Role of Semiconducting Compounds in Water Treeing of XLPE Cable Insulation

S.A. Boggs and M.S. Mashikian, Electrical Insulation Research Center, University of Connecticut Introduction
Water trees are known to be associated with reduction of dielectric strength and eventual failure of polyethylene-insulated cable which does not incorporate an effective moisture barrier [1,2]. However, past studies of this phenomenon often correlated poorly with data gathered from field-aged cable [3,4]. In particular, chemical analysis of water treed regions of laboratoryaged polyethylene demonstrated substantial differences from field-aged cable. Such results cast doubt on the usefulness of typical laboratory studies. A 1983 survey of solid dielectric cable technology conducted on behalf of EPRI indicated that several cable manufacturers in Europe and Japan placed great emphasis on the properties of the semiconducting shields used to manufacture power distribution and transmission cables. The carbon blacks used in North America differed substantially from those used by these offshore manufacturers. As a result of this finding, the Department of Energy initiated a project titled Interfacial Ageing Phenomena in Power Cable Insulation Systems. The findings of this project have been reported in several technical publications [4-7] which form the basis for the present summary. remains dry. This facilitates a direct comparison of the semicon-dielectric interface when maintained under wet and dry conditions. Ageing was carried out over long periods of time (typically 3500 and 7000 hours) at moderate stress (3.4 kV/mm or 85 V/mil and 2.6 kV/mm or 65 V/mil). Direct comparison of trees grown in this cell configuration and at these stresses with trees taken from field-aged cables indicated very similar tree chemical characteristics. Experiments were carried out using four commercial semiconducting insulation shield materials (C1 to C4) and four model shield materials (M1 to M4) formulated to vary such properties as the amount of sulfur in the shield. The dielectric used in all cases was a commercial cross-linkable polyethylene resin in the form of pellets which had been subjected to 100% optical inspection.

Raw Material Impurities

Analysis of the cell water showed that in all cases, the ion concentration of the distilled, deionized water increased during ageing, and after as little as 100 hours of ageing, many ion species could be identified which were not initially in the water. This effect was indeTable I [4] Contaminant Content of Raw Material (weight %) Sample C1 C2 C3 C4 C5 M1 M2 M3 M4 Surface .0513 .0306 .0994 .3992 .2484 .0818 .0180 .3892 .0494 Bulk .0746 .1038 .1072 .2970 .0286 .0355 .0860 .1430 .0581 Cleaned Surface .0087 .0096 .0100 .0110 .0010 .0090 .0013 .0101 .0091

Experimental Test Program

The test program was based on a sample configuration which incorporates the interface between the semiconducting compound and the polyethylene dielectric. The sample cell used in this project (Fig. 1) is a modification of a sample configuration originated by Union Carbide. This cell provides a well which allows one semiconducting layer to be maintained in a controlled, wet environment while the other semiconducting layer

Fig. 1. Test cell design which provides wet and dry semicon-dielectric interfaces [4].

Fig. 2. Contaminants on the surface of Compound C5 (a pellet of polyethylene resin).

Fig. 3. Detail of the interface between two pellets after melting. The defect in the interface caused by contamination on the surface of the pellets is obvious.

pendent of electrical stress. Various analytical techniques were used to evaluate contaminants in and on the raw material pellets. The results of this analysis are shown in Table I. In addition, the pellets were cleaned through bathing in hot, distilled, deionized water. As seen in Table I, the surface contamination generally differs from the bulk contamination. As well, the surface contamination can be reduced substantially through cleaning in hot, distilled water, which indicates that the contaminants are water soluble. The surface contamination is believed to come from processing water used during the pelletizing process. As seen in Fig. 2, the surface contamination is substantial and as shown in Fig. 3, it can interfere with the quality of the pellet-to-pellet interface. This effect may be much less pronounced in extruded cable; however, the ionic contaminants must still end up dispersed throughout the dielectric.

Results
Fig. 4 shows vented water tree length vs. ageing time for an old technology commercial semiconductive shielding compound while Fig. 5 shows a similar graph for a model shielding compound formulated with acetylene black. Note the difference in vertical scales. Obviously the cleaner model compound results in the growth of substantially fewer and smaller water trees. Evidently, tree growth is saturated by 7000 hours. As the tree growth was thought to be related to the supply of ions, tree growth might be limited as the supply of ions is depleted. While this could easily occur in the test geometry used during this project, it is less likely to occur in the field, as installed cables are subjected to ground water containing an ample supply of ions and which can pick up more ions from the cable conductor which is not included in this study. To test this hypothesis, water containing ions extracted from soil

Fig. 4. Vented water tree length distribution for several ageing times. The semiconducting compound was an old technology commercial shielding compound. The cell was aged at 3.4 kV/mm (85 V/mil) [7].

Fig. 5. Vented water tree length distribution for several ageing times. The semiconducting compound was formulated with acetylene black, and the cell was aged at 3.4 kV/mm (85 V/mil) [7].

Fig. 6. The importance of ions for tree initiation is demonstrated through comparison of the number of trees vs. time for cells filled with deionized, distilled water and cells filled with water containing ions extracted from soil and semiconducting shield material. In the case of distilled, deionized water, the ions from the sample shield become depleted after about 7000 hours and tree initiation stops. Tree initiation continues in the other samples, which have an ample supply of ions. Ageing was carried out at 3.4 kV/mm (85 V/mil) [7].

Fig. 7. Comparison of vented water tree length distributions for cells fabricated with cleaned and as-received old technology commercial shielding compound [7].

material after cleaning to remove water-extractable contamination. The effect of cleaning is dramatic. Previous literature indicates that surfactants (detergent-like materials which reduce surface tension) increase tree initiation and growth. However, the surfactants used in previous studies were ionic. Fig. 8 shows a comparison of tree growth for cells in which the semicon-dielectric surface was treated with an ionic surfactant, a nonionic surfactant, and no surfactant. As is clear from the figure, the effect on water treeing is the result of added ions, not the added surfactant. During the extensive tree counting required to assemble the data presented in the above figures, a number of effects were noted. For example, asperities at the semicon-dielectric interface did not generally result in

and from semiconducting compound was added to a cell after 7000 hours of ageing. As seen in Fig. 6, the number of vented water trees increased at a fairly steady rate for the samples which had an adequate supply of ions, whereas the number of trees leveled off for the sample which did not. Likewise, the effect of waterextractable contaminants on tree growth could be demonstrated. Fig. 7 shows a comparison of the vented water tree length distribution for cells manufactured with as-received old technology semiconducting shield and cells made with the same semiconducting

Fig. 8. Influence of ionic and nonionic surfactants on the number of vented water trees after 7000 hours of ageing at 3.4 kV/mm (85 V/mil). Evidently, water treeing is stimulated by ions rather than surfactants [7].

Fig. 9. Silicon ion profile as a function of position from the semiconducting compound into the dielectric. The transition is sharp for the dry electrode but is smeared out by ion migration from the wet semicon to the wet dielectric. The sample has been aged for 7000 hours at 2.6 kV/mm (65 V/mil) [4].

Fig. 10. Silicon ion profile as a function of position from a second semiconducting compound into the dielectric. The transition is sharp for the dry electrode but is smeared out by ion migration from the wet semicon to the wet dielectric. The sample has been aged for 7000 hours at 2.6 kV/mm (65 V/mil) [4].

Fig. 11. Change in chemical potential with change in ion concentration as calculated by Zeller for two water-filled cavities connected by a thin channel [9]. A change in chemical potential over about 1 eV is sufficient to drive an electrochemical process such as water treeing.

the growth of water trees unless they were accompanied by some form of contamination. Thus such asperities appear to have much less influence on water tree initiation than does contamination. Clearly, the above results suggest that ions are migrating from the semiconducting material into the dielectric and water tree. Several studies within the project demonstrated beyond any doubt that this can occur. For example, Figs. 9 and 10 show the profile of silicon (ion) concentration from within the semicon to within the dielectric for the wet and dry semicon-dielectric interfaces of the same samples. Clearly the transition is very abrupt on the dry side but has become smeared as a result of ion mobility on the wet side. Virtually no vented water trees grew at the dry semicon-dielectric interface, while many vented water trees grew on the wet interface.

3. The growth of water trees does not depend solely on ions originating from the semiconducting shields. Ground water will generally carry substantial ionic contamination. 4. The tree length and size distribution differs significantly for the semiconducting compounds tested, with the newer technology products which incorporate the cleanest carbon black showing a trend toward reduced propensity for the growth of vented water trees. 5. While the propensity toward treeing appears to depend on the degree of surface and volume contamination of the shield material pellets, the role of each impurity constituent has yet to be determined. 6. Surface contamination of the insulation pellets remains segregated at the interpellet interfaces and stimulates the initiation of bowtie trees.

Conclusions
1. As noted above, detailed comparisons of the chemistry of trees grown during this project with trees from field-aged cable demonstrated excellent correlation in all parameters which could be measured. Thus the test protocol employed in this study appears to mimic field ageing accurately. 2. As a result of the extensive testing carried out during this project, we can conclude that the initiation of water trees at a semicon-polyethylene interface requires ions and that the required ions are generally present in and on the semiconducting material. The concentration of water soluble ions on the surface of semiconducting material can be reduced through simple water extraction, and such reduction has a substantial effect on the number and length of water trees.

Technology Transfer
Various aspects of the technology developed during this Department of Energy-supported work have been transferred to Cablec Polymers, Inc., Dow Corning, Inc., Union Carbide, Elastimold Corporation, Cabot Corporation, Uniroyal, AT&T, Exxon, and BP Polymers. This research has resulted in substantial changes to semiconducting shield technology and compounds which have improved the reliability of solid dielectric cable.

Theoretical Context (Speculation)

A full theory for water treeing is still lacking. However, the outlines of a theory are available. H.R. Zeller has published two seminal papers in the field [8,9]. One paper outlines the basis for condensation of water within a polymer. Using basic thermodynamics, Zeller points out that water dispersed in a hydrophobic material which contains hydrophilic regions will condense

into those hydrophilic regions [8]. In the second paper, Zeller provides a credible basis for the driving function of water treeing [9]. He points out that the change in chemical potential with ion concentration is sufficient to drive water treeing. Fig. 11 shows the change in chemical potential (in electron volts) which accompanies the change in ion concentration from zero to the stated value for two small cavities connected by a small channel. Anything over 1 eV can drive a chemical reaction. Thus this mechanism has the potential to drive water treeing over a wide range of concentration. However, the driving function drops at sufficiently high and low concentrations. These computed data can be taken as qualitative and suggestive; they are not definitive computations of the driving force for a realistic geometry. Recently published experimental data indicate that water trees consist of cavities connected by channels of altered material [10]. Taken together, these results suggest that water treeing results from a localized chemical reaction which changes the polymer from hydrophobic to hydrophilic. Water and ions can travel along and condense into these hydrophilic paths from cavity to cavity. The combination of water, ions, and (possibly) cavities results in a chemical reaction at the channel tip which converts material from hydrophobic to hydrophilic and propagates the water tree as a myriad of such channels. Initially, the channels are probably not tunnels but rather paths of polymer in which the material has been reacted to change from hydrophobic to hydrophilic. Unfortunately, the channels tend to be from factions of a micrometre to a micrometre in diameter, so analysis of the material in a channel to determine the precise chemical reactions therein poses a substantial challenge which has yet to be overcome.

Matthew Mashikian was graduated from the American University of Beirut and received his Dr. of Engineering degree from the University of Detroit. Matt worked for ASEA from 1958 to 1962 as an application engineer for lightning arresters. From 1963 to 1979, he was in the Engineering Research Department of Detroit Edison where he rose to the position of Supervisor of Electrical Equipment and instrumentation. After early retirement from this position in 1979, he started his own consulting company, Mashikian & Associates, Inc. Since 1983, he has been Director of the Electrical Insulation Research Center at the University of Connecticut. Matt was elected a Fellow of the IEEE for his contributions to the technology of solid dielectric power cables. Matt is presently Secretary of the PES Insulated Conductors Committee and Chairperson of the DEIS Education Committee.

References
1. Lawson, J.H. and W.A. Thue. Summary of Service Failures of High Voltage Extruded Dielectric Cables in the United States. 1980 IEEE International Symposium on Electrical Insulation, pp. 100-104. 2. Lawson, J.H. and W. Vahlstrom. Investigation of Insulation Deterioration in 15 kV and 22 kV Polyethylene Cables Removed from Service - Part II. IEEE Trans. PAS-92, pp. 824-835 (1973). 3. Patsch, R. Water Treeing in Cable Insulation - Are Laboratory Tests Meaningful? 1988 IEE Conference on Solid Dielectrics, pp. 242-245. 4. Mashikian, M.S., J.H. Groeger, S. Dale, and E. Ildstadt. Role of Semiconducting Compounds in the Premature Ageing of XLPE Cable Insulation. 1988 IEEE International Symposium on Electrical Insulation, pp. 314-320, IEEE Publication 88CH2594-0. 5. Groeger, J.H., J. Henry, and A. Garton. Location and Concentration of Ionic Impurities in Polymeric Cable Insulation. 1988 IEEE International Symposium on Electrical Insulation, pp. 300-305, IEEE Publication 88CH2594-0. 6. Mashikian, M.S. and J.H. Groeger. Ionic Impurities in Extruded Cable Insulation: Analytical Detection Techniques, Sources, Nature, and Effects. Proceedings of the Jicable Conference, Versailles, 1987. 7. Mashikian, M.S. and J.H. Groeger. Ageing Phenomena at Cable-Shield Interfaces Affecting the Propensity of the Insulation to Develop Water Trees. Proceedings of the Jicable Conference, 1991. 8. Zeller, H.R. Thermodynamics of Water Treeing. IEEE Trans. EI-22, p. 677 - 681, 1987. 9. Zeller, H.R. Noninsulating Properties of Insulating Materials. 1991 Annual Report of the Conference on Electrical Insulation and Dielectric Phenomena. p. 19 - 47. 10. Moreau, E., C. Mayoux, C. Laurent, and A. Boudet. The Structural Characteristics of Water Trees in Power Cables and Laboratory Specimens. IEEE Trans. EI-28, No. 1, February 1993. pp. 54-64.

Acknowledgements
The experimental research described in this article was carried out by Matthew Mashikian, Joseph Groeger, and others at the Electrical Insulation Research Center (EIRC), University of Connecticut. The article was written by Steven Boggs, who recently joined EIRC. Steven Boggs was graduated from Reed College and received his Ph.D. and M.B.A. degrees from the University of Toronto. He conducted research for 12 years with Ontario Hydro, primarily in the areas of SF6 gasinsulated substations, solid dielectrics, and partial discharge detection. Prior to joining the Electrical Insulation Research Center as Associate Director, he was Director of Engineering and Research at Underground Systems, Inc. (Armonk, NY). Steve was elected a Fellow of the IEEE for his contributions to gas-insulated substation technology.