8 VISCOELASTICITY

Basic impulses and responses

creep impulse response stress relaxation

impulse

=G
elastic

(time)
response
viscous elastic viscous
 =   

liquid

viscoelastic viscoelastic

solid solid liquid

8.1 Two parameter models

isotropic body
ideal elastic element (spring) =G

ideal viscous element (dashpot)  =   

8.1.2 Kelvin (Voight)

retarded elasticity
 transition to equilibrium deformed state retarded by viscous resistance

spring = dashpot = 
 spring +  dashpot = 

d
G   
dt
Creep  = f (t) G  
d

(t  0)  = 0 ;  = 0 dt

introduce  = /G [s]

d
G   0  G
dt
 t
d
 
dt

0 
0 G 0

 0   t

 1  e  
G  
 

0
  deformation at equilibrium
G

 retardation time  viscosity

 stiffness of the spring
Reverse creep, Recovery (t  0)  = 0 ;  (0) =  d
G   
dt
t

   e 

Stress relaxation  = 0 (t  0) =0

 = 0 (t  0)   = f (t)

– step change of  at t = 0 – d/dt   –   

– when deformed  = 0 (= const.) – (t) = G0 (= const.)

no stress relaxation
Temperature dependence

G – only small effect, G  const.

 – decreases with T (WLF eq.)   – decreases with T (WLF eq.)
Dynamic straining (periodically changing)

 = 0 sint 0 – amplitude
Tc – time of a cycle, period
 – angular frequency (= 2f)
f – frequency (= 1/Tc)

spring  = G  = G0 sint

G0 = 0 – amplitude

response in phase with impuls

viscous element
d
  = 0  cost = 0 sin(t+/2)
dt

0 = 0 – amplitude

stress is ahead by /2 or deformation is lag behind by /2

viscoelastic materials – deformation is lag behind by angle 

lag angle 0    /2

deformation

stress response

in phase
stress components

out of phase
8.1.2 Maxwell

stress relaxation  spring = dashpot = 

 flow complicated with elasticity spring + dashpot = 

1 d  d
 
G dt  dt

Creep  = f (t) (t  0)  = 0 ;  = 0

d
0 0
dt   0  t
 t
0 
 d  
0 0

dt

(back creep, recovery): at t = t1 :  = 0

elastic recovery (reversible deformation) r = 0 = spring = 0/G

0
set (ireversible deformation) ir = dashpot = t
 1
 1 d  d
Stress relaxation  = 0 (t  0)  = 0  
G dt  dt
 = 0 (t  0)   = f (t)
d/dt = 0

 relaxation time
1 d 
 0
G dt G

 t
d dt
 
 

0 0

t

   0e 
8.2 Multi parameter models

8.2.1 Tucket
deformation of chem. bonds and
linear amorphous polymer intermolecular distances

deformation of polymer coils

Stress relaxation displacement of macromolecules

glass → irreversible, flow

rubber liquid

Creep
flow

glass rubber
8.2.2 Generalised Maxwell

real polymers →more i  wider transition region

G1 G2 G3 Gn

Relaxation modulus G(t) [= (t)/0] of generalised Maxwell model

j
G (t )  Ge   Gi e  t /  i the dependence of Gi on i is called relaxation spectrum
i 1

Relaxation modulus with continuous spectrum g():


G (t )  Ge   g ( )e  t /  d
0

instantaneous elastic response + delayed elastic r. + flow

(non relaxing) (relaxing)

– similarly generalized Kelvin for creep (retardation spectrum)

8.3 Introduction to fenomenological theory of linear viscoelasticity

linear viscoelasticity = direct proportionality between stress and deformation (response always at same time
after impulse – isochronical response)

(t) = G(t) 0

linear

nonlinear

linearity limits (stress 10 MPa)

plastics ca 1 %
rubbers 10 – 100 %
8.3.1 Viscoelastic functions

relaxation test
  (t ) 
G(t) – (time dependant) shear relaxation modulus of elasticity   
  0 
G(ti) = (ti)/0 – isochronical (ti) relaxation shear modulus of elasticity

creep test
  (t ) 
J(t) – (time dependant) creep compliance   
 0 

dynamic test
  
Gd – shear dynamic modulus of elasticity   0 
 0 
= complex modulus of elasticity G* = Gd (cos + i sin) = G + i G
  0 
G – storage modulus of elasticity (real component)   
 0 
  0 
G – loss modulus of elasticity (imaginary component)  
 
 0
also J and 
8.3.2 Boltzmann superposition principle

total response of many impulses is equal to sum of responses of individual impulses

t

example: (Maxwell) G  G0e 

two impulses: at time u1 :  =  (u1)

u2 :  =  (u2)
t

response: t  u1 1(t) = G(t – u1) (u1) = G0e    (u1 )
t

t  u2 2(t) = G(t – u2) (u2) = G0 e    (u 2 )

G(t) = 1(t) + 2(t)

d (u )
differential increments of deformation d = du
du
d (u )
corresponding responses d = G(t – u) d = G(t – u) du
du

d (u)
t
total stress response on deformation (u):  (t )   G(t  u) du
0
d u
Relationship between relaxation and dynamic behaviour
model B
relaxation behaviour G1
G(t )  G1et /   G2 G2

when t0 G(0) = G1 + G2

t G() = G2 () = 0 G2

dynamic behaviour deformation (u) = 0 sin u

t t t
d (u )
 (t )   G (t  u )du   G1 0 cos u  e (t u ) / du   G2 0 cos u  du
0
du 0 0

 (t )   2 2 
 sin t  G1  cos t  G1et /  
G(t) =  G1  G
0  1   2 2 2  1   2 2 1   2 2
 
at steady state:
 G´
G   G1  G2
1 
2 2


G   G1
1   2 2

( K  1)
tg  G1
1  K 2 2

where – transition intensity

G(0) Gd (  ) G1  G2
K  
G() Gd (  0) G2
8.3.3 Mechanical energy absorption
(and its conversion to heat)

absorbed energy w [J m-3]

energy absorbed during one period (Tc) : w – stored (elastic) energy (= 0)

w – lost (viscous) energy

Tc = 2/ w  G 02

1
heat flux Hd = w(Tc ) / Tc  G 0
2
2
8.4 Relaxation transitions in amorphous polymers
8.4.1 Secondary transition

transition between two elastic states at glassy region

example:

PMMA at 25 °C – transition intensity

relatively small (K = 1,5)
– rotation in (side) ester group

polycyclohexyl methacrylate (PCMA) at – 42 °C

– conformation transitions of cyclohexyl ring (chair  boat)

positive effect on mech. properties

– dian polycarbonate
8.4.2 Main transition

transition glass–rubber
large transition intensity – typically K = 1500
wide transition region (6 to 7 decimal orders)  a number of relaxation mechanism – wide spectrum
of relaxation times
loss factor maximum at lower frequency (e.g. 100times for NR) than corresponds to G´´ maximum

temperature ↑  frequency dependence shifted to higher frequencies

(the same curve shape, shift to the right in log-log scale)
 simple thermo rheological behaviour, WLF eq. can be used

Example:

vulcanised NR
8.4.3 Rubber – melt transition

Creep, e.g. PMMA při 110 °C :

compliance slightly  entanglements (physical network)
time  106 s – slope dlogJ(t)/dlogt increases to 1  entanglements relax, physical network tears 
irreversible deformation (flow)
 t t
compliance J    
0  J (t )

part of irreversible deformation (%)

irreversible irreversible compliance Jir(t) = t/

deformation

reversible reversible compliance Jr(t) = J(t)  t/

def.

region
rubber flow
The effect of MW on width of rubbery region and the position of flow region

Polystyrene
curve M [kg mol-1]
1 8.9
2 59
3 113
4 275
5 580

rubber region
- missing at low M
- widening with M
 PS  proportional to M 3.5 (M  40 kg/mol)
M (M  40 kg/mol)

critical mol. weight (Mcr), above that the dependence on M more steep
(„gel point“ of physical network)

M  Mcr log  = log cr  log (Mcr / M)

M  Mcr log  = log cr + log (M / Mcr)3,5

8.4.4 Time-temperature superposition

Superposition :

1. Reference temperature T0, e.g. 110 °C.

2. Log-log dependence at T0 is left in the place and

dependences at other temps. are shifted to
merge (super positioning)  one curve, so-
called generalised dependence of relaxation
modulus on time, which is valid for T0.
The shift log aT for every temperature differences T –T0 (temp. T) can be plotted

log aT = log t – log t0

aT = t/t0

1/t, 1/t0 measures of relaxation rates

1/aT – relative relaxation at T
(related to T0)

model B: t/ = t0/0 = const.  aT = T/To

(thermo rheologically simple polymer)

The temperature dependence of aT  WLF above Tg

8.4 Molecular theories

- Kelvin model
isolated chain → entropic spring, F1 = 2ktb2 r = k1 r
in zero viscosity environment → statistical theory of entropic elasticity
dr
in non-zero viscosity environment → F2 = k2
dt
F1 + F2 = F
dr
k1r  k2 F chain
dt
d
G    Kelvin
dt
 - flexible chain models  the simplest model by Raus:

conception:
 polymer chain divided into submolecules,
 beads connected with springs
springs: freely jointed chains the same in length
 only beads interact with viscous environment

Solution: generalised Maxwell model with m members

m  1 
relaxation modulus G(t) = NkT   
exp 

p 1  p 
if m  1 p = 1 / p2 , p = 1, 2, ... , m

k f ,s Z 2 a 2
1 = – end relaxation time
6 2 p 2 kT

– proportional to M 2 (no entanglements)

M 4,5 (entanglements)
– significantly depends on temperature (all members)
 simple thermo rheological behaviour
 verification of time – temperature equivalence superposition