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Physical Aging of Polymer Blends

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Polymer Blends Handbook

Abstract

The selection of polymers and polymer blends for use as specific materials requires the consideration of how these will withstand the environmental conditions to which these will be subjected. The long-term stability of a polymer will depend on its aging characteristics both physical and chemical.

Physical aging is the term used to describe the observed changes in properties of glassy materials as a function of storage time, at a temperature below the glass transition, T g . This phenomenon is important mainly when the materials have a substantial amorphous content. For these materials, a quench from above T g into the glassy state introduces a nonequilibrium structure which, on annealing at constant temperature, approaches an equilibrium state via small-scale relaxation processes in the glassy state. The aging process can be detected through the time evolution of thermodynamic properties such as the specific volume or enthalpy or mechanical methods such as creep, stress-relaxation, and dynamic mechanical measurements. Here, the fundamental principles of physical aging will be described, and models that quantitatively describe the aging process are briefly described.

Physical aging effects have practical implications and need to be considered when assessing the long-term stability of polymers and polymer–polymer mixtures. This chapter focuses on a discussion of the effect of blending on physical aging and gives a review of the different experimental methods that can be used to compare aging rates in blends to those of the individual components.

J. M. G. Cowie: Deceased.

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Authors and Affiliations

  1. Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, UK

    J. M. G. Cowie & V. Arrighi

Authors
  1. J. M. G. Cowie
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  2. V. Arrighi
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Corresponding author

Correspondence to V. Arrighi .

Editor information

Editors and Affiliations

  1. Industrial Materials Institute, National Research Council of Canada, Boucherville, Québec, Canada

    Leszek A. Utracki

  2. Department of Chemistry and Fire Retardant Research Facility, Marquette University, Milwaukee, Wisconsin, USA

    Charles A. Wilkie

Abbreviations

ABS

Acrylonitrile–butadiene–styrene

AIM

Acrylic Impact Modifier

AN

Acrylonitrile

BPAPC

Bisphenol-A polycarbonate

CCS-PS

Core cross-linked star PS

CPSF

Carboxylated polysulfone

C-F

Cowie–Ferguson model

Dil

Dilatometry

DSC

Differential scanning calorimetry

FTIR

Fourier-transform infrared spectroscopy

GD

Gibbs and Di Marzio theory

G-M

Gomez-Ribelles and Monleon-Padras model

HS

4-Hydroxystyrene

IPN

Interpenetrating network

KWW

Kohlrausch, Williams, and Watts function

Mech

Mechanical

NR

Natural rubber

PALS

Positronium annihilation lifetime spectroscopy

PB

Polybutadiene

PEEK

Polyether ether ketone

PEG

Polyethylene glycol

PEI

Polyether imide

PEMA

Poly(ethyl methacrylate)

PEO

Polyethylene oxide

PES

Poly(ether sulfone)

PHS

Poly(hydroxy styrene)

PiPMA

Poly(isopropyl methacrylate)

PLA

Poly(lactic acid)

PMA

Polymethacrylate

PMMA

Poly(methyl methacrylate)

PPO

Poly(p-phenylene oxide) or poly(2,6-dimethyl-1,4-phenylene ether) (PPE)

PPS

Polyphenylene sulfide

PS

Polystyrene (atactic)

PSF

Polysulfone

P-M

Petrie–Marshall model

PU

Polyurethane

PVAc

Polyvinyl acetate

PVC

Polyvinyl chloride

PVDF

Polyvinylidenefluoride

PVME

Poly(vinyl methyl ether)

P2VP

Poly(2-vinylpyridine)

PVP

Poly(N-vinyl pyrrolidone)

SAN

Poly(styrene-stat-acrylonitrile)

S

Styrene

SBR

Styrene butadiene rubber

SEBS

Hydrogenated styrene–butadiene–styrene block copolymer

SMA

Styrene-co-maleic anhydride

S-S

Theory of Simha–Somcynsky

TNM

Tool–Narayanaswamy–Moynihan model

VA

Vinyl alcohol

VAc

Vinyl acetate

A

Fitting constant

b V

Volume relaxation rate

C p

Heat capacity

C T

Adjustable temperature coefficient

C t

Adjustable time coefficient

ΔC p

Heat capacity change

D o

Creep compliance at zero time

D(t)

Creep compliance at time t

E o

Modulus at zero time

E(t)

Modulus at time t

G o

Stress-relaxation moduli at zero time

G(t)

Stress-relaxation moduli at time t

H

Enthalpy

H(∞)

Equilibrium enthalpy value

ΔH

Enthalpy change

Δh *

Effective activation energy

e+

Positively charged positron

I 3

Relative intensity of the oPs component

oPs

Ortho-positronium

Ps

Positronium

q

Cooling rate

r

Cavity radius

R

Gas constant

S c

Configurational entropy

t

Time

T

Temperature

t a

Annealing time

T a

Annealing temperature

t c

Characteristic time

T f

Fictive temperature

T g

Glass transition temperature

V

Specific volume

V ∞

Specific volume at equilibrium, at temperature T

x

Structural parameter

β

Parameter of KWW function

β T

Isothermal compressibility

δ

Departure from equilibrium

ε

Strain

Ï•(t)

Relaxation function

σ

Stress

μ

Shift factor

Ï„

Relaxation time

Ï„ 3

oPs lifetime

Ï„ o

Equilibrium relaxation time

ω c

Critical frequency

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Cowie, J.M.G., Arrighi, V. (2014). Physical Aging of Polymer Blends. In: Utracki, L., Wilkie, C. (eds) Polymer Blends Handbook. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-6064-6_15

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