Will Mars on the Rubber Industry: A Look Back 10 Years, Where We Are Now, A Look Ahead 10 Years

Q: With regards to fatigue life prediction methods, where was the rubber industry 10 years ago?

Will There was plenty of great academic work and good understanding of fundamentals, but the methods were only deployed – if at all – via “homebuilt” solutions that could never support a broad enough audience to really impact daily product design decisions.  Simulation methods and experimental methods shared theoretical foundations but they were poorly integrated.  They suffered from operational problems, noisy data and open-ended test duration.  It was possible to analyze a crack if you could mesh it, but the added bookkeeping and convergence burdens were usually not sustainable in a production engineering context.  Mostly, analysts relied on tradition-based crack nucleation approaches that would look at quantities like strain or stress or strain energy density.  These were not very accurate and they were limiting in many ways, even though they were widely used.  They left companies very dependent on build and break iterations.

Q: Where is the industry today?

Will: The early adopters of our solutions have been off and running now for a number of years.  Our critical plane method has gained recognition for its high accuracy when dealing with multiaxial cases, cases involving crack closure, cases involving strain crystallization.  Our testing methods have gained recognition for high reliability and throughput.  Our users are doing production engineering with our tools.  They are consistently winning on durability issues.  They are handling durability issues right up front when they bid for new business.  They are expanding their in-house labs to increase testing capacity and they are winning innovation awards from OEMs.  They are using actual road-load cases from their customers to design light-weight, just-right parts that meet durability requirements.  The automotive industry has lead adoption but aerospace, tires, energy, and consumer products are also coming up.  We have users across the entire supply chain: raw material suppliers, component producers and OEMs.  The huge value that was locked up because durability was previously so difficult to manage is now unlocked in new ways for the first time.  This has been the wind in Endurica’s sails for the last 10 years.

Q: Where do you see the industry in 10 years?

Will: In 10 years, OEMs will expect durability from all component producers on day 1, even for radical projects.  They will expect designs already optimized for cost and weight.  They will push more warrantee responsibility to the supplier.  They will monitor durability requirements via shared testing and simulation workflows.  Suppliers will pitch solutions using characterization and simulation to show their product working well in your product.  The design and selection of rubber compounds to match applications will enter a golden age as real-world customer usage conditions will finally be taken fully into account.  Where design and selection was previously limited by the budget for a few build and break iterations, and low visibility of design options, they will soon be informed by an almost unlimited evaluation of all possibilities.  Where simulation methods have traditionally had greatest impact on product design functions, we will also start to see rubber part Digital Twins that track damage accumulation and create value in the operational functions of a business.  Durability is definitely set to become a strong arena for competition in the next 10 years.

 

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EIE – Effect of Map Discretization on Interpolation Accuracy

Overview

The accuracy of the interpolated results performed by EIE is dependent on the discretization of the map. Specifically, the results will become more accurate as the map’s point density increases. This study uses a simple 2D model to quantify the accuracy of results interpolated from maps with different densities.

Model

A 1 mm x 1 mm rubber 2D plane strain model with two channels is used. The square’s bottom edge is fixed and the top edge is displaced in the x and y directions as shown below. The x displacement corresponds to channel 1 and the y displacement corresponds to channel 2. The working space of the model is defined by the x displacement ranging from 0 mm to 0.8 mm and the y displacement ranging from -0.08 mm to 0.8 mm.

Plane strain model with two channels

The model is meshed with 100 8-node, quadrilateral, plane strain, hybrid, reduced integration elements (shown below).

100 element mesh

History

We define as the benchmark reference solution a history that covers the model’s entire working space with a high density of points. An evenly spaced grid of 128×128 points for a total of 16384 points is used as the history (shown below). It is important that this history is more refined than the maps that we will create to ensure that we are testing all regions of our maps.

128×128 history points

These points are used to drive the finite element model and the results are recorded. For this study, we record the three non-zero strain components and the hydrostatic pressure (NE11, NE22, NE12, and HP) for each element at each time point. In summary, there are 4 result components, 100 elements, and 16384 time increments. This set of results is the reference solution since it is solved directly by the finite element model. We will compare this solution to our interpolated results to measure our interpolation accuracy.

Maps

Six maps with different levels of refinement are used to compute interpolated results for our history points. All of the maps structure their points as an evenly spaced grid. The first map starts with two points along each edge. With each additional map, the number of points along each edge is doubled so that the sixth and final map has 64 edge points. The map points for the six maps are shown below.

Six maps with increasing levels of refinement

The map points for these six maps are used to drive the finite element model’s two channels. The strain and hydrostatic pressure results from the FEA solutions are recorded at each map point in a similar way to how the results were recorded for the FEA solution that was driven by the history points. Next, EIE is used six times to interpolate the map point results at each resolution onto the high resolution reference history points.

We now have seven sets of history results: the true set of results and six interpolated sets of results.

Results

To compare our results, we look at the absolute difference between the sets of results. The absolute error is used, opposed to a relative error, since some regions of the model’s working space will give near zero strain and hydrostatic pressure. Division by these near zero values would cause the relative error to spike in those regions.

Since we have 100 elements and 4 components per element, there are a lot of results that could be compared. To focus our investigation, we look at the element and component that gave the maximum error. The figure below shows contour plots for each of the six maps for this worst-case element and component. The component that gave the maximum error was NE12. The title of each of the contour plot also shows the maximum error found for each of the plots.

Error contours for the worst-case element and component. Titles report the maximum log10 error.

You can see that the error decreases as the map density increases. Also, you can identify the grid pattern in the contour plots since the error gets smaller near the map points.

Plotting the maximum error for each of the maps against the number of map points on a log scale is shown below. The slope of this line is approximately equal to 1 which is expected since a linear local interpolation was used to compute the results.

Maximum error vs the number of points for each of the six maps
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Top 10 Reasons to Celebrate Endurica’s 10-Year Anniversary

In considering ways to capture the contributions and essence of Endurica LLC to celebrate its tenth year of existence – and educating myself some more about the company I joined a little more than a year ago – I decided to put together the following top 10 list.  Enjoy this informative snapshot of Endurica.

10 years of providing software and testing solutions for elastomer applications to #GetDurabilityRight in automotive, tire, aerospace, sealing, defense, consumer products, energy, and medical industries.

9 countries are using Endurica’s elastomer fatigue analysis software products (Endurica CL™, fe-safe/Rubber™, Endurica DT™, and Endurica EIE™) for finite element analysis (FEA).

8 specialized elastomer characterization modules are available in our Fatigue Property Mapping testing services.

7 years ago, the first training course was offered by Endurica. Today there are three courses that are each taught multiple times around the world every year.

6 is the number of full-time teammates working at Endurica LLC.

5 types of integrated durability solutions are offered by Endurica: FEA software, material characterization services, testing instruments, training, and consulting.

4 patents for Endurica’s innovative technology (3 granted plus 1 pending application). 

3 testing instruments are available in the Americas region through our partnership with Coesfeld GmbH & Co. KG (Germany).

2 members of the Endurica team received the Sparks-Thomas Award from the Rubber Division of the American Chemical Society for outstanding contributions and innovations in the field of elastomers.

1st (and only) commercial FEA software to predict when and where cracks will show up in an elastomer product with complex loading and geometry for users of Abaqus™, ANSYS™, and MSC Marc™.

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Just Because You Can Doesn’t Mean You Should

When you have an unmet simulation or testing need, should you build or buy the capability?

There are testing instruments and software packages available in the market – which have been improved through years of R&D and quality management – that can meet the needs of a technical team in their product development efforts. Despite these turn-key resources, we sometimes see a company tasking some of its engineers to build their own.

Why does this happen?

Companies hire smart and creative engineers and scientists with advanced degrees to populate their R&D centers. It is common, and even expected in many situations, for a graduate student to create customized equipment or software as a part of a Ph.D. or M.S. research project. Pushing the boundaries of science and technology often requires such development of devices or code. Also, limited research funding in academia can force students to build their own equipment. When young engineers start their industrial careers after graduate school, they carry with them the mindset of building and programming things themselves. These individuals excitedly offer to create when a new analysis or measurement need arises within a company, and managers like to encourage the enthusiasm of their technical staff.

But, even if your sharp engineer can build a DIY testing device or computer program that recreates the state-of-the-art commercial products created by teams of engineers across many years, is this an efficient and strategic use of the engineer’s abilities? If your company makes tires, for example, then shouldn’t you have your smart people focused on making better tires rather than making testing instruments or software?  What are the labor costs, and the opportunity costs, of your highly-skilled engineer building a piece of testing equipment compared to the price of the commercial instrument or relative to the return you could make on an actual improvement to your product? Unless you are in a position to surpass the commercial solution, there is no competitive advantage in the DIY solution. Once you have created your own solution, who will maintain and support it? Will you be able to keep it up to date with advances in technology? Do you have the capabilities and resources to validate your solution more strongly than the market has already validated the commercial solution?

Through my 15 years of experience in materials research and development in the tire and rubber industry, I have seen several pieces of home-built testing equipment collecting dust within companies. Either they were half finished and abandoned or could only be reliably operated by the creator who moved to another department or company.

There can be circumstances where the needed instrument or simulation product is not commercially available. Sometimes the capability exists in the marketplace, but it is not discovered because the maker mindset leads to a halfhearted search. For customized solutions, you may consider working with a vendor to leverage their expertise in creating the required device or program.

If your analysis and testing needs are in the rubber fatigue and lifetime area, please talk to us before you decide to invest in creating your own solutions. Our solutions embody decades of experience. They are the most competitive and strongly validated solutions you can buy. Endurica has specialized finite element analysis software that predicts elastomer durability for complex geometries and loads, and we offer testing instruments for accurately characterizing the fracture mechanics of elastomers through our partnership with Coesfeld GmbH & Co. KG. We can take you quickly to the forefront of fatigue management capabilities.

 

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Durability Simulation and the Value of Product Development Resources

What value does your company gain by deploying product development resources one way vs. another when it comes to durability?

R&D organizations are built around what it takes to get the product into production.  The costs of the organization include wages for the engineers and technicians, the costs of the capital equipment used in development and testing, and the overhead from administrative functions.  These are all fixed costs, and in the rubber industry it is typical to see R&D budgets that amount to somewhere between 1% and 5% of sales.

The R&D program lifecycle is iterative.  It goes something like this: design, build, test, qualify for production, launch product.  A quick way to understand product development costs is to look at how long it takes for one design-build-test-launch iteration.  If it takes your tech center one year per iteration, then the cost of one pass through the cycle is something like (company annual sales) x (R&D rate per annual sales)/(number of parallel development programs executing at a given time in your tech center).  For a $2B company with a 2.5% research budget and 10 development programs in the works, this works out to $5M/iteration.

How much of this cost is burned on durability issues?  Potentially all of it, at least within any one given iteration.  At worst, a non-qualifying test result leads to a “back to the drawing board” restart of the iteration.  The durability tests required for qualification can only be made after the prototype is in hand, so a restart means the whole team ends up revisiting and reproducing to correct a failed iteration.  Over the long run, if your iteration failure rate is 1 in 5 iterations (20%), that means you are burning $5M x 20% = $1M per product.

How much of this cost can realistically be avoided?  The big opportunity lies in the fact that the old “build and break” paradigm does not immediately hold accountable design decisions that lead to poor durability, and it does not have enough band-width to allow for much optimization.  A “build and break” only plan is a plan for business failure.  Poor decisions are only tested and caught after big investments in the iteration have all become sunk costs.  The advent of simulation has fueled a new “right the first time” movement that empowers the engineer to very rapidly investigate and understand how alternative materials, alternative geometries, or alternative duty cycles impact durability.  The number of alternatives that can be evaluated and optimized by an analyst before committing other resources is many times greater.  “Right the first time” via simulation is a model that is increasingly favored by OEMs and suppliers because it works.  Expect to halve your iteration failure rate.

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Integrated Durability Solutions for Elastomers

Will the durability of your new rubber product meet the expectations of your customers? 

Do you have a comprehensive capability that fully integrates all of the disciplines required to efficiently achieve a targeted durability spec?

Your engineers use finite element analysis (FEA) to model the elastomer component in the complex geometry and loading cycle for the desired product application.  One traditional approach to predicting durability is to develop a rough estimate of lifetime by looking at maximum principal strain or stress in relation to strain-life or stress-life fatigue curves obtained for the material using lab specimens in simple tension.  The difficulties and uncertainties with this method were discussed in a recent blog post.

 

A modern approach to elastomer durability is to use the Endurica CL™ durability solver for FEA.  This software uses rubber fracture mechanics principles and critical plane analysis to calculate the fatigue lifetime – which is the number of times the complex deformation cycle can be repeated before failure – for every element of the model.  This provides engineers with the ability to view lifetime throughout the FEA mesh, allowing them to modify design features or make material changes as needed to resolve short-lifetime areas.

A sound finite element model of the elastomer product in the specified loading situation and fundamental fatigue material parameters from our Fatigue Property Mapping™ testing methods are the two essential inputs to the Endurica CL software.  This is illustrated in the figure below.

The requisite elastomer characterization methods can be conducted by us through our testing services or by you in your laboratory with our testing instruments.  For some companies, consulting projects are a route to taking advantage of the software before deciding to license the unique predictive capabilities.  The following diagram shows how our products and services are integrated.

For companies that are just getting started with implementing our durability solutions, the following is a typical testing services and consulting project:

  1. We use our Fatigue Property Mapping™ testing methods, through our collaboration with Axel Products Physical Testing Services, to characterize the properties of cured sheets of rubber compounds sent to us by the client. The minimum requirements for fatigue modeling are crack precursor size and crack growth rate law, and these are quantified within our Core Fatigue Module.  Special effects like strain-induced crystallization and aging/degradation are accounted for using other testing modules when applicable.
  2. The client sends us the output files from their finite element analysis (FEA) of their elastomer part design for the deformation of their complex loading cycle. It is common for the goal to be a comparison of either two designs, two distinct loading profiles, two different rubber compounds, or combinations of these variations.  Our software is fully compatible with Abaqus™, ANSYS™, and MSC Marc™, so the simulations can be conducted on any of these FEA platforms.  In some situations where a client does not have their own FEA capabilities, one of Endurica’s engineers will set up the models and perform the analyses instead.
  3. The fatigue parameters and FEA model are inputted to Endurica CL fatigue solver to calculate values of the fatigue lifetime for every element of the model. The lifetime results are then mapped back onto the finite element mesh in Abaqus, ANSYS, or MSC Marc so that the problem areas (short lifetime regions) within the geometry can be highlighted.
  4. We review the results with the client and discuss any opportunities for improving the fatigue performance through design and material changes.

Advanced implementors of our durability solutions have licensed the Endurica CL software and are using our rubber characterization methods in their laboratories on a routine basis, with instruments provided through our partnership with Coesfeld GmbH & Co. (Germany).  One recently publicized example of a company using the Endurica approach to a very high degree is Tenneco Inc., which you can read about here.

We want to help you #GetDurabilityRight, so please contact me at cgrobertson@endurica.com if you would like to know more about how Endurica’s modern integrated durability solutions for elastomers can help enable a product development path that is faster, less expensive, and more confident.

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Wohler Curves or Fracture Mechanics?

Endurica uses a fracture mechanics based description of rubber’s fatigue behavior, rather than the classical Wohler curve (ie S-N curve) approach.  This is why:

1) Wohler curves in rubber show the combined effects of several nonlinear processes, but they do not easily deconvolve into useful information about the individual processes.  This means that Wohler curve users struggle to trace the causes of fatigue failures any deeper than the single monolithic empirical SN curve.  When the customer or the boss asks why the part is failing, Wohler curve users end up falling back on the old “rubber is mysterious” defense.  Meanwhile, users of critical plane analysis + fracture mechanics are hypothesis testing. They can check what events and what loading directions are most damaging, and what material parameters (crack precursor size, strain crystallization, threshold, crack growth rate law, thermal effects, etc.) can be exploited to gain leverage and solve the issue.

2) Fatigue failure in rubber is often dominated by “special effects”: dependence on strain level, dependence on R ratio, dependence on temperature, dependence on rate, dependence on ageing, etc. The Wohler curve crowd must choose between ignoring/oversimplifying these special effects, or running an experimental matrix that rapidly scales to an infeasibly huge size as more variables are added.  While fracture mechanics users obtain a wealth of information from a single test specimen (one test can probe many different strain levels, temperatures, rates, etc), Wohler curve users obtain 1 data point per tested specimen.  Look in the rubber technical literature and count the number of S-N-curves that are given, relative to the number of fatigue crack growth rate curves.  Google/scholar returns less than 2000 results for “rubber Wohler curve”, and 78700 results for “rubber crack growth curve”.  There is a reason that crack growth rate curves outnumber Wohler curves.

3) SN based methods are not conservative. Wohler curve users end up assuming that a crack will show up perpendicular to a max principal stress or strain direction.  This assumption only works when you have the very simplest loading cases, no compression, and no strain crystallization.  Users of fracture mechanics + critical plane analysis don’t worry about whether they have simple loading, finite straining,  out-of-phase loading, compressive loading, changing principal directions, and/or strain crystallization.  Critical plane analysis checks every possible way a crack might develop and is therefore assured to always find the worst case regardless of detailed mechanisms.

4) Wohler curves are messy. They depend strongly on crack precursor size, which naturally varies specimen-to-specimen, batch-to-batch, and between lab mix and factory processes.  During SN curve testing, the size of the crack is neither measured nor controlled.  This accounts for the extra scatter that is typical in these tests.  In fracture mechanics testing, on the other hand, the crack is measured and controlled, leading to more repeatable and reliable results.  Noisy data means that the Wohler curve crowd has trouble differentiating between material or design options.  Users of fracture mechanics benefit from cleaner results that allow more accurate discrimination with less replication.

A Wohler curve does have one valuable use.  The Wohler curve can be used to calibrate the crack precursor size for a fracture mechanics analysis. It only takes a few data points – not the entire curve, since the crack precursor size does not depend on strain level, or other “special effects” variables.  Our recommended practice is to run a small number of nucleation style tests for this purpose only, then leverage fracture mechanics to characterize the special effects.

The bottom line is that, for purposes of general fatigue life prediction in rubber, the Wohler curve method looses technically and economically to the fracture mechanics + critical plane analysis based method that is used in modern fatigue solvers.

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Fatigue Life Analysis of Free Surfaces

Free surfaces are critical in fatigue analysis because cracks in a physical part tend to form and grow fastest on such surfaces.  Extra care is required when analyzing free surfaces because typical 3D solid finite elements have their worst accuracy at the free surface (gauss points are not located on the free surface, and hydrostatic pressure profile does not conform adequately to element shape function).  Fortunately, the problem is not hard to resolve: free surfaces can easily be skinned with membrane elements.  Membrane elements are specially formulated to produce an exact state of plane stress.

Let’s look at fatigue life predictions that have been computed with a skin of membrane elements, and compare them with predictions computed from the underlying 3D solid elements.

To study the differences in fatigue life calculations, three simple loading cases were used: simple tension, planar tension, and bending. For each case the fatigue life is calculated for both the surface and solid elements.  The results are shown in the table below.

The fatigue life results show that the shortest life always occurred on the free surface. The life for the solid elements varied from 16% to 25% longer than the surface elements. In each case, the critical failure location was on the surface of the part and in the same location for both the solid and surface calculations. The colored contours of fatigue life are shown below for each of the cases.

Figure 1. Fatigue life on simple tension specimen. Isometric view.

 

Figure 2. Fatigue life on planar tension specimen. Cross-section view through the center of the specimen.

 

Figure 3. Fatigue life on bending specimen. Cross-section view through the center of the specimen.

 

Mesh refinement affects the fatigue life results. A mesh refinement study was performed on the bending case. The mesh refinement study consists of the standard mesh model shown above, a coarse mesh model and a fine mesh model. The number of elements in each model triples with each increase in mesh density. The results are shown below.

Figure 4. Mesh Density Analysis on bending specimen.

This mesh density analysis shows that as mesh density increases, the difference in the bulk and surface results decreases. The bulk and surface results converge to a single value. The amount that solid elements on the surface of the part extend into the interior of the part decreases as smaller elements are used. Since the smaller solid elements have a strain history closer to the surface they more closely match the surface element strains and the life results converge to a single value.

Bottom Line:  if you have free surfaces, skin your model with membrane elements for high accuracy results.  Refining your mesh at the surface may help somewhat, but skinning with membranes is far more reliable.

 

 

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Durability Simulation and the Value of Competitive Advantage

Durability simulation is impacting product development business models in several big ways.  There are cost and risk avoidance impacts.  There is a time-to-market impact.  There is a quality/warranty impact.  And the biggest impact may be competitive advantage.  It’s certainly been in the news.

Rubber component suppliers must compete to win the business of Original Equipment Manufacturers (OEMs).  Having plant capacity is not enough.  The OEM also wants to know that the supplier can meet their durability spec.  The OEM wants to know that if there is a problem down the road, the supplier knows how to find it and fix it quickly.  It is a strong competitive advantage to be able to show the OEM a simulation of the component operating under their loads, along with fatigue calculations that support their warranty.

What is the value of this advantage?

Let’s assume that you are competing with 2 other suppliers for a contract worth $1M.  Since there are 3 competitors (including yourself), you can say that before award, the contract is, statistically speaking, only worth 1/3 of $1M to each competitor.  But at award, the winner takes all, and this means that 2/3 of the ultimate contract value depends completely on being the best option of the three.

This result can be generalized for any number n of competitors.  The fraction of the contract value that competitive advantage wins is (n-1)/n.  Using this rule, we see that for 2 competitors, 1/2 of the contract value comes from competitive advantage.  For 10 competitors, 9/10 comes from competitive advantage.  The more competitors you have, the more valuable it is to have an advantage.

  • How much of your new business win depends on being good with durability issues?
  • Are you the best at solving durability issues? (and do your clients know it!)
  • How much should you be investing in competitive advantage?
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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 http://endurica.com/specifying-strain-crystallization-effects-for-fatigue-analysis/

 

 

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