Solid & Dry Lubricants

Inroduction
Dry lubricants or solid lubricants are materials which despite being in the solid
phase are able to reduce friction between two surfaces sliding against each other
without the need for a liquid oil medium.
Mineral oil-based fluid lubricants (oil and grease materials) function properly
where the designed surface areas and shaft speeds allow for the effective
formation of an oil film, as long as the machine operating temperature envelope
falls between -20C and 100C (-4F to 212F). The only absolute limits that
apply for fluid lubricants, regardless of the base oil type, are conditions that
cause a change in the state of the fluid that prohibits fluid film formation.
Fortunately, that is not the end of the story.
Various materials that protect interacting surfaces after the fluid film is lost have
been either discovered or created. These materials may be applied to a surface
in the form of an additive to a fluid lubricant, or in a pure form, and may also be
added
The four most commonly used solid lubricants are:
1. Graphite. Used in air compressors, food industry, railway track joints,
brass instrument valves, open gear, ball bearings, machine-shop works,
etc. It is also very common for lubricating locks, since a liquid lubricant
allows particles to get stuck in the lock worsening the problem.
2. Molybdenum disulfide (MoS2). Used in CV joints and space vehicles. Does
lubricate in vacuum.
3. Hexagonal boron nitride. Used in space vehicles. Also called "white
graphite."
4. Tungsten disulfide. Similar usage as molybdenum disulfide, but due to the
high cost only found in some dry lubricated bearings.

Graphite and molybdenum disulfide (MoS2) are the predominant materials used
as solid lubricant. . They are extracted from mined ore. In the form of dry powder
these materials are effective lubricant additives due to their lamellar structure.
The lamellas orient parallel to the surface in the direction of motion.

Even between highly loaded stationary surfaces the lamellar structure is able to
prevent contact. In the direction of motion the lamellas easily shear over each
other resulting in a low friction. Large particles best perform on relative rough
surfaces at low speed, finer particle on relative smooth surface and higher
speeds.
Other components that are useful solid lubricants include boron nitride,
polytetrafluorethylene (PTFE), talc, calcium fluoride, cerium fluoride and tungsten
disulfide
Typical applications
Solid lubricants are useful for conditions when conventional lubricants are
inadequate.

Reciprocating motion. A typical application is a sliding or reciprocating

motion that requires lubrication to minimize wear as for example in gear
and chain lubrication. Liquid lubricants will squeezed out while solid
lubricants don't escape and prevent for fretting corrosion and galling.
Ceramics. Another application is for cases where chemically active
lubricant additives have not been found for a particular surface, such as
polymers and ceramics.
High temperature. Graphite and MoS2 exhibit high temperature and
oxidizing atmosphere environments, whereas liquid lubricants typically will
not survive. A typical application include fasteners which are easily
tightened and unscrewed after a long stay at high temperatures.
Extreme contact pressures. The lamellar structure orient parallel to the
sliding surface resulting in high bearing-load combined with a low shear
stress. Most applications in metal forming that involve plastic deformation
will utilize solid lubricants.
In the following section the different materials used as solid lubricants will
be discussed in more detail showing the method of production and the
mechanism of their lubrication.
Graphite

Graphite as a lubricant dates to antiquity. It was first referenced in the mid-1500s

as being used as pencils. Graphite is a soft, crystalline form of carbon. It is gray
to black, opaque, has a metallic luster, and is flexible but not elastic. Graphite
occurs naturally in metamorphic rocks such as marble, schist and gneiss. It
exhibits the properties of a metal and a nonmetal, which makes it suitable for
many industrial applications. The metallic properties include thermal and
electrical conductivity. The nonmetallic properties include inertness, high thermal
resistance and lubricity. Some of the major end uses of graphite are in hightemperature lubricants, brushes for electrical motors, friction materials, and
battery and fuel cells.

Graphite is structurally composed of planes of polycyclic carbon atoms that are

hexagonal in orientation. The distance of carbon atoms between planes is longer
and therefore the bonding is weaker. The bonds between the carbon atoms in
the crystal structure of the layer are stronger than the carbon bonds between
layers. Graphite is comprised of carbon and water vapor. Each carbon atom is
bonded to three other surrounding carbon atoms. The flat rings of carbon atoms
are bonded into hexagonal structures, as shown in Figure 1. The hexagonal
carbon structure is referred to as a benzene ring. These plates exist in layers,
which are not covalently connected to the surrounding layers.

Figure 1. Graphite Lamella Lattice Structure

(Reference: Dynamic Coating, Inc.)

Graphite is best suited for lubrication in a regular atmosphere. Water vapor is a

necessary component for graphite lubrication. The adsorption of water reduces
the bonding energy between the hexagonal planes of the graphite to a lower
level than the adhesion energy between a substrate and the graphite. Because
water vapor is a requirement for lubrication, graphite is not effective in vacuum.
In an oxidative atmosphere graphite is effective at high temperatures up to 450C
continuously and can withstand much higher temperature peaks. The thermal
conductivity of graphite is generally low ~1.3 W/mK at 40C.
Graphite is characterized by two main groups: natural and synthetic. Synthetic
graphite is a high temperature sintered product and is characterized by its high
purity of carbon (99.5-99.9%). The primary grade synthetic graphite can
approach the good lubricity of quality natural graphite.

Natural graphite is derived from mining. The quality of natural graphite varies as
a result of the ore quality and post mining processing of the ore. The end product
is graphite with a content of carbon (high grade graphite 96-98% carbon), sulfur,
SiO2and Ash. The higher the carbon content and the degree of graphitization
(high crystalline) the better the lubricity and resistance to oxidation.
For applications where only a minor lubricity is needed and a more thermally
insulating coating is required, then amorphous graphite would be chosen (80%
carbon).
Molybdenum Disulfide
MoS2 is a mined material found in the thin veins within granite and highly refined
in order to achieve a purity suitable for lubricants. Just like graphite has MoS2 a
hexagonal crystal structure with the intrinsic property of easy shear.
MoS2 lubrication performance often exceeds that of graphite and is effective in
vacuum as well whereas graphite does not. The temperature limitation of
MoS2 at 400C is restricted by oxidation. The particle size and film thickness are
important parameters that should be matched to the surface roughness of the
substrate. Large particles may result in excessive wear by abrasion caused by
impurities in the MoS2, small particles may result in accelerated oxidation
Molybdenum was not discovered until the latter part of the 18th century, and
does not occur in the metallic form in nature. Despite this, its predominant
mineral - molybdenite - was used in ancient times (a 14th-century Japanese
sword has been found to contain molybdenum) but would have been
indistinguishable from other similar materials such as lead, galena and graphite.
Collectively, these substances were known by the Greek word molybdos, which
means lead-like.
Molybdenum remained a laboratory curiosity throughout most of the 19th century
until the technology for the extraction of commercial quantities became practical.
In 1891, the French company Schneider and Co. first used molybdenum as an
alloying element in the production of armor plates. It was quickly noted that
molybdenum was an effective replacement for tungsten in numerous steel
alloying applications because its density is only slightly more than half that of
tungsten.
Because there is no vapor present between lattice plates, MoS2 is effective in
high-vacuum conditions, where graphite will not work. The particle size and film
thickness are important parameters that should be matched to the surface
roughness of the lubricated component. Particle size selection is much larger for
rough cut surfaces, such as hobbed open gears, than for highly finished
surfaces, such as those found on bearings. Improperly matched particle sizes
may result in excessive wear by abrasion caused by impurities in the MoS2.

The temperature limitation of MoS2 at 400C (752F) is imposed by oxidation.

MoS2 oxidizes slowly in atmospheres up to 600F. In a dry, oxygen-free
atmosphere it can function as a lubricant up to 1300F. The oxidation products of
MoS2 are molybdenum trioxide (MoO3) and sulfur dioxide. MoS3 is hydroscopic
and causes many of the friction problems in standard atmosphere. MoO3 is a
preferred form of the metal used as an additive for various other metals, which is
its primary use.
The issue of where molybdenum disulfide should be used, versus graphite or
tungsten disulfide, is generally best addressed by a lubrication engineer. For
most commercial applications, these are relatively simple judgments. In
aerospace applications where unique environments and exotic materials are
employed, these questions often take substantial research to provide the best
answers.

Figure 2. Crystal Structure of MoS2

The low friction coefficients of MoS2 often exceed that of graphite.
Boron Nitride
Boron Nitride is a ceramic powder lubricant. The most interesting lubricant
feature is its high temperature resistance of 1200C service temperature in an
oxidizing atmosphere. Further Boron has a high thermal conductivity. Boron is
available in two chemical structures, i.e. cubic and hexagonal where the last is
the lubricating version. The cubic structure is very hard and used as an abrasive
and cutting tool component
PTFE
PTFE is widely used as an additive in lubricating oils and greases. Due to the low
surface energy of PTFE, stable unflocculated dispersions of PTFE in oil or water
can be produced. Contrary to the other solid lubricants discussed, PTFE does
not have a layered structure. The macro molecules of PTFE slip easily along

each other, similar to lamellar structures. PTFE shows one of the smallest
coefficients of static and dynamic friction, down to 0.04. Operating temperatures
are limited to about 260C.
Application methods
Spraying/dipping/brushing: Dispersion of solid lubricant as an additive in oil,
water or grease is most common used. For parts that are inaccessible for
lubrication after assembly a dry film lubricant can be sprayed. After the solvent
evaporates, the coating cures at room temperature to form a solid lubricant.
Pastes are grease like lubricants containing a high percentage of solid lubricants
used for assembly and lubrication of highly loaded, slow moving parts. Black
pastes generally contain MoS2. For high temperatures above 500C pastes are
composed on the basis of metal powders to protect metal parts from oxidation
necessary to facilitate disassembly of threaded connections and other
assemblies.
Free powders: Dry-powder tumbling is an effective application method. The
bonding can be improved by priory phosphating the substrate. Use of free
powders has its limitations, since adhesion of the solid particles to the substrate
is usually insufficient to provide any service life in continuous applications.
However, to improve running-in conditions or in metal forming processes a short
duration of the improved slide conditions may suffice
AF-coatings: Anti-friction coatings are "lubricating paints" consisting of fine
particles of lubricating pigments, such as molydisulfide, PTFE or graphite,
blended with a binder. After application and proper curing, these lubricants bond
to the metal surface and form a dark gray solid film. Many dry film lubricants also
contain special rust inhibitors which offer exceptional corrosion protection. Most
long wearing films are of the bonded type but are still restricted to applications
where sliding distances are not too long. AF-coatings are applied where fretting
and galling is a problem (such as splines, universal joints and keyed bearings),
where operating pressures exceed the load-bearing capacities of ordinary oils
and greases, where smooth running in is desired (piston, camshaft), where clean
operation is desired (AF-coatings will not collect dirt and debris like greases and
oils), where parts may be stored for long periods of time.

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