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VARIANINSTRUMENTS
AT WORK
ATOMIC ABSORPTION
Atomic AbsorptionSpectrophotometry for the Analysisof Wear Metals
in Oil Samples
Trevor McKenzie, Varian Techtron Pty. Limited,Mulgrave, Victoria, Australia.
AA-10January 1981
Table 1
Scope
This article outlines the procedures required for thedetermination of wear metals in oils. Samplingprocedures, sample preparation and atomicabsorption instrumentation requirements arediscussed with the view of implementing a viableSpectrometric 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 andSb, Be, Cd, Cr, Co, Mn, M
O
, Mi and V using the Carbon
Rod Atomizer have been listed in the accompanyingbibliography.
Introduction
Flame atomic absorption spectrophotometry hasbeen used extensively for a number of years to studytrace wear metals in used engine oil (1-5). Theinvestigation of trace metals in engine oil haspermitted the identification of wearing componentsbefore severe failure, without dismantling of theengine. Thus preventive maintenance can beperformed as needed and when convenient resultingin considerable cost savings and reduced down time.Spectrometric Oil Analysis Programs (SOAP) havebeen implemented by the Armed Services,Commercial Airlines, Railways, TractorManufacturers and large trucking firms as adiagnostic tool to monitor engine wear.In a spectrometric oil analysis program, the oil mustbe sampled at regular intervals under strict samplingconditions. 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 theconcentration of a particular metal, or the suddenappearance of a metal. Since different enginecomponents are composed of different alloys, theincrease of a particular metal can be used to identifyimpending failure of a specific component. Anincrease in chromium, for example, might suggestpiston wear, while an increase in copper may indicatebearing wear. An increase in silicon content couldsuggest improper air filtering leading to the entry ofabrasive dust into the engine. A list of metals found inaircraft engine oil and their origin is given in Table 1(81,76,82).
Metals Analyzed in Lubricating Oilsand Areas Associated with Possible TroubleElementPossible Trouble Areas
Aluminium
Alpistons (aircraft engines),
bearings (AI-Sm), push rods,air cooler, pump housings, oilpumps, gear casings, box
castings (aircraft)Antimony
Sb
Boron
BCadmium
CdChromiumCr
Copper
CuIron
Fe
LeadPb
MolybdenumM
O
NickelMagnesiumSiliconSilverSodiumTinTitaniumTungstenZinc
Ni
MgSiAg
Na
Sn
Ti
WZn
crankshaft and camshaftbearingscoolant leaksbearingscylinder liners, piston rings,alloyed steel, coolant leaks,seal rings (jet engines), platingon 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, bearingretainers; alloyed with Cu, Tipiston ringsplatings, engine valves;alloyed with bearing steelengine casing (jet engines),additive in oil, transmissionfluid, and certain syntheticfluidsair-borne dust, siliconlubricant (jet engines), sealmaterialsplatings (aircraft engines).bearings, piping (silversoldered), bearing cages (jet
engines)
coolant leaks (salt water,borax inhibitors) journal bearings, bearingcages, and retainerscasings (aircraft)bearing metalneprene seals, additives,galvanized piping; alloyed with
Cu, Al
 
Sample Collection
A wear metals program relies upon knowing thehistory of a particular engine. This history isdetermined by the analysis of five homogeneous andrepresentative oil samples, sampled at regular timeintervals. (It is upon these samples the criteria forwear is determined). The metal content in thesamples can be variable in amount and compositiondepending upon the engine’s alloy make up,components and age. A typical engine’s iron contentin oil with age is given in Figure 1.
Sample Preparation
There are three sample preparation methodspresently being employed prior to determination of
metals by flame atomic absorption: —
(a) Dilution of the oil sample in an organic solventsuch as Xylene or methyl isobutylketone (MIBK)followed by direct aspiration or injection into the
flame.
(b) Total acid digestion or ashing of the oil sampleand dissolution with an appropriate acid.(c) Filtration of the oil sample and digestion of theretained particulate matter by an acid such ashydrochloric acid.Each method of sample preparation has advantagesand disadvantages and the choice depends on therequirements of the wear metals program.The dissolution of the oil sample in an organic solventand comparison with a known set of organometallicstandards made up in the organic solvent is simpleand fast. However the method has been shown not tomeasure the total metal content since not all theparticulate metal aspirated is atomized (5). Theorganic solvent acts as combustible fuel which candisturb the flame conditions. Disruption of flameconditions can, however, be reduced by using anadjustable uptake nebulizer and flame microsamplingtechniques (80).Sample treatment by ashing is very time-consumingand although total metal content for iron, copper andchromium are determined accurately, volatile metalssuch as lead are lost during the ashing process.Filtration through a membrane filter (0.8 µm or 0.45µm) and digestion of the filter and particulates by anacid such as hydrochloric acid is also timeconsuming. A strong vacuum pump and heating of theoil sample is required to ensure that a large enoughsample is filtered for determination.Both the ashing and filtration methods permitaqueous standards to be used for calibration, but ifsulphuric and phosphoric acid are used duringsample treatment, a standard addition method or a setof matched matrix standards incorporating theseacids is required for calibration. The greatestdisadvantage to the filtration and ashing methods isthat they rely heavily upon strict sampling programs.The particulate metal will settle out very quickly fromoil and any deviation from the sampling program cangive anomalous results.
Figure 1
During the normal operation period there is very littlechange in metal content and, in order to gain reliableresults, strict sampling procedures are necessary.The following points should be considered whenimplementing a sampling program.1. The sample should be taken when the engine iswarm (normal running temperature) and from thesame location within the engine in order to obtain arepresentative sample. The method of samplingand sampling device may vary from engine toengine depending on design. A syringe with apiece of tubing of a length that will give a specificposition within the engine when inserted into thedip stick port would be adequate. A stainless steelsampling device of this type has been shown not tomarkedly affect the iron content of an oil sampleduring sampling. However, ensure that the probetubing does not come into contact with any movingparts of the engine when the sampling device isfully inserted.2. Any oil changes or top up additions of oil, togetherwith the amounts and the dates, should be listed ina log. This is extremely important for thecalculation of the metal content in the sample anddetermining a reliable history.3. The sample frequency relies on the expectedlifetime of the components; an increase in samplefrequency being implemented on approaching ofthe wear out period.4. In most cases a 20 mL sample is adequate foranalysis.2
 
A. Direct Aspiration of an Oil SampleDiluted
in an Organic Solvent
Dissolution of the oil sample and its direct aspirationis the most easily implemented and universally usedprocedure in Spectrometric Oil Analysis Programs.This section outlines the sample preparation andinstrumental 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 inan organic solvent.In our laboratory studies we determined Al, Fe, Cr, Cuand Si in a sample of used oil from a Bulldozer(SE30CD). The results of these studies are includedhere to illustrate the instrumental requirements andoperating conditions needed for fast, reliable routineSpectrometric Oils Analysis Programs.
Apparatus, Materials and Reagents
Instrument:Double Beam Atomic AbsorptionSpectrophotometer fitted withbackground correction (AA-475BD)Shaker:A shaking machine which canvigorously agitate the sample to ensurethat all particulate matter ishomogeneously distributed through the
oil sample.Oven:
Cable of heating sample to 60°C withinits sample container.
Glassware:
Assorted glassware, measuringcylinders 50 mL, 100 mL, syringes (10mL), standard flasks, adjustable diluter.Balance:
Having sensitivity of 0.1 g
Standards
A stock standard can be prepared fromorganometallic powders containing analyte metals in
an unused oil sample or can be obtained as a
convenient stock standard made up in oil. A set ofstandards over the required analytical range can beeasily prepared by appropriate dilution of the stockstandards. A list of suppliers is included in thebibliography (70-73).When preparing standards the following points mustbe considered.1. Viscosity of the standards and the samples are tobe matched. This can be achieved by adding therequired amount of blank oil to the standards.2. 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 thereforenecessary to quote the method and solvent usedas 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 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 dilutionwas used. The concentration of metals in ppm in themultiple standard are listed in Table 2.
Table 2
Metallo-Organic StandardsNational Spectrographic Laboratories, IncMultiple standard made up in oil in parts per million
(ppm)
MetalStandard 1Standard 2Standard 3Cu2552102
Fe
2548
103
Al
24
51
98Si
2451100Cr
51030
Sample: Used engine oil SE30CD from a bulldozer3. The analytical zero is established against a blankmade up from unused oil in accordance with thesample preparation procedure.4. Ideally, the standards and sample should give a
response between 0.1 and 0.8 Abs. This can
normally be achieved by appropriate dilution andby selecting a wavelength for the element thatcorresponds with the response and requiredconcentration range. However, this is not alwaysfeasible in fast routine analysis where matchedviscosities play a more important role. In manycases the burner position may have to be changedor 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 thedensity of the diluting organic solvent is known.
Table 3
List of Analytical Working Ranges of Metals
ElementAnalytical
Wave-
Comments
Working Range
lengthmg/kg
nmAg
0-10
328.1
Burner RotationAl0-60
309.2Cr
0-8357.910-40
425.4
25-100428.9Cu0-8
324.7
6-25
327.4
15-60
217.9
20-80
218.2Fe
0-10248.325-100372.0Mg0-1285.2Burner Rotation5-20
202.5
Na
0-2589.6Burner RotationNi0-12232.015-60341.515-60
352.4
35-140
351.5
Pb
0-20217.010-40283.0Si5-400
251.6
Sn0-200235.5Ti0-350364.3
Zn
0-2
398.8Burner Rotation
5. Where standards are made up from oil-solubleorganometallic powders it is necessary to dry thepowder over phosphorus pentoxide for 48 hoursbefore making up the standard.6. If the standards are to be stored for any lengthyperiod, a stabilizer which can be obtained from themanufacturer of the standards has to be added tothe standard.3
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