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IEEE Transactions on Dielectrics and Electrical Insulation

Vol. 16, No. 2; April 2009

509

Highly Sensitive Detection Method of Dibenzyl Disulfide and the Elucidation of the Mechanism of Copper Sulfide Generation in Insulating Oil
S. Toyama, J. Tanimura, N. Yamada, E. Nagao
Mitsubishi Electric Corporation Amagasaki, Hyogo 661-8661 and T. Amimoto Mitsubishi Electric Corporation Ako, Hyogo 678-0256, Japan

ABSTRACT
Highly sensitive detection method of dibenzyl disulfide (DBDS) in insulation oil was realized using solid phase extraction (SPE) with active alumina adsorbent followed by gas chromatography equipped with a mass spectrometry (GC-MS). The detection limit of DBDS is around 0.1 ppm. This method is also useful for detecting bibenzyl (BiBZ) and dibenzyl sulfide (DBS). The good relationship between the weight change of copper strip and BiBZ /DBS formation was obtained under heating with insulating oil containing DBDS and copper strip, so it was clarified that BiBZ and DBS are the byproducts of the copper sulfide generation with the chemical reaction between DBDS and copper. The chemical reaction formula between DBDS and copper was proposed based on the assumption that copper sulfide should be generated via Cu-DBDS complex. The temperature dependence of the weight change of copper strip before and after the heating in the insulating oil containing DBDS was quantitatively explained with the chemical reaction formula. Index Terms Copper, copper compounds, oil insulation, paper insulation, sulfur, sulfur compounds, transformers, transformer oil, chromatography.

1 INTRODUCTION
THE mechanism of copper sulfide generation in transformers and reactors has been intensively studied around the world [1]. It was revealed over the past several years that most of malignant oil contained dibenzyl disulfide (DBDS) [2, 3]. Highly sensitive analysis of DBDS is important for the diagnosis of the aging transformer and for the screening of the insulating oils. The analytical results of DBDS in insulating oils were reported by using gas chromatography equipped with atomic emission detector (GC-AED) or gas chromatography equipped with mass spectrometry (GC-MS) [2, 4]. The detection limit of DBDS using these methods seemed to be around 5-10 ppm. In the case of lower DBDS concentration, the peak of DBDS cannot be detected by means of the methods described in these reports, because the peak of DBDS is concealed behind many peaks of insulating oil. It is thought that solid phase extraction (SPE) or other pretreatment is the suitable choice for the isolation of DBDS from insulating oil.
Manuscript received on 14 February 2008, in final form 24 December 2008.

DBDS improved the lubricant effectiveness of mineral oil, so several researchers reported the mechanism of tribochemical reaction and the thermal decomposition of DBDS [5, 6]. Dibenzyl sulfide (DBS) and several compounds have been reported as the by-products generated from the chemical reaction of DBDS with iron. But the mechanism for the chemical reaction of copper and DBDS has not been cleared. The purpose of this study is to elucidate the mechanism of copper sulfide generation. As a first step, we develop an analytical method for highly sensitive detection of DBDS and by-products. We developed the analytical method for DBDS and by-products detection on the low order of ppm in insulating oil by using the conventional SPE technique and the gas chromatography. As the second step, we investigated the kinetics of copper sulfide generation. The rate of chemical reaction between DBDS and copper was obtained by the quantitative analysis of DBDS and by-products. Through the measurement of the chemical reaction rate, the chemical reaction mechanism of copper sulfide generation was elucidated.

1070-9878/09/$25.00 2009 IEEE

510

S. Toyama et al.: Highly Sensitive Detection Method of Dibenzyl Disulfide and the Elucidation of the Mechanism

2 EXPERIMENTAL PROCEDURE
2.1 ANALITICAL METHOD FOR DBDS, bibenzyl (BiBZ) and DBS A set of the calibration standard oils for the determination of DBDS, BiBZ and DBS was prepared by dissolving DBDS, BiBZ and DBS in commercial insulating oil in concentration from 0.3 to 180 ppm. The 500 mg calibration standard oils were diluted to 1 ml with hexane. Then, the diluted samples were penetrated into SPE cartridge. The adsorbent used in this study was a 100 mg chromatographic-grade active alumina. In this procedure, DBDS, DBS and BiBZ were adsorbed on the active alumina. The adsorbent was washed by 1 ml of hexane three times. The DBDS, DBS and BiBZ adsorbed on the active alumina were desorbed from alumina with 1ml of benzene. The benzene was analyzed by GC-MS (JMS-K9, JEOL). Injection amount into the GC-MS was 1 l with pulsed splitless injection method for avoiding deterioration of chromatographic peak shape. The analyzing column was HP-5 (250 m ID 30 m, Agilent). The temperature of injection was 300 C. The column temperature was initially held at 100 C for 5 min and then ramped to 300 C at 5 C /min and was held at 300 C for 15 min. The selected ion monitoring (SIM) method was used for the detection of BiBZ, DBS and DBDS. The condition of ionization was as shown below.
Table 1. The condition of detector parameter. Temperature Mass Range Monitoring Ion BiBZ DBS DBDS 250 C 35 to 500 (SCAN) 91 and 182 (15.4-17.0 min) 91, 123 and 214 (22.5-23.5 min) 91, 181 and 246 (28.0-29.0 min)

2.4 ANALYZING COPPER STRIPS SAMPLES After the heating, the external view of copper strips was investigated and the weight of the copper strip was measured using a microbalance. As a first approximation the weight change of the copper strip before and after the heating was proportional to the amount of generated copper sulfide.

3 RESULTS
3.1 ANALYSIS OF CALIBRATION STANDARD SAMPLES Figure 1 shows the gas chromatogram (M/Z=91) of the SPE effluent obtained for the calibration standard oil (1 ppm). (A) (B)

(B)

(C)

(A)

(C)

Figure 1. Gas chromatogram (M/Z=91) of effluent obtained from the calibration standard oil containing 1 ppm (A) BiBZ, (B) DBS and (C) DBDS by SPE technique.

2.2 PREPARING THE SAMPLE OIL WITH COPPER SULFIDE GENERATION The sample oil was prepared by dissolving DBDS or DHDS (dihexyl disulfide) in commercial insulating oil in a sulfur concentration of 300 ppm. The commercial insulating oil was non-corrosive one. The corrosivity of this oil was checked by CCD test according to CIGRE method (Siemens CCCD). 4 g of this insulating oil was sealed into 10cc vial with copper strip of 500 mg (15 mm 20 mm 0.2 mm). The vials containing the sample oil and the copper strip were heated for 1-24 h at the temperature of 135, 150 and 165 C. 2.3 ANALYZING OIL SAMPLES After the heating, concentrations of DBDS, DBS and BiBZ in the insulating oil were determined by the method described in the section 2.1.

Figure 2. Gas chromatogram of the same oil as Fig. 1 without SFE.

Peaks assigned for each compound, BiBZ, DBS and DBDS, were described in the figure. Each peak was detected clearly, because these peaks were not interfered by peaks of other compounds containing in the base insulating oil. Figure 2 shows the gas chromatogram (M/Z=91) for the 1 ppm calibration sample without using the SPE technique. Arrows in the Figure 2 show the retention time for BiBZ, DBS and DBDS. In this case, the detection of BiBZ, DBS and DBDS interfered with many compounds containing in

IEEE Transactions on Dielectrics and Electrical Insulation

Vol. 16, No. 2; April 2009

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the base insulating oil, like paraffin. These results indicate that the peaks of these compounds cannot be detected in the case of low concentration under a few ppm. Figure 3 shows the calibration curve for BiBZ, DBS and DBDS in the case using the SPE. Fine line shape correlation was obtained for each compound and the detection limit of the each compound is around 0.1 ppm. It is obvious that the SPE method with active alumina is powerful technique for detecting BiBZ, DBS and DBDS of low concentration in insulating oil.
250000 200000 Peak area 150000 100000 50000 0 - 50000 Concentration(ppm)
8000 6000 Peak area 4000 2000 0 -2000 0 0.5 1 1.5 Concentration(ppm)

under the different temperature conditions. The slight discoloration of copper strip was observed, but the color of copper strip differs from that of copper sulfide (black or gray with luster). Figure 4 shows the relationship between heating time and the weight change of the copper strip by heating. Copper strip was immersed in insulating oil containing 300
Table 3. Optical photographs of copper strips immersed in insulating oil with 300 ppm DHDS under the different temperature conditions.

135 C A

150 C

165 C

6h B

3h

1.5 h

12 h
0 5 10 15 20 25 30 35

6h

3h

Figure 3. Calibration curve of BiBZ, DBS and DBDS. (:BiBZ, :DBDS, :DBS) Inset graph is a close-up of lower concentration region.

24 h

9h

4.5 h

3.2 WEIGHT CHANGE OF COPPER STRIP DURING HEATING Table 2 shows optical photographs of copper strips immersed in insulating oil containing 300 ppm DBDS under the different temperature conditions. The considerable discoloration of copper strip resulting copper sulfide formation was observed after 3 h at 150 C, and after 1.5 h at 165 C. The discoloration of copper strip was not observed till 24 h at 135 C. Table 3 shows optical photographs of copper strips immersed in insulating oil containing 300 ppm DHDS
Table 2. Optical photographs of copper strips immersed in insulating oil with 300 ppm DBDS under the different temperature conditions.

ppm DBDS. The weight of copper strip increased with heating time at 165 C. The increase in the weight of copper strip can be explained in terms of the deposit of copper sulfide on the surface of copper strip. At 150 C, the weight of copper strip initially decreased, but increased with heating time after 3 h. The copper strip weight decreased with heating time at 135 C. This result showed that the copper was dissolved in insulating oil at least 135 C. Because of the low solubility of copper ion in the insulating oil, it is hard to explain that the copper ion was dissolved in insulating oil at 135 C. The increase in
15
Weight change of copper strip g/cm2)

10 5 0 -5 0 -10 -15 -20 Heating time h 10 20 30

135 C A

150 C

165 C

6h B

3h

1.5 h

12 h C

6h

3h

Figure 4. Weight change of copper strip immersed in insulating oil containing 300 ppm DBDS. ( : 165 C, : 150 C, : 135 C)

24 h

9h

4.5 h

solubility of copper ion could be explained in terms of the formation of copper complex. It is thought that a complex is formed by the reaction of copper with DBDS on the copper strip surface. Then DBDS-Cu complex was

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S. Toyama et al.: Highly Sensitive Detection Method of Dibenzyl Disulfide and the Elucidation of the Mechanism

dissolved in the insulating oil. Since the weight of copper strip decreased with heating time at 135 C, not only the formation of DBDS-Cu complex but also the dissolve DBDS-Cu complex into the insulating oil was more rapidly than the formation of copper sulfide. On the other hand, the formation of copper sulfide was more rapidly than that of DBDS-Cu complex at 165 C, the weight of copper strip increased with heating time. Copper sulfide formation involved the fission of C-S bond of DBDS-Cu complex and the formation of benzyl radical. The relative high stability of benzyl radical can be ascribable to the character as resonating molecule. Figure 5 shows the relationship between heating time and the weight change of the copper strip by heating. Copper strip was immersed in insulating oil containing 300 ppm DHDS. The weight of the copper strip decreased with heating time at 165 and 150 C. The decrease in the weight of copper strip suggests that the generated DHDS-Cu complex is dissolved in the insulating oil. DHDS-Cu complex is hard to generate the copper sulfide. Because the hexyl radical is more labile than benzyl radical, the fission of C-S bond of DHDS-Cu complex is hard to occur. The weight of copper strip slightly increased with heating time at 135 C. Induced dipole interaction of benzene ring enhanced the solubility of ions. Because there was no benzene ring in DHDS, the solubility of DHDS-Cu complex was probably insufficient to be dissolved all of DHDS-Cu complex in insulating oil at low temperature (e.g. 135 C). The DHDS-Cu complex was remained on the copper strip surface.
10
Weight change of copper strip ug/cm2)

than those in Figure 7. This suggested that BiBZ and DBS were not formed in the absence of copper strip. Figure 8 shows the relationship between the weight change of copper strip at 165 C and the decrease in DBDS concentration. The decrease in the concentration of DBDS was proportional to the increase in the weight change of copper

B A

Figure 6. Gas chromatogram of insulating oil with addition DBDS. (M/Z=91) (165 C 10 h with copper strip)

5 0 -5 -10 -15 -20 -25 Heating time (h) 0 10 20 30

B A

Figure 7. Gas chromatogram of insulating oil with addition DBDS. (M/Z=91) (165 C 10 h without copper strip)

Decresse in DBDS concentration (ppm)

Figure 5. Weight change of copper immersed in insulating oil containing 300 ppm DHDS. (: 165 C, : 150 C, : 135 C)

350 300 250 200 150 100 50 0 0 0.01 0.02 0.03 0.04 0.05 Weight change of cupper strip (%)

3.3 Analytical results of insulating oils Figure 6 and 7 show the gas chromatogram (M/Z=91) of insulating oil with addition DBDS heated at 165 C for 10 h with or without copper strip, respectively. It is apparent from Table 1 and Figure 4 that copper sulfide was formed under this condition. The peak C of DBDS in Figure 6 was much smaller than that in Figure 7, so DBDS concentration decreased in the presence of copper strip. On the other hand, the peak A of BiBZ and the peak B of DBS in Figure 6 were much bigger

Figure 8. . Relationship between weight change of copper strip and decrease in DBDS concentration.

IEEE Transactions on Dielectrics and Electrical Insulation

Vol. 16, No. 2; April 2009 Step 2.2 Formation of by-products 4C6H5CH2*+4C6H5CH2S* C6H5CH2CH2C6H5+2(C6H5CH2)2S+(C6H5CH2)2S2(2)

513

strip, so the copper sulfide was generated by the chemical reaction of DBDS with copper. As shown Figure 9, the good relationship between the weight change of copper strip and the concentration of BiBZ is obtained, so it is clarified that BiBZ is the by-products of the copper sulfide generation with the chemical reaction between DBDS and copper. Similar result was obtained from the relationship DBS and the weight change of copper strip, so DBS is also the by-products of the chemical reaction of DBDS with copper.
120
BiBZ concentration (ppm)

Equations (1) and (2) can be combined to give equation (3).


8Cu+3(C6H5CH2)2S2 4Cu2S+ C6H5CH2CH2C6H5+2(C6H5CH2)2S (3)

18
DBS concentration (ppm)

Furthermore, DBS formed in equation (3) react with copper.


2Cu+(C6H5CH2)2S Cu2S+ C6H5CH2CH2C6H5(4)

100 80 60 40 20 0 0 0.01 0.02 0.03 0.04 Weight change of copper strip (%)

15 12 9 6 3 0 0.05

Then, equations (3) and (4) can be combined to give equation (5).
4Cu+ (C6H5CH2)2S2 2Cu2S+ C6H5CH2CH2C6H5(5)

The principal chemical reaction will be determined by temperature and heating time. 4.2 THE RATE OF CHEMICAL REACTION Figure10 shows the concentration of generated BiBZ and DBS and DBDS at different temperature. The rate of chemical reaction is calculated from the slope. The rates of the chemical reactions obtained from the slopes are summarized in Table4. The rate of formation of DBDS-Cu complex is equal to the rate of the decrease in DBDS concentration from
Table 4. Rate of chemical reaction (mM/h). BiBZ 135 C 150 C 165 C 0.0013 0.0043 0.0193 DBS 0.0036 0.0056 0.0145 DBDS -0.0263 -0.0525 -0.2251

Figure 9. Relationship between weight change of copper strip and BiBZ concentration () and DBS concentration ().

4 DISCUSSION
4.1 THE CHEMICAL REACTION MECHANISM FOR THE FORMATION OF COPPER SULFIDE As described above, formation of BiBZ and DBS from DBDS was observed in the presence of copper strip. These by-products were created when copper sulfide generated on copper at high temperature. On the other hand, copper weight was decreased at low temperature. The decrease in the weight change of copper strip reflects the dissolution of copper ion into oil. Copper dissolution was caused by the formation of DBDS-Cu complex. It is suggested that copper sulfide formation on insulating paper should be occurred via DBDS-Cu complex at low temperature. Copper sulfide and the radical intermediates are generated by the decomposition of Cu-DBDS complex. These radical intermediates form BiBZ and DBS. The chemical reaction mechanism of copper sulfide generation can be estimated as follows.
Step 1: Formation of DBDS-Cu complex

2Cu+(C6H5CH2)2S2 (C6H5CH2)2S2-Cu2.(1) Step 2: Step 2.1: Formation of copper sulfide and by-products Formation of copper sulfide

(C6H5CH2)2S2Cu2 Cu2S+C6H5CH2*+C6H5CH2S**radical

equation (1).The rate of generation of copper sulfide is 4 times of the rate of the formation of BiBZ from equation (3). The rate of formation of copper sulfide is 2 times of the rate of the formation of BiBZ from equation (5). Figure 11 shows the temperature dependence of the rate of generation of copper sulfide (dot line obtained from equation (3) and dot-dash line obtained from equation (5)) and DBDS-Cu complex (solid line obtained from equation (1)). The rate of the formation of DBDS-Cu complex is higher than that of generation of copper sulfide at 135 C. So the weight of copper strip is decrease at this temperature. Since the rate of the formation of DBDSCu complex is lower than that of generation of copper sulfide at 165 C, copper sulfide is generated on the copper strip. The weight change of copper strip shown in Figure 4 can be explained from the comparison of the chemical reaction rate.

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S. Toyama et al.: Highly Sensitive Detection Method of Dibenzyl Disulfide and the Elucidation of the Mechanism

2 1.8
BiBZ concentration mM)

(a)
y = 0.1929x - 0.1031

0.16 0.14
DBS concentration mM)

(b)

y = 0.0145x - 0.0009

6
DBDS concentration (mM)

(c)
y = -0.0263x + 4.1951

1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 10


y = 0.0013x + 0.1406 y = 0.0043x + 0.1127

0.12 0.1 0.08 0.06 0.04 0.02 0 0 10

y = 0.0056x + 0.0034

5 4 3 2 1 0

y = -0.0525x + 4.6107

y = 0.0036x + 0.0043

y = -0.2251x + 4.9503

20

30

20

30

20 Heating time (h)

40

Heating time (h)

Heating time (h)

Figure 10. Concentration of (a) BiBZ, (b)DBS and (c)DBDS at different temperature.: 135 C, : 150 C, : 165 C.

1
Rate of reaction mM/h)

dependence of the weight change of copper strip before and after the heating in the insulating oil containing DBDS was quantitatively explained with the chemical reaction formula.

0.1

ACKNOWLEDGMENT
The authors would like to acknowledge Mr. Taninouchi, Mr. Kouan, Mr. Hosokawa and Mr. Kawashima in Mitsubishi Electric Corporation for their support and great advice from transformer designers.
0.0023 0.00235 0.0024 0.00245 Temperature -1) K 0.0025

0.01

0.001 0.00225

REFERENCES
[1] [2] CIGRE TF A2.31, Copper sulphide in transformer insulation, Electra, No. 20, pp. 20-23, 2006. F. Scatiggio, V. Tumiatti, R. Maina, M. Tuminatti, M. Pompili and R. Bartnikas, Corrosive Sulfur in Insulating Oils: Its Detection and Correlated Power Apparatus Failures, IEEE Trans. Power Del., Vol. 23, pp 508-509, 2008. R. Maina, F. Scatiggio, S. Kapila, V. Tumiatti, and M. Tumiatti and M. Pompilli, Dibenzyl disulfide (DBDS) as corrosive sulfur Contaminant in used and unused mineral insulating oils, Available: http://www.cigrea2.org/Site/Publications/download/DBDS_paper_ColorVersionID44 VER52.pdf M. Dahlund , L. Pettersson,, H. Onnerud, K. Gustafsson, R. Leandersson and S. Karlsson, Removing Corrosive sulphur Transformer Oil By Using Conventional On-Line Oil Reclaiming Technique, CIGRE SC A2 & D1 Colloquium, Belgium, PS2-10, 2007. S. Plaza, L.R. Comellas and L. Starczewski, Tribochemical chemical reactions of dibenzyl disulfide in boundary lubrication, Wear, Vol. 205, pp. 71-76, 1997. S. Plaza, R. Gruzinski, Homogenious and heterogeneous thermal decomposition of diphenyl disulfide, Wear, Vol. 194, pp. 212-218, 1996.

Figure 11. Relationship between the rate of chemical reaction and temperature. (: Step 1, : Step 2 (equation (5)), : Step2 (equation (3)).

5 CONCLUSION
Use of appropriate gas chromatography-mass spectrometry conditions using alumina-based solid phase extraction technique allowed the detection of BiBZ, DBS and DBDS of the low order of ppm. The good relationship between the weight change of copper strip and BiBZ /DBS generations was obtained under heating with insulating oil including DBDS and copper strip, so it was clarified that BiBZ and DBS is the by products of the copper sulfide generation with the chemical reaction between DBDS and copper. The chemical reaction formula between DBDS and copper with DBDS-Cu complex was supposed and the copper sulfide generation rate and DBDS-Cu complex generation rate were estimated. The temperature

[3]

[4]

[5]

[6]

IEEE Transactions on Dielectrics and Electrical Insulation

Vol. 16, No. 2; April 2009

515
E. Nagao was born in Japan on 2 August 1959. He received the B.S., M.S., and D.S. degrees in physics from Osaka University in 1983, 1985 and 1994, respectively. He joined Mitsubishi Electric Corporation in 1985 and has been engaged in research and development of materials, diagnosis and sensing technology for GIS, GCB and transformers. Dr. Nagao is a member of the Institute of Electrical Engineers of Japan and The Physical Society of Japan. T. Amimoto was born in Japan on 18 September 1969. He received the B.S. degree in chemistry from Ibaraki University in 1992. He joined Mitsubishi Electric Corporation in 1992 and has been engaged in research and development of material diagnosis for transformers. Mr. Amimoto is a member of the Institute of Electrical Engineers of Japan and The Japan Petroleum Institute

S. Toyama was born in Japan on 26 September 1960. He received the B.S. and M.S. degrees in chemistry from Osaka City University in 1984 and 1986, respectively. He joined Mitsubishi Electric Corporation in 1991 and has been engaged in the research of material analysis.

J. Tanimura was born in Japan in 1965. He received the B.S. and M.S. degrees in physics from Osaka University in 1988 and 1990, respectively. He joined Mitsubishi Electric Corporation in 1990 and has been engaged in research on material analysis, especially for microstructure analysis using TEM.

N. Yamada was born in Japan in 1960. He received the B.S. degree in mechanical engineering from Yamguchi University in 1982 and the M.S. degree in industrial mechanical engineering in 1985. He joined Mitsubishi Electric Corporation in 1985 and has been engaged in research and development of MEMS and Polymer processing. Mr. Yamada is a member of the Japan Society of Mechanical Engineers and the Japan Society of Polymer Processing.

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