The rubber compound
• Since a rubber compound is a mixture
of a number of different ingredients,
some of the ingredients might modify
the basic properties of the raw gum
elastomer within the compound.
The Basic Rubber Compound
• The basic compound formula
The term phr (parts per hundred rubber),
meaning parts of any nonrubbery
material per hundred parts of raw gum
elastomer (rubbery material)
Material Specific Formulation
Raw gum elastomer 100 SMR 20 100
Sulfur from 0 to 4 Sulfur 0.35
Zinc oxide 5 Zinc oxide 5
Stearic acid 2 Stearic acid 2
Accelerators from 0.5 to 3 MBS 1.4
TMTD 0.4
Antioxidant from 1 to 3 HPPD 2
Filler from 0 to 150 N330 Black 45
Plasticizer from 0 to 150 Aromatic petroleum oil 4
TOTAL 160.15
Vulcanization
• Converts a substance that is plastic,
moldable into one that is flexible and
elastic.
• Increases tensile strength, modulus,
hardness, abrasion resistance and
decreases elongation, hysteresis,
compression set and solubility.
• Excessive crosslinking can convert
the elastomer to a hard brittle solid.
• Longer crosslinks promote better
tensile and tear strength and better
fatigue properties.
• Shorter crosslinks provide better
oxidative and thermal stability and
lower compression set.
RUBBER CURING SYSTEMS
Over the years three special types of cure
systems have been developed. They are:
• efficient vulcanisation (EV) systems,
• semi-efficient vulcanisation (SEV)
systems and
• conventional vulcanisation (CV) systems.
The levels of accelerator and sulfur in CV,
SEV and EV systems are shown
Measuring Cure
The curve exhibits a number of features
which are used to compare cure:
- Maximum torque MH.
- tS2, T2 or T5 : there is a delay or induction
time before the torque or resistance value
begins to rise.
- T90 : is the time for the torque to increase
to:
90/100(MH − ML)+ ML
Cure rate: A rise in the value of torque with
time, the slope of the curve, gives the
measure of cure rate. Sometimes cure
rates of various cure systems are
compared with T90−ts2 data
Test Equipment and Conditions
• Cure characteristics were determined
using an MDR 2000EA rheometer.
• Test specimens were vulcanised by
compression molding at temperatures and
times indicated.
• Stress-strain properties were determined
according to ISO 37
• tear strength according to ISO 34/1.
• DIN abrasion ISO 4649.
• fatigue to failure ASTM 4482/85.
• hardness according to ISO 48.
• Ageing of the test specimens was carried
out in a ventilated air oven at 100 °C for 3
days (ISO 188).
• Heat build up and permanent set after dynamic
loading were determined using a Goodrich
Flexometer (Load 11 kg or 22 kg; stroke 0.445
cm, frequency 30 Hz, start temperature 100 °C)
according to ISO 4666/3-1982.
• Dynamic mechanical analysis was carried out
using a RDA-700 (prestrain 0.75%, frequency 15
Hz and temperature 60 °C) according to ASTM
D 2231.
• Vulcanisate network structure was
determined by equilibrium swelling in
toluene using the method reported by Ellis
and Welding. The volume fraction
• (Vr) obtained was converted into the
Mooney-Rivlin elastic constant (C1) and
finally into the concentration of chemical
crosslinks.
• The proportions of mono-, di-, and polysulfidic
crosslinks in the vulcanisates were determined
using thiol amine chemical probes.
• Following the cleavage of the poly- and disulfidic
crosslinks, the samples were treated with methyl
iodide to distinguish carbon-carbon based
crosslinks from monosulfidic crosslinks.
• The rubber to metal adhesion
characteristics were determined according
to ASTM 2229-85.
Sulfur-based cure system
A typical sulfur vulcanization is
composed of sulfur, a metal oxide (ZnO),
a fatty acid (to solubilize the oxide’s
metal) and one or more organic
accelerators.
Curing agent: Sulfur
• Sulfur is the most commonly used
curing agent for elastomers with
chemically unsaturated polymer
backbones (NR, SBR, BR, NBR, CR,
Polyisoprene…).
• Two forms: amorphous and rhombic
• The amorphous form, known as insoluble
sulfur (insoluble in rubber and most
solvents)
• The rhombic sulfur, a ring of eight sulfur
atoms, is soluble in rubber and the form
normally used for vulcanization
• About 1-3 phr are used for most rubber
products.
Activators
• A metal oxide plus fatty acid
• Not to activate the sulfur itself but to
activate the organic accelerators
Accelerators
• Not to be confused with a catalyst, which
remains fully available at the end of a
chemical reaction.
• Speeds up the rate of vulcanization.
• Affect the scorch safety, the cure rate, the
length and number of crosslinks which
form.
Accelerators may be classified in several
ways:
(a) inorganic or organic
(b) acidic or basic
(c) by chemical type or
(d) by speed of the cure, giving rise to the
terms slow, medium, semi-ultra and ultra
Functionally, accelerators can also be classified
into two broad categories:
Primary accelerators:
Primary accelerators are mercapto based
accelerators, generally efficient and confer good
processing safety to the rubber compounds,
exhibiting a broad vulcanisation plateau with
relatively low crosslink density.
• Secondary accelerators:
Some rubber compounds use only one
accelerator but most contain two, a primary at
about 1 phr and a secondary (or booster) at 0.1
to 0.5 phr.
These combinations cause faster vulcanisation
than each product separately and a
considerable activation of cure which is positive
for the general property spectrum of the
vulcanisates.
Accelerator comparison
Accelerator type Scorch safety cure rate crosslink length
None very slow very long
Guanidines moderate moderate medium-long
Mercaptobenzothiazoles moderate moderate medium
Sulfenamides long fast short-medium
Thiurams short very fast short
Dithiocarbamates least very fast short
• The sulfenamides are the most common
primary accelerators, they are frequently
used with secondary accelerators which
act as activators for the cure system.
Retarders
• The desired level of scorch safety
• The traditional retarders are acids (
benzoic acid, salicilic acid, phthalic
anhydrid)
N-(cyclohexylthio)phthalimidereact with
MBT to form cyclohexyldithiobenzothiazole
(CDB) and the CDB dissociates to accelerate
the cure.
Non-sulfur cure system
Elastomers with chemically saturated
backbones cannot be crosslinked
with sulfur and so require alternate
curing agents
Peroxides
• Also used with unsaturated elastomers
• Thermal decomposition into oxy radicals
• Abstract a hydrogen from the elastomer to
generate polymer radicals
• Form carbon – carbon crosslinks
• The most commonly used is dicumyl
peroxide (DCP)
• More thermally stable than sulfur
crosslinks.
• Poor tensile and tear strength.
• Cannot be used with butyl rubber
(depolymerization)
Difunctional compounds
• Diamines (hexamethylenediamine
carbamate) for fluoroelastomers
• P-quinone dioxime for butyl rubber (at
the polymer double bonds)
• Methylol terminated phenol-
formaldehyde resin for butyl rubber
(with SnCl2 activation)
Metal oxides
• Usually ZnO, but occasionnaly PbO are
used as crosslinking agent for
halogenated elastomers (Neoprene,
halobutyl, chlorosulfonated polyethylene)
• Form an oxygen crosslink plus metal
chloride salt.
Fillers
• While the cured raw gum elastomers
of NR and CR are mechanically
strong, most gums are weak when
vulcanized and they need reinforcing
fillers.
• There is a range of reinforcement
from very high to very low
Filler properties
• Partical size
• Surface area
• Structure
• Surface activity
Filler classification
• Reinforcing : precipitated silica, fume silica,
carbon black N220, N330 (10-100 nm).
• Semi-reinforcing: carbon black N550, N765, N
990, precipitated calcium carbonate, aluminum
silicate, calcium silicate, hard clay (0,1-1μm).
• Non reinforcing: soft clay, calcium carbonate
(wet ground), calcium carbonate (dry ground),
Magnesium silicate, Barium sulfate (1-10 μm)
Surface area
• High surface area more contact
available higher potential to
reinforce the rubber chains
Structure
• Aggregate properties-shape, density, size
– define their structure
Filler which exist as agregates reinforces
rather than discret particles (carbon black,
silica)
• The persistent structure that exists in the
rubber compound affects its process ability
and properties.
The higher structure the filler is, in
turn, the greater its reinforcing
potential
Surface activity
• A filler can offer high surface area
and high structure, but still provide
relatively poor reinforcement if it has
low specific surface activity.
The effect of a filler on rubber physical
properties can be related mainly to
how many polymer chains are
attached to the filler surface and how
strongly they are attached
Antidegradants
• The proper choice of elastomer, cure
system and filler will ensure that the
desired properties from a rubber product.
• Antidegradants are used to prevent these
properties from changing during service.
• The primary degradant effects are
oxidation and ozone attack.
Selection of antioxidants and
antiozonants
• The volatility (loss during compounding
and service).
• The solubility (be soluble in the rubber, but
insoluble in any liquids the product will
contact).
• Chemical stability (to heat, light, oxygen
and other compounding additives).
• Discoloration or staining.
Antioxidants
• Most elastomers are subject to
oxidation (unsaturated polymer
oxidize more readily than saturated
polymers).
• The reaction of oxigen with elastomer
causes both chain scission and
crosslinking.
• If chain scission dominates during
aging, the elastomer softens and
eventually becomes sticky (the usual
behavior of unfilled NR and IIR
vulcanisates).
• Most technical elastomer compounds
eventually harden and embrittle
during oxidation, a consequense of
the dominant crosslinking reactions.
Mechanism
Oxidation is initiated by the formation of
carbon radicals.
• The carbon radical add oxygen to
form peroxy radicals.
• The peroxy radicals add hydrogens
from the rubber to form
hydroperoxides and generate the
carbon radicals which continue the
cycle.
• The hydroperoxides decompose into
two oxy radicals (RO* + *OH) which
just accelerate the oxidation
degradation.
Primary antioxidants
• Scavenge radicals before they can
react with the elastomer.
- Staining/discoloring:
- Non staining/non-discoloring
Secondary antioxidants
• Destroy the hydroperoxides before
they can decompose into radicals.
• Used only to protect the raw
elastomer in storage and
manufacture, since they are
destroyed during vulcanization
Optimum use level
• Amin antioxidants: 1 - 2 phr
• The phenolics: 0.5 – 2 phr
Antiozonants
• Ozone, even when present in the
atmosphere at only a few part hundred
million, readily cleaves carbon-carbon
double bonds in elastomer.
• Under strain, this causes cracks to
form and propagate, leading ultimately
to product failure.
• Highly unsaturated rubbers (NR,
SBR) are readily cracked.
• Rubbers with low unsaturation (butyl)
or a deactivated double bond
(neoprene) are moderately ozone
resistant.
• Saturated elastomers (EPDM) are
totally resistant.
Processing aids
• Plasticizing function:
- Reduce elastomer viscosity
- Promote mold flow
- Improve milling and extrusion
- Facilitate incorporation of fillers
- Improve low temperature flexibility
- Provide soft vulcanizates
• The petroleum oils:
- parrafinic, naphthenic, aromatic
(depend on elastomer compatibility,
volatility, and expected ptoduct
service conditions.
• Vegetable oils ( castor oils, tall oils)
• Vulcanized vegetable oil products
Other additives
• Tackifiers
• Flame retardants
• Odorants
• Blowing agents
• Colors
• Abrasives
