Oxidation stability of gear lubricants

Once a proper gear lubricant is selected for a given application it should suffer a minimum chemical and physical change during use. One of the changes most likely to occur is oxidation  of  the oil  which ultimately  will  lead  to the formation of undesirable  products  and  changes in the characteristics  of the oil. Such changes may result in the formation of acidic  products which  may corrode  the metal  surfaces, in an increase  in viscosity  of  the  oil, or in production  of  insoluble  materials. Oxidation  of  lubricants  is  accelerated  by  high  temperatures or  by  the  presence of  certain catalysts, particularly  soluble  metals. The  immediate  effects  of  oxidation  may appear  beneficial  in  that  petroleum  acids formed  function  as  oiliness  agents, perhaps by  the formation  of  monolayers  of metallic  soaps. Ultimately, as oxidation of oil proceeds, the harmful effects become evident. The degradation of the oil by oxidation may result in not only the formation of acidic products but also asphaltenes, resins, or other polymers. Changes in the lubricant will  probably  be  accompanied  by  increase  in  viscosity , darkening  in  color, and  the  formation  of  sludge. Cases have been noted where gear oils became almost solid due to oxidation.

However, oxidation of gear lubricants can be retarded by addition of antioxidants or oxidation inhibitors. The use of such agents in most gear oils is wise since the environment for the lubricants is favorable for oxidation in that both air and heat are present and thin films of the oil are in contact with the air.

The mechanism of the action of antioxidants is generally considered to be that of chain breaking as the additive reacts with a “hot” molecule, thus being itself oxidized. In this process the oxidant molecule is destroyed, but with dissipation of the energy possessed by the “hot” molecule, so that the chain reaction is broken. Thus, the oxidation of hundreds or perhaps thousands of molecules of hydrocarbons is prevented, since the energy would be passed on from one molecule to the next in the normal chain reaction.

The suggestion was made by Larsen and Diamond^35 that antioxidants may be either inhibitors or retardants, the former acting to break reaction chains and the latter being converted into an inhibitor during the oxidation process. Three possibilities were given by Murphy et al.^42  for the possible disposition of such inhibitors after they had reacted: (a) the inhibitor is oxidized to a compound which is incapable of further antioxidant action; (b) the inhibitor is oxidized to a compound which still exhibits antioxidant action, but generally to a reduced extent; (c)  the inhibitor is capable of regeneration. The latter type of additive is the most desirable, provided the rate and degree of regeneration are high.

Specific compounds suitable as antioxidants will be suggested in a later section, but most of these agents fall in the following bellows: (a) various types of phenols, (b) certain sulfur bearing compounds, (c) numerous organic phosphites, and (d) certain of the amines. A number of additives function as dual purpose agents and thus, in some cases, a specific antioxidant may not be required.

Corrosion prevention by gear lubricants

Ellis et al.^22 consider that staining, tarnishing, and rusting are all  indications of corrosion. The thought is that light stain or tarnish represents the early stages of corrosion since, unfortunately these  changes do not proceed very far before pitting starts. Unreactive gear oils, which have not been subjected to excessive high temperature oxidation, have no tendency  to corrode  metals but, under moist or humid conditions or in the presence of  most salts or acids, do not offer proper protection against  rusting of ferrous  metal  surfaces such as gears. However, additives can be included in gear compounds which will provide rust prevention. Where conditions of incipient rusting prevail, the gears and other metal parts even to the inside of the gear case may require protection, particularly when idle. In such cases not only will the presence of a rust inhibitor but also the viscosity of the base oil be factors. Thus, the higher the viscosity of the gear lubricant, the slower this will drain from the metal surfaces and consequently the greater the rust prevention. Rusting may occur in different environments and various theories are offered as to the mechanisms of corrosion, but normally moisture and oxygen are the offenders

Most rust preventives are polar substances, such as long chain fatty acids, fatty amines, metal sulfonates, certain esters, oxidized petroleum fractions, etc. Such materials wet a metal surface preferentially and displace any water which may come in contact with the steel. The coating of polar substance then acts as a barrier against water reaching the metal surface.

As previously mentioned, controlled  corrosion due  to  EP  additives  is generally beneficial in  that  it  corrodes  away high  spots   on the gear  teeth after  which corrosion may decrease. With the proper selection of the chemical agents, these are not activated except under extreme conditions of load and /or temperature. Further, most of the EP additives which are  used  in  gear  lubricants will have little effect  upon  other  metals such  as bronze, copper, etc; at the bulk oil temperatures maintained  in normal  gear operation .