Polyalkylene Glycols
20 severe consequences to equipment and in extreme cases lead
EO-PO-46
PO-46
17 OSP-46
PAO-8
Alpha, GPa-1
14
11
8 the lubricant in these systems has never been more challenged.
5
25 40 55 70 85 100
Temperature, °C
FIGURE 6.7  Pressure viscosity coefficients of PAGs.
that PAGs can form much thicker films than mineral oils and
polyalphaolefins under high temperature conditions and this
may contribute to longer gear life [32].
6.6.11 Deposit Formation
Since the 1990s, there have been more and more reports of
equipment failures caused by sludge and varnish formation
in gas turbines due to the degradation of hydrocarbon oils
[33,34]. Deposit formation is also known to be an issue for
specific hydraulic systems and indeed automotive engine
oils. If left untreated, varnish build-up can result in severe
problems of critical components including increased bearing
and gear wear and servo valve failure. One of the fundamen-
tal reasons for this increase in failures is the fact that the
new equipment delivers more power and increases the stress
on the lubricant, causing excess frictional forces between
contacting surfaces, higher fluid reservoir temperatures, and
ultimately the premature thermal and oxidative degrada-
tion of the lubricant. When degradation happens, dangerous
sludge and varnish deposits can result. Controlling deposit
formation with hydrocarbon-based lubricants remains chal-
lenging especially when the equipment is operating at high
temperatures for extended periods.
In the 1980s, the lubricants industry faced similar chal-
lenges when using hydrocarbon oils to lubricate flooded
rotary screw air compressors. This was solved by transition-
ing the lubricant from hydrocarbon oils to synthetic PAGs.
Today, there are over 100,000 air compressors in service
using PAG technology and the problem of deposit formation
has been essentially eliminated.
PAGs minimize deposit formation and help maintain
equipment cleanliness and reliability in a different way to
hydrocarbon oils. The difference lies in the thermal and
oxidative breakdown products of hydrocarbon oils (mineral
oils and polyalphaolefins) compared to PAGs. Simplistically,
when hydrocarbon oils degrade they form high molecular
weight polar by-products that become insoluble in the hydro-
carbon base oil. Consequently, sludge develops over time
and in some cases varnish formation occurs. This can have
133
to catastrophic equipment failure. In contrast to hydrocarbon
oils, PAGs degrade to form smaller polar by-products, which
are soluble in the PAG lubricant. The net result is that sludge
formation is almost eliminated and equipment reliability
enhanced.
In the power generation industry, there are several exam-
ples where deposit formation has become a major issue. For
example, gear box failures in wind turbines are notorious and
Higher wind turbine towers continue to be built with longer
blades exerting huge loads on the gears, drive shafts, and bear-
ings. In addition, wind farm operators expect the gears to be
operational for more than 20 years. The average life of a gear
box is still only 5 years. Servicing wind turbines especially
those that are offshore incurs huge costs. Advancing lubrica-
tion technology beyond hydrocarbon oils using PAGs is today
being researched as a potential solution to improving deposit
and ultimately equipment reliability. An additional benefit of
using PAGs for this application is their excellent film-forming
properties compared to hydrocarbon oils resulting in much
lower frictional forces in the lubrication regime.
Hydrocarbon oils have been successfully used to lubricate
gas turbines for many decades using formulations based on
Group I mineral oils. With the gradual phasing out of Group
I base oils, formulators have developed newer products using
Group II and III mineral oils. However, their introduction
into the gas turbine industry has not been seamless and
varnish formation is a major concern particularly in North
America where the newer formulations have been adopted
faster. Typically, these formulations contain low levels of an
additive package (e.g., 1%–2%) containing antioxidants, cor-
rosion inhibitors, demulsifiers, and antifoams in the base oil.
However, the more paraffinic nature of the newer base oils
has resulted in the oxidative degradation products being even
less soluble in the base oil, accelerating sludge and varnish
formation. Problems associated with varnish formation have
been reported particularly with newer higher-efficient tur-
bines operating at higher firing temperatures and increased
power output. The economic consequences of a turbine fail-
ure in terms of equipment damage and lost power production
are huge and careful fluid selection and appropriate condi-
tion monitoring practices are critical. With global demand
for energy expected to double by 2030, reliable operation of
turbines is crucial for going forward. Higher-quality lubri-
cants, for example, those based on PAGs, could bring an end
to the challenges of deposit formation in gas turbines similar
to how history has taught us about the benefits of using PAGs
in air compressors.
In hydraulic circuits, sticking of servo valves due to var-
nish formation is also common [33]. This has been prevalent
for a number of years in systems operating at high tem-
perature using hydrocarbon oils but also with modern envi-
ronmentally friendly bio-based oils that use vegetable oil
feedstocks. The progression of hydraulic equipment to pro-
duce units with higher power output with smaller reservoirs
has led to elevated operating temperatures of hydraulic fluids.
134 Synthetics, Mineral Oils, and Bio-Based Lubricants

Consequently, the risk of thermal and oxidative degra­dation referred to as HF-C fire-resistant hydraulic fluids as defined
has increased and therefore the risk of varnish formation too. by the ISO-6743/4 classification [38]. Other fire-resistant
Formulators of hydrocarbon-based hydraulic fluids have fluid designations are shown in Table 6.8.
tried to address this challenge using new additive technolo- Other water-based hydraulic fluids include oil-in-water
gies. But, overtime additives deplete leaving the base oil vul- emulsions (HF-A) and water-in-oil emulsions (HF-B). These
nerable to degradation. It seems logical that lubricants using fluids also provide superior fire resistance properties over
non-hydrocarbon-based oils might solve these varnish chal- hydrocarbon oils, but are not as stable as water glycol flu-
lenges. High-performance synthetic hydraulic fluids based on ids and offer inferior lubrication performance. One challenge
PAGs are now able to solve these problems and keep equip- with water-based hydraulic oils is that they are much more
ment running deposit free with significantly extended service difficult to maintain [39] and are limited to use in equipment
intervals and reduced equipment downtime. operating under moderate temperatures and pressures. In
addition, it is common for hydraulic pumps to be derated.
Despite their limitations, the technology in formulating
6.6.12 Additive Solubility
good WGHFs continues to be advanced and new fluids have
Common lubricant additive groups generally have good solu- emerged. One of the key hydraulic pump test methods for
bility in PAGs; for example, aminic and phenolic antioxidants, assessing their wear performance is ASTM D7043 (formerly
amine phosphate antiwear and corrosion inhibitors, phospho- known as ASTM D2882) [40]. This method uses a rotary vane
thionate extreme pressure additives, triazole yellow metal pump operating at a pressure of 2000 psi, speed of 1200 rpm,
passivators, imidazoline corrosion inhibitors, and so on. and a temperature of 65°C. The wear rate of the ring and vanes
There are some additive families where solubility is more are measured after the 100 h test period. Fluids that result in
challenging. These include some viscosity index improvers, a wear rate of <1 mg/h are desired. Table 6.9 shows the wear
pour-point depressants, dispersants, and detergents. Many of rates of several anhydrous and water-based fluids but over a
these are used in automotive engine oils. However, some of 500 h test period. By extending the test time, a better assess-
these additive types are generally not required for PAGs. One ment of the condition of the fluid before and after the test can
example is viscosity index improvers. The use of these would
not have any significant benefit since most PAGs have inher- TABLE 6.8
ently good viscosity indices.
Fire-Resistant Hydraulic Fluid Classifications
One challenge pertains to conversions of equipment from
mineral oils to PAGs. If contamination occurs, some of the Typical R.I. Values—
additives that are used in mineral oils that are described ear- ISO-15029 Part 2 for
lier are not miscible in the PAG and this can leave it with a Fluid Types Classification ISO-46 Fluids
hazy appearance. Oil in water emulsions HF-A >100
containing >80%
water
6.7  TRADITIONAL PAG APPLICATIONS Water in oil emulsions HF-B 40–60
containing 35%–40%
6.7.1 Fire Resistant Water Glycol water
Hydraulic Fluids Water glycol hydraulic HF-C 80–90
fluids containing
WGHFs have been used in the steel, aluminum processing, >35% water
mining, and fluid power industries as fire-resistant alterna- Anhydrous PAG HF-DU 10–20
tives to mineral oils [35] for over 60 years. They were the first Anhydrous polyol ester HF-DU 10–15
commercial application of PAGs and have often been referred Phosphate ester fluids HF-DR 25–35
to as hydrolubes. In the past 60 years, innovation has con- Mineral oil No classification 0–10
tinued to occur in developing fluids that offer improved fire
resistance over hydrocarbon-based products and improved
equipment performance at higher operating pressures
[35–37]. These synthetic fluids contain water (35%–50%) to TABLE 6.9
provide fire resistance, a glycol for low-temperature stability, Modified ASTM D7043 Vane Pump Test
a PAG viscosity modifier, and a carefully designed additive Total Ring and Wear Rate KV40
package that includes boundary friction additives, multi- Vane Wear (mg) (mg/h) Change (%)
metal corrosion inhibitors, vapor-phase corrosion inhibitors, Conventional WGHF 63 0.126 27
air release components, and dyes. The choice of PAG can Advanced WGHF 21 0.042 11
influence the rheology and the stability of these fluids. Most Anhydrous PAG 8 0.016 0.5
fluids in service today use polymers designed from diol- (e.g., Anti-wear mineral oil 62 0.124 1.5
diethylene glycol) or triol- (e.g., trimethylolpropane) initiated Synthetic ester 11 0.022 14
PAGs with an EO/PO ratio of about 75/25 w/w and molecu- Vegetable oil 7 0.014 9
lar weights of at least 12,000 Da. These fluids are commonly