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USE OF RULERTM FOR THE DETERMINATION OF CRITICAL ANTIOXIDANT CONCENTRATION IN ESTER BASED HYDRAULIC FLUIDS Wilma van Leeuwen

Quaker Chemical BV, Industrieweg 1-13, 1422 AH Uithoorn, the Netherlands Email: leeuwenw@quakerchem.com ABSTRACT The steel and mining industry uses fire resistant hydraulic fluids which are based on biodegradable esters. These fluids contain antioxidant packages which slow down the oxidation processes of the ester. The antioxidants will deplete during use of the fluid until a certain critical level is reached at which the fluid will start to degrade / polymerise at a higher rate. At this point the fluid reached the end of its useful life. In order to estimate the remaining useful life of a fluid it is therefore important to know its critical antioxidant concentration. Two fire resistant fluids, which contain different antioxidant packages, were investigated in a laboratory ageing test in order to determine their critical antioxidant concentration. The concentration of the antioxidants was measured at regular time intervals with the RULERTM (Remaining Useful Life Evaluation Routine) which makes use of cyclic voltammetric techniques. The critical antioxidant concentration of the fluids was determined by comparing the antioxidant concentrations with the increase in acid number and viscosity. Field samples were collected from hydraulic systems of the steel industry. The antioxidant concentration, acid number and viscosity were measured. With the results the remaining useful life of the fluids was estimated. INTRODUCTION Fire resistant fluids, based on biodegradable esters, can degrade or polymerise as a result of oxidation processes. These fluids contain primary oxidation inhibitors like hindered phenols, amino phenols, aliphatic amines and 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 polymerisation reactions. Aminic oxidation inhibitors are active at higher temperatures in comparison to phenolic oxidation inhibitors and a combination of both types act synergistically. Secondary oxidation inhibitors eliminate peroxides, by reaction of ROOH to the harmless ROH, to prevent degradation reactions which lead to the formation of aldehydes and ketones which are easily oxidised into acids. A combination of primary and secondary oxidation inhibitors act synergistically. During use of the fluid the oxidation inhibitors (antioxidants, AO) will be depleted until a certain critical level is reached at which the fluid start to degrade / polymerise at a higher rate. At this point the fluid reached its useful life. In order to estimate the Remaining Useful Life (RUL) of a fluid it is therefore important to know its critical antioxidant concentration.

Presented at the STLE 98 Annual Meeting Detroit

The oxidation stability of two fire resistant hydraulic fluids, which contain different AO packages, was determined in a dry-TOST. The dry-TOST is a laboratory ageing test in which the rate of degradation / polymerisation of the fluid is determined by measuring the increase of acid number and viscosity. 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 commercial available apparatus which make use of cyclic voltammetric techniques (1). Field samples were collected from hydraulic systems of the steel industry. The AO concentration, acid number (AN) and viscosity were measured. With the results the RUL of the fluids was estimated. EXPERIMENTAL Test fluids Two fully formulated fluids (A and B), which are used in the steel and mining industry as fire resistant hydraulic fluids, were aged in a laboratory test. Fluid A and B are ISO 68, polyolester based, hydraulic fluids. Fluid A contains as AO package two different phenols (I and II) and an aromatic amine (I) and fluid B contains an aromatic amine (II) which is different from the one as used in fluid A. Field samples of fluid A, C and D were collected from hydraulic systems of the steel industry. Fluid C is an ISO 46, polyol ester based, hydraulic fluid which contain the same AO package as fluid A. Fluid D is an ISO 46, natural ester based, hydraulic fluid which contain a phenol (III) and an alkylated amine (III) as AO package. Measurement of AO concentration The RULERTM instrument, which make use of cyclic voltammetric techniques, was used for the measurement of AO concentration(s) in fresh fluids, laboratory aged fluids and field samples. The RULERTM instrument consists of a three electrode sensing system; a glassy carbon working electrode, a platinum wire as reference electrode and a platinum wire as auxiliary electrode (1). The samples (200-800 l) are diluted with a solvent containing a dissolved electrolyte. The instrument applies a controlled voltage ramp through the electrode into the prepared solution. As the potential increase, the AO oxidise 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). The peak value(s) and the total peak area of the oxidation peak(s) are stored as RULERTM Number(s) and RULERTM Area. The peak value(s) and peak area indicate the concentration of the AO when compared to a standard reference fluid. The peak value(s) and peak area depends of the type of AO measured and of the composition of 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. The voltage at which an antioxidant oxidise depends upon the used electrolyte and of the composition of the product. When more than one AO is present, overlap may occur between two or more oxidation peaks. In this case the total AO concentration is measured.

Presented at the STLE 98 Annual Meeting Detroit

Laboratory ageing test As laboratory ageing test a dry-TOST was used. The dry-TOST is a modified Turbine Oxidation Stability Test (TOST) in which fluid is aged at a temperature of 95 C, with an oxygen flow of 50 ml/minute, in presence of an iron/copper catalyst. The test was performed according ASTM D 943, except that no water was added to the fluid. During the test period, several samples were taken for analyses. From the samples the AN, viscosity at 40 C and AO concentration(s) were measured. Acid Number The AN was measured as the quantity of base, expressed in milligrams of Potassium Hydroxide per gram of sample (mg KOH/g), required to titrate the dissolved sample (in isopropanol) with 0.5 N KOH to a weakly pink endpoint, using a phenolphthalein indicator solution. Viscosity The kinematic viscosity at 40 C was measured according ASTM D 445. The time was measured in seconds, for a fixed volume of liquid, which flew under gravity through a capillary of a calibrated Cannon Fenske viscometer tube, at a closely controlled temperature of 40 C. The kinematic viscosity was calculated as the product of the measured flow time and the calibration constant of the viscometer tube. RESULTS Measurement of AO concentrations in fluid A and B From fluid A and B laboratory samples were prepared which contain 0, 10, 25, 50, 75, 90 and 100 % relative AO concentrations. These samples were used to check the sensitivity of the RULERTM for the measurement of phenolic and aminic AO. The sample which contained 100 % relative AO concentration was used as reference fluid for the RULERTM . All samples were measured in triplo. The average value of the RULERTM Number or RULERTM Area was used for calculation of the relative AO concentrations. Phenol I and II in fluid A were measured with 800 l of sample in ethanol with inorganic base at a voltage of 0-1.0 V (A mode; 0-11 seconds). Phenol I and II were measured as the total phenol concentration since the oxidation peaks of both phenols showed overlap. In figure 1 a RULER plot is shown of 100 vs. 50 % phenol I + II. The percentage phenol was calculated by comparing the RULERTM number of the first peak of the sample with the RULERTM number of the first peak of the reference. In figure 2 the results of the RULERTM measurements are shown for the total phenol concentration. Aromatic amine I in fluid A was measured with 600 l of sample in acetone/water with neutral salt at a voltage of 0-1.5 V (V mode; 0-17 seconds). In figure 3 a RULERTM plot is shown of 100 vs. 50 % aromatic amine I. The percentage aromatic amine I was calculated by comparing the RULERTM number of the first peak of the sample with the RULERTM number of the first peak of the reference. In figure 4 the results of the RULERTM measurements are shown for the aromatic amine I concentration. Aromatic amine II in fluid B was measured with 400 l of sample in acetone/water with neutral salt at a voltage of 0-1.5 V (V mode; 0-17 seconds). In figure 5 a RULERTM plot is shown of 100 vs. 50 % aromatic amine II. The percentage aromatic amine II was calculated by comparing the RULERTM area of the sample with the RULERTM area of the reference. In figure 6 the results of the RULERTM measurements are shown for the aromatic amine II concentration. Laboratory ageing test results of fluid A and B

Presented at the STLE 98 Annual Meeting Detroit

Fluid A and B were aged in a dry-TOST. Samples were taken at several time intervals for analyses. The percentage remaining phenol and/or aromatic amine in the samples was measured with the RULERTM and compared to the measured AN and viscosity. The results are given in figure 7 for fluid A and in figure 8 for fluid B. In the dry-TOST the useful life of the fluid is defined as the time in hours it takes to reach an AN increase of 2 mg KOH/g. Fluid A showed at its useful life a total phenol concentration of 10 % and an aromatic amine I concentration of 12 %. Fluid B showed at its useful life an aromatic amine II concentration of 20 %. These AO concentrations were taken for the dry-TOST as the critical AO concentrations for fluid A and B. RUL determination of field samples The useful life of a fluid depends of the hydraulic system in which it is used. Parameters which have influence on the useful life are; fluid bulk temperature; presence of hot spots; fluid leakage / addition of fresh fluid; contamination level and water content of the fluid. With the use of trend analysis the useful life of a fluid for a certain system can be determined. Based on years of practical experience it is known that fluid A and C reach the end of their useful life when the AN increase is 4-6 mg KOH/g and fluid D when the AN increase is 3-5 mg KOH/g. Several field samples of fluid A, C and D were collected from hydraulic systems of the steel industry. From fluid B no field samples were available. The phenolic and/or aminic AO concentrations of the samples were measured with the RULERTM . The phenols were measured in ethanol with inorganic base and the amines were measured in acetone water with neutral salt. From fluid D the aminic AO concentration could not be measured since the oxidation peak showed overlap with the oxidation peak of the phenolic AO. The measured AO concentrations were compared with the change in AN and viscosity at 40 C. The results are given in table 1. Since the useful life of a fluid is dependent of the hydraulic system in which it is used the RUL has to be estimated in relation to the system. The RUL is expressed as the ratio between the RUL and the useful life, e.g. the RUL is 1/4 when 3/4 of the useful life is passed. Based on the measured AN, viscosity and AO concentrations, the RUL of the fluid for each system was estimated. The results are given in table 1. In order to estimate the RUL more accurate, trend analysis of the AO concentration(s) of field samples will be very helpful but these results were not available yet at the moment this paper was writen. Fluid A in system 6 reached its useful life (AN increase of 5 mg KOH/g). The total phenol concentration of the fluid decreased to 62 % and the aromatic amine concentration decreased to 84 %. The critical AO concentrations as found for fluid A in the dry-TOST were 10 % (AN increase of 2 mg KOH/g). From these results it can be concluded that the ratio of the AN increase vs. the AO depletion in laboratory aged fluids is different compared to that of field samples. The critical AO concentration(s) as determined in the dry-TOST should therefore not be used to estimate the RUL of field samples.

Presented at the STLE 98 Annual Meeting Detroit

Fluid D in system 12, which exceeded its useful life, was for 50 % replaced with fresh fluid. After homogenisation the fluid was analysed again. The RULERTM plots (see figure 9a and 9b) showed two oxidation peaks. The first peak was identified as phenol III, the second peak indicated the presence of degradation product(s). After refreshment, the phenol concentration increased from 30 % to 60 % and the degradation product(s) almost disappeared. However, since the fluid still showed an AN increase of 3 mg KOH/g the estimated RUL is very limited. Acids catalyse the oxidation processes and the AN increase vs. AO depletion in system 12 will therefore proceed at a high rate. In this case, it would have been more cost effective to refresh the total system. Table 1. Phenol and/or amine concentrations compared to change in AN and viscosity at 40 C of field samples. System Fluid AN change Visc.change Phenol Amine RUL (mg KOH/g) (mm2/s) (%) (%) 1 A 0 0 101 1 2 A 0 -3 103 100 1 3 A +1 -5 96 103 1 1 4 A +3 0 82 99 /2 1 5 A +3 0 76 79 /4 6 A +5 0 62 84 0 1 7 C +2 -6 76 99 /2 8 C +7 1 0 50 0 1 9 D 0 +2 74 /2 1 10 D +2 +4 54 /8 11 D +4 +11 55 0 12 D +7 +13 30 0 13 D +8 +13 39 0 CONCLUSIONS The RULERTM is a quick method which is able to measure the total phenolic and/or aminic AO concentrations in ester based hydraulic fluids. The sensitivity of the RULERTM for the measurement of the relative AO concentration(s) in laboratory prepared samples was 2-7 % and depended of the type of AO and type of fluid measured. The RULERTM was successfully used for the determination of the critical AO concentrations in laboratory aged hydraulic fluids. The critical AO concentration for laboratory aged fluids can not be used to estimate the RUL of field samples. The RUL of field samples can be estimated by comparing the AO concentration(s) with the increase of acid number and viscosity at 40 C. Trend analyses of AO concentrations will give improved knowledge regarding the RUL of field samples. ACKNOWLEDGMENTS

Presented at the STLE 98 Annual Meeting Detroit

The author thanks J. Ameije, of Fluitec, for giving directions for the RULERTM measurements and S. Schellings and M. Raaphorst, of the authors laboratory, for carrying out the analysis. REFERENCES (1) Kaufmann R.E., Remaining Useful Life Measurements of Diesel Engine Oils, Automotive Engine Oils, Hydraulic Fluids, and Greases Using Cyclic Voltammetric Methods, Lubr. Eng. 51, 3, pp 223-229 (1995). (2) Herguth W.R., Philips S, Comparison of common analytical techniques to voltammetric analysis of antioxidants in industrial lubricating oils, Herguth laboratories, Vallejo, CA 94590. (3) Kaufmann R.E., On-Line and Off-Line Techniques for Monitoring the Thermal and Oxidative Degradation of Aircraft Turbine Engine Oils - Part I: Laboratory Evaluations, Lubr. Eng., 51, 11, pp 914-920 (1995). (3) Kaufmann R.E., Rapid, Portable Voltammetric Techniques for Performing Antioxidant, Total Acid Number (TAN) and Total Base Number (TBN) Measurements, Lubr. Eng., 54, 1, pp 39-46 (1998).

Presented at the STLE 98 Annual Meeting Detroit

100 100 90 80 70 60 50 40 30 20 10 0 82 86

RULER %

51 27 12 0 0 10 25 50 75 90 83 74 50 26 15 1 0 10 25 50 75 90 100 100 100

% total phenols

Figure 1. RULERTM plot of fluid A; 100 vs. 50 % of phenol I + II

Figure 2. RULERTM measurements of fluid A; phenol I + II concentration

100 90 80 70 60 50 40 30 20 10 0

RULER %

% aromatic amine

Figure 3. RULERTM plot of fluid A; 100 vs. 50 % aromatic amine I

Figure 4. RULERTM measurements of fluid A; aromatic amine I concentration


100 100 90 80 70 60 50 40 30 20 10 0 88 77 53 27 12 0 0 10 25 50 75 90 100

RULER %

% aromatic amine II

Figure 5. RULERTM plot of fluid B; 100 vs. 50 % of aromatic amine II

Figure 6. RULERTM measurements of fluid B; aromatic amine II concentration

Presented at the STLE 98 Annual Meeting Detroit

AO (%) and Viscosity 40C (mm/s)

100 90 80 70 60 65 50 40 30 20 10 1.4 0 0

6.0 AN (mg KOH/g) 5.0 75 3.3 4.0 3.0 2.0 12 10 24 48 72 96 120 144 168 192 216 1.0 0.0 240

Viscosity Amine Phenol AN

Ageing time dry-TOST (hours)

Figure 7. % phenol I + II and aromatic amine I, AN (mg KOH/g) and viscosity at 40C (mm2/s) vs. dry-TOST test hours of fluid A.
AO (%) and Viscosity 40C (mm/s)

100 90 80 70 60 69 50 40 30 1.3 20 10 0 0 48 96 144 192 240

4.0 3.3 3.5 3.0 69 2.5 2.0 1.5 20 1.0 0.5 0.0 288 336 384 AN (mg KOH/g) Viscosity Amine AN

Ageing time dry-TOST (hours)

AO (%) and Viscosity 40C (mm/s)

100 90 80 63 70 69 60 52 50 40 1.7 30 1.3 20 10 0 0 48

4.0 3.5 3.3 69 3.0 2.5 2.0 1.5 1.0 20 96 144 192 240 288 336 0.5 0.0 384 AN (mg KOH/g) Viscosity Amine AN

Ageing time dry-TOST (hours)

100 90 80 70 60 69 50 40 30 1.3 20 10 0 0

AO (%) and Viscosity 40C (mm/s)

4.0 3.5 63 69 52 1.7 3.0 2.5 2.0 1.5 1.0 20 48 96 144 192 240 288 336 0.5 0.0 384 AN (mg KOH/g) 3.3

Viscosity Amine AN

Ageing time dry-TOST (hours)

Figure 8. % aromatic amine II, AN (mg KOH/g) and viscosity at 40C (mm2/s) vs. dry-TOST test hours of fluid B.

Figure 9a System 12 before refreshment: Phenol concentration 30 %, AN increase +7 mg KOH/g, Visc. increase +13 mm2/s.

Figure 9b System 12 after 50 % refreshment: Phenol concentration 59 %, AN increase +3 mg KOH/g, Visc. increase +10 mm2/s.

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