1 1 Soft condensed matter Materials which are easily deformable by external stresses, electric or magnetic fields, or even by thermal fluctuations; typically possess structures which are much larger than atomic or molecular scales; the structure and dynamics at the mesoscopic scales determine macroscopic physical properties. http://www.seas.harvard.edu/weitzlab/ Polymers Colloids Amphiphiles (surfactants, lipid) Liquid crystals Molecular crystals Biological matter Soft condensed matter (Soft amtter) 2 Examination 08:00-12:00 Friday 12/12 VA Problem class P26 13:00-15:00 Thursday 4/12 FZ Summary P30 10:00-12:00 Tuesday 2/12 FZ Application of electronic polymers P26 08:00-10:00 Monday 1/12 VA and FZ Lab2 IFM 13:00-15:00 Thursday 27/11 OI Electronic polymers P34 10:00-12:00 Tuesday 25/11 OI Electronic polymers P22 08:00-10:00 Monday 24/11 VA and FZ Lab1 IFM 13:00-15:00 Thursday 20/11 NS Biopolymers P30 10:00-12:00 Tuesday 18/11 NS Soft Matter P26 08:00-10:00 Monday 17/11 NS Soft Matter P30 13:00-15:00 Thursday 13/11 FZ Crystalline polymers P30 10:00-12:00 Tuesday 11/11 VA Problem class P18 08:00-10:00 Monday 10/11 FZ molten state P30 13:00-15:00 Thursday 6/11 FZ Glassy amorphous state P30 10:00-12:00 Tuesday 4/11 FZ Polymer solution P26 08:00-10:00 Monday 3/11 FZ The rubber elastic state P26 13:00-15:00 Thursday 30/10 FZ Chain conformation P30 10:00-12:00 Tuesday 28/10 FZ Terminology and statistics P18 8:00-10:00 Monday 27/10 3 Insulating polymers Conductive polymers and others mostly base on research articles. Bokakademin in Kårallen, Campus Valla. 4 Chapter 1 Introduction to polymer physics Polymers Biopolymers (natural polymers) Synthetic polymers Biopolymers are produced by living system, for instance, silk, wool, more? Synthetic polymers produced by the chemical industry, plastics, rubbers, fibers (big scale, 10 6 ton/year) synthesized by researchers in labs (small scale, mg) 5 Polymer semiconductors n Polyacetylene S n Polythiophene n Poly (para-phenylene-vinylene) n Polyfluorene Some conjugated (semi-conducting) polymers Characterized by typical -electrical -optical properties They are versatile. 6 Why polymers are so useful? • The properties of polymers are very diverse and can be modified to meet the special requirements of applications http://www.konarka.com/ http://www.polymervision.com/ http://www.planete-energies.com/content/features/plastics/applications.html http://www.thinfilm.se/index.php?option=com_content&task=blogcategory&id=0&Itemid=59
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Soft condensed matterMaterials which are easily deformable by external stresses, electric or magnetic fields, or even by thermal fluctuations; typically possess structures which are much larger than atomic or molecular scales; the structure and dynamics at the mesoscopic scales determine macroscopic physical properties . http://www.seas.harvard.edu/weitzlab/
poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) (Baytron PH500 )
Y-H. Zhou, F. Zhang, et al., App. Phys. Lett., 92, 233308 (2008).
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Optical properties and structures of polymers
400 600 800 1000 1200 14000 .0
0 .2
0 .4
0 .6
0 .8
1 .0
1 .2
1 .4
1 .6
AM
1.5
(Glo
bal t
ilt,
wm
-2nm
-1)
W ave leng th (nm )
S S
NS
N
n
δδδδ-δδδδ+
δδδδ+
S S
NSN
NN
O
O
O
O
n
SS
S
N N
n
OO
APFO3 (Alternating polyfluorenes) APFO-Green5
LBPP1(Low bandgappoly phenylene)
F. Zhang, et al, APL 84(19), (2004), 3906.F. Zhang, et al, Adv. Mater. 18, 2169 (2006).
E. Perzon, et al, Adv. Mater. 19, 3308(2007).10
The variety of polymer materials
Physical state:
• Liquid: polymer melts and solutions (very viscous)
• Crystalline: polymer can crystallize, but usuallycrystallisation is not complete, semi-crystalline.
• Liquid crystalline: Some polymers can line up to form liquid crystalline materials.
• Glasses: amorphous solid.polymer glasses are verycommon, polystyrene, poly(methyl methacrylate)
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• Physics: Explain phenomenon, behavior and find correlationamong variables and rules.
• Polymer physics:Describe the properties of polymers and explain the correlation between microstructure and macroproperties.
microstructure macro propertiesdetermine
How?To modify property
Applications need special properties Design molecular structures12
1.1 Fundamental definitionPolymer (Macromolecule):
A substance composed of molecules by the multiple repetition of one or morespecies of atoms or group of atoms (constitutional repeating units ) linked eachother in amounts sufficient to provide a set of properties that do not varymarkedly with the addition of one or a few of the constitutional repeating unts. (Swedish chemist Jöns Jacob Berzelius invented in 1832 )
Polyethylene
n=103~106
polypropylene
n
Poly (para-phenylenevinylene)
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Oligomer: A molecule with only a few constitutinal repeating units.
Physical properties vary with n, mp (93-95°C, 211-214°C, 290°C, 280°C )
Mono mer:is the substance that the polymer is made
from.
poly propylenepropylene
Polymerization
Repeating unit
Monomer PolymerPolymerization
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BondsPrimary bond (covalent bond)
Secondary bond
Bond stability Physical properties(Modulus)
RT ~2.5kJ/mol (300K), 4kJ/mol at 500K
Bond energy
Bonds in polymers
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Covalent bonds
Ethane (C2H6)
Ethylene (Ethene)(C2H4)Two elements share an electron pair, form bond
Link the atoms of the polymerchains , which are very strong with dissociation energy 300-500 kJ/mol
σ and π bond
Difference between σ and π bond ?
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Secondary bondsThe interaction between atoms of different molecules
(important for the properties of polymers)Van der Waals bond ~10kJ/molDipole-dipole bond >10kJ/molHydrogen bond 10 ~50kJ/mol
u=ql dipole moment
Induced dipole moment
Dispersion forces (London forces)
acts between all atoms and molecules
Hydrogen bond
Dipole-dipole bond
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1.2 Configuration (”Permanent” stereostructure of a polymer )
Polymerization method determines configurationIf a polymer has more than one type of chemical group attached to eachmain chain carbon atom, then different arrangments of the groups in threedimensions are possible.
Isotactic( similar side groupsappear on the same side of the chain)
Syndiotactic( on alternate sides )
Atactic (random arrangement of the groups).
C2H2XY
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Polymers with double bonds
Stereoforms of 1,4-polybutadiene showing only the constitutional repeating unit with the rigid central double bond
Double bond is rigid and allows no torsion , and the cis and trans forms are not transferable into each other.
The entire structure of a polymer is generated during polymerization
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1.3 Homopolymer and copolymerHomopolymer consists only one type of monomer (A):
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
Copolymer consists 2 or more monomers (A, B,…): (why do we needcopolymers? )Block copolymer, Graft copolymer, Alternating copolymer, Random copolymer
Organize monomer 22
1.4 Molecular Architecture (organize chains)
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Structure properties
Linear polymer, atoms more or less arranged in a long chain(backbond)(102-103), if small chain (few atoms) attached (pendant group)
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
B B B
Branched polymer if B getting longer, comparable to the length of the backbone chain.
Profound effects on rheologicalproperties, chain mobility
linear or branced polymer soften or melt when heated, so that they can be moulded and remoulded by heating (Thermoplastics) . 24
Crosslinked polymer
Star polymer
Used as additives in motor oilhttp://www.diva-portal.org/kth/theses/abstract.xsql?dbid=4808
Sometimes there is no backbond at all. A polymer is built in such a way that branches keep growing out of branchesand more branches grow out of thosebranches. (Dendrimers )
heavily crosslinked polymers are normally rigid, can not melt on heating and they decompose if T is high enough (Thermosets) .
lightly crosslinked polymers are reversiblystretchable to high extensions (Rubber or elastomers)
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1.5 Conformation:A conformational state refers to the stereostructure of a
molecule defined by its sequence of bonds and torsion angles .
Example of conformational states of C7H16. The right-hand form is generated from the left-hand form by 120°torsion about the σ bond indicated by the arrow.
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The polymer characteristics, such as microstructure, architecture, degree of polymerization (n), chemicalcomposition of heteropolymer (copolymer) are all fixedduring polymerization and can not be changed withoutbreaking covalent bonds.
However, a single flexible macromolecule can adopt manydifferent conformations . Conformation is the spatial structure of a polymer determined by the relative locations of its monomers.
Conformation depends on Flexibility of the chainInteraction between monomers on the chainInteraction with surroundings
AttractiveRepulsiveRelative strength ofT
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How the interaction influence the conformation ?Consider a chain with n=1010 bonds, l ≈ 10-10m, contour length L=nl=1010×1010 ≈ 1mMagnify all lengths by 108, that is l ≈ 1cm
1. strong attraction between monomers, the conformation of the polymer is a denseobject called collapsed globule, V ≈ nl3 ≈ 104m3, R=3√V≈20 m, a classroom
2. No interaction between monomers, Random walk, R ≈n1/2l ≈ 103 m, a campus3. With excluded volume repulsions, R ≈ n3/5 l ≈10 km, a city4. With long-range repulsions, R ≈ nl ≈ 105 km, the order of the distance to the
Moon.
The multitude of conformations available for polymers is veryimportant for their properties
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• Cofiguration? How to change• Conformation? How to change• Why flexibility increase with T• Why rubber rapid response to external
force
More on conformation in Next Chapter
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1.5 Commen polymers
Most polyethylene applications are in the areas of film, molding, cable and pipe
Properties: Flexible at low temperature, colorless, non-toxic transparent. High density PE(HDPE) is hard, tough and resilient. Most of HDPE is used in manusfacture of containers. Low density PE(LDPE) is soft and has a rather lowwater vapor permeability, but high oxyg°en and aroma p ermeability and is sensitive to fats and oils. Tm ~ 137 °C, Tg -130 to - 80 °C
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The textile application is one of the largest polypropylene markets in size, being above 1700 kT in 2004 in Western Europe. Dishwasher, safe food containers, indoor and ourdoor carpets (easy to make colored PP and doesn’t absorb water).
Properties: PP has a high degree of crystallinity(isotactic) or high amorphous(atactic). The Tm, mechanical properties and transparencyare related to the crystallization, is a good insulator. PP is resistant to attack by polar chemicals, such as, soap, alcohols and its water absorption is very low, it reserves double duty as a plastic and as a fiber. Tm ~ 180 °C, Tg ~ -17 °C.
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PVC is useful plastic because it resists to fire and water. It is used to make raincoats and shower curtains and water pipe . PVC is commonly used in the construction sector, for example in window frames and shutters , pipe cabling and coating , etc. High amorphous ~11% crystallinity, Tg ~84 °C
PS is a inexpensive and hard plastic insulator, used in toys, the housingsof things like hairdryers, computers and kitchen appliancesTm ~270 °C, Tg ~100 °C
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PMMA is a clear colorless polymer, used extensively for optical application. It is an amorphous thermoplastic, that is, hard and stiff. PMMA has a good stability against UV radiation, but it has poor chemical resistance.
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1.6 Statistical molar mass (the mass of one mole)
MonodisperseThe sample is monodisperse if all polymers in a given sample
have the same number of monomers.
M=nMmon
Where n is the number of monomers in a polymer molecule, is the degree of polymerization, Mmon molar mass of monomer,
M the molar mass of a polymer
The molar mass distribution ranges over three to four orders of magnitude for many polymers
PolydisperseThe sample is made up of individualmolecues that have a distribution of degree of polymerization (depends on synthetic method)
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Molar mass dependence of the equilibriummelting point of oligo- and polyethylene.
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Average molar mass
The most commonly used averages are defined as follows. The number -average is given by:
where Ni is the number of molecules of molar mass Mi, and ni is the number fraction of those molecules.
The weight -average is given by:
where Wi is the mass of the molecules of molar mass Mi, and wi is the mass fraction of those molecules.
ii
i
ii
iii
n Mn
N
MNM ∑
∑
∑==
∑∑
∑
∑
∑===
iii
iii
iii
ii
iii
w MwMN
MN
W
MWM
2
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The z-average is given by:
The viscosity-average is given by:
where a is the exponent in the Mark-Houwink equation. It takes values between 0.5 and 0.8 depending on the combination of polymer and solvent.
∑
∑==
iii
iii
z
MN
MNM
2
3
a
iii
i
aii
v
MN
MNM
1
1
=
∑
∑ +
7
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A polymer sample consists of a mixture of threemondisperse polymers with molar masses 250000, 300000 and 350000g/mol in the ratio of 1:2:1 by numberof chains, calculate Mn, Mw and Mw/Mn.
Solution:Let the total number of chains with molar mass
250000g/mol be N, thenMn=(N×250000+2N×300000+N×350000)/(N+2N+N)=300000g/mol
Mw=…………………=304200g/mol
Mw>MnMw/Mn=1.014 (polydispersity index)
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The correlation of Mn, Mw, Mz and Mν
Mn≤Mv ≤Mw ≤Mz
All these averages are equal only for a perfectly monodispersepolymer.
In all other cases, the averages are different:M n <M v <M w <M z . The viscosity average is often relatively closeto the weight average.
Standard deviation ( σ) and Polydispersity index
The breadth of the molar mass distribution, measuring how widelyspread the values i a data set. If the data points are close to the mean, then σ is small.
1−=n
w
n
n
M
M
M
σ
n
w
M
M
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Experimental techniques for molar mass determinatio n
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1.7 Thermal transitions and physical structures
The logarithm of the relaxation modulus (10 s) as a function of temperature for semicrystalline (isotactic) polystyrene and fully amorphous (atactic) polystyrene in three "versions": low molar mass uncrosslinked, and high molar mass uncrosslinked and crosslinked.