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OXIDATIVE WEAR

Oxidative wear is the wear of dry unlubricated metals in the presence of air or oxygen. Atmospheric oxygen changes the friction coefficients and wear rates of dry sliding metals. Oxidative wear was found when changes in the chemical composition of wear debris generated. When the load and sliding speed were high enough to increase the frictional contact temperature to several hundred degrees Celsius, the wear debris changed from metallic iron to iron oxides. Oxidative or mild wear shows a moderate and stable coefficient of friction of about 0.3 -0.6 compared to much larger fluctuating values for severe wear.

Oxidative wear can be found in cases when a high process temperature causes rapid oxidation and the formation of thick oxide films.

The hole piercer used in the hot drawing of tubes is a good example of oxidative wear . A multilayer cap of scale and deformed metal accumulates at the tip of the piercer and the thickness of the scale (thick oxide film) can be as high as 0.1 [mm].

Kinetics of Oxide Film Growth on Metals at High and Low Temperatures


Oxide films are present on almost all metals and will form on any clean metal surface exposed to oxygen even at cryogenic temperatures. The oxidation rate of metals is dependent on temperature as is expected of a chemical reaction.
At low or ambient temperatures, e.g. 20C, the oxidation of metal is

initially rapid and is immediately followed by the passivation of the surface which limits the oxide film thickness. For example, the limiting film thickness can be as low as 2 [nm] (about 5 atom layers) for steels when the temperature is below 200C.

If the temperature of steel is increased to 500C, almost unlimited

oxidation occurs which results in a very thick oxide film, e.g. in the range of 1 - 10 [m]. The distinction between these two forms of oxidation is illustrated in Figure

The difference in oxidation kinetics results from much more rapid movement of oxygen or metal ions across the oxide film at high temperatures, when solid state diffusion is sufficient to ensure adequate transport of the metal or oxide ions necessary for a continuous film growth.
At low temperatures, the oxide films are form rapidly and effectively

suppress adhesive wear. If a system operates under mild oxidational conditions wear is greatly reduced. At high temperatures, however, oxidation resembles corrosion in its high rate of reaction and can become a direct cause of increased wear. This rapid oxidation at high temperatures forms the base of oxidative wear.

The high temperatures can either be imposed externally or can be due to high frictional heating at high speeds and loads as illustrated in Figure

Oxidative Wear at High Sliding Speeds


At sliding speeds above 1 [m/s] the surface flash temperatures can be as

high as several hundred degrees Celsius and if the load is low enough to permit mild wear, oxide films several micrometers thick can build up on the worn surface.

Under these conditions the oxidation proceeds very rapidly, especially

at the high contact spots. Because the oxide layers formed are thick enough to physically separate the wearing surfaces, it is reasoned that the oxidative wear which occurs must be due to the formation and removal of these thick oxide layers. At high speed, the thin oxide films present on unworn steel surfaces are rapidly destroyed and the friction and wear rates increase, initiating a period of severe wear. When each oxide layer reaches a critical thickness, it becomes too weak to withstand the load and frictional shear stress and is removed during the sliding.

Sequence of events associated with the formation and removal of oxide layers

At high sliding speeds any asperity of a surface is subjected to a random sequence of short periods of high temperature oxidation when contact is made with asperities of an opposing surface as shown

Periodic rapid oxidation between the asperities in dry high-speed sliding contact; d is average diameter of thick oxide patches

Oxidative Wear at Low Sliding Speeds


When a steel surface is exposed to air and subjected to low speed

sliding wear the initial thin (about 2 [nm]) films are rapidly worn away and a period of severe or adhesive wear results. At low sliding speeds below 1 [m/s] frictional temperature rises are not high enough to cause rapid oxidation at the asperity tips.

The fractured oxides and oxidized metallic wear particles compact to

form oxide islands on the worn surface. The area of these islands increases with the sliding distance and there is progressive reduction in the coefficient of friction.

The top surface of the islands is smooth and consists of plastically

deformed fine oxide debris and underneath this top layer there is mixture of much larger oxide and oxidized particles.

Oxidative Wear at High Temperature and Stress


When the temperature is progressively increased from close to ambient

to several hundred degrees Celsius, oxidative wear of a metal becomes more intense. The time necessary for the development of the wear protective, compacted oxide layers, is reduced and the quantity of oxidized wear particles and the thickness of the oxide film are dramatically increased. This is associated with the increase in oxidation rate at higher temperatures.

Usually the fractured fine metallic debris which remains on the worn

surface is oxidized and compacted into a glaze. As the glaze spreads over the worn surface the wear process becomes mild.

A practical example of this form of wear is found in gas turbine

components where thermal cycling causes slow periodic movements between contacting surfaces.

Formation of debris consisting of a mixture of oxide and metal

Oxidative Wear at Low Temperature Applications


Oxidative wear persists even at very low temperature applications, e.g. Rocket turbo pumps contain rolling bearings which operate under immersion in liquid oxygen or liquefied hydrocarbon gases. A comparative laboratory wear tests of ball bearings in liquid oxygen and liquid hydrogen revealed more rapid wear by liquid oxygen. The examination of worn bearings from space shuttle turbo pumps indicated that excessive damage was due to adhesive wear/shear peeling following the breakdown of the oxide scale formed on the balls and rings.

Transition Between Oxidative and Adhesive Wear


Sharp transitions, referred to as T1 and T2, between oxidative (mild) and adhesive (severe) wear are observed in metal-to-metal dry sliding contacts. The transition loads depend on the material properties of the sliding surfaces and their relative velocity.

Means of Controlling Corrosive and Oxidative Wear


Corrosion inhibitors based on strong adsorption to the corroding

surface can be effective in controlling corrosive wear, however, they may interfere with the adsorption lubrication of the sliding contact or else with an adjacent contact lubricated by the same oil or process fluid. Other types of inhibitors, e.g. those which involve the formation of a passive layer, are usually ineffective.

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