CHE/MSE 761

Polymer Blends & Alloys

Richard J. Spontak
Departments of Chemical & Biomolecular Engineering
and Materials Science & Engineering
North Carolina State University

Fall 2007
 Course at a Glance…

• Information provided: course syllabus

• Review of fundamental principles
• Commercially relevant systems
• Phase equilibrium: blends/copolymers
• Physical/reactive compatibilization
• Field and confinement effects
• Analytical methods
• Future prospectives
 Learning Objectives

• Predict/measure blend phase behavior

• Identify blends for use in applications
• Design blends with target properties
• Predict/measure copolymer behavior
• Describe the role of compatibilizers
• Use fields/confinement for alteration
• Deliver concise literature critiques
• Perform quantitative data analyses
Fundamentals: Chain Length

CH4 ----------------------------------------- 16
CH3 - CH3 ---------------------------------- 30
Gases
CH3 - CH2 _ CH3 --------------------------- 44 Increasing
CH3 - CH2 - CH2 - CH3 -------------------- 58 Molecular
weight
Liquids
CH3 - (CH2)6 _ CH3 -------------------------114

"Semi-solid"
CH3 - (CH2)30 _ CH3 -------------------------450

Solids
CH3 - (CH2)30,000 _ CH3 ----------------- 420030

Increasing
Molecular Weight
Fundamentals: Chain Length

• Paraffin wax is a
crystalline solid
• Increasing chain
length (n, DP) induces
crystal defects
• Crystals are separated
by amorphous regions
• Long PE chains connected
by entanglements
 Fundamentals: Amorphous

• Different
interpretations
of amorphous
regions differ
in local order

• Local order can

change due to
confinement
(crystals or
surfaces)
 Fundamentals: Properties

Melting temperature
• Melting temperature

• Glass transition

Glass transition
Molecular weight

log (Melt viscosity)

• Melt viscosity Molecular weight

Tensile strength
• Tensile strength log (Molecular weight)

• Polydispersity? log (Molecular weight)

Fundamentals: Polydispersity

• Chain or sequence
length
• Quantified by:
"Ni Mi
Mn =
"Ni
2
"Wi Mi "Ni Mi
Mw = =
"Wi "Ni Mi
PDI =Mw Mn >1.0
 Example Calculation

• 3 chain populations with 5 chains DP 100

5 mols of chain in each
• Number-average M: 5 chains DP 150

Mn =(5)(100)+(5)(150)+(5)(200)
(5)+(5)+(5)
5 chains DP 200

!
• Weight-average M:
Mw =(5)(100)2+(5)(150)2+(5)(200)2
(5)(100)+(5)(150)+(5)(200)
! • Polydispersity index: PDI = 161/150 = 1.07
 Fundamentals: Distributions

• Thermodynamics often governed by Mn

• Mechanical properties often governed !

by Mw
12 _ 1200000 _
Mn = 100,000
Mw = 104,500
10 ! 1000000

8
800000
Moles

Weight
6
600000

4
400000

2
200000

0
0 100000 200000 0
0 100000 200000
Molecular Weight Molecular Weight
 Fundamentals: Chain Size

• The size of a chain is

dictated by the size &
number of repeat units
 Coil or blob size C* ≈ 0.01

 Estimated by ideal chain or

random (Gaussian) coil
• Characteristic size is an C > 0.1

important consideration
in polymer systems Unperturbed: Rg = cM1/2

 Coil size < Lamellae/Assembly < Crystal/Domain

Fundamentals: Entanglements

• Entanglements distinguish
polymers from low-M
organics
• Properties dictated by entanglements
• In linear polymers, approximated by:
 600 carbon atoms along backbone
 200 repeat units
 For PS, Me ≈ 18,500
 Consider (200)(104) ≈ 20,000
 Fundamentals: Transitions

• Important regimes:
 Glass - high modulus
 Glass transition
 3-4 order drop
 Sensitive to M:
• Tg = Tg∞ - K/Mn non-polymer

 Leathery region

Glass transition
 Rubbery plateau
 Viscous liquid
• Time dependence? Molecular weight
Fundamentals: Viscoelasticity

• Due to their viscoelastic nature, time-

temperature superpositioning (tTS)
describes many polymer systems
• Creep compliance: J(t) = γ(t)/τ0
nLVE

τ γ J
LVE

time time time

Fundamentals: Time vs. Temp

• At long times, J(t) is

sigmoidal.
Relaxed,
J compliant

Unrelaxed,
stiff
• At other temperatures,
J(t) is shifted. log (time)

JR

• The tTS indicates that J log aT

mechanical processes JT(t) JTo(t)

speed up at high T Ju

log (time)
 Fundamentals: Using tTS

• The tTS can be used in

quantitative fashion:

• Shift factors:
 aT = t(T)/t(T0)
 Arrhenius: ln aT = Ea/RT + K
 WLF: log aT = C1(T - T0)/(C2 + T - T0)
 Example Calculation

• tTS principle of a semicrystalline polymer

 iPP exhibits the following compliance at 35°C
 J(t) = 1.2 t0.1 with J in GPa–1 and t in sec
 If Ea = 170 kJ/mol, what is J(t) at 40°C?
• For many crystalline and glassy polymers, Ea ≈ 120 kJ/mol

 Set To = 35°C and T = 40°C so that J40(a40t) = J35(t)

 Rearrange to obtain J40(t) = J35(t / a40)
 Determine a40 from Arrhenius expression (T [=] K);
a40 = 0.346
 Thus, J40(t) = J35(t / 0.346) = 1.2 (t / 0.346)0.1
 And, J40(t) = 1.33 t0.1
 Predict extended use behavior at long times by increasing T
Fundamentals: Time Issues

• Polymers in concentrated
solutions move via reptation
 Diffusivity ~ M-2
 Time ~ M3
 Plateau modulus ~ M0
 This occurs at ~8 Me
• Polymer diffusion at
interfaces during healing
 Wool theory (dynamic/static)
 Number of chains: ~t1/4M-5/4 (not t1/2)
 Fundamentals: Summary

• In polymeric systems, three important points

(EST) must be addressed:
 Entanglements: property development
 Characteristic Size: structure development
 Characteristic Time: dynamic changes

• In multicomponent polymer systems, each of

these plays a critical role:
 E: adhesion along polymer interfaces
 S: spatial distribution of species (morphology)
 T: evolution during phase separation
 Fundamentals: Exercise

• Consider EST
Fundamentals: Physical States

• Crystalline
 Chains enter into 3D register
 Mobility of chains extremely low
 Effective physical cross-links
 Responsible for melting (1st-order; Gc=Gl)
 Crystallization sensitive to
environmental conditions
 Confinement ' *
)
) 2 $e ,
,
 Cooling rate Tm =Tm,"1#)
)
,
,

l%&h
) ,

 Solvent
) ,
)
( f ,
+

!
 Fundamentals: Crystals

• Solution-crystallized polymers

Single crystals can be grown from solution.

Details of growth can be observed by TEM.
 Fundamentals: Crystals

• Melt-crystallized polymers
Side view Top view

Crystals grow in a high-

viscosity medium.

Confinement effects are

important.
 Fundamentals: Crystals

• Solvent-induced crystallization

Quasihomogeneous
PMMA/PVDF blend

After exposure to scCO2

Fundamentals: Crystallinity

• Measurement
 DSC (a)

 XRD Exotherm (b)

(c)

(d)

 Density a. PET as received

b. ambimilled for 20 min
c. ambimilled for 40 min
(e)
(f)

d. ambimilled for 1 hr

• Kinetics
e. ambimilled for 2 hrs
f. ambimilled for 36 hrs

40 80 120 160 200 240 280 320

Temperature (°C)

 Avrami equation: ln(1-x)=-Ktn

 Constant n depends on 2 factors
 Crystal dimension (sphere-3, disc-2, rod-1)
 Crystal initiation (Predetermined, Sporadic)
• nS = nP+1; nmax = 4.0 for sporadic spheres
 Fundamentals: Glasses

• Glass Temperature
Viscoelastic
 Amorphous liquid
 Mobility of
chains low
 High E Glass
Crystallization transition
 Creep
 Aging Melting
 Tg (2nd order)
 Vitrification
sensitive to
 Confinement
 Cooling rate Semicrystalline solid Glassy solid
 Solvent
 Fundamentals: Glasses

• 2nd-order phase
transition

• Starting with Sg=Sl:

 dTg/dP = TVΔα/Δcp
• Starting with Vg=Vl:
 dTg/dP = Δβ/Δα
 Fundamentals: Glasses

• Free-volume theory
 Iso-free volume (Simha & Boyer)
 Fractional free volume: ΔαTg = 0.113
 WLF equation (Williams-Landel-Ferry)
 log(η/η0) = -C1(T-T0)/(C2+T-T0)
 Yields a fractional free volume at Tg of 2.5%
• Kinetic theory
 Reveals how Tg shifts with exp. time frame
 Used in conjunction with PALS (o-positronium)
• Thermodynamic theory (Gibbs & DiMarzio)
 Variation with M, cross-link density, φ, P
Fundamentals: Other Motion

• Main-chain motion
 Schatzki crankshaft motion
 Needs at least 4 CH2 groups
• Side-chain motion
 Certain groups become mobile (locally)
• T|| transition
 Entire polymer molecule can move as a
single unit (no reptation)
 Still controversial
 Fundamentals: Example

• Consider polystyrene:
 160°C T|| Liquid(1) to liquid(2)
 100°C Tg (Tα) Long-range motion;
onset of reptation
 50°C Tβ Torsional vibration of
phenyl rings
 -143°C Tγ Motion due to carbon
backbone
 -225°C Tδ Wagging of phenyl
rings
Fundamentals: Mesophases

• Polymer chains show evidence of

structure (order; anisotropic alignment)
in the melt or solution state
 Temperature-induced: thermotropic
 Solvent-induced: lyotropic

• Examples:
 Block copolymers: microphase separation
 Liquid crystalline polymers: chain packing
Fundamentals: Microphases

Temperature
• Sequences on
a copolymer Viscoelastic
are repulsive liquid

• Sequences are
covalently Microphase
separation
linked together
Self-
• The chains assembled
self-assemble structures

to form various
(a)periodic
nanostructures
Fundamentals: Microphases

Biphasic

T
Decreasing
Temperature
Fundamentals: Nanostructure

• Examples of ordered nanostructures

Fundamentals: Nanostructure

SI30

SI48

100 nm
200 nm
Fundamentals: Nanostructure

• The number and types of ordered

nanostructures increases substantially
as the number of chemically dissimilar
blocks is increased.
Fundamentals: Microphases

• Microphase separation
is not limited to block
copolymers - +
+ -+
• Ionomers self-organize -

due to ionic interactions - +

+ -+
- - +
• Important in the design + -+
-
- +
of fuel-cell membranes + -+
-
 Fundamentals: LCPs

• Main chain or side chain architectures

Fundamentals: LCP Chemistry

• Common mesogenic units as building

blocks
Fundamentals: LCP mesophase

• Classified according to directional and

positional order

Nematic
Discotic

Cholesteric Smectic-A
Smectic-C
Fundamentals: LCP mesophase

LC transitions are 1st order;

heat is absorbed/evolved
Fundamentals: LCP mesophase

• Cholesteric ("twisted" nematic) exhibits a

visible pitch
• Commonly encountered
with cellulose derivatives
• Employed in
active matrix
displays
Fundamentals: LCP mesophase

• Side-chain LCPs have mesogenic units

as pendant groups
• Important in optoelectronic
devices
Fundamentals: LCP mesophase

• Mesogenic side groups often separate

from the flexible polymer backbone
• Can form bilayers or
"double combs"
Fundamentals: LCP mesophase

• LC mesophases are sensitive to external

fields: shear, electric and magnetic
• Some LCPs behave as
ferroelectrics (switches)
 Fundamentals at a Glance

• Importance of EST in designing multi-

component polymer systems
 Entanglements (mechanical properties)
 Size scales (morphology)
 Time scales (dynamics)
• Physical states and phase transitions
 Crystals: LRO; molecular registry; stability
 Glasses: SRO; free volume effects; aging
 Mesophases: µphase separation; LC
 Classes of Polymers

• Plastics
 Thermoplastics (semi-crystalline; glassy; 75-80%)
 Melt-processable; recyclable (non-conserved properties)
 Commodity and engineering polymers
 E.g., polyolefins, acrylics, nylons
 Thermosets (glassy)
 Networks formed by reactive monomers
 E.g., epoxides, phenolics (phenol+CH2O) Phenolic
resin -
• Elastomers "Bakelite"

 Cross-linked low-Tg polymers

 Physically or chemically cross-linked
 Rapid shape recovery; highly elastic
• Gels
 Polymer networks containing a liquid
 Polymer Production Figures

Source: C&EN, July 2, 2007

 Polymer Production Figures

Source: C&EN, July 2, 2007

 Blend Strategy

• Components
 State
 Properties
 Synergy
• Combination
 Processing
 Degree of
mixing
• Morphology
 Structuring
• Properties
 Application
• Recycling
 Energy requirements
 Post-life use
 Blend Structure

• Polymer blends are classified as either

 Miscible: one-phase (homogeneous)
 Immiscible: two-phase (heterogeneous)
 The phase diagram
is known & applies
 Incompatible
 Heterogeneous
 Cannot be processed
as single phase
 Phase diagram is not
known
 Most commercial blends
 Polymer Thermodynamics

• Lattice development
 Consider a solution of 2 different polymers on a cubic lattice
x x x x x x x o
x x x o o o x o
o o o o o o x o
o x x x x x x o
o o o o o o o o
 It has been shown by Flory, Huggins and Stavermann that the
free energy of mixing per unit volume is given by
φi = volume fraction of species i
!G mix "A ln "A "B ln "B #"A"B vi = volume of species i
= kT + + Ni = number of species i
V vAN A vBN B v*
v* = reference volume = (vAvB)1/2
 Phase Behavior

• A binary phase diagram typically (but not always) exhibits a

global maximum (upper critical solution temperature, UCST) or a
global minimum (lower critical solution temperature, LCST)
(a) Binodal, coexistence, cloud points
UCST where the chemical potential (µ) of polymer A(B)
in one phase equals that in the coexisting phase;
Homog Tc clear solution starts to appear opaque due to
Temperature

phase separation

(a) (b) Metastable regime

where the binary system phase-separates by the
(b) mechanism of nucleation and growth

φA,c (c) Spinodal, stability points

(c) where the 2nd derivative of the free energy with
Heterogeneous
respect to composition (const. T & P) equals 0;
φA within the spinodal envelope, phase separation
proceeds by spinodal decomposition
Phase Separation Mechanisms

• Nucleation and growth occurs by the formation of

pure, discrete nucleation sites that grow with time
• Spinodal decomposition occurs by an instability
wave that propagates in the material & coarsens

Spinodal decomposition (simulated)

Phase Separation Mechanisms

• Spinodal decomposition occurs by an instability

wave that propagates in the material & coarsens
 The result is a bicontinuous morphology
 Channels change composition with time

50/50 PB/dPB blend

 Quantitative Description

• Governing equations for phase separation

 Nucleation & growth dV vxeD
! , which yields d ! t1/nc with nc " 3
dt RT
 V = droplet volume, d = droplet diameter, v = specific volume of blend
 xe = equilibrium concentration at a given T, D = diffusion coefficient

 Spinodal decomposition
R(q)t 2 2
! – ! = " [A(q) cos(qr) + B(q) sin(qr)] e , where R(q) = –Mq (D + 2Kq )
q
 F = composition, A & B are constants, q = wave number, D = diffusivity
 R = Rayleigh factor, M = mobility constant, K = energy gradient term
 At the spinodal, q exhibits a maximum (qm), at which
1/2 2
D MDq m
qm = – and Rm = –
4K 2
 Critical Behavior

• The critical point (φA,c,Tc) on the binary phase

diagram identifies the maximum or minimum point
at which biphasic behavior is first observed.
 Good back-of-the-envelope calculation
 Can be obtained directly from the Flory-Huggins equation
2 –1
* 1/2
v 1 1 N AvA
!c = +
!A,c = 1 +
2 NAvA N BvB N BvB

 Here, Tc is determined from the T dependence of χ

 In the case of NAvA ≈ NBvB, these equations reduce to
2v*
!c = !A,c = 1/2
N AvA
 Rules of Thumb

• Most polymer pairs are at least immiscible

 Recall that isothermal mixing is governed by ΔGmix=ΔHmix–TΔSmix
 For polymers, ΔSmix is very small (unlike small molecules)
 Most polymer pairs mix endothermically (ΔHmix > 0)
!G mix "A ln "A "B ln "B #"A"B
= kT + +
V vAN A vBN B v*

• Most polymer pairs exhibit UCST behavior

 Immiscible at low T, but miscible at high T
 Most commercial polymer blends degrade before they become
a single (homogeneous) phase

• Polymer pairs exhibiting LCST behavior tend to exhibit

specific chemical interactions
 Miscible at low T, but immiscible at high T
 Phase Boundaries 1

• The binodal curve from the Flory-Huggins Theory

 These equations correspond to the condition of equal µi

'
!A '' ' N AvA "N AvA 2 2
' ''
ln + ! – ! 1– + !B – ! =0
Temperature

'' A A N BvB * B
!A v

'
!B ' '' N BvB "N BvB 2 2
' ''
ln + ! – ! 1– + ! – !A =0
'' A A N AvA * A
φA ! v
B

 For the case of comparable molecular volumes (NAvA ≈ NBvB),

v* "B
!(T) = ln
NAvA 1 – 2"A "A
 Phase Boundaries 2

• The spinodal curve is generally determined from

the conditions at which (∂2ΔGmix/∂φA2)T,P = 0

 From the Flory-Huggins theory, this yields

v* 1 1
!(T) = +
2 N AvA "A NBvB"B

 For the case of comparable molecular volumes (NAvA ≈ NBvB),

v*
!(T) =
2N AvA"A"B
 Considerations Regarding χ

• Since ΔSmix does not change very much, the phase

behavior of polymer blends depends strongly on χ,
which is a pairwise-specific parameter
 Governs macrophase separation in polymer blends
 Phase domains much larger than the size of individual chains
 Macroscopic domains are responsible for opacity
 Governs microphase separation in block copolymers
 Phase domains are on the same order as the block size
 Nanoscopic domains are too small to scatter light; transparent
 The χ(T) function is determined from homogeneous solns
 No interface or surface effects
 Chemically and thermally stable
 Usually performed by small-angle scattering (x-ray or neutron)
Role of χ in Phase Diagrams

• In general, χ(T) = A + B/T + C/T2. In most cases,

however, C = 0 so that
 UCST: B > 0 (χ decreases w/ increasing T)
 LCST: B < 0 (χ increases w/ increasing T)
Examples of Phase Diagrams

• What if C ≠ 0?
Examples of Phase Diagrams

• What if B = C = 0?
 χ ≠ χ(T)
 Sign on χ dictates
phase behavior
• Remember: meaningful
phase diagrams do not
exist for most com-
mercial polymer blends
(χ >> 0)
Where to Find χ(T)?
 The Meaning of Life via χ

• What is the physical meaning of χ?

 From regular solution theory:
 χ ~ [εAB - 1/2(εAA + εBB)]
 In principle, χ ≠ χ(M, φA)
 If χ < 0, AB interactions dominate; exothermic
 If χ > 0, like interactions dominate; endothermic
• It is not possible to accurately estimate χ
when χ < 0
 Exothermic mixing driven by site-specific
interactions or free-volume considerations
 Pure-Component Approach

• Most polymer pairs exhibit endothermic

mixing (ΔHmix > 0; χ > 0)
 Like interactions dominate
 Interactions derive from dispersion forces
 Corresponds to positive deviation from
Raoultian behavior
 Hildebrand solubility parameters can be
used to calculate χ
 Unlike χ values (pairwise-specific), solubility
parameters (δi) are pure-component values
and are often tabulated
 Solubility Parameter Physics

• Solubility parameters expressed in terms of √ c, where

c denotes cohesive energy density
 c = Δuvap/vliq
 c [=] energy/volume or pressure
 Provides a measure of the energy needed to break interactions
("bonds") of a species to permit the formation of bonds with a
different species
 δ [=] (J/m3)1/2 or (cal/cm3)1/2 {H} or MPa1/2
• Accurately describes dispersion forces
 Stronger interactions are less accurately accommodated
• Limitations
 Less dependable with complex interactions
 Cannot be used to predict LCST behavior
 Problematic with non-Gaussian chains (non-random ΔSmix)
Relationship between χ and δ

• For common binary polymer systems,

 χ = A + B/T = χS + χH

• For polymer-solvent systems,

 χ = K + vs(δ1 - δ2)2/RT, where K ≈ 0.34
 χmin = 0.34 when δ1 = δ2 (χ < 0.5; good solvent)

• For polymer-polymer systems,

 χ = <v>(δ1 - δ2)2/RT
 χmin = 0 when δ1 = δ2 (athermal mixing)
 Recall that Δhmix = χRTφAφB
 χ < 0 cannot be predicted by using δ
 Estimation Methods for δ

• Solubility parameters can be estimated via the

use of group contribution methods (GCMs)
 Account for each functionality present
 Each functionality contributes differently to a
thermodynamic property
 Many databases exist (van Krevelen, Properties of
Polymers)
 This methodology is not limited to δ
• Value of c is given by Σi Ecoh,i/v or (Σi Fi/v)2
 Here, Ecoh,i or Fi is a regressed contribution value
 Molar volume (v) obtained from M/ρ or other GCMs
GCM Procedure: Homopolymer

• Draw chemical structure & identify each chemical functionality

• Use the repeat unit or full chain in the calculations; be consistent
• Locate tabulated GCM values from a single source
• Example: high-M PS (1 CH2, 1 CH, 1 phenyl)

From van Krevelen:

Group Value of Fi
CH2 272
M of repeat unit: 104 g/mol CH 57
ρ of PS at 100°C: 1.00 g/cm3 C6H5 1504
V of PS at 100°C: 104 cm3/mol Total 1833

δ = Ftot / v = 17.6 (J/cm3)1/2, which agrees well with exp. values

 GCM Procedure: Copolymer

• For a random or alternating (not blocky or graft)

copolymer, weight the values of the contributions
according to composition
• Example: SAN

x CH2 1–x CH2

x CH 1– x CH
x CN 1– x C6H5

Total contributions:
1 CH2
1 CH
x CN
1– x C6H5
 Effective χ for Copolymers

• Addition of an AB random or statistical copolymer (1) to a C

homopolymer (2):
 Assume that the copolymer does not self-organize
!G mix "1 ln "1 "2 ln "2 #blend "1"2
= kT + +
V v1N1 v2N 2 v*
1/3
 where v* = v1,Av1,Bv2
! blend = fA! AC + fB!BC – fAfB! AB
[fi denotes the volume/monomer fraction of species i in the copolymer]

 Copolymer effect:
fAfB!AB > fA!AC + fB! BC so that !blend < 0
Phase Behavior of Copolymers
 Shortcomings of F-H Theory

• Shortcomings of the Flory-Huggins approach

 Does not account for free volume in polymers
 Lattice sites are either not occupied or not fully occupied

 Responsible for compressibility

 Becomes increasingly important as the system deviates from mean-
field behavior (e.g., as the molecular weight decreases)
 Addressed by Generalized Flory and Lattice Fluid Theories
 Does not account for specific chemical interactions
 Considered in version of F-H developed by Painter & Coleman
 Lattice Fluid Theory

• Basic premise: not all lattice sites are filled

r = 11 φ* = 0.31
r=7 φ* = 0.20
r=8 φ* = 0.23
r=9 φ* = 0.26
N0 = 5
Nr = 40
#m &
V = % "riNi + N0 (v 0 = (rN+ N0 ) v 0 = Nr v 0
$i '
Nr = total number of lattice sites
m Density :
r = " xiri (ave. DP)
i 1 rN rN
"˜ = = =
riNi r v˜ rN+ N0 Nr
)i* = = xi i
rN r Close# pack density : N0 = 0; "˜ = 1
 Generalized LF Theory

• Helmholtz free energy (A):

A #˜ $ * (1" #˜ ) m& * ) #˜ & * ,
=" + ln(1" #˜ ) + ' i ln+ i .
rNkT (1" %#˜ )kT #˜ i ri * (i -
) 1,/1+ (1" %#˜ )ln(1" %#˜ )2
" +1" .1 4
* r -0 %#˜ 3
m mm 2 ( 1+
where " *
= #% $i "ii + % % $i*$ j* & ijkT
* *
and ' = *1# -
i i< j z) r ,
!
Limiting case:
A % * m &i* ) &i* ,
If "˜ =1 and # = 0, then =$ +' ln+ .
! rNkT kT i ri * (i -
(F-H Theory)
 Sanchez-Lacombe Theory

• Consider another case:

A "˜ % * (1$ "˜ ) m& * ) "˜ & * ,
i
If "˜ <1 and # = 0, then =$ + ln(1$ "˜ ) + ' ln+ i .
rNkT kT "˜ i ri * (i -

• This is the Sanchez-Lacombe (S-L) theory

!
for polymeric systems (solutions or blends)
• In can also be written in its more common
PvT format
# "A &
Since P = -% ( , )˜ 2 + P˜ + T˜ [ln(1* )˜ ) + (1*1/r))˜ ] = 0
$ "V ' T
where T˜ =kT/+ * , P˜ =Pv 0/+ * and )˜ = )/) *

!
MC S-L Theory: Mixing Rules

• Many SL parameters are tabulated:

 T* = ε*/k
 P* = ε*/v0
 ρ* = M/rv0
• For multicomponent systems, mixing rules
are needed:
v0 = # "io v 0i P" = $ $ #i*# *j Pij"
i i j
wi wi
# $v rN #$ 1/2
"io = i 0i
"i* = i i= i # &
Pij" = %Pi"Pj" ( (1) *ij)
! wj ! rN wj $ '
% %
j # $v j #$
j 0j j

!
S-L Theory: Chemical Potential

• The final mixing rule:

T "
=
(# * ˜
i / T v
i ( i
+ / v j) j# * ˜
/ Tj)
$
# * * "
i # j (Pi + Pj ij ) 0
" $ 2P" v

T * *
#i + ( v i / v j ) # j RT

• !For multicomponent systems,

µi * $ ri ' $k * k k
* *
'
= ln"i + &1# ) + ri*˜ & , " j + ij # , , "i " j + ij )
RT % r( % j=1 i< j (
-/ *˜ P˜ v˜ 1 1/
i
+ ri .# + ˜ + (v˜ # 1)ln(1# *˜ ) + ln *˜ 2
˜
/0 T T r1 /3
i

!
Application of the S-L Theory

• Consider a blend of PDMS and PEMS

 UCST blend
160

140 (a)

 Cloud point decreases 120

(oC)
100

with increasing hydrostatic

cp
80

T
pressure 60

40

 Cloud point increases 20

75

with increasing CO2 50

(b)

pressure

(oC)
25

cp
• Can the phase behavior
!T
0

of a compressible blend
be modeled with S-L theory?
-25
0 10 20 30 40 50
P (MPa)
 The Sensitivity of χ(T)

150

• The reported temperature

(5)

100

dependence of χ leads to (4)

(oC)
50 (3)
very different behavior

cp
T
(1) (2)
0
32.0
-50
0.00 0.20 0.40 0.60 0.80 1.00
31.0 !
PDMS
15
(oC)

30.0 (b) (4) Determined from the data

of Kuwahara et al. (1995)
(5) Horiuchi et al. (1991)
cp

29.0 10 (3) (2)

T

3
" x 10
(5) (1)
(4)
28.0
5
(1) Meier et al. (1992, ! =0.54)
PDMS
(2) Meier et al. (1992, ! =0.30)
27.0 PDMS
(3) Meier et al. (1992, ! PDMS=0.82)
0.30 0.40 0.50 0.60
0
w 2.0 2.4 2.8 3.2 3.6 4.0
PDMS 3 #1
10 / T (K )
 Pressure Dependence of χ(T)

20

• Fitting the binodal with 16

20 30

the S-L theory yields χ(T,P), 10

3
! x 10
0
12
which can be decoupled
8

200 (a)
P (MPa) 4
2.0 2.4 2.8 3.2 3.6
3 "1
150 30 10 / T (K )
11.0
(oC)

20

! parameters (A, B)
10.0 3
"A x 10
100
10
cp

9.0
T

8.0
50 0 B
7.0

6.0
0 (b)
0.00 0.20 0.40 0.60 0.80 1.00 5.0
0 5 10 15 20 25 30
! P (MPa)
PDMS
Other Thermodynamic Models

• Statistical Associating Fluid Theory (SAFT)

 Uses chains composed of coalesced L-J spheres
 Calculates the residual A as a function of temperature and
density

• Polymer Reference Interaction Site Model (PRISM)

 Generally applicable at different levels of structural detail
 Can be used directly with blends (no mixing rules) and
polymers differing in architecture

• Lattice Cluster Theory (LCT)

 Extension of F-H Theory to include structural details of the
chains
 Can handle compressibility
 Other Valuable Uses of χ

• Helfand and Tagami model

 Infinite molecular weight (mean-field limit)
 Narrow interface approximation (NIA)

"~
(# A2 + #B2 ) ~ $ %1/2
$

"i ~ R g,i

!  χ also yields the PPO/SANS

interfacial
! tension
" ~ #1/2
 Literature Critique

• Purposes:
 Provide additional exposure to the literature
 Hone critical and succinct writing skills
• Objective: write a critical assessment of a
recent literature article
 Topic and sources:
 Phase behavior/thermodynamics of polymer blends
 Macromolecules, Polymer, Phys. Rev. Lett., Macromol. Rapid
Commun., J. Chem. Phys., Biomacromolecules, Macromol.
Chem. Phys.
 2007 only
 References:
 20, excluding websites, books, course notes or patents
 Literature Critique Details

• Format:
 Page 1
 Paper title and full bibliographic citation
 Your name, course name/number and date of submission
 Page 2
 Summary of paper (in your own words)
 Introduction to topic and motivation (in your own words)
 Identification of 5 strong points and 5 weak points (bulleted)
 Page 3
 Critical assessment of strong and weak points with citations
 Recommendation for reading with justification
 Potential improvements
 Page 4
 Full bibliographic references (with title and ending page no.)
• Timeline:
 Paper selection: provide 3 abstracts by 5 pm on Friday, Oct. 5
 Deadline: critique + full paper due by 5 pm on Friday, Oct. 12
 Exam I

• Take-home exam
 Individual basis - no teamwork
 Open (note)book
 Any evidence of collaboration: 0%
 Only on lectures available up to Oct. 4
• Open-ended questions and analyses
• Distributed to class on Oct. 7
• To be returned by 5 pm on Oct. 10
 Commercial Blends: Styrenic

• PS with polybutadiene (PB)

 High-impact PS (HIPS)
 Excellent processability
 Low moisture absorption, shrinkage
 Improved impact strength
 Composition-dependent modulus, toughness, transparency
 Consider replacing PB with ethylene-propylene rubber (EPR)

• PS with polyethylene (PE)

 Similar properties as PS/PB
 Commercial SEBS copolymers: compatibilizers

• Acrylonitrile-butadiene-styrene (ABS) with PB

 Excellent processability
 Weather- and scratch-resistant, impact strength
 Paintable
 Commercial Blends: Styrenic

• ABS with polyamide (PA, nylon)

 Compatibilization is required (PA matrix)
 Good processability
 Flow, high heat and chemical resistance
 Low-T impact strength
 Reduced moisture sensitivity
 Automotive & electrical applications (vibration dampening)

• ABS with polycarbonate (PC)

 Good processability
 High strength, stiffness and good dimensional stability
 Low-T impact strength
 Solvent resistance
 PC is often the matrix

• ABS with poly(vinyl chloride) (PVC)

 Compatibility between AN and PVC
 Good processability
 Excellent impact strength, flame retardance, solvent resistance
 Used in electrical housings and business machines
 Commercial Blends: Styrenic

• ABS with thermoplastic urethane (TPU)

 Blends can be processed in the solid state
 Intermediate hardness, good abrasion resistance
 High toughness and solvent resistance
 Low-T impact strength
 Reduced moisture sensitivity
 Automotive & electrical applications (vibration dampening)

• Brominated PS with PA
 Good flame retardance
 Good mechanical properties and dimensional stability
 Automotive & electrical applications

• Poly(styrene-b-butadiene-b-styrene) (SBS)
 Blend properties insensitive to processing
 Precursor to SEBS copolymers (weather resistance)
 Used primarily as an impact modifier
 Commercial Blends: PVC

• PVC with nitrile rubber (NBR)

 Good processability
 Ozone, heat and oil resistance
 Low-T flexibility
 Excellent weather resistance
 Used in weather stripping, tubing,
roofing, belts, membranes

• PVC with acrylics

 High impact strength, resilience, flame
retardance
 Electrical, solvent and abrasion resistance
 Used in weather-resistant applications

• PVC (and PVDC) with poly(methyl methacrylate) (PMMA)

 May exhibit LCST behavior: chlorination, PMMA tacticity/MW
 Improves rigidity and processability
 PMMA can serve as a compatibilizer for acrylic elastomers
 Commercial Blends: PMMA

• PMMA with polyolefins (PE and PP)

 Highly incompatible; requires compatibilizer
 Originally formulated as plastic paper/wood
 Good tear resistance with LLDPE and SEBS
 High impact strength and modulus

• PMMA with PC
 Can be miscible (LCST > 140°C)
 Modified PC chain ends: LCST > 300°C
 Tough, transparent, abrasion-resistant
 Biphasic blends (via SD) have high yield
stress, modulus and elongation at break

• PMMA with poly(vinylidene fluoride) (PVDF)

 Improved low-T impact strength
 Apparent miscibility depends on composition and molecular weight

Endothermic
 Compatibilized by EPR, reactive blending, radiation (electron/γ)
Crystallinity is non-linearly composition-dependent
(c)

 Properties may exceed those of homopolymers (synergy) (b)
(a)

 Biphasic behavior is detrimental at large strains -100 -50 0 50 100 150 200
Temperature (°C)
 PMMA/PVDF Foams

• Foams provide an alternative to dense polymers

 Less expensive (less material)
 Improved properties
 Lightweight
• Most polymer and blend foams are glassy
 Foaming occurs via introduction of blowing agent at high T & P
 A sudden drop in P or T induces a thermodynamic instability and
bubbles form via nucleation & growth
 The temperature must be quickly dropped to below the Tg to
lock-in the pores before they become too large
 Foaming operations can be conducted batch-wise or continuous
• PVDF/PMMA blend foams would be useful in the wire
and cable industry
PMMA/PVDF Foams

PVDF
PMMA/PVDF Foams

PMMA

a 20 µm

b 20 µm
 PMMA/PVDF Foams

1.40

Cell density (cell/cm )

1.30

Bulk density (g/cm )

3
10
10
a b 1.20

1.10
9
10
1.00

0.90

3
1 08 0.80
140 150 160 170 180 190 200
Temperature (°C)

c d 10 µm