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Laser-Interferometric Creep Rate Spectroscopy of Polymers

  • Vladimir A. BershteinEmail author
  • Pavel N. Yakushev
Chapter
Part of the Advances in Polymer Science book series (POLYMER, volume 230)

Abstract

Laser-interferometric creep rate meter (LICRM) and creep rate spectroscopy (CRS), as an original high-resolution method for discrete relaxation spectrometry and thermal analysis, were developed in the authors’ Materials Dynamics Laboratory at Ioffe Physical-Technical Institute of the Russian Academy of Sciences (Saint-Petersburg). In the last few decades they have been successfully applied to solving various problems of polymer physics and materials science, especially being combined with DSC, structural, and other techniques. CRS involves measuring ultra-precisely a creep rate at small tensile or compressive stress, typically much lower than the yield stress, as a function of temperature, over the range from 100 to 800 K. LICRM setup allows one to register precisely creep rates on the basis of deformation increment of 150–300 nm. The survey describes this method and summarizes the results of numerous studies performed with the LICRM setup and CRS technique for different bulk polymeric materials, films, or thin fibers. This approach provided new experimental possibilities superior in resolution and sensitivity compared to the conventional relaxation spectrometry techniques. Among such possibilities are discrete analysis of dynamics; creep on submicro-, micro- and meso-scales; revealing relations between stepwise microplasticity and morphology; kinetic information on creep at any temperature and deformation; polymer dynamics at interfaces; analysis of microplasticity, relaxations, and phase transitions in brittle materials; using creep rate spectra for non-destructive prediction of temperature anomalies in mechanical behavior of materials, etc. Considerable attention has been paid to combined CRS/DSC analysis of the peculiarities of segmental dynamics, nanoscale dynamic, and compositional heterogeneity in different kinds of complex polymer systems and nanocomposites.

Keywords

Complex polymer systems Deformation kinetics Dynamic heterogeneity Glass transition anomalies Laser interferometry Microplasticity vs morphology Polymer creep Relaxation dynamics 

Abbreviations

BCP

Block copolymer

BLS

Brilllouin light scattering

CNT

Carbon nanotube

CR

Creep rate (spectra, peaks)

CRS

Laser-interferometric creep rate spectroscopy

DBP

Dibutyl phthalate

DMA

Dynamic mechanical analysis

DMA(σ)

Dynamic mechanical analysis of the statically loaded solids

DRS

Dielectric relaxation spectrometry

DSC

Differential scanning calorimetry

FIRS

Far-infrared spectroscopy

FT-IR

Fourier-transform infrared spectroscopy

HDPE

High-density polyethylene

HEMA

2-Hydroxyethyl methacrylate

IPN

Interpenetrating polymer network

IRS

Infrared spectroscopy

LI

Laser interferometer; Laser interferometry

LICRM

Laser-interferometric creep rate meter

MAA

Methacrylic acid

MDS

Molecular-dynamics simulations

MMT

Montmorillonite (silicate nanolayers)

ND

Nanodiamond

NMR

Nuclear magnetic resonance

ODA

Oxydianiline

PAN

Polyacrylonitrile

PB

Polybutadiene

PBMA

Poly(n-butyl methacrylate)

PC

Polycarbonate

PCN

Polycyanurate

PDMS

Poly(dimethyl siloxane)

PE

Polyethylene

PEA

Poly(ethylene adipate)

PEG

Poly(ethylene glycol)

PEO

Poly(ethylene oxide)

PET

Poly(ethylene terephthalate)

PHEMA

Poly(2-hydroxyethyl methacrylate)

PI

Polyimide

PIA

Poly(imide-amide)

PMDA

Pyromellitic dianhydride

PMMA

Poly(methyl methacrylate)

PMPS

Poly(methylphenylsiloxane)

PMS

Poly(α-methylstyrene)

POM

Poly(oxymethylene)

PS

Polystyrene

PTFE

Poly(tetrafluoroethylene)

PTMG

Poly(tetramethylene glycol)

PU

Polyurethane

PVB

Poly(vinyl butyral)

PVC

Poly(vinyl chloride)

PVME

Poly(vinyl methyl ether)

PVP

Poly(vinyl pyrrolidone)

QENS

Quasi-elastic neutron scattering

RAF

Rigid amorphous fraction

SANS

Small-angle neutron scaterring

SAXS

Small-angle X-ray scattering

SEM

Scanning electron microscopy

TDI

Toluene diisocyanate

TEM

Transmission electron microscopy

TMP

Trimethylolpropane

TSDC

Thermally stimulated depolarization currents

UHMWPE

Ultrahigh-molecular-weight polyethylene

WAXD

Wide-angle X-ray diffraction

Symbols

E, Q

Activation energy

Q0

Activation energy of deformation

Qα

Activation energy of α-relaxation (glass transition)

Qβ

Activation energy of β-relaxation

ΔS

Activation entropy

vact

Activation volume

α

Activation volume of deformation

Vα

Activation volume of α-relaxation (glass transition)

Vβ

Activation volume of β-relaxation

REE

Average end-to-end distance for unperturbed macromolecule (random coil size)

Tβ

Beta-relaxation temperature

Ecoh

Cohesion energy

Tg′′

Completion glass transition temperature

\(\dot{\epsilon }\)

Creep rate (velocity of the moving mirror)

Tc

Crossover temperature in the Mode Coupling Theory

L

Deformation step in jump-like creep

vCRR

Donth’s cooperatively rearranging region

Δω

Doppler shift

νeq

Equivalent frequency

Qη

Flow activation energy

Tf

Flow temperature

ν

Frequency, Beat frequency

R

Gas constant

ΔTg

Glass transition range

Tg

Glass transition temperature

ΔCp

Heat capacity step

ω1

Incident laser beam frequency

I1

Incident laser beam intensity

Qi, Qi′′, Qi′′′

“Intermediate” relaxations activation energies

Ti, Ti′′, Ti′′′

“Intermediate” relaxations temperatures

EIMI

Intermolecular interactions energy

Q0− 1

Internal friction (DMA)

Qτ− 1

Internal friction under static loading [DMA(σ)]

B

Internal rotation barrier in chains

H

Jump sharpness in stepwise creep, Film thickness

A

Kuhn segment length

λ

Laser wavelength

C

Light velocity

Tll

“Liquid–liquid” transition temperature

tm

Maximal tangential stress

Tm

Melting point

Cm

Mobile fraction (NMR)

VM

Molar volume

σ

Normal stress

Nk

Number of monomer units in Kuhn segment

m

Number of monomer units per a kinetic unit (activation volume) of deformation

N

Number of oscillations (beats) in the interferogram

Mn

Number-average molecular mass

Tg

Onset glass transition temperature

Z

Parameter of cooperativity in segmental motion

qi

Partial energy barrier (per mole of monomer units) in deformation kinetics

\(\dot{{\epsilon }}_{0}\)

Pre-exponential factor (deformation kinetics)

Rg

Radius of gyration

ω2

Reflected laser beam frequency

I2

Reflected laser beam intensity

I

Resultant laser beam intensity

τsh

Shear stress

δ

Solubility parameter

Ts

Splitting (bifurcation) point

T

Temperature

t

Time

ε

Total creep value

V

Volume of monomer unit, Heating rate

Mw

Weight-average molecular mass

εy

Yield point deformation

σy

Yield stress (point)

Notes

Acknowledgements

The authors gratefully acknowledge the significant contributions which a number of our colleagues from the Ioffe Institute made to the study of the problems considered in this survey. We are grateful to the late Dr. G.S. Pugachev for his leading role in the development of the first LICRM setup. We would also like to express our deep gratitude to Dr. N.N. Peschanskaya, the author of numerous important studies in this field performed for over 30 years. We thank also our other co-authors in some of the CRS studies, Drs. A.B. Sinani, V.A. Marikhin, L.P. Myasnikova, and V.V. Shpeizman. Finally, we are grateful to Dr. V.M. Egorov and Mrs. L.M. Egorova for their long-time fruitful participation in the combined CRS/DSC studies.

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© Springer 2010

Authors and Affiliations

  1. 1.Ioffe Physical-Technical Institute of the Russian Academy of SciencesSaint-PetersburgRussia

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