CME3036 Process and Product Engineering CME3036/SJB/2011

Lubricant degradation

• Lubricant degradation chemistry

– Oxidation
– Antioxidants
» Primary antioxidants
» Secondary antioxidants
» Antioxidant synergies
CME3036 Process and Product Engineering CME3036/SJB/2011

Conditions in a diesel engine

CME3036 Process and Product Engineering CME3036/SJB/2011

Conditions in a piston ring pack

CME3036 Process and Product Engineering CME3036/SJB/2011

Lubricant oxidation
• Oils react with oxygen to form
– Organic acids, lacquers, coke, sludge
• Oxidation is usually the most important
life-limiting factor
• The oxidative stress on lubricants is
increasing as a result of:
– Engine design changes
– Smaller sump capacities
– Longer oil drain intervals
CME3036 Process and Product Engineering CME3036/SJB/2011

Initiation of Oxidation

• High temperature breaking of molecular

bonds to form very reactive free radicals, e.g.
R-R → 2R●
R-H + O2 → R● + HO2●
• NO2 in blowby gas can react with lubricant to
form free radicals
R-H + NO2 → R● + HONO
• Initiation can also be promoted by metal wear
particles
CME3036 Process and Product Engineering CME3036/SJB/2011

Lubricant oxidation
mechanism
R-R, R-H → R● Initiation
R● + O2 → ROO● Propagation
ROO● + RH → ROOH + R● [rate strongly depends
on lubricant molecule]

ROOH → RO● + HO● Chain

branching
2ROO● → Products Termination
CME3036 Process and Product Engineering CME3036/SJB/2011

Oxidation rate and lubricant

structure
ROO● + RH → ROOH + R●
Rate depends on how easily H atoms are
abstracted from the lubricant molecule R-H
CME3036 Process and Product Engineering CME3036/SJB/2011

Uninhibited oxidation

Because of chain branching, oxidation

accelerates in the absence of antioxidants:

Typically the extent of oxidation is mirrored by an increase in

acidity and viscosity
CME3036 Process and Product Engineering CME3036/SJB/2011

Effects of Oxidation
• Increase in acidity
– Carboxylic acids – corrosive to Pb in bearings
• Condensation and polymerisation reactions:
– Increase in viscosity
– Eventually sludge and deposits
– These cause blocking of filters and sticking of
piston rings
• Loss of additives
• Increase in metals content which gives
positive feedback further accelerating
oxidation
CME3036 Process and Product Engineering CME3036/SJB/2011

Oxidation in piston
environment
In-situ observations by FTIR in a running engine
CME3036 Process and Product Engineering CME3036/SJB/2011

Oxidation of a compressor oil

Carbon deposits in trunking leading from an air compressor