PFPE-PAMEA 2011

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PerfluoropolyethersPerfluoropolyethers

Stephen Whitlock

Performance Lubricants

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Synthetic LubricantsSynthetic Lubricants

Synthetic hydrocarbon Silicone

Polyalkylene glycol Silicate

Diester Phosphate ester

Polyolester Polyalkylbenzene

Polyphenylether

Fluorinated Lubricants

Chlorofluorocarbon

Fluorosilicone

Perfluoropolyether

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ChlorofluorocarbonsChlorofluorocarbons

Polychlorotrifluoroethylene (CF2CFCl)n

First synthesized in 1940s for uranium work.Range of products from light oils to waxes.Greases are commonly thickened with silica orPTFE.

May react with aluminum, can cause rusting ofsteel, may damage Buna, silicone rubber, naturalrubber, CTFE polymers, and PVC. Maximum safeoperating temp of 400F. Subject to thermalbreakdown above 580F. Soluble in most organicliquids. Non flammable and oxygen compatible.

Applications in chemical service such as chlorine,

metalworking lubricants, pump oils, etc.

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Fluorosilicone FluidsStrengths: High Viscosity Index

Wide Viscosity Ranges for High

and Low Temperature Applications

Water Repellant

Oxidation-Chemical-Thermal Stable

Low VolatilityGood Plastics Compatibility

Weaknesses: Poor Wear and Load Characteristics(Dimethyl- low, Phenylmethyl- Better, Fluoro- Best)

Highly Compressible

Applications: Specialty greases and fluids

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Perfluorinated Polyethers

Strengths: Highest Stability

Very wide Temperature Range

Very low Volatility

Non Flammable, Non Reactive

Compatibility with Elastomers, Plastics

Excellent Lubricity and Load Carrying

Weaknesses: Fewer additives available

Applications: Oxygen Service

Sealed for Life / Low Maintenance Needs

Vacuum Pump Fluids

Automobile Bearings

Oven Bearings and Chains

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Common Theme for UsesCommon Theme for Uses

High Temperature Applications whennothing else will work

Safe in oxygen

Chemically inert and non reactive Very long life performance in applications

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PFPE Oils & GreasesPFPE Oils & Greases

Used as:

Lubricant

Vacuum pump fluid

Functional fluid

Mold releaseSealant

In:

AerospaceAutomotive

Chemical

Computer

Oxygen system

Paper machinery

Petroleum handling

Power PlantSemiconductor

H-1Food applications

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PerfluoropolyetherStructures

Perfluoropolyether

Structures

Shielded

CF3CF2CF2-[-O-CF-CF2]x-O-CF2CF3

Non-Shielded Types

CF3-[-O-CF-CF2-]Y-[O-CF2-]mO-CF3

CF3-[-O-CF2-CF2-]Z-[-O-CF2]n-O-CF3

CF3CF2CF2-[-O CF2-CF2-CF2-]o-O-CF2CF3

CF3

CF3

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-60 -40 -20 0 20 40 60 80 100 140 160 180 200 240 260 300Temperature C

High Viscosity Range Normal Range

Continuous use

Low Viscosity Range

Petroleum

Diesters

PolyalphaolefinsPolyolesters

Silicones

PFPE-K

PFPE-Z

Comparison of Temperature Limits

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PFPE LubricantsPFPE Lubricants

Chemical Properties

Wont burn

High temperature stable Low evaporation rate

Insoluble

Non-reactive

High density of 1.9 vs standard oils

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PFPE Lubricants: Non-FlammablePFPE Lubricants: Non-Flammable

No flash point

No auto-ignition point

No reaction with

oxygenPFPE

Hydrocarbon

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PFPE Lubricants:

High Temperature Stability

PFPE Lubricants:

High Temperature Stability

Up to 650 F

No chemical breakdown

Breakdown products are volatile

No tars or deposits

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High Temperature StabilityHigh Temperature Stability

In oven at 232C for 40 hours

Hydrocarbon40% loss

PFPE0% weight loss

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PFPE Lubricants: SolubilityPFPE Lubricants: Solubility

Insoluble in:Hydrocarbons

Water

Steam

Chemical solvents

Acids and bases

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PFPE Lubricants: Chemically InertPFPE Lubricants: Chemically Inert

No chemical attack by or to:Boiling sulfuric acid

Fuming nitric acidHydrofluoric/ hydrochloric acid

Strong oxidizers

Water/steam

Molten/aqueous caustic

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Viscosity / Volatility

20C

vis

Approx

MW

Approx volatility

7 960 100% @ 250F

16 1180 30% @ 250F

36 1720 20% @ 250F

80 2275 7% @ 250F180 3150 3% @ 250F

550 4730 2% @ 250F

800 6250 1% @ 250F

1600 8250 < 1% @ 250F2700 11000 0 % @ 250F

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Viscosity-Temperature

Relationship

Viscosity-Temperature

Relationship

0 20 100

cSt10000

1000

100

10

Viscosity

Temperature (o C)

Silicone

PFPEK,YCTFE

PFPED

PFPEZ

-40

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700o F

PFPE Fluorinated OilCompatibility with Metals & Alloys in Air

PFPE Fluorinated Oil

Compatibility with Metals & Alloys in Air

650o F

600o F

550o F

371o C

343o C

316o C

288o C

Ni & Co.Monel

Ni/Co/CrSTEEL

Mg. Al, Cr

VTi (6AL6V2SN)

300 Series & 446 S.S.Bronze, A1

Ti (13V11Cr3A1)Ti (6A14V)

400 Series S.S., Tool &Bearing Steel

Cu

Ti (8 Mn)

Most Metals and Alloys are

Compatible Below 550o F (288o C)

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PFPE Fluorinated OilCompatibility with seals and plastics

PFPE Fluorinated OilCompatibility with seals and plastics

There are no reactions such asswelling or shrinking with plastics andelastomeric materials used in seals

or other components.No reaction with paints or other

components.

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Thermal & Oxidative DegradationProducts of PFPE Oils

Thermal & Oxidative Degradation

Products of PFPE Oils

C3F7[OCF(X)CF2]y OCF2CF3 :x=CF3,F

Inert Atm [02]600-650o F

CF3CF=CF2

+

CF3COF

+COF2

CF3CF=C0F

+

COF2

Secondary Rxs

CF3COOH, HF, CF3H. CO2CF3COFH2O

COF2

SiO2SiF4, CO2

H2O

CO2, HF

SiO2SiF

4

, CO2

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PFPE Oils and GreasesPFPE Oils and Greases

Clear oil is basic PFPE product

Different viscosity grades available Prepared by distillation

Greases made by thickening oils

Typically made with High-Temperature Thickenerssuch as Polytetrafluoroethylene (PTFE)

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PFPE Oils and GreasesPFPE Oils and Greases

Additives Only special soluble ones for oils Grease

Extreme pressureMolybdenum disulfide

Graphite

Anti-rust & high temperature anti-

corrosion Sodium nitrite Disodium Sebacate

Soluble additives from manufacturer of oils

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Typical Lubricants

Wear & Load Carrying Ability

Typical Lubricants

Wear & Load Carrying Ability

Oil

PFPEChlorofluorocarbonFluorosiliconeDiesterPetroleum oil

4-Ball Wear

Scar, mm*

0.360.370.430.610.69

Falex Pin/V-Block

Fail Load, LB.

>4500>4500

110023001300

* 20 kgf / 225o F / 1200 RPM / 60 min / 52100 steel on steel

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Extreme PressureExtreme Pressure

Falex Pin/V Block TestVery-high-pressure capableFalex Pin/V Block TestVery-high-pressure capable

Hydrocarbon on left shows welding,

PFPE on right has no welding

Hydrocarbon on left shows welding,

PFPE on right has no welding

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Typical ASTM D-3336 test results

2000+250C / 482F500 / 47-20 to +300PTFE / PFPE

5000+200C / 392F160 / 18-36 to +204PTFE / PFPE

5500+200C / 392F100 / 12.3-40 to +200PTFE / PFPE

4900+180C / 357F60 / 9-51 to +179PTFE / PFPE

Typical PFPE greases

400+177C / 350F29.3 / 5.6-54 to +177Organo-clay / PAO

500176C / 349F150 / ----- to +200Lithium complex / polyolester

600+150C / 300F-- / 31.8-23 to +177Microgel / hydrocarbon

750+177C / 350F115 / 12.2--Polyurea / hydrocarbon

Approx 3000 ***600

150C / 300F177C / 350F

116 / 12.3-29 to +177**Polyurea / hydrocarbonoil

Life, hoursTesttemperature

Viscosity40C/100CcSt

RecommendedTemp range, C

Competitive grease*(from manufacturers data sheets)

* Major corporate grease manufacturers

** This manufacturer claims the maximum operating temperature is the highest temperature at which the grease could be used with frequent (daily) relubrication.

*** Manufacturer claims this is nearly 10 times the life possible when using conventional lithium greases.

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Bearing Life Test

High Temperature Vacuum

Bearing Life Test

High Temperature Vacuum

0

1000

2000

3000

40005000

6000

7000

8000

900010000

PFPE Fluoro-

Silicone

Mineral o il

product

Silicone CTFE

Hours to Failure

NASA N85-11239, OCT 1984, 3600 RPM, 5 lb Load, 93.3 C, 1X10-6 Torr

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ApplicationsApplications

Steam resistant,long lasting,high pressure

grease

High performance automotivecomponent bearing grease

Inert low vaporpressure oils

Non migratingheat resistantgrease

Nato approved lifesupport systemsealing paste

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Aerospace / AviationAerospace / AviationHigh speed bearings

Synchronous motor bearings in gyroscope

Sealant / caulk for space suitsOxygen breathing systems-vehicle & space suit

Traction motors on lunar rover

Boeing wing flap actuator

O-ring lubricant

Assembly lubricant

Rocket engine assemblies

- Reduction gears- Turbine, pump, gimbal bearings

- Threaded fasteners

Harpoon missile rear main bearing (Max. temp. ->800o F)

De-icing hot air diversion seal lubrication

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Vapor Pressure / OutgassingVapor Pressure / Outgassing

Select grades have been developed for use in applicationssuch as aviation, aerospace and clean rooms where

outgassing is an issue or vacuum applications where vaporpressure is critical.

0.13 / 0.092%6 X 10-11TorrL-220

0.26 / 0.056%4 X 10-10TorrL-150

--8 X 10-13TorrLVP

0.22 / 0.023%8 X 10-8Torr240 AC

--5 X 10-6Torr240 AB

TML / CVCMVapor Pressure

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PFPE Automotive ApplicationsPFPE Automotive Applications

Assembly plant conveyors and chains

- High temperatures & loadsAnti-lock braking system ball screw- Compatible with brake fluids & elastomers

Fan-clutch ball bearing- Extended life, reduced warranty claims

Spark Plug Boot & Weatherstripping-Compatible lubricant

Race car CV joint, clutch, wheel bearing- High speeds, temperature & loads

Alternators, Sintered metal

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Automotive ApplicationsAutomotive Applications

Spark Plug Boots

Alternator Bearings

Clutch Pilot Bearings

Sintered Metal Bushings

Weatherstripping

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PFPE Industrial ApplicationsPFPE Industrial Applications

Bearings

- Corrosive environments- High temperatures

- Hard to lube areas

- Critical parts

Valves- Plug, ball

- Relief

Functional fluid- Sealant

- Hydraulic fluid

- Inert fluid

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The TrueCost

of Lubrication?The TrueCost

of Lubrication?

Price of the LubricantPlus

Cost of MaintenancePlus

Cost of Lost Production

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PFPE Applications: ValvesPFPE Applications: Valves

Valve Moving Parts

Packing- Good lubricity, reduces sticking, reduces emissions

- Low evaporation

- High temperature stability to 600o F

- No chemical breakdown- Insoluble

For:- Oxygen or Chlorine

- Strong acids, bases- Steam, water

- High temperature

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Control Valve LubricantControl Valve Lubricant

PFPE Grease

- Reducesticking

- Reduce

leaking

Operating Conditions

-High temperatures

-Corrosive chemicals

-Hydrocarbons

No Stick Slip with PFPEs

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Considerations in PFPE UseConsiderations in PFPE Use

Bearings free of all hydrocarbon or otherorganic residues

Lower thermal conductivity and thicker filmscould cause bearings and equipment to runslightly hotter

Not for use on aluminum bearing surfaces

Higher density - fill bearings by volume, notweight

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PFPE FuturePFPE Future

Lubrication requirements becoming more

demanding- New technology is pushing traditional design envelopes

- PFPEs have been identified as next generation aviation

lubricants by leading-edge designers

Lubricant purchase cost less important than

lifetime intervals- Reduced down-time and longer re-lube intervals

- Lubricated-for-life applications

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Additional ReferencesAdditional References

Synthetics, Mineral Oils and Biobased Lubricants,

Taylor and Francis Books, 2005, Chapter 8,

Perfluoroalkylpolyethers,

CRC Handbook of Lubrication, Volume III,

Perfluoroalkylpolyethers , T. W. Del Pesco, CRC Press,

Boca Raton, FL pp. 287-303, 1994.

PFPE manufacturer bulletins: DuPont Company,Wilmington DE

800-424 7502

Worldwide web on Internet:

HTTP://WWW.KRYTOX.COM

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PFPE-PAMEA 2011