Used grease analysis Smallest sample volume provides detailed information Author: Steffen Bots Co-author: Peter Weismann OELCHECK GmbH, Germany Presented at the 20" ELG! AGM April 2008, Lisbon - Portugal The analysis of used grease is a much more complicated process compared to used oil analysis. Only a few laboratories in the world specialise in the analysis of used greases using extremely small sample volumes. OELCHECK Germany performs such used grease analysis on a routine basis. The combination of analytical methods is selected based on the answers to questions posed to customers about their requirements. Special prepaid analysis kits are delivered. Results are provided within 24h from the time the sample is received in the laboratory. The data is interpreted by experienced mechanical engineers and recommendations are made in a detailed diagnostic report 1. A must: the proper sample taking technique The basic requirement for a valid sample result is proper sampling technique. It is obviously much more difficult to take a representative grease sample out of a bearing than to take an oil sample. Oelcheck supply a special kit for taking grease samples, so the sampling procedure can be standardized and becomes less complex. The kit consists out of: + areusable syringe which can operate under a high vacuum * a ttube, into which the grease is sucked by the syringe-operation ‘* a sample container marked as “pre-paid analysis kit" for the shipment of the used grease Steffen Bots studied industrial engineering at the University of Applied Science in Rosenheim. He graduated in 2004 with a diploma thesis on an inlernet based application for publishing and organising fresh oll information, ‘Since 2004 he nas been working as a member of the Technical Department at Oelcheck as an engineer with the following fiolds of responsibilities: evaluation of the laboratory results; creating diagnoste statements on laboratory reports; consulting services regarding questions about the laboratory reports; general tribological problems in the field of proactive maintenance. His experience is based on the evaluation of nearly 100,000 ‘samples and shares his experience during training courses and conferences. sb@wearcheck.de * asample information form with specific, questions for used greases * pre-addressed mailing envelope for the sample shipment * the complete content of the grease kit is packed in a robust red box (Fig.1) Figure 1: Typical test kit for taking a grease sample 2. How to take a grease sample Remove the inspection screw on a slew bearing. Remove the grease nipple from a rolling element bearing, if the bearing does not have a special grease sampling point. If the bearing is “filled for life" the shield or cover has to be removed or the seal lip has to be lifted, so that the used grease sample can be taken as close as possible to the area where the grease sample is representative and thus contains the most information. EUROGREASE | january/february/march 2009 a» Cut off approximately 10 cm of the supplied sampling tube. Mount the clean tube on the syringe. 4. Press the opening of the tube on the corresponding greased area. Operate the syringe and suck the used grease on a length of at least 1m (up to max. 5cm) into the sampling tube. Repeat the procedure on different sampling points of the same bearing. Usually 3 g by small bearings approximately 1g of grease is enough for the analysis. 5. Observe any colour changes. Avoid taking fresh grease too close to the re-greasing point. For trend analysis samples always should be taken at the same points. Assample of the fresh grease should be sent as a reference sample After sampling remove the tube from syringe, fold it and place it into the sample bottle. 9. Remove the sticky barcode label from the sample information form and stick it on the sample. 10. Complete the questions on the sample information form. Place the sample container and the sample information form into the mailing envelope and send it to the Oelcheck Laboratory (Fig.3). 2 Al 2 Figure 3: Shipment of a used grease sample ina tube Figure 4: Different samples from the Oelcheck laboratory 3. What are greases? Lubricating greases are not straight forward chemical substances. They contain approx. 90% of base oil and additives. The rest is thickener which works similar to a sponge and which holds the oil in suspension. Base oils of all types of mineral and synthetic oils are used. The additives are similar to those used in lubricating oils. Thickeners are mostly metallic soaps based on lithium, calcium, sodium, aluminium or a combination out of these metals. In the manufacturing process a sponge-like basic. grease structure is formed. During the grease cooking process, water is vaporized and replaced by base oil. In the final stage, the additives are added and the grease is homogenized and deaerated. The lubrication performance is provided by the base oils and additives but not by the thickener. The sponge like thickener is responsible for holding and releasing in a very slow way the liquid base oil to facilitate lubrication. Machine elements are lubricated by grease it continuous lubrication by oil is technically or practically not possible. Also if oil can drip-off lubrication points the oil should be replaced by the grease. For a selection of the right grease type it is important, that the grease will not melt at elevated temperatures but still remain sticky and flexible. It should always stick at the lubrication point. 28 EUROGREASE january/february/march 20094. Analytical methods for used greases Well-defined analysis kits for detailed information Oelcheck provides several analysis kits with pre- defined sets of analysis methods for lubricating greases. The experts of Oelcheck consult in the selection of the best analytical methods, the optimized kit, the sampling procedures and sample quantity. They also provide information regarding the analysis intervals. The tests packed in the analysis kits are sorted in a way that the kit with a higher number always contains all the tests of a kit with a lower number (like in kit 3 all tests of kit 1 and 2 are included). Additional tests can be performed. 4.1. Wear-additives and contamination elements by OES All grease samples at Oelcheck will be analyzed by the optical emission spectroscopy (OES) according to the Rotrode principal. Up to 21 elements can be checked providing information about wear, contamination and additives. » Wear metals include: iron, chromium, tin, copper, lead, nickel, aluminium, molybdenum, zine and, if present at all, particles of silver, vanadium, titanium antimony and tungsten. > Contamination elements: silicium, calcium, sodium, potassium and aluminium Additives or thickeners: magnesium, calcium, phosphorous, zinc, barium, silicium, aluminium, molybdenum and boron. - 4.1.1.Test principle Asmall quantity of approximately 0.3 g grease will be smeared on a Rotrode graphite wheel (Fig. 6). It is distributed over the radius of the 3 mm wide and 14 mm diameter electrode. According to the Rotrode-principle, in less than a minute all particles on the graphite electrodes are heated up in an arc which is created at 40.000 volts and provides temperatures of above 8.000°C. This temperature forces each of the elements present to create its characteristic light spectrum. The light beam will be distributed by means of a griter (prism principle) in its spectral colours (Fig.5). Figure 5: Spectro RDE device for metal detection Ina dark room, photomultiplier tubes are mounted in a radius behind slits such that so they can absorb only the light that is typical for the measured element. The voltage change caused by the intensity of the light is used to calculate the mass of the present metal. — ‘ Figure 6: Grease on a Rotrode graphite wheel 4.1.2. Result Of special interest for the diagnosis of bearing or grease-condition is the iron and chromium content, which are present as wear particles from the bearing material. Non-ferrous materials like copper, lead or tin are indicative of corrosive or abrasive wear from the bearing cage. If dust in the form of silicon or calcium (limestone) hard water containing minerals, like sodium, potassium or magnesium are present, this can be helpful in determining the reasons for the presence of wear metals. The metals content of a metallic soap or a comparison of the additive content between fresh and used grease can indicate whether the recommended grease is being used EUROGREASE januany/february’march 2009 294.2. Magnetic wear particles by PQ-Index The PQ-Index (Particle Quantifier Index) indicates the presence of magnetic iron particles. Index values between 0 and 9999 are independent of the particle size, giving information on all iron particles present. Because rust particles are non-magnetic, these are not measured. The test is performed at Oelchcel by the Analex Ferrous Debris Monitor PQ-90 A (Fig. 7). (eer Figure 7: Magnetic wear debris with the PQ-Index 4.2.4 Test principle The PQ-Index is based on the principle that iron and therefore iron wear particles are magnetic and can be detected by a magnet. If a grease sample contains magnetic iron wear particles, a magnetic field is disturbed. The change in the magnetic field can be measured. The test result, named as a PQ-Index will be recorded. In the PQ-90 A unit 2 magnetic coils are placed in such a way that the magnetic fields are in balance, During a test start, one of the magnetic coils functions as a sample coil while the other acts as a reference coil. On top of the 2 magnetic coils a sensor is mounted. 1g of the grease sample is placed in the cap of the sample bottle and set on the sensor. If the sample contains only traces of iron wear particles, only a small influence on the magnetic field is recorded. If the sample contains a high concentration of magnetic iron particles, the balance of the magnetic fields between the sample and the reference coil is changed. The "out of balance" signal is electronically filtered. The change is displayed as PQ-index. The index is dimensionless and can be related to the quantity of iron present in the grease. 4.2.2 Result The PQ-Index or Ferrous-Index gives information about the total content of magnetic wear particles. In contrast to the information about iron wear particles determined by OES. OES in used grease samples detects only particles up to 5 microns because larger particles are not excited. For the interpretation of the results, the difference between the iron content measured by the OES in mg/kg are compared with the PQ- Index. The following conclusion can be made: > An extremely high PQ-Index above 500 indicates independent of the iron wear by OES (mg/kg) an ongoing wear situation in combination with pitting formation and fatigue. A high PQ-Index above 100 and iron by OES in a similar range is typical for fatigue and a sign of "normal" wear. > Ahigh PQ-Index above 100 and a low iron reading by OES indicates pitting and actual wear with large particles. > Ahigh iron wear measured by OES (above 400 mg/kg) with a low PQ-Index (below 50) is a sign of corrosion and rust formation. y 4.3. Type and condition of the base oil using FTAR The FT-IR (Fourier-Transform Infra-Red) spectroscopy identifies the type and condition of the base oil in used grease. Also compared to the unused grease, contamination by another grease or depletion of additives can be determined. oe Figure 8 : FTIR device with ATR cell x0 EUROGREASE january/februarymarch 20094.3.1. Test principle The FT-IR spectroscopy is based on the principle that molecules present in a lubricant can absorb infrared light at wave lengths dependant on its structure. Changes in the used grease in comparison to the fresh grease reference spectrum are calculated using peaks at predefined wave numbers and interpreted as oxidation, water etc. A very small grease sample (less then 0.19) is applied onto an ATR cell. In the contact zone the grease sample will be exposed to infrared light. An infrared spectrum, showing the absorbance of the infrared light at the specific wave numbers will be recorded and interpreted 4.3.2. Result The infrared spectrum of a sample gives information about changes in the grease and contamination. Absorbance at peaks corresponding to oxygen-reactions indicate oxidation of the base oil. Changes in another region of the infrared spectrum are a sign of water and can be related to water analysis of the sample. By spectra-subtraction of used grease with reference grease, the FT-IR method show what kind of unknown grease is in use. Also a mixture of different greases in many cases is shown. The identification of the original grease and the base oil type can be found by a library search of reference spectra and supports the cause of a failure. The FT-IR can indicate whether synthetic or mineral oil base oils are used Ifa mineral oil is used as the base oil, the FT-IR will show whether the base oil is oxidized by operation for too long a time without regreasing or at too high a temperature. > If the grease contains zinc-phosphor EP additives the degradation of the additives can be seen. » Information about the water content in the grease is provided. Transmission 6T jure 9 : Typical FTIR spectrum for a used grease compared with a fresh grease 4.4, Water in used grease by Karl-Fischer Titration ‘As well as solid contaminates which can be identified by the OES-elements silicium, calcium or aluminium, water contamination is very often the cause for corrosion and bearing damage. Also often short regreasing intervals result from too much water. Unfortunately the determination of water in grease is not as easy as in oil. 4.4.1. Test principle For the water determination according to the Karl-Fischer method a small grease quantity (approx. 0.3 g) is filled into a glass vial and closed by a septic cap. In a small oven the sample is heated to approx. 120°C. The Volatilised water is transferred by nitrogen into a titration vessel in which an electrochemical reaction between the water and a Karl Fischer EUROGREASE | january/february/march 2009 31reagent takes place. A titration curve is recorded and the water content determined (Fig. 10). we Figure 10: Water detection according the KF method 4.4.2, Result Depending on grease type and application, the water content in a grease should not exceed the recommended limit values. Too much water in grease can have an impact on different damage mechanisms: > corrosion on all bearing metals > increased oxidation of the base oil > cavitation on parts with mixed friction > softening of the grease > water wash-out of the grease If the result for water according to the KF- method is compared to the elements determined by OES it can be shown whether the water in the sample is "hard"-water, which contains minerals like sodium or potassium or whether it is "soft'-water, like condensate or rain water. The comparison of KF-water and OES can also indicate, whether the water was already present in the fresh grease as a part of the production process, 4.5. Indication for wear and contaminates by sulphated ash Grease ash consists of components of the metallic soap solid contaminants, metal-organic grease additives and of wear metals. The quantity of the sulphated ash in comparison to reference grease is changed by the presence of wear particles and contaminants. Figure 11: Measurement of sulphated ash 4.5.1. Test principle The sulphated ash is determined by burning a small grease quantity of approximately 0.5 to 19 at a temperature of 775 °C. At this temperature all organic components are "burned by a treatment with concentrated sulphuric acid. The oxides in the ash are converted into the corresponding sulphates. The sulphated ash is the residue, remaining in the container when all organic components from base oil, thickener and contamination are volatilised. Only metallic oxides and the contaminants remain at 775 °C. The difference between the original and the ing quantity is given as sulphated ash by Result The increase of the sulphated ash content in grease samples in comparison with reference grease indicates contamination and wear. If the sulphated ash is completed by the metal detection by OES, itis possible to rate the ash as wear or as contaminant, by comparing the iron and chromium content with silicium and calcium content. The sulphated ash is changed by: > metallic wear particles, which indicate bearing wear > solid contaminants (dust- this may give information about the correct re-greasing intervals). metallic soap and organic thickeners (information on contamination by different grease types) solid lubricants like MoS2 metal-organic EP-additives vv 32 EUROGREASE | january/february/march 20094.8. Bleeding out characteristics Conventional grease consists of approx. 90% oil, The rest is thickener that looks, observed under a microscope, like a sponge. If the oil leaks out of the thickener it is called "bleeding". This “bleeding out” characteristic is influenced by the grease type and quality as well as by temperature, vibration or load. If oil is lost, the grease becomes dry and loses its lubrication properties. Re-greasing at shorter intervals can overcome the problem. Figure 12: Measurement of the bleeding out, characteristic for used greases 4.6.1. Test principle Aring with a diameter of 10mm and 3mm height is filled with approximately 1g of grease and placed on a defined filter paper. The arrangement is stored for 6 hours at 80°C in an oven. During this period the filter paper will absorb the oil out of the thickener. After completion of the test, the filter paper shows an oil spot that can be measured. The grease quantity that remains in the ring afer the test is scraped from the paper and compared to the original quantity. The difference will be recorded as bleeding outloss in % wt. Also the comparison of the diameter of the oil spot provides information with respect to. the reduction of remaining oil and the lubricity of the used grease. 4.6.2, Result Long term use without re-greasing, high temperature or oxidation will cause a separation of the oil from the grease thickener. To allow good interpretation of the oil loss, the bleeding out characteristic of the fresh grease or of the previously analyzed grease should be compared with the sample result. > the grease can be used without additional re-greasing if the bleeding out characteristic remains within a +/- 15% range > if less oil is bleeding out and the oil spot gets smaller the bearing should be re-greased because the grease maybe providing insufficient lubrication > if the used grease is losing much more oil than the fresh grease, the thickener is not stable enough to keep the oil in its structure. The grease is softer. Very often water has an impact on the increased bleeding out characteristic. The bearing should be greased at shorter time intervals. 4,7. Penetration and consistency For oils the viscosity is measured to assess oil fluidity. For greases the penetration or the consistency indicates whether the grease is soft or more solid or stiff. Grease penetration has nothing to do with the base oil viscosity. For used greases the consistency is measured by a penetrometer with a quarter cone. The penetration is used as an identifier and provides information whether it can be pumped by a central lubrication system or used for a certain application. Figure 13: Measurement of the penetration 4.7.1. Test principle 2g of the grease sample are filled at room temperature into a standard beaker. The tip of a standardized double cone touching the surface. Over a 5 second period how deep the cone penetrates into the grease is measured. Soft greases will have higher penetrations than hard greases. EUROGREASE january/february/march 2009 34.7.2. Result The consistency of the grease characterizes its ability to be deformed in an application. The consistency is grouped in NLGI classes from 000 to 6. If the used grease penetration is compared to the fresh grease, following information can be gathered: > ahigher penetration and therefore a softer grease indicates contamination by another grease. > Contamination with grease of different thickener types usually leads to softening > the penetration will be higher if there is by water or other liquid contamination > the grease will be softer if itis sheered by mechanical stress in a bearing. This destroys the soap structure and shears its long fibered components. the penetration is lower and the grease gets harder if it contains less base oil and more thickener. This may happen if base oil is lost by bleeding out because of vibrations or if it is vaporized by high temperature or oxidation ¥. 4.8. Instability of grease thickeners by dropping point: The dropping point indicates the temperature in °C at which a small sample volume under defined condition builds a drop. The test shows the end point of a softening process under static conditions. The dropping point should not be used as an indication of the temperature-limit for grease. Lubricating greases do not have a melting point like natural greases. They are not thinned in a uniform way, they get softer dependent on the thickener type. For the determination of the operating temperature of grease, the oxidation of the base oil and the destruction of the thickener but not the dropping point are more relevant (Fig. 14) Figure 14: Measurement of the dropping point 4.8.1. Test principle ‘Asmall sample volume of approximately 0.5 g is filled into a nipple has an associated thermometer. The test unit is heated until a drop is formed on the bottom opening of the nipple. The drop, consisting of a thickener and oil will fall into the test tube. The temperature, at which the drop formation starts, is recorded as "dropping point’. The test unit operates up to 300°C. 4.8.2. Result The dropping point only indicates whether grease is running at a specific operating temperature. The maximum operating temperature for a grease should be always far below the dropping point temperature. The base oil type and the thickener will determine how far below the dropping point the operating temperature can be. Usually the dropping point should be at least 50 °C higher than the operating temperature. If the analysis of used grease shows a lower dropping point compared to as the fresh grease, following problems might exist: > Contamination by a different thickener based grease. A mixture of different grease types lowers the dropping point. Due to the mixing of different greases, the product will become thinner; sometimes it looks like a semi-fluid grease. water or other liquids in the grease will thin- down the product in a way that it starts dropping at a much lower temperature > the grease has been so heavily worked in the lubrication area that the soap structure is sheered into such small particles, that the oil is no longer kept within the structure . In all cases of lowered dropping point, the problem can only be solved by the removal of the present grease, by a cleaning process or by re-lubrication at shorter intervals. 4.9. Oxidation and re-greasing intervals by RULER Besides of AW- , EP- or HD-additives which improve the anti-wear properties, a grease also contains anti-oxidants which avoid the base oil aging and oxidizing too quickly. Usually oxidation is observed by the FT-IR spectrum. This is especially so when synthetic base oils are used. The peaks in the spectrum present for the synthetic product and the peaks for oxidation are in the same region. The infrared spectrum therefore does not deliver any valuable information about oxidation or the aging of base EUROGREASE | january/february/march 2009oil based on temperature or operating time. One of the most important criteria for the recommendation of the optimum re-greasing intervals is missing With the RULER-test the content of oxidation inhibitors based on amines or phenols can be exactly determined. A comparison of the fresh grease can show the remaining useful lifetime of the grease and allows a prediction of the next re-greasing intervals. Figure 18: The RULER device 49.1. Test principle ‘Any grease containing aminic or phenolic oxidation inhibitors can be tested. In the sample tube, which simulates an electrolytic cell, 0.25 g of the grease sample is mixed with solvent and special sand. By shaking the sampling tube vigorously, the solvent-sand-mixture will free the anti-oxidants out of the base oil of the grease. Within 5 minutes the solid particles and the grease contaminants as well as the thickener and the base oil settle on the bottom of the glass tube. An electrode penetrates approximately ‘1cm into the upper phase of the electrolytic mixture were the additives concentrate. Using a voltametric principle, a defined current will be progressively applied to the electrode. As the potential increases, the anti-oxidants become chemically active and result in an increasing voltage up to a maximum that drops off with further increased applied current. The time dependent increase of the voltage is selected in the way that the typical curves of anti-oxidants can be measured. In the voltage curves the potential of the peak indicates the type of the additive. 4.9.2. Result The RULER value is a number representing the concentration of the oxidation inhibitors. The result is compared to a sample of the fresh grease. By trend analysis or a comparison of samples out of similar equipment, it can be observed by the Ruler, whether the oxidation inhibitor of a grease has been reduced. Based on this information, the remaining lifetime of the grease under similar conditions and the interval for the next re-greasing can be calculated (Fig. 16). Ruler Number ‘Seconds Figure 16 : Typical RULER diagram EUROGREASE | january/iebruary/march 2009 355. Summary 5.1. Predefined analysis kits for detailed used grease analysis, Oelcheck analysis kits contain test combinations for more than 25 single values. Even if only extremely small grease samples of less than 1g are available, the Oelcheck grease analysis is a well proven method for obtaining detailed information about the condition of the grease and of the bearing. The experienced Oelcheck personnel combine the data received from different test methods. In this way they can comment about wear and its cause or about reasons for bearing failures. Also information can be provided on the correct re-greasing interval or quantity. Based on the experience from more than 10.000 analysed grease samples at the OELCHECK laboratory, guidelines for the interpretation of wear in grease-lubricated applications can be provided: 5.2. Normal wear > amoderate increase of the OES wear- metals iron (Fe) up to 80 mg/kg, chromium (Cr) up to 10 mg/kg and copper (Cu) up to 50 mg/kg a small increase in the PQ-Index up to 60 water below 500 ppm. RULER value about 25% small differences in the bleeding out characteristics v vvvv 5.3. Corrosive wear > a relatively strong increase of most of the OES wear-metals > iron (Fe) above 150 mg/kg, chromium (Cr) above 15 mg/kg and/or copper (Cu) above 50mg/kg > PQ-Index less than 15% below the OES-iron (Fe). Rust particles are hardly magnetic, therefore grease containing rust particles will only show a low PQ-Index > more than 2% increase in the sulphated ash compared to a fresh grease > a decrease of the RULER value below 25% » awater content of more than 2.000 ppm. Increases in the sodium(Na) and potassium (K) contents, > TAN of more than 2 mgKOH/g above fresh grease. Oxidation of more than 20 A/cm. (The reason for rust and corrosion are usually water, acids or oxidation) 5.4, Fatigue wear > a moderate increase of the wear metals determined by the OES > iron (Fe) more than 50% lower than the value of the PQ-Index. The iron particles present in the grease, are too large to be detected by the OES-method. > the PQ-index is considerably greater than 300. ® the sulphated ash has increased by more than 2% > the bleeding out characteristics and the remaining oil content of the grease has changed significantly. (The reason for such a wear condition is that the bearing has reached the end of its lifetime or the grease is no longer suitable. Both reasons lead to pittings, spalling or similar damage) 5.5. Mechanical abrasive wear > a relatively strong increase of the OES. determined wear metals > iron (Fe) above 100 mg/kg, chromium (Cr) above 10 mg/kg > silicon (Si) very often also potassium (K), calcium (Ca) or aluminium (Al) above 50 mglkg > increase of the PQ-Index above 150 » increase of the sulphated ash of more than 2% The detailed interpretation of the analysis results and the individual data of an Oelcheck grease sample are clearly presented in a detailed laboratory report. Information about the individual test methods may be found on the internet: www.Oelcheck.de 36 EUROGREASE january/february/march 2009