

2. (10:25 AM, Invited) Serpe: STIMULI RESPONSIVE POLYMER-BASED SENSORS, MUSCLES,AND DRUG DELIVERY PLATFORMS

3. (10:45 AM, Oral) Li: POLYMER-BASED MATERIALS FOR BUILDING ARTIFICIAL MUSCLESAND THREE DIMENSIONAL STRUCTURES BY SELF-ROLLING

4. (11:05 AM, Oral) Alarifi: MECHANICAL AND THERMAL PROPERTIES OF CARBONIZED PANNANOFIBERS COHESIVELY ATTACHED TO SURFACE OF CARBON FIBER REINFORCEDCOMPOSITES

5. (11:25 AM, Oral) Goponenko: ELECTROSPUN NANOFIBROUS MATERIALS AS STIMULI-RE-SPONSIVE POLYMERIZED HYDROGELS

Wednesday, May 13, 2015 Starting: 9:45 AMW2_2: BIOT (Heritage Room)Session Chairs: Linxia Gu, Dimitry Papkov (Assistant: Yan Zou)

1. (9:45 AM, Keynote) Causin: NANOCELLULOSE-REINFORCED GELS FOR BIOMEDICAL AP-PLICATIONS

2. (10:25 AM, Invited) Schönherr: INFECTION DIAGNOSTICS WITH POLYMERIC VESICLESAND HYDROGELS FOR APPLICATION IN ADVANCED WOUND DRESSINGS AND BEYOND

3. (10:45 AM, Oral) Saunier: HOW ADDITIVE EXUDATION CAN AFFECT THE BIOCOMPATI-BILITY OF A POLYMERIC MEDICAL DEVICE: THE CASE OF A POLYURETHANE USED INIMPLANTABLE CATHETERS

4. (11:05 AM, Oral) Ding: ELECTROSPUN PHB/PCL/FUMED SILICA FIBROUS STRUCTUREFOR BONE TISSUE ENGINEERING

5. (11:25 AM, Oral) Andalib: BIOMIMETIC NANOFILAMENTARY POLYMER SCAFFOLDS ANDTHE MECHANISMS OF CELL-SCAFFOLD INTERACTION

6. (11:45 AM, Oral) Maleckis: ULTRAHIGH-PERFORMANCE NANOFIBERS FROM DNA ANDPROTEINS

7. (12:05 PM, Oral) Lyu: INVESTIGATION OF RUBBER FLOW DURING SHAPING OF AUTOMO-BILE TIRES

Wednesday, May 13, 2015 Starting: 1:00 PMW3: Young Plenary (Auditorium)Session Chair: Christopher Cornelius (Assistants: Trevor Gnuse, Yan Zou)

1. (1:00 PM, Young Plenary) Whittington: POLYMER CHARACTERIZATION OF MEDICAL DE-VICES FOR USE IN CANCER PATIENTS

Wednesday, May 13, 2015 Starting: 1:50 PMW4: Poster (Ballroom)Session Chairs: Michael Hess, Jean-Jacques Pireaux (Assistant: Trevor Gnuse)

1. (1:50 PM, Poster) Jayasinghe: INVESTIGATION OF SWELLING BEHAVIOR OF POLY(HEMA-CO-DMAEMA) HYDROGELS CONFINED IN AN ELASTOMERIC MOLD

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2. (1:50 PM, Poster) Schwahn: CONTROLLED CURING OF ACRYLATE: SYSTEM MODELINGAND APPLICATIONS IN STEREOLITHOGRAPHY

3. (1:50 PM, Poster) Adhikari: CHARACTERIZATION OF BAMBOO FLOURS REINFORCEDEPOXY RESIN COMPOSITES

4. (1:50 PM, Poster) Li: CHARACTERIZATION OF THE INFLUENCE OF DEPTH IN PHOTO CUR-ING OF ACRYLATE: A METHOD BASED ON RAPID-SCAN FTIR DURING LASER CURING ONAN ATR

5. (1:50 PM, Poster) Furgal: HIGH SURFACE AREA METHYLSILSESQUIOXANE POLYMER GELSBY FLUORIDE CATALYSIS

6. (1:50 PM, Poster) Stockdale: MANUFACTURING OF POLYIMIDE FIBER-REINFORCEDNANOCOMPOSITES

7. (1:50 PM, Poster) Zou: EFFECT OF CONSTRAINT ON STRUCTURE AND MECHANICALPROPERTIES OF CONTINUOUS POLYACRYLONITRILE-BASED STABILIZED AND CAR-BONIZED NANOFIBERS

8. (1:50 PM, Poster) Jasa: USING MOLECULAR DYNAMICS SIMULATIONS FOR CHARACTER-IZING MACROSCOPIC RESPONSE IN POLYCARBONATE

9. (1:50 PM, Poster) Hnatchuk: MODIFICATION OF POLY(VINYL CHLORIDE)

10. (1:50 PM, Poster)Hnatchuk: PROPERTIES OF EPOXY FILMS BASED ONMODIFIED PHENOL-FORMALDEHYDE OLIGOMERS

11. (1:50 PM, Poster) Chan: FTIR STRUCTURAL ANALYSIS OF EPOXY PAINTS ON STEELSTRUCTURE FOR COATING FINGERPRINTING CERTIFICATE FOR PAINT INDUSTRY

12. (1:50 PM, Poster) Viel: IMPACT OF COVER SLIDE ON RECRYSTALLIZATION FROM THEAMORPHOUS STATE OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPRO-PHYLLINE

13. (1:50 PM, Poster) Cosby: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS OF POLY-MERIZED IONIC LIQUIDS

14. (1:50 PM, Poster) Jiao: INTERPLAY BETWEEN ABSORPTION BROADENING ANDMORPHOL-OGY DETERIORATION IN TERNARY BULK HETEROJUNCTION SOLAR CELLS RESOLVEDBY SOFT X-RAY SCATTERING

15. (1:50 PM, Poster) Chen: OPTIMIZATION OF THE DISTRIBUTION OF PROPERTIES: USINGACRYLATE/EPOXY MIXTURES IN THE EXTENSION OF AN FGM PLATE WITH A HOLE

16. (1:50 PM, Poster) Daily: DIELECTRIC PROPERTIES AND KINETIC STUDY ON THE DEGRA-DATION OF BISMALEIMIDE RESIN

17. (1:50 PM, Poster) Jamil: MECHANISM OF MOLECULAR INTERACTION OF SUPERPLASTI-CIZER OLIGOMERS WITH HYDRATED CEMENT PHASES

18. (1:50 PM, Poster) Piorkowska: COMPARISON OF PROPERTIES OF STAR AND LINEARPOLY(L-LACTIDE)

19. (1:50 PM, Poster) Frazier: CHEMICAL MODIFICATION OF PROTEIN-BASED ADHESIVES FORCONSTRUCTION APPLICATIONS

20. (1:50 PM, Poster) Dargent: MOLECULAR DYNAMICS IN ELECTROSPUN FIBERS OF PLAS-TICIZED POLYLACTIDE

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21. (1:50 PM, Poster) Gakhutishvili: TRIBOLOGICAL PROPERTIES OF ANTIBACTERIAL POLY-MER COMPOSITES

22. (1:50 PM, Poster) Delpouve: LENGTH SCALE AT THE GLASS TRANSITION IN SEMI-CRYS-TALLINE COMPATIBILIZED POLYLACTIDE/CLAY NANOCOMPOSITES

23. (1:50 PM, Poster) Lin: HYDROGEN BONDING INDUCED NANOPHASE SEPARATION OF GI-ANT SURFACTANTS TOWARD SUB-10-NM HYBRID ORDER NANOSTRUCTURES

24. (1:50 PM, Poster) Liu: TWO-DIMENSIONAL NANO-CRYSTALS OF MOLECULAR JANUS PAR-TICLES

25. (1:50 PM, Poster) Alarifi: EFFECTS OF UV EXPOSURE ON PHYSICAL PROPERTIES OF CAR-BON FIBER/PPS THERMOPLASTIC COMPOSITES

26. (1:50 PM, Poster) Kaser: NANOMANUFACTURING POLYACRYLONITRILE NANOFIBERYARNS

27. (1:50 PM, Poster) Alharbi: INTEGRATING C60 NANOPARTICLES INTO TIO2 NANOFIBERSVIA ELECTROSPINNING PROCESS FOR ENHANCED ENERGY CONVERSTION EFFICIEN-CIES

28. (1:50 PM, Poster) Loubeau: AGEING OF A THREE-LAYER PAPER USED IN THE INSULATIONOF AN ELECTRICAL MOTOR FOR THE AUTOMOTIVE TRACTION

29. (1:50 PM, Poster) Schmidt: A STUDY OF THE EFFECTS OF SPIN COATING ON PVDF FILMS

30. (1:50 PM, Poster) Schönherr: INVESTIGATION OF ELECTRONIC PROPERTIES OF AGRAPHENE FIELD EFFECT TRANSISTOR

31. (1:50 PM, Poster) Ding: BROADBAND DIELECTRIC RELAXATION ANALYSIS ON THE REIN-FORCEMENT OF ANTHRACENE-FUNCTIONALIZED EPOXY COMPOSITES

32. (1:50 PM, Poster) Lobland: SYNTHESIS AND PROPERTIES OF REACTIVE OLIGOMERSBASED ON A PEROXY DERIVATIVE OF AN EPOXY RESIN AND 1,4- BUTANEDIOL

33. (1:50 PM, Poster) Ospina: SYNTHESIS AND CHARACTERIZATION OF POLYMERS WITH AN-TIBACTERIAL PROPERTIES BASE ON TRICLOSAN ACRYLATE

34. (1:50 PM, Poster) Bakhtiary Noodeh: USING CURING KINETICS TO CONTROL THE ME-CHANICAL PROPERTIES OF SIMULTANEOUS ACRYLATE/EPOXY IPNS DURING PHOTOCURING OF GRADED MATERIALS

35. (1:50 PM, Poster) Gafurov: MOLECULAR STRUCTURE PARAMETERS INFLUENCE ON DE-FORMATION MECHANICS OF AN ORIENTED CRYSTALLINE POLYMER

36. (1:50 PM, Poster) Lanyi: NOVEL CHART FOR REPRESENTATION OF MATERIAL PERFOR-MANCE AND RELIABILITY

37. (1:50 PM, Poster) Rezaei: U-SHAPED PROBES FOR CHARACTERIZATION OF POLYMERSUSING CONTACT RESONANCE ATOMIC FORCE MICROSCOPY

38. (1:50 PM, Poster) Dargent: STUDY OF AMORPHOUS AND CRYSTALLINE PHASES IN BIO-BASED NANOCOMPOSITE FILMS

39. (1:50 PM, Poster) Delpouve: MICROSTRUCTURE, AMORPHOUS PHASE DYNAMICS ANDBARRIER PROPERTIES IN MULTILAYER COEXTRUDED POLYLACTIDE

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40. (1:50 PM, Poster) Schamme: RELAXATION OF SHEAR-INDUCED PRECURSORS INPOLY(LACTIC ACID)

41. (1:50 PM, Poster) Hosseinabad: EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCEDCRYSTALLIZATION

42. (1:50 PM, Poster) Sterzynski: THE POSS AND MWCNT MODIFIED GLASS TRANSITION TEM-PERATURE TG OF POLY(VINYL CHLORIDE)

43. (1:50 PM, Poster) Saiter: INFLUENCE OF STRUCTURAL FEATURES OF POROGENMOLECULES ON THERMAL PROPERTIES AND POROSITY OF NANOPOROUS POLYCYA-NURATE-BASED FILM MATERIALS

44. (1:50 PM, Poster) Zare Rami: INVESTIGATION OF FRACTURE BEHAVIOR OF HETERO-GENEOUS POLYMER MIXTURES SUBJECTED TO VISCOELASTIC DEFORMATION USINGMICROSTRUCTURAL MODELING

45. (1:50 PM, Poster) Ding: POLAR PHASE GENERATION IN PVDF, THROUGH AMPHIPHILICIONIC LIQUID MODIFIED MULTIWALLED CARBON NANOTUBES: EFFECT OF ANION

Thursday, May 14, 2015 Starting: 8:30 AMTH1: Plenary (Henzlik 124)Session Chair: Yuris Dzenis (Assistants: Kaspars Maleckis, Zesheng Zhang)

1. (8:30 AM, Plenary) Cheng: GIANT POLYHEDRA AND GIANT SURFACTANTS BASED ONNANO-ATOMS: TUNING FROM CRYSTALS, TO QUASICRYSTALS, TO FRANK-KASPERPHASES: AN INTERCONNECTION BETWEEN SOFT AND HARD MATTER

Thursday, May 14, 2015 Starting: 9:45 AMTH2_1: FIC (Henzlik 124)Session Chair: Yuris Dzenis (Assistant: Kaspars Maleckis)

1. (9:45 AM, Keynote) Galeski: CRYSTALLIZATION AND MELTING PHENOMENA INNANOFIBER REINFORCED POLYMER NANOCOMPOSITES

2. (10:25 AM, Invited) Papkov: POLYMER CRYSTALLINITY AND TOUGHNESS: INCREASINGPLASTICITY OF CONTINUOUS POLYACRYLONITRILE NANOFIBERS THROUGH CRYSTAL-LIZATION SUPPRESSION

3. (10:45 AM, Oral) Sterzynski: ECOLOGICALLY FRIENDLY MULTILAYER WPC/SRC CON-STRUCTION MATERIALS; PRODUCTION, STRUCTURE AND PROPERTIES

4. (11:05 AM, Oral) Gonçalves: XANTHAM GUM AND CHITOSAN AS NATURAL ADHESIVESFOR CORK

5. (11:25 AM, Oral) Bin: TRANSCRYSTALLIZATION IN CARBON FIBRE FILLED POLY (L-LAC-TIC ACID) COMPOSITES UNDER TEMPERATURE GRADIENT

6. (11:45 AM, Oral) Alharbi: SYNTHESIS AND ANALYSIS OF ELECTROSPUN SRTIO3NANOFIBERS WITH NIOX NANOPARTICLES SHELLS AS PHOTOCATALYSTS FOR WATERSPLITTING

Thursday, May 14, 2015 Starting: 9:45 AMTH2_2: PPSC (Henzlik 53)Session Chairs: Eric Dargent, Lucia Fernandez-Ballester (Assistant: Zesheng Zhang)

1. (9:45 AM, Keynote) Lefebvre: IN-SITU SAXS/WAXS INVESTIGATIONS ON DEFORMATIONINDUCED STRUCTURAL EVOLUTIONS IN AMORPHOUS AND SEMI-CRYSTALLINE POLY-MERS

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2. (10:25 AM, Oral) Mokni: EFFECT OF THE SUBLIMATION TEMPERATURE ON THE MOR-PHOLOGY AND CRYSTALLINITY OF PARYLENE D DEPOSITED BY CVD

3. (10:45 AM, Oral) Piorkowska: NUCLEATION OF HIGH-PRESSURE-INDUCED GAMMA FORMIN ISOTACTIC POLYPROPYLENE IN NONISOTHERMAL CONDITIONS

4. (11:05 AM, Oral) Fernandez-Ballester: EFFECT OF COPOLYMER CONTENT ON FLOW-IN-DUCED CRYSTALLIZATION

5. (11:25 AM, Oral) Lugito: NOVEL APPROACHES TO ADVANCE UNDERSTANDING OF POLY-MER CRYSTALLIZATION

6. (11:45 AM, Oral) Ding: EFFECT OF TRI-ARM STAR-SHAPED IMIDAZOLIUM IONIC LIQUIDOLIGOMER WITH PEG SEGMENT ON THE CRYSTALLIZATION BEHAVIORS OF POLY(L-LACTIC ACID)

Thursday, May 14, 2015 Starting: 1:00 PMTH3: Flory Medal Talk (Henzlik 124)Session Chair: Jean-Jacques Pireaux (Assistants: John Jasa, Taylor Stockdale)

1. (1:00 PM, Prize Talk) Tashiro: CLARIFICATION OF MICROSCOPICALLY-VIEWED STRUC-TURE-PROPERTY RELATIONSHIP OF POLYMER MATERIALS

Thursday, May 14, 2015 Starting: 2:00 PMTH4_1: CSPM (Henzlik 124)Session Chairs: Joseph Alan Turner, Philip Yuya (Assistant: John Jasa)

1. (2:00 PM, Keynote) Yablon: ADVANCES IN ATOMIC FORCE MICROSCOPY (AFM) BASEDMETHODS TO CHARACTERIZE POLYMER MATERIALS ON THE NANOSCALE

2. (2:40 PM, Invited) Yuya: EFFECT OF GOLD NANOPARTICLE ENHANCEMENT ON NANOME-CHANICAL PROPERTIES OF CHITOSAN FILMS

3. (3:00 PM, Oral) Desyatova: CHARACTERIZATION OF THERMOMECHANICAL PROPERTIESOF RECOMBINANT RESILIN USING ATOMIC FORCE MICROSCOPY

4. (3:20 PM, Oral) Turner: SIMULTANEOUS QUANTIFICATION OF THE IN-PLANE AND OUT-OF-PLANE LOSS TANGENT OF POLYMERS USING CONTACT RESONANCE ATOMIC FORCEMICROSCOPY

Thursday, May 14, 2015 Starting: 2:00 PMTH4_2: NANO (Henzlik 53)Session Chair: Michael J. Serpe (Assistant: Taylor Stockdale)

1. (2:00 PM, Invited) Okamoto: EFFECT OF PARTICLE DISTORTION ON SAXS FROM OBDDSTUDIED USING PARACRYSTALLINE THEORY AND SELF-CONSISTENT FIELD THEORY

2. (2:20 PM, Invited) Matsuo: MECHANICAL AND DIELECTRIC PROPERTY OF POLYMER-FILLER COMPOSITES IN TERMS OF THERMAL FLUCTUATION-INDUCED TUNNELING EF-FECT

3. (2:40 PM, Oral) Song: REVERSAL NANOIMPRINTING AND FERROELECTRIC PROPERTIESOF P(VDF-TRFE) COPOLYMER NANOSTRUCTURES ON FLEXIBLE PET SUBSTRATE

4. (3:00 PM, Oral) Hnatchuk: POLYCARBONATE AND POLYURETHANE NANO AND MICRO-HYBRID FOAMS

5. (3:20 PM, Oral) Park: CHARACTERIZATION OF CRYSTALLINE THERMOSETTING UREA-FORMALDEHYDE RESINS

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Thursday, May 14, 2015 Starting: 4:00 PMTH5_1: BIOT (Henzlik 124)Session Chair: Holger Schönherr (Assistant: John Jasa)

1. (4:00 PM, Keynote) Castano: ADVANCED NATURAL MATERIALS: FROM RICE HUSK TOAEROSPACE SYSTEMS

2. (4:40 PM, Invited) Thomas: ROLE OF NANOPARTICLES IN COMPATIBILIZING IMMISCIBLEPOLYMER BLENDS

3. (5:00 PM, Oral) Gnuse: MECHANICALLY ACCURATE NANOFIBROUS VASCULAR GRAFTMATERIALS

4. (5:20 PM, Oral) Laskar: EVALUATION OF POTENTIAL APPLICATION OF UNUSUAL POLY-MERSOMES PREPARED FROM PH-RESPONSIVE DUAL HYDROPHILIC BIOCOMPATIBLERANDOM COPOLYMERS

Thursday, May 14, 2015 Starting: 4:00 PMTH5_2: PMMS (Henzlik 53)Session Chair: Zheng Li (Assistant: Taylor Stockdale)

1. (4:00 PM, Keynote) Saiter: PHYSICAL AGEING AND COOPERATIVE RELAXATION INGLASSY POLYMERS

2. (4:40 PM, Oral) Hagg Lobland: BRITTLENESS OF POLYMERS AND THE RELATION TOTOUGHNESS

3. (5:00 PM, Oral) Li: CHARACTERIZATION OF STRAIN-INDUCED ELASTIC ANISOTROPY,EQUILIBRIUM STRESS, AND MODELING OF THE THERMAL-MECHANICAL RESPONSE OFPEEK

4. (5:20 PM, Oral) Xu: VISUALIZED POLYMER PROCESSING: FAST COLLOIDAL PARTICLEREDISTRIBUTION AT NON-PLANAR SOLIDIFICATION INTERFACE

Friday, May 15, 2015 Starting: 8:30 AMF1: Plenary (Auditorium)Session Chair: Lucia Fernandez-Ballester (Assistants: Marzieh Bakhtiary Noodeh, Mohammad NahidAndalib)

1. (8:30 AM, Plenary) Segalman: USING BIOINSPIRED POLYMERS TO EXPLORE THE ROLE OFSEQUENCE ON CONTROLLING POLYMER PROPERTIES

Friday, May 15, 2015 Starting: 9:40 AMF2_1: PS (Auditorium)Session Chairs: Jean-Marc Saiter, Nicolas Delpouve (Assistant: Mohammad Nahid Andalib)

1. (9:40 AM, Keynote) Grande: DESIGN, SYNTHESIS, AND CHARACTERIZATION OF FUNC-TIONAL DOUBLY POROUS CROSSLINKED POLYMERS

2. (10:20 AM, Keynote) López: A NEW METHOD TO MODIFY POLY(ARYLENE ETHERS) WITHA MILD SULFONATION AGENT

3. (11:00 AM, Invited) Fors: DETERMINISTIC CONTROL OF POLYMER MOLECULAR WEIGHTDISTRIBUTION

4. (11:20 AM, Oral) Neupane: CONVERSION OF PAPER WASTE INTO BIOPLASTICS (POLY-LACTIC ACID)

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5. (11:40 AM, Oral) Bhajiwala: MORPHOLOGICAL STUDY OF SPHERICAL MAGNESIUMDICHLORIDE SUPPORTED TI BASED ZIEGLER NATTA CATALYST SYSTEM

Friday, May 15, 2015 Starting: 9:40 AMF2_2: RSP/MPP (Heritage Room)Session Chairs: Joseph Turner, Lucia Fernandez-Ballester (Assistant: Ehsan Rezaei)

1. (9:40 AM, Invited) Schubert: BINARY AND TERNARY BLENDS OF POLYPROPYLENE TYPES-INFLUENCE ON THE HOMOGENEITY OF BIAXIAL ORIENTED FILMS

2. (10:00 AM, Oral) Chaganti: PLASTICIZED POLY (3-HYDROXYBUTYRATE): BIOBASED OLE-GOMERIC DIISOCYANATE AS A TOUGHENER

3. (10:20 AM, Oral) Li: THE DYNAMIC FRACTURE BEHAVIOR OF PMMA

4. (10:40 AM, Oral) Wojtczak: ALL-POLYMER FIBRILLAR NANOCOMPOSITES

5. (11:00 AM, Oral) Akram: SOL-GEL DERIVED ORGANIC/INORGANIC HYBRID NANOCOM-POSITES FROM VEGETABLE OILS AS SURFACE COATING MATERIALS

6. (11:20 AM, Oral) Lin: CONTRIBUTION OF COLLAGEN FIBER UNDULATION TO MECHANI-CAL PROPERTIES OF TYPE I COLLAGEN GEL

Friday, May 15, 2015 Starting: 1:00 PMF3: Awards and Closing SessionSession Chairs: Michael Hess, Jean-Marc Saiter, Jean-Jacques Pireaux, Mehrdad Negahban (As-sistants: Wenlong Li, Ramin Hosseinabad, Marzieh Bakhtiary Noodeh)

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Monday, May 11, 2015 Starting: 8:30 AMM1: Short Course (Auditorium)

Session Chairs: Michael Hess, Brett ForsAssistants: Wenlong Li, Jase Kaser

Talks:

1. (8:30 AM, Short Course) Menard: DYNAMIC MECHANICAL ANALYSIS

2. (9:25 AM, Short Course) Schubert: RHEOLOGY AND PROCESSING

3. (10:20 AM, Short Course) Schönherr: CHARACTERIZATION OF POLYMERIC NANOSTRUC-TURES WITH COMBINED SCANNING PROBE AND FLUORESCENCE MICROSCOPIES

4. (11:15 AM, Short Course) Henning: MICROMECHANICS OF POLYMERS: MICRO- ANDNANOSCOPIC PROCESSES OF DEFORMATION AND FRACTURE

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Talk Number: 1 (Short Course)Time: Monday, May 11, 2015 8:30 AM Session: M1: Short Course (Auditorium)

DYNAMIC MECHANICAL ANALYSIS

Kevin P. Menard1

1 Thermal Analysis, PerkinElmer, USA

Dynamic Mechanical Analysis is one of the most powerful tools for understanding materials. This classwill cover the basics of the technique and it’s applications to polymers. After discussing the basics of thetechnique and its most common use in the polymer industry, we will move on to more complex applications.The effects of frequency and strain on temperature scan, methods of kinetics, humidity, UV irradiation, andimmersion testing will be discussed.

Kevin P Menard recieved his PhD from the Wesleyan University and did post doctoral research atRensselaer Polytechnic Institute. He has worked for Fina Oil and Chemical, General Dynamics, andPerkinElmer EH, where he is the Product Manager for Thermal Analysis. He has over 125 publications, 17patents, and authored the book "Dynamic Mechanical Analysis: A Practical Introduction."

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RHEOLOGY AND PROCESSING

Dirk W. Schubert1

1 Material Science, Institute for Polymer Materials, Germany

An overview from fundamental point of view will be given describing materials flow behavior. Correspondingsimple differential equations will be derived and solved for special cases. Aspects on linearity will beexplained to answer the question “What is a linear material behavior?” Shear thinning and relevantequations will be discussed to understand viscosity. Selected processed will be discussed where viscosityplays the main role.

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CHARACTERIZATION OF POLYMERIC NANOSTRUCTURES WITH COMBINEDSCANNING PROBE AND FLUORESCENCE MICROSCOPIES

Holger Schönherr1

1 Department of Chemistry & Biology, Physical Chemistry I, University of Siegen, Germany

This short course module will introduce scanning probe microscopy for studying polymer morphologies. Inparticular, I will focus on the fundamental principles and the basic modes of atomic force microscopy (AFM),the differentiation of different phases present in polymers (amorphous vs. crystalline) and the determinationof local mechanical properties. The probing of polymeric nanostructures, such as tubes, particles and hollowvesicular containers, by AFM will be complemented by simultaneous fluorescence microscopic approaches,which shed light onto the local nanoscale surroundings of incorporated tracer dye molecules.

Holger Schönherr studied chemistry and polymer chemistry & physics at the Universities of Mainzand Toronto and finished his diploma thesis with Helmut Ringsdorf in 1995. He obtained his Ph.D. at theUniversity of Twente, The Netherlands in 1999, working with G. Julius Vancso. Following a postdoctoral stayat Stanford University with Curtis W. Frank he joined the MESA+ Institute for Nanotechnology in Twenteas assistant (later associate) professor before joining the University of Siegen in 2008 as a tenured UniversityProfessor in Physical Chemistry. He was awarded among others with the Raphael-Eduard-Liesegang awardof the German Colloid Society (2011), the International POLYCHAR Materials Science Prize (2013) andthe Research Prize of the Faculty of Science and Engineering of the University of Siegen (2013). His researchinterests comprise the chemistry and physics of biointerfaces, self-assembled and nanostructured polymersystems, and surface analysis with atomic force microscopy. He is author of more than 170 papers in peerreviewed journals and published in the Springer Laboratory series a book on “Scanning Force Microscopy ofPolymers” (Holger Schönherr, G. Julius Vancso, 2010, Springer, Vienna).

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MICROMECHANICS OF POLYMERS: MICRO- AND NANOSCOPIC PROCESSESOF DEFORMATION AND FRACTURE

Sven Henning1

1 Biological and Macromolecular Materials, Fraunhofer Institute for Mechanics of Materials, Germany

The main aims of micromechanical analyses are the identification of property determining micro- andnanostructures and the description of the principal deformation phenomena that occur when mechanicalload is applied to the material, as there are, for instance, crazing, homogeneous deformation, shearband formation, micro- and nanovoid formation, fibrillation, etc. These processes can be correlated toa brittle, semiductile or ductile material behavior on the macroscopic scale. In that sense, the descrip-tion of micromechanical phenomena can contribute to the formulation of material laws predicting theresponse of a material to mechanical load. Micromechanical processes are the link between the morphology(predicted by synthesis, composition, and processing), loading conditions and resulting mechanical properties.

There are a number of different micromechanical techniques that can be adapted with respect to theactual problem. First of all, there are micromechanical in situ methods characterized by the application oftensile load, compressive or bending force using miniaturized testing devices inside the TEM, (E)SEM orAFM. Alternatively, microscopic analyses of deformation zones can be performed after mechanical testing exsitu with correlation to actual states of deformation. That approach also includes the inspection of fracturesurfaces and, to some extent, problems of failure analysis. Thirdly, micromechanical techniques also includethe application of miniaturized mechanical testing devices for small samples (e.g., micro-parts, biologicalsamples, nanofibers) or for mechanical testing of small amounts of materials from new syntheses. Finally,the micromechanical approach allows the measurement of local mechanical properties in microscopic regionsof interest.

The presentation also covers different preparation routes with a special emphasis on preparation bymeans of (cryo-)ultramicrotomy. The advantages of the different techniques are illustrated by a number ofexamples covering semicrystalline polymers, block copolymers, composites and nanocomposites with differentfiller geometries (particles, layered structures, carbon nanotubes) and biological/biomedical materials (bone,electrospun nanofibers).

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Monday, May 11, 2015 Starting: 1:00 PMM2: Short Course (Auditorium)

Session Chairs: Kevin P. Menard, Sven HenningAssistants: Marzieh Bakhtiary Noodeh, Mitchell Schmidt

Talks:

1. (1:00 PM, Short Course) Saiter: GLASS TRANSITION AND GLASS TRANSITION TEMPERA-TURE

2. (1:55 PM, Short Course) Blümich: SOLID-STATE NMR

3. (2:50 PM, Short Course)Guenet: BASICS OF SCATTERING TECHNIQUES: X-RAY, NEUTRONS,LIGHT

4. (3:45 PM, Short Course) Fors: PHOTOCHEMISTRY IN POLYMER SCIENCE

5. (4:40 PM, Short Course)Hnatchuk: FRICTION, WEAR AND SCRATCH RESISTANCE OF POLY-MERS

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Talk Number: 1 (Short Course)Time: Monday, May 11, 2015 1:00 PM Session: M2: Short Course (Auditorium)

GLASS TRANSITION AND GLASS TRANSITION TEMPERATURE

Jean-Marc Saiter1

1 Institut des Matériaux de Rouen, Universite de Rouen, France

We will look at the glass transition. When a liquid is cooled, a vitreous structure can be obtained if thecooling conditions (mainly the value of the cooling rate) are not compatible with the kinetic conditions toget a crystal. The temperature for which a transition between the liquid and the glassy materials occursis called the glass transition temperature. This glass transition temperature is not a material constant,because the glass transition does not separate two steady states that the material could reach by changingonly the temperature or the pressure. In other words the glass transition is not a thermodynamic transition.This particularity is also associated with the structural disorder that is frozen in at Tg.

We will consider the conditions that result in a glass, and then provide a description of a disorderedstructure, considering the consequence of structural disorder on the physical behavior of such materials. Wewill look at how the glass transition temperature can be correctly determined, what method can be used forthis evaluation, and the common errors that are generally made. We will conclude by looking at examplesof signals obtained by means of calorimetry so that students can have an idea of what to expect when doingsuch measurements.

Professor Saiter is Professor Exceptional Class and the Director of the Institute of Materials Re-search at the University of Rouen, Rouen, France. He has over 200 journal publications, and has beenone of the active members of the PolyChar Conference. He also is the founding member of the AdvancedMechanics and Materials Engineering International Laboratory and the first French Director.

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SOLID-STATE NMR

Bernhard Blümich1

1 Institut fuer Technische und Makromolekulare Chemie, RWTH Aachen University, Germany

Nuclear Magnetic Resonance (NMR) is one of the most powerful techniques to characterize materials andmolecules. While most other forms of spectroscopy probe electrons, NMR probes nuclei and takes a lookat matter from the inside of molecules. Since molecular motion in solids is slow, the chemical informationis obscured by anisotropic magnetic interactions between nuclei, leaving NMR relaxation and moleculardiffusion as the most simple NMR tools to characterize the physical properties of polymers. These quantitiescan be measured with far more simple instrumentation than needed for chemical analysis. The course givesan introduction to NMR with special emphasis on relaxation and diffusion measurements with compactinstrumentation drawing on applications to polymer morphology and aging. It will conclude with an outlookon desktop NMR spectroscopy for chemical analysis of polymer solutions.

ReferenceB. Blümich, S. Haber-Pohlmeier, W. Zia, Compact NMR, de Gruyter, Berlin, 2014

Prof. Blümich is Chair of Macromolecular Chemistry at RWTH Aachen University. He received hiseducation in Physics at the Technical University in Berlin and at Rensselaer Polytechnic Institute in Troy,N.Y. His research activities aim at understanding the macroscopic properties of advanced polymer andfunctional porous materials by NMR on a microscopic and molecular basis. To this end he develops andapplies NMR methods for NMR spectroscopy of liquids and solids, NMR imaging of heterogeneous materialsand fluid flow, and measurements of NMR relaxation and diffusion. Bernhard Blümich has pioneered anumber of methodical innovations concerning multidimensional NMR spectroscopy with noise excitation,1D and 2D methods of studying molecular motion in solids, solid sate imaging, and flow NMR. A growingfocus in his recent work is the development of magnets for compact NMR such as the NMR-MOUSE fornon-destructive materials testing and permanent magnets with homogeneous fields for chemical analysis by1H NMR spectroscopy under the fume hood. His publication record includes over 400 papers, 3 monographsand number of patents.

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BASICS OF SCATTERING TECHNIQUES: X-RAY, NEUTRONS, LIGHT

Jean-Michel Guenet1

1 Institut Charles Sadron, CNRS-Université de Strasbourg, France

In this short lecture we will present some basic knowledge about small-angle scattering techniques used inthe study of the structure of matter. Three types of radiations will be discussed as the basic principles fordescribing molecular structures are the same. They, however, do not necessarily interact with matter in thesame way. X-ray and light are both composed of photons and interact therefore with the electron clouds,yet the 3-order of magnitude discrepancy in wavelength makes that the correlations investigated, namelydistances explored in a sample, range from 1000-100 nm in the case of light down to 10-1 nm in the case ofX-rays. Conversely, neutron is a quantum particle with a given wavelength so that it behaves as X-ray andlight but interacts with the atomic nucleus instead. This allows one to toy with the so-called “contrast factor”in order to differentiate the various molecular structures present in a sample. Typical scattering sets-upwill be presented so as to provide some details about the experimental aspects. Various models of struc-tures of polymers and self-assembled systems will be described together with available experimental examples.

Professor Jean-Michel Guenet is the Director of ICS and the Head of Institute Charles Sadron (200employees) at CNR-University of Strasbourg. Dr. Guenet received his master from Paris XIII Universityand his Ph.D. from Strasbourg University. He is the author of over 170 peer-reviewed journal articles andthree books. He received the Dillon medal of the American Physical Society in 1990. Dr. Guenet hasgiven over 70 invited talked at international symposia and has been a visiting professor at Mons-HainautUniversity, Belgium, and Shizuoka University, Japan.

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PHOTOCHEMISTRY IN POLYMER SCIENCE

Brett Fors1

1 Department of Chemistry and Chemical Biology, Cornell University, USA

Having precise control over a polymer’s architecture and composition enables tuning of its function andallows the development of new technologies. Light has proven to be a highly unique reagent in polymersynthesis that can give both spatial and temporal control over polymerization and give rise to the formationof a diverse set of structures. On this basis, photochemistry in polymer science has seen significant attentionand been used for an array of applications. This short course will look at some of the important advancesin photomediated polymerizations over the last two decades, examine new developments in this field, andassess its future promise in materials science.

Brett P. Fors was born in Polson, Montana and carried out his undergraduate studies in chemistryat Montana State University (B.S., 2006). He went on to do his Ph.D. (2011) at the Massachusetts Instituteof Technology with Professor Stephen L. Buchwald, where he worked on the development and applicationsof Pd catalysts for C-N cross-coupling reactions. After his doctoral studies he became an Elings Fellow atthe University of California, Santa Barbara working with Professor Craig J. Hawker on new polymerizationtechniques that can be effectively regulated with light. In the summer of 2014 he joined the faculty at Cor-nell University and is currently an Assistant Professor in the Department of Chemistry and Chemical Biology.

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FRICTION, WEAR AND SCRATCH RESISTANCE OF POLYMERS

Witold Brostow1,2, Nathalie Hnatchuk1,2

1 Department of Materials Science and Engineering and Department of Physics, University of North Texas,USA2 International Council on Materials Education, University of North Texas, USA

Industry worldwide suffers huge losses every year because of a need to replace moving parts and elementsof structure as a consequence of wear. In this respect wear is similar to corrosion, but wear concerns allmoving parts while corrosion ‘attacks’ only some metals. The first step to mitigating wear is understandingtribology = the science and engineering of interacting surfaces in relative motion.

Important experimental techniques of determination of tribological properties include: determinationof static and dynamic friction with a ‘universal’ mechanical testing machine; determination of scratchresistance and sliding wear; pin-on-disk tribometry and profilometry for determination of dynamic frictionand wear and also of roughness.

Methods of mitigating wear used for metals cannot be used for polymers and polymer-based materi-als (PBMs). For metal parts one uses external lubricants; such lubricants are likely to be absorbed bypolymers, resulting in swelling and jamming of moving parts. However, methods of mitigating wear inPBMs exist and will be discussed also.

Recommended reading: W. Brostow, V. Kovacevic, D. Vrsaljko & J. Whitworth, Tribology of poly-mers and polymer-based composites, J. Mater. Ed. 2010, 32, 273.

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Tuesday, May 12, 2015 Starting: 8:20 AMT0: Opening (Auditorium)

Session Chair: Mehrdad NegahbanAssistants: Wenlong Li, John J. Bowen

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Tuesday, May 12, 2015 Starting: 8:45 AMT1: Plenary (Auditorium)

Session Chair: Jinsong HuangAssistants: Wenlong Li, John J. Bowen

Talk:

1. (8:45 AM, Plenary) Ade: SOFT X-RAY CHARACTERIZATION METHODS: UTILITY AND OP-PORTUNITY

Dr. Harald Ade, Distinguished Professor of Physics, North Carolina State University

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Talk Number: 1 (Plenary)Time: Tuesday, May 12, 2015 8:45 AM Session: T1: Plenary (Auditorium)

SOFT X-RAY CHARACTERIZATION METHODS: UTILITY AND OPPORTUNITY

Harald Ade1

1 Physics, North Carolina State University, U.S.A

Soft X-rays provide unique advantages to characterize systems with high spatial resolution, high composi-tional and bond-orientation sensitivity, with relatively little radiation damage. We will trace key developmentsteps in microscopy and scattering and exemplify the applications in a broad range of fields with a focuson application to characterize bulk heterojunction (BHJ) organic photovoltaics (OPVs). In these deviceselectron donating and electron accepting materials form a complex network of discrete and distributedheterointerfaces and charge transport pathways in the photoactive layer where critical photo-physicalprocesses occur. However, we have insufficient knowledge about the structural properties of these interfacesdue to their 3-dimensional arrangement and the paucity of techniques to measure local order and purity.Synchrotron radiation based soft x-ray methods can uniquely measure critical structural parameters, whichincludes molecular orientation correlations relative to donor/acceptor heterojunctions [1]. Using polarizedresonant soft X-ray scattering [2], the degree of molecular orientation, an order parameter that describesface-on (+1) or edge-on orientation (-1) relative to these discrete heterointerfaces, can be determined. Bymanipulating the degree of molecular orientation through choice of molecular chemistry and processingsolvent characteristics, the importance of this structural parameter on the performance of BHJ OPV devicesand charge transfer dynamics can be demonstrated. We will furthermore show how compositional variationscan be related to polymer crystal size [3] and how mobility and purity can relate to charge extraction andthus in turn to device performance [4,5]. A complete description of actual morphologies and theoreticalmodeling yet to be developed for OPVs will have to take these factors into account. Devices with efficienciesup to 10.8% will be discussed [6]. Complementary applications to milk, helical nanofibrillar liquid crystals,block copolymers and membranes will also be exemplified. Future plans and opportunities to improve envi-ronmental sample control, extend the energy range, and ptychography at the few nm level [7] will be discussed

1. J. R. Tumbleston et al., Nature Photonics 8, 386 (2014).2. B. A. Collins et al., Nat. Mater. 11, 536 (2012).3. W. Ma at al, Advanced Materials 26, 4234 (2014)4. S. Albrecht et al. J. Physical Chemistry Letters 5, 1131-1138 (2014).5. W. Liu et al., J. Am. Chem. Soc. 136, 15566-15576 (2014).6. Y. Liu et al., Nature Communications 5, 5293 (2014)7. D. Shapiro et al., Nature Photonics 8, 765-769 (2014)

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Tuesday, May 12, 2015 Starting: 10:00 AMT2_1: CMSP (Heritage Room)Session Chair: Bernhard Blümich

Assistant: John J. Bowen

Talks:

1. (10:00 AM, Keynote) Guenet: CHARACTERIZATION AND PROPERTIES OF HYBRID MATE-RIALS FROM POLYMERS AND SELF-ASSEMBLED SYSTEMS

2. (10:40 AM, Oral) Dargent: RELAXATION PROCESSES AND COOPERATIVITY IN COPOLY-MERS WITH A SIMILAR BACKBONE FLEXIBILITY

3. (11:00 AM, Oral) Pireaux: UNDERSTANDING (INDUCING, REPAIRING) ION BEAM DAMAGESIN POLYMERS - A POLYCHAR CONCERN

4. (11:20 AM, Oral) Delpouve: COUPLING APPROACHES FOR THE INVESTIGATION OF THEALPHA RELAXATION DYNAMICS IN INTERACTING NETWORKS

5. (11:40 AM, Oral) Adhikari: MORPHOLOGICAL, THERMAL AND ELECTRICAL PROPERTIESOF STYRENIC BLOCK COPOLYMER COMPOSITES WITH NANOCARBONS

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Talk Number: 1 (Keynote)Time: Tuesday, May 12, 2015 10:00 AM Session: T2_1: CMSP (Heritage Room)

CHARACTERIZATION AND PROPERTIES OF HYBRID MATERIALS FROMPOLYMERS AND SELF-ASSEMBLED SYSTEMS

Jean-Michel Guenet1

1 CNRS, Institut Charles Sadron, France

In this talk three types of hybrid materials made up from covalent polymers and self-assembling systemswill be presented. In all cases the formation of these hybrid materials is achieved through physical processes(heterogeneous nucleation, gelation, self-assembling).

Three cases will be reviewed and discussed: encapsulation of self-assembled filaments in polymer fib-rils, intermingled gels, sheathed of polymer fibrils with self-assembling molecules. The polymers used areisotactic polystyrene and syndiotactic polystyrene, and the self-assembling materials are bicopper-2-éthylehexanoatecomplex, OPV (oligo phenylene vinylene)and (3,5-Bis-(5-hexylcarbamoylpentyloxy)-benzoic aciddecyl ester) together with its decyl ester fluorinated counterpart.

Results on the formation thermodynamics as observed by DSC, the morphology as determined byAFM, some properties (magnetic) by SQUID, and the molecular structure as obtained by SANS, SAXSand EXAFS will be presented and discussed. All the experimental results show that a high degree ofcompatibility exists between all the components thus allowing one to prepare materials where one componentis finely dispersed within the other. The potential applications of these three systems will also be discussed.

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Talk Number: 2 (Oral)Time: Tuesday, May 12, 2015 10:40 AM Session: T2_1: CMSP (Heritage Room)

RELAXATION PROCESSES AND COOPERATIVITY IN COPOLYMERS WITH ASIMILAR BACKBONE FLEXIBILITY

Jorge A. Soto-Puente1,2, Bidur Rijal1, Laurent Delbreilh1, Kateryna Fatyeyeva2, Allison Saiter1,Eric Dargent1

1 AMME-LECAP EA 4528 International Laboratory, Normandie Université, France2 Laboratoire PBS, Normandie Université, France

The glass transition in polymeric materials is characterized by a temperature dependence of the segmentalrelaxation time close to Tg. The deviation of this dependence from an Arrhenius behavior could be quantifiedwith fragility [1].

Several approaches have been proposed to explain the correlation between the fragility and the coop-erative molecular mobility near to Tg [2,3]. Then, the concept of cooperative rearranging region (CRR) wasintroduced by Donth and defined as the smallest amorphous domain where conformational rearrangementphenomena can occur without causing rearrangements in the surrounding [4].

The poly (vinyl acetate) (PVAc) and its random ethylene copolymers, so-called poly (ethylene-co-vinyl acetate) (EVA) with a content of vinyl acetate (VAc) higher than 40 wt.% are completely amorphousmaterials [5]. As a consequence of the ethylene content increasing, the dipole-dipole interactions betweenthe polymer chains are expected to decrease. Generally, the published works correlate the fragility withthe chemical backbone stiffness [6]. The aim of this work is to correlate the fragility with the amplitude ofcooperative motions, by decreasing the dipole-dipole interactions (through the VAc content modification)and without changing the flexibility of the main chemical backbone. For this goal MT-DSC and broadbanddielectric spectroscopy measurements have been performed.

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UNDERSTANDING (INDUCING, REPAIRING) ION BEAM DAMAGES IN POLY-MERS - A POLYCHAR CONCERN

Jean-Jacques Pireaux1, Laurent Nittler1

1 Research Center in Physics of Matter and Radiation (PMR), University of Namur, Belgium

Different spectroscopies are available to characterize the elemental, chemical and molecular compositionof polymer materials in the bulk or micrometer range (IR, NMR...) and other ones to study surfaces andinterfaces in the nanometer range (XPS, ToF-SIMS...). For the latter subject, when it comes to analyzeand remove extreme surface contamination -as this may become extremely relevant for adhesion studies orbiocompatibilization properties-, one is generally using a soft ion beam or a plasma process to etch away thecontamination layer. In order to study thicker layers, Ar+ monoatomic ion beam etching appeared as thebest method to be used up to now , even if it is known that such monoatomic ion beams are inducing a lotof chemical and structural damages in the studied layer.

In the last few years, Argon ion cluster beams (Arn+) have been proven a very efficient method toetch away almost any kind of organic/polymer layer, practically without inducing any defect in the studiedlayer. In the present work, we propose to study with X-Ray Photoelectron Spectroscopy (XPS) and SRIMmodelling the use of such Arn+ beams in order to: (a) clean the surface of a PMMA layer, (b) to study thedamages induced by a monoatomic Ar+ beam (depending on the beam energy), and(c) remove those Ar+ -induced damages.

At the end, it will appear that Argon ion cluster beams (Arn+) are a good tool for healing a poly-mer surface of chemical and structural defects. We will show that, for a given cluster energy, there is aquite natural linear relation between the monoatomic ion beam damaged volume, and the fluence of ionclusters necessary to remove these damages. This suggests that the Arn+ erosion mechanism is in a firstapproximation mechanically driven.

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COUPLING APPROACHES FOR THE INVESTIGATION OF THE ALPHA RELAX-ATION DYNAMICS IN INTERACTING NETWORKS

Nicolas Delpouve1, Steven Araujo1, Wenlong Li2, Florian Batteux1, Li Tan2, Mehrdad Negahban2, Jean-MarcSaiter1

1 AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France2 AMME-A-TEAM, Department of Mechanical &Materials Engineering, University of Nebraska-Lincoln,Lincoln NE, USA

To date a wide number of models and theories have been developed in attempt to describe the moleculardynamics around the glass transition temperature and all assume that the molecular motions at thealpha-relaxation process are cooperative. Adam and Gibbs [1] first proposed the concept of cooperativerearranging region (CRR) defined as the smallest subsystem which, upon a sufficient thermal fluctuation,can undergo a conformational rearrangement independently of its environment. One of the challengesassociated to the relaxation investigation is to calculate the CRR size by means of experimental techniques.The approach of Donth [2] is a powerful empiric approach to investigate the CRR size since it relatesthe cooperativity volume to the fluctuation of the glass transition temperature directly obtained fromcalorimetric techniques. Many works refer to this approach to describe the molecular dynamics of theamorphous phase in polymeric systems at the glass transition [3,4] and in the liquid like state [5]. It ismoreover assumed that the cooperativity calculated from the equation of Donth depicts the level of weakinteractions in a material [6,7]. For some systems however, especially those exhibiting a very broad glasstransition, the strict use of Donth’s equation can lead to dramatically low values for the cooperativitylength. Another issue lies in the arbitrary determination of “the relaxing unit” which is particularly complexin crosslinked materials. In this work we propose to investigate a particular case combining these twomajor drawbacks: the reciprocal influence between two networks in terms of molecular dynamics in aninterpenetrating system. We will present our current challenges and the opportunities offered from couplingapproaches.

(1) Adam, G.; Gibbs, J. H. J. Chem. Phys. 2004, 43, 139-146.(2) Donth, E. J. Non-Cryst. Solids 1982, 53, 325-330.(3) Furushima, Y.; Ishikiriyama, K.; Higashioji, T. Polymer 2013, 54, 4078-4084.(4) Delpouve, N.; Delbreilh, L.; Stoclet, G.; Saiter, A.; Dargent, E. Macromolecules 2014, 47, 5186-5197.(5) Saiter, A.; Delbreilh, L.; Couderc, H.; Arabeche, K.; Schönhals, A.; Saiter, J.-M. Phys. Rev. E 2010, 81,041805.(6) Nakanishi, M.; Nozaki, R. Phys. Rev. E 2011, 84.(7) Paluch, M.; Pawlus, S.; Grzybowski, A.; Grzybowska, K.; Włodarczyk, P.; Zioło, J. Phys. Rev. E 2011,84, 052501.

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MORPHOLOGICAL, THERMAL AND ELECTRICAL PROPERTIES OF STYRENICBLOCK COPOLYMER COMPOSITES WITH NANOCARBONS

Rameshwar Adhikari1, Surendra Kumar Gautam2, Marco Liebscher3, Sven Henning4, Hai Hong Le3, RalfLach5, Wolfgang Grellmann5, Amit Das3, Gert Heinrich3

1 Central Department of Chemistry, Tribhuvan University, Nepal2 Department of Chemistry, Tri-Chandra Campus, Tribhuvan University, Kathmandu, Nepal3 Leibnitz Institute of Polymer Research, Dresden, Germany4 Fraunhofer Institute for Mechanics of Materials, Halle/Saale, Germany5 Center of Engineering, Martin Luther University Halle-Wittenberg, Germany

Styrenic block copolymers having different molecular architectures were compounded with multiwalledcarbon nanotubes and nanodiamond with the objectives of preparing composites with desired electricaland thermal conductivities. Melt mixing using microcompounder followed by compression molding allowedthe formation of nanocomopostes with well disperse nanofillers into the polymer matrix. The materialswere characterized with different microscopic, techniques, X-ray diffraction, microindentation hardnessmeasurement, and tensile testing, It was found that the matrix with co-continuous morphology is favors theformation electrically conducting polymers. The composites showed significant improvement in mechanicalproperties at low filler content. The observed properties of nanocomposites will be discussed in correlationwith block copolymer architecture, processing methods and observed morphology.

Keywords: block copolymer, polymer nanocompostes, electron microscopy, microhardness

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Tuesday, May 12, 2015 Starting: 10:00 AMT2_2: PEOD (Auditorium)Session Chair: Jinsong Huang

Assistant: Wenlong Li

Talks:

1. (10:00 AM, Invited) Ouyang: PEDOT:PSS FOR PEROVSKITE SOLAR CELLS

2. (10:20 AM, Invited) Xiao: UNDERSTANDING THE EFFECT OF DEUTERATED CONDUCT-ING POLYMER AND SOLVENT ADDITIVE ON THE PERFORMANCE OF ORGANIC PHOTO-VOLTAICS

3. (10:40 AM, Oral) Ulanski: OTFTS WITH ULTRATHIN LAYERS OF POLY(3-HEXYLTIOPHENE)

4. (11:00 AM, Oral) Xiao: UNIVERSAL FORMATION OF COMPOSITIONALLY GRADED BULKHETEROJUNCTION FOR EFFICIENCY ENHANCEMENT IN ORGANIC PHOTOVOLTAICS

5. (11:20 AM, Oral) Jo: CONDUCTING POLYMER/GRAPHENE COMPOSITE FOR SUPERCAPAC-ITOR

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Talk Number: 1 (Invited)Time: Tuesday, May 12, 2015 10:00 AM Session: T2_2: PEOD (Auditorium)

PEDOT:PSS FOR PEROVSKITE SOLAR CELLS

Kuan Sun1, Yijie Xia1, Jianyong Ouyang1

1 Department of Materials Science & Engineering, National University of Singapore, Singapore

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is the most successful conductingpolymer in terms of practical application. PEDOT:PSS can be dispersed in water and some polar organicsolvents. High-quality PEDOT:PSS films can be readily prepared by solution processing techniques, such ascoating and printing. PEDOT:PSS has high transparency in visible range and good thermal stability. Highlyconductive PEDOT:PSS can replace transparent conductive oxide as the transparent electrode of optoelec-tronic devices, while less conductive PEDOT:PSS can be used as the buffer layer. Here, I will present ourstudy on the application of highly conductive PEDOT:PSS as the transparent electrode of perovskite solarcells and the effects of perovskite precursors and solvents on the properties of PEDOT:PSS.

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Talk Number: 2 (Invited)Time: Tuesday, May 12, 2015 10:20 AM Session: T2_2: PEOD (Auditorium)

UNDERSTANDING THE EFFECT OF DEUTERATED CONDUCTING POLYMERAND SOLVENT ADDITIVE ON THE PERFORMANCE OF ORGANIC PHOTO-VOLTAICS

Kai Xiao1, Ming Shao1, Jong Keum1, Kunlun Hong1, Jim Browning2, Jihua Chen1, Wei Chen3, JacekJakowski1, Bobby Sumpter1, David Geohegan1

1 Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, USA2 Neutron Scattering Science Divisions, Oak Ridge National Laboratory, USA3 Material Sciences Division, Argonne National Laboratory, USA

The desired physical and optoelectronic properties of conjugated polymers strongly depend on the molecularstructure and film morphology. Therefore, understanding the structure-property-performance relationshipis crucial to the development of high performance organic electronic devices. Here, I will first reporta systematic study of the isotopic effects of deuterium substitution on the structure, morphology andoptoelectronic properties of regioregular poly(3-hexylthiophene)s (P3HT) with an integrated approachthat combines the synthesis of deuterated materials, optoelectronic properties measurements, theoreticalsimulation and neutron scattering. Interestingly, selective substitution of deuterium on the backbone or sidechains of P3HT contributes differently to the photovoltaic characteristic. Secondly, adding solvent additivehas been demonstrated to be an effective method to optimize the bulk heterojunction morphology, andimprove the efficiency of OPV. However, the key information of the nano-structural evolution occurring inthe transformation from casting solution to thin photoactive film is still lacking. We investigate the effects ofthe processing additive diiodooctane (DIO) on the morphology of high efficient PBDTTT-C-T:PCBM OPV,starting in the casting solution and tracing the effects in the spun-cast thin films. Our results reveal that DIOhas no observable effect on the structure of polymer donor and aggregation of fullerene acceptors in solution,however in the spun-cast films, it significantly promotes their molecular ordering and phase separation.Moreover, thermodynamic analysis provides a rationale for the effects of DIO on different characteristicsof phase segregation. Such information will guide the design of ternary blends to improved efficiency for OPVs.

This research was conducted at the Center for Nanophase Materials Sciences and the Spallation Neu-tron Source, which are sponsored at Oak Ridge National Laboratory by the Division of Scientific UserFacilities, U.S. Department of Energy.

[1] M. Shao, J. Keum, J. Chen, Y. He, W. Chen, J. F. Browning, J. Jakowski, B. G. Sumpter, I. N.Ivanov, Y. Ma, C. M. Rouleau, S. C. Smith, D. B. Geohegan, K. Hong, K. Xiao, Nature Comm. 5, 4180(2014).[2] M. Shao, J. K. Keum, R. Kumar, J. Chen, J. F. Browning, S. Das, W. Chen, J. Hou, C. Do, K. C.Littrell, A. Rondinone, D. B. Geohegan, B. G. Sumpter, K. Xiao, Adv. Funct. Mater., 24, 6467 (2014)

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Talk Number: 3 (Oral)Time: Tuesday, May 12, 2015 10:40 AM Session: T2_2: PEOD (Auditorium)

OTFTS WITH ULTRATHIN LAYERS OF POLY(3-HEXYLTIOPHENE)

Izabela Tszydel1, Lukasz Janasz1, Remigiusz Grykien1, Beata Luszczynska1, Tomasz Makowski2,Jacek Ulanski1

1 Department of Molecular Physics, Technical University of Lodz, Poland2 Department of Polymer Physics, Centre of Molecular and Macromolecular Studies of Polish Academy ofSciences, Poland

Flexible Organic Large Area Electronics (FOLAE) is quickly emerging technology offering possibility ofmass production of cheap and flexible electronic devices by using different printing techniques. Solutionprocessable conjugated polymers are main class of organic semiconductors suitable for FOLAE applicationsand Organic Thin Film Transistors (OTFTs) are basic building units of any electronic devices, therefore tran-sistors based on conjugated polymers are subjects of intensive investigations since many years. It is known,that in the OTFT the charge carrier transport occurs in few monolayers near the semiconductor/dielectricinterface, however there are only scares published data for OTFTs with ultra-thin semiconducting polymerlayers obtained by solution-based methods.

In our studies we have focused on determination of relationship between morphology of the very firstlayers of the conjugated polymer and performance of the OTFT. As a model conjugated polymer we havechosen the regioregular poly(3-hexyltiophene) (P3HT) with different molecular weights and with narrowmolecular weight distributions. Regioregular P3HT is well known p-type semi-crystalline polymer consistingof a π-conjugated backbone with head-to-tail arrangement of the thiophene units bearing pendent alkylside groups. We have found that by changing the conditions of processing (type of solvent, concentrationof the solution, speed of spin-coating, post-treatment annealing) one can get ultrathin layers with differentmorphology. These differences are reflected in different performances of the OTFTs, and in particular thecharge carrier mobility, as determined from the transistor characteristics, is very sensitive to morphology ofthe few first monolayers of P3HT.

Acknowledgements: This work was supported by grant 2013/08/M/ST5/00914 of the Polish NationalScience Centre and by grant Master9./2014 of the Foundation for Polish Science.

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UNIVERSAL FORMATION OF COMPOSITIONALLY GRADED BULK HET-EROJUNCTION FOR EFFICIENCY ENHANCEMENT IN ORGANIC PHOTO-VOLTAICS

Zhengguo Xiao1, Jinsong Huang1

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA

All of the current efficient organic photovoltaic devices have a bulk heterojunction (BHJ) structure. RegularBHJ films, formed from randomly mixed donors and acceptors in solution, inevitably have many breaksand dead ends, and have uniform distribution of donors and acceptors along the vertical direction whichdoes not match the gradient electron and hole current across the films. The nonideal morphologies in-evitably cause the charge recombination both in the BHJ films and at the metal/organic interface, in formsof geminate recombination, or bimolecular recombination. Compositionally graded BHJ films, donor en-riched at the anode and acceptor enriched at the cathode side, were proposed to facilitate the charge ex-traction and to reduce charge recombination in several highly efficient OPVs. However, the graded BHJswith preferred composition profiles were only observed in a few high efficiency material systems which re-quire special substrate surfaces and suitable surface energy differences between donors and acceptors forits formation. Here we report a universal method to form the compositionally graded BHJ using a sim-ple solvent-fluxing treatment of the wet BHJ films, in which the fluxing solvent brings the additives, aswell as fullerene-derivatives, toward the film surface. The graded BHJ significantly reduces bimolecu-lar charge recombination. The fluxing process also resulted in more uniform nanodomain distribution inthe plane of the films and higher charge carrier mobilities. An efficiency enhancement of 15∼50%, withhighest efficiency of 8.6% for poly[4,8-bis-(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl]-alt-[2-(2’-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl] (PBDTTT-C-T):C71-butyric acid methyl ester(PC70BM) system, was achieved for all of the solution-processed BHJ systems studied compared to thosedevices with regular BHJ films.

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CONDUCTING POLYMER/GRAPHENE COMPOSITE FOR SUPERCAPACITOR

Won Ho Jo1, Kyung Tae Kim1, Jin Woo Lee1

1 Dept of Materials Science and Engineering, Seoul National University, Korea

A water-soluble conducting polymer, poly(styrene sulfonic acid)-graft-polyaniline (PSSA-g-PANI), was syn-thesized and used to directly exfoliate graphite into graphene layers in aqueous media, because PANI inPSSA-g-PANI is strongly physisorbed onto graphene surface via strong interaction while PSSA in PSSA-g-PANI enhances water solubility. Hence, PSSA-g-PANI is expected to exfoliate directly graphite into graphenelayers and thus to disperse effectively the layers in aqueous media. As a consequence, PSSA-g-PANI/graphenecomposite films are easily fabricated by a solution process and used for supercapacitor electrode. The ca-pacitances of the composites depend upon the length and composition of PANI in PSSA-g-PANI. When thecapacitances of the composites with different PSSA-g-PANIs (different ratio of aniline (ANI) to styrene sul-fonic acid (SSA) in polymer) were measured by cyclic voltammetry, the composite with the ratio of ANI/SSA(50/50) in PSSA-g-PANI exhibits the highest specific capacitance of 480 F/g and 1449 F/g when the ca-pacitance was measured by cyclic voltammetry at a scan rate of 50 mV/s and Galvano curves at a currentdensity of 1 A/g, respectively, which are among the highest values of EDLC type supercapacitor, and thecomposite also shows superior cycle life with 90% retention of the initial specific capacitance after 1000 cyclesas compared to pseudo supercapacitor.

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Tuesday, May 12, 2015 Starting: 12:50 PMT3: Young Pleanary (Auditorium)

Session Chair: Lucia Fernandez-BallesterAssistants: Ramin Hosseinabad, Mitchell Schmidt

Talk:

1. (12:50 PM, Young Plenary) Stein: GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING:PRINCIPLES, MODELS, AND APPLICATIONS FOR NANOSTRUCTURED THIN FILMS

Dr. Gila Stein, Ernest J. and Barbara M. Henley Assistant Professor of Chemical and BiomolecularEngineering, University of Houston

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Talk Number: 1 (Young Plenary)Time: Tuesday, May 12, 2015 12:50 PM Session: T3: Young Pleanary (Auditorium)

GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING: PRINCIPLES,MODELS, AND APPLICATIONS FOR NANOSTRUCTURED THIN FILMS

Gila Stein1

1 Chemical and Biomolecular Engineering, University of Houston, USA

Grazing incidence small-angle X-ray scattering (GISAXS) is an emerging method for quantitative characteri-zation of nanostructured polymer films. This reflection-mode technique illuminates the sample with a shallowincidence angle and records off-specular scattering with an area detector. Analyzing these data is non-trivial,as models must include refraction corrections and account for multiple scattering events. In this talk, I willprovide an overview of the GISAXS experiment, and then discuss qualitative and quantitative approachesfor interpreting the data. I will present two case studies that illustrate how GISAXS measurements candetect confinement-induced behavior in block copolymer thin films: First, I will show that GISAXS detectscomplex symmetry transitions in thin films of spherical-domain block copolymers. These transitions (fromhexagonal to face-centered orthorhombic to body-centered cubic) are driven by packing frustration in theconfined geometry, and the equilibrium symmetry depends on the thickness of the film. Second, I willdiscuss domain orientations in thin films of lamellar copolymers on “nearly-neutral” substrates. Throughdetailed analysis of GISAXS data, we show that lamellae can bend near the bottom of the film. The extentof these deformations is controlled by preferential interactions with the underlying substrate, as well as thethickness of the film, and such defects have important implications for semiconductor manufacturing basedon block copolymer lithography.

About the speaker: Gila Stein earned her B.S. in Chemical Engineering at Drexel University (2002)and completed a Ph.D. in Chemical Engineering at the University of California, Santa Barbara (2006). Shethen moved to the National Institute of Standards and Technology, where she was a NRC postdoctoral fellowin the Center for Nanoscale Science and Technology (2007-2008). Since 2009, she has been an AssistantProfessor in the Chemical and Biomolecular Engineering department at the University of Houston. Dr.Stein’s research group studies the physics and chemistry of thin polymer films, emphasizing applications inthe microelectronics industry. She received a NSF CAREER award in 2012.

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Tuesday, May 12, 2015 Starting: 1:40 PMT4_1: CMSP (Heritage Room)

Session Chair: Christopher CorneliusAssistant: Ramin Hosseinabad

Talks:

1. (1:40 PM, Invited) Blümich: NMR-SPECTROSCOPY AND NONDESTRUCTIVE TESTING BYCOMPACT NMR

2. (2:00 PM, Oral) Tashiro: STRUCTURE FORMATION PROCESS OF POLY(VINYL ALCOHOL)-IODINE COMPLEX REVEALED BY IN-SITU TIME-DEPENDENT X-RAY DIFFRACTION MEA-SUREMENT

3. (2:20 PM, Oral) Salim: THERMAL DEGRADATION IN THE MELT REACTION BETWEENPOLY(3-HYDROXYBUTYATE-CO-3-HYDROXYHEXANOATE) AND EPOXIDIZED NATURALRUBBER

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Talk Number: 1 (Invited)Time: Tuesday, May 12, 2015 1:40 PM Session: T4_1: CMSP (Heritage Room)

NMR-SPECTROSCOPY AND NONDESTRUCTIVE TESTING BY COMPACTNMR

Bernhard Blümich1, Alina Adams1, Ernesto Danieli1, Tylor Meldrum2, Dirk Oligschlaeger1, KawarpalSingh1, Wasif Zia1

1 Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Germany2 Department of Chemistry, The College of William & Mary, USA

An introduction to compact NMR will be given with the focus on polymer analysis. Most NMR instrumentsare bulky and expensive. This is not so for compact NMR instruments, which employ small permanentmagnets instead of large superconducting magnets. Despite their low field strength they are useful fora variety of different investigations of macromolecules and macromolecular materials. For instance, high-resolution 1H and 13C NMR spectra of polymer solutions can be acquired within a few minutes with acompact desktop spectrometer directly in the chemical laboratory and even under the fume hood. Thesensitivity is good enough to monitor chemical reactions in real time and to distinguish raw rubber fromdifferent plantations (NR), different manufacturing processes. With stray-field sensors like the NMR-MOUSEextregistered only rubber products like tubes and tires could be characterized non-destructively in the pastin terms of depth profiles and local cross-link density. With the recent development of the MiniMOUSE, thelimiting instrument deadtime could be considerably reduced so that now not only the signal from amorphousdomains in semi-crystalline polymers can be detected but also the signal from crystalline domains. Inaddition to thermal and physical aging, temperature and solvent induced crystallization have been studied.Such investigations are closely related to studies of paint, paintings, and other objects of art and culturalheritage relevant to conservation science.

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Talk Number: 2 (Oral)Time: Tuesday, May 12, 2015 2:00 PM Session: T4_1: CMSP (Heritage Room)

STRUCTURE FORMATION PROCESS OF POLY(VINYL ALCOHOL)-IODINECOMPLEX REVEALED BY IN-SITU TIME-DEPENDENT X-RAY DIFFRACTIONMEASUREMENT

Kohji Tashiro1, Siti Munirah Saharin1

1 Department of Future Industry-oriented Basic Science and Materials, Toyota Technological Institute, Japan

Poly(vinyl alcohol) (PVA)-iodine complex is used for a optical polarizer for color display, sun glass etc. Bydipping PVA film into an iodine solution, the complex is formed not only in the amorphous region, as usedfor polarizer but also in the crystal region. We have analyzed the crystal structures of complexes usingX-ray diffraction data, and investigated the factors governing the complex formation. In the present paper,the structure changes in the formation process of the complexes have been investigated by performing thein-situ time-resolved X-ray diffraction measurement using a doubly-oriented anisotropic PVA film. (1) Inthe crystal structure of PVA itself, a couple of planar zigzag chains are linked together by intermolecularhydrogen bonds. These PVA chains are linked also between the unit cells with strong hydrogen bonds.(2) When the concentration of iodine solution is low (∼0.02M), the iodine ions invade into the amorphousregion and form the complex with PVA there.The iodine molecules exist as I5- ion. Most of the crystalregions are still remained as the crystalline state of PVA itself. (3) The PVA sample is dipped into a KI/I2aqueous solution of 0.05M∼1M concentration. As known from the Raman data, the I3- ions invade into thecrystalline region and form the complex with PVA chains. According to the X-ray sdiffraction analysis, thestructure consists basically of three layers: a layer of PVA chains connected by hydrogen bonds, and twolayers consisting of PVA-I3- complex. The occupancy of the iodine is about 0.3. The arrangement of these 3layers indicates that the PVA-iodine complex is formed by shifting the PVA chains from the original positionand iodine molecules enter the spaces created by such a shift of PVA chains. However, the invasion of I3- ionsis not perfect but some of PVA chains still remain in the original structure. (4) By dipping the PVA sampleinto more highly-concentrated iodine solution (∼3M), more perfectly-packed PVA-iodine complex is formed,in which all the PVA chains form the complex with I3- at an occupancy of 0.7. The planar zigzag planes ofPVA chains are almost commonly parallel to the rolled plane in the two cases of PVA itself and the complexof intermediate concentration. But, once the highly-concentrated PVA-I3- complex is formed, the a-axis isoriented in parallel to the rolled plane and the molecules rotate by 38o around the chain axis.

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THERMAL DEGRADATION IN THE MELT REACTION BETWEEN POLY(3-HYDROXYBUTYATE-CO-3-HYDROXYHEXANOATE) AND EPOXIDIZED NATU-RAL RUBBER

Yoga Sugama Salim1,2,3, Kumar Sudesh4, Seng Neon Gan3, Chin Han Chan2, Jean-Marc Saiter1

1 AMME-LECAP, EA4528, International Laboratory, Institute des Materiaux de Rouen, Université et INSAde Rouen, France2 Polymer Blends Research Laboratory, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450Shah Alam, Malaysia3 Department of Chemistry, Faculty of Applied Sciences, Universiti Malaya, 50603 Kuala Lumpur, Malaysia4 Ecobiomaterial Research Laboratory, School of Biological Sciences, Universiti Sains Malaysia, 11800Penang, Malaysia

Melt reaction between a member family of biodegradable copolyesters polyhydroxyalkanoate: poly(3-hydroxy-butyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx)] and epoxidized natural rubber (ENR) was investigated.P(3HB-co-3HHx) is known to exhibit random chain scission at temperature above its melting point. Thisrandom cleavage of P(3HB-co-3HHx) can be selectively grafted with natural rubber bearing a cyclic ethergroup. The temperature of investigated melt reaction was conducted at 195 oC. During the melt reaction,there is a time-dependence of mass loss as shown in thermogravimetric analysis. The plot of mass loss (inpercent, %) against weight fraction of ENR (wENR) exhibits an asymmetric bell curve. Highest mass loss at5 × t0.5,rb (t0.5,rb = half-time of isothermal reactive blends) was observed in the blends containing wENR= 30 wt% and wENR = 50 wt%, which was (14.1 ± 0.6)% and (13.0 ± 0.8)% respectively. The asymmetriccurve could be attributed to: (1) a heterogeneous reaction at the interface between P(3HB-co-3HHx) andENR. This means that in P(3HB-co-3HHx)-rich phase, there is a coexistence of dispersed ENR particleswith different size distribution and vice versa; and (2) further decomposition of P(3HB-co-3HHx) at prolongreaction time. However at wENR = 40 wt%, there is a percolation pathway in which it forms a continuousphase in both P(3HB-co-3HHx) and ENR (supported by SEM images). The mass loss for this particularblend composition at 5 × t0.5,rb was (9.5 ± 0.1)%. FTIR investigation confirms the molecular interactionsduring the course of melt reaction between P(3HB-co-3HHx) and ENR.

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Tuesday, May 12, 2015 Starting: 1:40 PMT4_2: DEMO (Auditorium)

Session Chair: Stephen DucharmeAssistant: Mitchell Schmidt

Talks:

1. (1:40 PM, Invited) Xu: ENHANCED SENSITIVITY OF PRESSURE SENSOR USING ELEC-TROACTIVE POLYMERS

2. (2:00 PM, Oral) Poddar: FLEXOELECTRIC EFFECT IN FERROELECTRIC AND RELAXORPOLYMERS OF VDF

3. (2:20 PM, Oral) Chan: RESPONSE OF SOLID POLYMER ELECTROLYTES TO ELECTRICFIELDS

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Talk Number: 1 (Invited)Time: Tuesday, May 12, 2015 1:40 PM Session: T4_2: DEMO (Auditorium)

ENHANCED SENSITIVITY OF PRESSURE SENSOR USING ELECTROACTIVEPOLYMERS

Chunye Xu1

1 Department of Polymer Science and Engineering, School of Chemistry and Materials; Hefei National Lab-oratory for Physical Sciences at the Microscale, University of Science and Technology of China, China

Electroactive polymers (EAPs) are smart materials that exhibit controllable response to external stimulus,promising in application for actuators, sensors and electrochromic devices. We developed a highly sensitiveflexible pressure sensor based on piezopolymer and silver nanowire (Ag NWs) composite. The compositenanofiber webs are made by electrospinning mixed solutions of poly(vinylidene fluoride) (PVDF) and AgNWs in the cosolvent of dimethyl formamide and acetone. FTIR and XRD results reveal that doping AgNWs into PVDF largely enhances the content of β phase in PVDF. The increase of β phase can be attributedto interactions between Ag NWs and the PVDF matrix, which force the polymer chains to be embedded intothe β phase crystalline. The sensitivity of the pressure sensors agrees well with FTIR and XRD characteristics.This study may provide a new method of fabricating high performance flexible sensors at relatively low costcompared with sensors based on [P(VDF-TrFE), (77/23)].

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Talk Number: 2 (Oral)Time: Tuesday, May 12, 2015 2:00 PM Session: T4_2: DEMO (Auditorium)

FLEXOELECTRIC EFFECT IN FERROELECTRIC AND RELAXOR POLYMERSOF VDF

Shashi Poddar1, Stephen Ducharme1

1 Physics and Astronomy, University of Nebraska Lincoln, United States of America

The flexoelectric effect yields a change in electrical polarization proportional to an inhomogeneous straingradient, and as such, is a more general phenomenon than the linear change in polarization due to stress,the piezoelectric effect, which requires a non-centrosymmetric crystal structure. The inhomogeneous straingradient becomes appreciable at the nanoscale and behaves as an applied electric field, capable of poling,switching, and rotation of polarization. The flexoelectric response is of practical interest, because it liftsthe symmetry restrictions that limit piezoelectric response, and therefore can be found in crystalline andamorphous materials alike, allowing much greater flexibility in material and device design. The theoreticalbackground laid down by Kogan and Tagantsev supposes the flexoelectric coefficient µ to be to be of orderke/a (∼ 0.1 nC/m), where k is the dielectric constant and a is the lattice constant of the material. Thepredicted scalability of the flexoelectric response with dielectric constant indicates that the flexoelectric effectshould also exhibit a strong enhancement near the Curie transition temperature for normal ferroelectricand near the dielectric relaxation temperature regimes. In our studies we investigated the flexoelectricresponse in ferroelectric and relaxor polymers of vinylidene fluoride. By using a simple cantilever measurementtechnique, while monitoring remanent polarization through the pyroelectric response, we are able to measurethe flexoelectric response in thin films as well as isolate and correct for piezoelectric contributions, whichwould otherwise dominate the flexoelectric measurement. We also investigated the temperature dependenceof the flexoelectric response in thin films of these materials. The ferroelectric samples were depoled tominimize piezoelectric response by heating them beyond their Curie temperature and then cooling in zeroapplied electric field. In both the relaxor ferroelectric polymer and the paraelectric state of the ferroelectriccopolymer, the flexoelectric coefficient was proportional to the dielectric constant over a limited range oftemperatures. The enhancements in flexoelectric response were also observed near the phase transitiontemperatures of both the forms. These organic polymer materials have a broader dielectric anomaly thanthe ceramic perovskites and thus, provides greater temperature stability for these enhancements.

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RESPONSE OF SOLID POLYMER ELECTROLYTES TO ELECTRIC FIELDS

Chinhan Chan1, Hans-Werner Kammer2, Laihar Sim3, Tan Winie1

1 Faculty of Applied Sciences, Universiti Teknologi MARA, Malaysia2 Department of Chemistry and Physics, Martin-Luther University Halle-Wittenberg, Germany3 Pusat Asasi, Universiti Teknologi MARA, Malaysia

The overview discusses in phenomenological way dielectric relaxation as a function of salt content in polymerelectrolytes with poly(ethylene oxide) (PEO) and epoxidized natural rubber (ENR). Impedance is seen askey quantity which images relaxation properties of those systems. It follows Debye relaxation at low saltconcentration. With increasing salt content one observes dispersion of relaxation time. The spectrum ofimaginary part of impedance displays two extreme values: maximum and minimum. Accordingly, one has todistinguish between low- and high-frequency branches. The maximum reflects chain relaxation. It shifts withincreasing salt content to higher frequencies, which is consistent with increase in glass transition temperature(Tg) under the same conditions. The minimum characterizes electrode polarization or formation of doublelayer at the electrode/electrolyte interface. The frequency where the minimum occurs might be seen asdiffusion frequency. It governs transport of charge carriers in the limit of low frequencies. Consequently,diffusion coefficient (Dion) changes as frequency omega (min) in dependence on salt content. Impedancespectrum of PEO displays two extreme values whereas the minimum in spectra of ENRs shifts to very lowfrequencies and is not experimentally accessible. As a consequence, relaxations in PEO can be discussed inthe DC range whereas those in ENRs are only approachable in the high-frequency region where frequencyomega >> omega (max). In any branch, the concentration of electrically active charge carriers is quite lowand changes only weakly with added salt content; the diffusion coefficient on the other hand, is high andincreases with salt content.

46

Tuesday, May 12, 2015 Starting: 3:05 PMT5_1: CMSP (Heritage Room)Session Chair: Yong-Rak KimAssistant: Ramin Hosseinabad

Talks:

1. (3:05 PM, Oral) Sun: INVESTIGATING ORGANIC MATERIALS USING SPECTROSCOPIC EL-LIPSOMETRY

2. (3:25 PM, Oral) Manhart: DESIGN OF ELASTOMER SURFACES WITH SPATIALLY CON-TROLLED TRIBOLOGICAL PROPERTIES APPLYING PHOTOLITHOGRAPHIC TECHNIQUES

3. (3:45 PM, Oral) Desai: ROLE OF EXTERNAL DONOR AND CO-CATALYST - ZIEGLER NATTACATALYST USING SPECTROSCOPY TECHNIQUE

4. (4:05 PM, Oral) Schamme: ROLE OF MOLECULAR MOBILITY AND FRAGILITY ON PHYSI-CAL STABILITY OF TWO AMORPHOUS PHARMACEUTICALS IN THE SUPERCOOLED ANDGLASSY STATES

5. (4:25 PM, Oral) Viel: MOLECULAR MOBILITY VS POLYMORPHISM OF CHIRAL PHARMA-CEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE

6. (4:45 PM, Oral) Denchev: STRUCTURE GRADIENTS BY MICROFOCUS SYNCHROTRON X-RAY DIFFRACTION IN SHELL-CORE POLYAMIDE MICROCAPSULES AND MOLDED COM-POSITES THEREOF

7. (5:05 PM, Oral) You: CHARACTERIZATION OF VISCOELASTIC-VISCOPLASTIC BEHAVIOROF POLYMERIC MATERIALS CONTAINING ALIPHATIC AND AROMATIC HYDROCARBONSDERIVATIVES

47


INVESTIGATING ORGANIC MATERIALS USING SPECTROSCOPIC ELLIPSOM-ETRY

Jianing Sun1, Greg Pribil1, James Hilfiker1, John Woollam1

1 Applications, J. A. Woollam Co., Inc, USA

Spectroscopic Elipsometry (SE) provides accurate film thickness (from sub-nanometers to microns), refrac-tive indices as well as structural conformation and anisotropy. The technique has been routinely used ingetting thickness of organic films in single layer or multiple-layer stack. SE determines the optical behaviorsof thin films in organic light emitting diodes (OLED) and organic photovoltaic (OPV). Such films presentanisotropy resulting from their conjugated molecular structure and conformation. The sensitivity to sub-nmfilm makes it an idea technique to monitor thin film absorption and desorption in bio- or surface chemistryapplications. Thermal behaviors of thin organic films are important for their mechanical, electrical orbiological applications. SE provides fast and non-destructive way to dynamically monitor their temperaturedependent behaviors. Applications in understanding temperature effects on glass transition and anisotropywill be demonstrated. Thermal responses of ultra-thin (below 20nm) free-standing films will for the firsttime be discussed.

Key Words: Spectroscopic ellipsometry, Refractive index, thickness, anisotropy, glass transition tem-perature

48


DESIGN OF ELASTOMER SURFACES WITH SPATIALLY CONTROLLED TRIBO-LOGICAL PROPERTIES APPLYING PHOTOLITHOGRAPHIC TECHNIQUES

Jakob Manhart1, Andreas Hausberger1, Inge Mühlbacher1, Raimund Schaller2, Armin Holzner2, WolfgangKern1,3, Sandra Schlögl1

1 Polymer Competence Center Leoben , GmbH, Austria2 Semperit Technische Produkte GmbH, GmbH, Austria3 Chair of Chemistry of Polymeric Materials, University of Leoben, Austria

Tribological properties of elastomer-based materials have gained increased attention in numerous fields ofapplication, ranging from the automotive industry to the health-care sector. In recent years, various routeshave been pursued towards the development of elastomer materials with improved tribological characteris-tics. The present contribution highlights a new approach for the preparation of functionalized and patternednatural rubber (NR) elements with tailored friction properties.By using versatile UV-induced thiol-ene chemistry, a two-step surface modification strategy has been de-veloped which enables controlled and patterned immobilization of micro-scaled inorganic particles onto di-ene-rubber surfaces, causing a tremendous change of chemical and physical surface properties. The chemicalcomposition of the modified surfaces was characterized by XPS, FTIR, zeta potential and water contact anglemeasurements. Physical transformation was monitored by means of optical, scanning electron and confocalmicroscopy in order to gauge surface topology and roughness whilst tribological studies were performed tocharacterize the friction properties in two dimensions.The results reveal that the attachment of selected micro-scaled particles provides a distinctive increase insurface roughness and a considerable decrease in the coefficient of friction. Both can be conveniently adjustedthrough the amount of particles immobilized onto the elastomer surface. The application of photolithographictechniques further promotes elastomer materials with precisely and spatially controlled tribological proper-ties. Whilst elastomer surfaces with randomly attached particles exhibit isotropic coefficients of friction,anisotropic friction properties can be accomplished by surface patterning. It is clearly evidenced that thisphotochemical modification route enables the well-defined production of surface textures and thus allows thedesign of elastomer surfaces with tailored friction properties.

49


ROLE OF EXTERNAL DONOR AND CO-CATALYST - ZIEGLER NATTA CATA-LYST USING SPECTROSCOPY TECHNIQUE

Bhavesh Kiritbhai Desai1

1 Reliance Research & Development center, Reliance Industries Ltd, Hazira, India

The roles of internal and external electron donors have been often discussed in abundant studies on MgCl2supported TiCl4 catalysts for propylene polymerization. Since Z-N catalyst and its polymerization is highlycomplex system and it is quite difficult to identify experimentally active species of polymerization in aheterogeneous MgCl2 support. The interaction of the electron donors with a central titanium atom ofthe active species is not well-understood. Due to heterogeneous nature of catalyst and also very complexpolymerization and catalyst reaction mechanism some advanced tool required to understand role of electrondonors (Lewis Base), supports, co-catalyst (Aluminum Alkyl) and also TiCl4 (Lewis Acid). In propylenepolymerization the interactions are very much important and are need to be understood for understandingthe polymerization mechanism in details.

External donor (p-isopropoxy methyl benzoate; PIPMB) & co catalyst (Triethylaluminium-TEAl)were interacted in 1:3 molar ratio. The resultant complexes formed by the interaction of ED and co catalystwere studied by spectroscopy at room temperature. 1H, 13C 1H & DEPT45, 90 & 135 NMR spectra ofwere recorded. The resultant complexes were also studied at 70o C to mimic the polymerization conditionsat slurry phase process. The strength of coordination bond (degree of coordination) was co related bymeasuring the chemical shift of carbonyl functionality through NMR spectra.

50


ROLE OF MOLECULAR MOBILITY AND FRAGILITY ON PHYSICAL STABIL-ITY OF TWO AMORPHOUS PHARMACEUTICALS IN THE SUPERCOOLED ANDGLASSY STATES

Benjamin Schamme1,2, Laurent Delbreilh1, Valérie Dupray2, Eric Dargent1, Gérard Coquerel2

1 Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France2 Crystal Genesis Unit, SMS Laboratory, France

In the pharmaceutical industry, crystalline active pharmaceutical ingredients (API) and/or excipients havebeen, so far, preferred for the formulation of drugs because of stability concerns [1]. However, a number ofpharmaceutical ingredients are prompt to get amorphized and it has been demonstrated that amorphousAPI can result in significant improvements of the dissolution rate and bioavailability with reference to thecrystallized solid. However, preparation methods as well as thermal and mechanical treatments employedduring formulation of the drug have been shown to affect physical stability of the amorphous API [2].

Beside the inherent out of equilibrium state of amorphous material, the molecular mechanisms gov-erning the kinetic stability of amorphous API remain unclear (as a large number of experimental factorsmay impact the process of crystallization) but need to be clarified in order to design reliable formulationprocesses [3]. Recent works have highlighted that molecular mobility could be a key factor to account for thephysical stability of amorphous substances. In particular the impact of glass fragility on physical stabilityof amorphous systems has been considered [4].

In view to contribute to this challenging inquiry, we characterized the amorphous state of two APIs:Biclotymol and Quinidine. Biclotymol possesses antiseptic properties and is used for the treatment ofotolaryngology infections while Quinidine acts as an antiarrhythmic agent. Based on Broadband DielectricSpectroscopy measurements conducted on these two compounds, this study shows that fragility could bea valuable parameter for understanding the mechanisms relating crystallization from amorphous state andstability (life expectancy) of amorphous materials. Dynamics of primary and secondary relaxations processesfor the two compounds have been carefully investigated in a wide range of temperatures and frequencies.Moreover, in situ crystallization mechanisms were explored through isothermal and non-isothermal coldcrystallization, within the framework of uncontrolled recrystallization processes from amorphous systems.

[1] Singhal, D; Curatolo, W. Adv. Drug Deliv. Rev. 2004, 56, 335-347.[2] Patterson, J; James, M; Forster, A; Lancaster, R; Butler, J; Rades, T. J. Pharm. Sci. 2005, 94,1998-2012.[3] Morris, K; Griesser, U; Eckhardt, C; Stowell, J. Adv. Drug Deliv. Rev. 2001, 48, 91-114.[4] Gupta, P; Chawla, G; Bansal, A. Mol. Pharmaceutics. 2004, 1, 406-413.

51


MOLECULAR MOBILITY VS POLYMORPHISM OF CHIRAL PHARMACEUTI-CAL COMPOUNDS: CASE OF DIPROPHYLLINE

Quentin Viel1,2, Clement Brandel2, Yohann Cartigny2, Gerard Coquerel2, Eric Dargent1, Samuel Petit2

1 LECAP, University of Rouen, France2 Crystal Genesis SMS, University of Rouen, France

Compared to the crystalline state, the amorphous state is an attractive solution for the pharmaceuticalindustry since the capacity of the molecule to be dissolved in liquids (not to be confused with “solubility”)is increased. Thus, a higher bioavailability of a targeted Active Pharmaceutical Ingredient (API) [1] canbe reached by amorphization of a crude product. However, physical instabilities related to the amorphousstate represent a significant limitation to the development of an amorphous drug product and for itssubsequent formulation. Consequently, the scientific and industrial communities try to understand thefactors affecting the crystallization route from the amorphous state [2]. There is a particular scientificinterest in understanding the role of molecular mobility in glass-forming materials during the process ofcrystallization [3]. The chiral drug Diprophylline (DPL) is used as a racemic solid (a 50/50 mixture of bothenantiomers) in oral dosage forms for treatment of pulmonary diseases. The molecule itself consists of a rigidheterocyclic group theophylline attached to a flexible propanediol moiety. Although the stable state of DPLenantiomeric mixtures consists of an usual equilibrium between a racemic compound (RI) and an enantiopureform (EI), we have found that annealing DPL glasses with various enantiomeric compositions (Xs) above theDPL glass transition (Tg = 37 oC) can induce the crystallization of two distinct metastable solid solutionslabelled ssRII and ssEII. The aim of the present study is to elucidate the impact of enantiomeric compositionin supercooled melts on the outcomes of DPL recrystallization from the amorphous state. Calorimetricmeasurements (DSC) and Broadband Dielectric Spectroscopy (BDS) analyzes have been used to characterizethe path/route of the molecules from the amorphous state (molecular mobility) until recrystallization atdistinct enantiomeric compositions.[1] Baird A.J., Taylor L., Ad Drug Rev, 64, 396-421, 2012[2] Bhugra C., Shmeis R., Pikal M., Journal of Pharmaceutical Sciences, 97, 10, 2008[3] Rodrigues A.C., Viviosa M.T., Affouard F, Correia T., Molecular Pharmaceutics, 11, 112-130, 2014

52


STRUCTURE GRADIENTS BY MICROFOCUS SYNCHROTRON X-RAYDIFFRACTION IN SHELL-CORE POLYAMIDE MICROCAPSULES AND MOLDEDCOMPOSITES THEREOF

Zlatan Zlatev Denchev1, Nadya Vassileva Dencheva1, Stephan V. Roth2

1 Polymer Engineering, I3N - Institute for Polymers and Composites, Portugal2 Photon Science at DESY, DESY, Germany

Polyamide microcapsules are of demand in many industries e.g., compression-and rotational molding, selectivelaser sintering, cosmetics etc. In bioengineering, polyamide-microcapsules can be attractive carriers forprotein or enzyme immobilization. The distribution of the solid filler in microcapsules is a function of themanufacturing conditions and is often of decisive importance for certain applications. Such measurementsare not possible by means of conventional X-ray techniques or electron microscopy due to the large size ofthe X-ray beam or sample preparation difficulties, respectively. This work reports on the measurements ofthe structure and composition gradients in novel microcapsules with polyamide 6 (PA6) porous shells anddiameters in the 25-50 angstrom range obtained by emulsion anionic polymerization. The microcapsuleswere loaded in situ with various amounts and types of inorganic, finely dispersed materials: nanoclays,carbon allotropes, and metal particles. Thin layers of the respective microcapsule samples were scannedalong two perpendicular axes with a 5x5 angstrom synchrotron beam in WAXS mode covering areas of3025 angstrom2. The microfocos WAXS results obtained showed irregular distribution of the filler withinthe PA6 microcapsules causing changes in the content of Î±- and ÎPA6 polymorphs in 121 shell sections of25 angstrom2 each. Similar measurements were performed with composite plates obtained by compressionmolding of certain amounts of the respective microcapsules. These unique WAXS studies helped characterizethe core nanostructure of the loaded PA6 microcapsules and how it transits into the molded part. In such away a direct relation was made between the reaction parameters of the microcapsule-forming polymerizationprocess and the nanostructure of the molded samples.

53


CHARACTERIZATION OF VISCOELASTIC-VISCOPLASTIC BEHAVIOR OFPOLYMERIC MATERIALS CONTAINING ALIPHATIC AND AROMATIC HYDRO-CARBONS DERIVATIVES

Taesun You1, Soohyok Im2, Yong-Rak Kim1

1 Civil Engineering, University of Nebraska-Lincoln, USA2 Civil Engineering, Texas A&M Transportation Institute, USA

Bitumen is a black or dark polymer, being composed of high molecular weight hydrocarbons and nonmetallicderivatives. Fine aggregate matrix (FAM) consisting of bitumen, air voids, fine aggregates, and fillers playsa significant role in evaluating the damage and deformation of entire bituminous mixtures. The simplicity,repeatability, and efficiency of the FAM testing make it a very attractive specification-type approach for eval-uating the performance characteristics of the entire bituminous mixtures. This study explores a linkage in thedeformation characteristics between the two length scales: bituminous mixture scale and its correspondingFAM scale. To that end, a simple creep-recovery test was conducted for both mixtures (i.e., bituminous mix-ture and its corresponding FAM phase) at various stress levels. Test results were compared and analyzed usingSchapery’s single integral viscoelastic theory and Perzyna-type viscoplasticity with a generalized Drucker-Prager yield surface. In particular, stress-dependent nonlinear viscoelastic and viscoplastic behaviors werecharacterized in addition to linear viscoelastic deformation characteristics, because the nonlinear viscoelasticand viscoplastic behaviors are considered significant in bituminous pavements that are subjected to heavyvehicle loads and elevated service temperatures. With a limited scope and test-analysis results at this stage,it was found that there is a strong link between the FAM and bituminous mixture in (linear and nonlinear)viscoelastic and viscoplastic deformation characteristics. This implies that the viscoelastic stiffness charac-teristics and viscoplastic hardening of typical bituminous mixtures could be estimated or predicted from thesimple FAM-based testing-analysis method, which can significantly reduce the experimental-analytical effortsrequired for bituminous mixtures.

54

Tuesday, May 12, 2015 Starting: 3:05 PMT5_2: DEMO (Auditorium)Session Chair: Chinhan ChanAssistant: Mitchell Schmidt

Talks:

1. (3:05 PM, Invited) Jonas: NANOIMPRINTED FERROELECTRIC/SEMICONDUCTING POLY-MER DEVICES

2. (3:25 PM, Oral) Sangoro: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS IN POLY-MERIZED IONIC LIQUIDS

3. (3:45 PM, Oral) Dencheva: FROM LOADED SHELL-CORE MICROCAPSULES TO THERMO-PLASTIC HYBRID COMPOSITES: A NEW PATHWAY FOR THE PREPARATION OF CONDUC-TIVE AND MAGNETIC POLYAMIDE COMPOSITES

4. (4:05 PM, Oral) Anada: DIVERSITY OF MICROSTRUCTURE OF POLYMER SOLID INVESTI-GATED BY MOTION OF IMPURITY IONS

5. (4:25 PM, Oral)Hagg Lobland: THERMOELECTRIC GENERATORS (TEGS) WITH LONG SER-VICE LIVES

55

Talk Number: 1 (Invited)Time: Tuesday, May 12, 2015 3:05 PM Session: T5_2: DEMO (Auditorium)

NANOIMPRINTED FERROELECTRIC/SEMICONDUCTING POLYMER DE-VICES

Ronggang Cai1, Tilia Patois1, Laurianne Nougaret1, Alain M. Jonas1

1 Bio & Soft Matter, University of Louvain, Belgium

For the fabrication of efficient organic devices, it is desirable to develop methodologies able to shapefunctional polymers into nanostructures, while simultaneously controlling essential attributes such as crystalorientation and size. In this context, nanoimprint lithography (NIL), initially developed as a nanolithographytechnique applied to amorphous polymers, proved to be well-suited to shape and control the structure of arange of liquid crystalline and semicrystalline polymers [1-3], such as semiconducting [4], electroluminescent,or ferroelectric polymers [5-7]. The reasons for this control stem from perturbed nucleation, confinementduring crystallization, and grapho-epitaxy.

As a side benefit of this process, the polymer is also shaped in an array of nanoobjects separated byregularly spaced cavities. This provides a unique opportunity to fabricate hybrid multifunctional layers, byfilling the so-created cavities by another material synergetically interacting with the first one. By using asemiconducting polymer as second component, we fabricated a series of memory devices, such as ferroelec-tric/semiconducting diodes [8], ferroelectric field effect transistors with a nanoimprinted top ferroelectriclayer [9], or a new type of ferroelectric transistor including a mixed semiconducting/ferroelectric active layer;we also realized organic solar cells containing nanoimprinted ferroelectric layers. In this communication, wepresent the specificities of the coupling between the ferroelectric polymer and the semiconducting polymerin the nanostructured bifunctional layers, and show how this may be used to develop new device architectures.

References[1] Nano Letters 2005, 5, 1738-1743;[2] Soft Matter 2010, 6, 21-28;[3] Handbook of Nanophysics. Nanoelectronics and Nanophotonics, Sattler, K. D., Ed. CRC: Boca Raton,2011; Vol. 6, pp 18.1-18.8;[4] Nano Letters 2007, 7, 3639-3644;[5] Nature Materials 2009, 8, 62-67;[6] Macromolecules 2013, 46, 8569-8579;[7] Macromolecules 2014, 47, 4711-4717;[8] ACS Nano 2014, 8, 3498-3505;[9] Appl. Phys. Lett. 2014, 105, 113113.

56


CHARGE TRANSPORT AND STRUCTURAL DYNAMICS IN POLYMERIZEDIONIC LIQUIDS

Joshua Sangoro1

1 Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, USA

Polymerized ionic liquids (PolyILs) are a novel class of functional polymers that combine the unique physic-ochemical properties of molecular ionic liquids with the outstanding mechanical characteristics of polymers[1-2]. This special mix of features might help to circumvent the key limitations of low molecular weight ionicliquids, namely, leakage and poor mechanical properties while utilizing their outstanding characteristicssuch as low vapor pressures, wide liquidus ranges, high thermal stability, high ionic conductivity, and wideelectrochemical windows. PolyILs have shown remarkable advantages when employed in electrochemicaldevices such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emittingelectrochemical cells, and electrochromic devices, among others. Despite their promising prospects asideal polymer electrolytes, the role of molecular structure, morphology, and polymer dynamics on chargetransport in PolyILs remains poorly understood.According to classical theories, the self-diffusion and ion transport in electrolytes are controlled by structuralrelaxation. These approaches predict similar temperature dependence for the dc conductivity and structuraldynamics. Although this prediction has been shown to hold reasonably well for low molecular weight aproticionic liquids [3], it fails for PolyILs [2]. In addition, the impact of morphology charge transport is notconsidered within the framework of these theories.In this talk, new insights obtained from both experimental studies employing broadband dielectric spec-troscopy, temperature-modulated differential scanning calorimetry, and scattering techniques along withmultiscale modeling investigations to elucidate charge transport and structural dynamics in a systematicseries of polymerized ammonium- and imidazolium- based ionic liquids will be presented. Detailed analysesreveal strong decoupling of these processes in the PolyILs, implying failure of the classical theories indescribing charge transport and molecular dynamics in these materials. In addition, the strong correlationobserved between ionic conductivity from dielectric experiments and morphologies from scattering studieswill be discussed.

References[1] Mecerreyes, D. Progress in Polymer Science 2011, 36, 1629.[2] Sangoro, J. R. et al., Soft Matter 2014, 10, 3536.[3] Sangoro, J. R.; Kremer, F. Accounts of Chemical Research 2012, 45, 525.

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FROM LOADED SHELL-CORE MICROCAPSULES TO THERMOPLASTIC HY-BRID COMPOSITES: A NEW PATHWAY FOR THE PREPARATION OF CON-DUCTIVE AND MAGNETIC POLYAMIDE COMPOSITES

Nadya Vassileva Dencheva1, Zlatan Zlatev Denchev1, Senentxu Lanceros-Méndez2, José Carlos Brêda1, FilipaMatos Oliveira1

1 Polymer Engineering, i3N - Institute for Polymers and Composites, Portugal2 ESM - Electroactive Smart Materials, University of Minho, Department of Physics, Portugal

Polyamide 6 microcapsules find various applications in biotechnology for protein and enzyme immobilizationto produce drug delivery systems, in solid-phase diagnostics, biosensors, biocatalysts, extracorporeal therapy,and bio-separation. Also, they have direct and potential applications in fields of industrial materials for lasersintering, electro-conductive and magnetic composites, etc. This work presents an original one-pot synthesisof polyamide 6 microcapsules containing in their cores finely dispersed inorganic payloads. The microcapsuleswere synthesized by suspension anionic polymerization of ε-caprolactam in non-polar hydrocarbon solventscarried out in the presence of metal micron-sized powders (Al, Cu, Zn or Fe) or carbon allotropes (carbonblack, carbon nanotubes, graphite and carbon nanofibers). Various composite materials were prepared bycompression molding of the resultant microcapsules. The morphology and crystalline structure of the micro-capsules and that of the respective composites were studied by SEM, light microscopy and thermal analyses(DSC and TGA). The mechanical properties in tension of the composites were evaluated as well as their elec-tromagnetic properties: volume conductivity, dielectric permeability and magnetic susceptibility. The resultsobtained suggest that loaded microcapsules can be obtained in high yields, with excellent dispersion of theconductive material and reaching electrical conductivities of semiconductors (in the case of carbon allotropes)or high dielectric constants (for metal loads) without any functionalization or compatibilization procedures.All this allowed the conclusion about the significant application potential of the suggested pathway.

58


DIVERSITY OF MICROSTRUCTURE OF POLYMER SOLID INVESTIGATED BYMOTION OF IMPURITY IONS

Yuichi Anada1

1 Business Administration and Information Science, Hokkaido Information University, Japan

A relatively large amount of non-crystalline part exists between crystallites in polymer solid generally. Inthe non-crystalline part, there are free spaces with various sizes. This inhomogeneity of free spaces resultsfrom a thermal motion of the polymer molecules with amorphous conformation under the spatial restrictionmade by crystallite morphology. The impurity ions mixed in processing in the crystalline polymers movethrough these inhomogeneous free spaces. Consequently, this motion of ions reflects the inhomogeneousmicro-structure of non-crystalline part. Actually, in previous study of our laboratory, plural kinds ofmotion of impurity ions is observed for the electric modulus as a function of frequency in low frequencyregion below 10 Hz. These plural motions reflect the inhomogeneity of non-crystalline part. Furthermore,the conductivity relaxation time of the ion motion analyzed for poly(vinyl chloride) plasticized withdioctyl phthalate (p-PVC), isotactic polypropylene (iPP) and low density polyethylene (LDPE) reflects thedifference of the micro-structure of non-crystalline part among these polymers. In the present study, theionic motion of impurity ions in poly(ethylene telephlalate) (PET) is investigated as continuation of this study.

Electrical measurement was made by the apparatus of Schlumberger SI1260 Impedance/Gain-PhaseAnalyzer with an amplifier of Keithley428. At the frequencies lower than 10Hz, the amplifier of Keithley428was used with the impedance analyzer. On the other hand, the amplifier was not used at frequencies higherthan 10 Hz. The three-Terminal-Configuration Electrodes were used. The thickness of the film of PET is0.1mm.

Frequency dependence of the loss permittivity of PET shows the characteristic of dc conduction be-low about 1Hz in frequency. The electric modulus-frequency curve shows the characteristic of singleconductivity relaxation, which is the Debye type dispersion. The conductivity relaxation time analyzedfrom this curve is 0.53 at 100oC. This value is similar to those of LDPE and plasticized poly(vinyl chloride)(p-PVC) but smaller than those of iPP. However, in a plot of conductivity relaxation time vs. permittivity,the location of PET is near p-PVC. This result suggests that the inhomogeneity of PET is similar to thatp-PVC.

59


THERMOELECTRIC GENERATORS (TEGS) WITH LONG SERVICE LIVES

Witold Brostow1, Gregory Granowski1, Haley E. Hagg Lobland1, Gerald Hu1, Nathalie Hnatchuk1, SanchitSachdeva1,2, Susmitha Sayana1,2, John B. White1,3

1 Dept. of Materials Science & Engineering and Dept. of Physics, University of North Texas, USA2 Texas Academy of Mathematics and Science, Texas, USA3 Marlow Industries, Inc., Dallas, USA

In 1821 the Estonian-German physicist Thomas Johann Seebeck discovered in the city now called Tallinnan effect later named after him. Namely, a temperature difference ∆T between two dissimilar electricalconductors or semiconductors in contact with each other produces a voltage V. Devices based on theSeebeck effect are called thermo-electric generators (TEGs). There is a very large ∆T between the ambienttemperature and the temperature of the car exhausts. This in principle makes possible creation of a newtype of hybrid cars, without heavy batteries and the need of frequent recharging these batteries. However,TE materials at temperatures such as 600oC undergo thermal degradation (oxidation, sublimation of somecomponents) fast. It is for this reason that hybrid cars based on the Seebeck effect do not exist.

Our solution to this problem consists in covering TEGs with high temperature polymers (HTPs)that survive without degradation 600oC. The coatings protect the devices from thermal degradation: oxygencannot penetrate inside, nothing can escape. This eliminates most polymers as candidates for HTPs;polyethylenes have melting temperatures at most at 130oC, other widely used polymers are not better.We do have HTPs that ‘survive’ temperature cycling up to 550oC or 600oC. Selection of HTPs is basedon determination of several characteristics: wettability of molten HTPs on TEGs determined by contactangles; HTP dehydration and curing cycles; differential scanning calorimetry (DSC); thermogravimetricanalysis (TGA); electrical resistivity (ER); energy-dispersive X-ray spectroscopy (EDS); Raman spectroscopy.

60

Wednesday, May 13, 2015 Starting: 8:30 AMW1: Plenary (Auditorium)

Session Chair: Li TanAssistants: Marzieh Bakhtiary Noodeh, Yan Zou

Talk:

1. (8:30 AM, Plenary) Laine: SYNTHESIS, PROCESSING AND PROPERTIES OF SILSESQUIOX-ANE MACROMONOMERS AND POLYMERS

Dr. Richard Laine, Professor and Director, Materials Science and Engineering, University of Michigan

61

Talk Number: 1 (Plenary)Time: Wednesday, May 13, 2015 8:30 AM Session: W1: Plenary (Auditorium)

SYNTHESIS, PROCESSING AND PROPERTIES OF SILSESQUIOXANEMACROMONOMERS AND POLYMERS

Richard M. Laine2,1, Joesph C Furgal3, Mozghan Bahrami1, David Pan2

1 Materials Science and Engineering, University of Michigan, U.S.2 Macromolecular Science and Engineering, University of Michigan, U.S.3 Chemistry, University of Michigan, U.S.

Synthesis, Processing and Properties of Silsesquioxane Macromonomers and Polymers

Cage compounds of the type [RSiO1.5]8,10,12 can be synthesized with a variety of functional groupsincluding systems with mixed functional groups. The cage, originally thought to be innocuous and insulatingcan now be shown to greatly influence the reactivity and photophysical properties of appended R groups.Trace amounts of fluoride anion can be used to catalyze the exchange or RSiO1.5 units between cages andthe introduction of RR’SiO units into the cage and/or the formation of polymeric materials. The judiciouschoice of reactants, reaction conditions and R groups provide access to polymers for coatings, very highsurface area microporous and hydrophobic materials as well as dendronizable beads on a chain polymers.General methods and specific outcomes will be discussed.

62

Wednesday, May 13, 2015 Starting: 9:45 AMW2_1: NANO (Auditorium)

Session Chair: Li TanAssistant: Marzieh Bakhtiary Noodeh

Talks:

1. (9:45 AM, Keynote) Dzenis: SIMULTANEOUSLY STRONG AND TOUGH CONTINUOUS POLY-MER NANOFIBERS AND NANOCOMPOSITES

2. (10:25 AM, Invited) Serpe: STIMULI RESPONSIVE POLYMER-BASED SENSORS, MUSCLES,AND DRUG DELIVERY PLATFORMS

3. (10:45 AM, Oral) Li: POLYMER-BASED MATERIALS FOR BUILDING ARTIFICIAL MUSCLESAND THREE DIMENSIONAL STRUCTURES BY SELF-ROLLING

4. (11:05 AM, Oral) Alarifi: MECHANICAL AND THERMAL PROPERTIES OF CARBONIZED PANNANOFIBERS COHESIVELY ATTACHED TO SURFACE OF CARBON FIBER REINFORCEDCOMPOSITES

5. (11:25 AM, Oral) Goponenko: ELECTROSPUN NANOFIBROUS MATERIALS AS STIMULI-RE-SPONSIVE POLYMERIZED HYDROGELS

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Talk Number: 1 (Keynote)Time: Wednesday, May 13, 2015 9:45 AM Session: W2_1: NANO (Auditorium)

SIMULTANEOUSLY STRONG AND TOUGH CONTINUOUS POLYMERNANOFIBERS AND NANOCOMPOSITES

Yuris Dzenis1

1 MME, UNL, USA

Simultaneously Strong and Tough Continuous Polymer Nanofibers and Nanocomposites

Yuris DzenisDepartment of Mechanical and Materials EngineeringNebraska Center for Materials and NanoscienceUniversity of Nebraska-LincolnLincoln, NE [email protected]

The bulk of nanomaterials research to date focused on nanoparticles. Nanofibers are becoming increasinglyavailable thanks to emerging nanomanufacturing technologies such as electrospinning. This presentationreviews recent theoretical and experimental breakthroughs on ultra-high-performance continuous nanofibersand nanocomposites, conducted by the author’s group. Nanomanufacturing, nanofiber characterization,modeling, and design issues are covered. Examples of novel synthetic and natural polymer nanofibers, theirassemblies, and nanocomposites are presented. Unique simultaneous increases in strength and toughnessof nanofibers with their diameter decrease are demonstrated for the first time and explained. Recentbreakthroughs on and prospects of nanofiber-reinforced supernanocomposites (defined as nanocompositesexceeding the properties of conventional advanced composites [3]) are presented. Recommendations on thecost-effective nanofiber manufacturing scale-up and macroscopic nanocomposite designs for near-to-mediumterm applications are formulated.

1. Dzenis Y. “Spinning Continuous Nanofibers for Nanotechnology”, Science, 304, 2004, 1917-19192. Dzenis, Y., "Structural Nanocomposites", Science, 2008, 319, 419-4203. Ritchie, R.O.; and Dzenis, Y., "The Quest for Stronger, Tougher Materials", Science, 2008, 320, 4484. Papkov, D., Zou, Y., Andalib, M.N., Goponenko, A., Cheng, S.Z.D., Dzenis, Y., "Simultaneously Strongand Tough Ultrafine Continuous Nanofibers,” ACS Nano, 2013, 7, 3324-3331 (cover feature ACS Nano,April, 2013; highlighted in Nature, 2013, 495, 284)

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Talk Number: 2 (Invited)Time: Wednesday, May 13, 2015 10:25 AM Session: W2_1: NANO (Auditorium)

STIMULI RESPONSIVE POLYMER-BASED SENSORS, MUSCLES, AND DRUGDELIVERY PLATFORMS

Michael J. Serpe1

1 Department of Chemistry, University of Alberta, Canada

The group’s research is focused on the development of novel polymer-based materials for solving environmen-tal and health-related problems. To solve these problems, the group primarily employs poly (N-isopropylacry-lamide) (pNIPAm)-based spherical particles as the active component in our technologies. PNIPAm-basedparticles (nano or microgels, depending on their diameter) are extremely porous, and are fully water solu-ble and swellable. Additionally, pNIPAm-based nano/microgels are responsive to temperature, shrinking indiameter as the temperature is increased to >32 oC and reswelling when they are cooled to < 32 oC. Ourgroup has exploited these properties for numerous applications. Today’s talk will highlight the group’s workon the development of these devices for sensing and biosensing, as muscles, and for controlled/triggered drugdelivery.

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Talk Number: 3 (Oral)Time: Wednesday, May 13, 2015 10:45 AM Session: W2_1: NANO (Auditorium)

POLYMER-BASED MATERIALS FOR BUILDING ARTIFICIAL MUSCLES ANDTHREE DIMENSIONAL STRUCTURES BY SELF-ROLLING

Xue Li1, Michael J Serpe1

1 Chemistry, University of Alberta, Canada

Poly (N-isopropylacrylamide) (pNIPAm) microgel-based materials can be made, which self-fold into three-dimensional structures in response to changes in the humidity of their environment. This material is composedof a semi-rigid polymer substrate coated with a thin layer of Au; the Au layer is subsequently coated with apNIPAm-based microgel layer and finally covered with a solution of polydiallyldimethylammonium chloride(pDADMAC). When the pDADMAC dries, it causes the material to deform, which is completely reversibleover many cycles as the environmental humidity is systematically varied. In this study, we found this materialwas able to do work and lift masses many times the mass of the material in response to changes in the humidityof its environment. We further investigated how the size and aspect ratio of the polymer substrate affectedthe self-folding behavior of the materials. From experimental observations, a set of empirical rules weredeveloped that can be applied to predict the folding behavior of such materials. Furthermore, these ruleshave allowed us to direct the folding of these materials into discrete three-dimensional objects, which arefully capable of unfolding and folding in response to humidity.

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MECHANICAL AND THERMAL PROPERTIES OF CARBONIZED PANNANOFIBERS COHESIVELY ATTACHED TO SURFACE OF CARBON FIBERREINFORCED COMPOSITES

Ibrahim Alarifi1, Dr. Ramazan Asmatulu1, Abdulaziz Alharbi1, Waseem S. Khan1

1 ME, Wichita State University, United States

Pre-preg carbon fibers of 10 peel plies were laid up at 0, 45, -45 and 45 stacking sequences on flat andsmooth Al plate, and then carbonized electrospun polyacrylonitrile (PAN) nanofibers were placed on topof the last ply prior to the vacuum curing in a vacuum oven. The PAN electrospun fibers were oxidizedat 280oC in an ambient condition for one hour, and then carbonized at 850oC for one hourr in Ar gasatmosphere. The resultant composite panels were cut into small pieces, and subjected to a number ofdifferent characterization techniques. Thermal Mechanical Analysis (TMA) measurements clearly showedthat a significant reinforcement was achieved for the pre-preg / carbonized PAN fiber composites becauseof the enhanced interfacial bonding between the PAN nanofibers and the matrix. Dynamic mechanicalanalysis (DMA) tests exhibited that glass transition temperature of carbonized PAN nanofiber/compositewas shifted, which may be helpful for the high-temperature applications of the present composites. Ramanspectroscopy peak around 897 cm-1 indicated the formation of the γ-phase of the carbonized PAN fibers.The highest stretching peak of CH2 group was recognized within the range of 185-200 cm-1 for thecarbonized fibers. The group of CâĽąN vibration peak also appeared at 1452 cm-1 spectrum. ThermalMechanical Expansion (TME) determined the coefficient of thermal expansion, indicating an improvementin stability of the composite material, which can be useful for the structural health monitoring, light-ning strikes and electromagnetic interference (EMI) shielding applications of the new carbon fiber composites.

Keywords: Electrospun PAN Nanofibers, Carbonization, Carbon Fiber Composites, Thermal andMechanical Properties.

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ELECTROSPUN NANOFIBROUS MATERIALS AS STIMULI-RESPONSIVE POLY-MERIZED HYDROGELS

Kazi I Jahan1, Alexander Goponenko1, Yuris A Dzenis1


Hydrogels are three-dimensional polymeric networks swollen in aqueous media without dissolution. Thereis a growing interest in hydrogel materials, especially in stimuli-responsive polymerized hydrogels (SRPH).These “smart” hydrogels respond to a change in their environment by increasing or decreasing theirvolume and dimensions, changing their mechanical properties, generating substantial force, etc. SRPHsare increasingly being used, for instance, as sensor-actuator systems for automatic regulation of a liq-uid flow, where the flow rate can be controlled by the fluid properties, like pH, temperature, and composition.

The main disadvantages of the bulk/film hydrogels are slow speed of response to stimuli and poormechanical properties. Therefore, SRPHs in a nanofibrous form are of high interest, because this form willprovide improved mechanical properties and fast response as well as developed porous structure. TheseSRPH can be achieved by the electrospinning process. Electrospinning is known to be a versatile andefficient tool for preparing fibrous materials with fiber diameters ranging from several micrometers down totens of nanometers.

In this study, both poly vinyl alcohol (PVA) - poly acrylic acid (PAA) and Dextran (Dex) - PAAnanofilamentary hydrogel (NFG) are fabricated by electrospinning and crosslinked thermally through esterformation between a hydroxyl group on one polymer chain and a carboxylic acid on the other. Swellingkinetics of NFG membranes in different pH solution were compared with bulk hydrogels. These studiesdemonstrate a higher degree of swelling and lower water retention abilities in NFG than bulk gels, becauseof easier diffusion of water molecules in NFGs. The response speed becomes very fast by reducing thecritical dimension of hydrogel to nano-scale. Also the mechanical properties of conventional bulk gelswere compared to the properties of aligned NFGs. Bulk gels from PVA-PAA and Dex-PAA demonstrateda similar mechanical behavior, while NFGs from these two polymer systems demonstrated a significantdifference in behavior and exhibit unusual size effect on mechanical properties at smaller diameters. Thesehydrogels with nanofilamentary structure and useful features, such as unusual volume phase transition,size-dependent mechanical properties, and sensitivity to environmental stimuli, reveal unique possibilitiesfor applications in smart actuator system and biochemical fields.

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Wednesday, May 13, 2015 Starting: 9:45 AMW2_2: BIOT (Heritage Room)

Session Chairs: Linxia Gu, Dimitry PapkovAssistant: Yan Zou

Talks:

1. (9:45 AM, Keynote) Causin: NANOCELLULOSE-REINFORCED GELS FOR BIOMEDICAL AP-PLICATIONS

2. (10:25 AM, Invited) Schönherr: INFECTION DIAGNOSTICS WITH POLYMERIC VESICLESAND HYDROGELS FOR APPLICATION IN ADVANCED WOUND DRESSINGS AND BEYOND

3. (10:45 AM, Oral) Saunier: HOW ADDITIVE EXUDATION CAN AFFECT THE BIOCOMPATI-BILITY OF A POLYMERIC MEDICAL DEVICE: THE CASE OF A POLYURETHANE USED INIMPLANTABLE CATHETERS

4. (11:05 AM, Oral) Ding: ELECTROSPUN PHB/PCL/FUMED SILICA FIBROUS STRUCTUREFOR BONE TISSUE ENGINEERING

5. (11:25 AM, Oral) Andalib: BIOMIMETIC NANOFILAMENTARY POLYMER SCAFFOLDS ANDTHE MECHANISMS OF CELL-SCAFFOLD INTERACTION

6. (11:45 AM, Oral) Maleckis: ULTRAHIGH-PERFORMANCE NANOFIBERS FROM DNA ANDPROTEINS

7. (12:05 PM, Oral) Lyu: INVESTIGATION OF RUBBER FLOW DURING SHAPING OF AUTOMO-BILE TIRES

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Talk Number: 1 (Keynote)Time: Wednesday, May 13, 2015 9:45 AM Session: W2_2: BIOT (Heritage Room)

NANOCELLULOSE-REINFORCED GELS FOR BIOMEDICAL APPLICATIONS

Valerio Causin1, Edmondo Maria Benetti2, Byungdae Park3, Nanang Masruchin3

1 Dipartimento di Scienze Chimiche, Università di Padova, Italy2 Department of Materials, ETH Zürich, Switzerland3 Department of Wood Science and Technology, Kyungpook National University, Republic of Korea

Drug delivery and tissue engineering pose great challenges for polymer scientists. Polymers have idealproperties under a number of aspects, but the multiple, and often contradictory, requirements of suchapplications involve a precise control over the several steps involved in the manufacturing of the finalmaterial, from the monomer to the finished item. This is vital in particular for the applications wherefeatures such as biodegradation behavior, biocompatibility, size and surface morphology critically governthe biological activity of the material.In this communication, the development of polymer-based materials for drug delivery and tissue engineeringapplications will be reported.Poly(oxazoline)s, polymers which display biodegradability, biocompatibility, antifouling properties anda relatively easy tunability of the chemical structure, were used. These materials were explored forpreparing degradable gels for drug delivery applications and for functionalizing polymeric scaffolds withbrush coatings acting as “first contact layers”. The mechanical properties of these gels were tuned by ad-dition of nanocellulose. The effect of such filler on the performance and on the drug release rate was evaluated.

Acknowledgement: This work was carried out in the framework of the executive programme for scientific andtechnological cooperation between the Italian Republic and the Republic of Korea. The contribution of Min-istero degli Affari Esteri, Direzione Generale per la Promozione del Sistema Paese, is gratefully acknowledged.

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Talk Number: 2 (Invited)Time: Wednesday, May 13, 2015 10:25 AM Session: W2_2: BIOT (Heritage Room)

INFECTION DIAGNOSTICS WITH POLYMERIC VESICLES AND HYDROGELSFOR APPLICATION IN ADVANCED WOUND DRESSINGS AND BEYOND

Katrin-Stephanie Tücking1, Simon Haas1, Mir Mortzea Sadat Ebrahimi1, Holger Schönherr1

1 Department of Chemistry & Biology, Physical Chemistry I, University of Siegen, Germany

The development of in situ approaches for point of care infection diagnostics receives currently considerableattention. In this context we investigate and develop polymer-based infection diagnostics for application in,among others, wound dressings and in food safety.Our core strategy is the implementation of selective trigger mechanisms that signal the presence of pathogenicbacteria via an easily discernible colorimetric signal. In our work we exploit bacterial enzymes as the triggerto break down reporter dye-filled capsules [1], to enzymatically release indicator species conjugated covalentlyto hydrogel materials [2] or digest polymers in nanoporous sensor membranes [3].The bacteria-sensing capsules are composed of amphiphilic block copolymers, which are assembled intopolymeric vesicles [1]. The enzymatic degradation of the vesicle wall by the enzymes of the pathogenic bacteriastaphylococcus aureus and pseudomonas aeruginosa result in the release of encapsulated dye molecules, whichis detected due to the change in color and / or fluorescence intensity. The detailed characterization of thepolymeric vesicles and the degradation kinetics by confocal fluorescence lifetime imaging microscopy (FLIM)is shown to provide the basis for the successful development of prototype dressings that respond to low levelsof enzymes in bacterial supernatants.The strategy was recently expanded to chitosan hydrogel-based sensing platforms, which are compatiblewith the implementation in infection-sensing wound dressings and food safety applications [2]. Thin filmsof the established wound dressing biopolymer chitosan were functionalized with fluorogenic or chromogenicsubstrates, which are released only upon selective enzymatic degradation, resulting in a pronounced increasein fluorescence emission intensity or color change, respectively. By exploiting various substrates, the detectionof staphylococcus aureus, pseudomonas aeruginosa as well as E. coli (EHEC) is shown to be feasible withour bacteria sensing hydrogels.Finally, it will be discussed how novel photonic structures can be exploited to detect bacterial enzymeswithout using dye molecules.References:1 K.-S. Tücking, S. Handschuh-Wang, H. Schönherr, Australian Journal of Chemistry, 2014, 67, 578-584.2 M. M. S. Ebrahimi, H. Schönherr, Langmuir, 2014, 30, 7842-7850.3 F. S. H. Krismastuti, H. Bayat, N. H. Voelcker, H. Schönherr, 2014, submitted.

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Talk Number: 3 (Oral)Time: Wednesday, May 13, 2015 10:45 AM Session: W2_2: BIOT (Heritage Room)

HOW ADDITIVE EXUDATION CAN AFFECT THE BIOCOMPATIBILITY OF APOLYMERIC MEDICAL DEVICE: THE CASE OF A POLYURETHANE USED INIMPLANTABLE CATHETERS

Johanna Saunier1, Micheal Nouman1, Emile Jubeli1, Jean-Marie Herry2, Christian Marlière3, AlexandreDazzi4, Margareth Renault2, Marie-Noëlle Bellon-Fontaine2, Najet Yagoubi1

1 EA 401 - UFR de pharmacie, Université Paris Sud, FRANCE2 BHM - UMR 1319 MICALIS, INRA - AgroPArisTech, FRANCE3 ISMO - UMR 8214, CNRS - Université Paris Sud, FRANCE4 LCP - UMR 8000, CNRS - Université Paris Sud, FRANCE

An important part of the implantable catheters are made of polyurethane (PU). Moreover the catheterscontain additives such as antioxidants or lubricants. The repartition of additives in the polymer is governedby thermodynamic and diffusion kinetic. As these molecules are small, they have indeed a high mobility andthey can migrate through the polymer matrix to the surface. Even if the concentration of these additives inthe bulk is commonly less than 0.5%, they can be present at very high concentration on the surface and theycan modify surface properties. In this communication we will present the case of a polyurethane catheter thatcan present blooming of antioxidant and lubricant on its surface. After having characterized the blooming bymicroscopy (AFM, AFM-IR), we worked on the catheter and on PU spincoated films and we showed how theinteractions of the material with biological media was modified by the blooming. The impact of the bacterialadhesion was studied by using a versatile and virulent pathogen bacterium, staphylococcus aureus, oftenimplicated in nosocomial diseases. The adhesion ability and the viability of the adhered cells were evaluatedand we try to correlate these results to the physical properties of the surface (hydrophobicity, topography,stiffness ...). Moreover the ability of the material to release additives at the solid or soluble state was studiedand correlated to cytotoxicity tests (MTT) realized after contact with endothelial cells (HUVECS).

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ELECTROSPUN PHB/PCL/FUMED SILICA FIBROUS STRUCTURE FOR BONETISSUE ENGINEERING

Yaping Ding1, Qingqing Yao2, Wei Li3, Judith Roether1, Aldo Boccaccini3, Dirk Schubert1

1 Department of Materials Science and Engineering, Institute of Polymer Materials, University of Erlangen-Nuremberg, Germany2 School of Ophthalmology & Optometry, Institute of Advanced Materials for Nano-Bio Applications, Wen-zhou Medical University, China3 Department of Materials Science and Engineering, Institute of Biomaterials, University of Erlangen-Nurem-berg, Germany

Bone tissue engineering is a novel approach to create bone graft in situ as alternative of autograft andallograft for bone defect repair and restoration. In bone tissue engineering, as one of the key player,scaffolds were designed to not only support the cell attachment, proliferation and differentiation, but alsowere able to degrade by the time of new tissue regeneration and then discharged from the body. Amongthe various scaffolds fabrication processes, with combining the dominant advantages of all components,Electrospinning of polymer/inorganic composites was one of the intensively studied approaches for threedimensional scaffolds fabrication owing to the fiber size down to nano level, the high porosity up to 95%, thehigh surface volume ratio, the conveniences, etc [1]. Here in this study, polyhydroxybutyrate (PHB)/ poly-ε-caprolactone (PCL)/fumed silica composite fibermeshes were prepared through electrospinning combinedwith the ultrasonication since the biopolymer blend was able to integrate the high stiffness and strength ofPHB and high elasticity of PCL, and fumed silica was reported to not only reinforce the polymer matrix, butalso induce higher cell vitality and improved cytocompatibility [2]. In this report, the influence of 0∼50wt%fumed silica addition on the composite fibrous scaffolds was investigated on the perspective of morphologies,mechanical properties, chemical structure, wettability, thermal properties and biological properties. TheSEM graphs showed that no severe aggregation occurred until 20wt% particles addition, and the fiberfilaments were fully covered with nanoparticles in case of 50wt% addition. The tensile strength and elasticmodulus was enhanced 14% and 20% by 1wt% silica addition, but decreased with further incorporation.All electrospun fiber meshes exhibited high hydrophobicity (all with WCA above 130oC); however, thecontact angles all reduced to different extent after 5 mins which is attributed to the hydrophilicity natureof the fumed silica. FTIR spectra were used to confirm the incorporation of silica nanoparticles, and thecrystallinity changes were analyzed through DSC measurements. At last, the cell response and cytotoxicityevaluation were conducted to testify the biological properties of the composite system.Reference[1] Y. Ding, et al, Eur. Polym. J. 2014, 55(1), 222-234.[2] Y. Wu, et al, J. Appl. Polym. Sci. 2012, 123(3), 1612-1620.

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BIOMIMETIC NANOFILAMENTARY POLYMER SCAFFOLDS AND THE MECH-ANISMS OF CELL-SCAFFOLD INTERACTION

Mohammad Nahid Andalib1, Jeong Soon Lee1, Ligyeom Ha1, Yuris Dzenis1, Jung Yul Lim1


Tissue engineered scaffolding materials require certain minimum requirements including cellular biocom-patibility, mechanical strength, degradation property, etc. to support successful regeneration of the dam-aged tissue. Electrospun nanofibrous scaffolds can fulfill many of these requirements, as they have advan-tages of biomimicking nanofilamentary architecture which can be tailored to match the mechanical com-pliance/strength of the target tissue, high surface area, controllable porous structure, and potential 3Dmicroenvironment for supporting cell-substrate and cell-cell interaction.Although nanofiber-based tissue engineering applications have reported some successes, very little is revealedregarding the molecular mechanism of cell-nanofiber interaction. We tested the hypothesis that cytoskeletaltension signaling, such as RhoA kinase (ROCK), may play a mediatory role in mesenchymal stem cell (MSC)alignment on nanofibers. To test this, we produced poly(L-lactic acid) nanofibers to have unidirectional andrandom orientations with same diameter (about 130 nm). We cultured MSCs on these aligned and randomnanofibers and flat PLLA control film and assessed the ROCK expression in MSCs on the test substrata bywestern immunoblotting. MSCs seeded on aligned nanofibers exhibited well-documented contact guidancebehavior by growing and aligning along the nanofibers. Importantly, we for the first time showed that ROCKexpression in MSCs was significantly increased for cells cultured on aligned nanofibers relative to cells on flatcontrol which suggested that ROCK is involved in MSC alignment on nanofibers. Furthermore, we demon-strated that if ROCK signaling in MSCs was interfered by molecular silencing (shRNA) or pharmacologicalinhibitor (Y-27632), cells on nanofibrous cultures displayed significantly decreased cellular lengths, in bothmajor and minor axis lengths.While cytoskeletal signaling such as ROCK may constitute one important regulatory mechanism, focal celladhesion signaling may form another vital mechanism for the nanofiber control of cells. Currently, we areconducting experiments to reveal the role of focal adhesion kinase (FAK) in cell response to nanofibers. Ob-tained data on the role of ROCK and FAK, each representing key molecular mechanosensors of cytoskeletaltension and focal adhesion, in MSC alignment and morphology on nanofibers will provide a new insight intonanofiber-based tissue engineering and regenerative medicine.

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ULTRAHIGH-PERFORMANCE NANOFIBERS FROM DNA AND PROTEINS

Kaspars Maleckis1, Yuris Dzenis1


Nucleic acids and polypeptides have several intriguing nanoscale properties which can be adapted in novelnano-structured and nano-sized devices, sensors and materials. Development of one-dimensional, continuousnanostructures of these polymers provide additional benefits, such as directionality of properties, easy ma-nipulation and high surface area. Typically such structures have been produced by bottom-up nanofacturingmethods, which rely on biopolymer capability to self-assemble at the molecular scale. While bottom-up ap-proach gives unprecedented control of the molecular structure, it has limitations in continuity and mechanicalintegrity of the nanofilaments. Alternative top-down nanomanufacturing methods, like electrospinning, allowone to overcome these limitations, however control of molecular structure and properties remains uncertain,since traditional polymer characterization methods cannot be applied to individual nanofilaments.Here we show a unique insight into structure and properties of individual electrospun DNA and other bi-ological polymer nanofilaments. We also demonstrate specially developed protocols of different character-ization methods that can be applied to individual polymer nanofilaments to study size-structure-propertyrelationships. Our results show that electrospinning enables production of continuous and uniform DNAnanofilaments within wide range of diameters (10-500nm) and high throughput. Mechanical tests of indi-vidual DNA nanofilaments through failure show extraordinary strength and toughness. These propertiesincrease as nanofiber diameters decrease, exceeding bulk properties of some of the high-performance syn-thetic materials and fibers. Structural studies of individual DNA nanofibers with different methods indicatepseudo-crystalline high orientation, but show no indication of crystalline packing. The resulting nanofibersand their constructs attract high interest for use in drug and gene delivery, tissue engineering, and biomedicaldevices.

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Talk Number: 7 (Oral)Time: Wednesday, May 13, 2015 12:05 PM Session: W2_2: BIOT (Heritage Room)

INVESTIGATION OF RUBBER FLOW DURING SHAPING OF AUTOMOBILETIRES

Min-Young Lyu1, Min-A Lee2, Seong-Yeol Park2, Sung-Hyun Choi3

1 Mechanical System Design Engineering, Seoul National University of Science and Technology, South Korea2 Product Design and Manufacturing Engineering, Seoul National University of Science and Technology,South Korea3 Central R & D Center, Hoonkook Tire Co., South Korea

Automobile tires consist of more than ten layers, including the tread, carcass, and sidewall. The tread,in direct contact with the road surface, has a significant effect on the performance of an automobile suchas breaking conditions, traction, noise and so on. It has grooves with a complex geometry that is moldedby a curing process. The short shot of the tread rubber in the mold affects the quality of the tire but,simultaneously, can lead to problems with the automobile performance. Consequently, investigation of theflow behavior of tread rubber during the curing process is important. This research undertakes a simulationand experiment using white rubber to investigate the flow behavior of tread rubber in a mold. Flow of therubber across the grooves of the mold is not observed in either the simulation or experiment. The simulationresults are in good agreement with those of the experiment.

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Wednesday, May 13, 2015 Starting: 1:00 PMW3: Young Plenary (Auditorium)

Session Chair: Christopher CorneliusAssistants: Trevor Gnuse, Yan Zou

Talk:

1. (1:00 PM, Young Plenary) Whittington: POLYMER CHARACTERIZATION OF MEDICAL DE-VICES FOR USE IN CANCER PATIENTS

Dr. Abby Whittington, Assistant Professor of Biomedical Engineering and Sciences, Virginia Tech

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Talk Number: 1 (Young Plenary)Time: Wednesday, May 13, 2015 1:00 PM Session: W3: Young Plenary (Auditorium)

POLYMER CHARACTERIZATION OF MEDICAL DEVICES FOR USE IN CANCERPATIENTS

Abby R. Whittington1

1 Chemical Engineering & Materials Science and Engineering, Virginia Tech, USA

Polymeric medical devices are becoming commonplace in the treatment of cancer patients to provide fluidsand medications, to offer insight into diagnosis, and to fill the voids created by removal of the tumor.Therefore there is a growing need to understand how the materials respond and are influenced by the hostileenvironment of generated around the tumor during caner treatment. My research group has begun focusingon the design and characterization of polyurethane devices for medical applications and how therapeuticradiation commonly used in cancer therapy influences the critical properties of such materials. This talk willfocus on the two main areas where therapeutic radiation is utilized: imaging and radiotherapy. The doses forimaging, while very low, pose a risk when repeated multiple times as in the case of placement and monitoringof peripherally inserted central catheters (PICC) for neonates. In radiotherapy, the dose levels are sufficientlyhigh to cause cross-linking and/or degradation of many polymers when exposed in the aqueous environmentof the body. An example of both applications will be explored.

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Wednesday, May 13, 2015 Starting: 1:50 PMW4: Poster (Ballroom)

Session Chairs: Michael Hess, Jean-Jacques PireauxAssistant: Trevor Gnuse

Talks:

1. (1:50 PM, Poster) Jayasinghe: INVESTIGATION OF SWELLING BEHAVIOR OF POLY(HEMA-CO-DMAEMA) HYDROGELS CONFINED IN AN ELASTOMERIC MOLD

2. (1:50 PM, Poster) Schwahn: CONTROLLED CURING OF ACRYLATE: SYSTEM MODELINGAND APPLICATIONS IN STEREOLITHOGRAPHY

3. (1:50 PM, Poster) Adhikari: CHARACTERIZATION OF BAMBOO FLOURS REINFORCEDEPOXY RESIN COMPOSITES

4. (1:50 PM, Poster) Li: CHARACTERIZATION OF THE INFLUENCE OF DEPTH IN PHOTO CUR-ING OF ACRYLATE: A METHOD BASED ON RAPID-SCAN FTIR DURING LASER CURING ONAN ATR

5. (1:50 PM, Poster) Furgal: HIGH SURFACE AREA METHYLSILSESQUIOXANE POLYMER GELSBY FLUORIDE CATALYSIS

6. (1:50 PM, Poster) Stockdale: MANUFACTURING OF POLYIMIDE FIBER-REINFORCEDNANOCOMPOSITES

7. (1:50 PM, Poster) Zou: EFFECT OF CONSTRAINT ON STRUCTURE AND MECHANICALPROPERTIES OF CONTINUOUS POLYACRYLONITRILE-BASED STABILIZED AND CAR-BONIZED NANOFIBERS

8. (1:50 PM, Poster) Jasa: USING MOLECULAR DYNAMICS SIMULATIONS FOR CHARACTER-IZING MACROSCOPIC RESPONSE IN POLYCARBONATE

9. (1:50 PM, Poster) Hnatchuk: MODIFICATION OF POLY(VINYL CHLORIDE)

10. (1:50 PM, Poster)Hnatchuk: PROPERTIES OF EPOXY FILMS BASED ONMODIFIED PHENOL-FORMALDEHYDE OLIGOMERS

11. (1:50 PM, Poster) Chan: FTIR STRUCTURAL ANALYSIS OF EPOXY PAINTS ON STEELSTRUCTURE FOR COATING FINGERPRINTING CERTIFICATE FOR PAINT INDUSTRY

12. (1:50 PM, Poster) Viel: IMPACT OF COVER SLIDE ON RECRYSTALLIZATION FROM THEAMORPHOUS STATE OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPRO-PHYLLINE

13. (1:50 PM, Poster) Cosby: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS OF POLY-MERIZED IONIC LIQUIDS

14. (1:50 PM, Poster) Jiao: INTERPLAY BETWEEN ABSORPTION BROADENING ANDMORPHOL-OGY DETERIORATION IN TERNARY BULK HETEROJUNCTION SOLAR CELLS RESOLVEDBY SOFT X-RAY SCATTERING

15. (1:50 PM, Poster) Chen: OPTIMIZATION OF THE DISTRIBUTION OF PROPERTIES: USINGACRYLATE/EPOXY MIXTURES IN THE EXTENSION OF AN FGM PLATE WITH A HOLE

16. (1:50 PM, Poster) Daily: DIELECTRIC PROPERTIES AND KINETIC STUDY ON THE DEGRA-DATION OF BISMALEIMIDE RESIN

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17. (1:50 PM, Poster) Jamil: MECHANISM OF MOLECULAR INTERACTION OF SUPERPLASTI-CIZER OLIGOMERS WITH HYDRATED CEMENT PHASES

18. (1:50 PM, Poster) Piorkowska: COMPARISON OF PROPERTIES OF STAR AND LINEARPOLY(L-LACTIDE)

19. (1:50 PM, Poster) Frazier: CHEMICAL MODIFICATION OF PROTEIN-BASED ADHESIVES FORCONSTRUCTION APPLICATIONS

20. (1:50 PM, Poster) Dargent: MOLECULAR DYNAMICS IN ELECTROSPUN FIBERS OF PLAS-TICIZED POLYLACTIDE

21. (1:50 PM, Poster) Gakhutishvili: TRIBOLOGICAL PROPERTIES OF ANTIBACTERIAL POLY-MER COMPOSITES

22. (1:50 PM, Poster) Delpouve: LENGTH SCALE AT THE GLASS TRANSITION IN SEMI-CRYS-TALLINE COMPATIBILIZED POLYLACTIDE/CLAY NANOCOMPOSITES

23. (1:50 PM, Poster) Lin: HYDROGEN BONDING INDUCED NANOPHASE SEPARATION OF GI-ANT SURFACTANTS TOWARD SUB-10-NM HYBRID ORDER NANOSTRUCTURES

24. (1:50 PM, Poster) Liu: TWO-DIMENSIONAL NANO-CRYSTALS OF MOLECULAR JANUS PAR-TICLES

25. (1:50 PM, Poster) Alarifi: EFFECTS OF UV EXPOSURE ON PHYSICAL PROPERTIES OF CAR-BON FIBER/PPS THERMOPLASTIC COMPOSITES

26. (1:50 PM, Poster) Kaser: NANOMANUFACTURING POLYACRYLONITRILE NANOFIBERYARNS

27. (1:50 PM, Poster) Alharbi: INTEGRATING C60 NANOPARTICLES INTO TIO2 NANOFIBERSVIA ELECTROSPINNING PROCESS FOR ENHANCED ENERGY CONVERSTION EFFICIEN-CIES

28. (1:50 PM, Poster) Loubeau: AGEING OF A THREE-LAYER PAPER USED IN THE INSULATIONOF AN ELECTRICAL MOTOR FOR THE AUTOMOTIVE TRACTION

29. (1:50 PM, Poster) Schmidt: A STUDY OF THE EFFECTS OF SPIN COATING ON PVDF FILMS

30. (1:50 PM, Poster) Schönherr: INVESTIGATION OF ELECTRONIC PROPERTIES OF AGRAPHENE FIELD EFFECT TRANSISTOR

31. (1:50 PM, Poster) Ding: BROADBAND DIELECTRIC RELAXATION ANALYSIS ON THE REIN-FORCEMENT OF ANTHRACENE-FUNCTIONALIZED EPOXY COMPOSITES

32. (1:50 PM, Poster) Lobland: SYNTHESIS AND PROPERTIES OF REACTIVE OLIGOMERSBASED ON A PEROXY DERIVATIVE OF AN EPOXY RESIN AND 1,4- BUTANEDIOL

33. (1:50 PM, Poster) Ospina: SYNTHESIS AND CHARACTERIZATION OF POLYMERS WITH AN-TIBACTERIAL PROPERTIES BASE ON TRICLOSAN ACRYLATE

34. (1:50 PM, Poster) Bakhtiary Noodeh: USING CURING KINETICS TO CONTROL THE ME-CHANICAL PROPERTIES OF SIMULTANEOUS ACRYLATE/EPOXY IPNS DURING PHOTOCURING OF GRADED MATERIALS

35. (1:50 PM, Poster) Gafurov: MOLECULAR STRUCTURE PARAMETERS INFLUENCE ON DE-FORMATION MECHANICS OF AN ORIENTED CRYSTALLINE POLYMER

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36. (1:50 PM, Poster) Lanyi: NOVEL CHART FOR REPRESENTATION OF MATERIAL PERFOR-MANCE AND RELIABILITY

37. (1:50 PM, Poster) Rezaei: U-SHAPED PROBES FOR CHARACTERIZATION OF POLYMERSUSING CONTACT RESONANCE ATOMIC FORCE MICROSCOPY

38. (1:50 PM, Poster) Dargent: STUDY OF AMORPHOUS AND CRYSTALLINE PHASES IN BIO-BASED NANOCOMPOSITE FILMS

39. (1:50 PM, Poster) Delpouve: MICROSTRUCTURE, AMORPHOUS PHASE DYNAMICS ANDBARRIER PROPERTIES IN MULTILAYER COEXTRUDED POLYLACTIDE

40. (1:50 PM, Poster) Schamme: RELAXATION OF SHEAR-INDUCED PRECURSORS INPOLY(LACTIC ACID)

41. (1:50 PM, Poster) Hosseinabad: EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCEDCRYSTALLIZATION

42. (1:50 PM, Poster) Sterzynski: THE POSS AND MWCNT MODIFIED GLASS TRANSITION TEM-PERATURE TG OF POLY(VINYL CHLORIDE)

43. (1:50 PM, Poster) Saiter: INFLUENCE OF STRUCTURAL FEATURES OF POROGENMOLECULES ON THERMAL PROPERTIES AND POROSITY OF NANOPOROUS POLYCYA-NURATE-BASED FILM MATERIALS

44. (1:50 PM, Poster) Zare Rami: INVESTIGATION OF FRACTURE BEHAVIOR OF HETERO-GENEOUS POLYMER MIXTURES SUBJECTED TO VISCOELASTIC DEFORMATION USINGMICROSTRUCTURAL MODELING

45. (1:50 PM, Poster) Ding: POLAR PHASE GENERATION IN PVDF, THROUGH AMPHIPHILICIONIC LIQUID MODIFIED MULTIWALLED CARBON NANOTUBES: EFFECT OF ANION

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Talk Number: 1 (Poster)Time: Wednesday, May 13, 2015 1:50 PM Session: W4: Poster (Ballroom)

INVESTIGATION OF SWELLING BEHAVIOR OF POLY(HEMA-CO-DMAEMA)HYDROGELS CONFINED IN AN ELASTOMERIC MOLD

Hasani Gaya Jayasinghe1, Yolanda Vasquez1

1 CHEMISTRY, OKLAHOMA STATE UNIVERSITY, USA

Hydrogels are versatile network polymeric materials that have a vast range of applications that includes scaf-folds for tissue engineering, drug delivery systems, and as sensors and actuators due to properties such as highretention of water, biocompatibility and ability to respond to external stimuli. The swelling of a hydrogeldepends on properties such as crosslinking density and the identity of the functional groups present in thehydrogel as well as the interactions between the hydrogel and the solvent. In addition to the chemical param-eters, swelling of the hydrogel can be significantly affected by confinement. In this study, we have prepareda poly(HEMA-co-DMAEMA) [poly(2-hydroxyethylmethacrylate-co-2-dimethylaminoethylmethacrylate)] hy-drogel and investigated the swelling of the hydrogel while confined by polydimethyl siloxane (PDMS), anelastomeric material. Around two-fold decrease in the swelling ratio was observed when PDMS was used asthe confining surface as compared to the free, unconfined hydrogel and when 60% ethanol was used as theswelling medium. We demonstrate that the swelling behavior of the confined hydrogel can be exploited tosuccessfully generate microscale patterns on to poly(HEMA-co-DMAEMA).

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CONTROLLED CURING OF ACRYLATE: SYSTEM MODELING AND APPLICA-TIONS IN STEREOLITHOGRAPHY

Evan Schwahn1, Wenlong Li1, Mehrdad Negahban1, Nicolas Delpouve2, Jean-Marc Saiter2, Steven Araujo2,Florian Batteux2

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States of America2 Department of Physics, University of Rouen, France

Rapid prototyping (RP) is widely used in industry for its ability to construct parts and/or prototypesquickly and affordably. Despite the recent advances in the field regarding part resolution and accuracy suchas that by Ruidong and Dichen [1], and also research into multi-material prototyping [2], there is still a needfor materials with properties that can be controlled and specified at any point within a part structure. Thiscontrol of properties within one material can eliminate the need for fasteners and other assembly practicesthat could otherwise be costly to manufacturers. The goal of this work was to provide a model for controlledcuring of acrylate resin that would allow the manufacture of a graded structure at the molecular level. Weuse the stereolithography rapid prototyping technique.To achieve this, rapid-scan FTIR was employed to study the curing kinetics of the acrylate resin in orderto determine control variables for the RP machine. The study provided information the energy exposureneeded to reach any degree of conversion desired for the acrylate system and yielded information about thedark cure effect (continued curing after termination of light exposure). Another control variable studied isthe laser beam profile overlap that results from successive linear scans. To achieve a uniform conversiondegree across the sample, it was determined that the energy profiles of successive scans over the same pointcould not added and related to the extent of curing. Instead, when a second exposure was overlapped withthe first, the overlapped area yielded a conversion degree up to 25% higher than would be expected for asingle exposure at the total energy. Because of this behavior, a study was done and the optimal beam profileoverlap for sample uniformity was found to be 35% beam overlap for the acrylate system. With informa-tion gained from these studies, a model was developed to predict the curing extent in the beam overlap region.

[1] Xie, Ruidong, and Dichen Li. “Research on the Curing Performance of UV-LED Light Based Stereolithog-raphy.” Optics & Laser Technology 44, no. 4 (June 2012): 1163-71. doi: 10.1016/ j.optlastec.2011.09.019.[2] Choi, Jae-Won, Ho-Chan Kim, and Ryan Wicker. “Multi-Material Stereolithography.” Journal of Mate-rials Processing Technology 211, no. 3 (March 1, 2011): 318-28. doi: 10.1016/ j.jmatprotec.2010.10.003.

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CHARACTERIZATION OF BAMBOO FLOURS REINFORCED EPOXY RESINCOMPOSITES

Rameshwar Adhikari1, Surendra Kumar Gautam2, Marco Liebscher3, Ralf Lach4, Wolfgang Grellmann4,Hanna Brodowsky3, Gert Heinrich3

1 Central Department of Chemistry, Tribhuvan University, Nepal2 Department of Chemistry, Tri-Chandra Campus, Tribhuvan University, Kathmandu, Nepal3 Leibnitz Institute of Polymer Research, Dresden, Germany4 Center of Engineering, Martin Luther University Halle-Wittenberg, Germany

Bamboo flours were subjected to different chemical modifications and carbonization and incorporatedinto epoxy resin with the aim of reinforcing the mechanical properties of the composite materials. Thecomposites were prepared by using amine hardened diglycidyl ether of bisphenol A (DGEBA) as polymermatrix which were characterized by thermogravimetric analysis (TGA), dynamic mechanical analysis andscanning electron microscopy (SEM).Both neat and carbonized bamboo flour filled composites showed significant reinforcement in mechanicalproperties. As shown by SEM investigations, the fillers were uniformly distributed in the matrix, thedistribution being much better in the composites with carbonized bamboo flour. This effect was reflectedalso in the mechanical properties of the samples. A significant increase in the glass transition temperaturein the composites relative to the neat epoxy resin was observed. The observed properties of composites willbe discussed in correlation with the phase morphology.Keywords: epoxy resin, polymer composites, electron microscopy, microhardness

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CHARACTERIZATION OF THE INFLUENCE OF DEPTH IN PHOTO CURINGOF ACRYLATE: A METHOD BASED ON RAPID-SCAN FTIR DURING LASERCURING ON AN ATR

Wenlong Li1, Mehrdad Negahban1, Nicolas Delpouve2, Jean-Marc Saiter2, Florian Batteux2, Steven Araujo2

1 Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States2 AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France

When photo curing a polymer system one becomes immediately concerned with the depth of penetration oflight into the system and with the uniformity of curing process. Both of these are related to the Beer-Lambertlaw of light penetration into the system. To use the Beer-Lambert law, which is given in an exponentialform for a homogeneous system, one needs to determine of the associated attenuation coefficient. This isnormally done by direct measurement of the light transmission using different thicknesses of the mediumusing a power meter. We have used a Rapid-Scan FTIR equipped with an ATR to demonstrate that one canget the Beer-Lambert attenuation coefficient directly while monitoring the curing kinetics. This also allowsto directly evaluate the validity of the one half power law used to model the effect of power on the curingkinetics. The process was demonstrated for the photo curing of an acrylate system.

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HIGH SURFACE AREA METHYLSILSESQUIOXANE POLYMER GELS BY FLUO-RIDE CATALYSIS

Joseph Furgal1, Honami Yamane2, Timothy Odykirk3, Eongyu Yi3, Richard Laine3

1 Chemistry/Macromolecular Science and Engineering, University of Michigan, USA2 Polymer Chemistry, Kyoto University, Japan3 Materials Science and Engineering, University of Michigan, USA

High surface area materials are of considerable interest for gas storage/capture as well as for slow release drugdelivery systems. The hydrophobic methylsilsesquioxane polymer gels are made by a simple and fast fluoridecatalyzed rearrangement of methyltriethoxysilane and bis-triethoxysilylethane (BTSE) at room temperature.These materials offer surface areas up to 1300 m2/g, pore sizes of 0.8 nm and thermal stabilities above 200oC. The gelation time and surface area can be controlled by adjusting the solvent volume (DCM), % fluoride(TBAF) and amount of cross-linking agent (BTSE). Polymers with other corners and linkers are also explored.

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MANUFACTURING OF POLYIMIDE FIBER-REINFORCED NANOCOMPOSITES

Taylor Stockdale1, Mohammad Nahid Andalib1, Anastasia Desyatova1, Stephen Cheng2, Yuris Dzenis1

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States2 Department of Polymer Science, University of Akron, United States

Continuous nanofibers are an emerging class of nanomaterials with property combinations unavailable inother materials, offering a great opportunity for composite applications. Polyimide (PI) is an attractivecandidate for use in composites due to its versatility, good chemical resistance, and high service temperature.Typical fabrication of PI fibers is completed in two steps. First a polyamic acid (PAA) solution is used tospin PAA fibers. The fibers are then converted to polyimide through an imidization process. A single stepfabrication method is of great interest as it would simplify the fiber manufacturing process, and prevent thefusion of fibers that can occur during imidization. Here we demonstrate the manufacturability of a thin,flexible, nanofiber-reinforced composite material based on electrospun PI nanofibers, produced in a single-step process from a soluble PI. PI nanofiber mats were used as reinforcement in two types of resins - epoxyand PI. The epoxy-based nanocomposites were manufactured by applying an epoxy resin to as spun nanofibermats and then curing at elevated temperatures under pressure. For PI/PI nanocomposites, thin PI filmswere first produced using a drawdown machine and another soluble PI. PI nanofiber mats were assembledbetween PI thin films and cured under pressure at temperatures above the Tg of the thin films, but below theTg of the nanofibers. PI/PI nanocomposite thicknesses were an order of magnitude lower than thicknessesof epoxy-matrix nanocomposites. SEM results confirmed that complete impregnation of nanofiber mats wasachieved and the resulting nanocomposites were optically transparent.

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EFFECT OF CONSTRAINT ON STRUCTURE AND MECHANICAL PROPER-TIES OF CONTINUOUS POLYACRYLONITRILE-BASED STABILIZED AND CAR-BONIZED NANOFIBERS

Yan Zou1, Dimitry Papkov1, Alexander Goponenko1, Yuris Dzenis1

1 Mechanical & Materials Engineering, UNL, USA

High-performance carbon fibers are the most commonly used reinforcements in structural advanced com-posites. Commercial high-strength carbon fibers are produced from polyacrylonitrile (PAN) by a two stageprocess that includes oxidative stabilization and carbonization at high temperature under inert atmosphere.Application of constraint and stretch of the precursor fibers during the stabilization stage is commonlybelieved to be responsible for the superior properties of carbon fibers. Such treatment prevents entropicshrinkage, and relaxation of the aligned polymer chains. Continuous carbon nanofibers (CNFs) can be pro-duced from electrospun PAN nanofibers (NFs) by stabilizing and carbonizing them. Mechanical properties ofindividual CNFs and NFs were not widely studied so far. Here we present a study of size effects in mechani-cal properties of individual stabilized and carbonized PAN NFs examined in a wide range of NF diameters,showing significant improvements in strength and modulus with the decrease in CNF diameter. In addition,graphitic structure, graphitic crystal orientation in CNFs was examined by Raman spectroscopy and electrondiffraction, showing significant improvements for smaller NF diameters, and as a result of physical constraintof the CNFs during the nano-manufacturing process. Comparison of mechanical properties of NFs stabilizedwith and without constraint show significant improvements in NF modulus for the constrained NFs. Thedemonstrated results indicate the potential for the development of next generation advanced fibers.

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USING MOLECULAR DYNAMICS SIMULATIONS FOR CHARACTERIZINGMACROSCOPIC RESPONSE IN POLYCARBONATE

John Jasa1, Lili Zhang3, George Gazonas2, Antoine Jérusalem3, Zesheng Zhang1, Mehrdad Negahban1

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States2 U.S. Army Research Laboratory, Aberdeen Proving Ground, United States3 Department of Engineering Science, University of Oxford, United Kingdom

Keywords: Molecular dynamics, continuum-level characterization, deformation gradient, Cauchy stress,multi-scale

Recently, there has been a push to accurately characterize amorphous glassy polymers using molecu-lar dynamics (MD) simulations. Our work uses MD to help bridge the gap between nanoscale simulationsand well-understood macroscale experiments. To do this, continuum parameters widely used in continuummechanics, such as deformation gradient and Cauchy stress, are constructed from MD simulations. Thesemethods are applicable to non-equilibrium and inhomogeneous systems, and can be used to evaluate anypart of a system, such as a molecule or particular region in the system. This information can be used tocreate continuum-like models based on MD simulations.

These continuum-like methods have been applied to systems of polycarbonate at various tempera-tures and strain rates. In addition to polymers, KcsA potassium channels, carbon nanotubes, and aluminumoxynitride have been investigated to show the versatility of the methods. The results from these simulationsand our analyses compare well with experimental results, especially in regards to stress-strain relationships.

With the proposed method, specific groups of atoms can be selected and analyzed in order to deter-mine areas of stress concentrations or derive properties for a portion of the system. This can be especiallyuseful to examine the material around cracks or to characterize the microstructure after impact loading.By using these methods on larger systems of 100,000s of atoms, the continuum properties are expectedto better mimic the expected continuum response. Additionally, the large systems allow focusing on localevents around, for example, cracks. Averaging of individual molecular response naturally provides a way tostudy the difference between affine and non-affine motions in large systems.

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MODIFICATION OF POLY(VINYL CHLORIDE)

Witold Brostow1, Olena Astakhova2, Bogdana Bashta2, Michael Bratychak2, Gregory Granowski1,Nathalie Hnatchuk1

1 Materials Science and Engineering, University of North Texas, USA2 Polymer Chemistry and Technology, Lvivska Politechnika National University, Ukraine

Oligomer products with various functional groups are widely used as crosslinking and modified agents ofdifferent polymer mixtures. The modification of Polyvinyl Chloride (PVC) based mixtures by oligomerswith carboxy and epoxy or peroxy functional groups have been studied.

The effect of incorporation of polyfunctional oligomers into the PVC material was investigated bythe weight loss. Samples were kept at 422 K during 7 days. Mixture IV is characterized by stable weightduring four days and the it starts losing weight, but still at a slower rate than other materials. This whilethe unmodified PVC containing a plasticizer started losing weight from the first day. These results correlatewell with those from TGA.

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PROPERTIES OF EPOXY FILMS BASED ON MODIFIED PHENOL-FORMALDEHYDE OLIGOMERS

Witold Brostow1, Olena Astakhova2, Michael Bratychak2, Nathalie Hnatchuk1, Halyna Zubyk1,2


The presence of different functional groups in the molecules of phenol-formaldehyde oligomers (PFOs)should improve properties of the final products. This applies in particular to protective coatings containingPFOs. We have synthesized PFOs which contain methacrylate or peroxide and hydroxyl groups based onthe Novolac PFO.

With oligomers so synthesized, we have created oligomeric epoxy films based on the ED-20 epoxyresin and oligoesteracrylate at 403 K for 75 minutes. The original Novolac PFO was studied for comparison.Films so obtained exhibit much stronger chemical resistance to aggressive environments and improvedproperties than the Novolac. We have also determined scratch resistance, the technique is described in [1].Much shallower residual depth is seen for an oligomer with methacrylic groups. Thus, such a material is agood candidate for protective coatings when strong scratch resistance is required.

Reference:1. W. Brostow, V. Kovacevic, D. Vrsaljko & J. Whitworth, Tribology of polymers and polymer-basedcomposites, J. Mater. Ed. 2010, 32, 273.

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FTIR STRUCTURAL ANALYSIS OF EPOXY PAINTS ON STEEL STRUCTUREFOR COATING FINGERPRINTING CERTIFICATE FOR PAINT INDUSTRY

Chinhan Chan1, Chonghup Ong2, Tan Winie1, Mk Harun1, Mh Hidzir1, Fi Saaid1, Jiayin Lee3

1 Faculty of Applied Sciences, Universiti Teknologi MARA, Malaysia2 , Norimax Sdn Bhd, Malaysia3 , Research Instruments (M) Sdn Bhd, Malaysia

Most of the oil and gas companies in Malaysia are facing challenge to ensure the fabrication & constructionworks are carried out in full compliance to the specifications. The general phenomenon is the jobs or projectsoffered by the oil and gas companies are secured at rock-bottom prices by the suppliers. The question is:has it been possible to maintain (or improve) the quality of the jobs despite the challenge of lower pricesor sometimes below the cost prices of suppliers. One of the identified and common challenges for the oiland gas companies is the failure of polymeric coatings on steel structures, which has led to huge cost ofrepainting jobs. This progressive study showcases the practicality and simplicity of the provision of CoatingFingerprint Certificate for 2-component epoxy coatings for the supply of polymeric coatings from local paintmanufacturers as quality assurance requirement of the coatings supplied. This will reduce the possibilityof failures of the polymeric coatings and hence enhance the quality, integrity and safety. Fourier-transforminfrared (FTIR) is a simple and reliable tool for the study of reproducibility of the epoxies and hardeners aswell as to differentiate different types of epoxies and hardeners without any intrusion of paint formulationswhen High Sensitivity Compare feature of the FTIR software is to be strictly followed. This algorithmdepends on x- (wavenumber) and y- (absorbance) vectors. This function is able to discriminate minutedifference of different components as well as the compositional change of the components among samples.Simple (and software assisted) step-by-step guides are proposed in this work for the generation of referenceFTIR spectrum from one sample, which subsequently is used to estimate the degree of similarity (r) with theFTIR spectra from other samples. Fingerprinting regions of FTIR for epoxy resin and hardener are proposedand the confidence level of acceptance for quality assurance and quality control (QA & QC) is suggested atmore or same at 90.0%. We conclude that, the structural analysis by FTIR for complete Coating FingerprintCertificate for epoxy resin and hardener is reproducible. Besides, rejection or acceptance of the samples canbe easily done by setting the threshold value at 0.90 using High Sensitivity Compare feature of the FTIRsoftware.

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IMPACT OF COVER SLIDE ON RECRYSTALLIZATION FROM THE AMOR-PHOUS STATE OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OFDIPROPHYLLINE

Quentin Viel1,2, Clement Brandel2, Yohann Cartigny2, Gerard Coquerel2, Eric Dargent1, Samuel Petit2

1 LECAP, University of Rouen, France2 Crystal Genesis SMS, University of Rouen, France

Althought two enantiomers of an active pharmaceutical ingredient (API) share the same chemical com-position, the spatial arrangement of atoms differs around the asymmetric center, which often results insignificantly different pharmacological properties. It is nowadays almost mandatory to commercialize onlyenantiopure samples. For this purpose, crystallization processes are economically advantageous and areoften employed at the industrial scale. Thus, crystallization of chiral APIs has been the subject of intenseresearch, but these investigations are rather focused on crystallization in solution. Hence, the fundamentalmechanisms related to nucleation and growth of chiral APIs from glassy materials remain largely unexploredas a consequence of our poor understanding of molecular arrangements, motions and interactions inamorphous materials. Consequently, the scientific and industrial communities try to understand thefactors affecting the crystallization route from the amorphous state [1-2]. There is a scientific interest inunderstanding the role of the confinement due to the cover slide in glass-forming materials during theprocess of crystallization [3].The aim of this study is to elucidate the impact of enantiomeric composition in supercooled melts onthe outcomes of DPL recrystallization from the amorphous state, with and without cover slide. HotStage Microscopy (HSM) analyzes, Calorimetric measurements (DSC), X-Ray Powder Diffraction (XRPD)and Raman spectroscopy have been used to characterize the polymorphism of the distinct enantiomericcompositions promoted by the cover slide effect.

[1] Yu L., Advanced Drug Delivery Reviews, 48, 27-42, 2001[2] Hancock B.C., Shamblin S.L., Zografi G., Pharmaceutical Research, 12, 6, 1995[3] Bhugra C., Shmeis R., Pikal M., Journal of Pharmaceutical Sciences, 97, 10, 2008

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CHARGE TRANSPORT AND STRUCTURAL DYNAMICS OF POLYMERIZEDIONIC LIQUIDS

James Tyler Cosby1, Maximilian Heres1, Joseph Minutolo1, Joshua Sangoro1

1 Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, United States

Charge transport and structural dynamics of polymerized imidazolium bis(trifluoromethylsulfonyl)imide ionicliquids are investigated by broadband dielectric spectroscopy and differential scanning calorimetry. Unlikenon-polymerized ILs, DC conductivity and structural dynamics show significant decoupling, especially atlow temperatures, due to the high mobility of the anion relative to the rate of structural relaxation. Ahomologous series of imidazolium based polymerized ionic liquids are investigated to determine the effect ofalkyl substitution of the polymer backbone on the physicochemical properties of these polyILs.

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INTERPLAY BETWEEN ABSORPTION BROADENING AND MORPHOLOGY DE-TERIORATION IN TERNARY BULK HETEROJUNCTION SOLAR CELLS RE-SOLVED BY SOFT X-RAY SCATTERING

Xuechen Jiao1, Xiaoyan Du2, Tayebeh Ameri3, Rainer Fink2, Harald Ade1

1 Physics, North Carolina State University, USA2 PhysikalischeChemie II, FAU Erlangen-Nürnberg , Germany3 I-MEET, FAU Erlangen-Nürnberg, Germany

In the past several years, P3HT:ICBA based ternary blends have been intensively investigated. Althoughvarious sensitizers were used to broaden absorption range, ternary BHJs show few successful cases. There-fore, fundamental understanding why ternary cells fail to achieve high efficiency is indispensable for thefuture development of ternary blend solar cells. Domain details inside active layers are considered crucial toinfluence device performance. However, due to the low material contrast between polymer and fullerene inconventional morphology characterization such as transmission electron microscope (TEM), unambiguousand quantitative study of morphology impact of sensitizer is still lacking. Resonant soft x-ray scatteringtechnique(R-SoXS) has emerged as a powerful tool for morphology study in polymer:fullerene blends dueto the strong material contrast it utilizes[1]. R-SoXS can probe inter-domain details or mass-thicknessvariation by tuning the incident photon energy to material contrast or vacuum contrast[2]. Here, wesensitized P3HT:ICBA by Si-PCPDTBT/C-PCPDTBT to broaden the absorption range. The domainspacing is quantitatively characterized by R-SoXS and reveals good correlation with device performance.Interestingly, although Si-PCPDTBT and C-PCPDTBT are very similar in terms of chemical structure andabsorption, the influence of Si-PCPDTBT/C-PCPDTBT on morphology are quite different. By tracking thedomain spacing evolution of ternary blends along with different Si-PCPDTBT/C-PCPDTBT concentration,it was found that incorporation of Si-PCPDTBT up to 20% does not influence active layer inter-domainspacing, while the incorporation of C-PCPDTBT disturbs active layer morphology even at low C-PCPDTBTconcentration. Through this study, we observed experimentally and quantitatively the morphology evolutionalong with different concentration of sensitizer and substantiated that in order to improve PCE of ternaryBHJs, at the moment of broadening the absorption range of active layer, it is also crucial to minimize thenegative influence of sensitizer on the active layer morphology.[1] Collins, B. A., Z. Li, et al. (2013). Advanced Energy Materials 3(1): 65-74.[2] Gann, E., A. T. Young, et al. (2012). Review of Scientific Instruments 83(4)

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OPTIMIZATION OF THE DISTRIBUTION OF PROPERTIES: USING ACRY-LATE/EPOXY MIXTURES IN THE EXTENSION OF AN FGM PLATE WITH AHOLE

Zhong Chen1, Mehrdad Negahban1

1 Mechanical and Material Engineering, University of Nebraska Lincoln, USA

We looked at optimization of property distribution in parts. As it will be shown, by changing the distributionof material properties, one can make an inhomogeneous part that is better than the best uniform part. Todemonstrate this, we looked at optimizing the distribution of properties in a plate with a hole that is underuniaxial extension. In this problem, for a uniform plate the hole creates a stress concentration that limits themaximum applied stress on the plate to one third the load carrying capacity of the material. We show thatfor real materials one can select material distributions that allows applied stresses close to the maximumcapacity of the best material (i.e. 3 times the load carrying capacity of the best uniform plate with a hole).

An acrylate/epoxy IPN plate with a hole was selected for the investigated. We modeled, as a func-tion of each components concentration, the real characterized values of the Young’s modulus, Poisson’s ratioand fracture strength. A finite-element-method analysis based tool was developed to optimized the propertydistribution for this problem. It is shown that by varying the content of epoxy from 70 to 100% in themixture, one can protect the hole, and thus use most of the material at 100% of its capacity, resulting inover two fold increase of the load carrying capacity of the part relative to the best uniform part.

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DIELECTRIC PROPERTIES AND KINETIC STUDY ON THE DEGRADATION OFBISMALEIMIDE RESIN

Connor Daily1, Nicola Bowler1

1 Materials Science and Engineering, Iowa State University, USA

Bismaleimide, a thermosetting resin, is attracting interest in the aerospace industry due to its epoxy-likeprocessability, but better high-temperature performance than epoxy. As this industry shifts towards usinghigher overall percentages of fiber-reinforced polymer-matrix composites, understanding how these systemsdegrade, in particular the polymer matrix component, becomes increasingly important. Additionally, thesematerials are now being exposed to a wider variety of environmental and physical conditions, as new areasof usage, for both primary and secondary roles, are being explored. In this context, the thermo-oxidativedegradation kinetics of bismaleimide are explored. Two model-free isoconversional methods, the Friedmanand Ozawa-Flynn-Wall methods, are used to analyze results from thermogravimetric analysis at a varietyof heating rates (2, 5, 10, 20, and 50 oC/min) from room temperature to 800 oC. From these methods, theactivation energies associated with particular degradation mechanisms have been determined. Additionally,the dielectric properties of the bismaleimide resin were measured as a function of frequency (0.10 Hz to 1MHz) and temperature (-115 oC to 240 oC) using spectroscopic techniques. Two dielectric relaxations, betaand gamma, were observed in the material, and their activation energies calculated.

97


MECHANISM OF MOLECULAR INTERACTION OF SUPERPLASTICIZEROLIGOMERS WITH HYDRATED CEMENT PHASES

Tariq Jamil1, Hendrik Heinz1

1 Polymer Engineering Department, University of Akron, United States

Understanding the action of organic additives on hydrated cement phases is essential to develop novel admix-tures and alternative cements with low carbon footprint. Due to the indirect nature of available experimentalinformation the true nanoscale morphology of hydrated cement surface and its interaction with additives hasremained elusive. Atomistic simulations at with the thoroughly validated PCFF-INTERFACE force fieldallow first quantitative insight into the interactions of polyacrylate oligomers containing polyethylene sidechains with tobermorite 14 A (h k l) surfaces in aqueous solution. The results show that the acrylate back-bone is more attracted to the surface than the polyethylene oxide side chains. In particular, carbonateions approach calcium ions on the tobermorite surface to form ion pairs. The adsorption energy on (001)tobermorite facets remains under -1 kcal per mol acrylate monomer. Detailed results for a range of differentpolymers and tobermorite facets (001) will be presented.

98


COMPARISON OF PROPERTIES OF STAR AND LINEAR POLY(L-LACTIDE)

Grzegorz Lapienis1, Ewa Piorkowska2, Joanna Bojda2, Michal Cichorek2

1 Department of Polymer Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy ofSciences, Poland2 Department of Polymer Structure, Centre of Molecular and Macromolecular Studies, Polish Academy ofSciences, Poland

The aim of the study is comparison of crystallization, structure and properties of 6 arm star-shapedpoly(L-lactide) (PLLA) with its linear analog.PLLAs with molar mass Mw of 140 kg/mol were polymerized in bulk at the temperature of 130 oC.The polymerization was initiated with dipentaerythritol in the presence of tin octoate as a catalyst [1].The resulting polymers contained a low content of unreacted L-lactide (≤ 0.5 mol %) and were furtherpurified by precipitation from methylene chloride solution into methanol, homogenized in the molten state,and analyzed by different methods. Crystallization, supermolecular structure, thermal, mechanical andrheological properties of both PLLAs were examined.

AcknowledgmentThis research project has been supported by the National Science Centre, Poland, grant No UMO-2013/09/B/ST5/03619.

References1. M. Srisa-ard, Y. Baimark, J. Appl. Sci., 2010, 10, 1937-1943.

99


CHEMICAL MODIFICATION OF PROTEIN-BASED ADHESIVES FOR CON-STRUCTION APPLICATIONS

Shane Frazier1, Wil Srubar1

1 Civil, Environmental, and Architectural Engineering, University of Colorado Boulder, United States ofAmerica

Wood and engineered wood are among the most common materials used in building and construction.A large percentage of engineered wood products contain adhesives that emit volatile organic compounds(VOCs). Research has shown that VOCs have the potential to cause short- and long-term health effects.Beyond health effects, commercially available wood adhesives are manufactured from nonrenewable sourcesand are not biodegradable. Recent research has focused on the synthesis and characterization of alternativeadhesives from renewable resources, including starch, lignin, and gelatin. While preliminary studieshave shown that gelatin exhibits promising mechanical and adhesive properties compared to commercialadhesives, one significant disadvantage that remains - especially if it is to be used as a construction material- is gelatin’s inherent hygroscopicity.

This presentation will highlight current research on evaluating the feasibility of gelatin-based mate-rials to serve as low-VOC construction adhesives. In this presentation, the effect of gelatin-to-waterconcentration and gelatin source (i.e., porcine vs. bovine) on mechanical properties, thermal properties,water and water-vapor absorption will be discussed. Given the wide range of material properties reported inthe literature, significant effort is currently being placed on correlating material properties to gelatin sourceand amino acid content. Specifically, food grade porcine and bovine, BioReagent grade Type A porcine skin,BioReagent grade Type B bovine skin, and pharmaceutical grade fish gelatin will be used in the synthesisand characterization of gelatin films with varying gelatin-to-water concentrations. To counter gelatin’shygroscopicity, the effect of chemical additives (e.g., tannic acid, silane) on mechanical and moisture barrierproperties will also be presented. Achievable mechanical properties, moisture resistances, and VOC contentsof the gelatin-based adhesives investigated herein will be discussed in comparison to commercially availablewood adhesives.

100


MOLECULAR DYNAMICS IN ELECTROSPUN FIBERS OF PLASTICIZED POLY-LACTIDE

Xavier Monnier1,4, Nicolas Delpouve1, Neil Basson4, Alain Guinault2, Sandra Domenek3, Allisson Saiter1,Peter E Mallon4, Eric Dargent1

1 AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France2 Laboratoire PIMM, UMR 8006, ENSAM-CNRS-CNAM, Paris, France3 UMR1145 Ingénierie Procédés Aliments, AgroParisTech, France4 Division of Polymer Science, Department of Chemistry and Polymer Science, University of Stellenbosch,South Africa

Polylactide (PLA) micro and nanofibers produced by the electrospinning process are used in severalfields including in applications for tissue engineering, filtration and electronics. The microstructure andmolecular dynamics of these electrospun fibers are tied to the macroscopic properties of the materials. Theelectrospinning process itself can lead to non-equilibrium microstructures due to the complex processesinvolved including the alignment and stretching of the molecules and the rapid solvent evaporation amongstothers. It is, therefore, important to understand both the microstructure and molecular dynamics, as thealpha relaxation processes, to gain an understanding of the properties of these materials. In this study,a thermodynamic approach was used to calculate the cooperativity length using modulated temperaturedifferential scanning calorimetry (MT-DSC). This technique has been widely used to provide evidence forthe effects of confinement [1], orientation [2], and plasticization [3] in many polymers including PLA.To our knowledge, no studies have been done on the effect of the electrospinning process on the cooperativityin PLA. In this work we investigate the cooperativity length at the glass transition in the bulk polymer andthe electrospun PLA fibers using Donth’s approach [4]. The possible correlations between the cooperativitylength and the inter- and intra-chain distances in the amorphous phase as determined [5] by wide angleX-ray scattering (WAXS) were also investigated.

1. Arabeche, K. et al. Fragility and molecular mobility in micro- and nano-layered PC/PMMAfilms. Polymer 55, 1546-1551 (2014).2. Delpouve, N., Delbreilh, L., Stoclet, G., Saiter, A. & Dargent, E. Structural Dependence of the MolecularMobility in the Amorphous Fractions of Polylactide. Macromolecules 47, 5186-5197 (2014).3. Dobircau, L. et al. Molecular mobility and physical ageing of plasticized poly(lactide). Polym. Eng. Sci.in press DOI: 10.1002/pen.23952 (2014).4. Donth, E. The size of cooperatively rearranging regions at the glass transition. J. Non-Cryst. Solids 53,325-330 (1982).5. Stoclet, G., Seguela, R., Lefebvre, J. M., Elkoun, S. & Vanmansart, C. Strain-Induced Molecular Orderingin Polylactide upon Uniaxial Stretching. Macromolecules 43, 1488-1498 (2010).

101


TRIBOLOGICAL PROPERTIES OF ANTIBACTERIAL POLYMER COMPOSITES

Witold Brostow1, Stevens Brumbley2, Marina Gakhutishvili1,4, Nathalie Hnatchuk4, Justin Youngblood4, Sun-dari Pokharel3

1 Department of Materials Science and Engineering, University of North Texas, U.S.A2 Department of Biological Sciences, University of North Texas, U.S.A.3 Department of Chemistry, University of North Texas, U.S.A.4 Faculty of Exact and Natural Sciences, Ivane Javakhishvili University, Georgia

One does not need to argue the importance of providing antibacterial activity to materials. The way itwas done earlier was simply using materials which can destroy bacterias. There are immediate problemssince some such materials including arsenic are highly toxic; they do destroy bacterias but not only .... Oneoption which has been used before our project began was using low molecular weight antibacterial agents.This represents progress as compared to ‘nude’ arsenic or arsenic oxide; however, toxicity is mitigated onlyto some extent while the service life is insufficient.

Our approach is different. We put arsenic (III) oxide into poly(vinyl chloride) (PVC). Sufficient an-tibacterial activity is achieved. The antibacterial material so obtained is non-irritant and non-toxic. Atthe same time, the PVC-based composite has high thermal stability as demonstrated by thermogravimetricanalysis (TGA, Perkin Elmer). Thermal transitions have been located by differential scanning calorimetry(DSC, Perkin Elmer). Still further, we have determined scratch resistance in a Microscratch Tester fromCSM, Peseux, Switzerland. Higher scratch resistance than in neat PVC has been demonstrated, includingstronger viscoelastic scratch recovery (the bottom of the groove goes up inside of 2 minutes).

Pertinent references:

[1] Patel M. B., Patel S. A., Ray, A., Patel R. M. Synthesis, characterization, and antimicrobial ac-tivity of acrylic copolymers. J. Appl. Polymer Sci. 2003; 89, 895-900.

[2] Tashiro T. Antibacterial and bacterium adsorbing macromolecules. Macromol Mater. & Eng.2001; 286, 63-87.

[3] MuÅĹoz-Bonilla A., Fernandez-Garcia M., Polymeric materials with antimicrobial activity. Progr.Polymer Sci. 2012; 37, 281-339.

102


LENGTH SCALE AT THE GLASS TRANSITION IN SEMI-CRYSTALLINE COM-PATIBILIZED POLYLACTIDE/CLAY NANOCOMPOSITES

Nicolas Delpouve1, Francesca Cicogna2, Werner Oberhauser3, Lucia Conzatti4, Elisa Passaglia2, AllissonSaiter1

1 AMME-LECAP EA 4528 International Lab., Normandie University, Université et INSA Rouen, France2 ICCOM, CNR UOS Pisa, Italy3 ICCOM, CNR Firenze, Italy4 ISMAC, CNR Genova, Italy

During the last ten years, great attention has been paid to the effects of interfaces and geometricalconfinement on the molecular dynamics of polymers [1,2,3]. One of the characteristic parameters describingthe glass transition is the cooperativity length which provides the average dimension of the alpha relaxationprocess. To investigate the cooperativity length from calorimetric measurements, the Donth’s approach [4]is the most appropriated. Previous works have highlighted that interfacial interactions between amorphouspolymer and exfoliated clays lead to a cooperativity length increase while confinement of polymer chains inthe galleries of clays (intercalated nanocomposite) produces a strong reduction of cooperativity [5]. In thiswork we propose to investigate the nature of the polymer/clay interactions thanks to the cooperativity lengthdetermination in Polylactide-based nanocomposites with the presence of polybutyrate adipate terephthalate(PBAT) compatibilizer. Polylactide (PLA) is a semi-crystalline polymer which thermal crystallization caneasily be tailored due to its slow kinetic, and can induce different crystalline forms (α and δ) depending onthe crystallization temperature [6,7], leading to strongly ordered or defective crystals. So this study aims atpicturing the dissociated or cumulated impact of compatibilization and crystallization on the cooperativityin exfoliated and intercalated morphologies.

(1) Schick, C. Eur. Phys. J. Spec. Top. 2010, 189, 3-36.(2) Napolitano, S.; Wübbenhorst, M. Polymer 2010, 51, 5309-5312.(3) Erber, M.; Georgi, U.; Müller, J.; Eichhorn, K.-J.; Voit, B. Eur. Polym. J. 2010, 46, 2240-2246.(4) Donth, E. J. Non-Cryst. Solids 1982, 53, 325-330.(5) Saiter, A.; Prevosto, D.; Passaglia, E.; Couderc, H.; Delbreilh, L.; Saiter, J. M. Phys. Rev. E 2013, 88,042605.(6) Righetti, M. C.; Tombari, E. Thermochim. Acta 2011, 522, 118-127.(7) Delpouve, N.; Saiter, A.; Dargent, E. Eur. Polym. J. 2011, 47, 2414-2423.

103


HYDROGEN BONDING INDUCED NANOPHASE SEPARATION OF GIANT SUR-FACTANTS TOWARD SUB-10-NM HYBRID ORDER NANOSTRUCTURES

Zhiwei Lin1, Stephen Z. D. Cheng1

1 Department of Polymer Science, The University of Akron, United States

Assemblies and fabrications of hybrid materials containing functionalized nanoparticles (NPs) have attractednumerous research interests over the past several decades. Giant surfactants are regarded as a library of newhybrid materials based on polymer-tethered molecular NPs. In this work, two series of giant surfactants,composed of a hydrophilic fullerene (AC60) NP tethered with a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) at the PS chain end (AC60-PS-PEO) or the junction point between two blocks (PS-(AC60)-PEO),were designed to investigate their assemblies in the bulk. It was revealed that the incorporation of AC60NPs induces the nanophase separation of intrinsically disordered PS-b-PEO with low molecular masses. Avariety of ordered nanostructures were formed including lamellae, double gyroids and cylinders with domainsizes smaller than 10 nm. Two pairs of topological isomers, AC60-PS50-PEO45 and PS50-(AC60)-PEO45,AC60-PS78-PEO45 and PS78-(AC60)-PEO45, were specifically investigated to reveal the topological effectson assembled giant surfactants. It was found that the similar ordered nanostructures with different domainsizes are resulted from assemblies of these topological isomers.

104


TWO-DIMENSIONAL NANO-CRYSTALS OF MOLECULAR JANUS PARTICLES

Hao Liu1, Chih-Hao Hsu1, Zhiwei Lin1, Kan Yue1, Wen-Bin Zhang2, Stephen Z. D. Cheng1

1 Department of Polymer Science, The University of Akron, U.S.A2 College of Chemistry and Molecular Engineering, Peking University, P. R. China

In this work, we report the molecular design, synthesis and self-assembly of a series of novel molecularJanus particles based on three nano building blocks (or called molecular nanoparticles, MNP), i.e., polyhe-dral oligomeric silsesquioxane (POSS) and hexa-molybdate, a Lindqvist-type polyoxometalate (POM), and[60]fullerene (C60) derivatives. These amphiphilic molecular Janus nanoparticles was produced by covalentlyconnecting hydrophobic crystalline BPOSS with a charged hydrophilic MNP. The rational strategy to ob-tain self-assembled two-dimensional (2D) nano-crystals with definite and uniform thickness was based onthe distinct interactions of the constitutional moieties. Symmetry breaking in both chemical compositionand geometric shape leads to the formation of bilayered molecular packing setting through crystallization insolution. In a polar solvent, individual two-dimensional (2D) nanosheets are formed with a thickness cor-responding to the stack of two molecular layers driven by the directional crystallization of the POSS cages.Aggregations of the nanosheets along the normal dimension are prevented due to the favored solvating inter-actions with the external ionic layers. This “bottom-up” fabrication of 2D nanosheets provides an alternativestrategy toward self-assembled 2D nanostructures.

105


EFFECTS OF UV EXPOSURE ON PHYSICAL PROPERTIES OF CARBONFIBER/PPS THERMOPLASTIC COMPOSITES

Khairul B. Mahat1, Ibrahim Alarifi1, Abdulaziz R Alharbi1, Dr. Ramazan Asmatulu1

1 ME, Wichita State University, United States

The recent attentions in the applications of the fiber reinforced thermoplastic composite have raisedsome concerns because of the ability and performance of the fiber reinforced thermoplastic compositeafter long-term exposures to environmental weathering (e.g., UV radiation, moisture, and oxygen). Thisweathering can be very destructive to the thermoplastic polymers; hence, a systematic study of the UVradiation effects on the properties of fiber reinforced thermoplastic composite is crucial for industrialapplications. The major objective of the project was to study the correlation between thermoplasticfabrication parameters and the final properties of composites. In this study, carbon fiber (CF) reinforcedpolyphenylene sulfide (PPS) thermoplastic composites were manufactured using high temperature pressafter optimizing the parameters. Subsequently, the effects of long term UV exposures on the thermal andmechanical properties of CF/PPS thermoplastic composites were investigated in detail. The test resultsshowed that the correlation between the processing parameters and the physical properties of the laminatecomposites were in all good agreements. The test results also revealed a significant decrease in the glasstransition temperature, as well as storage modulus, and tensile strengths. Furthermore, short (200 hrs) andlong (300 hrs) term UV exposures changed various thermal and mechanical properties of the thermoplasticPPS composites. This study can provide some preliminary knowledge to engineers and scientists in the fieldand develop new set of structural composites.

Keywords: PPS Films, Carbon Fibers, Thermoplastic Composites, UV Light Exposure, MechanicalProperties.

106


NANOMANUFACTURING POLYACRYLONITRILE NANOFIBER YARNS

Jase Kaser1, Dimitry Papkov1, Yuris Dzenis1, Yong Liu1

1 Mechanical & Materials Engineering, University of Nebraska-Lincoln, United States

Nanomanufacturing Polyacrylonitrile Nanofiber YarnsJase Kaser (Presenting), Dimitry Papkov, Yuris Dzenis, Yong Liu

Continuous nanofibers (NFs) are an emerging class of materials with unique property combinationsand the potential to produce the next generation of advanced fibers. Our previous research found extraor-dinary simultaneous increases in NF strength, modulus and toughness with the decrease of their diametersinto the ultrafine (<250nm) range. Handling and utilization of individual NFs with such small diametersis impractical for any macroscopic applications, and requires assembly of these NFs into yarns or othermacroscopic assemblies. During the manufacture of such assemblies, precision control over their differentaspects (such as pitch angle, yarn diameter, and NF diameter distribution within the yarn) is needed. Anovel nanomanufacturing process, which allows precision NF yarn production in “one-shot” was developed,and a parametric study of nanomanufacturing parameters and their impact on the yarn characteristics wasperformed. The manufacturability of nanofiber yarns with varying fiber diameter, yarn diameter, and pitchangle was demonstrated through control of the spinning distance, rotation speed of the disc collector andother process and solution parameters. Preliminary mechanical testing showed a significantly increasedstrain to failure compared to individual NFs, leaving large room for mechanical properties’ improvement andprocess optimization. The experimentally obtained mechanical properties were also compared with resultsfrom numerical simulations.

107


INTEGRATING C60 NANOPARTICLES INTO TIO2 NANOFIBERS VIA ELECTRO-SPINNING PROCESS FOR ENHANCED ENERGY CONVERSTION EFFICIEN-CIES

Manish A. Shinde1, Abdulaziz R Alharbi1, Ibrahim M. Alarifi1, Dr. Ramazan Asmatulu1

1 Mechanical Engineering, Wichita State University, United States

TiO2 nanofibers incorporated with C60 nanoparticles at 0, 2, 4, and 8wt.% were produced using elec-trospinning process. The chemical utilized for the electrospinning process included poly (vinyle acetate),dimetylfomamide, titanium (IV) isopropoxide and acetic acid in the presence and absence of C60 nanopar-ticles. The resultant nanofibers were heat treated at 300 oC for 2 hrs in a standard oven to remove allthe organic parts of the nanofibers, and then further heated up to 500 oC in Ar for additional 12 hrs tocrystalline the TiO2 nanofibers. SEM, TEM and XRD studies showed that C60 and TiO2 nanofibers werewell integrated in the nanofiber structures. The TiO2 and C60 nanofibers were then mixed in a solutionto form a paste which is then applied on a conductive glass by using a doctor blading technique to makevarious DSSCs. This technique enables to create solar cells with variable thicknesses of 7 µm to 45 µm.The ffects of the manufacturing technique, thickness of the paste, different percentages of C60 nanoparticleson overall efficiency of the solar cell were studied. This paper also includes the TiCl4 treatments, whichgreatly increases the efficiency of DSSCs. This study may guide some of the scientists and engineers to tailorthe energy bang gap structures of some of the semiconductor materials for different industrial applications,including DSSC, water splitting, catalyst, batteries, and fuel cell.

Keywords: Electrospinning, TiO2 Nanofibers, C60 Nanoparticles, Heath Treatment, DSCC, Efficiency.

108


AGEING OF A THREE-LAYER PAPER USED IN THE INSULATION OF AN ELEC-TRIC MOTOR FOR THE AUTOMOTIVE TRACTION

Florian Loubeau1,2,3, Pascal Rain1,2, Anne Durieux3

1 G2Elab, Univ. Grenoble Alpes, FRANCE2 G2Elab, CNRS, FRANCE3 Electric Materials Department, RENAULT SA, FRANCE

Electrical Insulation System (EIS) of the studied electric motor is composed of enameled wires, insulationpapers and impregnating resins. This EIS is subjected to various stresses: thermal (chemical kinetics,thermal expansion), environmental (water absorption, oxidation, various pollutions), mechanical (vibrations,frictions) and electrical (surge voltage applied by the inverter). In low voltage motors, thermal stress isconsidered as the most influent in the degradation of the EIS.

Thermal class of these materials is generally given by the suppliers and corresponds to a lifetime of20,000 hours at this temperature. Criterion for this end of life is chosen by the supplier. It can be a ratio ofmass loss, a relative decrease of Partial Discharge Inception Voltage (PDIV), or of the dielectric loss factor...To determine the thermal class of these materials according to a functional property of our application, thebehavior of materials during thermal aging was studied. Samples of papers, enameled wires, resin wafersand of a simple model of the EIS composed of these three materials were subjected to thermal aging at190oC, 205oC and 220oC.

Results coming from the mass losses of the NKN three-layer paper (Nomex extregistered polyaramide /Kapton extregistered polyimide / Nomex extregistered polyaramide) show a mechanism in two steps: thefirst part of the curve corresponds to a first order reaction and the second part to a zero order reaction.The first order reaction could correspond to a fast oxidation of structural irregularities and the zero orderreaction to the degradation of the structural unit. Apparent rate constants and activation energies havebeen calculated following the Arrhenius law.Physicochemical characterizations of the ageing by IR spectroscopy and dielectric spectroscopy were alsoperformed. IR spectroscopy shows for the Nomex a decrease of the N-H amide group absorption band andthe apparition of cyano groups. Regarding the Kapton, the imide group is more impacted by the degradationthan the ether group. Dielectric spectroscopy showed a decrease of the polarization and of the losses around10 000 Hz. This value is typically the frequency used by the inverters of electrical vehicles.

109


A STUDY OF THE EFFECTS OF SPIN COATING ON PVDF FILMS

Mitchell Schmidt1

1 Physics, University of Nebraska at Lincoln, USA

My research revolves around studying the properties of organic ferroelectrics. I specifically work withPolyvinylidene fluoride (PVDF). Ferroelectric properties have been studied for years as they hold greatpotential in a variety of fields including ferroelectric RAM, ferroelectric tunnel junctions and various sensordevices. To study the properties of PVDF, thin films of the material are created. Currently there are twoways to create thin PVDF films, Langmuir-Blodgett (LB) deposition and spin coating. LB deposition hasbeen utilized in our lab for years and thus is a very refined and useful technique. Spin coating on the otherhand has been only used in the creation of thick films and thus is not understood as well. My projectexamined the possible potential for creating uniform thin films with spin coating. Though spin coating hasbeen used in the creation of PVDF samples for years the creation of high quality samples below 50 nm hasbeen tricky. My role has been to attempt this by adjusting various parameters such as, spin speeds, solventsconcentration, quantity of solvent dispersed, time span of spinning and so on. Each parameter’s effect wasstudied in the creation and optimization of thin films. To test the effect of spin coating I utilized variousknown tests. The most basic test was to measure the capacitance as a function of voltage or temperature.Such scans indicate the level of crystalline structure in the material. Further test included doing pyro-electricscans which measured the induced polarization caused by laser beams. In addition AFM, PFM, XRD andellipsometry were all useful techniques to infer a sample’s thickness, roughness and quality.

110


INVESTIGATION OF ELECTRONIC PROPERTIES OF A GRAPHENE FIELD EF-FECT TRANSISTOR

Simon Schönherr1, Stefan Wagner2, Himadri Pandey2, Jasper Ruhkopf2, Max Lemme2

1 Department Q2, Fürst-Johann-Moritz-Gymnasium, Germany2 Graphene-based Nanotechnology, University of Siegen, Germany

Graphene is a material that has garnered enormous scientific and technological interest, since it was reportedfor the first time in 2004[1]. This interest is mainly due to the unique properties of graphene, includingits attractive electronic and mechanical properties as well as the excellent thermal conductivity. These area consequence of its two-dimensional structure consisting of a single atomic layer of carbon. Grapheneis therefore a promising material for field effect transistors (FETs)[2,3]. In this experimental study weinvestigated the electronic properties of graphene with a prototype of a graphene FET. In this prototype,in which the graphene channel is contacted by gold source and drain contacts, the current between sourceand drain is controlled by the gate voltage of a silicon back-gate. In a typical chip layout, 250 individualFET devices were fabricated on one chip[4]. The graphene was deposited by chemical vapor deposition.The transfer characteristics of the graphene-FET were characterized using a 3 point probe setup. The draincurrent flowing through the graphene channel was recorded as a function of the gate voltage. The transfercurves show a characteristic V shape. Drain currents were thus measured for positive as well as negativegate voltages. This ambipolar behavior confirms that graphene conducts both electrons and holes. Secondly,substantial drain currents were observed for all gate voltages between -5 V and +10 V: the minimum draincurrent is at least 60% of the maximum drain current over the gate voltage range. This observation can beexplained with the energy band diagram of graphene, which does not contain any band gap (zero band gapsemiconductor). Consequently, graphene-FETs in the investigated configuration with a single layer graphenechannel can probably not be seen as an alternative for silicon-based FETs in logic circuits because of thefact that the FET is always turned on. This behavior prevents the use of these FETs in a system, in whichthe difference between 0 and 1 (on & off) is the general principle. Nevertheless an application of graphenein high frequency circuits is still possible, especially because of the high carrier mobility of graphene[5].

[1] K.S. Novoselov et al. Science 2004, 306, 666[2] A.K. Geim et al. Nat Mater 2007, 6, 183[3] M.C. Lemme et al. IEEE Electron Device Lett. 2007, 28, 282[4] A.D. Smith et al. Accept. Solid State Electron. 2015[5] M.C. Lemme et al. MRS Bull. 2014, 39, 711

111


BROADBAND DIELECTRIC RELAXATION ANALYSIS ON THE REINFORCE-MENT OF ANTHRACENE-FUNCTIONALIZED EPOXY COMPOSITES

Rui Ding1, Sabrina Wells2, Jamie Messman2, Daniel Bowen2, Nicola Bowler1

1 Materials Science and Engineering, Iowa State University, United States2 Department of Energy’s National Security Campus, Honeywell FM&T, LLC, United States

Two polycyclic aromatic hydrocarbon (PAH) derivatives, namely anthracene (up to 5 wt.%,) and 2-aminoan-thracene (up to 10 wt.%) were dispersed in a model epoxy matrix as novel composite dielectrics. The dielectricrelaxation properties of anthracene-functionalized epoxy composites were investigated via broadband dielec-tric spectroscopy over the frequency range from 0.02 to 1,000,000 Hz and temperature range from -100 to130 oC. Within the measured domain, four phenomena, namely α-, β-, and γ-relaxation processes and ionicconductivity are identified for all the samples. The Havriliak-Negami (HN) dielectric relaxation model wasapplied to parametrically fit each relaxation and the characteristic relaxation times of the anthracene-func-tionalized epoxy composites were compared. A significant increase of glass transition temperature (Tg) isobserved in the system with coexistence of anthracene and 2-aminoanthracene, by both dielectric spectroscopyand differential scanning calorimetry (DSC).

112


SYNTHESIS AND PROPERTIES OF REACTIVE OLIGOMERS BASED ON A PER-OXY DERIVATIVE OF AN EPOXY RESIN AND 1,4- BUTANEDIOL

Witold Brostow1, Olena Astakhova2, Ostap Ivashkiv2, Olena Shyshchak2, Haley Lobland1


Oligomers products with various functional groups are widely used as crosslinking and modified agents ofpolymeric mixtures. We have synthesized an oligomer containing simultaneously peroxy and hydroxy groups.

The oligomer has the molecular mass M = 490 g/mol and active oxygen content 1.9 %. The pres-ence of hydroxy groups is confirmed by absorption band at 3384 cm-1 in IR-spectrum. The presence of theperoxy groups is confirmed by the band at 1380 and 1360 cm-1 and ether bond - at 1248 and 1040 cm-1(formed by the interaction of peroxide oligomer with butanediol).Our oligomer has been studied as active additive to epoxy-oligoesteric mixtures on the basis of an industrialdianic epoxy resin with the epoxy number 20.0 % and an oligoesteracrylate on the basis of triethyleneglycoland methacrylic acid with M = 280 g/mol. The synthesized oligomer constitutes 10/100 mass parts of themixture. The crosslinking was studied stepwise: first at room temperature and then at 383 and 423 Kfor 15, 30, 45, 60 and 75 minutes. The polymeric films so obtained are characterized by good adhesion tosubstrates, hardness between 0.7 and 0.8 in relative units and gel-fraction content 80-96 %.

113


SYNTHESIS AND CHARACTERIZATION OF POLYMERS WITH ANTIBACTE-RIAL PROPERTIES BASE ON TRICLOSAN ACRYLATE

Wilson Isidro Cardona1, Anny Catalina Ospina1, Carlos Alberto Pelaez1, Luis Fernando Giraldo1

1 Instituto de Química, Universidad de Antioquia, Colombia

In this research a monomer of triclosan acrylate was synthesized by reacting acryloyl chloride with triclosan inthe presence of a base. The monomer was polymerized by free radical bulk polymerization in order to obtainthe homopolymer of triclosan acrylate and the copolymers with styrene at different molar ratios. The finalpolymers were characterized by infrared spectroscopy, differential scanning calorimetry, thermogravimetricanalysis and gel permeation chromatography. The antibacterial activity for the polymers was determinateagainst Bacillus subtilis, Staphylococcus aureus and Escherichia coli. The results show that the monomerof triclosan and its homopolymer had the higher antibacterial activity and an important reduction in thebacterial population was also achieved with only 10 % of TCA in polystyrene. The glass transition temper-atures for the copolymers were between the Tg for the homopolymer of TCA (58 oC) and polystyrene (75oC), indicating a good compatibilization of both monomers. The higher number and weight average molec-ular weights for the copolymers were 12628 and 32941 g/mol, respectively. These polymers have potentialapplications in paint and coating industry and medical devices.

114


USING CURING KINETICS TO CONTROL THE MECHANICAL PROPERTIESOF SIMULTANEOUS ACRYLATE/EPOXY IPNS DURING PHOTO CURING OFGRADED MATERIALS

Marzieh Bakhtiary Noodeh1, Wenlong Li1, Steven Araujo2, Nicolas Delpouve2, Jean-Marc Saiter2, MehrdadNegahban1

1 Mechanical & Materials Engineering, University of Nebraska-Lincoln, United States2 LECAP, University of Rouen, France

Interpenetrating polymer networks (IPNs) are made from two or more polymer networks that are curedsimultaneously to achieve interpenetration, and can be usually made to express a range of characteristicsbetween those of the constructing networks [1]. One way to achieve grading with an IPN system is to varythe amount of the components. This can be used to vary not only mechanical properties, but also optical,electrical and other properties. The main issue is how to control the composition, yet obtain an IPN withgood properties. Normally the networks of IPNs with good characteristics are grown concurrently and, thus,this type of IPN is called a Simultaneous IPNs [2, 3]. We studied how one can control the curing kineticsfor photo cured systems to get Simultaneous IPNs of acrylate and epoxy with different final mechanicalproperties. Laser assisted UV-light curing on a Rapid Scan FTIR equipped with a temperature controlledATR was used to follow the construction of the networks and to design the controlling method. It is shownthat by this method one can get a wide range of properties starting from a single mixture. This UV-lightcontrolled process can be used in photolithography to vary properties in a 3D printing system.

115


MOLECULAR STRUCTURE PARAMETERS INFLUENCE ON DEFORMATIONMECHANICS OF AN ORIENTED CRYSTALLINE POLYMER

Ulmas Gafurov1

1 Composite Materials, Institute of Nuclear Physics, Uzbekistan

Taking into account that real crystalline polymer molecular and supra-molecular structure and theinterconnecting macromolecules have different conformation links we have carried out modeling of anoriented polymer deformation and creep molecular processes. We have considered two-phase model ofan oriented flexible-chain crystalline polymer type of linear polyethylene micro-fibrils of which consistof interchanging crystalline and amorphous regions. In the deformation molecular mechanics modelingthe Frenkel-Kontorova’s crowdion was used for condition of balance and longitudinal mobility of aninterconnection macromolecular chain.

The dislocation formation is stimulated by thermo-fluctuation and stressed load and is accompaniedmolecular chains exit of crystallites, elongation of amorphous section of interconnecting molecular chainand correspondingly lead to local loads relaxation on their amorphous sections as well as by conformationregroupings of these sections in some conditions especially for flexible chain polymer.

The load relaxation value and the dislocation evolution depends except of macromolecular chain pa-rameters mainly from dimension sizes of an interconnecting amorphous section and of initial local load onit, presence of cross-links, interpenetrating, loops in neighboring amorphous sections, defect structure ofpolymer crystallites. .

For high-oriented flexible-chain crystalline polymers at the certain values of slippage chains numberthere was the further discontinuous jump conformation structure (conformation straightening) of theinterconnecting amorphous section.

The dislocation forming thermo-activation energy values for various loads and the longitudinal sizesof crystal and amorphous regions are designed.

The dislocation moving to amorphous region lead to the interconnecting chain pulled into crystallitewith local load value increasing on amorphous section and the thermo-fluctuation energy dissipation.

In a real polymer there is the wide distribution over the amorphous and crystalline regions sizes. Asa result of this in the polymer being under external load the values of the local loads on the amorphoussections, correspondingly the activation energy for the dislocation formation and the velocity of the molecularchains longitudinal mobility and molecular deformation process will be also different.

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NOVEL CHART FOR REPRESENTATION OF MATERIAL PERFORMANCE ANDRELIABILITY

Franz Lanyi1, Peter Kunzelmann1, Dirk W. Schubert1

1 Institute of Polymer Materials, Friedrich-Alexander-University Erlangen-Nuremberg, Germany

In modern industrial production lines various process and material parameters determine the properties ofthe final product. Thus, a process optimization procedure has to take into account a large design spacecontaining several parameters. As a consequence the evaluation of the influence of single process parameterson the final product properties can be quite complicated. Usually a certain property of a product, forexample the mechanical strength, has to satisfy a defined specification. In terms of quality control not onlythe performance of the material but also the reliability of the specified values has to be considered.The Weibull statistic gives an interesting approach to evaluate both, material’s performance and reliability.Regarding the mechanical properties e.g. in terms of the stress at break the Weibull analysis leads to acharacteristic failure constant σb,0 at which 63.2 % of the samples will break. Additionally, the Weibullmodulus m can be regarded as a measure for the width of the distribution of the measuring results. Highvalues of m represent a narrow distribution and thus a better reliability. Moreover, the Weibull modulusm is independent of the absolute value of the measuring data. Therefore, it is possible to compare samplesproduced under different conditions. The standard deviation and the interquartile range are often used toquantify the scatter of empirical data. It is shown within this work that the Weibull modulus m can be amore precise discriminator for the evaluation of the reliability because it is rather stable against outlayingvalues.As an example this study concentrates on the mechanical properties of melt spun fibres consisting of blendsfrom polypropylenes with different molar masses produced under various process conditions. This workpresents a novel chart which allows one to compare different samples on the basis of the Weibull statisticswhereat the Weibull modulus m is plotted over σb,0. Defining a reference material, the m-σb,0-map canbe split into quadrants, whereat each quadrant designates an improvement or worsening of material’sperformance and reliability with respect to the reference. An evaluation in terms of performance andreliability of great sets of data is easily applicable. It will be shown that the Weibull statistic can also beapplied to the Young’s Modulus, the elongation at break and the tensile energy absorption.

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U-SHAPED PROBES FOR CHARACTERIZATION OF POLYMERS USING CON-TACT RESONANCE ATOMIC FORCE MICROSCOPY

Ehsan Rezaei1, Joseph Turner1


Contact resonance atomic force microscope (CR-AFM) methods have been commercially used to quantifythe elastic and viscoelastic properties of a variety of materials such as polymers, ceramics and biologicalmaterials. This approach involves measurement of the resonant frequencies of the AFM probe both for thefree case and the case for which the tip is in contact with a sample. Vibration models of the probe andtip-sample contact models are then used to determine the sample properties from the frequency behaviorand to create images of the sample properties. U-shaped AFM probes have been developed to allow localheating of samples and the resonances of these probes are much more complex. A simplified analytical modelof these U-shaped probes is described here. This three beam model (TBM) includes two beams clamped atone end and connected with a perpendicular cross beam at the other end. The sensitivities of the modesto the specimen properties are then examined using a tip-sample contact represented by three orthogonalKelvin-Voigt models for the vertical, lateral and axial stiffness of the contact. In this poster, we demonstratethe mode frequency sensitivity to the contact stiffness changes. The frequencies and mode shapes that resultfrom this model agree well with solutions created using the finite element method (FEM). As expected, themodes involving symmetric flexural motion of the legs are most sensitive to the vertical contact stiffnesswhile the modes associated with unsymmetric flexural motion of the legs are most sensitive to the lateralcontact stiffness. This work is anticipated to provide a simple analysis method allowing U-shaped probeswith CR-AFM to be used for polymers.

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STUDY OF AMORPHOUS AND CRYSTALLINE PHASES IN BIO-BASEDNANOCOMPOSITE FILMS

Sebastien Charlon1, Nadege Follain1, Laurent Delbreilh2, Eric Dargent2, Jeremy Soulestin3, MichelSclavons4, Stephane Marais1

1 PBS UMR6270, Université de Rouen, France2 AMME-LECAP, Université de Rouen, France3 Institute, Ecole de Mines de Bouai, France4 IMCN Institute, Catholic University of Louvain la Neuve, Belgium

With the emerging environmental concerns, many research works are focused on the use of biodegradablepolymers with the aim of reducing plastic pollution [1].

Among them, PolyButylene Succinate (PBS) and polyButylene Succinate Adipate (PBSA) are expectedto be promising candidates to substitute common polyolefins due their good properties (biodegradability,processability, chemical resistance, mechanical performances [2]. However, their softness and their poorbarrier properties [3] limit their use in industrial applications like packaging.

One of the relevant ways to significantly improve these characteristics is to incorporate nanofillers,even at low content. In this work, an optimized 5 wt% [4] nanoclay content (unmodified montmorillonite(MMT) and organo-modified montmorillonite (OMMT)) was introduced within PBS and PBSA matrices bymelt blending processing.

To date, a higher crystallinity degree for PBS-based films than for PBSA-based films was calculatedby X-ray diffraction and Differential Scanning Calorimetry (DSC) measurements. These experiments didnot reveal any microstructure variation with nanofiller loading. Polarized optical microscopy showed thatthe introduction of MMT lead to decrease spherulite sizes while the opposite effect was observed withthe incorporation of OMMT. Finally, Broadband Dielectric Spectroscopy (BDS) experiments exposed oneα-relaxation and two β-relaxations for both PBS and PBSA-based films, respectively associated to themotion of polymer chains and of small polar groups. Glass transition temperature determined from BDScurves was founded lower for PBSA than PBS, as observed by DSC measurements. Moreover, relaxationsare not modified by the presence of nanofillers, revealing that only the crystalline phase of polymer isaffected by the clay introduction.

[1] P. Bordes, E. Pollet, L. Avérous, Progress in Polymer Science, 2009, 34, 125-155[2] T. Fujimaki, Polymer Degradation and Stability, 1998, 59, 209-214[3] K. Okamoto, S.S. Ray, M. Okamoto, Journal of Polymer Science: Part B: Polymer Physics, 2003, 41,3160-3172[4] B. Alexandre, D. Langevin, P. Médéric, T. Aubry, H. Couderc, G.T. Nguyen, A. Saiter, S. Marais,Journal of Membrane Science, 2009, 328, 1316-1324

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MICROSTRUCTURE, AMORPHOUS PHASE DYNAMICS AND BARRIER PROP-ERTIES IN MULTILAYER COEXTRUDED POLYLACTIDE

Samira Fernandes Nassar1,2,3, Nicolas Delpouve1, Alain Guinault2, Laurent Delbreilh1, Cyrille Sollogoub2,Sandra Domenek3, Eric Dargent1

1 AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France2 Laboratoire PIMM, UMR 8006, ENSAM-CNRS-CNAM, Paris, France3 UMR1145 Ingénierie Procédés Aliments, AgroParisTech, France

The development of biopolymers for food-packaging applications implies combining ecofriendly characterand non-toxicity to specific industrial requirements as low-cost and good mechanical, thermal and barrierproperties. Polylactide (PLA) has exhibited promising applications in the past decades due to its perfor-mance in renewability, biodegradability, biocompatibility, and mechanical properties [1]. As one of the majorchallenges to consider producing high performance PLA packaging at a large scale lies in the improvementof its barrier properties, the tailoring of the PLA microstructure from thermal crystallization [2,3], drawing[4], or shish-kebab crystallization [5] has been strongly investigated in the recent years. New strategiesare actually studied to obtained stronger effects. One of them consists in the geometrical confinement ofthe polymer at the molecular scale using the layer-multiplying co-extrusion process combined eventuallywith annealing processes to create nanometric thickness layers. This technology is environmentally friendlyand health secured and has already proved its efficiency to improve the gas barrier properties for otherpolymers [6]. In this work we propose to design monolayer and multi-layer coextruded PLA and to analyzethe relationships existing between its microstructure and the resulting gas barrier properties. Eventually astransport properties are mainly governed by the diffusion in the amorphous phase, a picture of the moleculardynamics in the amorphous phase will be given.

(1) Auras, R.; Harte, B.; Selke, S. Macromol. Biosci. 2004, 4, 835-864.(2) Guinault, A.; Sollogoub, C.; Ducruet, V.; Domenek, S. Eur. Polym. J. 2012, 48, 779-788.(3) Cocca, M.; Lorenzo, M. L. D.; Malinconico, M.; Frezza, V. Eur. Polym. J. 2011, 47, 1073-1080.(4) Delpouve, N.; Stoclet, G.; Saiter, A.; Dargent, E.; Marais, S. J. Phys. Chem. B 2012, 116, 4615-4625.(5) Bai, H.; Huang, C.; Xiu, H.; Zhang, Q.; Deng, H.; Wang, K.; Chen, F.; Fu, Q. Biomacromolecules 2014,15, 1507-1514.(6) Carr, J. M.; Mackey, M.; Flandin, L.; Hiltner, A.; Baer, E. Polymer 2013, 54, 1679-1690.

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RELAXATION OF SHEAR-INDUCED PRECURSORS IN POLY(LACTIC ACID)

Manon Tesserau1, Ezequiel Morin2, Benjamin Schamme1, Constantine Tarawneh2, Antonella Esposito1, LiTan3, Eric Dargent1, Lucia Fernandez-Ballester3

1 Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France2 Transportation Center for Railway Safety, University of Texas - Pan American, United States3 Mechanical and Materials Engineering, University of Lincoln-Nebraska, United States

Semicrystalline polymers are usually processed from their molten state and subjected to intense shearand/or elongation flows [1]. Within the past few years, a whole array of studies has shown that flowhas a large impact on crystallization kinetics and morphology of semicrystalline polymers and therefore,on final properties [2]. Understanding flow induced crystallization (FIC) is thus of utmost importanceof the production of tailored-properties products, particularly with polymeric materials. Theoretical andexperimental work highlighted that final morphology is dictated by structures present in the melt at theearly stages of shear and crystallization [3]. These structures are called precursors and their nature iscurrently under investigation [4-5].

However, FIC studies were mainly focused on industrial polymers as polypropylene, polyethylene or randomcopolymers but fewer on biopolymers [6]. As one of the most promising biopolymers, Poly(lactic acid)(PLA) exhibits a reliable panel of performances in terms of availability, biocompatibility and biodegradability.

Using a commercial PLA, a fiber pull-out technique coupled with polarized optical microscope and ahot stage has been used, as in terms of sensitivity is the most powerful indicator of melt perturbations. Thedistinct morphological zones that happen after shear and relaxation (cylindritic or highly nucleated mor-phology and classical spherulitic morphology) have been used as an indicator of whether full reequilibrationhas been attained or not in the sheared melt. Quantitative data as lifetime of precursors, t*, has been inves-tigated in a wide range of relaxation temperatures and compared to other industrial semicrystalline polymers.

[1] Bove, L.; Nobile, M. R. 2002. Macromolecules Symposium. 185, 135-147.[2] Hsiao, B. S.; Yang, L.; Somani, R. H.; Avila-Orta, C. A.; Zhu, L. 2005. Phys. Rev. Lett. 94, 117802.[3] Kornfield, J.; Kumaraswamy, G.; Issaian, A. 2002. Ind. Eng. Chem. Res. 41, 6383-6392.[4] Balzano, L.; Kukalyekar, N.; Rastogi, S.; Peters, G. W. M.; Chadwick, J. C. Phys. Rev. Lett. 2008. 100,048302-048304.[5] Azzurri, F.; Alfonso, G. C. 2005. Macromolecules. 38, 1723-1728.[6] Xu, H.; Xie, L.; Chen, Y. H.; Huang, H. D.; Xu, J. Z.; Zhong, G. J.; Hsiao, B. S.; Li, Z. M. 2013. ACSSustainable Chem. Eng. 1, 1619-1629.

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EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED CRYSTALLIZATION

Ramin Hosseinabad1, Frederic Aubin1, Hugo Boitoit1, Eric Dargent2, Lucia Fernandez-Ballester1

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States of America2 Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France

Semi-crystalline polymers melts are often subjected to strong flows while undergoing processes. It is wellknown that flow can significantly alter the kinetics of crystallization and the resulting semi-crystallinestructure, which in turn deeply affects the material properties of the final product. Therefore, it isimportant to understand the basic mechanism and the variables that control flow-induced crystallization. Ingeneral, both the molecular structure and the processing conditions significantly impact the crystallizationprocess. Here, the role of co-monomer content and temperature on flow-induced crystallization are examined.

In this study, isotactic polypropylene and random ethylene co-monomers are subjected to short pulses ofhigh shear stresses at several crystallization temperatures. The critical shear stress for formation of a highlyoriented skin was studied for each of the polymer grades. It was found that for polypropylene homopolymer,the critical shear stress for crystallization temperature of 140C was smaller than that for 150C. However, thecritical shear stress was indistinguishable between 150C and 160C. For polypropylene with 3% co-monomer,the critical shear stress also increased when crystallization temperature was raised up from 140C to 150C.However, further temperature increase to 160C resulted in disappearance of the highly oriented skin layers:instead, a different morphology was obtained at the highest levels of shear stress, which was observed assomewhat bright areas under the polarizing optical microscope. Finally, polypropylene with 7% ethyleneco-monomer exhibited the same trend and value for critical shear stress at crystallization temperature of130C and 140C. In this case, however, rising the crystallization temperature to 150C resulted in almostcomplete disappearance of the highly oriented skin. The behavior of the real-time birefringence during andright after cessation of the shear pulse was examined. The observed trends and their relationship withsubsequent structure development for each of the three polymer grades will be discussed.

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THE POSS AND MWCNT MODIFIED GLASS TRANSITION TEMPERATURE TGOF POLY(VINYL CHLORIDE)

Jolanta Tomaszewska1, Tomasz Sterzynski2, Katarzyna Skórczewska1, Jacek Andrzejewski2

1 Faculty of Chemical Technology and Engineering, UTP UNIVERSITY OF SCIENCE AND TECHNOL-OGY, Poland2 Institute of Materials Technology, Poznan University of Technology, Poland

The aim of our studies was to modify specifically the poly(vinyl chloride) (PVC) by using of nanoadditiveslike polyhedral oligomeric silsesquioxane (POSS) and multi-wall nanotubes (MWCNT). As a nanofillerthree types of polyhedral oligomeric silsesquioxanes and multiwall carbon nanotubes were used. Thenanocomposites of PVC with various contain of fillers (concentration of POSS was in the range between 0.5and 10 wt.%, the MWCNT contain was between 0.01 wt.% and 0.05 wt.%) were prepared by melt mixingprocessing. As matrix the PVC compound in a form of dry blend, containing stabilizer and paraffin waxwas applied. The POSS and MWCNT were introduced into the PVC matrix by different procedures ofcompound preparation, followed by melt mixing.

Our interest was to determine the influence of the nanomodification on certain properties of PVC,like glass transition temperature; a property which determines the possible applications of this polymericmaterial, thus the temperature dependent macromolecular mobility.

The glass temperature was measured by means of dynamic mechanical analysis DMA, differentialscanning calorimetry DSC and dielectrical measurements. The effect of a fabrication way of the nanomodified PVC on the glass transition temperature has also been investigated.

By use of MWCNT always an increase of Tg of PVC with increasing concentration of the nanoaddi-tive was noted, signifying an important effect of nanotubes on the PVC chain mobility. The saturation - likeeffect was observed already by the MWCNT contain equal to 0.01-0.02 wt.%.

An opposite effect, i.e. a decrease of Tg was found in the case of PVC modification with polyhedraloligomeric silsesquioxane, particularly with 3-chloropropyl POSS and those containing methacryl and octylgroups. This observation may be an indication of a plastyfing effect, due to a possible introduction of POSSmolecules between the PVC macromolecules.

In every case, the higher was the frequency used in our experiment, the higher was the value of theTg .

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INFLUENCE OF STRUCTURAL FEATURES OF POROGEN MOLECULESON THERMAL PROPERTIES AND POROSITY OF NANOPOROUSPOLYCYANURATE-BASED FILM MATERIALS

Kristina Gusakova1, Jean-Marc Saiter2, Alexander Fainleib1, Olga Grigoryeva1, Daniel Grande3

1 Department of Heterochain Polymers and Interpenetrating Polymer Networks, Institute of MacromolecularChemistry of the National Academy of Sciences of Ukraine, Ukraine2 AMME-LECAP International Lab. Institute for Material Research, Université de Rouen, France3 Institut de Chimie et des Matériaux Paris-Est, UMR 7182 CNRS - Université Paris-Est Créteil Val-de-Marne, France

The present communication is focused on the investigation of the influence of molecular and structuralfeatures of porogens on thermal behaviour and porosity characteristics of nanoporous polycyanurate-basedfilm materials produced via the chemically-induced phase separation technique. For this purpose, severalhigh-boiling temperature (Tb ∼280-380oC) low-molecular phthalates were used as porogens. The molecularradius of all the phthalates was varied in the range of 0.405-0.545 nm. Miscellaneous investigations of bothisothermal (at 50, 100, 150 and 250oC for 48 h) and dynamic (starting from 30 up to 700oC at 20oC/min)heating of nanoporous films in either inert or air atmosphere were fulfilled. Isothermal annealing experimentsshowed similar kinetic behaviours for all the nanoporous PCN-based materials studied. Therefore, theidentity of processes occurred while annealing at 50-150oC was concluded. Standard TGA measurementsdemonstrated high thermal stability of all the samples before and after isothermal annealing (at T upto 150oC), regardless of the porogen structure. A drastic darkening and a significant decrease in thethermal stability of the nanoporous PCN-based samples annealed at 250oC confirmed the occurrenceof thermal-oxidative degradation at such an annealing temperature. The presence of nano-sized pores,before and after isothermal annealing, disregarding the temperature of annealing was confirmed usingseveral techniques, including SEM, N2 sorption, and DSC-based thermoporometry. A strong influence ofthe porogen structure was evaluated on the porosity characteristics, and consequently on the desorptionbehaviour of nanoporous PCN-based films annealed at 50-150oC. It was also established that the formationof the most thermodynamically stable porogen-containing PCN networks allowed for introducing largerporogen amounts, thanks to the deferment of the phase separation process. As a result, the generation ofrelatively more dense and homogeneous nanoporous structures could be achieved.This investigation could be useful for a possible prediction of long-term properties of porous film materialsderived from thermosetting densely crosslinked polycyanurates and related (co)polymers.Acknowledgements. The authors are thankful to the National Academy of Sciences of Ukraine andthe “Centre National de la Recherche Scientifique” for financial support through PICS project No 5700(Ukraine-France cooperation 2011-2013).

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INVESTIGATION OF FRACTURE BEHAVIOR OF HETEROGENEOUS POLY-MER MIXTURES SUBJECTED TO VISCOELASTIC DEFORMATION USING MI-CROSTRUCTURAL MODELING

Keyvan Zare Rami1, Yong-Rak Kim1, Taesun You1

1 Civil engineering, University of Nebraska Lincoln, USA

This paper presents a microstructural modeling of heterogeneous polymer mixtures where viscoelastic andfracture are significant sources of energy dissipation and failure-associated phenomena. Complex geometriccharacteristics of mixture microstructures are represented by an image technique, and individual mixtureconstituents such as elastic particles and surrounding viscoelastic matrix are characterized for their materialproperties. In addition, cohesive zones are embedded in the mixture microstructure to account for fracturewithin the mixture microstructure. A series of laboratory tests are performed to obtain elastic, viscoelastic,and fracture properties of the mixture components and overall damage-associated performance of the entiremixture. The computational microstructure modeling is validated by comparing simulation results with theexperimental test results of the mixture. The results presented in this paper clearly indicate that the effect ofmicrostructure and individual component material properties on the overall macroscopic damage-associatedbehavior of the heterogeneous media.

125


POLAR PHASE GENERATION IN PVDF, THROUGH AMPHIPHILIC IONIC LIQ-UID MODIFIED MULTIWALLED CARBON NANOTUBES: EFFECT OF ANION

Ali Bahader1, Haoguan Gui1, Huagao Fang1, Yu Li1, Shaojun Wu3, Yunsheng Ding1,2

1 Polymer Science and Engineering, Hefei University of Technology, China2 Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology,China3 Institute of optoelectronics, Hefei University of Technology, China

This study describe the effect of multiwalled carbon nanotubes (MWCNT), ionic liquid (IL) and IL modi-fied MWCNT on the crystallization and polar phase generation of melt crystallized PVDF. The surface ofMWCNT was modified with two types of ILs, 1-hexadecyl-3-methyl-imidazolium bromide [C16MIM][Br] and1-hexadecyl-3-methyl-imidazolium hexafluorophosphate [C16MIM][PF6]. The nanocomposites were charac-terized using FE-SEM, FTIR-ATR, XRD, DSC and EDX. Surprisingly, the results demonstrate that thepresence of IL accelerated the process of PVDF crystallization, because IL are well-known to act as a plas-ticizer for polymers and retard the crystallization process. Both, IL and IL-modified MWCNT are able togenerate β/γ phase/s of PVDF. The role of the anion also proved very effective, in terms of fast crystallizationprocess and β/γ phase generation.

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Thursday, May 14, 2015 Starting: 8:30 AMTH1: Plenary (Henzlik 124)Session Chair: Yuris Dzenis

Assistants: Kaspars Maleckis, Zesheng Zhang

Talk:

1. (8:30 AM, Plenary) Cheng: GIANT POLYHEDRA AND GIANT SURFACTANTS BASED ONNANO-ATOMS: TUNING FROM CRYSTALS, TO QUASICRYSTALS, TO FRANK-KASPERPHASES: AN INTERCONNECTION BETWEEN SOFT AND HARD MATTER

Dr. Stephen Z.D. Cheng, Frank C. Sullivan Distinguished Research Professor, Robert C. Musson Professor,Trustees Professor, NAE, Department of Polymer Science, The University of Akron

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Talk Number: 1 (Plenary)Time: Thursday, May 14, 2015 8:30 AM Session: TH1: Plenary (Henzlik 124)

GIANT POLYHEDRA AND GIANT SURFACTANTS BASED ON NANO-ATOMS:TUNING FROM CRYSTALS, TO QUASICRYSTALS, TO FRANK-KASPERPHASES: AN INTERCONNECTION BETWEEN SOFT AND HARD MATTER

Stephen Z. D. Cheng1

1 Department of Polymer Sceince, The University of Akron, USA

In order to create new functional materials for advanced technologies, both precise control over functionalityand their hierarchical structures and orders are vital for obtaining the desired properties. Among all thegiant molecules, giant polyhedra are a class of materials which are utilized by deliberately placing preciselyfunctionalized polyhedral oligomeric silsesquioxane (POSS) and fullerene (C60) molecular nano-particles(MNPs) (so-called “nano-atoms”) at the vertices of a polyhedron. Giant surfactants are polymer tail-tethered“nano-atoms” where the two components have drastic chemical differences to impart amphiphilicity. Thesegiant polyhedra and giant surfactants capture the essential structural features of their small-moleculecounterparts in many ways but possess much larger sizes, and therefore they are recognized as size-amplifiedversions of those counterparts. One of the most illustrating examples is a series of novel giant tetrahedral andgiant surfactants which possess precisely defined amphiphilic MNPs with different geometric combinations.When both geometrical and chemical symmetry are disrupted and these giant tetrahedra and surfactantsare functionalized they become building blocks for hierarchical ordered structures. A range of orderedsuper-lattice structures of this class of materials: crystals, quasicrystals and Frank-Kasper phases have beeninvestigated in the condensed bulk state and thin films, revealing the interconnections between soft matterand hard matter in sharing their common structures and fundamental behavior.

Speaker BackgroundProfessor Cheng received his Ph.D. in Chemistry from Rensselaer Polytechnic Institute in 1985 withProfessor Bernhard Wunderlich. Following a postdoctoral fellowship at RPI he joined the faculty in theDepartment of Polymer Science at the University of Akron in 1987. He served stints as Chairman of theDepartment of Polymer Science and Dean of the College of Polymer Science and Polymer Engineering andis currently the Frank C. Sullivan Distinguished Research Professor. Dr. Cheng is also a Member of theNational Academy of Engineering. His research interests center on the condensed states in polymers, liquidcrystals, surfactants and micelles, and focuses on the interactions, responses, dynamics, and structuresof materials on varying length and time scales in which the material itself embodies the technology. Hisresearch activities include investigations of transition thermodynamics and kinetics in metastable states,ordered structures and morphologies, surface and interface structures in electronic and optical materials andadvanced functional hybrid materials.

128

Thursday, May 14, 2015 Starting: 9:45 AMTH2_1: FIC (Henzlik 124)Session Chair: Yuris DzenisAssistant: Kaspars Maleckis

Talks:

1. (9:45 AM, Keynote) Galeski: CRYSTALLIZATION AND MELTING PHENOMENA INNANOFIBER REINFORCED POLYMER NANOCOMPOSITES

2. (10:25 AM, Invited) Papkov: POLYMER CRYSTALLINITY AND TOUGHNESS: INCREASINGPLASTICITY OF CONTINUOUS POLYACRYLONITRILE NANOFIBERS THROUGH CRYSTAL-LIZATION SUPPRESSION

3. (10:45 AM, Oral) Sterzynski: ECOLOGICALLY FRIENDLY MULTILAYER WPC/SRC CON-STRUCTION MATERIALS; PRODUCTION, STRUCTURE AND PROPERTIES

4. (11:05 AM, Oral) Gonçalves: XANTHAM GUM AND CHITOSAN AS NATURAL ADHESIVESFOR CORK

5. (11:25 AM, Oral) Bin: TRANSCRYSTALLIZATION IN CARBON FIBRE FILLED POLY (L-LAC-TIC ACID) COMPOSITES UNDER TEMPERATURE GRADIENT

6. (11:45 AM, Oral) Alharbi: SYNTHESIS AND ANALYSIS OF ELECTROSPUN SRTIO3NANOFIBERS WITH NIOX NANOPARTICLES SHELLS AS PHOTOCATALYSTS FOR WATERSPLITTING

129

Talk Number: 1 (Keynote)Time: Thursday, May 14, 2015 9:45 AM Session: TH2_1: FIC (Henzlik 124)

CRYSTALLIZATION AND MELTING PHENOMENA IN NANOFIBER REIN-FORCED POLYMER NANOCOMPOSITES

Andrzej Galeski1, Stanislaw Galeski1,3, Ewa Piorkowska1, Kinga Jurczuk1, Gilles Regnier2, Artur Rozanski1

1 Polymer Physics, Centre of Molecular and Macromolecular Studies, Poland2 PIMM, Arts et Metiers, ParisTech, 75013 Paris , France3 present address: Department of Physics, ETH, Zurich, Switzerland

Recently we have developed a method of transformation of solid polymer particles into nanofibers in-situduring compounding with other polymers in the molten state [1,2]. The prerequisite is a reduced numberof entanglements in the particles that allows to limit the strain hardening and facilitates the deformationinto nanofibers under shear forces during mixing. Polytetrafluoroethylene nanofibers obtained in this wayexhibit strong nucleation ability towards many polymer matrices, including isotactic polypropylene.

The crystallization kinetics in such systems can be analysed based on the probabilistic model andequally well in terms of extended volume developed to describe the overall crystallization kinetics innanocomposites with embedded finite length nanofibers exhibiting nucleation ability. The validity of themodel was confirmed by a computer simulation and also by comparison with the crystallization kineticsdata of polyamide 12 nanocomposites with carbon nanonubes. The overall crystallization kinetics inpolymer nanocomposites with nucleating nanofibers for isothermal and nonisothermal crystallization,length and orientation distribution of nanofibers, nucleation on nanofiber surfaces with different densityincluding transcrystallization, and curved nanofibers was described. Crystallization of nanocomposites ofPP with nucleating PTFE nanofibers and PA12 with MWCNTs was studied. Those nanofibers stronglynucleate crystallization and the slope of ln[-ln(1-alpha)] vs.ln(t) is close to 2, indicating 2-dimensional growth.

On the other hand transformation of solid polymer particles into long and thin nanofibers affectstheir melting behavior, reflected in a decrease of the melting temperature inversely proportional to nanofiberthickness. The interfacial tension causes also that nanofibers start to melt from their ends. We haveobserved a decrease of Tm of polymer nanofibers with decreasing thickness, following the Gibbs-Thomsonequation where interfacial tension plays also an important role. PE nanofibers cannot be very thin becausethey can melt even below 120 oC.

This research project has been supported by the statutory funds of CMMS PAS and from funds ofthe National Science Centre on the basis of the decisions number DEC-2012/04/A/ST5/00606.

1. K.Jurczuk, A.Galeski, E.Piorkowska, Polymer, 54, 4617-4628 (2013)2. K.Jurczuk, A.Galeski, E.Piorkowska, J. Rheol.,58, 589-605, 2014

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Talk Number: 2 (Invited)Time: Thursday, May 14, 2015 10:25 AM Session: TH2_1: FIC (Henzlik 124)

POLYMER CRYSTALLINITY AND TOUGHNESS: INCREASING PLASTICITYOF CONTINUOUS POLYACRYLONITRILE NANOFIBERS THROUGH CRYSTAL-LIZATION SUPPRESSION

Dimitry Papkov1, Yuris Dzenis1

1 Mechanical and Materials Engineering, University of Nebraska - Lincoln, USA

Strength of structural materials and fibers is usually increased at the expense of strain at failure and tough-ness. Polyacrylonitrile (PAN) is a popular precursor for production of carbon fibers. Electrospinning isan emerging technique that allows production of continuous polymer precursor nanofibers. Recently ourgroup reported significant scale effects in mechanical properties of individual electrospun polyacrylonitrilenanofibers. The nanofibers showed remarkable (two orders of magnitude) increases in strength and stiff-ness, as well as toughness (three orders of magnitude). The largest increases were recorded for the ultrafinenanofibers smaller than 250 nanometers. Structural investigations and comparisons with mechanical behaviorof annealed nanofibers allowed us to attribute ultrahigh ductility and toughness to low nanofiber crystallinityresulting from rapid solidification of ultrafine electrospun jets. Here we show that further reducing the crys-tallinity through changes in the system solvent from dimethylformamide to dimethyacetamide and additionof small amounts of plasticizer (ethylene carbonate) result in improved nanofiber plasticity and, subsequently,further improvements in nanofiber toughness. We further show that the observed size effects in mechanicalproperties shift to the intermediate diameter range (250-500 nm), offering the possibility of easier nanofiberprocessability and handling. For the first time we show experimental evidence of improved polymer chainorientation in individual nanofilaments with the decrease in their diameter. The described modificationsshow the ability to tailor the mechanical properties of the nanofibers in the strength/toughness propertyspace, which is highly desirable for safety critical applications in composites.

131

Talk Number: 3 (Oral)Time: Thursday, May 14, 2015 10:45 AM Session: TH2_1: FIC (Henzlik 124)

ECOLOGICALLY FRIENDLY MULTILAYER WPC/SRC CONSTRUCTION MATE-RIALS; PRODUCTION, STRUCTURE AND PROPERTIES

Artur Kosciuszko1, Tomasz Sterzynski2, Kazimierz Piszczek1

1 Polymer Division, Faculty of Chemcial Technology and Engineering, University of Technology and LifeScience, Bydgoszcz, Poland2 Faculty of Mechanical Engineering and Management, Polymer Division, Poznan University of Technology,Poland

The hybrid polymer composites composed of Wood Polymer Composite (WPC) and Self ReinforcedComposites (SRC) layer (-s) have been produced and characterized. The main idea was to produce amaterial with sufficiently high mechanical properties, easy to recycle after the end-of-life time. Accordingly,the material is composed of one polymer, in this case isotactic polypropylene (iPP), used in various forms,and a filler in a form of wooden flakes. On this way the full material recycling may be performed, makingthe reprocessing of this composite material possible.The sheets of SRC and WPC are placed alternatively, allowing to achieve a material with well-definedproperties, where as well as isotropic or/and anisotropic properties, depending on the of iPP fibers position(direction) in the SRC, may be realized.The difficulties appearing by the production of such composite materials, like constitution of temperatureprocessing windows where the iPP matrix will remains in molten state and the fibers are non-melted, as wellas the resolving of the adhesion problem between the SRC and the WPC will be presented and discussedfrom both, technological and structural point of view.

132


XANTHAM GUM AND CHITOSAN AS NATURAL ADHESIVES FOR CORK

Isabel Vale1, Carolina Gonçalves1, Diana Paiva1, Margarida Bastos1, Fernão Magalhães1

1 Chemistry - LEPABE, Faculty of Engineering of the University of Porto, Portugal

Composites based on cork (bark of Quercus suber L.) have been receiving increasing interest for differentapplications. Cork combines a unique set of properties like elasticity, resilience, impermeability, low density,and very low conductivity of heat, sound and vibration. Moreover, its use is supported by sustainableforest practices. Cork composites provide added design flexibility and environmental advantages, like easeof incorporation of pre and post-consumer wastes. But one increasing requirement has been the replacementof synthetic adhesives, like reactive polyurethane (PUR) or formaldehyde-based resins, by natural bindersfrom renewable resources. This presents particular challenges, especially when mechanical performance andwater resistance are needed.

The viability of using two widely available polysaccharides, xanthan gum (XG) and chitosan (CS) ascork binders was studied. The adhesives were used as water solutions with concentrations of 6 wt.%or lower. For XG, chemical oxidation was investigated as a strategy to provide water resistance andreactivity. Periodate oxidation allowed C-C cleavage between adjacent -CHOH groups, forming dialdehydes.NH2OH-HCl titration of the oxidized gum (XGox) indicated aldehyde contents of about 60%. 1H-NMRconfirmed formation of aldehyde groups.

Bond strength (BS) tests were performed on cork samples after drying the glued joints for 2 h at120 oC. Results showed that CS (6 wt.%) yielded similar BS as a reference PUR adhesive, being 50 %higher than XG. BS decreased as CS or XG concentrations were lowered, due to depletion of binder in theglued joint. When performing the tests after immersion of the glued samples in water for 24 h at 20 oC, XGshowed null BS, while CS displayed 40 % lower strength. This was expected considering that XG is solublein water while CS in insoluble, as long as nonacidic conditions are used.

Interestingly, XGox showed dry BS 76 % higher than XG and 15 % higher than CS. Wet BS wassimilar for XGox and CS. Oxidation of XG reduces its water solubility, as confirmed by total solublematter assays, due to decrease in hydroxyl content and possible self-crosslinking promoted by alde-hyde groups, which explains higher water resistance. On the other hand, aldehydes also allow forreaction with groups present in the cork structure, providing a covalent mechanism for increasing bondstrength and water resistance. Mixtures of XGox and CS did not yield better performances than XGox alone.

133


TRANSCRYSTALLIZATION IN CARBON FIBRE FILLED POLY (L-LACTIC ACID)COMPOSITES UNDER TEMPERATURE GRADIENT

Yuezhen Bin1,2, Shengnan Zhang1

1 Department of Polymer Science and Engineering, Dalian University of Technology, China2 State Key laboratory of Fine Chemicals, Dalian University of Technology, China

As a kind of biodegradable and biocompatible thermoplastic resin, Poly (lactic acid) is widely applied inpackaging and biomedical industries. Many researches dealt with the addition of filler in PLA to improveits crystallization rate. As well-known, the interfacial interaction between polymer matrix and filler playsa dominant role in the mechanical property of composites. Recently, it has been receiving more and moreattention that interfacial crystallization may contribute to interfacial bonding of the composite. In thisstudy, thin films of carbon fibre (CF)/PLA and nickel plating carbon fiber (NiCF)/PLA composites weremade via solution casting and the transcrystallization behavior of composites was investigated. Samples werecrystallized on the temperature gradient stage with temperature ranging from 363 K to 413 K. Polarizingmicroscope observation indicated that typical transcrystalline (TC) structure was formed in both CF/PLAand NiCF/PLA composite films. For each composite, nuclei density on single fiber decreased and radius ofTC increased as crystallization temperature (Tc) increased. In addition, nuclei density on single NiCF washigher than that on CF. SEM observation showed that NiCF had stronger ability to initiate heterogeneousnucleation due to the existence of nano-nickel particles. However, the radius of TC in short NiCF/PLAcomposite was smaller than that in CF/PLA at the same Tc. Crystallization kinetics analysis demonstratedthat the onset time of nucleation and the radius growth rate of TC increased as Tc increased. Furthermore,kinetics analysis revealed that final size of TC was influenced by competition between transcrystallizationon fiber surface and spherulitic crystallization around the fiber.

References1 Nanying Ning, Sirui Fu, Wei Zhang, et’al. Progress in Polymer Science, 2012, 37(10): 1425∼14552 Duigong Xu, Yuezhen Bin, Ping Tang. Macromolecules, 2010, 43(12): 5323∼5329

134


SYNTHESIS AND ANALYSIS OF ELECTROSPUN SRTIO3 NANOFIBERS WITHNIOX NANOPARTICLES SHELLS AS PHOTOCATALYSTS FOR WATER SPLIT-TING

Abdulaziz R Alharbi1, Ibrahim M. Alarifi1, Waseem S. Khan1, Dr. Ramazan Asmatulu1

1 Mechanical Engineering, Wichita State University, United States

Coaxial electrospinning process was used to produce core/shell SrTiO3- NiOx nanofibers. Poly(vinyl alcohol)(PVA) was dissolved in mixture with DI water and acetic acid at 10:90 weight ratios, and then titanium(IV) isopropoxide [C12H28O4Ti] and strontium nitrate [Sr(NO3)2] were added into the solution to form theinner (core) layer. Polyacrylonitrile (PAN) polymer was dissolved in dimethylformamide (DMF) with 10:90weight ratios. Nickel oxide [Ni2O3] was mixed with the solution to form the outer (shell) layer. This coaxialelectrospinning method generated uniform sized, defect-free fibers. The electrospun nanofiber samples wereannealed at 600 oC for 2 hours in air in order to remove the organic part and crystalline the amorphousSrTiO3- NiOx nanofibers. Water contact angles were determined to identify surface hydrophobicity ofthe nanofiber films. The UV spectrophotometer, fourier transform-infrared radiation (FT-IR), differentialscanning calorimeter (DSC) techniques were used to characterize structural properties of the SrTiO3- NiOxcomposite. The morphology and dimensions of the nanofibers were observed by scanning electron microscope(SEM). The images showed the fluctuation in the fiber diameters because of the two different polymericsolutions electrospun at the same time. The structures of the calcined nanofibers were determined byRaman spectroscopy, and X-ray diffraction (XRD), which clearly indicated the formations of SrTiO3 andNiOx nanofibers structures. The fabrication of such core/shell SrTiO3-NiOx nanofibers through coaxialelectrospinning suggests the further enhancement and development of photocatalytic behaviors of the newnanomaterials. This study can provide useful information for scientists, engineers, and manufacturersworking in the renewable energy and related fields, such as water splitting, sensors, solar cells, and catalysts.Keywords: Coaxial Electrospinning, Core/Shell SrTiO3 and NiOx Nanofibers, Calcination, Photocatalysts,Water Splitting.

135

Thursday, May 14, 2015 Starting: 9:45 AMTH2_2: PPSC (Henzlik 53)

Session Chairs: Eric Dargent, Lucia Fernandez-BallesterAssistant: Zesheng Zhang

Talks:

1. (9:45 AM, Keynote) Lefebvre: IN-SITU SAXS/WAXS INVESTIGATIONS ON DEFORMATIONINDUCED STRUCTURAL EVOLUTIONS IN AMORPHOUS AND SEMI-CRYSTALLINE POLY-MERS

2. (10:25 AM, Oral) Mokni: EFFECT OF THE SUBLIMATION TEMPERATURE ON THE MOR-PHOLOGY AND CRYSTALLINITY OF PARYLENE D DEPOSITED BY CVD

3. (10:45 AM, Oral) Piorkowska: NUCLEATION OF HIGH-PRESSURE-INDUCED GAMMA FORMIN ISOTACTIC POLYPROPYLENE IN NONISOTHERMAL CONDITIONS

4. (11:05 AM, Oral) Fernandez-Ballester: EFFECT OF COPOLYMER CONTENT ON FLOW-IN-DUCED CRYSTALLIZATION

5. (11:25 AM, Oral) Lugito: NOVEL APPROACHES TO ADVANCE UNDERSTANDING OF POLY-MER CRYSTALLIZATION

6. (11:45 AM, Oral) Ding: EFFECT OF TRI-ARM STAR-SHAPED IMIDAZOLIUM IONIC LIQUIDOLIGOMER WITH PEG SEGMENT ON THE CRYSTALLIZATION BEHAVIORS OF POLY(L-LACTIC ACID)

136

Talk Number: 1 (Keynote)Time: Thursday, May 14, 2015 9:45 AM Session: TH2_2: PPSC (Henzlik 53)

IN-SITU SAXS/WAXS INVESTIGATIONS ON DEFORMATION INDUCEDSTRUCTURAL EVOLUTIONS IN AMORPHOUS AND SEMI-CRYSTALLINEPOLYMERS

Jean-Marc Lefebvre1, Valérie Miri1, Gregory Stoclet1, Pepin Julie1, Roland Seguela2

1 UMET, CNRS/Univ Lille, France2 MATEIS, CNRS/INSA Lyon, France

The problem of thermally and mechanically-induced crystal phase transitions in semi-crystalline polymersbearing H bonds is of prime importance in materials where anisotropic intermolecular interactions (van derWaals vs H-bonding) result in the existence of crystal phases with sheet-like H-bonded structures. Materialsunder consideration are polyamides 11 and 6. The use of in-situ characterization of these polymorphicmaterials by wide angle and small angle X Ray scattering from a synchrotron source provides clear insightsinto the role of these transitions on the mechanical behavior under uniaxial and biaxial drawing. Thestructural characterization confirms the existence of a phase transition, the Brill transition, towards a HTphase with hexagonal symmetry for some specific crystal structures (α’ and δ’ in PA11, α defective inPA6). The most stable forms (α’ in PA11 and α in PA6) rebuild upon cooling. Under uniaxial drawing,polyamides exhibit ductility, whatever the original crystal form is; an order→disorder transition occurs forT<TBrill , which favors mesophase development (δ’ in PA11 and β in PA6), while above TBrill the HTphase is mechanically stable. In the case of biaxial stretching, phases with H-bonded sheet-like organizationare brittle, contrary to mesomorphic and HT phases. These findings underline the need to monitor thestructural evolution in order to achieve proper solid-state biaxial stretching in industrial processing.

With respect to the cold drawing behavior of PLA, a combination of in situ SAXS and AFM studiesallows identification of the elementary plastic deformation mechanisms involved. It shows that a brittleto ductile transition occurs when the draw temperature is increased and/or at decreasing strain-rate.Morphological studies reveal that the brittle behavior of PLA is correlated with the occurrence of crazing,whereas the ductile response implies dual plastic deformation mechanisms interacting in a rather unusualway. In particular, in situ SAXS reveals the formation of “shear band crazes” and a tentative explanation oftheir development is proposed. In addition this study shows shear banding, activated at high temperature,plays a dual role. While shear bands promote the formation of crazes, they also stabilize them during theirgrowth.

137

Talk Number: 2 (Oral)Time: Thursday, May 14, 2015 10:25 AM Session: TH2_2: PPSC (Henzlik 53)

EFFECT OF THE SUBLIMATION TEMPERATURE ON THE MORPHOLOGY ANDCRYSTALLINITY OF PARYLENE D DEPOSITED BY CVD

Marwa Mokni1,2, Abdelkader Kahouli1,2, Emmanuelle Giroud3, Vincent Mareau4, Fethi Jomni2, AlainSylvestre1

1 Genie electrical, Univ. Grenoble Alpes, G2Elab, France2 Physical, Univ. of Tunis El Manar (LMOP), Tunisia3 Material, Univ. Grenoble Alpes, Polytech Grenoble, France4 Material, Univ. Grenoble Alpes, INAC-SPRAM, France

In the family of parylenes, (Poly-dichloro-para-xylylene) (PPXD) was the object of few attentions untiltoday by the scientific community. However, its chemical structure seems to project some properties betweenPPX N and PPX C and so could be interesting to replace these latters for specific applications. In this way,thin and transparent PPXD has been prepared by Chemical Vapor Deposition (CVD) from vapor-phasepyrolysis of the cyclic tetrachloro-di-p-xylylene dimer. The dependence of (i) the sublimation temperature(120-160 oC), (ii) the deposition time (5-660 min) and (iii) the deposition rate on the physical propertiesof PPX D was investigated. Increasing sublimation temperature affects the surface morphology and thecrystallinity of the material. From Atomic Force Microscopy, one observes that the sublimation temperatureleads to an increase in the surface roughness from 4 to 5.4 nm. Wide Angle X-ray Diffraction (WAXD)experiments allow identifying a monoclinic crystalline-α-form with reflection (020) at 2θ=12oC. A significantdecrease in the crystalline phases of the polymer for higher sublimation temperatures is observed. Finally,crystalline phases are in depth investigated by polarized light microscopy.

138


NUCLEATION OF HIGH-PRESSURE-INDUCED GAMMA FORM IN ISOTACTICPOLYPROPYLENE IN NONISOTHERMAL CONDITIONS

Przemyslaw Sowinski1, Ewa Piorkowska1, Severine A.E. Boyer2, Jean-Marc Haudin3

1 Department of Polymer Structure, Centre of Molecular and Macromolecular Studies, Polish Academy ofSciences, Poland2 Department of Physics and Mechanics of Materials, P PRIME Institute, ISAE-ENSMA, UPR CNRS 3346,France3 Centre for Material Forming, MINES ParisTech, UMR CNRS 7635, France

Isotactic polypropylene (PP) under atmospheric pressure crystallizes usually in the monoclinic alpha ortrigonal beta phase, the latter requiring appropriate nucleating agents. Crystallization of the orthorhombicgamma form is facilitated by high pressure (P), although it requires also high temperature. Owing to itsunique structure with nonparallel chain alignment, it exhibits different mechanical properties than the alphaform [1]. Recently, we demonstrated [2] that alpha-nucleants can nucleate the gamma form under high P at200 oC. During processing crystallization is non-isothermal, hence our present study focuses on nucleationof the gamma form in PP under high P during cooling.

The study utilized PP 3250MR1, Arkema. Three alpha-nucleants, calcium salt of cis-1,2-cyclohex-anedicarboxylic acid, Hyperform HPN-20E, 1,3:2,4-bis(3,4-dimethylbenzylidene sorbitol), Millad 3988i,Milliken Chemicals, poly(tetrafluoroethylene) (PTFE) submicron particles [3], Dispersez 200W, Polysciences,and a known beta-nucleant - calcium pimelate, synthesized by us, were used. Neat PP and PP with 0.2wt% of the nucleants were crystallized in a cell described elsewhere [1,2], under P ranging from 100 to 300MPa, during cooling at approx. 8 oC/min and next analysed by different methods to examine crystallinity,contents of crystallographic forms and spherulitic structure.

Crystallization temperature (Tc) of all the materials increased with increasing P. HPN-20E and PTFEexhibited the highest Tc ; under 300 MPa Tc of PP with HPN-20E exceeded that of neat PP by 14 oCBoth, HPN-20E and PTFE increased also the gamma content and reduced the grain size. Calcium pimelatehad no such effect; it increased only the beta content. The effect of Millad depended on P. Under 100 MPait elevated Tc, and the gamma content, and strongly reduced the grain size, but the effect vanished withincreasing P.

The results show the possibility to nucleate the gamma form of PP under high P during cooling,hence to increase its content and Tc, and to reduce the grain size.

AcknowledgementCMMS PAN statutory funds and PAN/CNRS Collaborative Project 179990 High pressure crystallizationand structure of polymers based nanocomposites.

References1. Lezak E, Bartczak Z, Galeski A. Macromolecules 2006, 39, 48112. Sowinski P, Piorkowska E, Boyer SAE, Haudin JM, Zapala K. Colloid Polym Sci DOI: 10.1007/s00396-014-3445-z3. Masirek R, Piorkowska E. Eur Polym J 2010, 46, 1436

139


EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED CRYSTALLIZATION

Frederic Aubin1, Hugo Boitoit1, Ramin Hosseinabad1, Eric Dargent2, Lucia Fernandez-Ballester1

1 Mechanical and Materials Engineering, University of Nebraska at Lincoln, USA2 Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France

The effect of copolymer content on structure development during and after a short shear pulse has beenexamined for polypropylene-based materials containing between 0 and 7% mol ethylene content. Allmaterials have similar molecular weight Mw, polydispersity, and rheological behavior in the melt. Flowinduced crystallization experiments at fixed temperature and wall shear stresses up to σskin = 0.134MPashowed a similar critical shear stress for formation of a highly oriented skin (σskin) for 0 and 3% copolymercontent. In contrast, further increase in copolymer content up to 7% required a slightly higher σskin. In allcases, σskin was observed to plateau with increasing shearing time ts.

The relative amount of shish length/volume was estimated by applying a depth sectioning method tothe real-time optical measurements. Results indicate that as expected, for shear stress up to 0.123 MPa,shish length/volume is larger for higher σ for first increases and then levels off with sufficient ts for allmaterials. In contrast, at 0.134MPa, the relative shish length/volume for 0 and 3% copolymer contentis smaller than at 0.123. This unexpected behavior is shown to correlate with deviations in rheologicalbehavior and in the residual birefringence after flow.

140


NOVEL APPROACHES TO ADVANCE UNDERSTANDING OF POLYMER CRYS-TALLIZATION

Graecia Lugito1, Eamor M. Woo1

1 Chemical Engineering, National Cheng Kung University, Taiwan

Recently, more and more research on polymer morphology have been conducted in order to study the proper-ties - morphology correlation, which may bring us to the enhancement technique of polymer modification andmanipulation properties. Poly(trimethylene terephthalate) (PTT), a highly birefringent aromatic polyester,has been investigated to explore the correlation between crystal morphology, optical birefringence properties,and crystallization mechanism. PTT exhibits large and well-defined ring-banded spherulites which makeit a good candidate for the study of polymer crystallization and self-assembly. Optical interference colorsthat ornament the morphological image of PTT crystal under POM are found to be strongly related notonly to the sample thickness, but also to the lamellar structure and arrangement within the spherulites.Besides, banding patterns of the spherulites are also found to be varied with the curvature of the initialnucleus. Chemical etching using methylamine vapor has been carried out on bulk samples of PTT withdifferent angles of dissection to see the intricate lamellar structures in the spherulites. A novel crystallizationmechanism of PTT has been built from comprehensive analyses of morphology, optical colors, and chemicaletching approaches.

141


EFFECT OF TRI-ARM STAR-SHAPED IMIDAZOLIUM IONIC LIQUIDOLIGOMER WITH PEG SEGMENT ON THE CRYSTALLIZATION BEHAVIORSOF POLY(L-LACTIC ACID)

Yu Li1, Huagao Fang1, Di Zhang1, Pei Xu1, Haibing Wei1, Yunsheng Ding1,2

1 School of Chemistry and Chemical Engineering, Hefei University of Technology, China2 Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology,China

Crystallization kinetics of the poly(L-lactic acid) (PLLA) due to the incorporation of a kind of tri-armstar-shaped imidazolium ionic liquid oligomer with PEG segment (TSIL) has been studied. Crystallizationkinetic parameters, such as relative crystallinity, crystallization half time, crystallization rate constant andAvrami exponents, had been determined by both isothermal and non-isothermal techniques using differentialscanning calorimetry (DSC). The experimental results based on isothermal and non-isothermal methodsshow that the melt crystallization increases significantly with the incorporation of TSIL in the blends.During the isothermal crystallization process at the crystallization temperature of 90oC, 95oC, 100oC and105oC, respectively, addition of the 9wt% TSIL accelerates the crystallization of the PLLA greatly. Duringthe non-isothermal crystallization process, the crystallization behavior of the PLLA is found to be greatlydependent upon both the cooling rates and the concentration of TSIL. The growth of crystallized spheruliteshad also been monitored by polarizing optical microscope (POM), which confirms that the growth rate ofspherulites increases on the addition of TSIL in the blends, but the nuclear number decrease.In this article, we have also investigated the morphology of the spherulites for PLLA and TSIL/PLLAblends using POM. In the investigation, there are two kinds of spherulites observed under the POM at thecrystallization temperature of 108oC, 110oC and 115oC, respectively. When the weight content of TSIL isbelow 9wt%, the well-defined highly birefringent spherulites can be observed, and when the weight contentof TSIL is up to 9wt%, the spherulites tends to coarse which can be seen. It is amazing to find that theMaltese cross that we can find in the well-defined highly birefringent spherulites is not appeared in the coarsespherulites. The growth rate of the coarse spherulites is much faster than that of the highly birefringentspherulites. It is thought that the coarse spherulites nucleate and grow as the diffusion of the molecules ofthe TSIL at the interfaces between the TSIL and PLA, and the well-defined highly birefringent spherulitesjust nucleate and grow in the PLA matrix without the TSIL.

142

Thursday, May 14, 2015 Starting: 1:00 PMTH3: Flory Medal Talk (Henzlik 124)Session Chair: Jean-Jacques PireauxAssistants: John Jasa, Taylor Stockdale

Talk:

1. (1:00 PM, Prize Talk) Tashiro: CLARIFICATION OF MICROSCOPICALLY-VIEWED STRUC-TURE-PROPERTY RELATIONSHIP OF POLYMER MATERIALS

Dr. Kohji Tashiro, Principal Professor, Department of Future Industry-oriented Basic Science andMaterials, Graduate School of Engineering, Toyota Technological Institute

143

Talk Number: 1 (Prize Talk)Time: Thursday, May 14, 2015 1:00 PM Session: TH3: Flory Medal Talk (Henzlik 124)

CLARIFICATION OF MICROSCOPICALLY-VIEWED STRUCTURE-PROPERTYRELATIONSHIP OF POLYMER MATERIALS

Kohji Tashiro1

1 Future Industry-oriented Basic Science and Materials, Toyota Technological Institute, Japan

In these several decades, we have applied the various characterization techniques including synchrotron andneutron diffractions, FTIR/Raman vibrational spectroscopy, computer simulation and so on for the clarifi-cation of structure-property relationship of polymers from the microscopic point of view.[Structural Analysis using Quantum Beam and Vibrational Spectroscopy] We have been challenged to utilizea high-energy synchrotron X-ray beam of short wavelength and a highly-brilliant neutron beam for the de-tailed crystal structure analysis of polymers including even the determination of hydrogen atomic positions.Additionally, the combination of X-ray and neutron structure analyses or X-N method has allowed us toestimate the bonded electron density distribution along the polymer skeletal chain, giving us a chance todiscuss the physical property from the experimentally-clarified electron level.[Development of Simultaneous Measurement System to Trace the Structural Changes in the Phase Transi-tions] In order to trace the dynamic and hierarchical structural changes during the phase transitions, wehave developed the experimental system for the simultaneous time-resolved measurements of wide-angleX-ray diffraction, small-angle X-ray scattering, Raman scattering or FTIR spectra during heating/cooling,stretching/compression, and so on. As examples, the hierarchical structural changes occurring in the isother-mal crystallization from the melt or glass or in the tensile deformation process have been clarified for thevarious kinds of crystalline polymers.[Molecular Theoretical Study of Structure-Property Relationship of Polymer Crystals] The molecular theoryincluding lattice dynamics has been developed for the prediction of the 3D elastic constants tensor and stress-induced molecular deformation mechanism of polymer crystals, for example. This theoretical prediction ofmicroscopic deformation of polymer chain has been probed successfully by the performance of actual X-raystructure analysis of polymer crystal (polydiacetylene) under tension. The clarification of heterogeneousstress distribution in the mechanically-deformed polymer substance has been also succeeded by analyzingthe shifts of X-ray diffraction peaks, Raman peaks and IR peaks detected under the external stress, fromwhich the existence of taut tie chains was proposed, which is quite important for the solution of industrialproblems about the mechanical toughness of polymers.

144

Thursday, May 14, 2015 Starting: 2:00 PMTH4_1: CSPM (Henzlik 124)

Session Chairs: Joseph Alan Turner, Philip YuyaAssistant: John Jasa

Talks:

1. (2:00 PM, Keynote) Yablon: ADVANCES IN ATOMIC FORCE MICROSCOPY (AFM) BASEDMETHODS TO CHARACTERIZE POLYMER MATERIALS ON THE NANOSCALE

2. (2:40 PM, Invited) Yuya: EFFECT OF GOLD NANOPARTICLE ENHANCEMENT ON NANOME-CHANICAL PROPERTIES OF CHITOSAN FILMS

3. (3:00 PM, Oral) Desyatova: CHARACTERIZATION OF THERMOMECHANICAL PROPERTIESOF RECOMBINANT RESILIN USING ATOMIC FORCE MICROSCOPY

4. (3:20 PM, Oral) Turner: SIMULTANEOUS QUANTIFICATION OF THE IN-PLANE AND OUT-OF-PLANE LOSS TANGENT OF POLYMERS USING CONTACT RESONANCE ATOMIC FORCEMICROSCOPY

145

Talk Number: 1 (Keynote)Time: Thursday, May 14, 2015 2:00 PM Session: TH4_1: CSPM (Henzlik 124)

ADVANCES IN ATOMIC FORCE MICROSCOPY (AFM) BASED METHODS TOCHARACTERIZE POLYMER MATERIALS ON THE NANOSCALE

Dalia Yablon1

1 SurfaceChar, SurfaceChar, USA

AFM based characterization methods are uniquely suited to identify and discriminate polymer materialssince this microscopy is inherently based on a mechanical interaction between tip and sample. An ongoingchallenge for these kinds of characterization methods is quantitative measurement of nanoscale viscoelasticproperties.Recent progress has been achieved with advanced AFM methods to quantitatively measure the storagemodulus, loss modulus, and loss tangent of polyolefin containing blends. Both dynamic contact andamplitude modulation based AFM methods are applied to measure the properties of PP-PE-PS andPP-elastomer blends. The dynamic contact method show excellent sensitivity and accuracy where magneticactuation of the cantilever shows significant improvement in sensitivity to storage and loss modulus. Theloss tangent is also measured as a function of temperature, revealing important polymer transitions. Finally,the use of multifrequency AFM methods, where the AFM cantilever is excited at multiple eigenmodes, isshown to successfully discriminate materials in multi-component blends and materials.

146

Talk Number: 2 (Invited)Time: Thursday, May 14, 2015 2:40 PM Session: TH4_1: CSPM (Henzlik 124)

EFFECT OF GOLD NANOPARTICLE ENHANCEMENT ON NANOMECHANICALPROPERTIES OF CHITOSAN FILMS

Philip Yuya1

1 Mechanical & Aeronautical Engineering, Clarkson University, USA

Chitosan is a naturally derived polymer. It represents one of the most technologically important classes ofactive materials with applications in a variety of industrial and biomedical fields. However, they are usedin limited applications because of disadvantages such as poor electromechanical properties, high brittlenesswith a low strain at break, and sensitivity to water. In certain critical applications, the need arises to modifythe physical, mechanical and electrical properties of the polymer. When blends of polymer films with othermaterials are used for medical devices, as is commonly the case, device performance directly depends onthe nanoscale morphology and phase separation of the blend components. Here, chitosan reinforced bio-nanocomposite films with varying concentrations of gold nanoparticles were prepared through a solutioncasting method. Gold nanoparticles (∼ 32 nm diameter) were synthesized via a citrate reduction methodfrom chloroauric acid and incorporated in the prepared Chitosan solution. Uniform distribution of goldnanoparticles was achieved throughout the chitosan matrix and was confirmed by SEM images. Synthesisoutcomes and prepared nanocomposites were characterized using TEM, SAED, SEM, EDX, XRD, UV-vis,particle size analysis, zeta potential and FT-IR for their physical, morphological and structural properties.Nanoscale mechanical properties of the nanocomposite films were characterized at room temperature, humanbody temperatures and higher temperatures using instrumented nanoindentation techniques. The obtainedfilms were confirmed to be biocompatible by their ability to support the growth and proliferation of humancells in vitro. Statistical analysis on mechanical properties and biocompatibility results, were conducted.Results revealed significant enhancement on both the mechanical properties and cell adherence and prolif-eration. The results will enhance our understanding of the effect of nanostructures reinforcement on theseimportant functional polymeric thin films for potential biomedical applications.

147

Talk Number: 3 (Oral)Time: Thursday, May 14, 2015 3:00 PM Session: TH4_1: CSPM (Henzlik 124)

CHARACTERIZATION OF THERMOMECHANICAL PROPERTIES OF RECOM-BINANT RESILIN USING ATOMIC FORCE MICROSCOPY

Anastasia Desyatova1, Deepak Rudrappa2, Paul Blum2, Joseph Turner1

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA2 School of Biological Sciences, University of Nebraska-Lincoln, USA

Resilin is one of the most efficient biological elastomeric proteins known today with resilience of over 90%,long fatigue life and high elongation at failure. Recently produced recombinant resilins have demonstratedpromising mechanical properties for a wide range of engineering applications. However, their thermomen-chanical properties at the nanoscale have not yet been characterized. Here, recombinant pro-resilin wasmanufactured based on the first exon of the Drosophila CG15920 gene and crosslinked into a hydrogel usingruthenium-mediated rapid photochemical crosslinking. Thermomecanical properties of dehydrated resilingel specimens were characterized using nano Thermal Analysis (nano-TA) and glass transition temperatures(Tg) were obtained at scales less than 100 nm. The results show that Tg at the nanoscale is significantlylower than that measured using differential scanning calorimetry at the macroscale (115 oC versus 170-180oC). A thermal pre-treatment effect was also observed at the nanoscale with Tg gradually increasing up toits macroscopic value. The increase in Tg can be related to the additional thermal crosslinking not reportedpreviously. These results improve our understanding of thermomechanical properties of the crosslinked re-silin. The fact that resilin hydrogels can be thermally pre-treated allows manufacturing of resilin polymerswith heterogeneous tunable properties through nanoscale level pre-treatment [Support from the NebraskaCenter for Energy Sciences Research is gratefully acknowledged].

148

Talk Number: 4 (Oral)Time: Thursday, May 14, 2015 3:20 PM Session: TH4_1: CSPM (Henzlik 124)

SIMULTANEOUS QUANTIFICATION OF THE IN-PLANE AND OUT-OF-PLANELOSS TANGENT OF POLYMERS USING CONTACT RESONANCE ATOMICFORCE MICROSCOPY

Joseph Alan Turner1, Ehsan Rezaei1


Contact resonance atomic force microscope (CR-AFM) methods are relatively new measurement techniquesused to quantify the elastic and viscoelastic properties of numerous materials such as polymers, elastomers,and biological materials. This approach involves measurement of the resonant frequencies of the AFM probeboth for the free case and the case for which the tip is in contact with a sample. Vibration models of the probeand tip-sample contact models are then used to determine the sample properties from the frequency behaviorand to create images of the sample properties. More recently, U-shaped AFM probes were developed to allowlocal heating of samples and the resonances of these probes are much more complex. These probes haveone distinct advantage over rectangular AFM probes in that specific modes allow in-plane and out-of-planetip-sample motion to be excited independently at the same location. In this presentation, we demonstratethe use of this approach for measurement of the material loss tangent at local positions on several polymers.The excitation area is on the order of a few tens of nanometers offering the potential for a wide range ofheterogeneous polymers and polymer composites.

149

Thursday, May 14, 2015 Starting: 2:00 PMTH4_2: NANO (Henzlik 53)

Session Chair: Michael J. SerpeAssistant: Taylor Stockdale

Talks:

1. (2:00 PM, Invited) Okamoto: EFFECT OF PARTICLE DISTORTION ON SAXS FROM OBDDSTUDIED USING PARACRYSTALLINE THEORY AND SELF-CONSISTENT FIELD THEORY

2. (2:20 PM, Invited) Matsuo: MECHANICAL AND DIELECTRIC PROPERTY OF POLYMER-FILLER COMPOSITES IN TERMS OF THERMAL FLUCTUATION-INDUCED TUNNELING EF-FECT

3. (2:40 PM, Oral) Song: REVERSAL NANOIMPRINTING AND FERROELECTRIC PROPERTIESOF P(VDF-TRFE) COPOLYMER NANOSTRUCTURES ON FLEXIBLE PET SUBSTRATE

4. (3:00 PM, Oral) Hnatchuk: POLYCARBONATE AND POLYURETHANE NANO AND MICRO-HYBRID FOAMS

5. (3:20 PM, Oral) Park: CHARACTERIZATION OF CRYSTALLINE THERMOSETTING UREA-FORMALDEHYDE RESINS

150

Talk Number: 1 (Invited)Time: Thursday, May 14, 2015 2:00 PM Session: TH4_2: NANO (Henzlik 53)

EFFECT OF PARTICLE DISTORTION ON SAXS FROM OBDD STUDIED USINGPARACRYSTALLINE THEORY AND SELF-CONSISTENT FIELD THEORY

Shigeru Okamoto1

1 Materials Science and Engineering, Nagoya Institute of Technology, Japan

An ordered-bicontinuous double diamond (OBDD) structure in diblock copolymers was first discovered in1980s [1,2]. In mid 1990s, however, previously reported OBDD was reclassified to an ordered-bicontinuousdouble gyroid (OBDG) [3,4], which brought about many controversies. Recently theoretical study [5]suggested an OBDD structure in diblock copolymer/homopolymer blends. Our previous SAXS workreported experimental results of structural transition between OBDD and OBDG with temperature, whichwe analyzed by fitting with theoretical scattering profile calculated on the basis of a paracrystalline model.However, the theoretical SAXS intensity was not successfully matched while the peak positions wereperfectly matched. We consider that it is necessary to match the theoretical intensity with the experimentalone in order to clearly prove the existence of OBDD.A polystyrene-b-polyisoprene diblock copolymer (SI0426; Mn = 45000, fPS = 0.70), and a polyisoprenehomopolymer (PI0313; Mn = 18000) were used. DOP was added to the blend, SI0426/PI0313 (=75/25wt./wt.), by 40 wt.%. The total volume fraction of polyisoprene was 48.9 %. The structure was measuredby SAXS at BL40-B2 in SPring8.Theoretical profiles were obtained by Fourier transformation of a model prepared by translation of a unitmodel. Our previous work suggested the dry-brush PI homopolymers added were accumulated inside nodesof diamond networks to reduce the entropy loss of the block chains forming the nodes. However, this modeldid not have a good agreement with the experimental data as mentioned above. Then we introduced a newtype of distortion to a unit model to obtain ‘larger nodes and thinner rods’ or ‘smaller nodes and thicker rods’.

Theoretical profiles for various volume fractions without the distortion showed that higher-order maxima ismore strongly affected by the fraction, while the second maximum is much less affected. Thus we introducedthe distortion to nodes and rods as described above. The second peak intensity is most affected among thehigher-oreder maxima, and the profile for the ‘smaller nodes and thicker rods‘ model had better agreementwith the experimental profile.

REFERENCES[1] E. L. Thomas et al., Macromolecules, 1986, 19, 2197[2] H. Hasegawa et al., Macromolecules, 1987, 20, 1651[3] D. A. Hajduk et al., Macromolecules, 1994, 27, 4063[4] D. A. Hajduk et al., Macromolecules, 1995, 28, 2570[5] F. J. Marinez-Veracochea et al., Macromolecules, 2009, 42, 9058

151

Talk Number: 2 (Invited)Time: Thursday, May 14, 2015 2:20 PM Session: TH4_2: NANO (Henzlik 53)

MECHANICAL AND DIELECTRIC PROPERTY OF POLYMER-FILLER COMPOS-ITES IN TERMS OF THERMAL FLUCTUATION-INDUCED TUNNELING EFFECT

Masaru Matsuo1, Panpan Zhang1, Yuezhen Bin1, Rong Zhang1

1 Department of Polymer Science and Materials, Dalian University of Technology, China

Mechanical and dielectric property of polymer-filler composites in terms of thermal fluctuation-inducedtunneling effect and dielectric stabilities of polyimide (PI)-vapor grown carbon fiber (VGCF) composites wereinvestigated to investigate the thermal stability of the composites. VGCF/PI composites were fabricated byin situ polymerization to realize excellent dispersion of VGCFs in PI matrix. Adoption of VGCFs similar torigid carbon fibers is the strategy to investigate the conductive mechanism theoretically in terms of thermalfluctuation-induced tunneling conduction.[1-2] Dynamic tensile modulus and X-ray intensity under appliedelectric field were measured to investigate frequency-temperature dependence of the modulus by Joule heatas well as air heat in relation to the electron transfer mechanisms. Such simultaneous measurements forthe mechanical and structural properties under electric field provided important information about thecharacteristic of polymer-filler composites. As the results, good heat resistance of PI-VGCF compositeswas clarified to be attributed to very few thermal fluctuation of PI chain arrangement in spite of collisionbetween electrons flowed out from the VGCF gaps and atoms of PI chains.Based on the above thermal stability of the PI-VGCF composites, combination between DC componentof AC conductivity and DC conductivity by direct DC measurement was analyzed in terms of thermalfluctuation-induced tunneling through thin barriers in order to evaluate the average gap distance D betweenadjacent vapor grown carbon fibers (VGCFs) in polyimide (PI) matrix. The phase lags of resistances forcomplex impedance were evaluated by a two-circuit model with a 3.11 vol% and by a three-circuit model fora 6.28 vol% containing the Contact Phase Element. The distance D was calculated by computer simulationon the basis of the DC component of the AC conductivity. The values were 1.2 and 1.0 nm for the compositeswith 3.11 and 6.28 vol%, respectively, independent of the applied voltage range 0.1-0.5 V. These reasonablevalues accorded with those obtained by the direct DC measurement.References1) R. Zhang et al. Polymer J. 45, .1129 (2013),2) R. Zhang et al. J. Phys. Chem. B. 118, 2226 (2014)

152

Talk Number: 3 (Oral)Time: Thursday, May 14, 2015 2:40 PM Session: TH4_2: NANO (Henzlik 53)

REVERSAL NANOIMPRINTING AND FERROELECTRIC PROPERTIES OFP(VDF-TRFE) COPOLYMER NANOSTRUCTURES ON FLEXIBLE PET SUB-STRATE

Jingfeng Song1, Haidong Lu1, Shumin Li2, Li Tan2, Alexei Gruverman1, Stephen Ducharme1

1 Physics & Astronomy, University of Nebraska-Lincoln, USA2 Mechanical & Materials Engineering, University of Nebraska-Lincoln, USA

ABSTRACTPVDF and its copolymers have found increasing application in a wide range of flexible electronic technologies,such as nonvolatile memories, organic electronics, energy storage, and solid-state energy harvesting andconversion. Up to now, many studies of ferroelectric polymer nanostructures have applied the traditionaldirect nanoimprinting technique in which a hard mold is pressed against (PVDF)-based polymer film coatedon silicon wafer at raised temperature. The direct imprinting process often leaves a residual polymer layerbetween the imprinted structures, and more importantly, the required high pressure of 20∼128 bars ormore during the imprinting makes it unsuitable for flexible substrates since their mechanical strength arenot sufficient for high pressure processing at raised temperature. Based on these considerations, we havedeveloped a low pressure reversal nanoimprinting method and fabricated large area, residual-layer-freeP(VDF-TrFE) 2D nanograting and 3D nanopillar structures on flexible PET substrate. The reversalimprinting method is using low-cost polycarbonate and PDMS mold with no pretreatment necessary, andthe imprinted nanostructures showed very good piezoresponse. The low pressure reversal nanoimprintingmethod with a soft mold is a promising approach to fabricate functional polymer nanostructures on flexiblesubstrate for flexible electronics applications.

ACKNOWLEDGMENTWe thank Prof. Barry Cheung for fruitful discussions, Prof. You Zhou for assistance with SEM and Dr.Shah Valloppilly and Yunlong Geng for assistance with the x-ray data analysis. This work was supportedby the U.S. Department of Energy, Office of Basic Energy Sciences, under Award No. DESC0004530.

153


POLYCARBONATE AND POLYURETHANE NANO AND MICROHYBRID FOAMS

Witold Brostow1, Chong Bo1, Thomas Cloarec1, Nathalie Hnatchuk1, Yingji Wu1

1 Materials Science and Engineering, University of North Texas, USA

Metallic and polymeric foams have automatically light weight while their mechanical properties arecomparable to the respective solid materials. However, metallic foams corrode and recover poorly after largestresses. Polymeric foams have a large area of applications; varying a polymer matrix, we can obtain flexibleor rigid materials while adding different fillers can improve properties and lower an overall cost. We use asmatrices two commercial polymers, a polycarbonate (PC) and a polyurethane (PU).

We use both physical and chemical procedures to produce foams. The physical methods of creatingfoams require injecting carbon dioxide gas under pressure or else using a supercritical CO2. Along thechemical route, polymers undergo a chemical reaction with a foaming agent specific for each polymer.Depending on the chosen procedure and varying processing conditions such as time, temperature andpressure, we can control the sizes of pores in the foams. We use a variety of nano- and micro-fillers, suchas carbon black, nanoclay, silica and fly ash. The filler nature, its concentration, particles shape and sizemake a dramatic difference in the foam’s performance. Some of our fillers are quite inexpensive, includingeven industrial waste. Filler concentration in the foams is varied from 0 to 30 wt. % with step of 2.5 %.We observe a deterioration of mechanical properties of PC and PU foams when exceeding 30 % of the filler.Creating foams with fillers allows us to enhance thermophysical, mechanical and tribological properties ofmaterials while lowering the product cost at the same time. Since some of our fillers are actually wastes,recycling contributes to the environmental protection of our planet.

154


CHARACTERIZATION OF CRYSTALLINE THERMOSETTING UREA-FORMALDEHYDE RESINS

Byung-Dae Park1, Arif Nuryawan1, Valerio Causin2

1 Department of Wood and Paper Sciences, Kyungpook National University, Republic of Korea2 Department of Chemical Sciences, University of Padova, Italy

It is generally known that thermoset polymers such as epoxy resin and formaldehyde-based resins are es-sentially amorphous. In particular, urea-formaldehyde (UF) resin, a polymeric condensation product offormaldehyde with urea, is one of the most important thermosetting formaldehyde-based resins, and beingwidely used as wood adhesives. However, we here report that thermosetting UF resin of low formalde-hyde/urea (F/U) mole ratio contains crystalline structures either in liquid or cured state. We employedseveral characterization techniques, such as scanning electron microscopy (SEM), transmission electron mi-croscopy (TEM), wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS) to study thecrystalline structures of UF resins. These characterization results have revealed that UF resins with low F/Umole ratio contain crystalline structures, even in the contact with wood. The presence of crystalline struc-tures in UF resin indicates that a thermosetting polymer is a crystalline polymer. In addition, these resultsalso suggest that the crystallite formation in cured UF resin does not make contribution to its cross-linkingin the curing process, leading to a lower cross-linking density and consequent poor adhesion strength.

155

Thursday, May 14, 2015 Starting: 4:00 PMTH5_1: BIOT (Henzlik 124)

Session Chair: Holger SchönherrAssistant: John Jasa

Talks:

1. (4:00 PM, Keynote) Castano: ADVANCED NATURAL MATERIALS: FROM RICE HUSK TOAEROSPACE SYSTEMS

2. (4:40 PM, Invited) Thomas: ROLE OF NANOPARTICLES IN COMPATIBILIZING IMMISCIBLEPOLYMER BLENDS

3. (5:00 PM, Oral) Gnuse: MECHANICALLY ACCURATE NANOFIBROUS VASCULAR GRAFTMATERIALS

4. (5:20 PM, Oral) Laskar: EVALUATION OF POTENTIAL APPLICATION OF UNUSUAL POLY-MERSOMES PREPARED FROM PH-RESPONSIVE DUAL HYDROPHILIC BIOCOMPATIBLERANDOM COPOLYMERS

156

Talk Number: 1 (Keynote)Time: Thursday, May 14, 2015 4:00 PM Session: TH5_1: BIOT (Henzlik 124)

ADVANCED NATURAL MATERIALS: FROM RICE HUSK TO AEROSPACE SYS-TEMS

Victor M. Castano1

1 Centro de Física Aplicada and Tecnología Avanzada, Universidad Nacional Autónoma de México, Mexico

A review of the fundamental properties shared by many natural materials, from the standpoint of struc-ture/properties relationships will be presented as a general theoretical framework. Then, a number of specificexamples will be elaborated, with emphasis on the advance applications that have, are or can be attained,including fireproof building materials from rice husk, the bioproduction of nanoparticles from soil fauna,the removal of metal ions from water from chicken feathers, to the production of light, radiation-resistantmaterials for aerospace use from natural plants, and others in the biomedical arena. Finally, the future ofMaterials Science and Engineering, from a perspective of Nature-made raw materials, will be discussed.

157

Talk Number: 2 (Invited)Time: Thursday, May 14, 2015 4:40 PM Session: TH5_1: BIOT (Henzlik 124)

ROLE OF NANOPARTICLES IN COMPATIBILIZING IMMISCIBLE POLYMERBLENDS

Sabu Thomas1,2

1 Director,International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma GandhiUniversity,kottayam,Kerala, India2 School of Chemical Sciences, Mahatma Gandhi University,Kottayam,Kerala, India

The use of nanofillers in polymer system has brought about wide appreciation due to the excellentimprovement in property it imparts in a polymeric material .This in turn have benefitted hugely theindustrial sector. While blending of polymers is always done to enhance the properties of polymer products,the expected property is not always achieved due to the immiscibility faced by majority of the polymers.As reported by many research groups, the addition of nanoparticles is a useful and interesting methodfor compatibilization[3]. The use of nanofillers as a compatibilizer can impart significant changes to theimmiscible polymer blend system by various thermodynamic and kinetic phenomena.[1],[2]. Compatibilizerin polymer blend can act different roles to do the compatibilization. By the reduction in interfacial energybetween the two phases or by permitting a finer dispersion during mixing, or by providing a hindranceagainst gross segregation, or it can act by enhancing the interfacial adhesion. This paper will be presentinga brief account of the recent work done in immiscible polymer blends where various nanofillers like carbonnanotubes, nanoclay etc. were used as compatiblizers.[4-6]

1. M. Yoo., S. Kim & J. Bang, (2013). Journal of Polymer Science Part B: Polymer Physics, 51(7),494-507.2. Z. M. Zou, Z. Y. Sun, &, L. J. An (2014). Rheologica Acta, 53(1), 43-53.3. I. Labaume, J. Huitric, P. Médéric & T. Aubry (2013). Polymer, 54(14), 3671-3679.4. A. K. Zachariah, P. K. Mohammed and V. G. Geethamma, A. K. Chandra, P. K. Mohammedc and S.Thomas (2014). RSC Adv., 4, 580458058,DOI: 10.1039/C4RA11307A,5. A. K. Zachariah, S. Thomas, P. K. Mohammed and A. K. Chandra, patent le no.135/CHE/2012, 2012.6. H. J. Maria, N. Lyczko, A. Nzihou, K. Joseph, C. Mathew and S. Thomas, Appl. Clay Sci., 2014, 87, 120

158

Talk Number: 3 (Oral)Time: Thursday, May 14, 2015 5:00 PM Session: TH5_1: BIOT (Henzlik 124)

MECHANICALLY ACCURATE NANOFIBROUS VASCULAR GRAFT MATERIALS

Trevor Gnuse1, Kaspars Maleckis1, Jason Mactaggart2, Alexey Kamenskiy2, Yuris Dzenis1

1 Mechanical and Materials Engineering, University of Nebraska, United States2 Surgery, UNMC, USA

Cardiovascular disease is the leading cause of death and disability in the United States. Patients withadvanced stages of the disease frequently require surgical interventions involving replacement or bypass ofdiseased arterial segments with an arterial substitute, such as a patch or a graft. Despite the long history ofthis surgical procedure, in many cases patients experience complications, leading to unsatisfactory clinicalresults or even failure of the graft. Our findings suggest that major cause of these complications may be thedrastically different mechanical properties of the soft arterial tissue and available rigid graft materials.Here we present development and characterization of novel polymer nanofiber-based vascular graft materials.These materials were designed to mimic fiber networks of collagen and elastin in the native arteries andmanufactured using controlled electrospinning. Flexible process parameters allowed us to mimic importantmorphological features of arterial walls, such as orientation and buckling of filaments. This structuralmimicry in turn allowed us to closely match the key mechanical properties of the artery, such as non-linearity,compliance and anisotropy. In order to perform the complex multidimensional optimization of these graftswe used a set of different characterization methods, including structural studies with electron microscopy,polarized Raman spectroscopy, thermal analysis, and biaxial mechanical characterization of the nanofibrousconstructs. Furthermore we also characterized mechanical properties of individual nanofibers.Our results demonstrate that the developed nanofiber-based materials enable mimicking both structuralfeatures and key mechanical properties of different types of tissues. The methods developed can be used todesign and fabricate novel graft materials targeting individual patients, thus significantly reducing the risksof complications in the vascular graft bypass surgeries.

159

Talk Number: 4 (Oral)Time: Thursday, May 14, 2015 5:20 PM Session: TH5_1: BIOT (Henzlik 124)

EVALUATION OF POTENTIAL APPLICATION OF UNUSUAL POLYMERSOMESPREPARED FROM PH-RESPONSIVE DUAL HYDROPHILIC BIOCOMPATIBLERANDOM COPOLYMERS

Partha Laskar1, Sudip Kumar Ghosh2, Joykrishna Dey1

1 Chemistry, Indian Institute of Technology, Kharagpur, India2 Biotechnology, Indian Institute of Technology kharagpur, India

Polymeric nanocarriers are one of the important colloidal systems applied in the advancement of medi-cation research. Polymeric vesicles or polymersomes among several polymeric nanocarriers have such aparamount importance to play an integral role in drug delivery application to gene transfection. Since in-ception, polyethylene glycol (PEG) has been used as a hydrophilic modification of the various polymericsystems for personal care products to drug delivery systems. In contrast, we report here, for the firsttime, unusual polymersome formation by a series of pH-responsive dual hydrophilic random copolymers,cysteine-conjugated-poly[glycidyl methacrylate-co-mPEG] in different ratio, where methoxy poly(ethyleneglycol) methacrylate (mPEG) behaves as hydrophobe. All the three polymers were observed to decrease thesurface tension of water even without having any typical hydrophobe in their backbone and were found toform vesicular aggregates above a relatively low critical aggregation concentration (CAC). Their self-assemblyformation and microstructural properties were evaluated by steady-state fluorescence technique using vari-ous probes such as N-phenyl naphthylamine (NPN), pyrene and 1, 6-diphenyl-1, 3, 5-hexatriene (DPH). Thepresence of vesicular assembly by these polymers was confirmed by electron micrographs and light scatteringtechnique. The polymersomes are nearly monodisperse and quite stable at biological pH and temperature.Even the polymersome formation in water is devoid of any help of external stimuli (pH, temperature, light orionic strength) or usage of any hazardous organic solvent. All of them can be used as a depot for hydrophilicas well as hydrophobic cargo. All the polymersomes have shown high blood compatibility and literally nocytotoxicity up to very high concentration range. Their cell permeability efficiency was clearly observed byfluorescein isothiocyanate (FITC) tagged polymers. Interaction study with Human Serum Albumin (HSA) atbiological pH proves their adequate binding nature with the carrier protein without disturbing the secondarystructure of HSA. The polymers not only can encapsulate the guests in their vesicular assembly but alsocan release them with the change of pH especially at acidic pH. Thus these polymersomes may find a greatpotential in drug delivery application like intravenous delivery systems.

160

Thursday, May 14, 2015 Starting: 4:00 PMTH5_2: PMMS (Henzlik 53)

Session Chair: Zheng LiAssistant: Taylor Stockdale

Talks:

1. (4:00 PM, Keynote) Saiter: PHYSICAL AGEING AND COOPERATIVE RELAXATION INGLASSY POLYMERS

2. (4:40 PM, Oral) Hagg Lobland: BRITTLENESS OF POLYMERS AND THE RELATION TOTOUGHNESS

3. (5:00 PM, Oral) Li: CHARACTERIZATION OF STRAIN-INDUCED ELASTIC ANISOTROPY,EQUILIBRIUM STRESS, AND MODELING OF THE THERMAL-MECHANICAL RESPONSE OFPEEK

4. (5:20 PM, Oral) Xu: VISUALIZED POLYMER PROCESSING: FAST COLLOIDAL PARTICLEREDISTRIBUTION AT NON-PLANAR SOLIDIFICATION INTERFACE

161

Talk Number: 1 (Keynote)Time: Thursday, May 14, 2015 4:00 PM Session: TH5_2: PMMS (Henzlik 53)

PHYSICAL AGEING AND COOPERATIVE RELAXATION IN GLASSY POLY-MERS

Jean-Marc Saiter1, Mehrdad Negahban2

1 Institut des Matériaux de Rouen, Universite de Rouen, France2 Mechanical and Materials Engineering, University of Nebraska-Lincoln, U.S.A.

For many years researches have been engaged in describing the time dependent properties of glassy materials,with polymers accounting for a large portion of this effort. The particular difficulty is in the glass transitionrange where the characteristic relaxation times go from seconds when above the glass transition temperatureto years when below the glass transition temperature. Even though the glass transition phenomenon isstill today one of the unsolved problems of condensed matter theories, the fact is that all the glasses andall the liquids exhibit common behavior. These characteristics are: (a) Around the glass transition, themolecular movements are cooperative; (b) Blow the glass transition, the relaxations show physical ageing,are nonlinear, are non-exponential, show a characteristic time distribution, and display auto slow down.

We present a large series of data obtained from a wide number of different glasses, (organic and in-organic polymers) focused on the characterization of physical ageing and on the values of the cooperativedomains at their glass transitions. When measurements are performed on very old glasses, it clearly appearsthat the concept of the existence of one homogeneous glassy structure which relaxes during time cannotdescribe the behavior observed even if the material studied is a monoatomic glass (as for Selenium basedglasses). From this, we construct an understanding of how the concept of heterogeneities frozen in at Tg isimportant to describe the behavior of the glass during ageing.

162

Talk Number: 2 (Oral)Time: Thursday, May 14, 2015 4:40 PM Session: TH5_2: PMMS (Henzlik 53)

BRITTLENESS OF POLYMERS AND THE RELATION TO TOUGHNESS

Witold Brostow1, Haley E. Hagg Lobland1, Sahil Khoja1, Sameer Khoja1,2

1 Dept. of Materials Science & Engineering and Dept. of Physics, University of North Texas, USA2 Texas Academy of Mathematics and Science, University of North Texas, USA

Brittleness is an important feature of materials but one often described by only qualitative characterizations.A quantitative scale of brittleness for polymers was defined in 2006 [1]. Thus brittleness B is defined bya mathematical relationship between the elongation at break (by quasi-static mechanical testing) and thestorage modulus (by dynamic mechanical analysis). The scale of B applies to both neat and compositepolymers [2, 3], while researchers at the University of Sichuan demonstrated that the dimensional stabilityof laminates was inversely proportional to brittleness [4]. Furthermore, the usefulness of B is seen throughits connection to viscoelasticity of polymers [1, 2] and impact strength [3]. The frequent question of therelationship between brittleness and toughness, however, is not fully answered [5]. There exist multipledefinitions of toughness. Based on a comparison to impact strength, we have observed there is not a simpleinverse proportionality with B. The area under a stress-strain curve is another commonly used measureof toughness. We are examining the connection between brittleness and toughness so-defined. Throughour investigations we are arriving at better descriptions of these mechanical properties and improving ourcapacity for the prediction of polymer performance and service life.

[1] W. Brostow, H.E. Hagg Lobland & M. Narkis. Sliding wear, viscoelasticity and brittleness ofpolymers, J. Mater. Res. (2006) 21, 2422.[2] W. Brostow and H.E. Hagg Lobland, Predicting wear from mechanical properties of thermoplasticpolymers, Polym. Eng. & Sci. (2008) 48, 1982.[3] W. Brostow & H.E. Hagg Lobland. Brittleness of materials: Implications for composites and relation toimpact strength, J. Mater. Sci. (2010) 45, 242.[4] Chen J, Wang M, Li J, Guo S, Xu S, Zhang Y, Li T, Wen M (2009) Eur Polym J 45:3269-3281.[5] W. Brostow, H.E. Hagg Lobland and M. Narkis. The concept of brittleness and its applications. PolymerBull. (2011) 59, 1697.

163


CHARACTERIZATION OF STRAIN-INDUCED ELASTIC ANISOTROPY, EQUI-LIBRIUM STRESS, AND MODELING OF THE THERMAL-MECHANICAL RE-SPONSE OF PEEK

Wenlong Li1, Eric N. Brown2, Philip J. Rae2, George A. Gazonas3, Mehrdad Negahban1

1 Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States2 Los Alamos National Laboratory (LANL), Structure Property Relations, United States3 U.S. Army Research Laboratory, Aberdeen Proving Ground, United States

Poly-ether-ether-ketone (PEEK) is a high performance semi-crystalline polymer that appeared in the 1980s[1] and is extensively used in the chemical and mechanical applications due to its excellent chemical-resistanceproperties, toughness, and good high-temperature properties. Like many polymers and some metals, it canshow a substantial development of anisotropy in its response after plastic flow. We added experimentalresults on the development of anisotropy using ultrasonic, and equilibrium stress measurements throughcyclic loading [2] to the measurements of response under dynamic loading by Rae and Brown [3] to modelthe response of PEEK.Ignoring the possible recrystallization of PEEK during loading, we develop a preliminary thermo-mechan-ical model for PEEK that is capable to reproduce the experimentally evaluated equilibrium stress, thedevelopment of elastic anisotropy, and thermal-mechanical response at the loading rate from 0.0001 to 30001/s over a temperature range from -85oC to 140oC and for loading up to 40% compression. The modelis a multidimensional single-element nonlinear thermodynamically-consistent model. This model matchesthe measured thermo-mechanical response below the glass transition and correctly predicts the measuredtangent modulus at equilibrium.

1. Attwood, T.E., Dawson, P.C., Freeman, J.L., Hoy, L.R.J., Rose, J.B., Staniland, P.A.: Synthesisand properties of polyaryletherketones. Polymer 22, 1096-1103 (1981)2. Negahban, M., Goel, A., Delabarre, P., Feng, R.: Experimentally evaluating the equilibrium stress inshear of glassy polycarbonate. J. Eng. Mater. Technol. 128(4), 537-542 (2006)3. Rae, P.J., Brown, E.N., Orler, E.B.: The mechanical properties of poly (ether-ether-ketone) (PEEK)with emphasis on the large compressive strain response. Polymer 48, 598-615 (2007)

164


VISUALIZED POLYMER PROCESSING: FAST COLLOIDAL PARTICLE REDIS-TRIBUTION AT NON-PLANAR SOLIDIFICATION INTERFACE

Zhanping Xu1, Hongfeng Yu2, Li Tan1

1 Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States2 Computer Science and Engineering, University of Nebraska-Lincoln, United States

Freeze-drying has been widely used for polymer processing due to its accessibility, environment-friendlynature, and wide varieties of porous structures. However, freezing is also a complex process that requiresa major investigation of the process conditions and the formulations. Particularly, the mutual interactionbetween the growing solid-liquid interface and the solute content in the suspension plays a critical role inthe formation of different porous structures. We built a two-dimensional numerical model to simulation adirectional freezing in a colloidal suspension, with the focus of non-planar solidification interface and colloidalparticle redistribution. We will demonstrate an interactive platform by coupling simulation module with avisualization module through high performance GPU devices.

165

Friday, May 15, 2015 Starting: 8:30 AMF1: Plenary (Auditorium)

Session Chair: Lucia Fernandez-BallesterAssistants: Marzieh Bakhtiary Noodeh, Mohammad Nahid Andalib

Talk:

1. (8:30 AM, Plenary) Segalman: USING BIOINSPIRED POLYMERS TO EXPLORE THE ROLE OFSEQUENCE ON CONTROLLING POLYMER PROPERTIES

Dr. Rachel A. Segalman, Professor of Chemical Engineering and Materials, University of California, SantaBarbara; Director of AFOSR-MURI on Thermal and Electrical Transport in Organic and Hybrid Materials

166

Talk Number: 1 (Plenary)Time: Friday, May 15, 2015 8:30 AM Session: F1: Plenary (Auditorium)

USING BIOINSPIRED POLYMERS TO EXPLORE THE ROLE OF SEQUENCE ONCONTROLLING POLYMER PROPERTIES

Rachel Segalman1

1 Chemical Engineering and Materials, University of California Santa Barbara, U.S.A.

Chain shape and monomer sequence are two handles that affect polymer properties and self-assembly; how-ever, it is difficult to control these handles in conventional synthetic polymers without also changing otherfactors, such as chemistry. Polypeptoids, a class of sequence-specific bioinspired polymers, have a chain shapethat can be tuned by the introduction of monomers with bulky chiral aromatic side chains, allowing one toinduce a helical conformation while preserving the chemical nature of the side chains. Here, we examinethe rigidity of polypeptoid helices using small angle neutron scattering to measure the persistence length ofboth a helical and a non-helical peptoid chain. Incorporation of these polypeptoids into block copolymersenables a systematic study of the effect of chain shape on self-assembly while maintaining similar enthalpicinteractions. Because both the helical and non-helical peptoid blocks have similar flexibilities, it is shownthat the strength of segregation depends much more on monomer composition. These studies are a promisingbasis for further examining the effect of monomer sequence control on block copolymer self-assembly. In thistalk, I will also discuss the use of this model system to understand the role of sequence on chain collapse andglobule formation in solution, polymer crystallization, and potential application as surface active agents foranti-fouling.

167

Friday, May 15, 2015 Starting: 9:40 AMF2_1: PS (Auditorium)

Session Chairs: Jean-Marc Saiter, Nicolas DelpouveAssistant: Mohammad Nahid Andalib

Talks:

1. (9:40 AM, Keynote) Grande: DESIGN, SYNTHESIS, AND CHARACTERIZATION OF FUNC-TIONAL DOUBLY POROUS CROSSLINKED POLYMERS

2. (10:20 AM, Keynote) López: A NEW METHOD TO MODIFY POLY(ARYLENE ETHERS) WITHA MILD SULFONATION AGENT

3. (11:00 AM, Invited) Fors: DETERMINISTIC CONTROL OF POLYMER MOLECULAR WEIGHTDISTRIBUTION

4. (11:20 AM, Oral) Neupane: CONVERSION OF PAPER WASTE INTO BIOPLASTICS (POLY-LACTIC ACID)

5. (11:40 AM, Oral) Bhajiwala: MORPHOLOGICAL STUDY OF SPHERICAL MAGNESIUMDICHLORIDE SUPPORTED TI BASED ZIEGLER NATTA CATALYST SYSTEM

168

Talk Number: 1 (Keynote)Time: Friday, May 15, 2015 9:40 AM Session: F2_1: PS (Auditorium)

DESIGN, SYNTHESIS, AND CHARACTERIZATION OF FUNCTIONAL DOUBLYPOROUS CROSSLINKED POLYMERS

Daniel Grande1

1 Complex Polymer Systems Laboratory, Institut de Chimie et des Matériaux Paris-Est, France

Over the last decade, the preparation of doubly porous materials has particularly attracted the focus ofresearchers for the design of biocompatible scaffolds meant for biomedical applications. A hierarchicaldouble porosity may constitute a real benefit in the area of tissue engineering as the first porosity with poresizes higher than 100 µm may enable the seeding and development of suitable cell lines within the material,while the second porosity with pore diameters lower than 1 µm should permit to improve the nutrient andwaste flow though the material when the macropores are clogged at the last stage of the cell culture. In thiscontext, different methodologies have hitherto been developed for the design and synthesis of such materialsdisplaying a double porosity. Temperature-induced phase separation in combination with particle leachinghas recently been reported for the design of poly(L-lactic acid) (PLLA), gelatin or PLGA scaffolds. Gasfoaming combined with particle leaching also seems to be appropriate for the preparation of doubly porousPLLA- and PLGA-based frameworks when using dioxane/water as a porogenic solvent mixture and sodiumbicarbonate particles. In addition, High Internal Phase Emulsion (HIPE) templating has allowed for thegeneration of hydrophilic polymeric materials presenting a hierarchically-structured porosity.

In order to develop more robust and versatile approaches to biocompatible doubly porous crosslinkedpolymer materials, we propose novel porogen templating strategies through the use of two distinct typesof porogens, namely a macroporogen in combination with a nanoporogen. To generate the macroporosity,either CaCO3 or NaCl particles or sieved PMMA beads are used, while the second porosity is obtained byusing either hydroxyapatite nanoparticles or a porogenic solvent. Such straightforward methodologies basedupon porogen removal allow for the preparation of relatively well-defined doubly porous poly(2-hydroxyethylmethacrylate)-based materials. The porosity of the as-obtained biporous frameworks is characterized bymeans of nitrogen sorption measurements, mercury intrusion porosimetry, and scanning electron microscopy.Finally, the possibility to further functionalize such materials is investigated through an activation ofhydroxyl groups, and subsequent clickÂİ chemistry coupling with various amines.

169

Talk Number: 2 (Keynote)Time: Friday, May 15, 2015 10:20 AM Session: F2_1: PS (Auditorium)

A NEW METHOD TO MODIFY POLY(ARYLENE ETHERS) WITH A MILD SUL-FONATION AGENT

Natalia Andrea Agudelo1, Juliana Palacio1, Betty Lucy López1

1 Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia, Colombia

A series of sulfonated polymers from PEEK and PEES were obtained using acetyl sulfate as mild sulfonatingreagent. First the thermoplastics polymers poly(ether ether ketone) (PEEK) and poly(ether ether sulfone)(PEES) were synthesized by polycondensation reactions and characterized by gel permeation chromatography(GPC) and thermal analysis. The sulfonation reaction was performed in the temperature range of 40-60oCvarying the reaction time from 3h to 12h. The modification of these materials was confirmed by spectroscopytechniques such as Fourier transform infrared (FTIR). The degree of sulfonation (DS) was determined by 1HNMR spectroscopy, thermogravimetric analysis (TGA) and by titration method, finding interesting relationbetween the three used methods. The sulfonation degrees achieved values up to 38% at 40oC, 50% at50oC, and 65% at 60oC for PEES samples and for the sample of PEEK the sulfonation degree did notshow changes at the conditions evaluated. Additionally, there was not polymer degradation, which wascorroborated by FTIR and 1H NMR. Differential scanning calorimetry (DSC) and TGA studies were carriedout to investigate the thermal properties and stability of the sulfonated polymers. Finally was evaluatedthe modification of ABA triblock copolymers based on PEEK and PEES as middle block (B block) andpoly(methyl metacrylate) (PMMA) as end blocks (A block), under soft reaction conditions. The copolymerswill be evaluated as polymeric exchange membranes for fuel cells in future works.

170

Talk Number: 3 (Invited)Time: Friday, May 15, 2015 11:00 AM Session: F2_1: PS (Auditorium)

DETERMINISTIC CONTROL OF POLYMER MOLECULAR WEIGHT DISTRIBU-TION

Brett Fors1

1 Department of Chemistry and Chemical Biology, Cornell University, USA

A polymer’s dispersity (Ð) is a commonly reported parameter that reflects the ratio of its weight averageand number average molecular weights (Mw and Mn, respectively). Many polymer properties have beencorrelated with Ð, and values approaching unity are associated with controlled chain-growth polymerizations.However, Ð does not rigorously describe the distribution of polymer chain sizes in a given sample, and it hasbeen postulated that variations in the shape and composition of this distribution will influence properties.This presentation will detail a new modular approach for controlling the composition and shape of polymermolecular weight distributions. Through a temporally controlled initiation strategy using controlled radicalpolymerizations the length and molar quantity of polymer chains in a sample can be systematically controlled.This method provides simple access to new materials and allows for the relationship between molecular weightdistribution and polymer properties to be fully explored.

171

Talk Number: 4 (Oral)Time: Friday, May 15, 2015 11:20 AM Session: F2_1: PS (Auditorium)

CONVERSION OF PAPER WASTE INTO BIOPLASTICS (POLY-LACTIC ACID)

Bishnu Prasad Neupane1

1 School of Health and Allied Sciences, Pokhara University, Nepal

The broadly apposite bioplastic, poly lactic acid was synthesized by using deinked paper waste as substrateto Saccharomyces cerevisiae under controlled laboratory conditions. The substrate was initially subjected toacid hydrolysis followed by alkali neutralization to attain a ideal neutral pH for the growth of Saccharomycescerevisiae. At regular intervals the amount of reducing sugar present in the samples were tested using DNSmethod and the amount of sugar that was metabolized to alcohol and lactate were estimated using ferricammonium nitrate and ρ-hydroxy biphenyl method respectively. The lactic acid extract was concentratedusing a rotary vacuum evaporator and the amount was determined spectrophotometrically. The concentratedextract was used for polymerization in the presence of stannous chloride. This resulted in the production ofwhite amorphous wafers. Polymerization trial with stannous chloride was done with 1ml of purified extractwith 0.1g of stannous chloride.

172

Talk Number: 5 (Oral)Time: Friday, May 15, 2015 11:40 AM Session: F2_1: PS (Auditorium)

MORPHOLOGICAL STUDY OF SPHERICAL MAGNESIUM DICHLORIDE SUP-PORTED TI BASED ZIEGLER NATTA CATALYST SYSTEM

Hiren Manojkumar Bhajiwala1

1 Reliance Research & Development center, Reliance Industries Ltd, Hazira, India

The precursor of Ziegler-Natta catalyst plays an important role in maintaining the properties like porosity,morphology, particle size and circularity. Which are very much important to get desired resin properties[1-2]. These characteristic are monitored by various tools such as Scanning electron microscope (SEM) /Transmission Electron Microscopy (TEM) /video microscopy, Surface area etc. The particle growth and itsmorphology have been reported in many articles [3]. The catalyst morphology is a function of precursormorphology and the final resin morphology is dependent on catalyst fragmentation pattern. The detailunderstanding of the correlation between catalyst morphology and fragmentation pattern may be useful todesign a catalyst with desired performance. The several articles have explained fragmentation of catalyst[4].

The surface morphology, topology, shape and physical structure of polypropylene resin particle syn-thesized using Z-N catalyst is an exact replication of base material used for catalyst. The surfacemorphology of each stage precursor, catalyst and polymer resin has been studied using scanning electronmicroscope. The SEM images of spherical primary particle of precursor indicated, it was generated fromnumbers of tiny rod like secondary particle. The bunch of rod like tiny particle having lots of gape betweenthe each bunches, which forms porous structure of precursor. The supported Ti catalyst synthesized fromprecursor showed exact replication of parent particle with slightly increase particle size. The catalyst showedchange in surface morphology of secondary particle with very high surface area compare to precursor. Thedistribution of Ti on the support was found even on entire surface, which confirmed through energy dispersiveX-ray analysis (EDX). The morphology of polymer resin synthesized through slurry polymerization showsexact replication of catalyst to polymer particle with 10-15 time particle growth.

References1. R. Jamjah, G. H. Zohuri, J. Vaezi, S. Ahmadjo, M. Nekomanesh, M. Pouryari, J. App. Poly. Sci., Vol.101, 3829-3834 (2006).2. Zohuri, G. H., Ph.D. Thesis, University of Manchester Institute of Science and Technology (UMIST),Manchester, 1993.3. M. Abboud, P. Denifl, K.H. Reichert, J. App. Poly. Sci., Vol. 98, 2191-2200 (2005)4. F. J. Karol, B. E. Wagner, I. J. Levine, G. L. Goeke, A. Noshay, R.B. Seymour, Cheng, T. Plenum: NewYork, 1987.

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Friday, May 15, 2015 Starting: 9:40 AMF2_2: RSP/MPP (Heritage Room)

Session Chairs: Joseph Turner, Lucia Fernandez-BallesterAssistant: Ehsan Rezaei

Talks:

1. (9:40 AM, Invited) Schubert: BINARY AND TERNARY BLENDS OF POLYPROPYLENE TYPES-INFLUENCE ON THE HOMOGENEITY OF BIAXIAL ORIENTED FILMS

2. (10:00 AM, Oral) Chaganti: PLASTICIZED POLY (3-HYDROXYBUTYRATE): BIOBASED OLE-GOMERIC DIISOCYANATE AS A TOUGHENER

3. (10:20 AM, Oral) Li: THE DYNAMIC FRACTURE BEHAVIOR OF PMMA

4. (10:40 AM, Oral) Wojtczak: ALL-POLYMER FIBRILLAR NANOCOMPOSITES

5. (11:00 AM, Oral) Akram: SOL-GEL DERIVED ORGANIC/INORGANIC HYBRID NANOCOM-POSITES FROM VEGETABLE OILS AS SURFACE COATING MATERIALS

6. (11:20 AM, Oral) Lin: CONTRIBUTION OF COLLAGEN FIBER UNDULATION TO MECHANI-CAL PROPERTIES OF TYPE I COLLAGEN GEL

174

Talk Number: 1 (Invited)Time: Friday, May 15, 2015 9:40 AM Session: F2_2: RSP/MPP (Heritage Room)

BINARY AND TERNARY BLENDS OF POLYPROPYLENE TYPES-INFLUENCEON THE HOMOGENEITY OF BIAXIAL ORIENTED FILMS

Dirk W. Schubert1, Jochen Kaschta1, Stephan Seidl1, Peter Kunzelmann1

1 Material Science, Institute for Polymer Materials, Germany

Biaxial oriented polypropylene is one of the most used materials for industrial films and food packaging. Interms of environmental and economic issues, the reduction of the film thickness, increasing the homogeneity,enhancing the process efficiency and stability are in the focus of this work. To meet these demands, asystematic investigation on the biaxial stretching process was made in this study. Therefore, two commerciallinear polypropylenes with different molar mass and a commercial long-chain-branched polypropylene wereused to obtain binary and ternary blends to adjust the elongation behavior on the molecular level. Theblending was carried out using a cast film process on a twin-screw-extruder. The cast films obtained, wereinvestigated via biaxial stretching varying the preheat time, the temperature and the stretching speed. Thethickness distribution of the films, were used as the measure for film homogeneity, before and after the filmstretching process. The obtained results reveal efficient and stable film stretching process conditions and adesired polymer blend recipe.

175

Talk Number: 2 (Oral)Time: Friday, May 15, 2015 10:00 AM Session: F2_2: RSP/MPP (Heritage Room)

PLASTICIZED POLY (3-HYDROXYBUTYRATE): BIOBASED OLEGOMERIC DI-ISOCYANATE AS A TOUGHENER

Srinivasareddy Chaganti1,2, Rameshbabu Padamati1,2, Kevin O’connor3

1 The Centre for Research on Adaptive Nanostructures and Nanodevices, Trinity College Dublin, Dublin 2,Ireland2 School of Physics, Trinity College Dublin, Dublin 2, Ireland3 NovaUCD, Belfield Innovation Park, University College Dublin, Belfield, Dublin 4, Ireland

Poly (3-hydroxybutyrate)’s (PHB) food packaging applications are limited due to its poor mechanicalproperties, such as brittleness and low deformability. Although the mechanical properties of PHB have beenimproved by addition of plasticizers [1-4], there is a demand to further improve the deformability and tensiletoughness for food packaging applications.In the present work, the mechanical properties of PHB were tuned and enhanced by melt blending thepolymer with a biobased oligomeric diisocyanate synthesised from hexamethelene diisocyante. Oligomericdiisocyanate was found to positively influence mechanical properties of PHB. PHB’s strain at break andtensile toughness were improved with increasing weight fraction of oligomeric diisocyanate. The relativeelongation at break of PHB/oligomeric diisocyanate blends was increased by 275% and the tensile toughnesswas increased by 293%. PHB’s glass transition temperature width (∆Tg) was influenced by oligomericdiisocyanate. Glass transition onset temperature of PHB was shifted towards lower temperature withincreased weight fraction of oligomeric diisocyanate. The relative elastic modulus and storage modulus ofPHB/oligomeric diisocyanate blends at room temperature were decreased by 70% and 57% respectively.The degree of crystallinity of PHB was effected by oligomeric diisocyanate where PHB/oligomeric diiso-cyanate blends exhibited lower crystallinity compared to PHB. The changes in mechanical properties ofPHB/oligomeric diisocyanate blends were mainly due to efficient weakening of intermolecular interactions inthe amorphous regions of PHB, and also a slight decrease in crystalline order of PHB.* [email protected], [email protected]:1. Bibers I, Tupureina V, Dzene A, and Kalnins M. Mechanics of Composite Materials 1999;35(4):357-364.2. Choi JS and Park WT. Macromolecular Symposia 2003;197:65-76.3. Wang LA, Zhu WF, Wang XJ, Chen XA, Chen GQ, and Xu KT. Journal of Applied Polymer Science2008;107(1):166-173.4. Abdelwahab MA, Flynn A, Chiou BS, Imam S, Orts W, and Chiellini E. Polymer Degradation andStability 2012;97(9):1822-1828.

176


THE DYNAMIC FRACTURE BEHAVIOR OF PMMA

Zheng Li1, Guiyun Gao1, Jie Zhou1

1 Department of mechanics & Engineering Science, Peking University, China

Polymethyl methacrylate (PMMA) as a good transparent and typical tough engineering material is designedto exhibit brittle fracture behavior of material in this paper. Semi-Circular Bending (SCB) specimens arewidely used in experimental analysis of complicated fracture processes due to their simple geometry and easyloading control. Here SCB specimens of PMMA with different pre-crack angles and positions were employed.An optical method of caustics was applied to obtain the dynamic fracture properties of PMMA, such as thecrack initiation, crack propagation, stress intensity factor and fracture toughness, etc. During the dynamiccrack propagation, the dynamic fracture parameters could be determined by measuring the caustic patternsobserved by a high speed camera. Moreover, we also compared the fracture mode of different pre-crack anglesand positions. Finally, the interaction between cracks or crack and damage in dynamic fracture process wasalso investigated clearly by using this optical method. Results indicate that the fracture mode of SCBspecimen can be adjusted by pre-crack position and angle. The competition between cracks or influence ofdamage could also be observed. The optical method of caustics is a proficient method to analyze the dynamicfracture process and crack interaction.

177


ALL-POLYMER FIBRILLAR NANOCOMPOSITES

Kinga Jurczuk1, Malgorzata Wojtczak1, Andrzej Galeski1

1 Department of Polymer Physics, Centre of Molecular and Macromolecular Studies Polish Academy ofSciences, Poland

Polymers filled with ready-made polymer fibers may be substituted with success by nanocomposites withnanofibrillar inclusions formed during compounding. It was already reported that polytetrafluoroethylene(PTFE) nanofibers can be generated in situ by plastic deformation of chain-extended PTFE crystalsthrough shearing during compounding with different thermoplastic polymers [1, 2]. Now, we present howthe obtained method may be applied to other than PTFE crystalline polymers. Thus, HDPE powders weresynthesized via polymerization with controlled conditions like temperature and pressure. HDPE synthesiswas performed in toluene in the presence of methyl aluminoxane (MAO) and post-metallocene catalyst,so-called FI catalyst, fluorinated bis(phenoxy imine) titanium complex at 10oC and 1 bar under atmosphereof inert gas. The obtained polyethylene powder contained highly disentangled macromolecules, hence theywere capable of very large and easy deformation. The nascent powder consisted chain-extended crystals withmelting temperature around 140oC and degree of crystallinity of about 73%. The structure, thermal andrheological properties of HDPE powders were characterized by different experimental techniques (e.g. SEM,DSC, etc.). The all-polymer nanocomposites were produced by compounding of synthesized HDPE powdersat various concentration with various olefin copolymers at various processing conditions. The compoundingtemperature was maintained below the melting temperature of HDPE crystals.The studies revealed that HDPE crystals deformation efficiency can be affected by such factors: batchof HDPE powder, type and viscosity of polymer matrix and shear rate or time of compounding. Thosefactors influence significantly the composites morphology. For large single HDPE crystals with disentangledmacromolecules the deformation is easy and deformation ratios are large. The deformation of the HDPEcrystals leads to thin and strong nanofibers dispersed in the form of entangled network in the polymermatrix. The obtained fibrillar nanocomposites are characterized by drastic changes of rheological andmechanical properties in comparison to the polymer matrix..The authors are indebted for financial support of the studies from the project of the National ScienceCentre, Poland (DEC-2012/04/A/ST5/00606) 1.Jurczuk, K.; Galeski, A.; Piorkowska, E. Polymer 2013, 54,4617-4628 2.Jurczuk, K.; Galeski, A.; Piorkowska, J.Rheol. 2014, 58, 589-605

178


SOL-GEL DERIVED ORGANIC/INORGANIC HYBRID NANOCOMPOSITESFROM VEGETABLE OILS AS SURFACE COATING MATERIALS

Deewan Akram1,2, Eram Sharmin1,3, Sharif Ahmad1

1 Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi-110025, India2 Department of Chemistry, Faculty of Science, Jazan University, P.O.Box 2097, Jazan, Kingdom of SaudiArabia3 Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955, Kingdom of Saudi Arabia

Vegetable oils (VO) constitute the single, largest, easily available, low cost, non-toxic, non-depletable,biodegradable family yielding materials that are capable of competing with fossil fuel derived petro-basedproducts. They bear multi functional groups and find applications in the development of low molecularweight polymers such as alkyds, polyesters, polyesteramides, polyepoxies, polyols, and polyurethanes. VObased polymers generally lack high mechanical strength due to their long aliphatic (flexible) fatty acidchains. This can be overcome by the development of VO based organic/inorganic hybrids [O/IH], whichexhibit excellent combination of synergistic properties of both the organic and inorganic components.In the present work, synthesis, characterization and coating properties of VO based O/IH materials aredescribed. Polyols from Ricinus Communis [RO], Linseed oil [LO] and tetraethoxyorthosilane [TEOS]serve as organic and inorganic constituents, respectively. O/IH were prepared by “hydrolysis-condensation”reactions. The hydroxyl groups of polyols condensed with TEOS, by “one-pot, two-step” reactions, formingsilica anchored polyol based O/IH which on addition reaction with isocyanate formed polyurethane hybrids.In FTIR spectra, absorption bands at 800cm-1 (Si-O-Si sym str) and 1090.0cm-1 (Si-O-Si assym str)confirmed the formation of silica particles in O/IH. TEM micrographs of O/IH revealed the presence ofunagglomerated and spherical silica particles. Thermogravimetric analysis showed multiple degradationstages with the onset of degradation at 220oC-225oC. O/IH showed moderate to good antibacterial behavioragainst E.coli and S.aureus. The physico-mechanical and barrier resistance performance of RO and LOO/IH were conducted to evaluate their coating properties. LO based O/IH polyurethane coatings haveshown better corrosion protection efficiency compared to RO based O/IH polyurethane coatings.Keywords: Ricinus communis, Linseed oil, TEOS, Organic/Inorganic hybrid, Nanocomposites, TEM,Antibacterials, Coatings

179


CONTRIBUTION OF COLLAGEN FIBER UNDULATION TO MECHANICALPROPERTIES OF TYPE I COLLAGEN GEL

Shengmao Lin1, Linxia Gu1,2

1 Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA2 Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, USA

Type I collagen, a major component of the extracellular matrix (ECM) of soft tissues, is widely used inhydrogels for scaffold. The mechanical properties of collagen gel provide the basis of cell-scaffold interactionsand are essential in many scaffold design. Previous study has showed that the individual fiber structure(including fiber length, diameter and strength) affect the mechanical properties of collagen gel. Thermalundulation is another important characteristic and could be controlled by the temperature during the poly-merization. However, its contribution to mechanical properties has seldom been studied. In current study,the contribution of collagen fiber undulation was investigated through computational modeling. The col-lagen gel is modeled as three-dimensional random network of cross-linked fibers. Three different levels ofundulation along with straight collagen fiber network are compared together to unravel its effect on mechan-ical properties of the collagen gel. The results show that the stiffness of the collagen gel is reduced by theundulation of the collagen fiber. This work would enhance our understanding of collagen gel mechanics andbetter controlling its mechanical property under different polymerization condition.

180

Friday, May 15, 2015 Starting: 1:00 PMF3: Awards and Closing Session

Session Chairs: Michael Hess, Jean-Marc Saiter, Jean-Jacques Pireaux, Mehrdad NegahbanAssistants: Wenlong Li, Ramin Hosseinabad, Marzieh Bakhtiary Noodeh

Index

Adams, Alina, 40Ade, Harald, 95Ade, Harald (Speaker), 24Adhikari, Rameshwar (Poster), 84Adhikari, Rameshwar (Speaker), 30Agudelo, Andrea Natalia, 170Ahmad, Sharif, 179Akram, Deewan (Speaker), 179Alarifi, Ibrahim (Poster), 106Alarifi, Ibrahim (Speaker), 67Alarifi, M. Ibrahim, 108, 135Alharbi, Abdulaziz, 67Alharbi, R Abdulaziz, 106Alharbi, R Abdulaziz (Poster), 108Alharbi, R Abdulaziz (Speaker), 135Ameri, Tayebeh, 95Anada, Yuichi (Speaker), 59Andalib, Nahid Mohammad, 87Andalib, Nahid Mohammad (Speaker), 74Andrzejewski, Jacek, 123Araujo, Steven, 29, 83, 85, 115Asmatulu, Dr. Ramazan, 67, 106, 108, 135Astakhova, Olena, 90, 91, 113Aubin, Frederic, 122, 140

Bahader, Ali, 126Bahrami, Mozghan, 62Bakhtiary Noodeh, Marzieh (Poster), 115Bashta, Bogdana, 90Basson, Neil, 101Bastos, Margarida, 133Batteux, Florian, 29, 83, 85Bellon-Fontaine, Marie-Noëlle, 72Benetti, Maria Edmondo, 70Bhajiwala, Manojkumar Hiren (Speaker), 173Bin, Yuezhen, 152Bin, Yuezhen (Speaker), 134Blümich, Bernhard (Speaker), 18, 40Blümich, Bernhard (Chair), 25Blum, Paul, 148Bo, Chong, 154Boccaccini, Aldo, 73Boitoit, Hugo, 122, 140Bojda, Joanna, 99

Bowen, Daniel, 112Bowler, Nicola, 97, 112Boyer, A.E. Severine, 139Brêda, José Carlos, 58Brandel, Clement, 52, 93Bratychak, Michael, 90, 91Brodowsky, Hanna, 84Brostow, Witold, 21, 60, 90, 91, 102, 113, 154, 163Brown, N. Eric, 164Browning, Jim, 33Brumbley, Stevens, 102

Cai, Ronggang, 56Cardona, Isidro Wilson, 114Cartigny, Yohann, 52, 93Castano, M. Victor (Speaker), 157Causin, Valerio, 155Causin, Valerio (Speaker), 70Chaganti, Srinivasareddy (Speaker), 176Chan, Chin Han, 42Chan, Chinhan (Poster), 92Chan, Chinhan (Speaker), 46Chan, Chinhan (Chair), 55Charlon, Sebastien, 119Chen, Jihua, 33Chen, Wei, 33Chen, Zhong (Poster), 96Cheng, Stephen, 87Cheng, Z. D. Stephen, 104, 105Cheng, Z. D. Stephen (Speaker), 128Choi, Sung-Hyun, 76Cichorek, Michal, 99Cicogna, Francesca, 103Cloarec, Thomas, 154Conzatti, Lucia, 103Coquerel, Gérard, 51Coquerel, Gerard, 52, 93Cornelius, Christopher (Chair), 39, 77Cosby, Tyler James (Poster), 94

Daily, Connor (Poster), 97Danieli, Ernesto, 40Dargent, Eric, 51, 52, 93, 120, 121, 122, 140Dargent, Eric (Poster), 101, 119Dargent, Eric (Speaker), 27

182

Dargent, Eric (Chair), 136Das, Amit, 30Dazzi, Alexandre, 72Delbreilh, Laurent, 27, 51, 119, 120Delpouve, Nicolas, 83, 85, 101, 115Delpouve, Nicolas (Poster), 103, 120Delpouve, Nicolas (Speaker), 29Delpouve, Nicolas (Chair), 168Denchev, Zlatev Zlatan, 58Denchev, Zlatev Zlatan (Speaker), 53Dencheva, Vassileva Nadya, 53Dencheva, Vassileva Nadya (Speaker), 58Desai, Kiritbhai Bhavesh (Speaker), 50Desyatova, Anastasia, 87Desyatova, Anastasia (Speaker), 148Dey, Joykrishna, 160Ding, Rui (Poster), 112Ding, Yaping (Speaker), 73Ding, Yunsheng (Poster), 126Ding, Yunsheng (Speaker), 142Domenek, Sandra, 101, 120Du, Xiaoyan, 95Ducharme, Stephen, 45, 153Ducharme, Stephen (Chair), 43Dupray, Valérie, 51Durieux, Anne, 109Dzenis, Yuris, 74, 75, 87, 88, 107, 131, 159Dzenis, Yuris (Speaker), 64Dzenis, A Yuris, 68Dzenis, Yuris (Chair), 127, 129

Esposito, Antonella, 121

Fainleib, Alexander, 124Fang, Huagao, 126, 142Fatyeyeva, Kateryna, 27Fernandez-Ballester, Lucia, 121, 122Fernandez-Ballester, Lucia (Speaker), 140Fernandez-Ballester, Lucia (Chair), 37, 136, 166, 174Fink, Rainer, 95Follain, Nadege, 119Fors, Brett (Speaker), 20, 171Fors, Brett (Chair), 11Frazier, Shane (Poster), 100Furgal, Joseph (Poster), 86Furgal, C Joesph, 62

Gafurov, Ulmas (Poster), 116Gakhutishvili, Marina (Poster), 102Galeski, Andrzej, 178Galeski, Andrzej (Speaker), 130Galeski, Stanislaw, 130Gan, Seng Neon, 42

Gao, Guiyun, 177Gautam, Kumar Surendra, 30, 84Gazonas, George, 89Gazonas, A. George, 164Geohegan, David, 33Ghosh, Kumar Sudip, 160Giraldo, Fernando Luis, 114Giroud, Emmanuelle, 138Gnuse, Trevor (Speaker), 159Gonçalves, Carolina (Speaker), 133Goponenko, Alexander, 88Goponenko, Alexander (Speaker), 68Grande, Daniel, 124Grande, Daniel (Speaker), 169Granowski, Gregory, 60, 90Grellmann, Wolfgang, 30, 84Grigoryeva, Olga, 124Gruverman, Alexei, 153Grykien, Remigiusz, 34Gu, Linxia, 180Gu, Linxia (Chair), 69Guenet, Jean-Michel (Speaker), 19, 26Gui, Haoguan, 126Guinault, Alain, 101, 120Gusakova, Kristina, 124

Ha, Ligyeom, 74Haas, Simon, 71Hagg Lobland, E. Haley (Speaker), 60, 163Harun, Mk, 92Haudin, Jean-Marc, 139Hausberger, Andreas, 49Heinrich, Gert, 30, 84Heinz, Hendrik, 98Henning, Sven, 30Henning, Sven (Speaker), 15Henning, Sven (Chair), 16Heres, Maximilian, 94Herry, Jean-Marie, 72Hess, Michael (Chair), 11, 79, 181Hidzir, Mh, 92Hilfiker, James, 48Hnatchuk, Nathalie, 60, 102Hnatchuk, Nathalie (Poster), 90, 91Hnatchuk, Nathalie (Speaker), 21, 154Holzner, Armin, 49Hong, Kunlun, 33Hosseinabad, Ramin, 140Hosseinabad, Ramin (Poster), 122Hsu, Chih-Hao, 105Hu, Gerald, 60Huang, Jinsong, 35

183

Huang, Jinsong (Chair), 23, 31

Im, Soohyok, 54Ivashkiv, Ostap, 113

Jérusalem, Antoine, 89Jahan, I Kazi, 68Jakowski, Jacek, 33Jamil, Tariq (Poster), 98Janasz, Lukasz, 34Jasa, John (Poster), 89Jayasinghe, Gaya Hasani (Poster), 82Jiao, Xuechen (Poster), 95Jo, Won Ho (Speaker), 36Jomni, Fethi, 138Jonas, M. Alain (Speaker), 56Jubeli, Emile, 72Julie, Pepin, 137Jurczuk, Kinga, 130, 178

Kahouli, Abdelkader, 138Kamenskiy, Alexey, 159Kammer, Hans-Werner, 46Kaschta, Jochen, 175Kaser, Jase (Poster), 107Kern, Wolfgang, 49Keum, Jong, 33Khan, S. Waseem, 67, 135Khoja, Sahil, 163Khoja, Sameer, 163Kim, Kyung Tae, 36Kim, Yong-Rak, 54, 125Kim, Yong-Rak (Chair), 47Kosciuszko, Artur, 132Kunzelmann, Peter, 117, 175

López, Lucy Betty (Speaker), 170Lach, Ralf, 30, 84Laine, Richard, 86Laine, M. Richard (Speaker), 62Lanceros-Méndez, Senentxu, 58Lanyi, Franz (Poster), 117Lapienis, Grzegorz, 99Laskar, Partha (Speaker), 160Le, Hai Hong, 30Lee, Jiayin, 92Lee, Jin Woo, 36Lee, Min-A, 76Lee, Soon Jeong, 74Lefebvre, Jean-Marc (Speaker), 137Lemme, Max, 111Li, Shumin, 153Li, Wei, 73

Li, Wenlong, 29, 83, 115Li, Wenlong (Poster), 85Li, Wenlong (Speaker), 164Li, Xue (Speaker), 66Li, Yu, 126, 142Li, Zheng (Speaker), 177Li, Zheng (Chair), 161Liebscher, Marco, 30, 84Lim, Yul Jung, 74Lin, Shengmao (Speaker), 180Lin, Zhiwei, 105Lin, Zhiwei (Poster), 104Liu, Hao (Poster), 105Liu, Yong, 107Lobland, Haley (Poster), 113Loubeau, Florian (Poster), 109Lu, Haidong, 153Lugito, Graecia (Speaker), 141Luszczynska, Beata, 34Lyu, Min-Young (Speaker), 76

Mühlbacher, Inge, 49Mactaggart, Jason, 159Magalhães, Fernão, 133Mahat, B. Khairul, 106Makowski, Tomasz, 34Maleckis, Kaspars, 159Maleckis, Kaspars (Speaker), 75Mallon, E Peter, 101Manhart, Jakob (Speaker), 49Marais, Stephane, 119Mareau, Vincent, 138Marlière, Christian, 72Masruchin, Nanang, 70Matsuo, Masaru (Speaker), 152Meldrum, Tylor, 40Menard, P. Kevin (Chair), 16Menard, P. Kevin (Speaker), 12Messman, Jamie, 112Minutolo, Joseph, 94Miri, Valérie, 137Mokni, Marwa (Speaker), 138Monnier, Xavier, 101Morin, Ezequiel, 121

Nassar, Fernandes Samira, 120Negahban, Mehrdad, 29, 83, 85, 89, 96, 115, 162, 164Negahban, Mehrdad (Chair), 22, 181Neupane, Prasad Bishnu (Speaker), 172Nittler, Laurent, 28Nougaret, Laurianne, 56Nouman, Micheal, 72

184

Nuryawan, Arif, 155

O’connor, Kevin, 176Oberhauser, Werner, 103Odykirk, Timothy, 86Okamoto, Shigeru (Speaker), 151Oligschlaeger, Dirk, 40Oliveira, Matos Filipa, 58Ong, Chonghup, 92Ospina, Catalina Anny (Poster), 114Ouyang, Jianyong (Speaker), 32

Padamati, Rameshbabu, 176Paiva, Diana, 133Palacio, Juliana, 170Pan, David, 62Pandey, Himadri, 111Papkov, Dimitry, 88, 107Papkov, Dimitry (Speaker), 131Papkov, Dimitry (Chair), 69Park, Byung-Dae (Speaker), 155Park, Byungdae, 70Park, Seong-Yeol, 76Passaglia, Elisa, 103Patois, Tilia, 56Pelaez, Alberto Carlos, 114Petit, Samuel, 52, 93Piorkowska, Ewa, 130Piorkowska, Ewa (Poster), 99Piorkowska, Ewa (Speaker), 139Pireaux, Jean-Jacques (Speaker), 28Pireaux, Jean-Jacques (Chair), 79, 143, 181Piszczek, Kazimierz, 132Poddar, Shashi (Speaker), 45Pokharel, Sundari , 102Pribil, Greg, 48

Rae, J. Philip, 164Rain, Pascal, 109Regnier, Gilles, 130Renault, Margareth, 72Rezaei, Ehsan, 149Rezaei, Ehsan (Poster), 118Rijal, Bidur, 27Roether, Judith, 73Roth, V. Stephan, 53Rozanski, Artur, 130Rudrappa, Deepak, 148Ruhkopf, Jasper, 111

Saaid, Fi, 92Sachdeva, Sanchit, 60Sadat Ebrahimi, Mir Mortzea, 71

Saharin, Munirah Siti, 41Saiter, Allison, 27Saiter, Allisson, 101, 103Saiter, Jean-Marc, 29, 42, 83, 85, 115Saiter, Jean-Marc (Poster), 124Saiter, Jean-Marc (Speaker), 17, 162Saiter, Jean-Marc (Chair), 168, 181Salim, Sugama Yoga (Speaker), 42Sangoro, Joshua, 94Sangoro, Joshua (Speaker), 57Saunier, Johanna (Speaker), 72Sayana, Susmitha, 60Schönherr, Holger (Speaker), 14, 71Schönherr, Simon (Poster), 111Schönherr, Holger (Chair), 156Schaller, Raimund, 49Schamme, Benjamin (Poster), 121Schamme, Benjamin (Speaker), 51Schlögl, Sandra, 49Schmidt, Mitchell (Poster), 110Schubert, Dirk, 73Schubert, W. Dirk, 117Schubert, W. Dirk (Speaker), 13, 175Schwahn, Evan (Poster), 83Sclavons, Michel, 119Segalman, Rachel (Speaker), 167Seguela, Roland, 137Seidl, Stephan, 175Serpe, Michael J, 66Serpe, J. Michael (Chair), 150Serpe, J. Michael (Speaker), 65Shao, Ming, 33Sharmin, Eram, 179Shinde, A. Manish, 108Shyshchak, Olena, 113Sim, Laihar, 46Singh, Kawarpal, 40Skórczewska, Katarzyna, 123Sollogoub, Cyrille, 120Song, Jingfeng (Speaker), 153Soto-Puente, A. Jorge, 27Soulestin, Jeremy, 119Sowinski, Przemyslaw, 139Srubar, Wil, 100Stein, Gila (Speaker), 38Sterzynski, Tomasz (Poster), 123Sterzynski, Tomasz (Speaker), 132Stockdale, Taylor (Poster), 87Stoclet, Gregory, 137Sudesh, Kumar, 42Sumpter, Bobby, 33Sun, Jianing (Speaker), 48

185

Sun, Kuan, 32Sylvestre, Alain, 138

Tücking, Katrin-Stephanie, 71Tan, Li, 29, 121, 153, 165Tan, Li (Chair), 61, 63Tarawneh, Constantine, 121Tashiro, Kohji (Speaker), 41, 144Tesserau, Manon, 121Thomas, Sabu (Speaker), 158Tomaszewska, Jolanta, 123Tszydel, Izabela, 34Turner, Joseph, 118, 148Turner, Alan Joseph (Chair), 145Turner, Alan Joseph (Speaker), 149Turner, Joseph (Chair), 174

Ulanski, Jacek (Speaker), 34

Vale, Isabel, 133Vasquez, Yolanda, 82Viel, Quentin (Poster), 93Viel, Quentin (Speaker), 52

Wagner, Stefan, 111Wei, Haibing, 142Wells, Sabrina, 112White, B. John, 60Whittington, R. Abby (Speaker), 78Winie, Tan, 46, 92Wojtczak, Malgorzata (Speaker), 178Woo, M. Eamor, 141Woollam, John, 48Wu, Shaojun, 126Wu, Yingji, 154

Xia, Yijie, 32Xiao, Kai (Speaker), 33Xiao, Zhengguo (Speaker), 35Xu, Chunye (Speaker), 44Xu, Pei, 142Xu, Zhanping (Speaker), 165

Yablon, Dalia (Speaker), 146Yagoubi, Najet, 72Yamane, Honami, 86Yao, Qingqing, 73Yi, Eongyu, 86You, Taesun, 125You, Taesun (Speaker), 54Youngblood, Justin, 102Yu, Hongfeng, 165Yue, Kan, 105Yuya, Philip (Speaker), 147

Yuya, Philip (Chair), 145

Zare Rami, Keyvan (Poster), 125Zhang, Di, 142Zhang, Lili, 89Zhang, Panpan, 152Zhang, Rong, 152Zhang, Shengnan, 134Zhang, Wen-Bin, 105Zhang, Zesheng, 89Zhou, Jie, 177Zia, Wasif, 40Zou, Yan (Poster), 88Zubyk, Halyna, 91

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BURLINGTON NOR THERN/SANT A FE RAILROAD

Y STREET

9th

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10th

St.

11th

St.

12th

St.

13th

St.

14th

St.

20th

St.

16th

St.

17th

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18th

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19th

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'Y' St.

'R' St.

'Q' St.

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21st

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22nd

St.

23rd

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'S' St.

'T' St.

'U' St.

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14th

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Holdrege St.

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14th

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21st

St.

22nd

St.

21st

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22nd

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19th

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20th

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Sheldon St.

Dudley St.

Orchard St.

'W' St

Bessie St.

Court St.

Military Road

Claremont St.

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10th

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12th

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STREET DIRECTION

City Campus

Current as of June 9, 2014

1

1

1

1

1

1

1

2

1

1

3

3

5

7

9

1

1 1

1

8

11

1 10

116

Guest & Visitor ParkingGeneral Visitor Parking1. Metered Parking2. - Cashiered Facility (SDPG) - Pay on Exit (Credit/Debit) (14th & Avery Garage)3. Morrill Hall Visitor

Guest Parking5. Admissions Office6. CB3 & Athletics Performance Lab

Campus Affilated Visitor Parking 7. Business Services Complex 8. Facilities Management & Planning 9. Continuing Education Visitors10. Children’s Center 11. University Health Center Patient

STAD

IUM

DRI

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FacilitiesManagementShops

900 N. 22nd Street

Avery

ArchitectureUniversityPress

Center

Boat House

NebraskaHall

DevaneySports Center

TrackOfficeBldg.

NebraskaChampions

Club

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HuskerHall

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OthmerHall

TempleBldg.

AlexanderBuilding

TransportationSvcs.

AndersenHall

Mary RiepmaRoss MediaArts CenterVan BruntVisitors Center

HewitAcademicCenter

OsborneAthletic

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SchorrCenter

ManterHallRichards

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WoodsArt Bldg.

Hall

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BehlenLab

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KimballRecital Hall

WestbrookMusicBldg.

BusinessServicesComplex

LandscapeServices

UniversityPolice

FacilitiesManagement& Planning

Henzlik Hall

Mabel Lee Hall

CookPavilion

Colis

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PershingMilitary& NavalScience

HarperHall

SchrammHall

SmithHall

UtilityPlant

Ed Weir Track

StadiumDrive

ParkingGarage

UniversityHousingOffice

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HewitPlace

TeachersCollege Hall

Cam

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Hamilton Hall

Bessey Hall

Oldfather Hall

BurnettHall

AndrewsHall

MorrillHall

College ofBusinessAdministration

LoveLibrary

SheldonMuseum

of Art

CanfieldAdministration

Bldg.

SelleckQuad

CreditUnion

CatherHall

PoundHall

Neihardt

AbelHall

SandozHall

ScottEngineering

UniversityHealth Ctr.

SeatonHall Benton

HallFairfieldHall

WhittierBuilding

Union

U St.Apts.

420Univ

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KauffmanAcademic

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17th & RParkingGarage

Mueller

Avery Avenue

COURT STREET

17TH

STR

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14th &Avery

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TheCourtyards

TheVillage

HawksChampionshipCenter

WickAlumniCenter

New Hampshire St.

Charleston St.

KnollResidential

Center

19th & VineGarage

GaughanMulticultural

Center

JorgensenHall

Children’sCenter

UniversitySuites

18th & RGarage

50/50Apartments

EastsideSuites

OutdoorAdventures

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