NASA/TM--2002-211704

The Effect of Heating on the Degradation

of Ground Laboratory and Space Irradiated

Teflon ® FEP

Kim K. de Groh

Glenn Research Center, Cleveland, Ohio

Morgana Martin

Ohio Aerospace Institute, Brook Park, Ohio

July 2002
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NASA/TM--2002-211704

The Effect of Heating on the Degradation

of Ground Laboratory and Space Irradiated

Teflon ® FEP

Kim K. de Groh

Glenn Research Center, Cleveland, Ohio

Morgana Martin

Ohio Aerospace Institute, Brook Park, Ohio

Prepared for the

Sixth International Conference on Protection of Materials

and Structures From Space Environment

cosponsored by the ITL, UTIAS, MMO, AFOSR/NL, CRESTECH,

EMS Technologies, and MDRobotics

Toronto, Canada, May 1-3, 2002

National Aeronautics and

Space Administration

Glenn Research Center

July 2002
Acknowledgments

We would like to thank Dr. Stephen Pepper and Dr. Donald Wheeler of GRC for the use of, and characterization of,

their x-ray facility; Ed Sechkar of QSS Group, Inc. for build-up of the vacuum furnace facility; and Dr. Jim Gaier of

GRC for help with density gradient columns. We thank Joyce Dever of GRC for providing areal dose values for the

HST FEP. We also would like to acknowledge John Blackwood and Jackie Townsend of NASA GSFC, Ben Reed of

Swales Aerospace, and the HST Project Office for providing the retrieved HST material for this study

Trade names or manufacturers' names are used in this report for

identification only. This usage does not constitute an official

endorsement, either expressed or implied, by the National

Aeronautics and Space Administration.

NASA Center for Aerospace Information

7121 Standard Drive

Hanover, MD 21076

Available from

National Technical Information Service

5285 Port Royal Road

Springfield, VA 22100

Available electronically at http: / / gltrs.grc._aasa.gov/GLTRS
THE EFFECT OF HEATING ON THE DEGRADATION OF GROUND LABORATORY

AND SPACE IRRADIATED TEFLON ® FEP

Kim K. de Groh

National Aeronautics and Space Administration

Glenn Research Center

Cleveland, Ohio 44135

Morgana Martin

Ohio Aerospace Institute

Brook Park, Ohio 44142

Abstract

The outer most layer of the multilayer insulation (MLI) blankets on the Hubble Space Telescope (HST) is back

surface aluminized Teflon ® FEP (fluorinated ethylene propylene). As seen by data collected after each of the three

servicing missions and as observed during the second servicing mission (SM2), the FEP has become embrittled in

the space environment, leading to degradation of the mechanical properties and severe on-orbit cracking of the FEP.

During SM2, a sample of aluminized-FEP was retrieved from HST that had cracked and curled, exposing its

aluminum backside to space. Because of the difference in optical properties between FEP and aluminum, this

insulation piece reached 200°C on-orbit, which is significantly higher than the nominal MLI temperature extreme of

50°C. This piece was more brittle than other retrieved material from the first and third servicing missions (SM1 and

SM3A, respectively). Due to this observation and the fact that Teflon thermal shields on the solar array bi-stems

were heated on-orbit to 130°C, experiments have been conducted to determine the effect of heating on the

degradation of FEP that has been irradiated in a ground laboratory facility or in space on HST. Teflon FEP samples

were x-ray irradiated in a high vacuum facility in order to simulate the damage caused by radiation in the space

environment. Samples of pristine FEP, x-ray irradiated FEP and FEP retrieved from the HST during SM3A were

heat treated from 50 to 200°C at 25 ° intervals in a high vacuum facility and then tensile tested. In addition, samples

were tested in a density gradient column to determine the effect of the radiation and heating on the density of FEP.

Results indicate that although heating does not degrade the tensile properties of non-irradiated Teflon, there is a

significant dependence of the percent elongation at failure of irradiated Teflon as a function of heating temperature.

Irradiated Teflon was found to undergo increasing degradation in the elongation at failure as temperature was

increased from room temperature to 200°C. Rate of degradation changes, which were consistent with the glass I

transition temperatures for FEP, appeared to be present in both tensile and density data. The results indicate the

significance of the on-orbit temperature of Teflon FEP with respect to its degradation in the low Earth orbital space

environment.

1.0 Introduction

The HST was launched on April 25, 1990 into low Earth orbit as the first mission of NASA's Great Observatories

program. It is a telescope capable of performing observations in the near-ultraviolet, visible and near-infrared

wavelengths (0.115 to 2.5 gm). The HST was designed to be serviced on-orbit to upgrade scientific capabilities.

SM1 occurred in December 1993, after 3.6 years in space. SM2 was in February 1997, after 6.8 years in space.

SM3A was in December 1999, after 9.7 years in space. The fourth servicing mission, designated as SM3B, occurred

in March 2002. A future servicing mission is currently planned for mid 2003.

The HST is covered with two primary types of thermal control materials, radiators and multilayer insulation

blankets, which passively control temperatures on-orbit. 1 Both of these thermal control materials utilize metallized

Teflon FEP as the exterior (space-facing) layer. Metallized Teflon FEP is a common thermal control material used

on spacecraft, such as the Long Duration Exposure Facility, the Solar Max Mission spacecraft and HST, but it has

been found to degrade in the low Earth orbital (LEO) space environment. Teflon FEP is used as the outer layer of

thermal control insulation because of its excellent optical properties (low solar absorptance (as) and high thermal

NASA/TM 2002-211704 1
emittance(_)),inadditiontoitsflexibilityandlowmolecular weight.Ametallizedlayer(A1orAg)isappliedtothe

backsideoftheFEPtoreflectincidentsolarenergy.Theasand_of5mil(127gm)thickFEPwithanaluminized

backingare0.13and0.81,respectively. 2 Solarradiation(ultraviolet (UV)radiationandx-raysfromsolarflares),

electronandprotonradiation(omni-directional particlestrappedintheVanAllenbelts),thermalexposureand

thermal cycling,andatomicoxygenexposureareallpossibleLEOenvironmental factorswhichcouldpossibly

contributetothedegradation ofFEP.

Analysesofaluminized-FEP (A1-FEP) andsilvered-FEP(Ag-FEP) MLIblanketsretrievedduringSM1revealedthat

the5mil(127gm)thickFEPexteriorlayerwasembrittledonhighsolarexposuresurfaces. 3'4Surfaceswhich

receivedthehighestsolarexposureshadmicroscopicthrough-thickness cracksintheFEPatstresslocations. 3'4

Bondedsolarfacing2mil(51gm)A1-FEPonthesolararraydrivearm(SADA)powerharness, whichwasalso

retrievedduringSM1,hadmanycracksandatotallossofmechanical integrityinheavilystressedareas. 5 The

maximumtemperature duringthermal cyclingofthepowerharnessFEPwashigher(>130°C) 5thanthatoftheMLI

FEP(maximumtemperature of50°C)6.

DuringSM2,severecrackingofthe5milA1-FEPMLIouterlayerwasobservedonthelightshield(LS),forward

shellandequipment baysof thetelescope. Astronaut observations combinedwithphotographic documentation

revealedextensivecrackingoftheMLI inmanylocations, withsolarfacingsurfacesbeingheavilydamaged. 2

Figure1showstwolargecrackedareasontheLS.Averylargeverticalcrackcanbeseenearthecenterofthe

photograph, andasmallercrackedarea,inwhichfreestandingA1-FEPhadcurled-uptightly(withtheFEPsurface

incompression), islocatedabovetheverticalcrack.TheworstoftheMLIouterlayercrackswerepatchedduring

SM2.PriortopatchingtheupperLScrack,thetightlycurledA1-FEPouterlayerwascutoffandretrievedforpostmissionanalyses. Patchesof5milthick(127gm)A1-FEPwereplacedoverthetwoLScracks,andpatchesof2mil

thick(51gm)A1-FEPwereplacedovercracksinMLIonEquipment Bays8and10.Figure2showsoneofthese

crackedareasfromBay10.AsdeterminedthroughaHSTMLIFailureReviewBoard,embrittlement ofFEPon

HSTiscausedbyradiationexposure(lectronandprotonradiationwithcontributions fromsolarflarex-raysand

UVradiation) combinedwiththermal cycling. 6

SM2 sample

location

Figure 1. Two cracked areas in the MLI outer layer on the HST LS as witnessed during SM2. The astronauts have cut off the

curled upper LS material and are preparing to place a patch over the area.

NASA/TM 2002-211704 2
Figure2.Crackspresent i5milthickA1-FEPBay10MLI,photographed afterretrieval duringSM3A.

DuringSM3A,originalMLIfromBay10,whichexperienced 9.7yearsofspaceexposure, aswellas2milthick

A1-FEPpatchmaterial,whichexperienced2.8yearsof exposure, wereretrievedandavailablefordegradation

analyses. Post-retrieval analyseshaveshownthatFEPretrievedduringSM2after6.8yearsexposurewasmore

embrittled, witha 0%elongationto failure,thanFEPretrieved2.8yearslaterduringSM3A,after9.7years

exposure. 7'8BecausetheretrievedSM2material curledwiththeFEPsurfaceincompression, exposingthelower

emittanceA1surfacetospace, it experienced ahighertemperature extremeduringthermal cycling(_200YC)than

thenominal solarfacingMLIexperiences (u50YC).AsthiswastheonlysampleretrievedduringSM2,it was

importantto determinethedifferencebetweenthemeasuredpropertiesof thisexcessivelyheatedsampleand

nominallyheatedMLIFEP.AnotherbacksurfacemetallizedTefloninsulation, 2milthickA1-FEPthermal shields

thatcoveredthesolararraybi-stemsofthesecondpairofHSTsolararrays(SA-2),thermal cycledtoamaximum

temperatureof 130°Con-orbit.Becauseof thevarioustemperatures experienced byHSTFEPmaterials, it is

necessary tounderstand theeffectoftemperature onFEPdegradation onHST.Understanding temperature effectsis

important fordeterminingdegradation mechanisms, andforfacilitatingthepredictionofFEPdegradationnLEO.

Investigations havebeenconductedbydeGrohetal.ontheeffectsofheatingpristineFEPandFEPirradiatedin

groundfacilitiesorinLEO,asreportedinreferences7 and9. Forthisstudy,samplesof pristineFEP,x-ray

irradiatedFEPandSM3A-retrieved FEPwereheatedattemperatures of 50°Cto200°Cin25°Cintervalsinahigh

vacuumfurnaceandevaluatedforchangesintensilepropertiesanddensityinordertoimprovetheunderstanding of

thedegradationof thisinsulationmaterial intheLEOspacenvironment. X-rayswereusedforthesourceof

irradiationbecausex-raysfromsolarflaresarebelievedto contributeotheembrittlement ofFEPonHST,6and

becausepreviousgroundtestshaveshownthatsolarflarex-rayenergiesareenergeticenoughto causebulk

embrittlement in 127gmFEP.1°Also,themechanismofembrittlement ofpolymersisbelievedtobethesamefor

all formsof ionizingradiation, thereforex-rayexposureisaveryusefultechniqueforunderstanding radiation

damageeffectsinTeflon.

2.0Materials

2.1.PRISTINEFEPANDFEPFORX-RAYIRRADIATION

Teflon®FEPisaperfluorinated copolymer oftetrafluoroethylene (TFE)andhexafluoropropylene (HFP).TheFEP

material usedforx-rayirradiationfollowedbyvacuumheattreatment andfornon-irradiated heattreatment testswas

non-aluminized 5-railthick(127gin),andwaspurchased fromSheldahl (lot#96-16).

NASA/TM2002-211704 3
2.2. HSTSM3AA1-FEP

Aspreviouslymentioned, MLIblanketsoriginallyinstalledonHSTonBay10(exposedtothespaceenvironment

for9.7years)and2milA1-FEPpatchesinstalledonBay10duringSM2(exposedfor2.8years)wereretrievedby

astronauts duringservicingmissionSM3A.Figure3ashowsaclose-upoftheMLIandpatchesonBay10priorto

beingremovedfromHST.Fourdifferentmaterialswereretrieved: originalMLIfromthetopsectionofBay10

(TopMLI(TM)),originalMLIfromthebottomsectionofBay10(BottomMLI(BM)),andpatchesinstalledduring

SM2overportionsofTMandBM,designatedasTopPatch(TP)andBottomPatch(BP),respectively. Theouter

mostlayeroftheTMandBMmaterialswas5milthickA1-FEP.Retrievedpatchmaterial was2milthickA1-FEP.

TheA1was=1000A.

SamplesweresectionedfromvariousregionsoftheBM,TP,andBPsurfacesforpost-flight analysesandtheresults

arereportedinreferences 7,8and11.FortheBMsurface, regionsdesignatedasR1andR2refertotheareas

withoutapatchandcoveredbyapatch,respectively. AlargesectionoftheoriginalMLImaterial, whichwasnot

coveredbyapatchandthushadbeenexposedtothespaceenvironment for9.7years(sectionBM-R1),wascut

fromtheMLIblanketandprovidedfortheseheatingstudies.ThissamplesectioncanbeseeninFigure3b.

Becausethislargesamplewassectionedfromtheblanketin2001,whilemostsamplesforpost-flightanalyses

testingweresectionedshortlyaftertheDecember 1999flightin2000,thisparticularsampleisreferredtoasthe

SM3A2001BM-R1sample.The2001BM-R1samplewascarefullyexaminedandthelocationofallimpactsites

andcracksweredocumented inordertoavoidtheseareaswhenpunchingouttensilesamplesorcuttingdensity

samples.

Figure3. HSTEquipment Bay10material: (a)Bay10MLIandpatchesduringSM3Apriortoremoval fromHST,and(b)A

sectionofMLIblanket showingthelocationandsizeoftheSM3A2001BM-R1sample.

NASA/TM2002-211704 4
3.0 The HST Environment

Table 1 provides the space environmental exposure conditions for the retrieved SM2 and SM3A BM-R1 materials.

For the samples, the table lists the direction the surface faces with respect to the coordinate system for HST,

indicated by V2 and V3 axes (described below). The sample retrieved during SM2 faced the +V3 direction, which

is the solar facing surface of Hubble. Because this area had cracked and curled with the FEP surface on the inside of

the curl at some point during the mission, all environmental exposure conditions (except thermal cycling) are

indicated as being some amount less than the values calculated for the entire mission duration. Bay 10 faces the

V2 direction (SADA direction). The environmental exposure conditions of solar exposure hours, solar event x-ray

fluence, electron and proton fluence, and atomic oxygen fluence for FEP surfaces on HST vary depending on the

direction the surface was facing and position of nearby obstructing surfaces, whereas the number of thermal cycles

is independent of direction.

Table 1. Exposure Conditions for Retrieved HST FEP Materials.

Exposure SM2 FEP (LS, +V3) 12 SM3A BM-R1 MLI 7

(Bay 10, _2)

Thermal Cycles/Temperature Range

(cycles/°C)

Equivalent Solar Hours (ESH)

X-ray Fluence (J/m 2)

Electron Fluence (#/cm2), >40 keV

Proton Fluence (#/cm2), >40 keV

37,100_100 to +50°C

100 to +200°C when curled 52,550/ 100 to +50°C

< 33,638 13,598

1-8A*: <209 0.5-4 A*: < 13 1-8A: 62 0.5-4A : 3.9

< 1.95x 1013 2.74x 1013

< 1.95 x 101° 2.77 x 101°

* Values reported in Ref. 12 incorrectly assumed that +V3 surfaces always face direct sun.

Because the Bay 10 MLI surfaces, which approximately faced the V2 direction, were at an oblique angle to the

sun, Bay 10 MLI retrieved at SM3A actually received less equivalent solar exposure than the SM2 sample retrieved

2.8 years earlier. However, the SM3A BM-R1 MLI experienced many more thermal cycles, and higher electron and

proton radiation, and atomic oxygen fluence than the SM2 sample. The exposure levels for various retrieved

materials are affected by the solar activity, and it should be noted that there was a solar minimum between the SM2

to SM3A time period. More details of environmental exposures are provided in references 8 and 12.

4.0 Experimental Procedures

4.1 X-RAY EXPOSURE (PRISTINE FEP)

A modified X-ray photoelectron spectroscopy (XPS) facility was used to irradiate the pristine FEP tensile samples.

A copper target was irradiated with a 15.3 kV, 30 mA electron beam producing Cu x-rays (Cu Kc_ at 8048 eV, Cu L

at 930 eV). The tensile samples were located 30.5 mm from the target, and the Cu x-rays were filtered through a

2 gm A1 window (part of the x-ray tube). A 25 mil (635 gm) thick beryllium filter was placed over the FEP samples

to absorb the low energy Cu L components, which would contribute significantly to damaging only the surface. 13

The x-ray flux was 13.28 W/m2.14 The choice of target material, electron beam energy, and filter was chosen to

produce a high flux, uniform distribution of energy absorbed, versus depth in the film. The energy deposition rate,

or dose rate, versus depth below the surface for 127 gm FEP film at the specified exposure conditions are provided

by de Groh and Gummow in reference 15. The technique used to characterize the x-ray source and energy

deposition within the FEP film is described by Pepper and Wheeler in reference 13. Pepper et al. provide

quantitative characterization of the Cu x-ray source and the absorbed energy deposition rate within a 75 gm film in

reference 14. X-ray irradiated samples were stored under vacuum until they were tensile tested or vacuum heattreated.

NASA/TM 2002-211704 5
Thex-rayexposurewasnotintendedto simulatethefullextentof damageoccurringonHubble,buttocause

irradiationiducedpolymerdamage, andstillhaveenoughelongationatfailureremainingtoseetheeffectsdueto

heating.Basedonaseriesof priortests,it wasdeterminedthata2-hourexposurewouldprovidethedesired

reductionitensileproperties. 15Priortestsalsoindicatedthatthemaximumnumberof samplesthatcouldbe

uniformlyexposedatatimewastwo.Thesampleswerecenteredinaholderthatprovideda2.0x2.0cmexposure

area(thetensilesamplegaugelengthis= 1cm).Thetotalenergyabsorbedperunitareaintegratedthroughthefull

thickness(thearealdose,D)ofthe127gmfilmforthe2-hourexposurewas33.8kJ/m2J6

4.2 VACUUMHEATTREATMENT

PristineFEP,x-rayexposedFEPandHSTSM3AA1-FEPsampleswerevacuumheattreatedfrom50°Cto200°Cin

25°Cintervalsinahighvacuumfacilityadaptedwithatubefurnace.ATeflonlinedCupipewasplacedinsidethe

tubefurnacetopromoteuniformheating.Theexposuretemperature wasmonitoredwithathermocouple attachedto

aTeflonwitnesssample, heldincontact withthetestsamples.Thepressurewas106to 107torrduringheating.

Sampleswereheatedforatargettimeof72hours.

4.3 TENSILEPROPERTIES

Samplesfortensiletestingwere'dogbone'shapedanddie-cutusingatensilespecimendiemanufactured according

toASTMD638-95, typeV. Thetensilesampleswere3.18mmwideinthenarrowsection(neck),witha9.5mm

gaugelength.Samplesweretestedusingabench-toptensiletesterwitha4.54kgloadcellandatestspeedof

1.26cm/min.Ultimatetensilestrength(UTS)andelongationatfailureweredeterminedfromtheloaddisplacement

data.

4.4 DENSITYMEASUREMENTS

Densitymeasurements wereobtainedusingdensitygradient columnscalibratedusingglassfloatstandards ofknown

densities(+0.0001g/cm3).Thedensitysolventsusedwerecarbontetrachloride(CC14, P = 1.594 g/cm 3) and

bromoform (CHBr3, P = 2.899 g/cm3). The presence or absence of the thin (1000 A,) aluminized coating

(as removed by NaOH solution) was found to have no effect on the density of the A1-FEP samples.

5.0 Results and Discussion

5.1 ROOM TEMPERATURE TENSILE PROPERTIES

5.1.1 Pristine FEP

The room temperature (23°C) tensile data for pristine FEP are listed in Table 2. The UTS and percent elongation at

failure for 13 pristine FEP samples, was 24.1 + 1.5 MPa and 271.2 + 16.9%, respectively.

5.1.2 HST SM3A AI-FEP

The retrieved SM3A Teflon from HST, after 9.7 years in the space environment, is substantially degraded. The

tensile results for the as-retrieved SM3A FEP are listed in Table 2. If compared to the pristine FEP tested in this

study, the UTS of the retrieved HST FEP has decreased from 24.1 to 13.9 MPa, and the elongation at failure has

decreased from 271.2% to 55.3%. These correspond to decreases of 42.3% and 79.6%, respectively. These tensile

properties provide insight into the damage mechanism of Teflon in space. Because the UTS decreased, with the

decrease in elongation at failure of the space-exposed FEP, chain scission is identified as the primary degradation

mechanism on HST.

NASA/TM 2002-211704 6
Table2.TensileProperties ofVacuumHeat-Treated Pristine, X-rayIrradiated

madHSTRetrieved TeflonFEP.

VacuumHeat

Treatment

Temperature

Room

Temperature

23°C

Number of %Elongation Material Samples UTS(MPa) atFailure

PristineFEP 13 24.1+ 1.5 271.2 + 16.9

X-ray FEP 10 17.1 + 1.5 212.7 + 31

HST A1-FEP 4 13.9 + 0.4 55.3 + 9.3

Pristine FEP 4 23.4 + 0.7 264.1 + 12.6

50°C

(_+1oc) X-ray FEP 4 15.1 _+1.1 162.6 _+35.5

HST A1-FEP 4 13.9 _+0.3 46.5 _+4.1

Pristine FEP 6 22.5 _+1.5 259.6 _+14.2

75°C

(+ 2oc) X-ray FEP 8 15.3 + 0.2 134.9 + 46.3

HST A1-FEP 4 14.4 + 0.1 25.7 + 5.5

Pristine FEP 4 22.1 + 0.7 250.2 + 5.7

IO0°C

(+ loc) X-ray FEP 4 15.5 + 0.3 43.1 + 6.6

HST A1-FEP 4 14.5 + 0.2 10.4 + 1.1

Pristine FEP 4 22.5 + 0.8 254.7 + 8.3

125°C

(+ loc) X-ray FEP 4 15.8 + 0.2 23.8 + 4.9

HST A1-FEP 3 14.2 + 0.7 9.4 + 3.3

Pristine FEP 4 22.8 + 0.6 271.0 + 6.4

150°C

(+ 3oc) X-ray FEP 4 15.4 + 0.3 22.8 + 5.6

HST A1-FEP 4 14.2 + 0.3 8.7 + 4.2

Pristine FEP 3 22.1 + 0.8 287.4 + 11.1

175°C

(+ 12oc ) X-ray FEP 4 16.4 + 0.8 15.2 + 3.5

HST A1-FEP 4 14.9 + 0.8 7.9 + 2.0

Pristine FEP 4 23.7 + 0.8 306.8 + 9.6

200°C

(+ 4oc) X-ray FEP 2 16.1 + 0.4 9.7 + 5.2

HST A1-FEP 3 14.5 + 0.5 4.5 + 0.9

5.1.3 X-Ray Irradiated FEP

After x-ray exposure, the UTS and percent elongation at failure for 10 samples was 17.1 + 1.5 MPa and 212.7 +

31%, respectively. This is a 29.0% reduction in the UTS and a 21.6% reduction in percent elongation at failure due

to irradiation embrittlement. Density tests were conducted on pieces sectioned from a 200°C heated irradiated

tensile sample and indicated that the x-ray exposure was uniform across the length of the exposed area.

Although it was not the goal of this study to try to simulate the extent of damage on HST with the x-ray exposure, it

was decided to compare the areal dose for x-ray irradiated FEP with that experienced by the FEP on HST. The areal

dose for the 5 mil thick HST SM3A FEP is provided in Table 3.17 The total areal dose for the SM3A BM-R1 FEP

was 427.2 J/m 2. It should be noted that the HST FEP has an elongation at failure of 55% with an areal dose of only

427 J/m 2, while the x-ray exposed FEP was much less embrittled (213% elongation), after orders of magnitude

higher areal dose (33,800 j/m2). The factors that could contribute to these differences include the extreme

differences in the dose rates (i.e., time factor), the variation in ionizing species and energies, temperature differences

during irradiation exposure and the contribution from thermal cycling on HST (52,550 cycles from 100 to +50°C),

and possibly, surface effects from atomic oxygen and UV exposure in space. This stresses the difficultly in

conducting simulated space environment durability tests, and emphasizes the potential complication when

conducting durability testing based strictly on expected mission fluence or dose values.

Table 3. Areal Dose for HST SM3A FEP.

SM3A BM-R1 MLI (Bay 10, V2) Areal Dose (J/m 2)

X-rays, 1 to 8 A 29.80

X-rays, 0.5 to 4 A 0.72

Electrons, >40 keV 389.6

Protons, >40 keV 7.11

NASA/TM 2002-211704 7
5.2VACUUMHEATTREATMENT

5.2.1 Tensile Properties

The results of tensile tests for the pristine, ground-laboratory irradiated and HST FEP after vacuum heat treatment

are listed in Table 2 along with the room temperature data. The data are graphed in Figure 4. There was no

degradation in the tensile properties of vacuum heat-treated non-irradiated FEP, in fact, with this batch of FEP an

increase in the percent elongation at failure was observed for the higher temperatures (175 and 200°C). Although

heat treatment did not cause much change in the UTS of x-ray irradiated FEP with vacuum heat treatment, there was

a dramatic decrease in the percent elongation at failure, as can be seen in Figure 4. The elongation decreased from

212.7% at 23°C to only 9.7% after 200°C exposure. This corresponds to a 95% decrease. And as can be seen in the

graph, there is a rapid decrease in the elongation from 23°C to 100°C, with near complete losses of elongation from

125°C to 200°C. Only two of the original four x-ray samples heated to 200°C could be tensile tested because two

stuck together slightly during heating and then broke during separation.

Although the FEP retrieved from HST was significantly embrittled in its as-retrieved condition, it became even more

embrittled with vacuum heat treatment (even after vacuum heat treatment at 50°C, the maximum on-orbit

temperature). The space-exposed HST FEP followed a similar trend as the ground-laboratory x-ray irradiated FEP,

showing little changes in UTS and decreases in elongation from 23°C to 100°C, with near complete loss of

elongation with heating at 100°C and higher.

350

300

250

o

g 200

,- 150

0

cO 100

I.IJ

50

zx 2X

0 Pristine

o X-ray

zx HST

i

0 25 50 75 1O0 125 150 175 200

Vacuum heat treatment temperature, °C

Figure 4. Percent elongation at failure of pristine, ground laboratory x-ray exposed and retrieved HST Teflon FEP as a function

of vacuum heat treatment temperature.

5.2.2 Density

The density data for the pristine, ground-laboratory irradiated and HST space irradiated FEP, at room temperature

and after vacuum heat treatment, are listed in Table 4. The data are graphed in Figure 5. The standard deviation is

given when more than one sample was measured and averaged. As can be seen in the graph, the density of the

retrieved HST FEP is essentially the same as pristine FEP, and the room temperature x-ray irradiated FEP is just

slightly more dense than pristine FEP, even though these irradiated samples are significantly embrittled. This

indicates that although irradiation induces scission in the polymer chains, resulting in embrittlement, the actual

packing of the chains is not affected by irradiation exposure.

NASA/TM 2002-211704 8
Therewereverygradual increasesinthedensitywithheatingupto 75°Cforall samples. Significant increases

startedat100°C,withlargerincreasescorresponding tohighertemperatures. Althoughthedensityincreasedwith

temperatureforall samples, largerincreasesoccurredataparticulartemperatureforthesamplesthathadbeen

irradiatedeitherinspaceorinthegroundfacilitythanforpristineFEP.Theseresultsareconsistent withdeGroh's

previousstudiesthatshowpristineFEPincreases indensitywithheating, butFEPfromHSThasgreaterincreases in

densityforthesameheattreatment (200°Cexposure, reference7and9).Thisisattributedtoirradiation-induced

scissionofbondsinspace, whichallowsforgreatermobilityandcrystallization uponheatingthanthatwhichoccurs

withnon-irradiated FEP.Previousx-raydiffractionstudiesverifythatheincreasesindensitycorrelateoincreases

in polymercrystallinity. 7'9Thedensityresultsfurthersupportchainscissionastheprimarymechanismof

degradation ofFEPinthespaceenvironment.

Table 4. Density Data of Vacuum Heat-Treated Pristine, X-Ray Irradiated and HST Retrieved Teflon FEP.

HST FEP

Temperature Pristine FEP X-Ray FEP [SM3A 2001 BM-R1)

(°C) Density Std. Density Std. Density Std.

(g/cm 3) Dev. (g/cm 3) Dev. (g/cm 3) Dev.

23 2.1373 0.0011 2.1407 2.1376 0.0005

50 2.1379 2.1414 2.1376 0.0005

75 2.1379 2.1428 2.1389 0.0005

100 2.1393 2.1477 2.1407

125 2.1414 2.1585 2.1456

150 2.1473 2.174 2.1577

175 2.1507 2.1775 2.1647 0.0016

200 2.1631 2.1856 2.1696 0.0031

2.19

2.18

2.17

E

2.16

ell)

a

2.15

2.14

2.13

0 Pristine

o X-ray

_x HST

0

0 0

0

A

0

0

A

0

<>

I I I I I I I I

0 25 50 75 1 O0 125 150 175 200

Vacuum heat treatment temperature, °C

Figure 5. Density of pristine, ground laboratory x-ray exposed mad retrieved HST FEP as a function of vacuum heat treatment

temperature.

NASA/TM 2002-211704 9
Whencomparingthecurvesfortheelongationanddensitydata,it wasobservedthatineachsetof datathere

appearedtobeanoticeablechangeintheslopeofthedataaround100°C.Thedatawasthereforegraphedwith

linearfitsfortwosectionsofthedata.Thelineschosenwerebasedonthebestfit foreachindividual sectionof

data.TheresultingcurvesfortheelongationatfailureanddensitydataareshowninFigures6and7,respectively.

The"change-of-slope" temperature hasbeenhighlightedinthesegraphsattheintersectionofthetwolinearfits.

Thechange-of-slope temperature ofthepristineFEP(115°Cfortheelongationdataand126°Cforthedensitydata)

correlateswellwiththeglassI transitiontemperature (c_relaxation), whichislistedfrom= 83°Cto 150°Cinthe

literature, dependent onhexafluoropropylene (HFP)content. 9 EbyandWilsonreporttransitiontemperatures for

FEPwithdensities(2.136to 2.135g/cm3)similartothepristineFEPexaminedin thisreportat= 150°Cand

127°Cfor10.7and17.7mol%HFP,respectively. 18CommerciallyavailableFEPisreportedtobe20mol%

HFP,19whichwouldindicatethathetransitiontemperature forpristineFEPwouldbecloseto 125°Cbasedonthe

Ebystudy,whichisconsistent withthechange-of-slope temperatures forthepristineFEP.Anotherinteresting

observation isthattheirradiatedsampleshavelowerchange-of-slope temperatures thanpristineFEP.Forexample,

thetemperatureinwhichthedensityoftheground-laboratory irradiatedFEPstartstoincreasequicklyis 82°C,

whileit is 100°CfortheHSTretrievedFEPand126°CforpristineFEP.Theseresultsindicatethatirradiation

causeschangesinthepolymerstructureallowingincreasesincrystallization tooccuratalowertemperature than

whichit occursinpristineFEP.

o

II1

Q.

g

.-i

2

eO

e-

_o

ILl

350

300

250

Pristine

~115

200 <> Pristine

o X-ray

150 _ X-ray A HST

_o ~115.5

HST

,oo /

20 40 60 80 100 120 140 160 180 200

Vacuum heat treatment temperature, °C

Figure 6. Change in the slope of the percent elongation at failure data of pristine, ground laboratory x-ray exposed and retrieved

HST FEP as fimction of vacuum heat treatment temperature.

NASA/TM 2002-211704 10
¢o

E

t))

II1

a

2.19

2.18

2.17

2.16

2.15

2.14

2.13

2.12

2.11

2.10

Pristine ///_

o X-ray /o0

a

A

 -- Zne

X-ray | ~126

~82 HST

~1O0

20 40 60 80 1 O0 120 140 180 180 200

Vacuum heat treatment temperature, °C

Figure 7. Change in the slope of the density data of pristine, ground laboratory x-ray exposed and retrieved HST FEP as function

of vacuum heat treatment temperature.

6.0 Summary and Conclusions

The objective of this research was to determine the effects of heating on ground laboratory irradiated FEP and FEP

retrieved from the Hubble Space Telescope, in order to better understand the effect of temperature on the rate of

degradation, and on the mechanism of degradation, of this insulation material in the LEO environment. Samples of

pristine FEP, x-ray irradiated FEP and HST SM3A-retrieved FEP were heated from 50°C to 200°C in 25°C intervals

in a high vacuum furnace and evaluated for changes in tensile properties and density. Results indicate that although

heating does not degrade the tensile properties of non-irradiated Teflon, there is a significant dependence on the

degradation of the percent elongation at failure of irradiated Teflon as a function of heating temperature, with

dramatic degradation occurring at 100°C and higher exposures. The density of non-heated irradiated FEP (ground

or space irradiated) was essentially the same as pristine FEP, although these samples are significantly embrittled.

This indicates that irradiation induces scission in the polymer chains, resulting in embrittlement, but chain packing is

not affected. Gradual increases in the density occurred with heating from 23°C to 75°C for all samples, with

significant increases occurring at 100°C and higher exposures. Larger increases occurred for the irradiated samples

than for the pristine FEP. These results were consistent with previous studies that show pristine FEP increases in

density with heating, but irradiated FEP experiences greater increases for the same heat treatment. This is attributed

to irradiation-induced scission of bonds, which allows for greater mobility and crystallization upon heating than that

which occurs with non-irradiated FEP. Changes in the rate of degradation were present in both elongation and

density data. The change-of-slope temperatures of pristine FEP (115°C for elongation and 126°C for density)

correlate with the glass I transition temperature of FEP. The change-of-slope temperature of irradiated FEP was

lower than for pristine FEP, further indicating that scission damage has occurred. The tensile results and heated

density data support chain scission as the primary mechanism of degradation of FEP in the space environment. The

results show the significance of the on-orbit service temperature of FEP with respect to its degradation in the LEO

space environment.

NASA/TM 2002-211704 11
7.0 References

1. P.A. Hansen, J.A. Townsend, Y. Yoshikawa, D.J. Castro, J.J. Triolo, and W.C. Peters SAMPE International Symposium,

43,570, (1998).

2. J.H. Henninger, NASA RP 1121, 1984.

3. K.K. de Groh and D.C. Smith, NASA TM 113153, 1997.

4. T.M. Zuby, K.K. de Groh, and D.C. Smith, ESA WPP 77,385 (1995); NASA TM 104627, Dec. 1995.

5. M. Van Eesbeek, F. Levadou, and A. Milintchouk, ESA WPP_7, 403 (1995).

6. J.A. Townsend, P.A. Hansen, J.A. Dever, K.K. de Groh, B.A. Banks, L. Wang and C. He, High Perform. Polym. 11, 81 99

(1999).

7. K.K. de Groh, J.A. Dever, J.K. Sutter, J.R. Gaier, J.D. Gummow, D.A. Scheiman, and C. He, High Perform. Polym. 13,

$401 $420 (2001).

8. J.A. Dever, K.K. de Groh, R.K. Messer, M.W. McClendon, M. Viens, L.L. Wang. and J.D. Gummow, High Perform.

Polym. 13, $373 $390 (2001).

9. K.K. de Groh, J.R. Gaier, R.L. Hall, M.P. Espe, D.R. Cato, J.K. Sutter and D.A. Scheiman, High Perform. Polym. 12,

83 104 (2000).

10. B.A. Banks, K.K. de Groh, T.J. Stueber, E.A. Sechkar, and R.L. Hall, SAMPE International Symposium, 43, 1523 (1998);

also NASA/TM 1998-207914/REV1.

11. J.R. Blackwood, J.A. Townsend, P.A. Hmasen, M.W. McClendon, J.A. Dever, K.K. de Groh, B.B. Reed, C.C. He, and

W.C. Peters, SAMPE 2001 Conference Proceedings, May 6 10, 2001, Long Beach, CA, pp. 1797 1810.

12. J.A. Dever, K.K. de Groh, B.A. Banks, J.A. Townsend, J.L. Baxth, S. Thomson, T. Gregory, and W. Savage, High Perform.

Polym. 12, 125 139 (2000).

13. S.V. Pepper mad D.R. Wheeler, Review of Sci. Instruments, Vol. 71, No. 3, March 2000, 1509 1515.

14. S.V. Pepper, D.R. Wheeler, and K.K. de Groh, Proceedings of the 8th ISMSE and 5th ICPMSE Conference June 5 9, 2000,

Arcachon, France.

15. K.K. de Groh and J.D. Gummow, High Perform. Polym. 13, $421 $431 (2001).

16. S.V. Pepper, NASA Glenn Research Center, personal communication (1999).

17. Joyce Dever, NASA Glenn Research Center, personal communication (2002).

18. R.K. Eby and F.C. Wilson, J. of Applied Physics, 33, 2951 55 (1962).

19. Don Farrelly, DuPont, personal communication (1999).

NASA/TM 2002-211704 12
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1. AGENCY USE ONLY (Leave blank) 2. REPORT DATE 3. REPORT TYPE AND DATES COVERED

July 2002 Technical Memorandum

4. TITLE AND SUBTITLE 5. FUNDING NUMBERS

The Effect of Heating on the Degradation of Ground Laboratory and Space

Irradiated Teflon ® FEP

6. AUTHOR(S)

Kim K. de Groh and Morgana Martin

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration

John H. Glenn Research Center at Lewis Field

Cleveland, Ohio 44135-3191

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration

Washington, DC 20546-0001

WIJ-755-A4-06-00

8. PERFORMING ORGANIZATION

REPORT NUMBER

E- 13449

10. SPONSORIN G/MONITORING

AGENCY REPORT NUMBER

NASA TM--2002-211704

11. SUPPLEMENTARY NOTES

Prepared for the Sixth International Conference on Protection of Materials and Structures From Space Environment

cosponsored by the ITL, UTIAS, MMO, AFOSR/NL, CRESTECH, EMS Technologies, and MDRobotics, Toronto,

Canada, May 1-3, 2002. Kim K. de Groh, NASA Glenn Research Center, and Morgana Martin, Ohio Aerospace

Institute, Brook Park, Ohio 44142. Responsible person, Kim K. de Groh, organization code 5480, 216-433-2297.

12a. DISTRIBUTION/AVAILABILITY STATEMENT

Unclassified - Unlimited

Subject Categories: 18 and 27 Distribution: Nonstandard

Available electronically at hltp:/Igltrs.grc.na_sa.gov/G[2I'RS

This publication is available from the NASA Center for AeroSpace Information, 301-621-0390.

12b. DISTRIBUTION CODE

13. ABSTRACT (Maximum 200 words)

The outer most layer of the multilayer insulation (MLI) blankets on the Hubble Space Telescope (HST) is back surface aluminized Teflon ® FEP

(fluorinated ethylene propylene). As seen by data collected after each of the three servicing missions and as observed during the second servicing mission

(SM2), the FEP has become embrittled in the space environment, leading to degradation of the mechanical properties and severe on-orbit cracking of the

FEP. During SM2, a sample of alummized-FEP was retrieved from HST that had cracked and curled, exposing its aluminum backside to space. Because

of the difference in optical properties between FEP and aluminum, this insulation piece reached 200 °C on-orbit, which is significantly higher than the

nominal MLI temperature extreme of 50 °C. This piece was more brittle than other retrieved material from the first and third servicing missions (SM1 and

SM3A, respectively). Due to this observation and the fact that Teflon thermal shields on the solar array bi-stems were heated on-orbit to 130 °C,

experiments have been conducted to determine the effect of heating on the degradation of FEP that has been irradiated in a ground laboratory facility or in

space on HST. Teflon FEP samples were x-ray irradiated in a high vacuum facility in order to simulate the damage caused by radiation in the space

environment. Samples of pristine FEP, x-ray irradiated FEP and FEP retrieved from the HST during SM3A were heat treated from 50 to 200 °C at 25 °

intervals in a high vacuum facility and then tensile tested. In addition, samples were tested in a density gradient column to determine the effect of the

radiation and heating on the density of FEP. Results indicate that although heating does not degrade the tensile properties of non-irradiated Teflon, there is

a significant dependence of the percent elongation at failure of irradiated Teflon as a function of heating temperature. Irradiated Teflon was found to

undergo increasing degradation in the elongation at failure as temperature was increased from room temperature to 200 °C. Rate of degradation changes,

which were consistent with the glass I transition temperatures for FEP, appeared to be present in both tensile and density data. The results indicate the

significance of the on-orbit temperature of Teflon FEP with respect to its degradation in the low Earth orbital space environment.

14. SUBJECT TERMS

Hubble Space Telescope; Teflon®; Multilayer insulation; Embrittlement; Environment

effects; X-ray irradiation; Thermal vacuum tests; Temperature effects

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OF REPORT OF THIS PAGE OF ABSTRACT

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