High-Temperature Greases

Mike Johnson, Noria Corporation and Nicolas Samman, Petro-Canada

T here are many criteria to consider when selecting a
high-temperature grease for hot, grease-lubricated
equipment. The selection must include consideration
of oil type and viscosity, oil viscosity index, thickener
type, stability of the composition formed by the oil
and the thickener), additive composition and
properties, ambient temperature, operating
temperature, atmospheric contamination, loading,
speed, relubrication intervals, etc. With the variety of
details to resolve, the selection of greases that must
accommodate extreme temperature conditions poses
some of the more challenging lubrication engineering
decisions.
Given the variety of options, the potential for
incompatibility problems and high prices for a given
high-temperature product, the lubrication engineer must be selective and
discriminating when sourcing products to meet high-temperature requirements.
High-Temperature
High is relative when characterizing temperature conditions. Bearings running in a
steel mill roll-out table application may be exposed to process temperatures of
several hundreds of degrees, and may experience sustained temperatures of 250F
to 300F (120C to 150C). Automotive assemblers hang painted metal parts on
long conveyors and weave them through large drying ovens to dry painted metal
surfaces. Operating temperatures for these gas-fired ovens are maintained around
400F (205C).
In these two cases, the selection criteria differ appreciably. In addition to heat
resistance, the grease to be used in a hot steel mill application may require
exceptional load-carrying capability, oxidation stability, mechanical stability, water
wash resistance and good pumpability, and at a price suitable for large-volume
consumption. With all of the important factors to consider, it is useful to have a
grease selection strategy.
Selection Strategies
A reasonable starting point for selecting a high-temperature grease is to consider
the nature of the temperatures and the causes of product degradation. Greases
could be divided by temperatures along the lines in Table 1.
There is general correlation between a greases useful temperature range and the
expected price per pound. For instance, a fluorinated hydrocarbon-based (type of
synthetic oil) grease may work effectively as high as 570F (300C) in space
applications but may also cost hundreds of dollars per pound. The greases long-
term behavior is influenced by the causes of degradation, three of which are
particularly important: mechanical (shear and stress) stability, oxidative stability
and thermal stability. Oxidative and thermal stresses are interrelated. High-
temperature applications will generally degrade the grease through thermal stress,
in conjunction with oxidative failure occurring if the product is in contact with air.
This is similar to what is to be expected with most industrial oil-lubricated
applications.
Click Here To See Tables 1, 2, and 3.
Recipe for a High-Temperature Grease
Base Oils
When selecting lubricants for oil-lubricated applications, one often begins with the
consideration of base oil performance properties. This is also a good starting point
for grease products. Grease is composed of three components: the base oil, the
thickener and the additive package. There is a variety of options from which the
manufacturer creates the final product. Table 2 includes some of these options. 1
Base oils can be subdivided into mineral and synthetic types. Mineral oils are the
most widely used base oil component, representing approximately 95 percent of the
greases manufactured. Synthetic esters and PAO (synthetic hydrocarbons) are
next, followed by silicones and a few other exotic synthetic oils. 2
The American Petroleum Institute divides base oils into five categories that are
useful in initially selecting base oil by performance limits.
The Group I products are naphthenic and solvent-refined paraffinic petroleum
stocks with a high percentage of unstable unsaturated molecules that tend to
promote oxidation. Additionally, there are polar products that remain in the Group I
base oils called heterocycles (nitrogen, sulfur and oxygen- containing molecules).
Although the polar products are reactive, they help to dissolve or disperse additives
to produce the final product.
The Group II and Group III are mineral oils that experience extensive processing to
remove the reactive molecules and saturate (with hydrogen) the molecules to
improve stability. In a sense, these base oils are more like the Group IV synthetic
hydrocarbons (PAOs) than the Group I mineral oils. The oxidative and thermal
properties can be very good as a consequence of the removal of the reactive
heterocyclic molecules.
The Group IV synthetic hydrocarbons (SHC fluids) are produced by combining two
or more smaller hydrocarbons to synthesize larger molecules. These fluids may
have slightly better stability, but command a higher price. The Group V base oils
have a defined but different degradation path (not primarily thermal or oxidative).
Mineral and synthetic base oils degrade thermally in conjunction with oxidative
degradation if the product is in contact with air. The break point at which the
individual oil molecules in a highly refined (Group II+, Group III) mineral oil and
synthetic hydrocarbons will begin to unravel, releasing carbon atoms from the
molecular chain, is about 536F to 608F (280C to 320C). 3,4 The grease
manufacturer will select materials given their familiarity, and perhaps availability,
of the raw materials. If the manufacturer makes a particular type of synthetic base
fluid and is intimately familiar with the various destruction mechanisms of that
fluid, then it is likely that this type of synthetic base will often be selected for new
product development.
Thickeners
The materials selected as the grease thickeners may be organic, such as polyurea;
inorganic, such as clay or fumed silica; or a soap/complex soap, such as lithium,
aluminum or calcium sulfonate complex. The usefulness of the grease over time
depends on the package, not just the thickening system or the type of base oil. For
instance, silica has a dropping point of 2,732F (1,500C) as one extreme example.
5 However, because grease performance depends on a combination of materials,
this does not represent the useful temperature range. Some clay-thickened
(bentonite) greases may similarly have very high melting points, with dropping
points noted on the product data sheets as 500C or greater. For these nonmelting
products, the lubricating oil burns off at high temperatures, leaving behind
hydrocarbon and thickener residues.
The organic polyurea thickener system offers temperature range limits similar to
the metal soap-thickened grease, but additionally it has antioxidation and antiwear
properties that come from the thickener itself. Polyurea thickeners might become
more popular but they are difficult to manufacture, requiring the handling of several
toxic materials. While the thickener has a high dropping point, the composition
begins to thermally degrade at temperatures which limit its usefulness over time at
high temperatures. However, it does not have the pro-oxidant tendencies of the
metal soap-thickened greases. The exception is the calcium sulfonate complex
thickener system. Similar to the polyurea, it possesses inherent antioxidant, rust-
inhibiting properties, but in addition has inherent high dropping points and
EP/antiwear properties.
The third category option is the metal soap or complex soap thickener system.
Lithium complex-thickened grease has maximum temperature limits superior to
that of simple lithium grease, because the thickener offers higher thermal
degradation limits. Collectively, metal soap thickeners have thermal degradation
limits that range between 250F to 430F (120C and 220C). 6 However, unless
the grease composition is properly fortified against oxidation and thermal
degradation, the end product showing a dropping point of 500F (260C) or greater
would not be any more useful for long-term service than a grease with a low
dropping point.
Additives
The additives selected for grease manufacture must likewise be viewed as parts of
the whole rather than simply discrete parts that must withstand set test limits. The
additives tend to provide properties for greases in fashion similar to lubricating oils:
oxidation stability, corrosion resistance, wear resistance, low temperature flow
characteristics, water resistance, etc. The additive must be capable of working
synergistically with the thickener and the oil to lead to a balanced, stable mixture of
the three distinct components.
High-Temperature Grease Compatibility
Compatibility, or incompatibility, between high-temperature greases must be
addressed prior to selection. Because greases represent a complex mixture of
chemicals with a well-defined and engineered balance, the addition of unplanned
chemicals tends to upset the balance and degrade performance levels. Following
the Arrhenius rate rule, chemical reactivity doubles for each 10C rise in
temperatures, incompatibility issues are more pronounced at elevated
temperatures. The lack of compatibility shows up as grease thinning. If thinning
occurs, the user may relubricate to flush out the original product until the problem
ceases. Alternatively, the user has a more difficult choice to make, requiring
dismantling the equipment to remove the original product and cleaning the system.
The thickeners, additives and base oils may each have problems at differing
temperature ranges and time limits in use. Before converting major systems to a
new grease, exhaustive testing may be warranted to prevent significant cost and
time delay due to long-term maintenance problems.
While testing is warranted when changing between classes of thickeners, there is
relatively less potential for problems occurring when switching within families of
metal soap or complex soap-thickened products (lithium to lithium, lithium complex
to lithium complex, aluminum complex to aluminum complex, etc.). Greases will
generally soften when critical limits are reached (however hardening is also
possible), a consequence of the matrix between the additive, oil and thickener
becoming unstable and decomposing. It is difficult to determine exactly when the
decomposition will occur, considering temperature and time line. When variables
are introduced, such as a new mixture of chemicals (a result of grease mixing), it
becomes more difficult to predict the outcome. This points to the importance of not
mixing greases. With specially designed high-temperature grease products, these
issues can become more pronounced. Many of the exotic fluids used in very high-
temperature greases (fluorinated polyethers, perfluro-polyethers, phenal-
polyethers, silicones, etc.) will last longer than their thickening systems.
If a particular grease component is sensitive to moisture, then regardless of the
greases ability to withstand the heat alone, the use of the product must be
weighed against the risk of process moisture degradation of the grease. It could be
unwise to use a water-soluble glycol oil type of grease in an application that is
subject to high moisture, such as a conveyor wash system. Even though the fluid
may be capable of resisting thermal breakdown from the heat of the drying system,
the moisture poses a performance risk that may not be entirely eliminated.
How does one know if an application warrants a special-performance, high-
temperature product?
Because oils, additives and bases will react at various rates, there is something
good to be said about using simpler products. Consider whether the application is
intermittent or continuous high-temperature. If it is continuous - constant 392F
(200C) or greater - then go with the higher-tier product after appropriate testing.
If the temperature is intermittent, then a middle-tier product may be equally useful
with appropriately adjusted relubrication intervals.
Click Here To See Table 4.
Selecting a High-Temperature Grease
1. Determine the real temperature range. The operating temperature may be
less than what it seems. Use a contact or noncontact sensor to measure the
operating temperature of the grease. Does it exceed 392F (200C)?
2. Is it intermittent or continuous? If it is continuous, then look for a top-tier
product that meets the operational requirements.
3. Do heating and cooling cycles accompany machinery operating and
nonoperating intervals? Consider if moisture may be induced through either
atmosphere or impingement.
4. What is the reasonable relubrication interval or opportunity? If relubrication
is going to be difficult, then consider a top-tier product to achieve a lower
use cost even though its more expensive.
5. Consider any cosmetic issues. Can the product drip onto a component in
process? Relubrication frequency and volume must be balanced against
product contamination issues.
References
1. Lansdown, A. Lubrication and Lubricant Selection: A Practical Guide. p. 126.
2. Lansdown, A. Lubrication and Lubricant Selection: A Practical Guide. p. 126.
3. Lansdown, A. (1994). High Temperature Lubrication. p. 102.
4. Lansdown, A. (1994). High Temperature Lubrication. p. 108.
5. Lansdown, A. (1994). High Temperature Lubrication. p. 150.
6. Lansdown, A. (1994). High Temperature Lubrication. p. 150.
7. Lansdown, A. (1994). High Temperature Lubrication. p. 53.
Please reference this article as:
Mike Johnson, Noria Corporation and Nicolas Samman, Petro-Canada, "High-Temperature
Greases". Machinery Lubrication Magazine. May 2002
Issue Number: 200205
Machinery Lubrication
Lubricant Selection