CON-10

P184

REACTOR MODIFICATION OF HIGH PRESSURE LOW DENSITY POLYETHYLENE WITH DIENE AND ITS APPLICATION for HV and EHV EXTRUDED XLPE CABLES Dominic Kung, Borealis Compounds Inc., Port Murray, NJ Annika Smedberg, Borealis AB, Stenungsund, Sweden Rudi Peters, Borealis N.V., Belgium

Abstract
The use of crosslinked polyethylene (XLPE) produced by the high pressure polymerization process is well established. In the present study it is discussed how the reactivity of an LDPE material can be increased by copolymerizing ethylene with a diene comonomer in a high pressure reactor. It is also demonstrated how this material has been used to develop a material with improved scorch resistance together with a lower degassing burden without sacrificing crosslinking degree and electrical properties.

The electrical performance of cables has increased over the years thanks to the successful efforts on materials as well as of the cables as such. Examples are developments in cable designs and cable production processes, e.g. the introduction of triple (?) head extrusion, together with improvements of the consistency as well as the cleanliness of both the insulation and semiconductive materials. However, less effort has been made to improve the intrinsic properties of the material as such. This paper will discuss a special type of low density polyethylene (LDPE) material that offers opportunities to meet present and future requirements, e.g. productivity, on cable materials for use in HV and EHV cables without sacrificing quality. Base resin for XLPE manufacturing For XLPE insulated power cables the base is Low Density Polyethylene (LDPE). This polyethylene is produced in so called high pressure reactors via a free radical mechanism using pressures in the range of 1000 to 3500 bars and temperatures between 100 and 350 C. The resulting LDPE contains both long chain branches (LCB) as well as short chain branches (SCB). The presence of LCB has a pronounced effect on the molecular weight distribution (MWD),melt strength and shear thinning behaviour and provides the favourable and unique processing characteristics of LDPE. The SCB content affects properties like the melting point, degree of crystallinity, stiffness and mechanical properties. Both the LCB and SCB are inherent to the process which means that they are created without the addition of other monomers [1-4]. As one of the key requirements for materials to be used as insulation materials in power cables is a high level of cleanliness the tubular reactor technology is preferred. Besides the cleanliness, this reactor type also provides a tool to architecture a polyethylene to a wide range of desired end properties. The alternative high pressure reactor type is the autoclave reactor. This reactor uses rotating paddles within the reactor vessel and hence there will be contaminants generated from the moving parts. For this reason autoclave reactors should not be used in the manufacturing of HV/EHV XLPE compounds. Crosslinking In power cables the insulation as well as the semiconductive layers are crosslinked. The introduction of 1

Introduction
Crosslinked polyethylene (XLPE) has been used as an insulation material for more than 35 years. XLPE is today established globally as a reliable material for use in power cables and is widely used over a broad range of electrical stresses from low to extra high voltages, see Figure 1.

Figure 1. Example of conductor and insulation stresses of MV/HV/EHV cables. Important advantages of XLPE cables are low losses, low failure rates and a low impact on the environment. XLPE is currently the preferred insulation material in relation to paper and paper-propylene laminate fluid-filled insulated energy cables.
RVP-AI/2012 CON-10 PONENCIA RECOMENDADA
POR EL COMIT DE CONDUCTORES AISLADOS Y ACCESORIOS DEL CAPTULO DE POTENCIA DEL IEEE SECCIN MXICO Y PRESENTADA EN LA REUNION INTERNACIONAL DE VERANO, RVP-AI/2012, ACAPULCO GRO., DEL 8 AL 14 DE JULIO DEL 2012.

crosslinks in a material enhances a number of properties such as tensile strength, creep properties as well as deformation resistance at higher temperatures [5]. This leads to that the maximum operating temperature of the cable can be raised from 75 C for the thermoplastic version to 90 C for the crosslinked version. Similarly the crosslinked material can be exposed to a short-circuit temperature of 250 C instead of 150 C for the thermoplastic material [6]. A general description of the dicumylperoxide (DCP) initiated crosslinking mechanism is briefly summarized in Figure 2.

important is to have trained maintenance technicians for any dismantling and repair work. Cleanliness evolution Cleanliness of insulation is considered as the one of the most critical factor in the manufacturing of HV and EHV cables. Many studies have shown the degradation caused by large metallic contamination leading to a reduction of the electrical performance e.g. the breakdown stress. Thus the manufacturing technology of XLPE compounds needs to ensure the highest level of cleanliness in all points of the production chain. The Quality Control process is essential and at all inter-process points, samples should be taken to assure the cleanliness as well as the physical/chemical properties. Cleanliness is assessed by converting a representative sample of the polymer into transparent tape, and then establishing the concentration of any defect. To reach the required level of consistency and sensitivity the tape is inspected by automated optical system and the data processing is carried out by a microcomputer. Evolution of cleanliness can be seen in Figure 3.

CH3 C CH3 O O

CH3 C CH3

Heat
CH3

C CH3

Acetophenone
C CH3 C CH3 OH + CH3 O + CH3

. .
CH4 +

Cumylalcohol

Methane

.
Combination crosslink

Figure 2. A schematic illustration of the DCP initiated crosslinking of polyethylene.

When the temperature is raised the peroxide decomposes into radicals. These radicals then abstract hydrogen atoms from the surrounding polyethylene chains and so-called macroradicals are formed. A crosslink is created when two such macroradicals combine. In this paper this type of crosslinking is named combination crosslinking. As can be seen in Figure 2 one peroxide bond (-O-O-) can maximum give rise to one combination crosslinking point. In addition to the crosslinking reaction, methane and a number of polar by-products, such as acetophenone and cumylalcohol, are formed as well. Manufacturing of XLPE compounds To obtain a XLPE insulation compound with desired properties and cleanliness, additives such as stabilizers to provide thermo-oxidative stability and peroxide for crosslinking are added downstream the polymerization step. The process equipment is specially selected and designed in all parts and especially assigned and trained technicians are operating the production. Equally

Figure 3. Evolution of cleanliness of XLPE cable insulation material assessed by automation inspection system. This is a result of efforts that has been done to improve cleanliness of insulating materials focusing on an advanced measurement system, special clean base resin and stringent specifications. Sharp and conducting contaminants are considered to provide the highest risk to a cable but in practice they constitute a minority of the contaminant population. Smoothness evolution The semiconductive compounds have undergone a quality evolution similar to the evolution of insulation compound cleanliness but with respect to smoothness, see Figure 4. By employing automatic inspection devices operating online compounding processes have been continuously improved. The use of acetylene carbon black has offered a possibility to develop the smoothness level to so called Supersmooth or Enhanced Performance level.

diene modification results in a polyethylene material with a higher content of pendant vinyl groups.

Figure 4. Smoothness evolution of conventional and enhanced performance semiconductive compounds (sizes of surface defects on extruded tapes). Both these improvements, the high cleanliness of insulation materials and the very smooth semiconductive screens, together with the improved cable manufacturing practices have made it possible to reduce the insulation wall thickness of power cables. Figure 5 shows examples of significant reductions of XLPE insulation thicknesses for HV and EHV cables in recent years. Figure 6. Schematic illustration of a diene modified low density polyethylene. With this modification the crosslinking capability of LDPE is significantly improved. Detailed crosslinking experiments have shown that the vinyl groups are rapidly consumed after very short crosslinking times resulting in higher gel contents compared to a reference LDPE material crosslinked using the same conditions. It has been suggested that the vinyl groups are consumed in a socalled chain reaction and actually one single radical can give rise to several crosslinking points [9]. It has also been found that a crosslink originating from a reacted vinyl group contributes to the creation of the network structure in the same way as a network point formed by combination crosslinking [10]. Therefore in the diene modified LDPE, two concurrent crosslinking reactions are taking place; combination crosslinking and the chain reaction involving the vinyl groups. In the section below examples will be given on how this diene modified material has been used for the development of a material with a special combination of properties.

Insulation thickness
35 30

Thickness in mm

25
20 15 10 1980 1985 1990 1995 2010

132kV
154kV 275kV 400kV

Figure 5. Influence of insulation cleanliness and semiconductive screen smoothness on wall thickness of HV and EHV cables. Material developments to meet future demands As can be seen above a lot of efforts have been made to improve cleanliness and consistency of power cables materials as a first priority. Nevertheless development of the intrinsic polymer properties related to the productivity has been made as a next step. The high pressure reactor technology has proven to provide a solution resulting in an optimum balance of electrical, physical, extrusion and crosslinking properties. However, it is also an ideal basis for the development of engineered polymers that are better adjusted for future demands. One such example is the development of a high productivity base resin technology that is especially suited for power cables [7, 8]. This resin is a copolymer of ethylene and a diene and, as can be seen in Figure 6, this

Application examples
Materials The sample codes for the materials used for the exemplification of the application properties are summarized in Table 1. Table 1. Summary of material codes and material characteristics Sample Sample code MFR2 (g/10 min) DieneModifiedXLPE for HV Reference XLPE DM-XLPE Reference 2 2 3

Experimental Melt flow rate measurement (MFR) MFR2 is a measure of the viscosity of the material when testing the material with the 2.16 kg weight at 190 C. Monsanto scorch The torque evolution was measured in a Monsanto Rheometer at 140 C. The scorch time is defined as the time at which a 1 dNm torque increase over the minimum torque value is reached. Hot set measurements Samples were taken from crosslinked 20 kV cable cores produced on a CV line. A dumbbell shaped specimen was taken out from the inner part of the insulation layer in the cable core. The sample is marked with a reference length, put in an oven at 200 C with a 20 N/cm2 load. After 15 min the distance between the reference marks is measured. This is reported as the hot set elongation value. Determination of by-products Methane was determined by gas-chromatograph (GC) analysis and the amount of polar by-products (in this case acetophenone and cumylalcohol) was determined by extraction followed by analysis with a high pressure liquid chromatograph (HPLC). Samples for both these measurements were taken from extruded 30 kV cables. Directly after production of the cable a sample, including the insulation and the semiconductive layers, was taken from the cable core and the amount of methane gas as well as the total amount of polar by-products were determined. Tan measurements The tan was measured on a 10 kV cable core where the same type of semiconductive material has been used for the inner and outer semiconductive shield. Cable cores were produced on a CV line and after the production of the cable core it was heat treated for 72 h at 70C. The tan was then measured at 100 C and at a stress of 20 kV/mm. Electrical Breakdown (Eb(63%)) measurements The AC electrical breakdown strength was measured on a 20 kV/150 mm2 cable core where the same type of semiconductive material has been used for the inner and outer semiconductive shield. The cables cores were produced on a CV line and not thermally treated prior to measurement. The breakdown test procedure followed the CENELEC HD 605standard, thus steps of 12 kV every 5 min starting at 36 kV. The Eb value is reported with 90% confidence interval.

Results The recent material development for HV and EHV power cables has now been focused on reaching a lower degassing burden as well as enabling a more safe extrusion by reducing the risk of scorch (pre-crosslinking in the polymer extruder). A material with improved scorch can allow the cable makers to manufacture longer cable length without an increased risk of scorch. As a consequence of having longer cable length the number of joints might be reduced, thus reducing the risk of failures as the point when cable lengths are connected is considered as the weakest one in the cable line. The DMXLPE HV material presented is designed to fulfill both these requirements but with no sacrifice in the degree of crosslinking, crosslinking speed and electrical properties. To combine all these features in one product is really a challenge. Below application examples will be given to exemplify the mentioned improvements. For HV/EHV the actual amount of by-products formed, i.e. the degassing burden, is also important as there is a need to remove by-products or to reduce their concentrations before the cable can be used. The methane gas is the most critical component to remove due to safety aspects. The presence of polar by-products, such as acetophenone and cumylalcohol, contribute to dielectric losses and therefore their contents need to be reduced. The amounts of by-products formed in the DM-XLPE HV material have been compared with the amounts formed in the reference XLPE material using 30 kV cable cores produced on a CV line. The results are presented in Figure 7 and Figure 8.
%
100 90 80 70 60 50 40 30 20

Relative amount of methane

10 0
DM-XLPE Reference

Figure 7. Comparison of the relative initial amount of methane measured in freshly produced 30 kV cables insulated with DM-XLPE HV and XLPE reference materials respectively.

%
100 90

Relative total amount of polar by-products

high temperature and stress. As can be seen in Figure 10 the same low losses as in the reference XLPE material were measured in the DM-XLPE as well.
%
100 90 80 70 60 50 40 30 20 10 0 DM-XLPE Reference

80
70 60 50 40 30 20 10 0 DM-XLPE Reference

Relative tan d values measured on 10 kV cable cores

Figure 8. Comparison of the relative initial amount of total amount of polar by-products measured in freshly produced 30 kV cables insulated with DM-XLPE HV and XLPE reference materials respectively.

Figure 10. Comparison of tan values for the two materials measured on 10 kV cable cores. The breakdown strength is another important electrical property. The results for the two materials are presented in Figure 11.
%
100 90

As it is possible to balance the reactivity of the base resin with the diene technology, the amount of peroxide to reach a certain degree of crosslinking can be reduced. However, even if the amount of peroxide is reduced still the hot set elongation value, measured on the insulation layer in 20 kV cables produced under the same conditions (e.g. same line speed) on a CV line, has been determined to be in the range of 70-75% for both the DM-XLPE HV and the reference XLPE material. These values are well below the maximum allowed value of 175 % The scorch resistance of DM-XLPE HV material was compared with the reference XLPE material in the socalled Monsanto scorch test at 140 C. The longer the time until the selected torque value is reached the better the scorch resistance. The significant difference between the two materials can easily be seen from the data presented in Figure 9.
%
200 180 160 140 120 100 80 60 40 20 0 DM-XLPE Reference

Relative AC breakdown strength of 20 kV cable

80
70 60 50 40 30 20 10 0 DM-XLPE Reference

Figure 11. Comparison of the AC Eb (63%) measured on 20 kV cables. As demonstrated in Figure 11, it is indeed possible to combine improved scorch resistance and a lower degassing burden in one XLPE material while maintaining the crosslinking properties and the electrical properties.

Relative Monsanto Torque value measured at 140C

Conclusions
The high pressure tubular reactor technology has proven to provide a robust solution having an optimal balance of critical properties such as cleanliness, processing characteristics and dielectric strength that makes it especially suitable for the production of power cable insulation materials. It has also been demonstrated that with this technology it is possible to further modify the material by adding selected comonomers to the polymerization reactor to enhance existing properties and to produce new desirable properties. In this paper the characteristics of a LDPE material modified by copolymerizing ethylene with a diene is discussed. This 5

Figure 9. Monsanto scorch data for DM-XLPE HV compared to the XLPE reference. As electrical properties are very important for HV and EHV cables the tan as well as the Eb strength has been measured for both materials. The tan was measured at

diene modification significantly increases the reactivity of the material and this has been utilized to develop a material for use in HV and EHV applications focusing on reaching a more safe extrusion where the risk for scorch is reduced together with a lower degassing burden. Both these properties can be combined without sacrificing degree of crosslinking and electrical properties, measured via tan and electrical breakdown strength. References [1] K.W. Doak, in Encyclopedia of Polymer Science and Engineering, 6, 386 (1986) [2] A. Hill and K.W. Doak, in Crystalline Olefin Polymers, Eds. R.A.V. Raff and K.W. Doak, Interscience Publishers, XX, 267 (1965) [3] K.W. Doak and A. Schrage, in Crystalline Olefin Polymers, Eds. R.A.V. Raff and K.W. Doak, Interscience Publishers, XX, 301 (1965) [4] P. Ehrlich and G.A. Mortimer, Adv. Polym. Sci., 7, 336 (1965) [5] B- Sultan and M. Palmlf, Plast. Rubber Compos: Process Appl., 21, 65 (1994) [6] E. Peschke and R. von Olshausen, in Cable Systems for High and Extra-High Voltage, Erlangen and Munich, GmbH, Publicis MCD Verlag (1999) [7] B. Gustafsson, T. Magnusson, K. Alha and P. Rydin, EP647244B1 (1992) [8] A. Smedberg, T. Hjertberg and B. Gustafsson, J. Pol. Sci., A, Pol. Chem., 41, 2974 (2003) [9] A. Smedberg, T. Hjertberg and B. Gustafsson, Polymer, 38, 4127 (1997) [10] A. Smedberg, T. Hjertberg and B. Gustafsson, Polymer, 45, 4867 (2004)

Dominic Kung Borealis Compounds Inc. USA Senior Application Development Engineer Wire and Cable Dominic completed his Doctoral research in chemical engineering from Cornell University at Ithaca, New York before joining the chemical industry as a researcher. He has over 20 years of experience in the wire and cable technology and business development in various chemical companies. Dominic joined Borealis in New Jersey eight years ago and since then he has been involved in power cable product management and application development . He is currently serving as a board member at NEETRACGeorgia Tech and is also participating in various IEEE/PES working/discussion groups. Dominics main interests are in power cable compound and cable process technology, multi-phase polymer rheology, renewal energy and energy infrastructure development.

Rudi Peters Borealis Polymers NV Value Chain Manager Wire & Cable Rudi has 23 years of experience in the W&C industry, in a broad variety of functions and companies. In August 2006 he joined Borealis Polymers, as an Application marketing manager for the High Voltage cable business. Since October 2011 responsible for all Value Chain activities of W&C and member of the Global Management Team. His key focus will be to deliver profitable growth opportunities and to recognize, understand and communicate long term end-use needs towards the organization, by capturing early buy-in from the key stakeholders. Rudi is a member of the UMP of EUROPACABLE Rudi Peters holds a master in Applied Economics from the Limburgse Universitaire Campus Hasselt Belgium.