Physics of materials

Polymers
Gabriela Borcia

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023

 Physics of materials − Polymers

I. Generalities
II. Molecular interactions
III. Physical states and state transitions in polymers
IV. Physical properties of polymers

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023

 III.1. States of aggregation
“In physics, the state of aggregation of matter is understood to be
one of the characteristic forms in which matter can occur.
Historically, the distinction between states of matter was made on the
basis of qualitative properties, such as the solidity of the object, the
behavior of its atoms or its temperature, the traditional classification
being that of liquid, solid and gas.

However, thanks to research in physics, other states have been

discovered and raised that can occur in situations that, normally, are
not possible to replicate, such as extremely high or low temperatures.”

https://virtualpsychcentre.com/
the-9-states-of-aggregation-of-matter/

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 1

 III.1. States of aggregation
depending on pressure−temperature conditions

• gas
3 × fundamental • liquid
states of aggregation
• solid
(4 × ?)
• (plasma)

• intensity of thermal agitation rate of application

• of the force
•
packing density
capacity to retain shape and volume
?
• capacity to resist to external forces liquid ? solid

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 2

 III.1. States of aggregation
rate of application
of the force
liquid ? solid

“A pitch drop experiment is a long-term experiment which measures

the flow of a piece of pitch over many years. 'Pitch' is the name for
any of a number of highly viscous liquids which appear solid, most
commonly bitumen. At room temperature, tar pitch flows at a very
low rate, taking several years to form a single drop.”

https://en.wikipedia.org/wiki
/Pitch_drop_experiment
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 3
 III.1. States of aggregation
rate of application
of the force
liquid ? solid

“The best-known version of the experiment was started in 1927 by

Professor Thomas Parnell of the University of Queensland in Brisbane, Australia.
The eighth drop fell on 28 November 2000, allowing experimenters to calculate
the pitch as having a viscosity of approximately 230 billion times that of water.”

https://en.wikipedia.org/wiki
/Pitch_drop_experiment
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 4
 III.1. States of aggregation
depending on pressure−temperature conditions

• gas
3 × fundamental • liquid
states of aggregation
• solid

• intensity of thermal agitation

• packing density • thermal agitation
• capacity to retain shape and volume
? • structure
• capacity to resist to external forces

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 5

 III.1. States of aggregation

♦ no individual properties
• gas
♦ general gas laws

• liquid ♦ individual properties

• solid ♦ interaction energy of molecules > kinetic energy

• solid
macromolecules • liquid
• gas
T vaporization
>
T degradation (decomposition)
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 6
 III.2. Phase states

structure thermodynamics

structure → types and degrees of order in 3D space

• crystalline
• amorphous
• gas

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 7

 III.2. Phase states
structure → types and degrees of order in 3D space

• crystalline
− fundamental 3D structure consisting of highly regular pattern
of atoms or molecules − crystal lattice
− atoms or molecules in a crystal form a periodic or
repeating pattern in all three dimensions
− the internal structure of a crystal is highly organized
− 3D order on domains ~102-103 dimensions of atomic systems
− “long-range three dimensional order”

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 8

 III.2. Phase states
structure → types and degrees of order in 3D space

• amorphous
− no crystal lattice
− yet, order !
− order on domains ~ dimensions of atomic systems
− “short−range order”

• gas
− no order !
− gas phase ≡ gas state of aggregation

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 9

 III.2. Phase states
structure → types and degrees of order in 3D space

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 10

 III.2. Phase states
structure → types and degrees of order in 3D space

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 11

 III.2. Phase states
T
liquid amorphous
Tm − melting
Tm Tc Tc − crystallization
solid crystalline

liquid crystals − one-dimensional long-range order

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 12
 III.2. Phase states
structure thermodynamics

thermodynamics → phase =

“A simple description is that a phase is a region of material that is

chemically uniform, physically distinct, and (often) mechanically
separable. In a system consisting of ice and water in a glass jar, the
ice cubes are one phase, the water is a second phase, and the humid
air is a third phase over the ice and water. The glass of the jar is
another separate phase.”

https://en.wikipedia.org/
wiki/Phase_(matter)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 13

 III.2. Phase states

thermodynamics → phase =
region of space (thermodynamic system), uniform from point
of view of chemical composition and physical properties,
having a surface that separates it from the rest of the system
→ volume large enough
→ thermodynamic parameters / physical properties
(T, p, concentration, free energy, density, refraction index,
magnetization, etc.)

thermodynamic equilibrium !
∆ (thermodynamic parameters) phase transition

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 14

 III.2. Phase states
∆ (thermodynamic parameters) phase transition
• 1st order
transitions
• 2nd order
1st order → involve a latent heat
→ T constant during transition
→ discontinuous variation of thermodynamic parameters
→ system in “mixed-phase regime”
→ boiling (of water), melting (of ice) …

2nd order → “continuous phase transitions”

→ no heat exchange
→ discontinuous variation of the 1st derivative vs. T
→ ferromagnetic transition, superconducting transition,
Bose condensation (Bose−Einstein condensate −
superfluid Helium − “0 viscosity”) …
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 15
 III.2. Phase states
1st order → latent heat, T constant, discontinuous ∆ (parameters)

2nd order → no heat exchange, discontinuous ∆ (1st derivative) vs. T

V crystalline V amorphous
1st order 2nd order

melt
rubbery

crystalline glass
solid

Tm T Tg T

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 16

 III.2. Phase states
thermodynamic equilibrium ?!
polymers ↔ non-equilibrium, long durations

shellac (rom. „șerlac”)

(female lac bug resin) copal (rom. „copal”)
(tree resin)

amber (rom. „chihlimbar”)

(fossilized tree resin)

• natural resins
kinetic analysis
• most synthetic polymers ← ↓ T
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 17
 III.2. Phase states
H (enthalpy − heat)
H vs. T and cooling rate
1
solid
liquid
2
1−2−3−4 slow cooling
5
6 1−2−5−6 fast cooling
Ha 3
Hc
4

Tg
Troom Tg Tc T
glass transition !
(rom. „tranziția sticloasă”)
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 III.3. Physical states of amorphous polymers

chains flexibility specific states

• 1 × crystalline (semicrystalline)
(partially crystalline) !
4×
physical • viscous (viscous flow, viscoelastic)
states
• 3 × amorphous • rubbery (highly elastic)
• glassy (amorphous glassy)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 19

 III.3. Physical states of amorphous polymers
• viscous (viscous flow, viscoelastic)
3 × amorphous • rubbery (highly elastic)
• glassy (amorphous glassy)

• viscous (viscous flow, viscoelastic)

− intense thermal motion at all levels
→ structure unit
→ larger chain segments
→ the entire macromolecule
− similar to most liquids
− the substance flows when applying external stress
− very high viscosity ! (elasticity ?, plasticity ?)
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 20
 III.3. Physical states of amorphous polymers
• viscous (viscous flow, viscoelastic)
3 × amorphous • rubbery (highly elastic)
• glassy (amorphous glassy)

• glassy (amorphous glassy)

− no motions, except weak torsion oscillations of
small atom groups
− the molecules of the polymer are “frozen”
− the material is stiff and brittle
− ≡ in polymers and “small molecule” substances !

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 21

 III.3. Physical states of amorphous polymers
• viscous (viscous flow, viscoelastic)
3 × amorphous • rubbery (highly elastic)
• glassy (amorphous glassy)

• rubbery (highly elastic)

− only polymers !
− molecules large enough ⇒ segmental motion
→ structure unit
→ larger chain segments
→ the entire macromolecule
− very large reversible deformations
− long chains are packed in coils → mechanical stress → stretching
thermal motion → reversal to coiled structure
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 22
 III.3. Physical states of amorphous polymers
T
viscous

Tf
liquid amorphous rubbery

Tm Tc Tg
solid crystalline glassy

Tm − melting Tg − glass
Tc − crystallization Tf − flow

glass transition ! Tg
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 23
 III.3. Physical states of amorphous polymers
T
viscous ∆T ∆ (physical state)
Tf
physical states
rubbery
vs.
Tg temperature + molecular weight

glassy +
chemical structure
chain structure

T−M phase diagram

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 24

 III.3. Physical states of amorphous polymers

T T−M phase diagram

Gas
Boiling Visco
point elastic
Viscous zone
Rubbery
liquid

Tg

Glassy
Melting
point

M1 M2 M
amorphous polymer !

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 25

 III.3. Physical states of amorphous polymers

T Gas T−M phase diagram

Visco
elastic
Viscous zone Rubbery
liquid
Tm
Leathery
to rigid
Tg

Rigid

M amorphous−crystalline
polymer !
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 26
 III.3. Physical states of amorphous polymers
T−M phase diagram

amorphous amorphous−crystalline

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 III.3. Physical states of amorphous polymers

Tg technological importance !
• applications
Tf • processing

elastomer
rubbery
(deformable)
Tg T f > Td ?
glassy
plastomer
(rigid) flow → processing

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 28

 III.3. Physical states of amorphous polymers

Tg particular technological interest !

• mechanical properties
• electrical properties
• thermal properties
• permeability
• radiation absorption
…

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 29

 III.4. Study of physical states of polymers

(physical properties) vs. T !

mechanical
(mechanical properties) vs. T
spectroscopy

technique of material characterization in which the material deformation and

the flow behavior are analyzed by means of dynamic mechanical methods

deformation (strain) vs. T

(constant weak force)

thermomechanical curves

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 30

 III.4. Study of physical states of polymers
low-molecular-weight polymer

strain
strain

glassy fluid glassy rubbery viscous

Tg Tf T Tbr Tg Tf Td T

(Tbr − brittle temperature − brittle failure)

Typical thermomechanical curves:

• low-molecular-weight substance
• amorphous polymer, linear flexible chains

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 31

 III.4. Study of physical states of polymers
Relative strain (%)

glassy viscous
rubber-like thermal
state liquid,
elasticity destruction
melt

Tbr Tg Tf Td T

Typical thermomechanical curve:

• amorphous polymer, linear flexible chains

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 32

 III.4. Study of physical states of polymers

DPl DP
γ 1 2 3 4 5 6 7 8 9 10

γB
DPl !
l − “limit”

γA

Tg1 Tg2 Tg3 Tg4-10 T f5 T f6 T f7 T f8 T f9 T f10 T

T f1 T f 2 T f 3 T f 4
Thermomechanical curves for
polymer homologous series
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 33
 III.4. Study of physical states of polymers
DPl ! DP < DPl
l − “limit” Tg = T f
rubbery state
“small” molecule
→ mobile Tg ↑ vs. M

DP ↑ larger molecule !

DP ≥ DPl
Tg constant ! T f > Tg
DPl !
segmental motion T f ↑ vs. M

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 34

 III.4. Study of physical states of polymers

DPl ! DPl !
l − “limit” segmental motion

the lower limit of the macromolecular domain !

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 35

 III.4. Study of physical states of polymers
Relative strain

(1)
(2)

(3)

(4) (5)

Tg Tc Tm Tf Td
Temperature

“glass” “crosslink” “melting” “flow” “decomposition”

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 36

 III.4. Study of physical states of polymers

(1) amorphous polymer, linear flexible chains

(2) amorphous−crystalline polymer, linear chains
(3) crosslinked polymer, weak crosslinking degree
(4) thermosetting polymer (e.g., bakelites)
(5) rigid chains polymer (e.g., cellulose, PNA, aromatic PA …) or
highly crosslinked polymer (e.g., ebonite, formaldehyde resins …)
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 37
 III.4. Study of physical states of polymers

Tg

• specific volume
• dielectric constant
• NMR absorbance
• refraction index
• thermal dilatation
• thermal conductivity
PVAC
• ultrasound propagation
(polyvinyl acetate)
…

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 38

 III.5. Amorphous−crystalline polymers
polymers ? physical/chemical properties !
• structure unit
3 × structure levels • molecular structure
• supramolecular structure
(3D chains arrangement)

→ stereoregularity
→ long-range / short-range order
→ packing
→ crystallites
→ fibrils
polymer !
→ orientation
→ lattice defaults
etc.
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 39
 III.5. Amorphous−crystalline polymers
amorphous−crystalline character of polymers

crystalline ?
“small” molecule polymers
monocrystal amorphous matrix
amorphous < 1% +
crystalline regions

crystallites
~ 101−102 Å
biphasic structure
amorphous−crystalline amorphous > 50%

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 40

 III.5. Amorphous−crystalline polymers
amorphous−crystalline character of polymers

crystallites
(lamellae  plateletlike)
thickness ~ 50−500 Å
lateral dimension ~ 1−25 µm

biphasic structure
amorphous > 50%
amorphous−crystalline

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 41

 III.5. Amorphous−crystalline polymers

“A synthetic polymer may be loosely described as crystalline if

it contains regions of three-dimensional ordering on atomic
(rather than macromolecular) length scales, usually arising from
intramolecular folding or stacking of adjacent chains.”

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 42

 III.5. Amorphous−crystalline polymers
• microstructure
crystallization ? • suprastructure
• T
microstructure ― spatial arrangement of structural units
suprastructure ― spatial 3D arrangement of polymer chains

(a) amorphous polymer

(b) oriented amorphous polymer
(c) crystalline polymer

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 43

 III.5. Amorphous−crystalline polymers
• microstructure
crystallization ? • suprastructure
• T
♦ in the absence of tensile
(stretching) stress, the chains
assume an amorphous, or
disordered, arrangement
♦ on being stretched, the

!
molecules readily align into
an ordered crystalline
arrangement
oriented natural rubber !
♦ natural rubber also
amorphous crystallizes on cooling,
polymer “self-reinforcing” taking several hours
material to do so at −25 °C

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 44

 III.5. Amorphous−crystalline polymers
• microstructure
crystallization ? • suprastructure
• T
Tg < T < T f
Relative strain (%)

glassy viscous
rubber-like thermal
state liquid,
elasticity destruction
melt

Tbr Tg Tf Td T

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 45

 III.5. Amorphous−crystalline polymers
microstructure ― spatial arrangement of structural units
suprastructure ― spatial 3D arrangement of polymer chains

spatial ordering of the units ― NMR, IR spectroscopy

spatial ordering of chains ― electron microscopy, XRD

https://royalsocietypublishing.org/doi/10.1098/rsos.180394
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 46
 III.5. Amorphous−crystalline polymers

optical properties !
• crystallinity of polymers → degree of crystallinity

• ranging from 0 for a completely non-crystalline polymer

to 1 for a theoretically completely crystalline polymer

• polymers with microcrystalline regions are generally tougher

• polymers with a degree of crystallinity approaching 0 or 1

will tend to be transparent, while polymers with intermediate
degrees of crystallinity will tend to be opaque due to
light scattering by crystalline or glassy regions

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