Rubber Compounding

Rubber compounding involves the science and engineering of

rubbers and rubber additives, such as processing aids, fillers, and
curing agents, in definite proportions to obtain a uniform mixture
that will have desirable physical and chemical properties to meet
processing at low cost and end use performance.

From: Progress in Rubber Nanocomposites, 2017

Related terms:

Butadiene, Carbon Black, Elastomer, Graphene, Polytetrafluoroethylene, Styrene,

Zinc Oxide, Bisphenol A, Furan, Phenolic Resin

Multilayer Graphene/Elastomer Nanocomposites

Martin Böhning, ... Bernhard Schartel, in

Carbon-Based Nanofillers and Their Rubber Nanocomposites, 2019

6.2.4 Nanocomposite Preparation

Rubber compounding was performed on a two-roll mill (Lab Walzwerk

MT 6″×13″, Rubicon, Germany) in a three-stage process. In the first stage,

the rubber was mixed with zinc oxide, stearic acid, CB, and Struktol or

IPPD. Then the rubber/MLG masterbatch was added to the rubber

compound in the second stage. For the M-MLG route, the MLG was added

directly at this stage of compounding. Finally, the curatives (sulfur and

MBTS) were added in the third stage. For all compounds, the rolls were set

to a temperature of 50°C at a speed of 19 rpm with a friction ratio of 1.1:1

and a mixing time of 20 min. For the reference compounds without MLG

the second stage was not performed.

The same procedure was applied for the CIIR-based compounds

containing CB [26]. CB was added in the second processing stage on the

two-roll mill, with or without MLG masterbatch added at the same time.

Vulcanization was performed at 300 bar with curing temperatures of

180°C for CIIR and 150°C for the other materials. The curing times were

determined beforehand by a dynamic moving die rheometer (D-MDR 300,

MontechWerkstoffprüfmaschinen, Germany), as the time of maximum

torque (t100). For CIIR and NBR, the curing time was 20 min, for NR 18 min,

and for SBR 60 min.

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Characteristics of elastomer materials

Maziar Ramezani, Zaidi M. Ripin, in Rubber-Pad Forming Processes, 2012

3.3 Compounding
Rubber compounding or formulation refers to the addition of certain

chemicals to raw rubber in order to obtain the desired properties. The

well-known chemicals are crosslinking agents, reinforcements, anti

degradants and colorants. The crosslinking agents are required for

establishing the crosslinks to interconnect at molecular level thus

improving the strength and elasticity. Unformulated elastomers behave

like a high molecular weight with low elasticity and strength. Through

formulation long-chain molecules are chemically linked together, forming

networks and transforming the material from a viscous liquid to elastic

solid. This is what happens during vulcanization or curing, which

increases the strength and the modulus and decreases the hysteresis.

Sulphur is widely used as the vulcanization agent.

A deformed elastomer stores the input energy in terms of elastic potential

energy in the chains. This is released upon crack growth and acts as the

driving force for fracture to propagate. The remaining energy is dissipated

into heat through the molecular motions. Tight network of the molecular

chain due to high crosslink levels restricted the chain motion preventing

the network from dissipating much of the energy which causes brittle

fracture at low elongation. Too high crosslink level is undesirable and can

lead to brittle fracture and too little crosslinks may not be strong enough

to resist viscous flow failure. Therefore, the optimum density range of the

crosslinks for practical use needs to be determined.

Reinforcing agents of the rubber compound act as stress arrestor and are

required to have high specific area. This means that the particle must be

smaller than 1 μm in size. Typical fillers are carbon black and silica. A

primary particle size as small as 0.1 μm can be obtained which can give a

specific area of a few hundred square meters per gram of filler.

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Nanostructures and Compatibility in Rubber

Nanocomposites Containing Carbon Nanofillers

Carolina F. de Matos, ... Fernando Galembeck, in

Carbon-Based Nanofillers and Their Rubber Nanocomposites, 2019

1.5.2.2 Mechanochemical Grafting

Rubber compounding with carbon particles often involves intensive

mechanical processing and both components are susceptible to grafting

reactions. The mechanochemical reactions induced by mechanical energy

imparted to elastomer molecules have been used since Hancock

discovered the effects of “mastication,” that is the mechanochemical

degradation of a polymer [74].

Polymers exposed to triboplasma created by mechanical action undergo

chain breaking, free radical, or ion formation at the chain ends followed
by hydrogen abstraction, electron transfer, radical recombination-

producing grafts, and other events that have been demonstrated and

discussed in the contexts of tribochemistry, photochemistry, and

radiation chemistry [75].

Mechanochemical reactions may also happen when mixing CB or other

fillers, while grafted and block copolymers are obtained by comastication

of different rubbers. These reactions include the initiation of block or

graft copolymerization of vinyl monomers with rubber and they can also

allow rubber functionalization with reactants carrying suitable chemical

groups. Mechanochemical reactions may still take place within the

finished rubber goods, during their use, as in the thermo-oxidative aging

processes. Mechanochemistry is also used in modern recycling methods

applied to car tires and other rubber goods, especially in tire scrap

devulcanization [76].

Grafting on carbon particles has also been demonstrated, as in the case of

polyvinylpyrrolidone grafting on carbon nanofibers, in a thermal reaction

initiated by benzoyl peroxide. Another example describes CB

functionalization with atom transfer radical polymerization (ATRP)

initiating moieties by the reaction of surface carboxylic acid groups with

an ATRP initiator containing the hydroxy groups. Controlling initiator

density led to different polymer molecular weight distributions. Block

copolymer–grafted CB was also obtained and further polymer

modification yielded an amphiphilic core–shell grafted CB, dispersible in

water under basic conditions [77].

Polymer grafting of CB is thus an effective way for improving the

solubility and compatibility of CB. Currently, there are methods for

grafting polymers with well-controlled composition, structure, and

molecular weight onto the surface of CB, opening a number of new

possibilities to extend the applications of polymer–CB composites in

different areas [78].

Yang et al. [79] propose a generic mechanochemical grafting strategy to

prepare the organo-soluble CNTs. With this approach, the solvent

spectrum of the CNT suspension was extended by changing the chemical

composition of the grafted elastomer chains.

These few examples show that carbon surfaces are suitable sites for

anchoring preexisting and in situ grown polymer chains, participating

from chemical reactions that were intensively studied in solution, in

melts, and in solid states. Thus, mechanical action on mixed carbon

particles and rubber can produce chemical bonds between particles and

chains, forming amphipathic carbon–polymer entities that will contribute

to greater stability of the mixtures and to other effects, like increased

electrical resistance.

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Note on Reclaimed Rubber

V.C. Chandrasekaran, in Essential Rubber Formulary, 2007

Reclaimed rubber is a rubber compounding ingredient. Scrap rubber,

unlike scrap steel, undergoes a special process before it can be reused and

the rubber that is obtained at the end of this process is known as

reclaimed rubber. The rubber reclaiming industry is a specialized industry

that resembles its parent industry in development and growth. The use of

reclaimed rubber in rubber compounding gives several advantages and

therefore it deserves the special consideration of all rubber technologists.

The advantages of using reclaimed rubber are:

1. It is economic. Reclaim-added compounds are much cheaper. Even in a

high quality compound, reclaimed rubber if used in judicious

proportions can give considerable savings.

2. Ease of processibility in the mixing mill, extruder, calender, frictioning,

and skim coating operations.

3. Reclaimed rubber is uniform and is compatible with most

accelerators, and has a retarding effect on Vulcanisation.

4. Faster curing compounds can be made with reclaimed rubber.

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RUBBER PROCESSING

Peter A. Ciullo, Norman Hewitt, in The Rubber Formulary, 1999

Mastication
The first step in rubber compounding is mastication or polymer

“breakdown”. This is essentially development of the polymer's

viscoelasticity to make it receptive to the additives. Most synthetic

elastomers are produced with the uniformity in chemistry, viscosity and

stability that minimizes or precludes the need for mastication. This step

is, nevertheless, usually necessary for compounds containing a blend of

polymers to provide a uniform mixture prior to further compounding.

Natural rubber is characteristically widely variable in viscosity from lot to

lot, so that several lots are usually blended and masticated to control

viscosity and physical properties of the compound. The breakdown of

natural rubber promotes viscoelasticity by extending or disentangling the

polymer chains or by severing the chains. Breakdown cycles for both

natural and synthetic rubber are often facilitated by the inclusion of

plasticizers.

Polymer breakdown and subsequent compounding was historically

accomplished on open roll mills, although today these operations are

almost always performed in an internal mixer. The open mill consists of

two metal rolls which are jacketed for temperature control. These rolls

turn toward each other at fixed separations and often at different speeds.

This provides high shear mixing forces. Banbury® Mixers are the most
commonly used internal mixers today. They consist of two rotor blades

turning toward each other in an enclosed metal cavity. The cavity is fed

from a loading chute through which the rubber and in later steps the

fillers and compounding chemicals are added. Mixing shear, and

consequent mixing time, is determined by rotor shape, size, and speed. A

large Banbury can produce 500 kg of finished compound in a matter of

minutes.

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Other Types of Additive: Additives for Rubber

John Murphy, in Additives for Plastics Handbook (Second Edition), 2001

Table 19.1. Additives used in rubber compounding

Additive Function Typical chemicals used

Peptizers Chemically assist Thiobenzoate, zinc-2-

breakdown of rubber benzamidothiophenate, thio-β-

chains, to increase naphthol

efficiency of

mastication

Processing Soften and tackify Pine tar. mineral oil, wax, factice,

aids rubber, for easy coumarone-indene resins, petroleum

uniform mixing resins, high styrene resins, phenolic

resins

Plasticizers Plasticizing, Esters: phthalates, phosphates.

tackifying Polymerizable: ethylene glycol

dimethacrylate

Fillers: non- Mainly for cost Non-black: china clay, whiting,

black reduction: magnesium carbonate, hydrated

reinforcement from alumina, anhydrous/hydrated silicas

finely ground fillers (slate powder, talc, French chalk)

Fillers: Improved modulus, Carbon black (mainly from furnace

black tear strength, process)

abrasion resistance,

hardness; may also

assist cure

Anti- Protection from Staining (amines): phenyl

degradants attack by oxygen and naphthylamines. 4,4-dialkyl or

ozone dialkoxydiphenyl-amines. N,N-

dialkyl or diaryl-ρ-

phenylenediamines; staining

(phenols): styrenated phenols,

substituted phenols, σ- or ρ-bridged

substituted phenols

Vulcanizing Curing, cross- Accelerators: guanidines, thiazoles,

agents linking: control of sulphenamides, dithiocarbamates,

reaction to achieve thiuram sulphides, xanthates,

balance of optimum aldehydeamines; retarders: phthalic

properties without anhydride, N-nitroso diphenylamine;

scorch, in economic activators: zinc oxide/stearic acid

time

Source: Based on 'Polymer Science andTechnology of Plastics and

Rubbers'

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Processing of Fluoroelastomers

Albert L. Moore Sc.D., in Fluoroelastomers Handbook, 2006

6.2.2 Mill Mixing

Two-roll mills have been used for rubber compounding since the middle

of the nineteenth century. Originally they were also used for mastication

of natural rubber, to break down high molecular weight fractions.

However, such breakdown is generally not desirable for synthetic

elastomers, including fluoroelastomers, which are designed to have

molecular weight distributions optimized for various processing methods

and end uses. Mills are suited to low-volume production of specialty

fluoroelastomer compounds, but have been largely replaced with internal

mixers. In many production operations, mills are used for sheeting off

stock from internal mixers or for warm-up of compounds for sheet feed to

extruders or calenders.

A typical rubber mill is shown in Fig. 6.1.[1] The mill consists of two closely

spaced parallel, horizontal rolls made from hard castings supported by

strong bearings in a mill frame. The counter-rotating rolls are driven at

different speeds to maintain a friction ratio of 1.05 to 1.25, transporting

the rubber over the top of the roll to the nip area, then through the nip

with small adjustable clearance (usually 2–6 mm) to subject the stock to

high shear stresses. To get good mixing, the amount of stock and mill

clearances used should result in formation of a smooth band on one roll,

with a rolling bank of stock in the nip. The surface speed of the slow roll is

about 50 cm/s, allowing the mill operator to cut the band diagonally and

fold the cut portion over the remaining band for blending. The mill rolls

are hollow to allow flow of coolant for control of roll and stock

temperatures. A number of safety features are incorporated into mill

design, including shutoff switches and brakes to stop the rolls quickly,

means to move the rolls apart, and guards to keep hands and tools away

from the nip area. Stringent operator training and adherence to safe
procedures are necessary to avoid the inherent hazards involved in mill

operation.

Figure 6.1. Rubber mixing and sheeting mill.[1]

A typical mill mixing procedure is given in a 1975 DuPont product

bulletin.[2] The fluoroelastomer described is a VDF/HFP dipolymer

precompound, Viton® E-60C, containing about 2 phr Bisphenol AF and

0.55 phr BTPPC accelerator. The medium-viscosity polymer was designed

with a considerable high molecular weight fraction to impart enough

cohesive strength for good mill mixing. A batch size of about 40 kg is

recommended for a production-scale mill (about 50 cm diameter and 150

cm length). The compound recipe contains 100 phr E-60C precompound,

30 phr MT black, 6 phr calcium hydroxide, and 3 phr magnesium oxide.

The clean mill is cooled to about 25°C and the nip is adjusted to about 3

mm. The polymer is added to the mill for banding. Ordinarily, the

fluoroelastomer bands on the fast roll, but may be forced to the slow roll

by increasing the temperature slightly on the slow roll. The nip is adjusted

to about 5 mm to get a rolling bank in the nip. The banded polymer is cut

about three times from each side to get a uniform sheet on the roll. The

powdered ingredients are preblended and added at a rapid uniform rate

across the width of the nip. Loose filler that falls through the nip is swept

from the pan and added to the batch before cutting the sheet. Further

mixing is carried out by cutting and blending the sheet about four times

from each side. The mixed sheet is cut off the mill and cooled. About

fifteen minutes of milling time is usually adequate for the total operation

described. Cooling of the slab is accomplished by dipping in a water tank,

or by water spray or forced air. If water cooling is used, it is important to

dry the stock with forced air before storing it.

Mill mixing is difficult, especially on a production scale, for a number of

gum fluoroelastomers. Polymers with narrow molecular weight

distribution and low ionic end group levels may not have adequate

cohesive strength to form a smooth, hole-free band on a single roll. When

addition of powdered ingredients is attempted, the stock and loose fillers

may drop off the rolls into the pan. Subsequent consolidation of such a

batch is time consuming and messy at best. Very high molecular weight

fluoroelastomers undergo significant breakdown during initial passes

through a tight nip of a cold mill, with resultant deterioration of

vulcanizate physical properties. On the other hand, bimodal blends

(formed by latex mixing before isolation) have excellent milling

characteristics, with negligible breakdown of high molecular weight

fractions. High viscosity elastomers with considerable long-chain

branching and gel fractions may also break down during milling, possibly

improving subsequent processing characteristics (e.g., extrusion).

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Soft bio-composites from natural rubber (NR) and

marine products

S. Poompradub, in Chemistry, Manufacture and Applications of Natural Rubber,

2014

11.6 Sources of further information and advice

More information to guide the reader on the general information of the

historical background of rubber, compounding, vulcanization, and

manufacturing technologies of rubber products can be found in the

following:

• Bhowmick, A. K., Hall, M. M. and Benarey, H. A. (1994) Rubber Products

Manufacturing Technology, New York, Marcel Dekker.

• Brydson, J. A. (1988) Rubber Materials and their Compounds, London,

Elsevier Applied Science.

• Hofmann, W. (1989) Rubber Technology Handbook, Munich, Hanser

Publishers.

• Ohm, R. F. (1990) The Vanderbilt Rubber Handbook, Norwalk, CT, R. T.

Vanderbilt Company.

More information on the ecological principles governing marine life

throughout the world, oceanography and the effect of changes in the

carbonate chemistry on marine organisms and ecosystems can be found

in:

• Nybakken, J. W. (1997) Marine Biology: An Ecological Approach, New

York, Addison-Wesley.

• Riebessell, U., Fabry, V. J., Hansson, L. and Gattuso, J. P. (2010) Guide to

Best Practices for Ocean Acidification Research and Data Reporting,

Brussels, European Communities.

• Trujilo, A. P. and Thurman, H. V. (2008) Essentials of Oceanography,

Upper Saddle River, NJ, Pearson Education.

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Rubbers, Chemicals and Compounding for ‘O’ Rings
and Seals

V.C. Chandrasekaran, in Rubber Seals for Fluid and Hydraulic Systems, 2010

Styrene Butadiene Rubber (SBR)

Styrene butadiene rubber is generally marketed at lower viscosity grades

than NR and this permits its use in rubber compounding without

premastication. Mechanical or chemical peptizing (or dispersing as a

colloid, or suspension) is not required in SBR rubber. While most

properties of SBR are comparable with NR, in some respects, such as heat

build up, tack and gum tensile strength, SBR is inferior but addition of

resins and reinforcing fillers improves these properties acceptably.

Owing to its irregular molecular structure, SBR does not crystallize, so

reinforcing filler is required to achieve good physical properties. The best

of these is carbon black; other fillers give very inferior properties in SBR

to those achievable in a corresponding natural rubber compound.

Resistance to abrasion, and degradation under heat is better for SBR, but:

as it is less chemically reactive it is also slower to cure, requiring more

accelerators. Scorch problems are less likely to occur with SBR than with

NR especially with carbon filled compounds. It is compatible with NR,

butadiene rubbers, ethylene–propylene terpolymer (EPDM), nitrile and

chloroprene rubbers. The effect of the sulfur accelerator ratio on the

cross-link distribution in SBR is similar to NR. In general, a lower sulfur

level and a higher accelerator level are normally employed for SBR cure

systems.

Emulsion polymerized SBRs are used alone, as well when as blended with

butadiene or natural rubber. In addition with other diene rubbers, higher

levels of filler (75 phr of carbon black and plasticizer 20 phr, or more than

the quantity contained in oil-extended SBR) may be used.

Cold polymerized SBR is used in light duty products, such as hoses, or

molded goods. Its low resilience in black-filled compounds restricts its

use in products where high heat build up is likely, such as static seals.

Antidegradants can be added to SBR to provide protection during service.

Building tack can be improved by the addition of tackifying resins, or by

blending with natural rubber. The oil resistance of SBR can be improved

by blending nitrile rubbers into the compounds. Petroleum and coal-tar

type plasticizers are used to give easier processing, and reduced costs.

Solution polymerized SBRs are generally more expensive than the

emulsion types, and so are used in specialty applications, where higher

glass transition temperature (Tg) and grip while in contact with fluids are

required. This is particularly useful in high performance rotary seals.

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Rubber-clay nanocomposites

A. Mohammad, G.P. Simon, in Polymer Nanocomposites, 2006

12.1 Introduction
Since the early days of the rubber industry, fillers in the form of fine

particulates have been used in rubber compounding. Particulate fillers are

usually divided into two groups, inert fillers and reinforcing fillers. Inert

fillers are added to the rubber to increase the bulk and reduce costs. In

contrast, reinforcing fillers such as carbon black and silica are

incorporated in the rubber to enhance the mechanical properties, to

change the electrical conductivity, to improve the barrier properties or to

increase the resistance to fire and ignition.1,2 However, a minimum of 20

wt.% of the filler content is usually needed for a significant property

enhancement. This high loading of fillers may reduce the processability of

the rubber compounds and cause the end products to weigh significantly

more than the neat rubber, and thus limit their application in some

industries. The expansion of the polymer industry and the continuous

demand for new, low-cost composites with improved properties and

lower particle content are some of the many new and exciting challenges

for this industry.3,4

Nanocomposites based on layered silicates offer the possibility for new

paradigms of material properties. Although clay nanocomposites have

been prepared and tested for many thermoplastic and thermosetting

polymers, much less attention has been given to the rubber-clay

nanocomposites.5–11 Rubbery polymers with their low modulus stand to

gain much in terms of modulus and strength from the addition of

nanoparticles. In addition, the effect of clay addition on rubber tear

properties, fracture toughness and abrasion properties is only starting to

become known.

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