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Calcium Sulfonate Complex Greases
Calcium Sulfonate Complex Greases
Calcium Sulfonate Complex Greases
Calcium sulfonate
complex greases
Chemtura technology manager Wayne Mackwood examines grease’s chemical
composition, classifications, test procedures and additive packages.
MOST PEOPLE KNOW WHAT GREASES ARE and how they are used
KEY CONCEPTS as a lubricant. There are some disadvantages to grease when
compared to oil products, the biggest being reduced pump-
• Tribology’s
Tribol gy’s unsung
unsungg hero— ability. They’re also harder to replenish compared to oil lu-
grease—h many advantages
grease—has bricant systems, offer poorer cooling abilities, increase fric-
ooveer oil-based
over o basedd lubricants.
oil-b lubric t . tional drag and are harder to clean in-situ. They don’t offer
the ability to boost their properties when used with additives,
• Greases
G eases are made of three therefore making grease replenishment a necessity. Their low-
compon t : thickeners,
components: thickene , oils
l temperature performance might not be as good as oils, and
their thickeners oxidize and degrade. They also are not as
and additives.
generally recyclable as oils.
• The
he most important
p rtant grease
greaase However, greases do offer many advantages over oils. They
have a superior ability to seal out contaminants, and they drip
test is the ASTM D217 Grease
and mist less. They are the best choice when solid additives
Consistency Test, which like graphite are needed, and they’re very useful when operat-
ensures thee grease
g haas a
has ing in extreme conditions like high pressures and tempera-
cons stent
consistent
t t starting
ng point.
p int. tures, water contamination or shock loading. They also are
very important where there is intermittent operation.
This article is based on a Webinar originally presented by STLE University on August 5, 2015. “Calcium Sulfonate
Complex Greases” is available at www.stle.org: $39 to STLE members, $59 for all others.
Wayne Mackwood is the technology manager for detergents and greases for Chemtura Corp. and is based
in Toronto. He is an expert in the design, manufacture and use of calcium sulfonate complex grease. For more
than two decades he has developed over 150 grease formulations for the mining, steel production, paper and
pulp, power generation, transportation, food-processing and marine industries.
Most of his career Mackwood has served as a scientist with marketing and asset-management roles. He
is a member of STLE, NLGI and EGLI. He has previously served on STLE’s board of directors and is currently a
board member with NLGI. Mackwood has a bachelor’s of engineering and a master’s of engineering in materials
science with a focus on tribology from the University of Western Ontario.
You can reach Mackwood at wayne.mackwood@chemtura.com. Wayne Mackwood
CLASSIFYING GREASES a grease have been developed over the from 2010-2014. However, the big-
Greases can be classified and referred years: simple soaps, complex soaps and gest change in that time has been with
to in many ways, but the main way is non-soap thickeners. Simple soaps are calcium sulfonate complexes (CSC),
by consistency or stiffness as specified organic materials based around stan- whose production has almost doubled
by the National Lubricating Grease In- dard metals that when reacted form and where interest has grown in all re-
stitute (NLGI) grade. Greases also can metal salts. They typically have drop- gions of the world.
be referred to by thickener type such as ping points under 210 C. Lithium,
lithium or calcium grease. They can be calcium, sodium and aluminum are OILS AND ADDITIVES
classified by base oil types such as syn- typical metals used in simple soap Grease is mainly made up of base oils,
thetic or mineral, or by base oil viscos- thickeners. which can be any type from Groups I-V.
ity specified by the International Stan- Complex soap thickeners look like Most are made from Group I and II, but
dards Organization Viscosity Grade, simple soaps, but they have been fur- there are many made with synthetic oils
such as ISO 60 or ISO 100 grease. ther complexed and contain other ad- from Groups III, IV and V. A high per-
Some classify grease by its ability to ditives that react to create more robust centage of synthetic greases use PAO as
carry loads, whether it’s an EP or non- structures offering different properties. its base oil, and some PAG-based oil-
EP grease or by its application such The standard types of complex soap soluble greases are starting to be seen.
as food-grade grease, wheel bearing thickeners are lithium complex, alu- Natural and synthetic esters, silicones,
grease or steel mill grease. Others clas- minum complex, calcium complex and fluorocarbons and phosphate esters also
sify grease by color, which is the most calcium sulfonate complex, and their are used. Alkylated naphthalene base
unreliable method since in any given drop points are typically above 210 C. oils are becoming popular in greases
facility there might be several greases Non-soap thickeners can be reacted used for some specialty applications.
sharing the same color. products or dispersion-type gels whose Additives are the final components
high-speed dispersion causes fluids to of grease, and all of the same types that
THICKENERS thicken. They typically have high drop- can be found in lubricating oils can be
Greases are made of three components: ping points well above 210 C. Popular found in greases. Dyes and pigments
thickeners, oils and additives. Thicken- non-soap thickeners include polyurea, are popular for coloring grease, as well
ers are ways to gel the grease and typi- bentonite clay, silica, graphite, PTFE as tackifiers, antioxidants, anticorro-
cally range from 3%-35% of a grease and polymers. sion agents, rust inhibitors, metal de-
by volume. Oils in greases are the key Based on the latest data from the activators and EP or antiwear agents.
components that allow them to act as NGLI’s global 2014 Annual Grease Pro- Polymers and other water-resistant
lubricating fluids and typically com- duction Survey, lithium products still additives also are used, along with
pose 65%-95%. Additives impart or compose a large portion of the grease VI improvers. Pour point depressants
enhance specific performance aspects market. There have been changes in the are being investigated as to how they
to the lubrication and can range from different types of soaps used as thicken- may affect grease, but it is hard to say
1%-15% of grease’s volume. ers, but overall grease production has how effective they are at changing its
Many ways to thicken a fluid into remained the same or declined slightly properties.
30 Tornadoes have more intense winds than hurricanes. The fastest recorded hurricane
In simple CS greases, a very high Table 1 | CSC grease compatibility chart
content of thickeners are used, around
40%-50% in Grade 2 depending on the
base oil used. Thickener includes Ca
sulfonate, without the oil present in the
base, calcium carbonate and calcium
acetate, if present.
In complexed versions of the grease,
the manufacturing process includes a
key component that allows signifi-
cantly less thickeners to be used in the
product. The key complexing or co-
thickening agent that almost all manu-
facturers include is 12-Hydroxysteric
acid (12HSA). This allows thickener
content in Grade 2 grease, depending
on the processes used, to be reduced to Legend FC Fully compatible
SC Somewhat compatible – mixtures soften but remain grease like
as low as 15%-35%, with 30% being the NC Not compatible – mixtures soften severely and do not remain grease like
most common amount used.
The thickener in a CSC grease can
include Ca sulfonate (without oil), cal- (Table courtesy of Chemtura Corp.)
cium carbonate, Ca borate, Ca phos-
phate and Ca acetate (if present). Ca
borate, Ca phosphate and Ca acetate are
not necessarily required, but the final borate or calcium phosphate in the HOW GREASES ARE TESTED
properties of the grease may differ with complex grease increases its opacity. Grease is one of the most tested prod-
varying compositions. Some CSC greas- ucts and has the most tests written for
es are made without them. The 12HSA CSC COMPATIBILITY it. The ASTM specifies many tests, and
can be added at different stages, with Table 1 summarizes CSC compatibil- there are others developed by bearing
final properties dependent on when it is ity data compiled from industry litera- companies and industries where grease
added. When borate and phosphate are ture and work performed at Chemtura has found its way into the work. Some
used, they become part of the complex, Corp. on calcium sulfate complexes tests are quite old and are still used,
improving high temperature rheology over the years. In general, CSC greases and others may not be relevant.
and imparting better wear. are fully compatible with anhydrous The most important test for grease
Complex CSC grease looks more calcium and lithium complex products. is the ASTM D217 Grease Consistency
opaque than simple Ca sulfonate Substances highlighted in red are gen- Test that ensures the grease has a con-
grease, which looks more transparent erally not compatible. sistent starting point (see Figure 5 on
(see Figure 4). The presence of calcium When mixing incompatible sub- Page 32). A weighted cone is dropped
stances together in a bearing, mechani- into level grease and the depth of pen-
cal stability test or another application, etration is measured: the greater the
under certain conditions one or both of depth, the softer the grease. The pen-
the thickener structures typically will etration is measured after 60, 10,000
collapse, making the mixture lose con- and 100,000 double strokes. A change
sistency. Also, the dropping point may in consistency gives an indication of
reduce considerably below the original application stability. Performance also
point of each substance. can be compared when water is added
Compatibility between two greases as well.
depends on a number of factors: relative
concentration, the degree and duration NLGI CONSISTENCY CLASSIFICATION
of mixing, temperature and types and Greases are assigned a grade in units of
extent of external contamination. Rules 30 points, with a 15-point gap between
of thumb like these can be used to de- each grade to ensure no overlap. Many
Figure 4 | Complex CS grease has an opaque termine compatibility. But if used in an suppliers quote half grades such as 0.5
appearance. application is critical, as most are, it is or 1.5 indicating the grease is between
best to have the compatibility tested. grades, but they are not official. Grade
wind speed is approximately 200 mph. Tornado winds can be up to 300 mph. 31
Penetration Penetration After 10,000
Grease Worker Worker Plate After 60 Strokes or More Strokes
Figure 5 | Setup for testing the consistency of grease with the Grease Penetration Test.
000 is the softest. Grade 2 is the most the ASTM method, grease is tested up again rotated under load against three
common. Grade 3 has a consistency to a maximum of 316 C (600 F). stationary balls held tight in a metal
similar to peanut butter (see Figure 6). Greases also are tested for wear and cup filled with the test grease. Run at
The next most important test is load performance with the 4-Ball Wear 1770 rpm, 25 C for 10 seconds, this
the Dropping Point Test, specified by Test and the 4-Ball EP Test. The wear test starts at 80 kg and adds succes-
ASTM D2265 (see Figure 7). This tests test identifies wear and boundary wear sive loads to 800 kg or until welding
the temperature at which the thickener regimes. One ball is rotated under load occurs. The weld point is reported.
matrix can no longer hold oil, which against three stationary balls held tight The Load Wear Index is a measure of
is the point when the grease can no in a metal cup filled with the test grease. the wear associated during the testing.
longer serve its purpose. The dropping The test is run at 40 kg, 1200 rpm and The higher the number the better the
point temperature is not the melting 75 C for 60 minutes. The diameters of lubricant can protect against wear at
point of the grease. The higher the the circular scars formed on the three high loads.
dropping point temperature, the better. lower balls are measured in millimeters The two tests are very commonly
A thin smear of a small sample the size and averaged. The smaller the diameter referenced on grease specifications and
of a thimble is watched to see when the better protection afforded. datasheets. There continues to be much
droppable oil falls from a cup as the The 4-Ball EP Test pushes and goes debate in the grease and testing world
temperature is increased. According to beyond the wear regime. One ball is about how relevant either test is in real
Thermometer Bulb
Does Not Touch
Grease
Cup
Grease Sample
Applied to Walls
of Cup
Motor
Heater
Pump
Figure 8 | Setup for the Water Washout Test. Figure 9 | Comparing water resistance properties food-grade CSC and non-CSC greases with the
Water Washout Test.
world conditions. Better methods may and after one hour of testing to see how In the ASTM D4049 Water Spray
exist. But until new tests are widely ad- much of it has been removed from a Resistance Test, a weighed amount of
opted, these two and other tests will shielded packed bearing with a water grease is coated on a horizontal metal
continue to be used to characterize spray impinging on it (see Figure 8). A panel and is exposed directly to wa-
grease performance. motor spins a bearing and pumps wa- ter spray from above for five minutes
There are two other important ter running at 600 rpm, with a 5 cm3/s (see Figure 9). The panel is dried in
grease-specific tests: water washout and flow rate and either 79 C or 38 C water. an oven and the weight loss is used to
spray tests. In the ASTM D1264 Water The bearing is dried in an oven, and the determine the percent sprayed off. The
Washout Test, grease is weighed before weight loss after one hour is determined. less removed the better. While these Î Î Î Î Î
LEADING EDGE
People and specialty products
you can count on.
OXIDATION
• ASTM D5483-02 Pressure Dif-
ferential Scanning Calorimetry
• ASTM D3527 Wheel Bearing Life
Test
• ASTM D3336 High Speed Bearing
Life Test
Figure 11 | Two CSC greases offer superior performance in the Automotive Low Temperature
• FAG FE9 Test
Torque Test.
• Oven Panel Test
• ASTM D942 Bomb Oxidation properties and performance that CSC referenced for that reason more than
MECHANICAL STABILITY greases bring. for wheel bearing use.
• ASTM D1831 Roll Stability CSC greases used in automotive Chemtura performed industry tests
wheel bearings must meet many in- on two types of CSC products: ISO 150
BLEED/LEAKAGE
dustry requirements such as the NLGI with a mineral oil base and PAO50 with
• ASTM D6184 Cone Method Oil GC/LB Specification and ASTM D4950. a synthetic base. All CSC greases com-
Bleed These tests are similar to the SAE J310, patible with mineral oils met the specs
• ASTM D1742 Oil Bleed which has not been updated in several easily. They showed good oil separa-
• ASTM D4290, D1263 Wheel Bear- years. GC is most relevant now, with its tion and low spray out. In the 4-Ball
ing Leakage higher standards than GA and GB. In EP ASTM D2596 Test, both test results
MOBILITY/TORQUE chassis lubrication, LB is becoming the were good.
more important standard since most In the Bearing Life Test at low tem-
• ASTM D4693 and D1478 Low
chasses aren’t available to be lubricated peratures, the mineral oil passed the
Temperature Torque
aftermarket. In addition, other internal 80-hour minimum lifetime and last-
• ASTM D1092 Apparent Viscosity manufacturer specs may be present. ed 100 hours, and the synthetic PAO
• US Steel Mobility An NLGI working group is currently showed a lifetime improvement to well
• Lincoln Ventmeter investigating the relevancy of the NLGI over 200 hours (see Figure 10). This is
GC/LB test protocol. Using aftermarket typical for the synthetic technology.
CORROSION
grease in wheel bearings and chassis The Low-Temperature Torque Test
• ASTM D4048 Cu Corrosion points has significantly diminished. So (tapered roller bearing) (ASTM D4693)
• ASTM D1743 Bearing Corrosion far, the group has found that the spec showed similar results at the cold tem-
• ASTM D6138 Emcor Corrosion. is good for describing moderate- to perature at -40 C (see Figure 11). The
high-performance grease. It is probably mineral oil-based grease met the spec, Î Î Î Î Î
36 Hurricanes never form at the equator because they need the Coriolis Force, which is very weak at the equator, to spin.
ÎÎÎÎÎ ASTM D2266 4-Ball Wear Test (40 kg, 1200 rpm, 75 C, 60 minutes) tested several PAO-based and white oil-
based CSC formulations and compared
the results to Grade 1.5-2 aluminum
complex greases, anhydrous calcium
greases (which are not high tempera-
ture greases) and silica.
The performance of CSC grease
in the areas of load, water, shear and
temperature offered much-improved
performance over the other technolo-
gies. At the time of the testing, most of
the other greases were limited by their
choice of performance additives. That
landscape is changing now as more ad-
ditive chemistries are gaining approval
under the HX-1 program.
The CSC greases all performed very
Figure 12 | Comparing antiwear properties of food-grade CSC and non-CSC greases. well in the water-resistance test, which
is important in food industry equipment
that undergoes the worst case scenario
where water is used extensively to clean
but there was a noticeable improve- vibrations but no rolling motion, like the equipment. Compared to aluminum
ment in torque with the lower viscos- during transport. The CSC greases per- complexes, much less of the CSC greas-
ity synthetic PAO-based grease. These formed well on fretting wear tests. es was removed, all less than 1%.
findings are important to automobile CSC grease also showed excel-
users in the north that experience cold FOOD PROCESSING INDUSTRY lent antiwear properties in the ASTM
winter nights and want to be sure com- EXAMPLE D2266 4-Ball Wear Test, where silica
ponents are not damaged when first There is a lot of data available about indicated insufficient performance (see
starting in the morning. CSC grease performance in machinery Figure 12). In the ASTM D2596 4-Ball
Fretting wear is important in bear- used in the food processing industry. EP Test, CSC grease showed excellent
ings that have been packed in grease CSC grease obtained NSF H1 status in load carrying properties (see Figures
while the automobile is transported by 2001 and finds use in mixing, crush- 13 and 14). Also, all of the sulfonates
train or truck. Most fretting wear will ing, canning, bottling and package tested in the ASTM B117 Salt Fog Test
occur when there are high frequency manufacturing applications. Chemtura showed excellent corrosion resistance,
Figure 13 | How grease load carrying prop- Figure 14 | Comparing load carrying properties food-grade CSC and non-CSC greases.
erties are tested with the 4-Ball EP Test. ÎÎÎÎÎ
when very thin 1-mil thick coatings many performance advantages. bring excellent EP, wear, corrosion and
ran more than 1,000 hours (see Figure In a transportation roller bearing wide-temperature advantages to wind
15). Competitors were nowhere near as application in a hot rolling mill, very turbines, open gear in mining appli-
good and failed in less than 150 hours, short bearing lifetimes were seen with cations, on pin bushings and in bear-
typical of most food-grade industrial its standard NGLI 2 lithium grease ings. They also offer water resistance
greases. needing to be fed every eight hours. and mechanical stability to wet end
CSC greases are stable regardless of An ISO 460 CSC grease investigated for bearings, good corrosion resistance to
temperature during shear tests, while 7-10 days offered a significant improve- marine applications that use wire ropes
other thickener types softened with ment in performance and bearing life, and EP and wide temperature perfor-
time and heat. With water added to and extended the re-greasing interval mance to marine deck equipment.
roll stability tests, other products be- from eight to 24 hours. They’re used in power generation and
came much softer as their ability to gel In a similar steel mill bearing test, off-road construction industries and
was disrupted and the thickeners broke ISO 460 CSC grease tripled the bearing offer good heat, corrosion, EP, wear
down, depending on the thickeners life from 10 to 30 days with the origi- and radiation protection in motorized
used, but CSC greases remain stable. nal grease to more than 45 days. It also steam valve applications.
extended the re-greasing interval to 72
STEEL MILL EXAMPLE hours. (All figures courtesy of Chemtura Corp.)
Steel mills are the largest global con- In another steel environment us-
sumer of grease. In China alone there ing polyurea grease, shortened bearing
is an estimated 100,000 metric tons or lives were seen after the grease became
more of grease consumption in the steel thinner after contamination with water. FOR MORE INFORMATION
industry. Grease in these applications That effect was not seen after switching Chemtura Corp.: www.chemtura.com
are subject to high loads, high heat and to CSC grease.
water. Comparing ISO 460 CSC grease
to several commercial products found OTHER INDUSTRIES
in steel mills, the CSC grease did ex- In addition to these examples, CSC Debbie Sniderman is an engineer and CEO of VI
ceptionally well when operating tem- greases bring performance advan- Ventures, LLC, an engineering consulting company.
peratures were above 150 C, offering tages to a variety of industries. They You can reach her at info@vivllc.com.
40 The terms hurricane, typhoon and cyclone are different names for the same type of storm, a tropical cyclone.