EP0456679A1 - Formation d'un revetement metallique - Google Patents

Formation d'un revetement metallique

Info

Publication number
EP0456679A1
EP0456679A1 EP19900902310 EP90902310A EP0456679A1 EP 0456679 A1 EP0456679 A1 EP 0456679A1 EP 19900902310 EP19900902310 EP 19900902310 EP 90902310 A EP90902310 A EP 90902310A EP 0456679 A1 EP0456679 A1 EP 0456679A1
Authority
EP
European Patent Office
Prior art keywords
metal
compound
reagent
metals
paint
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.)
Withdrawn
Application number
EP19900902310
Other languages
German (de)
English (en)
Inventor
Michael Cox
Rajendra Joshi
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.)
BTG International Ltd
Original Assignee
BTG International Ltd
National Research Development Corp UK
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 GB898902311A external-priority patent/GB8902311D0/en
Priority claimed from GB898902310A external-priority patent/GB8902310D0/en
Priority claimed from GB898902312A external-priority patent/GB8902312D0/en
Application filed by BTG International Ltd, National Research Development Corp UK filed Critical BTG International Ltd
Publication of EP0456679A1 publication Critical patent/EP0456679A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds

Definitions

  • This invention relates to a method of forming a single-metal or mixed-metals coating on a surface, to a metallic paint, to a method of painting and to a method of spray-forming powders using the paint.
  • Metallic paints which comprise metal (e.g. zinc or aluminium) particles suspended in binder, pigment and volatile solvent. Such paints are easy to apply but cannot give a seamless coherent metal coating, which can be required in demanding and advanced technical applications.
  • metal e.g. zinc or aluminium
  • a metallic paint comprises a compound between the metal or each of the metals of the paint and a polydentate reagent, said compound(s) being dissolved in a paintable solvent.
  • An object is painted, according to the invention, by applying thereto a paint as set forth above, allowing the solvent to evaporate, and applying a gaseous or volatile substance which can decompose said compound(s) to release said metal(s).
  • Metal powder may be made by atomising the paint and applying a said gaseous compound.
  • the method of forming mixed-metal coatings on a surface comprises decomposing at the surface a fluid e.g. vapour comprising:
  • a first preferably volatile compound between a first metal and a polydentate reagent and a second preferably volatile compound between a second metal and the same or another polydentate reagent, wherein the reagent(s) is/are volatile, whereby the metals are co-deposited on the surface.
  • the reagent(s) and the compounds are preferably stable in air.
  • the decomposition preferably yields the reagent(s) directly, which accordingly may be recovered for re-use.
  • the said second metal is the surface and the said second volatile compound is formed from reagent liberated upon decomposition of the first volatile compound.
  • the decomposition of the polydentate reagent(s) to metal is by reduction.
  • the reduction is performed by a gas or gases.
  • the donor atoms of the said reagent(s) are any selection from N, O and S.
  • the said reagent (or one of said reagents) is a Schiff base or a ⁇ -diketone. Both theseare air-stable and non-toxic, unlike for example metal alkyls and metal carbonyls.
  • At least one may comprise ballasting substituents.
  • their relative vapour pressures can be varied so as to adjust the composition of the resulting metal mixture if other ways of altering the vapour composition are not available.
  • the substrate may be a metal or glass or ceramic (e.g. alumina) or a membrane requiring to be metallised.
  • UK Patent GB 2135984B the disclosure of which is imported by reference, claims a method of winning metal from ore, and discloses for that purpose compounds which may find use in this invention, such as, in the case of Cu(II), tetradentate Schiff base reagents.
  • ⁇ -diketones which may be used include for example 2,2,6,6 tetramethyl 3,5 heptadione (trivially called tert-butyl acetyl acetone), two molecules of which complex each copper atom:
  • surface oxide can be removed at low temperature (e.g. 300oC), below the onset of rapid diffusion. This feature improves the adhesion of deposited metal.
  • deposition temperatures of between 350 - 450 ⁇ 10°C and total gas flow (carrier and reductant) of 75 ⁇ 5 cm 3 /min were used.
  • EXAMPLE 1 NiCu alloy is deposited on mild steel.
  • Porosity of the resulting NiCu alloy deposit on the mild steel substrate was determined using a chemical staining technique, incorporating a sensitivity test for the substrate metal.
  • a piece of filter paper was dipped into a solution of hexacyanoferrate (III), then pressed lightly on to the thin deposit. Although a quantitive result was not obtained from the test, it gave an indication as to the porosity of the deposit, in that any holes in the deposit resulted in a blue stain on the filter paper.
  • NiFe alloy is deposited on mild steel by depositing Ni and relying on the freshly liberated ligand to react with the substrate iron, the iron complex then being decomposed alongside the nickel complex.
  • the nickel complex used was nickel bis 1,1,1-tr-fluoro-2,4-pentanedioate, Ni(tfa) 2 for short.
  • Ni(tfa) 2 was nickel bis 1,1,1-tr-fluoro-2,4-pentanedioate
  • NiCu alloy is deposited on silica glass/on alumina/on aluminium.
  • Example 5 aluminium substrate
  • the operating conditions were identical to Example 1.
  • Coating powder particles can radically alter their properties.
  • the coatings may only be a few atoms thick - less than 1% of the weight of the powder, yet be effective.
  • metallic copper is deposited on supermagnetic flakes, 1 ⁇ 2mm ⁇ 1 ⁇ 2mm ⁇ 1 /10mm for example, of iron neodymium boride Fe 14 NdB, known as Magnequench, or equally successfully on 5-micron Fe 14 NdB powder known as B14.
  • This copper provides a non-magnetic 'insulation'; on compressing the flakes (or powder particles), a small-domain highly magnetic material is obtained.
  • This task would be difficult to achieve using conventional metal paint, and is conventionally performed by tumbling the flakes with copper powder in a process known as 'tumble-co-milling', which cannot yield the same uniformity of magnetic insulation without greater volumetric dilution of the supermagnetic material.
  • a copper complex consisting of the compound 2,2,6,6-tetramethyl-3,5-heptadione described above, two molecules of which complex each copper atom, was used.
  • B14 is very pyrophoric and is therefore stored under cyclohexane.
  • the copper complex is dissolved directly into this, in an amount depending on the thickness of copper coating required after calculating the particle surface area; for magnetic purposes the coating thickness should be the minimum which will survive compression without rupturing.
  • the complex was calculated to amount to 1% (based on copper) by mass of the B14.
  • Example 6 the copper complex of Example 6 dissolved in cyclohexane or diethyl ether was brush painted onto a substrate, which was heated to 210°C for 1 hour in hydrogen. A continuous copper coating was left on the substrate, and the liberated ligand could be recycled to make further paint.
  • the copper complex of Example 6 in solution was jetted, through an atomising nozzle, as a fine spray into a chamber containing hydrogen at 250°C. Copper powder was recovered from the chamber. The liberated ligand could be recycled. Care must be taken to avoid an undue proportion of the complex from decomposing on the chamber walls and simply plating them, for example a cyclonic gas flow path may be established within the chamber so that the complex does not contact the chamber wall.
  • a mixture of such compounds may be used, in the same or separate sprays, to yield a mixture of liberated metals, in precalculated volumetric proportions of liquid to yield the metals in the desired ratios.
  • the metal is one or more of a mixture of copper and nickel.
  • a mixture of such metal powders may permit alloys to be made by pressures-sintering which would otherwise be unobtainable or only obtainable by extraordinary techniques such as implantation by nuclear bombardment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un procédé de formation d'un revêtement métallique sur une surface. Dans un mode de réalisation de l'invention, le procédé consiste à décomposer à la surface une vapeur comprenant: un premier composé volatil entre un premier métal et un réactif polydenté, ainsi qu'un second composé volatil entre un second métal et le même ou un autre réactif polydenté, le ou les réactifs étant volatils, de sorte que les métaux soient co-déposés sur la surface. Dans d'autres modes de réalisation de l'invention, on peut appliquer les composés sur la surface dans la phase liquide, sous la forme d'une peinture. Une telle peinture n'a besoin de contenir qu'un seul métal.
EP19900902310 1989-02-02 1990-02-01 Formation d'un revetement metallique Withdrawn EP0456679A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB8902310 1989-02-02
GB8902311 1989-02-02
GB898902311A GB8902311D0 (en) 1989-02-02 1989-02-02 Metallic paint
GB8902312 1989-02-02
GB898902310A GB8902310D0 (en) 1989-02-02 1989-02-02 Forming mixed-metal coating
GB898902312A GB8902312D0 (en) 1989-02-02 1989-02-02 Making metal powder

Publications (1)

Publication Number Publication Date
EP0456679A1 true EP0456679A1 (fr) 1991-11-21

Family

ID=27264297

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900902310 Withdrawn EP0456679A1 (fr) 1989-02-02 1990-02-01 Formation d'un revetement metallique

Country Status (5)

Country Link
EP (1) EP0456679A1 (fr)
JP (1) JPH04503085A (fr)
CA (1) CA2046335A1 (fr)
GB (1) GB2229453A (fr)
WO (1) WO1990008844A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008029691A1 (de) * 2008-06-24 2009-12-31 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Mischungen von Precursoren zur Herstellung von keramischen Schichten mittels MOCVD

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB872610A (en) * 1958-03-07 1961-07-12 Union Carbide Corp Gas plating of aggregates
US3092511A (en) * 1958-11-19 1963-06-04 Sperry Rand Corp Magnetic devices and preparation thereof
US3092510A (en) * 1959-03-02 1963-06-04 Sperry Rand Corp Magnetic devices and preparation thereof
US3242102A (en) * 1960-06-30 1966-03-22 Sperry Rand Corp Metal chelate polymers
US3071493A (en) * 1961-11-15 1963-01-01 Ethyl Corp Metal plating process
NL286046A (fr) * 1961-12-01
FR1406882A (fr) * 1963-09-13 1965-07-23 Ass Chem Co Perfectionnements apportés au revêtement de surfaces
NL6505307A (fr) * 1964-06-25 1965-12-27
SE306771B (fr) * 1965-09-14 1968-12-09 Asea Ab
GB1109890A (en) * 1965-12-21 1968-04-18 Int Nickel Ltd Preparation of finely divided metals
GB1249623A (en) * 1967-05-24 1971-10-13 Secr Defence Improvements in or relating to metal coatings
US3594216A (en) * 1969-06-19 1971-07-20 Westinghouse Electric Corp Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate
US3615888A (en) * 1969-09-04 1971-10-26 American Cyanamid Co Chemical treatment of metal
CA935336A (en) * 1970-05-29 1973-10-16 V. Melnikov Valery Method of depositing inorganic coatings from vapour phase
NL7117454A (fr) * 1970-12-24 1972-06-27
US4042163A (en) * 1974-08-23 1977-08-16 Schladitz Hermann J Method for the manufacture of a heat exchanger or heat transfer element
FR2314263A1 (fr) * 1975-06-13 1977-01-07 Anvar Procede de realisation d'un depot de corps a base de metal ou metalloide
FR2325621A1 (fr) * 1975-09-29 1977-04-22 Engelhard Mineral Chemical Cor Decoration pour matieres ceramiques ayant un aspect de metal blanc brillant
US4250210A (en) * 1977-12-27 1981-02-10 The International Nickel Co., Inc. Chemical vapor deposition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9008844A1 *

Also Published As

Publication number Publication date
JPH04503085A (ja) 1992-06-04
GB9002268D0 (en) 1990-03-28
CA2046335A1 (fr) 1990-08-03
GB2229453A (en) 1990-09-26
WO1990008844A1 (fr) 1990-08-09

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