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2014 | OriginalPaper | Chapter

7. Rheology of Polymer Alloys and Blends

Authors : Musa R. Kamal, Leszek A. Utracki, A. Mirzadeh

Published in: Polymer Blends Handbook

Publisher: Springer Netherlands

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Abstract

This chapter presents an overview of some of the important principles and characteristics associated with the rheological behavior of polymer blends. Initially, the chapter reports the observations and the scientific laws that illustrate and govern the rheological behavior of classical suspensions and emulsions of simple non-polymeric liquids. It is indicated that one of the main characteristics that differentiates the rheological behavior of polymer blends from that of simpler liquids is the viscoelastic nature of polymers and their blends. The discussion also points out the relationship between blend morphology and rheology and the importance of surface energy effects, such as interparticle and interfacial interactions. The general rheological characteristics of miscible polymer systems are considered. However, since the majority of polymers are immiscible, the rheological behavior of immiscible polymer blends is considered in more detail, with allowance for both thermodynamic and morphological factors. The influence of flow on morphology, as in phase separation, drop deformation, breakup, and fiber formation are discussed. Both viscous and viscoelastic characteristics of blend behavior are described, under the influence of shear and elongational flow fields. Various examples are presented, based on the study of rheological behavior of blends in both rheological testing devices (parallel plate, rotational, steady state, oscillatory, capillary, elongational, etc.) and processing equipment (extruders, mixers, molds, dies, etc.). In many cases, the observed rheological behavior is compared to the predictions of theoretical, computational, or empirical models.

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Glossary
Notations (Roman Letters)
a, b, k, K, n, u, β
Equation constants
av
Interfacial area density
BAB
Reduced binary thermodynamic interaction parameter, BAB = χABRT/V
B
Droplet width
bi
Segment length
ci
Lee and Park relaxation parameters
D
Deformation
d
Droplet diameter
d*
Equilibrium droplet diameter
D, DM, Ds
Diffusion, inter diffusion and self diffusion coefficient, respectively
Dp
Particle diffusion coefficient
E+
Threshold energy of coagulation
EDK
Macroscopic bulk breaking energy
F
Intrinsic thermodynamic function
f
Frequency
G*, G′, G″
Complex, storage and loss shear modulus, respectively
H(τ)
Relaxation time spectrum
\( \tilde{\mathbf{H}}\left(\boldsymbol{\upomega} \right) \)
Reduced frequency relaxation spectrum
\( {\tilde{\mathbf{H}}}_{\mathbf{G}}\left(\boldsymbol{\upomega} \right) \)
Gross’ frequency relaxation spectrum
Hmax
Maximum of the relaxation spectrum
hc
Critical separation distance
kB
Boltzmann constant
L
Droplet length
M
Onsager-type mobility factor
Mn, Mw, Mz
Number, weight and z-average molecular weight, respectively
N1 = σ11 − σ22
First normal stress difference
No,N
Initial and final number of particles respectively
No, N+
Number of coagulating drops, initially and at t = tc
NT
Total number of collisions per unit time
n
Number of particles
ni
Number of moles unit volume
P
Pressure
Pe
Peclet number
pr
Probability that two particles that have collided result in coalescence
q
Wave vector, or sinusoidal distortion
R
Ideal gas constant
Re
Reynolds number or real part of a complex function
R(q)
Fluctuation function
\( \overline{\mathbf{r}} \)
Reduced drop radius
〈r Θ 2 〉1/2
Unperturbed, average radius of gyration
rad
Radian
rN
Radius of the critical nucleus
S(q), S0
Virtual structure function
So, S
Interfacial area per unit volume of the blend for monodispersed spherical particles before and after coalescence, respectively
s
Spinodal
T
Absolute temperature
Tg
Glass transition temperature
t
Time
tb
Necessary time for breakup of droplets
tb*
Dimensionless breakup time
tc
Coalescence time
UCST
Upper critical solubility temperature
V
Volume
Vx/V
Volume fraction of emulsion undergoing uniform shear
z
Reduced frequency, f · τ
Notation (Greek Letters)
α
Orientation angle
αo
The distortion at t = 0
β12
Interlayer slip factor
χAΒ
Binary thermodynamic interaction parameter between polymers A and B
Δ
Thermodynamic distance from the spinodal; Δ ≡ 2((χN)s−N)
ΔΕ
Activation energy, e.g., of flow: ΔΕη
ΔGm
Gibbs free energy of mixing
ΔHm, ΔSm
Enthalpy and entropy of mixing, respectively
ε, \( \dot{\boldsymbol{\upvarepsilon}} \)
Hencky strain and Hencky strain rate in extension, respectively
ϕ1, ϕ2
Volume fraction of dispersed and matrix phase, respectively
ϕc
Volume fraction of the cross-linked monomer units
ϕi
Volume fraction of phase i at phase inversion
ϕm
Maximum packing volume fraction
ϕperc
Percolation threshold
γ, \( \dot{\boldsymbol{\upgamma}} \)
Shear strain and rate of shearing, respectively
η
Viscosity
ηo
Zero-shear viscosity
ηr
Relative viscosity
[η]
Intrinsic viscosity
η′
Dynamic viscosity
η*
Complex viscosity
η1, η2
Viscosity of dispersed and matrix phase, respectively
κ = σιφd/ν12
Capillary number
κcrit
Critical capillary number
Λ
Distortion wavelength
λ = η1/η2
Viscosity ratio
λs
Wavelength
ν 12 o
Interfacial tension in a quiescent blends
ν12
Interfacial tension coefficient between phase 1 and 2
ρ
Density
ρd
Droplet density
σ
Stress
σ11
Extensional stress
σ11 − σ22 = N1
First normal stress difference
σ12
Shear stress
sm
Stress in the matrix phase
σy
Yield stress
σy o
Permanent yield stress
τ
Relaxation time
t*
Mean relaxation time
Ω(Λ, λ)
Tabulated function for capillary instability
ω
Angular frequency
ωmax
Frequency at which \( \tilde{H}\left(\omega \right) \) is maximum
ωx
Crossover frequency
ψ1, ψ2
First and second normal stress difference coefficient, respectively
Abbreviations
ABS
Acrylonitrile-butadiene-styrene
EFM
Extensional flow mixer
EPDM
Ethylene-propylene-diene terpolymer
EPR
Ethylene-propylene rubber
EVAc
Ethylene-vinyl acetate copolymer
HDPE
High density polyethylene
HIPS
High impact polystyrene
IPN
Interpenetrating networks
LDPE
Low density polyethylene
LLDPE
Linear low density polyethylene
NG
Nucleation and growth
NR
Natural rubber
PA
Polyamide
PAA
Polyacrylic acid
PB
Polybutadiene
PC
Polycarbonate
PCL
Polcaprolactone
PE
Polyethylene
PEO
Polyethylene oxide (or polyethyleneglycol, PEG)
PEMA
Poly(ethyl methacrylate)
Phenoxy
Polyhydroxyether of bis-phenol A
PMMA
Polymethylmethacrylate
PnBA
Poly(n-butyl)acrylate
PP
Polypropylene
PPE
Polyphenyleneether
PS, PSD
Polystyrene, deuterated PS
PSF
Polysulfone
PVC
Polyvinyl chloride
PVME
Polyvinylmethylether
RMS
Rheometrics Mechanical Spectrometer
RSR
Rheometrics Stress Rheometer
SBR
Styrene-butadiene rubber
SBS
Styrene-butadiene-styrene three block copolymer
SD
Spinodal decomposition
SEBS
Styrene-ethylene/butene-styrene three block copolymer
SEC
Size exclusion chromatography
SIN
Simultaneous interpenetrating polymer networks
SSE
Single-screw extruder
TP
Thermoplastic resin
TS
Thermoset resin
TSE
Twin-screw extruder
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Metadata
Title
Rheology of Polymer Alloys and Blends
Authors
Musa R. Kamal
Leszek A. Utracki
A. Mirzadeh
Copyright Year
2014
Publisher
Springer Netherlands
DOI
https://doi.org/10.1007/978-94-007-6064-6_9

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