El proceso de la irradiación - Materiales complejos.pdf

7/28/2019 El proceso de la irradiacin - Materiales complejos.pdf

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Industrial Applications for Fibre-ReinforcedAdvanced Composites Aerospace Aircraft Sports Equipment Automobile Marine Miscellaneous Consumer Items Importance

High strength to weight and stiffnessto weight ratios

Annual Consumption: 1.5 x 1()6 kg/aGrowth: -15%/a


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Primary Components ofRadiation CurableFormulations

Multifunctional acrylates Acrylated oligomers Monofunctional diluent monomers Epoxies with radiation-initiators


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--Ro4o + 00 ---.ORPropagation0' + 00

Cyclohexene oxideRadiation Polymerization. 0 o4o.Initiation .WA"Y+'1. R + XGO

R

OOQOR

Er0R . X ORTermination .+ + X ---. 0" OOR + HX

...


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Typical PropertiesResins For Filament/Tape Winding

Epoxies* Acrylated EpoxiesuProperty #1 #2 #3 Difunc TetrafuncA B C DUltimate Tensile 85 60 90 65 75 50 60Strength (MPa)Tensile Modulus 3 2.5 3 3 3 3 3

(GPa)Elongation (%) 4-6 10 5 5 3 13 2Glass TransitionTemperature (OC) 145 100 175 120 120 85 180

* Thermally Cured; ** EB-Cured


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Relative Product Characteristicsfor Selected ResinsProperty Selected Resins

SR-399 SR-2000 SR-5000 SR-9503 SR-3000Abrasion Resistance X X X.................... .................... ........ . ..... ...... ..................... .. ... . ... . . . .. . ... .Adhesion X X X X.................... .................... .................... . . . .... . .... ... . . . . .. ...................Chemical Resistance X X.................... ..................... .................... ........ ............ ...................Flexibility X X X X.............................. . ........... . .................... .................... ...................Hardness X X.................... ..................... . . . . . .. . . . .. . . . . .. . . . . . . . . .. . . . . .. . . . . . .. . . . . . .. . . . . . .. . . . . .Impact Resistance X X........................................... .................... ..................... ...................Low Shrinkage X X X X.................... .................... .................... ..................... ...................Water Resistance ......X........... X X................... .................... ..................... ...................Weatherability X XX-imparts specified property to the cured polymer


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Gel FractionC3000 (Epoxy diacrylate)Gel Fraction, %

100

80

60

40

20

00...8 . , . 1 kGy/h+ 10 kGy/h* 6400 kGy /h

*

1000o k ~ ~ - . L . . . . l - i . L U . l . - _ . . . L . - . . L - . L . . . J . - L . L L U _ - - - - - - L - - - - L - - - L . - L - L L L . u J0.1 Dose, kGy


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Amount ofVolatiles Released fromSelectedMatrix Polymers During CuringCuring Curing Cycle VolatilesMethod Material @25C (mg/g)Electron CN-104 50-100 kGy < 0.005Electron CN-114 50-100 kGy < 0.005Electron Derakane470-36 50 kGy 0.75*Catalyst Derakane470-36 20 min 3.0Thermal Hysolepoxy 2 hr@ 150C 3.45RE-2039Thermal PMR-15 300C 1.38* blank=0.78


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Aerospatiale's Composites Program R&D started, early eighties Endorsed technology (1987) Commercial faci li ty approved (1988);operational in 1991 Designed to cure tape-wound productsDiameter, 0.1 to 4.0 mLength, 1.5 to 10.5 mThicKness, 1 to 10 cm 10 MeV, 20 kWaccelerator Cure time reduced, 100 to 8 hours


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Radiation Curing ofEpoxiesin Mixtures Epoxy - Catalyst Mixtures- The addition of primary amines, ferrocene,triphenylsulfonium borofluoride,phenyldiazonium borofluoride,diphenyldiazonium borofluoride andmaleic anhydride have been used to reduce thedose required for radiation polymerization ofcertain epoxies- No universal promoter discovered to date


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Curing and Rheological PropertiesCurina ~ l ' ! t viceCone. D O l ; ; P 1",,111 pFlrature Tg(E")Resin Initiator phr kG y nc C

Epon 862 UVI6974 3 20 104 102CD1012 3 120 143 156OPPI 2 60 147 154DW1 2 38 145 155

Taetix 123 UVI6974 3 22 94 92CD1012 3 74 165 180OPPI 2 48 164 164DW1 2 29 161 163

,


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Curing and Rheological Properties

Optimum initiator concentration 2-3 phr Curing dose changes with the initiator used Rheological properties change with the initiatorused


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Effect ofCure Temperatureon Internal Stress

250C;EB-5; IM-7; 2-ply; 50% RH

1330C;EB-5; IM-7; 2-ply; 50% RH


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Features ofEB-Curable ResinsFeatures EB-CurableE ) ox,' Thermoset t ingE )OXY


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Features ofED-Curable ResinsFeatures

EB-Curab leEpoxy

T he rm osc tt ingE p ( l x ~ '


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EB Curable AdhesivesAdvantages

Room temperature curing Internal stress much lower Energy efficient Faster curing cycle Lower volatile emmissions


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Effect ( r ~ BOU1d Gap30 , - - - - - - - - - - - - - - - - - - , , - - - - - - - .

9

I I Thermal. ~ E l e c t r o n ..

... - - .

6o ~

-:5 20C )cQ)" -- 15en" -co~ 10ena.j 5

8!. 25 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . - - -... -. -:2

Bond Gap, mmctite 363; sanded; 50 kGy dose


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Status Work started by Aerospatiale (- 1983) and by us(-1986) Led to Aerospatiale dedicating (1988-1991) a 10MeV, 20 kW electron accelerafor to production ofrocket motor casings (carbon fibre reinforcedacrylated epoxy) We demonstrated production of thin and thicklamil1ates of advanced composites using acrylatedepoxies Led to extensive collaboration with North Americanaerospace industry Developed .radiation curing of epoxies used byaerospace Industry Feasibility ~ t u d i e s on use of ~ ~ c h n o l o g y by theaerospace Industry very positive


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Adhesive Shear Strengths25 . - - - - - - - - - - - - - - - - - - - - - - - ,

roa..:E 20-c-')~ 15~-J)m10C1>.cCJ)a. 5ro....J

324 352 363 392Loctite Resins~ Specification I I Thermal ~ Electron

1m bond g ap ; s an de d; 50 kGy dose


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Concluding Remarks Electron processing of advancedcomposites l at the threshold ofcommercialization Several types of fibre-reinforcedcomposites can be electron processed Availabili ty of 10-MeV industrial electronaccelerators, important for this application Very large components can be radiation cured,witli large enough target room Ability to join composite ~ a r t s with radiationcurable aahesives, an adtied advantage

El proceso de la irradiación - Materiales complejos.pdf

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