Quantifying Polymer Crosslinking Density

Using Rheology and DMA

Keywords: Thermoset, crosslinking, polymer, crosslinking density, DMA, rheology RH102

ABSTRACT plate or a cone and plate. If the sample is in a stiff solid state,
then it is tested in the torsional mode. All rheological tests are
Thermosetting polymers have been widely used in a variety of conducted under a shear deformation mode, so the measured
industries, such as electronics, automotive, and aerospace. modulus is defined as G.
The performance of thermoset materials is strongly influenced
by the base polymer architecture, processing conditions, and
filler compositions. Examples of commonly used thermosets
include epoxies, crosslinked polyurethanes, and polyesters, filled
vulcanized rubber elastomers, and some formaldehyde foams.

The degree of crosslinking in a thermoset is a critical parameter

that has a major influence on the mechanical strength and visco- A DMA is used to measure the viscoelastic properties of sloid
elasticity of the material. For an unfilled thermosetting polymer, samples. The sample can be in a variety of different shapes such
the percentage of crosslinking (also called the crosslinking density) as thin film, rectangular bar, etc. The dynamic tests are conducted
can be quantitively calculated using both rheological and DMA under a linear deformation mode such as tension, bending, or
measurements. In this application note, we elaborate in detail on compression. Therefore, the reported modulus in a DMA test is
how to set up a rheological test method to measure the modulus defined as E.
of a thermoset in the rubbery plateau region and then, further, to
calculate the crosslinking density.

INTRODUCTION TO DYNAMIC MECHANICAL ANALYSIS

Dynamic oscillatory testing is a very important method for

characterizing thermoplastic and thermoset materials. It is usually
the best way to determine a material’s viscoelastic properties,
which can be related to molecular architecture, processability,
curing kinetics for thermosetting materials, and end-use
The relationship between these moduli is based on equation
performance [1].
(1), where ν is the Poisson’s ratio of the material. In general, the
In dynamic testing, one imposes a sinusoidal strain, at a particular Poisson’s ratio of polymeric materials ranges from 0.3 to 0.5.
frequency and measures the resultant stress, or vice versa.
E = 2G (1+ν) (1)
Imposing a sinusoidal strain and measuring the resultant stress in
a shear deformation mode is illustrated in Figure 1. Where γ is the The key parameters that one gets from a rheology and a DMA
shear strain; σ is the shear stress, and ω is the angular frequency. dynamic testing are shown in Table 1.

Parameter Symbol Equation

G* σ0/γ0
Complex Modulus (Pa)
E* τ0/ε0
G’ G*(cos(δ))
Storage Modulus (Pa)
E’ E*(cos(δ))
Figure 1. Illustration of dynamic oscillatory testing in a shear mode
G” G*(sin(δ))
Loss Modulus (Pa)
The ratio, σ0/γ0, is the complex modulus. The phase angle, δ, E” E*(sin(δ))
which is the shift between the input and the output sinusoidal
G”/G’ = sin(δ)/cos(δ)
waveform, is an indication of the viscoelastic nature of the material. Tan Delta Tan δ
E”/E’ = sin(δ)/cos(δ)
If δ is 0 rad (0º), the material is purely elastic; if δ is π/2 rad (90º),
the material is purely viscous. If 0 < δ < π/2 rad, the material is G*/ω, where ω is the
Complex Viscosity (Pa-sec) η* angular frequency
viscoelastic. (rad/sec)
In a dynamic rheological measurement, if the sample is a liquid or
soft solid (e.g., paste or gel), it is mostly tested between a parallel Table 1. Dynamic oscillatory parameters

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 Typical dynamic tests that can be performed on a rheometer and 109 1.5
a DMA include strain/stress sweeps, time sweeps, frequency 11.13 ºC
sweeps, temperature ramps, and temperature steps/sweeps. 108
1.2

Storage modulus G’ (Pa)

Loss modulus G” (Pa)
MEASURING AND CALCULATING THE CROSSLINKING

Tan(delta) tan(δ)
107
DENSITY OF A THERMOSET 0.9

109 10 106

0.6
108
105
8 Rubbery plateau
Storage modulus G’ (Pa)

107
Loss modulus G” (Pa)

0.3
104

Tan(delta) tan(δ)
106 6

105 103 0.0

Rubbery plateau -40 20 0 20 40 60 80 100 120
104 16.33 ºC 4
Temperature T (ºC)

103 Figure 3. Dynamic temperature ramp of a crosslinked adhesive

2
102 There are a number of references in the literature reporting using
Molten the modulus measured within the rubbery plateau region to
101
0
-40 20 0 20 40 60 80 100 quantitatively calculate the polymer crosslinking density [2,3].
Temperature T (ºC) First, the molecular weight between crosslinks can be calculated
from the G’ measured within the plateau region using equation (2)
Figure 2. Dynamic temperature ramp of a non-crosslinked adhesive
RTd (2)
MC =
Figure 2 shows a dynamic temperature ramp test result of a linear G’rubbery
polymeric adhesive sample. This measurement was conducted
using an 8 mm parallel plate geometry under shear deformation
Where Mc is the molecular weight between crosslinks, R is the
on a rheometer. The temperature ramp test was run from -30 °C to
universal gas constant, T is the absolute temperature and d is the
100 °C at a heating rate of 3 °C/min. The test frequency was set
density of the polymer.
at 1 Hz with a small strain that was within the linear viscoelastic
region of the sample. As can be seen from the test result, the glass Then, the crosslinking density of the polymer can be calculated
transition temperature (Tg, based on the peak of tan delta) of this using equation (3)
linear adhesive polymer is at 16.33 °C. Above Tg, the storage Mw
q=
modulus (G’) of the polymer shows a plateau over a temperature Mc (3)
window between 40 °C to 70 °C. Then at temperatures greater
than 70 °C, this polymer becomes molten with G” being greater Where Mw is the molecular weight of the monomer, and q is the
than G’, and the sample flows like a viscous liquid. The value of crosslinking density.
the rubbery plateau modulus (Ge) is correlated with the polymer
chain entanglement. Alternatively, researchers have reported using the DMA test results
for the calculation of the crosslinking density [4]. Equation 4 is
If the polymer is partially crosslinked, then its molten state will based on the assumption that E is 3 times greater than G, when
not be observed in a temperature ramp test. After Tg, the Poisson’s ratio is 0.5.
3RTd
rubbery plateau area will extend up to higher temperatures until MC =
E’rubbery (4)
the polymer starts to decompose. Figure 3 shows an example
temperature ramp test result of a partially crosslinked adhesive
Figure 4 shows the results of testing a series of rubber elastomers
sample. The storage modulus remains greater than loss modulus
with different amounts of crosslinking using a DMA in the
at temperatures above the normal molten temperature of the
tension mode. As can be seen from the graph, the measured
polymer without crosslinking. For a crosslinked polymer, the
rubbery plateau modulus increased with increasing the degree of
storage modulus value in the rubbery plateau region is correlated
crosslinking. In the meantime, the glass transition is also observed
with the number of crosslinks in the polymer chain.
to shift to higher temperatures.

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 104 ACKNOWLEDGMENTS

This paper was written by Dr. Tianhong Terri Chen, Senior

Applications Support Scientist at TA Instruments.
Storage modulus E’ (MPa) —

Increase
Loss modulus E” (MPa) —

103
crosslinking density
REFERENCES

1. C. W. Macosko, Rheology: Principles, Measurements, and

102
Applications; Wiley-VCH, New York, New York (1994)

2. F. Abd-El Salam, M. H. Abd-El Salam, M. T. Mostafa, M. R.

101 Nagy, M. I. Mohamed, Journal of Applied Polymer Science,
90, 1539–1544 (2003)

3. K.S. Santhosh Kumar et al. European Polymer Journal, 43

100 2504–2514, (2007)
-80 -70 -60 -50 -40 -30 -20 -10 0
Temperature T (ºC) 4. I. M. Barszczewska-Rybarek, A. Korytkowska-Walach, M.
Kurcok, G. Chladek, J. Kasperski, Acta of Bioengineering and
Figure 4. DMA temperature ramp tests on crosslinked elastomers with Biomechanics. Vol. 19, No 1, (2017)
different crosslinking density
5. L E Nielsen “Mechanical Properties of Polymers and
To simplify the test method and shorten the measurement Composites”, page 169, 2nd edition, Marcel Dekker, 1994
time, one can also program a short dynamic time sweep test
at a temperature that is within the rubbery plateau region, take For more information or to request a product quote, please visit
the measured storage modulus, then use equation (2) or (4) to www.tainstruments.com/ to locate your local sales office
calculate Mc. Please note that using the rubbery plateau modulus information.
to calculate the crosslinking density is only applicable to unfilled
thermoset polymers.

© TA Instruments 3 RH102