VULCANIZATION

OF RUBBER
ASSIGNMENT 4
PAULA VIEGAS GRECO DE OLIVEIRA 314011315

SCHOOL OF AMME Dr. ROD FIFORD

ABSTRACT
Rubber is a very important material, and has been used for many years. Even though
the natural rubber presented a great innovation, with its great property of elasticity, it
had some weaknesses when under heat or in cold situations. Because of this, this
material had to be improved to solve the problems it faced in several applications, and
to make possible to find other usages for it. This report will introduce the sequence of
facts that led to the discovery of vulcanization, describe the process, explain why it is
a significant engineering breakthrough and how it altered society.

INTRODUCTION
Rubber is part of a group of industrial
materials known as Engineering
Materials, which also include metals,
fibres, concrete, wood, plastics,
glasses, from which the modern
technology is dependent. It is a
polymeric material, discovered in
ancient Mesoamerica about 1600BCE,
differently from what until recently was
thought: that rubber originated in 19th
century Europe. The Mesoamerican
Figure 1: the Mesoamerican ancient rubber ball
rubber was used by the ancient Mayan
people to make balls, hollow human figures and as bindings used to grip axe heads to
their handles (i.e. as joints). This means that since the very ancient beginning rubber
had different usages and applications, going from a social activity to linkage tool 1.
Nonetheless, the application of this material was more expressive during and after the
19th century, when, similarly to the Mesoamerican material, rubber was obtained from
latex (a sap of certain plants that coagulates on exposure to air). In this period, this
elastic material was applied for many usages, such as door and window profiles,
hoses, belts and cables, gloves (very important for medical and industrial application,
to prevent accidents and infection), toy balloons, adhesives, office supplies and many
automotive pieces2. Therefore, rubber became a very important material for society,
pursuant the wide range of applications.

THE HISTORY OF VULCANIZATION

Even though the natural rubber had the fantastic property of elasticity, it had not
appreciable mechanical resistance at high temperatures (could easily deform when
warm) and was brittle when cold due to its long polymer chains (making it useless to
make articles with a good level of elasticity), what impeded it to be used for a long
period in situations that required thermal stability, such as automotive tyres and
dampeners. This material presented two big problems: it was difficult to work with solid
rubber and the artefacts became mushy and sticky under heat. It means that in
repetitive and high temperature and resistance applications natural rubber would
perish in a short period of time. At the same time, under low temperatures the rubber
articles became hard and rigid, until completely inflexible. As a result, a material with
great elasticity and mechanical resistance for applications with higher temperatures,
or with high temperature gradients started to be necessary, driving the engineers at
that time to research a try to discover a material with these properties.
Due to the necessity of a more stable rubber for several applications, during the 19th
century the engineers tried to discover a new process to improve this material.
Afterwards, in 1838, a manufacturing engineer called Charles Goodyear discovered,
accidentally, the vulcanization process. According to his description of the discovery,

available on his autobiography Gum-Elastica (written in

the third person), The inventor made some experiments
to ascertain the effect of heat on the same compound that
had decomposed in the mail-bags and other articles. He
was surprised to find that the specimen, being carelessly
brought into contact with a hot stove, charred like leather3.
On the other hand, there another scientist and engineer
called Thomas Hancock was the first to patent
vulcanization of rubber and actually he seemed to
understand the vulcanization process better than
Goodyear. Hancock got a British patent on 1844, and
Goodyear got his American patent three weeks later. The Figure 2: the scientist Charles Goodyear
American engineer claimed that he had discovered
vulcanization earlier, in 18394, and afterwards the invention is credited to him.
In his book, Goodyear gives several examples of the application of vulcanized rubber,
such as automotive springs (which require elasticity, high mechanical resistance and,
because of the conversion of friction to heat, require thermal stability as well), various
types of valves, stops, chains and hydraulic equipment. This means that, therefore,
rubber could be a great substitute for metal in many applications, being a cheaper and
lighter option, saving material, energy and, finally, money.

THE VULCANIZATION PROCESS

Generally, the process is considered to be irreversible and is much different from
thermoplastic processes (melt-freeze processes). The irreversible cure reaction called
vulcanization defines cured rubber compounds as thermoset materials, which do not
melt
on
heating,
turning
them
different
from
thermoplastic
materials5http://www.chemeurope.com/en/encyclopedia/Vulcanization.html.
The cure in a typical rubber compound comprises the cure agent (usually sulphur, but
can also be peroxide) together with accelerators, activators and antidegradants (to
prevent degradation by heat, oxygen and ozone). Sometimes, to prevent that the
process would star too early retarding agents can be added. The process consist in
adding the cure agent to modify the polymer through the crosslinks formed between
the polymer chains.
The reactive sites are allylic
hydrogen atoms, and these C-H
bonds are adjacent to C-C
double bonds. During the
vulcanization, some of the C-H
bonds are replaced by chains of
sulphur atoms that link with a
cure site (reactive site) of
another polymer chain, creating
bridges that contain between

Figure 3: molecular representation of a vulcanized polymer

one and eight atoms. The bridges created between the polymer chains prevent them
from moving independently, avoiding inelastic deformations under heat. The number
of sulfur atoms in the crosslink strongly influences the physical properties of the final
article: shorter bridges increase the heat resistance, while crosslinks with higher
number of atoms result in better dynamic properties (important for flexing movements
of the rubber article) but lower heat resistance.
There are different methods of vulcanization, but the economically most important is
the compression moulding (used for tires). It is based on increasing pressure and
temperature a typical temperature for a passenger tire is 10 minutes at 1706 and
the rubber article may adopt the shape of the mold. There are other methods of
vulcanization, and they differ by the type of cure agents, temperatures, pressures,
interval, accelerators, antidegradants, retarding agents and the environment of the
process. Some of these other methods can include hot air vulcanization or microwave
heated vulcanization, both continuous processes and used to make doors profiles for
cars.

THE ENGINEERING BREAKTHROUGH

Since the discovery of the process until present time, many different ways of
vulcanization had been discovered, improved and created. We can have several
distinct types of material just using the same idea: introduce a cure agent chain
between long polymeric chains, to increase the heat resistance and improve dynamic
properties, which are important for flexing movements of the object. With none of these
properties some movements, such as the movement of a side-wall of a running tire)
would rapidly lead to the emergence of cracks and, in the end, to failure of the rubber
article7.
The process of vulcanization was a great breakthrough for the usage of natural rubber
ate the period of its discovery. But until nowadays, many improvements of this process
were achieved, and it is now used
for other materials, including
artificial rubber (such as neoprene
or polychloroprene rubber8) and
silicones, increasing the range of
applications
on
vulcanized
materials.
Nowadays the process is used to
improve
the
properties
of
polymeric materials and increase
the possibilities of applications of
this type of material. Polymers are
used is a large range of
applications, and every day new
applications and new materials
are discovered. The vulcanization

Figure 4: vulcanized silicon rubber keypad

process is following this progress, and helps to decrease the costs and improve the
quality of many devices.
For those who like to cook, the pressure pan depends strongly on a great vulcanized
sealer to avoid the loss of pressure. For those who like watching TV, using a DVD
player or any device with a remote control, it is interesting to notice that the buttons of
the controllers are made of vulcanized silicon or rubber, to keep the stable and avoid
cracking for a very long period. At the same time, for those who like driving, or for
anyone who uses public transport, just look around and you will see vulcanized
materials everywhere: the tires of the cars/buses are made of vulcanized rubber, the
sealers of the windows and of the doors are made of vulcanized rubber or silicon, not
forgetting the automotive parts, such as springs, suspensions and cables.
What to say about medical applications? The risk of any object getting cracked and
failing inside the body is not acceptable, so thermal stability and great dynamic
properties are required for such application, what is possible because of the
vulcanization process.

CONCLUSION
The vulcanization of rubber revolutionized the use and applications of rubber, and later
of other materials, and changed the
face of the industrial world. It made
sealing gaps a much easier challenge
than using leather soaked in oil,
making possible the usage of steam
engines
working
with
higher
pressures. Besides, any application on
elastic materials which would be
submitted to repetitive work was
granted with this process, because it
made the materials last longer,
decreasing
expenses
and,
Figure 5: the pollution generated by vulcanized materials
consequently, increasing profits. But
the benefits do not remain on the industrial and financial aspects. It extend to daily life
and to the medical environment, turning everyone lives simpler, safer and also
cheaper.
However, as said in this report, the vulcanization process is irreversible. Consequently,
the vulcanized articles are difficult to be recycled, generating a huge amount of
garbage and increasing one of the biggest modern problems: pollution. The rubber
industry has been researching the devulcanization process for many year, to make
possible the recycling of this material without compromising the desirable properties.
This process involves treating rubber in granular form in order to restore its elastic
qualities and to enable the rubber to be reused. Furthermore, some smart solutions
had been used, and an interesting one is to mix the granular rubber with asphalt, to

increase the contact between the tire and the roads surface, and turn it safer for
drivers.
The conclusion made in this report is that the vulcanization process, despite of the
pollution problem, was a great benefit for society in many aspects, going from
industrial profits to safety in medical applications. Undoubtedly, it was a great
engineering breakthrough, changing the society in many aspects.

BIBLIOGRAPHY
Figure 1: A centuries-old latex ball made by the Olmec in what is now Mexico. Picture,
National Geographic, viewed 25 September 2014, http://s.ngeo.com/wpf/medialive/photos/000/211/cache/mesoamerican-rubber-balls-mayan-incanolmecs_21108_600x450.jpg
Figure 2: Charles Goodyear, painting, Chemistry Explained, viewed 25 September
2014. http://www.chemistryexplained.com/images/chfa_02_img0375.jpg
Figure 3: vulcanized rubber, showing the disulfide cross-links, figure, Meritnation,
viewed 25 September 2014,
http://www.meritnation.com/img/shared/discuss_editlive/3950778/2013_09_23_20_4
1_28/vulcanized%20rubber.png
Figure 3: Vulcanization of silicones, picture, Wikipedia: Vulcanization, viewed 25
September 2014,
http://upload.wikimedia.org/wikipedia/commons/6/60/Silicone_rubber_keypad_exam
ple_1.jpg
Figure 5: 15 Accidental Inventions That Were the Result of a Mistake, picture, Yur
Topic, viewed 25 September 2014
http://www.yurtopic.com/society/history/images/popular-inventionmistakes/vulcanized-rubber.jpg
1

Demand Media 2011, The history of rubber. Ancient Mayas invented ad used for
games, religious observances and tools. Essortment, viewed 25 September 2014.
http://www.essortment.com/history-rubber-21100.html
Natural rubber, Wikipedia, wikiarticle, viewed 25 September 2014,
http://en.wikipedia.org/w/index.php?title=Natural_rubber&redirect=no
2

and

Vulcanization, Wikipedia, wikiarticle, viewed 25 September 2014,

http://en.wikipedia.org/wiki/Vulcanization
4

and

5,

and

CHEMIE.DE Information Service GmbH 1997-2014, Vulcanization,

Chemeurope.Com, viewed 25 September 2014
http://www.chemeurope.com/en/encyclopedia/Vulcanization.html