hatisclaimedis:

1.Acompositeenginepart,comprising:
apiston
aconnectingrod
ametalsleeveforpivotallyreceivingandoperativelyconnectingsaidpistonandsaidconnectingrod
anamideimideresinouspolymericcoreforpositioningwithinsaidsleeve
saidmetalsleeveandpolymericcorecooperatingwitheachothertoformawristpin
saidpiston,connectingrod,core,andsaidsleevemaintainingtheirstructuralrelationship,shapeandintegrityatengineoperatingconditions.

2.Acompositeenginepartinaccordancewithclaim1whereinsaidcoreissubstantiallysolid.
3.Acompositeenginepartinaccordancewithclaim1whereinsaidsleeveandcoreareannularwithgenerallycircularcrosssections.
4.Acompositeenginepartinaccordancewithclaim1whereinsaidcorehasanoutsidediameterslightlygreaterthantheinsidediameterof
saidsleeveandsaidcoreandsaidsleeveareinpressfittingengagementwitheachother.
5.Acompositeenginepartinaccordancewithclaim1includingmeansforfixedlyconnectingsaidcoreandsaidsleeve.
6.Acompositeenginepartinaccordancewithclaim1whereinsaidmetalcomprisesaluminum.
7.Acompositeenginepartinaccordancewithclaim1whereinsaidmetalcomprisessteel.
8.Acompositeenginepartinaccordancewithclaim1whereinsaidcorecomprisesareactionproductofatrifunctionalcarboxylicacid
compoundandatleastonediprimaryaromaticdiamine.
9.Acompositeenginepartinaccordancewithclaim8whereinsaidcorecomprisesatleastoneofthefollowingmoieties:##STR8##wherein
onecarbonylgroupismetatoandonecarbonylgroupisparatoeachamidegroupandwhereinZisatrivalentbenzeneringorloweralkyl
substitutedtrivalentbenzenering,R1andR2aredifferentandaredivalentaromatichydrocarbonradicalsoffrom6toabout10carbonatoms
ortwodivalentaromatichydrocarbonradicalsoffrom6toabout10carbonatomsjoineddirectlyorbystablelinkagesselectedfromthegroup
consistingofO,methylene,CO,SO2,andSradicalsandwhereinsaidR1andR2containingunitsrunfromabout10molepercent
R1containingunitandabout90molepercentR2containingunittoabout90molepercentR1containingunitandabout10molepercent
R2containingunit.
10.Acompositeenginepartinaccordancewithclaim9whereinR1is##STR9##.
11.Acompositeenginepartinaccordancewithclaim9whereinZisatrivalentbenzenering,R1is##STR10##R2is##STR11##andwherein
theconcentrationrangerunsfromabout30molepercentoftheR1containingunitsandabout70molepercentoftheR2containingunitsto
about70molepercentoftheR1containingunitsandabout30molepercentoftheR2containingunits.
12.Acompositeenginepartinaccordancewithclaim9whereinsaidcorecomprisesfrom40%to100%byweightamideimideresinous
polymer.
13.Acompositeenginepartinaccordancewithclaim9whereinsaidcorecomprisesfrom65%to75%byweightamideimideresinous
polymer.
14.Acompositeenginepartinaccordancewithclaim9whereinsaidcorecomprisesafibrousreinforcingmaterialselectedfromthegroup
consistingessentiallyofgraphiteandglass.
15.Acompositeenginepartinaccordancewithclaim14whereinsaidcorecomprisesfrom10%to50%byweightgraphite.
16.Acompositeenginepartinaccordancewithclaim15whereinsaidcorecomprisesfrom30%to34%byweightgraphite.
17.Acompositeenginepartinaccordancewithclaim14whereinsaidcorecomprises10%to60%byweightglass.
18.Acompositeenginepartinaccordancewithclaim17whereinsaidcorecomprises30%to34%byweightglass.
19.Acompositeenginepartinaccordancewithclaim14whereinsaidfibrousreinforcingmaterialhasapolymericsizingthatsubstantially
maintainsitsstructuralintegrityatengineoperatingconditions.
20.Acompositeenginepartinaccordancewithclaim14whereinsaidcorecomprisesnotgreaterthan3%byweightpolytetrafluoroethylene.
21.Acompositeenginepartinaccordancewithclaim20whereinsaidcorecomprisesfrom1/2%to1%byweightpolytetrafluoroethylene.
22.Acompositeenginepartinaccordancewithclaim14whereinsaidcorecomprisesnotmorethan6%byweighttitaniumdioxide.

23.Aprocessforformingandconnectingacompositewristpin,comprisingthestepsof:
moldinganamideimideresinouspolymertoformacore
allowingsaidamideimideresinouspolymericcoretocoolbelowitsplasticdeformationtemperature
postcuringsaidcorebysolidstatepolymerization
pressfittingsaidcuredcoreintoametalsleeveand
pivotallyconnectingapistontoaconnectingrodbypivotallyfittingsaidsleeveinthewristpinholesofsaidpistonandsaidconnectingrod.

24.Aprocessinaccordancewithclaim23whereinsaidmoldingincludescompressionmolding.
25.Aprocessinaccordancewithclaim23whereinsaidmoldingincludesinjectionmolding.
26.Aprocessinaccordancewithclaim23whereinasubstantiallysolidcoreisformed.
27.Aprocessinaccordancewithclaim23whereinanannularcoreisformed.
28.Aprocessinaccordancewithclaim23whereinsaidsleeveisformedbycuttingandgrindingextrudedmetaltubing.
29.Aprocessinaccordancewithclaim23whereinsaidmetalcomprisesaluminum.
30.Aprocessinaccordancewithclaim23whereinsaidmetalcomprisessteel.
31.Aprocessinaccordancewithclaim23whereinsaidamideimidepolymerispreparedbyreactingatrifunctionalcarboxylicacidcompound
withatleastonediprimaryaromaticdiamine.
32.Aprocessinaccordancewithclaim31whereinsaidamideimidepolymercomprisesoneofthefollowingmoieties:##STR12##wherein
onecarbonylgroupismetatoandonecarbonylgroupisparatoeachamidegroupandwhereinZisatrivalentbenzeneringorloweralkyl
substitutedtrivalentbenzenering,R1andR2aredifferentandaredivalentaromatichydrocarbonradicalsoffrom6toabout10carbonatoms
ortwodivalentaromatichydrocarbonradicalsoffrom6toabout10carbonatomsjoineddirectlyorbystablelinkagesselectedfromthegroup
consistingofO,methylene,CO,SO2,andSradicalsandwhereinsaidR1andR2containingunitsrunfromabout10molepercent
R1containingunitandabout90molepercentR2containingunittoabout90molepercentR1containingunitandabout10molepercent
R2containingunit.
33.Aprocessinaccordancewithclaim32whereinR1is##STR13##.
34.Aprocessinaccordancewithclaim32whereinZisatrivalentbenzenering,R1is##STR14##R2is##STR15##andwhereinthe
concentrationrangerunsfromabout30molepercentoftheR1containingunitsandabout70molepercentoftheR2containingunitstoabout
70molepercentoftheR1containingunitsandabout30molepercentoftheR2containingunits.
35.Aprocessinaccordancewithclaim32whereinsaidpolymercomprisesfrom10%to50%byweightgraphitefibers.
36.Aprocessinaccordancewithclaim35whereinsaidpolymercomprisesfrom30%to34%byweightgraphitefibers.
37.Aprocessinaccordancewithclaim32whereinsaidpolymercomprisesfrom10%to60%byweightglassfibers.
38.Aprocessinaccordancewithclaim37whereinsaidpolymercomprisesfrom30%to34%byweightglassfibers.

Description:

BACKGROUNDOFTHEINVENTION
Thisinventionrelatestoengines,andmoreparticularly,toenginepartsandaprocessformakingthesame.
Traditionally,engineshavebeenmadeofmetal,usuallysteelorcastiron.Steelandcastironenginesareuseful,excepttheyarequiteheavy
andconsumeconsiderableamountsofgasolineordieselfuel.Conventionalenginesexertlargecompressiveforces,considerabletorque,
andsubstantialsecondaryharmonicvibrationswhichhavetobedampenedbycounterbalancingpistons,flywheels,dampeners,etc.The
movingmetalpartsofcastironandsteelenginesgeneratehighcentrifugal,reciprocating,andinertialforces,momentum,andloads.
Generally,theweightoftheengineadverselyaffectsitsperformance,efficiency,andpower.
Recently,ithasbeensuggestedtouseplasticenginepartsinautomotiveengines.SuchsuggestionshaveappearedintheDecember1980
issueofAutomotiveIndustriesatpages4043,inanarticleentitled,"What...aPlasticEngine!?"intheMay8,1980issueofMachineDesign,
Volume52,No.10,inanarticleentitled,"PlasticEngineIsOffAndRunning,"andinFrenchApplicationNo.2,484,042,publishedDec.11,
1981.
AnexperimentalprototypeenginewithconcealedplasticenginepartswasdisplayedattheSocietyofAutomotiveEngineers'(SAE)Showin
Detroit,Mich.inFebruary1980.
Overtheyears,amideimidepolymershavebeendevelopedforuseinmoldingandproducingvariousproducts,suchaswirecoatings,
enamels,films,impregnatingmaterials,andcookingutensils.Typifyingthesepriorartamideimideproducts,polymersandmoldingprocesses
arethosedescribedinU.S.Pat.Nos.3,546,1523,573,2603,582,2483,660,1933,748,3043,753,9984,016,1404,084,1444,136,085

4,186,2364,167,620and4,224,214.Thesepriorartproducts,polymers,andmoldingprocesseshavemetwithvaryingdegreesofsuccess.
Itis,therefore,desirabletoprovidealightweightenginepart.
SUMMARYOFTHEINVENTION
Animprovedlightweightcompositeenginepartisprovidedforuseingasolineanddieselpoweredautomotiveengines,truckengines,aircraft
engines,marineengines,singleandtwocylinderengines,suchaslawnmowerengines,portablegenerators,andotherinternalcombustion
engines.Thelightweightcompositeenginepartdecreasesgasolineandfuelconsumption,attentuatesnoiseforquieterperformance,and
permitsincreasedspeedofoperation.Thelightweightcompositeenginepartproduceshigherhorsepowerforitsweightthanconventional
engineparts,whilemaintainingitshape,dimensionalstability,andstructuralintegrityatengineoperatingconditions.Thelightweight
compositeenginepartdecreasescentrifugal,reciprocating,andinertialforces,momentum,andloadontheengine.
Thecompositeengineparthasagreaterstiffnesstoweightratiothanmetal,isflameresistant,andisstabletoheat.Thecompositeengine
partiscapableofeffectivelyfunctioningatengineoperatingtemperaturesandstartupconditionsduringhotandcoldweather.Thecomposite
engineparthashighmechanicalstrength,thermalstability,fatiguestrength,andexcellenttensile,compressive,andflexuralstrength.The
compositeenginepartisresistanttowear,corrosion,impact,rupture,andcreep,andreliablyoperatesinthepresenceofenginefuels,oils,
andexhaustgases.
Incontrasttometals,suchascastiron,steel,aluminum,titanium,andtothermosettingresins,suchasepoxyresin,thecompositeenginepart
canbeinjectionmolded.Injectionmoldingpermitsclosertoleranceswithlesssecondarymachiningoperationsforproductionefficiencyand
economy.Finishedsurfacesofinjectedmoldedcompositeenginepartsareofbetterqualityandhavefewerknitlines,seamsandflashesthan
doenginepartsmadefromcoldmetalforging,casting,fabrication,orotherconventionaltechniques.Ifdesired,someofthecompositeengine
partscanbeinsertmoldedorcompressionmolded.
Thelightweightcompositeenginepartismadeofdurable,impactresistant,hybridorcompositematerialwhichincludesspecialproportionsof
anamideimideresinouspolymer,preferablyreinforcedwithgraphiteand/orglassfibers.Theamideimideresinouspolymercanalsobe
blendedwithpolytetrafluoroethylene(PTFE)and/ortitaniumdioxide.Compositeenginepartswhichareinjectionmoldedorotherwisemade
fromamideimideresinouspolymershavebetterelongation,stiffness,moduli,andstrengthatengineoperatingconditionsthandoother
plastics,suchasepoxyresin,polyimides,aramids,polyphenylenesulfide,polytetrafluoroethylene,andnylon.Aparticularlysuitableamide
imideresinouspolymeriscommerciallyavailablefromAmocoChemicalsCorporationunderthetrademarkandproductdesignationTORLON.
Intheinventionofthisapplication,thecompositeengineparttakestheformofahybrid,compositewristpin.Thewristpinhasametalsleeve
whichpivotallyreceivesandconnectsapistonandaconnectingrod,andanamideimideresinouspolymericcorepositionedwithinthe
sleeve.Theannularsleevehasagenerallycircularcrosssectionandispreferablymadeofaluminumorsteel.Thecoreisgenerally
cylindrical,andcanbesolidorhollow.Preferably,thecorehasanoutsidediameterslightlygreaterthantheinsidediameterofthesleeveand
ispressfitintothesleeve.
Whilethethermoplasticcorecanbecompressionmolded,itispreferablyinjectionmoldedforclosertolerances,minimizedsecondary
machiningoperations,andenhancedstrength.Themoldedcoreisallowedtocoolbelowitsplasticdeformationtemperaturetosolidifyits
shape,andthenpostcuredbysolidstatepolymerizationtoincreaseitsstrength.Themetalsleeveispreferablyformedbycuttingandgrinding
extrudedmetaltubing.
Compositewristpinsdecreasesecondaryharmonicvibrations,fluttering,andengineshaking,andenhancemoreefficientcombustion
temperatures.
Amoredetailedexplanationoftheinventionisprovidedinthefollowingdescriptionandappendedclaimstakeninconjunctionwiththe
accompanyingdrawings.
BRIEFDESCRIPTIONOFTHEDRAWINGS
FIG.1isacrosssectionalviewofanautomotiveenginewithacompositewristpininaccordancewithprinciplesofthepresentinvention
FIG.2isaperspectiveviewofthecompositewristpin
FIG.3isaperspectiveviewofapistonwiththecompositewristpinand
FIG.4isacrosssectionalviewofthepistonandcompositewristpintakensubstantiallyalongline44ofFIG.3.
DETAILEDDESCRIPTIONOFTHEPREFERREDEMBODIMENT
Theautomotiveengine10ofFIG.1haslightweightcompositeenginepartstoreduceitsweight,decreasefuelconsumption,andimprove
engineperformance.Engine10isagasolinepowered,fourstroke,sparkignitionengine.TheillustratedengineisaV6enginewith6
cylindersarrangedinaVshapedfiringpattern.
Whilethecompositeenginepartsaredescribedhereinafterwithparticularreferencetotheillustratedengine,itwillbeapparentthatthe
enginepartscanalsobeusedinothertypesofgasolinepoweredautomotiveengines,aswellasindieselpoweredautomotiveengines,truck
engines,aircraftengines,marineengines,locomotiveengines,lawnmowerengines,portablegenerators,andotherinternalcombustion
engines.Thecompositeenginepartscanbeusedin1,2,4,6,8ormorecylinderenginesincludingVarrangedcylinderengines,aligned
cylinderengines,horizontallyopposedcylinderengines,rotaryengines,etc.
AsshowninFIG.1,engine10hasacastironblock11andhead12.Theblockhasmanychambersincludingacoolingchamber13andsix
combustionchambers14whichprovidecylinders.Theheadhasanexhaustmanifoldandanintakemanifold16whichcommunicatewiththe
cylindersandanoverheadcarburetor(notshown).Extendingbelowtheblockisanoilpan18.Extendingabovetheheadisarockerarm
cover20.Adistributor22withaninternalsetofsparkplugs(notshown)isprovidedtoignitethegaseousairmixtureinthecylinders.
Ametalcrankshaft24drivesthepistons26throughconnectingrods28.Acounterweight30oncrankshaft24balancesthepistons.The
crankshaft24drivesametalcamshaft32throughasetoftiminggears34and36.Thetiminggearsincludeacrankshaftgearordrivepulley34
mountedonthecrankshaft24,andacamshaftgearordrivenpulley36mountedonthecamshaft32.Afabricreinforced,rubbertimingbelt38
ortimingchaindrivinglyconnectsthecrankshaftgear34andthecamshaftgear36.Thecamshaftgear36hastwicethediameterandtwiceas

manyteethasthecrankshaftgear34,sothatthecamshaft18movesatonehalfthespeedofthecrankshaft.Insometypesofengines,the
crankshaftgeardrivesthecamshaftgeardirectlywithoutatimingbeltortimingchain.
Metalcams40aremountedonthecamshaft32toreciprocatinglydrivethevalvetrains46.Therearetwoorfourvalvetrainspercylinder
dependingonthetypeofengine.Eachvalvetrainhasavalvelifter48,apushrod50,arockerarm52,avalvespringretainer54,a
compressionspring56,andavalve58whichopensandclosestheexhaustmanifoldortheintakemanifold16.Theintakevalve58opensand
closestheintakemanifold16.Theexhaustvalveopensandclosestheexhaustmanifold.Thelifter48ridesuponandfollowsthecam40.The
pushrod50isseatedinarecessofthelifterandisconnectedtotherockerarm52byathreadedstud60andnut62.Thebottomendofthe
stud60isshapedcomplementarytothetopendofthepushrodtosecurelyreceiveandengagethepushrod.Therockerarm52pivotsupona
rockerarmshaft,fulcrumorpin62andreciprocatinglydrivesthevalvestem64ofthevalve58.
Thepiston26reciprocatinglyslidesagainstametallinerthatprovidesthecylinderwalls.Asetofpistonringsispressfitorsnapfitonthehead
ofthepiston.Thepistonringsincludeacompressionring66,abarrierring68,andanoilscraperring70.Thepistonispivotallyconnectedto
theconnectingrod28throughawristpin72andabushing74.Theconnectingrodispivotallyconnectedtothecrankshaft24throughasplit
ringmetalbearing76.
Inafourstrokeinternalcombustionengine,suchastheillustratedengine,eachpistonhasanintakestroke,acompressionstroke,apower
stroke,andanexhauststroke.Duringtheintakestroke,thepistonmovesdownwardandtheinletvalveisopenedtopermitagaseousair
mixturetofillthecombustionchamber.Duringthecompressionstroke,theintakeandexhaustvalvesareclosedandthepistonmovesupward
tocompressthegaseousairmixture.Duringthepowerstroke,thesparkplugisignitedtocombustthegaseousairmixtureinthecombustion
chamberandtherapidlyexpandingcombustiongasesdrivethepistondownward.Duringtheexhauststroke,theexhaustvalveisopenedand
thepistonmovesupwardtodischargethecombustiongases(exhaustgases).
Thepistons,aswellasconnectingrods,wristpins,barrierpistonrings,pushrods,rockerarms,valvespringretainers,intakevalves,and
timinggears,canbemadeofmetal,althoughitispreferredthattheyareatleastpartiallymadeofathermoplastic,amideimideresinous
polymertoreducetheweightoftheengine.Suchamideimideenginepartsarereferredtoascompositeengineparts.Insomeengines,the
exhaustvalvecanalsobeatleastpartiallymadeofathermoplastic,amideimideresinouspolymer.
AsshowninFIGS.24,thehybrid,compositewristpin72hasanannularmetalsleeve100,whichcoversathermoplastic,amideimide
resinouspolymeric,annularcore102.Thesleeveispreferablymadeofaluminumorsteel.Theoutersurfaceofthesleevefitsinthewristpin
holesofthepistonandconnectingrod,preferablywithinthewristpinbushingoftheconnectingrod,topivotallyreceiveandconnectthepiston
andconnectingrod.Themetalsleeveprovidesajacketwhichdistributestheloadexertedonthewristpinbythepistonandconnectingrod.
Theinnersurfaceofthesleevehasadiameterslightlysmallerthantheoutsidediameterofthecore102topressfittinglyreceiveandengage
thecore.Thesleeveandcorehavecircularcrosssections.
Theannularcore102providesanaxialoilholeextendingthroughthewristpin.Althoughahollowcoreispreferredforlighterweightand
enhancedlubrication,asolidcorecanbeused,ifdesired.
Thecompositewristpinisapproximately40%to70%lighterthanconventionalmetalwristpins.Advantageously,themetalsleeveand
thermoplasticcoremaintaintheirstructuralshapeandintegrityatengineoperatingconditions.Thecoefficientandrateofthermalexpansion
andcontractionoftheamideimidepolymericcorearesimilartothoseofthemetalsleeve,sothatthethermoplasticcoreexpandsand
contractscompatiblywiththemetalsleeveatengineoperatingconditions.
Thecorecanbecompressionmolded,althoughitispreferablyinjectionmoldedforclosertolerances,minimizedsecondarymachining
operations,andenhancedstructuralstrength.Theinjectionmoldingtemperature(polymermelttemperature)oftheamideimideresinous
polymerispreferablyfrom630F.to675F.,whichisslightlyabovetheplasticdeformationtemperatureofthepolymer.Themoldedcore
shouldbeallowedtocoolbelowitsplasticdeformationtemperaturetosolidifyitsshapeandpolymericorientation.Thetotalmoldingand
coolingtimerangesfrom15to30seconds,dependingonthegradeofthepolymericresinandthedesiredcrosssectionalthicknessofthe
core.
Thecooledmoldedenginepartprovidingtheblankisthenpostcuredbysolidstatepolymerizationbyprogressivelyheatingthemolded
enginepartbelowitsmeltingtemperaturetoenhanceitsdimensionalstrengthandintegrity.Thespecifictimeandtemperaturesdependupon
thedesiredsizeofthemoldedpart.
Inthepreferredmethodofpostcuring,themoldedenginepartispreheatedinthepresenceofacirculatinggasinanovenforaperiodoftime
suchthatamajorportionofthevolatilescontainedintheinjectionmoldedenginepartarevaporizedandremoved,whilesimultaneously
increasingthedeflectiontemperatureofthepolymerfromabout15F.to35F.withoutdeformationoftheenginepart.Preheatingcanbe
carriedoutbyheatingthemoldedpartfromaninitialtemperaturetoafinaltemperaturewitheithercontinuousorstepwiseincreasesin
temperatureoveraperiodoftime,oratasingletemperature,forasufficienttimetovaporizeandremovethevolatilesandincreasethe
polymer'sdeflectiontemperature.
Imidization,crosslinkingandchainextensiontakeplaceduringpreheating.Continuousorstepwisepreheatingincreasestensilestrengthand
elongationpropertiesofthemoldedengineparts.
Inordertoenhancethephysicalpropertiesofsmallermoldedengineparts,itispreferredtocontinuouslypreheatthemoldedpartfroman
initialtemperatureof300F.to330F.toafinalpreheatingtemperatureof460F.to480F.forabout40to60hours.Alternatively,themolded
enginepartcanbepreheatedinastepwisemannerfromaninitialpreheatingtemperatureof300F.to330F.for20to30hourstoafinal
preheatingtemperatureof410F.to430F.for20to30hours.
Generally,themoldedpartisheated(postcured)atatemperatureofabout330F.for24hours,about475F.for24hours,andabout500F.
for24hours.Morespecifically,themoldedarticleisheatedinthepresenceofacirculatinggasatabout5F.to25F.,andpreferablyabout5
F.to15F.,belowtheincreaseddeflectiontemperatureofthepolymerforaperiodoftimesuchthatsubstantialimidization,chainextension
andcrosslinkingtakeplacewithoutdeformationofthemoldedarticle.
Asaresultofsuchheating,waterandgasescontinuetobegeneratedandremoved,andthemolecularweightanddeflectiontemperatureof
thepolymerareincreased.Heatingiscontinuedforaperiodoftimesufficienttoincreasethedeflectiontemperaturebyabout15F.to35F.
Preferably,theheatingisatatemperaturerangingfromabout450F.to490F.foraperiodofatleast20hours.Thereafter,thetemperatureis

increasedtoabout5F.to25F.belowthepolymer'snewdeflectiontemperatureandheldatthenewtemperatureforasufficienttimeto
increasethepolymer'sdeflectiontemperaturebyabout15F.to35F.Preferably,suchheatingisatabout480F.to520F.foraperiodofat
least20hours.
Heatingiscontinuedinthismannertoincreasethepolymer'sdeflectiontemperaturetoitsmaximumattainablevaluewithoutdeformationof
themoldedarticle.Thefinalheatingstageiscarriedoutatabout5F.to25F.,andpreferablyfromabout5F.to15F.,belowthemaximum
attainabletemperatureforatleast20hours,andmostpreferablyatleast40hours.Theheatedpartisthencooled.
Inordertobestenhancethephysicalpropertiesofthemoldedenginepart,itispreferredtoheatthemoldedpartfromabout460F.toabout
480F.forabout20to30hours,thenfromabout490F.to510F.forabout20to30hours,andsubsequentlyfromabout495F.toabout
525F.forabout20to60hours.
Postcuringshouldbecarriedoutinthepresenceofacirculatinggaswhichflowsthroughandaroundthemoldedengineparttoremovewater
andgasesfromthepolymericresin.Theamountofcirculationandthecirculationflowpatternshouldbecoordinatedtomaximizeremovalof
waterandthegaseswithoutcausingsubstantialvariationsintemperature.Whileinertgases,suchasnitrogen,canbeused,itispreferredthat
thecirculatinggasbeanoxygencontaininggas,mostpreferablyair,becauseoxygentendstofacilitatecrosslinkingofthepolymer
molecules.Postcuringispreferablycarriedoutinacirculatingairoven,althoughitcanbecarriedoutinanyothersuitableapparatus.
Postcuredenginepartsareresistanttothermalshockattemperaturesofatleast500F.andexhibitsignificantlyimprovedtensilestrengthand
elongationascomparedwithuntreatedmolded,amideimideresinousengineparts.Amoredetailedexplanationofheattreatmentbypost
curingisdescribedinChenU.S.Pat.No.4,167,620,whichisherebyincorporatedbyreference.
Afterthemoldedenginepart(core)ispostcured,thecoreispressfitintothemetalsleeve.Themetalsleeveispreferablyformedbycutting
andgrindingextrudedmetaltubing.Thecorecanbeaxiallydrilledwithadrillpress,ifdesired.
Whilethemachiningoperationsdescribedabovearepreferablyconductedaftertheinjectionmoldedenginepartispostcured,oneormoreof
thesemachiningoperationscanbeconductedbeforepostcuringifdesired.
Thecompositeenginepartandthethermoplastic,amideimideresinouspolymercontainedthereinsubstantiallymaintaintheirshape,
dimensionalstabilityandstructuralintegrityatengineoperatingconditions.Usualengineoperatingtemperaturesdonotexceed350F.Oil
cooledengineoperatingtemperaturesrangefromabout200F.to250F.Advantageously,thecompositethermoplastic,amideimide
resinous,polymericenginepartisimperviousandchemicallyresistanttooil,gasoline,dieselfuel,andengineexhaustgasesatengine
operatingconditions.
Thethermoplasticresininthecompositeenginepartcomprises40%to100%,preferably65%to75%,byweightamideimideresinous
polymer.Thepolymerispreferablyreinforcedwithgraphitefibersand/orglassfibers.Inmoldedpartsthefibershaveanaveragelengthof6to
10milsandapreferreddiameterofabout0.2to0.4mils.Theratioofthelengthtodiameterofthefibersisfrom2to70,averagingabout20.
Whiletheabovefiberlengthsanddiametersarepreferredforbeststructuralstrength,otherlengthsanddiameterscanbeused,ifdesired.The
graphitefiberscanbegranulatedorchoppedandcanbeoptionallysizedorcoatedwithapolysulfonesizingorsomeotherpolymerwhichwill
maintainitsstructuralintegrityatengineoperatingconditions.Theglassfiberscanbemilledorchoppedandcanbesizedwithsilaneorsome
otherpolymerthatmaintainsitsstructuralintegrityatengineoperatingconditions.Choppedgraphiteandglassfibersarepreferablysized,
whilegranulatedgraphitefibersarepreferablyunsized.
Desirably,thethermoplastic,amideimideresinouspolymercomprises10%to50%,preferably30%to34%,byweightgraphitefibersor10%
to60%,preferably30%to34%,byweightglassfibers.Thepolymercanhaveasmuchas3%andpreferably1/2%to1%byweightpowdered
orgranularpolytetrafluoroethylene(PTFE)and/orasmuchas6%byweighttitaniumdioxide.Insomecircumstancesitmaybedesirabletoadd
morePTFE.
Thepolymer'smoldingcharacteristicsandmolecularweightcanbecontrolledtofacilitatepolymerizationwithanadditionalmonomer,suchas
trimelliticacid(TMA),andcanbepreparedwiththedesiredflowpropertiesbythemethodsdescribedinHansonU.S.Pat.No.4,136,085,
whichisherebyincorporatedbyreference.
Thepolymercanbeblendedwithgraphite,glass,PTFE,andtitaniumdioxidebythemethoddescribedinChenU.S.Pat.No.4,224,214,which
isherebyincorporatedbyreference.
Themostpreferredamideimidepolymerisreinforcedwith30%byweightgraphitefibersandhasthefollowingengineeringproperties:

TABLEI
______________________________________
ASTMTypicalTestPropertyValueUnitsMethod
______________________________________
MechanicalPropertiespsiD1708
TensileStrength
321F.
22,800
73F.
29,400
275F.
22,800

450F.
15,700
TensileElongation%D1708
321F.
3
73F.
6
275F.
14
450F.
11
TensileModuluspsiD1708
73F.
3,220,000
FlexuralStrengthpsiD790
321F.
45,000
73F.
50,700
275F.
37,600
450F.
25,200
FlexuralModuluspsiD790
321F.
3,570,000
73F.
2,880,000
275F.
2,720,000
450F.
2,280,000
CompressiveStrength
32,700psiD695
ShearStrengthpsiD732
73F.
17,300
IzodImpactft.lbs./in.
D256

73F.
0.9
ThermalProperties
DeflectionTemperatureF.
D648
264psi540
CoefficientofLinear
5106
in./in./F.
D696
ThermalExpansion
ThermalConductivity
3.6btuin.
hr.ft.2F.
C177
Flammability94V0Underwriters
94
Laboratories
LimitingOxygenIndex
52%D2863
GeneralProperties
Density1.42g/ccD792
Hardness"Rockwell"E
94
WaterAbsorption
0.26%D570
______________________________________
Thepreferred,glassreinforced,thermoplasticamideimideresinouspolymercomprises30%byweightglassfibersandhasthefollowing
properties:

TABLEII
______________________________________
ASTMTypicalTestPropertyValueUnitsMethod
______________________________________
MechanicalProperties
TensileStrengthpsiD1708
321F.
29,500
73F.
29,700
275F.

23,100
450F.
16,300
TensileElongation%D1708
321F.
4
73F.
7
275F.
15
450F.
12
TensileModuluspsiD1708
73F.
1,560,000
FlexuralStrengthpsiD790
321F.
54,400
73F.
48,300
275F.
35,900
450F.
26,200
FlexuralModuluspsiD790
321F.
2,040,000
73F.
1,700,000
275F.
1,550,000
450F.
1,430,000
CompressiveStrength
34,800psiD695
ShearStrengthpsiD732
73F.
20,100
IzodImpactft.lbs./in.

D256
73F.
1.5
ThermalProperties
DeflectionTemperatureF.
D648
264psi539
CoefficientofLinear
9106
in./in./F.
D696
ThermalExpansion
ThermalConductivity
2.5btuin.C177
hr.ft.2F.
Flammability94V0Underwriters
94
Laboratories
LimitingOxygenIndex
51%D2863
ElectricalProperties
DielectricConstantD150
103Hz4.4
106Hz6.5
DissipationFactor
D150103Hz
.022
106Hz.023
VolumeResistivity
61016
ohmsin.D257
SurfaceResistivity
11018
ohmsD257
DielectricStrength
835volts/mil.
GeneralProperties
Density1.56g/ccD792
Hardness"Rockwell"E

94
WaterAbsorption
0.24%D570
______________________________________
Theamideimidepolymersarepreparedbyreactinganaromaticpolycarboxylicacidcompound(acylhalidecarboxylicacidand/orcarboxylic
acidesters)havingatleastthreecarboxylicacidgroupssuchastrimelliticacid(TMA),4trimellitoylanhydridehalide(4TMAC),pyromellitic
anhydride,pyromelliticacid,3,4,3',4'benzophenonetetracarboxylicacidorananhydridethereof,oroxybisbenzenedicarboxylicacidoran
anhydridethereof.
Theamideimidepolymersarepreferablypreparedbyreactinganacylhalidederivativeofanaromatictricarboxylicacidanhydridewitha
mixtureoflargelyorwhollyaromaticprimarydiamines.Theresultingproductsarepolyamideswhereinthelinkinggroupsarepredominantly
amidegroups,althoughsomemaybeimidegroups,andwhereinthestructurecontainsfreecarboxylicacidgroupswhicharecapableof
furtherreaction.Suchpolyamidesaremoderatemolecularweightpolymericcompoundshavingintheirmoleculeunitsof:##STR1##andunits
of:##STR2##and,optionally,unitsof:##STR3##whereinthefreecarboxylgroupsareorthotooneamidegroup,Zisanaromaticmoiety
containing1to4benzeneringsorloweralkylsubstitutedbenzenerings,R1,R2andR3aredifferentandaredivalentwhollyorlargely
aromatichydrocarbonradicals.Thesehydrocarbonradicalsmaybeadivalentaromatichydrocarbonradicaloffrom6toabout10carbon
atoms,ortwodivalentaromatichydrocarbonradicalseachoffrom6toabout10carbonatomsjoineddirectlyorbystablelinkagessuchasO
,methylene,CO,SO2,Sforexample,R'OR',R'CH2R',R'COR',R'SO2R'andR'SR'.
Thepolyamidesarecapableofsubstantiallycompleteimidizationbyheatingbywhichtheyformthepolyamideimidestructurehavingtoa
substantialextentreoccurringunitsof:##STR4##andunitsof:##STR5##and,optionally,unitsof:##STR6##whereinonecarbonylgroupis
metatoandonecarbonylgroupisparatoeachamidegroupandwhereinZ,R1,R2andR3aredefinedasabove.Typicalcopolymersofthis
inventionhaveuptoabout50percentimidizationpriortoheattreatment,typicallyabout10toabout40percent.
Thepolyamideimidecopolymersarepreparedfromananhydridecontainingsubstanceandamixtureofwhollyorpartiallyaromaticprimary
diamines.Usefullytheanhydridecontainingsubstanceisanacylhalidederivativeoftheanhydrideofanaromatictricarboxylicacidwhich
contains1to4benzeneringsorloweralkylsubstitutedbenzeneringsandwhereintwoofthecarboxylgroupsareorthotooneanother.More
preferably,theanhydridecontainingsubstanceisanacylhalidederivativeofanacidanhydridehavingasinglebenzeneorloweralkyl
substitutedbenzenering,andmostpreferably,thesubstanceistheacylchloridederivativeoftrimelliticacidanhydride(4TMAC).
Usefullythemixtureofdiaminescontainstwoormore,preferablytwoorthree,whollyorlargelyaromaticprimarydiamines.Moreparticularly,
theyarewhollyorlargelyaromaticprimarydiaminescontainingfrom6toabout10carbonatomsorwhollyorlargelyaromaticprimary
diaminescomposedoftwodivalentaromaticmoietiesoffrom6toabout10carbonatoms,eachmoietycontainingoneprimaryaminegroup,
andthemoietieslinkeddirectlyorthrough,forexample,abridgingO,S,SO2,CO,ormethylenegroup.Whenthreediaminesare
usedtheyarepreferablyselectedfromtheclasscomposedof:##STR7##saidXbeinganO,CH2,orSO2group.Morepreferably,
themixtureofaromaticprimarydiaminesistwocomponentandiscomposedofmetaphenylenediamine(MPDA)andp,p'oxybis(aniline)
(OBA),p,p'methylenebis(aniline)(MBA),andp,p'oxybis(aniline),p,p'sulfonylbis(aniline)(SOBA),andp,p'oxybis(aniline),p,p'
sulfonylbis(aniline)andmetaphenylenediamine,orp,p'sulfonylbis(aniline)andp,p'methylenebis(aniline).Mostpreferably,themixtureof
primaryaromaticdiaminescontainsmetaphenylenediamineandp,p'oxybis(aniline).Thearomaticnatureofthediaminesprovidesthe
excellentthermalpropertiesofthecopolymerswhiletheprimaryaminegroupspermitthedesiredimideringsandamidelinkagestobe
formed.
Whentwodiaminesareusedtoachieveapolymerusefullycombiningthepropertiesofbothdiamines,itisusualtostaywithintherangeof
about10mole%ofthefirstdiamineand90mole%oftheseconddiaminetoabout90mole%ofthefirstdiamineand10mole%ofthe
seconddiamine.Preferablytherangeisabouta20to80moleratiotoaboutan80to20moleratio.Inthepreferredembodimentwhereinthe
acylchlorideoftrimelliticacidanhydrideiscopolymerizedwithamixtureofp,p'oxybis(aniline)andmetaphenylenediamine,thepreferred
rangeisfromabout30mole%oftheformerandabout70mole%ofthelattertoabout70mole%oftheformerandabout30mole%ofthe
latter.
Althoughembodimentsoftheinventionhavebeenshownanddescribed,itistobeunderstoodthatvariousmodificationsandsubstitutions,as
wellasrearrangementsofstructuralfeaturesand/orprocesssteps,canbemadebythoseskilledintheartwithoutdepartingfromthenovel
spiritandscopeofthisinvention.