Escolar Documentos
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MATERIALS
TAMPERE UNIVERSITY OF TECHNOLOGY
THE LABORATORY OF PLASTICS AND ELASTOMER
TECHNOLOGY
Kalle Hanhi, Minna Poikelisp, Hanna-Mari Tiril
Summary
On this course the students will get the basic information on different grades of
rubber and thermoelasts. The chapters focus on the following subjects:
- Introduction
- Rubber types
- Rubber blends
- Thermoplastic elastomers
- Processing
- Design of elastomeric products
- Recycling and reuse of elastomeric materials
The first chapter introduces shortly the history of rubbers. In addition, it cover
definitions, manufacturing of rubbers and general properties of elastomers. In this
chapter students get grounds to continue the studying.
The second chapter focus on different grades of elastomers. It describes the
structure, properties and application of the most common used rubbers. Some
special rubbers are also covered. The most important rubber type is natural rubber;
other generally used rubbers are polyisoprene rubber, which is synthetic version of
NR, and styrene-butadiene rubber, which is the most important sort of synthetic
rubber.
Rubbers always contain some additives. The following chapter introduces the
additives used in rubbers and some common receipts of rubber.
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Table of contents
Summary....................................................................................................................2
Table of contents........................................................................................................3
1. Introduction to elastomeric materials ................................................................5
1.1 Definitions of elastomeric materials and rubbers ..........................................6
1.2 Manufacturing process of rubbers .................................................................7
1.3 Behaviour of elastomers ................................................................................8
1.4 General properties of elastomers ...................................................................9
2. Classification of elastomers.............................................................................14
2.1 Natural Rubber (NR) ...................................................................................16
2.2 Isoprene Rubber, Polyisoprene (IR) ............................................................18
2.3 Butadiene Rubber, Polybutadiene (BR) ......................................................20
2.4 Styrene-Butadiene Rubber (SBR)................................................................23
2.4.1 The use of SBR in tyres ........................................................................26
2.5 Butyl Rubbers ..............................................................................................27
2.6 Nitrile Rubber, Nitrile-Butadiene Rubber, Acrylonitrile Rubber (NBR) ....29
2.6.1 Modified nitrile rubbers........................................................................30
2.7 Epichlorohydrin Rubbers.............................................................................31
2.8 Ethylene-Propylene Rubber (EPM), Ethylene-Propylene-Diene Rubber
(EPDM)................................................................................................................32
2.8.1 Typical Properties.................................................................................33
2.9 Chloroprene Rubber, Polychloroprene (CR) ..............................................35
2.10 Polyacrylate Rubbers (ACM) ....................................................................37
2.11 Polyurethane rubbers (AU, EU, PUR).......................................................38
2.12 Fluorocarbon Rubbers (FKM, FPM) .........................................................41
2.13 Silicone Rubbers (Q) .................................................................................44
2.14 Polysulphide Rubbers (T) ..........................................................................46
2.15 Ethylene-Vinyl Acetate Copolymer (EVA)...............................................47
2.16 Polypropylene Oxide Rubbers, Polypropylene Oxide-Allyl Glycidyl Ether
Copolymer (GPO)................................................................................................48
2.17 Chlorinated Polyethylene (CM, CPE), Chlorosulphonated Polyethylene
(CSM, CSPE).......................................................................................................49
3. Rubber blends ..................................................................................................50
4. Thermoplastic elastomers (TPE) .....................................................................51
4.1 Styrenic thermoplastic elastomers (TPE-S).................................................52
4.2 Elastomeric alloys........................................................................................53
4.2.1 Thermoplastic Olefin Elastomers (TPO, TOE) ....................................53
4.2.2 Thermoplastic Vulcanizates (TPE-V, TPV, DVR)...............................54
4.2.3 Melt-Processible Rubbers (MPR).........................................................55
4.3 Thermoplastic Urethane Elastomers (TPU, TPE-U) ...................................55
4.4 Thermoplastics Polyester-Ether Elastomer (TPE-E) ...................................57
4.5 Thermoplastic Polyamide Elastomers (TPE-A) ..........................................58
4.6 Comparison of different TPEs .....................................................................59
4.7 New development trends occuring in the field of TPEs ..............................59
5. Processing ........................................................................................................60
5.1 Processing of rubbers...................................................................................60
5.2 Processing of thermoplastic elastomers.......................................................60
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6. Design of elastomeric products .......................................................................61
6.1 Design process ...............................................................................................63
6.2 Elastomer selection......................................................................................63
6.3 Dimensioning of elastomer products ...........................................................65
6.3.1 Mechanical dimensioning.....................................................................65
6.3.2 The influence of hardness.....................................................................65
6.3.3 Shape factor ..........................................................................................65
6.3.4 Stiffness in different loading situations ................................................66
6.3.5 Allowed loadings for different rubbers.................................................67
6.4 Product shaping ...........................................................................................69
7. Comparison of Elastomer Properties. Data sources ........................................70
8. Recycling and reuse of elastomeric materials .................................................74
8.1 Why reclaim or recycle rubber? ..................................................................74
8.2 Recycling methods.......................................................................................75
8.2.1 Incineration ...........................................................................................75
8.2.2 Pyrolysis ...............................................................................................76
8.2.3 Grinding of vulcanized rubber waste....................................................76
8.2.4 Devulcanization ....................................................................................78
8.3 Utilization of unvulcanized rubber waste ....................................................80
8.4 Processing of recycled rubber......................................................................80
8.4.1 Unvulcanized rubber waste...................................................................80
8.4.2 Vulcanized rubber waste.......................................................................80
8.4.3 Devulcanized rubber waste...................................................................81
8.5 Applications of waste rubber .......................................................................82
8.6 Recycling of tyres ........................................................................................82
References................................................................................................................84
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1. Introduction to elastomeric materials
The natives of South America got the idea to exploit the latex of the Hevea
Brasiliensis rubber tree to produce waterproof footwear, among other products
from soaking their feet in the liquid, latex, tapped from the tree. From the Indian
word caa-o-chu (a weeping tree) are derived the words caoutchouc in English
and French, Kautschuk in German, caucho in Spanish and caucci in Italian. The
word rubber originates from the early applications of rubber, i.e. from the property
of caoutchouc to rub out pencil writing.
In the 18th century, when rubber appeared in Europe, it was used for the fabrication
of suspenders and straps. Different kinds of materials were impregnated with
rubber to make them waterproof. However, the performance of the rubber articles
was quite poor, because rubber was at that time still gummy and fluctuation in
temperature caused great changes in products. It was only in the year 1839 that
Charles Goodyear discovered nearly by accident the vulcanization of rubber, which
made rubber as an elastic material capable of preserving its characteristics over a
wide temperature range.
The idea of this part of the Virtual Education in Rubber Technology course is to
give students an extensive overview of elastomeric materials. The structure and
characteristics of most typical rubber and thermoplastic elastomers will be
examined during this course. In addition, the applications and testing of different
elastomers, their design and construction and the recycling of elastomeric products
will be treated.
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1.1 Definitions of elastomeric materials and rubbers
Low molar mass molecules which can react with the same or a
Monomer
different kind of monomers, thus composing a polymer.
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1.2 Manufacturing process of rubbers
The manufacturing process of synthetic rubber starts with the manufacturing raw
rubber. The first step in this process is polymerization. This is a chemical reaction
in which small molecules (monomers) are joined together to form large molecules
(polymers). The basics of polymerization are presented on VERT module organic
chemistry.
Natural rubber is collected in ready polymerized form. Thus, the manufacturing
process of natural rubber starts by mastication. Mastication is a process in which
molecules are physically or chemically shredded to make mixing and processing
easier. Mastication makes the rubber softer. Most synthetic rubbers do not need
mastication because they are made of shorter molecules. A peptizing agent prevents
reactions between the broken chains.
Rubbers consist of elastomer and additives. Additives may be for instance fillers
and vulcanization agents. The purpose of additives is e.g. to improve properties or
processability. Rubbers can be processed in many ways (e.g. by compression
moulding, injection moulding and extrusion). You can learn more about processing
on the VERT module Processing of elastomeric materials. During the process or
after it the rubber is vulcanized (cross-linked), due to which rubber elasticity and
dimensional stability appear. Vulcanization is explaind more deeply on the VERT
modules Rubber chemistry and Raw materials and compounds in rubber industry.
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After processing and vulcanization the rubber product often has to be finished e.g.
by cutting.
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The temperature range for the elastic behaviour of elastomers is limited by the
glass transition temperature (Tg). At temperatures lower than glass transition
temperature the movement of molecule chains is very restricted and the large
elastic deformations are not possible. Elastomers are rigid and fragile materials
below the glass transition temperature. The physical background of elastomeric
behaviour is described in more detail in the VERT section on rubber physics.
The property profiles of elastomers depend mainly on the choice of the particular
rubber, the compound composition, the production process and the shape and
design of the product. Moreover the type of loading, e.g. whether it is static or
dynamic, strongly influences elastomer properties. Satisfactory properties can be
obtained only by proper compounding of elastomers with chemicals and additives,
and by subsequent vulcanization in appropriate conditions. Depending on the type
and amount of rubber chemicals and additives in a compound, and depending on
the degree of vulcanization, a given rubber can yield vulcanizates with
considerably different properties with respect to hardness, elasticity or strength.
The following chapters will deal with the most frequently specified properties of
rubbers reference to the standards ASTM 2000, SFS 3552 and SIS 162602. A
comparison of the properties of different rubber types and also thermoplastic
elastomers is given in the next table.
Thermal expansion
The degree of thermal expansion of different rubbers varies considerably
depending e.g. on the elastomers and fillers and their properties in the rubber
compound. Generally speaking, the linear thermal expansion coefficient of
elastomeric materials is five 5 ... 20 -fold compared with e.g. that of steels.
Consequently, the heat shrinkage of moulded elastomer products can be several
percent.
Hardness
The hardness of rubber is determined and measured based on the protrusion depth
of a standardized body under well-defined conditions. Hardness measurement is
one of the most frequently measured properties of rubbers. Hardness is commonly
quantified using the IRHD or Shore 0 ... 100 scale. The hardness of a conventional
elastomeric product is around 50 ... 70 IRHD.
Tensile properties
In order to obtain tensile material properties, it is customary to define the stress
which is required for a certain deformation, strain (see figure below). Frequently,
the stress values corresponding 100 or 300 % deformation are chosen to describe
tensile stiffness ( s 100 or s 300 modulus). The modulus at the early stage of the
tensile test is called Young's modulus. The stress at the breaking point of the
sample is defined as tensile strength (MPa) and the breaking deformation compared
to the original length is defined as elongation at break (%). The values of the tensile
strength of rubbers and thermoplastic elastomers are taken as satisfactory/good on
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Properties of different rubbers
5 = exellent, 4 = really good, 3 = good, 2 = fair, 1 = poor
NR SBR IIR NBR ECO, CO CR AU, EU FPM Q EPDM CSM
Tensile strength , MPa 4-25 4-25 4-15 4-18 4-18 4-20 15-30 7-15 3-10 4-18 4-12
Break elongation , % 100-600 100-500 100-800 100-400 100-500 100-500 100-800 100-200 100-400 100-400 100-500
Operating temperature, C
- short-term 100 100 140 130 150 130 80 250 275 150 150
- cold -60...-30 -50...-20 -40...-10 -50...-10 -50...-10 -50..-20 -20...0 -40...-20 -80...-50 -60...-30 -40...-20
20-60 20-60 20-80 20-60 20-60 30-80 20-60 30-50 20-60 25-60 60-80
Compression set, % (C)
(70) (70) (100) (100) (100) (100) (70) (175) (150) (100) (100)
Elasticity 5 5 2 3-4 3 3-4 5 2 1-3 3 3
Resistance
Typical tensile curves of different plastics (A, B and C) and rubber (D).
Modulus of elasticity
As mentioned earlier, in assition to the tensile strength, the force is measured which
corresponds to a certain strain and is calculated to correspond to the original cross-
sectional area. This stress value is a measure of the stiffness of a rubber sample and
one of the most important measures for the evaluation of vulcanizates. The stress
value is often called modulus . The use of the word modulus is incorrect, however,
since the stress value is always taken for an area where Hooke's law (Young's
modulus with low strains) does not apply any more.
The statistical mechanical theory of rubber elasticity gives the following equation
for the force and stress:
shows that tension increases with rising temperature and an increasing degree of
cross-linking (decreasing Mc ). In addition, the stress depends on deformation
speed and the form of the deformed body. The shape of the body is typically
described by shape factor S.
Tear strength
Tear strength is defined as the resistance force which a rubber sample, modified by
cutting or slitting, offers to the propagation of the tear. A multitude of test
specimen configurations have been presented for tear test.
The force (kN) requires to tear the sample divided by the thickness (m) of the
sample is defined as the value of tear strength. Also the tear energy - which is
largely independent of sample geometry has gained importance in material
evaluation.
The values for the tear strength of elastomeric materials with good tear properties
are in the range 50-100 kN/m, and values over 100 kN/m are excellent. Natural
rubber is one of the best elastomers in this respect.
,
where h o is the initial height of the sample before deformation, h1 is the height
during deformation and h2 the height a certain time after deformation. Frequently,
the samples are stored in the compressed state at an elevated temperature in order
to simulate the requirements of gasket materials where changes due to aging effects
play a role.
Relaxation and creep express the time dependence of the stress or the deformation.
During the relaxation test the strain is kept constant and the change in stress is
monitored, while during the creep test the stress is kept constant and the time
dependent strain is measured. The stronger the viscous component, the more
pronounced relaxation or creep is.
Abrasion resistance
Abrasion resistance describes the durability of materials under wearing conditions.
Most rubbers have exceptionally good abrasion resistance, which is a consequence
of the ability of rubbers to creep over the irregularities of the wearing counterpart
in sliding. Good wearing resistance is typically achieved with vulcanized general-
purpose rubbers, NR, IR, SBR and BR. In an environment exposed to oil,
polychloroprene (CR) and nitrile rubber (NBR) are the rubbers with best abrasion
resistance. Buthyl and ethylene-propylene rubbers, on the other hand, have the best
abrasion resistance at elevated temperatures.
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Electrical properties
Most general-purpose elastomers, like natural rubber (NR) and a variety of
synthetic elastomers (e.g. SBR, IR, BR, EPDM, IIR, MQ), exhibit very low
electrical conductivity and are therefore suitable as electrical insulating materials.
However, some other types, like CR and NBR, contain electrically polarizable
groups or dipoles and are therefore less suitable as electrical insulators.
The range of electric conductivity of all elastomers can be affected extensively by
the composition of the compound or by the addition of insulating (e.g. light) fillers
or conducting substances, especially carbon blacks or anti-static plasticizers.
Rubber articles with a high electric conductivity can be produced, too, e.g. for the
prevention of static electricity build-up.
Chemical endurance
Some fluids can cause big volume changes in rubbers which derive from the in
filtration of the fluid into the macromolecules (swell) or from the dissolving of
rubber ingredients in the fluid (shrinkage). Water, acids and bases may also bring
about some hydrolysis in certain rubbers, leading to impairment of tensile
properties. Nitric acid and concentrated hydrochloric acid react with most rubbers
and vause them to deteriorate.
Dynamic properties
Elastomers are viscoelastic materials. It meansthat part of the deformation is
recovered after the load is removedand part of the deformation is permanent.
Dynamic properties of elastomers depend on temperature, type frequency of
loading and amplitude of deformation. Also shape of the product affects on
dynamic properties.
Values describing dynamic properties:
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Dynamic modulus E*
o E* = E' + iE''
Elastic modulus = storage modulus E'
o Represents the stiffness of the material
Viscous modulus = loss modulus E''
o Represents the amount of energy dissipated into heat under load
Tan delta, loss factor
o The ratio of loss and storage modulus
o The smaller the value of tan delta, the more elastic the material
o tan delta = E''/E'
2. Classification of elastomers
Rubber type 62
Rubber type 62 is a rubber type that has not been standardized. Butyl rubber (IIR),
chlorobutyl rubbers (CIIR) and bromobutyl rubbers (BIIR) are elastomers which
belong to this group. They have good ozone and weather resistance. In addition, the
gas permeability is low and they are resistant to vegetable oils, but not to mineral
oils.
Rubber type 63
Rubbers in this group have good oil resistance, but their ozone and weather
resistance are weak. Applications are products that come in contact with oils.
Nitrile rubber (NBR) is of rubber type 63.
Rubber type 631 is rubber that has developed from nitrile rubber. It has better
ozone, weather and heat resistance than nitrile rubber. Hydrogenated nitrile rubber
(HNBR) belongs to this group. Rubber type 632 is nitrile rubber blended with
polyvinylchloride (NBR/PVC). It has better oil, ozone and weather resistance than
NBR.
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Rubber type 64
Chloroprene rubber (CR) is representative of rubber type 64. It has good resistance
to vegetable oils and fairly resistance to good aliphatic and naphtenic oils. A
disadvantage is their poor resistance to aromatic oil.
Rubber type 65
Rubbers in this group have good weather and heat resistance and quite good oil
resistance. Polyacrylic rubbers (ACM) are in this group.
Rubber type 66
Rubber type 66 is not standardized. Polyurethane rubbers (AU, EU) belong to this
group. These rubbers are tough and have good weather and oil resistance. Their
heat resistance is poor.
Rubber type 67
Rubbers in this group (fluorocarbon rubbers (FPM)) have good weather, heat, oil
and chemical resistance.
Rubber type 68
Silicone rubbers (Q) belong to this group. They have good weather, cold and heat
resistance. Their mechanical properties are weak.
Rubber type 69
Epichlorohydrin rubbers (CO, ECO, GECO) belong to this group. They have
medium weather, oil and heat resistance.
Rubber type 70
Rubber type 70 comprises ethylene-propylene rubbers (EPDM, EPM). They have
good ozone, weather and heat resistance and poor oil resistance.
Other rubbers
These rubbers are not standardized:
CM, chlorinated polyethylene (medium weather and heat resistance)
CSM, chlorosulphonated polyethylene (good weather and acid resistance)
EVA, ethylenevinylacetate copolymer (resistant to aliphatic oils)
BR, butadiene rubber (good elasticity)
XNBR, carboxylated nitrile-butadiene rubber (tough and oil resistant)
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2.1 Natural Rubber (NR)
Natural rubber can be isolated from more than 200 different species of plants.
Commercially significant source of natural rubber is Hevea Brasiliensis. Nnatural
rubber is obtained from latex, which is the emulsion of cis-1,4-polyisoprene and
water. Latex is obtained from the tree by tapping the innerbark and collecting the
latex in cups. A stabilizing agent, such as ammoniac, can prevent too early
coagulation.
Cis-1,4-polyisoprene.
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Methods of processing latex into commercial grades of dry natural rubber and into
concentrated latex.
The operating temperature range for NR is -55...+70 C.
Advantages of NR:
good processability
excellent elastic properties
good tensile strength
high elongation
good tear resistance
good wear resistance
little dissipation factor - low heat build-up in dynamic stress
excellent cold resistance
good electrical insulator
high resistance to water and acids (not to oxidizing acids)
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Disadvantages of NR:
poor weather and ozone resistance
restricted high temperature resistance (short-time maximum temperature
100C)
swelling in oils and fuels: low oil and fuel resistance
unsuitable for use with organic liquids in general (even though
vulcanization considerably improves swelling resistance), the major
exception being low molecular weight alcohols
Applications:
tyres (60 - 70%)
tubes, conveyor belts and V-belts
coatings
gaskets
latex products
footwear
adhesives
There are also many modified types of natural rubber. There is e.g. oil-extended
natural rubber (OENR), which contains 20-30 % oil, epoxidized NR and
methacrylate grafted NR (Heveaplus MG). The purpose of these modifications is to
improve the properties of NR to meet the special needs of rubber manufacturers.
Polyisoprene rubber has the same basic chemical formula as natural rubber (NR)
and thus it is a synthetic version of NR. The study of materials comparable with
NR started at the beginning of 20th century, but because of the high price of raw
materials and the weak quality of polymers, industrial production was not begun.
Significant production was started in the 1970s, when cheaper monomers and
catalysts, which produce stereo-specific polymers in solution polymerization
became available.
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It is possible to create different kinds of isomeric structures using different catalysts
and polymerization conditions in the polymerization of isoprene monomers. The
structures which are exploitable are 3,4-, cis-1,4- and trans-1,4-polyisoprenes. Cis-
1,4 -polyisoprene is a synthetic substitute for natural rubber and trans-1,4-
polyisoprene is a hard thermoplastic material (Gutta-percha or Balata).
Cis-1,4-addition Trans-1,4-addition
1,2-addition 3,4-addition
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Advantages of synthetic IR:
toughness good abrasion resistance cold resistance competitive price
processability and adherence good uncured tack high tensile strength high
resilience good hot tear strength
resistance to many inorganic chemicals
Disadvantages of IR:
restricted life time at high temperatures and in oxidative conditionspoor oil
resistance needs protection against oxygen, ozone and light is not resistant
to hydrocarbons
unsuitable for use with organic liquids
IR is often used with other rubbers. By blending other rubbers with isoprene,
tensile and tear strength and flexibility are improved. Applications of IR are similar
to natural rubber:
tyres conveyor lines and transmission straps gaskets, tubes, paddings
footwear, sports equipment protective gloves
sealants and sealing materials
The forerunner of polybutadiene rubbers was Buna, which was prepared for the
first time in Germany in the 1920s. Buna was a compound of butadiene and
sodium. During World War I it was noticed that the cold resistance of Buna was
not good enough. For this reason, American rubber scientists polymerized
polybutadiene (BR) in 1954. BR rubbers have much better weather resistance than
Buna.
Using solution polymerization in hydrocarbon solvent typically performs the
polymerization of BR. Suitable catalysts are Ziegler-Natta combinations and
lithium and its compounds. The elastomer is often named according to its catalyst
or according to the metal in it. Abbreviations used are among others Li-BR
(lithium), Co-BR (cobalt) and Ni-BR (nickel).
Three different kinds of basic construction units can be formed in polymerization.
The catalyst and polymerization conditions affect the development of these units.
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Cis-1,4-form Trans-1,4-form
1,2-form
The properties of polymer are determined by the isomeric structures which appear
most. Butadiene rubbers can be divided in three groups according to the amount of
cis-units.
Cis-1,4-content, % 96 93 38
Trans-1,4-content, % 3 3 52
1,2-content, % 1 4 10
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Comparision the properties of BR and NR.
5 = excellent, 4 = very good, 3 = good, 2 = fair, 1 = poor
Butadiene Natural
rubber BR rubber NR
Hardness, IRH 40-80 30-90
Tensile strength at break, N/mm2 7-21 7-28
Elongation at break, % 100-600 100-700
Operating temperature range:
- maximum, C 80 80
- minimum, C -70 -55
Elasticity 5 5
Electrical properties 4 4
Resistance:
- weather and ozone 1-2 1-2
- acids 2-3 2-3
- alkalis 2-3 2-3
- water 3 5
- abrasion 4-5 4-5
- flame 1 1
- radiation 2-3 2-3
Gas permeability 3 3
Adherence 4 4
Tack to the metal 5 5
Residual compression, % (C) - 20-60 (70)
Disadvantages of BR:
poor processability
weak mechanical properties
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The processing of BR is really difficult. That is why it is usually blended with some
other rubbers, such as NR and SBR. In those blends, the purpose of BR is to reduce
heat build-up and improve the abrasion resistance of the blend. It also improves
flexibility.
Applications:
tyres (BR content typically 30-50%, blended with SBR and NR)
shoe soles
coatings of cylinders, V belts
gaskets, tubes
coatings
toys
transmission belts
conveyor belts
Cis-1,4-form Trans-1,4-form
1,2-form
Styrene
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most widely used polymerization technique, even though the solution method has
steadily increased its the market share.
In solution polymerization the polymerization typically occurs in dry hydrocarbon
solvent with anionic methyl-lithium catalyst. Depending on the specific
polymerization process, two different elastomer types can be formed. One type
contains segmented styrene and butadiene blocks (TPE), the other type is rubber
elastomer with random distribution of co-monomers in polymer.
Styrene-butadiene rubber can be vulcanized using sulphur, sulphur donor systems
and peroxides.
The processing method can affect on the properties of SBR considerably. Molar
mass, styrene content and the amount of units vary, depending on the
manufacturing technique. Examples are shown in the attached table.
Properties of emulsion polymerization and solvent polymerization.
Emulsion - SBR Solvent-SBR
Molar mass Mn, g/mol 145000 200000
Molar mass Mw, g/mol 651000 420000
Mw / Mn 4.5 2.1
Styrene content, % 23.5 18
Cis-1,4-content, % 18 35
Trans-1,4-content, % 65 54
1,2-content, % 17 11
Glass transition temperature Tg,
- 50.6 - 69.7
C
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Disadvantages:
inferior mechanical properties (require reinforcements)
adhesion properties
poor oil resistance
poor ozone resistance
do not resist aromatic, aliphatic or halogenated solvents
low elongation at break
SBR needs more reinforcement than natural rubber to achieve good tensile and tear
strength and durability. SBR also has lower resilience than NR.
Applications:
car tyres (blended with BR, IR and NR)
footwear
conveyor belts
hoses
toys
moulded rubber goods
sponge and foamed products
waterproof materials
belting
adhesives
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Tyre /10/
Varying the monomer content in SBR copolymer, used in tyre tread blends, can
modify the properties of tyres.
Monomer contents that are typical of tyre tread blends.
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2.5 Butyl Rubbers
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Disadvantages:
poor wear resistance
not resistant to hydrocarbon solvent and oil
relatively low elasticity
The properties of halogenated butyl rubbers are similar to those of basic butyl
rubber. However, they have lower gas permeability and better thermal, ozone,
weather and chemical resistance. Halogenated butyl rubbers are used in
applications that require rubber with a high vulcanization rate.
Applications:
inner tyres of cars and bicycles
steam hoses
coatings of fabrics and cables
base element of chewing gum
waterproof films
gutter gasket
inner tubes
pharmaceutical closures and membranes
vibration isolation
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2.6 Nitrile Rubber, Nitrile-Butadiene Rubber, Acrylonitrile Rubber
(NBR)
Poly-acrylonitrile-butadiene rubber is a copolymer of butadiene and acrylonitrile. It
was synthesized for the first time in 1930. It is used because of its good oil, fuel
and fat resistance. Acrylonitrile rubbers are also called just nitrile rubber.
NBR is produced by emulsion polymerization. The polymerization rates of
acrylonitrile and butadiene are different. Because of that, the content of monomers
in copolymer is not the same as the content of monomers in reaction mixture. The
polymer formed is random copolymer in which the acrylonitrile content varies
between 18 ... 50%. Changing the temperature or feeding with monomers can
modify the composition of the polymer.
Applications of NBR:
seals, hoses, joints
roll coverings
conveyor belts
containers
protective clothes and shoes
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Boots /6/ Gloves /9/
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2.7 Epichlorohydrin Rubbers
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Applications:
gaskets
oil and petrol tanks and hoses
belts, rolls
coatings of wires and cables
coatings of textiles
vibration isolator
membranes
resilient mountings
Dicyclopentadiene as a terpolymer
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Ethyldienenorborne as a terpolymer
1,4-hexadiene as a terpolymer
Ethylene-propylene rubbers are valuable for their excellent resistance to heat and
their oxidation, ozone and weathering resistance due to their stable, saturated
polymer backbone structure. Properly pigmented black and non-black compounds
are colour-stable.
As non-polar elastomers, they have good electrical resistivity as well as resistance
to polar solvents such as water, acids, alkalies, phosphate esters and many ketones
and alcohols.
Amorphous or low crystalline grades have excellent low temperature flexibility
with glass transition points of about -60C.
TUT 2007 33
Heat aging resistance up to 130C can be obtained with properly selected sulphur
acceleration systems and heat resistance at 160C can be obtained with peroxide-
cured compounds. Compression set resistance is good, particularly at high
temperatures, if sulphur donor or peroxide cure systems are used.
These polymers respond well to high filler and plasticiser loading, providing
economical (obs. low density too), easily processible compounds. They can
develop high tensile and tear properties, excellent abrasion resistance, as well as
improved flame retardance.
As the disadvantages of EP rubbers, bad oil and hydrocarbon resistance and poor
tack can be mentioned.
A general summary of properties (property ranges) is shown in the table below.
Compression Set B, % 20 to 60
* Range can be extended by proper compounding. Not all of these properties can
be obtained in one compound.
TUT 2007 34
Applications:
products of automotive industry: seals and hoses, isolators
gaskets and hosepipes, liners in building industry
roll covers
agricultural equipment: hoses, seed tubes, cushioning, silus
wire and cable
Polychloroprene was one of the first synthetic rubbers. The first chloroprene
monomers were prepared from acetylene. Nowadays they are synthesized from
butadiene, because it is an easier and safer route. Chloroprene is polymerized by
emulsion polymerization using potassium persulphate as free radical initiator. The
main component of the polymer usually is trans-1,4-units. In the vulcanizing of
CR, zinc oxide and magnesium oxide blend is usually used.
3,4- form
1,2- form
TUT 2007 35
Advantages of chloroprene rubber:
good abrasion resistance
good ozone resistance
good tear strength
good oil and solvent resistance
inflammability
good adhesion to metals
increased hardness in high-temperature environments
Disadvantages of CR:
High swelling in some oils, hot water, acids and some organic solvents
TUT 2007 36
2.10 Polyacrylate Rubbers (ACM)
Polyacrylate rubbers are elastomers that are prepared from acrylic esters (typically
ethyl and methyl acrylate) and reactive cure site monomer (carboxylic acid or
chloroethyl vinyl ether).
Examples of the structure of acrylate rubbers. Monomers are ethyl acrylate and
chloroethyl vinyl ether or carboxylic group.
TUT 2007 37
The preparation of polyacrylate rubbers is based on polymerization of acrylate and
metacrylate acids. The polymerization technique can be emulsion or precipitation
polymerization. In emulsion polymerization, the catalyst can be persulphate salt or
redox system. In precipitation polymerization, the catalyst can be peroxide. The
peroxides are solvents to monomer or atso-bis-isobytyro-nitril, which degrade
easily.
To make reactive sites for vulcanization, polyacrylate elastomers are
copolymerized with 1 ... 5 weight percent reactive component, such as carboxylic
acid or chloroethylene vinyl ether or epoxy compounds. Common vulcanization
agents are methylene dianiline or hexamethylene diamine carbamate, or
metalcarboxyl soaps, such as sodium- or potassium stearate. Sulphur acts as a
catalyst.
Properties of ACM:
excellent ozone and weathering resistance
very good heat resistance
good oil resistance
good elasticity
excellent flexing properties
resistant to oil and aliphatic solvents
low gas permeability
poor water, alkali and acid resistance
good heat aging resistance
low resistance to hot water
not highly corrosive to steel
Applications:
applications in automotive industry (e.g. boots, grommets and seals)
seals, hoses, wire coverings
adhesive formulations
Polyurethanes are named after the urethane group, which forms when the
isocyanate group reacts with the hydroxyl group of the alcohol. Depending on the
type and amount of feeding stocks and additives, polyurethanes can be thermosets
or thermoplastics.
TUT 2007 38
Polyurethanes are the single most versatile family of polymers there is.
Polyurethanes can be solid or microcellular elastomers (both cross-linked rubbers
and thermoplastic elastomers), foams, paints, fibres or adhesives. They can also be
processed with most processing methods known at present (see figure).
TUT 2007 39
MDI (diphenylmethane 4,4'-diisocyanate)
The polyurethane rubbers can be divided into castable and kneaded (millable)
polyurethanes according to their processing method.
Castable polyurethane rubbers are obtained in a one-step process or a two-step
process. In the one-step casting method polyol, di-isocyanate and chain extender
react and the product is formed in the same step. In the two-step casting method a
prepolymer is prepared first by the reaction between diisocyanate and polyol. In the
second step the molar mass and the length of the chains of the prepolymer are
increased and the structure is cross-linked with chain extenders. The second step is
often carried out in a mould at elevated temperatures. Extenders may be diols or
triols. The two-step casting is more used than one-step casting.
The cross-linking which forms the three-dimensional network in PUR can be
brought out, as described above, by multifunctional chain extenders or isocyanates,
but also with sulphur and peroxides (especially the kneaded PUR grades).
The properties of polyurethane rubbers depend on the structure of their chains.
Polyester-based polyurethane rubbers usually have better mechanical properties
and chemical resistance than polyether-based polyurethane rubbers. Polyether-
TUT 2007 40
based polyurethane rubbers have better properties in low temperatures and better
hydrolysis resistance.
Properties of polyurethane rubbers:
good abrasion and tear resistance
good tensile strength
hardness
good oxygen and ozone resistance
resistant to aliphatic hydrocarbons and oils
low friction coefficient
good insulator
Applications:
wearing surfaces of wheels and rollers
power transmission elements
seals
soles
Fluorocarbon rubbers are very stable materials because of the strength of the bond
between fluorine and carbon. The most typical grades of fluorocarbon rubbers are
based on vinylidene fluoride and hexafluoropropylene HFP monomers (see table
below), which are referred to as FKM in ASTM standards and FPM in ISO
standards. There are also fluorocarbon rubbers containing chlorine in vinylidene
monomers (e.g. CFCl = CF2), referred to as CFM rubbers. Fluorocarbon rubbers
are usually produced by emulsion radical polymerization. Peroxide compounds act
as initiators.
TUT 2007 41
Monomers used in fluorocarbon rubbers.
Monomer Structure
vinylidene fluoride
VF2
tetrafluoroethylene
TFE
chlorotrifluoroethylene
CTFE
hexafluoropropylene
HFP
1-hydropentafluoropropylene
HPTFP
perfluoromethylvinylether
FMVE
VF 2 + FKM Tecnoflon T
HPFP + TFE
TUT 2007 42
PFMVE + FKM ECD 006
TFE + X
Disadvantages:
low alkali resistance
relatively poor mechanical properties
limited elasticity at low temperatures
the tensile strength decreases substantially at elevated temperatures
high price
The fluorocarbon rubbers are used for special applications that require good heat,
oxygen or corrosion resistance and hot solvent and oil resistance.
Applications:
car and airplane seals and hoses
fire-resistant coverings
heat-resistant insulators
o-rings, shaft seals
gaskets, fuel hoses, valve-stem seals
TUT 2007 43
O rings /3/ V seal /3/
Silicone rubbers are inorganic polymers, since their main chain structure does not
include carbon atoms. As shown in the diagram, silicone and oxygen atoms
siloxane groups - form the polymer main chain. There are typically also some
pendant groups, usually methyl groups, attached to the polymer chain. The molar
mass of silicone rubbers can vary over a wide range, and consequently there are
liquid materials as well as traditionally resinous rubbers available.
TUT 2007 44
Silicone rubbers can be divided according to their pendant group structure.
Pendant group Rubber type
methyl CH3 MQ
phenyl C6H5 PMQ
vinyl CH2 = CH VMQ
vinyl CH2 = CH
PVMQ
phenyl C6H5
trifluoropropyl CF3CH2CH2 FMQ
vinyl CH2 = CH
FMVQ
trifluoropropyl CF3CH2CH2
In VMQ rubbers, some of the methyl groups (< 0.5 %) are replaced with vinyl
groups. This facilitates vulcanization and reduces deformation set of the rubber.
PMQ and PVMQ rubbers have phenyl groups (5...10 %) instead of methyl groups.
This improves the properties of the silicone rubbers at low temperatures.
Fluorosilicones (FMQ and FMVQ) have better solvent resistance than other
silicone rubbers.
Reinforcement fillers, such as silica, have to be used, because the mechanical
properties of pure silicone rubber are rather weak. For example, the tensile strength
of pure silicone rubber is worse than that of any other ruccer. However, the
mechanical properties of silicone rubber do not weaken at high temperatures as
much as in the case of other rubbers.
Advantages of silicone rubbers:
high temperature resistance, wide operating temperature range (even -100 ...
+300C)
UV light, oxygen and ozone resistance (peroxides have to be used for
vulcanization)
elasticity
non-toxic, odourless, tasteless
good release properties
good electrical insulation
good aging resistance at high temperatures
good resistance to low concentrations of acids, bases and salts
Disadvantages of silicones:
weak oil resistance (exception aliphatic oils)
low resistance to steam, acids and alkalis
weak mechanical properties without additives
large shrinkage in moulded articles
vulcanization to obtain good mechanical properties has to be carried out
with peroxides
price
TUT 2007 45
Applications:
electrical equipment and technical products in high temperatures
medical devices and hospital supplies
roll coverings
cable coverings and insulators
lining compounds
moulds
o-rings
seals for the aeronautics industry
Polysulphide rubbers are formed when dihalide reacts with sodium polysulphide.
Polysulphide rubbers have only one manufacturer, Morton International.
Polysulphide rubbers can be divided into four different groups: Thiokol A, FA, ST
and LP rubbers. A-type polysulphide rubbers have ethylene dichloride as a
dihalide, FA rubbers are produced from the blend of ethylene dichloride and
dichloroethylene form. ST-rubbers are produced from dichloroethyenel form and
trichloropropane. LP types are liquid polymers. They are formed by breaking down
a high molecular weight polymer in a controlled manner. The sulphur content of
type A is high (84 %), The sulphur content Fa types is 49 % and that of ST types 37
%.
TUT 2007 46
Properties of polysulphide rubbers:
excellent oil and solvent resistance
good weather and ozone resistance
bad smell
difficult to machine
narrow operating temperature range
they corrode copper
very good low-temperature properties
Applications:
paint, oil and fuel hoses
seals
paint and varnish rolls
roller coverings
TUT 2007 47
Properties of EVA:
excellent oxygen, ozone and light resistance
extremely good water and oil resistance
good heat resistance
no resistance to organic solvents
fire resistance
good tack to other materials
low price
poor tear resistance
low abrasion resistance
low elasticity due to the thermoplastic character
with reinforcements, high tensile strength can be obtained
Applications:
cable and wire coverings
seals
floor materials
some medical extrusions
hoses
Polypropylene oxide rubbers are copolymers of propylene oxide and allyl glycidyl
ether. The typical allyl glycidyl ether content is about 5 %. The polymerization
method is solution polymerization in hydrocarbon. Vulcanization can be done with
sulphur.
TUT 2007 48
Properties of polypropylene oxide rubbers:
good properties at low temperatures
good elasticity
good heat and cold resistance
excellent oxygen, ozone and UV light resistance
weak oil resistance
low internal damping
high price
broad temperature range
Applications:
vibration absorbers
engine mounts
body mounts
suspension bushing
seals
Chlorinated polyethylene .
Chlorosulphonated polyethylene.
TUT 2007 49
Chlorinated polyethylene can be cured using peroxides or radiation.
Chlorosulphonated polyethylene can be vulcanized with peroxides, metal oxides
and amines. Increasing chlorine content increases oil, fuel and solvent resistance,
but decreases low-temperature flexibility.
Properties of CM:
very good UV light resistance
good oil resistance
very good oxygen, ozone and light resistance
good tensile and breaking strength
low compression set (up to 150 C )
very good dynamic fatigue
excellent aging resistance
very good chemical resistance
good flame resistance
very good colour stability
Properties of CSM:
oxidation and ozone resistance
chemical resistance good
relatively difficult to process
high swelling in some types of oils
high compression set in high temperatures
good cold, heat and flame resistance
Applications:
cable and wire coverings
electrical insulator
floor materials
coated fabrics
hoses
pond liners
moulded goods
automotive tubes
boots
dust covers
3. Rubber blends
Rubber materials used in applications are always rubber blends. They contain basic
elastomer or masterbatch and additives. In this way the properties of the material
are improved or changed. Additives and fillers are presented on VERT module
TUT 2007 50
Raw materials and compounds in rubber industry. VERT module Reinforcing
materials in rubber products presents reinforcements.
The compositions of rubber blends are described in recipes. The basic recipes are
simple and they are standardized. These recipes can be modified when new blends
are developed. Recipes provide information the materials and the amounts used in
rubber blend. The amounts of constituents are usually given in parts per hundred
parts of rubber (phr).
The basic recipe for rubber vulcanized with sulphur.
Material phr
Sulphur 0-4
Zinc oxide 5
Stearic acid 2
Accelerator 0.5-3
Antioxidant 1-3
Filler 0-150
Plasticizer 0-150
Other additives 0-
Thermoplastic elastomers are a polymer group whose main properties are elasticity
and easy processability. The use of thermoplastic elastomers has grown noticeably
in recent decades.
Thermoplastic elastomers are a wide group of materials. These materials have
many advantages of which the most important are:
good properties at low temperatures
excellent abrasion resistance
damping properties
good chemical resistance
easy processability (compared to rubber)
recyclability
TUT 2007 51
Restrictive features of thermoplastic elastomers compared to rubbers are the
relatively low highest operating temperature (< 130 - 160C), small selection of
soft grades and high price of TPE's.
Thermoplastic elastomers are used in areas where elasticity over a wide
temperature range is required. The main applications are in the automotive industry
and sport accessories.
Thermoplastics elastomers can be divided into the following groups:
Styrene-diene block copolymer
Elastomeric alloys
Thermoplastic urethane elastomers
Thermoplastic ester-ether copolymers, TPE-E
Thermoplastic amide copolymer, TPE-A
TUT 2007 52
Advantages of styrenic TPEs:
high tensile strength and modulus
good miscibility
good abrasion resistance
good electrical properties
large variety in hardness
high friction coefficient (corresponds to that for NR)
colourless, good transparency
Disadvantages:
poor high temperature resistance (highest operation temperature, SBS 65C,
SEBS 135C)
weak oxygen, ozone and light resistance of SBS (exception SEBS)
poor oil and solvent resistance
Applications:
rubber products in car industry
cables and wires
shoe soles
adhesives
with thermoplastics in multi-component injection moulding and co-
extrusion
TUT 2007 53
good chemical resistance
excellent weathering resistance
low density
good processibility
low price
Applications:
buffers and outside profiles in car industry
wire and cable coatings
hoses
TUT 2007 54
The properties of thermoplastic vulcanizates:
small permanent deformation
good mechanical properties
good properties at low temperatures
fatigue durability
good liquid and oil resistance
Applications:
car components
tubes
electrical insulators
Melt-processible rubbers are very rubbery materials that look and feel like
traditional rubbers. However, they can be processed like thermoplastics. Melt-
processible rubbers have one phase structure, so they differ from other
thermoplastic elastomers that have a two-phase structure.
Properties of melt-processible rubbers:
excellent elasticity
stress-tensile behaviour corresponds to that of vulcanized rubbers
softness and flexibility
Polyurethanes are named after the urethane group, which is formed when
isocyanate group reacts with the hydroxyl group of the alcohol. Depending on the
type and amount of feeding stocks and additives, polyurethanes can be
thermoplastics, rubbers (PUR) or thermoplastic elastomers.
Thermoplastic polyurethane elastomers form from long (MW around 600 3000
g/mol) soft segments of linear polyester (TPE-AU) or polyethers (TPE-EU) and
short, hard urethane segments that are formed of di-isocyanate and small alcohol
molecule chain extender, e.g. butane diol.
TUT 2007 55
The structure of thermoplastic urethane elastomers : long ester or ether diol chains
and hard urethane segments
TUT 2007 56
The properties of TPAU and TPEU.
Property TPAU TPEU
Tensile strength ++ 0
Abrasion resistance ++ 0
Tear resistance ++ 0
Weather resistance + 0
Water absorption 0 +
Applications:
conveyor belts
footwear
cable and wire coatings
hoses
components of car industry
TUT 2007 57
Disadvantages:
small variety in hardness
low elongation at break (requires own design principles of products)
poor hydrolysis resistance
poor UV-light resistance
high price
Applications:
cable and wire coatings
gaskets
hoses, tubes
TUT 2007 58
4.6 Comparison of different TPEs
Some values for the comparison of different TPEs are given in the table below.
TPE-S TPE-V TPE-U TPE-E TPE-A
3
Density [g/cm ] 0.9-1.1 0.89-1 1.1-1.3 1.1-1.2
Hardness Shore A/D 30A-75D 60A-75D 60A-55D 40-72D 75-63A
Lowest util T. [oC] -70 -60 -50 -65 -40
Highest util. T. [oC] 70, 135 135 140 150 170
P(SBS)
Compression set at 100oC P F/G F/G F/G
F/G(SEBS)
Hydrocarbon resistance F/E G/E F/E G/E G/E
Hydrolysis resistance G/E G/E F/G P/G F/G
Price order [/kg] 2...5 3...6 4...7 6...8 7...10
Material innovations
New polymerization techniques, metallocene techniques
Foamed materials, e.g. supercritical gases
Electrical properties, conductivities
Paintability
Blends including nanofillers
Processing
Coextrusion, coinjection, overmoulding
Adhesion & joining
Milling, thermoforming, extrusion, injection & blow moulding (all
processing alternatives)
Recycling
Product innovations/development, hybrid products
Product design to maximize the benefits of TPEs
Smart products, functionality
Design
Food and health applications, bioapplications
TUT 2007 59
5. Processing
5.1 Processing of rubbers
The processing of rubbers starts by mixing elastomers and additives. After that
rubbers are shaped by using different kinds of processing methods. The possible
methods are calandering, extrusion, moulding techniques (e.g. compression
moulding and injection moulding) and dipping. The methods are presented in the
VERT module "Processing of elastomeric materials". After shaping, the rubber
product is vulcanized so that mechanical properties and dimensional stability
appear. Vulcanization may occur during the processing or after it in many
techniques.
Rubber process
The processing of rubbers is quite difficult. Rubber has high viscosity and that is
why high shear forces are needed in the processing. Vulcanization poses
restrictions too. The processing temperature of rubbers is typically 70-140oC.
TUT 2007 60
between TPs and TPEs lie in the values of processing temperatures and viscosity.
In the case of thermoplastics, the processing temperatures are usually higher (150-
250oC) and viscosity values are slightly lower than those for TPEs. However, as the
first approximation, the processing equipment for thermoplastics is mostly suitable
also for processing thermoplastic elastomers. The most common processing
methods for thermoplastic elastomers are injection moulding, extrusion and blow
moulding techniques. The methods are presented in the VERT module "Processing
of elastomeric materials". The viscosity of TPEs is significantly lower than the
viscosities of traditional rubber elastomers, which offers many processing
advantages for TPEs compared with rubbers.
TPE process
Benefits of TPE processing (comparison with rubbers):
No compounding
No vulcanization
Faster processing properties (short cycle times)
Standard thermoplastic processing equipment
Thermally stable
Recyclable
Colourable in a broad range of intensites
Clear grades available
Paintable
Printable
Weldable
Overmouldable onto a variety of different substrates
Foamable
TUT 2007 61
The important factors influencing the consumer:
Before the decision to buy: shop display, total interior of the shop, colors,
materials, functions, fashion content and price
When the product is in use: the products functions, ease of use and
required care
Requirements for the development project may be defined on the basis of customer
interviews. However, it is important to review these requirements, as often
customers do not really know what they want, or their wishes may be based on
history rather than the future market. The feasibility of various solutions is
evaluated by a feasibility study. The impact of each solution is tested in terms of
profitability.
The manufacturer of elastomer products can design the product according to the
customer's specific request or develop a new product and supply it for several
customers. Technical rubber products are often developed in line with the specific
request of the customer. A tyre is a good example of a product that is designed by
the manufacturer and then marketed for customers. The product design is often
made in co-ordination with the customer. An elastomer component is often part of
a bigger unit, which may include metal mountings and restrictions regarding size
and form.
It is important that the product meets the requirements of customers better than
products of competitors. It is also useful if the product is capable of further
development.
TUT 2007 62
6.1 Design process
TUT 2007 63
Mechanical resistance (including abrasion resistance)
Functionality at low and elevated temperatures
Weather and ozone resistance
Impermeability for gases and fluids
Elasticity and vibration damping properties
Long-term creep
Processability
Many methods that may facilitate elastomer selection have been developed. One
example is the selecting tree. By means of the selecting tree, it is easy to make
some basic choices. One way is to feed the criteria into a computer program and
obtain a recommendation regarding suitable material.
TUT 2007 64
6.3 Dimensioning of elastomer products
In dimensioning, the most important starting points to be taken into account at the
early stages of design are
Functionality
Predicting and ensuring against the risks of damage
Predicting lifetime
TUT 2007 65
6.3.4 Stiffness in different loading situations
Taking the shape factor S into account, dependences between compression stress s,
compression modulus Ec and shear modulus G (see picture below) can be written
in the form
s = F/A = Ec 1 + 2 k S2) x/h and Ec = G (3 + CS2),
where
F = Pressing force
A = Cross-sectional area
E = Compression module
G = Shear module
k = Parameter that depends on hardness of rubber (assumption k = 1)
x = Compression deformation
h = Height in stress direction
S = Shape factor
The equations above are most valid with the shape factor values 1 - 10. The factor
C depends also on the form of the sample, being typically between 4 (long stripe)
... 6 (round plate). The principal dependence of E c on shape factor is shown in the
picture below.
The stiffness of rubber constructions can be controlled with the help of the
equations above. The construction is shared with rubber plates whose shape factor
comprises more than single-layer structure. The method is, for example, used in the
case of bridge bearings where the load capacity has to be considerable.
TUT 2007 66
Compression modulus of natural rubber as a function of shape factor and
hardness.
It can be seen in the graphs that in practice the allowed deformation is for
Harder rubbers about 15 %
Softer rubbers 20 25 %
Again, the loading stress has to be < 1MPa in compression and 0.3 MPa in shear.
TUT 2007 67
Loading estimation graphs for rubber products having different hardness and
shape factors.
The greatest values allowed in mechanical loading depend on the rubber and also
on other stress factors (including chemical loadings).
TUT 2007 68
For example, in applications where long-term creep is a critical factor, dynamical
loadings have to be estimated separately. That is because they can generate greater
permanent deformations than static loadings.
Creep values for filled and non-filled natural rubber with static and dynamical
loading.
Loading in stretching has also to be taken into account. Stretching deformations
should be minimized, because rubber molecules are susceptible to aging reactions
caused by radiation, ozone and oxygen.
The creep depends on the composition of the elastomer. Thus, it is not possible to
draw conclusions on the grounds of theoretical modelling that is based on typical
properties of rubber types.
Rubber blends can contain 5 ... 20 components and thus it is obvious that properties
will vary significantly. For this reason the properties of new rubber blend should
first be measured since only then can the behaviour of the rubber be evaluated.
Dimensioning sets certain limitations. Before mould design, the structure of the
elastomer product has to be shaped so that local stresses are avoided in loading
situations. Weather-sensitive surfaces should not be exposed to stretch loadings.
The examples of designing for even loading are given in the figures below.
TUT 2007 69
Examples of applications that are used to achieve even distribution of loading
stress and to avoid tension in the rubber product.
There are numerous sources of information where data on elastomer properties are
available. Not the least important are the technical information services by the
material deliverers.
In the table below, we have picked up some examples of the general properties of
different elastomers and their chemical resistances.
http://www.timcorubber.com/definitions/Comparison_to_Elastomer_Properties.pdf
TUT 2007 70
Chemical resistance of rubbers
Generally Generally
Material Chemical Group
Resistant to Attacked by
Most moderate
wet or dry
Ozone, strong
chemicals,
Natural rubber, acids, fats, oils,
NR, IR Polyisoprene organic acids,
Isoprene greases, most
alcohols,
hydrocarbons
ketones,
aldehydes
Styrene, Butadiene
SBR, Butadiene, Styrene Similar to Similar to natural
Copolymer,
BR Butadiene natural rubber rubber
Polybutadiene
Petroleum
solvents, coal,
Isobutylene,
IIR Butyl Water and steam tar, solvents,
Isoprene, polymer
aromatic
hydrocarbons
Many
Ozone, ketones,
hydrocarbons,
Butadiene, esters, aldehydes,
fats, oils,
NBR Nitrile Acrylonitrile chlorinated and
greases,
copolymer nitro
hydraulic fluids,
hydrocarbons
chemicals
Similar to NBR
but with Ozone, ketones,
Butadiene, improved esters, aldehydes,
HNBR Hydrogenated nitrile Acrylonitrile chemical chlorinated and
copolymer resistance and nitro
higher service hydrocarbons
temperature
Ketones, esters,
Epichlorohydrin Similar to nitrile aldehydes,
CO 1
Epichlorohydrin polymer and with ozone chlorinated and
ECO
copolymer resistance nitro
hydrocarbons
TUT 2007 71
Strong oxidizing
Moderate
acids, esters,
chemicals and
ketones,
Chloroprene acids, ozone,
CR Neoprene chlorinated,
polymer oils, fats,
aromatic and
greases, many
nitro
oils, and solvents
hydrocarbons
Concentrated
oxidizing acids,
Chlorosulfonated
esters, ketones,
polyethylene with Similar to
CSM Hypalon chlorinated,
improved acid and Neoprene
aromatic and
ozone resistance
nitro
hydrocarbons
Concentrated
Similar to oxidizing acids,
Neoprene with esters, ketones,
CM, Chlorinated
Tyrin improved acid chlorinated,
CPE polyethylene
and ozone aromatic and
resistance nitro
hydrocarbons
Concentrated
Ozone,
acids, ketones,
hydrocarbons,
AU, esters,
Urethane Urethane polymer moderate
EU chlorinated and
chemicals, fats,
nitro
oils, greases
hydrocarbons
Mercaptons,
Ozone, oils,
chlorinated
solvents,
Organic hydrocarbons,
thinners,
T Polysulfide polysulfide nitro
ketones, esters,
polymer hydrocarbons,
aromatic
ethers, amines,
hydrocarbons
hetercocyclics
Moderate or
oxidizing Many solvents,
chemicals, oils, concentrated
Si, Organic silicone
Silicone ozone, acids, dilute
VMQ polymer
concentrated sodium
sodium hydroxide
hydroxide
TUT 2007 72
Moderate or
oxidizing
Fluorinated Brake fluids,
FSI, chemicals,
Fluorosilicone organic silicone hydrazine,
FVMQ ozone, aromatic
polymer ketones
chlorinated
solvents, bases
Steam, amines
Aromatic
and amine
hydrocarbons,
corrosion
Tetrafluoroethylene/ Fluorinated chlorinated
TFE/P inhibitors,
Propylene copolymer solvents, ethers,
caustics, high pH
limited in low
media, wet sour
temperatures
gas, oil
All aliphatic,
Ketones, low
aromatic and
Standard molecular weight
halogenated
FKM fluorocarbon esters and
Fluoroelastomer hydrocarbons,
#1 dipolymer 66% alcohols and
acids, animal
fluorine nitro-containing
and vegetable
compounds
oils
Greater
resistance to
Nitrogen-
Proprietary acid, base,
Zalak containing
fluorocarbon alcohol, amine
compounds
and ethers than
FKM
Fluorocarbon-
Best fluid containing
Fully fluorinated
FFKM Perfluoroelastomer resistance of any refrigerants
fluorocarbon
elastomer cause minor
effects
TUT 2007 73
8. Recycling and reuse of elastomeric materials
Rubber recovery can be a difficult process. However, there are many reasons, why
rubber should be reclaimed or recovered:
Final price can be half compared with the use of synthetic material.
Recovered rubber has some properties that are better than those of virgin
rubber.
Reclaiming rubber requires less energy in the total production process than
virgin material.
It is an excellent way to dispose of unwanted rubber products, which is
often difficult.
It conserves non-renewable petroleum products that are used to produce
synthetic rubbers.
Recycling activities can generate work in developing countries.
Many useful products are derived from reused tyres and other rubber
products.
If tyres are incinerated to reclaim embodied energy, they can yield
substantial quantities of useful power. In Australia, some cement factories
use waste tyres as a fuel source.
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8.2 Recycling methods
Basically waste rubber can be recycled in three ways: it can be used for energy by
combustion, it can be used in its original form through devulcanization, and it can
be used as ground powder.
Recovery Alternatives
Recovery type Recovery process
Product reuse Repair Retreading
Regrooving
Physical reuse Use as weight
Use of form
Use of properties
Use of volume
Material reuse Physical Tearing apart
Cutting
Processing to crumb
Chemical Reclamation
Thermal Pyrolysis
Combustion
Energy reuse Incineration
8.2.1 Incineration
Incineration is a good and economical method of disposing of rubber. The energy
content of rubber is about 32.6 MJ/kg, which is about 10 % less than heavy oil
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(37.7 MJ/kg) and 1.3 times the energy content of coal (25.1 MJ/kg). Rubber is
burned in a special incinerator. The purpose is to recover as much energy as
possible in as ecologically sound a manner as possible.
Incineration produces oxygen, carbon dioxide, water and some toxic gases. Using
sufficiently high temperatures can prevent the formation of toxic components, such
as dioxin.
8.2.2 Pyrolysis
Pyrolysis involves heating the rubber waste in the absence of oxygen. The
temperatures used in this process are typically 400-800C. The pyrolysis process
produces three principal products: pyrolytic gas (10-20%), oil (40-50%) and char
(30-40%). Char is a fine particulate composition of carbon black, ash, and other
inorganic materials, such as zinc oxide, carbonates and silicates. Other by-products
of pyrolysis may include steel, rayon, cotton, or nylon fibres from tyre cords. Each
product and by-product is marketable:
The gas has high calorific value.
The light oils can be sold as gasoline additives to enhance octane and the
heavy oils can be used as a replacement for number six fuel oil.
The char can substitute for carbon black in some applications, although
quality and consistency is a significant impediment.
The quality and quantity of pyrolytic products depend on the reactor temperature
and reactor design. Heating rate, reaction time and pressure are also important
process variables.
Pyrolysis does not pollute air significantly because most of the pyro-gas generated
is burned as fuel in the process. During burning, the organic compounds are
destroyed. The decomposition products are water, carbon dioxide, carbon
monoxide, sulphur dioxide and nitrogen oxides.
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1. Milling and grinding of dry material at ambient temperature (ambient grinding)
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Crumb rubber is measured by mesh or inch and it is generally defined as rubber
that is reduced to a particle size of 3/8-inch or less. Crumb sizes can be classified
into four groups:
large or coarse (9-5 mm or 3/8 and 1/4) (ambient grinding)
mid-range (10-30 mesh or 2-0.6 mm or 0.079-0.039) (ambient grinding)
fine (40-80 mesh or 0.425-0.180 mm or 0.016-0.007) (cryogenic and wet
grinding)
superfine (100-200 mesh or 0.149-0.074 mm or 0.006-0.003) (cryogenic
and wet grinding)
The chemical composition, the duration of breakdown and the ratio of thermal to
mechanical breakdown influence the physical properties of reclaim . Varying the
duration and ratio of the different breakdown steps allows the production of custom
reclaims differing in viscosity, tensile strength and other related properties. An
explanation of this effect is found in the selectiveness of the mechanical breakdown
step: it is primarily restricted to the carbon, i.e. to the carbon backbones of the
network, which are broken down, and preferably the longer chains. This leads to a
narrower molar mass distribution. The thermo-chemical breakdown step is random.
As a result, the percentage of low molar masspolymer, acting as a peptizer and
having no reinforcing effect on the network, increases and the tensile strength of
the cured reclaim decreases. These differences in reclaim quality influence the
properties of a compound containing different reclaims.
Recycled rubber powder obtained from ambient or cryogenically ground tyres can
be utilized as filler in rubber and other polymeric compounds. In cryogenically and
wet ground rubbers, smaller particle size allows recycled rubber to be used at
moderately high levels and still retain processability. The incorporation of GRP
into polymeric matrix typically impairs the mechanical properties of the resulting
composites. This is because of poor matrix-filler adhesion and the lack of reactive
sites on the particle surface. Thus, the related end products generally are used in
applications with low performance requirements. To overcome this problem
various surface treatments of GRP have been proposed:
Coating of the GRP
Interfacial compatibilizing
High-energy radiation such as plasma, corona and electron beam radiation
Reactive gas treatment
Chlorination
Surface grafting
Use of coupling agents
8.2.4 Devulcanization
Devulcanization is one of the new methods of recycling waste rubber products.
Devulcanization means the cleavage of cross-linking sulphur bonds in rubber
vulcanizates, without cleavage of the polymer chain bonds. Devulcanization is a
good way of utilizing rubber waste because it assumes renewal of the original
chemical formula of elastomers and provides a possibility of recovering elastomers
from rubber vulcanizate waste. It can also be incorporated into the compound in a
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considerably larger amount than surface-modified or non-modified rubber scrap. In
general, instead of adding one part of unmodified rubber scrap, about three parts of
surface-modified or about seven parts of devulcanized rubber can be added.
However, in practice a total devulcanization process is very difficult to carry out
since many problems are caused by accompanying chemical transitions such as
depolymerization, thermal destruction and oxidation that worsen the properties of
the recovered elastomers. The main problem is the very low thermal conductivity
of rubber and the extremely difficult selective regulation of the quantity of energy
carried to the cross-linking bonds. In practice, it is virtually impossible to achieve
such levels of energy evenly distributed in all materials. It is necessary to find
experimentally the optimal devulcanization conditions that lead to devulcanized
products with good properties.
In the initial stage of the devulcanization reaction, the polysulphide and disulphide
bonds are converted to monosulphide bonds by heat. Furthermore, the
monosulphide bond is broken by addition of shear stress and finally recycled
uncured rubber is obtained.
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8.3 Utilization of unvulcanized rubber waste
One of the most effective ways of reusing rubber waste is to incorporate it into new
rubber products in the form of fine ground powder (rubber scrap). Rubber scrap is
easy to apply using simple equipment and has a positive effect on the processing
behaviour of a compound.
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The main advantages derived from the use of reclaim concern the processing
behaviour of the compound. These advantages include:
Shorter mixing cycles, resulting in reduced processing costs
Lower mixing, calendering and extrusion temperatures, resulting in fast and
uniform calendering and extrusion
Improved penetration of fabric and cord
Lower swelling and shrinking during extrusion and calendering
In the processing of cryogenically ground rubber, certain particle sizes are more
suitable in specific applications:
Extrusion: 80-100 mesh cryogenically ground rubber is needed to avoid
fracturing and rough edges. In extrusion of thick section, 50-60 mesh
cryogenically ground rubber can be used, depending on the surface
smoothness of the final product. The optimum level of cryogenically
ground rubber to be added to virgin rubber is 5%.
Calendering: for optimum surface smoothness of products, whose thickness
is 1.5 mm or less, the compound requires 80-100 mesh cryogenically
ground rubber. Where smoothness is not so important/critical, 30-60 mesh
can be used. The optimum level of cryogenically ground rubber in
calendering is 10%.
Moulding: cryogenically ground rubber in all mesh sizes can be used
because all mesh sizes help in removing trapped air during moulding. The
cured rubber particles provide a path for the air to escape by bleeding air
from the part.
Mould flow: cryogenically ground rubber generally improves mould flow.
Shrinkage is usually less for compounds containing cryogenically ground
rubber. The shrinkage reduction is proportional to the amount of
cryogenically ground rubber in the compound. So less mould flashing was
found with increase in the percentage of cryogenically ground rubber.
Devulcanized rubber can be processed, shaped and vulcanized in the same way as
virgin rubber. There are also many benefits deriving from the use of devulcanized
rubber in rubber compounds:
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Shorter mixing cycles lower power consumption
Low calendering, mixing and extrusion temperatures greater uniformity
Improved penetration of fabric and cord
Increased tack with minimal effect on temperature variation
Low swelling and shrinkage during extrusion or calendering
Improved stability during curing in hot air or open steam
Better air venting
Improved reversion and aging performance on natural rubber
Lower raw material costs
Pavements
Sound barriers
Polymer mortars and concretes
Recycled rubber can be applied to the entire range of rubber products,
including tyres, technical rubber goods, conveyor belts, shoe soles and
industrial coatings.
Rubber powder can be applied to sport surfaces as a rubber mat when
bounded with a polymer binder, e.g. polyurethane, or just mixed with sand.
Whole tyres can be used for artificial reefs, breakwaters, erosion control,
playground equipment and highway crash barriers.
The methods of reusing rubbers are: product reuse, material reuse and energy
recovery. Most tyres of cars and vans can be retreaded. Tyre of car can be retreaded
once and tyres of vans 2 to 3 times. Retreated tyres should only be mounted on
low-speed rated cars. There must be an age-restriction for the acceptance of worn
tyres (e.g. 6 years); also careful inspection is required prior to starting buffing, and
afterwards during the processing. In addition, lower weight or longer running tyres
are becoming less suitable for retreading operations. Lifetime and driving distance
expectations for truck tyres have increased and retreading is common.
If a product cannot be reused, it can be used in secondary reuse. The biggest
secondary reuse applications of tyres are road building, noise barriers and landfills.
In those applications the tyre powder can act as insulator or lightening material
between different courses of other materials. Blasting mat and buffers in piers are
other uses.
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Examples of the amount of tyres in different secondary reuse applications.
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References
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/2/ http://www.scottsafety.com/fin/fsari.htm
/3/ http://www.ramikro.fi/frame.htm
/4/ http://www.ramikro.fi/frame.htm
/5/ http://www.ramikro.fi/frame.htm
/6/ http://www.nokianfootwear.fi/nfi/
/7/ http://www.ursuk.com/ursuit/pdf/fi_pelastus_koko.pdf
/8/ www.fipa-online.com
/9/ http://www.tamrex.fi/k%E4sineet3.pdf
/10/ http://www.nokiantyres.com/
/11/ http://www.ursuk.com/ursuit/pdf/heavy_light_fz_bz_res.pdf
/12/ http://www.itdg.org/docs/technical_information_service/recycling_rubber.pdf
/13/ ASTM 2000
/14/ SFS 3552
/15/ http://www.pslc.ws/macrog/urethane.htm
/16/ http://www.fbv.fh-frankfurt.de/mhwww/KAT/English/indexrubber.htm
/17/ http://www.pslc.ws/macrog/pb.htm
/18/ Simpson R.B (edit), Rubber basics, Rapra tevhnology Limited 2002
/19/ Morton, M. (edit), Rubber technology third edition, Chapman & Hall, 1995
/20/ Andersen, c., (edit), Lifespan of rubber materials and thermoplastic elastomers
in air, water and oil, IFP The Swedish Insitute for Fibre and Polymer Research,
1999
/21/ Franta, I., Elastomers and rubber compounding materials: manufacture,
properties and applications, Elsevier 1989
/22/ Lamminmki, J. Research on the utilization of waste rubbers in polymer
matrices, Licentiate thesis, Tampere University of Technology, Department of
Material Engineering, 2005.
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