Greenhouse Gas Reporting ProgramGreenhouseGasReportingProgramElectronics Manufacturing (Subpart I)Greenhouse Gas Reporting ofHeat Transfer FluidsKurt Werner, ktwerner@mmm.com651-733-84943M Electronics Markets Materials Division (EMMD)January 2011ElectronicsPresentation OverviewPresentationOverview•3M’Evolution of fluorinated fluidssEvolutionoffluorinatedfluids• Subpart I source categories•Relevant definitions and applicationsRelevantdefinitionsandapplications– Fluorinated GHG–Heat transfer fluid• Fluorinated heat transfer fluids–Chemical categories,suppliers,brands, pp ,• Likely consequences of Subpart I on reporting andfuture GHG emissions from heat transfer fluid use.Electronics23M Response to Environmental IssuesImpacting the Solvent MarketImpactingtheSolventMarketOzone DepletionClimate ChangePhotochemical SmogReplacement Materials for PFCs,SF6 CFC HCFC d HFCAir ToxicsSF6,CFCs,HCFCs, andHFCsIR RadiationGlobal WarmingVOC SmogCl + O3.OzoneDepletionElectronicsBoiling Point of Product FamiliesPFCsODSs, HFCs& HAPsNovec FluidsFC-3283PERC140120Novec-7500 130°PF-5070PF-5080TCAC3H7BrTCE1008 0Novec-720076°Novec-7300100PF-5060CFC-113HCFC-141bHCFC-225C3H7Br6 04 0Novec720076Novec-7100 61°Novec 1230 fluid49°PF-5050HCFC141b402 0Novec-7000 34°Novec 612, 64949HFC-227&HFC125CEA-410C3F8/C4F8OElectronicsBoiling Point in°C&HFC-125halonC3F8 /C4F8OGeneral Phys Chem Properties of 3M fluorinated fluidsNon-flammableThermally stableHigh purityHighpurityLow in toxicityHigh DensityL Vi itLowViscosityLow Surface TensionLow Heat of VaporizationNon-conductiveNon-corrosiveChemical stabilityElectronicsChemicalstabilityNovec FluidsHydrofluoroethersCFluoroketonesFOElectronicsSpecialty Chemicals Mix in % Sales (Feb 2010)90%100%60%70%80%

%PFC's40%50%60%

Percent %PFC'sGasNovec10%20%30%0% 1993 1 9 9 5 1997 1 9 99 2 0 0 1 2003 2005 2 0 0 7 2009ElectronicsSubpart I Source CategorySubpartISourceCategory• Consists of anyof the 5 followingproductionprocessesgp pthat usefluorinated GHGs* or N2 O. Facilities that usethese processes include, but are not limited to thosefacilities that manufacture MEMS LCDs PV andfacilitiesthatmanufactureMEMS,LCDs,PV,andsemiconductors (including LEDs):– Plasma etching;– Chamber cleaning;– Wafer cleaning;–Chemical vapor deposition;andp ;–Heat transfer fluiduseElectronics8Subpart I•Heat Transfer Fluids are Fluorinated GHGsHeatTransferFluidsareFluorinatedGHGsused for:–temperature controltemperaturecontrol,– device testing, and–soldering• Heat transfer fluids used in the electronicssector includeperfluoropolyethers,sectorincludeperfluoropolyethersperfluoroalkanes, perfluoroethers, tertiaryperfluoroamines, andperfluorocyclicethers.Electronics,andperfluorocyclicethers.9Fluorinated GHGFluorinatedGHG•Fluorinatedgreenhousegasmeans sulfur hexafluorideg(SF6), nitrogen trifluoride (NF3), and any fluorocarbonexcept for controlled substances as defined at 40 CFRpart 82 subpart A and substanceswith vapor pressurespart82,subpartAandsubstanceswithvaporpressuresof less than 1 mm of Hg absolute at 25 degrees C.Withthese exceptions, ‘‘fluorinated GHG’’ includes but is notf flimited to any hydroluorocarbon, any perfluorocarbon,any fully fluorinated linear, branched or cyclic alkane,ether,tertiaryamine or aminoether,anyy ,yperfluoropolyether, and any hydrofluoropolyether.Electronics10Heat Transfer Fluid Use inSemiconductor Manufacturing– Fluorinated Heat Transfer Fluids• Perfluorocarbons (PFCs) and Perfluoropolyethers (PFPEs)Sold by 3M under trade nameFluorinertTM–Soldby3MundertradenameFluorinert– Sold by Solvay under trade nameGaldenTM– GWPs>10,000• Hydrofluoropolyethers (HFPEs)–Sold bySolvayunder trade nameH-GaldenTMy– GWPs 3000 - 5000• Segregated Hydrofluoroethers (HFEs)– Sold by 3M under trade nameNovecTM– GWPs 55 - 290Electronics11PFCs and Hydrofluoroethers (HFEs)3M has developed the NovecTM product line to replace PFCswhere possiblewherepossiblePerformance FluidTM (PF)Product Code b.p. [°C] GWPFC 8 PF 0 03010 000FC-87,PF-5050,FC-3284, PF-5052 49 10,000FC-72, PF-5060 56 10,000FC-84, PF-5070 80 10,000FC-3255, FC-10410010,000Product Code b.p. [°C]GWPNovec 649 49 1HFE-7100 61 290FC 3255,FC 10410010,000FC-770 100 10,000FC-3283 128 10,000FC-8270 130 10,000FC-40 155 10,000HFE-7200 76 55HFE-7300 100 210HFE-7500 130 100FC-5311 174 10,000FC-43 174 10,000FC-70 215 10,000FC-5312 215 10,000GHGs exempt from reportingElectronics12Phased out before 2008Perfluoropolyethers (PFPEs) andHydrofluoropolyethers (HFPEs)Sold under TradenamesGaldenTM (HT)H d fl l thHydrofluoropolyethers(HFPEs)Product Code b.p. [°C] GWPHT-55 55 10,000HT-70 70 10,000E85 80 10,000HydrofluoropolyethersSold under Tradename H-GaldenTMProduct Code b.p. [°C] GWPZV60603000 000HT-90 90 10,000DET 91 10,000HT-110 110 10,000HT-135 135 10,000HT-17017010,000ZV60603000-5000ZV85 85 3000-5000ZV100 100 3000-5000ZV135 135 3000-5000ZT-130 100 3000-5000HT 17017010,000DO2-TS 165 10,000DO2 175 10,000HT-200 200 10,000LS-200 200 10,000ZT-150 130 3000-5000ZT-180 175 3000-5000DO3 203 10,000LS-215 215 10,000DO5 230 10,000LS230 230 10,000HS-24024010 000Heat transfer fluids exempt from reportingElectronics13HS 24024010,000HS-260 260 10,000GWP Range for Different Chemical ClassesPFCs, PFPEsHFPEsnon-flammable segregated HFEsnon-flammable HFCsElectronics140 2,000 4,000 6,000 8,00010,000 12,000 14,000 16,000Unintended Consequences of Subpart IUnintendedConsequencesofSubpartI•All the materials exempt from reporting have GWPs in the range ofAllthematerialsexemptfromreportinghaveGWPsintherangeof10,000x CO2e• All the low GWP substitutes will need to be reported as GHGs•There is already substantial use of heat transfer fluids that will beThereisalreadysubstantialuseofheattransferfluidsthatwillbeexempt from reporting (~50 %) and the market will increasinglymove to fluids that are exempt from reporting.•Selection of fluid based on reporting requirements will lead toSelectionoffluidbasedonreportingrequirementswillleadtoreduced energy efficiency (use of higher boiling fluids used at lowertemperatures)•The GHG reporting rule will likely result in dramatically increasedTheGHGreportingrulewilllikelyresultindramaticallyincreased(~100X) GHGs from these applications than otherwise would haveoccurred.Electronics15Vapor Phase SolderingVaporPhaseSoldering•Fluids are heated to boiling pointFluidsareheatedtoboilingpoint,therefore, they are used at 1 atm. vaporpressure.• At 25 degrees C. none of the fluids usedfor vapor phase soldering have vaporforvaporphasesolderinghavevaporpressures greater than 1 mmHg.N GHG i i f h•NoGHGemissionsfrom vapor phasesoldering will be reported.Electronics16IPCC and CARB benchmarking• IPCC reporting methodology does not narrowthe definition of heat transfer fluid via a vaporthedefinitionofheattransferfluidviaavaporpressure threshold.•Relevant CARB definitions:RelevantCARBdefinitions:– “Fluorinated Gases” means a compound that contains fluorineand exists in a gaseous state at 25 degrees Celsius and 1atmosphere of pressure. Fluorinated gases include, but are notlimited to: (A) hexafluoroethane (C2F6), (B) octafluoropropane(C3F8), etc.”– “Heat Transfer Fluid” means afluorinated fluid which prevents adevice, such as a semiconductor,from overheating by removingElectronicsexcess heat produced during a manufacturing process.”17Correcting the IssueCorrectingtheIssue• 98.92 GHGs to report.• (a) You must report emissions of fluorinated GHGs (asdefined in § 98.6) and N2O. The fluorinated GHGs thatitt d f l t i f t i d tiare emittedfrom electronics manufacturing productionprocesses include, but are not limited to, those listed inTable I–2 to this subpart. You must individually report, asappropriate:• (5) Any fluorinated GHG used as a heat transfer fluid.For purposes of this subparagraph the exception in theForpurposesofthissubparagraph,theexceptioninthedefinition of fluorinated GHGs in § 98.6 for substanceswith vapor pressures of less than 1 mm of Hg absolute atElectronics25 degrees C does not apply.18Summary• Vapor pressure of heat transfer fluids at 25 C is not predictive ofemissions.• Subpart I will increasingly lead to use of HTFs exempt fromreporting.• The exempt fluids have GWPs 100xhigher than fluids that must bereported as GHGs.• Systems will likely operate with less energy efficiency.• The GHG reportingrule will likelylead to increased GHG emissionsg yfrom this sector.• 3M would like to work with EPA to correctthe issueElectronics19Back-upElectronics20Publication AvailableElectronics21PFC Heat Transfer Fluid Use inSemiconductor Manufacturing• Heat Transfer Fluid Requirements– Dielectric or non-conductive• To keep the device being cooled electrically isolated• PFCs have electrical resistivity 7 orders of magnitude higher than DI Water– Non-contaminating• Volatile fluorinated fluids evaporate, leaving no residue–Temperaturerangepe a u e a ge• -100C to ~260C - Depends upon the application• The temperature range of applicationshas grown considerably in 20 years– Microwave Transparency•PFCs are transparent to microwave radiationPFCsaretransparenttomicrowaveradiation.– Thermal Stability• PFCs are among the most thermally stable organics fluids– Chemical Inertness•PFCs will not contaminate processes within thefabPFCswillnotcontaminateprocesseswithintheBecause Heat transfer fluids are used at elevated temperatures and pressures,vapor pressure at 25 deg C is not predictive of emissions Their fate is the atmosphereElectronics22vaporpressureat25degCisnotpredictiveofemissions.Theirfateistheatmosphere.Operating Temperature Range of Various CoolantsElectronics23