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W. Cully Hession
Professor of Biological Systems Engineering
204 Seitz Hall
Blacksburg, VA 24060
Enclosed is the requested Analysis of Potential Solutions for “Engineering a Greener Tire:
Protein-Activated Rubber Curing.” This report focuses on alternatives for rubber curing that
produce rubber products with similar properties of those produced with conventional practices.
Appendices are included at the end of this report, and describe the contributions from each team
member. The Analysis of Potential Solutions has been reviewed by Barbara DeButts, our
graduate student advisor.
Sincerely,
Potential Solutions
An alternative we will explore utilizes wheat gluten proteins as the activator in the
vulcanization process, meaning it can facilitate crosslinking of rubber chains with sulfur at faster
rates. The gluten supply from wheat crops has grown drastically, with the market expanding
from $3.8 billion to $4.6 billion in two years, since the food industry began producing more
gluten-free foods (Statista, 2017). Wheat gluten is a mixture of many proteins, with the largest
protein fractions being gliadin and glutenin. Wheat gluten proteins have the potential to activate
crosslinking because of their high amine content. Hydrolyzing the gliadin protein facilitates the
formation of nanostructures with potential for reinforcing the rubber matrix (Ridgley, 2011 and
Ridgley, 2013). Trypsin hydrolyzed wheat gluten (THWG) and trypsin hydrolyzed gliadin
(THGd) have been successfully used as a reinforcing material for unvulcanized rubber in past
studies (DeButts, 2017). Therefore, exploring the use of gliadin and/or wheat gluten protein as
the activator may provide additional benefits to the properties of the final product, such as
reinforcement (Bietz, 1996). Overall, THGd and THWG show great potential to replace zinc
oxide and stearic acid as the activator due to its chemical functionality, nanostructure-forming
ability, cheap cost, safety, and vast supply (Ridgley, 2011; Ridgley, 2013; DeButts, 2017).
One of the most basic alternatives for zinc oxide as it is currently used in the curing
process is simply reducing the amount of zinc added. Zinc oxide is traditionally added to the
curing process in the form of micro zinc oxide particles. In 2013, Panampilly and Thomas
demonstrated the vulcanization of rubber with nano zinc oxide rather than micro zinc oxide.
Decreasing the size of the size of the activator increases the surface area to volume ratio, and
allows the activator to be more accessible in the material; Panampilly and Thomas used this
property to their advantage by reducing zinc oxide molecular size. As a result, a smaller total
amount of zinc oxide needed to be included in order to obtain the same rubber properties as
rubber produced with micro zinc oxide since particle efficiency increased (Panampilly and
Thomas, 2013). Given the known success of micro zinc oxide as the activator in vulcanization,
nano zinc oxide serves as a viable alternative since it would decrease the amounts of harmful
chemicals both in and outside of a rubber processing plant while producing rubber with ideal
properties.
The last alternative considered for this analysis is the use of other metal oxides in rubber
vulcanization. Metal oxides other than zinc oxide, such as calcium oxide or magnesium oxide,
have been tested in rubber curing and were found to produce rubber with properties nearly
identical to rubber produced with zinc oxide or stearic acid. These other metal oxides have
similar properties compared to zinc oxide since the cation in the molecule (i.e., zinc) that has the
largest role in the reaction; therefore, they are considered to be a viable replacement for
conventional activators. One thing to note is that their curing rates are lower than that of zinc
oxide; as a result, curing with these activators requires longer periods of time. The only key
difference between the applications of zinc oxide versus other metal oxides is the metal oxides
require the use of tetra-methyl-thiuram disulphide in the reaction in order to receive optimal
results (Heideman, 2006).
Ranking Procedure
The main goal of this project is to replace zinc oxide and stearic acid in traditional rubber
curing procedures in an effort to reduce the harmful environmental effects of rubber production.
When comparing our different potential solutions, availability, cost, curing properties,
environmental health, and safety of the solutions were the main criteria measured. A decision
matrix with these criteria and our potential solutions was constructed and the solutions were
compared.
Reduction of zinc oxide and stearic acid: The elimination of harmful chemicals in the
leachate from the tire rubber is the main goal of this project. Their collective damage to the
environment and harm to industry employees make it the one of the largest areas of improvement
in the industry (Przybyszewska, 2009). Because reducing the amount of zinc oxide and stearic
acid, the two harmful chemicals used in the curing process, is the most important criterion for the
comparison of our possible solutions, this category has the highest weight. Complete elimination
of these chemicals would earn the solution a high score in this category and no elimination
would result in a score of zero.
Environmental-friendliness: The environmental impacts of the proposed solutions to
replace zinc oxide and stearic acid is another key component of our decision matrix; as a result, it
received a weight of 20 as one of the most important criteria. Zinc oxide and stearic acid are
known to produce damage to ecosystems surrounding rubber processing plants (Gualtieri, 2004).
It is important that the solution reduces the effects of these chemicals, but also does not introduce
other environmental toxins to the leachate. A high score in this category will be given to
solutions that do not introduce any additional environmental toxins, and a low score will be
given if the alternative produces environmental effects similar to zinc oxide and stearic acid.
Availability: Ideally, the alternative that we use to replace the zinc oxide and stearic acid
with would have high availability, as to not put strain on a product that already has a small
supply. To earn a high score in this category, the solution would be a renewable resource such
that using this material in the rubber industry would not deplete supplies. A material that is
extremely scarce would earn a low score in this category. This is an important component of our
comparison, which is why this category earned a weight of 20, equal to that of
environmental-friendliness.
Cost: Cost is always an important consideration in choosing a solution to any problem.
This category is viewed as a comparative cost analysis of each solution. In this category, the
solution with the lowest cost will earn the highest score and the solution with the highest cost
will earn the lowest score. This category was given a weight of 10 since it needs to be considered
among alternatives, but it is not one of the main factors of this project.
Safety: Conventional vulcanization activators are proven to cause detrimental health
effects to those working in the rubber industry (NIOSH, 1993). The safety of the workers who
operate industrial rubber processes is another criteria that we considered here. The processing of
chemicals has the potential to introduce toxic particles into the air at the plant, which can harm
the employees. A high score in the safety category is earned by an alternative that introduces no
toxins into the workplace, while a low score in this category would be given to the alternative
that produces similar health effects as zinc oxide and stearic acid. This category was given a
weight of 10 because safety is not something required of the replacement; however, it is a factor
that should be considered in order to improve vulcanization processes.
Curing Rate: The curing rate of the zinc oxide and stearic acid replacement must be
considered among these alternatives because the alternative will be used in curing reactions. We
aim to replicate the same, fast curing rate that these chemicals provide. The scores in this
category are comparative to the curing rates of the traditional use of zinc oxide and stearic acid.
A high score would be earned by an alternative that can produce curing rates equal to the
traditional rates while a low score will be given to the alternative that has low curing rates. This
was given a weight of 10 because it should be considered; however, there are additional
materials that may be included in curing reactions that improve reaction rates and the properties
of the product. These curing rates used to compare alternatives were found without the use of
reinforcing materials or curing additives, so it is important to remember they could fluctuate.
When comparing the three alternatives presented in this report, a scale of 1 through 5 was
used for each criterion, in which 5 is the maximum or ideal score. If literature did not include
evidence directly pertaining to the alternative, the alternative was given a neutral score of 3.
Each criterion was assigned a weight out of 100 in proportion to importance we placed on each
criterion when deciding which alternative is the best. The individual scores in each criteria for
each alternative was multiplied by its corresponding weight before the score for each alternative
was totalled.
Table 1. 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
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
Conclusion
Due to both human health and environmental concerns, the standard rubber curing
process is currently under scrutiny for its incorporation of hazardous materials such as zinc oxide
and stearic acid. Efforts to replace the use of these chemicals as activators in the vulcanization
process are underway, in the attempt to produce greener tires. Potential alternatives could
perhaps include the use of wheat gluten proteins, nano zinc oxide, or other metal oxides. When
comparing these potential solutions, availability, cost, curing properties, environmental health,
and safety of the solutions were the main criteria measured. A decision matrix with these criteria
and our potential solutions was constructed and the solutions were compared. After evaluation of
each alternative, the use of wheat gluten proteins was determined to be the best choice, with a
total score of 440 out of 500, compared to 270 and 360 for alternatives 2 and 3, respectively.
With regard to the primary goals of this project, including reduction of zinc oxide or
stearic acid, environmental-friendliness, and availability, Table 1 shows wheat gluten protein’s
scores were consistently the highest among the three alternatives. With the other three criteria,
wheat gluten proteins contained the highest score in two out of three categories. As a result, we
are going to pursue testing wheat gluten proteins with rubber vulcanization in the laboratory
since its total score of 440 far outmatched the other alternatives. Our final SuperPro model will
utilize wheat gluten protein in vulcanization reactions with specific reaction conditions
determined in the laboratory and curing additives in order to maximize wheat gluten protein’s
curing rates, as this was the only category wheat gluten scored lowly.
References
Bietz, J. A. & Lookhart, G. L. (1996). Properties and non-food potential of gluten. Cereal Foods
World, 41(5), 376-382.
DaNa2.0. Zinc Oxides - Material Information. Information about nanomaterials and their safety
assessment. Retrieved from
https://www.nanopartikel.info/en/nanoinfo/materials/zinc-oxide/material-information
DeButts, B. L., Hanzly, L. E., Barone, J. R. (2017). Protein-polyisoprene rubber composites. J.
Appl. Polym. Sci. http://dx.doi.org/10.1002/app.46026
Gualtieri, M., Andrioletti, M., Vismara, C., Milani, M., Camatini, M. (2005). Toxicity of tire
debris leachates. Environ. Int., 31, 723-730.
Heideman, G., Noordermeer, J.W.M., Datta, R.N., Baarle, B.V. (2006). Various ways to reduce
zinc oxide levels in S-SBR rubber compounds. Enschede, 197 p.
Lester, D. (2008). Gluten measurement and its relationship to food toxicity for celiac disease
patients. Plant Methods, 4(6).
NIOSH. (1993). Special NIOSH Hazard Review. Centers for Disease Control and Prevention.
Retrieved from https://www.cdc.gov/niosh/docs/93-106/default.html
Panampilly, B.; Thomas, S. (2013). Nano ZnO as cure activator and reinforcing filler in natural
rubber. Polymer Eng. & Sci., 53(6), 1337-1346.
Przybyszewska, M., Zaborski, M., Jakubowski B., Zawadiak, J. (2009). Zinc chealtes as new
activators for sulphur vulcanization of acrylnitrile-butadiene elastomer. eXPRESS
Polymer Letters, (3)4, 256-266.
Ridgley, D. M., Claunch, E. C., Barone, J. R. (2013). Characterization of large amyloid fibers
and tapes with Fourier Transform Infrared (FT-IR) and raman spectroscopy. Appl.
Spectrosc., 67 (12), 1417-1426.
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.
Saplakoglu, Y. (2017). Scientists genetically engineer a form of gluten-free what. Scientific
American. Retrieved from
https://www.scientificamerican.com/article/scientists-genetically-engineer-a-form-of-glut
en-free-wheat/
Statista. (2017). Global gluten-free food market size from 2013 to 2020 (in million U.S. dollars).
Retrieved from
https://www.statista.com/statistics/248467/global-gluten-free-food-market-size/
Tolcin, A. (2017). Zinc. US Geological Survey, Mineral Commodity Summaries. Retrieved from
https://minerals.usgs.gov/minerals/pubs/commodity/zinc/mcs-2017-zinc.pdf
Appendix A - Team Member Contributions
The Green Tire senior design team consists of Emily Berg, Danese Mozley, Rachel
Taitano, and Alison Waldman. Each member is expected to contribute equally to all assignments
and tasks during this project. All team members will attend weekly group meeting and meeting
with our Advisors (Dr. Barone and Barbara DeButts). If a team member is unable to make a
meeting, they will let the other members know ahead of time and will be filled in on the content
they missed. During meeting, notes will be taken in our shared Google drive. Each member has
the responsibility of completing their assigned task before the deadline and asking other team
members for assistance if needed. Emily will serve as the primary organizer of team
communication and weekly meetings.
WEEKLY RESPONSIBILITIES:
● Attend weekly meetings and communicate with team members via group messaging
● Update fellow team members on progress with weekly assignments
The following tasks were distributed for the Analysis of Potential Solutions:
Task Completed By
Cover Letter Emily
Cover Page Emily
Introduction Emily
Potential Solutions Emily
Ranking Procedure Alison
Results and Analysis Alison, Rachel
Summary and Conclusion Rachel
References Alison, Emily, Rachel
Appendix A Emily