Lecture 2


Polymer Physics I
 Class Announcements
• Lecture 2 optional reading:
– Coursework lecture notes
– Young & Lovell 10.3-10.3.3
– Painter & Coleman 7A-7D
– Grosberg chapter 5
– Jones 5.1-5.3
– Hamley 1.7, 2.3.1-2.3.2, 2.5.1-2.5.4
– Cowie 10.1-10.4
 Lecture 1 Review
chemical structure

density, packing of chains intermolecular bonding

Material Properties:
phase transitions degradation mechanics thermal properties

Applications:
absorbable bullet-proof circuit board
bone screws vests glue

Polymer scaling models: How much volume does a single

polymer chain take up? How does a single chain look?
 Scaling Laws
• “Soft matter is characterized by complexity, both in
structure and dynamics.” – Ian Hamley

• x~yz …..“x scales with y to the power z”

 Measurements of Chain Size
• Contour length
– Does not take thermal fluctuations into account
– Contour length = nl
contour length

bond length, l
 Measurements of Chain Size
• Contour length
– Does not take thermal fluctuations into account
– Contour length = nl
contour length

bond length, l

• Root-mean-square statistical average end-to-end

distance, 〈r2〉01/2
– As thermal fluctuations begin, the chain “wriggles”
– 〈 〉 denotes the thermal average
– Distance from one chain end to another

• Thought experiment: As thermal fluctuations increase,

what happens to 〈r2〉01/2?
 Measurements of Chain Size
• Root-mean-square radius of gyration, 〈Rg2〉01/2
– Average distance of a chain segment from the
center of mass of the coil
– Can be defined for branched polymers
(i.e., polymers with many ends)
– Can be defined for cyclic polymers
(i.e., polymers with no ends)
– Expression is often simplified to just Rg
– For ideal, linear chains: 〈r2〉01/2 = 61/2 〈Rg2〉01/2
– Y&L uses symbol 〈s2〉1/2
 Freely Jointed Chain Model
• Individual monomers are represented by
points connected by bonds
• Each bond can freely rotate in space
• Points and bonds do not take up any volume
• Similar to:
– Freely diffusing gas
– Brownian motion
– Random flight statistics
– “Drunkard’s walk”
〈r2〉01/2
 Freely Jointed Chain Model
• End-to-end distance between two segments in two-dimensions
OB2 = OA2 + AB2 - 2(OA)(AB)cosθ = r2
r2 = l2 + l2 - 2l2cosθ
r2 = 2l2 - 2l2cosθ
A

l θ l

〈r2〉01/2
O r B

• Add up these vectors for the entire chain of n segments

• Because θ will vary over all possible values, the sum of all these
terms will be zero (both in 2D and 3D)

〈r2〉0 = nl2, 〈r2〉01/2 = n1/2l

Cowie 10.2
 Freely Jointed Chain Model
• More accurate derivation uses summation

l ui+1 l ui
θ

〈r2〉01/2

n
r= Σ
i=1
lu i

n n n n
〈r•r〉 = l2 Σ Σ
i=1 j=1
〈u •u 〉 = 〈r 〉 = l Σ Σ δ = l
i j
2 2
i=1 j=1
ij
2 n

For i=j, δij = 1. For i≠j, δij = 0.

 Gaussian Chain
• Statistical analysis of a freely jointed chain
• Guassian chain is a random walk
β3 3 3/2 - 3r 2
P(r) = exp (-β2r2) = exp
π3/2 2π〈r 〉0
2 2〈r2〉0

where β = [3/(2 nl2)]1/2 = [3/(2 〈r2〉0)]1/2

• Probability distribution function for the location of the
chain end
〈r2〉0 = n l2
〈r2〉01/2 = n1/2l
 Coiled Nature of Polymers

• Freely jointed chain:

n = 10,000 segments and l = 0.3 nm
contour length = nl = 3,000 nm
r.m.s. end-to-end distance = 〈r2〉01/2

〈r2〉01/2 = n1/2l = (100)(0.3 nm) = 30 nm

• This is true at large length scales,

but at smaller length scales, the
chain can be restricted

• Why?
 Valence Angle Model
• Short range interactions between neighboring atoms
can restrict motion
• Example: steric repulsion
Φ

• Modified model: 〈r2〉0 = nl2 1 - cosθ

1 + cosθ
• C—C bond is restricted to θ = 109.5º, cosθ ~ -1/3
• 〈r2〉0 = nl2 (4/3)/(2/3) = 2nl2 so… 〈r2〉01/2 = 1.41n1/2l
• What about Φ?
 Stiff Chain Model
• Many polymer backbones, such as C—C bonds, can freely rotate
• Certain isomers are energetically favored (Newman projections).

Degrees of Rotation, Φ
 Stiff Chain Model
• Rotation about a single bond can dramatically affect the overall
polymer conformation

• 〈r2〉0 = nl2 1 - cosθ 1 + 〈cosΦ〉

1 + cosθ 1 - 〈cosΦ〉

• Can simplified into: 〈r2〉0 = σ2nl2 1 - cosθ

1 + cosθ
where σ = steric factor

• Experimental values of 〈r2〉0 are often reported as steric factors

Relating Theoretical and Experimental Values
• Steric factor, 〈r2〉0 = σ2nl2 1 - cosθ
1 + cosθ
• Characteristic ratio, C∞ = 〈r2〉0,exp
nl2
When C∞ = 1, the polymer follows the freely-jointed chain model

Polymer T (K) σ C∞
polypropylene - isotactic 408 1.53 4.67
polypropylene - atactic 408 1.65 5.44
natural rubber 293 1.67 4.70
polystyrene 308 2.23 10.00
poly(methy methacrylate) - isotactic 298 2.28 10.40
poly(methy methacrylate) - atactic 298 2.01 8.10
poly(methy methacrylate) - syndiotactic 308 1.94 7.50
Table 10.1, J. M. G. Cowie, Polymers: Chemistry & Physics of
Modern Materials, 2nd ed., p. 218.
 Chain Rigidity and Tacticity
• PMMA, poly(methyl methacrylate)
– Plexiglass
– Large, bulky side chains
– Steric hindrance affects bending
• Isotactic - All neighboring monomers overlap, C∞ = 10.40
• Atactic - Some neighboring monomers overlap, C∞ = 8.10
• Syndiotactic - No neighboring monomers overlap, C∞ = 7.50

AquaDom, Berlin
 Chain Rigidity and Tacticity
• PP, polypropylene
– Sides chains are much smaller than PMMA
– Isotactic PP can have an interesting conformation: helical coils
• Atactic PP, C∞ = 5.44
• Isotactic PP, C∞ = 4.67

PP PMMA
Syndiotactic

Isotactic
 Types of Polymer Models
• Discrete models
– Discrete step size
– Accounts for interactions between individual monomers

• Continuous models or “equivalent” models

– Continuously flexible chain, no set joints
– Step size must be chosen: Kuhn length

• Kuhn monomers
– Larger than “chemical” monomers
– Kuhn length is experimentally determined

• Important similarity
– At large length scales, all models converge
〈r2〉0 = nl2, 〈r2〉01/2 = n1/2l
 Worm-Like Chain
• Special case of the freely rotating chain model where Θ
is very small
• A good model for very rigid and semi-flexible polymers
• Step size is chosen by the persistence length
• Persistence length is the tendency to progress in one
direction
• Kuhn length ~ 2(lp), where lp is the persistence length
• Persistence length = bending rigidity/thermal energy
• Persistence length can change with:
– Solvent effects
– Steric hindrance
– Intermolecular bonding
 Worm-Like Chain
• Example: DNA, persistence length = 53 nm
– 0.34 nm base pair (i.e., chemical monomer)
– 10.5 bases/turn
– 3.57 nm per turn

• At small length scales:

– The chain seems rigid

• At large length scales:

– The 〈r2〉01/2 = n1/2l scaling reappears
– Kuhn length = 2(lp)
 Excluded Volume
• In all models discussed so far, the chain can freely cross itself
• Each link is only a vector with no volume
• These conditions are only met by specific solvent conditions
• These solvent conditions are defined as "theta" solvents
• The 0 in 〈r2〉01/2 denotes unperturbed “theta” conditions
– 〈r2〉01/2 ~ n1/2

• http://www.ph.biu.ac.il/~rapaport/anim_gif/polyfold_2_anim.gif
 Polymer-Solvent Interactions
• Polymer dimension is a balance between:
– Chain-chain interactions (generally repulsive)
– Chain-solvent interactions
• “Poor” solvents - polymer chains collapse
• “Good” solvents - polymer chains expand
– Excluded volume: space taken up by the chain
– Can be modeled by a self-avoiding random walk
– 〈r2〉1/2 ~ n3/5l
 Expansion Factors
• The expansion factor relates the perturbed and
unperturbed dimensions:

〈r2〉1/2 = α 〈r2〉01/2, α = expansion factor

• For poor solvents, α < 1
• For theta solvents, α = 1
• For good solvents, α > 1

• Solvent "quality" can change with temperature, pH,

ionic strength, etc.
• Example: hydrogel swelling
 Putting Polymer Expansion to Work
Self-folding all-polymer thermoresponsive microcapsules
Georgi Stoychev, Nikolay Puretskiy and Leonid Ionov
Soft Matter, 2011, 7, 3277-3279

Orange = PCL, poly(caprolactone), crosslinked hydrogel

Lavender = PNIPAM, poly(N-isopropylacrylamide), crosslinked hydrogel

PNIPAM is temperature sensitive: chains expand upon cooling

http://www.rsc.org/suppdata/sm/c1/c1sm05109a/movie%20s1.avi
 Take Home Message
• Polymer chains can alter their size by orders of magnitude

• At small length scales:

– The bond angles, preferred bond rotations, tacticity, structure,
bending rigidity, persistence length, etc. can alter the size

• At large length scales, all models converge:

– Polymers in ideal conditions (theta-solvent) follow a random walk
r ~ ln1/2
– Polymers in good solvents follow a self-avoiding random walk
r ~ ln3/5
 Concentration Regimes
• Dilute - excluded volumes do not overlap (all models discussed
so far are for dilute solutions)
– For theta solvents, 〈r2〉01/2 ~ n1/2
– For good solvents, 〈r2〉1/2 ~ n3/5
– Good solvent gone bad (coil-to-globule transition), 〈r2〉1/2 ~ n1/3
– Flexible chains undergo a gradual collapse
– Rigid chains undergo a quick collapse

• Semi-dilute solutions
– Excluded volumes just begin to overlap
– Because of the large excluded volume of a single chain, the weight
fraction required to reach semi-dilute conditions can be very small
 Concentration Impacts Viscosity
• Polymer solutions become more viscous as the concentration increases
• Increased friction and entanglements between chains
• Commonly used to test for polymer degradation

MW (Daltons)

IV (dL/g)
• Intrinsic viscosity = [𝜼] = lim (ηsp/c) as c➝0
• [𝜼] ~ excluded volume in solution [dL/g]
85:15 lactide-co-glycolide polymer
http://www.polymersolutions.com/dsv.html
 Concentrated Solutions
• Concentrated solutions
– Polymer melt (i.e., no solvent) or almost no solvent
– Chains only interact with other chains

– What type of scaling will 〈r2〉01/2 follow?

 Concentrated Solutions
• Concentrated solutions
– Polymer melt (i.e., no solvent) or almost no solvent
– Chains only interact with other chains
– Chain cannot tell if it’s interacting with itself or another chain
– Chains cannot avoid itself and instead follows a random walk
– Similar to theta solvents, 〈r2〉01/2 ~ n1/2
 Coil to Globule Transition
• Occurs when a good solvent goes bad
• Coil = extended chain
• Globule = collapsed chain
• Scaling is determined by chain rigidity
– Flexible chains undergo a gradual collapse
– Rigid chains undergo a quick collapse, 〈r2〉1/2 ~ n1/3
 Lecture 1 Review
chemical structure

density, packing of chains intermolecular bonding

Material Properties:
phase transitions degradation mechanics thermal properties

Applications:
absorbable bullet-proof circuit board
bone screws vests glue

Polymer scaling models: What happens if we stick one side of the

chain to a surface? What about adding charge to the chains?