Thermal Analysis & Rheology

RHEOLOGY SOLUTIONS
DETERMINING THE LINEAR VISCOELASTIC REGION IN POLYMERS
PROBLEM a series of creep curves is obtained such as those for
polystyrene in Figure 1. Replotting these curves as
Materials such as polymers exhibit viscoelastic behavior compliance, a viscoelastic function defined as strain
which is directly related to molecular structure and divided by stress, yields the results shown in Figure 2. In
formulation differences. To accurately evaluate the the polymer’s linear viscoelastic region, the compliance
relationships between molecular structure and viscoelastic curves should overlap. In this example, the curve pro-
behavior requires that experiments, such as rheological duced by Stress C does not overlap, indicating that the
measurements, be conducted in regions where the vis- linear viscoelastic region is exceeded.
coelastic properties observed are independent of imposed
stress or strain levels. That is, experiments must be In the dynamic oscillation approach, increasing cyclic
conducted in the linear viscoelastic region. levels of stress and strain are applied at a constant
frequency. The point at which a dynamic viscoelastic
SOLUTION function (either G* or η*) deviates by more than 10% from
a constant (plateau) value indicates departure from linear
Controlled stress rheology provides two techniques for viscoelastic behavior. Figures 3 and 4 illustrate the
determining a polymer’s linear viscoelastic region. These oscillatory stress and strain results respectively for
are creep and dynamic oscillation. In creep, a constant polystyrene. Departure from linear behavior occurs at
stress is applied to the material, and the resultant strain is about 9 k Pa in the former case and at about 20% strain in
monitored with time. By sequentially increasing the stress, the latter.

Figure 1. CREEP STRAIN (%) CURVES Figure 2. CREEP COMPLIANCE CURVES

140
140
0.0030

120
120
0.0025

100
100
Compliance (m /N)

0.0020
STRESS C
2
Strain(%)
(%)

STRESS C
(%)

80
80
Strain
Strain

0.0015 STRESSES
60
60 A & B (Linear
Region)
0.0010
40
40 STRESS B
STRESS A 0.0005
20
20
20

0.0000
00
0
0 100 200 300 400 500 600 700
00
0 100
100
100 200
200
200 300
300
300 400
400
400 500
500
500 600
600 700
700 Time (s)
(Time
Time
Time
(Time
Time (s)(s)
(s)
(s)
(s)

RS-23
 FIGURE 3. G* AND h* VERSUS SHEAR STRESS

35
10 35
10

G*

COMPLEX VISCOSITY η* (Pa . s)

COMPLEX MODULUS G* (Pa)

24
10 24
10
η*

13
10 13
10
2 3 4 5
10
1 10
2 10
3 10
4
Shear Stress (Pa)

FIGURE 4. G* AND η* VERSUS SHEAR STRAIN

5 5
3
10 3
10

G*
COMPLEX MODULUS G* (Pa)

COMPLEX VISCOSITY η* (Pa . s)

4
10
2 2
10
4
η*

3 3
1
10 1
10
0.1
1 1
2 10
3 100
4
% Strain

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Thermal Analysis & Rheology

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RS-23B