EP3003607B1 - Coulage en barbotine et sous pression de corps en métal réfractaire - Google Patents

Coulage en barbotine et sous pression de corps en métal réfractaire Download PDF

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Publication number
EP3003607B1
EP3003607B1 EP14806817.4A EP14806817A EP3003607B1 EP 3003607 B1 EP3003607 B1 EP 3003607B1 EP 14806817 A EP14806817 A EP 14806817A EP 3003607 B1 EP3003607 B1 EP 3003607B1
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EP
European Patent Office
Prior art keywords
approximately
powder
slip
refractory metals
mold
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EP14806817.4A
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German (de)
English (en)
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EP3003607A1 (fr
EP3003607A4 (fr
Inventor
Michael T. Stawovy
Maria Bozena WINNICKA
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Materion Newton Inc
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HC Starck Inc
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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
    • 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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution

Definitions

  • the present invention relates to slip casting with or without applied pressure, in particular to such slip or pressure casting of metal bodies.
  • Powder metallurgy techniques have been utilized in the fabrication of various types of finished metallic parts.
  • a flexible bag may be filled with metal powder and placed in a mold that approximates the final pressed shape and dimensions of the part.
  • the bag and mold are sealed, and cold isostatic pressing is utilized to form a pressed "green body" of the metal powder.
  • the green body may then be sintered in order to increase its density and subsequently machined to its final desired dimensions. While such powder metallurgy techniques are useful for particular applications, their utility is limited when the final parts have more complicated shapes. The more complicated the shape, the more excess powder must be placed in the bag and mold in order to prevent cracking during pressing.
  • the ratio of the weight of the sintered part to the new weight of the part in its final machined form may exceed 4:1, resulting in high machining, materials, and labor costs.
  • parts fabricated with such powder metallurgy techniques rarely achieve final sintered densities that exceed 94% of their theoretical densities.
  • Such parts may also have disadvantageously large grain sizes, e.g., greater than 40 microns.
  • slip casting Another powder metallurgy technique utilized for the production of complex shapes is slip casting, in which a "slip,” i.e., a suspension of fine metal powder in water, dispersing agents (for the stabilization of the powder against colloidal forces), one or more solvents (for control of slip viscosity and facilitating casting), and a binder for strengthening the cast shape are placed in a mold, the liquids are drawn away, and the resulting green body is sintered for densification and strength.
  • slip casting typically requires the use of a deflocculant or suspension aid to prevent the settling and agglomeration of the powder and to maintain a desirable slip viscosity.
  • Such deflocculants include, e.g., alcohols, other organic liquids, or alginates (i.e., ammonium and sodium salts of alginic acids).
  • alginates i.e., ammonium and sodium salts of alginic acids.
  • the use of such additives increases the cost, complexity, environmental impact and materials-handling requirements for a slip-casting process.
  • Document US3578478A describes a method of producing a shaped part in which a tungsten powder having discrete particle sizes is suspended in water for slip casting without separation of the particles.
  • metal parts are produced utilizing slip or pressure casting of metal powders having specific powder-size distributions that obviate the need for the use of added organic or inorganic suspension aids during casting.
  • the metal powders are suspended in a liquid that includes or consists essentially of water, e.g., deionized (DI) water, and poured into a mold for casting.
  • DI deionized
  • the liquid does not include any flocculating or deflocculating additives.
  • preferred embodiments utilize powders that consist essentially only of one or more metals and do not contain solid or powder agents such as binders or plasticizers.
  • the mold is porous (and may include or consist essentially of, e.g., gypsum), and the liquid in which the powder is suspended is drawn into the mold via capillary action.
  • the resulting green body is sintered to increase its density and final machining (if desired and/or necessary) is performed to shape the final part.
  • the metal powder may include or consist essentially of, e.g., one or more refractory metals.
  • the metal powder may include or consist essentially of tungsten (W), tantalum (Ta), niobium (Nb), zirconium (Zr), molybdenum (Mo), and/or titanium (Ti).
  • the slip does not exhibit dilatant or thixotropic flow, for example, when the slip is being poured into the mold; rather, the viscosity of the slip is preferably approximately constant as a function of the shear rate (i.e., with changes in shear rate) applied to the slip.
  • the slip and/or mold is not agitated (e.g., stirred, shaken, rotated, and/or vibrated) to promote mixing or settling of the metal powder within the slip; rather, the engineered particle size distribution of the powder particles within the slip provides resistance to powder settling within the slip before and during casting (i.e., the slip is colloidally stable rather than, e.g., colloidally unstable or even metastable, in preferred embodiments) while also facilitating low-resistance pourability of the slip itself in the absence of agitation.
  • no electrical voltage or current is applied to the mold or slip during the casting process to influence settling behavior.
  • the green bodies and molded parts are generally not functionally or mechanically graded, i.e., the parts exhibit few if any gradients in composition, microstructure, mechanical properties, porosity, residual stress, grain size, particle size, etc.
  • the mechanical and functional properties of bodies and parts fabricated in accordance with embodiments of the present invention e.g., grain size of unsintered or sintered parts, and/or powder particle size of slips and/or green bodies
  • embodiments of the invention feature slips that are substantially free of acidic or basic pH-modifying agents; such agents may have deleterious effects (e.g., corrosion and/or chemical reaction) on the metal powder particles utilized in preferred embodiments and are generally not necessary for engineering colloidal stability of slips described herein.
  • body As utilized herein, the terms “body,” “part,” and “article” refer to bulk three-dimensional objects (as opposed to mere grains of powder) with shapes as simple as a slab but also more complex shapes such as crucibles and other volumes having convexity and/or concavity.
  • the final shape (not considering any process-related shrinkage) is typically formed by casting (as opposed to bulk compression) and sintering, which may be followed by machining.
  • embodiments of the invention feature a method of producing a shaped part.
  • a powder is suspended in a liquid consisting essentially of water, thereby forming a slip.
  • the powder has a particle-size distribution d10 between 0.15 micron and 0.5 micron, d50 between 0.6 micron and 1 micron, and d90 between 2.4 microns and 3 microns, where a particle-size distribution dX of Y denotes that X% of particles have a size less than Y.
  • the slip is introduced into a mold having a shape approximately equal to a desired shape of the shaped part.
  • the particle-size distribution of the powder (i) substantially prevents separation of the powder from the liquid by agglomeration and/or sedimentation and (ii) maintains a substantially homogeneous distribution of powder particles within the liquid. Thereafter, at least a portion of the liquid drains out of the slip to produce a green body comprising or consisting essentially of the powder, and the green body is sintered to produce the shaped part.
  • Embodiments of the invention may include one or more of the following in any of a variety of different combinations.
  • the particle-size distribution of the powder may be d10 of approximately 0.3 micron, d50 of approximately 0.8 micron, and d90 of approximately 2.7 microns.
  • the shaped part may have a density between approximately 95% and approximately 99% of theoretical density, or even between 97% and 99% of theoretical density.
  • the shaped part may have a grain size (e.g., average grain size) between approximately 10 microns and approximately 20 microns.
  • the powder includes or consists essentially of one or more refractory metals.
  • the powder may include or consist essentially of tungsten, tantalum, niobium, zirconium, molybdenum, and/or titanium.
  • the green body may be sintered in hydrogen.
  • the green body may be sintered at a temperature between approximately 3000 °F (1649°C) and approximately 5000 °F (2760°C).
  • the powder may be produced by providing an initial powder having a particle-size distribution d10 of approximately 0.42 micron, d50 of approximately 1.8 micron, and d90 of approximately 3.8 microns, deagglomerating a portion of the initial powder, and blending the deagglomerated portion of the initial powder with a second portion of the initial powder.
  • the portion of the initial powder may be deagglomerated by ball milling.
  • the density of the green body may be between approximately 30% and approximately 40% of theoretical density.
  • the liquid may consist essentially of deionized water.
  • the mold may be porous. Substantially all of the liquid from the slip may drain into the mold to form the green body.
  • Neither the slip nor the mold may be agitated (e.g., shaken, stirred, vibrated, and/or rotated) after the slip is introduced into the mold and before the green body is produced.
  • a super-atmospheric pressure (which may be hydrostatic) is applied to the mold and/or to the slip during and/or after introducing the slip into the mold.
  • the powder may be substantially homogeneously distributed within the green body (i.e., there may be no noticeable gradients or bands in particle or grain size formed within the green body).
  • the mold may contain substantially only the slip.
  • the shaped part may be machined to a desired size and/or shape.
  • a method of producing a shaped part is provided.
  • a powder is suspended in water without flocculating or deflocculating additives, thereby forming a slip.
  • the slip is introduced into a mold having a shape approximately complementary to (i.e., enclosing a space for introduction of slip therewithin approximately equal to) a desired shape of the shaped part substantially without separation of the powder from the water (and/or settling or sedimentation of the powder within the water) thereduring.
  • at least a portion of the liquid is allowed to drain out of the slip to produce a green body including or consisting essentially of the powder, and the green body is sintered to produce the shaped part.
  • Embodiments of the invention may include one or more of the following in any of a variety of different combinations.
  • the powder may have a particle-size distribution (i) substantially preventing separation of the powder from the water by at least one of agglomeration or sedimentation and (ii) maintaining a substantially homogeneous distribution of powder particles within the liquid.
  • the particle-size distribution may be d10 between 0.15 micron and 0.5 micron, d50 between 0.6 micron and 1 micron, and d90 between 2.4 microns and 3 microns, a particle-size distribution dX of Y denoting that X% of particles have a size less than Y.
  • the powder may include or consist essentially of one or more metals (e.g., refractory metals such as tungsten).
  • a super-atmospheric pressure is applied to the mold and/or the slip during and/or after introducing the slip into the mold.
  • the mold may contain substantially only the slip.
  • consisting essentially of at least one metal refers to a metal or a mixture of two or more metals but not compounds between a metal and a non-metallic element or chemical species such as oxygen or nitrogen (e.g., metal nitrides or metal oxides); such non-metallic elements or chemical species may be present, collectively or individually, in trace amounts, e.g., as impurities.
  • the metal powder utilized in accordance with embodiments of the present invention has a particle-size distribution (PSD) that maintains an advantageous ratio between the powder sedimentation rate and the viscosity of the slip.
  • PSD particle-size distribution
  • the metal powder has a PSD d10 between 0.15 micron and 0.5 micron, e.g., 0.3 micron, a PSD d50 between 0.6 micron and 1 micron, e.g., 0.8 micron, and a PSD d90 between 2.4 microns and 3 microns, e.g., 2.7 microns.
  • Powders having desired PSDs may be prepared via, for example, deagglomeration and blending of commercially available powders.
  • the slip has a viscosity 0.7 and 1.3 Pa-s, and preferably between 0.9 and 1.1 Pa-s.
  • use of powders having conventional PSDs without suspension aids typically results in high sedimentation rates and low viscosities (e.g., below 0.5 Pa-s) unsuitable for slip casting.
  • a tungsten powder having a small Fisher sub-sieve sizer (FSSS) particle size is identified.
  • FSSS particle size represents the average particle size as determined by air permeability, assuming perfectly spherical powder particles.
  • the FSSS particle size of the starting powder is between 0.5 micron and 1 micron, e.g., 0.7 micron.
  • an initial powder may be HC70S tungsten powder having an FSSS particle size of 0.7 micron, available from H.C. Starck GmbH of Goslar, Germany.
  • Such powder may have a PSD d10 of 0.42 micron, d50 of 1.8 micron, and d90 of 3.8 microns.
  • All or a portion of the initial powder may be deagglomerated by, e.g., ball milling with tungsten carbide milling balls in order to reduce agglomeration of the powder or ultrasonification (i.e., application of ultrasound energy) for a time sufficient to reduce or substantially eliminate agglomeration of the powder.
  • ultrasonification i.e., application of ultrasound energy
  • a powder blend may be subsequently produced by blending an unmilled portion of the initial powder with a portion that has been deagglomerated in order to form a powder having the desired particle-size distribution.
  • An exemplary powder blend may include, e.g., between 60% and 80% (e.g., 70%) by weight unmilled powder and between 20% and 40% (e.g., 30%) by weight deagglomerated powder.
  • the resulting powder blend may have a PSD d10 of 0.3 micron, d50 of 0.8 micron, and d90 of 2.7 microns.
  • the powder is suspended in a liquid including or consisting essentially of water, e.g., DI water.
  • the resulting slip preferably contains between 30% and 40% (e.g., approximately 35%) of the solid particles by volume.
  • the slip 100 is poured into a porous mold 110, e.g., a mold including or consisting essentially of gypsum, resin, one or more polymeric materials (e.g., polystyrene), and/or plaster of paris, having the desired shape and dimensions for a pre-sintered part (i.e., the shape and dimensions that, after sintering, provide the part with substantially the final desired shape and dimensions).
  • external pressure is applied while filling the mold 110 with the slip 100, as described in more detail below.
  • the slip 100 may be pumped into the mold 110 at a pressure exceeding atmospheric pressure.
  • the density of the cast slip 100 may be, for example, between 30% and 40%, e.g., approximately 34%, as determined by gravimetric methods.
  • the liquid suspending the powder is then absorbed into mold 110, as shown in Figure 2 , resulting in a green body 200 shaped by the mold 110.
  • the green body 200 is removed from the mold 110 and subsequently sintered for densification, producing a sintered part 300.
  • High-pressure air and/or vacuum may be applied via lines 530, 540 (either together or in sequence) in order to facilitate removal of the green body 200 from the mold 110.
  • the green body 200 is sintered in a hydrogen ambient. The sintering may be performed at temperatures between approximately 3000 °F (1649°C) and approximately 5000 °F (2760°C), e.g., approximately 4000 °F (2204°C), for a time period between approximately 2 hours and approximately 7 hours, e.g., approximately 5 hours.
  • the part 300 may have a grain size smaller than approximately 30 microns, e.g., between approximately 10 microns and approximately 20 microns.
  • the density of part 300 may be between approximately 95% and approximately 99% of its theoretical density, e.g., approximately 97%.
  • the part may be utilized in its as-cast and as-sintered form, or may be machined into a desired shape, as, e.g., a crucible, a heat shield, a seamless tube, or other hollow or conical shape.
  • Figure 4 is an optical micrograph of the microstructure of a part 300 fabricated from W powder in accordance with embodiments of the present invention.
  • the grain size of the part 300 ranges between approximately 10 microns and approximately 20 microns.
  • the grains of part 300 have been revealed via etching with Murakami's etchant, known to those of skill in the art to be a mixture of potassium ferricyanide (K 3 Fe(CN) 6 ), potassium hydroxide (KOH), and water.
  • FIG. 5A depicts a pressure casting apparatus 500 that may be utilized in embodiments of the present invention.
  • apparatus 500 features a mold 110 partially or substantially encased within a pressure jacket 510 that may include or consist essentially of one or more mechanically strong and rigid materials capable of resisting the pressures imparted upon the slip while preventing deformation or fracture of the mold 110.
  • the pressure jacket 510 (and the mold 110) may be composed of multiple different parts that may be separated (see Figure 5C ) to facilitate removal of the cast part from the mold 110.
  • Pressure jacket 510 of Figures 5A-5C is depicted as being composed of pressure-jacket portions 510-1, 510-2.
  • the slip 100 is introduced into the mold 110 via a slip feed line 520 through which the slip 100 may be pumped under applied pressure.
  • the apparatus 500 also includes pressure lines 530, 540 for the introduction of, e.g., high-pressure air (or other gas, e.g., inert gas), to apply pressure to the slip 100 during casting.
  • air of a first super-atmospheric pressure i.e., having a pressure greater than atmospheric pressure
  • air of a second pressure less than the first super-atmospheric pressure or vacuum may be applied via the pressure line 540.
  • the applied pressure may be substantially hydrostatic pressure, and it may advantageously decrease the amount of time required for the casting process (due to, e.g., increased outflow of water from the slip 100 during casting) and/or increase the density (and/or improve other mechanical properties) of the resulting green body. Pressures of greater than approximately 10 bars, greater than approximately 20 bars, or even greater than approximately 40 bars may be applied during casting in accordance with various embodiments of the present invention.
  • Figure 5B depicts apparatus 500 after the slip 100 has been introduced into the mold 110 via the slip feed line 520.
  • pressure is applied to the slip 100 within the mold 110 as detailed above in reference to Figure 5A , resulting in a green body 200 shaped by the mold 110.
  • the pressure jacket 510 and/or mold 110 may be separated into multiple portions to facilitate removal of the green body 200 from the mold 110.
  • the green body 200 may be sintered for densification, producing a sintered part 300.
  • the green body 200 is sintered in a hydrogen ambient.
  • the sintering may be performed at temperatures between approximately 3000 °F (1649°C) and approximately 5000 °F (2760°C), e.g., approximately 4000 °F (2204°C), for a time period between approximately 2 hours and approximately 7 hours, e.g., approximately 5 hours.

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  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Powder Metallurgy (AREA)

Claims (14)

  1. Procédé de production d'une pièce façonnée, le procédé comprenant :
    - mettre en suspension, dans un liquide constitué d'eau, une poudre comprenant un ou plusieurs métaux réfractaires ayant une répartition granulométrique Fisher Sub-Sieve Sizer (FSSS) telle que déterminée par perméabilité à l'air en supposant des particules de poudre parfaitement sphériques de d10 entre 0,15 micron et 0,5 micron, d50 entre 0,6 micron et 1 micron, et d90 entre 2,4 microns et 3 microns, en formant ainsi une barbotine, dans lequel une répartition granulométrique dX de Y indique que X % de particules ont une taille inférieure à Y ;
    - introduire la barbotine dans un moule ayant une forme approximativement égale à une forme souhaitée de la pièce façonnée, la répartition granulométrique de la poudre comprenant un ou plusieurs métaux réfractaires (i) empêchant sensiblement une séparation de la poudre comprenant un ou plusieurs métaux réfractaires du liquide par au moins l'une d'une agglomération ou d'une sédimentation, et (ii) maintenant une répartition sensiblement homogène de particules de poudre comprenant un ou plusieurs métaux réfractaires à l'intérieur du liquide ;
    - ensuite, permettre à au moins une portion du liquide de s'écouler hors de la barbotine pour produire une ébauche crue comprenant la poudre comprenant un ou plusieurs métaux réfractaires, comprenant en outre l'application d'une pression super-atmosphérique à au moins l'un du moule ou de la barbotine pendant ou après l'introduction de la barbotine dans le moule ; et
    - fritter l'ébauche crue pour produire la pièce façonnée.
  2. Procédé selon la revendication 1, dans lequel la répartition granulométrique de la poudre comprenant un ou plusieurs métaux réfractaires est d10 d'approximativement 0,3 micron, d50 d'approximativement 0,8 micron, et d90 d'approximativement 2,7 microns, dans lequel le terme "approximativement" signifie ± 10 %.
  3. Procédé selon la revendication 1, dans lequel, après le frittage, la pièce façonnée a une densité entre 95 % et 99 % d'une densité théorique.
  4. Procédé selon la revendication 1, dans lequel, après le frittage, la pièce façonnée a une granulométrie entre approximativement 10 microns et approximativement 20 microns, dans lequel le terme "approximativement" signifie ± 10 %.
  5. Procédé selon la revendication 1, dans lequel la poudre comprenant un ou plusieurs métaux réfractaires comprend au moins l'un parmi le tungstène, le tantale, le niobium, le zirconium, le molybdène ou le titane.
  6. Procédé selon la revendication 1, dans lequel la poudre comprenant un ou plusieurs métaux réfractaires comprend du tungstène.
  7. Procédé selon la revendication 1, dans lequel l'ébauche crue est frittée dans l'hydrogène.
  8. Procédé selon la revendication 1, dans lequel l'ébauche crue est frittée à une température entre approximativement 1649 °C et approximativement 2760 °C, dans lequel le terme "approximativement" signifie ± 10 %.
  9. Procédé selon la revendication 1, comprenant en outre la production de la poudre comprenant un ou plusieurs métaux réfractaires par un processus comprenant :
    - prévoir une poudre initiale comprenant un ou plusieurs métaux réfractaires ayant une répartition granulométrique d10 d'approximativement 0,42 micron, d50 d'approximativement 1,8 micron, et d90 d'approximativement 3,8 microns ;
    - désagglomérer une portion de la poudre initiale comprenant un ou plusieurs métaux réfractaires, dans lequel le terme "approximativement" signifie ± 10 % ; et
    - mélanger la portion désagglomérée de la poudre initiale comprenant un ou plusieurs métaux réfractaires avec une seconde portion de la poudre initiale comprenant un ou plusieurs métaux réfractaires, dans lequel de préférence la portion de la poudre initiale comprenant un ou plusieurs métaux réfractaires est désagglomérée par broyage à boulets.
  10. Procédé selon la revendication 1, dans lequel une densité de l'ébauche crue est entre approximativement 30 % et approximativement 40 % d'une densité théorique, dans lequel le terme "approximativement" signifie ± 10 %.
  11. Procédé selon la revendication 1, dans lequel le liquide est constitué d'eau désionisée.
  12. Procédé selon la revendication 1, dans lequel (i) le moule est poreux et (ii) sensiblement l'intégralité du liquide de la barbotine s'écoule dans le moule pour former l'ébauche crue.
  13. Procédé selon la revendication 1, dans lequel ni la barbotine ni le moule ne sont agités après l'introduction de la barbotine dans le moule.
  14. Procédé selon la revendication 1, dans lequel la poudre comprenant un ou plusieurs métaux réfractaires est répartie de manière sensiblement homogène à l'intérieur de l'ébauche crue, ou, comprenant en outre l'usinage de la pièce façonnée à une taille et/ou à une forme souhaitée.
EP14806817.4A 2013-06-04 2014-05-28 Coulage en barbotine et sous pression de corps en métal réfractaire Active EP3003607B1 (fr)

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US201361830892P 2013-06-04 2013-06-04
PCT/US2014/039708 WO2014197246A1 (fr) 2013-06-04 2014-05-28 Coulage en barbotine et sous pression de corps en métal réfractaire

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EP3003607A1 EP3003607A1 (fr) 2016-04-13
EP3003607A4 EP3003607A4 (fr) 2017-02-22
EP3003607B1 true EP3003607B1 (fr) 2020-05-27

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US (1) US20140356216A1 (fr)
EP (1) EP3003607B1 (fr)
JP (1) JP2016524044A (fr)
KR (1) KR101675713B1 (fr)
CN (1) CN105263655A (fr)
TW (1) TWI599421B (fr)
WO (1) WO2014197246A1 (fr)

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US20180368339A1 (en) * 2016-11-30 2018-12-27 Reinierus Hendricus Maria van der Lee Solid state soil moisture sensor

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CN105263655A (zh) 2016-01-20
TW201507792A (zh) 2015-03-01
KR20160011675A (ko) 2016-02-01
EP3003607A1 (fr) 2016-04-13
WO2014197246A1 (fr) 2014-12-11
KR101675713B1 (ko) 2016-11-11
TWI599421B (zh) 2017-09-21
US20140356216A1 (en) 2014-12-04
EP3003607A4 (fr) 2017-02-22
JP2016524044A (ja) 2016-08-12

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