Project Title: Developing a Greener Tire: Protein-Activated Rubber Curing

Abstract
Tire processing accounts for approximately 60% of the world rubber market. In typical tire
rubber curing recipes, zinc oxide (ZnO) and stearic acid (STE) are used to activate the
vulcanization reaction. However, ZnO is poisonous to aquatic life and accumulates in the
environment. Additionally, concerns regarding the safety of those working in the rubber
processing plants have risen due to the use of ZnO. Gliadin, a component protein of wheat
gluten, has been shown to have potential to replace ZnO and STE as an activator in the rubber
curing reaction; this is due to the protein’s unique characteristics and crosslinking ability. Thus
far, the protein-activated cured rubber compounds exhibit lower crosslink density than the
industrial control compound. Here, we present a method that allows for the complete
replacement of commonly used zinc oxide and stearic acid with gliadin, while maintaining the
desired physical properties of traditional tire rubber. This material design was implemented into
a SuperPro rubber processing plant model to show how this material would be produced on
larger scales as well as the economic feasibility of this scale-up to industrial levels.

Acknowledgements
The Green Tire Team would like to thank our professor, Dr. Cully Hession, and our
advisors, Barbara DeButts and Dr. Justin Barone, for their contributions and endless guidance
throughout this project. Additionally, the Green Tire Team would like to thank the Biological
Systems Engineering Department for their supportive environment over the past three years.

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Contents
Problem Statement 4
Background 4
Goals and Objectives 5
Criteria and Constraints 5
Methods 6
Results 7
Conclusion 11
References 12
Appendix A: Economic Analysis 13
Appendix B: Decision Matrix 15

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Problem Statement
Rubber has many uses in today’s society; however, the most common use remains to be tire
production. Zinc oxide and stearic acid are activators conventionally used in tire rubber
vulcanization, and they produce harmful environmental effects and severe health consequences
for those working in rubber processing plants (Gualtieri et al., 2005 & IARC Working Group,
2012). The goal of this project is to utilize wheat gluten proteins as the activator in vulcanization
and minimize environmental toxicity and health effects through the use of natural proteins in
place of synthetic compounds. A rubber product, cis-1,4-polyisoprene, will be synthesized that
contains the same properties as tire rubber currently on the market; this process will be
implemented in a SuperPro model that reflects industrial-scale tire production with wheat gluten
proteins as the activator.

Background
Rubber is a hydrocarbon polymer which, when cured, is imbued with desirable properties for a
wide variety of commercial and consumer products, including tires, conveyor belt systems,
hoses, shoes, clothing, gloves, and toys. Traditionally, natural rubber is produced from products
of the Hevea brasiliensis tree, native to the tropical climates of South America and grown in
other such environments (e.g., South/Southeast Asia and West Africa). During the first half of
the 20th century, attempts to reproduce natural rubber compounds using synthetic chemistry were
successful. Further advances in rubber curing were achieved through the use of accelerator and
activator compounds, allowing for faster production rates in an industry setting; these
compounds include zinc oxide and stearic acid (Gent, 2017).

Rubber vulcanization requires a minimum of four materials: rubber (cis-1,4-polyisoprene),

sulfur, at least one accelerator, and an activator. Rubber consists of high molecular weight
polymer chains; without crosslinking, rubber does not have a permanent set required for high
fatigue and abrasion resistance. Sulfur acts as the atom that cross-links the cis-1,4-polyisoprene
polymers, thus giving the rubber material its permanent set, i.e. thermoset (Heideman et al.,
2005). Accelerators simply increase the rate of the reaction since rubber curing naturally occurs
at very low rates, thus it needs to occur more quickly for industrial use (Mark, 1994). Lastly, the
activator facilitates the cross-linking of the materials by forming an activator-accelerator to
increase the speed of the reaction (Ciesielski, pg. 33).

Recently, serious health and environmental concerns have arisen from the use of zinc oxide as an
activator in the standard rubber curing process (Das et al., 2011). This project investigates safer
alternatives to conventional activators, namely, wheat gluten proteins, in order to minimize the
harmful effects from vulcanized tire rubber throughout the material’s life cycle.

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Goals and Objectives
The goal of this project is to create a SuperPro model for industrial tire rubber production that
utilizes a more sustainable method of tire rubber curing. Ultimately, we will develop a method of
curing tire rubber with wheat gluten instead of conventional rubber activators, such as zinc oxide
and stearic acid, that will produce more sustainable rubber with the optimal physical properties
of traditional tire rubber. This method will be implemented in the SuperPro plant model, thus
allowing us to replace commonly used zinc oxide and stearic acid with wheat gluten protein,
gliadin.

In order to accomplish this goal, several objectives have been identified for this project. This
includes: 1) determining the appropriate quantity of wheat gluten proteins in parts per hundred
rubber (phr) needed in place of conventional activators (stearic acid, zinc oxide) and, 2)
establishing the appropriate phr of curing agent and accelerator required to mimic curing rates of
vulcanized rubber produced with standard activators. Finally, this project seeks to implement the
new curing process into a SuperPro plant model for rubber production.

Criteria and Constraints

When producing an environmentally friendly rubber curing package for use in tire production,
the aim is to make this option industrial feasible. In order to do this, criteria and constraints for
this rubber curing processing design have been implemented. The criteria of this design project
are that the design solution must include the use of gliadin from wheat proteins to replace
standard rubber curatives and that the final product must also possess the mechanical and
structural properties equivalent or superior to rubber cured with a standard activator system.
Gliadin from wheat proteins were chosen as the replacement activator due to their reinforcing
capacity, e.g., self-assembly through extensive hydrogen bonding, and crosslinking capacity
(Ridgley et al., 2011). In addition, the wheat protein supply has grown due to the boom of the
gluten-free foods industry, especially within the last decade. The final cured rubber material
must have comparable physical properties to that of rubber produced with zinc oxide and stearic
acid, since the goal is to implement this into the tire industry. Tire companies will not utilize this
final rubber design unless it performs as well as a conventionally cured rubber.

The constraints for this design are as follows: The process and the final cured rubber product
should be both environmentally friendly and non-hazardous to human health. The curing rates of
the synthetic rubber produced using wheat gluten protein should be similar to the curing rate of
synthetic rubber produced using stearic acid and zinc oxide. The final production design should
be economically feasible, ideally by carrying out the new production design under the same
reaction conditions and installed equipment as the standard rubber curing production processes.

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The material design should allow material costs for scaled-up production to be similar or less
than material costs for conventional rubber production.

Methods
Decision matrix description
Efforts to replace the use of zinc oxide and stearic acid as activators in the vulcanization process
are underway, in the attempt to produce greener tires. Potential alternatives considered included
the use of wheat gluten proteins, nano zinc oxide, or other metal oxides. When comparing these
potential solutions, reduction in zinc oxide and stearic acid, availability, cost, curing properties,
environmental health, and safety of the solutions were the main criteria evaluated. A decision
matrix (Appendix B) with these criteria and potential solutions was constructed and the solutions
were compared. Each of these criteria were weighted based on the relative importance within the
scope of this project. After evaluation of each alternative, the use of wheat gluten proteins was
determined to be the best choice, with the highest score compared to the other alternatives.

Material Selection
Before we could model our material design in rubber processing plant design in SuperPro, we
needed to synthesize rubber using wheat gluten protein, specifically trypsin hydrolyzed gliadin,
as the activator. Preliminary tire rubber samples showed that simply replacing ZnO and stearic
acid with gliadin yielded less than satisfactory tire rubber properties. As a result, we considered
various additives not commonly used, such as coupling agents, as well as different proportions of
accelerators, activators, and sulfur. The accelerator used in the synthesis of these rubber samples,
TBBS, was included in all samples; each sample had different amounts of silane, the coupling
agent, sulfur, and gliadin.

A variety of vulcanized rubber samples were produced using standard processing techniques, and
their physical properties were evaluated. The following properties of each sample were
evaluated: crosslink densities, hysteresis, curing kinetics, activation energies. After determining
the optimal material design for the final tire rubber product with properties similar to those of
conventional tire rubber, we implemented this design into a SuperPro model that scaled-up tire
rubber production with our curing package to industrial levels. An economic analysis was
completed to evaluate how cost-effective our final material design is compared to conventional
tire rubber.

Below in table 1 are the ASTM E-1136 standards used in the evaluation of the physical
properties of each tire rubber sample generated in the laboratory.

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 Table 1. ASTM E-1136 Standards
Parameter Value

Tensile sheet cure at 160 Celsius 15.0 minutes

Stress at 300% Elongation 11.4 +/- 1.0 MPa

Tensile Strength 15.2 MPa

Restored Energy (rebound or resilience) 39 +/- 2%

Results
Material Testing
Figures 1-3 show key results from testing the physical properties of the tire rubber samples
compounded using a variety of curing formulations; additional testing was performed and data
was generated, but these results illustrate the properties most relevant to industrial scale-up. The
IR Control represents the conventional tire rubber curing package, activated by ZnO and stearic
acid. Given that the goal of this project was to produce rubber with an alternative activator that
has similar properties to the IR Control, we were looking for the sample with the physical
properties as close to the control as possible.

Figure 1 shows the various crosslink densities of each tire rubber curing package tested in the
laboratory; the crosslink densities were calculated using data from swelling experiments in order
to determine how effective the wheat gluten protein, gliadin, was at crosslinking cis-1,4-
polyisoprene. A comparable crosslink density to the IR Control was desirable because
mechanical properties are heavily dependent on the crosslink density (Heideman et al., 2005).
The sample containing 8 phr trypsin hydrolyzed gliadin (THGd) and 8 phr sulfur (S) exhibited a
higher crosslink density compared to the IR Control and the THGd-activated samples tested;
therefore, this material design was adequately crosslinked to match the tire rubber.

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 Figure 1. Crosslink densities of various tire rubber samples

Figure 2 shows the degree of cure, i.e., crosslink conversion, as a function of time for each
laboratory formulation. Higher rates of cure are desirable for tire rubber since this is a crucial
unit operation in industrial tire production (Jong, 2017). The final design must be able to be
implemented into current tire rubber processing plants with minimal modifications; therefore, the
final tire rubber material design must have fast curing rates in order to closely match processes
currently used in industry.

Figure 2. Degree of cure vs. time for various tire rubber samples

Figure 3 displays percent hysteresis for each tire rubber sample in terms of percentage.
Hysteresis is the amount of energy that is lost to due unrecoverable deformation during repeated
loading and unloading cycles. Hysteresis is the energy lost or dissipated as heat during
deformation; it is the difference between the energy absorbed when the material is elongated and

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the energy released when the material is unloaded. A low percent hysteresis is desirable for tires
because tires are subjected to repeated loading/unloading cycles during use.

Figure 3. Hysteresis values (in %) for each vulcanized tire rubber formulation

Final SuperPro Model

The SuperPro model displayed in Figure 4 implemented the final material design into an
industrial-scale tire rubber plant. Many challenges were faced during this portion of the project
due to the minimal information available from industry on tire rubber plant design; Figure 4
represents our best attempt to model tire rubber production in the form of sheets to be used in tire
production.

The unit operations used for storage of the materials going into the final material include: SL-
101, SL-102, SL-103, and SL-104. Each material is a dry and powdery substance; therefore, silos
would serve as adequate storage spaces for solids. The unit operation SR-102 is used to shred the
polyisoprene prior to entering the reactor; this ensures large surface to volume ratios for each
piece of rubber, thus allowing for better mixing of the vulcanization materials inside the reactor.
R-101 represents the reactor, or the heated mixer, that would be used to combine all components
at high temperatures. The heat exchanger, HX-102, controls the temperature of the rubber before
entering the injection molder, IM-101. The injection molder is where the curing reaction takes
place while the material is flattened into sheets and the rubber vulcanizes. The final product of
this plant would be sheets of tire rubber; these sheets would be used in tire production elsewhere
due to the high complexity of tire designs, which was out of the scope of this project.

Alternative softwares were explored due to SuperPro’s limited unit operations applicable in
polymer processing; however, monetary costs limited our software tools to SuperPro. Ideally,
using Aspen Plus for Polymers would likely yield a more accurate plant design for tire rubber

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production due to the presence of diverse unit operations more suitable for polymer production
compared to SuperPro.

Figure 4. SuperPro model of industrial tire rubber processing plant

Economic Analysis
Appendix A shows the economic analysis performed for both the material costs contributing to
operational costs as well as the equipment costs for the SuperPro plant model displayed in Figure
4. A lack of information regarding conventional tire rubber processing plant design was made
available throughout this project due to trade secrets in industry; as a result, the model shown in
Figure 4 may not accurately depict a current tire rubber plant. Overall, our model may show
differences when compared to an actual tire rubber plant design; however, due to the nature of
this project, the material costs were the main concern.

Throughout this design we considered all necessary equipment for tire rubber production. We
came to the conclusion that our tire rubber material design would not require any significant
equipment changes compared to conventional tire rubber production; this is because the trypsin
hydrolyzed gliadin was added to the curing reaction in a solid form, so it would not need
additional equipment besides a storage silo. This was based on the assumption that the gliadin
would arrive to the tire rubber processing facility prepared for the reaction; therefore, additional
equipment would be needed if the gliadin did not arrive to the plant in the hydrolyzed and dried
form used for the vulcanization reactions. Prior research showed that gliadin preparation on an
industrial scale may require additional mixers and membrane separation equipment (Tatham et
al., 2000).

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The final equipment cost for the plant modeled in Figure 4, using pricing built into SuperPro, is
$4,171,000, as shown in table 4 of Appendix A; again, while this may seem like a high
investment, it would be very similar to a conventional tire rubber processing plant since no new
equipment was added, other than a storage silo, to accompany the utilization of gliadin in
vulcanization.

The material costs for both conventional tire rubber and tire rubber produced with gliadin are
shown in tables 2 and 3 of Appendix A. The tire rubber produced with gliadin is less expensive
to produce than the conventional rubber since the activator prices are different. Gliadin is
significantly cheaper than stearic acid and ZnO, based on bulk pricing estimates available at
Alibaba’s website; this results in a cheaper tire rubber product. The price comparison was
performed assuming that 8 phr THGd would replace 8 phr ZnO/STE. However, laboratory
studies demonstrated that 4 phr THGd was the minimum protein quantity necessary to activate
crosslinking. Therefore, the cost savings associated with THGd-activation may be greater than
those calculated here. Table 5 in Appendix A shows the cost to produce each unit of tire rubber
vs. the revenue for producing each unit. The selling price used in the SuperPro simulations was
taken from a Statista report that showed the price of rubber at the Singapore Commodity
Exchange in 2017; this comparison reflects the profitability of this product if it were immediately
implemented in Goodyear’s tire rubber production plants (Statista, 2017).

Conclusion
Conventional tire rubber curing packages contain hazardous materials, such as zinc oxide, that
cause environmental problems. Replacing these materials with a sustainable agricultural
material, such as gliadin from wheat protein, will improve environmental health and the safety of
those working in these processing plants. In the material design presented in this report, a
traditional rubber curing activator system of zinc oxide and stearic acid was replaced with wheat
gluten proteins, yielding a cured tired rubber with material properties comparable to
conventional tire rubber. Implementing this material design on an industrial scale should be
possible, as the same processing methods and equipment as the conventional rubber curing
package.

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References
ASTM. (2014). E1136-14: Standard specification for P195/75R14 radial standard reference test
tire. West Conshohocken, PA: ASTM Int.
Barnes & Co. (2017). Tire Manufacturing Industry. 2018 U.S. Industry & Market Outlook.
Das, A.; Wang, D.; Leuteritz, A.; Subramaniam, K.; Greenwell, C. H.; Wagenknecht, U.;
Heinrich, G. (2011). Preparation of zinc oxide free, transparent rubber nanocomposites
using a layered double hydroxide filler. J. of Materials Chem., 2011(20), 7194-7200.
Gualtieri, M., Andrioletti, M., Vismara, C., Milani, M., Camatini, M. (2005). Toxicity of tire
debris leachates. Environmental International, 31, 723-730.
Gent, A. N. (2017). Rubber. Britannica Online Encyclopedia.
Heideman, G.; Datta, R. N.; Noordermeer, J. W. M. (2005). Influence of zinc oxide during
different stages of sulfur vulcanization. Elucidated by model compound studies. J. of Appl.
Polymer Sci., 95(6), 1388-1404.
IARC Working Group on the Evaluation of Carcinogenic Risk to Humans. (2012). Occupational
exposures in the rubber-manufacturing industry. Chemical Agents and Related
Occupations. Lyon. International Agency for Research on Cancer. Retrieved from:
https://www.ncbi.nlm.nih.gov/books/NBK304412/
Jong, L. (2017). Reinforcement effect of soy protein nanoparticles in amine-modified natural
rubber latex. Industrial Crops & Products, 2017(105), 53-62.
Mark, J.E., Erman, B., Eirich, F.R. (1994). Science and technology of rubber. San Diego, CA:
Academic Press.
Ridgley, D. M.; Ebanks, K. C.; Barone, J. R. (2011). Peptide mixtures can self-assemble into
large amyloid fibers of varying size and morphology. Biomacromolecules, 12 (10), 3770-
3779.
Statista. (2017). Price of rubber at the Singapore Commodity Exchange from 2006 to 2017 (in
U.S. cents per pound). Retrieved from https://www.statista.com/statistics/653796/price-of-
rubber-per-pound/
Tatham A.S., Gilbert S.M., Fido R.J., Shewry P.R. (2000). Extraction, separation, and
purification of wheat gluten proteins and related proteins of barley, rye, and oats. In: Celiac
Disease. Methods in Molecular Medicine, 41, 55-73.

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Appendix A: Economic Analysis
Table 2. Conventional Rubber Production
Material phr Amount (kg/yr) Cost/kg Total Cost

Sulfur 8 149,760 $0.4/kg $59,904

TBBS 2 37,440 $3/kg $112,320

Zinc Oxide 5 93,600 $4/kg $374,400

Stearic Acid 2 37,440 $0.9/kg $33,696

cis-1,4-polyisoprene N/A 1,872,000 $2/kg $3,744,000

Total Production Cost $4,324,320

Table 3. Gliadin-based Rubber Production

Material phr Amount (kg/yr) Cost/kg Total Cost

Sulfur 8 149,760 $0.4/kg $59,904

TBBS 1.92 35,942 $3/kg $107,827

cis-1,4-polyisoprene N/A 1,872,000 $2/kg $3,744,000

Wheat Gluten Protein 8 149,760 $0.19/kg $28,455

(gliadin)

Total Production Cost $3,940,186

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 Table 4. Equipment Costs for SuperPro model
Equipment Name Process Identifier Size/Capacity Cost (USD)

Solids Storage - Sulfur SL - 101 314 L $81,000

Solids Storage - Latex SL - 102 3,922 L $81,000

Solids Storage - TBBS SL - 103 98 L $81,000

Solids Storage - Wheat Gluten (Gliadin) SL - 104 98 L $81,000

Shredder SR - 102 3,000 kg/h $98,000

Stirred Reactor R - 101 4,047 L $737,000

Heat Exchanger HX - 102 1.56 m^2 $12,000

Injection Molder (30 Units) IM - 101 43 entities/h $3,000,000

Total Equipment Costs $4,171,000

Table 5. Profitability
Unit Production Cost $7.25

Unit Production Revenue $41.68

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Appendix B: Decision Matrix
Table 6. Decision matrix to determine ideal design solution for replacement of zinc oxide and
stearic acid during the sulfur vulcanization process

Alternative 1: Alternative 2: Alternative 3:

Weigh
Criteria Wheat gluten Nano zinc Other metal
t
protein oxide oxides

Reduction of Zinc Oxide

30 5 2 5
or Stearic Acid

Environmentally-friendly
20 4 2 3
material

Availability 20 4 3 3

Cost 10 5 4 2

Safety 10 5 2 3

Curing rate 10 3 5 4

Weighted totals 500 440 270 360

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