Synthetic Sulfonate Greases

A Short Review of an Important Lubricant Technology

By Dr. Brett Chandler

1 of 8

Lubrication 101 A Brief Introduction

Our amazing industrialized world has come about through the remarkable ingenuity and
innovation of men and women who have turned abstract ideas and various raw materials
into functional devices and instruments that we depend on in our daily lives. While not
immediately obvious, all machines and instruments share one identical commonality they require lubricants to operate.
Simply put, lubrication science focuses on optimizing the separation of contacting
surfaces on moving components. For many, motor oil represents the most familiar
lubricant used in our automobiles yet is something the average person does not give much
thought about in how it functions. At the most basic level, oil separates surfaces by
forming a thin film. The thicker the oil is, the thicker the film becomes and the greater
the load that the contacting surfaces can support. The thickness of an oil is measured by
the oils viscosity, the greater the viscosity, the thicker the film. An oil without any
additives is referred to a Base Oil in the lubrication industry. Base oils are the foundation
of all commercial lubricants and serve two fundamental roles:

Reduce friction by forming a continuous fluid film to prevent direct contact

between moving parts under pressure. In Tech-Talk this is known as
hydrodynamic lubrication.
Transfer heat away from hot surfaces and supplies heat to cold surfaces.

In nearly all instances, base oil alone will not provide adequate lubrication and protection
to contacting surfaces. To remedy this, additives are added to the base oil. All fully
formulated oils are made using base oils as the foundation, and additives to meet specific
application requirements. So automotive oil will have different types and quantities of
additives compared to turbine oil or a lubricant used to remove rusty bolts from corroded
equipment, but could share the exact same base oil. Fundamentally, additives serve many
functions, but a few core roles include:

Provide wear protection by depositing a chemical film on surfaces when the

lubricant film becomes too thin to give full fluid film separation of rubbing
surfaces. In Tech-Talk this is known as boundary lubrication.
Reduce corrosion and inhibits rust formation.
Reduce the formation and build-up of sludge, varnish, and deposits.
Suspend and transport away particles, debris, and contaminants.

Greases represent a unique class of lubricants in that they can exist in a semi-solid or
solid physical state. An analogy to grease would be to that of a sponge filled with water.
The sponge provides the framework or matrix to hold the water. The different
consistencies result from the fact that grease makes up the only group of lubricants that
use a thickener or gelling agent. The thickening agent provides a physical matrix to the

2 of 8

base fluid and additives. All the components of a given grease can be classified into three
distinct groups

Base oil
Thickener
Additives

While varied in composition, typical multipurpose grease contains around 10 %

thickener, 85% base oil, and 5% additives. Grease is designed to serve many of the same
functions as a liquid lubricant; the base oil in grease lubricates moving metal parts.
Lubrication engineers classify greases as thixotropic gels. A thixotropic gel is a solid or
semi-solid that will flow under shearing forces and then resolidify when the force is
removed. As pressure increases, the grease will become more fluid-like and become
mobile. As soon as this pressure decreases or is removed the fluid-like grease reverts
back to the solid form. Since all greases contain base oil, they are able to serve the same
fundamental role that the base oil itself does. However, some of the important differences
between grease and a liquid lubricant include:

Grease, once applied stays putit does not easily wash away or drip off.
Grease functions poorly as a coolantit is ineffective at dissipating heat.
Grease does not wash away debris and contaminants; however, it does prevent
contaminants from entering the system.
Some grease can absorb considerable quantities of water and still lubricate
satisfactorily.
Grease is the lubricant of choice for machinery that operates intermittently or
under extreme conditions.
Grease is the lubricant of choice for parts that are not easily accessible and parts
that will go a long time before being supplied with fresh lubricant or are
lubricated for life when assembled.

In order to appreciate advancements in grease technology, it is best to review the three

component groups of the grease in more detail.
Base Oils

As previously mentioned, the base oil represents the majority component of grease. Base
oil viscosity is an important parameter in grease formulation and has some bearing on the
consistency (hardness) of the final grease. To thicken properly, the soap thickener should
be neither completely soluble in the base oil, nor completely insoluble and the base oil
should have some affinity (solvency) for the soap thickener. This careful balance can
result in the difference between good grease and great grease.
The most commonly used base oil for grease formulation is a mineral oil, as opposed to
synthetic oil. A mineral oil is a product of petroleum refining and the term "mineral oil"
or "rock oil" was first used to describe the petroleum hydrocarbons and associated

3 of 8

products that were produced from wells that tapped underground reservoirs in the late
1880s. Just as crude oils are often characterized as either paraffinic (long chain
molecules made up of carbon and hydrogen) or naphthenic (ringed structures made up of
carbon and hydrogen) depending on the relative quantities of paraffins and naphthenes
present, mineral base oils are also classified this way too. An important distinction is that
base oil does not have to be one or the other. Paraffinic oil will typically contain
predominantly paraffins, but a sizeable fraction of the oil may be naphthenes. As well,
naphthenic oil contains predominantly naphthenes, but may also contain paraffins.
Paraffinic oils have an advantage at high temperatures while naphthenic oils over good
low temperature performance. Due to increasing concerns over carcinogenic molecules
containing aromatic or polyaromatic structures, aromatic base oils have been replaced
with the naphthenic or paraffinic for use in grease formulation.
Conversely, synthetic base oils (oils that are artificially synthesized from crude oil
components) can also be used and have a number of superior properties. They can be
tailored to provide properties that are impossible to achieve with mineral based products.
These include:

Lower pour points (improved low temperature performance),

Improved high temperature stability,
Enhanced oxidative resistance (does not form varnish and sludge as easily or at
high temperatures)

While a great number of synthetic oils exist and can be used for specific applications,
PAO (Polyalphaolefin) synthetic base oils offer the aforementioned advantages and
represent the most commonly used synthetics for multipurpose grease. Greases made
from PAO synthetic base fluids exhibit excellent low temperature properties and can
offer low friction and optimum energy savings performance.
Additives
Additives are present in lubricants for a variety of reasons and are differentiated based on
whether they target the physical or chemical properties of the base oil or whether they
modify the metal surface the lubricant contacts. Not all additives used in lubricating oils
(e.g., detergents, dispersants) are appropriate for greases. Typical multipurpose grease
contains the following additives:
Antioxidants
Metal deactivators and corrosion inhibitors
Polymer additives
Friction modifier (FM), anti-wear (AW), and extreme pressure (EP) additives

4 of 8

Thickeners
The thickeners employed in greases are typically subdivided into three broad categories:
1) Soaps
2) Non-Soap Thickeners
3) Complex Soaps
Soap-thickened greases are the most common (about 46% of the North American
market), followed by the complex soap-thickened greases (about 40% of the same
market). The various nonsoap-thickened greases constitute only about 14% of the North
American market. The general trend in grease technology is the greater use of complex
soap thickeners. The nature of the soap thickener and the quantity used has the most
influence on the consistency of the grease.

Soap Thickeners
Soap is simply a cleansing agent made from the salts of vegetable or animal fats. In a
related fashion, the soap used to thicken a base oil to create grease is typically of
vegetable or synthetic origin but animal fats are still sometimes used. The soap content of
soap-thickened greases ranges from 5% to 20% by weight; increasing the soap content
increases the stiffness of the grease. While many different types of soap salts can be
made, over 80% of soap and complex soap-thickened greases use lithium soap. The
introduction of lithium soap-thickened greases in the 1940s and 1950s revolutionized the
grease industry and led to the introduction of multipurpose greases that could handle
increased temperatures over the prior calcium based soaps. The two most common
lithium soaps employed today in lubricating greases are lithium stearate and lithium 12hydroxystearate with the latter being the most preferred.
Non Soap Thickeners
Among the various types of nonsoap thickeners, the two most common types are
mentioned hereorgano-clay and polyurea. Clay based thickeners have the advantage
that they do not melt so are suitable for high temperatures, but perform poorly in wet
environments. Polyurea grease thickeners are produced within the base oil itself and can
support high temperatures ( >180 oC). They have an advantage in that they can be
formulated in such a way to produce only gaseous products upon thermal breakdown.
However, below 180 C, soap thickened greases are generally equal in performance. As
interesting aside - Japan relies heavily on polyurea grease more than any other country in
the world.

Complex Soap Thickeners

5 of 8

Greases with these thickeners contain the same soaps that are used to make soapthickened greases, but in addition, a second soap is added too. Often the preparation of
this thickener is carried out in two steps. The most common lithium complex grease is
based on 12-hydroxystearate and azelaic acid. Complex grease offers the advantage of a
higher dropping point than conventional grease. The addition of complementary salts is
advantageous in that it leads to an increase in the dropping point primarily because of the
increased thickener concentration. However, for the same reason, such thickened greases
are more restrictive for low-temperature applications. Because of their superior
properties, complex soap-based greases have become very popular and account for
approximately 20% of all greases sold worldwide.
A more recent addition to the complex soaps has been the introduction of the overbased
calcium sulfonate thickeners. This thickening system is unique in that it is the
combination of small spheres of calcium carbonate (limestone a basic inorganic
compound capable of neutralizing acids) with calcium sulfonate as the soap. The matrix
forms by coating sub-micron sized calcium carbonate spheres with the soap and the
interaction between these soap covered particles give the support to the base oil. An
analogy would be the use of yarn stuck to a golf ball. The yarn (soap) gets tangled with
the strands from other particles and can only be separated by enough force.
Greases manufactured from this thickening system have a number of advantages.
Exceptional corrosion protection
Resistant to shear forces and have load-carrying capacities that can be matched
only by greases of other soaps that contain large amounts of additives.
High dropping points (the point at which a thin film of grease will have enough
mobility to drip out of a small hole)
o Dropping points start around 220 oC and some grades can survive
operational temperatures up to 250 oC for several hours.
Well suited for centralized pumping systems
Extremely robust to water washout
Offer strong anti-wear protection without the use of additives.

These properties enable calcium sulfonate greases to be useful where a good resistance to
water washout is required, in high temperature applications as found in steel mills and in
extreme loading conditions associated with mining equipment. Increased usage in these
applications has resulted in the continued global growth of the calcium sulfonate greases
and makes the overbased sulfonate thickener arguably the best multipurpose technology
available today.
With all the significant advantages of the overbased sulfonate greases, one weaker
attribute is the low temperature performance. While it will meet the majority of
specifications for low temperature mobility and torque, it does not generally perform as
well as lithium complex products. This is attributed to the higher than normal thickener
content compared to most other technologies. However, when a normal mineral oil is
replaced with synthetic oil such as a PAO, it has been found to perform in line with many

6 of 8

lithium complex greases in low temperature performance. As an added bonus, this

synthetic-oil based sulfonate also works well at elevated temperatures.

Overbased Sulfonate Grease - Application Areas

PAPER MILLS
The primary considerations for a product to be successful in this environment include:
Superior corrosion resistance,
High Extreme Pressure Performance
Solid shear stability in the presence of water
Extended operating life under elevated temperatures.
Paper mills see significant use of premium (complex) type grease products to meet these
demanding requirements; Calcium sulfonate technology is ideally suited to this
environment particularly for its high resistance to corrosion. In press rollers, it has been
shown that overbased sulfonate greases do not soften as quickly as other complex soaps.
In the felt tensioning rollers (used in the drying process), overbased sulfonate grease have
shown a marked reduction in corrosion due to the high heat and humidity compared to
other soap based products.
STEEL MILLS
Typically this has been the domain of either Aluminum complex greases in North
American steel mills where water is concerned and Lithium Soap products where general
lubrication is required. Aluminum Complex greases have been used primarily where it is
believed that water wash-off is a critical property. The simple soap products have been
used primarily due to their low cost; however volumes used are typically high due to their
poorer expected service life. Overbased calcium sulfonate grease is ideally suited for use
in steel mills particularly in areas of elevated temperatures, shock loading and where
water may be mixed with the grease. While the cost may be more than a simple soap, the
significantly increased expected life dramatically reduces grease consumption and results
in a larger return on investment.
Use of overbased sulfonate grease has had excellent success in steel mills and has
observed reductions of grease consumption in the order of 40 to 50% in such areas as hot
strip mills and in roll neck bearings. Previous work has shown that overbased calcium
sulfonate complex grease was found to work successfully in spherical roller bearings of a
cold rolling mill and in the tapered roller bearings of a hot rolling mill. The new grease
provided excellent properties such as resistance to quench water washout, corrosion
protection, mechanical stability, pumpability, low oil separation, and high EP. The
excellent oxidation resistance coupled with good mechanical stability provided longer
bearing life over conventional grease products.
MARINE

7 of 8

Deck Grease
The multipurpose nature of overbased sulfonate grease would definitely be an asset in the
lubrication of bearings, gears, and wire ropes. The most significant properties required
for deck grease are:
Resistance to washout and wash-off,
Resistance to corrosion in a salt water environment,
Resistance softening at elevated temperatures,
Resistance to aging in service,
Excellent EP and AW characteristics.
As has been described previously, sulfonate grease technology meets and exceeds these
requirements; the intrinsic corrosion resistance is ideal for the marine environment.

Conclusions
Calcium Sulfonate Complex grease technology has been shown to have outstanding
extreme pressure/ anti-wear performance, corrosion resistance, mechanical stability,
oxidation resistance, water spray-off resistance and washout resistance. These properties
have been combined to provide a unique multipurpose grease for industrial and
automotive use. While there will always be a need for specific grease thickeners and
unique base oils in certain circumstances, overbased calcium sulfonate thickener
combined with synthetic base oils provides the technology necessary to meet the
multipurpose grease requirements of numerous applications and industries. The examples
and applications briefly reviewed in this paper are only a fraction of the total (current or
potential), where this technology can provide benefit.

8 of 8