Butyl Polymers

BLADDER TECHNOLOGY

BY
H. MANJUNATH

ExxonMobil Company India Pvt. Ltd.,

Bangalore Research & Development Technology Center,
Plot # 5, Road # 8, EPIP, Whitefield, BANGALORE-560 066

AP-ATD 02 033
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Butyl Polymers

Tyre curing Press

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Butyl Polymers

Tyre curing Bladders

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Butyl Polymers

Bladder Requirements

 Good Processing
 Good Molding
 Excellent heat aging
 Excellent flex and tear strength
 Low tension set (Low Set/High Elongation)
 Low compression set
 Impermeability

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Butyl Polymers

Basic Bladder Recipe

INGREDIENT PHR

 Butyl Polymer (Exxon Butyl 268) 100

 Activator (Neoprene W/Neoprene WRT) 5
 Carbon Black (HAF N330) 50
 Plasticizer (Castor Oil) 5
 Zinc Oxide (White Seal) 5
 Active Resin (Alkyl Phenol-Formaldehyde) 10

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Butyl Polymers

Polymer

Benefits of Butyl
 Excellent heat aging
 Good flex and tear resistance
BUTYL
 Low tension set
 Impermeability
 Low compression set

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Butyl Polymers

Butyl Polymers - Different Grades

Mooney Mole%
Grade Comments
Viscosity Unsaturation
B065 45 (1+8 @ 100ºC) 0.8 High elongation and
tension set; must be
used in blends

B165 45 (1+8 @ 100ºC) 1.2 Slightly high

elongation; slightly
lower flex; good for
large bladders

B068 51 (1+8 @ 125ºC) 0.8 Blend with B268

B268 51 (1+8 @ 125ºC) 1.6 Standard; good

property balance

B365 47 (1+8 @ 100ºC) 2.0 Low elongation; must

be used in blends
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Butyl Polymers

Guidelines for Polymer selection

 Lower unsaturation requires a faster cure system.
 Higher unsaturation gives a tighter cure and greater
elongation loss with age.
 In blends, as the amount of low unsaturation polymer is
increased, an increase in hot elongation, tension set, and aged
elongation will result.
Activators
 Resin cure requires a metal halide, normally ZnX2
 Using straight metal halide is very scorchy.
 Therefore, ZnO and halogen donor is used.
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Butyl Polymers

Sources of Halogen
 Neoprene* Good property balance
 HIIR Low tension set, low hardness, low modulus,
high compression set, softens with age
 Chlorowax Poor aging properties
 Hycar Poor aging properties
 Hypalon Poor aging properties
 Halo resin* Softens with age

*Most commonly used

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Butyl Polymers

Neoprenes as Activators
 GN Poor aging; scorchy
 GNA Scorchy
 *W Good processing
 *WRT Very crystalline resistant; needs more organic
accelerator
 TW Easy processing; good physicals
 *TRT Very crystalline resistant; good processing

* Most commonly used

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Butyl Polymers

Carbon Blacks
 Low particle size, high reinforcing blacks are best for steam aging
(ex: N242).
 High particle size, low reinforcing blacks are best for air aging (ex:
N660).
 Lower loading gives better air aging (ex: 35 phr).
 Higher loading gives better steam aging (ex: 65 phr).
 Acetylene black is best for heat conduction.
Best Balance: 50-55 phr N330
or
N330 / Acetylene Blend*
* Amounts are dependent on ability to disperse acetylene black.
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Butyl Polymers

Plasticizers

 Naphthenic Oils Poor steam aging; good dry aging

 Paraffinic Oil Poor steam aging; good dry aging
 Aromatic Oil Poor aging; steam and dry
 *Castor Oil Reduces marching modulus of resin
cure, lower unaged modulus, good
steam aging

* Most commonly used

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Butyl Polymers

Cure system for Butyl bladder

 Sulfur plus accelerators
 Sulfur donor
 Quinone dioximine
 Polymethylol phenol resins
Reactivity dependent upon:
 Unsaturation
 Resin molecular weight
 Zn or metal halide activator
 Halogen source
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Butyl Polymers

Resin cures of butyl compared to sulfur cure

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Butyl Polymers

Mixing

 Normally a two-stage mix in an internal mixer is used.

 The first stage batch size should be 10 - 20 % larger compared
to an SBR compound at equal gravity.
 The second stage should be 80% of the mixer volume.
 The butyl should be masticated for 45 seconds or preheated (24
hours @ 65°C) to give an internal bale temperature of 43 - 49°C.

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Butyl Polymers

Mixing - Normal mix

1st Stage 0 Add Butyl & Neoprene
45 sec. Add black & oil
160 - 175ºCDump
2nd Stage 0 Add masterbatch,
ZnO, and Resin
110 - 120ºC Dump

 If ZnO dispersion is a problem, the Neoprene and ZnO addition can

be reversed.
 If halo resin is used, add ZnO with the black.
 If stock is not strained, add Neoprene with the butyl and ZnO with the
black.

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Butyl Polymers

Tips on mixing
 Keep it clean.
 Add black to mixer before the oil, if they are added at the same
time.
 For maximum dispersion, add oil at 140°C.
 If black blend is used, add high structure black first.
 Use powdered resin.
 Add resin with last 1/3 of masterbatch and fold into stock on belt.
 Dump final hot enough to assure resin is melted and dispersed.
 Cool stock immediately and dry thoroughly.
 Do not use silicone or clay dips.
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Butyl Polymers

Slug Extrusion
 Keep clean.
 Keep mill banks at a minimum.
 Strip feed temperatures should be 85 - 95°C.
 Force feed extruder to minimize trapped air (power feed rolls).
 Maintain maximum back-pressure to eliminate porosity.
 Keep full water on screw to keep stock moving.
 Internal slug temperatures should be 95 - 120°C.
 Cool slugs as rapidly as possible.

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Butyl Polymers

Slug Handling
 Keep clean.
 Do not use a lubricant when cutting slug.
 Slugs should be approximately square for best molding.
 Slug weight should be 10% over the final trimmed bladder
weight.
 Slug should be skive cut and ends pressed together.
 Spliced slug should fit on mold ledge with no overlap or extra
pieces.
 Slug ends should not be heated before splicing.
 If slugs are to be preheated before cure, use a circulating air
oven (not a bank of lights) for uniform heating. Heat 1 - 4 hours
at 80°C depending on size.
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Butyl Polymers

Bladder Molding
 Mold should be clean and free of flash and plugged vents.
 If mold lube is used, use as little as possible.
 Mold and core temperature should be the same and should
never be less than the tire cure temperature.
 Higher temperatures give more stable cross links.
 Cure time and temperature should be set for optimum tension
set and compression set properties. These are longer than for
optimum tensile, modulus, elongation, and tear properties.
 If short cures are used to increase productivity, soak cure is a
must. Do not quench cool.

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Butyl Polymers

Bladder Molding - continued

 Press should close as rapidly as possible and reach maximum

hydraulic pressure within 30 seconds.
 Cores should be straight and tight.
 Mold halves should be aligned.
 Extrudates for injection molding should be 145 - 155°C.

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Butyl Polymers

Bladder usage
 Bladders should not be stored in an open state.
 Bladders should be protected from ozone if stored for a prolonged
period.
 Internal curing media should contain less than 150 pphm oxygen
and be as free as possible of metal compounds (especially copper).
 The clamping rings should be tightened to 10 - 15% compression
and the compression should be uniform around the bladder.
 The bladder should never see more than 65% circumferential and/or
20% lateral stretch.
 If the correct bladder size is not available, a smaller rather than
larger bladder should be chosen.

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Butyl Polymers

Process Tips
 Good Process enhances the Bladder life.
 It is recommended to use fresh Neoprene(Not older than 2 years),
which should be milled on two roll mill before putting into Banbury.
 Selection & Usage of Curing Resins
Resins with Methylol content of 8-12% only to be used.
Powdered & Fresh resin to be used.
Use White Seal grade Zinc Oxide(Mfd. Through French Process)
 Compound must be strained by duel mesh screen of 30:60/60:30,
before taken for slug extrusion. Strained stock is cooled either with
Air or Water and stored in clean area free from Talc.
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Butyl Polymers

Process Tips - continued

 In most of the bladder failures, the common cause is foreign material
which comes from carbon black. Establish the best supplier and
stringent quality control measure should ensure the allowed Grit
content in 325 (0.01%) & 100 (0.001%) mesh.

 Feed stock temperature should not exceed 80°C and also extruded
stock temperature is maintained at 110°C.

 Adequate nip gap (tighter) of two roll mill is to be maintained to avoid

air entrapment.

 A blender bar ensures uniform mixing.

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Butyl Polymers

Process Tips - continued

 Force feeding is a must in extruder to avoid air being sucked in and
causing porosity/Blister.

 Too much reduction in Mooney Viscosity can also cause porosity and
blister.A Mooney value below 40 units(ML 1+8 @ 100°C) is not good
sign and it indicates over mixing.

 Blank should be used in the same day for curing. Prolonged storage is a
potential source for contamination and hence the cool blanks to be
stored in wrapped polyethylene film and keep them away from dust/talc.

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Butyl Polymers

Process Tips - continued

 Use highest possible mould pressure to ensure good flow (Time to

reach max. pressure should be 30 seconds for PC & 45 sec. for TB)

 Avoid using work away in bladder compound mixing, the usage of

which is a potential source of lamination.

 Maintain cure temperature at least to 190°C. At higher curing

temperature more stable cross-link is reported. A little over cure is
always better than little under cure.

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Butyl Polymers

Process Tips - continued

 Post curing of bladder is a must. In the I stage, it is done in autoclave

for 30' @ 190°C or for 2-4 Hrs.@ 150°C, followed by storage at
room temperature for 30 days. Post curing stabilizes the cross-link.

 Cleanliness and good house keeping is very important.

 Deoxidization for hot water is important. Typical ingredients are

Sodium sulfite (Na2SO3.7H2O) 100 PPM or Hydrazine Hydrate
N2H4.H2O (31.2%), 20-30 PPM.

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Butyl Polymers

Typical properties of Exxpro™ BPC Exxpro™ Bladder

Bladder Compound
Control Compound A
Mooney Scorch @ 150ºC
T5 16 12.0 12.2
Stress/Strain Cured
T10 26 15.6 16.4
Tc90+2 @ 190ºC, Pulled
ODR Rheometer 1º Arc @ 190ºC
60 min. @ 190ºC
100% Modulus, MPa 1.7
ML, dNm 7.3 5.8 4.8
MH, dNm 30.3 300%
21.3 Modulus, MPa 14.0 5.1
Ts2, min, 2.4 Tensile,
2.6 MPa 4.1 5.5
Tc25, min, 4.6 %3.2
Elongation 4.3 334
Tc90, min. 26.4 5.9Aged 48 hrs @
Oven 9.0
Stress/Strain Cured 177ºC Pulled @ RT
Tc90+2 @ 190ºC, Pulled Hardness, Shore A 90
at RT
100% Modulus, MPa 5.5
Hardness 65 65 64
100% Modulus, MPa 1.6
300%
1.7
Modulus, MPa 1.4
--
300% Modulus, MPa 5.0 Tensile,
5.7 MPa 5.7 10.3
Tensile, MPa 12.7 % Elongation
12.3 12.6 246
% Elongation 664 692 653
Source: ExxonMobil Chemical Data 28
Butyl Polymers

Typical properties of Bladder Compound

Exxpro™ BPC Exxpro™ Bladder
Control Compound A Ex
Oven Aged 48 hrs @ C
177ºC Pulled 190ºC Die B Tear (lb/in)
100% Modulus, MPa 2.9 Unaged
1.8 @ RT 1.6208
Tensile, MPa 4.9 Unaged
3.0 @ 190ºC 4.1289
% Elongation 204 22148 hrs. @ 177ºC
Aged 278
Tension Sets Pulled @ RT 144
300% Tension Set 12.5 Pulled
15.6 @ 190ºC 12.5145
Aged 48 hrs. @ 177ºC DeMattia Flex Crack All three 2 of 3 s
200% Tension Set 25.9 Growth
31.3 @ 150ºC, Non- samples
18.8 broke b
Pierced (320 cycles/min) by 4 hrs.
Under 200% Elongation
in 170ºC Steam, % NOTE: Perkalink 900 is available from Flexys
Tension Set
24 hrs. 93.8 Ref: WO 96-072-24
100.0 100.0
48 hrs. 106.3 ExxonMobil
106.3 Chemical Company,
100.0 BPC
72 hrs. 100.0 125.0 100.0

Source: ExxonMobil Chemical Data 29

Butyl Polymers

Typical Bladder Failures And Remedies

Failure Possible Reason Comment

Delamination (rough  GPR contamination  Ensure mixers / extruders are free from
surface) GPR.
Delamination(smooth  Scorching  Reduce polymer unsats.
surface)  Lubricant / Solvent  Reduce resin level.
contamination.  Reduce Methylol content or resin.
 Improve black dispersion to reduce straining
temps.
 Improve flow properties.
 Do not use solvent cements in the process.
Surface hardening  Curative migration from  Clean bladder surface.
tyre  Consider use of brominated resin.
Vent cracking  Bladder too small.  Improve hot elongation.
 Poor ageing properties.  Reduce resin level.
 Reduce polymer unsats.
Bladder growth  Tension set too high  Increase cross-link density.
 Increase cure time or cure temp.
 Increase resin level.
 Increase methylol content.
Softening inside  Oxidation.  Oxygen in steam or water (max. 150 ppHm).
bladder.  Metal contamination  Check for presence of brass ferruls in the
(Cu, Ni, Mn, Co) bladder raising lowering mechanism.
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Butyl Polymers

Typical Bladder Failures And Remedies - continued

Failure Possible Reason Comment

Porosity  Check mixer / mill  Porosity caused by high extrusion temps

operating conditions. often causes scorching.
 Starvation.  Reduction in Mooney Viscosity.
 Straining / extrusion  Air being sucked into due to starvation.
temps too high.
Small Hard lumps in  Cured Neoprene.  First stage master batch should be strained.
bladder  Hard lumps in carbon  Neoprene is pre-masticated in two-roll mill
black. before adding in Banbury.
Tearing  Low hot elongation.  Change Carbon black Source.
 High grit content of  Improve hot elongation.
Carbon black.  Reduce resin level.
 Reduce polymer unsats.
Splice opening  Poor consolidation.  Do not use solvents or lubricants when
 Lubricant contamination. splicing the blank.
 Solvent contamination.
Poor surface on new  Dirty mold  Clean molds regularly.
bladder
Surface folds  Bladder too big.

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Butyl Polymers

BLADDER TECHNOLOGY
by
H. MANJUNATH

AP-ATD 02 033

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