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ICP OPTICAL EMISSION
application note
Analysis of wear metals in oil
Cindy Anderau, Ken Fredeen, Maryanne Thomsen, and Dennis Yates
PerkinElmer Instruments, 761 Main Avenue, Norwalk, CT 06859 USA
Introduction Table 1: Optima 3000 Operating Parameters
The concentration trends of wear
Plasma:
metals in engine lubricating oil can be
directly related to the engine com- Plasma Flow: 15 L/min.
ponents and can indicate component
Auxiliary Flow: 2.0 L/min.
wear. A sound engine maintenance
program which routinely measures Nebulizer Flow: 0.5 L/min.
wear metals in the lubricating oils not
Power: 1300 Watts
only reduces the expense of routinely
dismantling the engine for visual Viewing height: 15 mm above the load coil
inspection, but can indicate unexpected
wear before component failure. Sample Uptake rate: 1 mL/min.
The ICP-OES technique has gained Torch and Sample Introduction Assembly
popularity with this analysis in the last Nebulizer: Cone Spray
several years. It offers detection limits
that are far lower than required, good Injector: 1.2 mm i.d.; quartz
precision and, above all, speed. A new Torch: Corrosion-resistant demountable torch
high speed ICP-OES instrument was
used for this analysis with special
attention paid to speed of analysis, Reagents Maintenance of Torch
while still maintaining good detection Calibration standards were made Glassware
limits and precision. The results of this using Conostan S-21 blended stan- When running an organic matrix
investigation are described in this dard which contains 21 elements through an ICP system, carbon will
application study. (Ag, Al, B, Ba, Ca, Cd, Cr, Cu, Fe, build up on the torch glassware
Mg, Mn, Mo, Na, Ni, P, Pb, Si, Sn, and on the injector. Eventually (it
Experimental Ti, V and Zn) at 500 mg/g in a hydro- may take several days) the build-up
Instrumentation carbon oil. Single-element standards will cause the injector orifice to be
An Optima 3000™ radial-view ICP- were also used to rule out interfer- blocked thus degrading the perfor-
OES instrument was used. This ences and accurately select back- mance of the analysis. An easy way
instrument provides for the simulta- ground correction points. These to remove the carbon from the torch
neous determination of over 200 single-element standards were 5000 and injector is to burn it off by
wavelength regions during a single mg/g Conostan standards (Conostan putting them both in a muffle fur-
reading. It accomplishes this with the Division, Conoco Inc. P.O. Box 1267, nace at 550°C for several hours. For
use of a unique echelle spectrometer Ponca City Oklahoma 74601). this study, we left the glassware in
and segmented-array charge-coupled All standards were prepared using the furnace overnight.
device detector. The plasma source is a weight-by-weight dilution. Concen-
generated with a 40 MHz free- trations of 20 mg/g, 10 mg/g, 5 mg/g Results and Discussion
running generator. The free-running and 1 mg/g were used. Samples of Detection Limits and BECs
nature of the generator makes it ideal new and used lubricating oils ob- The elements selected for this
for difficult matrices such as organic tained from a customer were diluted analysis were based on those
solvents. Historically, ICPs have been 1:100 and also 1:10. The diluent used routinely determined by a customer.
difficult to ignite and/or keep stable in all cases was deodorized kerosene Wavelengths and background
when running organic matrices. This (Baker Analyzed, J.T. Baker Chemical
ICP is very forgiving to these harsh Co., Phillipsburg, NJ).
matrices and makes plasma ignition
very reliable and provides a stable
excitation source. The operating
parameters used are listed in Table 1.
correction points were chosen Table 2: Detection Limits and BECs (mg/L)
based on their freedom from
spectral interferences. This was Element Wavelength (nm) DL BEC
determined by comparing spectra of Mo 204.598 0.043 0.5
a single-element standard, the
multi-element standard, the kero- B 208.959 0.04 0.8
sene blank and a representative Si 212.412 0.027 0.7
used and new oil sample. Table 2
lists these elements, the wave- Zn 213.856 0.0036 0.18
lengths chosen, their detection P 214.914 0.07 1.5
limits and BECs. Detection limits
(DL) were determined using an Pb 220.353 0.086 2.2
integration time of 10 seconds and Fe 259.940 0.018 0.2
were the result of multiplying by
three the average SD of a blank run Cr 267.716 0.003 0.15
as a sample. Mg 279.079 0.05 1.5
Accuracy Sn 283.999 0.04 1.04
The accuracy of the calibration Mn 294.920 0.002 0.08
curve was confirmed by calibrating
with a 1-mg/g and 5-mg/g solution Al 308.215 0.021 0.8
of S-21 and the kerosene blank and Cu 324.754 0.0021 0.10
then analyzing NIST standard
1085 Wear Metals in Lubricating Ni 341.476 0.07 0.9
Oil. There are three types of data Ca 422.673 0.026 0.5
processing algorithms available in
the software for this instrument:
3-point parabolic fit, area integra- Table 3:Analysis of NIST SRM 1085
tion and multi-component spectral
fitting. The algorithm that provides Element Wavelength (nm) Certified Result (mg/g) Found (mg/g)
for the highest sample throughput is Mo 204.598 293 ± 2.5 299 ± 2.2
the area integration. Since the
analytical performance for this Si 212.412 (322) 295 ± 7.1
matrix was the same regardless of Pb 220.353 297.4 ± 9.6 302 ± 9.0
which technique was used, the area
integration was chosen since high Fe 259.940 296.8 ± 2.7 304 ± 2.2
sample throughput is desirable. The Cr 267.716 296.3 ± 3.3 289 ± 1.6
area that was integrated included 3
pixels in each subarray, one at the Mg 279.079 296.0 ± 3.1 296 ± 3.1
peak and one at either side of the Sn 283.999 296.0 ± 13.4 293 ± 3.0
peak. Integration time was 10
seconds. The results are shown in Al 308.215 (289) 290 ± 3.2
Table 3. Generally there was very Cu 324.754 295.1 ± 6.8 303 ± 3.8
good agreement between the
certified result and our result. The Ni 341.476 302.9 ± 6.8 302 ± 2.3
exceptions are Si, which is not
certified, and Cr. Our results were
consistently low for both of these The new and used oil samples from a customer were then analyzed. The
elements. results were expected to be around 100 mg/g for all wear metals for the used
oil samples, except Pb, which was expected to be around 15,000 mg/g, and
Fe, which was expected to be around 500 mg/g. The new oil samples were
specified to have the levels of Ca, Zn, P and Mg as shown in Table 4. The
samples were all diluted 1:100 before analyzing. The results shown are
corrected for the dilution.
Table 4: Comparison of Results of Oil Samples Expected and Found
Used Oil (mg/g) New Oil (mg/g) New Oil
Element Wavelength (nm) (this study) Used Oil Expected (this study) Reference (mg/g)
Mo 204.598 99 100 ND 0
B 208.959 99 100 ND 0
Si 212.412 149 100 ND 0
Zn 213.856 1098 1125
P 214.914 982 1030
Pb 220.353 14500 15000 ND 0
Fe 259.940 394 500 ND 0
Cr 267.716 104 100 ND 0
Mg 279.079 315 350
Sn 283.999 131 100 ND 0
Mn 294.920 97 100 ND 0
Al 308.215 99 100 ND 0
Cu 324.754 100 100 ND 0
Ni 341.476 84 100 ND 0
Ca 422.673 1472 1575
ND = Not Detected; Signal below the detection limit.
These results give us confidence that the Optima™ ICP-OES instrument is fully capable of providing accurate results for typical used and new oil samples.
Speed of Analysis limits are, generally, within a factor Conclusion
In optimizing the speed of the of 3 of the detection limits obtained The Optima ICP-OES instrument
analysis, the peak area integration at 10,000 ms, which are shown in provides excellent detection limits,
routine was used and 3 pixels per Table 2 (see Figures 4 – 6). At an accuracy and %RSDs for the
array were summed. This algorithm integration time of 500 ms, the time analysis of wear metals in lubricat-
was chosen because it had been for a set of 10 replicates to be com- ing oils. It also provides for a very
found to provide the highest sample pleted was 1 minute, 4 seconds. fast analysis with a single replicate
throughput without any sacrifice in Since wash or rinse out time measurement taking only 6 seconds
performance. Manual integration does significantly contribute to the to complete.
was used and a comparison of the speed of an analysis, the time to
detection limits and %RSDs for rinse out a 10 mg/g solution of all
several integration times was made. the wear metals in kerosene was
The shortest integration time used measured. It takes about 70 seconds
was 10 ms and the longest was 1000 for the signals to reach baseline.
ms. To maintain %RSDs of 1% or This wash time could be greatly
less an integration time of 500 ms reduced by using the fast pump
or longer must be used (see Figures speed of 4 mL/min between
1 – 3). At 500 ms, the detection samples.
Figure 1 Figure 4
Figure 2 Figure 5
Figure 3 Figure 6
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