5.

Solid-State Properties

Sang Ouk Kim

Soft Nanomaterials Lab.

National Creative Research Initiative Center for Multi-Dimensional Directed Nanoscale
Assembly Department of Materials Science and Engineering, KAIST

S F
O T
N N
A O
Various Solid Structures of Polymers

 Crystalline states of polymers - Crystalline structure have a significant

- Highly crystallized polymers: well- influence on the , , and
defined crystalline morphology other physical properties of the polymer
consisting of chain-folded .
joined in supramolecular structures
called .
ex) HDPE, i-PP
- Intermediately crystallized polymers:
regular crystalline units are linked by
unoriented, random-conformation
chains that constitute regions. Amorphous glassy polymer
cf) semicrystalline polymers
- Low crystalline polymers: .
defined crystalline microstructure in an
amorphous matrix
ex) PVC
- Amorphous polymers: no crystallinity
ex) , , .
Supramolecular Structure of Semicrystalline Polymer
Amorphous Polymers I

 Amorphous state of polymer  Chain Entanglement

- Long, randomly coiled polymer chains - Sufficiently polymer chains can
with sufficiently high-molecular-weight form flow restricting entanglements
are interpenetrated to form flow- - Analogous to a bowl of spaghetti
restricting . - Significant effect on properties,
- Polymer chains assume their . . .viscosity, and properties
dimension (stress relaxation, creep, and craze
1. Melt state (or molten state): formation).
- Sufficiently high thermal energy for the
random micro-Brownian motions of the
. .segments of each polymer chain
2. Glassy state
- Glass transition temperature (Tg): the
temperature where all .
segmental motions of polymer chain
ceased in the course of cooling from
melt.
- Below Tg: only short range molecular
motions ( relaxations)
Amorphous Polymers II

 Critical Molecular Weight  Reptation

- The polymer chain length or - A model describes how .
critical molecular weight (Mc) for the movement of polymer chains can occur
formation of . - motion of polymer chain within
- Chain flexibility ↑ → Mc . a tube
- M. W. entanglements (Me): - A successful model developed by to
typically Mc ≈ 2Me explain the polymer dynamics
Amorphous Polymers III

 Phenomenological model for glass  Tg vs. molecular structure

transition - backbone and substituent
1) Isoviscous state: Pa⋅s, viscosity groups: low Tg
increase rapidly around Tg
2) Isofree-volume state:
- Vf = V - V0, Vf : free volume, V: specific
volume, V0: occupied volume (from
group contribution method)
- free-volume for Tg
- Concept of free volume is important for
explaining time-temperature
superposition of viscoelastic properties,
melt viscosity, and permeability
3) Isoentropic state: conformational
entropy (Sc: a measure of the total
number of ways of arranging a polymer
molecule or collection of chains) goes to
. .
Amorphous Polymers IV

 Secondary relaxation process - The and of

- Small scale molecular motions occurs in secondary relaxation processes are
the region significantly related to the properties
- Limited motions of the main chain or of amorphous polymers (mechanical
rotations, vibrations, or flips of properties, gas permeability, etc.)
substituent groups. - Secondary motions are to the
ex) Schatzki crankshaft rotation -120 °C, onset of long-range, main-chain
phenyl ring rotation of PS -200 °C cooperative motions that mark the glass
transition
Crystalline Polymers I

 Low degree of crystallinity

- Generally, the crystallinity of a polymer
is low due to the of molecule
cf) polymer single crystal: solution
crystallized polymer

 Lamella
- Basic unit of polymer crystal, arrays of  Chain conformation in lamellae
folded chains
- The conformation of various
- Adjacent or nonadjacent reentry of flexible chain polymers
polymer chain
- Extended or planar zigzag conformation
- Typical thickness: 100~200 Å, which (all conformation)
correspond to repeating units of
polyethylene in each fold ex) PE, syndiotactic vinyl polymers, nylons
(hydrogen bonding), etc.
- Helical conformation
 Anisotropy of lamellae
ex) PP (31 or 3/1 helix): ,
- Various properties ( , , polyoxyethylene (72 or 7/2 helix):
. , etc.) of lamellae are anisotropic . .
due to covalent bonding
Crystalline Polymers II

 Spherulites  Thermal transitions of semicrystalline

- Large ( size) spherical aggregates polymers
of crystal - Tm: temperature where crystalline melts
- Lamellae are oriented or . - A crystalline polymer has both glass
. .to the radial direction of transition and crystal melting
spherulite
- mechanism
Crystalline Polymers III

 Chemical structure – crystallinity

relationship
- Symmetric regular chain structure:
favorable for close packing, high
crystallinity
ex) PE, Teflon, i-PVC, etc.
- Asymmetric irregular chain structure:
amorphous
Ex) a-PVC, a-PS, etc.
- and configuration
favors crystallization
- Specific interactions such as .
ex) a-PVA: partially crystalline
high Tm of nylon-6,6 (265 °C)
Crystalline Melting Temperature

 Equilibrium melting temperature  Melting temperature depression from

- The free energy of fusion per repeating equilibrium value
unit is given by - Kinetic effect from fast cooling rate
∆Gu = ∆H u − T∆S u - crystal size - impurities or
crystallization condition
- At equilibrium Tm, ∆Gu = 0 and - Diluent
therefore
1  R  Vu 
Tm0 =
∆H u
1
− 0 = 
Tm Tm  ∆H u
 (
 φ1 − χ 12φ12 )
∆S u  V1 

where R: ideal gas constant, Vu: molar volume

per repeating unit, V1: molar volume of the
diluent, φ1: volume fraction of diluent, χ1:
interaction parameter
Crystallization Kinetics

 Kinetic effect on crystallinity

- The crystallization rates for most of
polymers are order of the
cooling rates in conventional processes
- Crystallinity can be controlled by
processing condition (cooling rate)

 Crystallization rate
- Tg: , zero crystallization rate
- Tm: Lamellae melt as soon as ,
zero crystallization rate  Avrami equation
- Maximum at certain T between Tg and - Crystallization rate can be measured by
Tm, optimum balance of . dilatometry, calorimetry, IR spectroscopy,
and . optical microscopy
- Avrami equation
φ = 1 − exp(− kt n )
where φ: crystallization conversion, k:
temperature dependent constant, n: .
(dimension of crystallization)
Crystallinity Measurement

 Density measurement  X-ray diffraction

- Density of crystalline portion is different - X-ray: high energy photons with short
from that of amorphous portion wavelength of 0.5 to 2.5 Å, which interact
- Equipment: calibrated density with electrons
measurement column - Wide angle X-ray scattering (WAXS):
- Fractional density ρ − ρa . .scale structures (<10 Å ),
φ= crystallinity, crystal dimensions
ρc − ρa
ρa: density of totally amorphous sample, - Small angle X-ray scattering (SAXS): large
ρc : density of totally crystalline sample scale structures (10 to 104 Å), .
- Determination of crystallinity
Ic wc: weight fraction of
wc =
I c + KI a crystal
Thermal Transitions
 1st order transition 2) Isothermal compressibility coefficient (β)
- 1st derivatives of Gibbs free energy are  ∂ G   ∂V  ( β = − 1  ∂V 
2
−   =   = − βV )
discontinuous  ∂p T
2
 ∂p T V  ∂p  T
 ∂G 
- At constant pressure:  ∂T  = − S
 p 3) Thermal expansion coefficient (α)
- At constant temperature:
- Dilatometry
 ∂G 
  = V
 ∂  ∂G  
 
 ∂V 
  =   = αV ( α =  1  ∂V  )
 ∂T  ∂p T  p  ∂T  p  V  ∂T  p
 ∂p  T

 2nd order transition

- 2nd derivatives of Gibbs free energy are
discontinuous
1) Specific heat  Glass transition
∂ G
−
2
 ∂S 
 =  =
C ( C p =  ∂H  = T  ∂S  )
p
- 2nd order transition-like behavior
 ∂T 2   ∂T  p  ∂T  p
 p  ∂T  p T
- effect on transition temperature
Thermal Transition Measurement I
 Polymer thermal transition  Calorimetry
- The most frequently used techniques: - The most widely used methods
DSC, dilatometry, DMA, DEA
- The differential power needed to maintain
both the reference and sample pans at the
 Dilatometry (Oldest method) same temperature during a programmed
- change with temperature or time heating cycle

∆Q ∆C p
φ= φ =1−
∆H f (∆C )
p am
Thermal Transition Measurement II
 Heat distortion temperature (HTD)
- An oriented measure of transition temperature for polymers
- The temperature where a sample bar of standard dimensions (e.g. 127 × 13 × 3 mm)
deflects by 0.25 mm (0.01 in.) under a standard flexural load of 455 KPa (66psi)
placed at its center (ASTM Standard D648)
- Temperature limit for applications
- HDT of an amorphous polymer: slightly (10 to 20 °C) lower than the .
- HDT of a semicrystalline polymer: close to .
Chemical Structure – Thermal Transition Relationship
 Flexibility of main chain - Rigid side group
- Flexibility ↓ → Tg & Tm .
- Chain flexibility can be controlled by
the amount of or
nonrotational linkages

- Flexible side group

Glass Transition Temperature
 Molecular weight 2) Inverse rule of mixtures:
- relationship 1 W W
= 1 + 2
- Free volume theory: free volume T g T g ,1 T g , 2
increases with the number of chain ends
K
T g = T g∞ −  Pressure
Mn (Fox-Flory eq.)
where Tg∞: limiting value of Tg at , - Tg is relatively insensitive to pressure
molecular weight, K: constant value, - Tg- pressure relationship
(constant above M.W. of 10,000)
dTg ∆β
= = 25 K / kbar
dp ∆α

 Crosslink density
- Fox-Lshaek equation
 Composition (miscible blends) Tg = Tg , 0 + K c ρ c
1) Rule of mixtures
N Kc: polymer specific constant, ρc: # of
T g = ∑ Wi T g , i crosslinks per gram, Tg,0: glass transition
i =1

Wi: weight fraction of ith component temperature of uncrosslinked polymer

Deformation Mechanisms of Polymers I

 Response to mechanical strain  Crazing

- The strength of polymeric - When a brittle polymer is deformed to a
material is usually lower than those of certain level (the critical strain: εc), small
metals and ceramics cracks develop to the direction
cf) Kevlar fiber of deformation
1. Thermosetting resin - Light reflection: cloudiness or whitening
- mode of fracture: at
the stress-concentrated region
- Breakage of bonding at the
crack
2. Thermoplastic
- mode of transition
depending on temperature and strain rate
- At a low strain (usually below 1%):
. .deformation
- At a high strain (irreversible yield
behavior) crazing ( polymers)
or shear banding ( polymers),
Deformation Mechanisms of Polymers II
 Crazing II  Mechanical failure through crazing
- Unique morphology of polymers - The exact reason for crazing is uncertain
cf) crack - Crazes constitute the defects where brittle
- Thickness: a few nm ~ mm cracks initiate
- Polymer (0.6 to 30 nm in - The growth of craze by the breakdown of
diameter) stretched in the direction of the fibrillar microstructure to form
tensile deformation
additional voids → rapid propagation as a
- The microfibrils are surrounded by crack
. .(90 vol%)
- Optical anisotropy due to the of - Crazes are formed at the crack tip and act to
fibrils . .its advance
Deformation Mechanisms of Polymers III – Mechanical Test
 Shear banding  Various methods of mechanical testing
- Typical fracture mechanism for ductile - Static tests: force response to a constant
polymers . .→ modulus, strength, and
- Localized shear deformation at angle of elongation to failure
. .to the stretching or compressing
direction - Transient tests: force or strain response to
rapid strain ( ) or stress ( )
- Optical anisotropy due to the .
of polymer chain - Impact test: the required to fail
- No formation under rapid loading
- Fatigue: the of applied stress
required for failure
Tensile Properties of Polymers I

 Static Test - Tensile test  Stress–strain curve: brittle polymer

- The most common type: the force - Proportional limit: stress begins to deviate
required to keep constant strain rate from a stress-strain relation
(usually below %)
- Initial modulus: the initial .of the
stress-strain curve: (Hooke’s law)
- Secant modulus: slope of a line drawn from
the origin to some convenient point
ex) 1% strain → 1% secant modulus

Engineering stress: σ = F A0
Engineering strain: ε = ∆L L0 , (∆L = L − L0)
True stress: σ T = F A = σ L L0
True strain:  L
 
L 1
ε T = ∫  dl = ln 
0  l 
L
 L0 
Tensile Properties of Polymers II

 Modulus vs temperature - plateau region: ~ MPa,

entanglement effect
ρRT
Ep ∝
Me
- Far above Tg: second drop of modulus
(. .region)

2) Crystalline polymer
- The modulus is typically higher in the
secondary plateau due to effect
of crystallites dispersed in an amorphous
rubbery phase
1) Amorphous polymer - At Tm the crystallites melt and the modulus
- Below Tg : all glassy materials including drops in the viscous-flow region.
polymers have approximately same
value of GPa 3) Crosslinked polymer
- At Tg : rapid decrease to a secondary
plateau
Tensile Properties of Polymers III

 Temperature dependence of S-S 2) Curve 2 or 3: ductile polymers

curve (engineering plastics, polyamides, and
- Amorphous polymer can exhibit a range toughened (rubber-modified) plastics
of behaviors from to . - modulus, energy for failure
response upon the change of temperature - Yield stress → strain softening → draw
stress → fail or orientation hardening and
fail
- Necking: local decrease in cross sectional
area in gage region
- Cold drawing: necking stops at a certain
cross-sectional area and the neck
propagates along region
until the sample finally breaks

3) Curve 4: rubbery polymers

1) Curve 1: brittle polymers (polystyrene - Very low modulus, very high elongation at
at ambient temperature) break
- modulus, elongation at break - Strain-induced crystallization: increase in
stress at very high strain
Tensile Properties of Polymers IV

 Mechanical properties of various  Failure Envelope

polymers - The combined effect of and
- Influence from various parameters . .on the S-S curve
including the chemical structure of - Shear rate ↑ or testing temperature →
polymer, the conditions for sample ultimate strength .
preparation, M. W., M. W. D.
crystallinity, the degree of crosslinking
or branching
Creep I

 Creep  The responses of various materials

- Shear, torsion, flexure, compression as under creep
well as tensile measurement A: Ideally elastic: Hooke’s law ( ε = Dσ 0 = ε 0 ):
- Useful to check the response of a Spring
polymer under a load for periods B: Ideally viscous: Newton’s law of viscosity
- Strain is monitored with time under a ( σ = ηε ): Dashpot
constant value of stress ( σ 0) tσ  σ 
ε = ∫  0 dt =  0 t
ε (t ) η  η 
0

D(t ) =
σ0 C: Viscoelastic: elastic (initial response) +
D(t ) : creep compliance viscous (long-term response): combination
of springs and dashpots
Creep II, Stress Relaxation

 Simple instrumentation for creep test  Stress-relaxation experiments

- T ↑→ D(t ). . - The stress ( σ (t )) on a sample is measured
- leads to a master with time after a deformation
curve for creep (ε 0 )
σ (t )
E r (t ) =
ε0

E r (t ) : stress relaxation modulus

Impact Testing

 Various impact testings  Importance of impact strength in practical

- Izod and Charpy test: hammerlike weight application
strikes a specimen, the energy to break is - Test for energy property (beverage
determined from the loss in the of bottles or window replacement)
the hammer - Brittle polymers (polystyrene): impact
- Falling ball or dart test: the energy to break strength
is determined from the weight of the ball - Engineering plastics (polycarbonate): high
and the height from which it is dropped impact strength
- High speed tensile test: the energy to break  Chemical structure vs. brittleness
is determined from under stress- - Amorphous polymers with groups
strain curve and nonlinear backbones are brittle (high Tg)
- Unoriented crystalline in a polymer whose Tg is
above the testing temperature increases
brittleness
- Secondary relaxations
 High impact polystyrene (HIPS) or ABS
- Dispersing small particles within brittle
matrix to reduce brittleness
- Good adhesion to rubbery inclusions by .
the rubber and matrix polymer
Fatique Testing

 Fatigue Testing
- Fatigue life: of cycles of applied
stain at a a given level of stress that a
sample can sustain before complete
failure
- Maximum stress↑, temperature ↓ →
fatigue life .
- Endurance limit: maximum value stress
where failure will not occur under .
number of cycles of applied stress
- Typically the value of stress leading to
failure at a given fatigue life is %
of the static tensile strength
- Extremely important property to
evaluate engineering and composite
materials for applications or
when frequent periodic stress loading is
encountered (ex: plastic hinge joint)