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Polymers: Random walk model 13

Polymers:

Random walk model

Polymers

• So far, we mostly talked about glasses as a group of

nocrystalline materials

• Polymers are another important class of materials that are

often found in noncrystalline form

• Polymers are long molecules composed of repeating units known as monomers.

Poly

found in noncrystalline form • Polymers are long molecules composed of repeating units known as monomers.
found in noncrystalline form • Polymers are long molecules composed of repeating units known as monomers.

mer

found in noncrystalline form • Polymers are long molecules composed of repeating units known as monomers.
found in noncrystalline form • Polymers are long molecules composed of repeating units known as monomers.

Ancient polymers

• Originally natural polymers were used

– Wood

Cotton

Leather

– Rubber – Wool – Silk

• Oldest known uses (real or fictional)

– Rubber balls used by Incas

– Noah used pitch (a natural polymer) for the ark

• Synthetic polymers: second half of 20 th century

• Bioplymers: proteins, DNA, RNA

Polymers

• Most of polymers are organic in origin

high M Magnitude?
high M
Magnitude?

• Many are covalenetly bonded hydrocarbons (composed of C and H), and

sometimes oxygen, nitrogen, sulfur, silicon, chlorine, and/or fluorine

Examples
Examples
sulfur, silicon, chlorine, and/or fluorine Examples • Because of their large molecular weight ( M ),
sulfur, silicon, chlorine, and/or fluorine Examples • Because of their large molecular weight ( M ),
sulfur, silicon, chlorine, and/or fluorine Examples • Because of their large molecular weight ( M ),

• Because of their large molecular weight (M), also referred to as macromolecules

Low M

fluorine Examples • Because of their large molecular weight ( M ), also referred to as

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Random walk models

How do we describe the structure of an amorphous polymer?

We need a statistical average over the various conformations, able to provide us with as many information as possible è random walk model.

as many information as possible è random walk model . • • each step is uncorrelated

each step is uncorrelated with, or independent of, previous steps—steps forward and backward, left and right, up and down are all equally probable.

A random walk denotes a path of successive steps in which the direction of

It is a rather general model applicable to other problems in MS&E: gas diffusion or vacancy diffusion (you might know it under the term of Brownian motion)

(you might know it under the term of Brownian motion) • Variable angle random walk L

Variable angle random walk

under the term of Brownian motion) • Variable angle random walk L a t t i
under the term of Brownian motion) • Variable angle random walk L a t t i

Lattice random walk

under the term of Brownian motion) • Variable angle random walk L a t t i
under the term of Brownian motion) • Variable angle random walk L a t t i
under the term of Brownian motion) • Variable angle random walk L a t t i
under the term of Brownian motion) • Variable angle random walk L a t t i

Chain end-to-end distance

Let’s define r, R, and l R
Let’s define r, R, and l
R
Chain end-to-end distance Let’s define r, R, and l R Polymer schematic from The Physics of

Polymer schematic from The Physics of Rubber Elasticity by Treloar (2005) Fig. 3.3 p.45. By permission of Oxford University Press

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Chain end-to-end distance

Chain end-to-end distance • Because of the equal probability of steps in each direction, the average

• Because of the equal probability of steps in each direction, the average end- to-end vector of a random walk of N steps, taken over many possible conformations (time average), is zero

over many possible conformations (time average), is zero • The root-mean-square (rms) end-to-end distance, however,
over many possible conformations (time average), is zero • The root-mean-square (rms) end-to-end distance, however,

• The root-mean-square (rms) end-to-end distance, however, is finite, and characterizes the average spatial dimension traversed.

and characterizes the average spatial dimension traversed.
and characterizes the average spatial dimension traversed.

http://upload.wikimedia.org/wikipedia/commons/c/cb/Random_walk_25000.svg

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Chain end-to-end distance

Chain end-to-end distance Some math … 20

Some math

Structure-property relationship of polymers

Consequence of this analysis: polymer chain has a characteristic size that scales with n 1/2 . The average volume occupied by the coil is therefore much greater than the volume of the chain itself. In the melt or glassy state, many other chains will be found intermingled with a single chain •This is very different than in the case of small molecule systems, and leads to the unique rheological and mechanical properties polymers exhibit, like high viscosity and elasticity of polymers

polymers exhibit, like high viscosity and elasticity of polymers Volume of the chain and of the
polymers exhibit, like high viscosity and elasticity of polymers Volume of the chain and of the

Volume of the chain and of the occupied volume

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Self-avoiding random walk model

Self-avoiding random walk model • We made certain assumptions so far - which ones? In solutions,
Self-avoiding random walk model • We made certain assumptions so far - which ones? In solutions,
Self-avoiding random walk model • We made certain assumptions so far - which ones? In solutions,

• We made certain assumptions so far - which ones?

In solutions, polymers take on coil-like conformations, but are swelled due to monomer-solvent interactions

individual steps cannot cross each other

The swelling can be explained by the random walk model:

The swelling can be explained by the random walk model: ∝ N 3 / 5 R
∝ N 3 / 5
∝ N 3 / 5
can be explained by the random walk model: ∝ N 3 / 5 R 2 1

R 2

1 / 2

by the random walk model: ∝ N 3 / 5 R 2 1 / 2 SARWM

SARWM

by the random walk model: ∝ N 3 / 5 R 2 1 / 2 SARWM
by the random walk model: ∝ N 3 / 5 R 2 1 / 2 SARWM
22
22
2 R
2
R

1 / 2

RWM

N 1 / 2

Image from The Structure of Materials, Allen and Thomas,copyright 1999 John Wiley and Sons, Inc Reproduced with permission of John Wiley and Sons, Inc.

Polymer chain conformation

Collapsed coil n = 1/3

Polymer chain conformation Collapsed coil n = 1/3 R ∝ N 0 ν Random-walk coil n

R N

0

ν

Random-walk coil n = 1/2

Self-avoiding walk coil n = 3/5

conformation Collapsed coil n = 1/3 R ∝ N 0 ν Random-walk coil n = 1/2

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Assessment questions and keywords

1. How would you change the glass transition temperature of a non- crystalline material?

Keywords:

and keywords 1. How would you change the glass transition temperature of a non- crystalline material?
and keywords 1. How would you change the glass transition temperature of a non- crystalline material?
and keywords 1. How would you change the glass transition temperature of a non- crystalline material?
and keywords 1. How would you change the glass transition temperature of a non- crystalline material?

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Polymeric glasses and crystals

• Polymer glasses are rather common because of a large number of

possible polymer conformations

• However, crystallization of polymers is possible: ordered atomic arrangements involving molecular chains

From what we know so far, what is a guaranteed way to ensure noncrystallinity of a polymer?

Polyethylene unit cell

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Polymer tacticity

• For polymers having more than one side atom/group, the regularity and symmetry of the side group arrangement can significantly influence the properties

• Tacticity stereoregularity or spatial arrangement of R units along chain

isotactic – all R groups on side of chain

same

H

H

H

H

H

H

H

H

C

C C

C

C

C C

C

H

R

H

R

H

R H

R

same H H H H H H H H C C C C C C C

Polymer tacticity

syndiotactic R groups

alternate sides

atactic R groups randomly positioned

H

H

H

R

H

H

H

R

H

H

H

H

H

R H

H

C

C C

C

C

C C

C

C

C C

C

C

C C

C

H

R H

H

H

R H

H

H

R

H

R

H

H

H

R

C C C C C C C C C C C H R H H H
C C C C C C C C C C C H R H H H

Polymer tacticity

Polymer tacticity One example (apparently a simple one) is polystyrene: 9 Styrene: C 8 H 8
Polymer tacticity One example (apparently a simple one) is polystyrene: 9 Styrene: C 8 H 8

One example (apparently a simple one) is polystyrene:

Polymer tacticity One example (apparently a simple one) is polystyrene: 9 Styrene: C 8 H 8
Polymer tacticity One example (apparently a simple one) is polystyrene: 9 Styrene: C 8 H 8
Polymer tacticity One example (apparently a simple one) is polystyrene: 9 Styrene: C 8 H 8

9

Styrene: C 8 H 8

Thermoplastics and thermosets

What happens with properties of polymers with increased temperature?

1. Thermoplastics:

soften when heated (and eventually liquefy) and harden when cooled

process is reversible and may be repeated (materials can be recycled)

bonds between individual molecules is relatively week in thermoplastics (e.g. van der Waals bonding)

above glass temperature, polymer molecules can slide and c

examples: polyethylene, polystyrene, poly(vinil chloride)

Thermoplastics and thermosets

What happens with properties of polymers with increased temperature?

2. Thermosets (thermosetting polymers)

permanently hard (permanent curing), do not soften upon heating

network polymers that are covalently linked

at high temperature become damaged and degraded

examples: vulcanized rubbers, epoxies, polyamides

  at high temperature become damaged and degraded •   examples: vulcanized rubbers, epoxies, polyamides …

Fractals

can be described as "a rough or fragmented

geometric shape that can be split into parts,

each of which is (at least approximately) a reduced-size copy of the whole

self similarity

mass of a fractal does not scale with the dimension of the space

of a fractal does not scale with the dimension of the space M ∝ R D

M R D

M: mass R: characteristic length D: scaling exponent, that is different than the space dimension (e.g. a fractal in 3 dimensional space will have D 3

Examples of fractals

• Diffusion limited aggregation

• Electrodeposition

• Metal crystallization – dentritic growth

Non-crystalline materials: summary

Non-crystalline materials: summary 14
Non-crystalline materials: summary 14

Structure of materials - roadmap

Noncrystalline state •   liquids •   glasses Crystalline state and symmetry •   lattices
Noncrystalline state
•   liquids
•   glasses
Crystalline state and symmetry
•   lattices
•   space groups
•   diffraction
•   quasicrystals
Liquid-crystalline state
•   nematic
•   smectic
•   Processing and assembly
•   Properties
•   Applications
Microstructure imperfections
•   equilibrium defect
•   line defects
•   stacking faults
•   grain boundaries