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The Complete Book on Rubber Processing and Compounding Technology

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The Complete Book on Rubber Processing and Compounding Technology

Author: NIIR Board of Consultants and Engineers
Format: Paperback
ISBN: 8178330059
Code: NI174
Pages: 712
Price: Rs. 1,275.00   US$ 125.00

Published: 2006
Publisher: Asia Pacific Business Press Inc.
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Rubber products industry is an important resource based industry sector in India. Over the last decade the rubber industry has witnessed a steady and strong growth. Rubber can be deformed to a high degree of strain in a reversible manner and this special property finds use in fields as diverse as transportation, material handling, health care, and sport and leisure activities. The book covers manufacturing processes of rubber products, compounding of rubber, quality assurance, applications etc. Thus book is very useful for new entrepreneurs, existing units, technical institutions, technocrats etc.

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Contents

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1 RUBBERS: MATERIALS AND PROCESSING TECHNOLOGY
Natural Rubber Plantation
Tapping of Rubber Latex
Preservation and Coagulation of Latex
Chemical Nature of Natural Rubber Hydrobcarbon
Hydrogenated Rubber
Cyclized Rubber
Chlorinated Rubber
Rubbers from Stereo-regular Polymerization of Isoprene and Butadiene
Styrene-Butadiene Rubber (SBR)
Polychloroprene Rubber (CR)
Nitrile Rubber (NBR)
Butyl Rubber (IIR)
Ethylene-Propylene-Diene Terpolymer (EPDM)
Polysulphide Rubber (PSR)
Polyacrylic Rubber or Acrylate Rubber (ACR)
Fluorocarbon Rubber (FKM)
Introduction
Mastication and Mixing
Open Mill
Internal Mixers
Reclaimed Rubber
Fillers
Antidegradants
Accelerators
Retarders
Activators
Tyres
Belting and Hoses
Cellular Rubber Products
Miscellaneous Applications of Rubber
Passenger Tyre
Tube Compound for Car tyres
Conveyor Belts
Insulation Compound for Cables
Shoe Soles
2 MIXING TECHNOLOGY OF RUBBER
Two-roll Mills
Internal Batch Mixers
Continuous Mixers
Advantages of continuous mixing
Disadvantages of continuous mixing
Development of the Banbury Mixer
Operating Variables
Ram Pressure
Rotor Speed
Batch Size
Coolant Temperature
Unit Operations in Mixing
Single-Pass Versus Multiple-Pass Mixing
Types of Mix Cycle
Late Oil Addition
Upside-down Mixing
Sandwich Mixes
Analysis of Changes to the Mix Procedure
Acceleration of First-pass Compound
Mill Mixing of Speciality Compounds
Acceleration in Line with Internal Mixing
Testing of Raw Materials
Elastomers as Raw Materials
Fillers
Plasticisers and Process Oils
Small Ingredients
Control of Composition
Tracking the Mix Cycle
Compound Testing
Basic SPC Charting
Rheometer Data and its Meaning
Mixing Control Software
Peptisers in Natural Rubber
Effects of Temperature
Effects of Time
Effects of Use Level
Effects of Other Additives
Peptisers in SBR
Peptisers in Sulphur-containing Polymers
Additives to Increase Viscosity
Preventing Unwanted Chemical Reactions
Filler Treatments
Bin Storage Problems
Inspection of Banbury Mixers
Inspection at the Mezzanine Level
Side Cooling
Rotor Cooling
Rotors and Bearings
Rotor Bearing Lubrication
Dust Stops
Drop Door and Latch
Hydraulic System
Grease System
Dust Stop Lubrication
Drive Gears
Couplings
Inspection of the Banbury Platform
Ram and Cylinder
Heating Weight
Piston Rod
Weight Pin Assembly
Hopper Door
Air Line Filter
Hopper Operation
Mixer Maintenance and Lubrication
Each time the mixer is started
Once per shift
Once per day
Once per week
Once per month
Every six months
Anticipating Required Service
Dust Stop Maintenance
SSA Dust Stops
Assembly
Lapping
Running
Banbury Mixer — Hydraulic Dust Stops
Assembly
Run-in
Lapping
Production
Flushing
EPDM Expansion Joint Cover
Expansion Joint Intermediate Layer
Traffic Counter Treadle Cover
SBR/IR Belt Cover
EPDM Low Voltage Electrical Connector
Peroxide-cured Black-filled EPDM Compounds
EPDM Concrete Pipe Gasket
Injection-moulded NBR Gasket
CR/SBR Blend
Low Durometer CR/SBR Blend
Non-black CR for Injection Moulding
Hard Rubber Industrial Wheel
High Durometer NBR Masterbatch
NBR/PVC Cable Jacket
NBR/PVC/SBR Blend
Butyl Masterbatch
Butyl Masterbatch, Heat Interacted
Chlorobutyl/NR Blend
CSM CORD Jacket
Non-black Millable Urethane
Some Major Changes
Tempered Water
Power-controlled Mixing
Energy Conservation
Composition of EPDM Elastomers
Variables in EPM and EPDM Elastomers
Average Molecular Weight
Molecular Weight Distribution
Ethylene/Propylene Ratio
Type of Diene
Diene Level
How Processing Relates to Structure and Rheology
Practical Guidelines for Mixing EP Elastomers
Using Internal Mixers
Polymer Composition and Form
Filler/Oil Levels and Types
Cure Systems
Processing Aids
Mixing Process
Mixing Instructions
Fill Factor
Mixing Temperature
Machine Parameters
Ram Pressure
Coolant Temperature
Automation
Machine Condition
Downstream Processing Equipment
Using Two-roll Mills
Summary
Rework
Phase Mixing
Natural Rubber Viscosity Reduction
Measurement of Mixing Efficiency
Special Considerations
Raw Materials
Typical Formulations
Internal Mixing
Mill Mixing
Summary
Accounting Methods
Farrel Continuous Mixer
Operating Principles of the FCM
Commercial Applications for the FCM
Farrel Mixing Venting Extruder (MVX)
Designing the Rotor
Analysis of Dispersive Mixing
3 TECHNIQUES OF VULCANIZATION
Pressureless Vulcanization
Rubber Moulding
Factors of Mouding
Mouldin
Compression Moulding
Transfer Moulding
Injection Moulding
Helicure
Buffed Tread Crumb
Incineration and Pyrolysis of Tyres
Reclaimed Rubber
4 RUBBER VULCANIZATION
Physical Property Tests
Free Sulphur Determination
Solvent-swell Method
Mooney-Rivlin Equilibrium Modulus
Differential Scanning Calorimetry
Determination of Spring Constant
Sulphur Vulcanization
Peroxide Crosslinking
Resin Vulcanization
Electron Beam Vulcanization
Nitroso Compounds
Metal Oxides
5 RUBBER COMPOUNDING
General Compounding Principles
Tensile Strength
Tear Resistance
The Crescent Tear Test
The Hardness of Rubber
Set
Abrasion Resistance
Flex Cracking Resistance
Resilience
Heat Build-up
Temperature Resistance
Tyres
Retreading Materials
Conveyor Belting, Transmission Belting and Hose
Footwear
Rubber Roller
Medical Applications
‘O’ rings and Seals
Rubber Blends
Master Batches
Choice of Rubber
Fillers
Vulcanizing Agents
Peptizers
Accelerators
Activators
Anti-oxidants
Retarders
Softeners and Plasticizers
Rubber Crumb
Factice
Processing Aids
Special Purpose Additives
Unvulcanized compound properties
Vulcanized compound properties
6 RUBBER RECLAIMING
7 MANUFACTURE OF RUBBER PRODUCTS
Classification
Components
Tyre Building
Parts of a Conveyor Belt
Cover rubber
Manufacturing Process
Finished belt testing
PVC Belting
Steel Cord Belting
Design of Hoses
Hose Manufacture
Braided/spiralled hoses
Testing of Hose
Constructions
V-Belt Manufacture
Main Types of Power Transmission Belts
Preparation of Ingredients
Stability of Latex Compounds
Manufacture of Latex Products
Foaming and Gelling
Vulcanization
Classification and Terminology
Fabric Lined Water-proof Shoes
Canvas Shoes
Micro-cellular Soling
Manufacturing procedure
Types of Mountings
8 LATEX AND FOAM RUBBER
Selection of Raw Materials
Preparation of Raw Materials
Compounding and Design
Maturation
Processing and shaping
Dipped Goods
Latex Thread
Vulcanisation
Hot Air Cure
Hot Water Vulcanisation
Autoclave Vulcanisation
Radiation Vulcanisation
Ultrasonic Wave Curing
Testing of Rubber Products
Packing and Marketing
Conclusions and Recommendations

Manufacture of Latex Foam
Dunlop Process
Mechanism of Gelling
Compounding
Foaming and Gelling
Construction of Moulds
Curing
Washing
Drying
Finishing
Common Defects in Foam Making
Shrinkage
Foam Collapse
Setting
Complete Distortion of the Foam
Protein estimation protocol
Conlusion
9 SILICONE RUBBER
Electronics and Electrical Industries
Silicone Rubbers to Mimic Flesh
Silicone Polymers
Silicone Rubber Elastomers
Reinforcing Fillers
Semireinforcing or Extending Fillers
Additives
Curing Agents
Mixing
Freshening
Moulding
Extrusion
Calendering
Dispersion Coating of Fabric
Heavy-duty Hose
Bonding
Bonding Unvulcanised Silicone Rubber
Bonding Vulcanised Silicone Rubber
Post-baking
Condensation Cure—One-component
Condensation Cure—Two-component
Addition Cure
10 POLYBUTADIENE AND POLYISOPRENE
Polyisoprene
Cyclopolyisoprene
Gel and Branching
Polybutadiene
Isoprene
Butadiene
11 STYRENE BUTADIENE RUBBER (SBR)
Raw Materials
Production of Hydrocarbon Rubber
Manufacture of Emulsion SBR
Vinyl Content and Blockiness
Molecular Weight and Branching
Manufacture of Solution SBR
Property Control
Branching
Blending
Properties
Tg   Measurement
Molecular-weight Measurement
Dynamic Mechanical Measurements
Applications of SBR
12 RECLAIMED RUBBER
Whole Tyre Reclaim

Drab and Coloured Reclaims
Butyl Reclaim
Scrap-rubber Preparation
Reclaimed Rubber
Digester Process
Reclaimator Process
Pan Process
Engelke Process
Testing and Evaluations of Reclaimed Rubber
Millroom Operations
Special Strengths Through Reclaiming
Further Advantages of Reclaiming - Applications
Major Uses of Reclaimed Rubber
Automobile floor mat
Semi-pneumatic tyre
Butyl inner tube
Innerliner
Carcass
Applications
Process
Characterisation of Reclaimed Waste Latex Rubber (WLR)
13 NITRILE AND POLYACRYLIC RUBBER
Uses of Nitrile Rubber
Mixing and Processing
Latest Developments
Composition
Raw Polymer Characteristics
Physical Characteristics
Heat, Fluid, Low-temperature Resistance
Applications
Cure Systems
Reinforcing Agents
Plasticiscrs
Process Aids
Antioxidants
Mixing
Extrusion/Calendering
Compound Storage Stability
Vulcanisation
Bonding Characteristics
Solution Characteristics
Blends
Future Developments
14 RUBBER NATURAL
Agriculture
Exploitation
Latex Composition
Types and Grades
Production
Latex Concentrate
Processing
Chemistry
Physical Properties
Economic Aspects
Applications
15 HARD RUBBER
Ebonite
Hard Resin Rubbers
16 RECYCLING OF RUBBERS
Reclaiming Technology
Surface Treatment
Grinding and Pulverization Technology
Microwave Method
Ultrasonic Method
General Remarks
Use in New Tires
Rubber/Recycled Rubber Blends
Thermoplastic-Recycled Rubber Blend
E. Concrete Modified by Recycled Rubber
Asphalt Modified by Recycled Rubber
Use of Crumb Rubber in Soil

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Sample Chapters


(Following is an extract of the content from the book)
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Mixing Technology of Rubber

INTRODUCTION

This chapter deals broadly with the art and science of mixing rubber. Those unfamiliar with the nuts-and-bolts aspect of the industry may all too readily attribute artistic (or even magical) practice to the exotic ingredients and process techniques involved in manufacturing rubber articles. Others who have experienced the frustration when a composition does not quite meet a required physical property, lacks an anticipated attribute, or processes unsatisfactorily for no apparent reason, only to uncover remedies that are as difficult to explain as the symptoms, they will understand the phrase 'art and science'. These occurrences do not detract from the scientific achievements that have driven the art of mixing to its current level of sophistication.

The goal in mixing is to provide compositions having useful properties and suitable processability with as high a level of consistency as possible. The terms useful and suitable are determined by the application, for example, what is suitable for a sink stopper might not be suitable for an O-ring. In almost all applications there are criteria for the attributes that characterise whether a composition is suitably mixed; the criteria may vary, but they exist nonetheless. It is almost always the case that these criteria must be met with optimum efficiency, i.e., with the maximum output per expenditure of capital and energy.

In order to understand the reasons for the techniques and types of machinery employed in mixing, one must have some familiarity with raw materials, their physical forms, functions in the compound, and behaviour during processing. Several basic categories of ingredients are usually distinguished.

(a) Rubber or polymer-bales, clips, pellets or powder

(b) Fillers-powder, pellets

  • Reinforcing-carbon
  • Extending - clay, calcium carbonate, talc

(c) Plasticisers and lubricants-fluids, oils, waxes, process oil, ester plasticisers, processing aids, waxes, proprietary blends, stearic acid.

(d) Miscellaneous additives-powder, pellets, fluids

  • Antioxidants, antiozonants
  • Colourants
  • Release agents

(e) Vulcanising agents and accelerators-

  • Sulphur
  • Peroxides
  • Special ingredients

A knowledge of physical characteristics and forms leads to a certain amount of guidance regarding the most suitable type of mixer. For example, the knowledge that liquid additives need to be mixed into a liquid polymer would direct the technologist to certain types of equipment. But selection of the optimum mixer is not always possible, primarily because of economic factors. The organisation must often make do with what happens to be available; the ingenuity of the compounder lies in his or her ability to achieve specific results with the equipment on hand. On the other hand, given some degree of choice a more appropriate machine is usually available to improve mixing characteristics and, therefore, final properties. Early in the history of ruber compounding, almost simultaneously with Goodyear's discovery of sulphur vulcanisation it was found that kneading or softening the elastomer was useful in increasing its receptivity to incorporation of powders. This is the basis of mixing-masticating the elastomer to make it receptive to other ingredients, yet retaining sufficient stiffness to ensure adequete dispersion. (The more difficult an ingredient is to disperse, the higher the viscosity required during mixing ) This balance of mastication without undue shear softening can be achieved through several means.

1. Mixing with close temperature control.

2. Use of a specific sequence for adding materials.

3. In some cases, remixing after cooling (two-pass mixing).

These three considerations apply to mixing with all the most common types of equipment: two-roll mills, internal batch mixers, continuous mixers, extruders or combinations thereof.

MIXING MACHINERY FOR RUBBER

Two-roll Mills

Every mixer must provide two basic functions, both equally important-acceptable dispersion (intensive or dispersive mixing) and high uniformity (extensive or distributive mixing). The equipment used most often by the rubber technologist is the two-roll lab mill-a device for preparing small quantities of mixed compound. This mixing device is usually set for a ratio of roll surface frictional speed of about 1.25:1.

Roll Nomenclature

Diameter (D) Usually same for both rolls
Face length (L) Roll length (mill sizes expressed as D × L)
Roll gap Distance between rolls
Sank size Material sitting above gap
Banded roll Roll which material follows
Front roll Roll on operator's side
Slow roll Roll rotating at slowest speed
Fast roll Roll rotating at fastest speed
Friction ratio Roll speed ratio
Separating force Resultant force exerted by material in roll gap

The rolls are bored to permit cooling or heating the gap between the rolls adjustable within a range related to roll diameter. The mixing procedure is relatively standard. The operator places portions of elastomer on the mill, kneading the sample by multiple passes through the gap, until sufficient reduction in stiffness permits it to wrap and adhere to one roll. The gap is adjusted so that a reservoir of elastomer is always rotating above the nip. This reservoir is called the rolling bank. Rolling is rarely observed when the polymer has only limited elastomeric character at the milling temperature. In such cases the reservoir may flop about or break into discrete sections. This behaviour may often be corrected by a different choice of mill temperature on one roll or both, sometimes merely by using a different nip setting.

Powders are now added into the gap with frequent pan sweeping to recover increments which drop through. Process oil or plasticiser is also added usually after pan of the filler content has been incorporated. Only then does the mill operator begin to cut the rubber from one side of the mill, passing it to the other side, to cross-blend the batch. At the conclusion of mixing (usually determined by the judgement either of the operator or a supervisor) the batch is cut from the mill for cooling and storage. A major advantage of mill mixing is the high shear developed at the mill nip, this breaks up agglomerates and drives incorporation of ingredients. Furthermore, the massive surface exposure imparts good cooling, thereby maintaining the stiffness of the compound. And due to the roll friction ratio the rolling bank imparts further high shear.

The disadvantages of mill mixing usually far outnumber the advantages and may be listed as follows-

1. Length of the mixing cycles

2. Dependence on operator skills

3. Dust and dirt levels that are typical

4. Difficulty in standardising subjective procedures

5. Difficulty in controlling batch to batch uniformity.

Mills are used more in forming and breakdown applications than in actual mixing except for addition of curatives to pre-mixed masterbatch. The most common ratio of roll speeds in the past was 1.25:1, with the slower of the two rolls usually on what is most frequently the operator's side (often called the 'front' roll). Recent investigations have shown that the temperature rise of rubber on a two-roll mill is directly related to the sum of the speeds of two rolls. Therefore, whether the sum reduced by slowing the faster of two rolls (a change of friction ratio), or by reducing the speed of both rolls (maintaining the same friction ratio) the result is a reduction in rubber temperature build-up. Mills built in recent years have had lower total speed ratios closer to 1.1:1 and the fast roll at the front. In addition to improved processing of a broader range of elastomeric compounds, many such mills have also featured drilled rolls, permitting better temperature control and leading to easier compound release.

Internal Batch Mixers

The Banbury internal mixer was originally manufactured to replace the two-roll mill. The original nomenclature indicated the approximate number of 60" mills that a specific Banbury size could equal in output. The basic design of the machine includes two rotors that operate at a slight speed differential. The rotors are non-interlocking. Mixing or shearing action occurs between the rotors and the sides of the mixer and between the rotors themselves. The mixer is top loaded through an opening large enough to accommodate bales of elastomers (as well as the other ingredients). Pressure is exerted on the batch using a ram which closes the feed opening. Discharge of the batch occurs at the bottom of the mixing chamber. The rotor design is such that material in the chamber is constantly being displaced, corresponding to the cross-blending action of the mill operator cutting the batch on a two-roll mill. The compound is subjected to the shearing action of the rotors against the sides and the action of the rolling bank between the rotors.

The mixing chamber sides and the rotors are copied to maintain a high rate of shear during the mixing process. Improved cooling has been one of the most significant changes in modification of Banbury mixers over the years. The currently used cooling passages, called drilled sides impart an ease of heat transfer never before obtainable. In fact, the heat transfer efficiency of drilled-side mixers is so great that too much cooling can occur, leading to inefficiency when mixing certain types of compounds. This is corrected, and mixing generally much improved, by the use of a closed-circuit coolant tempering system. This system is used to dial in the proper temperature, optimising the degree of heat transfer and complementing the viscosity of a specific compound.

As with the two-roll mill, the sequence of ingredient additions is critical. In the case of the high viscosity elastomers, the polymer is usually added and masticated before the fillers are added; then the plasticisers and softeners are finally introduced. If the particular compound contains no curatives it is then discharged at an appropriate predetermined temperature. If the compound is a single-pass thermosetting composition, the curatives and accelerators are also added and the batch discharged at a lower temperature to prevent scorch (premature curing). The criterion for completion of the batch is often mixing to a specific temperature. Other criteria include elapsed time, and total power input into the batch. A combination of these observations is commonly used to judge the end-point and related to further processing of the batch during fabrication or to observe properties after vulcanisation. The selection of rotor speeds, mixer size and the extent of materials handling automation are all related to the demands of the specific sector of the rubber industry. At one extreme there is the massive quantity of compound mixed by tyre manufacturers, where most compounds are two-stage mixed (masterbatch and final) using high speed, automated materials handling equipment and large mixers. On the other hand, many custom compounders and mechanical goods manufacturers (who have a large number of recipes) prefer lower speeds and smaller machines and they have too great a variety of materials for totally automated handling. In many cases their compounds are mixed in a single cycle to reduce handling and inventories.

The major advantages of the internal batch mixer are as follows:-

1. Highly reproducible cycles

2. Minimum dependence upon operator skills

3. Large capacity and high output

4. Relatively short mixing cycles

5. Potentially clean factory operations.

But there are some disadvantages, compared to mill mixing:-

1. More rapid temperature rise in mixing

2. More time needed for cleaning equipment

3. Much higher initial investment.

Continuous Mixers

Compared to thermoplastics, continuous mixing of rubber compounds is a relatively new concept. The machinery available ranges from simple single screw extruders to twin rotor, multistage machines. All of these mixing extruders place a common demand upon materials; the ingredients need to be available in a free-flowing form capable of being continuously weighed and metered to the mixer. The continuous mixer receives the compound ingredients and disperses them to the extent needed to develop target physical properties. The required extent of mixing can be directly related to the ease or difficulty experienced with the same compound in batch mixing. Ingredients such as powders and liquids usually involve no undue problems in accurate continuous metering. The polymer, on the other hand, is often supplied in bales, requiring grinding or pelletising to provide a form suitable for continuous feeding. Recent demand has caused some polymer producers to offer a range of elastomers in pellets or powder form, thereby improving the option of continuous mixing. The advent of powdered rubber could revolutionise mixing. The advantage is that most or all of the distribution could be accomplished by using low power high intensity blenders. The resultant blend could then be fed to a simple relatively low horsepower mixer to masticate the compound and render it useful for fabrication. Vulcanisate properties often appear to depend upon a specific level of work input during mixing. In general, it is probably not significant whether this work is provided by a sequence of several machines or by a single mixer although the properties of all polymeric compositions are path-dependent to some degree.

With the advances that have been achieved in raw materials and product handling systems for batch mixers, it is sometimes hard to draw a clear line between batch and continuous systems. In developing the most useful configuration, the following considerations are suggested:

Advantages of continuous mixing

1. Very high product consistency is possible.

2. Automation level are highest.

3. Minor formulation changes are readily feasible.

4. Minimal floor space and ceiling height is required.

Disadvantages of continuous mixing

1. Supply of raw materials in free-flowing form may be costly.

2. Clean-up from compound to compound may be very extensive.

Development of the Banbury Mixer

The Banbury internal mixer was introduced to the rubber industry in 1917; the first mixers were supplied to Goodyear for mixing tyre compounds. For many years these mixers bore numerical designations for different sizes. These numbers approximated the quantity of 22" X 60" in mills that a specific Banbury mixer could replace. Soon after the first internal mixers were introduced, increases in speed, power and ram pressure made this relationship no longer meaningful.

The earliest mixers had the same basic fundamentals of operation as those which are in service today. A ram is necessary to push raw materials into the mixing chamber, two counter rotating rotors perform the mixing action, and a door at the bottom discharges the completed batch to a secondary piece of machinery. Improvements continued to increase the value of the design for mixing applications, despite changes in materials and in expectations.

The F-series Banbury mixers were introduced during the early 1970s. Unlike the earlier mixers, these F-series machines carried designations for each model which defined chamber volume. The F-series Banbury mixers not only introduced many new mechanical improvements, but were designed with the user in mind. Loading and discharge features and maintenance features were designed to emphasise the mixing capabilities of the machine rather than loading, unloading and maintaining.

When the F-series mixer hoppers were enlarged to accept bales and slabs of rubber more readily, the hopper door angle was steepened to assist in more rapid introduction of material to the mixing chamber. The junction between the hopper and the mixing chamber was provided with replaceable throat wear plates. These permit maintenance in an area subject to significant wear because of the action of the ram, well ahead of wear to the chamber. In the latest models, replaceable wear plates have been extended further into the hopper to increase the stiffness of the assembly.

The end-frames have been significantly strengthened and the access to the dust seals has been enlarged to assist maintenance or replacement. Within the mixing chamber the rotor end-plates have been converted to a one-piece design, eliminating occasional contamination associated with older, two-piece designs. This design also prevents the end-plate being dislodged from its fitting, reducing the incidence of mechanical failure. Rotor journals are now tapered, eliminating the need for bearing sleeves. Overall manufacturing tolerances have been reduced, lowering vibration and yielding longer useful service life.

The wall thickness of the sides has been increased by nearly a factor of 2 over older models, in response to the higher loads experienced with modern mixing procedures. The dual-circuit cooling design and the size and location of the bored cooling channels provide highly improved heat transfer. The discharge area has been significantly increased to permit more rapid batch discharge, reducing the interval between batches and adding to productivity. The toggle latch locking mechanism for the drop door has been made more positive in action but with lower moving parts, requiring less maintenance.

Rotor volumes are measured by immersion displacement, chambers' volumes by measurement and calculation. It is entirely feasible to convert an older D-series Banbury to the improved F-series equivalent. In many cases, the existing drive and hopper can be incorporated in the conversion. As shown in Figure 3, intensive mixing-the breakdown of agglomerates leading to a high level of dispersion- occurs by the action of the rotor against the side of mixing chamber. Extensive or distributive, mixing is accomplished by the continuous moving and shearing of the batch by the rotors; it occurs mainly between the rotors and the ram, and is influenced by the geometry of both. Intensive and extensive mixing must be considered, not only in machine design, but also with regard to mixing procedures.

Operating Variables

The major variables in mixer operation are ram pressure, charging procedure, rotor speed, batch size and coolant temperature. With a properly designed and well-maintained mixer, some selection of these variables will optimise the mixing of almost every rubber compound yet devised.

Ram Pressure

The major purpose for application of pressure to the ram is to drive the raw materials into the mixing chamber and to prevent their upward exit during mixing. Increasing ram pressure beyond this point is often found in practice, from a folkloric belief that it will speed the mixing action or otherwise improve it. In fact, it usually has the opposite effect. Too high a pressure can impede rotor action needed for extensive mixing.

The proper seated ram position is shown in Figure 4. The most popular ram configuration, now considered standard, is the single V-bottom.

Somewhat less popular is the double, gable V-bottom which facilitates addition of powder or liquid ingredients over the ram while it is in the down or mixing position. This procedure is not recommended as it increases wear and maximises hang-up of the compound from one batch to the next. It is in exactly the same category as dumping the batch with the ram in the down position. Nevertheless, both procedures retain popularity with those more interested in saving a few seconds of mix time than in machine life or batch to batch contamination. The flat-bottomed ram may still be found in older machines.

Because of the variation in air cylinder diameters, ram pressure should not be obtained from a pressure gauge on the supply line, but measured directly on the batch. Such data can then be transferred from one mixer to another. High ram pressure is useful in charging the mixing chamber, but a lower pressure is more desirable during the actual mixing. This has led to the development of multiple-ram pressure control systems. Two or three zones are pre-set with individual regulators to specific pressure levels. This may be automated or controlled by the mixer operator. It can include provision for relief of ram pressure if certain limits on power draw are exceeded, or even if the change in power draw indicates a likelihood that such limits may be reached. This is particularly useful in moderating power surges with upside-down and sandwich mixes. It also provides the means for staying below certain power plateaus that, in some locations, strongly affect plant utility costs.

The importance of ram pressure and position led to the development of the automatic sensing device shown in Figure 5. By means of its output graph the ram position indicator can provide a good profile of the mixing action and a guide to proper batch size. Typical profiles are shown in Figure 6. Here, three batches of the same compound are mixed to a total elapsed time T. The desired ram action is shown in Figure 6(b).

This is followed by a longer period of reduced ram action corresponding to distributive and dispersive mixing. Figure 6(a) shows an oversized batch of the same compound. Almost to the end of the batch, the mixer struggles to incorporate the excess of ingredients. Dispersion and uniform distribution will not be optimum if the ram does not reach a fully seated position in the first third of the mixing cycle. Figure 6(c) depicts the same batch below optimum batch size; the ram seats almost immediately; distributive and dispersive mixing are strongly impeded.

At optimum batch size, ram displacement charts can be used to fine tune the ram pressure programme so as best to approximate Figure 6(b). Besides this, batch to batch charts can spot equipment malfunction and aid in diagnosing improperly weighed batches.

Rubber Compounding

INTRODUCTION

Compounding is the development of rubber mixes which will effectively perform in service. At the same time, the mixes should be capable of being processed in the factory without much difficulty and at minimum cost. Chemically speaking, a rubber "compound" is not a compound, but is merely a mixture of rubber and compounding ingredients, ready for vulcanization. The simplest of all compounds, rubber plus vulcanizing agent, is of little use in most applications. Since it is the basic structure for most compounds, we have to consider how it can be compounded with reinforcing agents, anti-oxidants, and plasticizers to give the best combination of properties for a particular application.

General Compounding Principles

The scope of compounding consists of specifying the type and amount of various ingredients in a mix, the manner of mixing, the processing of the mixed compound, and the method and details of vulcanization. This essentially covers the requirements of end-use and service properties, processability, and cost. The three major decisions to be made by the compounder, considering all these factors in designing a compound, are connected with the choice of rubber, the level of reinforcement, and the type of vulcanization system to be employed. In general, these factors determine cost, mechanical and visco-elastic properties, resistance to degrading influences, processability, and special requirements such as flame resistance, low temperature flexibility and non-toxicity for application in contact with food-stuffs.

VULCANIZATE PHYSICAL PROPERTIES AND THEIR SIGNIFICANCE

Physical tests of quality are a means of measuring some fundamental physical property or attribute of a rubber compound. Service testing or product testing is more often than not connected with product design and manufacture. In practice, the failure of rubber articles occurs mainly by tearing, abrasion, or dynamic fatigue arising from crack propagation. Therefore, physical tests are often required for development of new materials or products or in developing new engineering uses of rubber. However, there is generally poor correlation between laboratory tests (particularly the static tests) and product performance. Despite this, laboratory tests have been developed due to the advantages of low cost, quick results, and the ability to compare many compounding variables primarily for screening purposes.

For many years, physical tests on vulcanizate properties such as tensile strength, hardness, abrasion resistance resilience, tear, compression, cut, and crack growth have been standardized in the rubber industry. We shall consider the individual tests and their significance. The tests have the following uses: (1) designing compounds to meet service conditions; (2) investigating product or process failures; (3) quality assurance of compound batches; and (4) quality control of raw material.

Tensile Strength

This is defined as the force on unit area of original cross-section which is required to break the test specimen, the condition being such that the stress is substantially uniform over the whole of the cross-section. The elongation at break is the maximum value of the elongation expressed as a percentage of the original length. The value of tensile stress (force/unit area) required to stretch the test piece from the unstrained condition to a given elongation (say 100 or 300 or 500%) is called the modulus or, more accurately, "tensile stress at a given strain".

Hooke's law is obeyed by metals, which undergo practically only elastic changes of shape below their yield point. However, in the deformation of rubber, we must differentiate between (a) an elastic deformation, (b) a plastic deformation and (c) an extension or residual deformation. The E modulus for metals is always the tension for an imagined elastic extension of 100%. In practice, this amounts to only 0.1% and then passes from purely elastic extension into plastic deformation. Thus for steel, the E modulus is 2,000,000 kg/cm2, i.e. under this stress, the extension would be 100%. However, the modulus of rubber is not a constant, as in the case of metals.

The modulus of rubber is not the ratio of stress/strain as used by engineers. It merely signifies the coordinates of a point on the stress/strain curve and is loosely used as a synonym for stiffness. Contrary to engineering practice, test results on rubber have no absolute meaning as they depend on the conditions of the test. Rubber specimens undergo gross changes in shape when stressed, unlike other high strength engineering materials. Rubber tensile machines can be used for various tests such as: (a) for the determination of tensile strength and elongation at break and (b) the determination of tensile stress values at given elongations. These are the so-called "modulus" values.

Physical properties can differ length-wise and cross-wise on a section of rubber compound due to anisotropy. In the direction of calendering, tensile strength is high and extensibility is low; across, the strength is relatively low and extensibility high. This phenomenon will be pronounced in the case of short-fibre reinforced rubber compounds.

Tensile test specimens can be tested at room temperature with standard Schopper-type machines of 0.5-5 KN capacity. The lower grip of such a machine moves at constant speed, while the upper grip is connected with a pendulum type dynamometer. The specimen is strained by a uniform movement of the lower grip, to which one end of the specimen is attached. The other end of the specimen is held by its upper grip. The pendulum is displaced from its normal position by a pull on the specimen and the amount of displacement indicate the force. The pendulum is lightly ratcheted to a notched sector so that after the specimen breaks, the pendulum and the pointer which is geared to it will remain stationary at the maximum load.

The pendulum moves with varying (usually increasing) angular velocity, i.e. there is angular acceleration. When this occurs:

FR = Mg D + I (dw/dt)

where F is force exerted by test piece, R radius of the dynamometer load, M mass of pendulum, I its moment of inertia, D horizontal displacement of mass, and angular acceleration of pendulum.

The pendulum-type machine is widely used by reason of its simplicity and lower cost, but it is subject to error mainly due to the pendulum inertia and the unavoidable friction in the pendulum bearings. The machine must be used within the range of 15-85% of its maximum force to reduce inaccuracy. Some machines have a constant rate of traverse of the lower grip (usually 50 ± 5 cm per minute), while others have a gear box to provide a range of speed. Movement of the upper grip occurs during deflection of the pendulum. This may cause variation in the straining rate of the specimen. Other machines have a heating chamber in which tests can be carried out at temperatures from approximately -18 °C to 100 °C.

The specimens used take the form of dumb-bells cut out from products. This design of a satisfactory test specimen takes into account two main problems in tensile testing. First, the difficulty of holding the rubber securely without any slipping, and second, the avoidance of high local stresses in the test piece which would cause premature rupture at the grips. The broader portions at the end of the dumb-bell are held in self-tightening grips which automatically tighten as the thickness diminishes during stretching. The broader portions are joined to the narrower central portion, i.e. the actual test section, by curved "shoulders" to avoid stress concentrations. The true length of the test specimen cannot be measured by recording the distance between the grips; this is done by marking the central portion of the piece with two parallel crosslines, the volume of rubber between the marks is regarded as being stretched uniformly. The dumb-bell pieces are punched from press moulded sheet, taking care to ensure that the cut be as clean as possible. For a complete determination of the force-extension curve, a record of the total course of the extension up to the point of break, taken with the help of an autographic recorder is required. Alternatively, readings at two or three load values, corresponding to the elongations of 100, 200, 500 or 700% may be taken.

Electrical-force measuring machines have been developed to overcome the inertia of the pendulum-type testing machine. In these devices, the load on the upper grip results in the deformation of a light but perfectly elastic metal ring. The extent of this deformation is then measured by electrical means. These instruments have a greater range, and force-extension graph or read out devices. There is negligible movement of the upper grip, and inertia effects are avoided. Most of them also have facilities for reverse motion to enable a retraction curve to be drawn, or for cycling tests. They also have cycling, automatic zeroing of load and extension outputs, and fast cross-head return, making them particularly suitable for repetitive quality control-type testing.

Tensile tests are almost invariably used either to indicate the quality of rubber vulcanizate or for purpose of quality control in production, but are seldom if ever, used in component design. Tensile strength in itself bears little relation to product service, as rubber is not normally used at such high elongations that there is a danger of failure due to tensile rupture even after moderate ageing.

As a service test, tensile strength tests are valueless but for many purposes of comparison, they are extremely useful. High tensile strengths coupled with a reasonable elongation at break can only be obtained with high quality rubber mixes and for this reason tensile strength is very often included in specifications, e.g. conveyor belt cover rubber. They are also useful for determining the curing characteristics of compounds-the cure condition giving the highest tensile strength being widely adopted as optimum cure. Deterioration of rubber on ageing can be followed by the drop in tensile strength. Effect of many compounding ingredients as well as that of pigment dispersion can be decided by tensile strength tests. Finally, as a control test, it is invaluable since any mistake in mixing or processing giving inferior product is indicated by a drop in tensile strength.

Unlike most other engineering materials, rubber can be compounded to give a wide range of elastic modulus values. This enables a product of fixed dimensions to be made in a variety of stiffnesses. Stiffness of rubber is equivalent to (modulus × area)/ thickness. In most applications, the modulus of rubber is more important in compression, shear and torsion, than in tension. In compression, the shape factor plays a significant part. Empirical curves have been compiled to illustrate this feature. Modulus measurements show less variations than values taken at rupture and thus, more reliable. Modulus is a useful property to measure as the compounder and designer generally have a reasonable idea of what level of modulus is most likely to suit the applications, e.g. it is generally thought that heat build up is less with low modulus casing compounds since they work under constant stress. However, modulus evaluations can be misleading because it is measured at an extremely low speed of deformation. It is believed that at high speed "dynamic" modulus may be different.

Elongation at break gives some indication of "chunking" tendencies in tyres. A high elongation is a good feature.

Ageing tests on tensile samples are traditional rather than technically useful. They can indicate disadvantages in cracking if the modulus increases rapidly on ageing, but ageing tests do not help in sorting out anti-crack anti-oxidants.

Tear Resistance

The measurement of tear strength of rubber from an initiating nick is carried out by tensile type tests using a specially shaped test piece which concentrates the stress in the region of the nick. This property is important in a number of products, e.g. tyre treads, tubes, cable sheaths, hose, etc. A very rough indication of resistance to tear may be obtained by nicking a piece of rubber and tearing by hand. The test which is now universally accepted employs a crescent shaped specimen cut by means of a die and press from a specially moulded slab of rubber. Differing test piece shapes are also used, but they tend to give diverging results.

The Crescent Tear Test

A test piece in the shape of a crescent is punched from thin rubber sheet. A small cut is made on the inside curve of the specimen to an accurate depth of 0.5 mm by means of a special cutter employing a razor blade. This specimen is then stretched in a tensile testing machine and the minimum force required to tear the test piece across the width of the uncut portion is then measured and reported.

The tear strength is dependent upon the width and thickness of the test piece and the test result is expressed as the load necessary to tear a specimen of standard width and thickness.

Tear strength = L × t1/t2

where L is the maximum force noted, t1 is the thickness of the standard test piece (2.5 mm), and t2 is the measured thickness of the specimen tested.

An important difference between tear testing and tensile strength testing is that while the applied force is uniformly distributed over the cross-section of the test piece in the latter, in tear testing, it is concentrated at the base of the nick. Tear values are influenced by the sample size and shape and therefore, care must be taken to simulate tear phenomena in service.

Compounds with high tear resistance such as those loaded with carbon black, give a jagged tear path. When tear resistance at elevated temperatures, i.e. hot tear is required, a heating chamber enclosing the specimen should be fixed to the tensile testing machine.

The tear resistance at elevated temperatures is important where the product may have to function at such temperatures in service and also where the product may have to be stripped hot from a mould which tends to hold it. At elevated temperatures, some synthetic rubbers are significantly weaker than others in tear resistance.

The Hardness of Rubber

Hardness is defined most simply as 'resistance to indentation'. The hardness of rubber has been widely used as a control test and many product specifications quote hardness as a guide to the type of compound required. In many cases, this may be the only property specified. Hardness tests may indicate the state of vulcanization or degradation in use. Compound hardness is greatly determined by the type and amounts of reinforcing filler used, softeners used and by the use of crosslinked resin system. The hardness value best suited for a product will need to be determined by practical trial or rig test.

Hardness measurements in rubber are different from those on metals as they are related to modulus determination at low strains and are not the permanent indentation made by a point. The indentation depth is converted into International Rubber Hardness Degrees (IRHD), the scale of which ranges from 0 (infinitely soft) to 100 (infinitely hard). The usual range of hardness covered is 30 to 90 IRHD. Shore A and IRHD, although not exactly equivalent, are the same within the limits of experimental error.

Hardness tests can be divided into two types; (a) accurate and reproducible standard laboratory testing, calling for a dead-load hardness tester and (b) routine checking, calling for a portable, spring-loaded, pocket type instrument.

Tests which are based on the measurement of the indentation of a rigid ball into the rubber test-piece under specified conditions use 'dead-load' instruments. The usual test is done on flat test-pieces 8-10 mm thick, atleast 9-10 mm from the edge. It may be possible to take test-pieces of much smaller dimensions from many components (2 ± 0.5 mm), and a 'micro-test' is then done with the result expressed in 'standard micro-hardness' which is approximately equivalent to the standard hardness.

Dead-load type hardness instruments are more reliable than spring loaded instruments because the applied force is controlled, whereas with the latter the pressure of the indent or foot will vary from operator to operator. The dead-load type instruments must be carefully levelled so that the spindle is substantially vertical. They are, therefore, more suitable for laboratory use.

Wallace (or Shore) hardness is defined as the resistance against the penetration of a body of specified shape applied under a specified spring loading. Spring loaded instruments are portable and thus more suitable for checking actual products. Their scales must be frequently checked as the springs are liable to incorrect setting, fatigue or elastic drift, and the indentors prone to wear or damage. The time of load application is not carefully controlled, and this can lead to errors. All spring loaded pocket type instruments are sensitive to applied pressure, and are therefore, subject to variation in results when used by different operators.

The special features of the different types of hardness measuring instruments are given in Table 1. The special feature of the indentors used in different hardness instruments are shown in Fig. 2.

Special Features of Hardness Measuring Instruments

Dead-load Spring loaded instruments
Type Hardness instrument Micohardness testers Wallace type Shore type
Indentor Ball 2.38 ± 0.01 mm diameter Ball, 0.4 mm diameter Hemispherical needle 5/64 in mm diameter Frusto conical needle 0.79 mm diameter face
Load 2.294 N/5.68 N 0.00814 N, 0.1537 N Depends on spring force 2.65 N Depends on spring
Foot 5mm diameter 0.02 N/mm2 3mm diameter 0.02 N/mm2 - -
Measurement of indenntation unit Dial gauge International Rubber hardness Degree (IRHD) Level surface required Suitable for laboratory use Dial gauge IRHD-samples less than 4 mm thick Level surface required Suitable for laboratory use on small samples Dial gauge Wallace hardness units Portable Suitable for checking products Dial gauge Shore "A" and shore "D" Portable Suitable for checking products

Set

Set is the amount of residual displacement in a rubber article after a distorting load has been removed irrespective of whether the load was in tension/compression/shear.

Tension set A dumb-bell specimen is stretched to a definite elongation and allowed to stand for a specified time. The tension is released, and after a definite time, the specimen is again measured. Increase in length calculated as a percentage of the original length is the tension set.

Generally, the lower the set, the better. One factor which influences the set is the state of cure. Under-vulcanized rubber has a high permanent set.

Compression set A moulded cylinder of rubber, used as the specimen which may be compressed at normal or elevated temperature to a pre-determined (in terms of percentage) height, is measured after compressing for a period of 24 hrs. This test is useful for rubber components which have to function under compression, e.g. rubber heels, compression buffers, etc.

Abrasion Resistance

The resistance to abrasion is an important property since it determines the useful life of a number of rubber products. However, abrasion tests are just as problematical as the other physical property tests and do not allow exact forecast of service behaviour.

The subject is extremely complex as the service conditions under which different products are abraded very considerably. When we consider such widely differing products as tyres, footwear, flooring and conveyor belts, it is evident that no single laboratory machine can cover the service conditions of these articles. Two main types of laboratory abraders are described below:

The DIN abrader consists of a cylindrical drum covered with emery paper. The specimen holder which contains the test specimen exerts a specified force on the emery paper. The test block is traversed slowly along the length of the cylinder, so as not to pass repeatedly over the same abrasive surface. Volume loss of the test specimen, before and after testing, is found out and the "abrasion resistance" compared against a reference sample.

Abrasion resistance = Volume loss of standard specimen/Volume loss of test specimen × 100.

The PICO abrader (ASTM 2228) abrades by means of knives of controlled geometry and sharpness. Standard rubbers are used for comparison and for checking the knives.

Laboratory abrasion test is an accelerated test. The different machines are all very useful in the laboratory to give a quick indication of abrasion resistance, but all of them have certain fundamental faults. The abrasive surface tends to become plugged up by the abraded particles. Abraded particles are also very much larger than those under actual service conditions. Although temperature has a large effect on wear rate, it cannot be controlled at the contracting surfaces during the test. The tests do not reproduce impact abrasion. Frequently, they are useless in comparing polymers, or for real development work with curatives, anti-oxidants or plasticizers.

Flex Cracking Resistance

Many rubber products must withstand repeated cycles of flexing without failure. During flexing small cracks may appear on the surface and these grow larger and deeper until they become large enough to cause failure. Therefore, information of flex cracking is important when designing compounds for tyre treads, belt covers, boot upper, etc.

"Flex cracking" has been defined as the occurrence and growth of cracks in the surface of rubbers when repeatedly subjected to a cycle of deformation.

Several laboratory test machines are available but as with abrasion resistance, these may not give a true assessment. It is, therefore, necessary very often to subject actual products to service type tests. The two popular machines are De Mattia machine and the Flipper machine.

De Mattia Machine The machine most widely used for soft rubber vulcanizates up to 70 IRHD is known as the De Mattia machine. This consists of a row of fixed grips and another parallel row of reciprocating grips which grip a moulded specimen. One of the clamps oscillates at high speed by a crank mechanism and by adjustment, the distance between the clamps and the stroke can be varied to give different degrees of flexing. The grips are set so that they approach each other to a distance of 18 mm and separate to a maximum of 75 mm at a rate of 7500 mm/min. The test piece is a flat strip, with a moulded transverse semicircular groove on which the strain is concentrated when the test piece is bent by bringing its ends nearer together. The cracking observed is compared with a series of descriptions and photographs contained in the standards.

The Flipper Machine This machine consists of a rotating disk on which specimens mounted in spots protrude from the periphery. These specimens are flexed by striking idler rolls. The specimens are flat mouldings having a ribbed portion at one end and grooves similar to those of the De Mattia test piece. The rotation or face ends are bent by contact with the idler rolls at the grooves. After test, the assessment and grading are done as described for the De Mattia machine.

Both the machines are compact and can be enclosed in a cabinet having elevated temperatures, ozonized air, or other means of accelerated ageing. The cut growth test differs from that of flex cracking in that the test piece is first punctured, at the base of the groove, by a chisel shaped tool with a blade 2 mm wide. The length of the cut is measured before and after various periods of flexing, the test result being the numbers of flexing cycles for pre-determined increases in this length.

Fatigue tests Fatigue may be defined as the deterioration in physical properties and eventual failure of rubber when repeatedly subjected to a stress well below its ultimate tensile stress. The onset of fatigue in rubber is characterized by the appearance of a series of cracks on the surface, which enlarge on repeated deformation, and eventually cause failure. Sudden section changes in the stressed/strained parts, or the rubber going through zero deflection (relaxation) in a plus-minus straining cycle will lead to fatigue failure of rubber.

For the dynamic testing of soft rubber, "fatigue testers" are used in which the life of the material is recorded, depending on the actual conditions, in revolutions, minutes or load cycles. The test results may be expressed either as the rate at which a cut extends, or as the number of cycles required to cause complete failure of the test piece. The test basically aims to establish on order of merit of materials and for comparison purposes, machines are designed to test many samples simultaneously. Test specimens may have a cut specially made to study cut propagation. The results are sensitive to the stress cycle used, particularly if this passes through zero. As the tests are run in air, it is probable that ageing effects will play an important part in the failure processes, so that these tests are often used for the evaluation of protective agents. Fatigue testing for service prediction is not easy and requires considerable efforts to identify the important test variables in the design and interpretation of the fatigue test.

In tyres, flex cracking occurs in the side walls and in the base of the grooves of the tread. Tyre failures, however, may occur due to cut growth and fatigue, accompanied by rise in temperature (heat build up) due to flexing.

Resilience

This property is one of the outstanding features of rubber. It shows the ability of a rubber vulcanizate to return the energy used to deform it. Low resilience values correspond to a higher internal friction and to a larger heat build-up on repetition.

The simplest form of resilience test involves the dropping of a steel ball into a rubber specimen and noting the height of rebound. Various rebound pendulums such as the Schob, Lupke, Dunlop, and Goodyear-Healey are in use.

The Healey pendulum springs from a predetermined height and rebounds to a height determined by the resilience of the rubber specimen.

The Dunlop tripsometer takes the form of an out of balance metal disc revolving on virtually frictionless bearing and which acts as a slow moving pendulum. The test-piece is placed against a rigid support so that it receives a blow at its centre. A circular scale is provided for measuring the angle of displacement. The measured quantity is the angle to which the disk rebounds after the hammer strikes the specimen.

Resilience is lower when rubber is over or under vulcanized and is also reduced by such fillers as carbon black. The higher the reinforcing properties of the black, the lower the resilience. Resilience is influenced by the state of cure and can, therefore, be used as a test for degree of vulcanization.

The rebound resilience test is a "single point" determination of damping characteristics. The picture obtained thus does not necessarily agree with the behaviour under high frequency dynamic load change. For complete characterization of damping curves, other methods are used. Usually, these use cylindrical rubber test pieces which are set in oscillation in an axial direction.

Heat Build-up

In the Goodrich flexometer (ASTM D623), the cylindrical rubber specimen is set in oscillation between anvils, one of which is connected to an eccentric and the other to a lever which can be loaded. The tests are carried out in a thermostat and the increases in temperature are measured by a thermocouple inserted into the anvil attached to the lever. The amplitude of the oscillations and the load can be varied. The effect of carbon black on hysterisis and heat build up is evident in flexometer tests. With a higher loading of carbon black, a temperature increase results, and the measured temperature increases linearly with the loading. As the degree of vulcanization increases, heat build up decreases.

Temperature Resistance

Exposure of rubber to low temperatures results in stiffening and eventual fracture as deformation occurs. The change is reversible and independent of the time of exposure, unless permanent damage has occurred due to deformation. (At high temperatures, however, the effects are irreversible and substantially time dependent).

Low temperature capability of rubber is determined by the Gehman Test, which compares the torsional modulus of rigidity at low temperatures with that at room temperature. The resistance of rubber strips to bending, twisting, and impact at low temperature, from -20°C to -80 °C, and sometimes lower, is determined by several methods. The methods generally used are Brittleness test, Brittleness temperature by impact. Young's modulus in Flexure and Gehman torsional apparatus for determining flexibility.

In the Gehman torsional apparatus, the cooling fluid is usually a mixture of solid carbon dioxide and methanol, and the test-piece is maintained at the required temperature at zero deflection in the cooling fluid, between a lower, fixed clamp and an upper clamp which is free to twist. The test piece is twisted at approximately constant speed through 90°, and the load required to twist the upper end of the sample through 90° is noted. There should be minimum tension in the test piece, so that it is allowed to change in length as it twists, and minimum friction in the bearings. The cooling fluid must also not affect the rubber. The rigidity modulus (at a particular temperature) is calculated from the expression.

G = L/Wt3K.180/pi. T/theta

where G is the rigidity modulus, L length of sample, t thickness of sample, W width of sample, q angle turned through is 90°, and K factor to indicate second moment of area of the sample.

The results are frequently expressed in a graphical form as shown in Fig. 5.

Heat resistance of rubbers is substantially affected by the presence of atmospheric oxygen, ozone, and contact with certain fluids, resulting in thermo-oxidative ageing. The physical properties of a rubber may also change if it continues to cure at elevated service temperatures by, for instance, the presence of uncombined sulphur. Volatile ingredients may be driven off by heat, resulting in a reduction in volume and an increase in the hardness of the material. Immersion of the rubber in a liquid excludes the effects of oxygen, but an increase in temperature may result in a change in dimension due to combined result of the swelling of liquid, absorption, and shrinkage due to extraction of plasticizer on other ingredients. Service temperatures recommended for liquid applications are likely to be significantly higher than those which would be appropriate to dry heat conditions.

COMPOUND PROPERTIES DESIRED FOR DIFFERENT RUBBER COMPOUNDS

Tyres

Different types of compounds are used for tread, side wall, casing, and beads. Tyre tread is the wearing surface and with the sidewall it protects the casing against damage. The compound must, therefore, be resistant to abrasion, tear, cracking, chipping, weathering, and heat ageing. Certain treads must be conductive. White sidewall or coloured side walls may also be used for some classes of tyres. Certain special applications, e.g. low temperature service in the Arctic or Siberia, requires good low temperature flexibility. Cheaper compounds with non-reinforcing fillers may be acceptable for treads such as for cycle tyres as the service conditions are less severe.

The tread must be cool running for durability. These requirements are met best with the use of two different compounds selectively distributed in the tread, i.e. a cap/base construction. The cap compound provides the desired wear and traction characteristics while the base compound is highly resilient and cool running. This combination reduces the tyre running temperature at the thickest portion of the tyre. Sidewall compounds, made separately from tread, require protective agents for resistance to heat ageing, flexing and ozone.

Casing compounds must ensure a good bond with tread and with the cord. They must be adequately heat and fatigue resistant and cool running. Bead compounds must be hard, bond well to the wire, and give the finished bead the desired degree of rigidity and flexibility. They should be heat resistant and must insulate one strand from another.

Tube compounds should have high extensibility, good air retention properties and should be heat resistant.

Flaps protect the inflated tube from damage from the rim surface in tubed tyres. The flap compound should be adequately hard and heat resistant.

Curing bags are used to pre-shape the green tyre and press the tyre against the mould surface through application of internal pressure and heat. The compound should be heat resistant as steam or hot water is circulated through the bag to heat up the green tyre from the inside.

Retreading Materials

Tread rubber is used for retreading worn out tyres. The compound must have a long shelf life in addition to good abrasion and heat resistance. For industrial trucks, bulky moulded objects, solid tyres, are used in slow moving vehicles carrying heavy loads. The compound must be hard, resilient, and relatively cheap. They are usually black and made of low grade material.

Conveyor Belting, Transmission Belting and Hose

Cover compounds are subject to rubbing abrasion of sand and hard materials. They must be abrasion resistant with good ageing and weathering properties. Heat resistant compounds will be required for application where hot substances, e.g. quenching cinders are carried. Oil resistant compounds are required for conveying oily or greasy substances.

Transmission belting carcass compound must be cool running and flex resistant as these belts have to transmit power at high speeds over relatively small pulleys. V-belt base compounds must be hard with good heat and flex resistance and cool running.

Hose compounds may be for lining, insulation, or cover. Lining compound protects the carcass from the deteriorating influence of the material to be carried. The compound must be resistant to deterioration from these influences, e.g. steam, oil, and chemical resistance. A hose lining is designed to withstand effects such as swelling, chemical attack, or abrasive wear, which might result from the material flowing through the hose.

Insulation compound bonds the outer layers of braiding and provides resistance to rupture when pressure or suction is applied. Compound should be soft and of low viscosity.

Cover compound protects the carcass from deterioration in service or storage, and should be abrasion and degradation resistant. A hose cover is designed to resist influences which might operate outside the hose. Usually, these are different from the internal influences and so the cover compound is usually different from that of lining.

A motor car radiator hose, carries water at low or moderate temperatures and without pressure. It must be cheap and have good heat ageing properties (being near the engine). As it must be produced in large numbers, it must be capable of fast extrusion and cure as well as of low volume cost. It must also have sufficient strength to resist splitting at the ends when fitted.

Footwear

The main requirements for rubber sole compounds are abrasion and flex resistance, hardness, traction, shape retention, and adhesion to the upper. A range of hardness 35 Shore A to 95 Shore A, and specific gravity from 0.40 (for sponge) to 1.65 (for slab soling) is in use. Quality and cost may vary according to the requirements for specific uses. Typical sole compounds use natural rubber with hard clay and white fillers, the types and amount adjusted to vary hardness and abrasion resistance. The shoe sole must have reasonable flex or cut growth resistance and also stitch tear resistance when it is attached to the upper by stitching with thread. High styrene resin with silica tiller may be used in blend with natural rubber/white fillers to achieve superior processing and abrasion resistance to replace leather soles. Heavy duty work shoes utilize clay and silicate pigments. Carbon blacks are used only in low proportion in order to avoid (floor) contact staining.

Foxing compounds must have good extrusion or calendering properties and must have good tack to both the sole and upper. These compounds include high grade natural rubber SMRL with whiting and titanium dioxide to adjust colour.

Rubber heels come in several varieties of sizes, thicknesses, and qualities for original equipment or replacement heels. They are compounded for attractive finishing characteristics, and for ease of attachment to automatic attaching and finishing machines. The compounds are loaded with hard clay, whiting and silicate fillers. Heel bases may be used between the heel and the sole in some shoes. These are economic, filled compounds. Reclaim (with carbon black) may be used if the part is not exposed to wear.

For hard rubber compounds used as top lifts or spike heels, nitrile rubber, reinforced with phenolic resin, may be used as polymer base. Ground walnut shell flour, silica, wood flock fibre etc. may be used in specialized applications to impart 'traction' or anti-slip characteristics.

For footwear compounds, whiting is the predominant filler for rubber boots, tennis shoes, gyro shoes, duck shoes and casual footwear where the elastomer is natural rubber. Shore A hardness of 50 to 70 are usually obtained in these compounds. Clays may be used with whiting to upgrade the compound quality or with silica fillers to reduce cost. Zinc oxide is normally used as an activator. Titanium dioxide and red-oxide are used as colouring pigments. Talc is used as an inert-filler similar to whiting for economic reasons.

The rubber compound for microcellular soling must be sufficiently soft to allow easy expansion during vulcanization. It usually contains 30-40 parts of high styrene resin. Reinforcing fillers like precipitated silica, calcium silicate, aluminium silicate, and clay are used. A blowing agent of the DNPT type is used to produce nitrogen during cure.

Rubber Roller

The rubber compound must have good metal to rubber bonding and building tack to facilitate plying up unvulcanized sheets.

Medical Applications

Rubber products for use in medical (surgical or pharmaceutical) applications are usually governed by some form of governmental specification. The selection of compounding ingredients for these applications should be done with care to ensure that they are physiologically inert or harmless.

'O' rings and Seals

For an external application, the 'O'ring is usually stretched over the piston into a groove where it will initially be at a maximum stretch of 8%. The section will reduce because of the stretch and on assembling the piston into the cylinder bore, the section will be compressed in order to attain the necessary sealing characteristics. Stress relaxation will occur when the section is under constant strain for a prolonged period and compression set will be observed over a period. For example, in a reciprocating application on a piston head, the 'O' ring will be pushed back and forth in its housing and may extrude out on both sides coupled with spiral twisting.

Squeeze-type seals operate by distorting under a compressive load, and the hardness selected must be sufficiently high to ensure adequate retention of sealing pressure. This can often be achieved by incorporating one or more plies of fabrics rather than by increasing the hardness of the mix which might adversely affect other properties. Dimensional effects on contact with liquids can be adjusted to achieve a small positive swell, capable of maintaining sealing efficiency, by compensating for seal wear and compression set. The choice of compound will depend on the effects of the fluid with which the seal will be in contact, the operational temperature, and mechanical conditions such as pressure, relative velocity and abrasion.

The basic design of a rubber compound must take note of three requirements: (1) the end-use and the service requirement of the product; (2) trouble-free processibility of the compound during manufacture; and (3) volume cost and availability of raw materials. Various types of rubber and compounding ingredients are specified in compounds to meet service requirements, processing requirements, and volume cost.

COMPOUNDING INGREDIENTS

Rubber: In India, as in other natural rubber growing countries, NR will most certainly be used in cases where the rubber compound does not have to withstand high temperature, direct sunlight or ozone, and where it does not come into contact with oils, solvents, or chemicals known to attack it. Synthetic rubbers, which are superior to natural rubber in these specific properties, are used depending upon the conditions of service of final product. The typical applications are listed below:

  • SBR: Used as general purpose rubber.
  • Butyl rubber: Low permeability, so used in tubes and inner liners. Good chemical resistance, so used in tank linings. Curing bags and bladders are made of resin-cured butyl to give good heat resistance.
  • BR: Good abrasion resistance and fatigue resistance. So it is used for tyre treads (in blends with NR and SBR), solid tyres, conveyor belts, shoe soles, golf balls, and anti-vibration mountings. BR has higher resilience, but as tear resistance is poor, it has to be compounded with higher black and oil, which lowers the resilience and such BR treads generate more heat than do treads based on NR.
  • Nitrile rubber: Good oil and solvent resistance.

Most polymers (including NR) can be "oil extended" and with higher black loadings, economic compounds can be developed.

Rubber Blends

Rubbers are often blended or copolymerized with another polymer, or chemically modified so as to enhance basic properties. Blends will be expected to have properties and price combining those of the individual components and thus, provide both technical and economic advantage. The addition of small amounts of a suitable rubber may improve properties such as oil or ozone resistance or improve processing behaviour. However, it generally does not improve the heat resistance.

Blends of emulsion and solution polymerized rubbers often give processing difficulties. The different rubbers being blended may have differences in viscosities and curing characteristics which may lead to processing difficulties and the final vulcanizate properties of the blend being inferior to the levels attainable with the individual rubbers. The properties adversely affected by non-compatible rubber blends include tensile strength, set, low temperature behaviour, and covulcanizability. Due to the reactivity difference in the blended phases and/or diffusion of vulcanizing agents (which are usually polar) from the less polar to the more polar phase, consistency of blending may be difficult to achieve under factory conditions. Inadequate covulcanization then leads to unfavourable mechanical properties such as inferior tensile properties, and poor dynamic behaviour.

Master Batches

A master batch is a mixture of rubber with one or more compounding ingredients in definite but higher concentrations than those in which they normally occur in a complete rubber mix. It is used for accuracy and efficiency in compounding, in order to avoid the addition of small amounts of accelerators, anti-oxidant, pigment etc.

Choice of Rubber

Natural Rubber (NR): Natural Rubber gum stocks can be compounded with tensile strengths, which are quite high compared to those of non-crystallizing rubbers. This is associated with the tendency of natural rubber to form crystallites when it is strained. Tensile strength can be further increased within limits by increase in crosslink density or at constant crosslink densities by addition of carbon black. Compression set ran be reduced by raising the crosslink density, but tensile, fatigue, and ageing properties are reduced slightly. In natural rubber compounds, silica is often added to provide high tear strength without a prohibitive increase in heat build-up.Semi-efficient vulcanization systems can give improved resistance to reversion and compression set at elevated temperatures. Soluble eV systems give low creep, stress relaxation, and compression set at elevated temperatures. They are not suitable for service at low temperatures for prolonged periods. The urethane crosslinking system gives vulcanizates with good resistance to high temperature ageing and suitable for arduous conditions. Air permeability of natural rubber compounds can be improved by use of natural rubber/chlorobutyl blends.

The use of gum natural rubber mixes is popular in articles such as gloves, surgical goods, toy balloons, elastic thread, and crepe soles.

From the processing stand point, natural rubber grades can be broadly divided into two groups: (a) viscosity stabilized grades such as SMR CV and SMR GP and (b) non-viscosity stabilized grades like RSS 1, RSS 3, SMR 10, and SMR 20. The viscosity stabilized grades do not require premastication prior to mixing and, therefore, mixing energy requirement is reduced.

Styrene Butadiene Rubber (SBR): SBR is generally marketed at a lower viscosity than NR and this permits its use in rubber compounding without premastication. Mechanical or chemical peptizing is not required. While most properties of SBR are comparable with NR, in some respects like heat build up, tack, and gum tensile strength, SBR is inferior to NR. But addition of resins and reinforcing fillers adequately improves the latter properties.

Owing to its irregular structure, SBR does not crystallize. A reinforcing filler is needed to achieve good physical properties with SBR. The best reinforcing agent is carbon black. Non-black fillers give very inferior properties in SBR to those they would give in a corresponding natural rubber mix. Abrasion resistance and resistance to degradation under heat are better for SBR than those of NR. SBR is less active chemically than NR and is thus slower curing, requiring more accelerators than NR. Scorch problems are less likely to occur with SBR than with NR, especially in black-filled compounds. SBR is compatible with NR, BR, EPDM NBR, and CR.

The effect of sulphur: accelerator ratio on the sulphur crosslink distribution is similar for SBR as for NR. In general, a lower sulphur level, and a higher accelerator level, is normally employed for SBR cure systems. In SBR, the use of eV systems tends to reduce resistance to flex fatigue cracking.

Emulsion SBR's are used alone as well as blended with BR or NR to improve the properties. In comparison with other diene rubbers, higher filler (75 pbw of carbon black) and plasticizer (20 pbw or more including the quantity contained in OE SBR) contents may be used. In addition to the cost benefit, the technical advantages in usage in car tread compounds include improved wet and dry grip while maintaining good abrasion resistance. Generally, N220, N375 or N339 carbon blacks and aromatic and naphthenic process oils are the preferred types.

Cold SBR is used for lighter duty tyres and in belting, hose, shoes, moulded goods, and other mechanical goods. Its low resilience compared to NR in black loaded compounds restricts its use in those tyre treads where a high heat build up is tolerable. SBR is not suitable for truck tyre treads, nor for elastic thread for golf-ball manufacture.

Anti-degradants are usually added to SBR to provide protection during service. Tack can be improved by the addition of tackifying resins or by blending with natural rubber. Generally SBR compounds are fabricated into composite articles with the use of natural rubber based solutions or insulation layers to obtain satisfactory building tack. Oil resistance of SBR can be improved by blending NBR into SBR based compounds. Plasticizers of the petroleum and coal-tar types are used to improve factory processing and to reduce costs.

Solution SBRs are generally more expensive than the emulsion types and are used in specialty applications; they consist of rubbers with different styrene and vinyl levels both of which raise the Tg and hence the wet grip. This is particularly useful in high performance radial car tyres and motor cycle treads.

Polybutadiene rubber: High cis BR is used in 20-30 parts along with 70-80 parts of NR in tyre treads. It is mainly used in truck tyre treads because of its high abrasion resistance and low heat-build-up. Tyre treads with NR/BR blends or SBR/BR blends give improved tread wear and reduced groove cracking. It is also used in the manufacture of mechanical goods and as a modifier for plastics to improve impact resistance.

Generally, BR is compounded with other non-polar elastomers. BR has limited compatibility with polar elastomers such as NBR (generally approximately 25% rubber hydrocarbon). Blends of BR are used partly due to the poor processing behaviour of polybutadiene as a homopolymer. BR does not respond to mastication and it does not band well on a mill and produces extrusions of rough appearance. It is generally advisable to mix all compounds containing high proportions of BR in internal mixers.

Curing of BR may be achieved by using conventional sulphur systems activated with metal oxide soaps (usually zinc oxide and stearic acid). In comparison with NR, BR requires less sulphur, but marginally higher accelerator levels, to achieve similar levels of crosslink density. Anti-degradants and accelerators are the same as for NR and SBR.

Acrylonitrile butadiene rubber (NBR): NBR does not strain-crystallize and without reinforcing fillers, NBR yulcanizates have poor tensile strength and low tear initiation resistance. Therefore, it is usual to have reinforcing fillers like carbon black or addition of phenolic resins or PVC to improve tensile strength to values which may be even higher than those obtained with NR. Very high hardness compounds can be prepared by using PF resins and NBR/PVC blends. With reinforced NBR vulcanizates, although the tear resistance is lower than for NR compounds, the fall off with higher rates of deformation and at higher temperatures is less than that for NR. NBR shows less abrasion loss than NR.

The incorporation of 30 pbw PVC into NBR compounds results in improved weather resistance and high resistance to swelling. The presence of PVC, however, produces stiffer compounds with lower resilience and inferior low temperature properties. To achieve optimum results, complete gelling of PVC with NBR at 160°C or higher temperature in the presence of an effective PVC stabilizer, such as a metallic soap type vinyl stabilizer, is necessary.

As NBR is susceptible to ozone attack, suitable antiozonants and waxes are to be added. NBR/EPDM blends (70/30 or 80/20 ratio) have a better ozone resistance than NBR compounds.

The heat resistance of NBR can be further enhanced by the use of semi-eV and eV cure systems, low sulphur, or sulphur donor systems. Plasticizers of low volatility should be chosen for heat stable compounds. Because of its strong polar properties, NBR is compatible only with polar plasticizers (DOP, DOS, DOS, etc.), i.e. esters of carboxylic acid or phosphoric acid.

NBR has low permeability to gases, this again depending on the ACN content. Generally, non-staining or slightly staining stabilizers are used in manufacture of NBR. The high polarity of NBR also influences its compatibility with certain compounding ingredients and non-polar rubbers. NBR is not compatible with SBR and BR. Good adhesion between NBR and textile can be achieved with NBR lattices or 50 : 50 blends of NBR and VP lattices in RFL dips.

NBR is a semi-conductor which can be made conductive (104 Wcm) by addition of FEF and acetylene blacks. Anti-static compounds may be prepared by addition of plasticizers for use in textile cots and aprons. NBR and NBR/PVC blends are used extensively as cable jacketing materials and portable electric cord.

The low temperature flexibility of NBR can be improved by the addition of adipate (DOA) or sebacate (DOS) type of plasticizers.

Isobutylene-isoprene rubber (IIR): Butyl rubbers, unlike many other polymers, do not break down on mastication or during the normal mixing process. The compound viscosity can be controlled by selection of the raw polymer grade, carbon black type and loading, oil type and loading, etc. Relatively high loadings of paraffinic or naphthenic oil are employed for typical butyl applications such as tubes or body mounts.

Tensile strength is highest in pure gum stocks, and increasing amounts of fillers generally reduces tensile strength. 50-100 phr carbon blacks (GPF or FEF) are added in practical compounds, and sometimes 100-150 phr of mineral fillers such as hard clay, platy talc, and silicas are also added. The recommended plasticizers are highly saturated materials of relatively low polarity, e.g. hydrocarbon oils, waxes, etc. "Heat treatment" procedures in which butyl and carbon blacks are subjected to high temperature (160-200°C) for at least 2-3 min mixing in the presence of "promoter" such as polyac (DuPont) or nitrol (Monsanto) generally give improved vulcanizate mechanical properties.

Butyl vulcanizates have high damping and this is more pronounced at lower temperatures. The maximum level of ozone resistance can be achieved when the lowest unsaturation grades of butyl are vulcanized to the highest possible state of cure. Plasticizers reduce ozone resistance. Excessively high-carbon black or light-coloured filler loadings should be avoided. Protective agents are not usually necessary but wax or EPDM can be employed to advantage.

Butyl vulcanizates are not serviceable in continuous contact with hydrocarbon oils and solvents as gross swelling will occur. However, butyl is resistant to polar solvents and vegetable/animal oils.

Strong acids and bases do not attack butyl nor do strong oxidizing or reducing solutions. However, concentrated nitric or sulphuric acids cause degradation. In compounding for minimum swell, the factors of greatest importance are high filler loadings, high reinforcement and maximum state of cure. Chemically sensitive fillers- for example, calcium carbonate, in a compound for use with mineral acids-must not be used.

The weathering properties of black butyl vulcanizates are outstanding. To protect non-black butyl compounds from sunlight, it is necessary to use adequate loadings of high opacity pigments, e.g. 15 phr Titanium dioxide or 45 phr zinc oxide.

The inertness of the polyisobutylene chain causes butyl rubber to be outstanding in resistance to heat and oxidation. However, low sulphur or sulphur donor systems with more thermally stable crosslinks show better effects on ageing than conventional sulphur cures. Resin cures are extremely stable towards heat and oxidation and these vulcanizates are preferred for high temperature service.

For general purpose insulation compounds, butyl rubber of low unsaturation grade with low sulphur and calcined clays (90-150 phr) or talc for low moisture absorption and high resistivity are selected. Whitings, calcium carbonates, and soft clay are used in lower voltage applications.

Butyl rubbers, unlike many other polymers, do not break down on mastication or during the normal mixing process. Relatively high loadings of paraffmic or napthenic oil are employed for typical butyl applications such as tube and body mounts. Compound viscosity is controlled by selection of butyl grade, carbon black particle size and structure, total filler and oil (plasticizer) loading, ratio, etc.

Mixing of butyl rubber compounds: Equipment which is used for processing diene rubbers must be thoroughly cleaned before it is used for butyl to avoid the possibility of contamination and delamination.

Internal mixing is preferable for efficient mixing of butyl compounds. The open mil mixing procedures are not generally suitable for butyl because of inherent high nerve, shrinkage, and resistance to breakdown, which preclude the formation of a mill band except under very specific conditions.

In internal mixing, close attention must be paid to batch weight (generally 10-15% higher than for NR/SBR to ensure full ram pressure during the mix), loading sequence, prewarming of rubber, black addition in stages, etc. As with other polymers, one or two stage mixing cycles are employed with butyl. Where mixing temperature exceeds the safe processing limit, curatives are added in a later stage.

Heat treatment of butyl rubber compounds is carried out by mixing a rubber/filler master batch at high temperature in the presence of a promoter such as dinitrosobenzene. This results in good carbon black dispersion and in better dimensional stability in extrusion and calendering processes.

There are five basic systems which are used for vulcanization of butyl rubber compounds (quantities in phr, approximate):

  • Sulphur 1.0, MBTS 1.0, TDEDC 1.5;
  • Sulphur 1.5, MBT 0.5, TMTD 1.0;
  • Sulphur donor, DTDM-2.0, TMTDS-2.0
  • Resin methylol phenol curing resin with halogenated polymers; and
  • Quinone dioxime cure; Red lead 5.0, p-quinone dioxime 2.0, stearic acid 1.0.

Sulphur cures: These are widely used in general purpose butyl compounds in conjunction with zinc oxide activation and (because the crosslinking sites are few), a combination of primary and ultra-accelerators. Stearic acid is not necessary as an activator, but is usually added as a process aid, i.e. as a mill release agent in soft butyl compounds; added late in the mixing cycle, stearic acid helps prevent sticking on the internal mixer drop mill.

Resin cures: These are used when maximum heat resistance is required, e.g. in tyre curing bags and bladders. Resin-cured butyl shows outstanding resistance to both dry heat and steam and can be compounded to give very low compression set. Heat-reactive, oil soluble, dimethylol phenol resins are used either in brominated form, or more commonly, as unmodified resin requiring halogen activation (which is provided by chloroprene in the presence of zinc oxide).

Quinone dioxime cures: Butylrubber is crosslinked by quinone dioxime in the presence of an oxidizing agent. These are used in cable compounds for fast, tight cures, where heat ageing and ozone resistance are of foremost importance. These compounds and scorchy are produce vulcanizates with lower than normal physical strengths.

Halobutyl rubber compounding: For halobutyl rubbers, zinc oxide is used as a vulcanizing agent with low levels of sulphur, stearic acid and sulphenamide accelerators. Bromobutyl shows higher cure reactivity than chlorobutyl. Both BIIR and CIIR will cure with zinc oxide but only BIIR will cure with sulphur alone, no zinc oxide or accelerator being necessary. BIIR can be cured with 0.5 phr sulphur, 1.3 phr MBTS, 3 phr zinc oxide and 1 phr stearic acid; levels of sulphur as low as 0.5 phr will give a rapid and reasonable degree of cure. ZDC can be used in small quantities (0.25-0.75 phr), with zinc oxide cures used in heat resistant applications and to improve compression set.

Peroxide vulcanization is also suitable for BIIR. While IIR degrades rapidly when heated in the presence of organic perioxides, BIIR can be cured with peroxides in combination with a co-agent. Vulcanizates with unusually low compression set, high heat resistance and excellent ozone resistance are produced.

Magnesium oxide and calcium stearate, when used alongwith the above accelerators in halobutyl rubbers, act as retarders. They also have an effect on cure time and state of cure besides increasing the scorch time.

Pre-crosslinked butyl This product is a terpolymer of isobutylene, isoprene and divinylbenzene, the last causing a high degree of pre-crosslinking. The pre-crosslinking increases the green strength, improves the dimensional stability and reduces the cold flow. The sealant and adhesive industry uses this product which resists sag and flow in preformed tapes for automotive and construction industries and improved ageing and weathering ability.

EPDM EPDM rubbers are amorphous terpolymers. Like other non-crystallizing polymers, mechanical properties of the unfilled EPDM are rather poor, and consequently, reinforcing fillers are added. As extraordinary mechanical properties are not required in applications where EPDM is commonly used, easily processable semi-reinforcing blacks are popular in EPDM compounds. Its low density makes it possible to use high extender oil and filler loadings for economy.

Oil extended EPDM's may be used for low hardness compounds. For high hardness compounds, blends with NR, SBR, high-styrene resins, or phenolic resins are also used.

Generally, the EPDM cure system will contain a thiazole (MBT, MBTS, etc.) in combination with a thiuram and/or a dithiocarbamate. For higher heat resistance, sulphur donor type accelerators may replace part or all of the elemental sulphur, e.g. 3 MBTS, 0.8 TMT, 1 ZDBDC, 0.8 DTDM, and 0.5-0.7 S.

The main chains of the EPDM molecule have no double bond and thus EPDM does not suffer deterioration due to molecular scission even after extended exposure to sunlight and high ozone concentrations. Because of their structure and composition, EPDM polymers are inherently resistant to ozone and weathering. The compounds are generally suitable for severe outdoor or high ozone applications without the need for anti-oxidants, waxes, or other special additives in black or non-black EPDM vulcanizates. Therefore, general purpose diene rubbers such as NR and SBR, which are inferior in those properties, are blended with EPDM.

Although EPDM does not possess the excellent low air permeability of butyl rubber, they are used at fairly low levels in inner tubes to improve low temperature properties, ageing, and processing characteristics.

There are a number of modifications which can be made in EPDM polymers. The different commercial grades currently available vary in polymerization process (solution or suspension), Mooney viscosity, relative molecular mass distribution, ethylene/ propylene ratio, and the third monomer (DCP or ENB) type and amount. Suitable grades may be chosen considering the process to be used, application requirements, and costs.

EPM (ethylene-propylene copolymer) does not have double bonds in the molecule. Hence peroxides are used for curing and the vulcanizates excel in heat resistance.EPDM may be crosslinked with sulphur or peroxide systems with unsaturation in the diene termonomer which is pendent or in a side chain. Peroxide cure systems may be necessary if the applications requires resistance to temperatures of 150-175 °C and a very low compression set.

Blending with NR, SBR rubbers is facilitated by the use of high diene EPDM (high unsaturation) rubbers. EPDM commercial grades contain a maximum of 15 double bonds per 1000 carbon atoms in contrast to SBR or BR with 150-250 double bonds per 1000 carbon atoms in the main chain. Thus, ozone, resistance to heat, and other atmospheric exposure hazards such as U.V. radiation and humidity are excellent.

EPDM may be considered as non-staining, non-migrating anti-ozonant, and is used in 15-30% blend with NK or SBR in white sidewall car tyres. Adhesion to textile of EPDM is somewhat difficult, but can be achieved by using dry bonding agents or incorporating SBR or VP lattices in RFL dips. EPDM compounds are not tacky and suitable tackifiers are necessary for operations involving bonding, knitting, or splicing in manufacturing.

EPDM has excellent electrical insulation properties, i.e. high dielectric strength, low power factors and corona discharge resistance, and radiation resistance. It has good low temperature flexibility and stays flexible above -50°C.

EPDM is resistant to polar solvents such as alcohol, glycol, ketone and phosphate ester, acids, alkalies, salt, and fats. EPDM compounds are used in tank linings where chemical resistance is important. EPDM compounds do not possess resistance to hydrocarbon oils and solvents.

Silicons rubber Low values of tensile strength are usual with unreinforced silicone rubbers. Hence, reinforcement is necessary. Unlike most organic rubbers, silicone rubbers can be either very difficult or impossible to crosslink with sulphur cure systems. The main chemical routes for the vulcanization of silicone elastomers are: (1) elevated temperature cures and (2) Room Temperature Vulcanizing (RTV) mechanisms. In elevated temperature cures, mostly organic peroxides are used. As the organic peroxides are inhibited by most carbon blacks, non-black reinforcing fillers such as precipitated silicas, titanium dioxide, and zinc oxide are used. Room temperature vulcanization is normally used with low-consistency silicone elastomers. Being of low consistency, the material can be easily extruded from a tube or other container and then cured in two-part or one-part systems.

As the uses of silicone elastomers are varied, various grades are available for specific uses, e.g. high strength, tough rubber, low compression set, wire and cable, etc. The rubbers suitable for low compression set applications do not also require elevated temperature post cure, following initial vulcanization.

Silicone rubber is the rubber of choice for high temperature service uses. In addition, it has excellent weather and thermal stability, ozone and oxidation resistance, good electrical properties, and extreme low temperature flexibility. The electrical properties of silicone rubber are very good in general but can be varied by compounding ingredients to suit applications such as wire and cable insulation and rubber insulating tapes. Silicone rubber is more permeable to gases than natural rubber and it behaves like a rather open screen.

Chloroprene rubber (CR) Chloroprene rubber grades are differentiated according to viscosity, crystallization tendency, degree of pre-crosslinking and the modifier type used in polymerization. Due to its high steric uniformity, CR vulcanizates from gum compounds or compounds with only inert fillers have higher tensile strength than those from similar SBR or NBR compounds, but not in the same range as that of similar NR based vulcanizates. With CR vulcanizates, tensile specifications have to be met often. CR compounds can be formulated according to the rules applicable for NR and SBR only in respect of fillers and plasticizers. CR is vulcanized with metal oxides; the formulation may sometimes contain sulphur, or it may be sulphur free. For general applications, a combination of zinc and magnesium oxides is used while lead oxide (litharge or red lead) gives good results where low water absorption is important. The allylic chlorine formed in the 1, 2 addition during polymerization in CR is present to the extent of 1.5 mole % and is the reactive site. The sulphur modified grades require no additional accelerator for vulcanization. In the case of mercaptan and XD-modified grades, ethylene thiourea increases the rate of cure and the modulus but reduces the storage stability of the compound.

The choice of anti-oxidants is also peculiar for CR. Diphenylamine derivatives or p-phenylene diamine anti-degradants with ozone protective waxes are used, and quinoline type anti-oxidants are avoided.

High tear resistance can be often obtained with reinforcing silica fillers with the addition of silanes. Other fillers may be used for special applications involving chemical resistance, as for example, (1) for flame resistance, antimony trioxide, zinc borate or aluminium hydroxide, usually with synthetic plasticizers like fire-retardant phosphoric acid esters, chlorinated waxes etc. (2) for resistance to hot water, silicate fillers, talc or chinaclay and (3) for chemical and acid resistance, fine particle talc.

Ester plasticizers reduce the glass transition temperature and improve the low temperature flexibility.

The mercaptan and XD grades are more heat resistant than the sulphur modified grades but while CR is better than NR, it is inferior to EVA, EPDM or IIR in this respect.

With appropriate compounding, the volume resistivity of CR can be raised to 5 × 1013 ohms cm, with a dielectric constant of about 6, a dielectric loss factor of about 0.045, and a dielectric strength of about 25 KV/mm. CR in thus suitable for cable sheating compounds and for low (up to 750 V) voltage insulation. In contrast, loadings of carbon blacks of high structure (conductive blacks) lead to conductive or antistatic vulcanizates with volume resistivity 102-1010 ohm cm.

To avoid sticking of CR compounds to the mill in processing, addition of stearic acid (0.5 to 1.0 phr), paraffin wax, low molecular weight polyethylene or polybutadiene as processing aids is often necessary. The temperature of compounds without accelerators should not be allowed to exceed 130 °C in processing because CR shows a tendency to cyclize at high temperatures. The effect of heat is cumulative and may result in progressive reduction of the processing safety. Therefore, mills at low friction ratios (1:1.1 or 1:1.2) are needed to minimize heat build up.

CR has a combination of several technically essential properties such as good mechanical properties, heat resistance, ozone and weathering resistance, flame resistance and adequate electrical properties for many applications, which are not obtained with other kinds of tonnage rubbers at a comparable price. Thus it has a broad application spectrum.

Reclaim: Apart from its role as a cheapening extender, reclaim in many cases aids processing considerably by reducing nerve. It is also a useful ingredient in stocks required for bonding to metal, as it confers improved adhesion. Batches containing reclaim are mixed more easily and rapidly. Where high physical properties are not necessary, it is possible to use large quantities of reclaim rubber. One balances performance, cost, and processing before making use of reclaim. It is better value for money than cheap fillers like clay and it assists processing. In higher proportions it can adversely affect physical properties like resilience, fatigue, and abrasion resistance.

Manufacture of Rubber Products

PNEUMATIC TYRES

A tyre is an annular toroidal-shaped inflatable envelope, made of rubber, which is reinforced with cord, enclosing coiled wire bead rings. It is fitted to a metallic rim which is secured to the vehicle.

A pneumatic tyre performs the following principal functions:

(a) It supports the weight of the vehicle. It transmits the forces on the vehicle to the ground, e.g.

(b) It helps to convert the engine torque to movement of the vehicle.

(c) It gives a more comfortable ride to the passengers or cargo in the vehicle by:

  • Acting as an additional spring in the suspension system.
  • Elastic deformation over undulations on the road.

(d) It permits cornering on the road at relatively high speeds by its capacity to generate higher cornering forces than would have been possible with a solid tyre.

Classification

Tyres may be classified in the following ways:

Tyre and Rim Notations. The tyre size which is prominently displayed on the sidewall indicates the approximate dimensions of the tyre. Many systems of tyre sizing are in vogue and the two most commonly used systems are explained below:

  • Size "9.00-20" indicates that the tyre has a section width of approximately 9" and is fitted on a rim of 20" nominal bead diameter.
  • For radial ply tyres, size 145/70R12 denotes a tyre with section width 145 mm, radial ply and nominal rim diameter code 12, and an aspect ratio of 70.

The ply rating of a tyre is also displayed on the sidewall, and indicates its load carrying capacity. It should be noted that it does not necessarily represent the number of casing plies. The actual load carrying capacity may be obtained by reference to published standards. In India, the Bureau of Indian Standards (BIS) has published this data. The ratio of tyre section height to width is called 'aspect ratio'.

Construction Tyres may be classified by the type of casing construction used and the principal physical difference between the casing constructions lies in the angles of the casing and breaker cords. The two basic casing constructions are as follows:

  • Cross ply The casing angle and the breaker angles are generally equal and in the region of 40°, with cords in alternate plies running in opposite directions.
  • Radial ply All the cords in the casing run in a radial direction and breaker cords are at a very low angle, i.e. almost circumferential.

All aspects remaining the same, the mileage potential of radials is the best.

Tread Pattern Design Tyres used on hard dry roads do not need patterned treads. However, on wet roads, the water acts as a lubricant between the tread rubber and the road, thus, drastically reducing the friction and hence grip of the tyre on the road. The pattern on treads helps to remove much of the water between the tyre and the road, thus improving the grip.

Tread patterns are of two basic types which are listed below. Various combinations of these types of patterns are in use which aim at providing specific properties for specific service uses and also to improve visual impact.

Fig. 3 shows in simplest terms the fundamentals of tread pattern design. The basic patterns have the following features:

  • Circumferential or ribbed pattern Its features are: Good lateral grip; even wear; and silent running.
  • Transverse cross-ribbed or lugged patterns Good fore- and aft grip; tendency to irregular wear and reduced grip; and noise on running are some of its properties. From these two basic patterns, others can be derived by addition and distortion. The simplest of these is produced by simple addition or combination of the basic two.
  • Square studs They have the features of-good grip in both directions; tendency to irregular wear; noise on running; and instability on cornering due to flexibility of units.
  • Ribs with side studs This is a simple commercial pattern. It is used for industrial tyres and for front wheel grader tyres. Its properties are: good resistance to wear; good steering due to longitudinal ribs; and side studs ensure that rotation and steering are maintained on soft surfaces.
  • Diamonds This was a well-known pattern for earth mover and other tyres. Properties were very similar to those of square studs, but slightly improved-good grip in all directions; somewhat reduced tendency to irregular wear; and reduced noise.
  • Improved ribs and side studs The basic properties are similar to those quoted under ribs with side studs for general on-and-off the road use.
  • Symmetrical transverse In this case, the simple transverse bar becomes a chevron, balanced about the centre line of the pattern. This type of pattern is widely used. The properties are: maximum grip and drive on rough and loose surfaces; tending to irregular wear if run on smoother roads; and no sideways reaction on drive or braking.
  • Asymmetrical transverse There have been a whole range of such designs, based on helical gear wheel designs. The properties can be altered by doing subtle changes to groove shape, tread radius, and shoulder contour. The basic types of highway tru