19nd March 2012

BASIC ON RUBBERS
RUBBER TESTING
Rubber - Definition

General Definition :-
Rubber Is a material . When we stretch It Can extent double the
size . If we release the stretch I t regain its original position

Technical Definition :-
Above the glass-rubber transition temperature, Tg .,
large parts of the chain are free to move; their thermal energy is high
enough to overcome the interaction forces, and the free volume increases
with increasing temperature. The polymer is , however, not yet in the liquid
condition; the coiled chains are mutually entangled,
Temperature
Tg : Glassy ----------------> Rubbery
Hard & Brittle Elastic & Flexible
Easy to break
 Brief History of Rubber:-
In 1839 Charles good year First discovered Vulcanization of Rubber
with sulphur .
Ever since natural rubber was processed to make pneumatic Tyres and
other rubber products. Rubber Natural and synthetic is a polymer which
is a chain of Hydrocarbon having Head to tail structure. eg. Poly
isoprene.

 
By substituting the functional group CH 3 by other
functional groups like N. Cl etc gave way to synthetic Rubbers like
Nitrile, Neoprene etc during the second world war by German when
Natural Rubber resources were cut off from Asia. Like that many
synthetic rubbers were developed using polymerization process
Rubber Classification
Max
Applicable (1) Max
Symb Curing
Type Rubber Service Application
ol temp
Polymer Temp(C)
Temp(C)
Rubber damper(insulator, bushing,
NR 70 160-170 stopper, coupling, pad, etc),
Tiretread(heavy duty truck)
Not used alone, blended with NR, EPDM,
160-170
IR 70 SBR, etc, and used for rubber damper,
weatherstrip, etc.
Tire tread, rubber damper,
160-180
SBR 100 weatherstrip, fluid brake line(brake
Elastomer
hose, cylinder cup, piston seal), etc.
of
Not used alone, blended with NR, etc,
Nonresista R 160-180
BR 70 and used for rubber damper(bushing,
nce
etc).
to Oil
Rubber damper(engine insulator, body
160-170
IIR 70 mount, etc), tire tube, cable cover,
etc.
Radiator hose, heater hose,
weatherstrip, rubber damper(muffler
EPM 180-200
70 hanger, etc), high tension cable,
EPDM
grommet, plug, fluid brake line
(cylinder cup, boot).
 Max
Max
Curing
Type Symbol Polymer Service Application
temp
Temp(C)
Temp(C)
Elastomer of Very
Oil hose, packing, oil proof
High Resistance SA PTR 100 170-180
sealing, etc
to Oil
Fuel hose, vacuum hose, oil seal,
NBR 120 170-180
O-ring, diaphragm, packing, etc.
Elastomer of High AU Rubber damper(bushing, stopper), ball
SB 120 170-180
Resistance to Oil EU joint boot, oil seal, etc.
CO,ECO Fuel hose, vacuum hose, oil seal,
140 170-180
AGE-ECO Diaphragm, O-ring packing, etc.
Constant velocity universal joint boot,
rack & pinion boot; outer cover of
CR 100 170-180
power steering, brake hose, etc;
Elastomer of weather strip, rubber damper, etc.
Moderate Resistance to SC Cover of fuel hose, vacuum hose,
Oil CSM 140 170-190 Weatherstrip, etc; high tension cable,
rubber cap, dust cover, etc.
High tension cable, cable cap, plug,
CM 140 170-190
and other electrical rubber part.
Elastomer of Very
MQ
High Resistance 180-200 High tension cable, cap, oil seal,
TA PMQ,VMQ 250
to Heat and check valve,gasket, packing, etc.
FVMQ
Low temperature
Elastomer of Engine oil cooler hose, oil seal,
ACM 220 170-180
High Resistance O-ring, etc.
TB
to Heat and Oil seal, check valve, packing, gasket,
FPM 250 180-200
High Temperature fuel hose, etc.
• Natural Rubber (NR)
NR has very goodabrasion resistance which, with its low relative cost,
makes it a significant choice for slurrypump liners and impellers as well as
for tank linings. It has very good dynamic mechanicalproperties and is
therefore used in tires, rubber springs and vibration mounts. have high
strength in gum vulcanizatesNR's good resilience, makes the gum excellent
for fine particle impact applications.
NR rubber gum vulcanizate has a very high elasticity, thus most of the
kinetic energy of an impacting particle is converted into deformation of the
vulcanizate
SBR
which then releases the energy by returning to its original
undeformed state
SBR are derived from petroleum oil. This applies to most elastomers, with the
obvious exception of NR. SBR represents half of all synthetic rubber production,
and is much consumed in tires, where it competes with and complements NR.
There are many subgroups of the raw gum elastomer, depending on the method
of synthesis of the polymer, such as whether it is solution or emulsion
polymerized, and the ratio of the two major
chemical building blocks styrene and butadiene.
POLY CHLOROPRENE RUBBER (CR)
The CR in the heading sta ds fo chloroprene rubber, more popul rly known as
Neoprene. Like all of the synthetic elastomers, CR is available to the rubber chemist in
a number of grades to aid in compound mixing (blending the raw gum elastomer with
a number of other ingredients to make the rubber compound) and to emphasize certain
properties, such as reduction of crystallization rate in the vulcanizate.
CR might be considered somewhat more specialized than the two previous elastomers
since it has a measure of both oil and weather resistance. The oil resistance would only
be considered moderate. CR has similar dynamic mechanical characteristics to
CR might be considered somewhat more specialized than the two previous elastomers
since it has a measure of both oil and weather resistance. The oil resistance would only
be considered moderate. CR has similar dynamic mechanical characteristics to NR,
including good mechanical strength when it is compounded as a gum vulcanizate. CR
has some ability to retard flame, which means that when a source of flame is removed,
the burning polymer will have a tendency to self extinguish, (this can be modified to
improve or unintentionally diminish this property), while NR, EPDM, and SBR for
example, will continue to burn. Upper continuous heat aging resistance temperature
limits are of the order of 90 "C. Like a number of elastomers this can be raised somewhat
by special compounding.
Acrylonitrile butadiene (NBR –Nitrile ) rubber:

NBR is called Buna-N but to many people in the industry, simply, nitrile. It is the workhorse of
the marketplace for its oil resistant properties. The grades offered differ in the percentage
of acrylonitrile (ACN) in the polymer chain as well as the overall viscosity of the polymer.
The higher the amount of ACN in the elastomer the better the oil resistance; the lower
end of the ACN distribution range being approximately equivalent to the oil resistance
of CR and therefore only having a moderate level of oil resistance. NBR also has superior
fuel resistance. The terms oil and fuel used here refers loosely to those products derived
from petroleum. The weather resistance of NBR is poor, similar to NR and SBR, although
it can be enhanced by blending with the plastic, polyvinyl chloride (PVC), at some 'cost'
to its low temperature properties. This latter attribute of NBR also varies with ACN
content; the lower the percentage of ACN in the polymer, the better the low temperature
flexibility, and the poorer the oil resistance.

The other major use for NBR is in the automotive

sector. However, as 'under the hood' temperatures increase with reduced airflow and
smaller engine compartments, NBR producers are searching for ways of increasing this
elastomer's upper region of heat aging resistance.
ETHYLENE PROPYLENE DIENE TERPOLYMER ( EPDM)

EPM is a copolymer consisting of ethylene and propylene units as part of the main polymer
chain. It can be cross-linked with peroxides or radiation but not sulfur. EPM is used as an
ethylene based plastic impact modifier and as a viscosity index improver for lubricating oils
EPDM is largely unaffected by weather with very good resistance to ozone. Dupont
literature [ 111 quotes EPDM products which were exposed to 10,000 parts per hundred
million of ozone for 1,000 hours in air, at room temperature, without cracking. Raw
gum elastomer manufacturers' literature [ 12, 13, 14, 151 indicate upper 'continuous'
heat aging temperature limits in air, anywhere from 126 "C to around 150 "C

The use of EPDM is dominant in roof membrane linings and extruded channels for
windows because of the above properties. EPDM has also been used as a blend with NR
in tire sidewalls to improve resistance to cracking by ozone attack. The excellent electrical
resistance of EPDM promotes its use in medium and high voltage cable covers. Its very
good resistance to water absorption, combined with good mechanical properties and
relatively low cost, make it a good choice for pond liners. Automotive applications of
EPDM would include radiator and heater hoses and weather strips. Metallocene catalyst
systems have recently been applied to the polymerization of EPDM [16, 171. This new
technology promises high precision in the control of the molecular architecture within
the polymer. This, as with all elastomers, translates to highly consistent processing of the
uncured compound and consistency of its final cured properties.
2.3.6
 Silicone rubber MQ MPQ MVQ and MPVQ
Most elastomers have a carbon main chain, while Q has a silicone oxygen backbone.
Silicone has an upper continuous heat aging temperature in the region of 205 "C. Caprin0
and Macander [20], give a table of estimated service life for Q as follows: 40 years at
90 "C, 2-5 years at 200 "C and two weeks at 315 "C. Moisture, such as might be found in
a poorly ventilated environment, can be a problem at high temperature [21]. Silicone is
among the best elastomers for both high and low temperature resistance. PVMQ heads
the low temperature list at around -100 "C. Silicone rubber has excellent ozone, weather
21

resistance and electrical insulation. Like CR, Q has a measure of flame retardant ability.
Mechanical properties such as tensile strength, are low, but change very little when
measured at higher temperatures; at 150 "C, it is catching up with other elastomers [22,
231. Oil resistance is about the same as that of CR; acid and alkali resistance are not good.
Applications include aerospace, medical, food contact, and automotive ignition cable. The
cost of the raw gum elastomer is higher than any of the rubbers mentioned so far.
 Hydrogenated nitrile HNBR (HSN)

It has all the attributes of NBR plus a very much higher heat resistance,
dependent on the grade chosen. It also has very good weather and abrasion resistance,
plus good mechanical strength. It is used in oilfields where it has resistance to amine
corrosion inhibitors and better hydrogen sulfide resistance than NBR. It has established
itself in automotive applications for timing belts, gaskets and O-rings, where higher
temperature resistant elastomers are needed. Peroxide cured HNBR has heat aging
resistance up to 150 "C, based on around 1,000 hours, while sulfur donor cured (see
sections 3.3.4 and 6.2.1) HNBR temperature resistance might drop to 135 "C. Cost is
somewhat less than conventional fluorocarbon rubber (FKM) on a weight basis, also
since the density (using g/cm3, which approximates to specific gravity) of HNBR is about
half that of FKM, more products can be made for the same weight purchased (
Fluorocarbon rubber FKM (FPM)
Based on vinylidene fluoride and hexafluoro-propylene
the grades available differ in the chemical building blocks which were used to construct
the polymer. Like silicone rubber, FKM has excellent high temperature resistance with an
upper continuous heat aging temperature limit of 205 "C. DuPont literature [24] quotes
continuous dry heat service to be >3,000 hours at 232 "C decreasing to >48 hours at 316
"C.
Polyacrylate ACM
This family of polymers exhibit oil resistance. Their heat aging temperature limit is between
150 "C and 175 "C. The major application areas are automotive engine and transmission
seals, gaskets and O-rings. The low temperature properties are not good, although some
grades are flexible to -40 "C.

Epichlorohydrin ECO CO and GECO

These halogenated polyethers are available in three forms: a homopolymer (CO), a
copolymer (ECO) and a terpolymer (GECO). Attributes found within this group are:
extremely low gas permeability, good oil and ozone resistance, and a good low and high
temperature range. The high temperature performance is better than that of nitrile. They
are used for automotive air ducts, fuel line hose tube and cover and some oilfield applications.

Chlorosulfonated polyethylene CSM

Best known as Hypalon this material has excellent ozone, acid, and weathering resistance
together with mild oil and heat aging resistance. It is used extensively for roofing, pond
liners and applications needing resistance to strong mineral acids
The symbols of polymer have been made in accordance with ASTM D 1418
(Designation of Synthetic Rubber and Latex).
RUBBER CHEMISTRY
Polymer

Just like a house built from bricks, the raw gum elastomer is also built from small
discrete units, called monomers. Both monomers and polymers are molecules, the
former are small, the latter are very large. Monomers are simple chemicals, such as
ethylene, propylene, isoprene, and butadiene, most of which originate from petroleum
oil. To a chemist a butadiene monomer would look like this: CH,=CH-CH=CH,.
All of the carbon atoms are linked together like a small chain. Two methods of
representing the structure are shown in Figure 6.1.

Figure 6.1 A butadiene molecule (monomer) used for creating BR

and other rubbers
The end carbon atoms have two bonds, linking them to the adjacent carbon atom.
These are called double bonds (also known as unsaturated bonds), and they are much
more chemically reactive than a single bond. It is the double bonds that allow the
carbon atom on the end of this small chain to link up with a carbon atom on the end of
another butadiene molecule, and start a ‘chain reaction’ (polymerization) to build up a
‘superchain’ containing thousands of monomers, all linked together.
 Vulcanization

Vulcanization is the process of cross-linking. Cured rubber is a much more dimensionally

stable and heat resistant material Vulcanization significantly increases the overall
elasticity, by locking the chains to each
other (see section 6.2.1), which greatly decreases the amount of slipping the chains can

Sulfur vulcanization
Sulfur links one chain to another through these double bonds. Elastomers such as
NR and SBR need only a small percentage of these double bonds to be utilized to produce
a useful product; however this leaves the larger percentage unused and therefore
vulnerable to attack by oxygen, ozone and heat.
EPDM,NR,SBR,IIR,BR ,NBR ,CR can be vulcanized by sulphur vulcanization
Peroxide Vulcanization

They do not need the reactivity of a double bond to cure, nor do they need accelerators,
although chemicals known as coagents are often used to improve overall vulcanization.
Peroxides typically react with the elastomer chains by removing hydrogen atoms from the
carbon backbone of the polymer, thus creating highly active sites on the chain, called
radicals, which attach to a similar site on another chain, creating a carbon to carbon cross-
link, which is stronger than a sulfur carbon link and more thermally stable
Polarity

The chemist uses the concept of polarity as a guide to determine how rubber will behave
in a liquid. Certain atoms in a polymer chain can preferentially draw electrons towards
themselves from their neighbors.

The chlorine atom, such as that in CR, draws electrical charge from the adjacent carbon
atom, causing the chlorine to be slightly negative (electronegative) and the carbon to be
slightly positive (electropositive j, as follows: This makes CR a polar elastomer. A chemical
group such as acrylonitrile (ACN) also has this ability in nitrile rubber.

Double bonds in a polymer chain also provide a measure of mobility for movement of
electrical charge, introducing somewhat less polarity than the chlorine atom or ACN
group. Double bonds are found in the main chain of NR, SBR and BR. EPDM has a
low level of polarity, consisting of only carbon and hydrogen atoms with little
unsaturation (the main chain has no double bonds) and no significantly electronegative
side groups.
How the chemist uses polarity
Rubber will swell the most in a liquid of similar polarity to itself. Thus EPDM (low
polarity) will swell little in methylene chloride or acetone (high polarity) and greatly in
paraffinic oil (low polarity). Nitrile rubber, on the other hand, will do the opposite;
hence its use as an oil resistant elastomer. However not all nitrile is created equal. It is
sold with the polymer chain containing different percentages of ACN. As that percentage
increases, so does the polarity of the rubber and thus the oil resistance improves. A low
ACN content might only confer the oil resistance of CR.
If the common elastomers are arranged in order of increasing polarity it looks like this:
EPDM, NR, SBR, CR, NBR. If the petroleum oils are arranged in the same way, it looks
like this: paraffinic, naphthenic, aromatic. A word of warning however, polarity is not
the only explanation for swelling, and there may be exceptions to the ‘rule’, nonetheless
it does explain quite a lot.
RUBBER TESTING
Test Classification in MS269-03
Training On Testing :-
1. ODR – Oscillating Die Rheometer

Temperature Condition:
Basically NR: 145-150°C ;SBR: 150°C ;NBR: 160°C ;
EPDM: 170-180°C

Flow induction period

The results obtained from the graph
1. Induction period and Flow time
2. Scorch Time (Ts2) can be defined as premature vulcanization before the compound flow is completed.
Normaly the cure should start only after the compound reaches full flow.
3. Initial Torque
4. Minimum Torque ML.
5. Maximum Torque. MH
Sample weight is 8.5- 9 gm as per standard
From Minimum Torque Level (ML) to 2 Point to get ts2. (Point: 2 lbf square) is the Scorch time
T90: Stabilizing torque (optimum X CrossLink density)
From the graph
2. Mooney Viscometer:-
 
Here the Viscosity is measured against resistance to shear.
Flow is inversely proportional to viscosity.ie:- If the compound flows more the viscosity will be less and
vice versa.
The instrument consists of a die and Rotor and the compound about
25 gms weight is placed in between the rotor in sandwich and shear is applied and the resistance of the
compound to shear is measured as viscosity in graphical output.
 
 
T3 (after Vmin 3 lbf square)
Vmin
 -It is process control testing. ML (1+4) AAA°C
Preheating Time
4 - Test Time
AAA – Temperature
 
The results obtained from the graph
1. Initial Viscosity.
2. Minimum Viscosity
3. T5
4. T35
T5: From Minimum Viscosity to 5 Point increased to get T5. (Point: 5 lbf square): Scorch Time
 
Time taken for optimum cure: Cure rate index T∆ = (T35-T5) = T30
 
3. Specific Gravity:
 Specific Gravity: Mass / Volume
= Wt in Air/ (Wt in air – Wt in water)
 This is based on Archimedes
 It is applicable for calculating batch Weight & process control

 
Lab Test– Mooney Viscosity
Description
Determines the Mooney Viscosity of unvulcanized compound.
Method
Cut sample from compound sheet using cutting die. Insert the specimen in the rotor & Keep the specimen on the machine as shown in the
pic . Click test start button.. Results for Mooney Viscosity , Scorch time expressed respectively MV , T5 ,T35 (mm:sec)

Samples Test

Rotor
Lab Test– Rheometer
Description
Determines the Curing characteristic of un vulcanized Rubber compound.
Method
Cut sample from compound sheet using cutting die. & Keep the specimen on the rotor as shown in the pic . Click test start button.. Results
for curing properties in terms of ts2,T90 (min), Tmin , Tmax (lb-inch)

Samples Test

Rotor
Lab Test– Tensile Strength & Elongation
Description
Determines the Tensile Strength, Elongation at Break and Modulus at Elongation of cured compound.
Method
Cut dumbbell from cured compound sheet using cutting die. Measure the thickness of the sample and clamp in tensometer grips. Apply the
contact arms of the extensometer to the sample, having first calibrated the appropriate sample length. Test runs at 500mm/min and is
complete when sample breaks. Results for Tensile Strength and Modulus at Elongation are expressed inKgf/cm2, while Elongation at Break is
expressed as a percentage. Test
Sample cutting

Gauge
 LabLab
Test–
Test Tear Strength
Summary – Tear Strength Test
Description
Determines the tear resistance of cured compound.
Method
Cut tear strength test piece from cured compound sheet using cutting die. Cut the sample so that the mill direction of the compound runs
parallel to the length of the cutting die. Measure the thickness of the sample and clamp in tensometer grips. Test runs at 500mm/min and
is complete when sample tears. Results are expressed in MPa.
Cut Test

Gauge
 Lab Test – Compression Set
Description
Determines the ability of compound to retain it’s elastic properties after prolonged compression at constant strain.
Method
Cut compression set pieces from cured compound, and measure the thickness. Place test pieces on the bottom plate of test jig. Place
appropriate spacers between the top and bottom plates. Tighten the bolts uniformly until the top plate comes into contact with the
spacers. Age in oven (set at required temperature) for appropriate duration. Once ageing complete, measure the thickness of the test
pieces again and calculate result based on thickness before / after ageing and spacer size.
Samples

Thickness Measurement Test Jig

Spacers
 Lab Test – Hardness Test
Description
Determines the Hardness ( Shore A & IRHD ) of Vulcanized Rubber compounds
Method
Mold the specimen by using lab press & Hardness Button Mold or Slab mold .
Shore A Hardness : Ensure the Specimen kept Flat surface Place the Durometer on the specimen applying force on the specimen . Reading
from the durometer should be noted after 3 seconds shows Shore A Hardness of the compound.
IRHD Hardness :Place the specimen ( 2mm slab cut piece ) on the centre of the specimen plate . Arrange the location by adjusting screws.
Push start Button . After 30 Seconds on the display shows IRHD of the vulcanized rubber compound
Shore A Hardness

Specimen Preparation

IRHD Hardness
 Lab Test – Abrasion Test

Description
Determines the Abrasion Resistance of the Vulcanized Rubber compounds
Method
Mold the specimen by using lab press. Insert the specimen on the specimen holder. After running of 1000 Cycles.
Weight difference of the specimen gives abrasion resistance of the compounds .

Abrasion Tester

Specimen

Sample weighing