Prediction of Remaining Grease Life a new approach and method by linear sweep voltammetry

Albert van den Kommer SKF ERC, Nieuwegein, The Netherlands Jo Ameye FLUITEC International, Brussels, Belgium
ABSTRACT This paper presents the results of research program to evaluate and predict the remaining grease life of greases used in deep groove ball bearings. The technique studied in this paper is based on linear sweep voltammetry1, which directly extracts the antioxidants out of the base oil into a working solution. By applying a controlled voltage ramp through the electrode inserted into the diluted grease sample, a current to flow will peak at the oxidation potential of the antioxidant. The height of the peak is related to the concentration of the additive in the solution. The components in a grease are predominantly base fluid containing specifically designed additives, like antioxidants. It is these additives, which provide the lubricants functions and also protect the base fluid from oxidative degradation. In a first step the precision of the voltammetric analysis was tested. Typically antioxidant peaks are detected from zinc dialkyl dithio phosphate, phenolic and amine type of antioxidants. In a second step a series of samples from different oxidation tests, were analysed using voltammetry. The results showed that the antioxidant capacity depleted with time, but that the rate of depletion varied depending on operating conditions. The voltammetric results were correlated to measurements results from other analytical techniques, i.e. High Performance Liquid Chromatography and Fourier Transfer Infra Red Spectroscopy. It is concluded that voltammetry (by mean of the RULER technology)(1) can determine rapidly the effective antioxidant concentration in greases. If the total effective antioxidant capacity depleted rapidly to a low level this could suggest the grease is inappropriate for the equipment particular duty cycle or re-lubrication of bearings is needed.

Introduction More and more lubricated-for-life bearings are used in applications, which demands the selection of a proper lubricant with sufficient grease life. Nowadays grease life is determined using standard test rigs (e.g. SKF ROF)(2), which have relatively long test durations. Decreasing grease life test time will shorten development time for customer application, but than a method is to be developed which can select grease candidates. The method must be capable to measure, or at least to monitor grease life. Another need to develop a method is related to customer needs. Customers are frequently asking for the remaining life of bearing greases, e.g. if they should re lubricate a bearing during a maintenance stop or how much longer they can run safely before having to re-lubricate. The parameters considered by a method found in literature (3), which are able to answer customer questions concerning remaining grease life, are: degree of oxidation, antioxidant depletion, oil content and total acid number (3). With these parameters as a baseline a new method is developed. A more complete method could be obtained by giving more attention to specific items like: S Location of sampling from the bearing S Type of grease With this project a method to monitor grease life is proposed, which is based on several analysis techniques measuring the relevant grease life parameters like antioxidant capacity and oil oxidation, based on degradation of grease samples in static and dynamic testing. The method could be a potential monitoring routine for lubricants in:

Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland

1) Real bearing applications, e.g. railway grease 2) Application developments, e.g. high temperature greases for automotive applications. KEYWORDS: Antioxidants (AO's), voltammetry, Fourier Transfer Infra Red Spectroscopy (FT-IR), High Performance Liquid Chromatography (HPLC), oxidation control, amines, phenols, remaining useful life. EXPERIMENTAL Fresh greases The fresh greases evaluated during this study were obtained from different commercial suppliers. Standard grease was selected for three types of application, i.e. Medium Temperature (MT), Extreme Pressure (EP) and High Temperature (HT). Details on the composition of the greases are given in Table 1.
Table 1. Composition of test greases Grease (type) Thickener type Li OH stearate Li OH stearate polyurea Oil type Base oil viscosity at 40 C [cSt] 72 170 70 Base oil content [%] 84 90 84

about 150 N, applied via an airpressurised system, while no radial load was set. Static oxidation test For the static oxidation test grease layers were put on steel coupons, having dimensions 100x32x6 mm. Before testing the coupons were vapour-phased cleaned using cyclo-hexane. Five layers of grease, 1 mm thick and with an area of 10x20 mm could be placed on each coupon. The coupons with grease samples were put in ovens. The MT and EP grease were degraded at 120 2 and the HT grease at 140 2C. Samples were taken after (about) 250, 500, 750, 1000, 1250, 1500 and 1750 hours. Linear Voltammetry The method for predicting the remaining useful life of grease is based on voltammetric analysis (1) as electroanalytic methods, in which a sample is mixed with an electrolyte and a solvent, and placed in an electrolytic cell. The voltammetric test results are based on current, voltage and time relationships at the cell electrodes. The cell consists of a fluid container with a small, easily polarized microelectrode, and a large non-polarizable reference electrode. The reference electrode should be massive compared to the microelectrode so that its behaviour remains essentially constant with the passage of small current: it remains unpolarized during the analysis period. In performing a voltammetric analysis, the potential across the electrodes varies linearly with time, and the resulting current is recorded as a function of the potential. With increased voltage to the sample in the cell, the various additive species under investigation i n the oil oxidize electrochemically. The data recorded during this oxidation reaction can then be used to predict the remaining useful life of the grease or oil type. A typical current -potential curve produced during the practice of the voltammetric test i s illustrated in figure 1.

A (MT) B (EP) C (HT)

mineral mineral ester

Oxidation test methods The laboratory-stressed greases were produced using a dynamic and a static oxidation test. Dynamic oxidation test The 6202 bearing was chosen as test element in a dynamic oxidation test. The bearings were vapour phased cleaned using cyclo-hexane, filled with about 880 milligrams of grease and capped with Zshields. They were run in a rig at a speed of 10.000 rpm and stopped after (about) 250, 500, 750 and 1000 hours. The test temperature for the MT and EP grease filled bearings was 120 5C, while the HT grease filled bearings were ran at 140 5C. The axial load on the bearings was
Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland

Initially the applied potential produces an electrochemical reaction with a rate so slow that virtually no current flows through the cell. As the voltage is increased (figure1), the electro-active species (such as antioxidants) begin to oxidize at the microelectrode surface, producing an anodic rise in the current. As the potential is increased (from 0 to 1.7 V at a rate of 0.1 V/second), the decreases in the electro-active species concentration at the electrode surface and the exponential increase of the oxidation rate lead to a maximum in the current-potential curve (figure 1); this is the oxidation wave. In this study the voltammetric method was performed with a commercially available voltammograph (RULER ) equipped with a glassy carbon-working electrode, a platinum wire electrode, and a platinum wire auxiliary electrode. After the grease samples (max. 200 mg) are diluted in an acetone/electrolyte mixture enhancing extraction of the antioxidants (AO[s]) into the solvent phase. The peaks produced by the voltammetric method (the oxidation wave) were then used to evaluate the remaining additives of the used oil samples. The peak of a zinc dialkyl dithio phosphate (ZDDP) additive is followed by an amine (PANA), and then by a phenol (BHT) (Figure 1).
Detection & Measurement of Oxidation Inhibitors
Phenyl - -naphthylamine
NH

Weigh between 0.05 and 0.2 grams of grease with small spatula. Wipe grease off towards bottom of bag, in a corner. Spread the grease around slightly to increase its exposure to the solvent. Pour green reagent from vial in bag. Use finger technique to massage grease in bag for 45-60 seconds. Pour (or pipette) as much solvent as possible back in vial. (Does not have to be all solvent because it is a concentration of AO that is important not the quantity of fluid, as long as it covers the probe tip.) Shake vial for 10 seconds. Let solution settle for about 15 seconds until clear liquid is evident on top Perform RULER test. The fresh grease is used as the 100% standard and the measurements of the used lubricant samples were expressed as percentage remaining additives. The repeatability of the percent-remaining additive measurements is between 2.5 and 4%.

Fourier Transform Infra Red spectroscopy Grease from the test bearings and the coupons was analysed by FT-IR spectroscopy to detect oil oxidation. Most samples were measured in a direct mode using the combination of a Nicolet Continu m IR microscope with a reflectance objective and Nicolet NEXUS FT-IR spectrograph with a KBr beamsplitter. Spectra were obtained after 16, 32 -1 or 64 scans at 4.0 cm resolution using a MCT/B detector. Several samples were analysed by an indirect mode using normal transmittance spectroscopy. A Nicolet 20SXC FT-IR spectrophotometer with a KBr beamsplitter was applied. Spectra were -1 recorded after 64 scans at 2.0 cm resolution. The path length used was 0.025 mm or a thin film.

Compound B

Linear Ramp (Voltage)

Current milli-amps

Compound A

ZDDP

Compound C

BHT OH
(CH3)3 C C(CH 3 )3

Solution Blank

CH 3

Voltage increases with time Figure 1- Voltammetry Voltage vs. Current for different antioxidants e.g. ZDDP, amine and phenol.

Voltammetric test procedures The RULER test procedures for greases, are slightly different than for oils; in order to enhance the extraction of antioxidants out of the oil phase, a small sample is put into a plastic bag. The following test procedures were applied:
Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland

High Performance Liquid Chromatography Grease samples were subjected to HPLC analysis to monitor AO content. An amount of 50 to 150 mg extracted oil was dissolved in 1 to 3 ml HPLC solvent to get a concentration of about 50 mg oil per ml. The HPLC solvent was a 1:1 mixture of chloroform and methanol to which 2 internal standards, i.e. mono chlorobenzene and dioctyl phthalate was added. The sample solution was filtered over a 0.5 m PTFE filter before injection in the Spectra Physics Spectra System HPLC instrument. A volume of 5.0 l is injected into a ChromSphe r C18 column (Chrompack, 250 x 4.6 mm, 5 m) and a separation of components is reached by applying a gradient using acetonitrile, dichloromethane and water as solvents. A FOCUS detector set at 254 nm UV-light is applied at 8.00 Hz sampling rate. The results were calculated and reported by a Spectra Physics Workstation using Spectra System software. RESULTS RULER Voltammogram of fresh and degraded MT, EP and HT grease samples are given in figures 2,3 and 4.

Figure 3. Voltammogram of EP-type of grease.

Figure 4. Voltammogram of HT-type of grease.

The RULER results from the voltammogram are presented in two different ways. The first parameter is Area Remaining Useful Life (RUL), which calculates the total concentration of all AO's in the lubricant. The second parameter is the Additive RUL, for each individual AO within the lubricant, by comparing individual AO peak heights. For this paper all data are represented by trending Area RUL%results, both for static and dynamic oxidation tests (see chapter discussion). FT-IR analysis Typical spectra of fresh and oxidised greases are given in figures 5, 6, and 7, for the MT, EP and HT grease respectively.
Fresh MT grease Grease after 500 hrs @ 120 C (static test) 1,0 Grease from bearing cage after 500 hrs at 120C (dynamic test)

0,8 Absorbance

0,6

oxidation

0,4

0,2

0,0 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)

Figure 2. Voltammogram of MT -type of grease. Figure 5. FT-IR spectra; fresh and oxidised MT grease.
Fresh EP grease Grease from cage after 500 hrs at 120C (static test) 0,25 Grease after 500 hrs at 120C (dynamic test)

0,20 Absorbance oxidation 0,15

0,10

0,05

Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland
0,00 3500 3000 2500 2000 1500 1000

HPLC analysis The analysis of extracted oils from fresh and tested grease samples was applied to detect AO's and to find correlation with the RULER method. An HPLC analysis example is given in figure 8, i.e. the chromatograms of fresh MT grease and grease after the dynamic test (250 and 450 hours).

Figure 6. FT-IR spectra; fresh and oxidised EP grease.

0,6

Fresh HT grease Grease from cage after 1015 hrs at 140 C (dynamic test)

0,5

Absorbance

0,4

oxidation

oxidation

0,3

0,2

0,1 0,0 3500 3000 2500 2000 1500 1000

Wavenumbers (cm-1)

Figure 7. FT-IR spectra; fresh and oxidised EP grease.

The MT and EP degraded grease samples show oxidation of the base oil. In the FT-IR spectra of these greases oxidation bands are found in the ranges -1 3000-3500 and 1500-1800 cm . A normalised measure of base oil oxidation (RO X) is defined as the ratio of: ROX = A ref / Aox where Aref is the height of the reference -1 band at 1375 cm ,and Aox is the height of the oxidation -1 band at about 1710 cm .

Figure 8. HPLC chromatograms of fresh and tested MT grease.

In the chromatogram of the fresh MT grease a high peak is shown (after about 13 minutes), which is the amine type of AO. Only amine types of AO's were detected, also in the EP and HT greases.

DISCUSSION Introduction In general the RULER method is applied on oil lubricated applications and has shown its usefulness as a condition monitoring routine. In the first phase of the study grease samples were subjected to filtration to separate thickener and oil ("indirect" method). Analysis of these oils by HPLC and RULER was executed to monitor the AO content, while the grease samples were analysed by FT-IR spectroscopy to monitor base oil oxidation.

The HT degraded grease samples did show much lower tendency to oxidation. There were changes seen in the FT-IR spectra of the HT samples, but these were not expressed in a measure for oxidation. Detailed results on trends in oxidation for the MT and EP grease are given in the paragraph discussion.
Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland

There was correlation between HPLC and the RULER method for the results obtained in the "indirect" method. The amine AO content as measured by HPLC and RULER shows the same trend; within 300 to 500 hours the amine content reached a 0% level; see figure 9.

RULER analysis MT grease The RULER method identifies two types of AO in the MT grease. The first and second peak in the voltammogram is related to an amine and a phenolic type, respectively; see figure 2. In the static oxidation test the parameter Area RUL% decreases from 100 to 0% in 1500 hours, while in the dynamic oxidation test a 10% level is reached after 1000 hours. (see figure 10)

100 80 60 40 20 0 0 200 400 time [hrs] 600 800 1000 AO amine HPLC - indirect AO amine RULER - indirect AO amine RULER - direct AO amine HPLC - direct

Figure 9. plots of the Amine AO content in MT grease samples by voltammetry and HPLC vs. hours from dynamic test.

Figure 10. plots of the Amine AO content by voltammetry and oxidation trend by FTIR vs. hours of oxidation from static and dynamic oxidation test on MT -type of grease samples.

In a second phase of the study the "direct" method to monitor the AO content was applied, i.e. directly dissolving the grease in the RULER test solution. Now, a higher level of amine AO content was found (see figure 9). While for a direct HPLC method, i.e. no filtration to separate oil and soap, but a dissolving of the grease in the HPLC solvent, still shows low AO levels. An explanation of the lower AO found by HPLC analysis can be clarified by: Loss of the additive during filtration, whereby the AO remains in the soap structure; Loss of the specific peaks in HPLC chromatograms, because (intermediate) reaction products are formed during the complex oxidation process. So, to monitor the AO content, the "direct" method was chosen to be the method applied for the RULER measurements.
Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland

EP grease Again the RULER method was able to detect two types of AO's in the grease (amine and phenolic type), while also the EP/AW additive in the form of zinc dialkyl dithio phosphate was found. The trends for the Area RUL% parameter obtained from the static and dynamic oxidation test were: from 100 to >10% in 1750 hours and from 100 to 20% in 750 hours, respectively. The trends are given in figure 11.

is of different order, although the depletion of the AO, expressed in RULER area, for MT and EP grease in dynamic and static test follows the same trends.
Figure 11. plots of the Amine AO content by voltammetry and oxidation trend by FTIR vs. hours of oxidation from static and dynamic oxidation test for EP-type of grease samples.

General The life of the MT and EP grease is about 3700 and 3200 hours, respectively, as determined in SKF R0F testing (2). The RULER method has shown that the Area RUL% parameter for both the greases in the dynamic test is decreased to the range 10 to 20% after about 1000 hours, while in the static test the range is 5 to 15% after 1750 hours. Comparing the trends for Area RUL% in the dynamic and static test gives an extrapolated Area RUL% level of <5% for the dynamic test after about 1500 hours. This means that the antioxidant is almost used up at about half the lifetime of the grease. The FT-IR spectroscopy results show that at half the lifetime of the grease the base oil oxidation level can be relatively high, expressed in the normalised oxidation measure. But, because of the complex nature of the changes in the degraded greases, resulting in non-linear changes in FT-IR spectra, there can be a large spread in the oxidation measure and so a clear correlation between grease life and oxidation level cannot be given. The FT-IR method is a quick method, which gives only qualitative information in respect to oxidation and presence of specific AO's. The HPLC method was not able to detect both types of AO's present in the greases. Besides the depletion of AO's by oxidation is not a straightforward process; during the oxidation process intermediate compounds are formed, which are perhaps not sensitive for the detection applied in the HPLC method. CONCLUSIONS When comparing the voltammetric procedure to existing grease and oil oxidation test methods, such as FT-IR, and HPLC, the following differences are apparent: Ease in use: the test procedure consists of sampling the grease, mixing

HT grease In case of the HT grease also at least two AO's were used in the formulation and also detected by means of the RULER method. This grease, based on a different thickener type and base oil than the MT and EP greases, seems to need other RULER conditions in respect to the sample amount and electrolyte. First RULER measurements were made on tested samples, which gave improper response to be used as trend results. Besides, FT-IR analysis of the polyurea grease did not result in a measure for oxidation in the same way as for the lithium greases. So, in this paper, no trends are given for the HT grease. A follow-up of the work is planned and than several polyurea type of greases will be studied. HPLC analysis The HPLC method was not able to measure the presence of both AO types; only the amine type was detected. The phenolic type of AO is not sensitive for ultra violet detection at 254 nm. However the AO gives a very specific peak in the IR -1 spectrum (band at about 3625 cm ), so by means of FT-IR spectrometry the presence of the phenol compound in degraded grease samples was obtained. When the "indirect method (separation of oil by filtration) was applied, a strong correlation was found between the RULER and HPLC results, but for the "direct" method the HPLC method did show clearly lower amine AO content. FT-IR analysis The FT-IR analysis of the degraded grease samples shows that base oil oxidation already starts in the first few hundred hours and not after all AO is used up; see figures 10 and 11. The base oil oxidation in static and dynamic oxidation testing for both greases
Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland

it with the 5 ml prepared test solution, inserting the probe, and measuring; Test method requires a very small grease sample volume (max.200 mg); Test avoids the extraction phase of oil with solvents; Portable technology, allowing on-site analysis; Quick test method (less than 5 minutes), which can be used for field analysis; Detects all present AO's compared to HPLC or FT-IR analysis method.

The RULER method, which measures remaining lubricant life, is a potential and reliable monitoring routine for lubricants in: 1) Real bearing applications, e.g. railway grease, or 2) Application developments, e.g. high temperature greases for automotive applications. ACKNOWLEDGEMENT The authors would like to thank Dr. H. Wittmeyer, Senior Vice President of SKF GTD, for permission to publish this work, and E.de Blic, Product Development Manager of SKF Electrical Division, for the support to publish this work. REFERENCES (1) Kauffman, R.E., STLE CRC Handbook of Lubrication and Tribology, (Vol III), Booser, E.R. ed., CRC Press, Boca Raton, FL, pp 89.( 1994 )
(2) SKF R0F, standard method for

grease life determination in 6204 rolling bearings. (3) H. Ito e.o ,Physical and Chemical aspects of Grease deterioration in sealed ball bearings, Lubrication Engineering, October 1988

Paper presented at the ELGI 2001 AM, May 9-11, Bern Switserland