10/5/24, 10:04 PM Rheology in Elastomer Technology

Vulcanization is the chemical process that transforms raw rubber into more durable and elastic
materials by forming crosslinks between individual polymer chains. Different vulcanization methods
use specific chemicals or conditions to initiate and control crosslinking, depending on the type of
rubber and desired properties of the final product. Below are detailed processes for each type of
vulcanization.

1. Sulfur Vulcanization

a. Conventional Vulcanization (CV)

Process:
1. Mixing: Sulfur (2-3 phr), accelerators (e.g., MBTS), activators (e.g., zinc oxide, stearic acid),
and other additives (antioxidants, fillers) are mixed with the rubber in an internal mixer or
on a two-roll mill.
2. Shaping: The rubber compound is shaped into the desired product using extrusion,
calendering, or molding techniques.
3. Vulcanization: The rubber is heated at 140-160°C in molds or in steam autoclaves. This
heat initiates the sulfur-accelerator reaction that forms polysulfidic crosslinks (chains with
multiple sulfur atoms between the rubber molecules).
4. Crosslinking: The sulfur atoms form bridges between adjacent polymer chains, resulting in
a rubber that has improved elasticity, tensile strength, and wear resistance.
Properties:
High elasticity and flexibility.
Susceptible to aging, heat degradation, and reversion (softening under prolonged
heating).
Applications: Tires, conveyor belts, general-purpose rubber products.

b. Semi-Efficient Vulcanization (Semi-EV)

Process:

1. Mixing: A reduced amount of sulfur (around 1 phr) and a higher dose of accelerators (e.g.,
CBS or TBBS) are used, along with zinc oxide, stearic acid, and fillers.
2. Shaping: The compounded rubber is shaped as desired.
3. Vulcanization: Heating the rubber to 140-160°C triggers crosslinking. Since less sulfur is
used, both polysulfidic and monosulfidic crosslinks (with fewer sulfur atoms) form,
providing a balance of properties.
Properties:

Better heat and aging resistance than conventional vulcanization.

Good mechanical properties and moderate flexibility.
Applications: Used in moderate-heat applications like automotive parts, conveyor belts.
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c. Efficient Vulcanization (EV)

Process:
1. Mixing: Very low amounts of sulfur (0.2-0.5 phr) and large quantities of fast accelerators
(e.g., TMTD, CBS) are mixed into the rubber with zinc oxide and other additives.
2. Shaping: The rubber is processed into the desired shape.
3. Vulcanization: The rubber is heated to 140-160°C. The reaction primarily
forms monosulfidic crosslinks, which provide superior thermal stability.
Properties:
Excellent heat, chemical, and aging resistance.
Stiffer and less flexible compared to conventional systems.
Applications: Heat-resistant products like hoses, seals, and automotive components.

2. Peroxide Vulcanization
Process:
1. Mixing: Peroxides (e.g., dicumyl peroxide, benzoyl peroxide) are mixed into the rubber
along with other additives (e.g., coagents like triallyl cyanurate or zinc oxide for faster
curing).
2. Shaping: The compound is extruded or molded into its final shape.
3. Vulcanization: The rubber is heated at 160-180°C, causing the peroxide to decompose
and form free radicals. These free radicals initiate the formation of carbon-carbon (C-C)
crosslinks between the polymer chains instead of sulfur-based crosslinks.
4. Crosslinking: The C-C bonds are stable and resistant to heat and oxidation, leading to
superior aging properties.
Properties:
Excellent heat, aging, and chemical resistance.
Lower elasticity compared to sulfur-vulcanized rubber.
Applications: EPDM rubber in seals, gaskets, wire insulation, automotive components.

3. Radiation Vulcanization
Process:
1. Pre-Mixing: Rubber and additives (fillers, antioxidants, plasticizers) are mixed together, but
no sulfur or accelerators are needed.
2. Shaping: The material is shaped by extrusion or molding.

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3. Irradiation: The shaped rubber is exposed to high-energy gamma rays or electron beams.
The energy from the radiation generates free radicals in the rubber.
4. Crosslinking: The free radicals initiate crosslinking between polymer chains without the
need for any curing agents, leading to strong, stable bonds.
Properties:
No residue from chemical vulcanization.
Excellent control over the crosslinking process.
Applications: Medical rubber products, food-grade rubbers, specialized electronics.

4. Resin Vulcanization
Process:
1. Mixing: A phenolic resin (typically alkylphenol-formaldehyde resin) is mixed with the
rubber. Fillers, plasticizers, and other additives are also included.
2. Shaping: The rubber compound is shaped by extrusion or molding.
3. Vulcanization: The resin-containing rubber is heated at temperatures around 150-180°C.
The phenolic resin reacts with the rubber to form crosslinks between the polymer chains.
4. Crosslinking: Unlike sulfur vulcanization, the crosslinks formed by resins are much
stronger and more heat-resistant, producing a harder, more rigid vulcanizate.
Properties:
High heat resistance and hardness.
Superior dimensional stability.
Applications: Tire inner liners, high-heat components, gaskets, industrial diaphragms.

5. Metal Oxide Vulcanization

Process:
1. Mixing: Chloroprene rubber (Neoprene) or halogenated rubbers (e.g., Butyl or EPDM) are
mixed with metal oxides (usually zinc oxide or magnesium oxide). In addition,
accelerators, fillers, and plasticizers are added.
2. Shaping: The compound is extruded or molded.
3. Vulcanization: The rubber is heated to temperatures of 140-160°C. The metal oxides react
with the halogenated rubber to form ionic crosslinks, instead of sulfur crosslinks.
4. Crosslinking: Ionic crosslinks give excellent heat and flame resistance.
Properties:

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Outstanding resistance to weathering, heat, and flame.

Better electrical insulation properties.
Applications: Flame-resistant cable coverings, automotive hoses, adhesives, weather-resistant
seals.

6. Urethane Crosslinking (Polyurethane Vulcanization)

Process:
1. Mixing: Polyurethane rubber (PU) is mixed with diisocyanates (e.g., toluene diisocyanate)
or polyisocyanates. These chemicals act as crosslinking agents. Other additives such as
fillers and plasticizers are included as well.
2. Shaping: The compound is shaped by molding or casting.
3. Vulcanization: At room or slightly elevated temperatures, the diisocyanates react with
hydroxyl groups in the polymer, forming urethane crosslinks.
4. Crosslinking: The urethane crosslinks provide high mechanical strength and durability.
Properties:
High abrasion and tear resistance.
Good mechanical properties and flexibility.
Applications: Rollers, bushings, coatings, and industrial parts requiring high wear resistance.

7. Sulfur Donor Vulcanization

Process:
1. Mixing: Sulfur donors (e.g., TMTD, DTDM) are used instead of elemental sulfur in the
rubber compound. These donors provide sulfur in a controlled manner to form more
stable, shorter crosslinks (monosulfidic).
2. Shaping: The rubber compound is extruded or molded.
3. Vulcanization: The rubber is heated to standard vulcanization temperatures (140-160°C),
and the sulfur donor releases sulfur for crosslinking.
4. Crosslinking: Shorter sulfur chains form, offering improved heat and aging resistance.
Properties:
Better heat resistance than conventional sulfur vulcanization.
Less reversion (softening at high temperatures).
Applications: High-performance tires, industrial rubber parts.

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10/5/24, 10:04 PM Rheology in Elastomer Technology

8. Microwave Vulcanization
Process:
1. Mixing: A standard rubber compound (containing sulfur or peroxide for curing) is
prepared.
2. Shaping: The rubber compound is extruded into profiles, tubes, or sheets.
3. Vulcanization: The shaped rubber is passed through a microwave oven. The microwaves
heat the rubber uniformly and rapidly, activating the curing agents (sulfur, peroxides) to
initiate crosslinking.
4. Crosslinking: Depending on the curing agent used, the crosslinks can be sulfur-based or
carbon-based (in peroxide systems).
Properties:
Rapid and uniform curing.
Suitable for continuous processing.
Applications: Hoses, profiles, rubber sheets, and tubing.

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