September 10,

2013

The Formation of Deposits in Lubricating Oil Systems

by Michael Holloway, CLS,
Business Development Manager

There are several reasons why deposits form in a

lubricating system. Typically, the oil undergoes a
transformation from one molecular structure to
another. This can be in the form of a mixture of a
contaminant such as fuel soot with motor oil, or
transmission sludge from debris and gear oil. It can also
be varnish or lacquer on a piston pump cylinder from
excessive temperature and load. More often it is the
breaking down of the base oil and the building up of a
new compound. This re-constitution develops through a
series of steps. The first step is the generation of a reactive compound or
free radicals. There are several ways in which these compounds develop.
Once in the system, they combine or polymerize into new compounds in
the form of deposits. Various environmental conditions can facilitate the
generation such as temperature, pressure, water, solvents, acids, caustics
and various metals.

When lubricants oxidize, they form reactive materials that can re-constitute
into different deposits. Oil analysis can help to identify the degree of
oxidation that has occurred. More sophisticated analysis may have to be
performed in order to identify the exact contaminant. The following are
several of the typical deposits that are formed and the problems that can
occur when lubricating oil breaks down.
Varnish: Found on bearings, cylinders, pistons, gears, vanes, pumps, and
turbines. Oil or fuel oxidizes, forming a gummy substance that develops
into a coating with highly cross-linked molecules that are insoluble in oil.
Varnish coating can lead to uneven gear wear due to unbalancing,
increased drag/energy demand and increased temperatures due to lack of
lubrication on metal surface, oil viscosity increase.

Lacquer: Found on bearings, cylinders, pistons, gears, vanes, pumps, and

turbines. When varnish is exposed to excessive temperatures and
pressure, it becomes baked on and ironed out, forming lacquer. Lacquer,
like varnish, can lead to uneven gear wear, increased drag/energy demand
and increased temperatures due to lack of lubrication on metal
surface. Lacquer is exceptionally difficult to remove.

Sludge: Found in oil pans, sumps, housings, reservoirs, and bearings.

Formation begins when contaminants begin to settle out of the oil. Sludge
develops with excessive accumulation of contaminants, leading to additive
depletion and oxidation. Sludge is composed of water, carbon residue,
oxidized oil, and acidic compounds, which can lead to further oil
decomposition. Sludge can restrict oil flow, leading to increased system
pressure, temperature, wear, and oil viscosity increase.

The following table describes the mechanism and contributing factors

contributing to the formation of varnish.

Contributing Factor Mechanism

When the base oil contains one or more of the
Inferior Base Oil following; light fractions, sulfur, low molecular weight
hydrocarbons.
Low concentrations of anti-wear agents and/or friction
modifiers produce wear metals and localized frictional
Insufficient Concentration
heat.
of Performance Additives
Low concentrations of demulsifiers can lead to
emulsified oil, which hastens oil oxidation.
Contaminants from external or internal sources can
Yellow Metals (copper,
catalyze oil oxidation and lead to deposits and additive
brass, bronze)
depletion.
Heat High ambient temperatures, operational heat (from
 kinetic energy or combustion), frictional heat (from
metal to metal contact), pressure (from aeration and/or
operation) can accelerate oil oxidation and additive
depletion.
By-products of combustion and/or external
Water contaminants can hasten oil oxidation and lead to
deposits, additive depletion.
Develops when base oil breaks down into reactive
species, produces sludge, varnish and/or other
Acids deposits, or external source such as acid washing.
Common forms are sulfuric acid, nitric acid and various
carboxylic acids.
External contamination breaks oil molecule into
Caustics and Solvents reactive species. The reactive species may
polymerize to form resinous deposits.

Testing for the Potential for Varnish

There are a few analytical techniques used to predict the onset of deposit
formation namely varnish. It should be noted that while one test may
provide an indication that varnish has the potential to form or is forming,
using several analytical techniques to establish the opportunity for varnish
to form provides a greater degree of confidence.

Color – when oil begins to oxidize the compounds that are getting created
will absorb various wavelengths of light rendering a sample dark. Color
testing is the quickest indication that oil has begun to oxidize. The degree
of oxidation can be understood if a base-line sample is used to compare.

Ultracentrifuge Sediment Rating – an ultracentrifuge will take full

advantage of the density of particulates, separating them from the oil
sample for further analysis. Suspended insoluble gums that represent
varnish precursors are pulled out of suspension due to the ultra-high
centrifugal force that normal centrifuges cannot obtain. This material is
then physically collected for observation and measurement.

Pentane Insolubles – pentane is a strong solvent but not strong enough to

dissolve the products of oxidation or the precursors to varnish. Determining
the insoluble population by filtering these insolubles and measuring the
weight per volume will provide insight into the rate and likelihood of varnish
formation.

MPC (Membrane Patch Colorimetry) - a sample is passed through a filter

media patch. The dark discoloration of filter patch identifies soft
contaminants (varnish precursors). This is reported in a numeric color
rating of the filter patch is based on the CIE ∆E (International Commission
on Illumination delta energy values).

Particle Count –particle count helps support an indication of a high level of

varnish potential due to the existence of suspended varnish precursors
when a low particle count is determined, while a high particulate weight by
pentane insolubles is measured. Varnish precursors are submicron in size
and would not normally be detected by standard particle count methods,
while the membrane filter used for the pentane insolubles test uses
submicron pore size for filtration.

RULER® (Remaining Useful Life Evaluation Routine) - measures

hindered phenolic and aromatic amine antioxidant content, the primary
antioxidants used in industrial oil and zinc-free turbine oil applications. By
measuring the depletion and available reactivity of these antioxidant
compounds in addition to routine performance tests, you can effectively
monitor the service life of used lubricants.

By combining these techniques and monitoring the overall oil condition as

well as wear metals and oxidation products, it is possible to accurately
predict the onset of oxidation in general and varnish in particular.