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RUBBER COMPOUNDING

INGREDIENTS :

PROTECTIVE
AGENTS
HASETRI

Introduction

Basically the ageing in the rubber article may be divided into


the following processes;

Oxidation at lower or higher temperatures (ageing in the


real sense)
Oxidation accelerated by metal heavy metal compounds
(Rubber poison)
Effect of heat in the presence of moisture (steam ageing,
hydrolysis)
Oriented crack formation by dynamic stress (fatigue)
Oriented crack formation by ozone under static &
dynamic condition
Random crack formation by high energy ultraviolet light
and oxygen (crazing, chalking effect)
Changes in surface luster (frosting)
Heat ageing with simultaneous exposure to swelling in
chemicals

HASETRI

Oxygen Ageing at Lower or Higher


Temperature
The chemical changes that a polymer experiences due to attack of
atmospheric oxygen is of the following types ;
1. Chain breakage (chain scission) mainly in NR leading to

Reduction in hardness and modulus


Loss in wear and tear properties (Tensile strength, Tear strength,
Abrasion resistance)
Loss in resilience
I ncrease in elongation at break

2. Chain crosslinking mainly in synthetic rubbers containing


vinyl groups leading to

Hardening (increase in Hardness and Modulus)


Loss in Tear Strength and Elongation at Break
Loss in fatigue resistance

HASETRI

Oxygen Ageing at Lower or Higher


Temperature
3. Chain modification of the polymer chain: Oxygen combines

to the chain giving rise to side-groups without breaking or


reforming the polymer chain. There becomes no loss in the
performance properties.
All of the above three reactions may occur simultaneously.
The properties which mostly affected due to oxygen attack
are:
I n NR

: Tensile strength

I n SBR, NBR, CR

Retention of Elongation at break

HASETRI

Accelerated oxidation in the presence


of heavy metal compounds (Rubber
Poison)
those of copper and manganese
Many heavy metal compounds

have a catalytic action on the oxidation of rubber blends and


vulcanisates.

I n particular even traces of e.g. 0.001 wt% of Cu and Mn


compounds in NR are able to accelerate the autooxidation of the
rubber and the vulcanisate and hence they are called rubber
poison.
Besides these rubber poisons other heavy metal compounds like
Fe++ especially poisonous in SBR. Co and Ni compounds also
accelerate ageing phenomena.
I n general standard antioxidants do not give protection against
heavy metal ions. I t is possible to protect the stock by
incorporating substances which react with the metal ion to give
stable coordination complex.

HASETRI

Fatigue

When a rubber article is subjected to prolonged mechanical stress, the article


periodically bends back and forth, cracks will slowly develop in the surface, they
will grow and leads to the breakage of the article.
The fatigue failure is initiated at minute flaws where stresses are high and
mechanical rupture at such points can lead to developments of crack. The cracks
develop perpendicular to the stress direction.
NR vulcanisates form these cracks relatively quickly but they grow slowly. SBR
shows slower start of crack but once the cracks are formed they grow faster. This
is connected to the low tear resistance to the SBR vulcanisates.
Higher temperature and higher frequency of stress change accelerate crack
formation. If higher ozone concentrations are also present dynamic crack
formation is accelerated.
The fatigue crack resistance not only depend on the type of rubber but also on the
crosslink density and type of crosslinks (higher crosslink density and sulfur rich
crosslink structures are preferred).

HASETRI

Crazing

When an unsaturated vulcanisate is exposed to


prolonged sunlight a small amount of non-orientated
cracks can develop on the surface.

The surface appears like an elephants skin.

The surface on prolonged irradiation becomes brittle


and the filler can chalk.

The vulcanisate in this case is not destroyed. This


phenomenon is only found in light coloured articles.
The carbon black filled and dyed articles do not exhibit
this phenomenon.

The crazing is more severe when the stock is a thin


one.

HASETRI

Frosting

The light coloured articles on exposure to warm,


moist, ozone containing atmosphere appears to be
dull coloured as compared to the previous gloss.

The whitish surface discolouration is known as


frosting.

Frosting is most likely to occur in the summertime


when ozone concentration in the atmosphere is
highest.

Frosting can be differentiated from bloom by heating


the rubber article.

The chemical bloom will redissolve in the warm


rubber, frosting is permanent.

HASETRI

Heat ageing in absence of oxygen


I n the presence of heat and in absence of oxygen, various
reactions can take place, e.g. in steam or in immersed oil
where the changes are as follows;
Thermal decomposition of crosslinks and also hydrolysis of
water sensitive structures (softening)
Continuation of inter or intra-molecular network
Formation (hardening)
Shifting in crosslinks without change in the total number
(no change)
I n hydrolysable rubbers e.g. polyurethane, EVA, Silicone and
others, steam ageing proceeds faster because of additional
breaking of C - N, C - O and Si - C bonds.

HASETRI

Ozone crack formation


Like in oxidation, the double bonds in the rubber backbone provide
the sites for attack by ozone.
The physical damage due to ozone attack is manifested in
formation of cracks in the direction perpendicular to the applied
stress.
The reaction of ozone with rubber is very rapid and occurs at the
surface of the rubber / rubber article.
I n case of unstretched rubbers, the reaction ceases when all
surface unsaturations are consumed, however, when the rubber is
stretched again, new unsaturation sites are formed at the surface
and ozone continues to react resulting in the formation and growth
of cracks.
Ozone has no effect under ordinary circumstances on saturated
rubbers. The speed of ozone crack formation depends strongly on
the temperature, humidity of the air and strain level.

HASETRI

HASETRI

Comparison of oxygen and ozone


Effect
Ozone,attack
O3
Oxygen, O2
Observed as

Discolouration,
cracking

Hardening or softening

Degradation
occurs at

Surface only

Throughout

Effect of
unsaturation

Diene only

Diene < Saturated

Effect of cure
system

No effect

Sulfur < Sulfur donor <


Peroxide

Temperature

Rate enhances

Rate doubles per 10o C


(rate enhances by 2.8 times
for NR and 2.2 for SBR)

Strain level

I ncreases crack
growth

No effect

HASETRI

Auto oxidation depends on the


following;

1. Nature of the polymer :

Presence of unsaturation in the polymer backbone - The


saturated polymers are less affected by oxygen than
unsaturated polymers
Reactivity of the double bond - presence of electropositive
groups e.g. - CH3 activate the double bond leading to fast
oxidation in NR and presence of electronegative groups like Cl, - CN etc. deactivates the double bond e.g. in CR and NBR
causing slow oxidative degradation.
Presence of vinyl side chains - e.g. in CR, SBR, NBR crosslinks
are formed during ageing.

HASETRI

Auto oxidation depends on the


following;
2.Type of crosslinkage:

Nonsulfur crosslinkages are comparatively more stable

Among the sulfur crosslinkages mono and to some


extent di-sulfidic crosslinkages are more stable
compared to poly-sulfidic. Poly-sulfidic crosslinkages
degrade under heat and produce free radicals which
starts oxidation chain reaction

3.

Degree of cure:
I n NR and I R, overcure gives higher degradation.
I n synthetic rubbers like SBR, CR overcure improves
resistance to oxidative degradation.

HASETRI

Mechanism of Oxygen attack


Oxidation is a free radical chain reaction. The attack by oxygen takes
place at the methylenic carbon atom in the chain. A hydrogen atom
is abstracted and in the presence of oxygen, an oxidative reaction
chain is initiated which, if unchecked propagates autocatalytically.
h
1. RH
------------->
R.
2.

R. + O2 ------------->

ROO.

3.
4.

ROO. + RH -----------> ROOH + R.


h
ROOH --------------> RO. + ROO. + H2O

5.

RO. + RH ----------->

ROH + R.

6. ROO. + RH --------------> ROOH + R.


Even if a small amount of combined oxygen is present, considerable
loss in performance properties occur e.g. if 1% combined oxygen is
present in a NR gum vulcanisate, 50% loss in TS occurs.

HASETRI

How an antioxidant performs its


function
I n order to prevent the autocatalytic reaction, an inhibitor must
break the chain either
1) By capturing the free radical formed and / or
2) By ensuring that the peroxides and hydroperoxides produced
decompose into harmless fragment without decomposing the
polymer and also ensure that no new free radicals (capable of
propagating the reaction chain) are formed.
The reaction scheme is as follows;
R.

ROO. +

AH -------------> RH + A.
AH ------------> ROOH + A.

ROOH + AH -------------> Harmless fragments

HASETRI

How an antiozonant performs its


action
The mechanism of ozone attack
on a double bond can be described
as;

O3
>C=C<

O3

>C

>C + OO(1)

C<

>C=O

O---O
>C

C<
O
(2)

I t is believed that the antiozonant reacts either with the (1) Zwitter
ion or the (2) Ozonide formed to make an inert protective film which
every time when broken, is repaired by formation of fresh film
produced by the reaction of rubber, ozone and antiozonant
(protective film theory).
The other concept (Scavenger theory) is that the antiozonant reacts
with ozone at a much faster rate than ozone reacts with the double
bond of rubber.

HASETRI

Chemical name of the different


antidegradants

Common
Chemical name
abbreviation
I PPD

N I sopropyl N Phenyl para phenylene diamine

6 PPD
77 PPD

N 1,3 dimethyl butyl N Phenyl para phenylene


diamine
N,N Di (1,4 dimethyl pentyl) para phenyl diamine

DPPD

N,N Diphenyl Para Phenylene Diamine

TMQ

Polymerised 1,2 dihydro 2,2,4 trimethyl quinoline

SP

Styrenated Phenol

ODPA

Octylated diphenyl amine

BPH

2, 2 methelyne - Bis (4- methyl-6-tert. butyl phenol)

BHT

2, 6- Di- tert. butyl-4-methyl phenol

MBI

2 - Mercaptobenzimidazole

MMBI

4- and 5- Methyl Mercaptobenzimidazole

HASETRI

Classsification of Antidegradants
Physical
Protectants

Chemical Protectants

Parrafin wax

Staining antioxidants with antiflexcracking and


antiozonant effects : IPPD, 6PPD, 77PD, DTPD

Microcrystalline Staining antioxidants with antiflexcracking effect but


wax
without antiozonant effect : PBN, ODPA, SDPA
(styrenated) , ADPA (acetonated)
Staining antioxidants without antiflexcracking or
antiozonant effect : TMQ
Nonstaining antioxidants with antiflexcracking effect
but without antiozonant effect: Styrenated Phenol (SP)
Nonstaining antioxidants without antiflexcracking and
antiozonant effect : BHT, BPH, MBI
Nonstaining antioxidants without antiflexcracking but
with antiozonant effect : Cyclic acetals, Enol ethers

HASETRI

Functions of waxes
Waxes brings out the antioxidants and antiozonants
to the surface of the compound for giving the surface
protection.
Paraffin Wax or MC Wax without addtion of
antioxidants and antiozonants can only give static
ozone protection to rubber products.
For dynamic ozone protection to rubber products
Waxes along with antioxidants and antiozonants are
required .
HASETRI

Important characteristics of Antidegradants


Staining / nonstaining / migratory staining / discolouring
Protective properties - Presence of active groups e.g. NH, - OH, - SH and their activity and ability to give
protection to the vulcanisate under the service condition.
Effect of curing characteristics
Solubility in rubber
Dispersibility in Rubber
Volatility
Migration characteristics
Nontoxicity
Economics

HASETRI

Application of different Antidegradants


Following points must be taken into consideration before using
an antidegradant ;

Which rubber is involved?


Rubbers having fairly good amount of unsaturations like NR, IR,
SBR, BR, and NBR: Mainly IPPD, 6PPD, 77PD, DPPD, TMQ
Rubber with low unsaturation (EPDM, IIR, partially unsaturated
HNBR): TMQ, ODPA and MBI
CR: ODPA, MBI acts as an accelerator for CR

Is freedom from staining or contact staining


demanded?
Products that stain heavily are the Paraphenylene diamine types,
the nonstaining types are BHT and SP types

HASETRI

Application of different Antidegradants

What must be protected ?

Surface effects (Cracking, chalking, embrittlement) or Bulk effects


(Hardening, softening, loss of strength.

What parts does anaerobic (non-oxidative) ageing play?

Antidegradants do not protect from heat as such . Special vulcanisation


systems are required here especially low sulfur systems, use of thiurams,
peroxides etc.

Is resistance to hydrolysis possibly required in addition to


resistance to oxidative degradation?

MBI and MMBI have given good results in steam aging of diene rubbers.
Rubbers with hydrolysable groups like EVA, AU are preferabily protected
with Carbodimides, all the ester grades are prestabilised.

Food and drug application: IPPD, DPPD, ODPA , BHT, SP, BPH,
are all approved by FDA

HASETRI

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