Vulcanization#Room temperature vulcanization

File:Roller-hockey-(Quad)-Ball.jpg ball obtained via vulcanisation.]]

In ancient Mesoamerican cultures, rubber was used to make balls, sandal soles, elastic bands, and waterproof containers.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 It was cured using sulfur-rich plant juices, an early form of vulcanization.{{Cite web|url=https://news.mit.edu/1999/rubber-0714|title=Rubber processed in ancient Mesoamerica, MIT researchers find|website=News.mit.edu|date=14 July 1999 |access-date=25 October 2021}}

In the 1830s, Charles Goodyear worked to devise a process for strengthening rubber tires. Tires of the time would become soft and sticky with heat, accumulating road debris that punctured them. Goodyear tried heating rubber in order to mix other chemicals with it. This seemed to harden and improve the rubber, though this was due to the heating itself and not the chemicals used. Not realizing this, he repeatedly ran into setbacks when his announced hardening formulas did not work consistently. One day in 1839, when trying to mix rubber with sulfur, Goodyear accidentally dropped the mixture in a hot frying pan. To his astonishment, instead of melting further or vaporizing, the rubber remained firm and, as he increased the heat, the rubber became harder. Goodyear worked out a consistent system for this hardening, and by 1844 patented the process and was producing the rubber on an industrial scale.{{Citation needed|date=May 2023}}

On 21 November 1843, a British inventor, Thomas Hancock took out a patent for the vulcanisation of rubber using sulfur, 8 weeks before Charles Goodyear in the US (30 January 1844). Accounts differ as to whether Hancock's patent was informed by inspecting samples of American rubber from Goodyear and whether inspecting such samples could have provided sufficient information to recreate Goodyear's process.

There are many uses for vulcanized materials, some examples of which are rubber hoses, shoe soles, toys, erasers, hockey pucks, shock absorbers, conveyor belts,{{Cite web|date=2020-01-27|title=A Guide to the Uses and Benefits of Vulcanised Rubber|url=https://www.martins-rubber.co.uk/blog/what-is-vulcanised-rubber-used-for/|access-date=2021-06-16|website=Martins Rubber|language=en-GB}} vibration mounts/dampers, insulation materials, tires, and bowling balls.{{Cite web|title=Vulcanized Rubber|date=April 6, 2019 |url=https://www.tech-faq.com/vulcanized-rubber.html|access-date=2021-06-16|language=en-US}} Most rubber products are vulcanized as this greatly improves their lifespan, function, and strength.

In contrast with thermoplastic processes (the melt-freeze process that characterize the behaviour of most modern polymers), vulcanization, in common with the curing of other thermosetting polymers, is generally irreversible.

Five types of curing systems are in common use:

1. Sulfur systems
2. Peroxides
3. Metallic oxides
4. Acetoxysilane
5. Urethane crosslinkers

File:The Employment of Women in Britain, 1914-1918 Q28267.jpg

{{Main|Sulfur vulcanization}}

The most common vulcanizing methods depend on sulfur. Sulfur, by itself, is a slow vulcanizing agent and does not vulcanize synthetic polyolefins. Accelerated vulcanization is carried out using various compounds that modify the kinetics of crosslinking;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}} this mixture is often referred to as a cure package. The main polymers subjected to sulfur vulcanization are polyisoprene (natural rubber) and styrene-butadiene rubber (SBR), which are used for most street-vehicle tires. The cure package is adjusted specifically for the substrate and the application. The reactive sites—cure sites—are allylic hydrogen atoms. These C-H bonds are adjacent to carbon-carbon double bonds (>C=C<). During vulcanization, some of these C-H bonds are replaced by chains of sulfur atoms that link with a cure site of another polymer chain. These bridges contain between one and several atoms. The number of sulfur atoms in the crosslink strongly influences the physical properties of the final rubber article. Short crosslinks give the rubber better heat resistance. Crosslinks with higher number of sulfur atoms give the rubber good dynamic properties but less heat resistance. Dynamic properties are important for flexing movements of the rubber article, e.g., the movement of a side-wall of a running tire. Without good flexing properties these movements rapidly form cracks, and ultimately will make the rubber article fail.

The vulcanization of neoprene or polychloroprene rubber (CR rubber) is carried out using metal oxides (specifically MgO and ZnO, sometimes Pb₃O₄) rather than sulfur compounds which are presently used with many natural and synthetic rubbers. In addition, because of various processing factors (principally scorch, this being the premature cross-linking of rubbers due to the influence of heat), the choice of accelerator is governed by different rules to other diene rubbers. Most conventionally used accelerators are problematic when CR rubbers are cured and the most important accelerant has been found to be ethylene thiourea (ETU), which, although being an excellent and proven accelerator for polychloroprene, has been classified as reprotoxic. From 2010 to 2013, the European rubber industry had a research project titled SafeRubber to develop a safer alternative to the use of ETU.{{cite web |title=A Safer Alternative Replacement for Thiourea Based Accelerators in the Production Process of Chloroprene Rubber |website=cordis.europa.eu |url=https://cordis.europa.eu/project/id/243756 |access-date=2024-04-25}}

File:Silicone rubber keypad example 1.jpg typical of LSR (Liquid Silicone Rubber) moulding]]

{{Main|RTV silicone}}

Room-temperature vulcanizing (RTV) silicone is constructed of reactive oil-based polymers combined with strengthening mineral fillers. There are two types of room-temperature vulcanizing silicone:

1. RTV-1 (One-component systems); hardens due to the action of atmospheric humidity, a catalyst, and acetoxysilane. Acetoxysilane, when exposed to humid conditions, will form acetic acid.{{cite web|title=MSDS for red RTV-Silicone|url=http://www.permatex.com/documents/msds/01_USA-English/81160.pdf |archive-url=https://ghostarchive.org/archive/20221009/http://www.permatex.com/documents/msds/01_USA-English/81160.pdf |archive-date=2022-10-09 |url-status=live|access-date=24 June 2011}} The curing process begins on the outer surface and progresses through to its core. The product is packed in airtight cartridges and is either in a fluid or paste form. RTV-1 silicone has good adhesion, elasticity, and durability characteristics. The Shore hardness can be varied between 18 and 60. Elongation at break can range from 150% up to 700%. They have excellent aging resistance due to superior resistance to UV radiation and weathering.
2. RTV-2 (Two-component systems); two-component products that, when mixed, cure at room-temperature to a solid elastomer, a gel, or a flexible foam. RTV-2 remains flexible from {{convert|−80|to|250|C|F}}. Break-down occurs at temperatures above {{convert|350|C}}, leaving an inert silica deposit that is non-flammable and non-combustible. They can be used for electrical insulation due to their dielectric properties. Mechanical properties are satisfactory. RTV-2 is used to make flexible moulds, as well as many technical parts for industry and paramedical applications.

• ISO 2921
• Polymer stabilizers
• Sulfur concrete
• Vulcanized fibre
• Vulcanizing shop

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Category:Chemical processes