10

Liquid Lubricants
and Lubrication

Lois J. Gschwender
Air Force Research Laboratory
David C. Kramer
Chevron Global Lubricants
Brent K. Lok
Chevron Global Lubricants
Shashi K. Sharma
Air Force Research Laboratory
Carl E. Snyder, Jr.
Air Force Research Laboratory
Mark L. Sztenderowicz
Chevron Global Lubricants
10.1 Introduction
10.2 Lubricant Selection Criteria
Operating Environment • Viscosity and Fluid-Film
Lubrication • Boundary Lubrication Performance • Stability •
Fire Resistance • Compatibility • Biodegradability and
Toxicity • Additive Susceptibility
10.3 Conventional Lubricants — The Evolution of Base
Oil Technology
Early Base Oil Processing • Solvent Refining • Additives
Improve Performance • Hydrotreating • Hydrocracking •
Catalytic Dewaxing and Hydroisomerization • Group II —
Modern Conventional Base Oils • Group III —
Unconventional Base Oils • Group IV — Traditional
“Synthetic Hydrocarbon” Base Oils (PAO) • Group III vs.
PAO Performance • Future Evolution
10.4 Synthetic Lubricants
Reasons For Use

10.1 Introduction
Liquid lubricants have been around for a long time and have evolved from the conventional mineral-oil
based to the more exotic synthetics. In this chapter, a systematic approach to the selection of a lubricant
will be addressed. The evolution of the base oil technology for the conventional lubricants will be
discussed in detail. Different classes of the synthetic-based specialty and high-temperature lubricants and
their key features will also be addressed.

10.2 Lubricant Selection Criteria

Although this chapter is primarily about liquid lubricants, it is worthwhile to spend a little time discussing
some of the other popular lubricant types, i.e., greases and solid lubricants and hard coatings, to get a
better idea of why liquid lubricants are selected most often. Also, the primary lubricant in grease is a
liquid lubricant, so greases will be discussed to a minor extent throughout this section.

10.2.1 Operating Environment

When selecting a lubricant for a specific application, a number of factors must be considered. First, and
most important, is the environment in which the lubricant must function; generally, that is the temper-
ature range of the application. However, there are sometimes other environmental considerations, e.g.,

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outer space, liquid oxygen, or other reactive medium. After the above factors have been considered, one
must decide which type of lubricant is required for the application. For some applications, greases can
be selected which provide a simple design for the lubrication system, i.e., pack the bearing or mechanism
with the appropriate grease. For other applications, solid lubricants or hard coatings are preferred. Again,
they provide a simple lubrication system, although they frequently require some kind of relubrication
process to provide long-time service.
Finally we come to the most widely used form of lubricant, the liquids. Besides providing for lubrication
of the mechanisms, they also provide damping and cooling. Cooling occurs by removing either the heat
from the environment, e.g., a turbine engine bearing compartment, or the heat generated by the friction
in the mechanism. By appropriate designing of the lubrication system, a liquid lubricant can control the
temperature of a mechanical assembly within a very narrow temperature range, if required. For example,
as a lubrication system using a pump to distribute the lubricant becomes hotter, the oil becomes less
viscous, flow increases, and therefore the oil removes more heat. The liquid and grease lubricants also
provide an efficient relubrication mechanism, i.e., if a grease or liquid lubricant film is broken, the grease
or liquid flows back into that contact area, once again providing lubrication. For this reason, liquid and
grease lubricants are more widely used than solid lubricants or hard coatings, but the solid lubricants
and hard coatings are gaining wider acceptance as improvements in performance and lifetime are being
achieved.

10.2.2 Viscosity and Fluid-Film Lubrication

As previously stated, the operational environment for a liquid or grease lubricant usually imposes some
specific property requirements on the lubricant and guides its selection. These property requirements
are both physical and chemical. Perhaps the most used physical property is the viscosity–temperature
relationship. The low temperature operational capability of a liquid lubricant is defined by the maximum
viscosity at which the lubricant can be pumped; for a grease it is defined by the maximum thickness at
which the mechanical assembly or bearing can operate. The high-temperature operating capability of a
liquid lubricant may be defined by the minimum viscosity that can provide fluid-film lubrication.
The lubricant has to be effective in both the fluid-film lubrication and the boundary lubrication
regimes. In fluid-film lubrication, a fluid film separates the interacting surfaces. In boundary lubrication
the interacting surfaces react with the lubricant components to form protective physisorbed, chemisorbed,
or reaction films. Fluid-film lubrication can be further divided into two broad categories — hydrodynamic
lubrication and elastohydrodynamic lubrication. In fluid-film lubrication, the physical properties of the
lubricant, such as viscosity, pressure–viscosity, and traction, determine the performance of the lubricated
contact. While fluid-film lubrication is the desired mode of operation, the boundary lubrication regime
cannot be avoided. Even in fluid-film lubrication, boundary lubrication occurs during start-up and
stopping, and during occasional asperity interaction during operation. Therefore, the material (both the
surfaces and the lubricant) properties that are important for the boundary lubrication regime are equally
important for fluid-film lubrication.
For thicker fluid films, a combination of higher viscosity and higher pressure–viscosity coefficient are
needed (Hamrock, 1994). Both these properties are affected by the molecular structure of the lubricant.
Linear and flexible structures provide better viscosity–temperature characteristics compared to the
branched and rigid structures. On the other hand, the branched and rigid structures have higher pres-
sure–viscosity coefficients at a given temperature. The pressure–viscosity coefficient for the branched and
rigid structures decreases more sharply with temperature increase than that for the linear and flexible
structures (Sharma et al., 1995). The lubricant selected should be able to maintain adequate film thickness
throughout the operating temperature range.
Lubricant traction coefficient (rolling/sliding friction coefficient) determines the power losses and
stability of the rolling-element bearings (Gupta, 1984). For lubricants, a lower traction coefficient is
desired for lower power loss and lower heat generation, whereas a higher traction coefficient is desired
for the traction-fluids. The molecular structures that result in higher film thicknesses also provide higher

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 16

14
MIL-PRF-83282 (No VI-improver)

Viscosity @ 40 oC, cSt

12

10

8
MIL-H-5606 (contains VI-improver)
6

4
0 500 1000 1500
Test Hours

FIGURE 10.1 Viscosity of fluid samples from pump tests.

traction coefficients. Thus, the branched and rigid structures result in higher traction coefficients com-
pared to the linear and flexible molecules (Hentschel, 1985). When selecting a lubricant, a balance must
be achieved between the film-thickness and the traction properties.
In the lubricant industry, the temperature response of viscosity is expressed as viscosity index (VI).
The less the oil viscosity changes with temperature, the better its lubricating performance at high and
low temperatures and the higher its VI. Generally, higher VI is preferred for lubricants. To increase the
viscosity index of a lubricant, high-molecular-weight VI-improving additives are sometimes added to
the lubricant. These additives increase the lubricant’s viscosity at the higher temperatures as well as at
the lower temperatures (to a lesser degree), thereby increasing the viscosity index of the lubricant. The
VI-improvers have been extensively used in automotive lubricants to formulate the multigrade oils. The
viscosity measurements under low shear rates do not directly translate into effective viscosity or film
thickness in the lubricated contact for the VI-improved fluids. Under the high-stress and shear conditions,
the VI-improved fluids do not contribute to the film thickness and traction to the predicted levels (Palacios
and Bajon, 1983; Sharma et al., 1993a). In aircraft hydraulic pump tests, the fluid viscosity dropped
sharply during the tests for the VI-improved fluid, whereas there was no viscosity loss for the non-VI-
improved fluids, as shown in Figure 10.1 (Sharma et al., 1998; 1999). It is interesting to note that the
sheared, reduced viscosity fluid did not adversely affect the pump performance, and perhaps an even
lower viscosity fluid would have worked equally well. Equivalent performance was shown in pump tests
with a lower viscosity (8 cSt @ 40°C) non-VI-improved fluid (Gschwender et al., 1988), and no viscosity
loss was observed. In selecting the lubricant viscosity for an application, one should not look just at the
low-shear viscosity, but also the effective viscosity in the contact inlet.

10.2.3 Boundary Lubrication Performance

When metal-to-metal contact occurs between two surfaces in a lubricated contact, the asperities on the
surfaces shear, thereby exposing a fresh metal surface. The appropriate lubricant reacts with the exposed
fresh metal to form protective surface films. The surface films thus formed are generally low-friction and
wear-resistant, and protect the surfaces from early failure/wear. During operation, these surface films can
wear and regenerate. Antiwear or lubricity additives are generally added to the base oil to enhance the
formation of the protective surface films during boundary lubrication. Thus, in boundary lubrication,
the chemistry of the lubricant along with the material properties of the interacting surfaces determines
the performance of the lubricated contact. Some metals perform better in boundary lubrication than
others. Surface coatings (Rai et al., 1999) can also enhance boundary lubrication performance. Therefore,
when selecting a lubricant, the lubricated surfaces should be given proper consideration.
While full-scale system/component testing is the best way to evaluate a lubricant’s performance, more
economical tests, such as the four-ball wear test (e.g., ASTM D4172) and Cameron–Plint reciprocating

© 2001 by CRC Press LLC

tribometer (e.g. Helmick et al., 1997), are available to measure the boundary lubrication performance of
a lubricant/formulation. The full-scale component tests are preferred because sometimes the laboratory
tests do not correlate with the lubricant’s performance in the application.

10.2.4 Stability
If the upper operating temperature limit for a liquid lubricant is not defined by the viscosity temperature
properties, it is generally defined by the stability of the lubricant. For greases, the viscosity at elevated
temperature is not generally the critical property. For greases, the upper operating temperature limit is
generally defined either by stability or volatility.
A lubricant must be stable in the environment in which it is being used so that it provides adequate
lubrication for a finite lifetime. Some mechanisms are “lubricated for life,” whereas other mechanisms
operate in such a severe environment that the lubricant must be changed on a regular basis. For example,
most automobiles require that the engine lubricant be changed every 3000 or 5000 miles, whereas most
small electric motor bearings do not require relubrication for their useful life. There are typically three
different stabilities to consider that are inherent properties of the base fluid when a class of lubricants is
selected for a specific application. They are thermal, thermal–oxidative, and hydrolytic. (For greases, a fourth
stability is the ability of the grease to remain a grease and not separate into the base fluid and the thickener.)
We must carefully analyze the environment in which the lubricant must operate to determine what
kind of stability is required. In an aircraft hydraulic system, for example, the lubricant, or in this case
the hydraulic fluid, is not exposed to much air or moisture since the aircraft hydraulic systems are generally
closed. Therefore, thermal stability is the most important stability for aircraft hydraulic fluids. On the
other hand, if a shipboard hydraulic system is the intended application, hydrolytic stability also becomes
very important since the lubricant will be operating in a wet environment.
Thermal–oxidative stability becomes important in air breathing systems, such as automotive engines,
aircraft engines, etc., where the lubricant will be exposed to both high temperatures and oxygen. This
puts another very severe limitation on the selection of the lubricant since many classes of lubricants have
limited thermal–oxidative stability. In applications where oxidative stability is of paramount importance,
e.g., lubrication of valves coming in contact with liquid oxygen, liquid lubricants must not contain any
hydrogen atoms and must be totally halogenated, e.g., chlorofluorocarbons or perfluorinated lubricants.
The various classes of liquid lubricants and their thermal, hydrolytic, and oxidative stabilities will be
discussed later in this chapter.

10.2.5 Fire Resistance

Another important property to consider when a liquid lubricant is selected is fire resistance. Liquid
lubricants can range from extremely flammable to nonflammable. Fire resistance is extremely important
in hydraulic fluids. Three different aerospace hydraulic fluids have been developed and are in use today
strictly to reduce the fire hazards in aircraft hydraulic systems. They are hydraulic fluids based on
phosphate esters, specifically AS1241, and synthetic hydrocarbons, MIL-PRF-83282 and MIL-PRF-87257.
Fire resistance is especially important for hydraulic fluids since they are used at high pressures (up to
5000 psi), which significantly enhances their potential ignition if the fluid is in the form of a spray. Hatton
described the many hazards involved with hydraulic fluids and some of the more widely used methods
to determine fire resistance, but even in his book, he failed to recognize one of the most important fire-
resistance characteristics, flame propagation (Hatton, 1966; Snyder et al., 1981). Most flammability test
methods concentrate on a fluid’s ignition characteristics, and, while that indeed is an important property,
they fail to assess the potential damage from a fire once ignited. The AS1241 and both MIL-PRF fluids
are ignitable, but they have extremely low flame propagation characteristics, making them significantly
safer to use (Snyder et al., 1981).
Although nonflammable hydraulic fluids have been developed, e.g., MIL-H-53119, a moderate-molec-
ular-weight chlorofluorocarbon, they have not found their way into applications as yet. This has been

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primarily due to the need to develop hydraulic systems around their unique properties, e.g., high density,
specific seal compatibility, etc., and the fact that no one is willing to accept the high risk associated with
being the first to use a new lubricant. Nonflammable lubricants are currently used only in small-volume
applications.

10.2.6 Compatibility
For a lubricant to be acceptable for a specific application, it must be compatible with all of the materials
with which it will come into contact. This is especially true when trying to replace an existing lubricant
with a new one. For this case, it is also important that the new lubricant be compatible and miscible
with the former one to facilitate the changeover process from the old to the new lubricant. Significant
costs could be experienced if parts of the system, e.g., O-rings, gaskets, and other seals, had to be replaced
in order to realize the benefits the new lubricant would bring to that application. Since it is difficult to
ensure that the new lubricant will not leak out of the system and get on other materials in the vicinity,
e.g., paint, wiring insulation, composites, etc., the new lubricant will need to demonstrate compatibility
similar to the old lubricant it is scheduled to replace. That has caused frustration over the years for
operators of hydraulic equipment who would like to take advantage of the greater safety afforded by the
fire-resistant hydraulic fluids based on phosphate esters. If this equipment was originally designed for
use with mineral oil or other hydrocarbon-based hydraulic fluids, many of the materials contained therein
will not be compatible with phosphate esters and would have to be changed if phosphate esters were to
be used. This has caused many of these operators to stay with the rather flammable hydraulic fluid they
have been using instead of exploring other options. In a number of cases, it has been possible to gain a
significant increase in fire resistance by converting to a synthetic hydrocarbon- or ester-based hydraulic
fluid that is compatible with all the materials of their systems. In addition, the compatibility of these
fluids with the previous fluid has made the conversion to the new fluid simple and cost effective.

10.2.7 Biodegradability and Toxicity

Biodegradability and toxicity have been combined because they both pertain to similar characteristics of
lubricants. The degree of biodegradability of a lubricant relates to the environmental friendliness of a
lubricant, whereas the toxicity of a lubricant relates to the friendliness of the lubricant to the user.
Biodegradability is becoming a more important property as environmental regulations become more
restrictive with regard to protecting the integrity of water supplies and the environment in general.
Toxicity has been an important issue for quite some time, and safety to the user will continue to gain
attention. So far, the most important aspect of a lubricant for a specific application is that it work well,
and the environmental friendliness is secondary. In the future, it could be that the environmental aspects
of the lubricant will take precedence over performance.

10.2.8 Additive Susceptibility

In order for a lubricant to perform its required function, it is typically necessary to formulate the base
oil with performance-improving additives. Some of these additives are typically oxidation inhibitors,
lubricity additives (both antiwear and friction modifying), rust inhibitors, antifoam additives, and, in
the case of greases, thickeners. It is critical that additives be effective in the base oils for a lubricant to
provide satisfactory performance. In the case of liquid lubricants, the additives must also be soluble. For
the majority of the hydrocarbon-based lubricants, this is not a problem. They have been in use long
enough for effective, soluble additives to have been developed. However, for some of the newer fluids,
e.g., the perfluoropolyalkylethers (PFPAE), the traditional additives are not soluble. Therefore, soluble,
effective additives have had to be developed. The lack of effective, soluble additives for the PFPAEs has
significantly delayed their introduction into the industry (Snyder and Gschwender, 1991). However, their
limited introduction speaks well for their unique properties, which will be discussed later in this chapter.
There can be cases where additive solubility is not an issue, but effectiveness is. This is the case for the

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polydimethylsiloxane fluids, a.k.a. silicones. Although typical antiwear additives like aromatic phosphates
dissolve in silicone fluids, they do not provide improved lubricity for metal-to-metal contacts. This has
prevented their widespread use as lubricants for wide-temperature-range applications for which they
would be ideal candidates due to their excellent viscosity–temperature properties. Additive susceptibility
is an important property to consider when selecting a class of lubricants for specific applications.

10.3 Conventional Lubricants — The Evolution of Base

Oil Technology
In this section, we cover some of the major milestones in the evolution of base oil technology used to
make “conventional” lubricants. Conventional lubricants are defined here as those that have historically
been formulated with mineral oils derived from crude oil. But we will see that as base oil technology
continues to evolve, the performance gap continues to close between conventional mineral-based oils
and the traditional “synthetic hydrocarbon” oils described later in the chapter.

10.3.1 Early Base Oil Processing

From its humble beginnings over 3000 years ago, base oil technology has seen many phases of evolution.
In the first phase, animal fats were used as lubricants. Ancient inscriptions dating back to 1400 BC show
beef and mutton fat (tallow) being applied to chariot axles. Very little changed over the ages except that
the oils sometimes came from more exotic animals such as whales.
In 1852 petroleum-based oils first became available. They were not widely accepted at first because
they did not perform as well as many of the animal-based products. Raw crude did not make very good
lubricant. The base oil industry was on the very steep part of the learning curve. But demand grew with
the appearance of the automobile. Soon lubricant manufacturers learned which crudes made the best
lubricants. Further improvements were made by refining the crude into narrow distillation cuts with
varying viscosity. By 1923 the Society of Automotive Engineers classified engine oils by viscosity; light,
medium, and heavy. Engine oils contained no additives and had to be replaced every 800 to 1000 miles.
In the 1920s more lubrication manufacturers started “processing” their base oils to improve their per-
formance. There were three popular processing routes.
10.3.1.1 Clay Treating
Clay was used to soak up and remove some of the worst components in the petroleum base oil. These
compounds were usually aromatic compounds and highly polar compounds containing sulfur and nitrogen.
10.3.1.2 Acid Treating
Concentrated sulfuric acid was used to react with the worst components in the base oil and convert them
into a sludge that could be removed. This process effectively cleaned up the oil, but it was expensive.
This technology has virtually disappeared from North America due to environmental concerns about
the acid and sludge (National Petroleum Refiners Association, 1999).
10.3.1.3 SO2 Treating
This was a primitive extraction process to remove the worst components in the lube oil by using a
recyclable solvent. Unfortunately, the solvent was highly toxic. Although it also has been virtually phased
out (National Petroleum Refiners Association, 1999), it was a useful stepping stone to conventional solvent
extraction.

10.3.2 Solvent Refining

By about 1930 solvent processing emerged as a viable technology for improving base oil performance
using a fairly safe, recyclable solvent. Most base oils in the world today still use this process. Solvent
refining for base oil manufacturing was pioneered mostly by Texaco and Exxon under trade names such

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 TABLE 10.1 API Base Stock Categories
Group Sulfur, Wt % Saturates V.I.

I >0.03 and/or <90 80–119

II <0.03 and >90 80–119
III <0.03 and >90 ≥120
IV All Polyalphaolefins (PAOs)
V All Stocks Not Included in Groups I-IV (Pale Oils and Non-PAO Synthetics)

as “Texaco MP,” “Duo Sol,” “DILCHILL,” and “EXOL.” About two thirds of the base oils in North America
are currently manufactured using this route. Solvent-refined base oils are commonly called Group I base
oils. Group I base oils are those having less than 90% saturates (>10% aromatics) and more than 300 ppm
sulfur. Table 10.1 shows all the base oil groups as defined by the American Petroleum Institute (API).
Solvents and hardware have evolved over time, but the basic strategy has not changed since 1930.
Solvent refining is still the most widely used route for making base oil.
Aromatics are removed by solvent extraction to improve the lubricating quality of the oil. Aromatics
make good solvent but they make poor-quality base oil. Aromatics are among the most reactive compo-
nents in the natural lube boiling range. Oxidation of aromatics can start a chain reaction that can
dramatically shorten the useful life of a base oil. The viscosity of the aromatic components also responds
poorly to changes in temperature (low VI).
Aromatics are removed by feeding the raw lube distillate (vacuum gas oil) into a solvent extractor
where it is contacted counter-currently with a solvent. Popular choices of solvent are furfural, NMP (N-
methylpyrrolidone), and a mixture of toluene and MEK (methylethyl ketone). Phenol is very rarely used
due to environmental concerns. Solvent extraction typically removes 50 to 80% of the impurities (aro-
matics, polars, sulfur, and nitrogen-containing species). The resulting product of solvent extraction is
usually referred to as a raffinate.
The second step is solvent dewaxing. Wax is removed from the oil to keep it from freezing in the sump
or crankcase at low temperatures. Wax is removed by diluting the raffinate with a solvent. This is done
to thin the oil and enhance the dewaxing rate. Popular dewaxing solvents are MEK/toluene,
MEK/MIBK(methylisobutyl ketone), or (rarely) propane. The diluted oil is then chilled to –10 to –20°C.
Wax crystals form, precipitate, and are removed by filtration.

10.3.3 Additives Improve Performance

Over the next several decades, the solvent refining process did not change very much. Improvements in
finished oil quality came mainly from the appearance of additives. Additives began to be widely used in
1947 when the API began to categorize engine oils by severity of service: regular, premium, and heavy
duty. Additives were used to extend the life only in premium and heavy-duty oils.
In 1950, multigrade oils were introduced which were formulated with polymers to enhance the hot
and cold performance of the oil. The additives changed the VI of the oil. This trend continued for several
more decades. Lubricant quality improved significantly only when the additive chemistry improved. This
was the only viable strategy for progress until a significant improvement in base oil quality was available.

10.3.4 Hydrotreating
Hydrotreating was developed in the 1950s and first used in base oil manufacturing in the 1960s by Amoco
and others. It was used as an additional “cleanup” step added to the end of a conventional solvent refining
process. Hydrotreating added hydrogen to the base oil at elevated temperatures in the presence of catalyst
to stabilize the most reactive components in the base oil, improve color, and increase the useful life of
the base oil. This process removed some of the nitrogen and sulfur-containing molecules but was not
severe enough to remove a significant amount of aromatics. This was a small improvement in base oil
technology that would become more important later.

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10.3.5 Hydrocracking
Hydrocracking is a more severe form of hydroprocessing. It is done by adding hydrogen at even higher
temperatures and pressures than simple hydrotreating. Molecules are reshaped and often cracked into
smaller molecules. A great majority of the sulfur, nitrogen, and aromatics are removed. Molecular
reshaping of remaining saturated species occurs as rings are opened and paraffin isomers are redistributed,
driven by thermodynamics with reaction rates facilitated by catalysts. Clean fuels are by-products of this
process. A primitive version of the hydrocracking process was attempted for lube oil manufacturing in
the 1930s but was soon abandoned for economic reasons when solvent refining appeared (Sequeira, 1994).
After WWII, more modern hydrocracking catalyst technology was imported from Germany. This
technology was commercialized for fuel production in the late 1950s by Chevron (Stormont,1959). In
1969 the first hydrocracker for base oil manufacturing was commercialized in Idemitsu Kosan Company’s
Chiba refinery using technology licensed by Gulf (Anonymous, 1972). This was followed by Sun Oil
Company’s Yabucoa refinery in Puerto Rico in 1971, also using Gulf technology (Sequeira, 1994).

10.3.6 Catalytic Dewaxing and Hydroisomerization

Then came first-generation catalytic dewaxing and hydroisomerization in the 1970s. BP, Shell, and others
used hydroisomerization technology coupled with solvent extraction to manufacture very high-VI base oils
in Europe. In the U.S., Mobil used catalytic dewaxing in place of solvent dewaxing, but still coupled it with
solvent extraction to manufacture conventional neutral oils. Catalytic dewaxing was a desirable alternative
to solvent dewaxing, especially for waxy high-VI oils. This process removed n-paraffins and waxy side chains
from other molecules by catalytically cracking them into smaller molecules. This lowered the pour point
of the base oil so that it flowed at low temperatures like a solvent dewaxed oil. In the case of hydroisomer-
ization, the majority of remaining aromatics were saturated, and the majority of remaining sulfur and
nitrogen species were also removed. Chevron was the first to combine catalytic dewaxing with hydrocracking
and hydrofinishing in its Richmond, California, base oil plant in 1984 (Zakarian et al., 1987). This was the
first commercial demonstration of an all-hydroprocessing route for lube manufacturing.
In 1994, the first modern wax hydroisomerization process was commercialized by Chevron in the same
plant. This was an improvement over earlier catalytic dewaxing because it lowered the pour point of the
base oil by isomerizing (reshaping) the n-paraffins and other molecules with waxy side chains into very
desirable branched compounds with superior lubricating qualities rather than cracking away the n-paraffins.
By combining three catalytic hydroprocessing steps (hydrocracking, hydroisomerization, hydrotreat-
ing), molecules with poor lubricating qualities are transformed and reshaped into higher-quality base
oil molecules. Pour point, VI, and oxidation stability could be independently controlled. This was
fundamentally different than the previous approaches that relied solely on subtraction. Among the many
benefits of this combination of processes is greater crude oil flexibility; that is, less reliance on a narrow
range of crude oils from which to make high-quality base oils. In addition, the base oil performance is
substantially independent of crude source, unlike solvent-refined base oil.

10.3.7 Group II — Modern Conventional Base Oils

The modern hydroisomerization process licensed by Chevron under the name ISODEWAXING gained
acceptance rapidly in the 1990s. In fact, about one third of all base oils manufactured in North America
are now manufactured using this process (Figure 10.2). ISODEWAXING technology is also moving
through Asia as well. Rapid growth of this technology in the U.S. prompted the API in 1991 to categorize
base oils by composition (API publication 1509), as shown in Table 10.1.
Most of the base oils made using modern hydroisomerization are categorized as Group II. Table 10.1
shows that they are differentiated from Group I base oils because they contain significantly lower levels
of impurities (<10% aromatics, <300 ppm sulfur). They also look different because Group II oils are
normally very clear, almost water-white. From a performance standpoint, improved purity means that
the base oil and the additives in the finished product can last much longer. This technology, along with

© 2001 by CRC Press LLC

 35
30
25

Percent
20
15
10
% Base Oil in
North America
5
0
1995 1996 1997 1998 1999

FIGURE 10.2 ISODEWAXING trend in North America.

specially designed additives, has already had a tremendous impact on finished oil performance. In some
applications, lubricating oils formulated with Group II base oils outperform expensive traditional “syn-
thetic hydrocarbon” oils made from PAO.

10.3.8 Group III — Unconventional Base Oils

The difference between Group II and III base oils is simply viscosity index (VI). Base oils with a
“conventional” VI (80 to 119) are Group II. Base oils with an “unconventional” VI (120+) are Group III.
They are also sometimes called unconventional base oils or UCBOs. Still another commonly used name
for these oils is VHVI, or very high VI base oils.
Group III base oils were not widely available in North America until a few years ago. Earlier generations
of Group III base oils (Min, 1998) were produced in Europe, primarily by Shell and BP, but were not
produced using the now commonly accepted all-hydroprocessing route. Consequently, they do not have
the exceptional stability and low temperature performance of these modern Group III oils. Fortunately
for North American consumers, those older-generation stocks are made and sold in different markets.
Many of these plants are being upgraded to modern technologies that will enable them to make the
modern Group III oils (Howell, 2000).
Modern Group III base oils perform at a level that is significantly higher than “conventional” base
oils, both Group I and Group II, and nearly match existing levels of performance in finished lube
applications already established by their traditional “synthetic hydrocarbon” counterparts. The most
notable exception, arctic oils, have very small market presence.
From a processing standpoint, the higher VI in modern Group III base oils is achieved by increasing
the temperature or time in the hydrocracker. This is sometimes collectively referred to as the “severity.”
Alternatively, the product VI could be increased simply by increasing the feed VI, which is typically done
by selecting the appropriate crude.
Group III base oils are now widely available in North America because they can be manufactured by
most of the companies that currently make Group II oils. Many companies have started adding them to
their “synthetic hydrocarbon” product lines.

10.3.9 Group IV — Traditional “Synthetic Hydrocarbon”

Base Oils (PAO)
Synthetic lubricants will be discussed in detail later in the chapter. However, we thought it would be
appropriate to say a few words about “synthetic hydrocarbon” base oils here because they are directly
influencing the future direction of mineral-based base oil technology.
The hydrogenated polyalphaolefin (PAO) commercial market can be traced as far back as the early
1970s when specialized products were formulated from PAOs (Bui, 1999). PAOs became a major con-
sumer-sought lubricant product when Mobil Oil commercially marketed its Mobil 1™ product 25 years
ago. However, Mobil’s involvement with “synthetic hydrocarbons” can be traced back to the 1960s when
the oil company resolved a problem plaguing military planes based on aircraft carriers. Mobilgrease 28
was developed to protect against wheel bearing failure caused by atmospheric cold temperatures. Mobil’s
SAE 5W-20 engine oil is derived from this base fluid technology. Since then, the PAO market has traveled

© 2001 by CRC Press LLC

a long and winding road battling a slow, steady growth and criticisms of the higher cost compared to
conventional oils. In the last 10 years, the PAO market significantly took off, first in Europe and then in
North America, experiencing as much as a double-digit growth. In part, the growth might be attributed
to the stricter lubricant specifications in Europe that created a market niche for synthetic hydrocarbons
and semisynthetic hydrocarbon products. The demand has since extended to North America and other
continents.
The use of the word “synthetic” in the lubricant industry has historically been synonymous with
polymerized base oils, such as PAOs, and other synthetics, such as esters, polyphenylethers, etc., which
are made from smaller molecules. Primarily this use evolved because these types of base oil were the only
components available for high-performance lubricants. That changed a number of years ago when some
lubricant manufacturers, primarily in Europe, began replacing PAOs with newly available Group III base
oils, which are made from feed molecules of substantially the same size as the final product. With the
recent availability of modern Group III base oils in North America, this practice is now spreading to
North America. This is currently causing a controversy in the lubricant industry, as some synthetic
hydrocarbon base oil producers and lubricant manufacturers see only polymerized base oils or other oils
made by combining smaller molecules as the true and only synthetic hydrocarbons.
PAOs have historically had superior lubricating performance characteristics, such as viscosity index,
pour point, volatility, and oxidation stability, that could not be achieved with conventional mineral oils.
Now, in modern base oil manufacturing, viscosity index, pour point, volatility, and oxidation stability
can be independently controlled. Modern Group III oils today can be designed and manufactured so
that their performance closely matches that of PAOs in most commercially significant finished lube
applications.

10.3.10 Group III vs. PAO Performance

As well-designed Group III base oils become abundant in the market place, the performance gap between
Group III and PAO (Group IV) is closing. Here are some key examples:
Pour Point — Pour point is the one place where Group III oils allegedly fall short of PAOs. While it
is certainly true that the pour point of the neat VHVI base oil is substantially higher than that of
a PAO of comparable viscosity, it is important to understand that what matters is the pour point
of formulated lubricants, which are comprised of both base oils and additives. Fully formulated
Group III-based lubricants are very responsive to pour point depressant additives, and where pour
point depressants may be used, these lubricants can demonstrate pour points of –50°C or below
when they are manufactured with modern isomerization catalysts. Products such as motor oils
made with the lighter-grade PAOs, on the other hand, typically have higher pour points than the
base fluid, so the gap in final product pour point between PAO-based and UCBO-based lubricants
is smaller than in the base fluids themselves. Moreover, it is entirely possible with modern Group
III manufacturing technology to produce base oils of even lower pour point, although this is not
currently common practice in the industry precisely because there is very little customer demand
or specifications for pour performance below –50°C.
Cold Crank Simulator — Viscosity in engine journal bearings during cold temperature startup is a
key factor in determining the lowest temperature at which an engine will start. Cold Cranking
Simulator (CCS) viscosity, as measured by ASTM D5293, is determined under conditions similar
to those experienced in engine bearings during starting. For base oils, this viscosity is determined
almost entirely by viscosity and viscosity index. Since VHVI stocks have a VI comparable to that
of 4 cSt PAO, one would expect comparable CCS performance. This is demonstrated in Figure 10.3,
where it can be seen that a 4 cSt Group III base oil with a kinematic viscosity of 4.2 cSt @ 100°C
and a VI of 129, and PAO 4, with a viscosity of 3.9 cSt and VI of 123, have similar CCS values,
both about half that of a 4 cSt Group II base stock of about 100 VI. This performance makes the
UCBO very effective for formulating fuel-efficient multiviscosity engine oils in the 0W-20 to
0W-50 range, one that has historically been achieved only with PAO-based product.

© 2001 by CRC Press LLC

FIGURE 10.3 Cold cranking performance of mineral oils and PAO.

FIGURE 10.4 Noack volatility of mineral oils and PAO.

Noack Volatility — Noack volatility of an engine oil, as measured by ASTM D 5800 and similar
methods, has been found to correlate with oil consumption in passenger car engines. Strict
requirements for low volatility are important aspects of several recent and upcoming engine oil
specifications, such as ACEA A-3 and B-3 in Europe and ILSAC GF-3 in North America. Figure 10.4
shows that from a blender’s perspective, Group III base oils are similarly effective as PAOs for
achieving these low volatility requirements in engine oil applications. The viscosity index of
modern Group III oils typically matches or exceeds that of PAO so they can match the volatility
of PAOs at a reasonable distillation cut width.
Oxidation Stability — Oxidation and thermal stability are among the most important advantages that
“synthetic hydrocarbons” bring to the table. Better base oil stability means better additive stability
and longer life. High stability is the key to making the premium-quality finished oils of the future
with longer drain intervals. Here Group III oils routinely challenge PAO performance.
The stability of modern Group III stocks depends mostly on their viscosity index, because VI is an
indication of the fraction of highly stable isoparaffinic structures in the base oil (Kramer et al., 1999).
However, because modern Group III stocks also undergo additional severe hydrofinishing after hydro-
cracking and hydroisomerization, they achieve an additional boost in stability because only trace amounts
of aromatics and other impurities remain in the finished stocks.
The benefit of all-hydroprocessed Group III base oils in oxidation stability is illustrated in Figure 10.5,
for hydraulic oils formulated by using the same additive system in four different base oils. Here, the time
required to reach an acid number of 2.0 (defined by neutralization of 2.0 mg of KOH/g of oil) in the
Universal Oxidation Test (ASTM D4871), a common measure of oil oxidation, was substantially longer
for the Group III formulation than for either the Group I or II products. Moreover, the performance of
the Group III product was essentially the same as that for the oil formulated with PAO. Table 10.2 lists
a variety of North American lubricants of which the authors are aware which are based upon all-
hydroprocessed Group III base stocks. These products include engine oils, industrial oils, and driveline
fluids like automatic transmission fluid, and are targeted at the same performance levels achieved by
traditional synthetic hydrocarbon formulations.

© 2001 by CRC Press LLC

FIGURE 10.5 Oxidation stability, acid number of hydraulic oils.

TABLE 10.2 Synthetic Quality Products Utilizing All-Hydroprocessed

Group III Base Stocks
Available Now Upcoming

Semi and full synthetic PCMO
Semisynthetic HDMO
DaimlerChrysler ATF+4®
Ford Mercon® V ATF
Compressor oil
GF-3 PCMO (semi and full synthetic)
Extended drain gear oil
High performance automotive (racing) oils
Motor oils
Gear and transmission oils

10.3.11 Future Evolution

Looking to the future, the trend is toward base oils with even higher purity, higher VI, lower volatility,
and longer life. The base oils will probably look even more like PAO as they become more concentrated
in isoparaffins, the most stable component in the base oil. It is likely that as base oil technology continues
to evolve, the base oils of the future will surpass current benchmarks such as PAO in the critical
performance areas such as oxidation stability and VI.
There are many possible routes for improving base oil quality. Continued evolution of the all-hydro-
processing route is one likely possibility. Selectivity toward desired molecular compositions could be
improved by improving the catalysts and the processing technology. Improving the feedstock can also
improve the product. Very paraffinic (waxy) feedstocks such as Fischer Tropsch wax from natural gas-
to-liquids plants can potentially be further processed into high-quality base oils. Volumes and applications
are expected to grow, as more ultra-waxy feedstocks become more widely available. Other competing
technologies are likely to emerge. New routes for manufacturing PAOs have been proposed that use
cheaper feedstocks such as ethylene and propylene rather than 1-decene (Heilman et al., 1999).
In summary, the conventional base oil technology evolved slowly from ancient times until the middle
of the 20th century. Then solvent refining brought base oil performance to a new level. Starting in the
1960s, hydroprocessing technologies were applied and combined to improve base oil purity and perfor-
mance. Group II base oils were born. An all-hydroprocessing route for Group II base oil manufacturing
was commercialized. Modern hydroisomerization technologies, such as ISODEWAXING became widely
accepted and have grown exponentially since 1995. They are now used to make one third of all base oils
in North America.
The next wave appears to be Group III base oils. They offer most of the performance advantages of
traditional PAO-based “synthetic hydrocarbon” oils at a fraction of the price. Most of the manufacturers
that make Group II base oils can make Group III base oils. As base oil technology and additive technology
continue to improve, mineral-based oils will continue to close the performance gap with traditional
“synthetic hydrocarbons.” Traditional “synthetic hydrocarbon” oils such as PAO should continue to
coexist with Group III oils as they have for years in Europe, but the widespread availability of high-
quality Group II and III mineral oils is accelerating the rate of change in the finished oil markets. New
improved base oils are helping the engine and equipment manufacturers meet increasing demands for
better, cleaner lubricants.

© 2001 by CRC Press LLC

10.4 Synthetic Lubricants

10.4.1 Reasons For Use

In this section we will present an overview of synthetic fluids with unique properties. Synthetic fluids
are selected because a mineral oil is deficient in some respect for a particular application. The U.S. military
has often led research and development into new synthetics because of military requirements for high
performance. Because of this and the authors’ backgrounds, many examples will be based on military
lubricants. Driving the use of these synthetics are cost, availability, performance, and safety.
10.4.1.1 Cost
Synthetic fluids are, as a rule, more expensive than mineral oils. An exception was a super-refined, deep
dewaxed paraffinic mineral oil, used as the base stock for the SR-71 aircraft hydraulic fluid, MIL-H-
27601A. MIL-H-27601A cost over $100 per gallon, when a less expensive hydrogenated polyalphaolefin-
based replacement was found. In cost analysis, an engineer must not only consider the initial acquisition
cost of the lubricant, but also the life cycle cost. In life cycle cost analyses, the synthetic lubricants are
often superior because equipment needs fewer repairs with synthetics, which are better inherent lubri-
cants. Often equipment can be lubricated for life, never needing further lubrication, or at least extending
maintenance intervals and thereby reducing down time.
10.4.1.2 Availability
Synthetic fluids are generally more available in good quality than even the more stable of the mineral
oils because the mineral oils come from various wells that may not be the same. Gradually as the better
crude oils are depleted, less stable crude oils are used. In several cases in the military, mineral oil products
no longer met the specifications that had been written around the original products. Synthetics, on the
other hand, can be made consistently, as long as the starting materials are the same.
10.4.1.3 Performance
Synthetic lubricants can be adjusted in the synthetic process to optimize property performance to a
particular application. With mineral oils, the refiners have some, but much less latitude to adjust prop-
erties. High-temperature thermal and oxidative stability of synthetics exceeds those of mineral oils. Also
viscosity–temperature range and low-temperature flow can be improved and controlled in synthetics by
controlling branching and chain length, for example. The upper limit may be from a thermal stability
limit or from a viscosity limit. (A fluid’s lowest useful viscosity depends on the application, but is generally
considered to be 0.5 to 1.0 cSt for adequate lubrication film formation in a bearing or other wear surface.)
The lower temperature limit may be either from limiting viscosity or from pour point, two distinct
properties of a fluid. The low-temperature viscosity depends on the application, e.g., size of fluid pumps,
length of tubing lines, and other impediments to flow. For gas turbine engine oils, for example, 19,000 cP
is considered the highest usable viscosity, while for hydraulic fluids in aircraft, 2100 cP is considered the
highest usable viscosity. Most often, any fluid class is available in a number of viscosity grades. The
commercial literature is often the best place to find current information to aid in selecting the proper
grade of a fluid. Selecting the proper fluid class, however, is not so simple and requires research to weigh
the pros and cons of the available fluid classes.
10.4.1.4 Safety
Flammability of lubricants is often a major consideration in the design of equipment, and even in
determining if a particular fluid should be used. Mineral oils are a distillation cut of a crude oil and so
the final oil’s flash point will be that of the most volatile part of the mixture. Synthetics, on the other
hand, can be more closely controlled to be essentially the same molecular weight throughout. This means
the flash point of synthetic oil will be higher for a certain viscosity of oil than it would be for a mineral
oil of the same viscosity. For a phosphate ester fluid, fire resistance is even greater because the phosphorous
atom acts as a fire suppressant.

© 2001 by CRC Press LLC

FIGURE 10.6 Polyalphaolefin — general formula.

Flammability testing is a science unto itself (Snyder et al., 1981). The potential threat of an application
must be considered, including ignition source, amount of oxygen present, air flow, temperature of the
surroundings, and materials present, to name a few.
10.4.1.5 Fluid Classes
10.4.1.5.1 Synthetic Hydrocarbons
Synthetic hydrocarbons have gone from the laboratory to a major industrial product. Hydrogenated
polyalphaolefin (PAO), Figure 10.6, is the most widely used synthetic hydrocarbon. It is most often
synthesized from C10 alpha unsaturated olefins using BF3 catalyst to make C20 , C30 , C40 , etc., finished base
oils. The synthesis conditions are adjusted to favor a certain molecular weight product, optimum viscos-
ity–temperature properties and low-temperature flow characteristics. The fluid is hydrogenated to remove
residual olefins and fully saturate the molecules.
PAOs have many of the advantages of highly refined paraffinic mineral oils such as those from now
mostly depleted Pennsylvania crude oils. In fact, PAOs resemble paraffinic oils chemically, as they are
largely straight chains, giving them high thermal stability and good viscosity–temperature index. Some
branching exists in PAOs, which prevents them from freezing (waxing) at cold temperatures. Mineral
oils must be dewaxed to remove the totally linear molecules to prevent low-temperature freezing (waxing).
PAOs are synthesized to avoid waxes. Ideal properties for a PAO are a careful balance of branch vs. linear
structure. PAOs in general have better lubricating ability than comparable mineral oils because there are
no other atoms besides carbon and hydrogen. The thermal stability of PAOs, when oxygen is excluded,
is quite high, as shown by the MIL-PRF-27601C fluid upper bulk oil temperature, 288°C. (The MIL-H-
27601A specification changed from a mineral oil to a PAO-based fluid when it became MIL-H-27601B,
as it is in the later revision MIL-PRF-27601C.) Also, PAOs respond to additives very similarly to mineral
oils except that additives tend to be less soluble in PAOs (especially the higher-molecular-weight oils)
than in mineral oils. PAOs cost less compared to other synthetic fluids.
The first major use of PAOs was in military hydraulic fluid, MIL-H-83282 (now MIL-PRF-83282)
(–40°C to 200°C), based on decene trimer PAO (Gschwender and Snyder, 1999). This was developed as
a fire-resistant fluid to counter the loss of military aircraft and lives from fires resulting from the use of
a highly flammable mineral oil-based hydraulic fluid, MIL-H-5606. Aircraft damage directly attributable
to hydraulic fluid fires went from over $10 million a year to fewer than $1 million a year with the
conversion of the majority of Air Force aircraft to MIL-PRF-83282. MIL-PRF-83282 is now the primary
hydraulic fluid for military aircraft in the U.S., Australia, and Israel, and is gradually going into European
military aircraft. Other PAO uses in the military are MIL-PRF-87257 (–54°C to 135°C), a fire-resistant
hydraulic fluid for cold climate operation; MIL-H-46170, similar to MIL-PRF-83282 but with a rust
inhibitor; MIL-PRF-27601 (–40°C to 288°C), the high-temperature hydraulic fluid mentioned earlier.
The C20, PAO decene dimer is widely used as a dielectric and cold plate coolant for military radar
systems (Flanagan et al., 1991), commercially as a solar heat transfer fluid and as a large computer coolant,
and as a shock absorber for higher priced automobiles. PAOs are also used in moisture-resistant, wide-
temperature greases, e.g., MIL-PRF-32014, and instrument oils. A small but critical higher-molecular-
weight PAO application is as oil or as grease for spacecraft (Jones et al., 1998). An important advantage
of the lower-molecular-weight PAOs is that they are readily biodegradable. MIL-PRF-87257 is a class 1
(the best) and MIL-PRF-83282 is a class 2 (second best) in the ASTM D5864 biodegradability test.

© 2001 by CRC Press LLC

 Decene trimer PAOs are often formulated as a major component of synthetic automobile engine oils,
although they are more popular in Europe than in the U.S. Because they are inherently good lubricants,
lower viscosity motor oils can be safely used, reducing viscous drag and engine wear. Often automobile
operators using synthetic motor oils extend the oil change intervals as well as engine life, greatly offsetting
the higher cost of the synthetic oil.
Another synthetic hydrocarbon fluid type, with a small but unique
niche, is multiply alkylated cyclopentanes (MACs) (Figure 10.7). In most
applications, these fluids are too expensive to be commercially viable, but
in spacecraft applications, they are being used more and more. Advantages
include low volatility and vapor pressure, low pour point, good antiwear
properties, and good additive response. The cyclopentane ring acts as an
anchor to which alkyl groups can be attached to produce lubricants with
good viscosity temperature properties and low pour points. The market FIGURE 10.7 Multiply alky-
for these fluids with unique properties will likely grow. lated cyclopentanes.
10.4.1.5.2 Esters
Hermann Zorn in Germany first researched ester lubricants in the 1930s as a replacement for aircraft
engine castor oil lubricants, notorious for sludge formation in higher temperature engines. In the U.S.,
the Naval Research Laboratory also experimented with esters in the 1940s. MIL-L-7808 first defined the
ester gas turbine oil requirements in 1951. Revisions of MIL-L-7808 have led to MIL-PRF-7808 K, with
Grade 3, a –54°C to 177°C (temperature given refers to the bulk oil temperature) fluid, and Grade 4, a
–51°C to 204°C fluid. The U.S. Navy, having less severe low temperature needs, has its own specification,
MIL-PRF-23699, with a standard STD type, a –40°C to 177°C oil, and a high temperature HTS type, a
–40°C to 204°C oil. Commercial aircraft also use this product as gas turbine engine oil.
The first ester lubricants were diesters and, as the temperature demands increased, esters became more
complicated, for example, trimethylolpropane, pentaerythritol, and dipentaerythritol esters, as shown in
Figure 10.8. Diesters are the least expensive, often similar in price to PAO fluids. As the ester functionality
increases, the costs also increase. Diesters have the best viscosity–temperature properties compared to
the more complicated esters. The pentaerythritol ester has very high autogenous ignition temperature
for a specific viscosity, a property very important in gas turbine engine applications where engine nacelles
are extremely hot and fires are disastrous. All esters are considered fire resistant compared to mineral
oils of comparable viscosities. Ester lubricants have excellent oxidative stability and can be tailored to
new applications. A wide variety of esters are commercially available. Esters are generally readily biode-
gradable because they react with water as the first step in degradation. One problem with esters in
application however, is unwanted hydrolysis, although beta blocking (having an alkyl branch on the
second carbon from the oxygen in the acid portion of the ester chain) does stabilize the molecule, both
hydrolytically and oxidatively.
Esters have many uses besides aircraft engines. Diesters are the base fluids for low temperature greases,
e.g., MIL-PRF-23827, gear oils, and instrument oils. Many of the synthetic automotive motor oils are
partially ester oils.

O O O
R-O-C(CH2)xC-O-R CH3CH2CH2-C-[CH2-O-C-R’]3

Diester Trimethyol Propane Ester

O O
C-[CH2-O-C-R"] 4 O-[CH2 -C-(CH2OC-R") 3]2

Pentaerythritol Ester Dipentaerythritol Ester

FIGURE 10.8 Gas turbine oil esters.

© 2001 by CRC Press LLC

 The U.S. Air Force is now developing the best possible thermally and oxidatively stable (–40°C to
232°C) ester for advanced engines (Gschwender et al., 2000). Improved and new higher-temperature fuels
and structural engine materials, and a desire for improved fuel efficiency are leading the way for higher-
temperature gas turbine engine oils. Problems in development programs with high-temperature perflu-
oropolyalkylether candidate gas turbine engine oils, as will be discussed later, reinforced the need to
develop the best ester-based gas turbine engine oil possible.
A recent advancement in esters is the polymer ester, a copolymer of alphaolefins and unsaturated diesters.
While they are more expensive than diesters, they have shown high benefit as antiwear blending fluids in
about 20 to 30% concentration with other base fluids. The unpaired electrons on the oxygen in the ester
are believed to bond to metal surfaces. Because the polymer esters often replace chlorinated cutting fluids,
they offer environmentally safer fluids with good antiwear and viscosity–temperature properties.
10.4.1.5.3 Phosphate Esters
Phosphate esters are widely used as excellent fire-resistant lubri-
cants. In most flammability tests they are superior to other fire-
resistant fluids unless significant amounts of halogens (chlorine,
fluorine, or bromine) replace the hydrogen in the molecules. The "
general structure is shown in Figure 10.9, although the triaryl phos-
phates are also used as fire-resistant fluids. FIGURE 10.9 Phosphate ester —
Advantages of phosphate ester fluids, besides their fire resistance, general formula.
include excellent lubricity and bulk modulus. Phosphate esters must
be closely monitored in the application to control hydrolysis (reaction with water) to form phosphoric
acid on one or more of the P–O–R sites. When properly monitored, they are used with great success.
Phosphate ester thermal and oxidative stability is fair, with improvements being made as described below.
Another issue in using phosphate esters is compatibility of paints, wiring, and elastomeric seals. These
materials must be carefully selected, excluding most materials typically used with mineral oils. For this
reason, equipment maintainers must use extreme care not to cross-contaminate phosphate ester fluid
with mineral oil, or other hydrocarbon fluids, and vice versa, as disastrous consequences will result. In
the U.S. Air Force, for example, any aircraft using phosphate ester fluids is maintained in a separate area
from aircraft using hydrocarbon-based fluids. Of synthetics, phosphate ester fluids are more expensive
than all except the highly halogenated oils and polyphenylethers.
Phosphate ester hydraulic fluids were introduced into commercial aircraft in the late 1950s and have
gone through many “type” improvements since then. The fluid is described in the Society of Automotive
Engineers document AS 1241. Currently Type IV, –54°C to 107°C, is used with low- and high-density
versions, Classes 1 and 2 respectively. Type V is a higher thermal stability version for use in newer, higher-
temperature commercial aircraft and is currently used in some aircraft.
Other uses of phosphate ester fluids are as lubricants, compressor fluids, coolants, brake fluids, and
greases. When the user properly maintains the fluid, phosphate ester fluids provide excellent fire resistance
in applications for which hydrocarbons are too flammable. Lower fire insurance rates may offset the extra
expense of phosphate ester initial cost and monitoring. The excellent antiwear properties of phosphate
esters, especially compared to water-based fluids, save on component replacement costs.
10.4.1.5.4 Silicon-Containing Fluids
Silicate ester and silicone fluids are illustrated by the formula in Figure 10.10. Both contain Si–O bonds
that impart unique properties to these fluids, namely very high viscosity–temperature index, low bulk
modulus, and low surface tension. Many authors attribute these properties to flexibility of the molecule
around the Si–O bond. These fluids are low volatility and have good fire resistance. The low surface
tension of the silicone and silicate ester fluids is generally undesirable in a lubricating application because
the oil tends to seep past seals to contaminate other surfaces. A third silicon-containing fluid is the
silahydrocarbon, a tetralkylsilane (Figure 10.11). This fluid has the advantages of the other silicon-
containing fluids, while their negative properties are minimized. While silahydrocarbons are not used
commercially as yet, they are promising for specialty applications.

© 2001 by CRC Press LLC

FIGURE 10.10 Silicon-containing fluids.

FIGURE 10.11 Silahydrocarbons.

10.4.1.5.5 Silicate Esters

The silicate esters, MIL-C-47220, were once widely used as dielectric and plate coolants in many military
radar systems, and as a high-temperature, –54°C to 177°C, hydraulic fluid, MIL-H-8446, in the B-58
aircraft. Silicate esters have excellent thermal stability and wide temperature range, but are very expensive.
A disiloxane silicate ester hydraulic fluid is still used in the supersonic Concorde commercial aircraft.
Both military specifications are now canceled. The silicate ester coolants have been largely replaced with
C20 PAO-based fluids (MIL-PRF-87252) in the radar cooling application. One major drawback to silicate
ester fluids is the hydrolysis of the Si–O–R bond to form a flammable alcohol and a gel. The alcohol is
a safety hazard and the gel is responsible for clogging system filters and, in dielectric applications where
the electronics are actually immersed in the coolant, the gel acts as a pathway for electrical arcing, disabling
the electronic system. The resulting black strings of decomposed fluid are known in the industry as “black
plague.” Most silicates are beta-blocked, that is, they have an ethyl group on the second carbon from the
O atom. This interferes with the hydrolysis reaction, but does not totally stop it. The replacement,
hydrolytically stable PAO-based fluids are also considerably less expensive than the silicate esters. While
PAOs are not as good in viscosity–temperature properties as silicate esters, they are miscible and com-
patible and have worked well as drain-and-fill replacements wherever tried.
10.4.1.5.6 Silicones
The R groups in the silicone fluids (Figure 10.10) can be methyl or other alkyl, phenyl, or alkyl, with
some of the hydrogen substituted with either chlorine or fluorine. The greater the ratio of Si and O to
hydrocarbon in the molecule, the higher the viscosity index, and the lower the thermal stability and
surface tension, and vice versa. When these fluids decompose thermally they create an undesirable gel,
similar to the gel from the hydrolytic decomposition of silicate esters. The chlorine or fluorine in some
silicone fluids improves their thermal stability and also their antiwear characteristics.
Silicone fluids have rather poor performance in wear properties of the base fluid by itself, and few
additives are soluble or effective for antiwear benefit. Silicone fluids are now primarily used in greases.

© 2001 by CRC Press LLC

The greases are useful as wide temperature range products because of their excellent viscosity–temper-
ature properties and good high-temperature performance. Currently, MIL-PRF-83261 is an alkyl substi-
tuted silicone-fluid grease, and MIL-PRF-83363 is a fluoroalkyl dimethyl copolymer-substituted silicone
fluid grease. Solubility of additives is less of an issue for greases, as partially soluble or even insoluble
additives can be used. Since much less grease is usually used, the higher cost of silicone greases is less of
an issue than when a liquid lubricant is used.
Other applications of silicone fluids are in synchronous motors, in precision equipment, with plastic
and rubber parts of refrigerators and recording tape, as dielectric coolants, as brake fluids, and as damping
fluids.
10.4.1.5.7 Silahydrocarbons
Silahydrocarbon fluids (Figure 10.11) were first synthesized and characterized in the 1950s (Rosenberg
et al., 1960). Their excellent, unique viscosity–temperature range and thermal stability were recognized,
but these fluids froze at rather high temperatures. In the 1970s, silahydrocarbons were synthesized with
good low-temperature properties by using various alkyl group lengths in the starting materials, allowing
a –54°C to 316°C missile hydraulic fluid to be developed (Gschwender et al., 1981; Snyder et al., 1982).
The fluid was never used, however, because the missile program was canceled. These fluids had one
silicon atom that acted as an anchor for the hydrocarbon chains, giving the fluids good viscosity–tem-
perature properties and low pour points.
In the 1990s, University of Dayton Research Institute under contract to Wright-Patterson Air Force
Base first synthesized high-molecular-weight silahydrocarbon spacecraft fluids with three or four silicon
atoms. The result was the first candidate space fluid that was unimolecular. These fluids have volatility
lower than any other space lubricant, except those based on Fomblin Z® perfluoropolyalkylether fluid.
In addition, they have lower torque in wear applications than PAOs or multiply alkylated cyclopentane
fluids, the newest synthetic space lubricants currently in spacecraft (Sharma et al., 1993b). Other varia-
tions of space silahydrocarbons have been synthesized under Air Force sponsorship. Recently NASA Glenn
Research Center conducted vacuum wear tests, finding silahydrocarbon space fluids to perform extremely
well (Jones et al., 1999).
Other advantages of silahydrocarbons are:
1. They are fire resistant.
2. The properties can be tailored to new applications by making them higher or lower molecular
weight.
3. They are compatible with other hydrocarbon fluids, an advantage in easy fluid conversion.
4. They have good bulk modulus; not quite as good as PAOs, but much better than other silicon-
containing fluids.
5. They have low traction properties, which means bearings operate with low internal friction.
The major disadvantages are they are not commercially available as of this writing and are more
expensive than other hydrocarbon synthetics.
Potential silahydrocarbon fluid applications include fire-resistant, wide-temperature-range hydraulic
fluids, space lubricants, and in niche commercial lubricants especially in precision bearings. Figure 10.12
shows the typical ASTM D92 flash points of hydraulic fluids. Three fluids with different base fluid
chemical classes, all have –54°C viscosities of less than 2500 cSt. The flash point of the fourth fluid (MIL-
PRF-83282), which has a –40°C viscosity of 2500 cSt, is also shown for comparison. The silahydrocarbon
has the highest flash point or the greatest safety margin, compared to the mineral oil (MIL-H-5606) and
PAO (MIL-PRF-87257) fluids (all –54°C operational fluids). Also, several commercially available additives
have been found to be both soluble and effective antiwear additives for silahydrocarbons.
10.4.1.5.8 Chlorotrifluoroethylene Polymers
Chlorotrifluoroethylene fluids (CTFEs) were developed in the 1940s for the Manhattan Project and have
enjoyed a niche market since then. They are represented by the formula Cl(CClFCCl2)nF. They are non-
flammable by any practical definition and can be used in contact with liquid oxygen and other aggressive

© 2001 by CRC Press LLC

FIGURE 10.12 Comparative ASTM D92 flash point of mineral oil, PAO, and SiHC.

materials totally unsuitable for hydrocarbon lubricant contact. CTFEs are more expensive than synthetic
hydrocarbon fluids but are a less expensive alternative to perfluoropolyalkylethers (PFPAEs) for demand-
ing applications.
CTFEs have good stability (up to 177°C) and excellent viscosity–temperature range. They have bulk
moduli almost as good as that of hydrocarbon fluids and much better than that of the PFPAEs. Another
advantage is they solubilize many of the commercially available hydrocarbon additives, although many
of those additives are ineffective in CTFE (Gschwender et al., 1992).
A major disadvantage of CTFE fluids is their high density, approximately double that of hydrocarbon
fluids. Also, they react with copper and low chrome steels, which should be avoided in components. Also,
as mentioned earlier, their cost is considerably higher than many people expect to pay for oil.
In the 1970s the U.S. Air Force selected a CTFE oligomer as the base fluid for a –54°C to 177°C
nonflammable hydraulic fluid, MIL-H-53119. Considerable research and development advanced the knowl-
edge of both the fluid and components designed for use with it. In the end, it was not selected for aircraft
application beyond test aircraft because it was considered too high a risk. MIL-H-53119 contains an additive
package with both an antiwear additive and an antirust additive to make it a usable, effective, nonflammable
hydraulic fluid. Extensive testing by the U.S. Air Force and others allayed concerns about the potential
toxicity and ozone depletion effects of CTFE. Current commercial applications of higher-molecular-weight
CTFE fluids are as gyroscope flotation fluids, vacuum pump oils, and metal-working lubricants.
10.4.1.5.9 Polyphenylethers
Polyphenylethers (PPEs) (Figure 10.13) were first developed as the gas turbine engine oil for the SR-71
reconnaissance aircraft in the 1960s. MIL-L-87100 was written to describe these fluids. PPEs have excellent
high-temperature oxidative stability, excellent bulk modulus, low volatility, and good fire resistance. Their
major disadvantages are poor low-temperature flow, which is partially improved by isomer mixtures of
meta and para linkage of the benzene rings by the oxygen atom, and poor lubricity. The five phenylether
with isomer mixture has a pour point of –4°C. In the SR-71, one scheme to keep the PPE liquid at lower
temperatures was to dilute it with solvent. After the engine heated from operation, the solvent would
boil out, leaving the PPE engine oil. Needless to say, today, such a plan would not be environmentally
acceptable. PPEs have poor inherent lubricating ability, and antiwear additives have not been highly
successful. Besides these problems, PPEs are quite expensive because of the many synthesis steps required

FIGURE 10.13 Polyphenylethers.

© 2001 by CRC Press LLC

FIGURE 10.14 Perfluoropolyalkylethers.

to produce them. Since the SR-71 aircraft was inactivated in the 1980s (except for a few test aircraft used
by NASA) PPEs, the 5- and 6-ring fluids, now have only a small market as electronic contact lubricants
and as vacuum pump oils.
10.4.1.5.10 Perfluorinated Fluids
Perfluoropolyalkylether (PFPAE) fluids were introduced in the 1960s and have been intensely studied
ever since, owing to their unique thermal and oxidative stability, nonflammability, and inertness to highly
reactive materials. Four classes are generally recognized, as shown in Figure 10.14. The physical properties
and stability of PFPAE fluids depend primarily on the carbon-to-oxygen ratio of the fluid and to a lesser,
but significant, extent on the amount of branching and the presence of less stable OCF2O linkage. Major
limitations of PFPAE fluids are high cost, corrosive wear in the presence of some metals, especially steel
and aluminum, and autocatalytic degradation in the presence of metal oxides/Lewis acids. Companies
that produce PFPAEs, the U.S. Air Force, NASA Glenn Research Center, and, more recently, the recording
media industry have led the research on PFPAE fluids.
To briefly summarize the experience in the authors’ laboratory on the types of PFPAE fluids, the K fluids
have the highest thermal and oxidative stability, but the poorest viscosity–temperature properties and highest
volatility. The Y fluids have viscosity–temperature and stability properties similar to the K fluids. The Z fluids
have exceptional viscosity–temperature properties and volatility, but the highest cost and the poorest thermal
and oxidative stability of the PFPAE fluids. Z fluids are also the most reactive to metals. M fluids are similar
to Z fluids, but cost less and have somewhat higher volatility. The D fluids, the newest commercially available
materials, have good viscosity–temperature properties and excellent thermal and oxidative stability, almost
as good as the K fluids. A further advantage of the D fluids is their lower cost compared to the other three
fluids. PFPAEs with functional end groups are used successfully for niche applications, such as by the
recording media industry as monolayer surface modifiers to reduce friction and stiction.
Soluble additives for PFPAE fluids were first synthesized by the U.S. Air Force (Tamborski and Snyder,
1977). Since then the PFPAE fluid producers and some other groups have expanded the list of additives
to combat corrosive wear and catalytic degradation (Srinivasan et al., 1993; Gschwender et al., 1993).
PFPAEs are used in contact with reactive materials in wide-temperature-range applications and where
a small amount of lubricant is sufficient. Greases based on PFPAE fluids, MIL-PRF-27617, are used in
aircraft high-temperature applications and in many commercial applications.

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© 2001 by CRC Press LLC

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For Further Information

An excellent book on lubricant classes and properties is Synthetic Lubricants edited by Reigh C. Gunderson
and Andrew W. Hart. The book is out of print, but if you are lucky enough to find one, it is a real treasure.
A newer, also excellent book, is Synthetic Lubricants and High-Performance Functional Fluids, edited by
Lester R. Rudnick and Ronald L. Shubkin.
The military technical reports (containing–TR–designations) referred to in this chapter are available
from DTIC (Defense Technical Information Center), 8725 John J. Kingman Road, Ste. 0944, Ft Belvoir,
VA 22060-6218. The military specifications referred to in this chapter are available from Standardization
Document Order Desk, Bldg. 4D, 700 Robbins Ave., Philadelphia PA 19111-5094.
Aerospace Standards AS1241, “Fire Resistant Phosphate Ester Hydraulic Fluid for Aircraft,” and
AIR1362, “Aerospace Hydraulic Fluid Physical Properties,” are available from SAE, 400 Commonwealth
Dr., Warrendale PA 15096.
Factory Mutual Research in Norwood, MA, is the most well-known organization for the testing and
certification of fire-resistant fluids and can be accessed at www.fmglobal.com.

© 2001 by CRC Press LLC