EP0024984B1 - Procédé de fabrication de pièces en alliage à base de titane par métallurgie des poudres - Google Patents

Procédé de fabrication de pièces en alliage à base de titane par métallurgie des poudres Download PDF

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Publication number
EP0024984B1
EP0024984B1 EP80401206A EP80401206A EP0024984B1 EP 0024984 B1 EP0024984 B1 EP 0024984B1 EP 80401206 A EP80401206 A EP 80401206A EP 80401206 A EP80401206 A EP 80401206A EP 0024984 B1 EP0024984 B1 EP 0024984B1
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EP
European Patent Office
Prior art keywords
powder
titanium
process according
titanium alloy
temperature
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
Application number
EP80401206A
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German (de)
English (en)
French (fr)
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EP0024984A1 (fr
Inventor
Pierre Blum
Jacques Devillard
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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Publication of EP0024984A1 publication Critical patent/EP0024984A1/fr
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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal

Definitions

  • the present invention relates to a process for manufacturing titanium-based alloy parts by powder metallurgy.
  • titanium exhibits an allotropic transformation at a temperature of 882 ° C; this temperature thus defines the stability domain of two phases: phase a of compact hexagonal structure which is stable below 882 ° C and the centered cubic ⁇ phase which appears above 882 ° C.
  • the methods for manufacturing titanium parts using sintering techniques generally consist in carrying out isostatic hot sintering under a pressure of 1 to 1.5 ⁇ 10 2 MPa, for 4 h, ie at a temperature of approximately 950 ° C. when one wants to maintain phase a in the case of pure titanium or when one wants to obtain the structure ⁇ + ⁇ in the case of titanium alloys, that is to say at a temperature of approximately 1050 ° C. when one wants to be located in the temperature range which corresponds to the ⁇ phase of pure titanium or its alloys.
  • parts made of titanium or of titanium alloys can be produced by conventional sintering processes, at pressures below 50 MPa and at temperatures below 900 ° C., starting from titanium powders or titanium alloys. , wrought and ground, but in this case the parts obtained are fragile due to significant intergranular oxygen contamination.
  • these sintering techniques do not allow parts of complex shape to be obtained directly, such as turbine blades with integrated blades, in particular having a "collar” structure, that is to say a heterogeneous structure characterized by the presence of large grains surrounded and welded together by finely crystallized grains.
  • the present invention specifically relates to a process for manufacturing titanium-based alloy parts by powder metallurgy, which overcomes the drawbacks of the aforementioned processes and which also makes it possible to obtain titanium alloy parts having the structure "in necklace ”.
  • the method as characterized above advantageously takes advantage of the fact that by locally modifying by coating with a suitable material such as copper, the surface composition of the particles of titanium powder or of titanium alloy, it is possible to during the sintering, an interstitial liquid phase appears on the surface of the powder grains and thus facilitate local deformations, which makes it possible to carry out the sintering at temperatures and pressures lower than those usually necessary for sintering powders having a particle size from 100 to 1000 ⁇ m.
  • the coating material which, in the case of copper, generally represents from 1 to 5% by weight, affects only the cortical zone of the grains without profoundly modifying the composition of the alloy . Also, during heating, the compression exerted during the temperature rise, that is to say when the coating material is still present on the surface of the grains, makes it possible to obtain a local deformation of the latter and their densification.
  • the coating material can be constituted by a titanium compound fusible at temperature T 1 , or preferably, by a material comprising an element capable of combining with the titanium of the powder to form a compound, by example a eutectic, fuse at temperature T 1 .
  • the coating may consist of this element or also of a compound or an alloy of this element.
  • the element used to form the coating is a betagen element such as iron, copper or nickel.
  • a betagen element such as iron, copper or nickel.
  • copper is used.
  • the sintering kinetics can be improved by locally modifying the phases of the alloy during densification.
  • titanium alloys of the TA 6 V type that is to say alloys comprising 90% of titanium, 6% of aluminum and 4% of vanadium, without addition of a betagenic element such as copper
  • a betagenic element such as copper
  • this two-phase structure ⁇ + ⁇ has a significant resistance to deformation, which does not promote densification.
  • a betagen element such as copper
  • the betagen element has a tendency to diffuse towards the center of the grains. Also, to obtain locally on the surface of the grains this single-phase structure ⁇ which promotes sintering, it is advantageous to carry out the heating and the application of the pressure quickly enough to avoid excessive diffusion. important of the betagen element and locally obtain a sufficient concentration of this element.
  • the powder is heated to the sintering temperature at a vi tesse of about 500 ° C / h to 1000 ° C / h.
  • the method of the invention has the advantage of leading to the production of titanium alloy parts having improved mechanical properties. Indeed, the fact of carrying out sintering in.
  • the fineness of the precipitation a depends in particular on the speed at which the parts obtained are cooled.
  • the powder of titanium or of titanium alloy having a particle size of 100 to 1000 ⁇ m, is prepared by the technique of fusion centrifugation.
  • this technique consists in bringing the end surface of a cylindrical ingot of titanium or titanium alloy to a melting temperature, driven in rotation about its axis; thus, under the action of centrifugal force, the titanium or the molten titanium alloy is ejected from the end surface of the ingot in the form of liquid droplets which, on cooling, are transformed by solidification into spherical particles having for most with a diameter between 100 and 1000 ⁇ m.
  • a titanium powder is used having particles with a diameter between 100 and 600 ⁇ m.
  • this melting-centrifugation technique when used to prepare the starting powder, it is preferable to subject said powder to a surface treatment before depositing said coating material on the latter.
  • This surface treatment can consist of a degreasing carried out for example by immersing the powder in pure trichlorethylene and then rinsing the latter with methanol.
  • this surface treatment is preferably a treatment to remove the surface layer rich in alphagene element, possibly present on certain particles.
  • the surface layer rich in aluminum powder particles by immersing these particles in sodium carbonate solution maintained at a temperature of about 60-70 ° C, and rinsing. successively the particles with water, acetic acid and water.
  • the coating is deposited on the titanium or titanium alloy powder by conventional techniques.
  • the coating consists of an element such as iron, copper or nickel or of compounds such as nickel-phosphorus or iron-phosphorus
  • chemical deposition techniques are used in particular.
  • the coating material is copper
  • the deposit by electrochemical displacement of copper is advantageously carried out from a solution, for example using a solution consisting of a mixture of a first solution containing copper sulphate, methanol and the aldehyde formic and of a second solution containing soda and double tartrate of potassium and sodium.
  • the coating operation is carried out at room temperature to avoid oxidation of the titanium.
  • the coating has a thickness of a few microns, for example from 1 to 5 ⁇ m.
  • the coated powder is introduced into a mold, then it is subjected to uniaxial compression while maintaining the mold at a temperature between T 1 and T.
  • the pressure exerted on the powder is between 10 and 30 MPa, and the duration of this compression is such that a complete densification of the powder is obtained.
  • a duration greater than 1 hour is requested, a duration of approximately 2 hours is sufficient to achieve this result.
  • This example relates to the preparation of a titanium alloy part from a powder of titanium alloy TA 6 V: alloy which comprises 90% of titanium, 6% of aluminum and 4% of vanadium.
  • Spherical particles having a diameter between 315 and 630 ⁇ m are prepared by the fusion-centrifugation technique from an ingot of this alloy.
  • the spherical particles thus obtained are subjected to a preliminary treatment with a view to removing the aluminum-rich surface layer from the powder particles.
  • the particles are immersed in a solution of 50 g per liter of sodium carbonate, maintained at a temperature of approximately 60-70 ° C, operating in fractions of 150 g of particles for two liters of solution; after immersion, the particles are rinsed with water, then the sodium carbonate is completely eliminated by immersing the particles in 2 liters of 5% acetic acid, and then rinsed twice with water.
  • 150 g of the powder particles are immersed in two liters of solution at room temperature, and the particles are kept in the solution until this solution is completely discolored, that is to say until when the reduction of the copper solution is complete. This operation lasts 3 to 4 days and the particles immersed in the solution are shaken from time to time to obtain a uniform deposit. The particles are then rinsed with water and etanol and dried at 60 ° C.
  • the particles thus coated comprise approximately -1.7% by weight, of copper and the thickness of the coating of each particle is of the order of 1 to 5 ⁇ m.
  • the coated particles are then introduced into an alumina mold obtained by hot spraying or with lost wax.
  • This mold has at its upper part a special cylindrical weight which makes it possible to add to the upper part of the mold an additional quantity of particles.
  • the mold is then placed inside a heating device by interposing between the walls of the mold and the device a refractory metal powder having a low sinterability at the temperature chosen for sintering.
  • the mold containing the powder is then brought to a temperature of approximately 950 ° C. and the mold is then maintained at this temperature under a maximum uniaxial pressure of 30 MPa, for a period of approximately two hours, which ensures complete densification of the powder.
  • the compression of the powder during sintering is carried out by means of a piston of refractory material which takes place at the top of the mold and can slide in the cylindrical counterweight in order to load inside the mold the additional quantity of powder initially placed in this feeder thus helping to eliminate the porosity in the sintered part.
  • the parts obtained After demolding, the parts obtained have a “collar” structure such as that shown in the drawing which corresponds to the presence of large grains (1) having the structure ( ⁇ + ⁇ ) surrounded by a phase (2) of structure exp with fine precipitation a.
  • oligocyclic fatigue resistance tests show that the titanium alloys sintered by uniaxial compression at 950 ° C between 10 and 30 MPa have properties similar to those of forged cast alloys. For example, after repeated stresses at 1Hz between 8 to 80 MPa at 20 ° C, the lifetime at break is 10 5 cycles for a TA e V sintered alloy with addition of copper at 950 ° C / 30 MPa and 10 4 cycles only for the same TA e V without addition, sintered by isostatic compression at 950 ° C / 10 2 MPa.

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  • Powder Metallurgy (AREA)
EP80401206A 1979-08-27 1980-08-22 Procédé de fabrication de pièces en alliage à base de titane par métallurgie des poudres Expired EP0024984B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7921441A FR2464112A1 (fr) 1979-08-27 1979-08-27 Procede de fabrication de pieces en alliage a base de titane par metallurgie des poudres
FR7921441 1979-08-27

Publications (2)

Publication Number Publication Date
EP0024984A1 EP0024984A1 (fr) 1981-03-11
EP0024984B1 true EP0024984B1 (fr) 1984-12-19

Family

ID=9229093

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80401206A Expired EP0024984B1 (fr) 1979-08-27 1980-08-22 Procédé de fabrication de pièces en alliage à base de titane par métallurgie des poudres

Country Status (4)

Country Link
US (1) US4381942A (oth)
EP (1) EP0024984B1 (oth)
DE (1) DE3069828D1 (oth)
FR (1) FR2464112A1 (oth)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4714587A (en) * 1987-02-11 1987-12-22 The United States Of America As Represented By The Secretary Of The Air Force Method for producing very fine microstructures in titanium alloy powder compacts
US4808249A (en) * 1988-05-06 1989-02-28 The United States Of America As Represented By The Secretary Of The Air Force Method for making an integral titanium alloy article having at least two distinct microstructural regions
US4851055A (en) * 1988-05-06 1989-07-25 The United States Of America As Represented By The Secretary Of The Air Force Method of making titanium alloy articles having distinct microstructural regions corresponding to high creep and fatigue resistance
US5234487A (en) * 1991-04-15 1993-08-10 Tosoh Smd, Inc. Method of producing tungsten-titanium sputter targets and targets produced thereby
JP2849710B2 (ja) * 1996-08-27 1999-01-27 工業技術院長 チタン合金の粉末成形法
RU2151027C1 (ru) * 1998-12-07 2000-06-20 Открытое акционерное общество "Всероссийский институт легких сплавов"(ОАО "ВИЛС") Способ изготовления центробежного колеса с лопатками
US6589310B1 (en) * 2000-05-16 2003-07-08 Brush Wellman Inc. High conductivity copper/refractory metal composites and method for making same
US6599466B1 (en) 2002-01-16 2003-07-29 Adma Products, Inc. Manufacture of lightweight metal matrix composites with controlled structure
EP1786943A4 (en) * 2004-06-10 2008-02-13 Howmet Corp THERMALLY PROCESSED MOLD PRODUCT BASED ON TITANIUM ALLOY QUASI BETA
GB0413135D0 (en) * 2004-06-12 2004-07-14 Rolls Royce Plc A method of manufacturing a component by consolidating a metal powder
US7833472B2 (en) * 2005-06-01 2010-11-16 General Electric Company Article prepared by depositing an alloying element on powder particles, and making the article from the particles
US8028812B2 (en) * 2007-07-23 2011-10-04 Gerald Martino Brake rotors for vehicles
EP2578336A4 (en) * 2010-05-31 2014-05-14 Toho Titanium Co Ltd TITANIUM ALLOY COMPOUND POWDER IN COMBINATION WITH A COPPER POWDER, CHROMIUM POWDER OR IRON POWDER, TITANIUM ALLOY MATERIAL WITH SAID POWDER AS A RAW MATERIAL AND METHOD OF MANUFACTURING THEREOF
CN103418785B (zh) * 2012-05-23 2016-05-25 北京航空航天大学 一种耐腐蚀钛/氧化钌复合粉体的制备方法
CN110937884A (zh) * 2019-12-05 2020-03-31 中国航发北京航空材料研究院 一种钛基合金粉末热等静压包套内腔隔离层的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379522A (en) * 1966-06-20 1968-04-23 Titanium Metals Corp Dispersoid titanium and titaniumbase alloys
US3341325A (en) * 1966-12-09 1967-09-12 Crucible Steel Co America Method for producing alloy-steel articles
CA989649A (en) * 1972-05-01 1976-05-25 Edward L. Thellmann Method of producing sintered titanium base articles
US3963485A (en) * 1972-05-01 1976-06-15 Gould Inc. Method of producing sintered titanium base articles
US3953205A (en) * 1973-06-06 1976-04-27 United Technologies Corporation Production of homogeneous alloy articles from superplastic alloy particles
CA1042735A (en) * 1974-07-12 1978-11-21 Sherritt Gordon Mines Limited Copper coated composite powders and method of production thereof
DE2448738C3 (de) * 1974-10-12 1978-08-03 W.C. Heraeus Gmbh, 6450 Hanau Metallischer Dünnschicht-Verbundwerkstoff
GB1444530A (en) * 1975-06-11 1976-08-04 Council Scient Ind Res Production of composite powders

Also Published As

Publication number Publication date
US4381942A (en) 1983-05-03
FR2464112A1 (fr) 1981-03-06
DE3069828D1 (en) 1985-01-31
EP0024984A1 (fr) 1981-03-11
FR2464112B1 (oth) 1983-01-14

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