Rapid and Cost-effective Determination of the Remaining Useful Life (RUL) of Industrial Lubricants by Voltammetric Techniques

Jo Ameye, Fluitec International 272 Leo Street, Dayton, OH 45404-1006 (937) 223-8602 ; e-mail: j.ameye@fluitec.com

Abstract In the last 5 years a substantial increase of industrial on-site oil analysis programs have been implemented, as a direct result of industrial demand to increase machine reliability and reduce downtime costs. To ensure these increasing operational requirements, lubricant formulations are also undergoing major modifications. It is apparent that these factors would motivate end-users to add new techniques to accepted techniques like RPVOT (previously known as RBOT), TAN, and HPDSC. One of the new techniques is portable and proactive and uses voltammetry to assess the Remaining Useful Life (RUL) of lubricants directly on-site. But how are professionals in lubrication management finding the right balance between routine off-site oil analysis techniques, and on-site, quick, RUL assessing techniques? What is the relationship between oxidation, known as a failure root cause, and proactive RUL information? How does voltammetry work, and why does it enable cost-effective, routine RUL assessment for a wide variety of industrial lubricants? This paper will present the added value of combining oil analysis data, such as portable voltammetric techniques (RULER), with data from specialized oil analysis laboratories. By monitoring RUL this would significantly contribute, at a financial acceptable cost, to any proactive maintenance program.

1) Remaining Useful Life of Lubricants

When we look at the wide variety of industrial lubricants, from hydraulic, gear, and bearing lubricants over to combustion engine lubricants, there are different important trends influencing the evolution of these products: The need for machine reliability and availability is increasing (with deregulation in the power generation industry as an example) Downtime cost reduction Machine load factors are increasing (e.g., paper and steel industries) The trend to extend lubricant life by applying newer and improved technologies of additives and oil base-stocks (hydrotreated petroleum and synthetic basestocks) Environmental and performance requirements (lower volatility, extended warranties, better fuel economy)

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

On-site lubricant monitoring to identify abnormal operating conditions has been the answer to these strategic evolutions through the implementation of the Remaining Useful life (RUL)-monitoring procedure.

What is the Remaining Useful Life? The use of antioxidants, natural and synthetic, to improve the durability of oil has been an accepted practice since the 1940s. To control oil degradation, antioxidants are present in a wide range of industrial lubricants to increase their thermal-oxidative stability. Since the antioxidants are depleted with equipment operating time, they eventually become ineffective (unless they are replenished by lubricant or additive additions), allowing large changes to occur in the physical and chemical properties of the lubricant. The key parameter to prevent these above mentioned operating problems is the combination of good quality base oil with a supplemental antioxidant package. These antioxidants added alone or in synergistic combinations extend the operating life of the oil by improving its oxidation stability. During their use in the lubrication systems, the oxidation inhibitors (antioxidants, AO) will deplete to a certain critical level at which point the fluid will 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) [1] [2]

Figure 1: Plots of percent-remaining useful life (RUL), viscosity (40C) and Total Acid Number vs. hours of stressing time and remaining useful life at 150C (lab. Stressing test) of a typical railroad diesel engine oil. The plots in Figure 1 show that the commonly monitored properties such as viscosity and acidity (Total Acid Number) are insensitive to changes in the RUL of a lubricant. TAN tests also do not discriminate between acids generated by oxidation, acidic additives and acidic contaminants making trending of oxidation by TAN difficult [3]. The basic mechanism of oxidative degradation [3] and the role that different antioxidants play, begins at the formation of oxygenated hydrocarbons, such as alcohols,

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

acids, and sludge. These oxygenated species are preceded by the formation of reactive (harmful) compounds, better known as free radicals, hydroperoxides and peroxides. Its exactly here that antioxidants act in 2 ways: primary antioxidancy by removing radicals or secondary antioxidancy by decomposing hydroperoxides to form nonreactive products which do not participate in further oxidation of the lubricant. Currently, common primary antioxidants are phenols and amine types, while secondary antioxidants are usually sulfur or metal containing additives. With the growing interest of predicting oil change out, measuring antioxidant concentration is useful in estimating the Remaining Useful Life (RUL) during the lubricant lifetime. This would provide savings in operating costs, and also allow users to identify lubricants being degraded at an accelerated rate by abnormally operating equipment. A nice example of this trend is the power generation industry, which has in recent years improved dramatically the thermal efficiency of its industrial equipment. This has been achieved by installing a combination of a gas turbine and a steam turbine to reach higher efficiencies in the range of 50 to 65% (Combined cycle applications). But this advance in technology demands a stronger performance to control oxidation under conditions of high temperatures, which are typical for gas turbine operation. Typically as operational temperature increases, the oil film temperatures will increase and reach levels of 140 to 150 C. Conclusions on RUL We can conclude from the above chapter that an oil analysis program requires the following information on the lubricant condition, in order to be classified as proactive: Proactive information on RUL% is preferred over measurements of oxidation (reactive) such as TAN increase, color change, or viscosity increase. S Antioxidant depletion rates (trending) will help to identify the root causes of oxidation. RUL information on 1 oil sample is too limited to contribute, but an oil analysis frequency adapted to the equipment, will result in a useful trending graph. S Turn the alarm signals generated by the RUL information into actions, in order to prevent severe lubricant oxidation. Earlier papers [7] have indicated that large batches of lubricant can be saved from severe oxidation, by topping off the reservoir, as long as remaining concentration of antioxidants is not below warning levels, between 30 and 50%. S Oxidation information, based on RUL, needs always to be referred to the newest (latest batch) oil, especially for long life lubricants.
S

Techniques capable of performing evaluations of remaining antioxidant concentration, and logically RUL, can be covered in following basic categories: 1) thermal-oxidative stressing techniques like RPVOT, TOST, HPDSC 2) electrochemical voltammetric techniques (RULER) 3) instrumental techniques FTIR, HPLC

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

In this paper we will focus on the combination and added value of voltammetric techniques with the RPVOT (Rotating Pressure Vessel Oxidation Test) technique, or previously known as RBOT (Rotating Bomb Oxidation Test).

2) How do Voltammetric techniques work?

The voltammetric method [4] was performed with a commercially available Voltammograph (RULER). The RULER portable instrument consists of a three electrode sensing system: with a glassy carbon working electrode, a platinum wire electrode, and a platinum wire auxiliary electrode. The oil samples (200 - 400l max.) are diluted in a prepared solvent vial, which results in the extraction of the antioxidants into the solvent phase. The voltage of the auxiliary electrode was scanned from 0.0 to 1.5 V at a rate of 0.2 V/second. As the potential increases, the antioxidants 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 (Figure 2). Basically, 4 steps have to performed during the analysis: S Sampling 200 to maximum 400 l of oil S Mixing it into the prepared 5ml-solvent vial S Insert probe into the vial S Start & run the test via the software, followed by automatic data calculation These 4 steps should not take longer than 5 minutes for any experienced lubricant operator. The peaks produced by the voltammetric method are used to evaluate the remaining antioxidants of the used oil samples. The applied voltage ramp and measured current are stored in the RULER data acquisition software as a graph in which seconds (voltage) are plotted against a RULER number (current) (figure 3). The peak value(s) and the total peak area of the oxidation peak(s) are stored as RULER Number(s) and RULER Area and indicate the concentration of the AO when compared to a standard reference fluid. The new oil is used as the 100% RUL. (Figure 3). Several previous studies have found that the repeatability of the percent-remaining additive measurements is between 2.5 and 4% RSD [5, 6, 7]

Figure 2: Cyclic Voltammetry Voltage vs. Current for different antioxidants.

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

Figure 3: Voltammograph showing the comparison between a new oil (upper line) and a used turbine oil. The commercial remaining useful life evaluation rig (RULER), Figure 4, is specifically designed to perform voltammetric analysis for different type of lubricants [5]. steam and gas turbine oils hydraulic fluids (mineral, synthetic, and biodegradable) industrial and gear lubricants aircraft jet engine oils greases marine, truck, and railroad diesel engine oils

Figure 4: Portable RULER Condition Monitoring Instrument

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

3) How can RUL data contribute to your existing oil analysis programs? Before answering this question we need to focus on what motivates lubricant management professionals to perform on-site oil analysis: Achieve quick oil analysis results (if necessary quick retest). Proactive maintenance: use and transfer the results into actions (as analysis is done by people who know the operating conditions of the equipment). Reduce Total cost of ownership (p.e. machine downtime). Combine and transfer data into data acquisition programs (trending) at the plant level. Quality control of incoming batches. Adapt the oil analysis frequency in function of the % Remaining Useful Life. Knowing these important factors, and relating it back to the growing importance of antioxidants in lubricant formulations, we see different reasons why voltammetric techniques will contribute to on-site oil analysis programs: S Low cost of analysis RUL data can be obtained with voltammetry at a fraction of the cost of RPVOT (see table 1). S Trending capabilities by combining the antioxidant depletion trends with particle. counting, water analysis and viscosity analysis, the operator can detect abnormal operating conditions. By analyzing oil samples drawn for equipment on a regular basic, lubricant technicians will be able to chronicle when and how fast antioxidants depleted. S Proactive information test and monitor the onset and propagation of oxidation, which will result in greater understanding of lubricant oxidation, and make proactive decisions. Figure 5 is an example how the RULER gives proactive information. This case shows (steam turbine lubricant) when RUL% is approaching the 30%, how quickly Total Acid Number starts to increase and achieves a value of 0.23 mg KOH/g oil. Based on the TAN increase, the power station decided to change the oil from the main steam turbine reservoir (prediction by RUL% would have allowed earlier planning of oil change). S Portable technique light weight instrument for on-site oil analysis. S Data-exchange capabilities in a Windows CE environment exchange data over IrDA connections. 75
RUL% AO

0.3

RUL % Area

50

0.2
TAN

25

TAN

0.1

0
Dec-98 Mar-99 Jun-99 Sep-99 Dec-99 Mar-00

Figure 5: Industrial case showing correlation between RUL% and Total Acid Number (mg KOH/g oil)

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

Before we compare RPVOT and Total Acid Number with voltammetric techniques (RULER), we must describe first the RPVOT test. Description of Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure Vessel, ASTM D2272 RPVOT test, in accordance with ASTM D2272-98, determines the test life of new or in-service oil by measuring the time period of sample oxidation under conditions of heat and pressure. The method forces a reaction between oil sample, oxygen, water and copper catalyst under accelerated conditions. The reactants are in contact under an oxygen pressured vessel charged to 90 psi and are heated to a temperature of 150C. The stainless steel vessel is rotated axially during the whole test, while the oxygen pressure is measured via gauge or transducer. The test is complete when the pressure drops 25.4 psi below the maximum employed by the system, indicating the oil oxidation process has started, and expressed in minutes of RPVOT. Table 1: comparison between RPVOT, TAN and RULER oil analysis techniques RPVOT Cost Instrumental Operational Ease of operation Sample size Sample preparation Analytical procedure Safety requirements Analysis time Sample preparation Analytical procedure Duplicate analysis without resampling Instrument for RUL evaluations Standardized test On-site condition monitoring capability Disposal cost $15 30 K $100 150 50 ml Moderate Minimal Moderate < 10 min >1h No Yes Yes ASTM D-2272 No High $3K $25 5 ml Extensive Extensive Extensive < 10 min > 10 min No No Yes ASTM D-664 No Very high $ 10 K $7* 0.4 ml Minimal Minimal Minimal < 2 min < 1 min Yes Yes No Yes Low TAN RULER

* :cost of 5-ml prepared test solution vial

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

From the table 1, it is clear that all 3 techniques have their strengths and weaknesses, but if we keep the focus on the implementation into condition monitoring programs, as described on page 4, voltammetric techniques have several operational and financial advantages over RPVOT techniques. 1. With the newer generation of lubricants, under pressure of environmental and performance requirements, RPVOT test times of industrial lubricants have increased to values higher than 1000 minutes for some types of oils. Obviously the RULER has a significant time advantage. 2. For equipment with higher oil analysis frequency e.g. monthly or bimonthly, the cost of analysis and time delay is gives an advantage to the RULER. Small sample size (e.g. bearing housings) allows RUL% estimation. 3. RULER can be used as a screening test to monitor loss of antioxidant additives, which can prompt the analyst to obtain RPVOT tests when needed. For low RUL% (< 20%) it is advised to perform RPVOT analysis, to measure the overall oxidation resistance of the lubricant (due to primary, and secondary antioxidants and basestocks contribution to RPVOT life). 4. RULER can be used for incoming oil batch control or to monitor oil replenishments on a wide variety of oils. 5. RULER is not a replacement for RPVOT (RBOT), but can be an effective way to implement a proactive oil monitoring and changeout program. As part of this comparison study, we present a technical case at a power station where both RPVOT and RULER techniques have been in service for more than 2 years, and present this complementarity. 4) Practical case Power Generation Plant For this part of the program, measurements were taken from a power station in Europe, with Frame-9 Gas turbines for a total output of 2000 MW. Each turbine is equipped with a 35,000 liter oil reservoir, using a mineral based turbine oil. The power station performs oil analysis every 6 months through an outside laboratory with following parameters: Viscosity RPVOT Water Color ISO Cleanliness level Currently the power station is implementing a Predictive Maintenance Program, where the lubricant sampling and analysis plays an important role as diagnostic tool. Turbine and hydraulic fluids have been in service 2 years, and have the following voltammetric characteristics (see Figure 6 for the voltammograph, detecting broad peak of aromatic amines as antioxidants).

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

Figure 6: Voltammograph of industrial gas turbine lubricant Table 2: Analytical data ISO VG 32 turbine oil Measurements TAN Colour RPVOT Viscosity (40C) mm2/s Water RUL % Amines New Oil 0.07 mg KOH/g oil L 2.0 > 1500 min 32,1 < 0.05 % 100%

Every six months the power station was receiving an RPVOT result for oxidation control of their gas turbine and hydraulic fluids. They did not want to increase their off-site analysis program and decided the following: Efficiently analyze oil samples with the RULER every 2 months, to determine their RUL%, and complement this with their off-site (6 months) analysis results. S Select the optimum oil analysis frequency for hydraulic, pump lube oil and gas turbine lubricants S The power stations main objective was to increase the on-site fluid control, eventually resulting in improvements of productivity.
S

Figure 7 summarizes all the oil analysis data for 1 of the 5 turbines, during the past two years of service. Figure 8 presents the trending curves of the RUL% for the 5 turbines.

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

1400 1200
RBOT ( min )

80 60 40 20

1000 800 600 400 200 0

4 8 0 0 3 1 4 2 5 30 11 93 37 50 61 30 04 70 19 64 99 11 13 14 16 18 19 22 26 28 05

R.B.O.T. RUL% TAN(*100)

Visc.40C Color

Operating Hours

Figure 7: Oil analysis data for gas turbine lubricants, expressing RPVOT (min), RUL%, TAN (mg KOH/g oil * 100), Viscosity (40C), and Color ( ASTM) vs. operating hours

Trending AO % for GT 3,4, 5, 6, 7

100 95

Remaining Antioxidant %

90

EC3 EC4 EC5 EC6 EC7

85

80

75

70

65

4380 8066 10119 12534 13116 14799 16260 17869 21368 24193 Operating Hours

Figure 8: Trending graphs for 5 gas turbine fluids vs. operating hours With this case we also clearly see that when antioxidants stay above 50 % and Total Acid Number below the oil company specification, then RPVOT is not needed and will save the end user money and time. Other research programs [7, 8] have confirmed this conclusion.

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

RUL% ANTIOXIDANTS

1600

100

10

With the data from the past 2-years we can also conclude that the parameters like viscosity, color and water stay relatively stable, and fluctuations are probably caused by top-ups of fresh oil (which are reflected by the AO concentrations). The implementation of the RULER has been a complete success for the power station, corresponding to the initial objectives and showing following benefits: S Increased capabilities of the oil condition monitoring program: rapid and costeffective. S Optimization of the combination between off-site and on-site oil analysis programs, with a review of the oil change intervals. S Quality control advantages for incoming batches. This advantage of quality control, has been reported by several other N. American power stations using the RULER. In a specific case at a nuclear power station, RULER measurements determined that a barrel of oil had abnormally low RUL%, below the warning limit specified by the power station. The on-site RULER measurements kept the oil reservoirs of the coolant pumps from being replenished with this fresh" oil. It appeared that the oil barrel had suffered from auto-oxidation during 3 years of storage and that the oil was no longer in a condition to guarantee efficient lubrication. Time and cost savings played a major role here. 5) General conclusions RUL-information vs. RPVOT data The main point we see here is that RUL% (antioxidant) trending by voltammetry and RPVOT, give similar results. RULER is not a replacement for RPVOT, but is an effective way to implement a proactive oil monitoring and changeout program. So from the operators (lubricant operators) point of view, the motivation for using new, portable techniques can be easily defended, with the following financial benefits: S Analysis costs: by finding the ideal combination between on-site RUL data, and the off-site oil analysis programs. Generally RULER is used as a screening technique for RUL (oxidative health) estimation, and will prompt the analyst to perform off-site tests like RPVOT or FTIR, only where necessary. S Repair costs: with on-site and trending analysis at the right oil analysis frequency, control the presence of destructive contaminants. S Downtime costs: prevent equipment downtime by controlling oxidation, and extending time between machine inspections. S Lubricants costs: change oil at the right moment/ quality control A specific case here is the Reactor Recirculation Motors, in nuclear power stations, which can only be maintained during outage (refueling). If we imagine that an oil sample was taken late, e.g. as station chemical laboratory are not staffed to provide samples, and that oil analysis (particle counts, water analysis) showed that one of the reservoirs had a lot of water in it. As time is an important issue during outages, the following actions can be taken:

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

11

 Filter the specific reservoirs (30 to 40 gallons) to take out all kinds of contaminants from the reservoir, and to restore the oil. Check particle counts and water. Check RUL%, on-site and if RUL% numbers on all the reservoirs trend with the previous results. A specific power station reported 75-80 RUL%, and this is after 6 years of service. FTIR can show correlation for both Amine and Phenolic inhibitors. These actions will save easily about $50,000 in maintenance, new lube, and disposal costs.
S

Quality costs: Quality control of incoming batches of oil

Oil change recommendations We refer here to warning limits, as specified in ASTM standard procedure, ASTM D6224 (Standard Practice for In-Service Monitoring of Lubricating Oil for Auxiliary Power Plant Equipment), with specific levels of In-Service oil for remaining antioxidants and RPVOT set at 25% of the new oil. By using these limits, in function of the criticality of the application, we are convinced lubricant specialists will be able to prevent the oil from entering the dangerous zone of severe oxidation, leading to irreversible base-stock oxidation. Study Groups in ASTM are evaluating how to modify this practice using the latest condition monitoring techniques, like voltammetry. Of course warning limits issued by oil company technical centers, as well the specialized oil analysis laboratories, are to be applied. Other applications using voltammetry as RUL screening technique Lubricating oils in equipment such as gears, diesel engines, pumps, compressors, hydraulic systems, and electro-hydraulic control systems Also greases belong to the list of applications for quick, easy and on-site RUL assessment. Beside the long list of power generation applications, we experienced a significant increase of on-site oil analysis programs at pulp and paper plants. Especially the hydraulic fluids, with very low leakage rates, as well the gear oils (e.g. on the dry part of the paper plant) require a continuous oil analysis by monitoring: Cleanliness levels (ISO classes) Water contamination by ingression RUL% measurement One specific N. American paper plant was able to implement RULER technology into their condition monitoring program, and kept lubricants RUL% above the warning limit. Knowing water, cleanliness and temperature as major root causes for oil degradation, and eventually equipment failure, it helped them to quickly take actions towards the oils condition and if necessary even replace the oil in the system. Also all incoming oil batches are checked on their quality with the RULER technology, in order to assure that the right amount of oil and additives are replenished.

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

12

From a standpoint of an equipment supplier, we see several tremendous positive evolutions, regarding on-site oil analysis. High expectations are set towards the return on investments and benefits from the combination of vibration and oil analysis techniques as the two biggest components of reliability-based maintenance programs.

References: 1. Kauffman, R.E. and Rhine, W.E., Assessment of Remaining Lubricant life, Rep.No. AFWAL-TR-86-2024, Nov. 1986 (NTIS AD-A177 186) 2. Kauffman, R.E., Techniques to evaluate the remaining useful lubricant life of gas turbine engine lubricating oils, 44th Meet. Mechanical Failures Prevention Group Proc., Vibration Institute, Willowbrook, IL, 1990, 121. 3. Richard N. Wurzbach, Oxidation Stability and Strategies for Extending Lubricant Life, Practicing Oil Analysis 1999 Conference Proceedings, Tulsa, OK, 1999, 264273 4. Kauffman, R.E., Method for Evaluating the Remaining Useful Life of a Hydrocarbon Oil U.S. Patent n. 4, 764, 258 (1988) 5. Kauffman , R.E. Remaining Useful Life measurements of Diesel Engine Oils, Automotive Engine oils, Hydraulic fluids, and Greases using cyclic voltammetric methods, Lubrication Engineering, STLE, Volume 51, 3, 223 229 6. Jefferies, A, RULER and Used Engine Oil Analysis Programs, Lubrication Egineering, STLE, Volume 54, 5, 29-34 7. Van Leeuwen, Wilma; Use of RULER for the Determination of Critical Antioxidant Concentration in Ester Based Hydraulic Fluids, Quaker Chemical, Presented at the STLE 98, Detroit Annual Meeting, and AISE 98, September , Annual Meeting 8. William R. Herguth and Dr. Sidney Phillips, Comparison of Common Analytical Techniques to Voltammetric Analysis of Antioxidants in Industrial Lubricating oils

Presented at Oil Analysis 2000 Conference, Tulsa, Oklahoma, 24-26 October 2000

13