GEAR SOLUTIONS MAGAZINE

CFD SIMULATION OF POWER LOSSES AND LUBRICANT FLOWS IN GEARBOXES

CFD Simulation of Power

Losses and Lubricant
Flows in Gearboxes
ISSUE FOCUS
Lubrication
Broaching

COMPANY PROFILE
JM Performance Products
MARCH 2018

MARCH 2018
Your Resource for Machines, Services, and Tooling for the Gear Industry gearsolutions.com
 HOT D. SCOTT MACKENZIE, PHD, FASM

SEAT
SENIOR RESEARCH SCIENTIST-METALLURGY
HOUGHTON INTERNATIONAL INC.

OIL QUENCHANTS – UNDERSTANDING THE CHEMISTRY (PART III)

In this issue, a discussion of the mechanism of quench oil, focusing on oxidation,
thermal degradation, contamination, and additive depletion.

In the last two installments, the effects of base oil and additives on the
performance of quench oil were described. In Part III, the mechanism of
quench oil oxidation will be discussed.
The life of quench oil is dependent upon its thermal stability. The
thermal stability is a function of the quality of the base oil, the antioxidant
package used, and the presence of heat and catalysts. Premium quality
heat-treating quenching and martempering oils are formulated from
refined base stocks (usually paraffinic) of high thermal stability with addi-
tives to improve performance and increase tank life. These additives are a
combination of specially chosen ingredients compatible with the base oil;
in particular, carefully selected and tested antioxidants, which retard the Fig. 1: Deposits on ring gears due to severely degraded quench oil.
aging process. Quench oils degrade due to four primary reasons:
• Oxidation
• Thermal Degradation
• Contamination
• Additive Depletion
The degradation of quench oil is aggravated by residues on parts,
washer residues from oil reclaimed from washers; high energy density
heater or radiant tubes, and excessive peak temperatures. The addition
of robust additive packages prolongs a quenchant life and provides for
repeatable quenching.
Oxidation of quench oil is caused by exposure to oxygen. As operat-
ing temperatures increase, the kinetics of oxidation approximately double
with each 10° C. This is especially true with mar-tempering oils because
of their elevated temperature of use.
Thermal degradation is from exposure to temperatures that cause the
base oil and additive package to change. This results in the formation of
insoluble products of reaction that can cause deposits on parts and sludge
Fig. 2: Effects of oxidation on the cooling curve of a high viscosity martempering oil.
the quench tank. Oxidation shows a destabilization of the vapor phase, and an increase in the nucleate
Contamination can be from many sources. Water, dust, scale, and boiling to convection transition temperature.
soot are not the direct result of oil degradation but can contribute to other
degradation issues. Soot can act as nucleation sites for thermal degradation tant part in chain initiation reaction. Typically, reactions are slow
products, and it can mimic oxidized oil. at room temperatures but become increasingly faster above 100° C.
Additive depletion is normal and expected. The anti-oxidants are This is why, for high-quality quenching oil, “cold” oils (those used
consumed as part of their function. Anti-oxidants are replenished as below 80 ° C) do not experience the severe oxidation with attendant
make-up oil is added. increases in viscosity and Total Acid Number (TAN) than martem-
Oil degradation is manifested by a viscosity increase, acidity increase pering oils experience (Figure 2). There are generally two types of
(as measured by Total Acid Number), varnish and lacquer deposits, sludge, initiation reactions:
and changes in the quench speed [1]. Examples of staining of parts are
shown in Figure 1. RH+O 2  R•+HOO•
There are many papers covering the mechanism of oxidation of oils 2RH+O 2  2R•+H 2 O 2
and the function of antioxidants [1-5]. There are three primary steps in
the oxidation of oil: Chain Initiation; Chain Propagation and Branching; There is a second class of reactions that are catalyzed by the
and Termination. presence of iron or copper. These are hydroperoxide decomposition
initiation reactions:
CHAIN INITIATION
The oxidation mechanism of quenching oils is very complex. The Fe +3 +ROOH  Fe +2 ROO•+H+
presence of iron and copper catalyze the reactions and play an impor- Fe +2 +ROOH  Fe +3 +RO•+HO –
24 gearsolutions.com
CHAIN PROPAGATION AND BRANCHING The first two reactions are a chain scission step that forms two
The chain propagation step involves the reaction to produce addi- lower molecular weight hydrocarbon fragments and the formation
tional radicals that propagate the oxidation sequence. Alkyl radicals of an alkyl radical. These reactions affect the physical properties of
(R•) react with oxygen in the oil and create peroxy radicals (ROO•). the oil quenchant by decreasing the viscosity, increasing the volatility
These peroxy radicals react with additional hydrocarbon molecules and decreasing the flashpoint, and finally, by increasing the polarity
to produce hydroperoxides (ROOH) and additional akyl radicals: of the quenchant. The alkyl radials are then free to react with oxygen
in the propagation steps above. The scission that occurs is very rare
R•+O 2  ROO• in quenchants, but can occur in other lubricants.
ROO•+RH  ROOH+R• The last reaction above is a chain termination that consumes two peroxy
radicals and produces an alcohol and a carbonyl compound. The polarity of
Additional chain branching occurs by several different reactions. the hydrocarbon will increase, but the molecular weight will be unchanged.
This is dependent on the base oil and the temperature. Examples This also means that the viscosity, flashpoint will also be unchanged.
are shown below:
FORMATION OF CARBOXYLIC ACIDS
ROOH  RO•  +HO• As the oxidation increases, the acid levels from the formation of
RO•+RH  ROH+R carboxylic acids increase. This increase leads to further oxidation
HO•+RH  H 2 O+R• because the carboxylic acids promote oxidation. This is why, once
oil starts to oxidize, it does so in an exponential fashion, with the
There are many other initiation, propagation, and chain branch- oxidation rapidly increasing. Carboxylic acids are formed by the
ing reactions that have been reviewed elsewhere [1, 2]. oxidation of aldehydes and ketones. This is measured by ASTM
The side reactions of the formation of aldehydes and ketones are D664. It is a measure of the amount of organic acids present in the
probably the most important in maintenance of quench oils because oil, and is useful for determining when staining is likely, or the oil
their subsequent reactions eventually form sludge and deposits. While is reaching the end of its useful life. For most oil quenchants, when
there are a number of different paths that lead to the formation of alde- the TAN (Total Acid Number) is greater than 1.5-2.0, it is indicative
hydes and ketones, the most accepted mechanisms are shown below: of staining or deposits on parts being quenched.

RR'HCO•  RCH=O+R' CONDENSATION REACTIONS

RR'R''CO  R R'C=O+R'' As oils become increasingly oxidized, whether in the quench tank, or
2RR'CHOO•  R'RC=O+RCHOHR'+O2 in oxidation tests, the viscosity increases. This occurs by condensation

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reactions that become important as the levels
of aldehydes and ketones increase. These reac-
tions are known as Aldol Condensations [1]. It
is this reaction that causes varnish on parts and
sludge in quench tanks.

SLUDGE AND DEPOSIT FORMATION

The condensation products described in
the above section have a limited solubil-
ity in the quenchant. These are high
molecular weight oligomers. These are
molecules that have a few monomer units,
in contrast to a polymer that can have
an unlimited number of monomers. As
oil oxidizes the amount of carboxylic Fig. 3: Overall schematic of the oxidation of quench oil.
acids will increase. These acids are very
effective catalysts for Aldol condensation
reactions. These then convert the low molecular weight carbonyl can also act as a nucleation site for the formation of oligomers
compounds into higher molecular weight oligomers. formation, resulting in oligomers coated soot particles. These
As the reactions progress, chemical changes in the oligomers accumulate at the bottom of the quench tank in low velocity
will result in making them insoluble in the quench oil. At this areas, and are deposited on parts. The overall oxidation reac-
point the insoluble oligomers will precipitate from the quench tions are shown in Figure 3.
oil and create sludge on the bottom of the quench tank, and In the next installment, examples of the effect of base oil
deposits on the hot metal part. and additive packages on the oxidation resistance of quench
The higher kinetic rate of aromatic group oxidation increases oil will be discussed, as well as methods to help mitigate the
sludge and deposits. Because paraffinic oils have fewer aromatic effects of oxidation.
groups than naphthenic oils, paraffinic oils are preferred for
quenchants. Metal scale and soot, base oil sulfur, additive sulfur REFERENCES
can also promote the formation of sludge and deposits. Soot 1. G. Totten, C. Bates, N. Clinton, “Handbook of Quenchants
and Quenching Technology,” ASM International, Metals
Park, OH, 1993
2. Scott, G., Atmospheric Oxidation and Antioxidants, Elsevier
Publishing Company, Amsterdam, 1965.
3. Shlyapnikov, Y. A., “Antioxidant Stabilization of Polymers,”
Russ. Chem. Rev., Vol. 50, 1981, pp.581–600.
4. Colclough, T., “Lubricating Oil Oxidation and Stabilization,”
Atmospheric Oxidation and AntioxidantsVolume II, G. Scott,
Ed., Elsevier Science Publishers B. V., Amsterdam, 1993,
pp. 1-70.
5. Rasberger, M., “Oxidative Degradation and Stabilization of
Mineral Oil Based Lubricants,” Chemistry and Technology
of Lubricants, R. M. Motier and S. T. Orszulik, Eds., Blackie
Academic and Professional, London, 1997, pp. 98-143.
6. V. Gatto, W. Moehle, T. Cobb, and E. Schneller, “Oxidation
Fundamentals and Its Application to Turbine Oil Testing,”
J. ASTM, April 2006, V3 #4, p.1
7. AL-Malaika, S., “Autoxidation,” Atmospheric Oxidation
and Antioxidants Volume I, G. Scott, Ed., Elsevier Science
Publishers B. V., Amsterdam, 1993, pp. 45-82.
8. Uri, N., “Mechanism of Autoxidation,” Autoxidation and
Antioxidants Volume I, W. O. Lundberg, Ed., John Wiley
& Sons, Inc., New York, 1961, pp. 133-170.
9. March, J., “The Aldol Condensation,” Advanced Organic
Chemistry, 3rd ed., John Wiley & Sons, Inc., New York,
1985, pp. 829-834.

ABOUT THE AUTHOR D. Scott MacKenzie, Ph.D., FASM, is senior

research scientist-metallurgy at Houghton International Inc. Go online to
www.houghtonintl.com.

26 gearsolutions.com