LAAN-A-CP-E027$

Inductively Coupled Plasma Atomic Emission Spectrometry

Application
News Analysis of Additive Elements, Wear Metals, and
Contaminants in Used Lubricating Oil According to
ASTM D5185: ICPE-9820
No. J114$
Q Introduction carbon deposition at the tip of the torch. With the
Analysis of lubricants added to engine oils such as those Shimadzu ICPE-9820, however, the vertical orientation of
used in automobiles and ships is an effective as well as the plasma torch and adoption of a plasma torch that
important way to diagnose the state of the engine and suppresses carbon deposition has nearly completely
other equipment. eliminated the deposition of carbon originating from the
According to ASTM International Standard D5185 1), sample. Therefore, even in analysis of organic solvent
inductively coupled plasma (ICP) atomic emission samples such as kerosene, xylene and MIBK, the ICPE-
spectrometry with organic solvent dilution is specified for 9820 eliminates the need to introduce oxygen to
measurement of additive elements, wear metals and suppress the precipitation of carbon.
contaminants present in used lubricants. Also, the Japan Also, since the Shimadzu ICPE-9820 adopts a vacuum
Petroleum Institute standard JPI-5S-44-2011 stipulates the spectrometer, elements such as S with a wavelength in
use of ICP atomic emission spectrometry in Japan for the vacuum ultraviolet region can be analyzed at a low
analysis of Fe, Cu, Al, Pb, Cr and Sn in used lubricating oil.2) running cost without the need for costly high-purity gas,
Here, using the Shimadzu ICPE-9820 multi-type ICP atomic typically required with a purge-type spectrometer.
emission spectrometer, we conducted analysis of 22 Table 1 Analytical Conditions
elements specified according to ASTM D5185 in samples : ICPE-9820

Instrument
consisting of a used lubricant (commercially available Radio Frequency Power : 1.40 k:
automotive lubricating oil) and, as a reference, the same, Plasma Gas Flowrate : 16.0 L/min
but unused lubricating oil, both of which were diluted with Auxiliary Gas Flowrate : 1.40 L/min
organic solvent. The ICPE-9820, which adopts a vertically- Carrier Gas Flowrate : 0.70 L/min
oriented plasma torch which reduces the possibility of Sample Introduction : Nebulizer, 10UES
Misting Chamber :2UJDQLFVROYHQW chamber
carbon precipitation, provides stable analytical results for Plasma Torch : Torch
organic solvent samples without requiring the flow of Observation 5aGLDO (RD)
oxygen through the system.
Q Analysis
Q Samples
The calibration curve method – internal standard method
- Used lubricating oil (commercially available automotive was used to conduct analysis of 22 elements (Al, Ba, B, Ca,
lubricant, used for approximately 4000 km) Cr, Cu, Fe, Pb, Mg, Mn, Mo, Ni, P, K, Si, Ag, Na, S, Sn, Ti, V,
- Same lubricating oil as above, but in unused state Zn) specified according to the ASTM standard.
Q Sample Preparation Q Analytical Results
Approximately 10 g of each sample was weighed and then Table 2 shows the analytical results. Excellent results near
diluted with 100 mL of kerosene. The standard solutions 100 % were obtained in the dilution test for the high-
were prepared by appropriately diluting with kerosene the concentration elements and the spike-and-recovery test for
SPEX oil-based 21-element mixed standard solution the low-concentration elements, both with respect to the
(500 μg/g), the Conostan® and SPEX oil-based single- used lubricating oil. In addition, the analytical results
element standard solution (5000 μg/g), and the Tokyo obtained in analysis of the unused lubricating oil are also
Kasei Kogyo Co., Ltd. heavy oil sulfur content standard listed for reference.
sample (1.05 % by weight). The spectral line profiles for Fe and P are shown in Fig. 1.
For validation of the measurement values, the above The calibration curves for Fe, Mg and S are shown in Fig. 2.
standard solution was added to the used lubricating oil to
prepare a 5 mg/L solution to serve as a low-concentration Q Conclusion
element spike-and-recovery test sample. In addition, for Using the ICPE-9820, dissolved elements in used
high-concentration elements, the used lubricant was lubricating oil can be analyzed stably without the
diluted 50-fold with kerosene to prepare a diluted test introduction of oxygen.
sample.
Finally, the Conostan® oil-based Y (yttrium) single-element Q References
standard solution (5000 μg/g) was diluted with kerosene 1) ASTM International Standard D5185
and added to all the samples as the internal standard Standard Test Method for Determination of Additive Elements, Wear
element so as to occupy a fixed concentration in all the Metals, and Contaminants in Used Lubricating Oils and Determination
samples. of Selected Elements in Base Oils by Inductively Coupled Plasma Atomic
Emission Spectrometry (ICP-AES)
Q Instrument and Analytical Condition
2) T h e J a p a n P e t ro l e u m I n s t i t u t e S t a n d a rd J P I - 5 S - 4 4 - 2 0 1 1
Measurement was conducted using the Shimadzu ICPE-
Method for Analyzing Fe, Cu, Al, Pb, Cr and Sn Contents in Used
9820 multi-type ICP atomic emission spectrometer. The Lubricating Oil Using Solvent Dilution - Inductively Coupled Plasma
measurement conditions are shown in Table 1. Atomic Emission Spectrometry
When conducting analysis of organic solvent samples
with most conventional ICP instruments, oxygen must
typically be introduced into the plasma torch to suppress
Application No. J114A
News

Table 2 Analytical Results of Lubricating Oil

Used lubricant Used lubricant

Used lubricant Unused Detection limit
Element spike recovery dilution test
(μg/g) lubricant (μg/g) (μg/g)
rate (%) (%)
Ag < 100 - < 0.02
Al 10 101 - 6.51 0.3
B 65.9 - 98 121 -
Ba 0.123 101 - < 0.02
Ca 3970 - 98 2250 -
Cr 1.03 101 - < 0.01
Cu 0.65 100 - < 0.02
Fe 10.8 101 - 0.43 0.01
K 22.1 99 - < 0.6
Mg 10.4 100 - 5.48 0.02
Mn 0.618 101 - 0.139 0.002
Mo 184 - 98 183 -
Na 2.5 100 - < 0.4
Ni < 102 - < 0.05
P 756 - 99 731 -
Pb < 100 - < 0.5
S 3980 - 100 3810 -
Si 8.96 103 - 5.07 0.03
Sn < 100 - < 0.5
Ti < 100 - < 0.01
V < 103 - < 0.02
Zn 872 - 97 882 -
Spike recovery rate (%) = (C1-C2)/B×100 (C1: Spiked sample quantitative value; C2: Non-spiked sample
quantitative value; B: Spike concentration)
Dilution test (%) = I/S ×100 (I: Quantitative value of sample before dilution; S: Quantitative value of 5-fold diluted
sample ×5)
Detection limit: DL = 3×σBL× κ (σBL: Standard deviation of background intensity;κ: Concentration/intensity)
<: Less than the detection limit

Fe 259.940 nm
P 213.618 nm
10000
15000
Standard sample Standard sample
Used lubricant
7500
Intensity

Intensity

10000
Unused lubricant
5000

5000 Used lubricant

2500
Unused lubricant

0 0

Fig. 1 Spectral Profiles of Fe and P

Fe 259.940 nm Mg 285.213 nm S 182.037 nm

45 45 150
40 40
35 35 125
30 30 100
Intensity

Intensity

Intensity

25 25
20 20 75
15 15 50
10 10
5 5 25
0 0 0
r = 0.99999 r = 0.99999 r = 1.00000
0.0 2.5 5.0 7.5 10.0 0.0 2.5 5.0 7.5 10.0 0 250 500
Concentration (mg/L) Concentration (mg/L) Concentration (mg/L)

Fig. 2 Calibration Curves of Fe, Mg and S

Second Edition: Jul. 2015

First Edition: Apr. 2015

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