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“MECHANIICAL PROPERTIES OF POLYMERS”

(PPE-301)

Submitted To:
Dr. Atif Javaid

Submitted By:
Omer Khalid (2015-PE-46)

“Department of Polymer and Process Engineering


University of Engineering and Technology, Lahore”
TABLE OF CONTENTS

 Eyring equation.
 Postulates.
 Assumptions.

 Mathematical derivation.

 Applications of Eyring equation.


 Applications to creep.
 Applications to stress relaxation.

 Applications to yield behavior.

 References.
EYRING EQUATION

For the determination of stress relaxation and the creep simultaneously standard linear model or
Zener model is used. But it is limited up to the linear viscoelastic behavior but it does not represent
non-linear viscoelastic behavior (after yield point). For the representation of this behavior Eyring
modified the Zener model.

POSTULATES:
Eyring states that:
 In polymer deformation is a process of thermally activation.
 In polymer deformation the motion of molecular chain segments is above the activation
energy barrier (Δ𝐻).
 We can modify Zener model to allow the dashpot to move by activated process.

ASSUMPTIONS:
The macroscopic deformation is either due to intramolecular or intermolecular process.
Intermolecular process is mainly due to the chains sliding, chains scission, etc. and intramolecular
process is due to chains conformation (rotation of bonds). And the frequency v of these
deformations depends on “How easily the chain segment crosses the potential energy barrier Δ𝐻?”
In the absence of any stress there’s exist a dynamic equilibrium which states the amount of chain
segments crossing energy barrier (Δ𝐻) must be same in all directions.

MATHEMATICAL DERIVATION:
Arrhenius equation states that the frequency of the movement of chains segment at dynamic
equilibrium is given by the expression:
𝑣=𝑣0𝑒𝑥𝑝(−Δ𝐻/𝑘𝑇)
Where,
 𝑣 = frequency of the movement of chains segment.
 k= Boltzmann's constant (1.381 x 10-23 J/K),
 Δ𝐻 = potential energy or activation energy barrier.
 T= Absolute temperature (K)
Figure 1. Potential energy curve vs direction of flow curve

From figure 1 we infer that as we move forward by the application of stress (σ), this stress linearly
shifts the energy barrier (Δ𝐻) by a factor βσ. Where β has the dimensions equal to volume. So the
new potential barrier in forward direction is potential barrier at the start of deformation less the
linear shift factor βσ.
So, the frequency in the forward direction is given by Arrhenius equation modified according to
above discussion

𝑣1=𝑣0(𝑒𝑥𝑝−(Δ𝐻−𝛽𝜎)/𝑘𝑇)

Similarly, in the backward direction the frequency is given by the expression:

𝑣2=𝑣0(𝑒𝑥𝑝−(Δ𝐻+𝛽𝜎)/𝑘𝑇)

For the net flow of chain segments in the forward direction, the frequency(𝑣2) in the backward
direction must be smaller than frequency in forward direction.

𝑣1−𝑣2=𝑣0(𝑒𝑥𝑝−Δ𝐻/𝑘𝑇)(𝑒𝑥𝑝𝛽𝜎/𝑘𝑇−𝑒𝑥𝑝−𝛽𝜎/𝑘𝑇)

As we know that
Sinhx = (ex – e-x)/2

𝑣1−𝑣2=𝑣0′(𝑒𝑥𝑝−Δ𝐻/𝑘𝑇 )(sinh(𝛽𝜎/𝑘𝑇))
Where, 𝑣0′= (2)𝑣0

If we assume that this net flow is directly link with the change in strain rate, then

𝑑𝑒/𝑑𝑡= e˙= e˙o 𝑒𝑥𝑝(−Δ𝐻/𝑘𝑇)(sinh(𝑉𝜎/ 𝑘𝑇))

Where,
 V=Molecular event activation volume, which replaces 𝛽 and it varies material to material.
 e˙ = time dependent strain
This equation defines an “activated viscosity”, which is then substituted in the disport of Zener
model in order to find the relationship between stress and strain after the yield point (non-linear
viscoelastic region).

APPLICATIONS OF EYRING EQUATION:

Eyring equation is applicable to


 Creep
 Stress Relaxation
 Yield behavior.

APPLICATIONS TO CREEP:

Dorn and Sherby determined the creep behavior of Glass PMMA at various temperatures. They
found that creep rate can be expressed in terms of following equation:

e˙ = f1(T) f2(σ/T) f3(e)


Where,
 f1(T) is the function of T
 f2(σ/T) is the function of σ
 f3(e) is the function of e

According to Eyring equation:

 f1(T) is expressed in terms of exponential of thermally activated process.


 f2(σ/T) is expressed in terms of exponential of hydrostatic stress component, giving the
measurement shear, tensile and pressure’s activation volume.

APPLICATIONS TO STRESS RELAXATION:


Consider the following model which consist of an elastic spring with an Eyring dashpot attached
in series, which leads to derive the simple relation for stress relaxation curve during tension. The
total strain in this model is sum of both strains (in elastic spring and Eyring dashpot.)

𝑒 = 𝑒𝐸 + 𝑒𝑉

Where,
 𝑒𝐸 represents the strain in elastic spring
 𝑒𝑉 represents the strain in Eyring dashpot.
Figure 2. Spring and Eyring/ viscous dashpot in series (“This figure is taken from mechanical
properties of solid polymers by I. M. WARD and J. SWEENEY”)

Differentiating the above equation with respect to time

𝑑𝑒/𝑑𝑡= 𝑑𝑒𝐸/𝑑𝑡 + 𝑑𝑒𝑣/𝑑𝑡 …….………. (1)


Replace the time rate of viscous strain using Eyring equation:

𝑑𝑒v/𝑑𝑡= e˙v = e˙o (𝑒𝑥𝑝−(Δ𝐻/𝑘𝑇))(sinh(𝑉𝜎/𝑘𝑇)) ………………(2)

Converting sinh to exponential function and consider the flow in the forward direction we will
obtain the following expression:
e˙V = e˙0 (exp (− Δ H/ kT) (1/2 exp(Vσ/ kT)) = Aexp(Bσ)
Where A and B have been introduced as constants.
Substituting the value of e˙V in expression 1
𝑑𝑒/𝑑𝑡=1/𝐸(𝑑𝜎/𝑑𝑡) + 𝐴𝑒𝑥𝑝(𝐵𝜎) …………. (3)
As we know during stress relaxation strain remains constant w.r.t time so 𝑑𝑒/𝑑𝑡 =0
0=1/𝐸(𝑑𝜎/𝑑𝑡) + 𝐴𝑒𝑥𝑝(𝐵𝜎)
On integrating by the method of separating variables and applying limits from 0 to t. we get
σ0 − σ = (1/B) (ln (1 + t/c))
Where, σ0 corresponds to stress at t=0 and c is the constant of integration.
This expression is known as Guiu and Pratt expression. This expression is highly effective for the
representation of stress relaxation curves for polymers.
APPLICATIONS TO YEILD BEHAVIOUR:
Consider the model as shown in figure 2, which consist of an elastic spring with an Eyring dashpot
attached in series. When the constant strain rate from the unloaded state, is applied on the system
low stress will be produced which results in stretching of an elastic spring and causing low strain
rate in Eyring/viscous dashpot. When the stretching in spring increases the stress would also
increase and so does strain rate in viscous/Eyring dashpot up to a point when the total strain rate
applied is equal to the strain rate in viscous/Eyring dashpot. At this condition there is no more
extension in the elastic spring, and the stress in the spring which is equal to total stress applied on
the systems becomes constant. This state corresponds to the yield behavior.
From equation 1 setting deE/dt=0 and substituting the value of dev/dt from equation 2(for forward
direction of flow only) we get:

e˙ =𝑑𝑒/𝑑𝑡=𝐴𝑒𝑥𝑝(𝐵𝜎𝑌)
On rearranging,

σY = (1/B) (ln (e˙/A)) where, σY is the yield stress

On substituting the values on A and B, we get,

σY = (RT/ν) (ln[ (2e˙/e˙0 )(exp Δ H/kT)]) .

From this relation we obtain a relation between σY/T and ln(ė). Results from this equation when
compared from experimental data it yields realistic behaviors at both temperature i.e. before and
after glass transition temperature (Tg).

REFERENCES:

 “MECHANICAL PROPERTIES OF SOLID POLYMERS” by “I.M.WARD and


J.SWEENEY.”

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