November 5th, 2017

W. Cully Hession
Professor of Biological Systems Engineering
204 Seitz Hall
Blacksburg, VA 24060

Dear Dr. Hession,

Enclosed is the requested Technology Review for “Engineering a Greener Tire:

Protein-Activated Rubber Curing.” This written review covers the current science and
technology that is used to produce rubber for greener tire production. This includes a review of
the chemistry of natural and synthetic rubber as well as a brief explanation of the current tire
market and manufacturing processes. The Appendices of this review include the results from
brainstorming sessions with the group members, challenges that we will encounter with this
project and our plans to address them, a project timeline for the rest of the year, and an outline of
team member responsibilities. The Technology Review has been reviewed by Barbara DeButts,
our graduate student advisor.

Sincerely,

Emily Berg Rachel Taitano Alison Waldman

Enclosure: Technology Review

 Engineering a Greener Tire
Protein-Activated Rubber Curing

BSE 4125 - Technology Review

November 5, 2017

Team Name: Green Tire

Team Members: Emily Berg,
Rachel Taitano, Alison Waldman
Advisor: Dr. Justin Barone
Introduction
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
20​th​ 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. In recent years
however, serious health and environmental concerns have arisen from the use of these chemical
compounds in the standard rubber curing process. Here, we analyze alternative, environmentally
conscious additives for rubber curing that minimize health and environmental safety concerns
associated with current rubber curing processes.

Review of State of Technology

Natural rubber, also called natural latex, is a milky sap that is produced in hundreds of
species of plants (Woodford, 2008). However, the overwhelming majority of the world’s natural
rubber is produced by​ Hevea Brasiliensis​ trees (Matador, 2007). This tree species is commonly
grown for rubber production on plantations in tropical conditions such as Southeast Asia,
Western Africa, and South America. Once the trees on these plantations have grown to a mature
age, workers will slash a small strip of their bark which allows their milky sap to drain from the
tree. The sap will drain from this small slash for five to six hours while it is collected in a small
bucket attached to the side of the tree (Matador, 2007). The sap, a colloidal suspension of water
and rubber particles, is a natural isoprene polymer (Woodford, 2008).
Unprocessed natural rubber can be sticky when warm and brittle when cold, which does
not make it particularly useful in rubber applications. Further processing is needed to give
natural rubber the right characteristics so it can be used industrially. Epoxidized natural rubber
(ENR) is produced when formic acid is added to coagulate the sap into a paste-like consistency
(Perera, 1984). The semi-solid sap is then rolled out into sheets, cured with sulfur, and laid out
to dry. The sap has now fully transformed from a liquid to a solid. This method of processing
natural rubber is considerably more environmentally friendly than the processing of
petroleum-based synthetic rubbers. Formic acid will biodegrade without loading wastewater with
phosphate nor nitrate (BASF, 2012), and sulfur is a naturally occurring element that is nontoxic
to the environment at low levels.
Due to the challenges associated with sourcing and shipping natural rubber from Asia,
many synthetic rubber formulations have been developed which are easily industrially produced
in the Americas. However, natural rubber has superior properties to synthetic rubber and some
high performance products are exclusively made from natural rubber, such as airplane tires.
Natural rubber has high tensile strength which makes it resistant to tearing or chipping, adheres
well to itself and other materials, and is environmentally friendly (Hygenic, 2017). However,
natural rubber can be known to rapidly degrade when exposed to extreme conditions. Synthetic
rubber is not environmentally friendly because it is a petroleum product whose production
releases many harmful chemicals into the environment. Compared to natural rubber, synthetic
rubber is more resistant to extreme temperatures and abrasion (Hygenic, 2017). These properties
makes synthetic rubber a longer-lasting product than natural rubber.
Tires are produced industrially from both natural and synthetic rubber. The process
begins when rubber stock is mixed with additives that serve as activators, antioxidants,
vulcanizers, reinforcing agents, pigments and more (Beliczky, 1995). These components are
mixed together in large batches under high temperature and shear conditions before they are
extruded into sheets of rubber “dough”. Polyester fabric is then introduced into the process by a
calendering method which applies a layer of rubber to each side of the fabric for reinforcement.
Cotton threads are then adhered to the rubberized fabric which creates pathways along the rubber
for air ventilation during the tire production. Steel cables are coated in rubber to create the bead,
the inner ring of the tire that holds the tire onto the wheel (Beliczky, 1995). Two beads are then
placed onto a drum where they are covered in various sheets of rubber to produce different parts
of the tire such as the main body, side walls, and tread. Once all the layers are combined, the tire
is cured in a mold. The process of curing rubber is called vulcanization.
 Sulfur vulcanization refers to the process by which crosslinks are formed between rubber
chains using sulfur. Such systems usually involve activators to initiate vulcanization and
accelerators to increase reaction kinetics (Mark, 1994). The most common activator system used
in rubber curing are zinc oxide and stearic acid, which form a complex with an accelerator to
speed up the rate at which vulcanization can occur, reducing the processing time from hours to
minutes (Ciesielski, pg. 33). Curing mixtures often contain approximately 5 and 2 parts per
hundred (phr) zinc oxide (ZnO) and stearic acid (STE), respectively, but this may vary
depending on the type of rubber being produced (Amari, 1999). While inclusion of ZnO and STE
has been shown to improve thermal conductivity, abrasion resistance, and heat resistance in
rubber, both occupational safety and environmental concerns have risen in the last few decades
due to processing with these chemicals (Moezzi, 2012; Amari, 1999).
Zinc oxide and stearic acid act as activators in the rubber vulcanization, or curing,
process by decreasing vulcanization time and improving vulcanization properties, such as tensile
strength, elongation break, and resistance to material swelling. In order to replace zinc oxide
with a different activator for vulcanization, the mechanism zinc oxide uses needs to be clarified.
Heideman et al. showed that zinc oxide played a key role in vulcanization by delaying the
consumption of crosslink precursors in the vulcanization reaction; this directly delayed the
timing of the crosslink reactions required to produce polymers within the rubber stock. Sulfur
crosslinks, the goal of the vulcanization reaction, became shorter in length and decreased in
number as zinc oxide was consumed during long reactions; this was presumed to be a result of
reversion reactions taking place after long periods of vulcanization (Heideman et al., 2005).
For more than a century, curing innovation within tire production has been relatively
stagnant since Charles Goodyear discovered vulcanization methods in 1839. Equipment and
manufacturing processes have been optimized within industrial plants; however, very little
research with regard to non-conventional activators has been performed within the tire industry
(Gent, 2017). Due to developing health and environmental concerns, various approaches are
being studied in an effort to reduce or replace the use of toxic chemicals in the curing process.
Globally, zinc oxide production is approximately 10​5​ tons per year, a majority of which is
used in rubber curing processes (Das, 2011). The release of zinc and other curing chemicals into
the environment during production, disposal, recycling, and through normal wear of tires is a
primary environmental concern (Heideman, 2006). In a 2004 study performed by Councell et
al., the concentration of anthropogenic zinc was positively correlated with traffic density
(Councell, 2004). Many studies have focused on the effects of tire debris leachates on aquatic
environments (Gualtieri, 2004). Preliminary studies found that leachates from both new and used
tires submerged in water negatively impacted growth and development of certain types of fish
and were shown to inhibit metabolic functions in aquatic microorganisms (Day, 1993). In a later
study, it was further demonstrated that zinc inhibits algal growth, the extent of which was found
to be correlated to particle aggregation, rather than quantity (Gualtieri, 2004).
Additional health and safety concerns have developed in regards to rubber processing and
the effects of any leachates on human populations. During the curing process, workers may be
exposed to chemical fumes from the heated rubber products, which may include volatile
chemical byproducts (IARC Working Group, 2012). In the late 1900s, multiple studies
demonstrated deaths due to lymphatic, hematopoietic, lung, and stomach cancers in populations
of workers employed in the tire industry, with an increased risk of bladder cancer specifically
reported from workers at a plant manufacturing rubber antioxidants and accelerators (NIOSH,
1993). Substances used in the curing processes have been linked to respiratory problems such as
emphysema (Beliczky and Fajen). Often, these health effects cannot be tracked back to one
individual chemical, as many chemicals may be involved and chemical formulations may
change. Health concerns for the general population are similar to those reported for aquatic
environments, as many recycled rubber products are used in recreational fields, mulch, asphalt,
or even playground materials.
Efforts to replace zinc oxide and stearic acid in the vulcanization process have begun due
to these harsh environmental and health effects. Recent approaches have focused on minimizing
zinc levels in rubber compounds. In a study by Heideman et al., the authors found that a
minimum of 1phr zinc can be used in the curing process, while still maintaining the necessary
physical properties (Heideman, 2006). Alternatively, use of zinc clay in the vulcanization
process was shown to produce characteristics comparable to rubber cured using zinc oxide
(Heideman, 2006). Additionally, Panampilly et al. successfully utilized nano zinc oxide rather
than the conventional addition of micro zinc oxide as the activator for rubber production. Nano
zinc oxide improved curing rates and the energy storage modulus of the final material, a property
crucial for rubber products, while simultaneously decreasing curing times; these improvements
to zinc oxide performance were due to the increased surface area from the smaller zinc oxide
particles. While the final rubber material still contains safety and environmental concerns due to
the use of zinc oxide in the vulcanization process, the dangers are significantly minimized due to
the use of smaller amounts of zinc oxide; smaller masses of zinc oxide can be used when the
particles are composed of nano zinc oxide rather than micro zinc oxide due to the larger surface
area to volume ratios (Panampilly and Thomas, 2013). Alternatively, other metal oxides such as
magnesium or calcium oxide have been shown to produce similar cure characteristics when used
as activating agents, yet these compounds may lead to unforeseen environmental effects and are
therefore not an ideal, long-term solution (Heideman, 2006).
Recently, studies have been conducted in attempts to fully replace the zinc oxide and
stearic acid used in rubber processing. In 2011, Das et al. explored the use of a layered double
hydroxide mineral filler particle for an accelerator in the vulcanization process and mineral
sheets as the reinforcing filler for the rubber scaffold; stearate anions were used as the activator,
so this method eliminated the need for conventional stearic acid and zinc oxide activators. The
layered double hydroxide nano-particle contained zinc; zinc ions are crucial for the formation of
crosslinks during vulcanization, so the replacement for zinc oxide and stearic acid needed to
contain zinc so it would have the ability to transport zinc ions for successful rubber curing.
Overall, this particle design allowed for a 10-fold reduction in zinc used in vulcanization, thus
reducing environmental and health risks. Rubber processing with the layered double hydroxide
particle yielded more efficient curing reactions compared to conventional zinc oxide-activated
reactions. This method has been successfully implemented in the production of a range of
rubbers, including natural rubber, acrylonitrile butadiene rubber, and polychoroprene rubber
(Das et al., 2011).
While our goal is to replace zinc oxide and stearic acid with wheat gluten as the activator
in vulcanization, other studies have been completed in an effort to utilize organic materials
contained in biomass, such as cellulose or glucose, in order to improve synthetic rubber
properties in a sustainable manner; very few studies exist regarding the total replacement of zinc
activators in tire production with greener or safer alternatives. Beyond chemical reduction, the
use of non-conventional additives for the improvement of synthetic rubber mechanical
properties, such the use of soy protein as a reinforcer in natural rubber latex production, has also
been recently explored. This surge in soy protein nanoparticle use is due to its vast supply of
roughly 340 million tons, biodegradability, safety, and relatively lightweight yet strong material.
Soy protein was exploited as a reinforcer in rubber due to the previous knowledge that including
natural fillers, such as starch and cellulose, improve stress-loading capacities while limiting
polymer chain displacement, both key properties required for high-value rubber products.
Adding amine groups has been shown to improve non-covalent bonding interactions between
natural fillers and rubber composites; these non-covalent interactions are important factors for
producing successful rubber products. This study aimed to improve mechanical properties of
natural rubber composites containing soy proteins by increasing amine content in the final
product while not compromising vulcanization; this was done by propagating diallylamine and a
free-radical initiator to the natural rubber, and evaluating the final rubber properties. The results
of this study showed that the addition of amine groups to natural rubber with soy protein acting
as the reinforcing filler improved curing rates while minimizing negative impacts on polymer
cross-linking. The mechanical properties of the final rubber product showed improved tensile
strength while producing no impact on linear viscoelasticity; additionally, the modified rubber
latex contained higher rolling resistance than conventional carbon black-based rubber, showing
significant potential for tire tread applications (Jong, 2017). Soy protein has yet to be studied
with the manufacturing of other rubber products; however, this study shows a promising future
regarding the demand for soy in the rubber industry due to its positive effects on material
properties and small environmental impact.
Another study completed in 2005 by Angellier et al. highlighted potential for the use of
biomass-derived fillers as a structural stimulus in rubber products. The report discussed the
successful implementation of chemically-modified starch nanocrystals into natural rubber; this
starch served as a component creating additional non-covalent bonding potential for the
enhancement of the required mechanical properties, such as the bulk modulus and material
swelling when under stress. Utilizing starch in natural rubber products creates more potential for
the conversion of biomass into value-added products. Starch nanocrystals proved to be a much
more sustainable method of producing synthetic rubber with improved mechanical properties;
however, the natural rubber latex provided in this study was produced by conventional means,
and does not solve the issue of zinc oxide toxicity or the infeasibility of organic rubber
production (Angellier et al., 2005).
Coupling agents are used to facilitate the compatibility between two dissimilar phases,
such as hydrophobic rubber matrix and a hydrophilic protein filler. The performance of these
agents depends on many reaction parameters, such as the mixing order, the reaction temperature,
and mixing time; these experimental parameters will affect the mechanical properties of the final
product. In 2002, a study was done in the Netherlands to determine effects from varying
temperatures and mixing times on the final silica-filled tire tread compounds. Silica has been
investigated as a potential material for tire tread due to its high wear resistance and wet grip;
additionally, a silane coupling agent was used to increase compatibility between silica and
rubber. The dump temperature and minimum mixing time were found to have the largest impact
on rubber products (Reuvekamp et al., 2002). Another study highlighted the importance of the
silane coupling agent injection timing on the final rubber compound properties when silica is
used as a reinforcing filler. The study showed that while adding the reagent earlier in the reaction
may have optimized rubber content, sheet forming was damaged; similarly, delaying the addition
of the reagent improved sheet formation and decreased bound rubber content (Jeong et al., 2016).
While neither of these studies examined the replacement of zinc oxide or stearic acid in the
vulcanization process, they support the idea that there is a desire to include as many safe
materials with smaller environmental impacts as possible in the tire industry through a variety of
experimental parameters. Many of these optimized parameters interfere with each other, thus
requiring the performance of a “balancing act” during experimental trials.
Throughout the course of this project, we will explore wheat gluten as a total replacement
of zinc oxide and stearic acid in vulcanization. According to the National Agricultural Statistical
Service (NASS), wheat is the third largest commodity crop produced in the U.S. Gluten, the
protein component of wheat, can be hydrolyzed into peptides which, through extensive hydrogen
bonding, form beta-sheet nanostructures with superior properties (Ridgley, 2011 and Ridgley,
2013). There are many challenges associated with replacing zinc oxide with wheat gluten
proteins, such as identifying the reaction mechanisms responsible for protein-activated rubber
curing, and optimizing the system to achieve similar kinetics and mechanical properties to a
typical Zn-activated vulcanizate. Proteins have specific properties and applications that vary
depending on the protein’s structure; Ridgely et al. highlights properties of wheat gluten that
show potential for use as an activator in a material with repeating subunits. Wheat gluten
contains both gliadins and glutenin. The varying solubilities between these two macromolecules
allow for various conformations to occur depending on the protein’s environment; Ridgely et al.
found that combining various proportions of gliadin, glutenin, and amylase resulted in the fibers
having very different physical characteristics (Ridgley, 2011). Additionally, another study by
Ridgely et al. showed that proteins can readily self-assemble into repeating subunits. The study
showed that wheat gluten commonly forms fibers and ribbons when contained in an aqueous
solution; however, processing conditions (i.e., pH, temperature) affect the protein’s morphology
(Ridgley, 2012). These characteristics of wheat gluten are important to know when utilizing it as
an activator in a reaction due to the specificity of the protein.
Previously, literature reviews have indicated that gluten could perhaps be used in a
variety of processing applications due to these properties. Applications may include packaging
films and coatings, inks, and laundry detergents. Wheat gluten proteins have also been used as a
reinforcing agent in certain rubber products and as a binder or matrix material in generation of
composite materials (Bietz, 1996; Ferrero, 2013). Within the past two decades, limited
investment opportunities have prevented further research into wheat gluten use in this manner,
however new dietary standards have developed focusing on minimizing the amounts of gluten
found in grain-based products, thus leading to an excess of gluten that mainly goes to waste.
Globally, the market for gluten-free foods has risen from $3.8 to over $4.6 billion in just two
years, from 2013 to 2015. In the upcoming years, this value is expected to increase to
approximately $7.6 billion by 2020 (Statista, 2017). At the same time, industry tire sales are
expected to rise from $16.3 billion in 2015 to over $19.4 billion by 2019, such that an investment
in more environmentally-conscious tire production may be extremely profitable (Barnes & Co.,
2017). Wheat gluten could perhaps be one solution to safer tire production, as the demand for
gluten-free products is clearly on the rise.
Ultimately, full replacement of zinc oxide and stearic acid with wheat gluten proteins will
also need to produce rubber materials with physical properties comparable to those achieved
using current standard rubber curing processes. ASTM standards for both the physical properties
of tire tread compounds can be found below in Table 1 (ASTM, 2014).

A significant cost challenge will arise due to changing the reaction conditions as well as
the activator in the rubber curing process; one of the main costs to consider is whether any
equipment needs to be replaced or added in a rubber processing plant due to the new curing
agents. We could not find any literature that discussed rubber processing plant designs for
synthetic rubber tires, likely due to the companies wanting to keep trade secrets; however, a
number of studies discussed replacing conventional fillers with natural materials. There was no
mention of new equipment; however, it is likely that more sets of existing equipment would be
needed in order to account for the longer mixing periods and additional drying steps due to the
utilization of a wider range of materials (Angellier et al., 2005).
The most important challenge that must be taken into consideration for our project is the
complete elimination of zinc oxide and stearic acid as activators for sulfur vulcanization of
synthetic rubber. Some studies did not mention the use of either zinc oxide or stearic acid, such
as the report detailing starch substitution in natural rubber, and they usually focused on the
structural properties gained from adding the natural material to the rubber rather as a reinforcing
filler rather than investigating replacements for vulcanization activators (Angellier et al., 2005).
Many studies that did utilize natural fillers often required the utilization of small amounts of zinc
oxide and stearic acid for vulcanization (Jong, 2017). We expect more challenges to arise when
mimicking reaction conditions and reagents with the complete absence of zinc oxide and stearic
acid; however, it is required that we do not use stearic acid or zinc oxide in the reaction due to
their dangerous impact on health, safety, and the environment.

Summary and Conclusions

Overall, the production of an environmentally friendly rubber at an industrial scale has
not yet become a reality. While it has been established that activators used in the standard rubber
curing process pose a significant threat to both the environment and human health and safety,
adequate research into alternatives has not been conducted to date. Much of the research
conducted in the past two decades has focused mainly on reducing the amount of zinc and stearic
acid present in cured rubber products, yet little progress has been made in regards to fully
replacing these chemicals in the vulcanization process. Wheat gluten proteins present an
extremely viable pathway to environmentally-conscious tire production, as these compounds
possess similar physical properties and would simultaneously utilize a product that is
increasingly going to waste. We will anticipate the need to utilize another biological material
(i.e., cellulose, soy protein) as a reinforcing agent for the final rubber product.
With regard to the project deliverable, more information regarding rubber processing
plant design will be needed in order to develop an accurate SuperPro model; the vulcanization
technology’s parameters developed in the laboratory with wheat gluten will be known at the end
of this project, but current information regarding industrial rubber production plants is
inadequate.
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Appendix A - Brainstorming Session Results: Potential Design Solutions
Goal​: Create a chemical process that allows for the replacement of Zinc Oxide and Stearic Acid
with Wheat Gluten proteins:
● Replicate the same physical properties as traditionally produced synthetic rubber
○ Need to determine what these properties are
■ Specifically commercial automobile tires
● Use the same industrial equipment used to produce synthetic rubber so that our new
formulation would not have the added cost of replacing equipment
○ This would also make the transition to protein-activated rubber much easier in
general
○ Determine the equipment that is currently used in the rubber industry
■ Research if these pieces of equipment can be used with wheat gluten
proteins
● Get trained by Barb in the laboratory procedures she currently uses to produce her rubber
samples
○ Determine reaction kinetics to replicate synthetic rubber
○ Use wheat gluten proteins and produce rubber samples in the lab
■ Test these samples for their physical properties, compare the properties
determined above
● Cost analysis to determine if gluten proteins would be more economically feasible
compared to other proposed green alternatives for rubber production
○ Reproduce our rubber processing method in SuperPro for economic evaluation
● Explore the use of other biological materials as additional reinforcing materials
○ Soy protein
○ Cellulose
● Potential inclusion of materials containing zinc ions to help vulcanization
○ Zinc clay
Appendix B - Challenges encountered and plans to address
The tire industry is dominated by large private companies who do not publicly publish
their manufacturing techniques to maintain control of the market. Additionally, there are no
current “environmentally friendly” tire formulations being manufactured in which gluten
proteins are being utilized. Some alternatives have been investigated, such as soy protein and
silica; however, most studies have not had their findings used in an industrial setting regardless
of their initial success. Furthermore, current green alternatives to rubber production are focused
in applications outside of tire manufacturing, and may not be applicable for use in tires. Because
of these gaps in our knowledge, it is currently a challenge for our group to focus on the design
aspect of this project rather than the research aspect of how to use gluten proteins in rubber
formulation. As a team, we will continue to search for more information about the industrial
production of rubber which we hope will include more information about the equipment used in
industrial laboratories and manufacturing plants. This information will be used to design our
final deliverable, a SuperPro model of a rubber processing facility using wheat gluten as the
activator.
Appendix C - Project Timeline for Key Tasks: Gantt Chart
Appendix D - Team Member Responsibilities
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 Technology Review:

Task Completed By
Cover Letter Alison
Cover Page Rachel
Introduction Rachel
Review of State of Technology Alison, Emily, Rachel
Summary and Conclusion Emily, Rachel
References Alison, Emily, Rachel
Appendix A Alison, Emily
Appendix B Alison, Emily
Appendix C Alison, Rachel
Appendix D Alison

General Editing and Review Barbara DeButts