Vulcanization

Vulcanization (Brit ish: Vulcanisation) is a range of processes for hardening rubbers.[1] The t erm
originally referred exclusively t o t he t reat ment of nat ural rubber wit h sulfur, which remains t he
most common pract ice. It has also grown t o include t he hardening of ot her (synt het ic) rubbers
via various means. Examples include silicone rubber via room t emperat ure vulcanizing and
chloroprene rubber (neoprene) using met al oxides.

Worker placing tire in a mold before vulcanization.

Vulcanizat ion can be defined as t he curing of elast omers, wit h t he t erms 'vulcanizat ion' and
'curing' somet imes used int erchangeably in t his cont ext . It works by forming cross-links bet ween
sect ions of polymer chain which result s in increased rigidit y and durabilit y, as well as ot her
changes in t he mechanical and elect rical propert ies of t he mat erial.[2] Vulcanizat ion, in common
wit h t he curing of ot her t hermoset t ing polymers, is generally irreversible.

The word vulcanizat ion is derived from Vulcan, t he Roman god of fire and forge.

History

Rubber—lat ex—had been known for t housands of years in Mesoamerican cult ures, used t o make
balls, sandal soles, rubber bands, and wat erproof cont ainers. Rubber was processed for specific
applicat ions wit hin t he Azt ec empire — rubber and lat ex goods were processed and const ruct ed,
and t hen shipped t o t he capit al for use or furt her dist ribut ion.[3]

Early rubber t ube t ires in t he 19t h cent ury would grow st icky on a hot road, unt il debris would get
st uck in t hem and event ually t he t ires would burst .

Charles Goodyear, in t he 1830s, was working t o improve t hose t ube t ires. He t ried heat ing up
rubber in order t o mix ot her chemicals wit h it . This seemed t o harden and improve t he rubber,
t hough t his was due t o t he heat ing it self and not t he chemicals used. Not realizing t his, he
repeat edly ran int o set backs when his announced hardening formulas did not work consist ent ly.
One day in 1839, when t rying t o mix rubber wit h sulfur, Goodyear accident ally dropped t he
mixt ure in a hot frying pan. To his ast onishment , inst ead of melt ing furt her or vaporizing, t he
rubber remained firm and, as he increased t he heat , t he rubber became harder. Goodyear quickly
worked out a consist ent syst em for t his hardening, which he called vulcanizat ion because of t he
heat involved. He obt ained a pat ent in t he same year, and by 1844 was producing t he rubber on
an indust rial scale.

Applications

There are many uses for vulcanized mat erials, some examples of which are rubber hoses, shoe
soles, t oys, erasers, shock absorbers, conveyor belt s,[4] vibrat ion mount s/dampers, insulat ion
mat erials, t ires, and bowling balls.[5] Most rubber product s are vulcanized as t his massively
improves t heir lifespan, funct ion, and st rengt h.
 Overview

In cont rast wit h t hermoplast ic processes (t he melt -freeze process t hat charact erize t he
behaviour of most modern polymers), vulcanizat ion, in common wit h t he curing of ot her
t hermoset t ing polymers, is generally irreversible.
Five t ypes of curing syst ems are in common
use:

1. Sulfur syst ems

2. Peroxides

3. Met allic oxides

4. Acet oxysilane

5. Uret hane crosslinkers

Vulcanization with sulfur

The most common vulcanizing met hods depend on sulfur. Sulfur, by it self, is a slow vulcanizing
agent and does not vulcanize synt het ic polyolefins. Accelerat ed vulcanizat ion is carried out using
various compounds t hat modify t he kinet ics of crosslinking;[6] t his mixt ure is oft en referred t o as
a cure package.
The main polymers subject ed t o sulfur vulcanizat ion are polyisoprene (nat ural
rubber) and st yrene-but adiene rubber (SBR), which are used for most st reet -vehicle t ires. The
cure package is adjust ed specifically for t he subst rat e and t he applicat ion. The react ive sit es—
cure sit es—are allylic hydrogen at oms. These C-H bonds are adjacent t o carbon-carbon double
bonds. During vulcanizat ion, some of t hese C-H bonds are replaced by chains of sulfur at oms
t hat link wit h a cure sit e of anot her polymer chain. These bridges cont ain bet ween one and
several at oms. The number of sulfur at oms in t he crosslink st rongly influences t he physical
propert ies of t he final rubber art icle. Short crosslinks give t he rubber bet t er heat resist ance.
Crosslinks wit h higher number of sulfur at oms give t he rubber good dynamic propert ies but less
heat resist ance. Dynamic propert ies are import ant for flexing movement s of t he rubber art icle,
e.g., t he movement of a side-wall of a running t ire. Wit hout good flexing propert ies t hese
movement s rapidly form cracks, and ult imat ely will make t he rubber art icle fail.

Vulcanization of polychloroprene

The vulcanizat ion of neoprene or polychloroprene rubber (CR rubber) is carried out using met al
oxides (specifically MgO and ZnO, somet imes Pb3O4) rat her t han sulfur compounds which are
present ly used wit h many nat ural and synt het ic rubbers. In addit ion, because of various
processing fact ors (principally scorch, t his being t he premat ure cross-linking of rubbers due t o
t he influence of heat ), t he choice of accelerat or is governed by different rules t o ot her diene
rubbers. Most convent ionally used accelerat ors are problemat ic when CR rubbers are cured and
t he most import ant accelerant has been found t o be et hylene t hiourea (ETU), which, alt hough
being an excellent and proven accelerat or for polychloroprene, has been classified as reprot oxic.
The European rubber indust ry has st art ed a research project SafeRubber[7] t o develop a safer
alt ernat ive t o t he use of ETU.

Vulcanization of silicones

An example of a silicone rubber keypad typical of LSR (Liquid Silicone Rubber) moulding

Room-t emperat ure vulcanizing (RTV) silicone is const ruct ed of react ive oil-based polymers
combined wit h st rengt hening mineral fillers. There are t wo t ypes of room-t emperat ure
vulcanizing silicone:

1. RTV-1 (One-component syst ems); hardens due t o t he act ion of at mospheric humidit y, a
cat alyst , and acet oxysilane. Acet oxysilane, when exposed t o humid condit ions, will form
acet ic acid.[8] The curing process begins on t he out er surface and progresses t hrough t o it s
core. The product is packed in airt ight cart ridges and is eit her in a fluid or past e form. RTV-1
silicone has good adhesion, elast icit y, and durabilit y charact erist ics. The Shore hardness can
be varied bet ween 18 and 60. Elongat ion at break can range from 150% up t o 700%. They
have excellent aging resist ance due t o superior resist ance t o UV radiat ion and weat hering.
2. RTV-2 (Two-component syst ems); t wo-component product s t hat , when mixed, cure at
room-t emperat ure t o a solid elast omer, a gel, or a flexible foam. RTV-2 remains flexible from
−80 t o 250 °C (−112 t o 482 °F). Break-down occurs at t emperat ures above 350 °C (662 °F),
leaving an inert silica deposit t hat is non-flammable and non-combust ible. They can be used
for elect rical insulat ion due t o t heir dielect ric propert ies. Mechanical propert ies are
sat isfact ory. RTV-2 is used t o make flexible moulds, as well as many t echnical part s for
indust ry and paramedical applicat ions.

See also

Polymer st abilizers

Vulcanized fibre

References

1. Akiba, M (1997). "Vulcanization and crosslinking in elastomers". Progress in Polymer Science. 22 (3):
475–521. doi:10.1016/S0079-6700(96)00015-9 (https://doi.org/10.1016%2FS0079-6700%2896%29000
15-9) .

2. James E. Mark, Burak Erman (eds.) (2005). Science and technology of rubber. p. 768. ISBN 0-12-
464786-3. {{cite book}}: |author= has generic name (help)

3. Tarkanian, M., & Hosler, D. (2011). America’s First Polymer Scientists: Rubber Processing, Use and
Transport in Mesoamerica. Latin American Antiquity, 22(4), 469-486. doi:10.7183/1045-6635.22.4.469

4. "A Guide to the Uses and Benefits of Vulcanised Rubber" (https://www.martins-rubber.co.uk/blog/what-i

s-vulcanised-rubber-used-for/) . Martins Rubber. January 27, 2020. Retrieved June 16, 2021.

5. "Vulcanized Rubber" (https://www.tech-faq.com/vulcanized-rubber.html) . Retrieved June 16, 2021.

6. Hans-Wilhelm Engels, Herrmann-Josef Weidenhaupt, Manfred Pieroth, Werner Hofmann, Karl-Hans

Menting, Thomas Mergenhagen, Ralf Schmoll, Stefan Uhrlandt “Rubber, 4. Chemicals and Additives” in
Ullmann's Encyclopedia of Industrial Chemistry, 2004, Wiley-VCH, Weinheim.
doi:10.1002/14356007.a23_365.pub2 (https://doi.org/10.1002%2F14356007.a23_365.pub2)

7. SafeRubber, an alternative accelerator to the development of rubber (http://www.saferubber.eu/)

8. "MSDS for red RTV-Silicone" (http://www.permatex.com/documents/msds/01_USA-English/81160.pdf)

(PDF). Retrieved June 24, 2011.
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