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WO1989005870A1 - Depot par pulverisation - Google Patents

Depot par pulverisation Download PDF

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Publication number
WO1989005870A1
WO1989005870A1 PCT/GB1988/001106 GB8801106W WO8905870A1 WO 1989005870 A1 WO1989005870 A1 WO 1989005870A1 GB 8801106 W GB8801106 W GB 8801106W WO 8905870 A1 WO8905870 A1 WO 8905870A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
base material
metal
addition
alloy
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.)
Ceased
Application number
PCT/GB1988/001106
Other languages
English (en)
Inventor
Alan George Leatham
Andrew Ogilvy
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.)
Sandvik Osprey Ltd
Original Assignee
Osprey Metals Ltd
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 GB878729159A external-priority patent/GB8729159D0/en
Priority claimed from GB888816181A external-priority patent/GB8816181D0/en
Application filed by Osprey Metals Ltd filed Critical Osprey Metals Ltd
Publication of WO1989005870A1 publication Critical patent/WO1989005870A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal

Definitions

  • This invention relates to the spray deposition of a molten metal, metal alloy or non-metal in which a stream of molten metal, metal alloy or non-metal e.g. ceramic is atomised into droplets by high velocity atomising gas at a temperature less than the molten stream.
  • the atomising gas used is normally either nitrogen or argon.
  • the porosity of the deposit varies according to the atomising gas used and the metal or metal alloy being atomised.
  • the article "Spray Forming" constituting report number 85CRD073 of May 1985 of General Electric reported on an evaluation of disc preforms of Rene 80. Atomisation was conducted with both argon and nitrogen and respective densities of 99.4% and 99.9% were measured. The lower density of the argon sprayed preforms was found to be due to argon bubbles being trapped within the deposit causing porosity.
  • the alloying is limited by macrosegregation during solidification or, in the case of powder metallurgy, by precipitation in the teeming nozzle during atomisation.
  • powder metallurgy by precipitation in the teeming nozzle during atomisation.
  • the alloy constituents from a metal precipitates (e.g. aluminium oxide and nitride) form in the pour nozzle restricting flow and causing blockage.
  • An object of the present invention is to provide an improved method of spray deposition.
  • the object is making improved and new alloys.
  • a method of spray deposition comprising the steps of: teeming a stream of molten metal or metal alloy or non-metal base material through an atomising device, directing atomising gas at a temperature less than that of the liquid stream to break up the stream of the base material into a spray of atomised droplets, and applying an addition or a reactant material which is deliberately added for at least one of: reaction with the base material, reaction with the atomising gas, diffusion within the base material, and evolution of a gaseous phase within the base material.
  • a method of producing an alloy by spray deposition comprising the steps of atomising a stream of molten metal particles by subjecting the stream to atomising gas directed at the stream, and introducing into the spray of atomised or atomising particles of the base material, or into the molten stream just prior to atomising, solid or molten particles of a different metal, metal alloy, ceramic or a non-metallic material to form an alloying addition to the base material and co-depositing the particles of the base material and the alloying material under controlled conditions such that the deposit formed comprises an alloy of the base material and the alloying addition.
  • Partial or complete alloying can occur on deposition or on subsequent cooling or may be finally completed by diffusion during subsequent heat treatment or hot working.
  • the injection of particles composed of metals of a low atomic number can be particularly beneficial as diffusion can occur very rapidly.
  • the invention also provides a method of injecting into the spray of atomised particles of a base alloy, solid or molten particles of a metal alloy, ceramic or non-metallic compound which during flight or subsequently on or after deposition, reacts with the base alloy to form a dispersoid composed of constituents from both the base alloy and the injected solid or molten particles.
  • a spray deposit of an alloy is formed where the alloy has been formed by the co-deposition of atomised particles of a base material and applied particles of an alloying addition or a reactant.
  • the alloying addition particles are suitably applied by generating a fluidised bed of particles in a gas stream from the bed into the spray so that the alloying addition particles are co-deposited with the atomised base material particles.
  • other techniques can be used including screw feeding.
  • Liquid metals can be added to the main spray using a second spraying device arranging the relative atomising rakes to provide the required volume of weight fraction of alloying or reactant addition.
  • a method of forming a deposit from gas atomised metal or metal alloy comprising doping the metal or metal alloy and/or the atomising gas with a material which will react on deposition to reduce the porosity in the deposit which would otherwise have been present without the addition of said material.
  • this aspect of the invention envisages deliberately adding reactive gas to the ato isinng gas and/or deliberately adding a reactive element to the alloy to form a constituent which would not normally be acceptable in conventional forming techniques due to segregation problems but which, in the rapid solidification of an atomising process, improves the density and/or the microstructure of the deposit.
  • the deposit formed in accordance with the method of the invention may be of any shape, for example bar, strip, plate, disc, tube or intricately shaped articles or may be a coating. It may also be used in the as deposited form or subsequently hot or cold worked or thixotropically formed.
  • the reaction product formed in the deposit need not be solid. Co-depositing a thermally unstable particle with the base metal so that the particle vapourises when entrapped by the depositing metal droplets will form a "foamed" metal structure.
  • the particle or the product of a reaction between the particle and the matrix would be a material that vapourises or decomposes to gas in the matrix.
  • pre-expanded polystyrene beads may be used. These are readily available as particles of about 0.1 mm in size. The extent and size of the porosity could be controlled by adjusting the liquid content of the depositing metal and the volume fraction and size of the injected particles.
  • the applied addition is solid and particulate so as to be co-deposited with the base material it is very important that the heat extraction is carefully controlled by control of the atomising conditions and the temperature and rate of injection of the applied particles.
  • an atomised spray will typically have a range of droplet sizes (e.g. 10-300 microns, approximating to a log-normal .size distribution) and these arrive at different temperatures and states of solidification at the collector surface.
  • the cooling rate in flight is mainly determined by the size of an individual particle.
  • the coarse particle e.g. 300 micron
  • the fine particles e.g. 10 microns
  • the majority of particles of an intermediate size will be deposited in the semi-solid/semi-liquid condition or fully liquid undercoated condition.
  • the surface onto which the particles of the base material and the alloying or reactant addition are co-deposited is not at too low a temperature as this leads to individual particle of the base alloy retaining its -own indentity.
  • the surface onto which the particles are co-deposited must not be at too high a temperature as a thick layer of molten alloy can build up on the surface of the deposit and subsequently be ejected from the surface by the high velocity gas and/or any motion of the collector.
  • the conditions of co-deposition are controlled in such a manner that a layer of semi-solid/semi-liquid metal of controlled thickness is maintained at the surface of the deposit throughout the co-deposition, so that individual particles from the base alloy lose their identity in the semi-solid/semi-liquid layer.
  • the atomised particles of the base material in which dendrite solidification has occurred during flight are impacted at high velocity onto the surface of the deposit resulting in dendrite fragmentation.
  • the fine pre-solidified particles and the coarse fully molten particles of the base alloy add to the solid and liquid content of the surface of the deposit.
  • the deposit surface consists of a mixture of dendrite fragments of the base material particles, pre-solidified particles of the base material and liquid metal from the base materials together with the alloying or reactant addition.
  • the fine pre-solidified particles of the base material, alloying or reactant addition and the dendrite fragments partially re-melt in the liquid metal, aided partly by the release of latent heat and the metal solidifies uniformly and rapidly as the atomising gas flows over the surface of the deposit.
  • the alloy or reactant addition may then melt and/or diffuse into the base material to form a deposit of the desired integrated alloy, or alternatively, the material may chemically react with the matrix alloy or some constituent of the matrix alloy or of the gas or with a specially added constituent to the gas to reduce porosity in the deposit or to form a second stable phase.
  • Post heat treatment or hot working may be necessary in some cases to complete the diffusion or reaction processes.
  • the addition need not be applied by the introduction of separate particles which co-deposit into the base material.
  • the atomisation of copper with nitrogen as the atomising gas invariably results in 1 to 4% porosity in the deposit. This is because nitrogen is inert with respect to copper.
  • the porosity in the end product may be reduced to less than 1%.
  • aluminium nitride is normally detrimental to the properties of an ingot due to segregation the formation of large precipitates
  • the rapid solidification of a spray forming process means that the nitride is small and evenly dispersed and does not constitute a problem.
  • the copper desposit so formed has a large grain size. If it is desired to reduce the grain as well, this can be achieved by the addition of small amounts of oxygen in the atomising gas (suitably by the inclusion of air) which will provide a deposit with a finer grain size and still with less than 1% porosity.
  • the free grain size produced during spray deposition can be retained in the copper alloy if the grain boundaries are prevented from moving after solidification is completed. This is achieved by forming very fine oxide particles during atomisation that pin the boundaries and so produce a material at room temperature with a grain size of 15-25 ⁇ . Two similar melts can be combined to produce a base alloy having extra precipitate formed by reaction between two or more compounds of the two melts.
  • a high aluminium stainless steel melt may be mixed with a high oxygen stainless steel melt to produce an alloy containing a fine dispersion of alumina.
  • two copper melts, one containing zirconium and one containing boron can be co-deposited so that an alloy with a fine dispersion of zirconium boride would be formed.
  • Nickel base alloy where pores as large as 100 microns might be present in the deposited material leaving a porosity of 3 to 5%.
  • a reactive addition such as aluminium and titanium which can be combined with nitrogen trapped in the deposit, the pore sizes can be reduced to less than 5 micron and the overall porosity to less than 1%.
  • This example relates to producing an alloy whose composition prevents successful atomisation because of nozzle blocking problems.
  • gas atomised powders cannot be produced for subsequent compaction into solid parts.
  • spray deposits cannot be produced for the same reason.
  • the application of aluminium powder into the spray allows a much higher aluminium content to be achieved whilst avoiding blockage of the pouring nozzle.
  • the aluminium powder co-deposited with the stainless steel base material melts in the deposit because of its lower melting point (660°C) and the aluminium diffuses very rapidly into the steel. In this way it is possible to produce a stainless steel/aluminium alloy having up to 20% aluminium. This can provide a material with increased corrosion resistance and improved metallurgical properties.
  • the base material is a titanium alloy which is atomised and to which is applied particles of silicon carbide of a fine particle size e.g. 10 micron.
  • the titanium reacts with the silicon carbide causinng precipitation of fine titanium carbide in a titanium matrix.
  • This examples relates to the application of an addition to the metal to reduce porosity in the final deposit and to the atomising gas to modify the structure of the deposit.
  • a copper, 0.5. wt% aluminium alloy was melted and poured from a crucible via a zirconia nozzle into the gas atomising chamber.
  • High purity nitrogen gas was used to atomise the stream.
  • the gas to metal ratio used was 0.63 cum/kg.
  • a rotating ceramic disc was used to collect the spray and a solid deposit was built-up. After 5 seconds spraying time (20% of total spray) a small amount of air was added to the atomising gas which raised the chamber O y content from 20 ppm to 500ppm 0- . There was no noticeable effect on the spray.
  • the first material sprayed had noticeably less porosity than pure copper atomised previously under the same conditions. It is believed that this is due to a reaction between the aluminium in the copper alloy and a small amount of nitrogen atomising gas which remains trapped.between droplets forming every fine precipitates of aluminium nitride.
  • the nitrogen expands in the hot deposit to form gas porosity.
  • the grain size of the nitrogen atomised alloy was 200 microns whereas with some 0- in the atomising gas the grain size was reduced to 20-30 micron.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Procédé de dépôt par pulvérisation dans lequel on ajoute à dessein un agent d'addition ou une matière de réaction, afin d'obtenir une diffusion ou une réaction avec une matière de base atomisée. L'agent d'addition peut être des particules d'un métal différent, un alliage de métaux, une matière céramique ou non métallique introduite dans le courant ou la vaporisation afin de former un agent d'addition d'alliage avec la matière de base, produisant un alliage dont la compositon empêche la production réussie par une technologie métallurgique classique ou des poudres. Dans un autre mode, l'agent d'addition peut réduire par réaction la porosité dans un dépôt en formation, qui sans cela se produirait. Dans un tel cas l'agent d'addition peut être un gaz réactif ajouté au gaz d'atomisation, ou une matière réactive ajoutée à dessein à la matière de base, afin de réagir avec le gaz d'atomisation piégé. On peut également déclencher une réaction afin de provoquer l'évolution d'un gaz de sorte que l'on peut produire un métal poreux ou moussé.
PCT/GB1988/001106 1987-12-14 1988-12-14 Depot par pulverisation Ceased WO1989005870A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB878729159A GB8729159D0 (en) 1987-12-14 1987-12-14 Spray deposition
GB8729159 1987-12-14
GB8816181.5 1988-07-07
GB888816181A GB8816181D0 (en) 1988-07-07 1988-07-07 Production of alloys

Publications (1)

Publication Number Publication Date
WO1989005870A1 true WO1989005870A1 (fr) 1989-06-29

Family

ID=26293200

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1988/001106 Ceased WO1989005870A1 (fr) 1987-12-14 1988-12-14 Depot par pulverisation

Country Status (2)

Country Link
AU (1) AU2821089A (fr)
WO (1) WO1989005870A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307556A3 (fr) * 1987-09-12 1990-07-11 Karl-Hermann Busse Poudre pour la préparation de matériaux durs en un temps de réaction limité pour le remplissage de fils creux pour revêtement par chalumeau à arc électrique
FR2659581A1 (fr) * 1990-03-02 1991-09-20 Gen Electric Procede pour la formation d'un article ayant une composition d'alliage variable.
WO1992004475A1 (fr) * 1990-09-04 1992-03-19 Olin Corporation Incorporation de particules de ceramique dans une matrice a base de cuivre pour former un materiau composite
US5209787A (en) * 1990-07-27 1993-05-11 Olin Corporation Surface modification of copper alloys
US5213638A (en) * 1990-07-27 1993-05-25 Olin Corporation Surface modified copper alloys
EP0552004A1 (fr) * 1992-01-16 1993-07-21 United Kingdom Atomic Energy Authority Procédé de dépôt d'une couche de revêtement sur un substrat
EP0552479A1 (fr) * 1992-01-17 1993-07-28 Wieland-Werke Ag Procédé pour améliorer la flexibilité de demi-produits en alliage de cuivre
US5320689A (en) * 1990-07-27 1994-06-14 Olin Corporation Surface modified copper alloys
US5336342A (en) * 1989-07-26 1994-08-09 Olin Corporation Copper-iron-zirconium alloy having improved properties and a method of manufacture thereof
US5371937A (en) * 1990-07-02 1994-12-13 Olin Corporation Method for producing a composite material
US5390722A (en) * 1993-01-29 1995-02-21 Olin Corporation Spray cast copper composites
US5749938A (en) * 1993-02-06 1998-05-12 Fhe Technology Limited Production of powder
US5980604A (en) * 1996-06-13 1999-11-09 The Regents Of The University Of California Spray formed multifunctional materials
EP1130128A1 (fr) * 2000-02-29 2001-09-05 Robert Bosch Gmbh Procédé et appareil de dépôt d'un revêtement par pulvérisation d'un liquide
GB2366298A (en) * 2000-06-29 2002-03-06 Ford Global Tech Inc Forming metal foam structures by cold-gas spraying
US8871356B2 (en) 2007-03-14 2014-10-28 Sandvik Osprey Limited Brazing piece, a method of making a brazing piece, and a method of brazing and components made from said brazing piece
JP2017218633A (ja) * 2016-06-08 2017-12-14 積水化学工業株式会社 複合粒子の製造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1102522B (de) * 1952-05-03 1961-03-16 Felix Ritter Von Rueling Heissspritzverfahren zur chemischen Behandlung von Oberflaechen
FR1412272A (fr) * 1963-10-23 1965-09-24 Deloro Stellite Ltd Procédé d'application de revêtements superficiels d'alliages sur des métaux
FR2012909A1 (fr) * 1968-07-12 1970-03-27 Johnson Matthey Co Ltd
US3663206A (en) * 1968-11-27 1972-05-16 British Iron And Steel Ass The Treatment of molten material
BE852018A (fr) * 1977-03-02 1977-07-01 Centre Rech Metallurgique Procede pour fabriquer des tuyeres d'injection
US4066117A (en) * 1975-10-28 1978-01-03 The International Nickel Company, Inc. Spray casting of gas atomized molten metal to produce high density ingots
GB1531222A (en) * 1975-12-10 1978-11-08 Vandervell Products Ltd High strength bearing materials
JPS59222566A (ja) * 1983-05-30 1984-12-14 Kawasaki Heavy Ind Ltd 耐熱構造体の製造方法
EP0156760A2 (fr) * 1984-03-12 1985-10-02 MANNESMANN Aktiengesellschaft Procédé et installation pour la fabrication d'un outil de travail à chaud
EP0198613A1 (fr) * 1985-03-25 1986-10-22 Osprey Metals Limited Procédé de fabrication de produits métalliques

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1102522B (de) * 1952-05-03 1961-03-16 Felix Ritter Von Rueling Heissspritzverfahren zur chemischen Behandlung von Oberflaechen
FR1412272A (fr) * 1963-10-23 1965-09-24 Deloro Stellite Ltd Procédé d'application de revêtements superficiels d'alliages sur des métaux
FR2012909A1 (fr) * 1968-07-12 1970-03-27 Johnson Matthey Co Ltd
US3663206A (en) * 1968-11-27 1972-05-16 British Iron And Steel Ass The Treatment of molten material
US4066117A (en) * 1975-10-28 1978-01-03 The International Nickel Company, Inc. Spray casting of gas atomized molten metal to produce high density ingots
GB1531222A (en) * 1975-12-10 1978-11-08 Vandervell Products Ltd High strength bearing materials
BE852018A (fr) * 1977-03-02 1977-07-01 Centre Rech Metallurgique Procede pour fabriquer des tuyeres d'injection
JPS59222566A (ja) * 1983-05-30 1984-12-14 Kawasaki Heavy Ind Ltd 耐熱構造体の製造方法
EP0156760A2 (fr) * 1984-03-12 1985-10-02 MANNESMANN Aktiengesellschaft Procédé et installation pour la fabrication d'un outil de travail à chaud
EP0198613A1 (fr) * 1985-03-25 1986-10-22 Osprey Metals Limited Procédé de fabrication de produits métalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, vol. 9, no. 91, (C-277)(1814) 19 April 1985; & JP-A-59222566 (KAWASAKI JUKOGYO) 14 December 1984 *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307556A3 (fr) * 1987-09-12 1990-07-11 Karl-Hermann Busse Poudre pour la préparation de matériaux durs en un temps de réaction limité pour le remplissage de fils creux pour revêtement par chalumeau à arc électrique
US5336342A (en) * 1989-07-26 1994-08-09 Olin Corporation Copper-iron-zirconium alloy having improved properties and a method of manufacture thereof
FR2659581A1 (fr) * 1990-03-02 1991-09-20 Gen Electric Procede pour la formation d'un article ayant une composition d'alliage variable.
US5371937A (en) * 1990-07-02 1994-12-13 Olin Corporation Method for producing a composite material
US5213638A (en) * 1990-07-27 1993-05-25 Olin Corporation Surface modified copper alloys
US5209787A (en) * 1990-07-27 1993-05-11 Olin Corporation Surface modification of copper alloys
US5320689A (en) * 1990-07-27 1994-06-14 Olin Corporation Surface modified copper alloys
US5120612A (en) * 1990-09-04 1992-06-09 Olin Corporation Incorporation of ceramic particles into a copper base matrix to form a composite material
WO1992004475A1 (fr) * 1990-09-04 1992-03-19 Olin Corporation Incorporation de particules de ceramique dans une matrice a base de cuivre pour former un materiau composite
EP0552004A1 (fr) * 1992-01-16 1993-07-21 United Kingdom Atomic Energy Authority Procédé de dépôt d'une couche de revêtement sur un substrat
EP0552479A1 (fr) * 1992-01-17 1993-07-28 Wieland-Werke Ag Procédé pour améliorer la flexibilité de demi-produits en alliage de cuivre
US5390722A (en) * 1993-01-29 1995-02-21 Olin Corporation Spray cast copper composites
US5749938A (en) * 1993-02-06 1998-05-12 Fhe Technology Limited Production of powder
US5980604A (en) * 1996-06-13 1999-11-09 The Regents Of The University Of California Spray formed multifunctional materials
EP1130128A1 (fr) * 2000-02-29 2001-09-05 Robert Bosch Gmbh Procédé et appareil de dépôt d'un revêtement par pulvérisation d'un liquide
GB2366298A (en) * 2000-06-29 2002-03-06 Ford Global Tech Inc Forming metal foam structures by cold-gas spraying
US6464933B1 (en) 2000-06-29 2002-10-15 Ford Global Technologies, Inc. Forming metal foam structures
GB2366298B (en) * 2000-06-29 2004-03-24 Ford Global Tech Inc Forming metal foam structures
US8871356B2 (en) 2007-03-14 2014-10-28 Sandvik Osprey Limited Brazing piece, a method of making a brazing piece, and a method of brazing and components made from said brazing piece
JP2017218633A (ja) * 2016-06-08 2017-12-14 積水化学工業株式会社 複合粒子の製造方法

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Publication number Publication date
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