Viscoelasticity

Rheology: The study of deformation or flow behavior exhibited by materials. Therefore, according to Rheology, which is regarding to the science of flow, viscous flow and elasticity are only two extreme forms of the possible types of behavior of matter.

All materials have viscoelasticity, which is a combination of viscosity and elasticity in varying amounts. When this viscoelasticity is measured dynamically, there is a phase shift between the force applied (stress) and the deformation (strain) which occurs in response. The tensile stress and the deformation (strain) are related via the elasticity modulus G as follows: =G or S = GE

Polymers are not ideal energy elastic bodies; they are viscoelastic materials. In such cases the deformation (strain) lags behind the applied stress.
For low molecular weight solids and liquids exhibit their characteristic flow behavior according to Hookean equation and Newton equation respectively.

spring

E (elongation)

Spring model (Hookean)

An ideal solid behavior obey Hookes law.

load

t1

t2

T (time)

t1 - load apply to solid materials (spring) solid elongates to a certain length instantaneously t1 t2 extended length remains, as long as load is retained

t2 - load applied is removed solid goes back to original length instantaneously

For ideal solid, it elongates instantaneously upon applying load and retracts instantaneously when unloaded elasticity eg. A deformation behavior of an ideal solid - elastic deformation and is time- independent Plot of stress-strain (S- E) or force elongations From the plot it shows the applied stress, S is proportional to a resultant strain, E, and is independent of the rate of strain, (dE/dt) Hookes law, S = GE

S (tegasan)

hard

soft

Elasticity modulus - a quantity represents for material resistance to deform, eg. Hardness.

Dash pot Model

An ideal liquid behavior obey Newtons law.

Elongation vs time plot E B

A t1 t2 t

piston Viscous liquid

t1 - force apply to viscous liquid the piston elongates to a certain position until force is released at time t2

t2 flow stops but the material (piston) not recovers its original position or shape
The deformation is permanent and time-dependent viscous flow

Stress strain plot S Applied stress (s) is proportional to strain rate dE/dt but is independent of strain Newtons law

S dE/dt
S = (dE/dt) E= S

= liquid viscosity
- The higher the liquid viscosity the lesser is its flowing tendency.

This flow behavior can be compared to the a shock absorber (dash pot). In the dash pot, the viscous liquid is does not allow the piston to move past, even an attempt to pull the piston forcibly is made. Its will move slowly. On releasing the force, the piston cannot move back to it original place because of the viscous liquid permanent deformation (displacement)

With both two basic models, the spring and dash pot way help us to studying and understanding the deformation behavior of many materials.

Steel spring with G represents the behavior of a elastic solid

Dash pot with liquid of viscosity represents the behavior of viscous flow

G Hookes model Newtons model

Maxwell and Voigt Models

W
Maxwell Model spring and dash pot in series Voigt Model spring and dash pot in parallel

Maxwell Model spring and dash pot in series Maxwell studied behavior of some metals, copper and lead found to be exhibited deformation as below: E

A copper wire when loaded, immediately elongates to a certain length and then continues to elongate slowly. While unloading retracts immediately as much as a first elongation, and remains permanent lt set at that length.

Etotal = Espring + Edash pot

B D Etotal = S S + G t

Plot of S versus E
A t1 t2 S t

AB = CD represent the spring model elasticity of deformation BC elongation and set at D represent the viscous flow of deformation

Voigt Model spring and dash pot in parallel Voigt studied behavior of a rubber band being stretched E

When loading it elongates and upon unloading regain it original shape. It look like spring elastic, but is not true!! When applying a small load at t1 the material elongates slowly and continuously till the load is released at t2, On releasing load, recovery is not intantaneous but rather slowly and continuously and also complete to original shape.

t1

t2

Stotal = Sspring + Sdash pot

Stotal = GE +

dE
dt E

Stress-strain curves for different types of polymeric materials

S
5 4

3
1 2

The curves appearance depending on egs. Tg, degree of crosslinking and crystallinity of the polymeric materials

1. Soft and tough (amorphous) 2. Soft and weak (highly crystalline) 3. Hard and tough (partially crystalline) 4. Hard and strong (amorphous 5. Hard and brittle (amorphous)

Burger Model

Burger Model Represents the combination of deformation behavior of the polymeric materials
3 4 2 5 1

G1

G2

n1

t1

t2

n2

1. 2. 3. 4. 5.

Exhibit instantaneous elongation Exhibit delayed elongation Exhibit instantaneous recovery Delay recovery Permanent set, deformed state!!

Maxwell model

Voigt model

Standard Linear Solid model

Schematic of Maxwell-Wiechert Model

Relaxation and Retardation (creep)

If an elastomeric polymer is stretch rapidly and release it back immediately the material exhibits elasticity and regain it original shape. But what happen if it is slowly stretched and keep it under stretch for a longer time? Or what happen after a long time being stretched under a minimum load and then the load is released? The polymer behave like a viscous flow characteristic and shall undergo greater degree of permanent deformation.

Relaxation

Retardation (creep)

t1

t3

t2 S E

creep

Maxwell Model for Relaxation

Et = Espring + Evisco
dE = dt
1 dS + G dt

S/G + (S/)t
remember! ln a = x a = ex

dE =0 dt S dS S So

=
G

1 dS G dt

S So

G t

=e

t =

dt
dt

G t = So exp

S ln So
ln

trelax = S

G t trelax

S So

= So exp

trelax; time taken for the stress to fall to a value 1/e of So or from S0 to 0.37 S0

So
0.37

trelax

Voigt Model for Retardation

St = Sspring + Svisco = GE + dE/dt

Quiz: prove the equation

E tret =

= G

S G

1 - exp

t tret

tred; time taken for the elongated model at Eto recover (after release of load) to 0.63E value

0.63E

tred

Schematic representation of conformation assumed by polymer molecules undergoing relaxation and retardation (creep)

Under creep (retardation) the position of the molecule within the material does not change but only their conformation does!
unstrained

under relaxation, molecules take an enough long time to slip into new position

Time Temperature Superposition

It is often important to know how polymeric materials will behave (eg. relaxation and creep) at a fixed temperature but over a long period of time.
Measurements over long time periods (perhaps years) may not be feasible. Fortunately, it was found that by obtaining stressrelaxation or creep data over short time periods but at several different temperatures it is possible to estimate long-time behavior.

According to the time-temperature superposition method, one first obtains modulus data (e.g. tensile modulus) for different frequencies, ( note that ( t = 1/ ), then each constant temperature curve is shifted along the log-time axis which is equivalent to dividing every value of it abscissa by a constant factor. The constant factor which brings a curve at a particular temperature T into alignment with the one at the reference temperature is known as the temperature shift factor, aT

aT = t / tr

tr - time at tr tr - ref. temperature

In other words, the time-temperature superposition principle says that E(T,t) = E (Tr, tr) The dependence of aT on temperature is given by the Williams-Landel-Ferry (WLF) relationship Log aT = - C1 ( T Tr ) C2 + T - Tr

C1, C2 constants for the given polymer. When Tr =Tg ; C1 and C2 can be approximated by C1 = 17.44 and C2 = 51.6 If C1 and C2 are not known each curve is shifted to the reference temperature (Tr) and aT is determined ( aT = t/Tr ). Subsequently, C1 and C2 are determined by plotting

(T-Tr)
Log aT

vs ( T-Tr )

i.e

(T-Tr)
Log aT

= - 1/C1 ( T-Tr ) C2/C1

e.g. : Time-temperature superposition (polyisobutylene) : Tensile (Young modulus E ( t ) vs time on a log-log scale r