Defining the Temperature Dependence of Strain Crystallization in Endurica

Crystallization requires the suppression of molecular mobility, which in natural rubber can happen either by reducing the temperature or by increasing the strain.  Crystallization of natural rubber can be extremely beneficial to durability.  Nonrelaxing conditions (ie R>0) can increase life by factors of more than 100!  So, what happens if you have both high mean strain and high temperature?

This was the question studied in 2019 by Ruellan et al.  They constructed Haigh diagrams for a filled natural rubber at 3 temperatures: 23 degC, 90 degC and 110 degC.  They completed a large experimental study using dumbbell shaped specimens with a matrix consisting of approximately 4 R ratios x 4 amplitudes x 3 temperatures = 48 conditions.  Their results show that the increase of fatigue life with increasing mean strain at constant amplitude disappears as temperature is increased.  In particular, notice how at 23 degC each life contour (shown in red) has a strongly defined minimum force amplitude that lies near the R=0 line.  Also notice how, at higher temperatures, the life contours start to reflect a decrease of life with increasing mean strain.

This interesting effect can easily by replicated in the Endurica fatigue solver by letting the strain crystallization effect depend on temperature.  The material definition we have used in this quick demo is given below in both the old hfi format and the new Katana json format.  I have highlighted in yellow those parts of the definition which reflect the temperature dependence.

In the material definition, we have reflected two behaviors:

  1. the increase of crack growth rate with temperature (ie the RC parameter), and
  2. the decrease of strain crystallization with temperature (ie the Mars-Fatemi exponential strain crystallization parameter FEXP).

We have plotted the resulting Haigh diagrams in the Endurica viewer, and directly overlaid Ruellan’s results for comparison.  Although the x and y scales in Ruellan’s results are shown in terms of total specimen force and ours are shown in terms of strain, a quite satisfying match is nonetheless achieved for the interaction of temperature with the mean strain effect.  It is especially satisfying that such rich behavior is so compactly and so accurately described by means of the Mars-Fatemi crystallization parameter.

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Strain-Induced Crystallization in High Cis Butadiene Rubber: Fact or Fiction?

There is an ongoing drive to create synthetic rubber that can give mechanical performance matching the properties of natural rubber (NR) – excellent strength, tear resistance, and fatigue crack growth resistance – which are attributed to the ability of NR to strain crystallize.  I have attended several technical conferences in the tire and rubber field where I have witnessed presentations about new grades of polybutadiene (butadiene rubber (BR)) with high cis-1,4 structure, wherein a claim is made about the improved ability of the BR to undergo strain-induced crystallization (SIC) for better mechanical properties in tires and other rubber applications.  Similar statements can be found in technical marketing materials and in patents.1,2  To what extent is this true?  This post takes a closer look at this topic.

It is first useful to show why strain-induced crystallization is key to the unique mechanical properties of natural rubber.  One of the most conclusive studies on the function of strain-induced crystals to slow the growth of cracks in cyclic fatigue is the work by Brüning et al.3  The movie below from this research shows an edge crack region in NR reinforced with 40 phr of N234 carbon black that is experiencing cyclic deformation from 0% to 70% planar tension at a frequency of 1 Hz.  Each pixel at each time in the video represents a wide-angle X-ray diffraction pattern collected in real time while stretching in a synchrotron X-ray beam, with red color used to indicate crystallinity and black for purely amorphous regions.  You can see the crystals form during stretching which self-reinforces the rubber at the crack tip region to resist further growth of the crack.  These experiments are very revealing, but they are extremely difficult and expensive to perform, as they require scattering analysis expertise, specially designed stretching devices with precise spatial control, and access to one of the few national laboratory sites where synchrotron X-ray studies can be performed.

Stereoregular polymers can crystallize in a window bounded by the glass transition temperature (Tg) and the melting temperature (Tm). When stretched, a polymer can crystallize at temperatures above its normal melting temperature due to melting temperature elevation caused by the well-known chain orientation/entropy effect.4  Chain orientation results in an increase in melting temperature from Tm to Tm,SIC.  This is shown schematically in the figure below for NR and BR.  The Tg and Tm for BR are significantly lower than the values for NR.  Therefore, even after perfecting the structure of polybutadiene to achieve >98% cis-1,4 structure though catalyst and process innovations, BR still has an intrinsic disadvantage compared to NR when it comes to SIC in the common temperature range where durable rubber components are employed.

 

Gent and Zhang5 recognized the lower Tm,SIC for BR compared to NR for samples crystallized in uniaxially strained conditions.  Ultra high cis BR with 98% cis content did not show any evidence of strain-induced crystallization at 23 °C whereas NR clearly exhibited SIC in a study by Kang and coworkers.6  In an investigation by Toki et al.,7 it was necessary to reduce the temperature to 0°C before high cis BR showed a crystalline X-ray scattering pattern at a strain of 5 (500% elongation).

As an aside, I will caution the use of the entropy-driven melting temperature increase as the only explanation for strain-induced crystallization above the normal Tm.  Natural rubber is quite a slow crystallizing polymer in the unstretched state, even when annealed in the prime crystallization regime midway between Tg and Tm.  In stark contrast, strain-induced crystallization occurs very fast in NR which highlights the complexity of behavior beyond the over-simplification given in the figure above.

So, why is there not more focus on synthetic high cis-1,4-polyisoprene which has the same polymer microstructure and strain crystallization window as NR?  The short answer is that the butadiene monomer is much more commercially available than isoprene at many synthetic rubber plants around the world.  I remember the early years in my industrial R&D career when I was working with some very talented polymer chemists at Bridgestone / Firestone.   I was developing new molecular architectures for improved synthetic rubber to use in various tire compounds.  The chemists told me that they could make almost any polymer design I wanted, as long as it could be made from styrene and/or butadiene.  This restriction reflected the fact that these two monomers were the commonly available feedstocks at the commercial plants where the polymers would eventually be produced.

In closing, it is a fact that high cis polybutadiene can strain crystallize at sub-ambient temperatures, but it is fiction that it will strain crystallize in the same manner as natural rubber at room temperature and above.

Do you want to see if your rubber will really exhibit strain-induced crystallization in a practical way that is relevant to end-use applications?  Contact me (via email: cgrobertson@endurica.com) to learn more about the Non-Relaxing Module in Endurica’s portfolio of testing services that was specifically developed to efficiently highlight SIC effects.8-10

References

1 http://arlanxeo.de/uploads/tx_lxsmatrix/sustainable_mobility_01.pdf

2  S. Luo, K. McKauley, and J. T. Poulton, “Bulk polymerization process for producing polydienes”, U.S. Patent 8,188,201, granted May 29, 2012 to Bridgestone Corporation.

3 K. Brüning, K. Schneider, S. V. Roth, and G. Heinrich, “Strain-induced crystallization around a crack tip in natural rubber under dynamic load”, Polymer 54, 6200 (2013).; movie provided to Endurica LLC by the authors (movie to be used only with permission from Karsten Brüning).

4 P. J. Flory, “Thermodynamics of crystallization in high polymers. I. Crystallization induced by stretching”, Journal of Chemical Physics 15, 397 (1947).

5 A. N. Gent and L.-Q. Zhang, “Strain-induced crystallization and strength of elastomers. I. cis-1,4-polybutadiene”, Journal of Polymer Science Part B: Polymer Physics 39, 811 (2001)

6 M. K. Kang, H.-J. Jeon, H. H. Song, and G. Kwag, Strain-induced crystallization of blends of natural rubber and ultra high cis polybutadiene as studied by synchrotron X-ray diffraction”, Macromolecular Research 24, 31 (2016).

7 S. Toki, I. Sics, B. S. Hsiao, S. Murakami, M. Tosaka, S. Poompradub, S. Kohjiya, and Y. Ikeda, “Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X-ray diffraction”, Journal of Polymer Science Part B: Polymer Physics 42, 956 (2004).

8 K. Barbash and W. V. Mars, “Critical Plane Analysis of Rubber Bushing Durability under Road Loads”, SAE Technical Paper 2016-01-0393, 2016, https://doi.org/10.4271/2016-01-0393.

9 W. V. Mars and A. Fatemi. “A phenomenological model for the effect of R ratio on fatigue of strain crystallizing rubbers”, Rubber Chemistry and Technology 76, 1241 (2003).

10 https://endurica.com/specifying-strain-crystallization-effects-for-fatigue-analysis/

 

 

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Specifying Strain Crystallization Effects for Fatigue Analysis

Endurica CL and fe-safe/Rubber provide several material models for defining cyclic crack growth under nonrelaxing conditions.  Nonrelaxing cycles occur when the ratio R is greater than zero.  R is defined as

R = (T min)/(Tmax)

where T is the energy release rate (note that T will always be greater than or equal to zero).

The crack growth rate under nonrelaxing conditions is, in general, a function of both Tmax and R. For purposes of calculation, it is convenient to define an “equivalent” energy release rate Teq that gives the same steady state rate of crack growth as the operating condition on the nonrelaxing crack growth curve, but which is instead on the fully relaxing crack growth curve.  In other words,

f(Teq) = f(Tmax, R).

Using this scheme, you can set up models for both amorphous and strain-crystallizing rubbers, depending on your definition of Teq.  Amorphous rubbers follow the well-known Paris model, and strain-crystallizing rubbers follow the Mars-Fatemi model (or you can define a lookup table).

Paris Model (Amorphous):

The Paris model is the simplest to derive, as it does not involve any material parameters.  It defines the equivalent energy release rate as

Teq = ∆T = Tmax (1-R)

This definition is only suitable for rubbers that do not strain-crystallize.

For strain-crystallizing rubbers, one of the other two models should be used.

Mars-Fatemi Model (Strain-crystallizing):

The Mars-Fatemi model accounts for strain crystallization by treating the power-law slope, F, of the Thomas fatigue crack growth rate law   r = rc (Tmax/ Tc) ^ (F(R))as a function of R, where

F(R) = F0e^(F4R)

or

F(R) = F0 + F1R + F2R^2 + F3R3

The exponential version is more compact, but the polynomial version is more flexible.

By substituting F(R) into the fatigue crack growth rate equations for relaxing and nonrelaxing cases, and doing a bit of algebra, the following relationship is obtained

Teq (Tmax, R) = Tmax,R ^(F(R)/F(0)) Tc^(1-(F(R)/F(0)))

 

Lookup Table (Strain-crystallizing):

The most flexible and accurate way to define strain crystallization is via a lookup table.  The lookup table takes R as an input and returns x(R) as an output.  This function can be defined as the fraction x(R) by which the nonrelaxing crack growth curve is shifted between the fully relaxing crack growth curve (x=0), and the vertical asymptote at Tc (x=1), at a given R.

x(R) = (log(T) - log(Teq))/(log(Tc) - log(Teq))

This can be rearranged into the desired Teq (Tmax,R) form, as follows

Teq = (Tmax ^(1/1-x(R)) Tc ^-(x(R)/1-x(R)))

Comparisons:

Visualizing the differences between the models helps gain a better understanding of how strain crystallization can affect fatigue performance.  Since all of these models can be represented in the same form of Teq(Tmax,R), we show 2-D contour plots of Teq with R on the x-axis and ∆T on the y-axis.  ∆T is used instead of Tmax to make it easier to compare back to the simple Paris model.

2D contour plots of Teq with R on the x-axis and ∆T on the y-axis. ∆T is used instead of Tmax to make it easier to compare back to the simple Paris model.

From the figures above, we see that for the Paris model, the equivalent energy release rate depends only on ∆T.  When using this model, changes in R will have no effect on fatigue performance (when ∆T is also held constant).

For strain-crystallizing rubbers, changes in R should influence fatigue performance.  This is seen in the figures for the Mars-Fatemi and lookup table models.

The Mars-Fatemi example uses the following parameters:

Parameters used in the Mars-Fatmi example

The lookup table example uses Tc=10.0 kJ/m2 and Lindley’s data for unfilled natural rubber (P. B. Lindley, Int. J. Fracture 9, 449 (1973)).

For these models, there is a significant decline in Teq as R increases.  This effect is most pronounced when Tmax is much smaller than the critical energy release rate Tc.  Also, there is a point where the effect is reversed (around R=0.8 in these examples) and the high R-ratio starts to have a negative effect on fatigue performance.

Implications:

A material’s strain crystallization properties’ impact on fatigue performance under non-relaxing conditions should not be ignored.  Whether you are seeking to take advantage of strain-crystallization effects or simply comparing the results of different materials/geometries/loadings, strain-crystallization should be accurately represented in your simulations.

Follow these tips to take advantage of strain crystallization and help ensure your fatigue performance is the best it can be.

  • Take advantage of Endurica’s material characterization service (the FPM-NR Nonrelaxing Module generates the strain crystallization curve) or use your own in-house testing to create an accurate strain crystallization model of your material (the nonrelaxing procedure is available for the Coesfeld Tear and Fatigue Analyser).
  • Use output requests like DAMAGE_SPHERE, CEDMINMAX and CEDRAINFLOW to observe R-ratios for your duty cycles.

 

References

  1. B. Lindley, Int. J. Fracture 9, 449 (1973)

Mars, W. V. “Fatigue life prediction for elastomeric structures.” Rubber chemistry and technology 80, no. 3 (2007): 481-503.

Mars, W. V. “Computed dependence of rubber’s fatigue behavior on strain crystallization.” Rubber Chemistry and Technology 82, no. 1 (2009): 51-61.

Barbash, Kevin P., and William V. Mars. Critical Plane Analysis of Rubber Bushing Durability under Road Loads. No. 2016-01-0393. SAE Technical Paper, 2016.

 

 

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