APPLICATION NOTE 44426
Lubricating oil analysis according to ASTM D5185
using the Thermo Scientific iCAP PRO XP ICP-OES
Author Introduction
Sanja Asendorf, The cost of unscheduled maintenance of engines and machinery can be
Application Specialist, high, not only in materials and labor, but also in lost profits due to downtime.
Thermo Fisher Scientific, Therefor the analysis of used lubricating oil for wear metals, contaminants
Bremen, Germany and additive elements is a valuable diagnostic tool to schedule preventative
maintenance. Once the oil has been sampled, analysis by ICP-OES is very
Keywords useful for aiding with maintenance scheduling, basing decisions on the results
Additives, Contaminants, of analysis. The high temperature source of an ICP-OES, which dissociates
Used oil, Wear metals any organometallic compounds and also its ability to handle difficult organic
solvent matrices makes the ICP-OES an ideal technique. This allows the oil to
be directly aspirated into the instrument after a simple dilution, negating the
Goal need for any time consuming digestion sample preparations and consequently
This application note describes enabling faster turnaround times.
the analysis of lubrication
oils in accordance with
standard test method ASTM
D5185 for “Determination
of Additive Elements, Wear
Metals, and Contaminants
in Used Lubricating Oils and
Determination of Selected
Elements in Base Oils by
ICP-OES”.
Standard method ASTM D5185 Sample and standard preparation
Scope Prior to any sample or stock standard being diluted, it
The standard method ASTM D5185 is for “Determination was homogenized by sonication. For very viscous oils,
of Additive Elements, Wear Metals, and Contaminants the sample can be pre-heated to 60 ˚C.
in Used Lubricating Oils and Determination of Selected
Elements in Base Oils by ICP-OES”. A total of 22 elements The yttrium oil-based standard was diluted (by weight)
can be determined by this test method and it is generally in xylene to give a final concentration of 10 mg·kg-1. This
used as a rapid screening method to monitor the condition solution was used for all dilutions, the yttrium being used
of the equipment using the oil and to define when as an internal standard. For all samples and standards,
preventative action is needed. The metallic analytes must the final solution contained 10% oil (by weight) to ensure
be oil soluble for accurate quantification. The quantification that differences in viscosity were minimized. To achieve
of insoluble particles such as small particles (greater than this, base oil was added if required to the standards prior
a few micrometers) of metal dislodged from a mechanical to dilution with the solvent.
part is not possible when using this method and any
attempt to do so will result in low recoveries. This is due A blank was obtained by diluting the base oil in the
to the plasma not fully atomizing larger particles. It should dilution solvent ten-fold. The standards were prepared
also be highlighted that obtaining a representative sample by diluting the stock standard by weight with the dilution
would be difficult in such cases. solvent to give the required concentration. All samples
were diluted ten-fold by weight with the diluent solution.
Summary of test method
An aliquot of a homogenized sample is diluted by weight Instrument parameters
with a suitable solvent (such as mixed xylenes). Standards The peristaltic pump was fitted with Solvent Flex pump
are prepared in the same manner. The concentration tubing to introduce the sample and remove waste
of metals within a sample is then determined by direct from the spray chamber. A concentric nebulizer was
analysis using ICP-OES. used in conjunction with a baffled spray chamber. This
combination was selected because it reduces the overall
Instrumentation amount of solvent reaching the plasma and shows
The Thermo Scientific™ iCAP™ PRO XP Radial good efficiency at removing large particles from the
ICP-OES was chosen for the analysis. The radial sample aerosol. The plasma was then ignited and the
instrument configuration was selected for its high appropriate parameters set (see Table 1).
matrix tolerance and reduced matrix interferences.
The iCAP PRO XP ICP-OES is fully compatible with the Table 1. Instrument parameters.
Teledyne CETAC ASX-7400 Stirring autosampler which
ensures good homogeneity of the solutions analyzed. Parameter Setting
Sample Solvent Flex orange/white
Pump tubing
Drain Solvent Flex white/white
Method development
Pump speed 30 rpm
Reagents
Spray chamber Baffled glass cyclonic
The following reagents and standards were used in this
Nebulizer Glass concentric
work: Xylene (Fisher Scientific, Loughborough, UK);
Nebulizer gas flow 0.35 L·min-1
Conostan® base oil (Conostan® SCP SCIENCE,
Auxiliary gas flow 1.5 L·min-1
Baie- D’Urfé, Canada); S21 Conostan oil-based standard
900 mg·kg-1 (Ag, Al, B, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Coolant gas flow 12 L·min-1
Mo, Na, Ni, P, Pb, Si, Sn, Ti, V, Zn); Conostan oil-based Center tube 1 mm
standard 5000 mg·kg-1 S; Conostan oil-based standard RF power 1150 W
5000 mg·kg-1 Y. Radial viewing height 12 mm
Repeats 3
The standard reference material (SRM) NIST SRM 1085c - Exposure time 15 s
Wear Metals in Lubricating Oil (approximate concentrations Uptake time 45 s
300 mg·kg-1) was analyzed as a check sample. Wash time 30 s
2
Using the intuitive wavelength selection tool of the The measured value of the check is required to be within
Thermo Scientific™ Qtegra™ Intelligent Scientific Data ±5% of the certified value for the analysis to continue,
Solution™ (ISDS) Software, wavelengths were selected both after the initial calibration and at regular intervals
that were most likely to be free from interferences in every fifth sample.
this matrix. ASTM D5185 also gives a non-exhaustive
list of suggested wavelengths that can be used as a Results
guideline. Once each of the samples and standards were The results of the sample analysis can be seen
analyzed the subarray plots were examined and changes in Table 3. Although the iCAP PRO XP Radial
were made to correct for interferences and optimize ICP-OES is capable of detecting low concentrations,
background corrections, as necessary. From the results as demonstrated by the results of elements such as
obtained it was found that no mathematical correction magnesium, ASTM D5185 expects detectability in the low
factors such as Inter-Element Correction (IEC) were mg·kg-1 range for most elements to be sufficient. Focus is
required. The wavelengths used for analysis and internal on trend analysis and identification of high concentrations
standard correction are shown in Table 2. of wear metals and additives in the oil/engine under
study. The recovery of the check standard was better
Table 2. Analytic and internal standard wavelength used as well as than ±5% for the 5 analyses performed (Table 3). As
detection limit.
described in the standard method, certified standards
Element and Internal standard DL should be regularly analyzed to verify accuracy and
wavelength (nm) wavelength (nm) (µg·kg-1)
precision of the instrument calibration.
Ag 338.289 Y 324.228 6.7
Al 308.215 Y 324.228 33
Table 3. Concentration results and average recovery of the
Al 396.152 Y 324.228 15 certified reference material analysis.
B 208.959 Y 324.228 17
Element and Average Reference Average
Ba 233.527 Y 224.228 2.1 wavelength concentration value recovery CRM
Ca 184.006 Y 224.229 28 (nm) (n=5) (mg·kg-1) (mg·kg-1) 1085c
Cd 214.438 Y 224.230 1.2 Ag 298.2 298 100.1
Cr 267.716 Y 360.073 2.2 Al 298.4 292 102.2
Cu 324.754 Y 324.228 2.3 Al 297.3 292 101.8
Fe 238.204 Y 324.228 4.1 B 318.8 304 104.9
Mg 279.553 Y 360.073 0.3 Ba 294.0 306 96.1
Mo 281.615 Y 360.073 7.1 Ca 312.6 299 104.6
Na 589.592 Y 324.228 16 Cd 304.4 301 101.1
Ni 231.604 Y 324.228 10 Cr 301.3 302 99.8
P 178.284 Y 224.229 54 Cu 309.6 298 103.9
Pb 220.353 Y 224.229 30 Fe 314.0 301 104.3
S 180.731 Y 224.229 9.9 Mg 296.1 300 98.7
Si 212.412 Y 224.229 19 Mo 304.8 305 99.9
Sn 283.999 Y 324.228 23 Na 305.1 300 101.7
Ti 334.941 Y 324.228 1.0 Ni 312.9 306 102.3
V 309.311 Y 324.228 1.6 P 293.3 304 96.5
Zn 213.856 Y 324.228 2.2 Pb 301.5 303 99.5
S 313.6 - ND
Analysis Si 305.7 293 104.3
Xylene was aspirated for a period of 10 minutes Sn 297.0 298 99.7
prior to analysis. The method ASTM D5185 calls for Ti 298.2 300 99.4
wavelength profiling to be carried out prior to analysis. V 299.1 285 105.0
Due to the stability and intelligent design of the Zn 293.3 285 102.9
iCAP PRO XP ICP-OES, this is not needed. The instrument *ND: not determined
was calibrated by running a 3 point calibration and then a
check standard was run (NIST 1085c).
3
Conclusion
The design of the Thermo Scientific iCAP PRO XP
Radial ICP-OES enables for its high matrix tolerance
which makes it ideal for such challenging analysis.
High speed of analysis is accomplished by covering the
whole wavelength range within just one simultaneous
acquisition making the iCAP PRO XP Radial ICP-OES
the perfect fit for high throughput environments.
The removable and easily cleaned interface parts reduce
downtime, due to maintenance, to a minimal. The system
is capable of meeting the requirements of the standard
method ASTM D5185 which details direct analysis of
lubricating oils for wear metals and additives. Also low
analysis time per sample is achieved with the
iCAP PRO Series ICP-OES, which is often a requirement
for analyzing used oil samples in laboratories facing
both a high volume of samples and the constraint for
fast turnaround analysis times. Time is undeniably a
key factor in preventative maintenance and reducing
downtime costs.
Find out more at thermofisher.com/ICP-OES
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AN44426-EN 0919C
