Getting to Know Grease Thickeners: Soap vs. Non-Soap
A grease typically consists of three components: base oils, additives, and thickeners. The NLGI Lubricating Grease Guide Seventh Edition states a thickener is “the solid particles which are relatively uniformly dispersed to form the structure of lubricating grease in which the liquid is held by surface tension and other physical forces."
Thickeners are what help distinguish greases from oils. Without thickener, a lubricating base oil would migrate. Thickeners are often compared to sponges as they play a critical role in keeping an oil in place. Aside from their role in maintaining the structure of a grease, different types of thickeners can offer increased thermal, shear, and oxidative stability as well as water resistance. Historically, thickeners have been classified as soaps or non-soaps.
Soap Thickeners
Soap thickeners are relatively low cost with good water resistance and work stability. Soap thickened greases consist of simple, mixed and complex soaps.
There is a wide variety of soap greases to choose from and they all have different physical properties where the application requirements dictate which soap is best. The different types of soap thickeners include lithium 12-hydroxy stearate soaps, lithium stearate soaps, calcium soaps, sodium soaps and aluminum soaps. Simple metallic soaps are made by reacting the metallic alkali with a monobasic organic acid.
Lithium Soaps
Lithium 12-hydroxy stearate greases are the most widely used soap greases. Lithium soaps are very efficient thickeners. Lithium greases prepared from them have good lubricity, shear stability, thermal resistance (as measured by the “dropping point”, typically between 190-220 °C), and relatively low oil separation. Lithium greases are traditionally used in automotive and industrial applications such as bearings.
Calcium Soaps
Greases prepared from calcium soaps have improved water resistance over the lithium greases and good shear stability. Calcium soap greases do not have good thermal resistance (dropping points range from 135-145 °C) and are typically only used in applications that operate up to 110 °C.
Sodium Soaps
Sodium soap greases have high dropping points (typically 175 °C) but are generally limited to operating conditions not higher than 120 °C due to poor oxidative stability and high oil bleed. They also don’t have good water resistance. Sodium soaps do provide good shear stability and lubricity.
Aluminum soaps
Aluminum soaps have excellent oxidation resistance and good water resistance. However, these greases have low thermal resistance (dropping point of only 110-115 °C) but users limit its operating conditions to less than 80 °C. When aluminum soap greases get too hot from bearing heat, they form stringy gels that cause sharp increases in torque and therefore additional work is required to turn the bearing
Mixed soap greases were developed to improve the short comings of individual simple soap greases. The most common mixed soap grease is lithium/calcium as the lithium will improve the high temperature resistance of the resulting grease while the calcium improves the water washout and cost. The combination of sodium/calcium has also been used where the calcium improves the water resistance without lowering the operating temperature of the grease. The calcium will also shorten and smooth the coarse fibers of the sodium soap.
Lastly, there are the complex soaps which are formed by reacting the alkali with a blend of a monobasic acid and a dibasic acid. Complex greases typically result in improved temperature resistance and can handle applications where there are short temperature excursions up to 175 °C; higher is possible provided that the base oil used is stable at that temperature. The heat resistance of a grease can be measured by a temperature sweep test using a controlled stress rheometer. In this test, a simple soap grease will lose its structure as the temperature approaches that of its dropping point. However, a good complex soap grease will have a significantly more stable structure and as the temperature approaches 300 °C may not show an apparent loss of structure.
Non-Soap Thickeners
Non-soaps are split into two main categories. The first group is comprised of thickeners that undergo a chemical reaction to form the thickener, such as calcium sulfonates and polyureas. The second group is a dispersion of particles in oil that includes silica, organo-clays, polytetrafluoroethylene (PTFE’s), and carbon black.
Polyurea greases are generally considered to be high performance greases as they perform well in high temperature, continuous use bearing applications. One of the key properties of polyurea thickened greases is their excellent anti-oxidant capability. Polyurea greases are also characterized by dropping points in excess of 250 °C and low oil separation as measured by ASTM D6184. Typical applications for polyurea greases are precision ball bearings and electric motor bearings.
Calcium sulfonate greases are characterized by their unique inherent properties. Most other thickeners do not bring any tribological performance to the grease, but calcium sulfonate thickeners provide good anti-wear, extreme pressure and corrosion resistance. The water resistance for water spray off tests per ASTM D4049 depends on the base oils used and is generally considered fair, but can be improved by incorporating polymers into the grease. However, when testing calcium sulfonate greases on the water washout test per ASTM D1264, they have very good resistance to water. They also possess good thermal stability and have dropping points above 350 °C. Calcium sulfonate greases have been used successfully in a broad range of applications such as rolling equipment, pulp and paper industries, mining and construction, automotive, and the marine industry.
Silica greases resemble an aero gel which will yield excellent heat resistance and oxidative stability as the thickener is non-melting and therefore when tested for dropping point, do not give a value. The upper operating temperature of a silica grease is determined by the base oil with which it is paired. Silica inherently has poor water resistance. However, it can be treated with various silanes to make it water resistant which is important for electrical connector and damping applications. Silica is also a very efficient thickener as it has a large surface area.
Organo-clay greases are smooth textured greases based on either bentonite, hectorite, or montmorillonite. They have outstanding heat resistance, since the thickener will not melt, and when tested for dropping point, do not give a value. They have good oxidative stability and are usable at least up to the temperature that the constituent oil evaporates. These greases also have excellent water resistance. Clay greases do have fair shear stability and tend to soften quite a bit when worked.
PTFE greases are generally considered to be high temperature greases that have good thermal stability, water resistance, shear stability, and lubricity. PTFE greases typically have dropping points over 260 °C. PTFE is typically used to thicken PFPE base oils which result in greases that can have low outgassing properties which make them ideal candidates in space and semicon applications. Another advantage to PTFE/PFPE greases is that they have excellent material compatibility with plastics and elastomers. A drawback to PTFE is that it is an inefficient thickener and typically can require up to 50% thickener depending upon the stiffness of the resulting grease. PTFE can also be used to thicken other base oil chemistries such as PAOs and silicones which are used in automotive and damping applications. PTFE is classified under the per- and polyfluoroalkyl substances (PFAS) umbrella of chemicals. For more information regarding the efforts we are making to comply with PFAS regulations, please contact one of our experts
There are a few carbon blacks that have decent thickening efficiency and are employed to produce electrically conductive greases. The resulting greases are high-temperature products that are used in bearings to allow static discharge to pass through the bearing instead of building up, arcing, and causing damage to the rolling element. These greases have good thermal stability but have surprisingly poor water resistance. Typical applications for these greases have been in treadmills, laser printers, copiers, and computer equipment.
The chart below summarizes the key characteristics of each thickener we have discussed. In addition, you'll find a list of applications where these thickeners have been successful.
Thickener | Key Characteristics | Applications |
---|---|---|
Soap Thickeners | ||
Lithium Soaps | Good lubricity, shear stability, thermal resistance, low oil separation | Bearings in automotive and industrial |
Calcium Soaps | Improved water resistance over the lithium greases, good shear stability | Used in applications that operate up to 110 °C, bearings of water pump, wheel bearings, and agricultural vehicles |
Sodium Soaps | High dropping points (typically 175 °C), good shear stability and lubricity | Bearings in aerospace, wheel bearings, universal joints, and axle journal boxes |
Aluminum Soaps | Excellent oxidation resistance, good water resistance | Vibrating screens, elevator drive motors and governors where reversing motion occurs, and large electric motors with bearings operating at high linear speeds |
Non-Soap Thickeners | ||
Polyurea | Performs in high temperatures, low oil separation | Precision ball-bearings and electric motor bearings |
Calcium Sulfonate | Good anti-wear, extreme pressure and corrosion resistance, good thermal stability | Rolling equipment, pulp and paper, mining and construction, automotive, and marine |
Standard Silica | Excellent heat resistance and oxidative stability, large surface area | Electrical connector and damping |
Organo-Clay | Outstanding heat resistance, good oxidative stability, excellent water resistance, fair shear stability | Military/aviation, industrial equipment, low speed bearings operating at high temperatures |
Polytetrafluoroethylene (PTFE) | Good thermal stability, water resistance, shear stability, and lubricity, excellent material compatibility with plastics and elastomers | Automotive and damping |
Carbon Blacks | Good thermal stability, performs in high-temperature | Treadmills, laser printers, copiers, and computer equipment |