EP0525325B1 - Procédé pour la préparation d'articles frittés denses - Google Patents

Procédé pour la préparation d'articles frittés denses Download PDF

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Publication number
EP0525325B1
EP0525325B1 EP92108827A EP92108827A EP0525325B1 EP 0525325 B1 EP0525325 B1 EP 0525325B1 EP 92108827 A EP92108827 A EP 92108827A EP 92108827 A EP92108827 A EP 92108827A EP 0525325 B1 EP0525325 B1 EP 0525325B1
Authority
EP
European Patent Office
Prior art keywords
binder
mould
green body
process according
mixture
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
EP92108827A
Other languages
German (de)
English (en)
Other versions
EP0525325A1 (fr
Inventor
Arie Dr. Ruder
Hans Peter Dr. Buchkremer
Rudolf Prof. Hecker
Detlev Dr. Stöver
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
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 Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP0525325A1 publication Critical patent/EP0525325A1/fr
Application granted granted Critical
Publication of EP0525325B1 publication Critical patent/EP0525325B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C24/00—Coating starting from inorganic powder
    • 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
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/26—Producing shaped prefabricated articles from the material by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor ; specially for manufacturing articles starting from a ceramic slip; Moulds therefor
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a method for producing porous or dense sintered workpieces from metal, a metal alloy or from ceramic materials, in which a green body is first formed from a mixture of the metal present as a powder, the metal alloy or the ceramic material and a binder debindered, sintered and the sintered body is compressed, if necessary, by hot isostatic pressing (HIP process).
  • HIP process hot isostatic pressing
  • a viscous mixture of powder and binder has previously been produced, and this mixture has been pressed into the predetermined shape under a pressure of a few hundred bars. Quite apart from the fact that in this procedure narrow cavities of the form to be filled can be inaccessible to the viscous mass, it also shows that during the subsequent binder removal or sintering process to which the viscous mass filled under pressure is subjected to the binder does not completely escape from the mass or the green body, so that undesired residues can remain in the workpiece.
  • the green body is removed from the mold after drying and is thus ready for further processing.
  • the casting compound is expediently produced in a separate vessel, after which it is poured into the mold through a sprue or a funnel.
  • Adequate filling of the form is achieved by gravitation and can be accompanied by targeted vibration of the form. External vibrations and / or rotations of the shape by hand or mechanically are useful for this.
  • the solvent can be removed from the mass filled into the mold under normal pressure and at room temperature. However, this drying process can also take place at elevated temperature and / or under a slight negative pressure or can be accelerated thereby.
  • the filling can be built up in several steps using different materials.
  • a procedure which is expedient for this is that mixtures formed from different materials are poured into the mold one after the other, so that the poured-in mass and thus also the green body formed thereafter consists of layers of different composition arranged one above the other.
  • a second is poured onto the first. This process is complete Filling of the mold continued, so that a layer system green body composed of different materials with a graduated structure, for example with regard to material, porosity, grain / particle size distribution, arises.
  • Another variant of the method is that the mixture is poured in via / or around a green body previously introduced into the mold or an already finished workpiece.
  • an inner or outer coating (s) or covering of a solid part that has already been produced can be produced, the casting compound being poured into the cavities and the surface to be coated after being introduced into a suitable mold.
  • the casting compound can also be applied with a brush or sprayed on and then further processed with good success.
  • Composite materials or graded materials can be produced by introducing the insert component into the premix or by introducing them into the mold before casting.
  • the general rule is that the proportion of the binder in the mixture should be such that it is sufficient to solidify the mass to form a manageable green body.
  • the amount of binder required for this can easily be determined by means of a few preliminary tests; it is in the range between 2 and 5% by volume.
  • green bodies with a binder content of 0.02 (2.00% by volume) with particle sizes of approx. 20 ⁇ m have considerable strength. However, when using larger particles with the same binder content, the strength is still sufficient to ensure safe handling of the green bodies.
  • the binder content can be varied by controlled addition or evaporation of the liquid, volatile solvent component (carrier). In practice, the maximum volume fraction is limited by the solubility limit of the binder in the solvent or by the relative natural porosity, which is approximately 26% for ideally packed spherical particles.
  • the binder condenses as a thin film on the powder particles during the removal (evaporation) of the solvent (carrier) and a rapid, continuous removal of the solvent (carrier) through the free particle spaces takes place.
  • the final strength of the green body is achieved after the solvent has been completely removed (Carrier) and after the binder has solidified at room temperature (possibly also at elevated temperature) as a solid network with connecting bridges between adjacent powder particles.
  • the green body After the green body has been formed, it is subjected to a thermally activated debinding and sintering treatment.
  • the green body is heated to remove the binder.
  • This debinding process is not limited to a specific time-temperature program (profiles, sequences, cycles), although some sub-steps are required to enable complete binder removal.
  • a typical procedure is for the green body to be heated to a temperature in the range from 280 to 420 ° C. at a rate of 3-10 ° C./min and, depending on the size of the body, to be kept at this temperature until the binder is removed.
  • the body is then heated to sintering temperature up to a rate of> 10 ° C / min.
  • High temperatures promote the rapid splitting of the binder into a vapor that sublimes outside the green body either in the atmosphere or pumped out by a vacuum system. The splitting and removal takes until the binder has burned out.
  • Materials such as superalloys, stainless steel, titanium alloys and aluminum alloys, iron materials, ceramic powders such as zirconium oxide, chromium oxide, lathane oxide, perovskite, aluminum oxide and silicon oxide can be used as the material for the workpieces to be produced be provided.
  • Wax, shellac, PMMA and alcohol, trichlorethylene, toluene (toluene) are mentioned as binders.
  • the sintering of the green bodies produced by the process according to the invention was carried out using specific, known schemes for each material. Density measurements showed that the sinterability of the materials is not affected by the process itself.
  • the end product can be sintered to a closed porosity. The sintered parts with closed porosity can therefore be compacted containerless up to the theoretical density by HIP.
  • Chemical analyzes of end products produced by the method according to the invention showed no increase in the concentration of contaminants related to the chemical composition of the binder, such as oxygen, carbon, nitrogen and hydrogen.
  • the overall composition was within the nominal concentrations of the starting products.
  • the materials were mixed in a tumble mixer for 2 hours.
  • the mixture was poured into a two-part stable Teflon mold, which consisted of two eccentrically arranged cylinders (20 and 10 mm ⁇ and 10 or 15 mm in length).
  • the product reached high strength after 14 hours of drying time in the air or after 4 hours of drying in a desiccator, so that handling is easy.
  • the total process time was 12.4 hours.
  • the density of the sintered part was 96% of the theoretical density (Archimedean method) of the material and the chem. Analysis showed no deviation from the nominal composition of this material.
  • the mixture was poured into a four-part stable Teflon mold, with the dimensions 80x20x1 mm. After 2 hours of drying in air, the product reached high strength, so that handling is possible.
  • the total process time was 4.27 h.
  • the density of the sintered part was 92.5% of the theoretical density of Ti6A14V and the chem. Analysis showed within the measurement accuracy the same composition as that of the starting powder.
  • the mixture was applied to the substrate with a brush.
  • the 50 ⁇ m thick layer produced in this way was then air-dried for half an hour.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Ceramic Products (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Claims (10)

  1. Procédé de fabrication d'éprouvettes frittées, poreuses ou compactes, à base de métal, d'un alliage métallique ou de matières céramiques, dans lequel on moule d'abord un corps vert à partir d'un mélange du métal, de l'alliage de métal ou de la matière céramique, à l'état pulvérulent, et d'un liant, et ensuite, on débarrasse ce corps vert du liant et on le fritte, caractérisé en ce qu'on forme d'abord le mélange de poudre, de liant, dont la proportion dans le mélange est dosée d'une manière telle qu'elle suffit à la solidification du mélange de poudre et de liant pour former le corps vert, et qui représente 2 à 5 % en volume du mélange, et d'un solvant pour le liant, les quantités relatives de liant et de solvant étant dosées de façon que le liant soit complètement dissous dans le solvant, et, par ailleurs, les quantités de poudre, de liant et de solvant étant dosées de manière que la masse ainsi formée (masse à couler) destinée à être coulée dans le moule permettre un remplissage libre du moule (par gravitation) ou au moins un remplissage contraint du moule à une pression légèrement supérieure à la pression atmosphérique, après quoi cette masse est coulée dans le moule prédéfini formé d'un matériau non poreux, appliquée ou vaporisée et ensuite séchée, le solvant étant éliminé par évaporation, et le liant subsistant solidifiant le mélange de poudre et de liant, de sorte qu'un corps vert est formé.
  2. Procédé selon la revendication 1, caractérisé en ce que la masse est introduite dans le moule pendant que celui-ci est soumis à des secousses de manière appropriée.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la masse coulée située dans le moule est soumise à un vide pendant le séchage.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la masse coulée située dans le moule est maintenue à une température constante pendant le séchage.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que des mélanges formés à partir de matériaux différents sont coulés successivement dans le moule, de sorte que la masse coulée, et donc aussi le corps vert qui sera formé ultérieurement, est formée de couches empilées ayant des compositions différentes.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que le mélange est verse sur ou autour d'un corps vert préalablement introduit dans le moule ou d'une pièce à usiner déjà finie.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le corps vert est chauffé à une température comprise entre 280 et 420°C, à une vitesse de 3 à 10°C/minute, et, selon la dimension du corps formé, il est maintenu à cette température jusqu'à l'élimination du liant.
  8. Procédé selon la revendication 7, caractérisé en ce qu'ensuite, le corps vert est chauffé à une température de frittage à une vitesse > 10°C/minute.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce qu'on effectue le chauffage dans des conditions de vide poussé ou de vide très poussé.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que le corps fritté est compacté par compression isostatique à chaud (procédé HIP).
EP92108827A 1991-06-22 1992-05-26 Procédé pour la préparation d'articles frittés denses Expired - Lifetime EP0525325B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4120706A DE4120706C2 (de) 1991-06-22 1991-06-22 Verfahren zur Herstellung poröser oder dichter Sinterwerkstücke
DE4120706 1991-06-22

Publications (2)

Publication Number Publication Date
EP0525325A1 EP0525325A1 (fr) 1993-02-03
EP0525325B1 true EP0525325B1 (fr) 1996-03-06

Family

ID=6434559

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92108827A Expired - Lifetime EP0525325B1 (fr) 1991-06-22 1992-05-26 Procédé pour la préparation d'articles frittés denses

Country Status (3)

Country Link
EP (1) EP0525325B1 (fr)
AT (1) ATE134922T1 (fr)
DE (2) DE4120706C2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19963698A1 (de) * 1999-12-29 2001-07-12 Gkn Sinter Metals Gmbh Dünne poröse Schicht mit offener Porosität und Verfahren zu ihrer Herstellung

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19535444C2 (de) * 1995-01-20 1999-07-22 Scholz Paul Friedrich Dr Ing Verfahren zum pulvermetallurgischen Herstellen von Gegenständen sowie auf diese Weise hergestellte Gegenstände
DE19528031A1 (de) * 1995-07-31 1997-02-06 Krebsoege Sinterholding Gmbh Flachdichtung aus Metall
DE19716595C1 (de) * 1997-04-21 1998-09-03 Forschungszentrum Juelich Gmbh Dünne, feinporige, metallische Innenschicht eines Rohres
DE19717460A1 (de) * 1997-04-25 1998-10-29 Karlsruhe Forschzent Verfahren zum Herstellen poröser oder dichter Keramik, insbesondere supraleitende Keramik
DE19722004A1 (de) * 1997-05-27 1998-12-03 Fraunhofer Ges Forschung Verfahren zur Herstellung eines Metall- oder Keramikwerkstücks
DE19748742C1 (de) * 1997-11-05 1999-07-01 Karlsruhe Forschzent Verfahren zur Herstellung von schmelztexturierten Volumenproben auf der Basis der Hochtemperatursupraleiter Nd¶1¶Ba¶2¶Cu¶3¶O¶7¶(Nd-123)
DE19801440C2 (de) * 1998-01-16 2001-08-16 Forschungszentrum Juelich Gmbh Kostengünstiges Verfahren zur Herstellung einer Elektroden-Elektrolyt-Einheit
KR20010041043A (ko) 1998-04-17 2001-05-15 게카엔 진터 메탈스 게엠베하 다공의 소결 금속판 제조 방법
US5989493A (en) * 1998-08-28 1999-11-23 Alliedsignal Inc. Net shape hastelloy X made by metal injection molding using an aqueous binder
DE19841573C2 (de) * 1998-09-11 2000-11-09 Karlsruhe Forschzent Verfahren zum Herstellen von mechanisch festen, elektrisch leitenden Verbindungen zwischen Hochtemperatursupraleitern (HTSL)
DE19936734C1 (de) * 1999-08-06 2001-02-15 Fraunhofer Ges Forschung Verfahren zur Herstellung eines Metall- oder Keramikwerkstücks
DE10027551B4 (de) * 2000-06-02 2005-09-29 Hesse, Thomas, Dipl.-Ing. Verfahren zur Herstellung von Formkörpern aus einer plastisch verarbeitbaren Formmasse auf der Basis von Bienenwachs, Lösungsmittel und sinterfähigen Pulvern und eine Verwendung der Formmasse
DE102005024623B4 (de) * 2005-05-30 2007-08-23 Beru Ag Verfahren zum Herstellen eines keramischen Glühstiftes für eine Glühkerze

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US4491559A (en) * 1979-12-31 1985-01-01 Kennametal Inc. Flowable composition adapted for sintering and method of making
US4554130A (en) * 1984-10-01 1985-11-19 Cdp, Ltd. Consolidation of a part from separate metallic components
US5006493A (en) * 1986-03-31 1991-04-09 The Dow Chemical Company Novel ceramic binder comprising poly(ethyloxazoline)
GB8621712D0 (en) * 1986-09-09 1986-10-15 Mixalloy Ltd Flat products
US4882110A (en) * 1987-01-27 1989-11-21 Air Products And Chemicals, Inc. CO2 copolymer binder for forming ceramic bodies and a shaping process using the same
WO1988007901A1 (fr) * 1987-04-09 1988-10-20 Ceramic Systems Corporation Moulage et coulage de precision utilisant des systemes fortement charges
DE4037258A1 (de) * 1989-11-24 1991-05-29 Asea Brown Boveri Verfahren zur herstellung eines komplizierten bauteils ausgehend von pulvern

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19963698A1 (de) * 1999-12-29 2001-07-12 Gkn Sinter Metals Gmbh Dünne poröse Schicht mit offener Porosität und Verfahren zu ihrer Herstellung
US7306753B2 (en) 1999-12-29 2007-12-11 Gkn Sinter Metals Gmbh Method of making a thin porous layer

Also Published As

Publication number Publication date
DE4120706C2 (de) 1994-10-13
DE59205549D1 (de) 1996-04-11
EP0525325A1 (fr) 1993-02-03
ATE134922T1 (de) 1996-03-15
DE4120706A1 (de) 1992-12-24

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