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ANTI-OXIDANTS AND CONTAMINATION CONTROL

ANTI-OXIDANTS AND CONTAMINATION CONTROL. YOUR EQUIPMENT’S HEALTH DEPENDS ON THEM. LUBRICANTS. To appreciate the need for the monitoring of anti-oxidants and contamination a brief look at the composition of a typical modern lubricant is beneficial.

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ANTI-OXIDANTS AND CONTAMINATION CONTROL

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  1. ANTI-OXIDANTS AND CONTAMINATION CONTROL YOUR EQUIPMENT’S HEALTH DEPENDS ON THEM ABN 78 087 393 020 Ph 02 9644 9100

  2. LUBRICANTS To appreciate the need for the monitoring of anti-oxidants and contamination a brief look at the composition of a typical modern lubricant is beneficial. The next slide depicts the components of a lubricant and describes their function in the lubrication process. Each component of the lubricant wheel is hyperlinked to the appropriate description of the additive or base oil allowing you to progress as fast or a slow as you want through the information provided. Use the button to proceed. Once a better understanding of the lubricant is realised, the need to monitor these properties becomes more evident for the continued protection of the lubricant as well as the compartment. CONTINUE ABN 78 087 393 020 Ph 02 9644 9100

  3. BASE OIL POUR POINT DEPRESSANT ANTI-OXIDANT BLENDED TOGETHER TO PRODUCE LUBRICANTS TO SPECIFICATION ANTI-FOAM ADDITIVE CORROSIONINHIBITOR DETERGENT& DISPERSANTADDITIVES VISCOSITYINDEXIMPROVER ANTI-WEAR and EP ADDITIVES ABN 78 087 393 020 Ph 02 9644 9100 CONTINUE

  4. MINERAL BASE OILS Base oils transport additives to areas where protection is needed. The lubricating oil fractions from the refinery after purifying and de-waxing are referred to as mineral base oils. They are made up of: Normal paraffinic (or saturated) molecules, most stable to oxidation Branched chain paraffinic molecules (naphthenics), less stable to oxidation Aromatic (or unsaturated) molecules, prone to oxidation Base oils are classified by Group Numbers: GROUP I Normal Paraffin content 50 % typical Naphthenic content 45 % typical Aromatic content 5% typical GROUP II Normal Paraffin content 65 % typical Naphthenic content 34 % typical Aromatic content 1% typical GROUP III Normal Paraffin content 85 % typical Naphthenic content 15 % typical Aromatic content 0% typical ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  5. SYNTHETIC BASE OILS AlthoughGROUP III oil based products can be marketed as synthetic or semi-synthetic products, they are not truly synthesised in the true sense of the word. The two main types of synthetic oils are: POLYALPHAOLEFIN (PAO) and ESTER based synthetic oil are chemically manufactured from appropriate raw materials. GROUP IVPAO base oils are manufactured using unsaturated hydrocarbon molecules called olefins. The simplest olefin is ethylene gas which can be manufactured synthetically or obtained as a product from the crude oil refining process and is usually the olefin of choice for manufacture of PAO base oils. By combining individual molecules of ethylene (known as an alpha olefin) in a process called polymerisation saturated long chain paraffinic hydrocarbons are produced. Oil produced in this way is very oxidation stable. Being a synthetically produced hydrocarbon, these base oils are compatible with mineral base oils. GROUP V These oils are synthetically manufactured by reacting organic chemicals together to form a very stable ester in the form of an oil. They are typically characterised by being very light (ISO 22-ISO 32) grade, very stable to oxidation and fluid at very low temperatures. Polyol ester base oils have higher viscosities. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  6. Treatment of metal surfaces to prevent corrosion due to entrapped air is catered for by the inclusion of a CORROSION INHIBITOR similar to that supplied in cooling systems. The inhibitor acts in two main ways: • wetting the exposed surfaces with a layer of additive • react preferentially with air and water thus preventing its attack on metals surfaces. • Typically the corrosion inhibitors are of the amine and phosphate type compounds which absorb oxygen and prevent rusting. They also react with acidic by-products of wear to prevent attack on vulnerable metal surfaces. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  7. Frictional forces within a lubricated system tend to generate wear by metal to metal contact. The heat generated by this contact is so severe that the metals weld together and further motion of the surfaces tears these welded sections apart creating a rough surface and wear debris. An additive called ANTI-WEAR Additive utilises the heat generated to chemically bond with the metal surfaces and prevent future welding and in doing so retards the wear effect. A typical engine anti-wear additive is Zinc Dialkyl DithioPhosphate (ZDDP) sometimes referred to merely as zinc anti-wear additives. ZDDP also acts as an Anti-oxidant. Extreme pressure (EP) additives are typically composed of Phosphorus/Sulphur compounds which bond to the moving surfaces under heat of welding and shearing of the metal to metal contact. This bonding imparts a “slippery” surface on the moving components exposed to wear and provides a better surface to counteract wear. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  8. Multigrade oils have been introduced into the modern lubricated equipment to give them the capability to lubricate at cold starting to minimise start-up wear while being able to provide the specified lubrication at operating temperature. Base oils by themselves have a characteristic “thinning out” when the temperature increases from cold start to operating temperature. The relationship between increasing temperature and corresponding decrease in viscosity (thickness) of the oil is known as the Viscosity Index (VI). To increase the natural VI of the oil and thus increase the lubrication ability of the oil at elevated temperatures, an additive called a VISCOSITY INDEX IMPROVER is added to the blended oil. VI Improvers are typically long chain hydrocarbon compounds. The VI improver retards the thinning out of the oil when heated but does not interfere with the lubricant when cold. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  9. Air is a lousy lubricant. Air entrapment in lubricated components permits metal to metal contact and results in excessive wear. An additive must be included to permit the air to quickly dissipate from the oil. This is called ANTI-FOAM additive and is generally in the form of a silicone type oil in the order of up to 10 parts per million. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  10. ANTI-OXIDANTS are chemicals added to a lubricant to protect the base oil of the lubricant and thereby protecting the equipment being lubricated. • The anti-oxidant additives are designed to be sacrificially consumed during the life of the lubricant and are the first of the additives in an oil to deplete. • If the Anti-oxidant level depletes to below 30% of the original concentration, it can no longer completely protect the lubricant nor the equipment. • Anti-oxidants operate in several ways. • reacting with entrapped air to prevent varnish formation in the base oil. • preventing formation of degradation by-products in the oil in high friction areas. • neutralise the effects of metallic wear particles that could lead to degradation of the oil. • neutralise the effects of moisture that could lead to degradation of the oil. • Conventional Anti-oxidant additives are amines and phenols. In some cases anti-wear additives such as Zinc Di Alkyl Di ThioPhosphate (ZDDP) have an anti-oxidant effect and can also be monitored. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  11. Detergents in oil clean surfaces within the lubricated compartments (usually engines). These additives also keep the material removed in suspension until it can be removed by the system filters or by change-out. These additives chemically protect oil from attack and neutralise acids that are formed by fuel combustion. Dispersants are chemicals which when added to oils assist the detergent additive keep the contamination which it has cleaned from surfaces as well as other introduced contaminants such as water (and soot in engines) in suspension until the contamination can be removed. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  12. In cold climates, the oil may freeze and starve the lubricated components of oil causing wear. An additive that inhibits the freezing characteristics of the oil (in much the same way as glycol in the cooling system inhibits freezing of the water) is blended into the oil. This additive is the POUR POINT DEPRESSANT The name POUR POINT relates to the temperature at which the lubricant can just flow., ie a couple of degrees cooler, the oil will, in fact, NOT FLOW. ABN 78 087 393 020 Ph 02 9644 9100 MAIN DIAGRAM

  13. ABN 78 087 393 020 Ph 02 9644 9100

  14. Lubrication of a Compartment requires an Oil with Additives to: • Prevent wear • Clean & Disperse (For engines) • Counter Oxidation • inhibit corrosion • Keep the Oil Fluid • Reduce Foaming AND filtration to KEEP THE OIL CLEAN ABN 78 087 393 020 Ph 02 9644 9100

  15. MAXIMISING THE OIL LIFE IN EQUIPMENT Although the lubricant is still considered the cheapest replaceable item in large plant and equipment, the oil has a finite cost, both to purchase as well as dispose of, and to obtain full value, the oil should be changed out only when it can no longer effectively protect the oil and the moving surfaces. The additive in the oil formulation that provides this protection is the ANTI-OXIDANT which can be measured using RULER. ABN 78 087 393 020 Ph 02 9644 9100

  16. RULER Oil Condition Monitoring • R emaining • Useful • L ife • Evaluation • R outine ABN 78 087 393 020 Ph 02 9644 9100

  17. RULER Oil Condition Monitoring Definition: Remaining Useful Life of lubricants = Length of equipment operating time from the time a lubricant is sampled based on anti-oxidant level readings of a standard for the lubricant ABN 78 087 393 020 Ph 02 9644 9100

  18. %RUL RULER Oil Condition Monitoring Remaining Useful Life dependent on: OPERATING CYCLE ANTI-OXIDANT TYPE BASE OIL OXIDATION STABILITY PRESENCE OF METALS &/OR WATER ABN 78 087 393 020 Ph 02 9644 9100

  19. Anti-Oxidant Depletion RULER Oil Condition Monitoring RULER & Oil Degradation: R.U.L. 100% 50% 0% Operating Time (hours; months; km …) Viscosity Critical Point TAN ABN 78 087 393 020 Ph 02 9644 9100

  20. Critical Point In the service life of a lubricant the anti-oxidant (AO) additive incorporated into the formula preferentially depletes until a stage is reached where there is insufficient AO left to FULLY protect the base oil(s) and the equipment. This point is referred to as the CRITICAL POINT and is typically set at 30% RUL. Continued use of the lubricant after the critical point has been reached will result in escalating values for Total Acid Number (TAN) and viscosity due to oil oxidation. Oil oxidation is evidenced by formation of lacquers/varnishes and gums which renders the oil unsuitable for redosing with additives. Redosing with AO or changing out of the lubricant prior to achieving the critical point will enhance the longevity of oil, if redosing, and the equipment makingRULERa true maintenance PRO-ACTIVE CONDITION MONITORING TOOL ABN 78 087 393 020 Ph 02 9644 9100

  21. RULER Oil Condition Monitoring What are RULER APPLICATIONS ? • Petrol engine oil • Diesel engine oil • Aircraft engine oils • Steam turbine oils • Gas turbine oils • Hydraulic oils • Compressor lubricants • Transmission fluids • Greases ABN 78 087 393 020 Ph 02 9644 9100

  22. RULER Oil Condition Monitoring What is RULER METHOD ? LUB OIL/FLUID SOLVENT EXTRACTION OF ADDITIVES OIL PHASEADDITIVES Substrate +oil in solution settles down to electrolytic cell bottom of vial ABN 78 087 393 020 Ph 02 9644 9100

  23. RULER Oil Condition Monitoring auxiliary working electrode electrode Cyclic Voltage reference 0 - 1,5 V electrode 11 / 17 sec. RULER Probe Solvent + Additives mixture+ RULER Sand + Oil & Insolubles CE320 INSTRUMENT ABN 78 087 393 020 Ph 02 9644 9100

  24. ABN 78 087 393 020 Ph 02 9644 9100

  25. RULER Oil Condition Monitoring + QUALITATIVE C U R R E N T QUANTITATIVE – PEAK HEIGHT & QUANTITATIVE – PEAK AREA ADDITIVE B ADDITIVE A V O L T A G E ABN 78 087 393 020 Ph 02 9644 9100

  26. RULER Oil Condition Monitoring S T A N D A R D ABN 78 087 393 020 Ph 02 9644 9100

  27. RULER Oil Condition Monitoring T E S T ABN 78 087 393 020 Ph 02 9644 9100

  28. RULER Oil Condition Monitoring RULER TRENDING: Successive samples measurement antioxidant additive depletion rate PROACTIVE FLUID & MACHINE CONDITION MONITORING ABN 78 087 393 020 Ph 02 9644 9100

  29. 3500 hours 500 hours 3000 hours 2000 hours RULER Oil Condition Monitoring T E S T S ABN 78 087 393 020 Ph 02 9644 9100

  30. RULER Oil Condition Monitoring T R E N D I N G ABN 78 087 393 020 Ph 02 9644 9100

  31. RULER Oil Condition Monitoring CE320 RULER IS A VALUABLE TOOL FOR • Detecting abnormally operating equipment • : • Used oil condition monitoring • Incoming lubricant batch control • Additive replenishment/top-up detection • Detecting abnormally operating equipment • Predicting & extending oil change intervals ABN 78 087 393 020 Ph 02 9644 9100

  32. RULER augments standard analysis methods Diagnostic oil analysis programs are a “jigsaw” puzzle of many pieces in which all pieces are required to give a full picture of oil and equipment condition. RULER supplies the vital piece which can can tell how long the lubricant can last and how much protection it can supply to the lubricated component. • RULER technology has been investigated and is now included in ASTM list of methods as ASTM D6810-02 and ASTM D6971-04 ABN 78 087 393 020 Ph 02 9644 9100

  33. RULER Oil Condition Monitoring RUL (%) Operating Time FRESH Oil replenishment CHANGE in operating conditions NORMAL Trending ABN 78 087 393 020 Ph 02 9644 9100

  34. ANTI-OXIDANT DEPLETION can: be a reflection of normal wear – rate would generally be linear with the slope of the rate line indicating the severity of the wear. % R U L SOME WEAR MORE WEAR SEVEREWEAR TIME ABN 78 087 393 020 Ph 02 9644 9100

  35. ANTI-OXIDANT DEPLETION can: % R U L TIME be a reflection of changing wear – rate would increase indicating change in wear. Change may be due to: INGRESS OF EXTERNAL SOLID CONTAMINATION e.g dirt INGRESS OF EXTERNAL LIQUID CONTAMINATION e.g. moisture CHANGE IN LOAD CHANGE IN OPERATOR USE OF A LIGHTER VISCOSITY OR DIFFERENT OIL FOR TOP-UP OR CHANGE PRODUCTION OF WEAR PRODUCING PARTICLES IN SYSTEM RATE CHANGE POINT ABN 78 087 393 020 Ph 02 9644 9100

  36. FILTRATION One of the major factors affecting the useable life of a lubricant is its cleanliness. Accordingly it is appropriate to provide a few details of filtration and the various classes of cleanliness commonly encountered Filtration is the physical or mechanical process of retention or “capture” of particles in a fluid by the passage of the fluid through a porous filter medium. ABN 78 087 393 020 Ph 02 9644 9100

  37. ROLLER 3-5 MICRON . OIL FILM FRICTIONAL AREA INNER RACE The lubricant is separating loaded surfaces by means of a fluid film of between 3 and 5 micron in thickness. The next slide gives a comparison of micron sizes ABN 78 087 393 020 Ph 02 9644 9100

  38. COMPARATIVE SIZES IN MICRONS GRAIN OF SALT 120 HUMAN HAIR 80 FLOOR DUST 40 WHITE BLOOD CELLS 20 TALCUM POWDER 10 BACTERIA 3 ABN 78 087 393 020 Ph 02 9644 9100

  39. MONITORING SOLIDS FOR THEIR EFFECT ON LUBRICANTS Solids of any size are detrimental to the operational efficiency of lubricated components leading to wear of moving surfaces and degradation of the lubricant by depletion of anti-oxidants and then oxidation of the base oil. Having looked at the monitoring of the properties of the lubricant and assessing the lubricant’s condition, particularly the RULER determinations of active anti-oxidant content, it is just as wise to inspect the cleanliness of the lubricant to determine the effectiveness of the filtration in the system. The PODS instrument depicted in the following slide is typical of the affordable particle counting technology for industry that makes testing on-site a reality in the same way as RULER. ABN 78 087 393 020 Ph 02 9644 9100

  40. ABN 78 087 393 020 Ph 02 9644 9100 PODS - PORTABLE OIL DIAGNOSTIC SYSTEM

  41. ABN 78 087 393 020 Ph 02 9644 9100

  42. CLASSIFICATION OF FILTRATION • MACRO FILTRATION - >2 MICRON IN SIZE • MICRO FILTRATION - 2 MICRON TO 0.2 MICRON IN SIZE • ULTRA FILTRATION - < 0.2 MICRON IN SIZE ABN 78 087 393 020 Ph 02 9644 9100

  43. FILTRATION PROCESS • Gravitational separation from fluid- achieved by rotational forces applied to the fluid eg Glacier or Spinner • Depth retention - direct interception and / or adsorption • Surface retention - direct interception and / or adsorption ABN 78 087 393 020 Ph 02 9644 9100

  44. FILTER RATINGS ABSOLUTE RATING Diameter of largest hard spherical particle permitted to pass NOMINAL RATING Based on % of largest particles permitted to pass BETA RATING Ratio of upstream particles of nominated size with downstream particles ABN 78 087 393 020 Ph 02 9644 9100

  45. BETA RATING Ratio of upstream particles of nominated size with downstream particles BETA RATIO EFFICIENCY 1 0 % 2 50 % 20 95 % 50 98 % 100 99 % 200 99.5 % 1000 99.9 % Usual specification ABN 78 087 393 020 Ph 02 9644 9100

  46. FILTRATION All filters will reduce the solid matter contamination to the appropriate micron size withoutdetriment to the properties of the lubricant, that is, they cannot remove the additives from the oil formulations. Even polymers employed as viscosity index improvers and tackifiers will pass through the filters as they are dissolved in the oil base. A good rule of thumb to use when considering filtration of oil is "If It Can Be Removed By Filtration It Shouldn't Be There". ABN 78 087 393 020 Ph 02 9644 9100

  47. SAE AS 4059(c) – Aerospacestandard recording particles counted per 100 ml for all size ranges from 4 micron to to greater than70 micron ISO 4406 (c)International Standard recording particles counted per ml for size ranges from >4 micron to to >14 micron Condition Monitoring Programmes should include Particle Size Distribution analysis for Hydraulic and Transmission and Drive systems that incorporate forced lubrication and filtration to gauge the effectiveness of the filtration. ABN 78 087 393 020 Ph 02 9644 9100

  48. INTERNATIONAL STANDARD 4406(c) MEASUREMENT RANGE: >4um / >6um / >14um MORE THAN LESS THAN ISO CODE 5 000 000 particles/ml 10 000 000 particles/ml 30 2 500 000 5 000 000 29 1 300 000 2 500 000 28 640 000 1 300 000 27 320 000 640 000 26 160 000 320 000 25 80 000 160 000 24 40 000 80 000 23 20 000 40 000 22 10 000 20 000 21 5 000 10 000 20 2 500 5 000 19 1 300 2 500 18 640 1 300 17 320 640 16 160 320 15 80 160 14 40 80 13 20 40 12 10 20 11 etc…….. ABN 78 087 393 020 Ph 02 9644 9100

  49. ISO REPORTING > 4 MICRON / >6 MICRON/ >14 MICRON INCLUDES INCLUDES INCLUDES SILT FINE WEAR COARSE WEAR &/OR DIRT &/OR DIRT &/OR DIRT + + FINE WEAR COARSE WEAR &/OR DIRT &/OR DIRT + COARSE WEAR &/OR DIRT ABN 78 087 393 020 Ph 02 9644 9100

  50. SAE AS 4059(c) MAXIMUM CONTAMINATION LIMITS (particles/100ml) Size – ISO 11171 Calibration (Projected Area Equivalent Diameter) >4um(c) > 6um(c) > 14um(c)>21um(c)>38um(c) >70um(c) 000 00 0 1 2 3 4 5 6 7 8 9 10 11 12 195 390 780 1560 3120 6250 12 500 25 000 50 000 100 000 200 000 400 000 800 000 1 600 000 3 200 000 76 152 304 609 1220 2430 4860 9730 19 500 38 900 77 900 156 000 311 000 623 000 1 250 000 14 27 54 109 217 432 864 1 730 3 460 6 920 13 900 27 700 55 400 111 000 222 000 3 5 10 20 39 76 152 306 612 1 220 2 450 4 900 9 800 19 600 39 200 1 1 2 4 7 13 26 53 106 212 424 848 1 700 3 390 6 780 0 0 0 1 1 2 4 8 16 32 64 128 256 512 1 020 CLASSES ABN 78 087 393 020 Ph 02 9644 9100

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