EP0365460A1 - Méthode de préparation de revêtements sur pièces mécaniques par techniques P/M - Google Patents

Méthode de préparation de revêtements sur pièces mécaniques par techniques P/M Download PDF

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Publication number
EP0365460A1
EP0365460A1 EP89500102A EP89500102A EP0365460A1 EP 0365460 A1 EP0365460 A1 EP 0365460A1 EP 89500102 A EP89500102 A EP 89500102A EP 89500102 A EP89500102 A EP 89500102A EP 0365460 A1 EP0365460 A1 EP 0365460A1
Authority
EP
European Patent Office
Prior art keywords
paste
additive
binder
metallic
way
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.)
Granted
Application number
EP89500102A
Other languages
German (de)
English (en)
Other versions
EP0365460B1 (fr
Inventor
Antonio Romero Fernandes
Jesus Acedo Rosas
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.)
Sintermetal SA
Original Assignee
Sintermetal SA
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 Sintermetal SA filed Critical Sintermetal SA
Priority to AT89500102T priority Critical patent/ATE97701T1/de
Publication of EP0365460A1 publication Critical patent/EP0365460A1/fr
Application granted granted Critical
Publication of EP0365460B1 publication Critical patent/EP0365460B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat

Definitions

  • This invention applies to a method to obtain coatings on mechanical parts by P/M (Powder Metallurgy) techniques by means of a paste conventionally applied on the required surface of a substrate to coat.
  • This paste is set up by a binder and metallic and/or ceramic powders.
  • Powder Metallurgy offers unique advantages, as for instance to obtain materials composed by a metallic matrix with non metallic inclusion or selflubricating materials with oil containing prorosity. For this and other reasons, several P/M methods have been developed to obtain coatings on substrate parts.
  • the most common method to apply coatings on substrate parts is the single-axis pressing of two powder layers of different composition which form parts composed by two differente materials after sintering.
  • the limit in this case is the impossibility of filling a die and densifying powders over non flat surfaces, for instance on spherical and conical surfaces.
  • Another application method is the injection moulding of a plastified mixture in a cavity where the substrate part is an insert or part of the mould. This method is especially suitable to large series.
  • a paste like product can be also applied by forming a sheet from which shapes are cut and sticked to the substrate part.
  • coatings can be obtained by any method for paste application, as for instance a brush, smoother, centrifugation etc.
  • the binder ratio varies according to the powder grain size or according to the specific powder surface.
  • the binder may be of wax basis, being formed, for instance, by wax and petrolatum or of polymeric basis, being formed, for instance by polymetylmetacrilate dissolved in toluene or of water based, formed, for instance, by a solution of cellulosic glue or by a combination of various.
  • the materials of the substrate part have only the limitation of being compatible with the temperature and atmosphere used when sintering the coating.
  • the pastes may be also used for manufacturing parts without substrate, i.e. totally formed by the coating material, by means of coating a substrate of the required shape and detachable after sintering, as for instance graphite.
  • Binder forming always comprises a thermal treatment stage for binder removal before sintering the powders. This stage is the most critical of the process, since faults easily appear, as for instance distortion of the part shape of cracks and craters on the surface. To avoid these defaults a very slow warmup and a very long process duration are necessary, resulting in a high cost, and consequently in a necessary limitation of the process to very specific applications.
  • binder composition influences the shaping properties of the paste and the coating behaviour during thermal treatment.
  • Pastes based on wax are very plastic at room temperature, consequently they are easily formable. However, as the temperature increases, its viscosity reduces and, therefore, they tend to flow and distort during the removal stage.
  • Pastes based on cellulose or water solved polysaccharides harden with temperature and retain well the shape during binder removal, but they have poor formability and its viscosity at room temperature is very affected by solvent losses during storage or handling.
  • Thermoplastic polymers with solvents also harden when heating and solvent evaporation, but they soften again when temperature further increases. They are easily conformable, but they are affected by distortion during removal and variable viscosity with solvent losses.
  • the minimum temperature to assure total removal of a organic type binder is 500o C and the most favorable atmosphere is oxidant.
  • the total process with usual heating speeds of 0,5o C per minute has a duration of 9 to 10 hours and results in very rusty parts.
  • This oxidation is used to furnish a cementing skeleton among the particles as the binder is disappearing.
  • it is negative for the sintering stage in major or minor degree, according to the alloy elements, since the oxide reduction requires high temperatures and longer exposure times to reducing atmospheres.
  • the dimensional change in sintering depends upon the oxidation degree and in the case of bronzes very much.
  • coatings of this type need a slow heating speed at the critical binder removal stage.
  • coatings of this type need a slow heating speed at the critical binder removal stage.
  • coatings are very thin (between 10 and 50 microns) or they are conceived for very concret applications, as for instance the coating described in the US license No. 4.596.692 from Morishita and others, or they use a specific and concret binder as mentioned in the US licence No. 4.491.559 from Kennametal Inc. which contains metal particles of tungsten carbide.
  • the method subject to this invention allows coatings which admit a fast temperature increase from the moment of removing the water based vehicle or the polar solvent without outflow nor distortion after the binder removal has been finished.
  • the coating obtained according to the method subject of this invention shows an excellent homogeneity and after debinding a suitable strenght for hadling on trays, pallets and trucks without more care than usual in manufacturing plants.
  • Coating pastes obtained according to this invention allow fast heating from 120o C approximately and without shape distortions, cracks or craters and in a reducing, neutral or oxidant atmosphere and even in vacuum.
  • the coating accordingly the invention allows shorter debinding and is more flexible on alloy elements oxigen affinity than the methods known until now.
  • the method according to the invention is characterized by performing the operation after the conventional paste is obtained, of slowly adding at atmospheric pressure and at a temperature ranging between 10o and 50o C an additive formed by a solution in a polar solvent, preferably of metallic free or complex ions; homogenizing the paste mixture and the additive by mechanical agitation; application of the product obtained in that way on the surface of the substrate part to coat, by any known way; performing of a first binder removal stage, by conventional application of heat until nearly 120o C by a temperature increase of approximately 0,5o C per minute, and a second and last binder removal stage with faster temperature increase. Then the part is ready to be submitted to the known coating sintering operations and finishing.
  • the mentioned additive is closen among those which do not produce precipitates at atmosphere pressure below 80o C. They precipitate between 80 and 100o C and their precipitates are stable below 200o C.
  • the mentioned additive is chosen in such a way that its free metal ions are compatible with the alloy of the metal and/or ceramic powders which form part of the conventional paste to which the additive is added.
  • Spherical bronze 70% Sn, particle size ranging between 250 and 125 microns was mixed with a binder formed by 80% petrolatum and 20% of Hoechst wax tipe C in a proportion of 93% powder and 7% binder.
  • This paste was applied on a cylindrical surface of P/M steel parts 2% copper, density 6.8 g/cc, forming a 1.2 mm thickness.
  • binder cycles were tested in an oven with air atmosphere with different heating speeds. In this way the cycle represented in figure 1, curve a, was determined as the shortest and still free of distortions and cracking.
  • An identical paste to the previous one was prepared but adding 2% of an additive formed by 17% of copper sulphate and 83% of water. Tests to determine the shortest cycle were performed and the cycle represented in figure 1, curve b, was obtained. It is noted that the presence of the additive according to this patent allows the reduction of binder removal practically to half the time.
  • a mixture of atomized iron powder with particle size below 100 microns and atomized nickel powder with particle size below 50 microns in a proportion of 96% iron and 4% nickel was prepared. This mixture was then mixed with a binder formed by 80% petrolatum and 20% Hoechst wax type V in a proportion of 90% to 10%.
  • the obtained paste was conformed as in the previous examples and submitted to removal cycles producting in all cases a coating overflow. To this paste was added 1% of an additive formed by 40% in weight of iron ammonic oxalate and 60% water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pinball Game Machines (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Control Of Vending Devices And Auxiliary Devices For Vending Devices (AREA)
  • Chemically Coating (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
EP89500102A 1988-10-17 1989-10-14 Méthode de préparation de revêtements sur pièces mécaniques par techniques P/M Expired - Lifetime EP0365460B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89500102T ATE97701T1 (de) 1988-10-17 1989-10-14 Herstellungsverfahren von beschichtungen auf mechanischen teilen durch p/m-techniken.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES8803147 1988-10-17
ES8803147A ES2009355A6 (es) 1988-10-17 1988-10-17 Procedimiento para preparar recubrimientos aplicables por tecnicas pulvimetalurgicas en piezas mecanicas.

Publications (2)

Publication Number Publication Date
EP0365460A1 true EP0365460A1 (fr) 1990-04-25
EP0365460B1 EP0365460B1 (fr) 1993-11-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP89500102A Expired - Lifetime EP0365460B1 (fr) 1988-10-17 1989-10-14 Méthode de préparation de revêtements sur pièces mécaniques par techniques P/M

Country Status (4)

Country Link
EP (1) EP0365460B1 (fr)
AT (1) ATE97701T1 (fr)
DE (1) DE68910937T2 (fr)
ES (1) ES2009355A6 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555760A2 (fr) * 1992-02-10 1993-08-18 Hüls Aktiengesellschaft Procédé pour le traitement de la surface d'un corps
EP0597230A2 (fr) * 1992-11-10 1994-05-18 Degussa Aktiengesellschaft Procédé pour la préparation de couches resistantes à l'usure et sans fissures sur des substrats métalliques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1185901B (de) * 1943-02-17 1965-01-21 Dr H C Hans Vogt Verfahren zum Herstellen von Sintermetallueberzuegen
US4371589A (en) * 1976-08-24 1983-02-01 Warner London Inc. Process for depositing protective coating and articles produced
US4626406A (en) * 1985-10-28 1986-12-02 Inco Alloys International, Inc. Activated sintering of metallic powders
DE3628363A1 (de) * 1986-08-21 1988-02-25 Mtu Muenchen Gmbh Verfahren zum herstellen von schutzschichten

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1185901B (de) * 1943-02-17 1965-01-21 Dr H C Hans Vogt Verfahren zum Herstellen von Sintermetallueberzuegen
US4371589A (en) * 1976-08-24 1983-02-01 Warner London Inc. Process for depositing protective coating and articles produced
US4626406A (en) * 1985-10-28 1986-12-02 Inco Alloys International, Inc. Activated sintering of metallic powders
DE3628363A1 (de) * 1986-08-21 1988-02-25 Mtu Muenchen Gmbh Verfahren zum herstellen von schutzschichten

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555760A2 (fr) * 1992-02-10 1993-08-18 Hüls Aktiengesellschaft Procédé pour le traitement de la surface d'un corps
US5318799A (en) * 1992-02-10 1994-06-07 Huls Aktiengesellschaft Process for tempering the surface of a body
EP0555760A3 (en) * 1992-02-10 1994-09-14 Huels Chemische Werke Ag Method for tempering the surface of a body
EP0597230A2 (fr) * 1992-11-10 1994-05-18 Degussa Aktiengesellschaft Procédé pour la préparation de couches resistantes à l'usure et sans fissures sur des substrats métalliques
EP0597230A3 (fr) * 1992-11-10 1995-03-01 Degussa Procédé pour la préparation d'une couche de protection d'usure sur substrats métalliques.

Also Published As

Publication number Publication date
DE68910937D1 (de) 1994-01-05
EP0365460B1 (fr) 1993-11-24
ES2009355A6 (es) 1989-09-16
DE68910937T2 (de) 1994-06-01
ATE97701T1 (de) 1993-12-15

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