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MICROCHEMICAL JOURNAL 57, 245–250 (1997)

ARTICLE NO. MJ971475

Extraction Efficiencies of Emulsions for 21 Elements in Oil and


Transmission Fluids by Inductively Coupled Plasma Spectroscopy

Terry L. Thiem1 and Jeff D. Watson


Department of Chemistry, U.S. Air Force Academy, Colorado Springs, Colorado 80840
Received December 2, 1996; accepted January 7, 1997

Wear metals, especially transition metals, are key indicators of the condition of specific
components within an engine, whether it be a car, truck, or jet. Determination of these elements
can greatly reduce the chance of engine failure. Traditionally this is done by atomic absorption
spectroscopy (AAS) or inductively coupled plasma spectroscopy with organic solvent dilution
with methyl isobutyl ketone, xylene, or kerosene. This, however, creates a large quantity of
organic waste that is expensive to dispose of following analysis. Several groups have used acid
extraction with emulsions with great success. In this study aqueous standards that are much
easier and less expensive to dispose of are used with inductively coupled plasma spectroscopy.
Twenty-one elements are determined from a 300 mg/g base oil solution. Extractions of 30W oil,
10W30 oil, and transmission fluid were completed to establish a baseline for subsequent analysis
of used oil by this method. q 1997 Academic Press

INTRODUCTION
The analysis of lubricating oils as a basis for determining engine condition is
common practice for systems where large amounts of lubricating oils are involved or
where engine wear is critical (1). Engine wear patterns and oil contamination originat-
ing from dirt and leaks can be traced by contaminant element determination, thus
allowing the problem to be fixed prior to engine failure. Spectrometric oil analysis
was first applied by the railroad in the early 1940s in an effort to detect wear in
diesel locomotive engines. The technology was later adopted by the U.S. military for
monitoring of wear metals in automobile and jet engines. Considering the tremendous
cost savings to be achieved in reduced maintenance and repair activities, as well as
improved operational reliability of weapon systems, the Air Force has maintained a
continued interest in research to improve the capability to detect and identify the
extent of engine internal wear (2).
In the early 1980s, the Air Force used primarily rotating-disk electrode-atomic
emission spectroscopy (RDE-AES) and flame atomic absorption spectrophotometry
(FAAS) for trace metal analysis. X-ray fluorescence (XRF) spectroscopy is also com-
monly used for the determination of additive elements in fresh oil. Inductively coupled
plasma (ICP) spectroscopy offers high sensitivity and multielement capability when
applied to the determination of wear metals. The problem with attempting direct
analysis is that the viscosity of the lubricating oils is too high for traditional nebulizers.

1
To whom correspondence should be addressed. Present address: Polymer Research Division, Bayer
Corporation, P.O. Box 500, New Martinsville, WV 26155.

245
0026-265X/97 $25.00
Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.

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246 THIEM AND WATSON

TABLE 1
ICP Operating Parameters

Power 1.0 kW
Oscillator 40.68-MHz Flagg oscillator
Coolant 14 LPM
Nebulizer 40 psi
Pump rate 1.0 ml/min

The most common solution is to dilute the sample with a low-viscosity organic solvent
such as methyl isobutyl ketone, xylene, or kerosene prior to nebulization. This method
is quick but creates a large amount of organic waste that must be disposed of following
analysis. An alternative method to organic dilution is the use of acidic emulsions.
Several emulsifiers and combinations of emulsifiers have been used in an attempt to
reduce the amount of organic waste produced in the analysis of trace metals in organic
matrixes. Borszeki et al. determined sulfur and trace metals in oil products using two
different types of emulsifiers, one for the sulfur determination and the other for the
trace metals (3). The sulfur emulsifier consisted of 50% of a 1:1 mixture of metal-free
mineral oil and oleic acid (C18:1 fatty acid)–morpholine salt, 35% oleic acid–polyethyl-
ene glycol [PEG(300)] ester, and 15% polypropenyl succinic acid–PEG(300) diester.
For the trace metal analysis a mixture of 50% of a 1:1 mixture of metal-free mineral
oil and petroleum sulfonate–sodium salt, 35% oleic acid–PEG(300) ester, and 15%
polypropenyl succinic acid–PEG(300) diester. For S, Al, Cr, Cu, Ni, and Pb the error
in their analysis based on certified samples was less than 5%.
Lead in gasoline was determined by Cardarelli et al. using emulsions that were
stabilized with 2-propanol or a mixture of ethanol and a surface-active agent (4). The
detection limit for lead was 0.07 mg/liter when using the 217.0-nm line. Other studies
used emulsions for the determination of additives containing calcium (5), barium (6),
zinc (7), dissolved lead (8), and total iron (9) in used oils without the need for

TABLE 2
Percentage Recovery Using Emulsions (HCl)

ICP analysis Recovery ICP analysis Recovery


Element (mg/ml) (%) Element (mg/ml) (%)

Ag 0.40 { 0.08 8.0 Mo 4.98 { 0.13 99.6


Al 4.46 { 0.36 89.2 Na 1.55 { 0.04 31.0
B 5.52 { 0.51 110.4 Ni 4.48 { 0.19 89.6
Ba 3.30 { 0.09 66.0 P 2.39 { 0.11 47.8
Ca 5.07 { 0.19 101.4 Pb 4.65 { 0.44 93.0
Cd 5.22 { 0.09 104.4 Si 3.39 { 0.04 67.8
Cr 4.63 { 0.12 92.6 Sn 5.05 { 0.16 101.0
Cu 5.00 { 0.45 100.0 Ti 5.04 { 0.28 100.8
Fe 4.55 { 0.20 89.0 V 5.49 { 0.10 109.8
Mg 4.72 { 0.21 94.4 Zn 4.48 { 0.17 89.6
Mn 5.28 { 0.11 105.6

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EXTRACTION EFFICIENCY BY ICP SPECTROSCOPY 247
TABLE 3
Percentage Recovery Using Emulsions (HNO3)

ICP analysis Recovery ICP analysis Recovery


Element (mg/ml) (%) Element (mg/ml) (%)

Ag 0.83 { 0.03 16.6 Mo 5.07 { 0.20 101.4


Al 3.63 { 0.09 72.6 Na 1.44 { 0.02 28.8
B 6.33 { 0.29 126.6 Ni 4.29 { 0.06 89.6
Ba 2.56 { 0.13 51.2 P 2.63 { 0.07 52.6
Ca 4.27 { 0.13 85.4 Pb 5.08 { 0.09 101.6
Cd 5.40 { 0.23 108.0 Si 5.02 { 0.13 100.4
Cr 2.96 { 0.08 59.2 Sn 5.28 { 0.24 105.6
Cu 5.19 { 0.14 103.8 Ti 4.23 { 0.51 84.6
Fe 4.21 { 0.20 84.2 V 4.63 { 0.09 92.6
Mg 5.27 { 0.27 94.4 Zn 4.08 { 0.21 81.6
Mn 5.01 { 0.16 100.2

organometallic standards. In this study we report the extraction efficiencies of 21


elements in a base oil standard using a variety of different acidic emulsions followed
by a baseline determination of two different oils and transmission fluid.

EXPERIMENTAL
Instruments
The ICP analysis was completed using a Leeman Lab PS Series 1000 Sequential ICP
(Leeman Labs, Lowell, MA) with an Echelle spectrometer and Hildebrand Grid nebu-
lizer. This system is a completely computer-controlled sequential instrument allowing
multielement analysis using two wavelengths. Multiple wavelengths were used as a
check of the instrumental results. Instrumental conditions are given in Table 1.

TABLE 4
Percentage Recovery Using Emulsions (H2SO4)

ICP analysis Recovery ICP analysis Recovery


Element (mg/ml) (%) Element (mg/ml) (%)

Ag 1.77 { 0.20 35.4 Mo 4.69 { 0.18 93.8


Al 3.62 { 0.42 72.4 Na 1.18 { 0.03 23.6
B 5.65 { 0.23 113.0 Ni 4.06 { 0.11 81.2
Ba 2.04 { 0.09 40.8 P 3.93 { 0.16 78.6
Ca 4.28 { 0.34 85.6 Pb 3.65 { 0.13 73.0
Cd 4.51 { 0.09 90.2 Si 5.18 { 0.22 103.6
Cr 4.73 { 0.18 94.6 Sn 5.67 { 0.27 113.4
Cu 5.02 { 0.07 100.4 Ti 4.44 { 0.20 88.8
Fe 3.97 { 0.20 89.0 V 4.98 { 0.42 99.6
Mg 5.12 { 0.67 102.4 Zn 4.19 { 0.18 83.8
Mn 4.82 { 0.38 96.4

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248 THIEM AND WATSON

TABLE 5
Percentage Recovery Using Emulsions (HCl/HNO3)

ICP analysis Recovery ICP analysis Recovery


Element (mg/ml) (%) Element (mg/ml) (%)

Ag 6.25 { 0.18 125.0 Mo 4.23 { 0.08 84.6


Al 3.10 { 0.07 62.0 Na 1.20 { 0.04 24.0
B 5.15 { 0.12 103.0 Ni 3.64 { 0.04 72.8
Ba 3.02 { 0.12 60.4 P 3.13 { 0.09 62.6
Ca 3.70 { 0.14 74.0 Pb 4.28 { 0.04 85.6
Cd 4.88 { 0.06 97.6 Si 4.91 { 0.05 98.2
Cr 3.32 { 0.06 66.4 Sn 5.62 { 0.12 112.4
Cu 4.41 { 0.06 88.2 Ti 4.10 { 0.14 82.0
Fe 4.45 { 0.20 89.0 V 4.28 { 0.12 85.6
Mg 4.47 { 0.10 89.4 Zn 5.21 { 0.14 104.2
Mn 4.34 { 0.05 86.8

Sample Preparation
The extraction efficiencies were determined using a 300 mg/g 21-element oil stan-
dard (SPEX, Edison, NJ). One milliliter of the 300 mg/g 21-element oil standard was
placed in a Teflon beaker and 5 ml of acid or acid mixture was added. This was
allowed to react for 10 min. Following this, 50 ml of doubly deionized water and 4
ml of the 20% Triton X-100 solution were added. This mixture was stirred for 2 min
and allowed to settle for 3 min prior to analysis. This produced 60 ml of solution and
therefore a concentration of 5 mg/ml. The oil and transmission fluid samples were

FIG. 1. Comparison of extraction efficiencies.

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EXTRACTION EFFICIENCY BY ICP SPECTROSCOPY 249
TABLE 6
Base Metals in Diluted Oils/Transmission Fluid

Transmission Transmission
30W 10W30 fluid 30W 10W30 fluid
Element (HCl) (HCl) (HCl) (HNO3) (HNO3) (HNO3)

Ag 0.30 { 0.01 0.42 { 0.03 0.46 { 0.01 0.38 { 0.01 0.39 { 0.01 0.41 { 0.01
Al 0.31 { 0.01 0.32 { 0.01 0.31 { 0.01 0.26 { 0.01 0.30 { 0.01 0.31 { 0.01
B 0.67 { 0.01 0.28 { 0.01 1.14 { 0.02 0.37 { 0.01 0.20 { 0.01 0.94 { 0.01
Ba 0.19 { 0.01 0.20 { 0.01 0.19 { 0.01 0.19 { 0.01 0.20 { 0.01 0.19 { 0.01
Ca 1.20 { 0.07 0.84 { 0.03 0.22 { 0.01 0.51 { 0.01 1.56 { 0.09 0.20 { 0.01
Cd 0.26 { 0.01 0.26 { 0.01 0.28 { 0.01 0.26 { 0.01 0.24 { 0.01 0.25 { 0.01
Cr 0.30 { 0.01 0.29 { 0.01 0.27 { 0.01 0.46 { 0.01 0.21 { 0.15 0.23 { 0.01
Cu 0.19 { 0.01 0.19 { 0.01 0.19 { 0.01 0.21 { 0.01 0.17 { 0.01 0.18 { 0.01
Mg 0.23 { 0.01 0.64 { 0.01 0.22 { 0.01 0.23 { 0.01 0.96 { 0.01 0.22 { 0.01
Mn 0.18 { 0.01 0.18 { 0.01 0.18 { 0.01 0.17 { 0.01 0.17 { 0.01 0.17 { 0.01
Mo 0.21 { 0.01 0.17 { 0.01 0.14 { 0.01 0.31 { 0.01 0.12 { 0.01 0.12 { 0.01
Na 1.09 { 0.01 1.15 { 0.01 1.00 { 0.02 0.69 { 0.01 0.91 { 0.03 0.97 { 0.02
Ni 0.19 { 0.01 0.19 { 0.01 0.19 { 0.01 0.21 { 0.01 0.18 { 0.01 0.18 { 0.01
P 3.66 { 0.08 3.81 { 0.07 3.71 { 0.04 2.58 { 0.03 2.81 { 0.08 3.34 { 0.10
Pb 1.23 { 0.05 1.43 { 0.09 1.33 { 0.04 0.61 { 0.02 0.44 { 0.02 0.47 { 0.01
Si 0.36 { 0.01 0.20 { 0.01 0.13 { 0.01 0.15 { 0.01 0.03 { 0.01 0.08 { 0.01
Sn 2.25 { 0.06 1.95 { 0.04 2.07 { 0.06 5.00 { 0.15 1.09 { 0.11 1.14 { 0.05
Ti 0.14 { 0.01 0.15 { 0.01 0.15 { 0.01 0.19 { 0.01 0.19 { 0.01 0.18 { 0.01
V 0.17 { 0.01 0.18 { 0.01 0.16 { 0.02 0.16 { 0.01 0.15 { 0.01 0.17 { 0.01
Zn 6.97 { 0.11 10.50 { 0.25 0.19 { 0.01 0.91 { 0.02 4.67 { 0.12 0.12 { 0.01

analyzed using the same method described above. Aqueous standards were made by
diluting 1000 mg/ml standards (Aldrich, Inc.).
RESULTS AND DISCUSSION
Four different acid/acid combinations were attempted in this study, namely, HCl,
HNO3 , H2SO4 , and HCl/HNO3 in a 75/25 ratio. The extraction efficiencies of these
acids are given in Tables 2–5 and graphically in Fig. 1. The extraction efficiencies
ranged from 8.0% for Ag in HCl to 126.6% for B in HNO3 .
From the graph and Tables 2–5 both HCl and HNO3 have very good extraction
efficiencies for the elements of interest in this study. The results from the acid extrac-
tion for baseline determination of the oils and transmission fluid are given in Table
6. These are the diluted values and therefore would have to be multiplied by 60 to
obtain the actual values in the oil/transmission fluid.
CONCLUSION
The use of emulsions greatly reduces the amount of organic waste that must be
disposed. It has been shown that with the correct acid or acid combination, extraction
efficiencies near 100% can be realized for many different elements. Low extraction
efficiencies for Ag and Pb in HCl are due to the formation of insoluble chloride salts.
HNO3 is recommended if Ag and Pb are important to the analysis.

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250 THIEM AND WATSON

ACKNOWLEDGMENT
The authors thank Frank J. Seiler Research Laboratory for their generous support of this project.

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