EP1575745B1 - Verfahren zur herstellung eines keramischen artikels durch druckgiessen - Google Patents

Verfahren zur herstellung eines keramischen artikels durch druckgiessen Download PDF

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Publication number
EP1575745B1
EP1575745B1 EP20030782563 EP03782563A EP1575745B1 EP 1575745 B1 EP1575745 B1 EP 1575745B1 EP 20030782563 EP20030782563 EP 20030782563 EP 03782563 A EP03782563 A EP 03782563A EP 1575745 B1 EP1575745 B1 EP 1575745B1
Authority
EP
European Patent Office
Prior art keywords
slip
deposit
deflocculant
solution
mold
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
EP20030782563
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English (en)
French (fr)
Other versions
EP1575745A1 (de
Inventor
Thierry Chartier
Marie-Pierre Comte-Gautron
Gilles Gasgnier
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.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
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Publication of EP1575745A1 publication Critical patent/EP1575745A1/de
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Publication of EP1575745B1 publication Critical patent/EP1575745B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B28B13/00—Feeding the unshaped material to moulds or apparatus for producing shaped articles; Discharging shaped articles from such moulds or apparatus
    • B28B13/02—Feeding the unshaped material to moulds or apparatus for producing shaped articles
    • B28B13/0215—Feeding the moulding material in measured quantities from a container or silo
    • B28B13/0275—Feeding a slurry or a ceramic 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
    • B28B1/265—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 pressure being applied on the slip in the filled mould or on the moulded article in the mould, e.g. pneumatically, by compressing slip in a closed mould
    • 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
    • B28B13/00—Feeding the unshaped material to moulds or apparatus for producing shaped articles; Discharging shaped articles from such moulds or apparatus
    • B28B13/02—Feeding the unshaped material to moulds or apparatus for producing shaped articles
    • B28B13/021—Feeding the unshaped material to moulds or apparatus for producing shaped articles by fluid pressure acting directly on the material, e.g. using vacuum, air pressure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249968—Of hydraulic-setting material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/24997—Of metal-containing material

Definitions

  • the invention relates to the manufacture of ceramic articles.
  • the document CA 2124863 has a device for mixing two slips of distinct compositions before injection into the mold and a method of manufacturing a ceramic article comprising the step of casting a slip under pressure in a mold to form a deposit.
  • the document US 5948335 presents an injection process in which the composition of the slip is modified by adding polymers to the slip prior to injection.
  • Die Casting consists of shaping articles from a slip identical to that used in plaster mold casting. This time, the mold is porous resin and the slip is injected under a pressure ranging from 8 to 40.10 5 Pa approximately. This deposit is made by pressure filtration through the mold of most of the water that was used to initially suspend the various components of the ceramic. Thus the formation of the part is accelerated and as soon as it is formed the mold can be opened to proceed with demolding. As soon as this operation is complete, the mold can be closed again for a new casting cycle.
  • the mold does not require drying, its average life is 20,000 cycles and it is not no need to have more than one or two molds per piece type, which greatly reduces the bulk of the workshop.
  • the pressure casting cycles depend to a large extent on the rheological characteristics of the slip. These characteristics can be regulated by additives called deflocculants whose action can be purely electrostatic, purely steric or electro-steric.
  • deflocculants whose action can be purely electrostatic, purely steric or electro-steric.
  • the characteristics of the slip must allow a casting cycle as fast as possible while preserving good mechanical behavior of the part after pouring. This means that the freshly formed part must be strong enough to undergo the various handling required by demolding and finishing. These constraints lead most of the time to adjust the slips identically for the CSP and for conventional casting, while the CSP would allow even better yields if the slips were under-deflocculated. Unfortunately, the use of such slip, if it allows a speed of forming parts faster, leads to a poor firming of the ceramic in the mold and an irreversible deformation of the parts during demolding.
  • the repulsive forces between the mineral particles are high and the particles can move independently of each other. They will therefore be able to settle individually and rearrange into a denser deposit (high relative density, low porosity), incompressible and homogeneous.
  • a denser deposit high relative density, low porosity
  • incompressible and homogeneous because of the high degree of compactness of the deposit, casting speeds are low.
  • the attraction forces are strong and the particles will move and settle by agglomerates.
  • the deposit thus formed will be less dense (high porosity), compressible (rearrangement of particles under the action of pressure) and heterogeneous.
  • the casting speeds will in this case be higher because of a higher porosity.
  • the objective of the user is to accelerate the speed of formation of the deposit in order to increase the profitability of the machine.
  • this acceleration is limited by the capacity of the deposit formed to eliminate the residual water and thus allow the gripping of the article during the opening of the mold. This means that if the slip is "set" so that the rate of formation of the deposit is as fast as possible, the article can not be demolded without being deformed because it behaves like a thixotropic solid.
  • An object of the invention is to accelerate the manufacture by die casting without threatening the mechanical strength of the part from demoulding.
  • Another object of the invention may be to allow the manufacture of traditional ceramic articles by die casting.
  • the filtering step makes it possible to compact the relatively sparse deposit formed in the previous step.
  • This post-treatment consists in passing through the deposit a solution containing the deflocculant. It can be assumed that during this post-filtration process, the deflocculant molecules will be able to adsorb to the surface of the particles and thus increase the repulsion forces. The particles will then be able to "move” and rearrange into a denser deposit with the help of pressure (higher mechanical strength of the green part). The piece then has mechanical characteristics suitable for its demolding and finishing.
  • the manufacturing device 2 is schematically illustrated in FIG. figure 1 .
  • the tank 4 is able to receive a slip 8 while the tank 6 is able to receive a filtration solution containing a deflocculant.
  • the device comprises a mold 12 of die casting of a conventional type which may have a horizontal or vertical joint plane. It also comprises means 14 capable of injecting under pressure into the mold 12 in turn the slip 8 and the solution 10. These means may be formed by two independent injectors respectively assigned to the injection of the slip 8 and the solution 10, following two separate circuits upstream.
  • the device comprises means 16 for purging or cleaning the downstream circuit connecting the injection means of the solution to the mold 12.
  • the mold 12 comprises two high and low end portions 13 and 13.
  • Each of the upper and lower parts has an internal chamber in which a supply duct coming from the outside of the mold opens out and forms the injection means 14.
  • upper part 13 has a cavity 33 and the lower part has an advance 25 able to enter the cavity 33 when the two mold parts are assembled in a male-female connection.
  • the step 25 occupies only a part of the cavity 33 so that the remainder of the cavity 33 forms the molding chamber for the formation of the workpiece 30 to be molded.
  • the portions of the upper and lower parts contiguous to the enclosure are made of porous materials.
  • Several ducts 29 are formed in each of the upper and lower parts.
  • the conduits 29 are rectilinear, parallel to each other and separated from each other by identical intervals. They extend in the direction 37 in which the two upper and lower parts are movable relative to each other to allow the mold to extract the formed part.
  • the ducts 29 extend to the right of the cavity 33, without however reaching it so that they are blind.
  • the ducts of the lower part 15 penetrate into the projection 25.
  • the ducts 29 connect the main supply duct to the core of the porous material.
  • the mold 12 further comprises a lateral duct 39 extending in one of the two upper and lower parts, for example the upper part 13, from the outside of the latter opening directly into the chamber 33.
  • the slip 8 is injected under pressure into the mold 12 to form a deposit 20, and then the solution 10 is injected into the mold.
  • the slip 8 comprises a powder suspended in an aqueous solution.
  • the solid phase represents in mass 70% of the slip.
  • the slip has a density of 1.77.
  • the aqueous solution comprises in very small quantities the deflocculant marketed by the firm Zschimmer and Schwartz under the name PC 67, so that the suspension is considered as under-deflocculated. In this case, the flocculant represents 0.06% of the mass of the slip.
  • the slip is injected in this case via the lateral duct 39, the water evacuating through the porous material then the ducts 29.
  • this slip makes it possible to obtain a relatively low density deposit after the evacuation of a portion of the water through the wall of the mold.
  • Solution 10 is an aqueous solution of deflocculant PC 67 representing by mass between 0.10 and 4.70% of the solution (for example up to 1% by weight of the final article 30).
  • the solution 10 is injected here from the lateral channel 39.
  • the solution passes through the deposit 20 and the water escapes through the wall of the mold and then the vertical ducts 29.
  • the mold is opened and water and compressed air are injected to take off the part made with respect to the two mold parts. This injection takes place via the conduits 29.
  • the intermediate product 20 is removed for finishing in a manner known per se (cooking, etc.) to obtain the article 30 of the figure 6 .
  • the figure 4 presents the kinetics of filtration of the deflocculant solutions whose concentration varies from 0 to 4.70% through the deposition 20. Two behaviors can be observed.
  • the figure 5 presents the specific resistance of the deposits after and before treatment. It clearly appears that the resistance of the deposits after treatment (curve in solid line) is 2 times higher than that obtained by simple casting (curve in dashed line). This result shows that the porous structure of the deposit has been modified (rearrangement of the particles into a denser structure).
  • This post-filtration method therefore makes it possible to obtain a denser deposit by rearranging the particles during this process.
  • the compaction mechanism of the deposit may be the following.
  • the figure 2 illustrates the deposition after pouring of the flocculated suspension 8.
  • the large quartz particles 22 whose zero charge point is towards a pH of 2 are negatively charged in the suspension where the pH is around 7-8. These particles will therefore repel by electrostatic repulsion.
  • the small particles of kaolin 24 have a point of zero load towards 8-9. These uncharged particles in the suspension will therefore agglomerate together and around the quartz particles 22 of the makes attractive forces of Van der Walls and electrostatic respectively.
  • the deposit obtained from the casting of this suspension will therefore be formed of blocks of quartz particles surrounded by kaolin with a large porosity allowing rapid flow of the liquid phase.
  • the figure 3 illustrates the deposition after injection of the solution 10.
  • the deflocculant contained in the solution will be able to be absorbed on the kaolin particles 24 and charge negatively.
  • the deflocculant is negatively charged (COO group - in the case of a polyacrylate). These particles will then be able to repel by repulsive forces (electro-steric) and thus individually rearrange in a denser deposit (lower porosity and higher mechanical resistance).
  • the arrows 26 represent the flow of the filtrate.
  • a second application of the invention is to apply the principle to slip "that does not flow well" such as earthenware and sandstone or other slip containing a high proportion of clay.
  • slips that does not flow well
  • the method described here makes it possible to use such slips in CSP whereas this was not the case previously in the design of the process and the machines.
  • the purge of the system carrying the deflocculant solution must be complete before the new injection of slip so as not to produce an involuntary defloculation of the latter.
  • the purge means 16 is activated to clean the portion of circuit to be borrowed by the solution 8 during the next cycle.
  • the invention is applicable to any type of ceramic. It will thus be applicable to traditional clay ceramics used for the arts of the table or sanitary. It will also be applicable to technical ceramics (such as those based on silicon nitride or silicon carbide) for example for the manufacture of electronic component supports or refractory materials.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Producing Shaped Articles From Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Claims (8)

  1. Verfahren zur Herstellung eines Gegenstands (30) aus Keramik, das die Schritte umfasst, die aus Folgendem bestehen:
    - Zuführen eines Keramikschlamms (8) unter Druck in eine Gussform (12), um eine Ausscheidung (20) zu bilden; und
    - Filtrieren durch die Ausscheidung (20) einer Lösung (10), die ein Mittel zur Flockungsverhinderung enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Keramikschlamm (10) ausgeflockt ist.
  3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass der Keramikschlamm (10) Kaolin enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Keramikschlamm (10) Ton enthält.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Keramikschlamm (10) Quarz enthält.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Mittel zur Flockungsverhinderung maximal 3% der Masse des Gegenstands (30) entspricht.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Mittel zur Flockungsverhinderung maximal 5% der Masse der Lösung (10) entspricht.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Mittel zur Flockungsverhinderung zwischen 0,20% und 3% der Masse der Lösung (10) entspricht.
EP20030782563 2002-11-15 2003-11-14 Verfahren zur herstellung eines keramischen artikels durch druckgiessen Expired - Lifetime EP1575745B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0214305 2002-11-15
FR0214305A FR2847195B1 (fr) 2002-11-15 2002-11-15 Procede de fabrication d'un article en ceramique par coulage sous pression
PCT/FR2003/003379 WO2004045818A1 (fr) 2002-11-15 2003-11-14 Procede de fabrication d’un article en ceramique par coulage sous pression

Publications (2)

Publication Number Publication Date
EP1575745A1 EP1575745A1 (de) 2005-09-21
EP1575745B1 true EP1575745B1 (de) 2013-07-24

Family

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EP20030782563 Expired - Lifetime EP1575745B1 (de) 2002-11-15 2003-11-14 Verfahren zur herstellung eines keramischen artikels durch druckgiessen

Country Status (7)

Country Link
US (1) US20060134399A1 (de)
EP (1) EP1575745B1 (de)
JP (1) JP4561362B2 (de)
AU (1) AU2003290201A1 (de)
ES (1) ES2431838T3 (de)
FR (1) FR2847195B1 (de)
WO (1) WO2004045818A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3072378B1 (fr) 2017-10-12 2019-11-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Dispositif et procede de fabrication de pieces en ceramique par voie cryogenique

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1694563A (en) * 1927-02-02 1928-12-11 Donald W Ross Method of molding ceramic materials
US2521128A (en) * 1948-05-29 1950-09-05 Stark Brick Company Casting of ceramic articles
US4983423A (en) * 1988-05-24 1991-01-08 Ceramem Corporation Method of forming a porous inorganic membrane on a porous support using a reactive inorganic binder
JP2800955B2 (ja) * 1991-09-06 1998-09-21 新東工業株式会社 焼結用原形体の成形方法
US5788891A (en) * 1994-05-09 1998-08-04 Gauckler; Ludwig J. Method for the forming of ceramic green parts
CA2124863C (en) * 1994-05-18 1999-06-29 National Research Council Of Canada Slip casting process and apparatus for producing graded materials
US5972263A (en) * 1995-06-13 1999-10-26 Ecc International Ltd. Process for producing clay compositions for use in slip casting
JP2002255630A (ja) * 2001-02-26 2002-09-11 Toto Ltd 衛生陶器

Also Published As

Publication number Publication date
WO2004045818A1 (fr) 2004-06-03
JP2006506255A (ja) 2006-02-23
FR2847195A1 (fr) 2004-05-21
US20060134399A1 (en) 2006-06-22
ES2431838T3 (es) 2013-11-28
FR2847195B1 (fr) 2005-07-29
JP4561362B2 (ja) 2010-10-13
EP1575745A1 (de) 2005-09-21
AU2003290201A1 (en) 2004-06-15

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