Greenhouse Gas Reporting Program Greenhouse Gas Reporting Program

Electronics Manufacturing (Subpart I)

Greenhouse Gas Reporting of 

Heat Transfer Fluids

Kurt Werner, ktwerner@mmm.com

651-733-8494

3M Electronics Markets Materials Division (EMMD)

January 2011

Electronics
Presentation Overview Presentation Overview

• 3M s’ Evolution of fluorinated fluids Evolution of fluorinated fluids• Subpart I source categories• Relevant definitions and applications Relevant definitions and applications

– Fluorinated GHG– Heat transfer fluid

• Fluorinated heat transfer fluids

– Chemical cate

g , pp , ories, suppliers, brands

• Likely consequences of Subpart I on report

future GHG emissions from heat transfer flu

Electronics

2
3M Response to Environmental Issues 

Impacting the Solvent Market Impacting the Solvent Market

Ozone DepletionClimate ChangePhotochemical Smog

Replacement Mater

Air Toxics SF6 CFC HCFC 

SF6, CFCs, HCFCs

IR Radiation

Global Warmin

g

VOC Smog

Cl + O .

3

Ozo

Depl

Electronics
Boiling Point of Product Famili

ODSs, HFCs PFCs& HAPs 

Novec 

FC-3283

PERC

140120

Novec-7500 

PF-5070

PF-5080

TCA 

C

3

H

7Br

TCE 

100

8 0 Novec

-7200 

Novec-7300 

CFC-113 PF-5060

HCFC

-141b

HCFC-225 

C

3

H

7Br

6 04 0

Novec 7200 Novec-7100 

Novec 1230 fl

PF-5050

HCFC 141b

4

0

2 0 Novec-7000 

Novec 612, 64

HFC-227 &HFC 125

CEA-410 C3F8/C4F8O

Electronics Boiling Point in 

°

C

&HFC

-125

halon

C3F8 /C4F8O
General Phys Chem Properties of 3M fluorinate

 Non-flammable Thermally stable High purity High purity Low in toxicity High Density L Vi it Low Viscosity Low Surface Tension Low Heat of Vaporization Non-conductive Non-corrosive Chemical stability

Electronics

Chemical stability
Novec Fluids

Hydrofluoroethers

Fluoro

Electronics
Specialty Chemicals Mix in % Sales (Feb 2010)

90%

100%

60%70%80%

%

40%50%60%

Percent %

10%20%30%

0%

1993

1995

1997

1999

2001

2003

2005

2007

2009

Electronics
Subpart I Source Catego

Subpart I Source Catego

• Consists of an

y gp p of the 5 followin

g

production 

pro

that use fluorinated GHGs* or N2 O. Facilities t

these processes include, but are not limited to th

facilities that manufacture MEMS LCDs PV anfacilities that manufacture MEMS, LCDs, PV, an

semiconductors (including LEDs):

– Plasma etching;– Chamber cleaning;– Wafer cleaning; – Chemical va

pp ; or de

position; and 

– Heat transfer fluid use

Electronics

8
Subpart I

• Heat Transfer Fluids are Fluorinated 

Heat Transfer Fluids are Fluorinated 

used for:

– temperature control temperature control,

– device testing, and 

– soldering

• Heat transfer fluids used in the electr

sector include sector include perfluoropolyethers perfluoropolyethers,

perfluoroalkanes, perfluoroethers, ter

perfluoroamines, and perfluorocyclic 

Electronics

, and perfluorocyclic 

9
Fluorinated GHG Fluorinated GHG

• Fluorinated 

g g reenhouse 

gas means sulfur hexaf

(SF6), nitrogen trifluoride (NF3), and any fluorocexcept for controlled substances as defined at 4part 82 subpart A and substances part 82, subpart

A and substances with vapor pr

with vapor pr

of less than 1 mm of Hg absolute at 25 degrees these exceptions, ‘‘fluorinated GHG’’ includes bu

limited to any hydrof f luorocarbon, any per

fluoroc

any fully fluorinated linear, branched or cyclic alether, y ,y tertiar

y amine or aminoether, an

y

perfluoropolyether, and any hydrofluoropolyethe

Electronics 10
Heat Transfer Fluid Use in 

Semiconductor Manufacturin

g

– Fluorinated Heat Transfer Fluids

• Perfluorocarbons (PFCs) and Perfluoropolyethers (PFPEs)

– Sold by 3M under trade name Sold by 3M under trade name Fluorinert Fluorinert

TM

– Sold by Solvay under trade name GaldenTM– GWPs>10,000

• Hydrofluoropolyethers (HFPEs)

– Sold b

y y Solva

y under trade name H-GaldenTM

– GWPs 3000 - 5000

• Segregated Hydrofluoroethers (HFEs)

– Sold by 3M under trade name NovecTM– GWPs 55 - 290

Electronics 11
PFCs and Hydrofluoroethers (HF

3M has developed the NovecTM product line to replac

where possible where possible

Performance FluidTM (PF)Product Code b.p. [°C] GWPFC 8 PF 0 0 FC-87, PF-5

0

5

0 30 10 000 ,

FC-3284, PF-5052 49 10,000FC-72, PF-5060 56 10,000FC-84, PF-5070 80 10,000FC-3255, FC-104 100 10,000

Product Code b.p. [°C] GWPNovec 649 49 1HFE-7100 61 290 FC 3255, FC 104 100 10,000

FC-770 100 10,000FC-3283 128 10,000FC-8270 130 10,000FC-40 155 10,000

HFE-7200 76 55HFE-7300 100 210HFE-7500 130 100

FC-5311 174 10,000FC-43 174 10,000FC-70 215 10,000FC-5312 215 10,000

GHGs exempt from reporting

Electronics 12

Phased out before 2008 
Perfluoropolyethers (PFPEs) and 

Hydrofluoropolyethers (HFPEs)

Sold under TradenamesGaldenTM (HT)

H d fl l th

Hydrofluoropolyethers (HFPEs)

Product Code b.p. [°C] GWPHT-55 55 10,000HT-70 70 10,000E85 80 10,000

H

y

drofluoropolyethers

Sold under Tradename H-GaldenTMProduct Code b.p. [°C] GWP

HT-90 90 10,000 ZV60 60 3000 000DET 91 10,000HT-110 110 10,000HT-135 135 10,000HT-170 170 10,000

ZV60 60 3000-5000ZV85 85 3000-5000ZV100 100 3000-5000ZV135 135 3000-5000

HT 170 ZT-130 100 3000-5000 170 10,000DO2-TS 165 10,000DO2 175 10,000HT-200 200 10,000LS-200 200 10,000

ZT-150 130 3000-5000ZT-180 175 3000-5000

DO3 203 10,000LS-215 215 10,000DO5 230 10,000LS230 230 10,000HS-240 240 10 000

Heat transfer fluids exempt from 

Electronics 13

HS 240 240 10,000HS-260 260 10,000
GWP Range for Different Chemical Cla

PFCs, PFPEs

HFPEs

non-flammable segregated HFEs

non-flammable HFCs

Electronics 14

0 2,000 4,000 6,000 8,000 10,000 12,00
Unintended Consequences of Sub

Unintended Consequences of Sub

• All the materials exempt from reporting have GWPs in the 

All the materials exempt from reporting have GWPs in the 

10,000x CO2e

• All the low GWP substitutes will need to be reported as G

• There is already substantial use of heat transfer fluids tha

There is already substantial use of heat transfer fluids tha

exempt from reporting (~50 %) and the market will increasmove to fluids that are exempt from reporting.

• Selection of fluid based on reporting requirements will lea

Selection of fluid based on reporting requirements will lea

reduced energy efficiency (use of higher boiling fluids usetemperatures)

• The GHG reporting rule will likely result in dramatically inc

The GHG reporting rule will likely result in dramatically inc

(~100X) GHGs from these applications than otherwise wooccurred.

Electronics 15
Vapor Phase Soldering Vapor Phase Soldering

• Fluids are heated to boiling point Fluids are heated to boiling point, 

therefore, they are used at 1 atm. va

pressure.

• At 25 degrees C. none of the fluids u

for vapor phase soldering have vapofor vapor phase soldering have vapo

pressures greater than 1 mmHg.

• N GHG i i f h No GHG emissions 

from vapor p

has

soldering will be reported.

Electronics 16
IPCC and CARB benchmarkin

• IPCC reporting methodology does not nar

the definition of heat transfer fluid via a vathe definition of heat transfer fluid via

a va

pressure threshold. 

• Relevant CARB definitions: Relevant CARB definitions:

– “Fluorinated Gases” means a compound that contains 

and exists in a gaseous state at 25 degrees Celsius an

atmosphere of pressure. Fluorinated gases include, bulimited to: (A) hexafluoroethane (C2F6), (B) octafluorop(C3F8), etc.”

– “Heat Transfer Fluid” means a fluorinated fluid which p

device, such as a semiconductor, from overheating by 

Electronics

excess heat produced during a manufacturing process

17
Correcting the Issue Correcting the Issue

• 98.92 GHGs to re

port.

• (a) You must report emissions of fluorinated GH

defined in § 98.6) and N2O. The fluorinated GHGare emitt d f l t i f t i d 

itt

e

d

from elec

tronics manu

fac

turing pro

d

processes include, but are not limited to, those lTable I–2 to this subpart. You must individually r

appropriate:

• (5) Any fluorinated GHG used as a heat transfer 

For purposes of this subparagraph the exceptioFor purposes of this subparagraph, the exceptio

definition of fluorinated GHGs in § 98.6 for subswith vapor pressures of less than 1 mm of Hg ab

Electronics

25 degrees C does not apply.

18
Summary

• Vapor pressure of heat transfer fluids at 25 C is not predi

emissions.

• Subpart I will increasingly lead to use of HTFs exempt fro

reporting.

• The exempt fluids have GWPs 100x higher than fluids tha

reported as GHGs.

• Systems will likely operate with less energy efficiency.• The GHG repg y orting rule will likely lead to increased GHG 

from this sector.

• 3M would like to work with EPA to c

the issue

Electronics 19
Back-up

Electronics 20
Publication Available

Electronics 21
PFC Heat Transfer Fluid Use in 

Semiconductor Manufacturin

g

• 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 t

– Non-contaminating

• Volatile fluorinated fluids evaporate, leaving no residue

–

T

e pe a u e a ge mpe

r

atu

r

e r

a

nge

• -100C to ~260C - Depends upon the application• The temperature range of applications has grown considerab

– Microwave Transparency

• PFCs are transparent to microwave radiation PFCs are transparent to microwave radiation.

– Thermal Stability

• PFCs are among the most thermally stable organics fluids

– Chemical Inertness

• PFCs will not contaminate processes within the PFCs will not contaminate processes within the fab

Because Heat transfer fluids are used at elevated temperatures and prevapor pressure at 25 deg C is not predictive of emissions Their fate is th

Electronics 22

vapor pressure at 25 deg

C is not predictive of emissions. Their fate is th
Operating Temperature Range of Various Coolants

Electronics 23