Experiences with RULER Oil Analysis Instrument for Quick Determination of Remaining Useful Life on Jet and Diesel

Engine Lubricants

Jo Ameye - FLUITEC International Nieuwbrugstraat, 73 B-1830 Brussels Steve Lee DERA Pyestock, Fuels & Lubricants Centre Farnborough, Hants UK

Abstract: This paper presents the results of research to monitor the Remaining Useful Life (RUL) by means of cyclic voltammetric methods of aircraft turbine and diesel generator lubricants. The cyclic voltammetric method used to monitor the antioxidants of different lubricants was the RULER instrument. The RUL is the length of equipment operating time from the time a lubricant is sampled, until the antioxidants are depleted allowing large changes in the basestocks physical properties to occur (resulting in excessive oil degradation, component wear, and eventual equipment malfunction). Therefore, the ability to predict the RUL of lubricants would eliminate the need for scheduled changes, i.e. oil changes performed based on RUL and not time, contributing to a Condition Monitoring Program. The first part of the program focused on the use of the RULER on laboratory aged fluids, namely ester-based aircraft turbine lubricants, detecting aromatic amine type of antioxidants. In the second part, the RUL was monitored (for various antioxidants) on field oil samples obtained from marine diesel generators and helicopters. Results showed that the cyclic voltammetry could be used to accurately measure the RUL, regardless of oil formulation or stressing conditions. For both parts, the results were then correlated to existing analysis methods, like viscosity, volatility, TAN and TBN. Also the results of this research demonstrate that Remaining Useful Life measurements made by the RULER can be used for oil analysis programs to quantify the additive levels of incoming batches of lubricants, as part of the specifications and quality control program. Keywords: antioxidants, Remaining Useful Life, Oxidation, jet turbine lubricants, diesel lubricants
1. Introduction to the Cyclic Voltammetry: Jet engine lubricants, based on polyolester based oil, can degrade or polymerize as a result of oxidation processes. To inhibit this oxidation of the oil, antioxidants are added to the oils basestock. These are mainly primary oxidation inhibitors like phenols, aminophenols, aromatic amines and/or secondary oxidation inhibitors like sulphurised phenols and phosphites. The primary oxidation inhibitors react with free radicals (from ROO to ROOH) to prevent polymerization reactions. Aminic oxidation inhibitors are active at higher temperatures in comparison to phenolic oxidation inhibitors and a combination of both types act synergistically.

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Secondary oxidation inhibitors eliminate hydroperoxides oxidizing to acids, by reaction of ROOH to the less harmful hydroperoxide (ROH.) degradation reactions, increasing the formation of aldehydes and oxidized into acids. A combination of primary and secondary oxidation inhibitors act synergistically. During use of the fluid in the lubrication systems of aircraft turbine engines, the oxidation inhibitors (antioxidants, AO) will be depleted until a certain critical level is reached at which the fluid start to degrade / polymerize at an accelerated rate. At that moment the fluid reaches a point allowing large changes in the basestocks physical properties to occur, i.e. the end of the Useful Life of the oil (figure 1). In order to estimate the Remaining Useful Life (RUL) of a fluid it is therefore important to know its critical antioxidant concentration.

Figure 1: Graph of the percent Remaining Useful Life (RUL), viscosity (40C), and total acid number vs. hours of stressing time and Remaining Useful Life at 175C for a typical aircraft engine oil.
2. Experimental RULER Analyzer: In order to determine the critical antioxidant

level of the fluids the remaining AO concentration was measured with the Remaining Useful Life Evaluation Routine (RULERTM). The RULERTM is a commercially available apparatus, which makes use of a cyclic voltammetric technique (1), for fresh fluids, laboratory-aged fluids and field samples. The RULERTM instrument consists of a three electrode sensing system: a glassy carbonworking electrode, a platinum wire as reference electrode and a platinum wire as auxiliary electrode (1). The samples (200-400 l) are diluted with a solvent containing a dissolved electrolyte. The instrument applies a controlled voltage ramp through the electrode into the prepared solution at the bottom surface of the electrode. As the potential increases, the AO oxidize at the carbon electrode surface. The oxidation releases electrons to the electrode causing current, which is linearly related to the additive concentration in the solution. The applied voltage ramp and measured current are stored in the RULERTM data acquisition software as a graph in which seconds (voltage) are plotted against a RULERTM number (current) (figure 2). The peak value(s) and the total peak area of the oxidation peak(s) are stored as RULERTM Number(s) and RULERTM Area and indicate the concentration of the AO when compared to a standard reference fluid. The peak value(s) and peak area depends on the type of AO measured in the fluid. Therefore, the reference material should be of a comparable composition as the sample to be measured. The voltage range of the peak value(s) is related to the identity of the AO (figure 2). The voltage at which an AO oxidizes depends upon the used electrolyte and of the type of AO.

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In the case of jet turbine lubricants, a solution based on an acetone/neutral electrolyte mixture is used to mainly detect aromatic amines, hindered phenols and phenothiazine type of AO. For diesel combustion and generator lubricants, a solution based on an ethanol/acidic electrolyte mixture is used, in order to detect the amines or ZDDP type of AO.

Figure 2: Cyclic Voltammetry voltage vs. current for different antioxidants. Tested oils: Different recent research programs (2) (6) have demonstrated the suitability of RULER techniques on laboratory-stressed oils, as well field oil samples, e.g. C-130 military aircraft (6). To assess the value of these programs, 3 experimental cases are presented in this paper: Case 1: RULER correlation & evaluation on jet lubricant oxidation tests. Case 2: RULER evaluation on diesel generator lubricants (Royal Navy UK). Case 3: RULER evaluation on helicopter engine & gearbox lubricants (Dutch Navy).
3. Case 1: Analysis of Aircraft Turbine Oil Following Oxidation Test (DEF STAN

05-50 Part 61 Method 9) A programme of work was carried out at the Defence Evaluation and Research Agency (DERA), Fuels and Lubricants Centre, to evaluate the RULER instrument as a technique for determining the degree of oil degradation following laboratory oxidation of an aircraft turbine engine lubricant. The oxidation method used was Defence Standard 05-50 Part 61 Method 9. This involves two different procedures. The first is referred to as Temperature Parameters - Oxidative Stability. The second is referred to as Effective Life - Oxidative Stability. 3.1. Temperature Parameters - Oxidative Stability Experimental: A weighed volume of oil contained in a glass boiling tube assembly is inserted into a heating block. Water saturated air is bubbled through the sample which is maintained at constant temperature for 192 hours. After measurement of volatilisation loss, the sample is restored to its original weight by addition of fresh lubricant and then examined in respect of viscosity, acidity increase and insolubles content. A number of separate tests are carried out in order to establish the temperatures at which, after 192 hours; there is a volatilisation loss of 15% w/w; an acidity increase of 1.0 mg KOH/g; a viscosity increase of 15%; an insolubles content of 0.05% w/w; the formation of a gel (solidus). The samples examined in this report had undergone this test for 192 hours at 185, 190, 195, 200, 205, 210 and 215C. Samples taken following completion of the above tests were analysed with the RULER using 100l of test oil and 100l of water in the RULER red solution. (Figure 3a)

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Results: The RUL% initially decreases (Figure 3b), in these samples, with the increasing test temperature until a minimum at 200C. Then the RUL% starts to quickly rise through to 215C (Figure 4). This occurs because the oxidation test severely volatilises light end base oil components from the oil at the higher temperatures (Figure 4) leaving little sample to test. The stressed oil sample is made up with fresh oil so that viscosity (Figure 3) and TAN measurements (Figure 4) can be made. Consequently we are almost measuring the RUL% of unstressed fresh oil at the higher temperatures where the most make-up oil is used. TAN and viscosity also rise significantly after 200C indicating severe oxidation of the oil. In fact, the temperatures at which most of the parameters (TAN increase etc.) reach their critical limits are in the region of 195 to 200C.

Figure 3a - b: RULER graph turbine oil Trend Graph AO Depletion Turbine oil
Figure 3. Aircraft Turbine Oil RUL and Volatility vs Oxidation Test Temperature 70 300

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Figure 4: Aircraft Turbine Oil RUL%, volatility, viscosity, and TAN(*10) vs. Oxidation test temperature Discussion: Only one peak was detected for the fresh oil samples and so the software only measures one peak (at the same voltage as the fresh oil peak) in each of the used samples. Some antioxidants form breakdown products (dimers and trimers) as a nature of their action. These polar oxidation products are valuable antioxidants in themselves but can change the conductivity of the solution causing the original antioxidant peak to gradually shift. This causes problems for the software as it only looks for the peak within a narrow voltage range and so can give low RULER numbers for that peak (as peak measurement is automatic). Care must be taken with the results in such cases and manual measurements of the RULER number are sometimes necessary. This limitation of the software can be overcome. The voltage range (either side of the fresh oil peak) can be changed in a configuration file while emerging dimer and trimer peaks (once you know at which voltage

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they occur) can be measured by retesting the standard (fresh oil), manually adding peaks at the relevant voltages in the standard and then retesting the used oils. The new peaks will then be measured since all measurements are referenced to the fresh oil standard. In conclusion, it would have been ideal to take RUL% measurements before any make-up oil was added. Nevertheless, the RUL% measurements did reflect the chemical changes taking place in the samples when compared to viscosity, volatility and TAN measurements, with the RUL% reaching its minimum at approximately the same temperatures as TAN increase etc. reached their critical limits. The RULER only detects one peak here while the lubricant is known to contain two secondary aromatic amine antioxidants. These consequently have very similar oxidation potentials, which cannot always be differentiated by the RULER technique. Nevertheless, the RULER is still capable of measuring total antioxidant (RUL% area), which is the most important parameter for using this instrument in the field. 3.2. Effective Life - Oxidative Stability Experimental: The procedure for Effective Life - Oxidative Stability is the same as that described above for Temperature Parameters, except that the temperature is kept constant and the time period varied. The test duration at which the same parameters (TAN increase etc.) reach the same critical points described under the Temperature Parameters method are determined. The samples analysed in this exercise were heated to 250C for 0.5, 1.5, 2.5, 3.5, 4.5, 5.5, 6.5, 7.5, 8.5, 9.5 and 18 hours. Samples taken following completion of the above tests were analysed with the RULER using 100l of test oil and 100l of water in the RULER red solution. Results: The RUL% of the samples falls rapidly up to 3.5 hours of test, where it reaches a minimum (Figure 5). Again, make-up oil is used so that viscosity and TAN determinations can be made. Volatility (Figure 5) is not as severe as the previous method and so the amount of make-up oil used is less than before. Nevertheless a gentle rise in RUL% of the samples from 3.5 to 18 hours can be observed, attributable to make-up oil. The viscosity increase results (Figure 5) show an almost linear rise through to 18 hours. Similarly the TAN results (Figure 5) show an almost linear rise up to 9.5 hours at which point the TAN plateaus at this value to 18 hours. This would suggest that the antioxidant is having little or no effect throughout the test.
Figure 6. Aircraft Turbine Oil Effective Life, Ruler No ,Volatility , Viscosity, TAN v Test Duration 70 160 140

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Figure 5: Aircraft Turbine Oil Effective Live RUL%, Volatility, Viscosity(@40C), TAN vs. Test Duration

Discussion: Once the oil has less than 20% RUL% then the antioxidant becomes ineffective leaving the base oil open to oxidative degradation. This state is achieved by 3.5

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hours and from this point on the base oil can be regarded as relatively unprotected. This is born out by the fact that both the TAN and viscosity increases reached their critical limits at between 2.5 and 3.5 hours..
4. Case 2 :RULER Trend Analysis of Engine Oil From Diesel Generators

Experimental: A candidate crankcase lubricating oil (RULER graph see Figure 6) was examined in a field trial in the diesel generators onboard a Royal Navy vessel. The lubricant charge was used for 600 hours. Samples were taken every 25 hours and principally analysed in the laboratory at the DERA Fuels and Lubricants Centre for viscosity, TBN and RUL%. Results: The results for the RUL% analysis, versus engine run time, are shown in figure 7 as well as the correlation of the RUL% results with viscosity increase (%) and base number loss (%), versus engine run time (Figure 8) Discussion: During the operation of this trial, the lubricating oil was topped up three times due to a leaking oil filter housing. The top-ups were 5 litres at 125 hours, 5 litres at 275 hours and 10 litres at 425 hours. These, significant top ups (in a 35 litre sump) can quite clearly be seen in the RULER results at those corresponding hours. Also, whilst the movements in RUL% for each of the additives does not exactly follow the movement in TBN, as an overall trend there is reasonable correlation with TBN and viscosity. From the additive trending figures one can see the difference in depletion rate between the 2 type of antioxidants ( ZDDP-type and Organic type of antioxidant). More experience with placement of the antioxidant peaks in the RUL traces and with solvent choice would have yielded a smoother antioxidant (RUL) depletion over time. This may then give a correlation with viscosity increase, FTIR carbonyl peak increase or TBN depletion. A more in depth statistical analysis would then be required. Even so, the potential for this technique in field trending is evident from the above results. The instrument (with the appropriate software, solvent system and probe) is also capable of determining TBN and TAN. This added facility strengthens the case for the instrument to be used in a off-line condition monitoring field role.

Figure 6: RULER Graph for Diesel Generator Lubricant

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Figure 7: RULER Trending Graphs for Additive1 (antioxidant) and Additive 2 (antiwear)
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5. RULER evaluation on helicopter engine & gearbox lubricants (Dutch Navy).

Experimental: This case presents the results from an oil condition-monitoring program, on helicopter turbine and gearbox lubricants at the Royal Netherlands Navy site, Marine Vliegbasis De Kooy (Den Helder Netherlands). This Navy site has in operation approximately 20 GKN Westland Lynx Helicopters since 1980. The Lynx Helicopters are equipped with 2 Rolls Royce GEM42 turbine engines, which is described in figure 9. Via a lubricant reservoir of 8 litres lubricant, type O-160 (Defence Standard 91-100/2), the jet lubricant is circulated over the main shaft bearings, followed by the gearbox. Fresh oil is topped up regularly, and the rate of top-up is dependent from engine to engine (varying between 0.05 and 0.1 l/h).

Figure 9: Schematic Rolls Royce GEM42 engine and Lynx Helicopter

Before 1997, the helicopter base was performing an oil condition-monitoring program based on the Spectrophotometric Oil Analysis Program (SOAP) (7) (wear metal) analysis program on site with a sampling frequency of every 25 hours. As this analysis is not focussing on the oxidation control, and that the helicopter base wanted to increase the preventive aspect of oil condition monitoring programs, RULER analysis was introduced. As the Royal Netherlands Navy MOD Chemical Laboratory (Scheikundig Laboratorium Den Helder) is using the RULER analysis method on

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regular basis, it was decided early 1997 to add the antioxidants analysis method to the SOAP program. The O-160 lubricant (Figure 10a+b) consists of polyol ester base oil, blended mainly with v Additive 1: phenothiazine anti-wear agent v Additive 2: aromatic amine (DOPDA) antioxidants

Figure 10a + b RULER graph O-160 standard (normal used oil vs. abnormal used oil) The oil is sampled with a volume of 200 l, prepared in an acetone/electrolyte-patented solution, in order to extract the Antioxidants. In order to perform oxidation control via trend analysis, the lubricant was sampled every 25 operating hours, for a selection of 20 helicopters. RULER analysis was performed in the laboratory (Scheikundig Laboratorium Den Helder), in combination with SoapAnalysis. Following trends of the different helicopter lubricants were achieved, where you can see how the Antioxidant depletion is expressed vs. the operating time (See figure 11 13).
Engine 5012-9002-9023-9033 Additive #1
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Fig 11: Trend analysis for phenothiazine on engines 5012-9002-9023-9033

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Fig 12: Trend analysis for aromatic amines on engines 5012-9002-9023-9033

Engine 5020 - Add #1 & 2
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Fig 13: Trend analysis for phenothiazine (Add 1) and aromatic amine (Add 2) for engine 5020 Discussion: From these trending reports it can be concluded that: a) All engines show a quick and continuous depletion of the phenothiazine additive (Add # 1), but a clear distinction can be made between the engines with high top-up rate, and the engines with low top-up rate. b) The concentration RUL% (Remaining Useful Life %) of the phenothiazine is fluctuating differently for all engines and this phenomenon can be explained by the different top-up rates of fresh oil. c) For engine n 5020, it can be seen that the concentration of phenothiazine has decreased to a RUL% of lower than 20%. As a consequence of this low concentration, the aromatic amine (Add #2) starts also to deplete faster (Fig.13). Based on this abnormal additive depletion, this engine has shown a damage at the main labyrinth of the gearbox bearing, resulting in hot air suction and contact with the lubricant. d) The trend of the aromatic amine antioxidant depletion is also engine dependent. Here we see a differentiation between i) Engines with a RUL% varying between 95 and 105%, which represents a stable and normal oxidation process. (engines with high top-up rate) ii) Engines where the RUL% for the aromatic amine antioxidants is stable in a first phase followed by a second phase where RUL% starts to decrease continuously (engine 5020). (engines with low top-up rate) e) A special attention goes to the engine 9073, which went through a major engine failure (September 1997). From the data available it was concluded that the last sample before (bearing) damage had a RUL% for the phenothiazine of 18% RUL. f) Further research was necessary to understand the behaviour of the phenothiazine and the aromatic amine, as well their interaction. This research work will be presented in the next chapter, where we will simulate oxidation tests on the 0-160 lubricant. g) The RULER analysis results showed very clearly when a total drainage and/or top-up with fresh oil has occurred (see figures 11-13).

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h) Further condition monitoring of the above mentioned engines in the next months will result in additional experiences, and eventually lead to specifications for predicting correct oil change intervals.
6. Oxidation Test Results on O-160 jet lubricant

Experimental: In order to understand the oxidation process on 0-160 lubricants and the relation to the RULER analysis of field results for the 2 main additives, different oxidation tests were performed at the UDRI (University of Dayton Research Institute). Sets of 6-12 glass vials (with each 100l-sample volume) were heated isothermal in a drilled out aluminium block at the following temperatures: 125C 150C 175C 200C 250 C. At prescheduled time intervals (15 minutes up to 1 hour) a glass vial was removed, cooled and diluted with analysis solvent and consequently analysed with the RULER. Oxidation tests were done also in glass vials containing metal discs (copper and iron) to quantify the catalysis effect of metal (wear) surfaces on the oxidation reaction (and logically the depletion of the Antioxidants). The oxidation tests results are presented in the following graphs (Figures 14-15) were additive depletion are expressed vs. the time. The following conclusions can be made from this test: a) The phenothiazine depletes first and the depletion rate increases with increasing temperature (Figure 14 and 15) b) The depletion of phenothiazine is accelerated with the presence of copper (Figure 14) c) The aromatic amine antioxidant has a slow depletion rate than phenothiazine. It can be seen from the graphs (Figure 14 & 15) that as soon as the phenothiazine achieves a low concentration (20%) the aromatic amine starts to deplete as well. These results are in line with the field sample analysis results.
Chart 4 - 175 C TESTS ON GLASS, STEEL AND COPPER

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Chart 3 - 200C test ON GLASS
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Figure 15: Graph of oxidation test on 0-160 in glass vials at 200C

7. Conclusions

v There was good correlation between RUL% results and the degree of oil degradation as shown by more traditional means (TAN increase etc.) for each of the applications described above. This indicates that RUL% measurements are at least complimentary to the more traditional techniques and, in some cases, might obviate the need for such measurements, particularly where a good relationship has been established. v A case of field experience with helicopter gear oils, showed significant advantages by controlling oxidation on the turbine oils with the RULER instrument, in order to predict the correct oil change intervals. Further field experiences needs to be acquired in order to assess the condition monitoring program. v In field use, where individual antioxidant peaks are less important than the RUL of the total remaining antioxidancy, then the area% result is more significant than individual peak results. v As a research tool, tracking depletion of (and appearance of new) peaks is within the capabilities of this instrument. For use as a laboratory research technique it would be advantageous if the software were more sophisticated and configurable. Especially if recalculating RUL results when the identified peaks for the original standard have changed. Ad-hoc analysis can be time consuming when the correct solvent system or combination of solvent systems is not known. The opposite is true if used as a field tool (which the instrument was designed for), where significant experience of repeating the same analysis on the same oil in the same solvent system would prevail. In this scenario the software is probably a little over complicated. v The technique does rely heavily on familiarity with the solvent / lubricant interaction. As stated above, time is needed to familiarise with these parameters before undertaking ad-hoc analyses. v The instrument (with the appropriate software, solvent system and probe) is also capable of determining TBN and TAN. This added facility strengthens the case for the instrument to be used in a off-line condition monitoring field role.

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References: (1) Kauffman, R.E., Rapid Determination of Remaining Useful Lubricant Life, in CRC Handbook of Lubrication and Tribology, Vol III, Booser, E.R., ed., CRC Press, Boca Raton, FL. P 89. (1994) (2) Kauffman, R.E. and Rhine, W.E., Assesment of Remaining Lubricant Life. Report N AFWAL-TR-86-2024, Aero Propulsion Laboratory, Wright-Patterson AFB, Ohio. (1986) (3) Saba, C.S., Smith H.A., Keller, M.A., Kauffman, R.E. and Jain, V.K. Lubricant Performance and Evaluation, Report N AFWAL-TR-89-2008, Aero Propulsion Laboratory, Wright-Patterson AFB, Ohio. (1989) (4) Kauffman, R.E., Development of a RULLET Part III: Cyclic Voltammetric Methods. Lubrication Engineering, 45.11.pp 709-716 (1989) (5) Kauffman, R.E., Method for Evaluating the Remaining Useful Life of a Lubricant;, U.S. Patent N. 4.744.870 (1988). (6) Kauffman, R.E., On-line and Off-line Techniques for Monitoring the Thermal and Oxidative Degradations of Aircraft Turbine Engine Oils Part I: Laboratory Evaluations Lubrication Engineering, 51.11.pp 914-921 (1995) (7) U.S.Natl.Bur. Std. Tech. News Bulletin 57(6), 135 (1973)

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