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Article history: In this paper, Dielectric Spectroscopy (DS) was employed to analyze the oxidation degradation process of
Received 29 September 2010 engine lubricating oil qualitatively and quantitatively compared with Fourier Transform Infrared Spec-
Received in revised form 15 March 2011 troscopy (FTIR). It was found that both DS and FTIR can directly obtain the degradation features from
Accepted 15 March 2011
the spectral data. With the combination of DS and multivariate calibration (Partial Least Square PLS),
Available online 23 March 2011
three main oil monitoring properties including Oxidation Duration (OD), Total Acid Number (TAN) and
Insoluble Content (IC) can be determined quantitatively and accurately. It was proved that operating
Keywords:
temperature had more influence on DS data than excitation amplitude. The results in the article show
Engine lubricating oil
Oil monitoring
that DS can be developed into an effective oil monitoring/analysis method.
Fourier transform infrared spectroscopy © 2011 Elsevier B.V. All rights reserved.
(FTIR)
Dielectric spectroscopy (DS)
Multivariate calibration
0924-4247/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.sna.2011.03.033
L. Guan et al. / Sensors and Actuators A 168 (2011) 22–29 23
Dielectric and electrochemical impedance analysis methods are new analysis idea is explained in our previous publication too
relatively fast, simple, inexpensive and free from the difficulties [32].
associated with the current standard testing methods. Moreover, The monitoring sensor for oil condition, especially for engine
dielectric and electrochemical properties are related with the lubricating oil should be easy to be cleaned and is able to extract
chemical composition and physical structures of engine lubricating sufficient dielectric information. Interdigitated comb capacitor sen-
oil. sor is a good and practical selection, which has been applied for
Dielectric spectroscopy (DS) is an analytical technique on oil analysis widely [27,31–33]. So the measuring sensor for engine
the interaction between dielectric material and electromagnetic lubricating oil in this article is a type of interdigitated comb capac-
energy in the radio-frequency and microwave range, which is a itor sensor too.
powerful structural detection technique for dielectric materials. In this article, DS is employed to examine the oxidative degra-
What DS studies is the dependence of materials’ dielectric prop- dation of engine lubricating oil and to determine the Oxidation
erties on wavelength or frequency. The difference between DS Duration (OD), Total Acid Number (TAN) and Insoluble Content (IC)
and EIS: the main interest of DS is on the intrinsic electric mate- properties. All the DS analysis results are discussed compared with
rial properties. The complex permittivity ε*(ω) or conductivity the Fourier Transform Infrared spectroscopy (FTIR).
*(ω) spectra can be easily evaluated from Z*(ω) with the help of
sample dimensions; the focus of EIS is mostly on the properties
2. Experimental
of electrode/material interfaces and the materials under test are
often electrolytes or ion conductors. Petroleum products including
2.1. Samples
engine lubricating oil are all typical dielectric materials. So DS is
more suitable than EIS for engine lubricating oil analysis.
All the samples were prepared with the device illustrated in
At present, DS technique enables researchers to make sound
Fig. 1. The main function of the device is to oxidize the virgin sam-
contributions to contemporary problems in modern physics. DS
ples under given oxidation conditions. The air flow generated by
has been employed to quality sensing application of agricultural
the air pump and the copper wire catalyst are used to accelerate
product [29,30]. Our previous publications have investigated the
the oxidization process.
correlations between DS data and petroleum products’ compo-
According to the sample preparation device, three types of vir-
sition and quality indexes by means of multivariate calibration,
gin engine lubricating oils were employed to produce three series
which include classification of virgin engine lubricating oils by SAE
of samples with different degrees of degradation. The three virgin
and source [31] and determination of clean gasoline octane num-
engine lubricating oils are listed in Table 1.
bers [32]. It is already proved that DS is a practical and effective
For each series of samples, three types of properties including
analysis method to obtain rich composition and structure infor-
Oxidation Duration (OD), Total Acid Number (TAN) and Insoluble
mation of complex mixture systems. Especially, with the help of
Content (IC) were recorded. OD values were recorded according
chemometrics multivariate calibration methods the direct relation-
to sampling time. TAN and IC properties were respectively deter-
ships between DS data and quality properties can be established
mined by TAN&TBN Analyzer and Insoluble Content Analyzer made
efficiently, which is more effective than the interpretation of EIS
by Beijing China Invent Instrument Technology Ltd. Company. The
results by means of complex equivalent circuit (EC) models. The
samples with three properties are shown in Tables 2–4.
Table 1
Information on three virgin engine lubricating oils.
Table 2
Sample list generated by set one.
Table 3
Sample list generated by set two.
2.2. FTIR apparatus and method For this study, the sine waveform was selected; amplitudes were
4 V, 6 V, and 8 V; frequencies ranged from 50 kHz to 16 MHz and
The FTIR instrument used in this work was Perkin Elmer 1725X frequency interval was 200 kHz; measurement temperatures were
FT-IR spectrometer. A pair of well-polished KBr windows with 40 ± 1 ◦ C and 100 ± 1 ◦ C.
0.05 mm spacer creating a fixed thin film was used to acquire the A type of interdigitated comb capacitor sensor is fabricated and
sample spectral data. During spectra measurement, a blank KBr employed in this article. The construction of the sensor is shown
window spectra was collected and used as reference for sample in Fig. 2. The sensor is fabricated by printed circuit board (PCB)
absorbance calculation. And then the sample was injected into the technique.
blank KBr windows and the sample spectra were collected in the The comb electrodes of the sensor are made of gold plated cop-
range of 400 to 4000 cm−1 at 4 cm−1 resolution. per layers with 35 m height h. The copper finger width and spacing
L. Guan et al. / Sensors and Actuators A 168 (2011) 22–29 25
Table 5
Peak area results of set one.
No. S1 S2 S3
Table 6
Peak areas results of set two.
No. S1 S2 S3
Table 7
Peak areas results of set three.
No. S1 S2 S3
Table 8 ferent from the peak area or height changing feature in MIR
Predicted results based on MIR peak areas in correlation coefficient.
spectra.
Property Set one Set two Set three (2) Similar characteristics can be obtained under different testing
Oxidation duration (min) 0.9905 0.9723 0.5796 conditions. For example, at 40 ◦ C and 100 ◦ C testing tempera-
TAN (mgKOH/g) 0.8670 0.4918 0.1138 tures and at 4Vpp, 6Vpp and 8Vpp excitation signal amplitudes
Insoluble content (mg/g) 0.9385 0.9718 0.9131 have almost the same testing results.
(3) Characteristic band peak features cannot be seen from the spec-
tra data of DS, which is different from MIR and somewhat
coefficients between the predicted and the measured were listed
similar with NIR. It can be difficult to assign specific features
in Table 8.
to specific chemical components.
As shown in Table 8, poor correlation coefficients for TAN were
obtained for three series. For set one and set two, the correlation
coefficients for OD and IC were relatively acceptable. For set three, 3.2.2. Quantitative calculation based on DS data
only IC property had good predicted results. As DS is based on the interaction of an external field with
the electric dipole moment of the sample, it is difficult to assign
3.2. DS measurements specific features to specific chemical components of the sam-
ple like MIR analysis. However characteristic ingredient and
3.2.1. DS spectra features analysis structure information of the sample can be obtained from DS
DS spectra of all three series of samples were collected and data. In order to find out the relationship between DS data
shown in Fig. 4. From Fig. 4 we can conclude the main features and usual chemical and physical properties such as TAN and
of DS spectra: insolubles, multivariate (multiple frequencies) calibration tech-
niques (e.g. principal components analysis PCA, partial least
(1) The output DS spectra of DSAP have the shift trend to the lower squares PLS, or artificial neural networks) are often employed
frequency range as oxidation duration increases, which is dif- [31,32].
Fig. 4. DS spectra (a) set one at 40 ◦ C. DS spectra (b) set one at 100 ◦ C. DS spectra (c) set two at 40 ◦ C. DS spectra (d) set two at 100 ◦ C. DS spectra (e) set three at 40 ◦ C. DS
spectra (f) set three at 100 ◦ C.
L. Guan et al. / Sensors and Actuators A 168 (2011) 22–29 27
Table 9
Predictive results of sample set one based on DS data.
Table 10
Predictive results of sample set two based on DS data.
Table 11
Predictive results of sample set three based on DS data.
Table 12
Predicted results of all samples based on transformed DS data.
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