US3700496A - Application of metal coatings by the seizure method - Google Patents

Application of metal coatings by the seizure method Download PDF

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Publication number
US3700496A
US3700496A US32967A US3700496DA US3700496A US 3700496 A US3700496 A US 3700496A US 32967 A US32967 A US 32967A US 3700496D A US3700496D A US 3700496DA US 3700496 A US3700496 A US 3700496A
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US
United States
Prior art keywords
metal
coating
alloy
aluminum
glass
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.)
Expired - Lifetime
Application number
US32967A
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English (en)
Inventor
Emile Plumat
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.)
AGC Glass Europe SA
Original Assignee
Glaverbel Belgium SA
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
Priority claimed from GB1489170A external-priority patent/GB1303742A/en
Application filed by Glaverbel Belgium SA filed Critical Glaverbel Belgium SA
Application granted granted Critical
Publication of US3700496A publication Critical patent/US3700496A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/023—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/263—Metals other than noble metals, Cu or Hg
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/17—Deposition methods from a solid phase

Definitions

  • Metal coatings are applied to article surfaces by frictional contact between the surface and a scriber of the metal to be deposited, the metal being a special alloy of aluminum and at least 0.1% by weight of at least one secondary metal giving the alloy a Brinell hardness of not more than 100.
  • This invention relates to the metallizing of surfaces of vitreous, vitrocrystalline and ceramic materials, and to articles of those materials having metallized surfaces.
  • seizure method Another method of metallizing a substrate which has special advantages ofits own is the so-called seizure method the essential characteristic of which is the transfer of metal to the substrate by friction between the substrate and a metallic scribing member which may, for example, be in the form of a disc rotated in contact with the substrate.
  • Another object of the invention is to facilitate the application of metal layers by the seizure method.
  • a further object of the invention is to provide an improved scribing member for applying such layers.
  • a scribing member composed of an alloy selected from a range of United States Patent 0 Patented Oct. 24, 1972 aluminum alloys.
  • suitable alloys Will be given hereafter.
  • the invention is not however restricted to the use of those particular alloys.
  • the present invention includes any article having at least one surface portion of vitreous, vitrocrystalline or ceramic material, on which a coating of metal has been applied by the seizure method, characterized in that the coating is composed of an aluminum alloy and has a maximum resistance of 0.3 ohm per square.
  • the coating has a maximum resistance of 0.06 ohm per square.
  • vitrocrystalline denotes a material which has been formed by heat-treating a wholly vitreous material to produce one or more crystalline phases.
  • ceramic denotes a refractory composition comprising a mass of crystals which have been formed into a coherent mass with or without a binder.
  • a surface coated by the seizure method will exhibit microabrasions. Such microabrasions do not materially lower the tensile strength of glass any more than the superficial scratches which almost inevitably appear during normal handling of glass products.
  • the substrate surface should preferably be at least free of fissures or cracks which are large enough to be visible to the naked eye.
  • fissures become dangerous for the mechanical strength when their gravity is such that they become visible.
  • Acceptable and not visible fissures may be 0.7 mm. long, 30 microns deep I and have a width which cannot be distinguished by an optical microscope.
  • Not acceptable and visible fissures either have larger sizes or are accumulated with a so strong density that shells appear.
  • glass surfaces to which metal has been frictionally transferred from prior art scribing members have "been found to either exhibit very high electrical resistance or possess visible fissures which substantially lower their tensile strength.
  • the preferred aluminum alloys specified hereinafter, enable coatings to be formed which have a resistance of less than 0.3 ohm per square, and even less than 0.06 ohm per square.
  • the preferred alloys comprise aluminum and at least 0.1% by weight of a secondary metal or metals, a eutectic mixture of which, with aluminum, contains less than 20% by weight of such other metal, said alloy having a liquidus temperature not exceeding the melting temperature of the aluminum by more than 40 C. (thus not exceeding 700 C.), and having a maximum electrical resistivity of 4 microhm-cm. Alloys meeting these specifications can be very readily applied by the seizure method, particularly to ordinary glass, without subjecting the substrate to forces which would be harmful.
  • an aluminum-based alloy which has the above specifications and comprises at least one metal in the following group: antimony, bismuth, cadmium, indium, lead, tellurium and silicon.
  • Aluminumbased alloys containing these secondary metals often.have
  • alloys which preferably, but not necessarily, have the specifications just defined, containing aluminum and a content of at least 0.1% by weight, based on the total weight of the alloy, of a secondary metal or metals, at least part of such content being dissolved in the aluminum and the rest, if any, being contained in a separate phase constituting less than 12% by weight of the alloy.
  • an aluminum-based alloy which has these latter specifications and comprises at least one metal selected from the following group: silver, copper, magnesium and zinc.
  • These metals are soluble in the solid state in aluminum, in various amounts, on condition that cooling is carried out at suitable speeds from the solidus temperature down to a temperature which is near the room temperature. If too high a quantity of the secondary metal is in a separate phase this adversely affects the quality of the metal coating.
  • speeds of about 10 C. per minute allowed the obtainment of alloys which did not contain much metal in a separate phase; very high speeds (of about 600 C. per minute) and very slow speeds (of about 1 C. per minute) have generally resulted in non-satisfactory alloys. In any case, it is easy to adjust the cooling speed in such a way that an alloy of low separated phase( s) content is obtained.
  • the aluminum alloy used has a Brinell hardness of not more than 100. In the most preferred embodiments, the alloy used has a Brinell hardness of not more than 55.
  • a eutectic composition is considered to form a single phase even if it is not impossible to observe the coexistence of two different finegrained phases, under very considerable magnification. More particularly, when using a secondary metal which forms a eutectic mixture with aluminum, it is preferred to use the eutectic composition itself, so that the alloy consists of a single phase in the broad sense just referred to.
  • the invention particularly includes articles comprising a sheet of glass bearing a coating of aluminum alloy on at least one strip-like zone less than 2 mm. in width, the coating having a maximum resistance of not more than 0.3 ohm per square, and preferably not more than 0.06 ohm per square.
  • a sheet has a transparency which is only slightly less than that of the sheet of glass prior to application of the coating.
  • the coating strip or strips has or have an attractive shiny appearance.
  • the coating strip or strips enable the sheet to be appreciably heated by the passage of substantial electric currents.
  • the coated sheets can be produced quite inexpensively and the coated glass sheets have a mechanical strength com parable with the strength of uncoated glass sheets which have been in use for some months.
  • the coating or coatings on an article according to the invention can be formed using a scribing member in the form of a body which has a circular profile and is mounted for rotation in contact with the body to be coated.
  • the invention includes methods of forming articles as hereinbefore defined.
  • the invention also includes aluminum alloys suitable for forming a coating as hereinbefore referred to, and particularly includes aluminum alloys suitable for that purpose and having one or more of the compositional features hereinbefore referred to, and the aluminum alloys specifically identified in this specification.
  • the invention also includes scribing members, e.g., discs, formed of an aluminum alloy according to the invention.
  • FIG. 1 is a front elevational view of a vehicle window coated according to the invention.
  • FIG. 2 is an edge view of the window of FIG. 1.
  • a glazing 1 is formed by a sheet of thermally tempered ordinary soda-lime silica glass curved to form a vehicle rear window.
  • Eight parallel linear-metal deposits 2, the outermost of which are indicated at 5, are produced by the rotation of a metal disc in contact with the glass accompanied by relative bodily displacement between the disc and the glass sheet to cause metal to transfer from the disc to the sheet along the indicated longitudinal lines.
  • a coating of silver is formed on each of two end contact zones 3 by applying a suspension of metallic silver in benzene.
  • the silver coatings have a fairly low resistance and serve to distribute electric current to the various conductive strips 2.
  • Terminals 4 are soldered to the end zones 3 using an ordinary tin solder. The resulting rear window can be successfully heated by connecting the terminals 4 to a source of electric current.
  • FIG. 2 illustrates in simplified form a scriber disc 8 made of a material according to the invention.
  • the disc 8 is supported and rotated by a motor 9 via a support and drive link 10 which could have any suitable form.
  • the motor can be mounted on a stationary support and the glass sheet 1 can be carried by any type of carriage capable of moving the sheet past the disc 8 as the disc rotates about its axis.
  • the illustrated rear window and the method of forming the coating strips 2 are defined by the following data:
  • Length of strips 1 m.
  • Width of strips 0.8 mm.
  • Thickness of deposits 5-10 microns Distance between strips: 30 mm.
  • Diameter of disc mm.
  • a reduction in the electrical resistance per unit length of the strips can be obtained by using a thicker disc, in-
  • creasing the disc speed increasing the pressure and/or reducing the speed of movement of the glass in relation to the disc.
  • the electrical resistance per unit length of a strip is reduced by half when the speed of rotation of the disc is doubled.
  • a thicker disc produces a wider deposit and this has the effect of reducing visibility through the rear window, whilst excessive pressure spoils the glass and may cause interruptions in the layer and result in a rapid misshaping of the disc.
  • the speed of translational movement of the glass in contact with the disc may be higher during formation of the central portion of each strip than when forming the strip end portions.
  • the variation in speed can be carried out stepwise or, preferably, continuously. Strips of different resistances can also be deposited; for instance the outermost strips can have a higher resistance than the other strips.
  • the formation of the coatings in the illustrated window do not materially reduce the mechanical strength of the thermally tempered glass sheet.
  • the mechanical strength immediately after formation of the metal deposits was close to that of an identical thermally tempered (but uncoated) window after a few weeks or months of use.
  • the conductive strips formed with this scribing member have substantially identical electrical properties to those in the previous example.
  • the glass substrate showed evidence of flow at the coatings lines, the surfaces of the glass being about 0.5-1.0 micron lower beneath the coatings than in the regions between coating strips.
  • zinc can be in solid solution in aluminum at room temperature on condition that the alloy is cooled with suitable cooling speed from the solidus temperature.
  • a suitable cooling speed is about C. per minute.
  • alloys used in the above examples are sufficiently corrosion-resistant and their properties do not substantially deteriorate in use on a vehicle rear window.
  • the invention has uses apart from the manufacture of vehicle windows. Rcsistances for electrical applications can be made according to the invention and the substrate may bear the coating metal over its entire surface instead of on spaced zones. Linear deposits can, for example, be formed side by side or with a slight overlap, to form an all-over coating.
  • the invention can be used for applying conductive coatings to form contact zones, like the zones 3 in FIG. 1, for feeding electric current to conductive coating strips which may also be applied according to the invention or by some other method, such as deposition in vacuo, for example.
  • Other examples are ceramic or glass 6 bodies bearing aluminum alloy coatings formed preparatory to the making of ceramic-to-metal or glass-to-metal seals.
  • a deposit formed according to the invention can be coated over with a deposit of the same or some other composition, metallic or not, by any other method, for instance, by electrolysis or spraying.
  • the aluminum-based alloy deposits can be protected by anodic oxidation.
  • the following table gives data relating to four sheets of glass (denoted I-IV) each bearing an alloy coating along twelve strip-like linear zones 1 meter in length, 0.6 to 0.7 mm. in width and 10 to 15 microns in thickness, the zones being at a spacing of 30 mm.
  • the coatings on each of the four sheets were applied from a disc scribing member having a diameter of mm. and a thickness of 0.5 mm. and the disc was rotated at 30 r.p.rn. and exerted a pressure of 3 kg. on the glass surface during each coating pass along the glass sheet, the speed of such pass being 0.6 meter/min.
  • Four difierent scribing discs were used: a different one for each sheet of glass.
  • the table gives the compositions of the aluminum alloys forming the different discs and data relating to the electrical properties of the alloy coatings on the sheets:,
  • An article having at least one surface portion composed of a vitreous, vitrocrystalline or ceramic material and carrying on such surface portion a coating of a metal applied by the seizure method, the metal comprising an alloy composed of aluminum and at least 0.1% by weight of a substance constituted by at least one of silicon and at least one second metal, the substance being of a type which forms a eutectic mixture with aluminum containing less than 20% by weight of such substance, said alloy having a liquidus temperature not exceeding the melting temperature of pure aluminum by more than 40 C. and having a maximum resistivity of 4 microhm-cm., and said coating having a maximum resistance of 0.3 ohm per square.
  • said alloy is further composed of at least 0.1% by weight of at least one further metal, at least part of said further metal being dissolved in the aluminum and any remainder of the further metal being present in a separate phase which constitutes less than 12% by weight of the alloy.
  • An article having at least one surface portion composed of a vitreous, vitrocrystalline or ceramic material and provided with a metal coating applied to such surface portion by the seizure method, said coating being composed of an alloy comprising aluminum and at; least 0.1% by weight of at least one second metal, at least part of said second metal being dissolved in the aluminum and any remainder of the second metal being present in a separate phase which constitutes less than 12% by weight of the alloy, and said coating having a maximum. resistance of 0.3 ohm per square.
  • An article having at least one surface portion composed of a vitreous, vitrocrystalline or ceramic material and a metal coating applied to such surface portion by the seizure method, the coating metal being constituted by an alloy composed of aluminum and at least one second metal and having a Brinell hardness of not more than 100, the coating having a maximum resistance of 0.3 ohm per square.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Ceramic Products (AREA)
US32967A 1969-05-02 1970-04-29 Application of metal coatings by the seizure method Expired - Lifetime US3700496A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
LU58564 1969-05-02
GB1489170A GB1303742A (es) 1969-05-02 1970-03-26

Publications (1)

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US3700496A true US3700496A (en) 1972-10-24

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US32967A Expired - Lifetime US3700496A (en) 1969-05-02 1970-04-29 Application of metal coatings by the seizure method

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US (1) US3700496A (es)
AT (1) AT316786B (es)
BE (1) BE749167A (es)
CA (1) CA968649A (es)
CH (1) CH523207A (es)
DE (1) DE2021385A1 (es)
ES (2) ES379246A1 (es)
FI (1) FI52330C (es)
FR (1) FR2046314A5 (es)
IE (1) IE34212B1 (es)
IL (1) IL34398A (es)
NL (1) NL7006408A (es)
NO (1) NO129343B (es)
SE (1) SE371426B (es)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900634A (en) * 1972-07-21 1975-08-19 Glaverbel Glazing panel with conductive strips
US4065848A (en) * 1976-03-15 1978-01-03 Normand Dery Method of applying and repairing rear window defroster

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900634A (en) * 1972-07-21 1975-08-19 Glaverbel Glazing panel with conductive strips
US4065848A (en) * 1976-03-15 1978-01-03 Normand Dery Method of applying and repairing rear window defroster
US4244774A (en) * 1976-03-15 1981-01-13 Normand Dery Apparatus to apply pre-glued strips of resistive material to a car rear window

Also Published As

Publication number Publication date
IL34398A (en) 1974-01-14
SE371426B (es) 1974-11-18
NO129343B (es) 1974-04-01
ES186351Y (es) 1974-07-16
FI52330C (fi) 1977-08-10
BE749167A (fr) 1970-10-20
NL7006408A (es) 1970-11-04
ES186351U (es) 1973-11-01
FR2046314A5 (es) 1971-03-05
AT316786B (de) 1974-07-25
DE2021385A1 (de) 1970-11-12
CH523207A (fr) 1972-05-31
IE34212B1 (en) 1975-03-05
CA968649A (en) 1975-06-03
FI52330B (es) 1977-05-02
IE34212L (en) 1970-11-02
ES379246A1 (es) 1973-04-01
IL34398A0 (en) 1970-06-17

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