Polymer Compounds Used In High Voltage Insulators by Cc R. Allen Bernstorf Randall K. Niedermier David. S. Winkler Principal Engineer - Manager Polymer Chemist Insulators Polymer Development of Hubbell Power Systems The Ohio Brass Company CS» CHIO/BRASS POWER SYSTEMS Hubbell / Ohio Brass P.0. Box 1001 + Wadsworth, Ohio 44281-0901, Tol (S73) 682-5521 Fax (573) 682-8714, NOTE: Because Onio Brass has # pity of eaminuous product improvement, we reserve te right to change design ans specications without notice. EU 1407-HR1 ©Copyright 1998 Hubbell / Ohio Brass Printed in U.S.A.Sample Polymer Specification Purpose: To ensure a suitable seroice life of polymer insulating materials, I. Material Design Tests ~ The following must be performed to certify a material for use in production. 1. No carbonization or tracking, 2. No current flow at the end of 90 seconds. The sample must pass 15,000 test cycles. checking or becoming hydrophilic, ‘he sample is judged to have passed this test i it exceeds 8,000 hours of exposure without damage. 3- Corona Cutting: Samples 5 cin by 7 cm are subjected to mechanical stress of 300,000 Placed 1 mm from the surface of the sample and energized at 12 ki? must pass 1,000 hours of exposure to this test, reaction. The time to this reaction must exceed 300 minutes are tested to determine tear strength of the material. The minimum acceptable tear strength is 100 Ib,/in. IL Other Requirements The manufacturer must supply upon request a listing of routine tests performed to ensure production compliance with design tests. 2. Ultraviolet Test: Samples of the rubber must be tested in a QUV tester or equivalent. These samples must be exposed to high ultraviolet and high humidity without cracking, mictostrain by bending samples around a grounded electrode needle-like electrode is The sample is judged to have passed this test if there is no splitting or cutting, Samples z & Z & 3 wa z é & g 5 8 is a 4 3 A é 2 8 a 3 3 3 & = Z 5 B 3 é é s 3 Z couusxtermal polymer insulation material in the assembled product must be of the same compound. Box jovt re Caciome/ seniee, =} Tol 7a ope 5 Ldn} ( otopyniny Aen Hubbell OFFS’ Bjass),_ TW 2 : we sh wr Fax 79y652-9714 ee al ea Pate waa © \References 1. The Vanderbilt Rubber Handbook, pp. 2. The Vanderbilt Company, Inc., Connecticut, (1990). 2. Fundamentals of Polymer Science, P.C. Painter, M.M. Coleman, pp. 24-25, Technomic Publishing Company, Inc. (1994) 3. The Vanderbilt Rubber Handbook, pp. 3. The Vanderbilt Company, Inc., Connecticut, (1990). Science and Technology of Rubber, F.R Eich, pp: 89-91, Academic Press, New York, (1978) Rubber Technology, M. Morton, pp. 371, Van Nostrand Reinhold Company, New York, (1973). ‘The Vanderbilt Rubber Handbook, pp. 126-127. The Vanderbilt Company, Inc., Connecticut, (1990). x Rubber Technology, M. Morton, pp. 370. Van Nostrand Reinhold Company., New York, (1973) 2 The Vanderbilt Rubber Handbook, pp. 234. The Vanderbilt Company, Inc., Connecticut, (1990), Royalene EPDM Rubber Handbook, Comparative Property Chart, Uniroyal Chemical Company, Connecticut, (1988). 10. Basic Compounding and Processing of Rubber, pp. 6. Rubber Division, American Chemical Society,ino., The University of Akron, Akron, OH 44325, (1985), 11. Compounders' Pocket Book - Chemicals for the Rubber Industry, pp. 189-190. Monsanto Rubber Chemicals Division, Akron, OH 44313, (1981) 12, Concise Encyclopedia of Polymer Science and Engineering, pp. 1048. John Wiley and Sons, Inc., New York, (1990) 13,14. Silicone Chemistry, J.L. Speier, M.J. Hunter, Reprinted from International Science and Technology, New York, (1968). 15. Concise Encyclopedia of Polymer Science and Engineering, Pp. 1049. John Wiley and Sons, Inc., New York, (1990). 16. Basic Compounding and Processing of Rubber, pp. 6. Rubber Division, American Chemical Society,inc., The University of Akron, Akron, OH 44325 (1985). 17. Basic Compounding and Processing of Rubber, pp. 6. Fubber Division, American Chemical Society,inc., The University of Akron, Akron, OH 44325, (1985).EPM/Silicone Alloy | 400 No Failure, End of Test ESP [ 400 No Failure, End of Test EPDM: 20 Failure EPDM, 400 No Failure, End of Test Silicone Rubber, 400 No Failure, End of Test Table 4, Oxidative Stabilily Test Results EPDM;, EPDM, and Silicone Rubber, are commercially available insulating compounds from different manufactures. Ohio Brass first developed these test techniques in the mid 1960s for evaluating the characteristics of polymer insulating compounds, and over the intervening years has continued to improve the methods. Twenty-five years of experience have indicated that materials which perform well in these tests will offer decades of satisfactory service in field use. Summary This paper has presented details on the types of polymers used for high voltage insulators. There are many factors which must be considered while designing a polymer compound for use as high voltage insulation.letime. Electrical insulation that may be subject to corona must be made from a properly compounded EPR or silicone rubber. The presence of corona combines UV and heat with a high level of ozone. The Ohio Brass corona cutting chamber combines this with mechanical sirose tr accelerate the Gegradation of a polymer. Polymer insulator samples are subject to a mechanical stress of @pProximately 300,000 microstrain by bending the sample over a grounded electrode, Corona is continuously generated by applying 12 kV to a needlelike electrode placed 1 Tam above the strained surface of the sample. Under a combination ot stress and MATERIAL TIME, HRS COMMENTS EPM 404 Failure EPM/Silicone Ali 1.290 Failure ESP 3.250 ‘Test Terminated EPDM. 2.780 Test Terminated Silicone Rubber, 348 Failure Silicone Rubber, 1,650 Test Terminated Table 3. Corona Cutting Test Results Silicone rubber, silicone rubbers and EPDM; are commercially available insulating compounds from different manufactures, Oxidative Stability Antioxidants are incorporated into a polymer compound to inhibit the attack of oxygen and ozone on the compound's chemical composition. The effectivensee of an antioxidant is very important in electrical insulation applications. An oxidative stability test measures the time to deplete the anti-oxidants within a material tinder controlled conditions. Oxidative stability is measured by using the thermal analysis Hechniaue of differential scanning calorimetry (DSC). The DSC meceures the amount of heat flowing into (endothermic) or out of (exothermic) the sample as a function of the material's temperature, Oxidation is a highly exothermic process and is readily studied by DSC techniques. A test Sample is rapidly heated in a nitrogen atmosphere to the test temperature ef 200°C. The elmosphere is then changed to oxygen and the temperature is maintanen until the sample begins to oxidize. When the sample oxidizes or decomposes, an exothermic MATERIAL TIME, MINUTES: COMMENTS | EPM 20-26 FailureThe negative effects of UV radiation for a polymer include: J. razing, checking or cracking of the surface 2. loss of hydrophobicity 3. discoloration, exposure test. Under accelerated testing methods, like ASTM G53 (QUV), a good polymer compound Should be capable of sustaining 10,000 hours of exposure without crazing, cracking or MATERIAL, TI COMMENTS EPM Loss of Hydrophobicity EPM/Silicone Alloy Loss of Fy ‘drophobicity ESP Still Hydrophobic™ EPDM, Checking of Surface EPDM» Loss of Hydrophobicit Silicone Rubber, 39,000 Still Hydrophobic* Table 2. QUV Test Resulis - “indicates ‘ongoing test EPDM:, EPDM, and silicone rubber, are commercially available insulating compounds from different manufactures, Corona, porana discharges form at the surface of an insulator when the elecitic field intensity on ihe surface exceeds the breakdown strength of ait wren is about 15 kV/cm. Corona generation is dependent on atmospheric conditions such as air density, humidity, and Se ee ty Of the insulator. The effects of corona are radio interference, TV interference, noise generation, ozone production, and energy loss. Corona accelerates the aging of polymers, By generating ozone and UV light. The UV light produced is of short wavelengths and includes the spectra of light damaging to polymers. The electric discharge subjects the insulate, {0 severe electrical strain and chemical degradation. Continued degradation May render the polymer unusable AFailure is judged by one of three criteria: J. carbonization or tracking of the sample's surface; 2 the sample remains conductive at the end of ne 90 second cycle; or 3. erosion creates a hole in the sample, MATERIAL CYCLES COMMENTS Porcelain) 50,000 No Failure EPM 50.000 No Failure EPWMiSilicone Alloy 22.700 Failure ESP. [50,000 No Failure. Silicone Rubber, 16,000 Failure EPDM, 1,800 | Failure Table 1. Tracking Test Results Silicone Rubber, and EPDM, are commercially available insulating compounds, Ultra Violet Polymer insulating compounds are exposed to UV Tadiation not only from sunlight, but aiso from corona and dry band arcing. Resistance 1 degradation resulting from ultra the pray season, time of day, elevation and latitude. Acteloraton ss the effects occurs in ihe presence of moisture on the polymer's surface, Polymer compounds for use in outdoor and high Po ioh eu Hetefore, be evaluated in the combined precesne oe UV radiation and high humidity.Comparison of Polymer Compounds in Use Today Again, the other compounds listed are commercially available for any insulator manufacturer to purchase, Desian Tests While there are several standardized (e.g, ASTM, ANSI, CEA CSAN, IEC) tests to evaluate insulating materials, few of these are Particularly suited to proper assessment of the characteristics required for outdoor high voltage insulation. As a consequence, Ohio reseed Specialized tests for evaluating materiaie es its polymer insulator A polymer compound's suitability for long term use in high voltage insulators is assessed by means of design tests. By necessity, given that an insulators lifetime is measured in Gecades, design tests involve accelerated aging or conditioning, Good polymer compounds used for high voltage insulation should be tested for the ability 'o resist tracking, erosion, corona, oxidation and ultie-vislet (UV) radiation exposure, 4 polymer compound must exhibit excellent resistance to tracking and erosion. Polymers Bearade by erosion and tracking due to the heat generate by leakage currents and dry band arcing, Since each polymer differs in terms oF tracking resistance, one of the ways to differentiate various compounds is to subject them to + tracking test.Processing aids are added to a rubber compound to help mold flow and release, as well as aid in the mixing of the compound. Fillers Fillers are used to reinforce the base elastomer which can increase the physical properties or impart certain processing characteristics. There are two types of fillers: reinforcing and extending, The reinforcing type can improve tensile strength, modulus, tear strength and abrasion resistance of a compound, ‘An extending filler is a loading or non-reinforcing material. It may be used to impart some desirable property. Alumina trihydrate (ATH) is used in nearly all insulator compounds to impart a high resistance to electrical tracking and inflammability. Coupling Agents A coupling agent provides a chemical bond between the filler and the elastomer. The coupling agent is a bridge between the ATH and the polymer. This can greatly improve the electrical properties, modulus and tensile strength. Plasticizers and Softeners Plasticizers and softeners are used to either aid mixing, modify viscosity or provide flexibility at low temperatures. Many ingredients in this group may also be considered as processing aids. Special Purpose Materials Special purpose materials are used for a specific purpose which is not normally required in the majority of rubber compounds. Antifungal agents, blowing agents, colorants, re-odorants, the Ohio Brass silicone material and materials which assist the compatibilization of silicone to the matrix are examples of special purpose materials. Formulation Testing/Material Characterization Polymer insulating materials are typically formulated to provide performance characteristics equivalent to, or better than that of porcelain. Because of the different physical properties of porcelain and polymers, a comparison is usually made only on short term electrical characteristics of complete insulators - e.g. wet and dry 60 Hz flashover, critical impulse flashover. However, many physical properties of a polymer material must be understood and properly controlled to give the material the characteristics necessary to serve a long life as a high voltage insulating polymer. Once a compound has been formulated to meet the desired criteria, various types of design tests are conducted. These tests ensure the formulation exhibits the required characteristics for use in high voltage insulators.Compounding {G. the field of polymer technology, rubber compounding is a complex subject. Compounding is part art, part science. The compounder's ability to select and combing polymers and additives to obtain a mixture that will develop the necessary physical and chemical properties can take years to master [17] A practical compound formulation can consists of 10 or more ingredients. Each ingredient has a specific function and each has an impact on properties and processibility. The remainder of this section will be dedicated to brief descriptions of the ingredients and their functions, Elastomers 4s discussed in previous details, the most important step in compounding is the selection of the elastomer, or base polymer. The selection of an elastomer should be based on the properties desired and processibility of that elastomer, Vuleanizing Agents Vuleanizing agents are ingredients used to cause a chemical reaction, resulting in the Cross-linking of elastomer molecules. Through chemical cross-linking, an elastomeric compound is converted from a soft, tacky material to a sii lemperature-stable material. There are many types of vulcanizing or curing agents used. Organic peroxides are the most widely used for high voltage ineulation. Coagents Goagents protect the already cross-linked bonds between the polymer and vulcanizing agent from being torn apart. This assures that bonds are not broken as fast as new bonds are generated. There are two types of coagents: type | and type Il. Type | coagents increase the Fe date (Speed) and cure state (stiffness) of the compound. Type II coagents increase the cure state but do not effect cure rate, Antidegradants Antidegradants are used to retard the deterioration of a rubber compound by oxygen, ozone, heat and light Im the selection of antidegradants the following factors must be considered: 1. type of protection desired 2. chemical activity 3. persistence (volatility and extractability) 4, discoloration and staining Processing AidsComparison of Polymers in Use Today EPR EXRs are among the best weathering resistant synthetic polymers [8]. Because of EPR's salurated polymer backbone (*) it has excellent electrical, chemical and mechanical resetance in Superior aging and color stability. In general all EPs have outstanding resistance to Neat, oxygen, ozone and sunlight. In fact, the resistance of EPDM rubber to Sunlight is rated equal to thet of silicone rubber [8], (10), [11] There are a variety of EPM and EPDM polymers available today, each offering different Gombinations of characteristics. The selection of a particular polymer has to be made on the basis of a thorough evaluation of the characteristics and their significance lor the intended application, Silicone Rubber As ghown on the previous pags, silicone rubber contains a repeating silicon-oxygen backbone and has organic methyl groups attached to a significant proportion of the elfcon atoms by silicon-carbon bonds [12]. Silicone rubber is classified as an "organo silicon" Shee trorteck This is due to the very important bond between carbon (organic) and silicon (inorganic) [14]. Silicone rubber is not inorganic. eacause of the silicon-oxygen backbone, silicone rubber is resistant to sunlight, heat and 's lexible over a wide range of temperatures. But, unlike the EPA backbone, the alcne ivgen bond is susceptible to heterolytic cleavage, i.e., attack by acids and bases (15). Silicone rubber has low physical properties compared to EPR based matoraie 16} ‘moisture than EP rubber. As ie the case for EPRs, many different silicone polymers are commercially available, but relatively few are suitable for high voltage applications, Extensive evaluation analys and testing are required to ensure an appropriate match of material charactoristioe Lain application needs. EPDM/Silicone Alloy Recognizing the only beneficial characteristic of silicone rubber = hydrophobicity - but desiring a compound which had the excellent mechanical properties that EPDM can Provide, Ohio Brass developed an alloy of EPDM and silicone which combines the bect Properties of these two materials. This compound is called ESP. () Backbone refers to the C-C chain found in EPR materials and the Si-O found in silicone,H H H HCH HCH HCH | | nCl-Si-Cl + 2H,o = nHO-Si-OH + 2HCL -; [si-o], | | | HCH HCH HCH H H H Dimethyidicioro Dimethyisilane dio! Polydimethyl Siloxane siloxane qhe word polymer is Greek for “many parts", thus Polyethylene translates to "many ethylenes*, and in some cases it may be a liquid. As ‘n* and “m” increases (molecular weight increases), the polymers Physical Properties are improved [3]. As mentioned above, Polymers are very large molecules, winere in the ease of EPR, the "n" and “m" can be ag high as 1,000,000 [4]. In the case of silicone rubber "n" is in the range of 3,000 to 10,000 5) Sra is normally manufactured in a continuous process in large reactors. The monomers, Ginyiene, propylene and sometimes a diene {in Ihe case of EPDM), along with the Galalyst are metered into the reacior and the polymorisatnn takes place almost instantly anon temperature. After polymerization, the ‘pole ix cooled, dewatered, dried, So0led ‘again and compressed into bales 6). tne Cor Polymer is now ready for compounding (2) roseular weight. Once separated, they are polymerized te higher molecular weight in the presence of catalysts (7. Now the silicone tubers ready for compounding (#) (#) = Once the polymer has been manufactured, it needs 'o be compounded into a suitable material for use in high voltage insulators. Polymer compounding is the produc ol mixing the polymers discussed above, with cine chemicals to Produce a polymer compound which has specific Properties for an application Examples of polymer compounds could be Chewing gum, a garden hose, tires, Solid rocket fuel, and of course, electrical insulators, Polymer compounding willbe discussed in more detail in a later sectionPOLYMER COMPOUNDS USED IN HIGH VOLTAGE INSULATORS Introduction Since their introduction in the early 1970s, Polymer insulators have been increasingly pepe oe! ilies as suitable replacements for porcelain and glass insulators. This Peres resents details to the non-chemist on the types of Polymers used in compounds for high voltage insulation, ‘The polymers that will be discussed are ethylene propylene polymers, which include sinylene propylene rubber (EPR) and ethylene Propylene diene monomer (EPDM), silicone rubber (POMSO) and an alloy of EPDM and PDMSO. Polymer Composition A polymer is composed of very large molecules. Each molecule contains atoms arranged one after another in a chain-like manner. The chain-like arrangement repeats in regular ELGPS: 0 the structure can be wrtlen as certain segmnente nian repeat "n" times [1] Each polymer is commonly named after the raw material uced ty make it. For example: H H HH HH HCH HCH nC=C = [c-c} H | H | HH HH ne=-c 5 [c-¢], HH HH Ethylene Polyethylene Propylene Polypropylene H Hq HCH HCH HH H | HH H | nC=C + mc=c > [c-c], - [C-clm HH HoH HH HH Ethylene Propylene Ethylene Propylene Rubber Chemical Structures [2]