L D-Ai84 956 MOLECULAR-LEVEL SYNTHESIS AND CHARACTERIZATION OF / METAL-POLYMER INTERFACE .(U) MASSACHUSETTS UNIV AMHERST DEPT OF POLYMER SCIENCE AND ENGINE S L LING ET AL. UNCLASSIFIED 23 RUG 87 RRO-2896i 4-MS DAAG29-84-K-0852 F/G 7/6 N1 IENE. IIIIIIII
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L D-Ai84 956 MOLECULAR-LEVEL SYNTHESIS AND CHARACTERIZATION OF /METAL-POLYMER INTERFACE .(U) MASSACHUSETTS UNIV AMHERST
DEPT OF POLYMER SCIENCE AND ENGINE S L LING ET AL.UNCLASSIFIED 23 RUG 87 RRO-2896i 4-MS DAAG29-84-K-0852 F/G 7/6 N1
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Molecular-Level Synthesis and Characterizationof Metal-Polymer Interfaces
DTICFinal Report
SCEP 17W7
Shaw Ling Hsu and Thomas J. McCarthy
August 23, 1987
U.S. Army Research Office
DAAG 29-84-K-0052
Polymer Science and Engineering DepartmentUniversity of Massachusetts
Amherst, Massachusetts 01003
Approved for Public ReleaseDistribution Unlimited
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07 9 1 6 41
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The view, opinions and/or findings contained in this report are those of the Authorsand should not be construed as an official Department of the Army position, policyor decision, unless so designated by other documentation.
Accesion ForNTIS CRA&Ir1 IC TAB C]
U 'l- mnno uce i -
D- is' r~ /
/ "! A. 4aj'i,2 ,t Codes!
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UNCLASSIFIED MASTER COPY -FOR REPRODUCTION PURPOSESSECURITY. CLASSIFICATION OF THIS PAGE
IlncIq -_Qi f i p2a. SECURITY CLASSIFICATION AUTHORITY 3. DISTRIBUTION /AVAILABILITY OF REPORT
2b. DECLASSIFICATION /DOWNGRADING SCHEDULE Approved for public release;distribution unlimited.
4. PERFORMING ORGANIZATION REPORT NUMBER(S) S. MONITORING ORGANIZATION REPORT NUMBER(S)
ARP 20961.4-MS6a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION
University of Massachusettl (ff aplicable) U. S. Army Research Office
6c. ADDRESS (City. State, and ZIP Code) 7b. ADDRESS (City, State, and ZIP Code)
Amhert, MA01003P.O0. Box 12211
Amhert, MA01003Research Triangle Park, NC 27709-2211 IBa. NAME OF FUNDING /SPONSORING 8b. OFFICE SYMBOL 9. PROCUREMENT INSTRUMENT IDENTIFICATION NUMBER
ORGANIZATION I(if applicable)U. S. Army Research Office DAAG29-84-K-0052
9 c. ADDRESS (City, State, and ZIP Code) 10. SOURCE OF FUNDING NUMBERS
P. 0. Box 12211 PROGRAM PROJECT TASK IWORK UNIT
Research Triangle Park, NC 27709-2211 ELMN NO I OIOCCSINN
11 TITLE (Include Security Classification)
Molecular-Level Synthesis and Characterization of Metal-Polymer Interfaces
12 ERONL UTORS)Shaw Ling Hsu and Thomas J. McCarthyOI EPR 3b. TIME COVERFfl 14. 0 EPOR T (Year onrh, Day) 5.PAECON13a. TYPE F RNAL FROM J1.L 4/1L5/.871 1. 1 F ~U ut17AE
16 SUPPLEMENTARY NOTATIONThe view, opinions and/or findings contained in this report are thoso
ofIhe authiqr(s),and sh uld not be const I d sa fcialje artmerit of the Army Positic-..
17COSATI CODES 18. SUBJEC-T TERMS Continue on rev.ers.e iI'necessary and identify by block number)
FIELD GROUP SUB-GROUP metal, polymer, interface, surface, adsorption Ithin film, reflection-absorption spectroscopy
9 ARS CT (Continue on reverse if necessary and identifyj by block number)
Two separate, but interacting research groups began a program entailing molecularlevel syntheses and characterization of metal-polymer interfaces. Two general
$ synthetic routes were followed: In one case, a metal surface (platinum) was cleanedof its oxide layer by carrying out a hydrogenation reaction (hexene or cyclohexene)using the metal surface as the catalyst. Under these conditions, platinum oxide isIunstable and is reduced to platinum(O) and water. The reaction was thendeliberately poisoned with 4-picoline. Monitoring the kinetics of hydrogenationbefore and after the addition of the poison allowed us to determine thatv-70% of thehydrogenation sites were ligated. The amount of 4-picoline that adsorbed wasdetermined by elemental analysis, gravimetric analysis and UV-vis analysis of the ~
20 DISTRIBUTION /AVAILABILITY OF ABSTRACT 21. ABSTRACT SECURITY CLASSIFICATIONOUNCLASSIFIED/UNLIMITED 0 SAME AS RPT. 0QOTIC USERS Unclassified
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00 FORM 1473,e4 MAR 83 APR edition may be used until exhausted SECURITY CLASSIFICATION OF THIS PAGEAll other editions are obsolete. UNCLASSIFIED
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solution. The surface-confined picoline was then deprotonated to render the ligated--"1 lithium reagent which was used to initiate the polymerization of styrene. The thin
6"if i film of polystyrene prepared in this manner was irreversibly attached to theplatinum surface. The platinum-polystyrene interface was studied by a range ofanalytical techniques. In the other case, a metal-polymer interface was prepared bypolymer adsorption: Polystyrene containing one terminal thiol group and styrene-propylene sulfide block copolymers were allowed to adsorb on evaporated goldfilms supported on glass. The resulting supported films were characterized by X-ray photoelectron spectroscopy, external reflectance infrared spectroscopy andscintillation counting of radioisotope-labelled polymers. The polymers adsorbrapidly and irreversibly and the polymer monolayers can be washed with freshsolvent without desorption. e effects of molecular weight, concentration andsolvent power on adsorban were determined for thiol-terminated polystyrene.The effect of propylene sulfid block size on the number of adsorbed chains for aseries of styrene-propylene sul e block copolymers was determined. Thetechnique of doubly modulated larization Fourier transform reflectance infraredspectroscopy has developed as perlaps the most useful characterization method forthin films on metallic surfaces. The retical calculations were carried out todetermine the theoretical limits of thi technique and the technique has beenperfected using thin films of discotic Ii uid crystals on gold surfaces. Well-resolved infrared spectra of thiol-termi .ted polystyrene monolayers on gold wereobtained over the spectral range of 4000- 00 cm-1.
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SECUAITV CLASSIFICATION OF THIS PAGE
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Molecular-Level Synthesis and Characterizationof Metal-Polymer Interfaces
Introduction
Surface interactions between metals and polymers are central to a
range of applications: corrosion inhibition, adhesive joint strength,