EP0270265B1 - Fabrication d'un composite métallique par pulvérisation de métal liquide - Google Patents

Fabrication d'un composite métallique par pulvérisation de métal liquide Download PDF

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Publication number
EP0270265B1
EP0270265B1 EP87309972A EP87309972A EP0270265B1 EP 0270265 B1 EP0270265 B1 EP 0270265B1 EP 87309972 A EP87309972 A EP 87309972A EP 87309972 A EP87309972 A EP 87309972A EP 0270265 B1 EP0270265 B1 EP 0270265B1
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EP
European Patent Office
Prior art keywords
metal
streams
particles
sprays
substrate
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.)
Revoked
Application number
EP87309972A
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German (de)
English (en)
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EP0270265A1 (fr
Inventor
Richard Michael Jordan
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.)
Rio Tinto Alcan International Ltd
Original Assignee
Alcan International Ltd Canada
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Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10607385&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0270265(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Alcan International Ltd Canada filed Critical Alcan International Ltd Canada
Publication of EP0270265A1 publication Critical patent/EP0270265A1/fr
Application granted granted Critical
Publication of EP0270265B1 publication Critical patent/EP0270265B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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    • 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
    • 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 is concerned with a method of making a composite metal deposit by spray casting.
  • the technique of spray casting is well known and comprises the steps of atomising a stream of molten metal to form a spray of hot metal particles by subjecting the stream to a relatively cold gas directed at the stream, and depositing the spray on a substrate.
  • the provision of rapid and controlled cooling permits the production of deposits having unusual microstructures, which can be rolled or formed into shaped articles. But with only one source of molten metal, there is a limit to the range of compositions and microstructures that can be obtained.
  • US Patent No 4674554 describes a spray casting method which includes the step of applying to the stream or spray fine, solid particles of a material of different composition from the metal. The particles are incorporated in the deposit.
  • refractory particles e.g. of alumina or silicon carbide can result in metal matrix composites having enhanced properties.
  • US Patent 4522784 describes a casting method in which two streams of molten metal are mixed just prior to casting, the smaller stream having a higher temperature than the larger stream and being chosen so that a fine intermetallic precipitate is formed during and prior to casting. With the DC casting methods described, it is difficult to remove heat fast enough from the system to prevent to resolution of the intermetallic precipitates.
  • GB 1359486 describes a spray casting technique for casting two immiscible metals of different density. A single flow of molten metal consisting of concentric streams of the two metals is atomised and the drops collected on a substrate. The range of alloy compositions that can be cast in this way is quite restricted.
  • This invention provides a convenient way of making composite metal deposits by spray casting, which is characterized over the above prior art by the fact that separate streams of molten metal are atomised separately. As a result, there is much less restriction on the compositions of the two metals.
  • GB 1083003 describes a method of making bearing materials by spraying Al and Pb simultaneously onto a backing strip. This results in a microstructure comprising alternating regions, of size corresponding (substantially) to the molten spray droplets, of Al and Pb.
  • US 3826301 contains a similar disclosure.
  • the invention provides a method of making a laminated metal article having consecutive layers of deposited metal compositions wherein the compositions of any two consecutive layers in the laminated article are different which method comprises providing at least two metal streams and a substrate, atomising each of the metal streams to form at least two sprays of hot metal particles by subjecting each of the metal streams to relatively cold gas directed at the said metal streams, depositing metal particles from one of the said streams onto the substrate to form a first layer thereon, depositing metal particles from another of the same metal streams onto the first layer to form a second layer and, if desired, depositing in a consecutive manner layers of metal particles from any of the said sprays such that any two consecutive layers have different compositions whereby a laminate is produced, wherein the atomisation conditions are controlled such that the metal particles of the sprays are partially or fully liquid but supercooled on impact to the extent that solidification takes place immediately on impact or that deposition on the substrate is followed by immediate solidification.
  • the first and second metal streams may be provided by gravity flow from holding vessels containing supplies of the molten metals.
  • the invention contemplates the use of two, three or more molten metal streams, each being atomised separately, and references to first and second metal streams should be construed accordingly.
  • Atomisation conditions may be chosen, as is known in the art, to control the size, velocity, direction and temperature of the sprays of hot metal particles.
  • the particles of molten metal spread out in a conical spray pattern which may be of circular cross-section or may be modified, as known in the art, to form a different cross-section or a more even spread of metal particles.
  • the substrate may be a metal surface, which may for example be flat or tubular with the metal spray to be deposited on the inner or the outer surface. It is generally preferred that the metal particles be still at least partially liquid on impact, otherwise the deposit may be too porous.
  • the metal spray is partially or fully liquid but supercooled on impact, so that solidification takes place immediately on impact and there is no need to extract large amounts of heat through the substrate.
  • fibres, whiskers or particles of refractory material e.g. carbon or silicon carbide
  • refractory material e.g. carbon or silicon carbide
  • particles of refractory material can be incorporated in the first and/or second spray by the technique described in US-A-4674554 noted above.
  • Three (or more) sprays may be used.
  • the spray patterns of two may be superimposed and operated simultaneously to form one layer of the laminate structure.
  • the result therefore, is a laminated structure in which alternate layers have a microstructure resulting from the two simultaneously operated sprays.
  • two superimposed sprays may be chosen to interact as described in the aforesaid US patent 4522784.
  • the spray patterns of the first and second sprays may, but need not, overlap; that is to say, the two sprays may be arranged to impact on the same or different areas of the substrate.
  • the substrate may be translated, or reciprocated, or rotated in order to pick up the two metal sprays.
  • the two spray patterns of the two sprays do overlap, then it is necessary to operate the two sprays alternatively in order to achieve the desired laminated structure. In order to operate both sprays continuously, it is therefore preferred that the two spray patterns can be arranged not to overlap, and to reciprocate or rotate the substrate so that alternating layers of the two metals are deposited thereon.
  • the laminated deposit comprises at least two layers of each metal in alternating superimposed relationship.
  • the thickness of the alternating layers has a significant effect on the properties of the laminate.
  • each layer preferably has a thickness in the range 0.01-100 mm, particularly 1-10 mm.
  • the as-sprayed deposit may be subjected to rolling. For many purposes it is preferred that each layer in the rolled product have a thickness of from 10 to 500 ⁇ m, particularly 30 to 200 ⁇ m.
  • Figures 1 to 3 are a schematic diagram of a system for making a composite metal deposit according to the invention.
  • the system comprises first and second furnaces 10 and 12 for supplying first and second streams of molten metal, which are atomised (by means not shown) to form first and second sprays, 14 and 16, of hot metal particles.
  • the spray patterns overlap, and each spray is operated in turn while the other is shut off.
  • the sprays are deposited in turn on a substrate 18, whose position and orientation are controlled by means 20.
  • the metal sprays and the substrate are contained within a spray chamber 22, which is closed except for an exit vent for gas and any overspray powder.
  • a refractory material contained in a stream of carrier gas is supplied via a pipe 26 to the region where the first metal is atomised, and becomes incorporated in the first metal spray 14.
  • the substrate 18 might be maintained stationary, so as to build up a composite metal body thereon; or it might be translated, rotated or reciprocated in order to build up a uniform composite metal layer.
  • the substrate 18 might have taken the shape of a mould, with the intention of working the deposit while on the substrate to form a shaped article.
  • Figure 2 corresponds to Figure 1, except that the spray patterns of the two metal sprays 14 and 16 are shown as being non-overlapping. In this case, the sprays are operated continuously and the substrate 18 is reciprocated in order to obtain a deposit consisting of alternating layers of first and second metal.
  • the spray patterns of the two metal sprays 14 and 16 are shown as partly overlapping when they impact on cylindrical substrate 18 which is caused to rotate round a horizontal axis 28.
  • a fibre 30 is supplied from a spool 32 and becomes incorporated in the deposit.
  • the first metal or alloy mentioned will generally be present in the deposit in a volume concentration as great or greater than the second metal or alloy.
  • Laminated material was sprayed using a combination of 6061 Al alloy from on atomizer and 7475 Al alloy + SiC from the other atomizer.
  • Both crucibles used were alumina with zirconia nozzles.
  • the atomizing gas was nitrogen.
  • the collector was an aluminium plate 300 mm long by 150 mm wide. The plate was reciprocated beneath the sprays at a frequency of 1Hz.
  • the conditions for the 7475 alloy were the same apart from the melt temperature which was 710°C.
  • SiC particulate (F600) was fed to the 7475 spray only, SiC was fed at a rate of 1.72 kg/min to the atomizing nozzle.
  • the as - sprayed material was consolidated by hot rolling at 430°C to approximately 2 mm in thickness and then further cold rolling to 1 mm. Any as - sprayed porosity was found to close up during this process to form a fully consolidated product.
  • the sheet was solution heat treated by holding for at least 30 min at 500°C and cold water quenching. The material was artificially aged for 20 hr at 120°C.
  • results illustrate that the combination of the two materials in the laminate can result in improvements in mechanical properties over the individual constituents.
  • results indicate an improvement in strength and ductility over 6061 and an improvement in ductility and crack initiation and propagation energy (indicating improved toughness) over the 7475 alloy with SiC.
  • results also indicate a significant improvement in the properties (notably ductility) over that of the 6061 alloy with SiC.
  • the thickness of the laminated regions is highly important in controlling the final properties of the material - specifically in this instance the ductility and toughness of the laminate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Metal Rolling (AREA)

Claims (9)

  1. Procédé de fabrication d'un article métallique stratifié comportant des couches successives de compositions de métal déposées, les compositions de deux couches successives quelconques dans l'article stratifié, étant différentes, et ce procédé comprenant la mise en oeuvre d'au moins deux courants de métal et d'un substrat, l'atomisation de chacun des courants de métal pour former au moins deux jets de particules métalliques chaudes, en soumettant chacun des courants de métal à un gaz relativement froid dirigé vers ces courants de métal, en déposant les particules métalliques de l'un de ces courants, sur le substrat afin de former une première couche sur celui-ci, en déposant les particules métalliques de l'autre de ces mêmes courants de métal, sur la première couche pour former une deuxième couche et, si on le souhaite, en déposant successivement des couches de particules de métal à partir de l'un quelconque de ces jets de telle façon que deux couches quelconques successives, aient des compositions différentes, de sorte que l'on produit un stratifié ; les conditions d'atomisation étant ajustées de telle façon que les particules métalliques des jets, soient partiellement ou complètement liquides, mais sur-refroidies au moment de l'impact selon un degré tel que la solidification a lieu immédiatement au moment de l'impact, ou que le dépôt sur le substrat est suivi par une solidification immédiate.
  2. Procédé selon la revendication 1, dans lequel on dépose des fibres, des trichites ou des particules de matériau réfractaire sur le substrat, de telle façon qu'elles soient incorporées dans le dépôt métallique composite cohérent.
  3. Procédé selon la revendication 1, dans lequel des particules de matériau réfractaire sont introduites dans au moins un des courants de métal, ou dans au moins un des jets de particules métalliques chaudes.
  4. Procédé selon la revendication 1, dans lequel on emploie deux courants de métal, et on introduit un matériau réfractaire dans l'un des courants de métal ou dans le jet formé à partir de l'un des courants de métal, de telle façon que l'on produise un stratifié dans lequel les couches successives de métal déposées, ne contiennent pas toutes les deux des particules réfractaires.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel les métaux des courants de métal, sont des alliages différents dérivés du même métal de base.
  6. Procédé selon la revendication 5, dans lequel le métal de base est l'aluminium.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel on met en oeuvre deux courants de métal, et dans lequel l'article métallique stratifié comprend au moins deux couches de chaque métal alternativement superposées.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel l'article métallique stratifié est ensuite laminé.
  9. Procédé selon la revendication 8, dans lequel, après laminage, chaque couche déposée, a une épaisseur de 10 à 500 µm.
EP87309972A 1986-11-14 1987-11-11 Fabrication d'un composite métallique par pulvérisation de métal liquide Revoked EP0270265B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8627308 1986-11-14
GB868627308A GB8627308D0 (en) 1986-11-14 1986-11-14 Composite metal deposit

Publications (2)

Publication Number Publication Date
EP0270265A1 EP0270265A1 (fr) 1988-06-08
EP0270265B1 true EP0270265B1 (fr) 1992-07-01

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ID=10607385

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87309972A Revoked EP0270265B1 (fr) 1986-11-14 1987-11-11 Fabrication d'un composite métallique par pulvérisation de métal liquide

Country Status (10)

Country Link
EP (1) EP0270265B1 (fr)
JP (1) JPS63145762A (fr)
KR (1) KR880006378A (fr)
CN (1) CN1011389B (fr)
AU (1) AU612609B2 (fr)
BR (1) BR8706130A (fr)
CA (1) CA1269284A (fr)
DE (1) DE3780131T2 (fr)
GB (1) GB8627308D0 (fr)
ZA (1) ZA878404B (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3941853C1 (fr) * 1989-12-19 1991-04-11 Mtu Muenchen Gmbh
CA2025302A1 (fr) * 1989-12-26 1991-06-27 John R. Rairden, Iii Composite microlamine, renforce, a matrice metallique
GB9210763D0 (en) * 1992-05-20 1992-07-08 Lucas Ind Plc Improvements in and relating to thixoformable layered materials and articles made from them
DE4235303A1 (de) * 1992-10-20 1994-04-21 Wieland Werke Ag Rotationssymmetrisches Halbzeug mit über den Querschnitt variierenden Eigenschaften
GB2310866A (en) * 1996-03-05 1997-09-10 Sprayforming Dev Ltd Filling porosity or voids in articles formed by spray deposition
DE19955789A1 (de) * 1999-11-19 2001-05-23 Basf Ag Verfahren zur kombinatorischen Herstellung einer Bibliothek von Materialien
DE10009598A1 (de) * 2000-02-29 2001-09-06 Bosch Gmbh Robert Verfahren und Vorrichtung zur Abscheidung einer Beschichtung auf einem Substrat durch Versprühen einer Flüssigkeit
US6911129B1 (en) * 2000-05-08 2005-06-28 Intematix Corporation Combinatorial synthesis of material chips
DE102004031164B4 (de) * 2004-06-28 2008-03-20 Federal-Mogul Burscheid Gmbh Eingusskörper mit Außenbeschichtung zur Herstellung von Verbundkörpern
CA2520705C (fr) * 2004-11-02 2012-12-18 Sulzer Metco Ag Appareil de projection a chaud et egalement processus de projection a chaud
DE102006051936B4 (de) * 2006-11-01 2014-03-20 Zollern Bhw Gleitlager Gmbh & Co. Kg Verfahren zur Herstellung zweier miteinander verbundener Schichten und nach dem Verfahren herstellbares Funktionsbauteil
CN102151828A (zh) * 2011-03-18 2011-08-17 西南交通大学 多坩埚多喷嘴喷射成形制备梯度材料的方法
FR2991216B1 (fr) * 2012-05-29 2014-07-04 Snecma Procede de compactage de peintures anodiques avec collision des jets de sablage
EP2874159A3 (fr) * 2013-05-14 2015-10-07 Longke Electronics (Huiyang) Co., Ltd. Électrode de combinaison de métal de base de composant céramique électronique et procédé de fabrication correspondant
CN104087891B (zh) * 2014-07-12 2016-06-22 卢玉锋 一种喷射及喷涂法制备复合金属材料的方法及装置
JP6481154B2 (ja) * 2014-10-18 2019-03-13 エムテックスマート株式会社 粉粒体の塗布方法
CN104561884B (zh) * 2014-12-22 2017-01-04 浙江灿根机械制造有限公司 压力机球碗自动复合铜层装置及采用该装置复合铜层方法
CN105458263B (zh) * 2015-12-10 2018-05-11 安徽相邦复合材料有限公司 一种铝基复合材料-铝合金夹层板的制备方法
US20170216918A1 (en) * 2016-02-02 2017-08-03 Melissa E. Orme-Marmarelis Methods and systems for fabrication using multi-material and precision alloy droplet jetting
CN207699655U (zh) * 2017-06-30 2018-08-07 爱普科斯电子元器件(珠海保税区)有限公司 一种电子元件复合电极的制备装置

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933264A (en) * 1955-06-28 1960-04-19 Bullen Russell Hose delivery guide
US2993264A (en) * 1955-12-23 1961-07-25 Gen Electric Protective coating for molybdenum
GB1083003A (en) * 1964-10-23 1967-09-13 Glacier Co Ltd Hot metal spraying of bearing materials
GB1410169A (en) * 1971-06-17 1975-10-15 Johnson Matthey Co Ltd Method of making composite layered structures by spraying
BE790211A (fr) * 1971-10-22 1973-02-15 British Steel Corp Appareil en vue de former des revetements protecteurs sur des articles en carbone
BE790453A (fr) * 1971-10-26 1973-02-15 Brooks Reginald G Fabrication d'articles en metal
GB1484023A (en) * 1974-08-07 1977-08-24 Mebac Inc Metal member having a non-skid surface and method of making same
FR2311101A1 (fr) * 1975-05-13 1976-12-10 Kawasaki Heavy Ind Ltd Procede de traitement d'une surface de glissement utilisant un revetement par explosion de fil
GB1531222A (en) * 1975-12-10 1978-11-08 Vandervell Products Ltd High strength bearing materials
GB8629373D0 (en) * 1986-12-09 1987-01-21 Alcan Int Ltd Billet/tube

Also Published As

Publication number Publication date
JPS63145762A (ja) 1988-06-17
CN1011389B (zh) 1991-01-30
ZA878404B (en) 1988-05-05
BR8706130A (pt) 1988-06-21
AU612609B2 (en) 1991-07-18
DE3780131D1 (de) 1992-08-06
CA1269284A (fr) 1990-05-22
AU8119187A (en) 1988-05-19
CN87107803A (zh) 1988-07-27
GB8627308D0 (en) 1986-12-17
EP0270265A1 (fr) 1988-06-08
DE3780131T2 (de) 1993-01-14
KR880006378A (ko) 1988-07-22

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