WO1991004349A1 - Procede de revetement en continu d'un metal avec de l'oxyde de titane, et equipement utilise a cet effet - Google Patents

Procede de revetement en continu d'un metal avec de l'oxyde de titane, et equipement utilise a cet effet Download PDF

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Publication number
WO1991004349A1
WO1991004349A1 PCT/US1990/005377 US9005377W WO9104349A1 WO 1991004349 A1 WO1991004349 A1 WO 1991004349A1 US 9005377 W US9005377 W US 9005377W WO 9104349 A1 WO9104349 A1 WO 9104349A1
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WO
WIPO (PCT)
Prior art keywords
substrate
metal
chamber
alloy
coating
Prior art date
Application number
PCT/US1990/005377
Other languages
English (en)
Inventor
Ibrahim M. Allam
David J. Rowcliffe
Original Assignee
Sri International
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 Sri International filed Critical Sri International
Publication of WO1991004349A1 publication Critical patent/WO1991004349A1/fr

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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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—Apparatus
    • C23C2/0036—Crucibles
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath

Definitions

  • This invention relates to dip coating of a substrate metal in a molten alloy.
  • M K 1 is used to indicate a metal such as titanium which is to be selectively oxidized and H M 2 M is used to indicate a more noble metal, such as nickel, which is not to be oxidized.
  • M x indicates a metal which reacts with a suitable molecular species to form an oxide, a carbide, a nitride, a boride or a ⁇ ilicide and M 2 indicates a metal which, under the reaction conditions, does not form an oxide, a carbide, etc. It will be understood that M x includes mixtures of two or more such metals and M 2 includes a mixture of two ormore such metals.
  • a substrate metal is dipped into a molten alloy such as a eutectic titanium-nickel alloy (28.5% Ni, 71.5% Ti, commonly designated as Ti-28.5 Ni) , it should be exposed to the molten alloy for a period short enough to minimize or control the extent of migration of a component of the alloy into the substrate and vice versa.
  • a molten alloy such as a eutectic titanium-nickel alloy (28.5% Ni, 71.5% Ti, commonly designated as Ti-28.5 Ni)
  • a single vessel within which are provided a receptacle for holding a body of molten alloy and there are also provided means for melting the alloy and holding it at the desired temperature, means for introducing the substrate metal into the molten alloy and for bringing the substrate metal up to an elevated temperature suitable for dipping in the molten alloy before it is dipped into the alloy, means for removing the substrate metal after it has been dip coated and for holding it at a temperature and for a time sufficient to anneal the coating of alloy and means for removing the coated substrate from the annealing zone. Means are also provided, where the metal M x is to be selectively oxidized, to maintain an atmosphere * trough the annealing step which has a very low parti? pressure of oxygen such that neither M x nor M 2 is oxidized.
  • means are also provided to expose the alloy coating to an atmosphere and at a temperature such that M x will oxidize and M 2 will not oxidize.
  • Means are also provided to remove the coated, or coated and oxidized, substrate from the apparatus without cooling the heated parts of the apparatus much below their normal operating temperatures and without admitting a large quantity of ambient air and to introduce a new specimen of uncoated substrate without major cooling and entry of ambient air.
  • the substrate metal should be heated approximately to the temperature of the molten alloy, and after dipping or dipping and before oxidizing the coating should be annealed. Thereafter the alloy coating is oxidized at a high temperature and in an atmosphere low in oxygen such that the more readily oxidizedmetal M x is oxidized and the other metal (M 2 ) remains unoxidized.
  • Figure 1 is a block diagram illustrating the method
  • Figure 2 is a view in vertical mid-section of a preferred apparatus together with auxiliary equipment for carrying out the method of the invention.
  • the numeral 10 indicates that portion of the apparatus and the method whereby the concentration of oxygen is controlled to avoid or minimize oxidation when desired and to provide an oxygen partial pressure for selective oxidation when desired.
  • the numeral 11 indicates that portion of the apparatus and method wherein the alloy (or physical mixture) of metals M x and M 2 is melted and wherein the metal substrate is dipped into the molten alloy.
  • the numeral 12 indicates that part of the apparatus and of the method wherein the alloy coating is annealed and selectively oxidized.
  • the numeral 13 indicates that part of the apparatus and method in which the coated and oxidized metal substrate is removed from the system and uncoated substrate metal is introduced into the system.
  • the various lines indicate the flow of materials such as purging gas, inert gas, vacuum, introduction of uncoated substratemetal, removal of coated andoxidized substrate metal.
  • the apparatus is generally designated by the reference numeral 25. It comprises an elongated tube 26 of suitable refractory material such as alumina and which is of a diameter suitable for the purpose, for example 12 centimeters outside diameter and walls 0.6 centimeter thick. Surrounding an intermediate portion of the tube 26 is an electric furnace 27, for example a Kanthal furnace, which will bring the interior of that portion of the tube 26 embraced by it to a suitable operating temperature wi- in the tube 26. Within the tube 26 is a tube 28 also of refractory material and of smaller outside diameter, for example 5 centimeters, which supports at its upper end a crucible 29 of suitable refractory material. Both the inner tube 28 and crucible 29 may be made of alumina.
  • thermocouple 30 is provided within the tube 28 in close proximity to the crucible and its leads extend down through a fitting 31 to the exterior and to a suitable measuring instrument.
  • the fitting 31 may be in the form of a water cooled brass fitting provided with an epoxy seal 33.
  • a line 34 having in it a valve 35 is connected at one end (not shown) to a source of gettered argon, e.g. gettered over calcium at 650*C.
  • This line, which enters the tube 28 through the fitting 31, is one of several such lines used to purge the system of oxygen and fill it with an inert gas (argon for example) containing a desirably low partial pressure of oxygen, for example 10 "16 atmosphere or less.
  • a molten bath 35 of alloy e.g. a Ti-28.5 Ni eutectic alloy. This bath will have to be replenished from time to time but is large enough to coat a large number of metal substrate pieces without replenishment.
  • This equipment includes water cooled brass flanges 36 secured to the upper end of tube 26 including an epoxy seal 37. Secured within the flanges 36 is a section 38 of pipe constructed of brass and water cooled by coil 39 to the upper end of which is secured a housing 40 which houses a stainless steel heat reflector 41 at the end of a handle 42 which enters through the outer (righthand as viewed in Figure 2) end of the housing. The housing is air tight and a seal 43 allows the handle, and with it the reflector 41 to move between the position shown in which it reflects heat into the tube 26 and to the right to clear the tube 26.
  • the seal 43 may be water cooled.
  • a duct 44 water cooled by coil 45 and secured at its upper end to a gate valve structure 46 which may be of conventional construction but which serves, when open, to permit a fresh piece of uncoated substrate to be inserted and a coated substrate to be removed.
  • This gate valve provides the only access of the interior of the equipment to the ambient air and is of a design to minimize entry of ambient air.
  • a cooling chamber 47 water cooled by coil 48.
  • a duct 49 which has a branch 50.
  • a rod 55 extends through a seal 56 into the equipment through the duct 49, the cooling chamber 47, the gate valve 46, the housing 40, the duct 38 and the tube 26 into the crucible 29.
  • the rod 55 is provided with a suitable means (not shown) to attach to a substrate metal such as shown at 58 which may be provided with one or more holes, lugs or other means for this purpose.
  • a tube 59 connects the space between o-rings in seal 56 to a source of vacuum.
  • a tube 60 near the lower end of gate valve 46 is connected to a source of gettered argon.
  • the branch line 50 mentioned above is connected through a valve 61 to a source of vacuum and between its junction with the tube 49 and the valve 61 it is connected to an oxygen sensor 65, to a vacuum pressure gauge 66 and through a valve 67 to a line 68 connected to a source of gettered argon.
  • a specimen of substrate metal 58 suitably cleaned and free of rust and/or other undesirable surface impurities, is introduced through the gate valve 46 which is then closed. Vacuum is applied through line 50 and tube 59 until a desirable degree of vacuum is achieved.
  • the crucible 29 is, of course, filled to a suitable level with the alloy which is used for coating. Instead a mixture of components of the alloy may be used in finely divided form.
  • the rod 55 will be above the gate valve 46 until the metal substrate is introduced, after which it is lowered and connected to the substrate.
  • the heat reflector will also be in retracted position at this time.
  • gettered argon having a suitably low oxygen partial pressure is introduced through lines 34, 60 and 68 until, as indicated by the oxygen sensor 65, the desired oxygen partial pressure is achieved, for example below 10 "16 atmosphere.
  • the furnace 27 is turned on and the crucible 29 and its contents are brought up to the desired temperature for melting the alloy or formelting and alloying the metal mixture.
  • this temperature is 942*C.
  • the molten alloy may be heated somewhat above this temperature but preferably not greatly above it, for example to 1050*C, to avoid damage to the substrate and to retard migration of metal of the substrate into the coating and vice versa.
  • the substrate will be lowered by the rod 55 into the upper region of tube 26 above the crucible until its temperature reaches or closely approaches the temperature of the bath of molten alloy. Then the substrate will be lowered by the rod 55 into the molten alloy 35 in the crucible 29 and will be held there for a suitable time to accomplish coating while minimizing or controlling migration of components of the substrate into the alloy and vice versa.
  • a suitable time to accomplish coating while minimizing or controlling migration of components of the substrate into the alloy and vice versa.
  • a dipping time of about 5 seconds will be suitable.
  • the rod 55 will be pulled up into the upper region of the tube 26 above the crucible 29 and will be held there for a long enough time while maintaining a suitable temperature for annealing of the coating to occur.
  • a suitable time is 30 minutes and a suitable temperature is 900*C.
  • the coated metal substrate will be oxidized by admitting argon containing a suitable concentration of oxygen, for example a partial pressure of oxygen of 10 "16 , to selectively oxidize the titanium without oxidizing the nickel, the temperature being, for example 900*C.
  • argon containing a suitable concentration of oxygen for example a partial pressure of oxygen of 10 "16 , to selectively oxidize the titanium without oxidizing the nickel, the temperature being, for example 900*C.
  • the coated, selectively oxidized substrate will be lifted by the rod into the cooling chamber 47 to cool to a temperature convenient for handling in the ambient atmosphere, e.g.20*C.
  • a temperature convenient for handling in the ambient atmosphere e.g.20*C.
  • the reflector is placed in the position shown in Figure 2 overlying the tube 26. This will conserve heat by reflecting heat coming from the lower portion of the tube and from the molten alloy and the crucible which can, therefore, be maintained in suitable condition to receive the next specimen of substrate.
  • the cooled, coated oxidized substrate is then lowered into gate valve 46, which is opened to remove the specimen to be quickly replaced by another, uncoated specimen. Gettered argon continues to be admitted to bring the oxygen partial pressure to within the desired range.
  • the gate value is closed.
  • the alloy coating instead of being selectively oxidized, maybe selectivelynitridedusing, for example ammonia as the source of nitrogen, or selectively carbided using methane as the source of carbon, or selectively borided using boron hydride as the source of boron or selectively silicided using silane as the source of silicon.
  • selectivelynitridedusing for example ammonia as the source of nitrogen, or selectively carbided using methane as the source of carbon, or selectively borided using boron hydride as the source of boron or selectively silicided using silane as the source of silicon.
  • step of selective oxidation may be omitted resulting in a substrate coated with a layer of alloy which may become oxidized during use or during exposure to the atmosphere.
  • the metal used in the crucible may be a single metal rather than an alloy.
  • the substrate need not be metallic. It may, for example, be a ceramic material or any other material to which a metal coating may be applied by dip coating, to which the coating will adhere when it solidifies and which is not destroyed or seriously damaged by the molten metal.
  • Eutectic alloys are preferred whose eutectic points are not so high as to cause melting or excessive migration of components of the substrate into the alloy or to damage the substrate. That is to say, a eutectic alloy is preferred which melts at its eutectic point below the melting point of the substrate. However such eutectic alloys need not be used in all cases.
  • Metal and other substrates which may be treated by the method and in the equipment of the invention include structural steel, pressurevessel steels, carbon steels, super alloys such as described in U.S. Patent 4,483,720, stainless steels, cast iron, non-ferrous metals such as nickel and Monel 100, copper and its alloys, refractory metals and alloys, cemented carbides such as WC-3 to 25 Co, and ceramics.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Appareil et procédé de revêtement de substrat métallique avec un alliage, consistant à tremper le substrat dans un bain d'alliage en fusion. L'appareil et le procédé réduisent au minimum l'entrée d'air ambient pendant l'introduction du substrat métallique non revêtu et lors de l'extraction du substrat métallique revêtu. De tels moyens comprennent une chambre fermée ayant un orifice d'entrée, une section de refroidissement située au-dessus de l'orifice d'entrée, une section de préchauffage et de recuit se trouvant sous l'orifice d'entrée, un four et une section à creuset pour la fusion de l'alliage et le revêtement du substrat, des moyens pour abaisser successivement le substrat non revêtu dans la section de préchauffage/recuit, puis dans le creuset, de relèvement du substrat revêtu pour le faire passer dans la section de préchauffage/recuit, de relèvement dans la section de refroidissement, puis d'abaissement dans la section à orifice puis d'extraction. Un réflecteur de chaleur est prévu au-dessus du creuset pour conserver la chaleur pendant que le substrat revêtu est refroidi.
PCT/US1990/005377 1989-09-22 1990-09-20 Procede de revetement en continu d'un metal avec de l'oxyde de titane, et equipement utilise a cet effet WO1991004349A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41105089A 1989-09-22 1989-09-22
US411,050 1989-09-22

Publications (1)

Publication Number Publication Date
WO1991004349A1 true WO1991004349A1 (fr) 1991-04-04

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PCT/US1990/005377 WO1991004349A1 (fr) 1989-09-22 1990-09-20 Procede de revetement en continu d'un metal avec de l'oxyde de titane, et equipement utilise a cet effet

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JP (1) JPH04501888A (fr)
CA (1) CA2041662A1 (fr)
WO (1) WO1991004349A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU176793A1 (ru) * В. И. Першин, С. А. Малинский , А. П. Мельников Механизм фокусировки длиннофокусных объективов в фотоаппаратах типа «фоторужье»
US1343842A (en) * 1920-01-03 1920-06-15 Robert J Piersol Process and apparatus for metal-plating
SU383529A1 (ru) * 1971-10-25 1973-05-23 Физико технический институт Белорусской ССР , Белорусский институт механизации сельского хоз йства Способ обработки расплавленного металла ультразвукол!
US4483720A (en) * 1981-11-27 1984-11-20 S R I International Process for applying thermal barrier coatings to metals
DE3413240A1 (de) * 1984-04-07 1985-10-17 Möhl und Schmetz Anlagenbau GmbH, 5000 Köln Verfahren und einrichtung zum aufbringen einer zinkschicht auf teile aus guss oder stahl

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU176793A1 (ru) * В. И. Першин, С. А. Малинский , А. П. Мельников Механизм фокусировки длиннофокусных объективов в фотоаппаратах типа «фоторужье»
US1343842A (en) * 1920-01-03 1920-06-15 Robert J Piersol Process and apparatus for metal-plating
SU383529A1 (ru) * 1971-10-25 1973-05-23 Физико технический институт Белорусской ССР , Белорусский институт механизации сельского хоз йства Способ обработки расплавленного металла ультразвукол!
US4483720A (en) * 1981-11-27 1984-11-20 S R I International Process for applying thermal barrier coatings to metals
US4483720B1 (fr) * 1981-11-27 1987-03-10
DE3413240A1 (de) * 1984-04-07 1985-10-17 Möhl und Schmetz Anlagenbau GmbH, 5000 Köln Verfahren und einrichtung zum aufbringen einer zinkschicht auf teile aus guss oder stahl

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Journal of Vacuum Science & Technology A, Volume 4, No. 6, Second Series, November-December 1986, (Woodbury, NY.US), I.M. ALLEN: "Dip Process Thermal Barrier Coatings for Gas Turbines", pages 2652-2655 see page 2652, Point I and II *
PATENT ABSTRACTS OF JAPAN, Volume 6, No. 149 (C-118) (1027), 10 August 1982 & JP, A, 57/70275 (Mitsubishi Jukogyo K.K.) 30 April 1982 see the Abstract *
Soviet Inventations Illustrated, Week B43, 5 December 1979, & SU, A, 383529, (Ivanov), 5 February 1979 see the Abstract *
Soviet Inventions Illustrated, Week B44, 12 December 1979, & SU, A, 176793 (Kostornov) 19 February 1979 see the Abstract *

Also Published As

Publication number Publication date
JPH04501888A (ja) 1992-04-02
CA2041662A1 (fr) 1991-03-23

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