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MAT373
4. Solid Lubricants

© A Matthews 2014

1. INTRODUCTION
Solid lubricants are used in environments where conventional liquid lubricants (ie, oils and
greases) would be unsuitable.

Examples:
• High temperatures.
• Very low temperatures (cryogenic).
• High vacuum (eg, in space).
• Highly corrosive conditions.
• Radioactive or biologically hazardous environments.
• Hygenic environments (eg, food processing).

Furthermore, solid lubricants can provide virtually permanent lubrication, thereby reducing
or eliminating maintenance.

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1. INTRODUCTION (cont.)
Dry bearings, which are usually based on polymeric materials, are
sometimes employed as an alternative to using metal-based systems that
are fed with solid lubricants.
However, some applications (especially the first 3 examples above) may be
restricted, due to rapid changes in the mechanical properties of most
polymers with temperature and possible "outgassing" effects under vacuum
conditions.
Nevertheless, they can provide the additional benefits of being cheap and
easy to manufacture, they rarely undergo seizure and can offer weight
savings.

2. TYPES OF SOLID LUBRICANT

2.1. Background

Essentially, the common factor with all solid lubricant materials is that they
can be sheared easily in at least one direction within their micro structures; it
is this effect that reduces the friction coefficient when such a material is
present between two rubbing surfaces. They can be grouped into 3
categories: (i) soft metals, (ii) lamellar solids and (iii) polymers.

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2.2. Soft metals

Soft metals, such as lead, indium, tin and gold can be sheared relatively easily. Being soft,
however, means that they cannot support heavy loads without deforming. Therefore, for
solid lubrication applications, they are normally used as thin coatings on harder (stronger)
metal surfaces. The friction coefficients obtained with soft metal lubrication are usually not
very low, typically 0.1 - 0.3 against other metals. Friction depends critically on the soft metal
film thickness: there is a compromise between load support (better with thin films) and
effects related to film continuity, such as a risk of penetration by asperities (less of a
problem with thicker films). The optimum thickness is usually between 0.1 and 1.0 μm and
films are applied by electroplating or physical vapour deposition techniques (such as
vacuum evaporation, sputtering or ion plating).

2.2. Soft metals (cont.)

Soft metal films are mainly used as lubricants in vacuum conditions, since many can be
sensitive to reaction with gases present in the atmosphere and this may affect their
performance, particularly at elevated temperatures. At low speeds and loads, they can be
used at temperatures close to their melting points (eg, up to about 300 °C for lead) but at
higher speeds and loads, frictional heating may cause localised melting.

Main benefits:
most can be used to moderately high temperatures (low speeds and loads), good
conductors of heat and electricity.

Main limitations:
coefficients of friction are usually not very low, potential reactions in air restrict applications.

Note that thicker soft metal-based films are often used in liquid lubricated conditions (eg,
journal bearings in car engines) and these are discussed later in the course.

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2.3. Lamellar solids

A material with a layered structure can be useful as a solid lubricant, if the bonding
between layers is much weaker than that within each layer. Examples include: graphite,
molybdenum disulphide (MoS2), tungsten diselenide (WSe2) and cadmium iodide (CdI2).
Graphite and MoS2 are the most commonly used lamellar solid lubricants.

2.3.1. Graphite
Graphite is a grey-black crystalline form of carbon, in which
the carbon atoms are arranged hexagonally in layered sheets
(Fig (1)). There are strong (covalent) bonds between the
carbon atoms within each layer but the bonds between the
layers are weak (van der Waals) forces. Therefore, the layers
in graphite crystals are relatively strong but the crystals will
split easily between layers. The low friction properties would
seem to arise from the weak bonds allowing the layered
sheets to slide over each other; however, it has been found
that the presence of condensed vapours, most commonly
water vapour, are also necessary for low friction. Therefore,
graphite is not a good lubricant in vacuum or in dry
Fig (1): Structure of graphite.
atmospheres. The mechanism by which vapours can reduce
friction is believed to be associated with vapour molecules
decreasing the effects of van der Waals forces between
adjacent layers.

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2.3.1. Graphite (cont.)

Another effect observed with graphite is that its friction
coefficient decreases as the normal load is increased.
The general explanation for this is that a film of graphite
forms on the surfaces being lubricated, so that the
interface region consists of graphite rubbing on
graphite. As the load is increased, the layered sheets at
the film surface are encouraged to tilt more in the
direction of motion, as shown in Fig (2). When a
reversal in direction occurs, the friction coefficient
increases slightly and then decreases, as the layered
sheets re-adjust. Typically, for high quality graphite in Fig (2): Sheet orientation effects.
the presence of water vapour, the friction coefficient can
vary from 0.05 at high contact loads to 0.15 at low
loads.

2.3.1. Graphite (cont.)

As the temperature rises in normal atmospheres, the moisture is driven off from
the graphite and becomes inadequate at about 200 °C. The friction coefficient
can then increase to the order of 0.3 - 0.4, making the graphite a mediocre dry
lubricant. Above about 350 °C, however, it becomes an effective lubricant again,
and it has been suggested that this may be due to some interaction with metal
oxides produced from the surfaces being lubricated. Graphite cannot be used at
temperatures above about 540 °C in air, since it begins to oxidise rapidly.

Main benefits:
can be used up to about 540 °C; low friction coefficients (particularly at high
loads); good performance in the presence of liquids.

Main limitations:
good performance depends on the presence of a condensable vapour, hence
unsuitable in vacuum or very dry environments.

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2.3.2. Molybdenum disulphide

There are numerous compounds, such as disulphides and
diselenides of molybdenum, tungsten and niobium, which have very
similar crystal structures and lubricant performance. Molybdenum
disulphide is the only one in this group that occurs naturally (in
"molybdenite", the main ore of molybdenum); therefore, it is cheaper
(since it only needs refining from the raw state) and much more
widely used than any of the other compounds in the group.

The structure of MoS2 is shown schematically in Fig (3). Here,

individual layers of the lamellar structure are either molybdenum
(black circles) or sulphur (white circles). Each layer of molybdenum
atoms is sandwiched between two layers of sulphur atoms, to make
a triple layer of atoms that are covalently bonded to each other. Thus Fig (3): Structure of molybdenum disulphide.

each triple layer is actually a single layer of MoS2 molecules. The

triple layers are joined to each other only by weak van der Waals
forces that exist between the adjacent layers of sulphur atoms, hence
the crystal can split easily between the MoS2 layers, giving rise to low
friction characteristics.

2.3.2. Molybdenum disulphide (cont.)

MoS2 adheres more strongly than graphite to metal and other surfaces and, like
graphite, the friction coefficient is load dependent for broadly similar reasons; a film of
MoS2 forms on the surfaces being lubricated, so that the interface region consists of
MoS2 rubbing on MoS2. Initially, the MoS2 may be applied to just one surface as a
bonded film (because of its excellent adhesion properties) and a transfer film of MoS 2
would form quickly on the mating surface. Typically, the friction coefficient of such
films can vary from about 0.03 at high contact loads to 0.2 at low loads.

The main advantage that MoS2 has over graphite is that its low friction characteristics
do not depend on the presence of absorbed vapours. Therefore, it can be used in
vacuum or very dry environments. In fact, it is well suited to vacuum conditions, since
oxidation problems do not arise. Satisfactory lubrication up to 1000 °C in high vacuum
has been claimed. In the presence of air, however, oxidation effects limit the
maximum usable temperature to about 450 °C.

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2.3.2. Molybdenum disulphide (cont.)

Main benefits:
excellent performance in vacuum; temperature limit approaches 1000 °C in
vacuum and about 350 °C in air; low friction coefficients (particularly at high
loads); excellent adhesion to bearing surfaces; very high load-carrying
capacity.

Main limitations:
poorer film adhesion to bearing surfaces in the presence of a liquid;
exposure to most contaminants (including moisture) can increase the
friction coefficient.

2.3.3. Lamellar solids - methods of application

(i) Powders:

They can be applied as dry powders or as dispersions in fluids (water, oil or alcohol).
Graphite dispersions are commonly used as mould and tool lubricants. Although MoS 2 may
not adhere so well to bearing surfaces in the presence of a liquid, dispersions of MoS 2 in
lubricating oils are widely used. There seems to be some uncertainty in the value of using
MoS2 in vehicle engine oils: some results have indicated a slight increase in engine wear,
other results have shown a small reduction in fuel consumption; also, it is said that MoS 2 is
deposited as a thin solid film at the piston-cylinder interface, and this can offer short term
protection in the event of complete oil loss.

For highly loaded bearings, it is useful to know that a 3 to 5% concentration of MoS2

particles in lubricating grease gives a substantial increase in load carrying capacity.
Furthermore, if grease is lost from the bearing, a residual film of MoS2 on the surfaces can
continue to give satisfactory lubrication for some time.

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2.3.3. Lamellar solids - methods of application (cont.)

(ii) Films:

Thin films will often form during the operation of surfaces rubbing together after adding a
lamellar solid as a dry powder or as a sprayed dispersion in a volotile solvent. Due to the
excellent adhesion of MoS2 to surfaces, a film can be purposely made by rubbing or
"burnishing" MoS2 powder onto a metal surface with a cloth; this will produce a glossy blue-
black film about 0.1 μm thick. Thicker films can be made by the repeated addition of
powder followed by burnishing, up to about 10 μm thick.

Lamellar solid lubricants (mainly MoS2) may be incorporated in an organic binder such as
epoxy resin and applied in a solvent base to surfaces by spraying, brushing or dipping. A
hard varnish-like film is produced after baking, that is 2 to 40 μm thick. For high
temperature use, an inorganic binder, such as a silicate, should be used.

In recent years, MoS2 films 0.2 to 2 μm thick, with very low friction coefficients (0.01 or less),
have been produced by a process known as magnetron sputtering (a form of physical
vapour deposition).

2.3.3. Lamellar solids - methods of application (cont.)

(iii) Solid blocks:

Although polymeric-based dry bearings are commonplace, applications involving high

temperatures and electrical conductivity usually need alternative solutions:

The simplest form is made by heating a mixture of petroleum, coke (distilled

bituminous coal) and a binding agent in a high temperature furnace so that they
become graphitised; depending on the heat treatment, components range from low
load applications such as electrical brushes to high load applications such as thrust
and journal bearings.

Alternatively, a metal composite, in which the lamellar solid lubricant is mixed with a
metal powder, can be compacted and sintered so that the lubricant is incorporated in a
heat conducting metal matrix. These may also be used as self-lubricating bearings,
electrical brushes and other low friction components.

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2.4. Polymers
2.4.1. PTFE (Polytetrafluoroethylene)
The most effective and widely used polymer for sliding
applications is PTFE. Fig (4) shows that it has a smooth
molecular profile; also, the large F atoms have a significant
screening effect on any net charges in the vicinity of the C
atoms, hence the attractive (van der Waals) forces
between adjacent long chain molecules are very weak.
Fig (4): Side and end views of the PTFE molecule
Thus PTFE molecules can slide easily over each other.

For tribological applications, the ease at which the molecular chains can slip over each other
results in chain orientation and the formation of a transfer film between rubbing surfaces; it is
this effect that is largely responsible for the low friction properties of PTFE. Common with
other polymeric materials and lamellar solid lubricants, the friction coefficient is load
dependent; thus for pure dry PTFE sliding against metals, friction coefficients as low as 0.03
can be obtained at high loads (and low speeds to minimise heating effects from friction), but
these can increase to 0.1 or more at low loads.

2.4.1. PTFE (Polytetrafluoroethylene) (cont.)

PTFE can be used at up to about 300 °C (it melts at 335 °C). PTFE is commonly
used in the form of a solid component (eg, a bearing), from which the transfer film is
generated and constantly replenished; however, PTFE cannot be injection moulded –
therefore machining from block, sintering, or compression moulding are the only
viable manufacturing methods. It can also be applied in the form of a dispersion (eg,
as a spray) to leave a residual film on bearing surfaces. The wear rate of pure PTFE
tends to be very high and it deforms slowly (creeps) under load; thus fillers or some
form of reinforcement is commonly used to reduce these effects. The presence of
liquids can interfere with transfer film formation; see Section 3 for further details.

Main benefits:
can achieve friction coefficients as low as 0.03 under high loads; usable from about -
200 °C to about +300 °C; highly resistant to chemical attack.

Main limitations:
the presence of liquids can be detrimental to low friction and wear performance; pure
PTFE has poor load carrying capacity; PTFE cannot be injection moulded.

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2.4.2. Other polymers

Polymers other than PTFE tend to be used (in the form of solid components, such as
bearings) only at low loads and speeds in dry sliding applications, or they are utilised
in environments where there is marginal or intermittent lubrication from liquids, oils or
grease to minimise the possibility of seizure. Examples:

(i) Nylons:

Easy to manufacture, these are much stronger, stiffer, and more creep resistant than
pure PTFE. They form transfer films on metal counterfaces and friction coefficients
are about 0.1 to 0.2 at low speeds, depending on the load and temperature. Surface
melting effects from friction restrict their use at higher speeds (> 1 m/sec) and they are
susceptible to moisture absorption (some types more than others), which make them
soften and swell. Typically, nylons can be used up to about 130 °C.

2.4.2. Other polymers (cont.)

(ii) Polyethylene:

Easy to manufacture but generally poor dry running tribological properties and the
temperature limit is about 75 °C. It is sometimes used in the high density form
(HDPE) for bushes running in water, but damage is said to occur if they run dry. The
ultra-high molecular weight form (UHMWPE) is, however, commonly used as bearing
material in artificial hip and other prosthetic joints.

(iii) Epoxy resins:

These give friction coefficients of about 0.2 against metals and are useful up to 200
°C, but they would not normally be used on their own for dry bearing applications.
Epoxies are more usually employed as matrix materials for dry bearing composites.

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3. POLYMERIC-BASED DRY BEARINGS

3.1. Background
The main polymer that is used as a solid lubricant is PTFE, as highlighted in
Section 2.4. A dry-running bearing, on the other hand, is usually made from a
polymeric-based composite; this may be a PTFE matrix or some other
polymeric-based matrix which incorporates PTFE particles or other solid
lubricants to reduce friction effects. As mentioned in Section 1, polymeric dry
bearings have certain benefits and limitations compared with more
conventional bearings, and the following gives more details:

3.1. Background (cont.)

Benefits:

(i) Usually maintenance-free.

(ii) Usually cheap and easily formed.
(iii) Low friction possible without additional lubricant.
(iv) Rarely undergo seizure.
(v) Wear rates on smooth counterfaces << soft metals.
(vi) Generally chemically inert.
(vii) Some can readily deform, allowing conformity to mating parts, resulting
in less critical alignment and tolerance requirements.
(viii) Low weight.

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3.1. Background (cont.)

Limitations:

(i) Low softening and melting points.

(ii) Low strength.
(iii) Low modulus (affects dimensional stability).
(iv) Fluid absorption may occur (detrimental to performance).
(v) Wear rates on rough surfaces >> soft metals.

3.1. Background (cont.)

The types of additive that are incorporated into polymeric bearings are:

(i) Fillers or fibres for improving stiffness and (for fibres) strength, to increase
load carrying capacity and reduce wear rate (eg, carbon, glass).
(ii) Additives for friction reduction (eg, MoS2, graphite, PTFE).
(iii) Additives for increasing thermal conductivity to improve heat
dissipation (eg, bronze, silver).

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