Perfluoropolyethers

Stephen Whitlock

Performance Lubricants

Synthetic Lubricants
Synthetic hydrocarbon Polyalkylene glycol Diester Polyolester Polyphenylether Silicone Silicate Phosphate ester Polyalkylbenzene

Fluorinated Lubricants
Chlorofluorocarbon Fluorosilicone Perfluoropolyether

Chlorofluorocarbons
Polychlorotrifluoroethylene (CF2CFCl)n First synthesized in 1940s for uranium work. Range of products from light oils to waxes. Greases are commonly thickened with silica or PTFE. May react with aluminum, can cause rusting of steel, may damage Buna, silicone rubber, natural rubber, CTFE polymers, and PVC. Maximum safe operating temp of 400F. Subject to thermal breakdown above 580F. Soluble in most organic liquids. Non flammable and oxygen compatible. Applications in chemical service such as chlorine, metalworking lubricants, pump oils, etc.

Fluorosilicone Fluids
Strengths: High Viscosity Index Wide Viscosity Ranges for High and Low Temperature Applications Water Repellant Oxidation-Chemical-Thermal Stable Low Volatility Good Plastics Compatibility Poor Wear and Load Characteristics
(Dimethyl- low, Phenylmethyl- Better, Fluoro- Best)

Weaknesses:

Applications:

Highly Compressible Specialty greases and fluids

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

Common Theme for Uses

High Temperature Applications when nothing else will work Safe in oxygen Chemically inert and non reactive Very long life performance in applications

PFPE Oils & Greases

Used as:
Lubricant Vacuum pump fluid Functional fluid Mold release Sealant

In:
Aerospace Automotive Chemical Computer Oxygen system Paper machinery Petroleum handling Power Plant Semiconductor H-1 Food applications

Perfluoropolyether Structures
CF3 Shielded CF3CF2CF2-[-O-CF-CF2]x-O-CF2CF3 Non-Shielded Types CF3 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

Comparison of Temperature Limits

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

Petroleum Diesters Polyalphaolefins Polyolesters Silicones PFPE-K PFPE-Z

High Viscosity Range

Normal Range Continuous use

Low Viscosity Range

PFPE Lubricants
Chemical Properties
Wont burn High temperature stable Low evaporation rate Insoluble Non-reactive High density of 1.9 vs standard oils

PFPE Lubricants: Non-Flammable

No flash point No auto-ignition point

Hydrocarbon PFPE

No reaction with oxygen

PFPE Lubricants: High Temperature Stability

Up to 650 F No chemical breakdown Breakdown products are volatile No tars or deposits

High Temperature Stability

In oven at 232C for 40 hours

Hydrocarbon 40% loss

PFPE 0% weight loss

PFPE Lubricants: Solubility Insoluble in:

Hydrocarbons Water Steam Chemical solvents Acids and bases

PFPE Lubricants: Chemically Inert

No chemical attack by or to:

Boiling sulfuric acid Fuming nitric acid Hydrofluoric/ hydrochloric acid Strong oxidizers Water/steam Molten/aqueous caustic

Viscosity / Volatility
20C vis 7 16 36 80 180 550 800 1600 2700 Approx MW 960 1180 1720 2275 3150 4730 6250 8250 11000 Approx volatility 100% @ 250F 30% @ 250F 20% @ 250F 7% @ 250F 3% @ 250F 2% @ 250F 1% @ 250F < 1% @ 250F 0 % @ 250F < 1% @ 500F

Viscosity-Temperature Relationship
Viscosity

cSt 10000 1000 100

PF PE K, PF Y PE D
PFP EZ

CT FE

Silico ne

10 -40

20

100

Temperature (o C)

PFPE Fluorinated Oil

Compatibility with Metals & Alloys in Air

700o F Ni & Co.

Monel

371o C

Ni/Co/Cr STEEL 650o F 343o C Mg. Al, Cr V Ti (6AL6V2SN) 300 Series & 446 S.S. 316o C 600o F Bronze, A1 Ti (13V11Cr3A1) Ti (6A14V) 550o F 400 Series S.S., Tool &Bearing Steel 288o C Cu Ti (8 Mn)

Most Metals and Alloys are Compatible Below 550o F (288o C)

PFPE Fluorinated Oil

Compatibility with seals and plastics

There are no reactions such as swelling or shrinking with plastics and elastomeric materials used in seals or other components. No reaction with paints or other components.

Thermal & Oxidative Degradation Products of PFPE Oils

C3F7[OCF(X)CF2]y OCF2CF3 :x=CF3,F Inert Atm
CF3CF=CF2 + CF3COF + COF2

600-650o F

[02]
CF3CF=C0F + COF2

Secondary Rxs
CF3COF

H2O SiO2

CF3COOH, HF, CF3H. CO2 SiF4, CO2

H2O COF2 SiO2 SiF4, CO2 CO2, HF

PFPE 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 Thickeners such as Polytetrafluoroethylene (PTFE)

PFPE Oils and Greases

Additives
Only special soluble ones for oils Grease
Extreme pressure
Molybdenum disulfide Graphite
Anti-rust

& high temperature anticorrosion

Sodium nitrite Disodium Sebacate Soluble additives from manufacturer of oils

Typical Lubricants Wear & Load Carrying Ability

Oil PFPE Chlorofluorocarbon Fluorosilicone Diester Petroleum oil 4-Ball Wear Falex Pin/V-Block Scar, mm* Fail Load, LB. 0.36 0.37 0.43 0.61 0.69 >4500 >4500 1100 2300 1300

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

Extreme Pressure
Falex Pin/V Block Test Very-high-pressure capable
Hydrocarbon on left shows welding, PFPE on right has no welding

Typical ASTM D-3336 test results

Competitive grease*
(from manufacturers data sheets)

Recommended Temp range, C

Viscosity 40C/100C cSt

Test temperature 150C / 300F 177C / 350F 177C / 350F 150C / 300F 176C / 349F 177C / 350F

Life, hours

Polyurea / hydrocarbon oil Polyurea / hydrocarbon Microgel / hydrocarbon Lithium complex / polyol ester Organo-clay / PAO Typical PFPE greases PTFE / PFPE PTFE / PFPE PTFE / PFPE PTFE / PFPE
* Major corporate grease manufacturers

-29 to +177** --23 to +177 --- to +200 -54 to +177

116 / 12.3 115 / 12.2 -- / 31.8 150 / -29.3 / 5.6

Approx 3000 ***

600 750+ 600+ 500 400+

-51 to +179 -40 to +200 -36 to +204 -20 to +300

60 / 9 100 / 12.3 160 / 18 500 / 47

180C / 357F 200C / 392F 200C / 392F 250C / 482F

4900+ 5500+ 5000+ 2000+

** 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.

Bearing Life Test High Temperature Vacuum

Hours to Failure
10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 PFPE FluoroSilicone Mineral oil product Silicone CTFE

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

Applications
Non migrating heat resistant grease Steam resistant, long lasting, high pressure grease

Nato approved life support system sealing paste

High performance automotive component bearing grease

Inert low vapor pressure oils

Aerospace / Aviation
High speed bearings
Synchronous motor bearings in gyroscope Sealant / caulk for space suits Oxygen 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

Vapor Pressure / Outgassing

Select grades have been developed for use in applications such as aviation, aerospace and clean rooms where outgassing is an issue or vacuum applications where vapor pressure is critical. Vapor Pressure TML / CVCM 240 AB 240 AC LVP L-150 L-220 5 X 10-6 Torr 8 X 10-8 Torr 8 X 10-13 Torr 4 X 10-10 Torr 6 X 10-11 Torr -0.22 / 0.023% -0.26 / 0.056% 0.13 / 0.092%

PFPE Automotive Applications

Assembly plant conveyors and chains
- High temperatures & loads

Anti-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

Automotive Applications

Spark Plug Boots Alternator Bearings Clutch Pilot Bearings Sintered Metal Bushings Weatherstripping

PFPE Industrial Applications

Bearings
- Corrosive environments - High temperatures - Hard to lube areas - Critical parts

Valves
- Plug, ball - Relief

Functional fluid
- Sealant - Hydraulic fluid - Inert fluid

The True Cost of Lubrication?

Price of the Lubricant Plus Cost of Maintenance Plus Cost of Lost Production

PFPE 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

Control Valve Lubricant

PFPE Grease - Reduce sticking - Reduce leaking
Operating Conditions -High temperatures -Corrosive chemicals -Hydrocarbons

No Stick Slip with PFPEs

Considerations in PFPE Use

Bearings free of all hydrocarbon or other organic residues Lower thermal conductivity and thicker films could cause bearings and equipment to run slightly hotter Not for use on aluminum bearing surfaces Higher density - fill bearings by volume, not weight

PFPE 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

Additional 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

 . .

K-CHAIN

The CF2O & CF2CF2O are shielded and by this could not be attacked as easy as nonshielded CF2O groups

F F | | FCF FCF F F F | F F F | F F F F F | | | | | | | | | | | | | FCCCOCCOCCOCCOCCOCCF | | | | | | | | | | | | | F F F F F | F F F | F F F FCF FCF | | F F

Y-CHAIN
The CF2O & are not completely shielded and by this could be more easily attacked than shielded CF2O groups

F F | | FCF FCF F | F F F F F | F F F F F F | | | | | | | | | | | | | | FCOCCOCOCCOCOCCOCOCCOCOCF | | | | | | | | | | | | | | F F F F | F F F F F | F F F FCF FCF | | F F