EP0513238B1 - Bogenspritzen von rasch abgekühlten aluminiumlegierungen - Google Patents

Bogenspritzen von rasch abgekühlten aluminiumlegierungen Download PDF

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Publication number
EP0513238B1
EP0513238B1 EP91905287A EP91905287A EP0513238B1 EP 0513238 B1 EP0513238 B1 EP 0513238B1 EP 91905287 A EP91905287 A EP 91905287A EP 91905287 A EP91905287 A EP 91905287A EP 0513238 B1 EP0513238 B1 EP 0513238B1
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EP
European Patent Office
Prior art keywords
rapidly solidified
alloy
wire
substrate
arc
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
EP91905287A
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English (en)
French (fr)
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EP0513238A1 (de
Inventor
Michael S. Zedalis
Paul S. Gilman
Santosh K. Das
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.)
Honeywell International Inc
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AlliedSignal Inc
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Publication date
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Publication of EP0513238A1 publication Critical patent/EP0513238A1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B22F9/008—Rapid solidification processing
    • 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
    • C23C4/131—Wire arc spraying

Definitions

  • This invention relates to a process for improving the properties of materials, and more particularly to a process for producing a metallic coating from a rapidly solidified metal.
  • Spray metallizing consists of heating a metal to a molten or semi-molten condition by passing it through a high temperature heat source, and depositing it in a finely divided form on a substrate.
  • the molten or semi-molten particles flatten out on impacting the substrate and adhere to its surface.
  • Subsequently deposited particles also flatten out, and adhere to those previously deposited, thus the structure of sprayed deposits is lamellar.
  • the sprayed metal deposits resemble the derivative wire or powder chemically, but their physical properties, especially their microstructure, are quite different from those of the original wrought metal. Cohesion is achieved through mechanical and metallurgical bonding.
  • certain materials can be fused to form a dense and uniform coating that is metallurgically bonded to the substrate.
  • Fused coatings usually are required for protecting the substrate material during service at high temperatures, in abrasive and corrosive environments, or for developing a surface of uniformly high hardness.
  • sprayed aluminum coatings on steel require heating to above 482°C to metallurgically bond the costing to the steel.
  • the material may be subsequently heated at 732°C to 1093°C to provide a dense, uniform coating metallurgically bonded to the base metal.
  • problems may arise due to the spray metallizing of aluminum coatings and subsequent diffusing of the aluminum spray coating from the formation of coarse aluminum-iron intermetallics dispersed within the deposited particles and at the coating/substrate interface. These intermetallics are very brittle and can degrade the mechanical properties of the component, for example, by forming a brittle layer between the components. Also, because the sprayed aluminum coating requires a thermal diffusing treatment, conditions may exist wherein the substrate material may not be properly heat treated. Problems may be encountered with welded aluminum coated steel parts. The alloying of the aluminum and iron can create a loss of ductility and lowering of corrosion resistance in the weld and heat-affected zone. Finally, because of the mismatch in the coefficient of thermal expansion between the sprayed aluminum coating and the substrate, the coating may degrade and spall off during high temperature exposure.
  • the present invention provides an economical and efficient process for arc spraying an aluminum base alloy onto a substrate which does not have a fiber reinforcing material thereon in which no subsequent thermal treatment is required.
  • properties as high temperature strength and stability, corrosion and oxidation resistance and compatibility with the substrate, of an aluminum spray metallized coating, are improved in accordance with the invention by arc spraying a rapidly solidified, high temperature aluminum alloy onto a designated substrate.
  • This procedure referred to hereinafter as arc spraying, results in the formation of a high temperature spray metallized coating.
  • Subsequent thermal treatments, such as heating the costing to above the solidus of the alloy, heretofore required to adhere the coating to the substrate are virtually eliminated.
  • Deposition and retention of a rapidly solidified alloy onto a substrate are effected in a single process step.
  • the coated substrate exhibits improved ambient and elevated temperature mechanical and physical properties due to the microstructure of the rapidly solidified coating.
  • the invention provides a process for producing a rapidly solidified aluminum base alloy coating, comprising the steps of: (a) forming a rapidly solidified aluminum base alloy into a wire; and (b) arc spraying said wire onto a substrate which does not have a fiber reinforcing material thereon.
  • Wire having a diameter suitable for arc spraying may be fabricated directly by a friction actuated process or by conventional wire drawing techniques, and sprayed onto a substrate using arc spraying techniques to form a nearly fully dense spray metallized coating. Moreover, the attractive properties of the rapidly solidified wire are retained. This process may be repeated such that the subsequent spraying is done on top of the sprayed coating.
  • the sprayed metal coatings may then be finished by typical metal finishing operations such as machining, grinding, burnishing and polishing provided that the precautions usually followed for sprayed metallized coatings are followed. Also components having the spray metallized coatings can withstand moderate forming operations such as drawing, spinning, brake and roll forming, and embossing.
  • the arc sprayed coatings are suitable for use in components requiring corrosion, oxidation and elevated temperature protection for use as aerospace components such as turbine blades, turbine vanes and fasteners; automotive components such as exhaust pipes, intake valves and cylinder barrels; and industrial components such as heat exchangers, fasteners for chemical piping and boilers, reactor tubes, and heat treating equipment.
  • aerospace components such as turbine blades, turbine vanes and fasteners
  • automotive components such as exhaust pipes, intake valves and cylinder barrels
  • industrial components such as heat exchangers, fasteners for chemical piping and boilers, reactor tubes, and heat treating equipment.
  • Applications such as molds appointed for subsequent casting may arise that specifically utilize the higher temperature capability, i.e. hardness, of the rapidly solidified coating.
  • the arc sprayed layers can be used for repairing coatings as well as engineering shapes made directly from the rapidly solidified materials.
  • the coating can be applied to a substrate to repair a surface defect thereof.
  • the arc sprayed layers can also be used to make the preforms for various composite materials wherein the substrate consists of continuous or woven fibers, bundles, whiskers or particulate made from a hard or semi-hard material such as refractory carbides, oxides or nitrides.
  • the rapidly solidified alloys may be combined with a reinforcing phase to form a composite as described in WO-A-89/06287 prior to being formed into a wire.
  • the aluminum base, rapidly solidified alloy appointed for use in the process of the present invention has a composition consisting essentially of the formula Al bal Fe a Si b X c wherein X is at least one element selected from Mn, V, Cr, Mo, W, Nb, Ta, "a" ranges from 1.5-8.5 at %, "b” ranges from 0.25-5.5 at %, “c” ranges from 0.05-4.25 at % and the balance is aluminum plus incidental impurities, with the proviso that the ratio [Fe+X]:Si ranges from 2.0:1 to 5.0:1.
  • the alloy include aluminum-iron-vanadium-silicon compositions wherein the iron ranges from 1.5-8.5 at %, vanadium ranges from 0.25-4.25 at %, and silicon ranges from 0.5-5.5 at %.
  • Another aluminum base, rapidly solidified alloy suitable for use in the process of the invention has a composition consisting essentially of the formula Al bal Fe a Si b X c wherein X is at least one element selected from Mn, V, Cr, Mo, W, Nb, Ta, "a" ranges from 1.5-7.5 at %, “b” ranges from 0.75-9.5 at %, “c” ranges from 0.25-4.5 at % and the balance is aluminum plus incidental impurities, with the proviso that the ratio [Fe+X]:Si ranges from 2.01:1 to 1.0:1.
  • Still another aluminum base, rapidly solidified alloy suitable for use in the process of the invention has a composition consisting essentially of the formula Al bal Fe a Si b X c wherein X is at least one element selected from Mn, V, Cr, Mo, W, Nb, Ta, Ce, Ni, Zr, Hf, Ti, Sc, "a” ranges from 1.5-8.5 at %, "b” ranges from 0.25-7.0 at %, and "c” ranges from 0.05 to 4.25 at %, the balance being aluminum plus incidental impurities.
  • Still another aluminum base, rapidly solidified alloy that is suitable for use in the process of the invention has a composition range consisting essentially of 2-15 at % from the group consisting of zirconium, hafnium, titanium, vanadium, niobium, tantalum, erbium, 0-5 at % calcium, 0-5 at % germanium, 0-2 at % boron, the balance being aluminum plus incidental impurities.
  • a low density aluminum-lithium base, rapidly solidified alloy suitable for use in the present process has a composition consisting essentially of the formula Al bal Zr a Li b Mg c T d , wherein T is at least one element selected from Cu, Si, Sc, Ti, B, Hf, Cr, Mn, Fe, Co and Ni, "a” ranges from 0.05-0.75 at %, "b” ranges from 9.0-17.75 at %, "c” ranges from 0.45-8.5 at % and “d” ranges from 0.05-13 at %, the balance being aluminum plus incidental impurities.
  • the powder can be composed of rapidly solidified alloy combined with the particles of a reinforcing material present in an amount ranging from 0.1 to 50 percent by volume, the powder having been ball milled to enfold metal matrix material around each of the particles.
  • the metal alloy quenching techniques used to fabricate these alloys generally comprise the step of cooling a melt of the desired composition at a rate of at least 105°C/sec.
  • a particular composition is selected, powders or granules of the requisite elements in the desired portions are melted and homogenized, and the molten alloy is rapidly quenched on a chill surface, such as a rapidly moving metal surface, an impinging gas or liquid.
  • the aluminum alloy When processed by these rapid solidification methods the aluminum alloy is manifest as a ribbon, powder or splat of substantially uniform microstructure and chemical composition.
  • the substantially uniformly structured ribbon, powder or splat may then be pulverized to a particulate for further processing.
  • the rapidly solidified aluminum alloy particulate has properties that make it amenable to direct friction actuated extrusion into wire, as well as numerous powder metallurgy techniques used to fabricate such powders, including vacuum hot degassing and compacting the rapidly solidified powder into near fully dense billets at temperatures where the majority of the adsorbed gases are driven from the powder surfaces and that decomposition of any dispersed phases does not occur.
  • the billets may thereafter be compacted to full density in a blind died extrusion press, forged, or directly extruded into various shapes including profiled extrusions and wire.
  • the substrate may be water or gas cooled, or may be heated directly or indirectly during the processing.
  • the optimum substrate temperature is dependent on the rapidly solidified alloy and the dispersed phases which must be formed during solidification.
  • the rapidly solidified alloy in the form of a wire is arc sprayed to form a coating.
  • the arc spraying step comprises the steps of (i) striking an arc between two strands of said wire to melt the tips thereof; and (ii) atomizing said melt in said arc by impinging a high pressure inert gas thereagainst.
  • Arc spraying involves initially striking an arc between two strands of a conductive metal wire and essentially atomizing any molten metal which forms in the arc by impinging a high pressure inert gas onto the molten wire tips. Since arc spraying is a consumable process, wire is continually fed and the arc and metal source are maintained.
  • the rapidly solidified alloy must be provided as a wire that can range in size from 0.05 cm to 0.25 cm in diameter and more preferably from 0.1 cm to 0.18 cm in diameter, the optimum wire diameter depending on the alloy composition, the voltage across the wires and the feed sizes physically allowed by the arc spraying apparatus.
  • the wire suitable in diameter for arc spraying may be fabricated directly by a friction actuated process or by conventional wire drawing techniques.
  • Arc spraying may be performed for varying lengths of time depending on the thickness of the sprayed preform required. The attractive microstructure and mechanical and physical properties of the rapidly solidified wire are retained. This process may be repeated such that subsequent spraying is done on top of the sprayed coating, and multi-layered coatings may be fabricated.
  • the sprayed coatings require no diffusion treatment as the arc sprayed material retains the attractive microstructure and mechanical and physical properties of the rapidly solidified wire.
  • alloy A a rapidly solidified alloy having a diameter of 0.16 cm and the composition aluminum balance, 4.06 at % iron, 0.70 at % vanadium, 1.51 at % silicon
  • FIG. 1 is a scanning electron photomicrograph of the surface of wire arc sprayed coating composed of rapidly solidified aluminum based iron, vanadium and silicon containing alloy matrix deposited on planar flow cast aluminum based iron, vanadium and silicon containing ribbon. Individual areas or splats corresponding to solidified droplets of sprayed molten alloy were observed. The coating was uniform and contiguous.
  • Fig. 2 is a light photomicrograph of a cross section of a wire arc sprayed preform composed of rapidly solidified aluminum based iron, vanadium and silicon containing alloy matrix deposited on planar flow cast aluminum based iron, vanadium and silicon containing ribbon. Some porosity was observed, however, discrete primary intermetallic compound particles were not seen in the matrix alloy A microstructure indicating that solidification of the arc sprayed wire occurred at a rate rapid enough to suppress the formation of coarse primary dispersoid particles.
  • TEM Transmission electron microscopy
  • Samples were prepared by mechanically grinding off the planar flow cast alloy A substrate and thinning the sample to approximately 25 micrometers in thickness.
  • TEM foils were prepared by conventional electro-polishing techniques in an electrolyte consisting of 80 percent by volume methanol and 20 percent by volume nitric acid. Polished TEM foils were examined in a Philips EM 400T electron microscope.
  • a transmission electron photomicrograph of a wire arc sprayed coating composed of rapidly solidified aluminum based iron, vanadium and silicon containing alloy fabricated by the present invention is shown in Fig. 3.
  • the microstructure of the deposited layer was observed to be composed of fine 50-100 nm diameter Al13(Fe,V)3Si dispersoids uniformly distributed in an aluminum solid solution matrix. This microstructure is very similar to that typically observed in the planar flow cast, rapidly solidified alloy A ribbon as well as in components consolidated from rapidly solidified powder particles using powder metallurgical techniques.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)

Claims (8)

  1. Verfahren zum Herstellen einer sprühmetallisierten Beschichtung aus rasch erstarrtem Aluminium, welches die folgenden Verfahrensschritte umfaßt:
    (a) Formen einer rasch erstarrten Legierung auf Aluminiumbasis zu einem Draht; und
    (b) Lichtbogensprühen des Drahtes auf ein Substrat, auf welchem kein Faserverstärkungsmaterial ist.
  2. Verfahren nach Anspruch 1, bei dem die rasch erstarrte Legierung eine im wesentliche gleichförmige Struktur besitzt.
  3. Verfahren nach Anspruch 1 oder 2, bei dem die rasch erstarrte Legierung auf Aluminiumbasis durch Bilden einer Schmelze aus der Legierung auf Aluminiumbasis und Abschrecken der Schmelze auf einer sich bewegenden Kühlfläche mit einer Geschwindigkeit von wenigstens 10⁵°C/sec. hergestellt wurde.
  4. Verfahren nach Anspruch 1 oder 2, bei dem die rasch erstarrte Legierung auf Aluminiumbasis durch Abschrecken einer Schmelze der Legierung an einem auftreffenden Gas oder einer Flüssigkeit zur Bildung eines Pulvers mit einer Geschwindigkeit von wenigstens 10⁵°C/sec. hergestellt wurde.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem der Verfahrensschritt (b) des Lichtbogensprühens die Verfahrens schritte (I) des Zündens eines Lichtbogens zwischen zwei Strängen des Drahtes zum Schmelzen ihrer Spitzen; und (II) des Zerstäubens der Schmelze in dem Lichtbogen durch Aufprallen eines inerten Gases hohen Druckes gegen dieselbe umfaßt.
  6. Verfahren nach Anspruch 5, bei der Draht einen Durchmesser von 0,05 cm bis 0,25 cm besitzt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem das Beschichten am Substrat zum Reparieren eines Oberflächenfehlers desselben erfolgt.
  8. Verfahren nach Anspruch 8, bei dem das Substrat eine rasch erstarrte Aluminiumlegierung ist.
EP91905287A 1990-01-18 1991-01-15 Bogenspritzen von rasch abgekühlten aluminiumlegierungen Expired - Lifetime EP0513238B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US46707290A 1990-01-18 1990-01-18
US467072 1990-01-18
PCT/US1991/000301 WO1991010760A2 (en) 1990-01-18 1991-01-15 Arc spraying of rapidly solidified aluminum base alloys

Publications (2)

Publication Number Publication Date
EP0513238A1 EP0513238A1 (de) 1992-11-19
EP0513238B1 true EP0513238B1 (de) 1994-06-08

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EP91905287A Expired - Lifetime EP0513238B1 (de) 1990-01-18 1991-01-15 Bogenspritzen von rasch abgekühlten aluminiumlegierungen

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EP (1) EP0513238B1 (de)
JP (1) JPH05502911A (de)
DE (1) DE69102422T2 (de)
WO (1) WO1991010760A2 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2468119C2 (ru) * 2008-04-30 2012-11-27 Улвак, Инк. СПОСОБ ПОЛУЧЕНИЯ РЕАГИРУЮЩЕЙ С ВОДОЙ Al ПЛЕНКИ И СОСТАВЛЯЮЩИЙ ЭЛЕМЕНТ ПЛЕНКООБРАЗУЮЩЕЙ КАМЕРЫ
DE102012200378A1 (de) 2012-01-12 2013-07-18 Federal-Mogul Burscheid Gmbh Kolbenring

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991007157A1 (fr) * 1989-11-10 1991-05-30 Didier Couineau Dispositif pour un lit medical multifonctionnel

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1497398A (en) * 1975-04-15 1978-01-12 British Steel Corp Arc-sprayed protective coatings
GB2015035A (en) * 1978-02-17 1979-09-05 Bicc Ltd Fabrication of Metallic Materials
US4232056A (en) * 1979-04-16 1980-11-04 Union Carbide Corporation Thermospray method for production of aluminum porous boiling surfaces
NO850403L (no) * 1985-02-01 1986-08-04 Ingard Kvernes Aluminiumbasert artikkel med beskyttelsesbelegg og fremgangsmaate til fremstilling derav.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991007157A1 (fr) * 1989-11-10 1991-05-30 Didier Couineau Dispositif pour un lit medical multifonctionnel

Also Published As

Publication number Publication date
WO1991010760A3 (en) 1991-09-05
DE69102422D1 (de) 1994-07-14
WO1991010760A2 (en) 1991-07-25
EP0513238A1 (de) 1992-11-19
JPH05502911A (ja) 1993-05-20
DE69102422T2 (de) 1994-10-27

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