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BLADDERCAREINSERVICE
SamirMajumdar

,GRReddy

EXELRUBBERLIMITED,HYDERABAD

**

1.INTRODUCTION
Withongoingliberalizationprocesstherehasbeenadrasticchangein
theIndianEconomyandthereissignofpositivegrowthofboth
AgriculturalandIndustrialproduction.Tyreindustrygrowthinany
countryisdrivenfromgrowthonthetransportation.Indias
transportationgrowthisbasicallydrivenfromagriculturalgrowth.
HistorictrendofagriculturalgrowthinIndiais78%whereas,for
tyreindustry,itis56%andtheexceptionalyearis2003wherethe
tyreindustryhasalreadyshowntomorethan10%.
Theaveragegrowthofvitaltrucksegmenthasbeenrecordedtoabove
12%.Averagemonthlyproductionin2003isTruck0.9m,PC
0.773m,LCV0.383m.Scootertyregrowthratehasbeen9%with
0.7moftyrespermonthandMCgrowthrateby7%withaverage
productionof1.3mtyrespermonth.
Asontoday,themajortyreplayersare;ApolloTyresLtd,MRFLtd.,JK
TyresLtd.,BirlaTyresandGoodYearIndiaLtd.Togethertheyproduce
65Ktonsofmaterialsand4.0millionoftyrespermonth.Experts
predictthatnumberofplayersinIndianmarketwillshrinklikewhat
hashappenedworldwideyetgrowthofIndianTyreIndustryisevident
becauseoffollowing:
Economicalgrowthof89%(8.4%bytheendof2003),one
ofthefastestintheworld.
ContinuedthrustontheinvestmentplanbyGovt.ofIndia.

Forexreservesofmorethan$100billion
Ahugepopulationofabove1.0billion
Averageincomeoflowermiddleclassandmiddleclasspeople
areincreasingduetoeconomicalgrowthontheinvestment
policybyGovernmentofIndia.
ConstraintsofIndianRailwaystometthegrowingdemandfor
passengerandgoodstransport.

Forallcorrespondences.

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**
ManufacturerofTwo/ThreeWheelerTyres,InnerTubesofallsizes,Curing
AirbagsandBladders,SpliceJawsandTurnupBladdersforTyrebuildingmachines
andothermouldedrubberitems.

Roadtransportisthemajorlinkforessentialgoodstotherural
massesandtransportationoffarmproducetothecities.
DevelopmentofgoldenquadrilateralandNorthSouth&East
WestCorridorsNationalHighways.
Moreandmorecapacityutilizationbytyreindustries.
Continuedthrustofexportsbyalltyreindustries(2530%
growth)
Easyfinancingforvehiclepurchase.
Theyear2003wasaboomperiodforIndiantyreindustries.Itis
expectedthattheindustrygrowthof20032004wouldbebetween11
12%.AppearesthatApollotyrewillbeleadinginthemarketsharein
theabovefinancialyear.Themarketshareofthemajorplayers
duringAprilOct.2003(ATMA)are:
TYRECO.
SHARE(%)
Apollo
26

JK
24

MRF
18

CEAT
16

BIRLA
10

GOODYEAR
5

OTHERS
1

TOTAL
100%

Tyrebecameoneofthecrucialcomponentfrombicycletoairplanesfor
transportofgoodsandpeopleparticularlyontheonsetofTheWorld
WarI(19141918).TheWorldWarII(193945),however,further
acceleratedmakingspecialtypeoftyresduetodifferentrequirement
ofvehicleinwar.
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3
ThestoryoftheinventionofthepneumatictyrebyR.W.Thomson(
1846)andsubsequentreinventionbyJ.B.Dunlop(1888)iswell
known.ThewordTyreispracticallyderivedfromthewordattire,
meaningaprotectivecovering.
TirespelledbyAmericansisclosedtoattire.
CuringBladderistheessentialcomponentoftyremanufacturing
process.Allpneumatictyresarecuredwithcuringbladderbeitwith
OTR,TB,LCV,PC,MCorBC.
Therearevariousreasonsonthecausesofpoorbladderlifebutone
importantcausecouldbeduetopoorprocessingofbladdercompound
andpoorhandlingofbladderontheshopfloor.
Thedispersionlevelofbladdercompoundvariesfrom50%to>
98%indifferenttyreindustries.Highlevelofdispersionofthe
ingredientsalsoimprovesthebladderlife.Itistheartofprocessing
technologyhowoneachievesthedispersionlevelgreaterthan90%.In
majorcasesforbetterbladderlife,bladdercareinserviceisrequired
togivemoreattentionthanmodifyingcompoundingand/or
processing.
Particularlyindevelopingcountries,bladdercareinserviceplaysa
verysignificantroleforthelifeofthebladder.Infact,themajor
failureofbladderintyreindustriesofdevelopingcountriesisdueto
theadverseconditionsonwhichthebladderhasbeenexposedto.
Wewouldliketodiscusshereonbladdercareinservicewithrespect
to:
TheProduct
Properties
Ingredients
Compounding
Manufacturing
Averagelife
Bladdercareinservice
Summary

2.THEPRODUCT
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4
Agreentyreiscuredwithcompressionmouldinginatyrecuring
press.Outsidetyrei.e.treadandsidewallportionisheatedbymould
whichisnormallyheatedwithsteam.Theinsidetyrei.e.thebeadand
innerlinerportionwillbeheatedthroughbladder.Infact,abladderis
theheattransformationdevice,whichisheatedeitherbysteam,hot
waterorbybothorbyheatednitrogen.
Abladdercanbestressedupto2530%insidethecuringpressand
shouldbecapabletohold1835kg/cmpressuretogivehighdegree
oftyrematerialconsolidation.Agoodbladdershould,therefore,give
thefollowingperformances:
Bestair/steam/waterimpermeability
Goodheattransfer
Capableofretaininghighpressure
Capabletogivehighdegreeoftyrematerialconsolidation
Highdegreeofflexibilitytotakecareofcyclicchangesinstress
underwater/nitrogen/steampressureaswellasdeformation
undervacuum.
Highdegreeofresistancetogrowth,whichcancausebuckle
problemandsubsequentscrapofthetyre
HighdegreeresistancetoOzone/Oxygen/Heatdegradation
3.PROPERTIES
Basedontheaboveperformancerequirementofthecuringbladder,
thefollowingelastomeric
andvulcanizatepropertieshavebeen
suggestedbyexperts:
Butylrubberwithhighlevelofimpermeabilityandlowlevelof
unsaturation.
Averagehardness6070ShoreA
%Elongation>600
Tensilestrength>140kg/cm.
Tensionset12%max.totakecareofbladdergrowthinservice.
ACarbonCarbonbondcrosslinksystem,capableofhighest
heatresistance.
4.INGREDIENTS
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5
RecommendedcompoundformulationisButyl95.0100.0/
NeopreneWRT5.07.0/HAFblack50.060.0/Castoroil5.0
7.0/StearicAcid1.0/ZnO5.0andCuringResinSP10455.0
10.0Phr.
Eachrawmaterialsgivenabovehasdistinctfunctionstoachievethe
desiredpropertiesofcuringbladder.Criterionsforagoodbladder
compoundsare:
Shouldmixwell(dispersion).
Canbeprocessedsatisfactorily(scorchsafety).
Shouldhavegoodflowsothatmouldssatisfactorily.
Shouldhavegoodphysicalproperties.
Shouldexhibitgoodheat,steamageingandozoneproperties.
Shouldhavelowestpossibletensionsetbuthighestpossible
elongation.
Functionsofingredientarediscussedbelow:
4.1.ButylRubber
Itisacopolymerofisobutyleneandisoprenerubber.Ithasveryhigh
levelofgas/steam/moistureimpermeability.Impartsveryhighheat
resistance/ageingresistancewhencrosslinkedwithMethylolPhenol
Resin.Normaldoseiseither100.0phror95.0phr.Ifbetterflow
propertiesarerequiredforaspecificreasoneg.Injectionmolding,low
unsaturation/lowmooneygradesareusedorblended.
4.2.N330
Itisareinforcingfillerandithelpsinmaintainingthemooneyfor
processabilityandvulcanizatepropertiesaftercure.Normaldosein
theindustryis50.0phr.Increasingblacklevelsresultingreater
embrittlementuponairaging,butshowsbetterresistancetoreversion
.The50partslevelappearstobeagoodcompromiseforthebladder
application.Ingeneral,50phrloadingisverycommonintyre
industries,inafewcasesthereareusesbetween5560phrloading.
Insomecases,highstructureHAF(N347)isalsousedinbladder
stocksatalevelof5060phrwhichgivesagoodbalanceof
properties.OtheralternativecarbonblacksareFEF(N550)and
ISAF(N220)combination.TheHAF(N330)andISAF(N220)black
Page 6

6
combinationalsoexhibitthebestbalanceofpropertiesforthebladder
application.Ingeneral,thesmallestparticleblack(SAF/N110)shows
thebestresistancetoreversioninsteam,whileinresistancetoair
aging,itwassomewhatpoorerthantheotherblacks.

AcetyleneBlack,SAF(N110)andISAF(N220)blackaregenerallyhard
togetgooddispersion.Acetyleneblackisreportedtogivebetterheat
transfer(cansaveatleast10%ofcuringtime)thananyother
conventionalblackbutithasnotyetbeenpopularizeddueitsproblem
tohaveinadequatedispersioninbladdercompoundandeventuallyit
reducesthebladderlifeconsiderably.
4.3.CastorOil
Itisaprocessingaid.Ithelpsinthedispersionofblack.Thisisanoil
ofvegetableoriginandchemicallyitisRicinoleicAcid(bp226.8C).
Itshighboilingpointhelpstoretainelongationatelevated
temperature.Acidmediumhelpstoactivatecrosslinkingsystem.
Castoroilisusedalmostexclusivelyforbladdercompoundsbuta
highviscositylowvolatilityparaffinicoiloroleicacidoil(bp
285.6C)canalsobeusedasareplacement.Theseoilscanactnot
onlyasaplasticizerforthecompoundbutalsoasanreleaseagent
betweenthebladderandthetyreliner.
Themoisturecontentandthepurityoftheseprocessingoils(Oleicacid
orhighviscosityparaffinicoilorcastoroil)willplayavitalroleinthe
dispersionandageingpropertiesofthecompound.Thenormaldose
is5phrandsuchalowdoseoftheseoilsresultsinstockswitha
considerablyhighermodulusandretensionofthephysical
properties.However,theoildosecanvaryfrom5.0to7.0phr
dependingontheprossabilityrequirement.
4.4.Neoprene
Itisanactivatorforthecrosslinkingsystemofmethylolphenolresin
andbutylrubber.Thereisnosignificantdifferencesinoriginalandaged
physicalpropertieswithGNorWRTcatgoriesofneoprene.However,
WRTismorestable,lesscrystalline,betterdispersiblethanGNgrade
soWRTisoftenused.Dosagescanvaryfrom5to7phrinthe
compoundingformulation.
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7
TheresincureofthebutylbladdercompoundisaFriedelCrafts
typeofreaction,viaametalhalide,normallyZnX

.Whenusinga
standaredphenolicresintheactivatorisusallyachlorinatedorganic
chemicalorpolymer.Theonlyexceptionstothisisbrominated
resinwhichisalsousedasthecurativeforbutylandthiscontains
bromineinthepolymer.Inordertoachievegoodresultsof
activatoritisbettertouseneoprenefresh(notolderthan2yrs.from
dateofmanufacture)andneopreneshouldbemilledontworoll

millbeforeputtingintobanburyforbetterdispersion.
Besidesneoprene,whichhasbeenwidelyacceptedintyreindustryas
thebestactivator,otheractivatorsare;Chlorobutyl,Chlorowax,
ChloroSulphonatedPolyethyleneetc.Theaboveactivatorshavemuch
theoreticalimportance,practically,neopreneisusedallover,though,
itisacostlypolymer.
4.5.StearicAcid
Itisnotabsolutelynecessaryinbladdercompoundformulation,yet,
withcomparativelylowlevelofprocessingoil,stearicacidhelpsin
carbonblackdispersion.Acidmediumalsohelpsintheactivationof
crosslinking.Italsohelpsinreleasingfrommould.Only1.0phris
sufficient.
4.6.ZincOxide
Thisisanactivator.Infactzincoxidehelpsintheformationofmetal
halidewithneoprenewhichhelpsincrosslinkformation.Normaldose
is5.0phrbutatleast2.0phrisnecessaryforbestretentionof
physicalproperties.
4.7.MethylolPhenolResin
AlmostallbladderstocksintheworldarecuredbyastandaredAlkyl
PhenolFolmaldehyderesincontainingamethylolgroup.Althoughmost
bladderstocksarecuredbyneopreneactivatedMethylolPhenol
Resin,itispossibletouseabrominatedresinaswell,suchas,
SchenectadySP1055,whichisselfactivatingandcaneliminatethe
useofneopreneastheactivator.However,itistobenotedthatshelf
lifeofanyhalogenatedorganiccompoundisveryimportantforits
activity.
Page 8

8
Simplyreplacedwithbrominatedresin,itmayresultinprocessing
difficultiesduetoaScorchproblem.Insuchcases,alower
concentrarionofbrominatedresinorblendofbrominated/non
brominatedresinshouldbeconsidered.Resinlevelshouldalsobe
adjustedwhenadifferentlevelofunsaturationinpolymerisused.
AlkylPhenolFolmaldehyderesinisthevulcanizingchemical,which
givescarboncarboncrosslinkwithbutylrubberviamethylolphenol
group.Resinlevelsabove10phroffernoadvantageinheat
resistance.Bestpropertyretentionafteragingisexhibitedatthe5.0
phrlevel,whichistheborderlineforadequatecure.However,
between5and10phrconstitutethebestcompromiseforthebladder
applicationintyreindustry.Inmostcasesitisusedbetween78phr.
5.COMPOUNDING

Recommendedcompoundformulationisalreadydiscussed.
Compoundingformulationforcuringbladderwillbesimilarinall
industriesexceptforthechangesinthemodulusandhardnessthat
mayberequiredbyindividualtyreindustriesduetoprocessing
differences.Yet,scorchyness,mouldflowandheatdegradationarethe
commonproblemincuringbladder.
Wewilldiscusshereon:
Flowimprover
Scorchretarder
Improveonheatresistance.
5.1FlowImprover
Goodflowpropertiesandgoodknittingpropertiesofthestockare
importantcriteriatoassurethesufficientleveloflife.Theseproperties
areimportantespeciallyforlargesizebladderse.g.TB,OTRbladder
andinjectionmolding.
Typicalapproachesare:
Increasethelevelofprocessoil
BlendwithlowMooneyviscositybutyl
AddprocessingaidslikeSTRUKTOLWB16/RUBID16or
STRUKTOLWS180(about2Phriseffectvetouseinthe
compounds).
Page 9

9
5.2ScorchRetarder
Typicalscorchretardersforbutylandneoprenebasedcompounds
are:
Magnesiumstearate0.250.5phr
Reduceresinlevel
Evaluateresinswithlowmethylolcontent
Intyreindustry,however,thelatertwoareextensivelypracticed.Best
propertyretentionafteragingisexhibitedatthe5.0phrlevel,which
istheborderlineforadequatecure.78phrisverypopularinthe
industry,incaseofscorchyproblem,itcanbetriedanywherebetween
57phr.
Methylolcontentinmostcasesvariesfrom812%andthisisthe
specificationsbymostofthebladderproducingunits.Incaseof
scorchy,specificationof
710%methylolcontentcouldbewellmanaged.
Inmostcasesthescorchyproblemisduetoimproperstrainingof
compoundstock.Bladdercompoundiscomparativelyharderthan
innertubecompoundandhastobeprocesseddifferently.During

straining,compoundisrequiredtobesoftandadequatecutsand
foldsaretobeprovidedonthetworollmillbeforefeedingforthe
straining.Strainingmeshesshouldbechangedatdesirednumberof
batches.
5.3.HeatResistance
Resincuredbutylcompoundsalreadyhavegoodresistancetoheat
andozone/oxygenattackandthecompoundformulationisquite
internationalandhaslittlevariation.However,thereisstillsome
roomtoimproveontheheatresistanceandozoneattacklike:
UseButylwithlowunsaturationlevel.
Blendwithlowunsaturationbutyl.
Noprocessoilinthecompoundingformulation.
Anitoxidants.
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10
Whenthecontentsinthecentralmechanismsystemincludedissolved
oxygenbeyondcertainlimit,thereisnosignificantdifference
reportedwithlowerunsaturationlevelofbutyl.
Itisknownthattheretentionofphysicalpropertiesafterageingwith
orwithoutantioxidantsarealmostidentical.Noantioxidantsare
recommended,therefore,forcuringbladder.However,1.0phrof
crystallinewaxhelpsnotonlyinfillerdispersionbutalsoonretaining
glossysurfaceofbladder.Sometimeroughsurfaceofbladder
complaintcouldbetakencareofbyadditionofwax.
6.MANUFACTURING
Compoundformulationofbladdercompoundwillbesimilarinalltyre
industries.Itisthestateofartontheprocessingtechnologythat
givestheconsistencyandhigherlifeexpectancyoftheproduct.
Processingofbladderisdifferentindifferentindustries.Bottomlineis
howonegetsbetterdispersionatlowestpossiblecostandhowone
getsthebestproductatlowestpossiblecost.Finallytheproductwillbe
judgedbythenumberofheatshavebeengivenbytheproduct,
highertheheatsloweristhecostperkgoftyreproduction.
Aflowsheetdiagramofthebladdermanufacturingisshownbelow:
Masterbatch
Straining
FinalBatch
Straining
(mixinginbanbury)
(mixinginbanbury)
Splice

BlankSplicing
Cooling
Extrusionof
blanks
Jamming
Prewarming
Curing
Postcuring
Postcuring
atroom
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11
OfBlank
@200C
@150C(24hrs.)
temperaturefor
(upto210C)
(1530days)
Transport
Storage
7.AVERAGELIFE
Itisalwaysadebatableissueontheaveragelifeofbladder.Thisis
becausedifferenttyreindustryusesdifferentconditiontouseof
bladder.
bladderlifealsovariesonthetypeofmoulding
likecompressionvs.injectionmoulding.
Itisreportedthatbladderwithinjectionmouldingprovidesbetterlife.
Thereasonisobviousbecauseofthefactthatbladdergaugecanbe
controlledpreciselywithinjectionmouldingandabladderwiththin
gauge,curecyclecouldbereducedtotheextentof1020%andthe
flexlifeincreasestomanyfolds.Presenttrendofbladder
manufacturingisthinnergaugeatthecentersuchthatitgivesbetter
flexibilityinthatregionaswellasbetterheattransfer.
Theaveragelifeofdifferentbladdercanbesummarizedbelow:
BC6001800
PC300800
TB100500
OTR1550
ThemostImportantthingishowthiscuresarespread.Forexample,
400curescanbespreadover5to620cureswhichisconsideredto
bebadbutifitisspreadover350to450whichcouldbeabetter

product.
8.BLADDERCAREINSERVICE
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12
Thereareseveralmethodstoimprovetheperformanceofbladderlike
:
changeinformulation
changeinthemixing
changeinblankpreparation
changeindesignofbladder
changeinseverityofuse
changeintyrecuringtemperatureetc.
Bladdercareinservicetellsushowbladdershouldbehandledduring
its
service,thatis,afterithasbeenfixedwiththepress.Preciselyittells
abouttocontroloxygenlevelinthecentralmechanismsystemand
caretobetakenduringitsservice.Butwewouldalsodiscusshereon
uniformityinmixingandcaretobetakenduringcuring,postcuring
andstorage.
8.1Uniformityinmixing
Thedispersionlevelofbladdercompoundvariesfrom50%to>
98%indifferenttyreindustries.Highlevelofdispersionofthe
ingredientsalsoimprovesthebladderlife.Itistheartofprocessing
technologyhowoneachievesthedispersionlevelgreaterthan90%
withoutalteringthecompoundingingredients.
Inmostcasesbutylcompoundmixingisdoneintwostages.First
stageormasterbatchcontainsallingredientsexceptthecuratives
andinthesecondstageorfinalbatch,onlycurativesareadded.In
somecasesbothneopreneandresinstogetherorzincoxideandresin
togetherwillbeaddedinthefinalstage.
Useofmotherbatchesofneoprene,zincoxideandresinsarealso
populartohavegooddispersioninthecompoundandcanbetried
bothinbanburyaswellasinopenmillmixing.
Motherbatchesofzincoxide,neopreneandcuringresinmaybe
madewithproportionatequantityofbutyl,carbonblackandprocess
oilsuchthattheactualbatchcontainsthedesiredlevelofbutyl,
processoil,carbonblackandingredientsinmotherbatches.
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13

Bladdercompoundcanalsobemixedinsinglestage.Masterbatchis
mixedinbanburywhichisdumpedat180
0

C+andthenaddmother
batchofresinandneopreneonthedumpmillafterapplying23cuts
onmill.Inthiscasestrainingcanbedoneonlyonce.
Inordertogetbetterdispersionandhigherdumptemperature,the
useofbanburyvolumeisveryimportant.Incaseofmasterbatch,
thenormalbatchweightis1020%higherthanthatusedforGPR
basedcompound.Forbutylbasedcompound,itisbettertouse
banburyfillfactorbetween0.85to1.0forbetterdispersionofcarbon
blackandzincoxideinbutylrubber.Thedumptemperatureof
masteriskept180
0

C+.
Forfinalbatch,thebatchweightisnormally80%ofthemasterin
thesamebanburyandthedumptemperatureismaintainedbetween
100110
0

C.Banburybatchweightiscalculatedinthefollowing
manner:
Baburybatchweight(kg)=Banburyvolume(liter)xFillFactorx
Comd.Sp.Gr.
Onemayrememberthatthebanburyvolumeindicatedby
manufactureristhetotalvolumeofwaterhavingspecificgravity1.0
withramdownanddischargedoorinclosedconditions.
Abanbury,having50literofcapacity,fillfactorof1.0andcompound
specificgravityof1.12shouldhave56kgofbatchweight(50x1.12
x1.0=56).Foraverynewbanbury,itisdesiredtokeepfillfactor
around0.85becauseveryhighbatchweighthasalwaysadverseeffect
onthedustsealsandasaresult,optimumbatchweightisalways
determinedpracticallyaroundthecalculatedbatchweightwhich
shouldprovideadequatemixingindesiredmixingtimeandshould
provideadequatedumptemperaturewithoutaffectingdustseals.
Itisdesiredthatthestartingtemperatureofmasterandfinalbatch
arekeptaround80
0

C.Infact,adequatemixingtimeanddump
temperaturewilldependon:
Typeofbanbury(2wing/4wingchamberandTangentsystem/
Interlockingsystem).
Banburyvolumeloading.
Banburystartingtemperature.
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Black:OilratiointheMasterBatch.
Sequenceofloading.
Dumptemperature.
Cleanlinessandgoodhousekeepingoftheentirebladdermixingarea
isveryimportant.
8.1.1.Someimportantparametersinmixing
Duetodifferenceincocurecharacters,butylrubbercannotbe
blendedwithGPR.
Duringmixingofcarbonblackwithbutylrubber,enoughtime
orshearingforceistobeprovidedforbetterdispersionbecause
butylhascomparativelyloweraffinitytowardscarbonblackthen
GPR.
Combinationofdifferenttypesofcarbonblackaregoodprovided
dispersionisalsoequallygood.Differenttypeofcarbonblack
willhavedifferentaffinityforbutylrubberduetothedifference
insurfacearea.
Carbonblackwithhighersurfaceareawillprovidebettergreen
strengthbutdifficulttogetdispersedinbutylrubber.If
dispersionofaboveblackisinadequate,thiscancreateproblems
asporousextrusions,laminationandblisterinvulcanizate.
Mineralfillersarenotrecommendedinbladdercompound
formulationasthismaycausedieplatingproblem.Downtime,
scrapandrejectionsoftenincreaseduetotheuseofmineral
filler.
Thekeyrequirementforprocessingaidsistoimproveuponthe
processabilitywithminimumeffectonthevulcanizates.Use
processoilasminimumaspossible.
Butylrubberinbladdercompoundshouldalwaysbe
premasticatedeitherinbanburyorinopenmillmixing.This
increasestheacceptanceofingredients.Incaseofdifficultyin
premastication,butylisrecommendedtokeepathothouse(60
80
0

C).InhothouseFIFOsystemshouldbefollowed.
Page 15

15
8.2.Moulding/Vulcanization
Itissuggestedtowarmuptheblankfor24hours@80
0

Cinoven

whichhasaircirculatinginsidetopreventlocalhotspotsespeciallyfor
largebladderswhichhavelargecrosssectionalvolumeandneedgood
mouldflow.Itisbettertohavedifferentsizesofovenfordifferent
sizesofslugs.Priortomoulding,mouldshouldbecompletelyfreefrom
therubberflashfrompreviousmolding.Asageneralguideline,
bladdersshouldbecuredatahighertemperaturethantheyare
expectedtoencounterduringthetyrecure.
Advisedtousehighestpossiblemouldpressuretoensuregoodflow
oninsidethemould.Avoidusingworkawayinbladder
compound.Blendofworkawayisthepotentialsourceof
lamination.Incaseworkawayismore,use
inextruderwithout
blendingwithokaystock.Avoidusingdifferentworkawaytogether
becausedifferentworkawaywillhavedifferentheathistoryandwill
tendtobehavedifferentlyinbladdermouldwhichtendstogive
laminationinthevulcanizate.Compoundwithhigherheathistoryin
theprocessingwilltendtodegradefasterinuse.
Maintaincuretemperatureatleastto190C.Athighercuring
temperature(210C)morestablecrosslinkisreported.Alittleover
cureinbladderisalwaysbetterthanalittleundercure.Mould
shouldbeclosedasfastaspossible.Maintainmouldclosingpressure
insuchawaythattherubberflowisasfastaspossible.Itisbetter
thatmouldsqueezingtimeiskeptminimumat2minutesbeforethe
mouldisclosedfinallyforcuring.Itisdesiredthatrubberflowtakes
simultaneouslybothonthetopaswellasonthebottom.Watchfor
properventingofmouldstoavoidcoldspot.
Itissuggestedtowarmuptheblankfor24hours@80
0

Cinoven
whichhasaircirculatinginsidetopreventlocalhotspotsespeciallyfor
largebladderswhichhavelargecrosssectionalvolumeandneedgood
mouldflow.Itisbettertohavedifferentsizesofovenfordifferent
sizesofslugs.Priortomolding,moldshouldbecompletelyfreefrom
therubberflashfrompreviousmolding.Asageneralguideline,
bladdersshouldbecuredatahighertemperaturethantheyare
expectedtoencounterduringthetirecure.
Page 16

16
8.3.PostCuring
Postcuringofbladderisamust.IntheIststageitisdoneinautoclave
for30'at190Corfor24hrs.@150C,dependingonthe
thicknessofbladder.Thiswillbefollowedbyroomtemperaturepost

curing(2ndstage)for30days.Postcuringhelpstogetbetter
stabilizationofthebladdercrosslinksystemandeventuallyoffers
betterbladderlife.
8.4.BladderStorage
Asageneralrule,bladdersthatarestoredinthewarehouse(open
andoutofUVlight.)approximately24weeksaftercuring,exhibit
betterlifethanthoseusedimmediatelyaftercuring.Thisisdueto
crosslinkstabilizationandstressrelaxationatroomtemperaturefora
periodof1530days.Postcuringnotonlystabilizesthecrosslink
butalsohelpstosweatingwateraswell,whichiseliminatedduring
crosslinkformations.
Bladdershouldnotbestoredinfoldedcondition.Oxidativecracks
generatesonthestressedregionwhenthebladderisfolded.Bladder
shouldbestoredin
dark,awayfromsunlight/UVlight.
8.5.Oxidativedegradation
Softeningorbecomingstickyisoneoftheindicationofthe
degradationofinsidebladderduetooxygenattack.Thedegraded
andthestickymaterialcouldbedegradedpolymerofbutyl.Oneof
themostcommonmethodtotakecareofthisproblemistocontrolthe
dissolvedoxygenbychemicalmethod.
Manycaseshavebeenreportedtohavebladderfailuredueto
oxidativedegredation.Inordertopreventthis,deoxidationofhot
waterisimportant.TypicalingrediantsareSodiumSulphite(Na
2

SO
3

.7
H
2

O)100ppmor2030ppmofHydrazinehydrateN
2

H
4

H
2

O(31.2%).
Freeoxygencontentinhotwatershouldbebelow150pphm.Itis
betterthatthefreeoxygencontentismonitoredinthelaboratoryon
periodicchecks.
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17
Oxygencontentmayalsogoupiforingsinthebladderiswornout.
EPDMbased(heatresistance)Oringsarereportedtohave

prolongedservice.
Centralmechanismshouldnotcontaincopperorbrassmetalasit
acceleratestherateofoxidationinthemedium.
Bladdershouldnotbestoredinfoldedcondition.Oxidativecracks
generatesonthestressedregionwhenthebladderisfolded.Bladder
shouldbestoredin
dark,awayfromsunlight(UVlight).
Alltheabovepointsgivetheinformationsonthesourceofthe
oxidativedegradation.However,degradationproblemcouldbe
minimizedbycontrollingoxygenlevelinthecentralmechanism
system.
8.6.Oxygenlevelincentralmechanism
Centralpostmechanismisasystemonwhichbladderisfixedtoa
centralmetalpost,bothtopringandbottomringareclamped.Desired
stackingheightandstretchingheightaremaintained.Beforeactual
curingstartsthebladderissubjecttowarmupwithsteamandshould
undergocertainnumbersofcyclicshapinganddeshaping.
Centralmechanismissubjecttocontainsteam/hotwater/cold
water/gas/(oftencalledasinternal)andvacuuminacyclic
sequence.
8.6.1.Internal
Curingmediumisoftencalledasinternal.Hotwateristhecuring
mediafortyrecureandthemajorcauseforinsidebladder
degradationisduetodissolvedoxygeninthesystem.Inorderto
preventthis,deoxidationofhotwaterisimportant.Treatmentofhot
watercanbedonewithchemicalslikeoxygenscavengerorwith
contactheater(Deaerator).Itisadvisablethatthefreeoxygen
contentismonitoredinthelaboratoryonperiodicchecks.Nitrogengas
curinghasbeenproventobethebestagainstoxidativedegradation.
Typicalcuringmediumsusedintyreindustriesare:
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18
Steam/Hotwaterwithchemicaloxygenscavenger.
Steam/Hotwaterwithcontactheater(Deaerator).
Steam/Hotinertgas.
Thequalityofhotwater(degreesofdissolvedoxygen)affects
degradationofinsideofthebladderandwecanseethreephasesof
technologicaldevelopmentsinthisarea.
8.6.1.1.Steam/Hotwaterwithchemicaloxygenscavenger:
Beforechemicaltreatmentfordeoxydation,desaltingofwateris
important.Theuseofchelatecompound,Disodiumsaltof

ethylendiaminetetraaceticacidorEDTAcanapproximately
eliminate90%Butionexchangersarethebesttechnologynowbeing
practicedallover,whichcantakecare>99%desalinity.
Littleconservativewayofeliminationofdissolvedoxygenfromhot
wateristheuseofcertainspecialchemicalssuchas,oxygen
scavengerandtypicalusagesareSodiumsulphite(Na
2

SO
3

.7H
2

O)
100ppmorHydrazineHydrate
N
2

H
4

.H
2

O(31.2%),2030ppm.Freeoxygencontentinhotwater
shouldbebelow150pphm.
Thisprocedureishowever,notpowerful/effectiveandinconvenientto
control,so,veryoftenthissystemresultedinseveredeteriorationof
insideofbladder(verystickyandgrownupunevenly).Majorproblem
inthissystemisinmostcasesthedissolvedoxygencontentisnot
analyzedproperlyandsystematically.Laboratorypersonnelshouldbe
maderesponsibletomonitorandcontrolthedissolvedoxygenlevelin
hotwater.
8.6.1.2.Steam/Hotwaterwithcontactheater(Deaerator):
ThisisaveryactivetypetoeliminatedissolvedoxygenbyDeaerator
physicallyanditisquiteeffectivetoremovedissolvedoxygenalthough
itneedsinvestment.Inmanycasesthedeaerationequipmentisnot
thereorunfortunatelyitisusedincorrectly.
Thecontactheaterremovesoxygenandfreecarbondioxidefromhot
watersoastoprotectpiping,steeltanksandotherequipmentsfrom
corrosion.Othernotableeffectistoprolongthebladderlifeby
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19
preventingdegradationofbladdercompoundwhichcontactshot
water.
Advantagesexperiencedare:
Markedlyreducetheinsidedeteriorationofbladderandimprove
thelife,
Easymaintenanceofhotwatersupplypipelines(nocorrosionof

insideofstealpipes).

Dissolvedoxygenisgenerallycontrolledatbelowthan0.1ppm.
8.6.1..3.Steam/Hotinertgas(Nitrogen).
Thisisrelativelynewtechnologywhichgiveslotofsignificant
advantages.FieldtestswithNitrogenhavebeendonebyseveral
companieswhichhavesupportedtheexpectedbenefitsof:

Increasedbladderlife(50%)

Reducedcycletime

Reducedoperatingcost(energysaving)
Increasescomponentadhesionduetohigherconsolidationwith
higherpressure
Togetmaximumbenefits,highpurityNitrogengasisneededand
perfectsealingatallconnections(pipelines,bladderclampingetc)are
required.
8.6.2.Oring/diaphragmofcentralmechanism
Oxygencontentmayalsogoupiforingsorthesealinginthe
bladderisofpoorqualityoriswornout.EPDMbased(heat
resistance)Oringsarereportedtogiveprolongedservice.Aperiodic
replacementalwaysgivesbetterresults.
8.6.3.Metalcontaminationinhotwater/steam
Centralpostmechanismshouldnotcontaincopperorbrassmetalasit
acceleratestherateofoxidationinthemedium.
8.7.Qualityofgreentyre
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20
Thisisparticularlyrelatedtothequalityofinnerpaintandthe
applicationofit.Waterbasedinnerpaint,compoundedwithmica,
givesbetterresistancetooxidativedegradationonoutersurface.
Uniformapplicationofinnerpainthelpstopreventflowofcuratives
fromgreentyretothebladder.Highercurativeabsorption/
adsorptionalsoincreasestheageingofbladder.
8.8.Servicecondition
ThefirstthumbruleistomaintainFIFOsystem.Bladdershavebeen
cured,postcuredinautoclaveandalsopostcuredinroom
temperatureisnowreadytobefixedonthepress.Veryoldbladderis
subjecttooxidativedegradationandmaynotgiveadequatelife.
Bladdershouldnotbestoredandtransportedinfoldedcondition.

Oxidativecracksgeneratesonthestressedregionwhenthebladderis
folded.Bladdershouldbestoredindark,awayfromsunlight/UV
light.
Itisbettertomaintainthecontinuityofcuringofbladder.Once
bladderismountedonthepress,shouldberemovedonlywhenthe
bladderhasgivenfull(adequate)life.Abladderdiscontinuedfrom
curingissubjecttogiveroughsurfaceoroxidativedegradationon
storage.
Veryhighvacuumofbladderisnotnecessary,onlyaround150mm
w/gisgoodenoughbutshouldnotgobeyond200mmw/g.Vacuum
shouldnotcausetotouchthebladdertocentralpost.Highvacuum
causesfastercrackgenerationonthebladder.
Assemblingofthevulcanizedbladderisveryimportant.Careshouldbe
takenspeciallyforfixingtheclampareauniformlyandavoidgivingtoo
muchstresstoonearea.Fittingshouldbesuchthatitdoesnot
produceunnecessarystressonthebladder.Maintainproperstretching
heightandstackingheightofbladderinuseinthepress.
Itisknownfactonthebladderrelatedproblemsduringseasonal
changesanditissevere,particularly,inwinter.Unlikedeveloped
countries,tyreindustriesindevelopingcountriesarenotoperating
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21
underaircondition.Seasonalrelatedproblemsinairconditionedplant
aremuchless.
MostofourIndiantyreindustriesarewithoutairconditioning
arrangementandeventuallywefindproblemsduetoseasonal
changes.Normally,incaseofcompoundprocessingthecontrolof
mooneyviscosityandthecontrolofscorchplaysavitalroletocopeup
withtheprocessduringseasonalchanges.
Whenabladderiscuredandexposedtowinterforalongertime,it
mayshowstretchrelatedprobleminservice.
Itisdesiredthatabladderafterassembledandfixedinthepress
shouldundergoatleast23hours/23curecyclesprewarming
sessionsbeforeitissubjectedtocuring.Theprewarmingtimecould
belessinsummertime.Prewarmingincludesheatingwith
steam/domeandgivingatleast10timescyclicshapinganddeshaping
inthepressbeforeinitiationofcuringoftyres.Thiswillenablethe
bladdertosustainstressandstraininactualconditionwithminimum
problems.
Notethatsufficientscrewholesarethereforassemblyinordertoavoid
slippageunderstretch.Thescrewholesaretobeseparatedfromone

anotheruniformly.Bettertousepneumaticscrewtightdevicefor
tightningclampringswithtorquewrench.
Usehoistforbladderassemblyandassembledbladdershouldnotbe
keptinafoldedconditiononthefloor.Useforklifttohandlebladder
intheshopfloor.
Correctbladdertyrefittingisimportanttomaximizethebladderlife.
Userightsizeofbladdersothattheoverallstretchisnotmorethan
25%.Itisnotnecessarythatsamebladdershouldbeusedfor
differentaspectratiotyreordifferentsectionalwidthoftyrethough
therimdiaofthetyremaybethesame.
Bladderserviceconditionisveryimportanttohavehigherlife.High
purityNitrogengascurehasshownimprovementonbladderlife.Very
highvacuumofbladderisnotnecessary,onlyaround150mmw/gis
goodenoughbutshouldnotgobeyond200mmw/g.Highvacuum
causesfastercrackgenerationonthebladder.
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22
Waterbasedinnerpaintbasedcompoundedwithmicagivesbetter
resistancetooxidativedegradationonoutersurface.Uniform
applicationofinnerpainthelpstopreventflowofcurativesfromgreen
tyretothebladder.Highercurativeabsorption/adsorptionincreases
theageingofbladder.
8.10.Assessmentofbladderlife
Bladderisoneofthepartsoftyrecuringpressesandservicecondition
haswidevariationbyplants(curingmediumforbladders),typeof
bladders(openendtypeorclosedendtype)andcuringpressitself
(variationoffittingtothepresse.g.clampdesignandfastening),
thereforeitisverynecessarytorecordthebladderlifewith
statisticallymeaningfulmannerwihichneeds
followingclarifications.
Kindofcuringmedium.
Typeofbladders(BOM,BagwellorRollingintypes).
Bladdersize.
Tiresize.
Machinenumber.
Heats(bladderslife).
Failuremodeswithclarificatione.g.
Brokenatbeadclamping(upperorlower).
Delamination(whicharea).
Blistering(localizedareaorevenly).

Insidesoftening(localizedareaorevenly).
Bladdersurfacecracks(everywhereoratcornersofventgrooves).
Growth(localizedareaorevenly).
Statisticallymeaningfuldatawillgiveeasierfocusingtopinpointthe
areastotakecountermeasures.Forexample,ifonegetsfrequent
problemondelamination,itistobetakencareintheprocessingonly.
Letusseehowoneshouldsystematicallyproceedonthedelamination
part.
Delaminationistheseparationbetweentwolayerswithinthebladder
gauge.Thishappensmainlyduetofourfactors:
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23
Contamination
Airtrapment
Workaway
Impropermouldflowinthemould
Delaminationoccurifmica,dustortalcgetsontothesurfaceofthe
blank.Beforemoulding,themouldshouldbemaintainedcleanwith
outaddinganymouldlubricant.Chromiumplatedmouldgivesbetter
results.
Itisalsocausedbyairentrapment.Careshouldbetakenminimumair
trapmentduringmixingandinmillingasalreadydiscussed.Itisbetter
tousehighersizeextruder8.0or10.0forlargersize(20.0&>
20.0).
Avoidusingworkawayinbladdercompound.Blendof
workawayisthepotentialsourceoflamination.Incaseworkaway
ismore,useinextruderwithoutblendingwithokaystock.Avoid
usingdifferentworkawaytogetherbecausedifferentworkawaywill
havedifferentheathistoryandwilltendtobehave(flow)differentlyin
bladdermouldwhichtendstogivelaminationinthevulcanizate.
Compoundwithhigherheathistoryintheprocessingwilltendto
degradefasterinuse.
Mouldshouldbeclosedasfastaspossible.Maintainmouldclosing
pressureinsuchawaythattherubberflowisasfastaspossible.Itis
desiredthatrubberflowtakessimultaneouslybothonthetopaswell
asonthebottom.Itisbetterthatmouldsqueezingtimeiskept
minimumat2minutesbeforethemouldisclosedfinallyforcuring.
Forbladderorintyreorinanyrubberindustriesallproblemscould
betakencareifrightlogicortherightreasoningiscultivatedina
systematicmanner.Itisdefinitelyateamwork.Mostimportantpart
isgatheringrightinformationatrighttime.

9.SUMMARY
Particularlyindevelopingcountries,bladdercareinservice
playsaverysignificantroleforthelifeofthebladder.Infact,
themajorfailureofbladderintyreindustriesofdeveloping
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24
countriesisduetotheadverseconditionsonwhichthebladder
hasbeenexposedto.
RecommendedcompoundformulationisButyl95.0100.0/
NeopreneWRT5.07.0/HAFblack50.060.0/Castor
oil5.07.0/StearicAcid1.0/ZnO5.0andCuringResin
SP10455.010.0Phr.
Compoundformulationofbladdercompoundwillbesimilarinall
tyreindustries.Itisthestateofartontheprocessing
technologythatgivestheconsistencyandhigherlifeexpectancy
oftheproduct.
Processingofbladderisdifferentindifferentindustries.Bottom
lineishowonegetsbetterdispersionatlowestpossiblecostand
howonegetsthebestproductatlowestpossiblecost.Finallythe
productwillbejudgedbythenumberofheatshavebeengiven
bytheproduct,highertheheatsloweristhecostperkg.oftyre
production.
Beforemoulding,blanksaresplicedandprewarmedat80Cfor
24hrs.dependingonthethickness.Prewarmblankshelpsin
goodflowinsidethemould.Splicingofblankscanalsobedone
onlineafterextrusion.
Forcuttingblank,coldknifeisusedandiscutinasinglelength
havingaverageweightcloseto1015%higherthantheweight
ofthecuredbladder.
Beforeputtingtheblankinthemould,ensurethatthemouldis
clean,freefromlubricants,ifany,orflashfrompreviouscure.
Usehighestpossiblemouldpressuretoensuregoodflowinside
themould.
Delaminationoccurifmica,dustortalcgetsontothesurfaceof
theblank.
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25
Beforemoulding,themouldshouldbemaintainedcleanwithout
addinganymouldlubricant.Chromiumplatedmouldgives

betterresults.
Delaminationisalsocausedbyairentrapment.Careshouldbe
takenminimumairtrapmentduringmixingandinmilling.Itis
bettertousehighersizeextruder8.0or10.0forlargersize
(20.0&>20.0)ofbladder.
Avoidusingworkawayinbladdercompound.Blendof
workawayisthepotentialsourceoflamination.Incasework
awayismore,useinextruderwithoutblendingwithokay
stock.
Avoidusingdifferentworkawaytogetherbecausedifferentwork
awaywillhavedifferentheathistoryandwilltendtobehave
differentlyinbladdermouldwhichtendstogivelaminationin
thevulcanizate.
Compoundwithhigherheathistoryintheprocessingwillshow
resistancetoflowinthemouldandtendtodegradefasterin
use.
Maintaincuretemperatureatleastto190C.Athighercuring
temperature(210C)morestablecrosslinkisreported.A
littleovercureinbladderisalwaysbetterthanalittleunder
cure.
Mouldshouldbeclosedasfastaspossible.Maintainmouldclosing
pressureinsuchawaythattherubberflowisasfastas
possible.Itisbetterthatmouldsqueezingtimeiskept
minimumat2minutesbeforethemouldisclosedfinallyfor
curing.Itisdesiredthatrubberflowtakessimultaneouslyboth
onthetopaswellasonthebottom.
Postcuringofbladderisbetter.IntheIststageitisdonein
autoclavefor30'at190Corfor24hrs.@150C,depending
onthethicknessofbladder,followedby(2ndstage)
storageatroomtemperatureforaperiodof1530days.
Postcuringstabilizesthecrosslinkandalsohelpstosweating
water,whichiseliminatedduringcrosslinkformations.
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26
Thethumbruleofbladdercuringisalittleovercureofbladder
isalwaysbetterthanalittleundercure.Alittleundercure
bladderissubjecttofasteroxidativedegradation.
Asageneralguideline,bladdersshouldbecuredatahigher
temperaturethantheyareexpectedtoencounterduringthetyre
cure.
Duringmoulding,itisadvisedtousehighestpossiblemould

pressuretoensuregoodflowinsidethemould.
Mouldshouldbeclosedasfastaspossible.Itisbetterthat
mouldsqueezingtimeiskeptminimumat2minutesbeforethe
mouldisclosedfinallyforcuring.
Itisdesiredthatrubberflowtakessimultaneouslybothonthe
topaswellasonthebottom.Watchforproperventingofmoulds
toavoidcoldspot.
Bladdershouldnotbestoredandtransportedinfolded
condition.Oxidativecracksgeneratesonthestressedregion
whenthebladderisfolded.Bladdershouldbestoredindark,
awayfromSun
light/UVlight.
Beforechemicaltreatmentfordeoxydation,desaltingofwateris
important.Theuseofchelatecompound,Disodiumsaltof
ethylendiaminetetraaceticacidorEDTAcanapproximately
eliminate90%.
Ionexchangersisthelatesttechnologyandisnowbeing
practicedallover,whichcantakecare>99%desalinity.
Specialchemicalsareknownasoxygenscavengersuchas,
Sodiumsulphite(Na
2

SO
3

.7H
2

O)100ppmorHydrazine
Hydrate
N
2

H
4

.H
2

O(31.2%),2030ppm.Freeoxygencontentinhot
water
shouldbebelow150pphm.
Page 27

27
Hotwaterwithcontactheater(Deaerator)ismuchmore
effectivetoeliminatedissolvedoxygenthanchemicaltreatment.
Inmostcasesthedissolvedoxygencontentisnotanalysed
properlyandsystematically.Laboratorypersonnelshouldbe
maderesponsibletomonitorandcontrolthedissolvedoxygen
levelinhotwater.

Assemblingtothevulcanizedbladderisveryimportant.Care
shouldbetakenspeciallyforfixingtheclampareauniformly
andavoidgivingtoomuchstresstoonearea.
Notethatsufficientscrewholesarethereforassemblyinorderto
avoidslippageunderstretch.Thescrewholesaretobe
separatedfromoneanotheruniformly.Bettertousepneumatic
screwtightdevicefortightningclampringswithtorquewrench.
Usehoistforbladderassemblyandassembledbladdershould
notbekeptinafoldedconditiononthefloor.Useforkliftto
handlebladderintheshopfloor.
Correctbladder/tyrefittingisimportanttomaximizethe
bladderlife.Userightsizeofbladdersothattheoverallstretch
isnotmorethan25
%.
Itisnotnecessarythatsamebladdershouldbeusedfor
differentaspectratiotyreordifferentsectionalwidthoftyre
thoughtherimdiaofthetyremaybethesame.
Bladderserviceconditionisveryimportanttohavehigher
life.HighpurityNitrogengascurehasshownimprovementon
bladderlife.
Veryhighvacuumofbladderisnotnecessary,onlyaround150
mmw/gisgoodenoughbutshouldnotgobeyond200mm
w/g.Highvacuumcausesfastercrackgenerationonthebladder..

Maintainproperstretchingheightandstackingheightof
bladderinuseinthepress.
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28
Beforeloadingthetyre,properwarmupofbladderis
important.Warmupincludes(a)puttingsteaminsidefor
one/twocurecycle(b)atleast10timescyclicshapingand
deshaping.
MaintainFIFOsystem.Veryoldbladdermaynotgiveadequate
life.
Itisbettertomaintainthecontinuityofcuringofbladder.A
bladderdiscontinuedforcuringissubjecttogiveroughsurface
oroxidativedegradationonstorage.
Waterbasedinnerpaintbasedcompoundedwithmicagives
betterresistancetooxidativedegradationonoutersurface.
Uniformapplicationofinnerpainthelpstopreventflowof

curativesfromgreentyretothebladder.Highercurative
absorption/adsorptionincreasestheageingofbladder.
Cleanlinessandgoodhousekeepingoftheentirebladder
processingareaisveryimportant.
11.REFERENCES
1.IsobutyleneBasedPolymersforcuringMembers,H.Nagano,
ExxonChemicalInternationalAsia,PolymerTechnologyCentre
Tsurumi,Yokohoma,Japan.
2.BagoMaticBladderCompoundingAndProcessingGuidelines,C.
Moore,EssochemEuropeInc.,Machelan,Belgium.
3.CuringMembers,S.Kamano,ExxonChemicalJapanLtd.,
ElastomersDepartment,Tsurumi,Yokohama.
4.MoreUniformBladderLifeWithResinDispersion,A.H.
Johansson,PhD,RheinChemic,USA,inTireTechnology
International(8492),1995.
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29
5.UnderstandingMixingPartI,SamirMajumdar,RubberChem
Review(1723),March,1996.
6.UnderstandingMixingPartII,SamirMajumdar,RubberChem
review(1726),April,1996
7.IsobuthyleneBasedElastomers:WorldWideStatusandFuture
Outlook,D.H.Price,J.P.Cross,H.C.WangandS.Majumdar,
presentedinInternationalRubberconference,Chennai,Dec7
9,1998.
8.RubberProcessingMineralOil,Dr.SamirMajumdar,Presentedat
RubberProcessingOilSeminar,SriLanka,August24,1999.
9.CuringBladder,S.Majumdar,ShanghaiButylSeminar,Shanghai
RegalEstateHotel,Shanghai,Aug27Sept.03,2000.