SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE ...

SYNTHETIC LUBRICANTS
AND HIGH-PERFORMANCE
FUNCTIONAL FLUIDS
***
Copyright © 1999 Marcel Dekker, Inc.
Second Edition, Revised and Expanded
edited by
Leslie R. Rudnick
Infineum USA, L.P.
Linden, New Jersey
Ronald L. Shubkin
Albemarle Corporation
Baton Rouge, Louisiana
MARCEL DEKKER, INC. NEW YORK • BASEL

ISBN: 0-8247-0194-1
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Copyright © 1999 Marcel Dekker, Inc.

Preface to the Second Edition
The objective of this second edition is to provide up-to-date information on the many synthetic
lubricants that are available in order to meet the increasingly severe demands placed on them.
In addition to including all chapter subjects that appeared in the first edition, this edition contains
new chapters in each of the three parts: fluids, applications, and trends. In Part I, on fluids, there
are new chapters on poly(internal)olefins, polyphenyl ethers, polymer esters, and highly refined
mineral oils.
In Part II, on applications, the chapter on gear oils from the first edition has been split
into automotive gear lubricants and industrial gear oils in this one. There is also a new chapter
on refrigeration lubes. In Part III, on trends, the chapter on automotive trends has been
separated into four chapters, each representing a different region of the globe: Europe, the
United States, Asia, and South America. Because these markets are at different stages of
development and are growing at greatly different rates, it is appropriate that these regions be
evaluated separately.
In addition to the textual material, most authors of the fluids chapters have included a list of
commercially available fluids related to their chapter, giving the properties and in some cases performance
data for the fluids described.
The last chapter of this second edition is a compilation of lubricant-related terms and
acronyms. It includes the abbreviations of many organizations around the globe that are involved
in the lubricants industry in one way or another.
Finally, an extensive index has been included to facilitate use of this book. All in all, this
second edition will be a valuable reference for the status of synthetic lubricants and highperformance
functional fluids as we approach the next millennium.
Leslie R. Rudnick: I wish to extend thanks to all of my colleagues (and especially Ron
Shubkin), who encouraged me to begin and complete this book. This edition is the collection of the
efforts and expertise of over 50 contributors recognized as experts in their respective areas of work.
The best aspect of this project has been the opportunity to meet and interact with the many contributors.
It is my sincere hope that we will continue to share our areas of interest long after this project
is complete. This project would not have progressed as efficiently had it not been for the excellent
guidance and advice received from Rita Lazazzaro and Eric Stannard of Marcel Dekker, Inc.
I would especially like to thank Kelli Swatsworth, who helped with all the correspondence
and typing. I would also like to thank my wife, Paula, and my family for their understanding and
support while I worked on this book.
Ronald L. Shubkin: The preparation of the first edition of Synthetic Lubricants and High-
Performance Functional Fluids afforded me an opportunity to meet and get to know one of the
finest groups of people I have ever had the pleasure to work with—the authors of the individual
chapters. For this opportunity, I will always be grateful.
Much has changed in the few years since the original publication. It was with great satisfaction
(and relief) that I was able to coax Les Rudnick into joining me as the coeditor of the
Copyright © 1999 Marcel Dekker, Inc.
iii

iv Preface to the Second Edition
second edition. In fact, since my responsibilities have now taken me far from the synthetic lubricants
area, Les has indeed been the primary force behind this second edition. Thank you, Les.
It has been a job well done.
Copyright © 1999 Marcel Dekker, Inc.
Leslie R. Rudnick
Ronald L. Shubkin

Preface to the First Edition
While in many applications the primary function of a synthetic fluid is lubrication, it is by no
means the only function. Heat transfer, power transmission, electrical insulation, and corrosion
inhibition are only a few of the other tasks that fluids may be expected to perform. In many
instances the requirements of the tasks exceed the performance capabilities of natural fluids, and
the synthesis of new products to meet the extraordinary demands is necessary. In other cases, synthetic
fluids have proven to be more cost-effective than natural products in meeting the requirements
of a given application. In still other cases, environmental or toxicological considerations
have mandated the use of synthetic functional fluids, which are relatively nontoxic in comparison
to many naturally derived fluids. Synthetic fluids, designed to provide performance characteristics
above and beyond those available from fluids derived from most natural sources, are the
subject of this book.
The intention of this book is to provide a one-volume overview of the various types and uses
of synthetic functional fluids currently available. The first section of the book is devoted to the
different fluids. Each chapter is focused on a particular class of compounds and is authorized by
a recognized expert in the field. The fluids covered include all the well-established commercial
products as well as some experimental fluids that have the potential of becoming commercialized
in the near future. To the extent possible, each chapter includes a discussion of:
Historical Development
Chemistry
Property and Performance Characteristics
Manufacture, Marketing, and Economics
Outlook
The second section of the book deals with applications. These chapters focus on specific
application areas for which synthetic fluids are either currently used or being seriously considered
for use. Again, the authors are recognized experts in the application area. The chapters
cover:
Historical Development
Synthetic Fluids Appropriate to Application
Comparative Performance Data
Current Commercial Practice
The third and last section of the book deals with long-range trends in the use of synthetic
fluids in major industries or areas of interest. The authors of these chapters have been chosen
because of their ability to take a long-term view. They have been asked to consider not only
where their field of interest is today, but where it is headed in the future. They have in effect
been asked to become prognosticators of future developments in synthetic functional fluids.
Copyright © 1999 Marcel Dekker, Inc.
v

vi Preface to the First Edition
Some chapters in this section of the book deal with industrial markets, whereas other chapters
deal with economic and environmental trends. The chapters on industrial markets deal with:
Current Equipment and Fluids
Developmental Equipment and Fluids
Long-range Trends
I am particularly pleased to be able to conclude this book with a chapter on the environmental
impact associated with the use of synthetics. There are two critical areas of concern. The first
involves the conservation of our planet’s limited supply of natural resources. Synthetics extend
these assets not only by simple replacement but, in many applications, by dramatically increasing
service lifetimes. The second area of environmental concern involves toxicity and
biodegradability. In both areas, synthetics are becoming recognized as environmentally responsible
solutions to a sensitive issue.
I wish to extend my gratitude to all of my colleagues and friends who encouraged and supported
my efforts to bring this work together. Thanks also to Ethyl Corporation, the management
of Ethyl’s Research and Development Division, and the Ethyl Industrial Chemicals Division for
their support in this undertaking. I especially wish to thank those people in Ethyl’s Research and
Developmental Department with whom I have had the good fortune to work on the PAO project.
Special thanks also goes to Ms. Norma Delaune, who helped me in handling the correspondence
and in preparation of the tables and graphs. Finally, a word of thanks to my wife, Swee—without
her encouragement and understanding I could never have finished the project.
Copyright © 1999 Marcel Dekker, Inc.
Ronald L. Shubkin

Introduction
The publication of the second edition of Synthetic Lubricants and High-Performance Functional
Fluids comes at a milestone in the way we have chosen to record and order historical events. Very
shortly we shall enter a new millennium in our accounting system—a time that seems appropriate
to reflect on the past and prognosticate on the future. When we do this, we realize that we live
in a time like no other. At no time in our history has change and real improvement in the human
condition come at so rapid a pace. Even a subject as seemingly mundane as lubrication has shared
in and significantly contributed to the exhilarating pace of progress.
In the most fundamental sense, a lubricant may be defined as a substance that has the ability
to reduce friction between two solid surfaces rubbed against each other. The use of natural
products to achieve this effect dates to antiquity. Art decorations on the inner wall of the
Egyptian tomb of Tehuti-Hetep (ca. 1650 B.C.) indicate that olive oil on wooden planks was
used to facilitate the sliding of large stones, statues, and building materials. Egyptian chariots
dating to 1400 B.C. have been uncovered that have small amounts of greasy materials, presumed
to be either beef or mutton tallow, on the axles. In addition to animal fat and vegetable oil, petroleum
products have been used for lubrication in a primitive fashion for more than a millennium.
In fact, Herodotus (484–424 B.C.) described methods of producing bitumen and a lighter oil
from petroleum.
The first synthetic hydrocarbon oils were produced by the prominent chemists Charles
Friedel and James Mason Crafts in 1877. Standard Oil Company of Indiana commercialized a
synthetic hydrocarbon oil in 1929, but it was unsuccessful because of a lack of demand. However,
the onset of World War II, and the subsequent shortages of petroleum feedstocks in Germany,
France, and Japan, revitalized interest in synthetic lubricants. Moreover, the German disaster at
the Battle of Stalingrad in 1942 demonstrated the inadequacy of petroleum products in extremely
cold weather. Because the lubricants used in tanks, aircraft, and other military vehicles gelled,
the engines used in the vehicles could not be started. An intense German research effort to find
alternative lubricants ensued, which led to the first manufacture of synthetic products by olefin
polymerization.
Interest in ester-based lubricants appears to date back to the Zurich Aviation Congress in
1937. Triesters were later synthesized from fatty acids and trimethanolethane. These materials
performed so well that more than 3500 esters were prepared and evaluated in Germany between
1938 and 1944. Meanwhile, the first diester base stocks were developed in the United States at
the Naval Research Laboratory between 1942 and 1945. The British began using esters in 1947
as lubricants for turboprop aircraft, in which conventional mineral oils failed to give satisfactory
performance at high temperatures. With the introduction of jet engines, the problem became even
more complex because of the need for lubrication at very low temperatures to the front of the
engine and at very high temperatures to the rear. The need for fire-resistant hydraulic fluids in
aircraft further spurred the development of synthetics.
Copyright © 1999 Marcel Dekker, Inc.
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viii Introduction
From the end of World War II until the mid-1970s, a variety of synthetic fluids were developed
to meet the ever-increasing demands of the newer and more efficient high-performance
engines and machines being developed. The use of synthetics, however, was limited to applications
in which the required performance characteristics could not be met by petroleum-based
products.
The oil embargo of 1974, and the subsequent escalation of petroleum prices, brought about
a new and urgent need for the conservation of oil reserves and the development of alternative raw
materials. By early 1987, the pressures on the world petroleum supply had abated, but the lessons
of the late 1970s had not been forgotten. The increased emphasis on cost-effectiveness had a
twofold effect on the growth of synthetics. First, the fluids themselves were found to offer advantages
of longer drain intervals, less downtime, and greater fuel efficiency. Second, a new generation
of engines was being developed that required fluid performance characteristics that were
becoming increasingly difficult to achieve with mineral oil-based products.
Finally, in the 1990s there is a new urgency to the concept of environmental responsibility.
This development has led to an increased need for functional fluids that are both biodegradable
and low in toxicity.
As the new millennium begins, we ponder the role of synthetic fluids in the years,
decades, and even millennia to come. Looking back, we recall that as recently as 1859, lubrication
functions were performed by natural oils and fats. Starting soon after the drilling of the
first oil well that year, mineral oils began to displace natural oils and fats. By the 1970s, mineral
oils had essentially displaced natural oils and fats, but synthetics were starting to come
into use. At the end of the 1990s, synthetics still account for only a low percentage of the total,
but their use is certainly on the rise. The idea that synthetic lubricants could ever totally displace
mineral oils seems far-fetched, but estimates of worldwide crude oil reserves indicate
that we may run out of crude oil sometime in the next century. Will synthetic oils displace
mineral oils, or will alternative technologies displace both? Only time will tell. In the interim,
however, synthetic oils have proven their value and promise to make their impact on the third
millennium.
Copyright © 1999 Marcel Dekker, Inc.
Ronald L. Shubkin

Contents
Preface to the Second Edition iii
Preface to the First Edition v
Introduction vii
Contributors xiii
Part I. SYNTHETIC HIGH PERFORMANCE FLUIDS:
Chemistry, Technology, and Commercial Importance
1. Poly(a-olefins) 3
Leslie R. Rudnick and Ronald L. Shubkin
2. Poly(internal olefins) 53
G. Corsico, L. Mattei, A. Roselli, and Carlo Gommellini
3. Esters 63
Steven James Randles
4. Phosphate Esters 103
Michael P. Marino and Douglas G. Placek
5. Polymer Esters 141
Uwe Wallfahrer and Lynnette Bowen
6. Polyalkylene Glycols 159
Paul L. Matlock, William L. Brown, and Nye A. Clinton
7. Alkylated Aromatics 195
Margaret M. Wu
8. Perfluoroalkylpolyethers 215
Gregory A. Bell, Jon Howell, and Thomas W. Del Pesco
9. Polyphenyl Ether Lubricants 239
Manuel E. Joaquim
10. Polychlorotrifluoroethylene 253
Dale A. Ruesch and Louis L. Ferstandig
Copyright © 1999 Marcel Dekker, Inc.
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x Contents
11. Silicones 267
Clay Quinn, Frank Traver, and Kedar Murthy
12. Silahydrocarbons 287
F. Alexander Pettigrew
13. Phosphazenes 297
Robert E. Singler and Frank J. Gomba
14. Dialkyl Carbonates 313
Giuseppe Fisicaro and Giampaolo Gerbaz
15. Cycloaliphatics 325
Edward W. Casserly and Clifford G. Venier
16. Polybutenes 357
John D. Fotheringham
17. Highly Refined Mineral Oils 393
Ronald A. Phillipps
18. Comparison of Synthetic Fluids 413
Wilfried J. Bartz
Part II. APPLICATIONS
19. Automotive Crankcase Oils 441
Stephen C. Lakes
20. Automatic Transmission Fluids 461
James F. Landry
21. Automotive Gear Lubricants 477
Stephen C. Lakes
22. Industrial Gear Lubricants 499
Dennis A. Lauer
23. Synthetic Grease 519
Paul A. Bessette and David S. Stone
24. Compressors and Pumps 539
Kenneth C. Lilje, Glenn D. Short, and J. William Miller
25. Refrigeration Lubes 563
Steven James Randles
26. Hydraulics 595
Andrew G. Papay and Leslie R. Rudnick
Copyright © 1999 Marcel Dekker, Inc.

Contents xi
27. Metalworking Fluids 625
William L. Brown
Part III. TRENDS
28. Automotive Trends in Europe 669
R. David Whitby
29. Automotive Trends in the United States 707
Cynthia D. Ontiveros
30. Automotive Trends in Asia 719
R. David Whitby
31. Automotive Trends in South America 751
R. David Whitby
32. Industrial Trends 767
Raymond B. Dawson and Mark E. Kerkemeyer
33. Trends Toward Synthetic Fluids and Lubricants in Aerospace 785
Carl E. Snyder, Jr. and Lois J. Gschwender
34. Environmental Impact 793
Bradley F. Droy and Steven James Randles
35. Commercial Developments 807
R. David Whitby and E. Ian Williamson
Lubricant-Related Terms and Acronyms 841
Leslie R. Rudnick and Edward F. Zaweski
Index 857
Copyright © 1999 Marcel Dekker, Inc.

Wilfried J. Bartz Technische Akademie Esslingen, Ostfildern, Germany
Contributors
Gregory A. Bell E.I. du Pont de Nemours & Company, Inc., Deepwater, New Jersey
Paul A. Bessette Nye Lubricants, Inc., New Bedford, Massachusetts
Lynnette Bowen Akzo Nobel Chemicals Ltd., Tunbridge Wells, England
William L. Brown Union Carbide Corporation, Tarrytown, New York
Edward W. Casserly Pennzoil Products Company, The Woodlands, Texas
Nye A. Clinton Union Carbide Corporation, Tarrytown, New York
G. Corsico EURON, Milan, Italy
Raymond B. Dawson Albemarle Corporation, Baton Rouge, Louisiana
Thomas W. Del Pesco E.I. du Pont de Nemours & Company, Inc., Deepwater, New Jersey
Bradley F. Droy Toxicological & Environmental Associates, Inc., Baton Rouge, Louisiana
Louis L. Ferstandig Halocarbon Products Corporation, River Edge, New Jersey
Giuseppe Fisicaro AgipPetroli, Rome, Italy
John D. Fotheringham BP Singapore Pte. Ltd., Singapore
Giampaolo Gerbaz AgipPetroli, Rome, Italy
Frank J. Gomba United States Naval Academy, Annapolis, Maryland
Carlo Gommellini AgipPetroli, Rome, Italy
Lois J. Gschwender Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio
Jon Howell E.I. du Pont de Nemours & Company, Inc., Deepwater, New Jersey
Copyright © 1999 Marcel Dekker, Inc.
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xiv Contributors
Manuel E. Joaquim Santovac Fluids, Inc./Findett Corporation, St. Charles, Missouri
Mark E. Kerkemeyer Amoco Chemical, Lisle, Illinois
Stephen C. Lakes Henkel Corporation/Emery Group, Cincinnati, Ohio
James F. Landry Castrol Specialty Products, Downers Grove, Illinois
Dennis A. Lauer Kluber Lubrication NALP, Londonderry, New Hampshire
Kenneth C. Lilje CPI Engineering Services, Inc., Midland, Michigan
Michael P. Marino* FMC Corporation, Philadelphia, Pennsylvania
Paul L. Matlock Union Carbide Corporation, Tarrytown, New York
L. Mattei EURON, Milan, Italy
J. William Miller J. William Miller & Associates, Inc., Midland, Michigan
Kedar Murthy GE Silicones, Waterford, New York
Cynthia D. Ontiveros Amoco Petroleum Products Research Center, Naperville, Illinois
Andrew G. Papay Ethyl Petroleum Additives, Inc., St. Louis, Missouri
F. Alexander Pettigrew Ethyl Corporation, Richmond, Virginia
Ronald A. Phillipps Ronald A. Phillipps & Associates, Oxfordshire, England
Douglas G. Placek FMC Corporation, Princeton, New Jersey
Clay Quinn GE Silicones, Waterford, New York
Steven James Randies ICI Wilton, Middlesbrough, Cleveland, England
A. Roselli EURON, Milan, Italy
Leslie R. Rudnick Infineum USA, L.P., Linden, New Jersey
Dale A. Ruesch* Halocarbon Products Corporation, River Edge, New Jersey
Glenn D. Short Consultant, Detroit, Michigan
Ronald L. Shubkin Albemarle Corporation, Baton Rouge, Louisiana
*Retired.
Copyright © 1999 Marcel Dekker, Inc.

Contributors xv
Robert E. Singler United States Military Academy, West Point, New York
Carl E. Snyder, Jr. Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio
David S. Stone Nye Lubricants, Inc., New Bedford, Massachusetts
Frank Traver GE Silicones, Waterford, New York
Clifford G. Venier Pennzoil Products Company, The Woodlands, Texas
Uwe Wallfahrer Akzo Nobel Central Research, Düren, Germany
R. David Whitby Pathmaster Marketing, Ltd., Woking, England
E. Ian Williamson The College of Petroleum and Energy Studies, Oxford, England
Margaret M. Wu Mobil Technology Company, Paulsboro, New Jersey
Edward F. Zaweski Amoco Chemicals, Naperville, Illinois
Copyright © 1999 Marcel Dekker, Inc.