EP1575745B1 - Method of producing a ceramic article by means of pressure casting - Google Patents
Method of producing a ceramic article by means of pressure casting Download PDFInfo
- 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
Links
- 238000005266 casting Methods 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 19
- 239000000919 ceramic Substances 0.000 title claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 33
- 239000002245 particle Substances 0.000 description 18
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 238000004512 die casting Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229910052571 earthenware Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QYLJIYOGHRGUIH-CIUDSAMLSA-N Arg-Ile Chemical compound CC[C@H](C)[C@@H](C(O)=O)NC(=O)[C@@H](N)CCCNC(N)=N QYLJIYOGHRGUIH-CIUDSAMLSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000010111 plaster casting Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
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- 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)
Description
L'invention concerne la fabrication d'articles en céramique.The invention relates to the manufacture of ceramic articles.
Le coulage sous pression (CSP) d'une barbotine (suspension aqueuse des différentes matières minérales constituant la « formule » de la céramique) est une technique répandue dans les secteurs des céramiques traditionnelles que sont les arts de la table et la fabrication de produits sanitaires. La technique dérive du traditionnel coulage en moule plâtre qui est la méthode ancestrale utilisée pour produire des pièces de forme complexe. Ce mode de fabrication comporte néanmoins un certain nombre d'inconvénients que le coulage sous pression résout en partie :
- prise lente (formation des pièces),
- démoulage différé (nécessité d'attendre le raffermissement des pièces en moule avant démoulage),
- séchage nécessaire des moules après quelques utilisations,
- courte durée de vie des moules (moins de 150 cycles),
- encombrement important (stock de moules).
- slow grip (forming parts),
- delayed release (need to wait for the firming of mold parts before demolding),
- necessary drying of the molds after a few uses,
- short life of the molds (less than 150 cycles),
- large size (mold stock).
Divers documents ont tenté de résoudre ces inconvénients dans le cadre du coulage traditionnel.Various documents have attempted to solve these disadvantages in the context of traditional casting.
Le document
Le document
Le coulage sous pression consiste à mettre en forme des articles à partir d'une barbotine identique à celle utilisée dans le cas du coulage en moule en plâtre. Cette fois, le moule est en résine poreuse et la barbotine est injectée sous une pression pouvant aller de 8 à 40.105Pa environ. Ce dépôt est réalisé par filtration sous pression au travers du moule de la majeure partie de l'eau ayant été utilisée pour mettre initialement en suspension les différents composants de la céramique. Ainsi la formation de la pièce est accélérée et dès que celle-ci est formée le moule peut être ouvert pour procéder au démoulage. Dès cette opération terminée, le moule peut être refermé pour un nouveau cycle de coulage. Le moule ne nécessite pas de séchage, sa durée de vie moyenne est de 20.000 cycles et il n'est pas nécessaire d'avoir plus d'un ou deux moules par type de pièce, ce qui réduit considérablement l'encombrement de l'atelier.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.
Les cycles de coulage sous pression dépendent en grande partie des caractéristiques rhéologiques de la barbotine. Ces caractéristiques peuvent être réglées par le biais d'additifs appelés défloculants dont l'action peut être purement électrostatique, purement stérique ou électro-stérique. Les caractéristiques de la barbotine doivent permettre un cycle de coulage aussi rapide que possible tout en préservant un bon comportement mécanique de la pièce à l'issue du coulage. Cela signifie que la pièce fraîchement formée doit être suffisamment résistante pour subir les diverses manutentions nécessitées par le démoulage et la finition. Ces contraintes conduisent la plupart du temps à régler les barbotines de façon identique pour le CSP et pour le coulage classique, alors que le CSP permettrait des rendements encore meilleurs si les barbotines étaient sous-défloculées. Malheureusement, l'emploi de telles barbotines, s'il permet une vitesse de formation des pièces plus rapide, conduit à un mauvais raffermissement de la céramique dans le moule et à une déformation irrémédiable des pièces lors du démoulage.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. 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.
Il faut préciser à ce stade que la structure et la vitesse de formation du dépôt lors du coulage sous pression sont les résultats de deux types de mécanismes suivant le degré de défloculation de la barbotine en suspension.It should be noted at this point that the structure and rate of formation of the deposit during die casting are the results of two types of mechanisms depending on the degree of deflocculation of the slurry in suspension.
Dans les suspensions défloculées, les forces de répulsion entre les particules minérales sont élevées et les particules peuvent se déplacer indépendamment les unes des autres. Elles vont donc pouvoir se déposer individuellement et se réarranger en un dépôt plus dense (forte densité relative, faible porosité), incompressible et homogène. Mais, du fait du degré élevé de compacité du dépôt, les vitesses de coulage sont faibles.In the deflocculated suspensions, 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. However, because of the high degree of compactness of the deposit, casting speeds are low.
Dans les suspensions floculées, les forces d'attractions sont fortes et les particules vont se déplacer et se déposer par agglomérats. Le dépôt ainsi formé sera moins dense (forte porosité), compressible (réarrangement des particules sous l'action de la pression) et hétérogène. Par contre, les vitesses de coulage seront dans ce cas plus élevées du fait d'une porosité plus forte.In the flocculated suspensions, 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. On the other hand, the casting speeds will in this case be higher because of a higher porosity.
D'autre part, toutes les barbotines n'ont pas le même comportement au coulage. La nature minéralogique des constituants joue un rôle très important vis à vis des caractéristiques rhéologiques. Pour simplifier, les barbotines réalisées à partir de kaolins (telles les porcelaines ou les vitréous) « coulent bien » au sens du coulage classique, ce qui signifie que leur défloculation est facile et que les vitesses de prise obtenues sont élevées. En revanche, les barbotines à base d'argiles (telles les faïences ou les grès) ne coulent pas bien, ce qui signifie qu'elles sont difficiles à défloculer et que les vitesses de prise obtenues sont mauvaises. C'est la raison pour laquelle la grande majorité des produits réalisés dans le secteur des céramiques traditionnelles en coulage sous pression sont des porcelaines et des vitréous. Les producteurs de faïence et de grès ne peuvent généralement pas accéder à cette technologie du fait des piètres caractéristiques rhéologiques intrinsèques de leurs suspensions.On the other hand, all the slips do not have the same casting behavior. The mineralogical nature of the constituents plays a very important role with respect to the rheological characteristics. For simplicity, the slips made from kaolin (such as porcelain or vitreous) "flow well" in the traditional casting sense, which means that their deflocculation is easy and that the setting speeds obtained are high. On the other hand, clay-based slips (such as earthenware or sandstone) do not flow well, which means that they are difficult to deflocculate and the resulting setting speeds are poor. This is why the vast majority of products made in the field of traditional die-casting ceramics are porcelains and vitreous. The producers of faience and sandstone can not generally access this technology due to the poor intrinsic rheological characteristics of their suspensions.
L'objectif de l'utilisateur est d'accélérer la vitesse de formation du dépôt afin d'augmenter la rentabilité de la machine. Or, cette accélération est limitée par la capacité du dépôt formé à éliminer l'eau résiduelle et ainsi permettre la préhension de l'article lors de l'ouverture du moule. Cela signifie que si l'on « règle » la barbotine de telle sorte que la vitesse de formation du dépôt soit la plus rapide possible, l'article ne pourra pas être démoulé sans subir de déformation car il se comporte comme un solide thixotrope.The objective of the user is to accelerate the speed of formation of the deposit in order to increase the profitability of the machine. However, 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.
Un but de l'invention est d'accélérer la fabrication par coulage sous pression sans menacer la résistance mécanique de la pièce à compter du démoulage. Un autre but de l'invention pourra être de permettre la fabrication d'articles en céramiques traditionnelles par coulage sous pression.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.
A cet effet, on prévoit selon l'invention un procédé de fabrication d'un article en céramique, comprenant les étapes consistant à :
- couler une barbotine sous pression dans un moule pour former un dépôt ; et
- filtrer sur le dépôt une solution contenant un défloculant.
- casting a slip under pressure in a mold to form a deposit; and
- filter on the deposit a solution containing a deflocculant.
Ainsi, l'étape de filtrage permet de compacter le dépôt relativement peu dense formé à l'étape précédente. Ce post-traitement consiste à faire passer à travers le dépôt une solution contenant le défloculant. On peut supposer qu'au cours de ce processus de post-filtration, les molécules du défloculant vont pouvoir s'adsorber à la surface des particules et augmenter ainsi les forces de répulsion. Les particules vont alors pouvoir se « déplacer » et se réarranger en un dépôt plus dense avec l'aide de la pression (tenue mécanique plus élevée de la pièce crue). La pièce a alors des caractéristiques mécaniques convenables pour assurer son démoulage et sa finition.Thus, 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.
Le procédé selon l'invention pourra en outre présenter au moins l'une quelconque des caractéristiques suivantes :
- la barbotine est floculée,
- la barbotine comprend du kaolin,
- la barbotine comprend de l'argile,
- la barbotine comprend du quartz,
- le défloculant représente au maximum 3% en masse de l'article,
- le défloculant représente au maximum 5% en masse de la solution,
- le défloculant représente entre 0,20% et 3% en masse de la solution .
- the slip is flocculated,
- the slip includes kaolin,
- the slip includes clay,
- the slip includes quartz,
- the deflocculant represents a maximum of 3 % by mass of the article,
- the deflocculant represents a maximum of 5% by weight of the solution,
- the deflocculant represents between 0.20% and 3% by weight of the solution.
D'autres caractéristiques et avantages de l'invention apparaîtront au cours de la description suivante présentant notamment un mode préféré de réalisation à titre d'exemple non limitatif. Aux dessins annexés :
- la
figure 1 est une vue schématique d'un mode de réalisation du dispositif de l'invention, - les
figures 2 et 3 sont deux vues schématiques de la structure de l'article à l'échelle microscopique à l'issue respectivement de la première étape et de la deuxième étape du procédé de l'invention, - la
figure 4 présente des courbes illustrant pour différentes compositions de la solution de filtrage l'évolution de la masse du filtrat en fonction du temps, - la
figure 5 est une courbe illustrant la résistance spécifique du produit intermédiaire en fonction de sa concentration en défloculant, - la
figure 6 est une vue en coupe de l'article obtenu au moyen de l'invention, et - la
figure 7 est une vue en coupe plus précise du moule de lafigure 1 .
- the
figure 1 is a schematic view of an embodiment of the device of the invention, - the
Figures 2 and 3 are two schematic views of the structure of the article at the microscopic scale at the end of the first step and the second step respectively of the method of the invention, - the
figure 4 presents curves illustrating, for different compositions of the filtering solution, the evolution of the mass of the filtrate as a function of time, - the
figure 5 is a curve illustrating the specific resistance of the intermediate product as a function of its deflocculant concentration, - the
figure 6 is a sectional view of the article obtained by means of the invention, and - the
figure 7 is a more precise sectional view of the mold of thefigure 1 .
Le dispositif 2 de fabrication est illustré schématiquement à la
Il comprend deux réservoirs 4 et 6. Le réservoir 4 est apte à recevoir une barbotine 8 tandis que le réservoir 6 est apte à recevoir une solution de filtration 10 contenant un défloculant.It comprises two
Le dispositif comprend un moule 12 de coulage sous pression d'un type classique qui pourra avoir un plan de joint horizontal ou vertical. Il comprend également des moyens 14 aptes à injecter sous pression dans le moule 12 à tour de rôle la barbotine 8 et la solution 10. Ces moyens pourront être formés par deux injecteurs indépendants affectés respectivement à l'injection de la barbotine 8 et de la solution 10, suivant deux circuits séparés en amont.The device comprises a
Le dispositif comprend des moyens 16 de purge ou de nettoyage du circuit aval reliant les moyens d'injection de la solution au moule 12.The device comprises means 16 for purging or cleaning the downstream circuit connecting the injection means of the solution to the
On a illustré plus précisément à la
Les portions des parties haute et basse contiguës à l'enceinte sont réalisées en matériaux poreux. Plusieurs conduits 29 sont ménagés dans chacune des parties haute et basse. Les conduits 29 sont rectilignes, parallèles entre eux et séparés les uns des autres par des intervalles identiques. Ils s'étendent suivant la direction 37 suivant laquelle les deux parties haute et basse sont mobiles l'une par rapport à l'autre pour permettre d'extraire du moule la pièce formée. Dans les deux parties haute et basse, les conduits 29 s'étendent au droit de la cavité 33, sans toutefois atteindre celle-ci de sorte qu'ils sont borgnes. Les conduits de la partie basse 15 pénètrent dans l'avancée 25. Dans chacune des parties haute et basse, les conduits 29 relient le conduit d'amenée principal au coeur du matériau poreux. Le moule 12 comprend en outre un conduit latéral 39 s'étendant dans l'une des deux parties haute et basse, par exemple la partie haute 13, depuis l'extérieur de celle-ci en débouchant directement dans la chambre 33.The portions of the upper and lower parts contiguous to the enclosure are made of porous materials.
Dans le présent mode de mise en oeuvre de l'invention, on injecte la barbotine 8 sous pression dans le moule 12 pour former un dépôt 20, puis on injecte dans le moule la solution 10.In the present embodiment of the invention, the
Dans la première étape, le coulage est effectué sous une pression de 20.105 Pa. La barbotine 8 comprend une poudre en suspension dans une solution acqueuse. La poudre est constituée ici de 50% de kaolin et de 50% de quartz. Elle présente un diamètre de grains médian tel que
On injecte la barbotine en l'espèce par le conduit latéral 39, l'eau s'évacuant à travers le matériau poreux puis les conduits 29.The slip is injected in this case via the
L'injection de cette barbotine permet d'obtenir un dépôt 20 relativement peu dense après évacuation d'une partie de l'eau à travers la paroi du moule.The injection of 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.
Dans la deuxième étape, l'injection a également lieu sous pression de 20.105 Pa. La solution 10 est une solution acqueuse de défloculant PC 67 représentant en masse entre 0,10 et 4,70% de la solution (par exemple jusqu'à 1% en masse de l'article final 30). On injecte la solution 10 ici à partir du canal latéral 39. Au cours de cette deuxième étape, la solution traverse le dépôt 20 et l'eau s'échappe à travers la paroi du moule puis les conduits verticaux 29.In the second step, the injection is also carried out under a pressure of 20 × 10 5 Pa. 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
A l'issue d'une période adaptée, on ouvre le moule et on injecte de l'eau et de l'air comprimé pour décoller la pièce réalisée par rapport aux deux parties de moule. Cette injection a lieu via les conduits 29. Le produit intermédiaire 20 en est ôté en vue de sa finition d'une façon connue en soi (cuisson, etc) pour obtenir l'article 30 de la
Différentes concentrations massiques (masse de défloculant/masse totale de la solution 10) ont été testées, comprises entre 0 et 4,70% (soit 0 à 1% par rapport à la masse de solide). Pour chaque essai, la cinétique de filtration a été caractérisée (mesure de la masse de filtrat recueilli au cours du temps, calcul de la résistance spécifique c'est-à-dire de la résistance au passage de l'eau) ainsi que la structure du dépôt obtenu (porosité, diamètre des pores, résistance mécanique).Different mass concentrations (mass of deflocculant / total mass of the solution 10) were tested, ranging between 0 and 4.70% (
La
En absence de défloculant, le filtrat passe à travers le dépôt très rapidement. Il n'y a pas de temps mort avant le début de l'écoulement du filtrat.In the absence of deflocculant, the filtrate passes through the deposit very quickly. There is no time-out before the start of the filtrate flow.
En présence de défloculant, l'écoulement du filtrat à travers tout le dépôt n'est effectif qu'au bout de 114, 169, 222 et 128 s pour des concentrations en défloculant en masse de 0,10, 0,45, 0,65 et 4,70% respectivement. Ce temps mort augmente donc avec la concentration en défloculant sauf pour la concentration la plus élevée.In the presence of deflocculant, the flow of the filtrate through the entire deposit is only effective after 114, 169, 222 and 128 s for mass deflocculant concentrations of 0.10, 0.45, 0, 65 and 4.70% respectively. This dead time therefore increases with the concentration of deflocculant except for the highest concentration.
On a également étudié la variation de la vitesse d'écoulement du filtrat au cours de la filtration des solutions de défloculant dont la concentration varie de 0 à 4,70% à travers le dépôt. Pour des temps supérieurs au temps mort, le débit d'écoulement du filtrat est indépendant du temps mais varie légèrement avec la concentration en défloculant.The variation in the flow rate of the filtrate during the filtration of deflocculant solutions whose concentration varies from 0 to 4.70% through the deposition was also studied. For times longer than the dead time, the flow rate of the filtrate is time independent but varies slightly with the deflocculant concentration.
La
Des tests de résistance mécanique en flexion ont été également réalisés sur les dépôts après traitement et séchage. Les résultats sont présentés dans le tableau ci-dessous. CD indique la concentration en défloculant en pourcentage en masse dans la solution et σ est la contrainte à la rupture de flexion 3 points, en MPa.
Il apparaît que le dépôt obtenu après filtration d'une solution contenant 4,70% de défloculant a une résistance mécanique 2 fois supérieure à celle obtenue pour les autres dépôts. Cette variation importante de résistance mécanique montre que la structure du dépôt a été modifiée.It appears that the deposit obtained after filtration of a solution containing 4.70% deflocculant has a
Les essais de post-filtration mettent en évidence les points suivants :
- L'écoulement de la solution 10 contenant le défloculant n'est effectif qu'au bout de 100 à 200 s contrairement à l'eau pour laquelle l'écoulement se fait sans temps mort. Ce résultat montre qu'en présence de défloculant, le passage de la solution entraîne des modifications de la structure poreuse avant qu'elle puisse s'écouler à travers toute l'épaisseur du dépôt. Avec l'eau seule, l'écoulement à travers l'épaisseur du dépôt ne provoque pas de modification de la structure puisque son écoulement se fait sans temps mort.
- The flow of the solution 10 containing the deflocculant is effective only after 100 to 200 s unlike the water for which the flow is done without a dead time. This result shows that in the presence of deflocculant, the passage of the solution causes modifications of the porous structure before it can flow through the entire thickness of the deposit. With the water alone, the flow through the thickness of the deposit does not cause a modification of the structure since its flow is without a dead time.
Après traitement, la résistance spécifique du dépôt est augmentée ainsi que sa résistance mécanique. Cette augmentation montre que l'écoulement d'une solution de défloculant à travers un dépôt peu dense permet le réarrangement des particules en une structure plus compacte (plus résistante mécaniquement et plus homogène).After treatment, the specific resistance of the deposit is increased as well as its mechanical strength. This increase shows that the flow of a deflocculant solution through a low density deposit allows the rearrangement of the particles into a more compact structure (more mechanically resistant and more homogeneous).
Cette méthode de post-filtration permet donc d'obtenir un dépôt plus dense grâce au réarrangement des particules au cours de ce processus.This post-filtration method therefore makes it possible to obtain a denser deposit by rearranging the particles during this process.
Le mécanisme de compaction du dépôt est peut-être le suivant. La
La
Sur ces deux figures, les flèches 26 représentent l'écoulement du filtrat.In these two figures, the
Le coulage sous pression d'une barbotine, de préférence, floculée, suivi d'un post-traitement visant à réorganiser le dépôt de particules afin de le rendre apte à subir le reste du procédé de fabrication ouvre certaines perspectives en matière de CSP.Pouring a slip, preferably flocculated, followed by a post-treatment to reorganize the deposition of particles to make it suitable for the rest of the manufacturing process opens up some prospects for CSP.
En effet, il améliore le rendement de fabrication des produits réalisés avec des barbotines "qui coulent bien" (porcelaines, vitréous). On peut ainsi diminuer de façon sensible la durée du cycle de coulage en injectant une barbotine floculée puis en procédant à la défloculation in situ par post-traitement.Indeed, it improves the production yield of products made with slip "that flow well" (porcelain, vitréous). It is thus possible to significantly reduce the duration of the pouring cycle by injecting a flocculated slip and then carrying out deflocculation in situ by post-treatment.
Une seconde application de l'invention consiste à appliquer le principe aux barbotines "qui ne coulent pas bien" telles que les faïences et les grès ou toute autre barbotine contenant une forte proportion d'argile. Le procédé décrit ici permet en effet la mise en oeuvre de telles barbotines en CSP alors que ce n'était pas le cas précédemment dans la conception du procédé et des machines.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. 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.
L'application de l'invention aux machines antérieures de coulage sous pression est relativement simple :
Le système 14 de pompage et de distribution sous pression devra de préférence être capable de véhiculer des suspensions de viscosité supérieure aux viscosités couramment utilisées dans l'art antérieur,
- The
system 14 for pumping and dispensing under pressure should preferably be capable of conveying suspensions of viscosity higher than the viscosities commonly used in the prior art,
La purge du système véhiculant la solution de défloculant devra être complète avant la nouvelle injection de barbotine afin de ne pas produire une défloculation involontaire de cette dernière. Ainsi, après injection de la solution 10 en post-traitement, on active les moyens de purge 16 pour nettoyer la portion de circuit devant être empruntée par la solution 8 durant le cycle suivant.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. Thus, after injection of the solution 10 in post-treatment, the purge means 16 is activated to clean the portion of circuit to be borrowed by the
Bien entendu, on pourra apporter à l'invention de nombreuses modifications sans sortir du cadre de celle-ci.Of course, we can bring to the invention many changes without departing from the scope thereof.
L'invention est applicable à tout type de céramique. Elle sera ainsi applicable aux céramiques traditionnelles argileuses utilisées pour les arts de la table ou les sanitaires. Elle sera également applicable aux céramiques techniques (telles que celles à base de nitrure de silicium ou de carbure de silicium) par exemple pour la fabrication de supports de composants électroniques ou de matériaux réfractaires.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.
Claims (8)
- Method of producing a ceramic article (30), comprising the steps consisting in:- casting a slip (8) under pressure into a mold (12) in order to form a deposit (20); and- filtering a solution (10) containing a deflocculant through the deposit (20).
- Method according to Claim 1, characterized in that the slip (10) is flocculated.
- Method according to either of Claims 1 and 2, characterized in that the slip (10) comprises kaolin.
- Method according to any one of Claims 1 to 3, characterized in that the slip comprises clay.
- Method according to any one of Claims 1 to 4, characterized in that the slip (10) comprises quartz.
- Method according to any one of Claims 1 to 5, characterized in that the deflocculant represents at most 3% by weight of the article (30).
- Method according to any one of Claims 1 to 6, characterized in that the deflocculant represents at most 5% by weight of the solution (10).
- Method according to any one of Claims 1 to 7, characterized in that the deflocculant represents between 0.20% and 3% by weight of the solution (10).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0214305A FR2847195B1 (en) | 2002-11-15 | 2002-11-15 | METHOD FOR MANUFACTURING A CERAMIC ARTICLE BY PRESSURIZED CASTING |
FR0214305 | 2002-11-15 | ||
PCT/FR2003/003379 WO2004045818A1 (en) | 2002-11-15 | 2003-11-14 | Method of producing a ceramic article by means of pressure casting |
Publications (2)
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EP1575745A1 EP1575745A1 (en) | 2005-09-21 |
EP1575745B1 true EP1575745B1 (en) | 2013-07-24 |
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EP20030782563 Expired - Lifetime EP1575745B1 (en) | 2002-11-15 | 2003-11-14 | Method of producing a ceramic article by means of pressure casting |
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US (1) | US20060134399A1 (en) |
EP (1) | EP1575745B1 (en) |
JP (1) | JP4561362B2 (en) |
AU (1) | AU2003290201A1 (en) |
ES (1) | ES2431838T3 (en) |
FR (1) | FR2847195B1 (en) |
WO (1) | WO2004045818A1 (en) |
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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 (en) * | 1991-09-06 | 1998-09-21 | 新東工業株式会社 | Forming method for sintering prototype |
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 (en) * | 2001-02-26 | 2002-09-11 | Toto Ltd | Sanitary chinaware |
-
2002
- 2002-11-15 FR FR0214305A patent/FR2847195B1/en not_active Expired - Lifetime
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2003
- 2003-11-14 US US10/534,845 patent/US20060134399A1/en not_active Abandoned
- 2003-11-14 ES ES03782563T patent/ES2431838T3/en not_active Expired - Lifetime
- 2003-11-14 JP JP2004552800A patent/JP4561362B2/en not_active Expired - Fee Related
- 2003-11-14 WO PCT/FR2003/003379 patent/WO2004045818A1/en active Application Filing
- 2003-11-14 EP EP20030782563 patent/EP1575745B1/en not_active Expired - Lifetime
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US20060134399A1 (en) | 2006-06-22 |
FR2847195A1 (en) | 2004-05-21 |
AU2003290201A1 (en) | 2004-06-15 |
EP1575745A1 (en) | 2005-09-21 |
WO2004045818A1 (en) | 2004-06-03 |
JP2006506255A (en) | 2006-02-23 |
JP4561362B2 (en) | 2010-10-13 |
ES2431838T3 (en) | 2013-11-28 |
FR2847195B1 (en) | 2005-07-29 |
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