EP1026704A2 - Isolateur modifié en surface et procédé - Google Patents

Isolateur modifié en surface et procédé Download PDF

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Publication number
EP1026704A2
EP1026704A2 EP99125571A EP99125571A EP1026704A2 EP 1026704 A2 EP1026704 A2 EP 1026704A2 EP 99125571 A EP99125571 A EP 99125571A EP 99125571 A EP99125571 A EP 99125571A EP 1026704 A2 EP1026704 A2 EP 1026704A2
Authority
EP
European Patent Office
Prior art keywords
insulator
preparation
iii
tin
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99125571A
Other languages
German (de)
English (en)
Other versions
EP1026704B1 (fr
EP1026704A3 (fr
Inventor
Peter Dr. Jenkner
Eckhard Just
Johannes Liebermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa GmbH, Siemens AG filed Critical Degussa GmbH
Publication of EP1026704A2 publication Critical patent/EP1026704A2/fr
Publication of EP1026704A3 publication Critical patent/EP1026704A3/fr
Application granted granted Critical
Publication of EP1026704B1 publication Critical patent/EP1026704B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
    • H01B19/04—Treating the surfaces, e.g. applying coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y10T428/31612—As silicone, silane or siloxane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a surface-modified insulator Process for surface modification of an insulator and its use a preparation containing fluoroorganosilane and / or siloxane therefor.
  • Isolators are used in many places in technology, for example as High voltage insulators in substations or in transmission lines. It is desirable that insulators be used under difficult operating conditions, especially when contaminated by dirt, salt or other deposits as long as possible the high technical Requirements met.
  • a foreign layer deposited on the surface of the insulator affects the electrical insulation.
  • countermeasures are complex designs with large screen overhang and long Creepage distances selected. They must also be heavily soiled Surfaces are cleaned manually at regular intervals.
  • EP 0 497 189 B1 teaches a process for producing a water and oil repellent adsorbed film, in which a pretreated by roughening Substrate surface, which is also aksive on its surface Has hydrogen groups with a non-aqueous solution surface-active material is brought into contact, the active Material a fluorocarbon group and a chlorosilyl group or one Contains fluorocarbon group and an alkoxy group.
  • chlorinated hydrocarbons are used as solvents, which today are comparatively expensive and are also extremely harmful to health. Examples of applications include high voltage insulators and Spark plugs mentioned.
  • a coating of the mentioned type under difficult operating conditions not permanent, because the Bonding to the insulator is not sufficient.
  • Such water, solvent or dispersant Compositions are generally considered to be hydrophobic and at the same time oleophobic and dirt-repellent finish from Substrates or for special modification of the surface properties of the substrates used, for example for metals, metal oxides, fillers, Pigments, glass, enamel, ceramics, building materials, structures, fibers, textiles, Natural materials, plastics, paints.
  • This modification can also be to form a protective layer against UV radiation, mechanical, act thermal and chemical influences.
  • scratch-resistant, anti-corrosive, antiicing, antifouling, or antibacterial antithrombic properties can be achieved.
  • Organofunctional groups have said fluoroorganofunctional Siloxanes as a rule Si-bonded hydroxyl or alkoxy groups, the one enable later connection to the substrate. However, here too not satisfactory, d. H. permanent connection of the coating reached the substrate.
  • fluoroalkylsilanes are used for coating the Surface of inorganic fillers use, which in turn in an insulating high polymer material for the production of water-repellent dielectric materials are dispersed.
  • a such procedure is usually very complex and for the Modification of the entire surface of workpieces, in particular glass or ceramic, not applicable.
  • the present invention is therefore based on the object of an isolator with a water, oil and dirt-repellent coating with satisfied providing adhesive properties.
  • composition fluoroorganofunctional silanes and / or siloxanes receives, the majority of silanol groups containing fluoroorganofunctional silanes and / or siloxanes, if one at least one fluorine-functional chlorosiloxane or alkoxysilane, optionally further organochlorosiloxanes or organoalkoxysilanes, at least a metal salt of aluminum (III), tin (II) tin (IV) iron (III) or titanium (III) and at least one mineral acid in the presence of a small amount Water, preferably 1 ppm by weight to 2% by weight, mixes, if appropriate partially hydrolyzed and optionally condensed or oligomerized.
  • the Metal salt can be used in combination with the mineral acid and in particular act as a catalyst when using said preparation.
  • Figures 1 to 3 show preferred embodiments of insulators, cf. also the legend.
  • the insulator can be made of a ceramic, glass or one insulating plastic.
  • the ceramics e.g. B. a clay ceramic Porcelain or a steatite, can be unglazed or with a glaze in Be provided in the form of a glass-like melt.
  • Said preparation stands out when used for coating of the insulator, also called the insulator base, by a special rapid and complete reaction with the usually polar, i.e. H. hydrophilic surface of the insulator.
  • the application of the said Preparation causes a homogeneous, highly cross-linked on the isolator Coating that excellently even under the influence of weather, such as rain, heat, cold, UV exposure, completely and permanently chemical remains bound and this is advantageous for long-term behavior is.
  • a coating can be produced in a simple and economical manner on insulators so that the surface of the modified insulator a particularly good beading effect, a high roll angle and thus also has a low tendency to become contaminated.
  • the inherently hydrophilic The surface of a glaze or a glass is thereby suitably Water-repellent, like a coating with silicone, but it is coating according to the invention much more resistant.
  • coatings according to the invention have in excellently oleophobic, d. H. Oil repellent properties.
  • the coating according to the invention is further characterized by a excellent pH resistance, thermal resistance and special UV resistance out.
  • the coating according to the invention their excellent adhesion to the substrate surface especially as Surface coating for a high voltage insulator for use in the Transmission of electrical energy indoors and outdoors is suitable. This can significantly improve the behavior of the foreign layer and an increase in the breakdown voltage, especially below Moisture exposure to precipitation (rain, fog, spray - especially in the maritime sector). This means that even complex, mostly manual cleaning work is significantly reduced become.
  • An object of the present invention is therefore a surface-modified Insulator, which by coating the insulator body with a Preparation is available that contains at least one fluoroorganofunctional silane and / or siloxane, at least one mineral acid and at least one Metal salt of aluminum (III), tin (II) tin (IV) iron (III) or titanium (III) contains.
  • Said preparation preferably contains a mineral acid from the series Hydrogen chloride, nitric acid, phosphoric acid or sulfuric acid.
  • said preparation has one Metal salt content of 0.01 to 10 wt .-% and a content of Mineral acid from 0.001 to 5% by weight, with the metal salt being chlorides, Nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, sulfates or Hydrogen sulfates preferred.
  • the said preparation suitably also contains a dissolving or Dispersant.
  • a dissolving or Dispersant can contain a aromatic or aliphatic hydrocarbon or an alcohol or Have water or a mixture thereof.
  • Methanol, ethanol, n-propanol, i-propanol, n-butanol, acetone, cyclohexane, n-hexane or toluene used as a solvent As a rule, the solution or dispersant the remaining proportions of said preparation to 100%.
  • an insulator is preferably coated by Dipping, spraying, painting or polishing, if necessary, the Follow coating after thermal treatment.
  • it can treated workpiece in a heating oven for a period of 1 minute up to 24 hours at 50 to 350 ° C, particularly preferably over 20 to Heated to 150 ° C for 60 minutes.
  • the isolator obtained advantageously has a fluoroorganofunctional one and metal salt-containing coating, which is usually 0.1 to 1,000 nm is thick.
  • the thickness of the layer mentioned is preferably 0.5 to 50 nm, particularly preferably at 1 to 15 nm.
  • the present invention thus also relates to a method for Modification of the surface of an insulator, which is characterized by that you have a preparation that contains at least one fluoroorganofunctional silane and / or siloxane, at least one mineral acid and at least one Metal salt of aluminum (III), tin (II) tin (IV) iron (III) or titanium (III) contains, applies to the insulator body and, if necessary, thermally aftertreated.
  • the metal salt is preferably used for said preparations solid or liquid or dissolved form.
  • metal salt metal chlorides are preferred - in particular aluminum (III) chloride, Tin (II) chloride, tin (IV) chloride, titanium (III) chloride and iron (III) chloride,
  • the metal salt is suitably used in a total amount of 0.01 up to 10% by weight, based on the finished preparation.
  • the coating process according to the invention is carried out d. H. for surface modification of insulators, as follows:
  • the insulator or base body to be treated can be pre-cleaned.
  • the cleaning can mechanically and / or chemically, for example by brushing, Neutralization with acid or alkali at a pH from 0 to 14 and optionally subsequent rinsing with demineralized water or degreasing the Substrate surface with an appropriate solvent. So you can Prepare used or new insulator for treatment. You can use the isolator, suitably an unused one, but also according to the invention without carrying out a special pre-cleaning to treat.
  • the insulator is usually coated by Dipping, spraying, brushing or polishing in said preparation or by a combination of the coating methods mentioned.
  • the treatment time is usually a few seconds up to approx. 1 hour, preferably at about 1 to 20 minutes, the duration in some Cases for the homogeneity of the coating, but usually not for the thickness of which is decisive.
  • Treatment can be a Drying time from 10 seconds to 24 hours at temperatures of 50 up to 350 ° C. Drying usually takes place at 100 to 200 ° C over a period of 10 to 120 minutes.
  • the drying process can be done in air, in vacuum or under a protective gas, for example under argon or nitrogen.
  • the base body of the insulator can be, for example, ceramic, glass, enamel, Metal oxides or plastics, d. H. organic polymers such as casting resins different chemical functions and compositions, e.g. B. Epoxy resin or silicone, e.g. B. silicone rubber act.
  • the metal salt present in the preparation used results in Connection with the mineral acid the binding and condensation of the fluorine-functional silane or siloxane to the insulator in surprising good, lasting and therefore advantageous way.
  • Cast resin plates, glazed and unglazed porcelain test specimens are used as substrates.
  • the porcelain used is identical for all substrates.
  • a gray and a brown glaze are used as glazes, which differ only in the color pigments used in each case.
  • the gray glaze contains metal oxides of cobalt as color pigments.
  • the brown glaze contains metal oxides of iron, chromium and magnesium as color pigments.
  • fluoroalkylsilane systems are used.
  • composition is 1.0% by weight of DS F 8261, 1.0% by weight of H 2 O, 0.2% by weight of hydrochloric acid, 0.12% by weight of SnCl 2 x6H 2 O and 97, 68% by weight ethanol.
  • the solution is used after a ripening time of 24 h.
  • hydrophobic properties are checked by a static contact angle measurement (H 2 O) in accordance with DIN EN 828.
  • the coated test specimens are boiled in demineralized water for 5 h. After that, the hydrophobicity is again determined by a static Contact angle measurement checked.
  • the ceramic of the insulators is an alumina porcelain from Type C120 according to DIN-EN 60 672. Porcelain or ceramics from others Composition makes no difference.
  • the coated long rod insulator was made by dipping it into a preparation as already described in Example 1.
  • the isolators are each in one suitable room and hung with a predetermined intensity of rain sprinkled at a given angle.
  • the breakdown voltages are determined from an oscillogram. There will be five each Rollover tests carried out.
  • the determined breakdown voltage for the uncoated long rod insulator was 376 kV, the breakdown voltage determined for the coated Isolator was 405 kV. This means that the coated insulator despite smaller creepage distance (11 shielding ribs) only with a higher voltage showed a rollover. Technically, the result means a profit of 9.1% of the voltage to be insulated per mm of insulation length.
  • the shape of the connector caps doesn't matter. This type is often used as a rail isolator.
  • the ceramic is again a C120 alumina porcelain.
  • the high-voltage insulators are included Washed trisodium phosphate. Then the High-voltage insulators preconditioned according to IEC 507 (1991). The preconditioned high-voltage insulators are subjected to a standing test each subjected to predetermined salt mass concentration in air. Each The exam lasts at least one hour, provided that none is found Rollover instead. It is at a test voltage of 15 kV (AC voltage) each the maximum standing salt mass concentration determined in accordance with IEC 507 (1991), page 19, d. H. the highest Standing salt mass concentration at which the examined High voltage insulator with a maximum of one flashover in three attempts shows within the one-hour trial period.
  • the determined standing salt mass concentration lies with the coated one High voltage insulator one salt level higher than IEC 507 (1991) with the uncoated high voltage insulator.
  • the isolators designed according to Example 3 become one Salt spray test according to Example 4 subjected. So it becomes an 11-shielded coated long rod insulator with a 22-shielded, uncoated long rod insulator compared.
  • the 11-shielded, coated long rod insulator shows the same Standing salt content like the 22-shielded, uncoated long rod insulator. This means in practice that the coating has a creepage distance of can be saved at least 30%.
  • FIG. 1 shows an insulator 1 in the form of a high-voltage insulator partially broken representation shown.
  • the insulator 1 has one Insulator body 2 made of a ceramic K and connection caps 4 for Connection and / or for carrying current-carrying lines.
  • the Base body 2 is a substantially cylindrical stem 5 with a Number of plate-shaped ribs 6 formed thereon.
  • the Ceramic K not shown here, is superficial with a glaze overdrawn.
  • On the surface of the glazed ceramic K des Insulator body 2 is a water and oil repellent Coating B according to the invention by dipping the insulator body 2 applied in a preparation as described in Example 1.
  • Figure 2 is also a partially broken representation coated according to the invention, designed as a high-voltage insulator Isolator 7 shown.
  • the number of Ribs 6 of the insulator base body 2 made of ceramic K are reduced.
  • the length of the Insulators 7 and 1 are identical here. However, there are only two ribs 6 available.
  • FIG. 3 shows an isolator 10 designed as a high-voltage isolator, where compared to the insulators 1 and 7 according to Figure 1 and Figure 2 of Insulator body 2 made of ceramic K is reduced to the shank 5.
  • Umbrellas to increase the leakage current leakage between the two Connection caps 4 are not provided here.
  • the insulator 10 is additionally protected against dust deposits.
  • the isolator 10 is considerably cheaper to produce, since the ceramic material K of the screens 6 is saved.
  • the manufacturing costs for the insulator 10 are also significantly lower than for insulators 1 and 7, since the complex shape for the screens 6 not applicable.
  • the expensive twisting off of the screens 6 from the still unbaked, soft molded body 2 is eliminated.

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  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Insulators (AREA)
  • Insulating Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Organic Insulating Materials (AREA)
EP99125571A 1999-02-03 1999-12-21 Isolateur modifié en surface et procédé Expired - Lifetime EP1026704B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904133A DE19904133B4 (de) 1999-02-03 1999-02-03 Oberflächenmodifizierter Isolator und Verfahren zur Modifizierung der Oberfläche eines Isolators
DE19904133 1999-02-03

Publications (3)

Publication Number Publication Date
EP1026704A2 true EP1026704A2 (fr) 2000-08-09
EP1026704A3 EP1026704A3 (fr) 2001-10-10
EP1026704B1 EP1026704B1 (fr) 2005-09-07

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EP99125571A Expired - Lifetime EP1026704B1 (fr) 1999-02-03 1999-12-21 Isolateur modifié en surface et procédé

Country Status (7)

Country Link
US (1) US6426150B1 (fr)
EP (1) EP1026704B1 (fr)
JP (1) JP2000222959A (fr)
AT (1) ATE304210T1 (fr)
BR (1) BR0000247A (fr)
DE (2) DE19904133B4 (fr)
NO (1) NO20000561L (fr)

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WO2016180396A1 (fr) * 2015-05-12 2016-11-17 Iph Institut "Prüffeld Für Elektrische" Gmbh Garniture de câble haute tension et procédé de réalisation d'une garniture de câble haute tension

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DE10320765A1 (de) * 2003-05-09 2004-11-25 Degussa Ag Mittel zur Beschichtung von Metallen zum Schutz vor Korrosion
DE10336544A1 (de) * 2003-08-05 2005-02-24 Degussa Ag Zweikomponentenbeschichtungssystem für die Ausstattung glatter Oberflächen mit "Easy-to-clean" - Eigenschaften
WO2005063413A1 (fr) * 2003-12-19 2005-07-14 Omg Americas, Inc. Catalyseur modificateur de surface
DE10361893A1 (de) * 2003-12-19 2005-07-21 Degussa Ag Spezielles Verfahren zur Herstellung von Fluoralkylgruppen tragenden Siliciumverbindungen durch Hydrosilylierung
DE102004025767A1 (de) * 2004-05-26 2005-12-22 Degussa Ag Stabile Lösungen von N-substituierten Aminopolysiloxanen, deren Herstellung und Verwendung
DE102004037043A1 (de) * 2004-07-29 2006-03-23 Degussa Ag Blockkondensate organofunktioneller Siloxane, deren Herstellung, Verwendung sowie deren Eigenschaften
US20070202339A1 (en) * 2004-08-09 2007-08-30 Nippon Steel Chemical Co., Ltd. Epoxy Resin Composition And Epoxy-Polysiloxane Coating Composition
DE102005060402A1 (de) * 2005-12-15 2007-06-21 Degussa Gmbh Lagerstabile Beschichtungszusammensetzung für eine abriebfeste und witterungsbeständige Ausstattung glatter anorganischer Oberflächen mit "Easy-to-clean"Eigenschaften
DE102005060401A1 (de) * 2005-12-15 2007-06-21 Degussa Gmbh Lagerstabile Beschichtungszusammensetzung für eine abriebfeste und witterungsbeständige Ausstattung glatter anorganischer Oberflächen mit "Easy-to-clean"-Eigenschaften
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EP2622124A1 (fr) * 2010-09-27 2013-08-07 Unilever NV Composition et procédé de traitement de substrats
US9278374B2 (en) * 2012-06-08 2016-03-08 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Modified surface having low adhesion properties to mitigate insect residue adhesion
CN104276765B (zh) * 2013-07-08 2016-11-02 中国科学院重庆绿色智能技术研究院 超疏水透明玻璃的制备方法
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016180396A1 (fr) * 2015-05-12 2016-11-17 Iph Institut "Prüffeld Für Elektrische" Gmbh Garniture de câble haute tension et procédé de réalisation d'une garniture de câble haute tension
CN107615608A (zh) * 2015-05-12 2018-01-19 Iph高能电工测试研究所有限公司 高压电缆附件以及生产高压电缆附件的方法
RU2681207C1 (ru) * 2015-05-12 2019-03-05 Ипх Институт "Прюффельд Фюр Электрише Хохляйстунгстехник" Гмбх Арматура для высоковольтного кабеля и способ изготовления арматуры для высоковольтного кабеля
US10476251B2 (en) 2015-05-12 2019-11-12 IPH Institut “Prueffeld fuer elektrische Hochleistungstechnik” GmbH Set of high-voltage cables and method for producing a set of high-voltage cables
CN107615608B (zh) * 2015-05-12 2020-11-27 Iph高能电工测试研究所有限公司 高压电缆附件以及生产高压电缆附件的方法

Also Published As

Publication number Publication date
DE19904133B4 (de) 2007-02-08
ATE304210T1 (de) 2005-09-15
DE59912524D1 (de) 2005-10-13
NO20000561D0 (no) 2000-02-03
JP2000222959A (ja) 2000-08-11
EP1026704B1 (fr) 2005-09-07
BR0000247A (pt) 2000-09-12
NO20000561L (no) 2000-08-04
US6426150B1 (en) 2002-07-30
DE19904133A1 (de) 2000-09-28
EP1026704A3 (fr) 2001-10-10

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