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Mechanical Properties of Polymers

Deformation of Materials
plastic Lo L L rubber

Effective spring constant of the material: Material dependent property (modulus):

Youngs modulus (E) specifies resistance of the material to elongations at small deformations.

k = F / L F/A M= L / L0

Dependence of the Modulus vs Temperature

Dependence of the Modulus vs Time

Schematic modulus-time curve for a polymer at constant temperature

Specific-volume vs Temperature

Specific-volume data for poly(vinyl acetate) used to determine glass transition temperature Tg.

Phenomenological Treatment of Viscoelasticity

Elastic Modulus
Stress force per unit area X F Y

Z F

F F E = = A YZ
Tensile strain resulted form application of uniaxial stress

X = X

Tensile modulus and the tensile compliance:

E 1 = E= D
Units: dynes/cm2 (dynes per square centimeter), or N/m2 (Newton per square meter)

Elastic Modulus
Shear deformation X X Z Y F Shear strain: X F Shear stress:

F = ZX X = = tan Y

Shear modulus G and shear compliance J are defined as

1 G= = J

Deformation at Constant Volume


Initial state F Deformed state Material stress ij is a stress produced by the deformed material. Fx x

xx

Fx = Ax

Ax y

Deformation at Constant Volume


Force balance at the boundary pAx xxAx pAy yyAy xxAx

xx = xx + p xx = xx p

or rearranging

yy = p xx = xx yy

Deformation at Constant Volume


Hooks law

ij = G ij

where ij is a deformation tensor The definition of the deformation should be consistent with the shear experiment u u

ij =

x j

xi
u y y u y y u y y

where x1=x, x2=y and x3=z Tensile experiment

xx

u x u x = + = 2 x x

yy =

=2

Deformation at Constant Volume


Relation between Shear and Youngs modulus

xx = xx yy = G ( xx yy ) = G (2 ( ) ) = 3G
Using the definition of the Youngs modulus

E = E = xx
E = 3G
Sample does not change volume!!!

Poissons Ratio
1 1 1 Volume change upon deformation 1+ 1- 1-

V = (1 + )(1 ) 1 (1 2 )
2

No volume change when the Poissons ratio =1/2 General relation between Shear and Youngs modulus

E G= 2(1 + )

Elastic Properties of Polymers as Compared to Other Materials (T=300K)

Understanding the mechanical response on the molecular level


The elastic properties of solids (glasses) is a result of the Intermolecular forces between the atoms. The force acting between atoms at small deformations is equal to

F = k ( x a)
a Deformed sample The area per atom is equal to a2 and the tensile stress is written as

k ( x a) k ( x a) = = = E 2 a a a
Youngs Modulus E=k/a

Understanding the mechanical response on the molecular level


The constant k is obtained by expanding intermolecular potential around the equilibrium separation a
2 dU x 1 ( ) U ( x) = U (a ) + ( x a ) 2 dx 2 2

k ( x a) 2 + ... = const + 2 x=a

Thus, we find

dU ( x) 2 k= dx 2

For a potential U(x)=f(x/a) which has a minimum value at x=a


dU ( x) 2 k= dx 2 =
x=a

x=a

int
a2

f (1)
''

E=

int
a3

f '' (1)

Molecular Rearrangements
Liquid t~ 10-10 sec

Solids

t>>100 sec

Polymer chain

t~100 sec

t~ 10-9 sec T>>Tg

Linear Viscoelasticity
Viscose Response of a Liquid The Newtonian liquid obeys the equation v

d d = = dt dt
+ e viscose

where is the viscosity of liquid e v

Linear viscoelasticity = elastic

d = G + dt

e e

v v

Readings:
Ch. 1,2 p.p.1-33, M. T. Swah, W. J. MacKnight, Introduction to Polymer Viscoelasticity. Ch. 6. p.p. 162-174 D. I. Bower, An Introduction to Polymer Physics

Creep response of material to a constant stress, . Liquid Strain

/Geq

In these experiments the strain is monitored as function of time, (t). The creep compliance J(t) is defined as the ratio of the time dependent strain (t) and the applied stress

Jeq

Solid Time

(t ) J (t )

Stress-relaxation - response of materials to a constant strain, . In these experiments the stress is monitored as function of time, (t). Solid Liquid Time The stress relaxation modulus G(t) is defined Geq as the ratio of the time dependent stress (t) and the applied strain Stress

(t ) G (t )

Mechanical Models of Viscoelastic Materials

The Maxwell Model


This model consists of a spring and dashpot in series For spring s, s, G

s = G s

d, d, For elements connected in series

d d For the dashpot d = dt

=s =d
d 1 d = + dt G dt

and

= s +d

The Maxwell Model


Creep experiment: deformation at constant stress d/dt=0

d 1 d = + = dt G dt
Solving the equation with initial conditions at time t=0

0 (t ) 1 t = J (t ) = + (t ) = 0 + t G 0
This illustrates that the compliance of the Maxwell model increases without limit, a behavior characteristic for viscoelastic fluids.

The Maxwell Model


Creep experiment:

(t)

(t)

0 Time

The Maxwell Model


Stress relaxation experiment: deformation at constant strain d/dt=0

d 1 d 1 d = + = dt G dt G dt
Solving the equation

= dt = , where = G dt t ln( (t )) = ln 0 (t ) = 0 exp


The stress decays to zero at infinite time!!!

dt

(t ) 0 t t G (t ) = exp = G exp = 0 0

The Maxwell Model


The response of the Maxwell model in a stress relaxation experiments corresponds to an elastic solid at t<< and to a viscose fluid at t>>.

t G, for t << G (t ) = G exp 0, for t >>

The Maxwell Model


Stress-relaxation experiment: (t) 0

(t)
G0

Time

The Voigt Model


This model consists of a spring and dashpot in parallel For spring s, s, G d, d,

s = G s

d d For the dashpot d = dt


For elements connected in parallels

= s +d

and

=s =d

d = G + dt

The Voigt Model


Creep experiment: deformation at constant stress =0

d 0 = G + dt
0
Solution of this equation is

t (t ) = 1 exp G

G , where = is retardation time

The Voigt Model


Creep experiment:

(t)

(t) 0/G

Time

The Voigt Model


Stress relaxation experiment: deformation at constant strain d/dt=0

d = G + dt

= G

This model can not describe stress relaxation !!!!

More Complicated Models


Generalized Maxwell Model Voigt-Kelvin Model

.. {Gi, i} {Gi, i}

These models describe systems with multiple relaxation times.

Generalized Maxwell Can Describe Relaxation Process in Real Polymers

The Boltzmann Superposition Principle


The strain from any combination of small step stresses is the linear combination of the strains resulting from each individual step i applied at time ti

(t)
2 1 (t) t1 t2 2J(t-t2)

1J(t-t1)

The Boltzmann Superposition Principle


For the multi-step loading program:

(t ) = 1 J (t t1 ) + 2 J (t t 2 ) + 3 J (t t3 ) + ..
For continuously changing stress:
t

d (t s ) dt s (t ) = J (t t s )d (t s ) = J (t t s ) dt s
t

For the strain experiments

d (t s ) dt s (t ) = G (t t s )d (t s ) = G (t t s ) dt s
t t

Creep and Recovery


(t)
0 t1 t2

(t)

Dynamic Measurements
A sinusoidal strain with angular frequency

(t ) = 0 sin (t )

Elastic solid:

(t ) = G (t ) = G 0 sin(t )

The stress is perfectly in phase with the strain for Hookean solid.

Dynamic Measurements
Newtonian liquid:

d (t ) (t ) = = 0 cos(t ) = 0 sin(t + ) dt 2
The stress is out of phase with the strain for Newtonian liquid.

Dynamic Measurements
In general, the linear response of the viscoelastic materials always has stress oscillate at the same frequency as the applied strain, but the stress leads strain by a phase angle

(t ) = 0 sin(t + )
The stress can be separated into two orthogonal functions that oscillate with the same frequency, one in phase with the strain and the other out-of-phase with the strain by /2

(t ) = 0 [G ' ( ) sin(t ) + G " ( ) cos(t )]

G() is the storage modulus

G() is the loss modulus

Examples: Elastic solids: G() =G and G()=0 Newtonian liquids: G() =0 and G()=

Dynamic Measurements
We can rewrite storage and loss modulus in terms of phase angle

sin(t + ) = cos( ) sin(t ) + cos(t ) sin( )


Using

(t ) = 0 [G ' ( ) sin(t ) + G " ( ) cos(t )]


and

(t ) = 0 sin(t + ) = 0 [cos( ) sin(t ) + cos(t ) sin( )]


One obtains

0 ' G ( ) = cos( ) 0

0 G ( ) = sin( ) 0 G " ( ) tan( ) = ' G ( )


"

Application to the Maxwell Model


For the time dependent strain and stress

(t ) = 0 sin (t )

(t ) = 0 sin(t + )
d 1 d = + dt G dt

Substitution to the Maxwell model

results in

0 sin(t + ) 1 0 cos(t ) = 0 cos(t + ) + G


0 cos( ) 1 0 = 0 sin( ) + G

Collecting terms at cos(t) and sin (t) one has

sin( ) 1 0 = 0 cos( ) + 0 G

Application to the Maxwell Model


Rewriting the last equations in terms of loss and storage modulus

G ' ( ) +

G " ( )

0=

G " ( ) +

G ' ( )

Solving this system of equations for G and G one arrives at


2 2 G ' ( ) = G 1 + 2 2

G " ( ) = G

1 + 2 2

1 G " ( ) tan ( ) = ' = G ( )

Readings:
Ch. 3 p.p.51-66, M. T. Swah, W. J. MacKnight, Introduction to Polymer Viscoelasticity. Ch. 7. p.p. 187-204 D. I. Bower, An Introduction to Polymer Physics