WO2013013688A1 - Process for preparing coated push-rods and/or pole housings for electrical contacts and connecting elements - Google Patents

Process for preparing coated push-rods and/or pole housings for electrical contacts and connecting elements Download PDF

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Publication number
WO2013013688A1
WO2013013688A1 PCT/EP2011/003776 EP2011003776W WO2013013688A1 WO 2013013688 A1 WO2013013688 A1 WO 2013013688A1 EP 2011003776 W EP2011003776 W EP 2011003776W WO 2013013688 A1 WO2013013688 A1 WO 2013013688A1
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WO
WIPO (PCT)
Prior art keywords
sol
push
rod
process according
pole housing
Prior art date
Application number
PCT/EP2011/003776
Other languages
French (fr)
Inventor
Dietmar Gentsch
Thorsten FUGEL
Original Assignee
Abb Technology 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 Abb Technology Ag filed Critical Abb Technology Ag
Priority to PCT/EP2011/003776 priority Critical patent/WO2013013688A1/en
Priority to EP11754290.2A priority patent/EP2737511A1/en
Publication of WO2013013688A1 publication Critical patent/WO2013013688A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
    • H01H33/60—Switches wherein the means for extinguishing or preventing the arc do not include separate means for obtaining or increasing flow of arc-extinguishing fluid
    • H01H33/66—Vacuum switches
    • H01H33/662—Housings or protective screens
    • H01H33/66207—Specific housing details, e.g. sealing, soldering or brazing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H9/00—Details of switching devices, not covered by groups H01H1/00 - H01H7/00
    • H01H9/02—Bases, casings, or covers
    • H01H2009/0285—Casings overmoulded over assembled switch or relay
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
    • H01H33/60—Switches wherein the means for extinguishing or preventing the arc do not include separate means for obtaining or increasing flow of arc-extinguishing fluid
    • H01H33/66—Vacuum switches
    • H01H33/662—Housings or protective screens
    • H01H33/66207—Specific housing details, e.g. sealing, soldering or brazing
    • H01H2033/66223—Details relating to the sealing of vacuum switch housings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
    • H01H33/60—Switches wherein the means for extinguishing or preventing the arc do not include separate means for obtaining or increasing flow of arc-extinguishing fluid
    • H01H33/66—Vacuum switches
    • H01H33/662—Housings or protective screens
    • H01H33/66207—Specific housing details, e.g. sealing, soldering or brazing
    • H01H2033/6623—Details relating to the encasing or the outside layers of the vacuum switch housings

Definitions

  • the present invention relates to a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements, to such a coated push-rod and/or pole housing and to the use of the process for preparing coated push-rods and/or pole housings.
  • BMC bulk moulding compound
  • push-rods and/or pole housings used for electrical contacts or connecting elements are made of a thermoplastic material in order to provide a mechanical strengthening of the overall electrical contact or connecting element and/or to protect the electrical conductive body of the electrical contact or connecting element from dust and humidity.
  • thermoplastic materials are used in a great variety and are well known in the art.
  • thermoplastic materials can absorb water (so called water up-take), which may have an adverse effect on the mechanical and dimensional stability of such electrical contact or connecting element and may further lead to a severe damage of the electrical conductive body inside such an electrical contact or connecting element.
  • Push-rods and/or pole housings used for electrical contacts or connecting elements and which are made of a thermoplastic material are thus only suitable for outdoor applications to a limited extent.
  • a first aspect of the invention relates to a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material for electrical contacts or connecting elements, the process comprising the following steps:
  • the sol is formed by using a hydrolytic sol/gel-process in the presence of water.
  • the sol is formed by using a non- hydrolytic sol/gel-process in the absence of water.
  • the sol is formed by using sol/gel forming components selected from the group comprising alkoxides, metal alkoxides, metal oxides, metal acetates, metal nitrates, metal halides, wherein the metal includes at least one of silicon, aluminum, boron, magnesium, zirconium, titanium, alkaline metals, alkaline earth metals, or transition metals, platinum, molybdenum, iridium, tantalum, bismuth, tungsten, vanadium, cobalt, hafnium, niobium, chromium, manganese, rhenium, iron, gold, silver, copper, ruthenium, rhodium, palladium, osmium, lanthanum and lanthanides.
  • sol/gel forming components selected from the group comprising alkoxides, metal alkoxides, metal oxides, metal acetates, metal nitrates, metal halides, wherein the metal includes at least one of silicon,
  • the sol/gel forming components are selected from metal alkoxides and preferably the sol/gel forming components are selected from the group comprising Ti(n-butoxy) 4 and Zr(n-propoxy) 4 .
  • the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material, or bulk moulding compound (BMC), in liquid, pulpy or pasty form, preferably by painting, spraying, spin coating, roll coating, dipping, ink-jet-printing and/or electrophoresis.
  • the conversion of the sol into a solid material is performed by hydrolysis of the sol, aging, crosslinking and/or drying.
  • the drying is obtained by a thermal treatment in the range of about -100 °C to 200 °C, preferably in the range of about -50 °C to 175 °C, more preferably in the range of about -25 °C to 150 °C, about 0°C to 00 °C, and most preferably from about 10 °C to 100 °C, optionally under reduced pressure or vacuum.
  • thermoplastic material of the push-rod and/or pole housing is selected from the group comprising polyethylene, polypropylene, polystyrene, polyamide, polyacetate, polycarbonate, acrylonitrile butadiene styrene, polymethyl methacrylate, polyethylene terephthalate polyvinyl chloride and bulk moulding compound (BMC).
  • a further aspect of the invention relates to a coated push-rod and/or pole housing made of a thermoplastic material for electrical contacts or connecting elements obtainable by the inventive process.
  • Another aspect of the invention relates to the use of the inventive process for preparing a coated push-rod and/or pole housing.
  • Fig. 1 schematically shows a sectional illustration through an exemplary pole part comprising a push-rod and/or pole housing according to at least one embodiment.
  • Fig. 2 shows a flow diagram of a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements according to an exemplary embodiment of the invention.
  • BMC bulk moulding compound
  • the sol/gel-process is widely applied in order to build up different types of networks.
  • the linkage of the components under formation of the sol or gel can take place in several ways, e.g. via hydrolytic or non-hydrolytic sol/gel-processing as known in the prior art.
  • the present invention utilizes a sol/gel technology to prepare coated push-rods and/or pole housings made of a thermoplastic material or bulk moulding compound (BMC) for use in electrical contacts or connecting elements.
  • BMC bulk moulding compound
  • a “sol” is a dispersion of colloidal particles in a liquid, and the term “gel” connotes an interconnected, rigid network of pores of submicrometer dimensions and polymeric chains whose average length is typically greater than a micrometer.
  • the sol/gel- process may involve mixing of the precursors, e.g.
  • the sol/gel forming components into a sol, optionally adding further additives or materials, applying the sol onto a substrate in the form of a coating, gelation of the mixture, whereby the colloidal particles are linked together to become a three-dimensional network, aging of the gel to increase its strength; converting the gel into a solid material by drying from liquid and/or dehydration or chemical stabilisation of the network, and densification of the material to produce structures with ranges of physical properties.
  • Such processes are described, for example, in Henge and West, The Sol/Gel-Process, 90 Chem. Ref. 33 (1990).
  • sol/gel as used within this specification may mean either a sol or a gel.
  • the sol can be converted into a gel as mentioned above, e.g. by aging, curing, raising of the pH, evaporation of solvent or any other conventional method.
  • the inventive push-rods and/or pole housings for example exhibit the advantageous property that they can be easily prepared at low temperature from sols and/or gels.
  • sols/gels prepared in accordance with the process of the present invention are suitable for coating of almost any type of push-rods and/or pole housings made of a thermoplastic material or bulk moulding compound (BMC).
  • BMC bulk moulding compound
  • thermoplastic material is a material that will repeatedly soften when heated and harden to a rigid material when cooled without any degradation of the material.
  • thermoplastic material used for preparing a push-rod and/or pole housing is preferably one or more material selected from the group comprising PE (polyethylene), PP
  • the sol utilized in the process of the present invention can be prepared from any type of sol/gel forming components in a conventional manner. The skilled person will - depending on the desired properties and requirements of the push-rods and pole housings to be produced - select the suitable components/sols based on his professional knowledge.
  • the sol/gel forming components may be selected from alkoxides, oxides, acetates, nitrates of various metals, e.g. silicon, aluminum, boron, magnesium, zirconium, titanium, alkaline metals, alkaline earth metals, or transition metals, and from platinum,
  • molybdenum iridium, tantalum, bismuth, tungsten, vanadium, cobalt, hafnium, niobium, chromium, manganese, rhenium, iron, gold, silver, copper, ruthenium, rhodium, palladium, osmium, lanthanum and lanthanides, as well as combinations thereof.
  • the sols may be derived from at least one sol/gel forming component selected from alkoxides, metal alkoxides, colloidal particles, particularly metal oxides and the like.
  • the metal alkoxides that may be used as sol/gel forming components may be conventional chemical compounds that may be used in a variety of applications. These compounds have the general formula M(OR) x wherein M is any metal from a metal alkoxide which e.g. may hydrolyze and polymerize in the presence of water. R is an alkyl radical of 1 to 30 carbon atoms, which may be straight chained or branched, and x has a value equivalent to the metal ion valence.
  • Metal alkoxides such as Si(OR) 4 , Ti(OR) 4 , AI(OR) 3 , Zr(OR) 3 and Sn(OR) 4 may be used.
  • R can be the methyl, ethyl, propyl or butyl radical.
  • suitable metal alkoxides can include Ti(isopropoxy) 4 , Ti(n-butoxy) 4 , AI(isopropoxy) 3 , AI(sec-butoxy) 3 , Zr(n-butoxy) 4 and Zr(n-propoxy) 4 .
  • the suitable metal alkoxides are selected from the group comprising Ti(n-butoxy) 4 and Zr(n-propoxy) 4 .
  • sols can be made from silicon alkoxides such as tetraalkoxysilanes, wherein the alkoxy may be branched or straight chained and may contain 1 to 25 carbon atoms, e.g. tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or tetra-n-propoxysilane, as well as oligomeric forms thereof.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • alkylalkoxy- silanes wherein alkoxy is defined as above and alkyl may be a substituted or
  • methyltrimethoxysilane MTMOS
  • methyltriethoxysilane methyltriethoxysilane
  • ethyltriethoxysilane methyltrimethoxysilane
  • ethyltrimethoxysilane methyltripropoxysilane, methyltributoxysilane, propyltri- methoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, isobutyltri-methoxysilane, octyltriethoxysilane, octyltrimethoxysilane, methacryloxydecyltrimethoxysilane (MDTMS), aryltrialkoxysilanes such as phenyltrimethoxysilane (PTMOS), phenyl-triethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane, phenyl-tri-(3-glycidyloxy)-silane-oxide (TGPSO), 3-aminopropyltrimethoxysilane, 3-aminopropyl-triethoxysilane, 2-
  • fluoroalkyltriethoxysilanes with a partially or fully fluorinated, straight chain or branched fluoroalkyl residue of about 1 to 20 carbon atoms e.g. tridecafluoro- 1 ,1 ,2,2-tetrahydrooctyltriethoxysilane and modified reactive flouroalkylsiloxanes which are available from Degussa AG under the trademarks Dynasylan ® F8800 and F8815; as well as any mixtures of the foregoing.
  • the sol/gel components used in the sols may also comprise colloidal metal oxides, preferably those colloidal metal oxides which are stable long enough to be able to combine them with the other sol/gel components.
  • colloidal metal oxides may include, but are not limited to, Si0 2 , Al 2 0 3 , MgO, Zr0 2 , Ti0 2 , Sn0 2 , ZrSi0 4 , B 2 0 3 , La 2 0 3 , Sb 2 0 5 and ZrO(N0 3 ) 2 .
  • Si0 2 , Al 2 0 3 , ZrSi0 and Zr0 2 may be preferably selected.
  • Further examples of the at least one sol/gel forming component include aluminumhydroxide sols or -gels, aluminumtri-sec-butylat, AIOOH-gels and the like.
  • colloidal sols may be acidic in the sol form and, therefore, when used during hydrolysis, it may not be necessary to add additional acid to the hydrolysis medium.
  • colloidal sols can also be prepared by a variety of methods.
  • titania sols having a particle size in the range of about 5 to 150 nm can be prepared by the acidic hydrolysis of titanium tetrachloride, by peptizing hydrous Ti0 2 with tartaric acid and, by peptizing ammonia washed Ti(S0 4 ) 2 with hydrochloric acid.
  • Such processes are described, for example, by Weiser in Inorganic Colloidal Chemistry. Vol. 2, p. 281 (1935).
  • the molar ratio of the added water and the sol/gel forming components may be in the range of about 0.01 to 100, preferably from about 0.1 to 75, more preferred from about 0.2 to 50.
  • the sol/gel components are suspended in water.
  • further solvents or mixtures thereof, and/or further additives such as fillers, surfactants, crosslinkers and the like may be added.
  • the solvent may contain salts, buffers such as PBS buffer or the like to adjust the pH value, the ionic strenght etc.
  • Further additives like catalysts for controlling the hydrolysis rate of the sol or for controlling the crosslinking rate may be added.
  • Non-hydrolytic sols may be similarly prepared as hydrolytic sols, but essentially in the absence of water.
  • Non-hydrolytic sol/gel processing in the absence of water may be accomplished by reacting alkylsilanes or metal alkoxides with anhydrous organic acids, acid anhydrides or acid esters, or the like.
  • the sol may thus be formed from at least one sol/gel forming component as described above in a nonhydrous sol/gel processing, and the anhydrous organic acid, acid anhydride or acid ester can be selected from formic acid, acetic acid, acetoacetic acid, succinic acid maleic acid, crotonic acid, acrylic acid, methacrylic acid, partially or fully fluorinated carboxylic acids, their anhydrides and esters, e.g. methyl- or ethylesters, and any mixtures of the foregoing.
  • Suitable inorganic acids include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid as well as diluted hydrofluoric acid.
  • Suitable bases include, for example, sodium hydroxide, ammonia and carbonate as well as organic amines.
  • Suitable catalysts in non- hydrolytic sol/gel processes include anhydrous halide compounds, for example BCI 3 , NH 3 , AICI3, TiCI 3 or mixtures thereof.
  • solvents including water-miscible solvents, such as water- miscible alcohols or mixtures thereof.
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol and lower molecular weight ether alcohols such as ethylene glycol monomethyl ether may be used.
  • the sol may be further modified by the addition of at least one crosslinking agent to the sol.
  • crosslinking agent may be selected from the group comprising isocyanates, silanes, diols, di-carboxylic acids, (meth)acrylates, for example, 2-hydroxyethyl methacrylate, propyltrimethoxysilane, 3-(trimethylsilyl)propyl methacrylate, isophorone diisocyanate, polyols, glycerine and the like.
  • Further additives may include, e.g., drying-control chemical additives such as glycerol or any other suitable liquid that can be suitable for controlling the conversion of the sol to a gel and a solid material.
  • drying-control chemical additives such as glycerol or any other suitable liquid that can be suitable for controlling the conversion of the sol to a gel and a solid material.
  • the formed sol may be applied onto the surface of the push-rod and/or pole housing made of thermoplastic material in liquid, pulpy or pasty form, for example, by painting, spraying, spin coating, roll coating, dipping, ink-jet-printing or electrophoresis.
  • Coated push-rods and/or pole housings may also be obtained by a transfer process, in which the gels are applied to the push-rod and/or pole housing as a lamination.
  • the coated push-rod and/or pole housing can be cured, and subsequently be thermally treated. It is possible to successively apply a plurality of thin layers to provide a more uniform and thicker coating on the surface of the push-rod and/or pole housing.
  • the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material in that the surface of the push-rod and/or pole housing is at least partially coated with the sol.
  • the surface of the resulting push-rod and/or pole housing is thus at least partially coated.
  • the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) in that only the outer surface exposed to dust and humidity is substantially coated with the sol.
  • BMC bulk moulding compound
  • the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) in that the complete surface is substantially coated with the sol.
  • BMC bulk moulding compound
  • the surface of the push-rod and/or pole housing may be treated before the formed sol is applied onto the surface of the push-rod and/or pole housing.
  • the surface of the push-rod and/or pole housing is wetted with an appropriate solvent.
  • Any suitable solvent can be used, like saturated hydrocarbon solvents such as hexane, heptane and the like and other organic solvents like
  • the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) ay be treated with a laser.
  • the formed sol applied onto the surface of the push-rod and/or pole housing can be converted into a solid material. Conversion of the sol into a gel may be accomplished by, e.g., hydrolysis of the sol, aging, curing, crosslinking, raising of pH, drying or any other conventional method.
  • the sol may be first converted into a gel and subsequently converted into the inventive coated push-rod and/or pole housing, or the sol may be directly converted into the solid.
  • the sol may preferably be converted into the solid material at room temperature.
  • the conversion step can preferably be achieved by drying, for example by air-drying at room temperature or thermal drying.
  • the thermal drying is carried out in the range of about -100 °C to +200 °C, preferably in the range of about -50 °C to 175 °C, more preferably in the range of about -25 °C to 150 °C, about 0°C to 100 °C, and most preferably from about 10 °C to 100 °C or at about room temperature. Drying or aging may also be performed at any of the above temperatures under reduced pressure or in vacuo. Such thermal drying may be carried out in a heat oven or by using IR or UV radiation or by other methods known to the skilled person.
  • the conversion of the sol into the solid or semi-solid material can be performed under various conditions.
  • the conversion can be performed in different atmospheres, e.g. inert atmospheres such as nitrogen or noble gases such as argon, or any mixtures thereof.
  • Suitable conditions such as temperature, atmosphere and/or pressure may be applied depending on the desired property of the final material and the components used to form the material.
  • the sol applied onto the surface of the push-rod and/or pole housing creates a thin, uniform, and dense film on the surface of the object being ' treated.
  • the benefit of the sol- gel coating is that the film adheres extremely well to the surface of the push-rod and/or pole housing made of thermoplastic material.
  • the sol provides the beneficial characteristic of being a smooth and hard coating which is highly resistant to mechanical stress and scratches and, furthermore, shows a highly reduced water uptake behavior resulting in a push-rod and/or pole housing with a higher mechanical and dimensional stability under outdoor conditions.
  • the sol applied onto the surface of the push-rod and/or pole housing creates a thermally stable sol-gel film that seals the thermal sensitive surface of the push-rod and/or pole housing made of thermoplastic material or bulk moulding compound (BMC).
  • FIG. 1 An exemplary embodiment is schematically illustrated in Fig. 1 showing a sectional illustration through an exemplary pole part according to at least one embodiment.
  • a vacuum interrupter 40 is embedded in a pole housing made of a thermoplastic material 10 and further comprising a bottom connection part 30 and an upper connection part 50, a flexible connection 60 and a push-rod made of a thermoplastic material 70.
  • the pole housing 10 as well as the push-rod 70 are coated by the process of the present invention.
  • Fig. 2 shows a flow diagram for a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material for electrical contacts or connecting elements.
  • a sol is formed from suitable hydrolytic or non-hydrolytic sol/gel forming components.
  • the formed sol is applied onto the surface of the push- rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC).
  • BMC bulk moulding compound

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Abstract

The present invention relates to a process for preparing a coated push -rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements, to such a coated push-rod and/or pole housing and to the use of the process for preparing coated push -rods and/or pole housings. High mechanical and dimensional stability under outdoor conditions is provided. The process comprises steps of forming a sol from hydrolytic or non-hydrolytic sol/gel forming components, and applying the sol onto the surface of the push -rod or pole housing. The coating of the pole housing or push-rod is used for a UV protection layer.

Description

Process for preparing coated push-rods and/or pole housings for electrical contacts and connecting elements
FIELD OF THE INVENTION
The present invention relates to a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements, to such a coated push-rod and/or pole housing and to the use of the process for preparing coated push-rods and/or pole housings.
BACKGROUND OF THE INVENTION
In general, push-rods and/or pole housings used for electrical contacts or connecting elements such as pole parts are made of a thermoplastic material in order to provide a mechanical strengthening of the overall electrical contact or connecting element and/or to protect the electrical conductive body of the electrical contact or connecting element from dust and humidity. Such thermoplastic materials are used in a great variety and are well known in the art.
However, thermoplastic materials can absorb water (so called water up-take), which may have an adverse effect on the mechanical and dimensional stability of such electrical contact or connecting element and may further lead to a severe damage of the electrical conductive body inside such an electrical contact or connecting element. Push-rods and/or pole housings used for electrical contacts or connecting elements and which are made of a thermoplastic material are thus only suitable for outdoor applications to a limited extent. SUMMARY OF THE INVENTION
It is an object of the invention to provide push-rods and/or pole housings for electrical contacts or connecting elements which are made of a thermoplastic material and which are easy to prepare and inexpensive in their application and which provide a high mechanical and dimensional stability under outdoor conditions.
This object is achieved by the subject-matter of the independent claims. Further exemplary embodiments are evident from the dependent claims and the following description.
A first aspect of the invention relates to a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material for electrical contacts or connecting elements, the process comprising the following steps:
a) forming a sol from suitable hydrolytic or non-hydrolytic sol/gel forming components;
b) applying the formed sol onto the surface of the push-rod and/or pole housing made of a thermoplastic material, and
c) converting the applied sol into a solid material.
According to an embodiment of the inventive process, the sol is formed by using a hydrolytic sol/gel-process in the presence of water.
According to an embodiment of the inventive process, the sol is formed by using a non- hydrolytic sol/gel-process in the absence of water.
According to an embodiment of the inventive process, the sol is formed by using sol/gel forming components selected from the group comprising alkoxides, metal alkoxides, metal oxides, metal acetates, metal nitrates, metal halides, wherein the metal includes at least one of silicon, aluminum, boron, magnesium, zirconium, titanium, alkaline metals, alkaline earth metals, or transition metals, platinum, molybdenum, iridium, tantalum, bismuth, tungsten, vanadium, cobalt, hafnium, niobium, chromium, manganese, rhenium, iron, gold, silver, copper, ruthenium, rhodium, palladium, osmium, lanthanum and lanthanides.
According to an embodiment of the inventive process, the sol/gel forming components are selected from metal alkoxides and preferably the sol/gel forming components are selected from the group comprising Ti(n-butoxy)4 and Zr(n-propoxy)4.
According to an embodiment of the inventive process, the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material, or bulk moulding compound (BMC), in liquid, pulpy or pasty form, preferably by painting, spraying, spin coating, roll coating, dipping, ink-jet-printing and/or electrophoresis. According to an embodiment of the inventive process, the conversion of the sol into a solid material is performed by hydrolysis of the sol, aging, crosslinking and/or drying.
According to an embodiment of the inventive process, the drying is obtained by a thermal treatment in the range of about -100 °C to 200 °C, preferably in the range of about -50 °C to 175 °C, more preferably in the range of about -25 °C to 150 °C, about 0°C to 00 °C, and most preferably from about 10 °C to 100 °C, optionally under reduced pressure or vacuum.
According to an embodiment of the inventive process the thermoplastic material of the push-rod and/or pole housing is selected from the group comprising polyethylene, polypropylene, polystyrene, polyamide, polyacetate, polycarbonate, acrylonitrile butadiene styrene, polymethyl methacrylate, polyethylene terephthalate polyvinyl chloride and bulk moulding compound (BMC).
A further aspect of the invention relates to a coated push-rod and/or pole housing made of a thermoplastic material for electrical contacts or connecting elements obtainable by the inventive process.
Another aspect of the invention relates to the use of the inventive process for preparing a coated push-rod and/or pole housing.
These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject matter of the invention will be explained in more detail in the following text with reference to exemplary embodiments which are illustrated in the attached drawings.
Fig. 1 schematically shows a sectional illustration through an exemplary pole part comprising a push-rod and/or pole housing according to at least one embodiment.
Fig. 2 shows a flow diagram of a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements according to an exemplary embodiment of the invention.
The reference symbols used in the drawings, and their meanings, are listed in summary form in the list of reference symbols. In principle, identical parts are provided with the same reference symbols in the figures. DETAILED DESCRIPTION
The sol/gel-process is widely applied in order to build up different types of networks.
The linkage of the components under formation of the sol or gel can take place in several ways, e.g. via hydrolytic or non-hydrolytic sol/gel-processing as known in the prior art. The present invention utilizes a sol/gel technology to prepare coated push-rods and/or pole housings made of a thermoplastic material or bulk moulding compound (BMC) for use in electrical contacts or connecting elements.
A "sol" is a dispersion of colloidal particles in a liquid, and the term "gel" connotes an interconnected, rigid network of pores of submicrometer dimensions and polymeric chains whose average length is typically greater than a micrometer. For example, the sol/gel- process may involve mixing of the precursors, e.g. the sol/gel forming components into a sol, optionally adding further additives or materials, applying the sol onto a substrate in the form of a coating, gelation of the mixture, whereby the colloidal particles are linked together to become a three-dimensional network, aging of the gel to increase its strength; converting the gel into a solid material by drying from liquid and/or dehydration or chemical stabilisation of the network, and densification of the material to produce structures with ranges of physical properties. Such processes are described, for example, in Henge and West, The Sol/Gel-Process, 90 Chem. Ref. 33 (1990).
The term "sol/gel" as used within this specification may mean either a sol or a gel. The sol can be converted into a gel as mentioned above, e.g. by aging, curing, raising of the pH, evaporation of solvent or any other conventional method.
The inventive push-rods and/or pole housings for example exhibit the advantageous property that they can be easily prepared at low temperature from sols and/or gels.
Particularly, sols/gels prepared in accordance with the process of the present invention are suitable for coating of almost any type of push-rods and/or pole housings made of a thermoplastic material or bulk moulding compound (BMC).
A thermoplastic material is a material that will repeatedly soften when heated and harden to a rigid material when cooled without any degradation of the material. Such
thermoplastic material used for preparing a push-rod and/or pole housing is preferably one or more material selected from the group comprising PE (polyethylene), PP
(polypropylene), PS (polystyrene), PA (polyamide), PLA (polyacetate), PC
(polycarbonate), ABS (acrylonitrile butadiene styrene), PMMA (polymethyl methacrylate), PET (polyethylene terephthalate), PEEK (polyetheretherketon) and PVC (polyvinyl chloride). The sol utilized in the process of the present invention can be prepared from any type of sol/gel forming components in a conventional manner. The skilled person will - depending on the desired properties and requirements of the push-rods and pole housings to be produced - select the suitable components/sols based on his professional knowledge. The sol/gel forming components may be selected from alkoxides, oxides, acetates, nitrates of various metals, e.g. silicon, aluminum, boron, magnesium, zirconium, titanium, alkaline metals, alkaline earth metals, or transition metals, and from platinum,
molybdenum, iridium, tantalum, bismuth, tungsten, vanadium, cobalt, hafnium, niobium, chromium, manganese, rhenium, iron, gold, silver, copper, ruthenium, rhodium, palladium, osmium, lanthanum and lanthanides, as well as combinations thereof.
In some exemplary embodiments of the present invention, the sols may be derived from at least one sol/gel forming component selected from alkoxides, metal alkoxides, colloidal particles, particularly metal oxides and the like. The metal alkoxides that may be used as sol/gel forming components may be conventional chemical compounds that may be used in a variety of applications. These compounds have the general formula M(OR)x wherein M is any metal from a metal alkoxide which e.g. may hydrolyze and polymerize in the presence of water. R is an alkyl radical of 1 to 30 carbon atoms, which may be straight chained or branched, and x has a value equivalent to the metal ion valence. Metal alkoxides such as Si(OR)4, Ti(OR)4, AI(OR)3, Zr(OR)3 and Sn(OR)4 may be used.
Specifically, R can be the methyl, ethyl, propyl or butyl radical. Further examples of suitable metal alkoxides can include Ti(isopropoxy)4, Ti(n-butoxy)4, AI(isopropoxy)3, AI(sec-butoxy)3, Zr(n-butoxy)4 and Zr(n-propoxy)4.
In a preferred embodiment, the suitable metal alkoxides are selected from the group comprising Ti(n-butoxy)4 and Zr(n-propoxy)4.
In another exemplary embodiment, sols can be made from silicon alkoxides such as tetraalkoxysilanes, wherein the alkoxy may be branched or straight chained and may contain 1 to 25 carbon atoms, e.g. tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or tetra-n-propoxysilane, as well as oligomeric forms thereof. Also suitable are alkylalkoxy- silanes, wherein alkoxy is defined as above and alkyl may be a substituted or
unsubstituted, branched or straight chain alkyl having about 1 to 25 carbon atoms, e.g., methyltrimethoxysilane (MTMOS), methyltriethoxysilane, ethyltriethoxysilane,
ethyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, propyltri- methoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, isobutyltri-methoxysilane, octyltriethoxysilane, octyltrimethoxysilane, methacryloxydecyltrimethoxysilane (MDTMS), aryltrialkoxysilanes such as phenyltrimethoxysilane (PTMOS), phenyl-triethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane, phenyl-tri-(3-glycidyloxy)-silane-oxide (TGPSO), 3-aminopropyltrimethoxysilane, 3-aminopropyl-triethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, triaminofunctional propyltri-methoxysilane (Dynasylan® TRIAMO, available from Degussa AG, Germany), N-(n-butyl)-3- aminopropyltrimethoxysilane, 3-aminopropylmethyl-diethoxysilane, 3- glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxy-silane, vinyl- trimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxy-silane, Bisphenol-A- glycidylsilanes; (meth)acrylsilanes, phenylsilanes, oligomeric or polymeric silanes, epoxysilanes; fluoroalkylsilanes such as fluoroalkyltrimethoxy-silanes,
fluoroalkyltriethoxysilanes with a partially or fully fluorinated, straight chain or branched fluoroalkyl residue of about 1 to 20 carbon atoms, e.g. tridecafluoro- 1 ,1 ,2,2-tetrahydrooctyltriethoxysilane and modified reactive flouroalkylsiloxanes which are available from Degussa AG under the trademarks Dynasylan® F8800 and F8815; as well as any mixtures of the foregoing.
The sol/gel components used in the sols may also comprise colloidal metal oxides, preferably those colloidal metal oxides which are stable long enough to be able to combine them with the other sol/gel components. Such colloidal metal oxides may include, but are not limited to, Si02, Al203, MgO, Zr02, Ti02, Sn02, ZrSi04, B203, La203, Sb205 and ZrO(N03)2. Si02, Al203, ZrSi0 and Zr02 may be preferably selected. Further examples of the at least one sol/gel forming component include aluminumhydroxide sols or -gels, aluminumtri-sec-butylat, AIOOH-gels and the like.
Some of these colloidal sols may be acidic in the sol form and, therefore, when used during hydrolysis, it may not be necessary to add additional acid to the hydrolysis medium. These colloidal sols can also be prepared by a variety of methods. For example, titania sols having a particle size in the range of about 5 to 150 nm can be prepared by the acidic hydrolysis of titanium tetrachloride, by peptizing hydrous Ti02 with tartaric acid and, by peptizing ammonia washed Ti(S04)2 with hydrochloric acid. Such processes are described, for example, by Weiser in Inorganic Colloidal Chemistry. Vol. 2, p. 281 (1935). Where the sol is formed by a hydrolytic sol/gel-process, the molar ratio of the added water and the sol/gel forming components, such as alkoxides, oxides, acetates, nitrides or combinations thereof, may be in the range of about 0.01 to 100, preferably from about 0.1 to 75, more preferred from about 0.2 to 50.
In a hydrolytric sol/gel processing procedure which can be used in exemplary
embodiments of the invention, the sol/gel components are suspended in water. Optionally, further solvents or mixtures thereof, and/or further additives such as fillers, surfactants, crosslinkers and the like may be added. The solvent may contain salts, buffers such as PBS buffer or the like to adjust the pH value, the ionic strenght etc. Further additives like catalysts for controlling the hydrolysis rate of the sol or for controlling the crosslinking rate may be added.
Non-hydrolytic sols may be similarly prepared as hydrolytic sols, but essentially in the absence of water.
Non-hydrolytic sol/gel processing in the absence of water may be accomplished by reacting alkylsilanes or metal alkoxides with anhydrous organic acids, acid anhydrides or acid esters, or the like. The sol may thus be formed from at least one sol/gel forming component as described above in a nonhydrous sol/gel processing, and the anhydrous organic acid, acid anhydride or acid ester can be selected from formic acid, acetic acid, acetoacetic acid, succinic acid maleic acid, crotonic acid, acrylic acid, methacrylic acid, partially or fully fluorinated carboxylic acids, their anhydrides and esters, e.g. methyl- or ethylesters, and any mixtures of the foregoing.
In general, according to the degree of crosslinking desired in the resulting sol, either acidic or basic catalysts may be applied, particularly in hydrolytic sol/gel processes. Suitable inorganic acids include, for example, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid as well as diluted hydrofluoric acid. Suitable bases include, for example, sodium hydroxide, ammonia and carbonate as well as organic amines. Suitable catalysts in non- hydrolytic sol/gel processes include anhydrous halide compounds, for example BCI3, NH3, AICI3, TiCI3 or mixtures thereof.
To affect the hydrolysis in hydrolytic sol/gel processing steps of the present invention, the addition of solvents may be used, including water-miscible solvents, such as water- miscible alcohols or mixtures thereof. Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol and lower molecular weight ether alcohols such as ethylene glycol monomethyl ether may be used.
In certain exemplary embodiments of the present invention, the sol may be further modified by the addition of at least one crosslinking agent to the sol. Such crosslinking agent may be selected from the group comprising isocyanates, silanes, diols, di-carboxylic acids, (meth)acrylates, for example, 2-hydroxyethyl methacrylate, propyltrimethoxysilane, 3-(trimethylsilyl)propyl methacrylate, isophorone diisocyanate, polyols, glycerine and the like.
Further additives may include, e.g., drying-control chemical additives such as glycerol or any other suitable liquid that can be suitable for controlling the conversion of the sol to a gel and a solid material.
The formed sol may be applied onto the surface of the push-rod and/or pole housing made of thermoplastic material in liquid, pulpy or pasty form, for example, by painting, spraying, spin coating, roll coating, dipping, ink-jet-printing or electrophoresis. Coated push-rods and/or pole housings may also be obtained by a transfer process, in which the gels are applied to the push-rod and/or pole housing as a lamination. The coated push-rod and/or pole housing can be cured, and subsequently be thermally treated. It is possible to successively apply a plurality of thin layers to provide a more uniform and thicker coating on the surface of the push-rod and/or pole housing.
The formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material in that the surface of the push-rod and/or pole housing is at least partially coated with the sol. The surface of the resulting push-rod and/or pole housing is thus at least partially coated. In one exemplary embodiment of the present invention, the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) in that only the outer surface exposed to dust and humidity is substantially coated with the sol. Such application of the sol results in a coated push-rod and/or pole housing in which the outer surface exposed to dust and humidity is substantially coated with the sol. In another exemplary embodiment, the formed sol is applied onto the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) in that the complete surface is substantially coated with the sol. Such application of the sol results in a coated push-rod and/or pole housing in which the complete surface of the push-rod and/or pole housing is substantially coated with the sol.
In order to obtain a better adhesion between the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) and the sol, the surface of the push-rod and/or pole housing may be treated before the formed sol is applied onto the surface of the push-rod and/or pole housing.
In one preferred embodiment, the surface of the push-rod and/or pole housing is wetted with an appropriate solvent. Any suitable solvent can be used, like saturated hydrocarbon solvents such as hexane, heptane and the like and other organic solvents like
isopropanol, methanol, ethanol, benzene, acetone and 1 ,2-dichloroethane. However, solvents that are poorly wetting, such as water, are to be avoided.
Alternatively or additionally, the surface of the push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) ay be treated with a laser. The formed sol applied onto the surface of the push-rod and/or pole housing can be converted into a solid material. Conversion of the sol into a gel may be accomplished by, e.g., hydrolysis of the sol, aging, curing, crosslinking, raising of pH, drying or any other conventional method. The sol may be first converted into a gel and subsequently converted into the inventive coated push-rod and/or pole housing, or the sol may be directly converted into the solid. The sol may preferably be converted into the solid material at room temperature.
The conversion step can preferably be achieved by drying, for example by air-drying at room temperature or thermal drying. In exemplary embodiments of the present invention, the thermal drying is carried out in the range of about -100 °C to +200 °C, preferably in the range of about -50 °C to 175 °C, more preferably in the range of about -25 °C to 150 °C, about 0°C to 100 °C, and most preferably from about 10 °C to 100 °C or at about room temperature. Drying or aging may also be performed at any of the above temperatures under reduced pressure or in vacuo. Such thermal drying may be carried out in a heat oven or by using IR or UV radiation or by other methods known to the skilled person. The conversion of the sol into the solid or semi-solid material can be performed under various conditions. The conversion can be performed in different atmospheres, e.g. inert atmospheres such as nitrogen or noble gases such as argon, or any mixtures thereof. Suitable conditions such as temperature, atmosphere and/or pressure may be applied depending on the desired property of the final material and the components used to form the material.
The sol applied onto the surface of the push-rod and/or pole housing creates a thin, uniform, and dense film on the surface of the object being' treated. The benefit of the sol- gel coating is that the film adheres extremely well to the surface of the push-rod and/or pole housing made of thermoplastic material. Additionally, the sol provides the beneficial characteristic of being a smooth and hard coating which is highly resistant to mechanical stress and scratches and, furthermore, shows a highly reduced water uptake behavior resulting in a push-rod and/or pole housing with a higher mechanical and dimensional stability under outdoor conditions. Furthermore, the sol applied onto the surface of the push-rod and/or pole housing creates a thermally stable sol-gel film that seals the thermal sensitive surface of the push-rod and/or pole housing made of thermoplastic material or bulk moulding compound (BMC).
An exemplary embodiment is schematically illustrated in Fig. 1 showing a sectional illustration through an exemplary pole part according to at least one embodiment. In the pole part shown in Fig. 1 , a vacuum interrupter 40 is embedded in a pole housing made of a thermoplastic material 10 and further comprising a bottom connection part 30 and an upper connection part 50, a flexible connection 60 and a push-rod made of a thermoplastic material 70. In the exemplary embodiment illustrated in Fig. 1 , the pole housing 10 as well as the push-rod 70 are coated by the process of the present invention.
Fig. 2 shows a flow diagram for a process for preparing a coated push-rod and/or pole housing made of a thermoplastic material for electrical contacts or connecting elements. ln step 201 of Fig.2, a sol is formed from suitable hydrolytic or non-hydrolytic sol/gel forming components. In step 202, the formed sol is applied onto the surface of the push- rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC). In step 203, the sol is converted into a solid material.
While the invention has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive; the invention is not limited to the disclosed embodiments. Other variations to the disclosed embodiments can be understood and effected by those skilled in the art and practising the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.
LIST OF REFERENCE SYMBOLS
10 pole housing
20 coating
30 bottom connection part
40 vacuum interrupter
50 upper connection part
60 flexible connection
70 push-rod

Claims

1. A process for preparing a coated push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements, the process comprising the following steps:
a) forming a sol from suitable hydrolytic or non-hydrolytic sol/gel forming components;
b) applying the formed sol onto the surface of the push-rod and/or pole housing made of a thermoplastic material, and
c) converting the applied sol into a solid material.
2. Process according to claim 1 , wherein the sol is formed by using a hydrolytic sol/gel-process in the presence of water.
3. Process according to claim 1 , wherein the sol is formed by using a non-hydrolytic sol/gel-process in the absence of water.
4. Process according to any one of claims 1 to 3, wherein the sol is formed by using sol/gel forming components selected from the group comprising alkoxides, metal alkoxides, metal oxides, metal acetates, metal nitrates, metal halides, wherein the metal includes at least one of silicon, aluminum, boron, magnesium, zirconium, titanium, alkaline metals, alkaline earth metals, or transition metals, platinum, molybdenum, iridium, tantalum, bismuth, tungsten, vanadium, cobalt, hafnium, niobium, chromium, manganese, rhenium, iron, gold, silver, copper, ruthenium, rhodium, palladium, osmium, lanthanum and lanthanides.
5. Process according to claim 4, wherein the sol/gel forming components are selected from metal alkoxides, preferably the sol/gel forming components are selected from the group comprising Ti(n-butoxy)4 and Zr(n-propoxy)4.
6. Process according to any one of claims 1 to 5, wherein the formed sol is applied onto the surface of the component made of a thermoplastic material or bulk moulding compound (BMC) in liquid, pulpy or pasty form, preferably by painting, spraying, spin coating, roll coating, dipping, ink-jet-printing and/or electrophoresis.
7. Process according to any one of claims 1 to 6, wherein the conversion of the sol into a solid material is performed by hydrolysis of the sol, aging, crosslinking and/or drying.
8. Process according to claim 7, wherein the drying is obtained by a thermal treatment in the range of about -100 °C to 200 °C, preferably in the range of about -50 °C to 175 °C, more preferably in the range of about -25 °C to 150 °C, about 0°C to 100 °C, and most preferably from about 10 °C to 100 °C, optionally under reduced pressure or vacuum.
9. The process according to any one of claims 1 to 8, wherein the thermoplastic material of the component is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyamide, polyacetate, polycarbonate, acrylonitrile butadiene styrene, polymethyl methacrylate, polyethylene terephthalate, polyetheretherketon and polyvinyl chloride.
10. A coated push-rod and/or pole housing made of a thermoplastic material or bulk moulding compound (BMC) for electrical contacts or connecting elements obtainable by a process according to any one of claims 1 to 9.
1 . Use of the process according to any one of claims 1 to 9 for preparing coated push-rods and/or pole housings.
12. Use of UV - protection layer by using the coating of the pole housing or the push rod.
PCT/EP2011/003776 2011-07-28 2011-07-28 Process for preparing coated push-rods and/or pole housings for electrical contacts and connecting elements WO2013013688A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080142485A1 (en) * 2005-08-22 2008-06-19 Abb Technology Ag Method for producing breaker pole parts for low-voltage, medium-voltage and high-voltage switchgear assemblies, and breaker pole part itself
US20080272613A1 (en) * 2007-05-01 2008-11-06 Weiss Keith D Encapsulated plastic panel and method of making the same
DE102009019493A1 (en) * 2009-05-04 2010-11-18 Bayer Materialscience Ag Polar soluble UV absorber
EP2278601A1 (en) * 2009-07-20 2011-01-26 ABB Technology AG Embedded pole part with an isolating housing made of thermoplastic material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080142485A1 (en) * 2005-08-22 2008-06-19 Abb Technology Ag Method for producing breaker pole parts for low-voltage, medium-voltage and high-voltage switchgear assemblies, and breaker pole part itself
US20080272613A1 (en) * 2007-05-01 2008-11-06 Weiss Keith D Encapsulated plastic panel and method of making the same
DE102009019493A1 (en) * 2009-05-04 2010-11-18 Bayer Materialscience Ag Polar soluble UV absorber
EP2278601A1 (en) * 2009-07-20 2011-01-26 ABB Technology AG Embedded pole part with an isolating housing made of thermoplastic material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HENGE, WEST: "The Sol/Gel-Process", CHEM. REF., vol. 90, 1990, pages 33, XP000125925, DOI: doi:10.1021/cr00099a003
WEISER, INORQANIC COLLOIDAL CHEMISTRY, vol. 2, 1935, pages 281

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