Atomic Absorption Spectrophotometry for the Analysis of Wear Metals in Oil Samples

Application Note
Atomic Absorption

Authors
Trevor McKenzie

Scope
This article outlines the procedures required for the determination of wear metals in oils. Sampling procedures, sample preparation and atomic absorption instrumentation requirements are discussed with the view of implementing a viable Spectrometric Oil Analysis Program (SOAP). Particular consideration is given to the determination of Al, Cr, Cu, Fe, Mg, Na, Ni, Pb, Si, Sn, Zn and Ti using flame atomic absorption spectroscopy. Comprehensive methods for the trace metals analysis of As, Se and Hg by vapor generation techniques and Sb, Be, Cd, Cr, Co, Mn, MO, Mi and V using the Carbon Rod Atomizer have been listed in the accompanying bibliography.

Introduction
Flame atomic absorption spectrophotometry has been used extensively for a number of years to study trace wear metals in used engine oil [15]. The investigation of trace metals in engine oil has permitted the identification of wearing components before severe failure, without dismantling of the engine. Thus preventive maintenance can be performed as needed and when convenient resulting in considerable cost savings and reduced down time. Spectrometric Oil Analysis Programs (SOAP) have been implemented by the Armed Services, Commercial Airlines, Railways, Tractor Manufacturers and large trucking firms as a diagnostic tool to monitor engine wear. In a spectrometric oil analysis program, the oil must be sampled at regular intervals under strict sampling conditions. This program permits the observation of trends in the metal content of the oil. Wear of a specific component is heralded by an increase in the concentration of a particular metal, or the sudden appearance of a metal. Since different engine components are composed of different alloys, the increase of a particular metal can be used to identify impending failure of a specific

component. An increase in chromium, for example, might suggest piston wear, while an increase in copper may indicate bearing wear. An increase in silicon content could suggest improper air filtering leading to the entry of abrasive dust into the engine. A list of metals found in aircraft engine oil and their origin is given in Table 1 [81,76,82].
Table 1. Metals Analyzed in Lubricating Oils and Areas Associated with Possible Trouble Possible trouble areas Al pistons (aircraft engines), bearings (AI-Sm), push rods, air cooler, pump housings, oil pumps, gear casings, box castings (aircraft) crankshaft and camshaft bearings coolant leaks bearings cylinder liners, piston rings, alloyed steel, coolant leaks, seal rings (jet engines), plating on compression rings, chromate (cooling system) bearings, bushes, (Cu-Pb-Sn). sleeves, bearing cages, coolant core tubes, valve guides, thrust washers; alloyed with S, Ti piston rings, ball and roller bearings, gears, pump gears, cylinder liners, valve guides, rust bearings (Pb-Sn, Cu-Pb-Al), thrust bearings (Cu-Pb), bearing cages, bearing retainers; alloyed with Cu, Ti piston rings platings, engine valves; alloyed with bearing steel engine casing (jet engines), additive in oil, transmission fluid, and certain synthetic fluids air-borne dust, silicon lubricant (jet engines), seal materials platings (aircraft engines). bearings, piping (silver soldered), bearing cages (jet engines) coolant leaks (salt water, borax inhibitors) journal bearings, bearing cages, and retainers casings (aircraft) bearing metal neprene seals, additives, galvanized piping; alloyed with Cu, Al Figure 1.

Element Aluminium

Antimony Boron Cadmium Chromium

Sb B Cd Cr

Copper

Cu

During the normal operation period there is very little change in metal content and, in order to gain reliable results, strict sampling procedures are necessary. The following points should be considered when implementing a sampling program. The sample should be taken when the engine is warm (normal running temperature) and from the same location within the engine in order to obtain a representative sample. The method of sampling and sampling device may vary from engine to engine depending on design. A syringe with a piece of tubing of a length that will give a specific position within the engine when inserted into the dip stick port would be adequate. A stainless steel sampling device of this type has been shown not to markedly affect the iron content of an oil sample during sampling. However, ensure that the probe tubing does not come into contact with any moving parts of the engine when the sampling device is fully inserted. Any oil changes or top up additions of oil, together with the amounts and the dates, should be listed in a log. This is extremely important for the calculation of the metal content in the sample and determining a reliable history. The sample frequency relies on the expected lifetime of the components; an increase in sample frequency being implemented on approaching of the wear out period. In most cases a 20 mL sample is adequate for analysis.

Iron Lead

Fe Pb

Molybdenum MO Nickel Magnesium Silicon Silver Sodium Tin Titanium Tungsten Zinc Ni Mg Si Ag Na Sn Ti W Zn

Sample Collection
A wear metals program relies upon knowing the history of a particular engine. This history is determined by the analysis of five homogeneous and representative oil samples, sampled at regular time intervals. (It is upon these samples the criteria for wear is determined). The metal content in the samples can be variable in amount and composition depending upon the engines alloy make up, components and age. A typical engines iron content in oil with age is given in Figure 1.

Sample Preparation
There are three sample preparation methods presently being employed prior to determination of metals by flame atomic absorption: Dilution of the oil sample in an organic solvent such as Xylene or methyl isobutylketone (MIBK) followed by direct aspiration or injection into the flame. Total acid digestion or ashing of the oil sample and dissolution with an appropriate acid. Filtration of the oil sample and digestion of the retained particulate matter by an acid such as hydrochloric acid.

Direct Aspiration of an Oil Sample Diluted in an Organic Solvent

Dissolution of the oil sample and its direct aspiration is the most easily implemented and universally used procedure in Spectrometric Oil Analysis Programs. This section outlines the sample preparation and instrumental conditions for the analysis of the metals Ag, Al, Cr, Cu, Fe, Mg, Na, Ni, Pb, Si, Ti and Zn using flame atomic absorption for oil samples dissolved in an organic solvent. In our laboratory studies we determined Al, Fe, Cr, Cu and Si in a sample of used oil from a Bulldozer (SE30CD). The results of these studies are included here to illustrate the instrumental requirements and operating conditions needed for fast, reliable routine Spectrometric Oils Analysis Programs.

Each method of sample preparation has advantages and disadvantages and the choice depends on the requirements of the wear metals program. The dissolution of the oil sample in an organic solvent and comparison with a known set of organometallic standards made up in the organic solvent is simple and fast. However the method has been shown not to measure the total metal content since not all the particulate metal aspirated is atomized [5]. The organic solvent acts as combustible fuel which can disturb the flame conditions. Disruption of flame conditions can, however, be reduced by using an adjustable uptake nebulizer and flame microsampling techniques [80]. Sample treatment by ashing is very time-consuming and although total metal content for iron, copper and chromium are determined accurately, volatile metals such as lead are lost during the ashing process. Filtration through a membrane filter (0.8 m or 0.45 m) and digestion of the filter and particulates by an acid such as hydrochloric acid is also time consuming. A strong vacuum pump and heating of the oil sample is required to ensure that a large enough sample is filtered for determination. Both the ashing and filtration methods permit aqueous standards to be used for calibration, but if sulphuric and phosphoric acid are used during sample treatment, a standard addition method or a set of matched matrix standards incorporating these acids is required for calibration. The greatest disadvantage to the filtration and ashing methods is that they rely heavily upon strict sampling programs. The particulate metal will settle out very quickly from oil and any deviation from the sampling program can give anomalous results.

Apparatus, Materials and Reagents

Instrument Shaker Double Beam Atomic Absorption Spectrophotometer fitted with background correction (AA-475BD) A shaking machine which can vigorously agitate the sample to ensure that all particulate matter is homogeneously distributed through the oil sample. Cable of heating sample to 60 C within its sample container. Assorted glassware, measuring cylinders 50 mL, 100 mL, syringes (10 mL), standard flasks, adjustable diluter. Having sensitivity of 0.1 g

Oven Glassware Balance

Standards
A stock standard can be prepared from organometallic powders containing analyte metals in an unused oil sample or can be obtained as a convenient stock standard made up in oil. A set of standards over the required analytical range can be easily prepared by appropriate dilution of the stock standards. A list of suppliers is included in the bibliography [70-73]. When preparing standards the following points must be considered. Viscosity of the standards and the samples are to be matched. This can be achieved by adding the required amount of blank oil to the standards. The standards can be prepared on a weight per weight, weight per volume, or volume per volume basis in the chosen organic solvent. It is therefore necessary to quote the method and solvent used as the concentration units are not equivalent to each other. In our laboratory study the standards were prepared from a multiple standard containing Fe, Si, Al, Cr and Cu and
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diluted in Xylene on a volume per volume basis. The viscosity of the sample and standards on dilution were found to be similar when a 1:4 dilution was used. The concentration of metals in ppm in the multiple standard are listed in Table 2.
Table 2. Metallo-Organic Standards National Spectrographic Laboratories, Inc Multiple standard made up in oil in parts per million (ppm) Standard 1 Standard 2 Standard 3 102 103 98 100 30

Table 3.

List of Analytical Working Ranges of Metals Analytical working range mg/kg 010 060 08 1040 25100 08 625 1560 2080 010 25100 01 520 02 012 1560 1560 35140 020 1040 5400 0200 0350 02 Wavelength nm 328.1 309.2 357.9 425.4 428.9 324.7 327.4 217.9 218.2 248.3 372.0 285.2 202.5 589.6 232.0 341.5 352.4 351.5 217.0 283.0 251.6 235.5 364.3 398.8

Element Ag Al Cr

Comments Burner Rotation

Metal

Cu

Cu 25 52 Fe 25 48 Al 24 51 Si 24 51 Cr 5 10 Sample: Used engine oil SE30CD from a bulldozer

Fe Mg Na Ni

BurnerRotation BurnerRotation

The analytical zero is established against a blank made up from unused oil in accordance with the sample preparation procedure. Ideally, the standards and sample should give a response between 0.1 and 0.8 Abs. This can normally be achieved by appropriate dilution and by selecting a wavelength for the element that corresponds with the response and required concentration range. However, this is not always feasible in fast routine analysis where matched viscosities play a more important role. In many cases the burner position may have to be changed or the nebulizer adjusted to achieve the required response of the sample and standards. Table 3 lists on a weight for weight basis the analytical working ranges for the metals Ag, Al, Cr, Cu, Fe, Mg, Na, Ni, Pb, Si, Sn, Ti and Zn. Conversion to other concentration units can be easily determined if the density of the diluting organic solvent is known. Where standards are made up from oil-soluble organometallic powders it is necessary to dry the powder over phosphorus pentoxide for 48 hours before making up the standard. If the standards are to be stored for any lengthy period, a stabilizer which can be obtained from the manufacturer of the standards has to be added to the standard. Where high levels of accuracy and precision are required, a standard addition method is recommended. However, a standard addition method is time consuming, requires an accurately prepared blank and the calibration must be linear over the analytical working range. Details of the standard addition method are given in Analytical Methods for Flame Spectroscopy by Varian Techtron, 1971.

Pb Si Sn Ti Zn

Burner Rotation

Organic Solvents
A number of organic solvents have been used for diluting oil samples for the determination of wear metals in oil. The most common solvents presently used are 4-methyl-pentan-2-one (MIBK), m-Xylene and cyclohexanone. A more comprehensive list of organic solvents for use in atomic absorption listing Flash Point, Boiling Point and Specific Gravity is presented in Varians AA at Work AA-6 Safety Practices using Organic Solvents in Flame Atomic Absorption Spectroscopy [20]. The procedures presented in publication AA-6 are to be strictly followed when operating Agilent atomic absorption spectrophotometers. Data regarding organic solvents can normally be obtained from the manufacturers or other technical publications [77,78].

Instrumental Requirements
There are a variety of atomic absorption spectrophotometers available. The most suitable instrument for implementation of a routine wear metals program using the dissolution of the sample in an organic solvent method is a double beam, background corrected atomic absorption spectrophotometer. A single beam atomic absorption instrument does not accommodate inconveniences arising from drift in the light source and flame absorption arising from aspiration of an organic solvent.
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Background Correction
Background Correction can be used to reduce errors that may arise from flame absorption. Figure 2 using Fe standard 1 (Table 2) shows that the flame with no background correction absorbs at the wavelength at which Fe is determined. Although the analytical zero can be set using the blank reagent, a negative digital value results after removal of the sample. This can often be disconcerting when a large number of results are required. The background correction will also compensate for particulate matter that may be aspirated, thus a more accurate measurement of the soluble fraction will be gained. Elimination of Flame Absorption resulting from Aspiration of the Organic Solvent in the Analysis of Iron at 248.3 nm in Xylene.

Double Beam
During a wear metals analysis at low absorbance levels (<0.1 abs), baseline drift resulting from lamp fluctuations can cause significant errors. To overcome drift in the single beam mode constant zeroing of the instrument using a blank must be carried out. This can be inconvenient, especially in a long program, and can be overcome by using the double beam mode. Figure 3 shows a comparison between double beam and single beam for Cr using standard 1 (Table 2). Drift of 20% is observed over an eight minute period using single beam while none is observed over the same period using double beam. Elimination of drift arising in the light source by using a double beam system for determining Cr in Xylene Standard 1.

Adjustable Nebulizer
The aspiration of an organic solvent changes the fuel conditions in the flame. By reducing the uptake rate the disturbances occuring in the flame can be minimized. Figure 4 shows that while maximum sensitivity for iron in MIBK is obtained at 6 mL/min uptake, the solvent uptake rate may be reduced by a factor of two for a loss of only 10% in response. Figure 5 shows that a more linear calibration is obtained at lower uptake rates.

Figure 2.

A single beam instrument can be used but constant zeroing using the analytical blank is required and this, apart from being an encumbrance to the operator, will extend the time of the analysis.

Figure 4.

Figure 3.

Table 4 shows the experimental conditions used in our laboratory.

Table 4. Wavelength Sht Lamp nm nm current Cu 324.8 Fe 248.3 Cr 357.9 Al 309.3 Si 251.6 0.5 0.2 0.5 1.0 1.0 3 5 5 10 20 Nebulizer uptake rate mL/min Flame 3.0 3.0 3.0 3.5 3.5 Air/C2H2 Air C2H2 Air C2H2 N2O/C2H2 N2O/C2H2 Measurement time (sec) Mode 6 6 6 6 6 Conc.

Figure 5.

Operating Conditions.

Sample Preparation for Dilution of Oil and Organic Solvent Procedure

The oil sample (20 mL or 20 g) is diluted with the appropriate organic solvent to a total of either 100 mL or 100 g and aspirated into the flame of the atomic absorption spectrophotometer. In our study the oil sample (20 mL) and the multiple standards were diluted in Xylene (1:4, oil:Xylene, v/v). Other dilution ratios may be required depending on the metal content of the sample. It is important that the standards are matched to similar viscosities, especially if the dilution ratio is less than 1:4. The results of this study are listed in Table 5 while Figures 6 and 7 show typical recorder traces for iron and aluminium determined in a bulldozer oil.
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The instrumental conditions for the elements listed in Table 2 can be obtained from Analytical Methods for Spectroscopy by Varian Techtron Ply. Ltd.

Calibration and Measurement

The concentration mode (CONC) permitted the direct entry of standard values and a direct reading of the sample concentration on the digital display. All measurements carried out in our analysis used double beam and background correction. The absorbance of the standards and sample were monitored on a chart recorder and the measurements taken after 4 seconds aspiration when the absorbance signal stabilized.
Table 5. Results of Laboratory Study Metal Cu Fe Al Si Cr Concentration ppm 1.91 14.1 6.9 5.4 1.6

Because the samples and standards were diluted to the same degree there was no need to change the concentration values of the standards entered into the instrument. This permitted the direct readout of the sample concentration. The concentration of the metal in the diluted sample as a result of dilution was 0.2 of the values quoted in Table 5 and Figures 6 and 7.

Flame Microsampling
As previously mentioned, the aspiration of large quantities of organic solvent can cause large disturbances within the flame. Where this disturbance is excessive, or when several elements are to be determined from a very small sample volume, flame microsampling can be used. Flame microsampling can be achieved by the injection of a small aliquot (50200 L) into the flame via a small teflon cup attached to the polyethylene capillary which is connected to the nebulizer. The precision for ten injections of a similar concentration is better than 2% RSD as shown in Figure 9. Flame microsampling determines the iron content in wear metal to be 14.3 ppm which compares favorably with the direct aspiration of the sample shown in Figure 6.
Figure 6. Iron in wear metal sample diluted with xylene.

Figure 7.

Aluminium in wear metal sample diluted with xylene.

The oil sample (2 g) was treated with concentrated sulphuric acid (2 g) and heated on a hot plate until dry in a Vycor crucible. The crucible was transferred to a muffle furnace and ashed at 550 C until all traces of carbon were removed. This was indicated by the absence of a charcoal colour and took about 30 minutes. After cooling the sample was treated with concentrated hydrochloric acid (6 mL) and filtered through a Whatman 541 filter paper. The solution was then made up to 25 mL with distilled water and its absorbance compared to a set of matched aqueous iron standards. In cases where matrix matching is not possible, a standard addition method is recommended. Many interferences from the formation of refactory compounds in air/acetylene can be overcome by using a nitrous oxide/acetylene flame.

Conclusions
A modern double beam, background corrected atomic absorption spectrophotometer permits direct reading of sample concentration, is simple in operation and allows routine on-site analysis for Spectrometric Oil Analysis Programs.

Figure 8.

Iron in xylene.

References
Determination of Metals in Oils
The references are arranged into the following four sections: General Flame Methods 141 Carbon Rod Atomization Methods 4263 Organic Matrix Digestion Procedures 6469 Suppliers of Metallo-organic standards 7075

Figure 9.

Response of standard 3 iron in xylene.

Ashing of Oil Samples

The procedure for ashing oils is based upon the method by Milner Glass, Kirchner and Yurick [79]. The sample volume for decomposition will be determined by concentration of the metals of analytical interest in the sample. The analytical procedure for the analysis of iron used in our laboratory is as follows.

A comprehensive text for the determination of trace metals in petroleum is presented in reference 40 and was prepared from papers presented at the symposium Analysis of Petroleum for Trace Metals held at the 169th National Meeting of the American Chemical Society. Listed in the publication are methods developed by five petroleum companies for 13 elements of environmental interest (As, Be, Cd, Cr, Co, Pb, Mn, HG, MO, Ni,V, Se, Sb) using vapor generation, flame and the carbon rod atomizer. The methods are well documented and easy to implement and extensively referenced. Annual Reports on Analytical Atomic Spectroscopy (reference 24) which has been published since 1971, contains a section on Petroleum and Petroleum Products and should be consulted for recent developments in the analysis of Petroleum Products.

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