Fuel 81 (2002) 12271232

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Adsorption and surface properties of silica with transformer insulating oils q

Amane Jada a,*, Abdelouahed Ait Chaou a, Yves Bertrand b, Olivier Moreau c
b

Institute de Chimie des Surfaces et Interfaces, 15 rue Jean Starcky, B.P. 2488, 68057 Mulhouse, France veloppements, Electricite de France, CIMA 8, Les Renardie res, BP 1. F-77818 Moret-sur-Loing Cedex, France Division Recherche et De c partement Machines Electriques, Division Recherche et De veloppements, Electricite de France, Service Mate riel Electrique, De ne ral de Gaulle, 92 141 Clamart Cedex, France 1 Avenue du Ge Received 22 January 2001; revised 19 December 2001; accepted 7 January 2002; available online 12 February 2002

Abstract The presence of polar species in transformer insulating oil may cause degradation and electric discharges in the power transformer. Such oil polar fraction can originate either from the neat oil and/or from its oxidative degradation in the power transformer. The aim of this study is to examine the relation between the insulating oil and the electrical properties of its polar fraction in order to predict eventual failure in the power transformer. We investigate at ambient temperature the adsorption of the polar fractions of various transformers insulating oils (a new and two used oils) from the neat oils onto silica particles. The adsorbed amount was higher for the used oils as compared to the new one. Infrared spectra of the polar fraction indicate the presence of hydroxyl, aromatic and carboxyl functional groups that are found in the asphaltenes compounds. Microelectrophoresis study of the oil polar fraction covered silica particles gives negatively charged oil polar fraction. Such oil surface charge depends on the pH and results from the ionisation of the oil acidic surface groups. Finally, we obtain a good correlation between the amount of the oil polar fraction and the magnitude of the zeta potential at the water/oilsilica interface. q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Asphaltenes; Adsorption; Silica; Zeta-potential

1. Introduction Insulating oils are used in the electric power transformer mainly to transfer heat. However, static electrication due to the insulating liquid ow causes failure and electric discharges in the power transformers [111]. Further, the presence of small amount of sulphur in the oil can promote dissolution of copper (cupric corrosion by sulphur), which functions as degradation catalyst of the oil. In order to overcome static electrication and oil degradation, we add the benzotriazole (BTA) to the insulating oil in some manufactures researches [2]. This molecule adsorbs easily from the oil onto the pressboard and metallic cooper. Hence, the addition of the BTA to the oil inhibits charge separation on the pressboard and reduces the oil degradation [2]. The static electrication, which is due to the liquid ow, results from the charge generation at oil/pressboard interface. In this process, it is generally assumed that the
* Corresponding author. Tel: 133-3-896-08709; fax: 133-3-896-08799. E-mail address: a.jada@univ-mulhouse.fr (A. Jada). q Published rst on the web via Fuelrst.comhttp://www.fuelrst.com

pressboard and the oil acquire, respectively, a negative and a positive charge, due to preferential adsorption onto the pressboard of negative ions present in the oil (impurities, additives). Static electrication occurs if the energy of oil ow is sufcient to separate these ions from the oil/pressboard interface. Previous simulation studies [12], on static electrication, have shown that charge generation at oil/ pressboard interface results not only from the transfer of ionic species from the oil to the pressboard, but also from the pressboard to the oil. In that work, the authors consider two modelling approaches for simulation studies. According to these models, charge generation at oil/pressboard interface can be due either to adsorption onto the pressboard of negative ions present in the oil, or to diffusion in the oil of positive ions coming from the pressboard. Such positive ionic species may be the protons H 1 that result from the dissociation of the alcohol radicals in the cellulose. The two modelling approaches considered in the simulation studies [12] were in accordance with the experimental observations. Several authors [1322] have studied the process of the electrical charge generation at solid/organic liquid interface. From these works, it was concluded that the solid acquires

0016-2361/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved. PII: S 0016-236 1(02)00019-4

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electrical charges either by preferentially adsorbing ions, possibly still associated in structures, or by ion formation resulting from surface groups dissociation, which are being held in some lyophilic structure. Therefore, the occurrence of the static electrication in power transformer suggests the presence of an electrical double layer at the oil/pressboard interface. Mineral transformer oil is mainly a mixture of hydrocarbon compounds of three classes: alkanes, naphtenes and aromatic hydrocarbon. Polar compounds found in the transformer oil are a minor part of the constituents, and usually contain heteroatoms, such as, oxygen, nitrogen, or sulphur, which may greatly inuence the chemical and electrical properties of the oil. These heteroatoms are mainly associated with the oil aromatic structures, such as pyridine, pyrazine, pyrrole, carbazole, indole, or benzoic acid groups and can result in their stabilisation in aqueous medium. Further, nitrogen and oxygen atoms can be involved in various acid and basic functional groups, such as carboxylic acid, ether, ester, aldehyde, ketone, amine and amide [2325]. In addition, Waldo et al. [26] showed that sulphur atom is essentially present in thiophene and organic sulphur form. The insulating oil polar fraction can result either from the neat oil and/or from its oxidative degradation in the power transformer. It is mainly made of charged particles in the oil, which deteriorates transformer insulation by decreasing electrical strength. It is useful to know the amount and the charge of this polar fraction to predict future failure in power transformer. The object of this work is to establish a relationship between the chemical and the electrical properties of the transformer insulating oil polar fraction. For this purpose, we have extracted the polar fractions of various transformers insulating oils from their neat oils by using silica gel as solid support, and we have examined their surface compositions and charges. 2. Experimental 2.1. Materials de France supplied the three oils used in this Electricite work. Two oils, respectively, UO1 and UO2, were used in power transformers, while the third oil, NO, is new oil. The silica substrate used is a silica gel 60 for column chromatography purchased from Merck, having specic surface area 480540 m 2 g 21. The solid particles size 40 60 mm, which are aggregates of primary particles having size of about 12 nm. 2.2. Extraction and adsorption onto silica of the oil polar fraction The silica gel 60 was preliminary heated at 100 8C during 1 day, a weight amount (2 g) of the dried silica was placed in a stoppered bottle and a known volume (50 cm 3) of the neat

oil was added. The resulted dispersion was allowed to stand few days at ambient temperature, until the adsorption equilibrium was reached. Then, the oil fraction covered silica substrate was separated from the dispersion and washed several times with n-hexane to remove the residual nonpolar oil fraction adsorbed on silica. Finally, the oil polar fraction covered silica solid substrate was placed in an oven, until all the residual n-hexane was driven off into vapour. 2.3. Preparation of the oil polar fraction covered silica particles aqueous dispersions The silica dispersions were prepared by introducing a given amount of the oil covered silica particles (0.1%) in the 10 23 M NaCl aqueous solutions. The resulted dispersions were ultrasonicated for few minutes and the pH values of the systems were varied in the range 39 by adding to the dispersions small amounts of sodium hydroxide (NaOH) or hydrochloric acid (HCl) aqueous solutions. The nal silica dispersions were then shaken for few days, until electrical equilibrium was reached. The nal pH values were measured prior the zeta potential measurements. 2.4. Infrared measurements Infrared spectra of the sample were recorded on BRUKER (IFS 66, IFS 66/S, IFS 48) apparatus with a golden gate single reection diamond attenuated total reectance (ATR) accessory, purchased from GRASEBY SPECAC. In this technique, the sample (the neat oil or the oil polar fraction) is held in intimate contact on an ATR crystal and internal reection occurs, when the infrared radiation enters the ATR crystal (diamond). The crystal design enables total internal reection of the radiation that creates an evanescent wave at the crystal surface. Such evanescent wave extends into the sample, which is in contact with the crystal. The spectra were an accumulation of 100 scans and ranged from 4000 to 600 cm 21. We have recovered the oil polar fraction from the oil polar fraction covered silica solid substrate by using ethanol as eluent. The resulted ethanol solution was then placed in a vacuum rotary evaporator to drive out the residual solvent and to yield the pure oil polar fraction, which was investigated by the infrared spectroscopy. 2.5. Zeta potential measurements The electrokinetic potential or zeta potential of the silica dispersions was measured at ambient temperature using the microelectrophoresis method. The measurements were made with a Zetaphoremeter II model Z3000, having cell section of 0.5 0.2 cm 2, apparent cell dimension of 1504 mm and a micrometer calibration with objective 20.X: 50 mm. This apparatus purchased from SEPHY, converts the electrophoretic mobility Ue into the zeta potential z according to the Smoluchowski's equation [27,28]: z h=1Ue ; where h and 1 are, respectively, the viscosity

A. Jada et al. / Fuel 81 (2002) 12271232 Table 1 Amounts of the oil polar fractions adsorbed on the silica and maximum values of the zeta potential in water of the oil covered silica particles Insulating oil Reference in the text Amount of the polar fraction adsorbed on the silica (in gram of the polar fraction per 100 cm 3 of the neat oil) (%) 0.05 0.36 0.20 Maximum value of the oil polar fraction covered silica particles zeta potential (mV) 2 35 2 45 2 70

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New oil Used oil Used oil

NO UO1 UO2

and the permittivity of the aqueous medium. At least, we achieve three experiments with each dispersion. The values of the zeta potential were reproducible within ^2 mV.

3. Results and discussion 3.1. Infrared spectra of the neat oil and its polar fraction Table 1 presents the amounts of the oil polar fractions found in various insulating oils. As can be observed in the table, the amounts of the polar fractions are higher in the used oils as compared to the new one. The Fourier transform infrared spectra (FTIR) of the neat oils NO, UO1 and UO2, obtained in the region 4000600 cm 21, are presented, respectively, in the Fig. 1(a)(c). As can be seen in the gures, the neat oils from different origins display similar infrared spectra and are of high aliphatic index. These spectra show three stretching and two bending absorption peaks, respectively, in the regions 30002800 and 1450 1370 cm 21, due to the alkyl CH bonds. In addition, Fig. 1(a)(c) indicates that the used oils UO1 and UO2 as compared to the new one NO, are not degraded. It is useful to know the structure of the insulating oil polar fraction, which is the oil active specie that can cause electric discharges and failure in the power transformer. Knowing the structure of such oil polar fraction will allow us a better understanding of its adsorption properties and the polarisation that occurs at the pressboard/insulating oil interface. Fig. 2(a) and (b) shows infrared spectra of, respectively, UO1 and UO2 polar fractions. Hence, we can observe different features, when we compare the spectra to those of the neat oils, in the region 18001600 and 34003100 cm 21. The spectra in Fig. 2(a) and (b) indicate also that the oil polar fractions contain associated phenolic groups due to hydrogen bonding, carboxylic groups, and aromatic groups. These groups absorb, respectively, in the regions, 3400 3100, 18001700, and around 1600 cm 21. Moreover, Fig. 2(a) and (b) shows that the amount of the polar groups, i.e. phenolic, carboxylic and aromatic groups, increase from the UO1 to UO2 oil. On the other hand, the infrared spectra of the asphaltenes as studied by others authors [2931], present various absorption bands, which are found in the spectra of oil polar fractions investigated in the present work. These absorption bands are usually assigned to the

CH bonds of alkyl, the CH and the CyC bonds of aromatic compound, the CyO bonds of carbonyl groups, and the OH bonds of alcohol. Accordingly, the infrared spectra of the UO1 and UO2 oil polar fractions presented in Fig. 2(a) and (b) are consistent with the structure of the asphaltenes. Thus, the asphaltene compounds contain oxygen atoms, which are involved in various acidic functional groups of linear or aromatic structures analogous to carboxylic acid, and phenolic acid groups. Such groups, as determined by infrared spectroscopy, refer to the family of compounds containing the carboxylic or phenolic, which are bounded by alkyl chains to the condensed aromatic rings of asphaltenes. 3.2. Electrical properties of the oil polar fraction The electrical properties of the oil polar fractions were determined by measuring the zeta potential of the oil polar fraction covered silica particles. The analysis of the oil polar fraction electrical properties provides a way of examining charged particles in the oil, when the transformer is in equilibrium operation. Such charged particles can adsorb from the oil onto the pressboard and hence cause failure in the transformer. Further, varying the pH of the aqueous dispersion allows us to control the polarity of the oil polar fraction covered silicawater interface and its inuence on the acidity of the oil surface functional groups. Fig. 3 indicates the variation of the zeta potential versus the pH, for various oil polar fraction covered silica aqueous dispersions. The negative values of the zeta potential of the aqueous dispersions observed in the pH range 39 indicate negative oil polar fraction surface charges. For the bare silica, the negative surface charge observed is due to the ionisation of the surface hydroxyl groups. The properties of such silica are determined by the surface chemical activity, which in turn depends on the concentration, the distribution, the type of hydroxyl groups, the presence of siloxane bridges; and on the porous structure of the silica. Several studies [32,33] conrm the presence of silanol (SiOH) groups on silica surface. In addition, in the capillary electrochromatography on silica columns, used for separation of organic compounds, the efciency depends on the silica particle size [34]. The mechanism of the surface charge generation at the

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Fig. 1. (a) Infrared spectra of the NO neat oil. (b) Infrared spectra of the UO1 neat oil. (c) Infra red spectra of the UO2 neat oil.

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bare SiO2 water interface is mainly due to the adsorption of hydroxyls (OH 2) onto an amphoteric silica site. The isoelectric point, i.e. the pH at which the zeta potential z 0; for this system can be obtained only by extrapolation, since it occurs at about pH 2.5. Further, the acid side of the z -pH curve is not accessible to electrokinetic measurements. On the other hand, the negative surface charge observed in Fig. 3 for the oil polar fraction covered silicawater interface, is attributed to the ionisation of the oil polar fraction acidic groups. These groups, the carboxylic acid and phenolic acid groups, have respectively, pKa , 4 and 4 , pKa , 9 values [3537]. The important feature exhibited by these used oil polar fractions, UO1, and UO2, when compared to the bare silica, is the increase in the magnitude of the zeta potential at pH values above 4. This behaviour is due to the increase of the concentration of the oil surface groups, i.e. the carboxylic acid and phenolic acid. However, the nonused oil NO shows slight variations in the zeta potential, within the experimental error range ^2 mV. Fig. 3 indicates also an increase in the plateau levels z max (see Table 1) from the UO1 to the UO2, in a good agreement, with the increase of their respective polar group amounts, as observed on their FTIR spectra. The change in the surface charge observed for the oil polar fractions in the aqueous medium is related to the nature and the amount of acidic groups present at their surfaces. In addition, an arrangement of oil components on the silica surface will occur in water, which will give

rise to the acidic groups development at the oilwater interface. This surface arrangement is due to the differences in the afnity of the various oil components for water and silica. It is likely that the polarity of charging at the oil polar fraction/silica interface may resemble to the same charging that occurs at the oil/pressboard interface in the power transformer. In fact, the surface of the paper or on the pressboard, used in the transformer, contains polar groups, such as hydroxyl (OH) that we nd also on the silica surface. In these groups, the hydrogen and the oxygen atoms are, respectively, positively and negatively polarised, due to the large electronegativity of the oxygen atom. Such positive polarised hydrogen has an afnity for the phenolic groups that belongs to the oil polar fraction. Hence, in the transformer, the pressboard may selectively adsorb the family of compounds containing the phenolic groups, which are bounded by alkyl chains to the condensed aromatic rings of the oil polar fraction. Further, according to Fowkes [38], the acidbase interactions between the acidic groups at the surface of a solid and the basic groups of the molecules of a liquid are very specic. The energy of such interaction is proportional to the enthalpy of the complex or adducts formation of the acidbase pair and to their surface concentration. Thus, in the pH range 39, acidbase complexes between the acidic groups of the oil polar fraction and the ions OH 2 of the aqueous solution form at the solidwater interface. Therefore, an increase of the oil polar fraction surface charge with the increase

Fig. 2. (a) Infrared spectra of the insulating oil UO1 polar fraction. (b) Infrared spectra of the insulating oil UO2 polar fraction.

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methods seems to be a good tool for analysis of the surface charge and the structure of the particles included in the insulating oil and hence to prevent electrical discharges in power transformer. References
[1] Shimizu S. IEEE Trans Power Appar Syst 1979;PAS-98(July/ August). [2] Okubo H. Transaction A 79 051-4, IEEE Winter Power Meeting, New York, 1979 (and references cited therein). [3] Tamura R. IEEE Trans Power Appar Syst 1980;PAS-99(1) IEEE PES Summer Meeting, Vancouver, British Columbia. [4] Crofts DW. In: Erdman HG, editor. Electrical insulating oils, STP 998, Philadelphia: American Society for Testing and Materials, 1988. p. 136. [5] Roach JF, Templeton JB. In: Erdman HG, editor. Electrical insulating oils, STP 998. Philadelphia: American Society for Testing and Materials, 1988. p. 119. [6] Lemesch G, Praxl G. Proceedings of the Ninth International Symposium on High Voltage Engineering, Graz 1995, vol. 1, No. 1006. [7] Artana G, Touchard G, Moreau O. J Electrostat 1997:40(41);129. [8] Touchard G, Grimaud PO, Romat H, Moreau O. IEEE Trans Dielectr Electl Insul 1994;1(4):728. [9] Romat H, Touchard G, Moreau O. EPRI: TR-105019, 1994. p.2.8.1 2.825. [10] Moreau O, Artana G, Romat H, Touchard G. Proceedings of ICDL96 Conference, 1996. p. 405. [11] Washabaugh AP, Zahn M. IEEE Trans Dielectr Electl Insul 1996;3(2):161. [12] Moreau O, Augier F, Touchard G. Proceedings of ESA-IES Joint Symposium on Electrostatics 1998. p. 12. [13] Dutta PK, Holland RJ. Fuel 1983;62:732. [14] Dutta PK, Holland RJ. Fuel 1984;63:197. [15] Labib ME, Williams RJ. J Coll Interf Sci 1987;115:330. [16] Labib ME. Coll Surf 1988;29:293. [17] Fowkes FM. Adv Ceram 1987;21:411. [18] Fowkes FM, Jinnai H, Mostafa MA, Anderson FW, Moore RJ. ACS Symp Ser 1982;200:307. [19] Lyklema J. Adv Coll Interf Sci 1968;2:65. [20] Siffert B, Jada A, Eleli Letsango J. J Coll Interf Sci 1994;163:324. [21] Siffert B, Jada A, Eleli Letsango J. J Coll Interf Sci 1994;167:281. [22] Siffert B, Eleli Letsango J, Jada A, Papirer E. Coll Surf 1994;92:107. [23] Ignasiak T, Strausz OP, Montgomery DS. Fuel 1977;56:359. [24] Moschopedis SE, Speight JG. Fuel 1976;55:334. [25] Christy AA, Dahl B, Kvalheim OM. Fuel 1989;68:430. [26] Waldo GS, Mullins OC, Penner-Hahn JE, Cramer SP. Fuel 1992;71:53. [27] Shaw DJ. Introduction to colloid and surface chemistry. London: Butterworths, 1980. [28] Hiemenz PC. Principle of colloid and surface chemistry. New York: Marcel Dekker, 1986. [29] Yen TF, Wu WH, Chilingar GV. Energy Sources 1984;7:203. [30] Guiliano M, Mille G, Kister J, Muller JF. J Chim Phys 1988;85:963. [31] Pieri N, Planche JP, Kister J. Analysis 1996;24:113. [32] Morrow BA, Lang SJ. J Phys Chem 1994;98:13319. [33] Tripp CP, Hair ML. J Phys Chem 1993;97:5693. [34] Bartle KD, Carney RA, Cavazza A, Cikalo MG, Myers P, Robson MM, Roulin SCP, Sealey K. J Chromatogr A 2000;892:27990. [35] Salou M, Siffert B, Jada A. Coll Surf 1998;142:9. [36] Salou M, Siffert B, Jada A. Fuel 1998;77:339. [37] Salou M, Siffert B, Jada A. Fuel 1998;77:343. [38] Fowkes MF. In: Mittal KL, Anderson Jr HR, editors. Acidbase interactions: relevance to adhesion science and technology. The Netherlands: VSP, 1991.

Fig. 3. Variation of zeta potential versus the pH for the aqueous dispersions of the bare silica and the silica covered with insulating oil polar fractions.

of the pH should result from an increase of the concentration of the acidbase surface complexes. Finally, the two methods used in this work, microelectrophoresis and infrared spectroscopy, seem to be suited to investigate the surface composition and functionalities of oil polar groups, which may be present in the transformer insulating oil. Hence, we nd a good correlation between the amount of the oil polar fraction, the peak area of various oil polar groups, obtained by FTIR spectra, and the magnitude of the zeta potential at the water/oilsilica interface. The use of the two methods to investigate insulating oils is useful to predict future failure in the power transformers. 4. Conclusions At ambient temperature oil polar fractions adsorb from various transformers, insulating oils (a new and two used oils) onto the silica gel. The microelectrophoresis measurements in water of the various oil covered silica particles, gives negatively charged oil polar fraction that resembles to asphaltenes molecules. Further, the FTIR analysis of such oil polar fraction indicates the presence of phenolic carboxylic and aromatic polar groups. We nd a good correlation between the amounts of the oil polar groups; their functionalities and the magnitude of the zeta potential at the water/oil covered silica interface. In the power transformer, the oil polar fraction may adsorb from the oil onto the pressboard leading to static electrication. The use of microelectrophoresis and infrared