US20030098530A1 - Production method for ceramic structure and production method for ceramic honeycom structure - Google Patents

Production method for ceramic structure and production method for ceramic honeycom structure Download PDF

Info

Publication number
US20030098530A1
US20030098530A1 US10/267,049 US26704902A US2003098530A1 US 20030098530 A1 US20030098530 A1 US 20030098530A1 US 26704902 A US26704902 A US 26704902A US 2003098530 A1 US2003098530 A1 US 2003098530A1
Authority
US
United States
Prior art keywords
ceramic
water
production method
added
lubricant
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.)
Abandoned
Application number
US10/267,049
Inventor
Kazuhiro Inoguchi
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.)
Denso Corp
Original Assignee
Denso Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denso Corp filed Critical Denso Corp
Assigned to DENSO CORPORATION reassignment DENSO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INOGUCHI, KAZUHIRO
Publication of US20030098530A1 publication Critical patent/US20030098530A1/en
Priority to US12/654,495 priority Critical patent/US8747729B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006Honeycomb structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/20Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein the material is extruded
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/11Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels comprising two or more partially or fully enclosed cavities, e.g. honeycomb-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/30Extrusion nozzles or dies
    • B29C48/32Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/362Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using static mixing devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/375Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/385Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/195Alkaline earth aluminosilicates, e.g. cordierite or anorthite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/62625Wet mixtures
    • C04B35/6263Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/636Polysaccharides or derivatives thereof
    • C04B35/6365Cellulose or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02Natural products
    • C10M159/08Fatty oils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/268Throttling of the flow, e.g. for cooperating with plasticising elements or for degassing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/76Venting, drying means; Degassing means
    • B29C48/765Venting, drying means; Degassing means in the extruder apparatus
    • B29C48/766Venting, drying means; Degassing means in the extruder apparatus in screw extruders
    • B29C48/767Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2709/00Use of inorganic materials not provided for in groups B29K2703/00 - B29K2707/00, for preformed parts, e.g. for inserts
    • B29K2709/02Ceramics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/60Multitubular or multicompartmented articles, e.g. honeycomb
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/60Multitubular or multicompartmented articles, e.g. honeycomb
    • B29L2031/608Honeycomb structures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034Physico-chemical characteristics of the mixtures
    • C04B2111/00129Extrudable mixtures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3218Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • C04B2235/3436Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445Magnesium silicates, e.g. forsterite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602Making the green bodies or pre-forms by moulding
    • C04B2235/6021Extrusion moulding
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/14Composite materials or sliding materials in which lubricants are integrally molded

Definitions

  • This invention relates to a production method for a ceramic structure or a ceramic honeycomb structure.
  • the method includes extrusion a ceramic material by use of a dedicated die.
  • the invention particularly relates to an improvement of a extrusion rate during extrusion.
  • a honeycomb structure assembled into an exhaust gas purification apparatus of an automobile is one of the structures produced from ceramics such as cordierite (refer, for example, to Japanese Unexamined Patent Publication (Kokai) No. 8-11528).
  • This honeycomb structure includes a cylindrical outer cladding, partitions arranged in grid form inside the outer cladding and a large number of cells separated by partitions and penetrating in an axial direction.
  • a ceramic material containing ceramic powder, water, a binder and a lubricant is mixed and kneaded, extruded, and then dried and sintered.
  • the extrusion rate can be improved to a certain extent when a bigger extruder is used to increase the pressure. In this case, however, the temperature of the resulting molding rises and the shape of the extrusion cannot be retained. Therefore, a cooler for cooling the extruder must be added or the capacity of the cooler must be increased. As a result, the setup cost increases.
  • the invention aims at providing a production method for a ceramic structure capable of increasing the extrusion rate coefficient described above in the extrusion of ceramic structures.
  • a first aspect of the invention provides a production method for a ceramic structure comprising the steps of mixing and kneading a ceramic material containing at least a ceramic powder and water, extruding the mixture so kneaded, and drying and sintering a extrudate, wherein a water-insoluble liquid lubricant (hereinafter merely called a “lubricant” in some cases) consisting of acyl glycerin as its main component and/or its derivative is added to the ceramic batch material.
  • a water-insoluble liquid lubricant hereinafter merely called a “lubricant” in some cases
  • a water-insoluble liquid lubricant consisting of acyl glycerin, and/or a derivative, as a main component is added to the ceramic batch material.
  • a water-soluble lubricant has been used in the past for the ceramic batch material that is kneaded to a clay form by use of water, and the invention employs an entirely novel ceramic batch material.
  • the invention can make the resistance in extrusion of the ceramic batch material smaller and the extrusion rate coefficient greater than when the water-soluble lubricant is added as in the prior art technologies.
  • the reason is assumed as follows.
  • the water-insoluble liquid lubricant that is incompatible with water but is uniformly dispersed in the ceramic batch material kneaded into the clay form, leaches to the clay surface when a pressure is applied during extrusion, wets the friction surfaces of a cylinder and barrel of an extruder and the die, and reduces the coefficient of friction.
  • This phenomenon is analogous to squeezing of a material of vegetable oil such as soybean oil and rapeseed oil.
  • water-soluble lubricants according to the prior art have high affinity with water and are bonded to the ceramic power material together with water. Therefore, even when the pressure is applied during extrusion, the lubricants do not leach to the clay surface. Therefore, only the limited amount of the water-soluble lubricants existing on the clay surface can contribute to lubrication performance. Even when a high pressure is locally applied, these lubricants cannot be concentrated on that portion, and cannot reduce the coefficient of friction, either.
  • the lubricant consisting of acyl glycerin and/or its derivative among the water-insoluble liquid lubricants can secure a relatively large gap between the ceramic raw material and the friction surface of the die, though the reason has not entirely been clarified. It is assumed that the greater the adsorption force of the lubricant to the die, the smaller becomes the coefficient of friction.
  • the invention can make the extrusion rate coefficient, described above, in extrusion of the ceramic Structure greater than in the prior art technologies. Therefore, the invention can suppress a drop in the rate when a ceramic structure having a shape that involves a large die resistance during extrusion is extruded. In consequence, the invention can improve productivity while keeping the quality of the ceramic structure and its shape retainability.
  • a second aspect of the invention provides a production method of a ceramic honeycomb structure having partitions arranged in a honeycomb shape, comprising the steps of mixing and kneading a ceramic batch material containing at least ceramic powder, water, a binder, extruding the mixture so kneaded, and drying and sintering a extrudate, wherein a water-insoluble liquid lubricant that is a water-insoluble liquid at a temperature of extrusion is added to the ceramic batch material.
  • the water-insoluble liquid lubricant that is a water-insoluble liquid at a temperature of extrusion is added to the ceramic batch material.
  • This is extremely revolutionary in the production of the ceramic honeycomb structure because the water-soluble lubricant has been employed in the past.
  • the invention uses a ceramic batch material having an entirely novel construction. In comparison with the case where the water-soluble lubricant is added as in the prior art technologies, the resistance when extruding the ceramic honeycomb structure by extruding the ceramic batch material can be reduced, and the extrusion rate coefficient can be increased.
  • the second invention can make the extrusion rate coefficient greater in extrusion of the ceramic honeycomb structure greater than in the prior art technologies, the drop of the extrusion rate can be suppressed when a ceramic honeycomb structure, having a shape that has a large die resistance in extruding, is extruded.
  • the second invention can further suppress die cracking resulting from the increase of the pressure and extrusion defect resulting from die deflection. For these reasons, the second invention can improve productivity while keeping the quality of the ceramic honeycomb structure and its shape retainability.
  • FIG. 1 is an explanatory view showing a construction of an extruder in Example 1;
  • FIG. 2 is an explanatory view showing a construction of a honeycomb structure in Example 1;
  • FIG. 3 is an explanatory view showing a clearance between a ceramic batch material and a friction surface of a die when using polyoxyethylene polyoxypropylene monobutylether (PPBE) as an example of existing lubricants;
  • PPBE polyoxyethylene polyoxypropylene monobutylether
  • FIG. 4 is an explanatory view showing a clearance between the ceramic batch material and the friction surface of a die when rapeseed oil (Canola oil) (triacyl glycerin) is used in Example 1;
  • FIG. 5 is an explanatory view showing a relation between a extrusion pressure and a extrusion rate in Example 2;
  • FIG. 6 is an explanatory view showing a relation between an addition amount of rapeseed oil and a extrusion rate ratio in Example 3;
  • FIG. 7 is an explanatory view showing a relation between a extrusion pressure and a extrusion rate in Example 4.
  • FIG. 8 is an explanatory view showing a relation between the number of revolutions of a motor and a extrusion rate in Example 5;
  • FIG. 9 is an explanatory view showing a relation between the number of revolutions of a motor and a motor current in Example 5;
  • FIG. 10 is an explanatory view showing a relation between a liquid ratio in a ceramic batch material and hardness in Example 6;
  • FIG. 11 is an explanatory view showing a relation between a water-insoluble liquid lubricant and a kinematic viscosity (cSt) in Example 6;
  • FIG. 12 is an explanatory view showing experimental points of a lubricant content and a water content (moisture ratio) with respect to a matrix in Example 7;
  • FIG. 13 is an explanatory view showing an optimum range of lubricant content and water content (moisture ratio) in a matrix in Example 7.
  • the first invention described above can use a water-insoluble liquid lubricant consisting of acyl glycerin, and/or a derivative, as a main component.
  • liquid lubricant herein used excludes those grease-like liquid lubricants that have an extremely high viscosity at normal temperature.
  • the water-insoluble liquid lubricant consisting of acyl glycerin, and/or a derivative, as the main component preferably has a viscosity of 15 to 45 cp at 50° C. In this case, handling of the water-insoluble liquid lubricant becomes easier when an automatic line is set up. When the viscosity is less than 15 cp, the viscosity is so low that a sufficient effect cannot be acquired in extrusion at a high pressure. When the viscosity exceeds 45 cp, on the other hand, the viscosity is so high that an extrusion rate cannot be improved.
  • rotary viscometers known generally such as a B type, a C type, a BH type, an E type, and so forth, can be employed for the measurement.
  • Acyl glycerin is called “acyl glycerol” according to the IUPAC nomenclature, and includes monoacyl glycerin, diacyl glycerin and triacyl glycerin. Triacyl glycerin among them is a main component of natural fat. It is expressed by a chemical formula in which three aliphatic acids are bonded with one glycerin:
  • each of R 1 , R 2 and R 3 is an alkyl group of an aliphatic acid).
  • the aliphatic acids R 1 , R 2 and R 3 in the chemical formula given above include various kinds.
  • Examples of the water-insoluble liquid lubricant consisting of triacyl glycerin, and/or a derivative, as its main component are various vegetable oil such as rapeseed oil, soybean oil, sunflower oil, cotton seed oil, and so forth.
  • methyl cellulose on the basis of 100 wt % of ceramic powder is added to the ceramic batch material.
  • Methyl cellulose increases plasticity, improves shape retainability when extrusion is conducted, and improves dry strength of a dried ceramic structure.
  • the addition amount of methyl cellulose is les than 2.0 wt % (to be added), an improvement effect of plasticity and bonding power during drying due to its addition cannot be expected.
  • the addition amount of methyl cellulose exceeds 8.0 wt % (to be added), on the other hand, a problem occurs that volume shrinkage becomes excessively great after sintering.
  • the amount of ceramic powder is 100 wt % as the unit of the addition amount
  • the amount of the component to be added to ceramic powder is expressed as wt % (to be added) and when the overall ceramic bath is expressed as 100 wt %, the component contained in the batch material is expressed by wt % (to be contained).
  • the water-insoluble liquid lubricant consists of triacyl glycerin as the main component.
  • the addition amount of the water-insoluble liquid lubricant is preferably at least 0.5 wt % (to be added) on the basis of 100 wt % of ceramic powder.
  • the effect of improving the extrusion rate coefficient brought forth by the addition of the water-insoluble liquid lubricant is small if the addition amount of the water-insoluble liquid lubricant is less than 0.5 wt % (to be added)
  • the addition amount is preferably limited from the aspects of saturation of the addition effect and the increase of the cost.
  • the main component of the aliphatic acid constituting triacyl glycerin described above is preferably an aliphatic acid having 18 carbon atoms.
  • Concrete examples are stearic acid, oleic acid, linolic acid, linolenic acid, elaidic acid, cis-vaccenic acid, vaccenic acid and other aliphatic acids- Triacyl glycerin constituted by these C18 aliphatic acids is liquid at normal temperature, has a suitable viscosity and is most suitable as the water-insoluble liquid lubricant.
  • a saponification value of triacyl glycerin is preferably not greater than 200. In this case, the effect of improving the extrusion rate coefficient can be sufficiently acquired.
  • the water-insoluble liquid lubricant that is a water-insoluble liquid at the temperature of extrusion is added to the ceramic batch material.
  • a binder such as methyl cellulose is generally added to the batch material to impart plasticity and to obtain dry strength.
  • the temperature of the material is controlled to about 10 to about 30° C. with a center temperature at about 20° C.
  • the water-insoluble liquid lubricant suitable for this purpose preferably has a kinematic viscosity of 30 cSt to 120 cSt at 20° C.
  • the kinematic viscosity described above may belong to the following four viscosity grades stipulated in ISO viscosity classification for industrial lubricant oil (ISO 3448-1975 and JIS K2001 “Viscosity Classification of Industrial Lubricant Oil” applied correspondingly to the former), that is, ISO VG22, ISO VG32, ISO VG46 and ISO VG68.
  • the sum of water and the water-insoluble liquid lubricant contained in the ceramic batch material is preferably 18.0 to 24.5 wt % (to be contained) on the basis of 100 wt % of the total ceramic batch material.
  • the viscosity of the material becomes so high that the extrusion pressure exceeds the die strength, or the ceramic batch material becomes powdery and dusty with the result that plasticization cannot be attained (the material does not become clay-like) and extruding becomes substantially impossible.
  • the sum of water and the water-insoluble liquid lubricant is preferably 20.0 to 22.5 wt % (to be contained) on the basis of 100 wt % of the overall ceramic batch material as will be later described.
  • Shape retainability is of importance in a thin ceramic honeycomb structure, and to retain the shape, the sum of the contents is more preferably not greater than 22.5 wt % (to be contained) Since the extrusion pressure becomes greater in the thin ceramic honeycomb structure, the sum of the content is more preferably at least 20.0 wt % (to be contained) to obtain an excellent extrusion condition.
  • the binder described above is methyl cellulose, and the content of the binder is preferably 2.0 to 8.0 wt % (to be added) when the content of ceramic powder is 100 wt %.
  • the reason for limitation of the methyl cellulose content in this case is the same as that of the first invention.
  • the ceramic honeycomb structure described above has partitions arranged in the honeycomb shape. Therefore, it has large resistance particularly when passing through the die, and the extrusion rate coefficient is likely to become small. In this sense, the application of the invention is extremely effective.
  • the thickness of the partitions is preferably not greater than 150 ⁇ m. In this case, because the resistance becomes great when the ceramic honeycomb structure passes through the die, and the application of the invention is further effective.
  • the honeycomb structure is preferably extrusion-molded by use of a die having slits for forming the partitions described above, and a width of the slit is preferably not greater than 150 ⁇ m.
  • a width of the slit is preferably not greater than 150 ⁇ m.
  • the water-insoluble liquid lubricant is triacyl glycerin and when the amount of ceramic powder is 100 wt %, the addition amount of the water insoluble liquid lubricant is preferably 1.0 to 8.0 wt % (to be added).
  • the addition amount of the water-insoluble liquid lubricant exceeds 8.0 wt % (to be added) in the case of a ceramic honeycomb structure having a complicated shape, large amounts of oil are burnt and scattered during a degreasing process at the time of sintering, and sintering cracks are likely to occur.
  • the amount is less than 1.0 wt % (to be added), the remarkable effect of improving the extrusion rate cannot be obtained in comparison with the existing level. Therefore, the addition amount of the water-insoluble liquid lubricant is preferably 1.0 to 8.0 wt % (to be added).
  • the main component of the aliphatic acid constituting triacyl glycerin described above is preferably an aliphatic acid having 18 carbon atoms in the same way as in the first invention.
  • the saponification value of triacyl glycerin is preferably not greater than 200 in the same way as in the first invention
  • a production method of a ceramic structure according to this example will be explained with reference to FIGS. 1 to 4 .
  • a method of producing a ceramic structure 8 by the steps of mixing and kneading a ceramic batch material 88 containing at least ceramic powder and water, extruding the mixture, and drying and sintering the resulting extrudate, this example added a water-insoluble liquid lubricant consisting of acyl glycerin and/or its derivative as a main component to the ceramic batch material 88 .
  • This example produced a honeycomb structure including an outer cladding 81 , partitions 82 arranged in a grid form inside the outer cladding 81 and a large number of cells 80 separated by the partitions 82 and penetrating in an axial direction, and consisting of cordierite as the main component.
  • talc, kaolin, alumina and aluminum hydroxide powder that were components capable of changing to cordierite after sintering were used as ceramic powder that constituted the ceramic batch material 88 described above.
  • a water-insoluble liquid lubricant consisting of methyl cellulose, water and acyl glycerin and/or its derivative as the main component was added to the powder mixture to form the ceramic batch material 88 .
  • Rapeseed oil consisting of triacyl glycerin as the main component, more concretely rapeseed oil containing 97% of triacyl glycerin, 0-8% of diacyl glycerin and 0.1% of monoacyl glycerin by weight ratio, was used as the water-insoluble liquid lubricant consisting of acyl glycerin and/or its derivative as the main component.
  • symbol C represents carbon
  • symbol a in a:b as the suffix to C represents the number of carbon atoms and b represents the number of double bonds.
  • the ceramic batch material 88 was kneaded in a kneader 3 and was extruded by use of a screw type extruder 1 as shown in FIG. 1.
  • a screw type extruder 1 as shown in FIG. 1.
  • Each of the extruder 1 and the kneader 3 included inside a cylindrical frame 11 , 31 a screw 15 , 35 having a screw plate 150 , 350 that was helically wound.
  • the crew 15 , 35 was driven for rotation by a motor 17 , 37 connected to its rear end.
  • a material charging hole 39 was provided to the upper part of the frame 31 of the kneader, and the ceramic batch material 88 was charged through this charging hole 39 .
  • the kneaded ceramic batch material 88 was extruded from a distal end portion 38 of the kneader 31 and was then charged into a material charging hole 19 of the extruder 1 .
  • the material charging portion to the extruder 1 was kept as a whole under vacuum by a vacuum pump 195 to suppress entrapment of the ceramic batch material into air.
  • a die 2 for shaping was arranged at the distal end of the extruder 1 .
  • the die 2 had grid-like slits 20 corresponding to the shape of the partitions 82 of the honeycomb structure 8 to be produced.
  • the ceramic batch material 88 was charged into the extruder 1 , was moved forth by the revolution of the screw 15 and was thereafter extruded from the die 2 . In this way, the honeycomb structure 8 was extruded and extruded.
  • honeycomb structure 8 so extruded was serially cut into a desired length and was passed through subsequent drying and sintering steps to give complete products.
  • rapeseed oil as the water-insoluble liquid lubricant consisting of triacyl glycerin as described above was added to the ceramic batch material 88 . Therefore, in comparison with the case where a conventional lubricant was added, the extrusion rate coefficient in extrusion could be drastically improved and presumably for the following reason.
  • the water-insoluble liquid lubricant such as triacyl glycerin was not dissolved in water but was dispersed in the ceramic batch material. Therefore, when the pressure was applied during extrusion, the lubricant leached to the clay surface, lubricated the cylinder, the barrel and the friction surface of the die and could thus decrease the coefficient of friction. The greater the pressure applied in this case, the greater became the amount of the lubricant leaching from inside the clay. Consequently, even when the pressure locally increased, a necessary amount of lubricant was concentratedly supplied to that portion, and the coefficient of friction could be efficiently lowered.
  • a water-soluble lubricant was highly hydrophilic and was strongly bonded to the ceramic material as an aqueous solution. Therefore, even when the pressure was applied during extrusion, the lubricant did not leach to the clay surface.
  • Synthetic lubricants well known in the past includes polyoxyethylene-polyoxypropylene-monobuthylether (trade name: “Uniloob”) expressed by the following formula:
  • This synthetic lubricant became water-soluble and water-insoluble depending on a polymerization ratio of propylene oxide and ethylene oxide. Since this lubricant was used in combination with water in the field of ceramics, it was generally used while the ratio of ethylene to oxide was set to 40% or more. In this case, the oxygen ion (O ⁇ ) of ethylene oxide was adsorbed to the iron ion (Fe + ) of the die 2 , for example, between the die 2 and the boundary 89 surface of the solid content of the ceramic batch material as shown in FIG. 3.
  • the water-insoluble liquid lubricant consisting of triacyl glycerin as the main component in this example could be arranged between the die 2 and the boundary surface 89 of the solid content of the ceramic batch material while the molecule of the aliphatic acid remained upright as shown in FIG. 4. Further, the acyl glycerin had a carbonyl group (COO ⁇ ) and exhibited a stronger adsorption force to the iron ion (Fe + ) than to the oxygen ion (O ⁇ ). Therefore, the water-insoluble liquid lubricant (rapeseed oil) consisting of triacyl glycerin as the main component of this example was more difficult to peel from the die 2 than the conventional water-soluble lubricant.
  • Example 1 conducted experiments by comparing the case where PPBE (C1) was used as the conventional water-soluble lubricant with the cases where water-insoluble liquid lubricants consisting of four kinds of acyl glycerin as the main components were used.
  • Rapeseed oil (E1), soybean oil (E2), safflower oil (E3) and linseed oil (E4) consisting of triacyl glycerin as the main component were used as the water-insoluble liquid lubricants consisting of acyl glycerin as the main component.
  • a batch type kneader was used as a kneader, a screw type extruder for an experimental use was used as a extruding machine, and a die having a slit width of 150 ⁇ m and 400 mesh (400 cells/in. 2 ) was used as a die.
  • Honeycomb structures having an outer diameter of ⁇ 500 mm were extruded.
  • FIG. 5 shows the measurement result.
  • the abscissa represents the extrusion pressure (MPa/cm 2 ) and the ordinate does the extrusion rate (m/min).
  • Symbols C1 and E1 to E4 respectively represent the results when the lubricants (C and E1 to E4) were used.
  • the extrusion rates at the same extrusion pressure could be much more improved when the water-insoluble liquid lubricants (E1 to E4) consisting of triacyl glycerin as the main component were used than when the conventional water-soluble lubricant (C1) was used.
  • the extrusion rate coefficient could be improved.
  • This example used rapeseed oil as a typical example of the water-insoluble liquid lubricant consisting of acyl glycerin as the main component, and a test was carried out to determine an optimum range of its addition amount.
  • test condition was as follows.
  • the addition amount of methyl cellulose was fixed at 5 wt % (to be added) on the basis of 100 wt % of ceramic powder, and the addition amount of water was fixed at 26 wt % (to be added) on the basis of 100 wt % of ceramic powder.
  • the addition amount of rapeseed oil was changed within a range of 0.5 to 10.0 wt % (to be added) on the basis of 100 wt % of ceramic powder For comparison, a case where rapeseed oil was not added at all was also tested.
  • a batch type kneader was used as a kneader for kneading the ceramic batch material, and an FM-30 vacuum extruder, a product of Miyazaki Steel Co., was used as a extruding machine.
  • An FM-30 vacuum extruder a product of Miyazaki Steel Co., was used as a extruding machine.
  • a die having a slit width of 150 m and the number of cells of 400 cells/in. 2 was used.
  • Ceramic batch materials having mutually different addition amounts of rapeseed oil were used and each extrusion rate with respect to a extrusion pressure was measured to determine the extrusion rate coefficient for each addition amount of rapeseed oil.
  • the extrusion rate coefficient when rapeseed oil was not added was set to 1, and a ratio to this value was determined as a extrusion rate ratio.
  • FIG. 6 shows the result.
  • the abscissa represents the addition amount (wt % to be added) of rapeseed oil, and the ordinate does the extrusion rate ratio.
  • the result is represented as E 5 .
  • the addition amount of rapeseed oil as the lubricant consisting of acyl glycerin as the main component was preferably less than 10.0 wt % (to be added).
  • the addition amount of rapeseed oil was preferably small.
  • the addition amount was preferably not greater than 8.0 wt % (to be added).
  • the hardness of the ceramic batch material could be regulated by the addition amount of water
  • a ceramic batch material having suitable hardness could be obtained by adjusting the addition amount of rapeseed oil and the addition amount of water.
  • the die used for extrusion in this example had a slit width of 3 mil (76.2 ⁇ m) and the number of cells of 400 cells/in. 2 , and a honeycomb structure having an outer diameter of ( ⁇ 107 mm was molded.
  • composition of the ceramic batch material was fundamentally the same as that of Example 3, and the addition amount of rapeseed oil as the lubricant was fixed at 3 wt % (to be added).
  • a large-scale screw type vacuum extruder for a production plant (not shown) was used as a kneader and a extruding machine.
  • FIG. 7 shows the test result.
  • the abscissa represents the extrusion pressure (MPa/cm 2 ) and the ordinate represents the extrusion rate (m/min).
  • Symbol E6 represents the case of the addition of rapeseed oil and C2 does the case where PPBE was added.
  • This example used linseed oil as the lubricant consisting of acyl glycerin as the main component, and actually extruded a honeycomb structure having a partition thickness of 4 mils (101.6 ⁇ m), the number of cells of 600 cells/in. 2 and an outer shape of ⁇ 120 mm. The result was compared with the case where the water-soluble lubricant (PPBE) was used in the same way as in Example 4.
  • PPBE water-soluble lubricant
  • extrusion was carried out while the number of revolutions of a motor for turning a screw shaft of a screw type extruder and a motor current were respectively measured to examine the relations between these values and the extrusion rate.
  • FIGS. 8 and 9 show the test result.
  • the abscissa represents the number of revolutions of the motor (rpm) and the ordinate represents the extrusion rate (m/min).
  • the abscissa represents the number of revolutions of the motor (rpm) and the ordinate represents the motor current (A).
  • Symbol E7 represents the case where linseed oil was used and C3 represents the case where PPBE was used.
  • This example used rapeseed oil, linseed oil and soybean oil as the water-insoluble liquid lubricants consisting of triacyl glycerin as the main component.
  • Each ceramic batch material for a ceramic honeycomb structure containing the lubricant in a blend ratio tabulated in Tables 1 to 3 was kneaded in a batch type kneader. The clay hardness (plasticity) was examined, and the ceramic honeycomb structures were extruded by use of a vacuum extruder in the same way as in Example 3 to evaluate extrudability and the extrusion rate.
  • clay hardness plasticity: workability index, stipulated in former JIS P2574 abandoned in 1998) is the value measured by use of a pencil-shaped spring type penetrometer ordinarily used in this field.
  • a higher numerical value represents a higher hardness and a smaller numerical value represents a lower hardness.
  • a relatively high extrudability could be obtained at a liquid ratio of 18 to 24.5 wt % (to be contained) and a hardness (plasticity coefficient) of 9 to 11 and preferably a liquid ratio of 20 to 22.5 wt % (to be contained) and a hardness of 9.6 to 10.7.
  • the inclination of the relation between the clay hardness (plasticity coefficient) and the liquid ratio became somewhat different depending on the kind of the lubricant presumably because of the difference of the viscosity of the lubricant at the measurement temperature.
  • Pa ⁇ s is used in due form as the unit of viscosity (coefficient of viscosity)
  • cP centi-poise
  • 1 Pa ⁇ s 1 ⁇ 10 3 cP.
  • the kinematic viscosity was measured by use of an Ostwald viscometer as a kind of capillary viscometer.
  • FIG. 11 shows the measurement result.
  • the abscissa represents the temperature and the ordinate represents the kinematic viscosity (cSt).
  • the kinematic viscosity at 20° C. was 43.1 cSt for the soybean oil, 86.8 cSt for rapeseed oil and 45.8 cSt for linseed oil.
  • the kinematic viscosity at 40° C. was 27.1 cSt for soybean oil, 47.6 cSt for rapeseed oil and 28.1 cSt for linseed oil.
  • the measurement result by the E type viscometer at 50° C. was 22.0 cp for soybean oil, 24.2 cp for rapeseed oil and 18.2 cp for linseed oil.
  • the liquid ratio was fixed at 21.35 wt % (to be contained) by adjusting the water content on the basis of the result of Example 6, rapeseed oil was used as the lubricant in the same way as in Example 3, and a extruding test was carried out by changing the addition amount of the lubricant within a range of 1 to 10 wt % (to be added).
  • Table 5 and FIG. 12 show the blend proportions (experimental condition) of the test product.
  • Table 4 and FIG. 12 show also the blend proportion (experimental condition) of Example 3, too.
  • the abscissa represents the addition amount of the water-insoluble liquid lubricant in terms of wt % (to be added) and the ordinate represents the water content (addition amount of water) in terms of wt % (to be contained).
  • a plurality of lines drawn slantingly in the diagram represents the total content (liquid ratio) of water and the water-insoluble liquid lubricant contained in the ceramic batch material in terms of wt % (to be contained). The lines respectively represent from below 18.0 wt % (to be contained), 20 wt % (to be contained), 22.5 wt % (to be contained) and 24.5 wt % (to be contained).
  • the range of the liquid ratio in this case was at least 20.0 to 22.5 wt % (to be contained).
  • FIG. 13 shows an optimum range of water and the lubricant for producing a ceramic honeycomb structure by combining the conditions described above with the suitable range of content of the lubricant consisting of triacyl glycerin as the main component.
  • This diagram has the same fundamental construction as that of FIG. 12, and the suitable ranges of the liquid ratio and the water-insoluble liquid lubricant are hatched.
  • TABLE 4 Condition and result of Example 3 wt % (to be contained) ratio wt % (to be added) ratio of material of material evaluation result

Abstract

This invention provides a production method for a ceramic structure capable of making a extrusion rate coefficient, in extruding of a ceramic structure, greater than that of prior art technologies. In a production method for a ceramic structure by the steps of mixing and kneading a ceramic batch material containing at least ceramic powder and water, extruding the mixture so kneaded, and drying and sintering a resulting extrudate, a water-insoluble liquid lubricant consisting of acyl glycerin and/or a derivative is added to the ceramic batch material.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0001]
  • This invention relates to a production method for a ceramic structure or a ceramic honeycomb structure. The method includes extrusion a ceramic material by use of a dedicated die. The invention particularly relates to an improvement of a extrusion rate during extrusion. [0002]
  • 2. Description of the Related Art [0003]
  • A honeycomb structure assembled into an exhaust gas purification apparatus of an automobile, for example, is one of the structures produced from ceramics such as cordierite (refer, for example, to Japanese Unexamined Patent Publication (Kokai) No. 8-11528). This honeycomb structure includes a cylindrical outer cladding, partitions arranged in grid form inside the outer cladding and a large number of cells separated by partitions and penetrating in an axial direction. [0004]
  • To produce this ceramic honeycomb structure, a ceramic material containing ceramic powder, water, a binder and a lubricant is mixed and kneaded, extruded, and then dried and sintered. [0005]
  • In the honeycomb structure described above, it has been required to reduce the thickness of the partitions and the cell width, in order to improve the performance of the exhaust gas purification apparatus. To satisfy this required, the slit width for forming the partitions must be reduced in the die used for extrusion. [0006]
  • However, the reduction of the slit width of the die for extrusion affects an extrusion step and eventually, productivity of an overall production process. In other words, when extrusion is conducted by use of an extruder using a die that has a reduced slit width, an extrusion pressure at the same extrusion rate is higher than when the slit width is great. Therefore, so long as the extruder having the same pressurization performance as that of existing extruders is employed, the extrusion rate unavoidably drops. The drop of this extrusion rate governs the overall production process of the honeycomb structure, and productivity drops. [0007]
  • The extrusion rate can be improved to a certain extent when a bigger extruder is used to increase the pressure. In this case, however, the temperature of the resulting molding rises and the shape of the extrusion cannot be retained. Therefore, a cooler for cooling the extruder must be added or the capacity of the cooler must be increased. As a result, the setup cost increases. [0008]
  • When the pressurization force is excessively increased, the die used for extrusion is broken, or extrusion defect occurs due to deflection of the die. Therefore, an increase in the pressurization force is limited. [0009]
  • For these reasons, development of a technology that can acquire a higher extrusion rate at a lower extrusion pressure than ever has been desired to extrude a honeycomb structure as the ceramic structure described above. In other words, when a extrusion pressure and a extrusion rate are plotted on the abscissa and the ordinate, respectively, and their relation is expressed by a graph, and when the gradient (rate/pressure) is defined as “extrusion rate efficiency”, development of a technology capable of increasing this extrusion rate coefficient has been desired. [0010]
  • If such a technology was available, the technology could be applied to the production of ceramic structures, having a sheet form and various other forms, besides the honeycomb structure described above. [0011]
  • SUMMARY OF THE INVENTION
  • In view of the problems with the prior art technologies described above, the invention aims at providing a production method for a ceramic structure capable of increasing the extrusion rate coefficient described above in the extrusion of ceramic structures. [0012]
  • A first aspect of the invention provides a production method for a ceramic structure comprising the steps of mixing and kneading a ceramic material containing at least a ceramic powder and water, extruding the mixture so kneaded, and drying and sintering a extrudate, wherein a water-insoluble liquid lubricant (hereinafter merely called a “lubricant” in some cases) consisting of acyl glycerin as its main component and/or its derivative is added to the ceramic batch material. [0013]
  • To extrusion-die a ceramic structure, it is necessary to impart plasticity to a ceramic batch material as its starting material. Therefore, water has ordinarily been added in the past to the ceramic batch material, and a water-soluble additive such as a lubricant having high compatibility with water is further added. [0014]
  • In the invention, a water-insoluble liquid lubricant consisting of acyl glycerin, and/or a derivative, as a main component is added to the ceramic batch material. This is revolutionary in view of the fact that a water-soluble lubricant has been used in the past for the ceramic batch material that is kneaded to a clay form by use of water, and the invention employs an entirely novel ceramic batch material. In this way, the invention can make the resistance in extrusion of the ceramic batch material smaller and the extrusion rate coefficient greater than when the water-soluble lubricant is added as in the prior art technologies. [0015]
  • The reason is assumed as follows. The water-insoluble liquid lubricant, that is incompatible with water but is uniformly dispersed in the ceramic batch material kneaded into the clay form, leaches to the clay surface when a pressure is applied during extrusion, wets the friction surfaces of a cylinder and barrel of an extruder and the die, and reduces the coefficient of friction. [0016]
  • This phenomenon is analogous to squeezing of a material of vegetable oil such as soybean oil and rapeseed oil. The greater the pressure applied, the greater becomes the amount of the lubricant leached from inside the clay. Therefore, even when the precessure locally increases, a necessary amount of the lubricant leaches concentratedly to that portion and reduces the coefficient of friction. [0017]
  • In contrast, water-soluble lubricants according to the prior art have high affinity with water and are bonded to the ceramic power material together with water. Therefore, even when the pressure is applied during extrusion, the lubricants do not leach to the clay surface. Therefore, only the limited amount of the water-soluble lubricants existing on the clay surface can contribute to lubrication performance. Even when a high pressure is locally applied, these lubricants cannot be concentrated on that portion, and cannot reduce the coefficient of friction, either. [0018]
  • The lubricant consisting of acyl glycerin and/or its derivative among the water-insoluble liquid lubricants can secure a relatively large gap between the ceramic raw material and the friction surface of the die, though the reason has not entirely been clarified. It is assumed that the greater the adsorption force of the lubricant to the die, the smaller becomes the coefficient of friction. [0019]
  • The invention can make the extrusion rate coefficient, described above, in extrusion of the ceramic Structure greater than in the prior art technologies. Therefore, the invention can suppress a drop in the rate when a ceramic structure having a shape that involves a large die resistance during extrusion is extruded. In consequence, the invention can improve productivity while keeping the quality of the ceramic structure and its shape retainability. [0020]
  • A second aspect of the invention provides a production method of a ceramic honeycomb structure having partitions arranged in a honeycomb shape, comprising the steps of mixing and kneading a ceramic batch material containing at least ceramic powder, water, a binder, extruding the mixture so kneaded, and drying and sintering a extrudate, wherein a water-insoluble liquid lubricant that is a water-insoluble liquid at a temperature of extrusion is added to the ceramic batch material. [0021]
  • When a ceramic honeycomb structure is extrusion, water-containing minerals such as talc, kaolin, and so forth, are used as the main material of the ceramic batch material. Therefore, large quantities of water having high compatibility with them have been used in the past. Therefore, it has been believed that additives such as a lubricant must be water-soluble. [0022]
  • In the second invention, the water-insoluble liquid lubricant that is a water-insoluble liquid at a temperature of extrusion is added to the ceramic batch material. This is extremely revolutionary in the production of the ceramic honeycomb structure because the water-soluble lubricant has been employed in the past. In other words, the invention uses a ceramic batch material having an entirely novel construction. In comparison with the case where the water-soluble lubricant is added as in the prior art technologies, the resistance when extruding the ceramic honeycomb structure by extruding the ceramic batch material can be reduced, and the extrusion rate coefficient can be increased. [0023]
  • Because the second invention can make the extrusion rate coefficient greater in extrusion of the ceramic honeycomb structure greater than in the prior art technologies, the drop of the extrusion rate can be suppressed when a ceramic honeycomb structure, having a shape that has a large die resistance in extruding, is extruded. The second invention can further suppress die cracking resulting from the increase of the pressure and extrusion defect resulting from die deflection. For these reasons, the second invention can improve productivity while keeping the quality of the ceramic honeycomb structure and its shape retainability.[0024]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is an explanatory view showing a construction of an extruder in Example 1; [0025]
  • FIG. 2 is an explanatory view showing a construction of a honeycomb structure in Example 1; [0026]
  • FIG. 3 is an explanatory view showing a clearance between a ceramic batch material and a friction surface of a die when using polyoxyethylene polyoxypropylene monobutylether (PPBE) as an example of existing lubricants; [0027]
  • FIG. 4 is an explanatory view showing a clearance between the ceramic batch material and the friction surface of a die when rapeseed oil (Canola oil) (triacyl glycerin) is used in Example 1; [0028]
  • FIG. 5 is an explanatory view showing a relation between a extrusion pressure and a extrusion rate in Example 2; [0029]
  • FIG. 6 is an explanatory view showing a relation between an addition amount of rapeseed oil and a extrusion rate ratio in Example 3; [0030]
  • FIG. 7 is an explanatory view showing a relation between a extrusion pressure and a extrusion rate in Example 4; [0031]
  • FIG. 8 is an explanatory view showing a relation between the number of revolutions of a motor and a extrusion rate in Example 5; [0032]
  • FIG. 9 is an explanatory view showing a relation between the number of revolutions of a motor and a motor current in Example 5; [0033]
  • FIG. 10 is an explanatory view showing a relation between a liquid ratio in a ceramic batch material and hardness in Example 6; [0034]
  • FIG. 11 is an explanatory view showing a relation between a water-insoluble liquid lubricant and a kinematic viscosity (cSt) in Example 6; [0035]
  • FIG. 12 is an explanatory view showing experimental points of a lubricant content and a water content (moisture ratio) with respect to a matrix in Example 7; and [0036]
  • FIG. 13 is an explanatory view showing an optimum range of lubricant content and water content (moisture ratio) in a matrix in Example 7.[0037]
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The first invention described above can use a water-insoluble liquid lubricant consisting of acyl glycerin, and/or a derivative, as a main component. The term “liquid lubricant” herein used excludes those grease-like liquid lubricants that have an extremely high viscosity at normal temperature. [0038]
  • The water-insoluble liquid lubricant consisting of acyl glycerin, and/or a derivative, as the main component preferably has a viscosity of 15 to 45 cp at 50° C. In this case, handling of the water-insoluble liquid lubricant becomes easier when an automatic line is set up. When the viscosity is less than 15 cp, the viscosity is so low that a sufficient effect cannot be acquired in extrusion at a high pressure. When the viscosity exceeds 45 cp, on the other hand, the viscosity is so high that an extrusion rate cannot be improved. [0039]
  • To measure the viscosity (cp) described above, rotary viscometers known generally such as a B type, a C type, a BH type, an E type, and so forth, can be employed for the measurement. [0040]
  • Acyl glycerin is called “acyl glycerol” according to the IUPAC nomenclature, and includes monoacyl glycerin, diacyl glycerin and triacyl glycerin. Triacyl glycerin among them is a main component of natural fat. It is expressed by a chemical formula in which three aliphatic acids are bonded with one glycerin: [0041]
    Figure US20030098530A1-20030529-C00001
  • (where each of R[0042] 1, R2 and R3 is an alkyl group of an aliphatic acid).
  • The aliphatic acids R[0043] 1, R2 and R3 in the chemical formula given above include various kinds. Examples of the water-insoluble liquid lubricant consisting of triacyl glycerin, and/or a derivative, as its main component are various vegetable oil such as rapeseed oil, soybean oil, sunflower oil, cotton seed oil, and so forth.
  • Preferably, 2.0 to 8.0 wt % (to be added) of methyl cellulose on the basis of 100 wt % of ceramic powder is added to the ceramic batch material. Methyl cellulose increases plasticity, improves shape retainability when extrusion is conducted, and improves dry strength of a dried ceramic structure. When the addition amount of methyl cellulose is les than 2.0 wt % (to be added), an improvement effect of plasticity and bonding power during drying due to its addition cannot be expected. When the addition amount of methyl cellulose exceeds 8.0 wt % (to be added), on the other hand, a problem occurs that volume shrinkage becomes excessively great after sintering. [0044]
  • In the invention, when the amount of ceramic powder is 100 wt % as the unit of the addition amount, the amount of the component to be added to ceramic powder is expressed as wt % (to be added) and when the overall ceramic bath is expressed as 100 wt %, the component contained in the batch material is expressed by wt % (to be contained). [0045]
  • The water-insoluble liquid lubricant consists of triacyl glycerin as the main component. The addition amount of the water-insoluble liquid lubricant is preferably at least 0.5 wt % (to be added) on the basis of 100 wt % of ceramic powder. When the water-insoluble liquid lubricant consisting of triacyl glycerin as the main component is used, the effect of improving the extrusion rate coefficient brought forth by the addition of the water-insoluble liquid lubricant is small if the addition amount of the water-insoluble liquid lubricant is less than 0.5 wt % (to be added) There is no upper limit to the addition amount of the water-insoluble liquid lubricant from the aspect of the improvement of the extrusion rate coefficient, the addition amount is preferably limited from the aspects of saturation of the addition effect and the increase of the cost. [0046]
  • The main component of the aliphatic acid constituting triacyl glycerin described above is preferably an aliphatic acid having 18 carbon atoms. Concrete examples are stearic acid, oleic acid, linolic acid, linolenic acid, elaidic acid, cis-vaccenic acid, vaccenic acid and other aliphatic acids- Triacyl glycerin constituted by these C18 aliphatic acids is liquid at normal temperature, has a suitable viscosity and is most suitable as the water-insoluble liquid lubricant. [0047]
  • A saponification value of triacyl glycerin is preferably not greater than 200. In this case, the effect of improving the extrusion rate coefficient can be sufficiently acquired. [0048]
  • Next, in the production method of the ceramic honeycomb structure according to the second invention, the water-insoluble liquid lubricant that is a water-insoluble liquid at the temperature of extrusion is added to the ceramic batch material. [0049]
  • In the case of the ceramic honeycomb structure, a binder such as methyl cellulose is generally added to the batch material to impart plasticity and to obtain dry strength. When the temperature is too high, in this case, the resulting extrusion becomes so soft that shape retainability cannot be secured. Therefore, extrusion is carried out while the temperature of the material (at the time of extrusion) is controlled to about 10 to about 30° C. with a center temperature at about 20° C. [0050]
  • Therefore, the water-insoluble liquid lubricant suitable for this purpose preferably has a kinematic viscosity of 30 cSt to 120 cSt at 20° C. [0051]
  • Therefore, a sufficient effect can be obtained when the ceramic honeycomb structure is extruded while the material temperature is controlled to 10 to 30° C., too. [0052]
  • Incidentally, the kinematic viscosity described above may belong to the following four viscosity grades stipulated in ISO viscosity classification for industrial lubricant oil (ISO 3448-1975 and JIS K2001 “Viscosity Classification of Industrial Lubricant Oil” applied correspondingly to the former), that is, ISO VG22, ISO VG32, ISO VG46 and ISO VG68. [0053]
  • The sum of water and the water-insoluble liquid lubricant contained in the ceramic batch material is preferably 18.0 to 24.5 wt % (to be contained) on the basis of 100 wt % of the total ceramic batch material. [0054]
  • When the sum of water and the water-insoluble liquid lubricant contained in the ceramic batch material exceeds 24.5 wt % (to be contained), the raw material becomes so soft that the ceramic honeycomb structure undergoes deformation due to its own weight and cannot retain the shape after extruding even when the material temperature is regulated. [0055]
  • When the sum of water and the water-insoluble liquid lubricant contained in the ceramic batch material is smaller than 18.0 wt % (to be contained), the viscosity of the material becomes so high that the extrusion pressure exceeds the die strength, or the ceramic batch material becomes powdery and dusty with the result that plasticization cannot be attained (the material does not become clay-like) and extruding becomes substantially impossible. [0056]
  • When the thickness of partitions of the ceramic honeycomb structure is smaller than 150 μm, that is, when extrusion is carried out by use of a die having a slit width of smaller than 150 μm, the sum of water and the water-insoluble liquid lubricant is preferably 20.0 to 22.5 wt % (to be contained) on the basis of 100 wt % of the overall ceramic batch material as will be later described. Shape retainability is of importance in a thin ceramic honeycomb structure, and to retain the shape, the sum of the contents is more preferably not greater than 22.5 wt % (to be contained) Since the extrusion pressure becomes greater in the thin ceramic honeycomb structure, the sum of the content is more preferably at least 20.0 wt % (to be contained) to obtain an excellent extrusion condition. [0057]
  • In the second invention, the binder described above is methyl cellulose, and the content of the binder is preferably 2.0 to 8.0 wt % (to be added) when the content of ceramic powder is 100 wt %. The reason for limitation of the methyl cellulose content in this case is the same as that of the first invention. [0058]
  • The ceramic honeycomb structure described above has partitions arranged in the honeycomb shape. Therefore, it has large resistance particularly when passing through the die, and the extrusion rate coefficient is likely to become small. In this sense, the application of the invention is extremely effective. [0059]
  • The thickness of the partitions is preferably not greater than 150 μm. In this case, because the resistance becomes great when the ceramic honeycomb structure passes through the die, and the application of the invention is further effective. [0060]
  • The honeycomb structure is preferably extrusion-molded by use of a die having slits for forming the partitions described above, and a width of the slit is preferably not greater than 150 μm. When the slit width of the die for extruding the honeycomb structure is not greater than 150 μm in the honeycomb structure, the extrusion rate coefficient drops particularly at the time of extrusion. Therefore, when the slit width is not greater than 150 μm in the honeycomb structure, too, the application of the invention is further effective. [0061]
  • In the second invention, too, the water-insoluble liquid lubricant is triacyl glycerin and when the amount of ceramic powder is 100 wt %, the addition amount of the water insoluble liquid lubricant is preferably 1.0 to 8.0 wt % (to be added). [0062]
  • When the addition amount of the water-insoluble liquid lubricant exceeds 8.0 wt % (to be added) in the case of a ceramic honeycomb structure having a complicated shape, large amounts of oil are burnt and scattered during a degreasing process at the time of sintering, and sintering cracks are likely to occur. When the amount is less than 1.0 wt % (to be added), the remarkable effect of improving the extrusion rate cannot be obtained in comparison with the existing level. Therefore, the addition amount of the water-insoluble liquid lubricant is preferably 1.0 to 8.0 wt % (to be added). [0063]
  • In the second invention, too, the main component of the aliphatic acid constituting triacyl glycerin described above is preferably an aliphatic acid having 18 carbon atoms in the same way as in the first invention. [0064]
  • In the second invention, too, the saponification value of triacyl glycerin is preferably not greater than 200 in the same way as in the first invention [0065]
  • EXAMPLE 1
  • A production method of a ceramic structure according to this example will be explained with reference to FIGS. [0066] 1 to 4.
  • In a method of producing a [0067] ceramic structure 8 by the steps of mixing and kneading a ceramic batch material 88 containing at least ceramic powder and water, extruding the mixture, and drying and sintering the resulting extrudate, this example added a water-insoluble liquid lubricant consisting of acyl glycerin and/or its derivative as a main component to the ceramic batch material 88.
  • Hereinafter, an explanation will be given in detail. [0068]
  • This example produced a honeycomb structure including an [0069] outer cladding 81, partitions 82 arranged in a grid form inside the outer cladding 81 and a large number of cells 80 separated by the partitions 82 and penetrating in an axial direction, and consisting of cordierite as the main component.
  • First, talc, kaolin, alumina and aluminum hydroxide powder that were components capable of changing to cordierite after sintering were used as ceramic powder that constituted the [0070] ceramic batch material 88 described above. A water-insoluble liquid lubricant consisting of methyl cellulose, water and acyl glycerin and/or its derivative as the main component was added to the powder mixture to form the ceramic batch material 88.
  • Rapeseed oil consisting of triacyl glycerin as the main component, more concretely rapeseed oil containing 97% of triacyl glycerin, 0-8% of diacyl glycerin and 0.1% of monoacyl glycerin by weight ratio, was used as the water-insoluble liquid lubricant consisting of acyl glycerin and/or its derivative as the main component. [0071]
  • The aliphatic acid composition (mol %) consists of C[0072] 16.0=4.0%, C18.0=1.8%, C18.1=57.8%, C18.2=21.8%, C18.3=11.2%, C20.1=1.9% and C22.1=1.0%. Here, symbol C represents carbon, symbol a in a:b as the suffix to C represents the number of carbon atoms and b represents the number of double bonds.
  • Next, the [0073] ceramic batch material 88 was kneaded in a kneader 3 and was extruded by use of a screw type extruder 1 as shown in FIG. 1. Each of the extruder 1 and the kneader 3 included inside a cylindrical frame 11, 31 a screw 15, 35 having a screw plate 150, 350 that was helically wound. The crew 15, 35 was driven for rotation by a motor 17, 37 connected to its rear end.
  • A [0074] material charging hole 39 was provided to the upper part of the frame 31 of the kneader, and the ceramic batch material 88 was charged through this charging hole 39. The kneaded ceramic batch material 88 was extruded from a distal end portion 38 of the kneader 31 and was then charged into a material charging hole 19 of the extruder 1. The material charging portion to the extruder 1 was kept as a whole under vacuum by a vacuum pump 195 to suppress entrapment of the ceramic batch material into air.
  • A [0075] die 2 for shaping was arranged at the distal end of the extruder 1. The die 2 had grid-like slits 20 corresponding to the shape of the partitions 82 of the honeycomb structure 8 to be produced.
  • To conduct extrusion, after being kneaded by the [0076] kneader 3, the ceramic batch material 88 was charged into the extruder 1, was moved forth by the revolution of the screw 15 and was thereafter extruded from the die 2. In this way, the honeycomb structure 8 was extruded and extruded.
  • The [0077] honeycomb structure 8 so extruded was serially cut into a desired length and was passed through subsequent drying and sintering steps to give complete products.
  • In this embodiment, rapeseed oil as the water-insoluble liquid lubricant consisting of triacyl glycerin as described above was added to the [0078] ceramic batch material 88. Therefore, in comparison with the case where a conventional lubricant was added, the extrusion rate coefficient in extrusion could be drastically improved and presumably for the following reason.
  • The water-insoluble liquid lubricant such as triacyl glycerin was not dissolved in water but was dispersed in the ceramic batch material. Therefore, when the pressure was applied during extrusion, the lubricant leached to the clay surface, lubricated the cylinder, the barrel and the friction surface of the die and could thus decrease the coefficient of friction. The greater the pressure applied in this case, the greater became the amount of the lubricant leaching from inside the clay. Consequently, even when the pressure locally increased, a necessary amount of lubricant was concentratedly supplied to that portion, and the coefficient of friction could be efficiently lowered. [0079]
  • In contrast, a water-soluble lubricant was highly hydrophilic and was strongly bonded to the ceramic material as an aqueous solution. Therefore, even when the pressure was applied during extrusion, the lubricant did not leach to the clay surface. [0080]
  • In consequence, only a very small amount of the water-soluble lubricant existing on the clay surface contributed to lubrication performance. Even when a high pressure was locally applied, the lubricant did not concentrate on that portion and the frictional force reducing effect could not presumably operate sufficiently. [0081]
  • Synthetic lubricants well known in the past includes polyoxyethylene-polyoxypropylene-monobuthylether (trade name: “Uniloob”) expressed by the following formula: [0082]
    Figure US20030098530A1-20030529-C00002
  • This synthetic lubricant became water-soluble and water-insoluble depending on a polymerization ratio of propylene oxide and ethylene oxide. Since this lubricant was used in combination with water in the field of ceramics, it was generally used while the ratio of ethylene to oxide was set to 40% or more. In this case, the oxygen ion (O[0083] ) of ethylene oxide was adsorbed to the iron ion (Fe+) of the die 2, for example, between the die 2 and the boundary 89 surface of the solid content of the ceramic batch material as shown in FIG. 3. Therefore, though PPBE described above had a relatively large molecular weight and an elongated molecule, the elongated molecule did not remain upright and a sufficient distance could not be secured between the die 2 and the boundary surface 89 As the adsorption force of the oxygen ion (O) was relatively small, the water-soluble lubricant was likely to peel from the die 2.
  • On the other hand, the water-insoluble liquid lubricant consisting of triacyl glycerin as the main component in this example could be arranged between the [0084] die 2 and the boundary surface 89 of the solid content of the ceramic batch material while the molecule of the aliphatic acid remained upright as shown in FIG. 4. Further, the acyl glycerin had a carbonyl group (COO) and exhibited a stronger adsorption force to the iron ion (Fe+) than to the oxygen ion (O). Therefore, the water-insoluble liquid lubricant (rapeseed oil) consisting of triacyl glycerin as the main component of this example was more difficult to peel from the die 2 than the conventional water-soluble lubricant.
  • Presumably because the water-insoluble liquid lubricant consisting of triacyl glycerin as the main component was used as in this example, lubrication performance could be improved and the extrusion rate coefficient could be increased. [0085]
  • EXAMPLE 2
  • To further clarify the effect of Example 1, this example conducted experiments by comparing the case where PPBE (C1) was used as the conventional water-soluble lubricant with the cases where water-insoluble liquid lubricants consisting of four kinds of acyl glycerin as the main components were used. [0086]
  • Rapeseed oil (E1), soybean oil (E2), safflower oil (E3) and linseed oil (E4) consisting of triacyl glycerin as the main component were used as the water-insoluble liquid lubricants consisting of acyl glycerin as the main component. [0087]
  • A batch type kneader was used as a kneader, a screw type extruder for an experimental use was used as a extruding machine, and a die having a slit width of 150 μm and 400 mesh (400 cells/in.[0088] 2) was used as a die. Honeycomb structures having an outer diameter of Φ500 mm were extruded.
  • To prepare a ceramic batch material, 5 wt % (to be added) of methyl cellulose, 25.9 wt % (to be added) of water and 2.7 wt % (to be added) of various lubricants on the basis of 100 wt % of ceramic powder were added to a ceramic powder. [0089]
  • The extrusion rate relative to the extrusion pressure in extrusion by the screw extruder described above was measured. [0090]
  • FIG. 5 shows the measurement result. In the diagram, the abscissa represents the extrusion pressure (MPa/cm[0091] 2) and the ordinate does the extrusion rate (m/min). Symbols C1 and E1 to E4 respectively represent the results when the lubricants (C and E1 to E4) were used.
  • As can be understood from the diagram, the extrusion rates at the same extrusion pressure could be much more improved when the water-insoluble liquid lubricants (E1 to E4) consisting of triacyl glycerin as the main component were used than when the conventional water-soluble lubricant (C1) was used. In other words, the extrusion rate coefficient could be improved. [0092]
  • It could be understood from this result that the extrusion rate coefficient could be drastically increased in extrusion of the honeycomb structure when the lubricant consisting of triacyl glycerin was used as the water-insoluble liquid lubricant. [0093]
  • EXAMPLE 3
  • This example used rapeseed oil as a typical example of the water-insoluble liquid lubricant consisting of acyl glycerin as the main component, and a test was carried out to determine an optimum range of its addition amount. [0094]
  • The test condition was as follows. [0095]
  • First, a ceramic powder that had the same composition as in Example 1, and methyl cellulose, water and rapeseed oil were added to 3 kg in total of ceramic powder. The addition amount of methyl cellulose was fixed at 5 wt % (to be added) on the basis of 100 wt % of ceramic powder, and the addition amount of water was fixed at 26 wt % (to be added) on the basis of 100 wt % of ceramic powder. The addition amount of rapeseed oil was changed within a range of 0.5 to 10.0 wt % (to be added) on the basis of 100 wt % of ceramic powder For comparison, a case where rapeseed oil was not added at all was also tested. [0096]
  • A batch type kneader was used as a kneader for kneading the ceramic batch material, and an FM-30 vacuum extruder, a product of Miyazaki Steel Co., was used as a extruding machine. A die having a slit width of 150 m and the number of cells of 400 cells/in.[0097] 2 was used.
  • Ceramic batch materials having mutually different addition amounts of rapeseed oil were used and each extrusion rate with respect to a extrusion pressure was measured to determine the extrusion rate coefficient for each addition amount of rapeseed oil. The extrusion rate coefficient when rapeseed oil was not added was set to 1, and a ratio to this value was determined as a extrusion rate ratio. [0098]
  • FIG. 6 shows the result. In this diagram, the abscissa represents the addition amount (wt % to be added) of rapeseed oil, and the ordinate does the extrusion rate ratio. The result is represented as E[0099] 5.
  • In the diagram, the extrusion rate ratio when 2-7 wt % (to be added) of PPBE as a conventional water-soluble lubricant was added was also plotted as C[0100] 1. It could be understood by comparing them that when the addition amount of rapeseed oil was at least 1.0 wt % (to be added), a extrusion rate coefficient higher than that of the prior art could be sufficiently obtained.
  • It was thus clarified that when the addition amount of rapeseed oil was at least 0.5 wt % (to be added), the effect of improving the extrusion rate coefficient could be obtained and when it was at least 1.0 wt % (to be added), the extrusion rate coefficient higher than that of the prior art could be obtained. [0101]
  • On the other hand, when the addition amount of rapeseed oil was increased, the ceramic batch material became so soft, as a whole, that shape retainability of the extrudate became lower. In this example, when the addition amount of rapeseed oil exceeded 10.0 wt % (to be added), shape retainability dropped and a desired honeycomb shape could not be obtained. [0102]
  • Therefore, it could be concluded that the addition amount of rapeseed oil as the lubricant consisting of acyl glycerin as the main component was preferably less than 10.0 wt % (to be added). [0103]
  • From the aspect of the cost, the addition amount of rapeseed oil was preferably small. To obtain reliable improvement of the extrusion rate coefficient and to reduce the cost, therefore, the addition amount was preferably not greater than 8.0 wt % (to be added). [0104]
  • Since the hardness of the ceramic batch material could be regulated by the addition amount of water, a ceramic batch material having suitable hardness could be obtained by adjusting the addition amount of rapeseed oil and the addition amount of water. [0105]
  • Though this example represented the case where rapeseed oil was used as the lubricant, substantially similar effects could be obtained when other lubricants consisting of triacyl glycerin as the main component were used. [0106]
  • It was of course possible to add the conventional water-soluble lubricant to the lubricant consisting of acyl glycerin as the main component. The water-soluble lubricant hardly exhibited the effect of improving the extrusion rate coefficient in this case, but provided a lubrication effect with respect to other equipment such as a water pump. [0107]
  • EXAMPLE 4
  • In this example, an extremely thin honeycomb structure having a partition thickness of 3 mil (76.2 μm) was actually extruded, and the effect of the lubricant consisting of acyl glycerin as the main component was confirmed. [0108]
  • In other words, the die used for extrusion in this example had a slit width of 3 mil (76.2 μm) and the number of cells of 400 cells/in.[0109] 2, and a honeycomb structure having an outer diameter of (Φ107 mm was molded.
  • The composition of the ceramic batch material was fundamentally the same as that of Example 3, and the addition amount of rapeseed oil as the lubricant was fixed at 3 wt % (to be added). [0110]
  • For comparison, a test was also carried out by the use of a ceramic batch material containing 3 wt % (to be added) of PPBE as the water-soluble lubricant. [0111]
  • A large-scale screw type vacuum extruder for a production plant (not shown) was used as a kneader and a extruding machine. [0112]
  • FIG. 7 shows the test result. In the diagram, the abscissa represents the extrusion pressure (MPa/cm[0113] 2) and the ordinate represents the extrusion rate (m/min). Symbol E6 represents the case of the addition of rapeseed oil and C2 does the case where PPBE was added.
  • It can be understood from the diagram that when rapeseed oil as the lubricant consisting of acyl glycerin as the main component was used, the extrusion rate, that is, the extrusion rate coefficient, could be drastically improved at the same extrusion pressure in comparison with the prior art when the honeycomb structure having extremely thin partitions of 76.2 μm was extruded. [0114]
  • EXAMPLE 5
  • This example used linseed oil as the lubricant consisting of acyl glycerin as the main component, and actually extruded a honeycomb structure having a partition thickness of 4 mils (101.6 μm), the number of cells of 600 cells/in.[0115] 2 and an outer shape of Φ120 mm. The result was compared with the case where the water-soluble lubricant (PPBE) was used in the same way as in Example 4.
  • The addition amount of linseed oil was 3 wt % (to be added). The rest were the same as in Example 4. [0116]
  • In this example, extrusion was carried out while the number of revolutions of a motor for turning a screw shaft of a screw type extruder and a motor current were respectively measured to examine the relations between these values and the extrusion rate. [0117]
  • FIGS. 8 and 9 show the test result. In FIG. 8, the abscissa represents the number of revolutions of the motor (rpm) and the ordinate represents the extrusion rate (m/min). In FIG. 9, the abscissa represents the number of revolutions of the motor (rpm) and the ordinate represents the motor current (A). Symbol E7 represents the case where linseed oil was used and C3 represents the case where PPBE was used. [0118]
  • It can be understood from FIG. 8 that when the number of revolutions of the extrusion screw was the same, the extrusion rate of the case (E6) where linseed oil was used became substantially twice at the same number of revolutions in comparison with the extrusion rate of the case (C[0119] 3) where the water-soluble lubricant was used.
  • It could be understood from FIG. 9 that the motor current value at the same number of revolutions became lower in the case (E7) where linseed oil was used than in the case (C3) where PPBE was used, and the motor load at the same number of revolutions dropped. This was presumably because the friction between the ceramic batch material and the die decreased when linseed oil was used as the lubricant consisting of acyl glycerin as the main component. Further, when the lubricant consisting of acyl glycerin as the main component was used, life of the die could be extended due to the decrease of the friction of the die. [0120]
  • EXAMPLE 6
  • This example used rapeseed oil, linseed oil and soybean oil as the water-insoluble liquid lubricants consisting of triacyl glycerin as the main component. Each ceramic batch material for a ceramic honeycomb structure containing the lubricant in a blend ratio tabulated in Tables 1 to 3 was kneaded in a batch type kneader. The clay hardness (plasticity) was examined, and the ceramic honeycomb structures were extruded by use of a vacuum extruder in the same way as in Example 3 to evaluate extrudability and the extrusion rate. [0121]
  • Tables 1 to 3 and FIG. 10 illustrate the evaluation results. FIG. 10 shows the clay hardness (plasticity) with respect to the proportion of the total weight of water and the lubricant (hereinafter called “liquid ratio”; unit=wt % (to be added) in the total weight of the material. [0122]
  • Here, clay hardness (plasticity: workability index, stipulated in former JIS P2574 abandoned in 1998) is the value measured by use of a pencil-shaped spring type penetrometer ordinarily used in this field. When a distal end of the penetrometer is inserted into the clay, a higher numerical value represents a higher hardness and a smaller numerical value represents a lower hardness. [0123]
  • It could be understood from FIG. 10 that in all the cases of rapeseed oil, linseed oil and soybean oil, the clay hardness became higher as the sum of the lubricant and water, that is, the liquid ratio, became smaller (plasticity coefficient became greater) irrespective of the ratio of the lubricant and water, and the clay hardness became lower as the liquid ratio became greater (plasticity coefficient became small), and that they had a strong correlation. Therefore, when the lubricant consisting of triacyl glycerin as the main component was added to the raw material of the ceramic honeycomb structure, the clay hardness (plasticity) could be easily regulated by regulating the addition amount of water in accordance with the necessary amount of the lubricant. It was estimated that the extrudability of the ceramic honeycomb structure could be easily regulated. [0124]
  • In this example, a relatively high extrudability could be obtained at a liquid ratio of 18 to 24.5 wt % (to be contained) and a hardness (plasticity coefficient) of 9 to 11 and preferably a liquid ratio of 20 to 22.5 wt % (to be contained) and a hardness of 9.6 to 10.7. Incidentally, the inclination of the relation between the clay hardness (plasticity coefficient) and the liquid ratio became somewhat different depending on the kind of the lubricant presumably because of the difference of the viscosity of the lubricant at the measurement temperature. [0125]
  • For reference, the relation between the temperature of the water-insoluble liquid lubricant used for the test and the kinematic viscosity was examined in this example. Incidentally, the kinematic viscosity (kinematic viscoelasticity) is the quotient obtained by dividing the viscosity (coefficient of viscosity) by the density (ρ) of the liquid. Its unit is mm[0126] 2/s or cSt, and 1 mm2/s=1 cSt. Though Pa·s is used in due form as the unit of viscosity (coefficient of viscosity), cP (centi-poise) is customarily used, and 1 Pa·s=1×103 cP.
  • In this example, the kinematic viscosity was measured by use of an Ostwald viscometer as a kind of capillary viscometer. FIG. 11 shows the measurement result. In the diagram, the abscissa represents the temperature and the ordinate represents the kinematic viscosity (cSt). [0127]
  • It could be understood from the diagram that the kinematic viscosity at 20° C. was 43.1 cSt for the soybean oil, 86.8 cSt for rapeseed oil and 45.8 cSt for linseed oil. The kinematic viscosity at 40° C. was 27.1 cSt for soybean oil, 47.6 cSt for rapeseed oil and 28.1 cSt for linseed oil. [0128]
  • For reference, the result of measurement obtained by using an E type viscometer and a BH type viscometer (products of Tokyo Keiki Co.) as a kind of rotary viscometer is also shown. [0129]
  • The measurement result by the E type viscometer at 50° C. was 22.0 cp for soybean oil, 24.2 cp for rapeseed oil and 18.2 cp for linseed oil. [0130]
  • The measurement result by the BH type viscometer was available only for linseed oil, and was 100 cp at 10° C., 60 cp at 25° C. and 45 cp at 33° C. [0131]
    TABLE 1
    lubricant: linseed oil
    ceramic batch material
    methyl liquid
    cellulose lubricant water ratio evaluation result
    ceramic powder wt % wt % wt % wt % extrusion
    Experiment weight weight (to be weight (to be weight (to be (to be hard- rate
    No. (g) wt % (g) added) (g) added) (g) added) contained) ness extrudability ratio
    1 3000 100 150 5.0 30 1.0 660 22.0 18.0 12.4 X 1.38
    2 3000 100 150 5.0 90 3.0 780 26.0 21.6 9.9 1.90
    3 3000 100 150 5.0 150  5.0 900 30.0 25.0 7.5 X 1.93
    4 3000 100 150 5.0 30 1.0 780 26.0 20.5 10.7 1.40
    5 3000 100 150 5.0 90 3.0 900 30.0 23.9 8.3 Δ 1.85
    6 3000 100 150 5.0 150  5.0 660 22.0 20.5 10.7 1.95
    7 3000 100 150 5.0 30 1.0 900 30.0 22.8 9.1 Δ 1.35
    8 3000 100 150 5.0 90 3.0 660 22.0 19.2 11.6 Δ 1.92
    9 3000 100 150 5.0 150  5.0 780 26.0 22.8 9.1 Δ 1.98
  • [0132]
    TABLE 2
    lubricant: rapeseed oil
    ceramic batch material
    methyl liquid
    cellulose lubricant water ratio evaluation result
    ceramic powder wt % wt % wt % wt % extrusion
    Experiment weight weight (to be weight (to be weight (to be (to be hard- rate
    No. (g) wt % (g) added) (g) added) (g) added) contained) ness extrudability ratio
    1 3000 100 150 5.0 30 1.0 660 22.0 18.0 11.8 X 1.48
    2 3000 100 150 5.0 90 3.0 780 26.0 21.6 10.1 1.97
    3 3000 100 150 5.0 150  5.0 900 30.0 25.0 8.6 X 1.98
    4 3000 100 150 5.0 30 1.0 780 26.0 20.5 10.7 1.44
    5 3000 100 150 5.0 90 3.0 900 30.0 23.9 9.1 Δ 1.95
    6 3000 100 150 5.0 150  5.0 660 22.0 20.5 10.7 2.05
    7 3000 100 150 5.0 30 1.0 900 30.0 22.8 9.6 Δ 1.43
    8 3000 100 150 5.0 90 3.0 660 22.0 19.2 11.2 Δ 1.92
    9 3000 100 150 5.0 150  5.0 780 26.0 22.8 9.6 Δ 1.98
  • [0133]
    TABLE 3
    lubricant: soybean oil
    ceramic batch material
    methyl liquid
    cellulose lubricant water ratio evaluation result
    ceramic powder wt % wt % wt % wt % extrusion
    Experiment weight weight (to be weight (to be weight (to be (to be hard- rate
    No. (g) wt % (g) added) (g) added) (g) added) contained) ness extrudability ratio
    1 3000 100 150 5.0 30 1.0 660 22.0 18.0 11.0 X 1.38
    2 3000 100 150 5.0 90 3.0 780 26.0 21.6 9.8 1.86
    3 3000 100 150 5.0 150  5.0 900 30.0 25.0 8.8 X 1.90
    4 3000 100 150 5.0 30 1.0 780 26.0 20.5 10.2 1.39
    5 3000 100 150 5.0 90 3.0 900 30.0 23.9 9.1 Δ 1.87
    6 3000 100 150 5.0 150  5.0 660 22.0 20.5 10.2 1.95
    7 3000 100 150 5.0 30 1.0 900 30.0 22.8 9.5 Δ 1.36
    8 3000 100 150 5.0 90 3.0 660 22.0 19.2 10.6 1.96
    9 3000 100 150 5.0 150  5.0 780 26.0 22.8 9.5 Δ 1.92
  • EXAMPLE 7:
  • In this example, the liquid ratio was fixed at 21.35 wt % (to be contained) by adjusting the water content on the basis of the result of Example 6, rapeseed oil was used as the lubricant in the same way as in Example 3, and a extruding test was carried out by changing the addition amount of the lubricant within a range of 1 to 10 wt % (to be added). [0134]
  • When the addition amount of the lubricant was 10 wt % (to be added) in Example 3, shape retainability could not be secured and the resulting extrudate underwent deformation. In this example, the extruding test was carried out at a constant liquid ratio by adjusting the water content. Therefore, extrudability hardly changed even when the addition amount of the lubricant was changed from 1 to 10 wt % (to be added), and an excellent extrusion could be obtained even at 10 wt % (to be added). Moreover, the extrusion rate could be increased when the addition amount of the lubricant was increased in the same way as in Example 3, and its effect could thus be confirmed. [0135]
  • It was found, however, that when the extrudates were sintered, the sintering shrinkage ratio became greater in extrudates having a greater addition amount of the lubricant, and sintering cracks became likely to occur when the addition amount exceeded 8 wt % (to be added). [0136]
  • Therefore, the liquid ratio and extrudability were further examined while the addition amount of the lubricant was kept at 3 wt % (to be added) and 5 wt % (to be added), at which a high extrusion rate could be stably obtained, and the water content was changed. [0137]
  • Table 5 and FIG. 12 show the blend proportions (experimental condition) of the test product. Table 4 and FIG. 12 show also the blend proportion (experimental condition) of Example 3, too. In the diagram of FIG. 12, the abscissa represents the addition amount of the water-insoluble liquid lubricant in terms of wt % (to be added) and the ordinate represents the water content (addition amount of water) in terms of wt % (to be contained). A plurality of lines drawn slantingly in the diagram represents the total content (liquid ratio) of water and the water-insoluble liquid lubricant contained in the ceramic batch material in terms of wt % (to be contained). The lines respectively represent from below 18.0 wt % (to be contained), 20 wt % (to be contained), 22.5 wt % (to be contained) and 24.5 wt % (to be contained). [0138]
  • It was found from Tables 4 and 5 that when the liquid ratio was less than 1.0 wt % (to be contained), the clay hardness was so high (the plasticity coefficient was so great) that the extrusion pressure rose and extruding could not be carried out due to the limit of the die strength. [0139]
  • It was also found that when the liquid ratio exceeded 24.5 wt % (to be contained), the clay hardness was so low (the plasticity coefficient became so small) that shape retainability could not be secured and the ceramic honeycomb structure underwent deformation. [0140]
  • Particularly when a ceramic honeycomb structure having thin walls was produced by use of a die having a small slit width, the product strength became small and shape retainability could not be secured easily. In addition, the die resistance increased. Therefore, the range of the liquid ratio in this case was at least 20.0 to 22.5 wt % (to be contained). [0141]
  • Incidentally, though this example represented the case of rapeseed oil as the lubricant, substantially similar results could be obtained when other lubricants consisting of triacyl glycerin as the main component were used. [0142]
  • FIG. 13 shows an optimum range of water and the lubricant for producing a ceramic honeycomb structure by combining the conditions described above with the suitable range of content of the lubricant consisting of triacyl glycerin as the main component. This diagram has the same fundamental construction as that of FIG. 12, and the suitable ranges of the liquid ratio and the water-insoluble liquid lubricant are hatched. [0143]
    TABLE 4
    Condition and result of Example 3
    wt % (to be contained) ratio
    wt % (to be added) ratio of material of material evaluation result
    Experiment ceramic methyl liquid extrusion
    No. powder cellulose water lubricant water lubricant ratio extrudability rate ratio
    1 100 5.0 26.0 0.0 19.85 0.00 19.85 X 1.00
    2 100 5.0 26.0 0.5 19.77 0.38 20.15 1.07
    3 100 5.0 26.0 1.0 19.70 0.76 20.45 1.54
    4 100 5.0 26.0 1.5 19.62 1.13 20.75 1.79
    5 100 5.0 26.0 2.0 19.55 1.50 21.05 1.88
    6 100 5.0 26.0 2.5 19.48 1.87 21.35 1.91
    7 100 5.0 26.0 3.0 19.40 2.24 21.64 1.93
    8 100 5.0 26.0 3.5 19.33 2.60 21.93 1.94
    9 100 5.0 26.0 4.0 19.26 2.96 22.22 1.95
    10 100 5.0 26.0 5.0 19.12 3.68 22.79 Δ 1.96
    11 100 5.0 26.0 8.0 18.71 5.76 24.46 Δ 1.97
    12 100 5.0 26.0 10.0 18.44 7.09 25.53 X 1.97
  • [0144]
    TABLE 5
    Condition and result of Example 7
    wt % (to be contained) ratio
    wt % (to be added) ratio of material of material evaluation result
    Experiment ceramic methyl liquid extrusion
    No powder cellulose water lubricant water lubricant ratio extrudability rate ratio
    1 100 5.0 27.5 1.0 20.60 0.75 21.35 1.53
    2 100 5.0 26.5 2.0 19.85 1.50 21.35 1.89
    3 100 5.0 25.5 3.0 19.10 2.25 21.35 1.95
    4 100 5.0 24.5 4.0 18.35 3.00 21.35 1.98
    5 100 5.0 23.5 5.0 17.60 3.75 21.35 1.99
    6 100 5.0 22.5 6.0 16.86 4.49 21.35 2.00
    7 100 5.0 20.5 8.0 15.36 5.99 21.35 2.01
    8 100 5.0 18.5 10.0 13.86 7.49 21.35 1.99
    9 100 5.0 32.0 3.0 22.86 2.14 25.00 X 1.91
    10 100 5.0 30.2 3.0 21.86 2.17 24.00 Δ 1.94
    11 100 5.0 27.5 3.0 20.29 2.21 22.50 1.95
    12 100 5.0 23.3 3.0 17.71 2.29 20.00 1.96
    13 100 5.0 20.8 3.0 16.17 2.33 18.50 Δ 1.93
    14 100 5.0 18.5 3.0 14.63 2.37 17.00 X
    15 100 5.0 30.0 5.0 21.43 3.57 25.00 X 1.95
    16 100 5.0 28.2 5.0 20.38 3.62 24.00 Δ 1.98
    17 100 5.0 21.3 5.0 16.19 3.81 20.00 2.00
    18 100 5.0 18.8 5.0 14.62 3.88 18.50 Δ 1.99
    19 100 5.0 16.5 5.0 13.05 3.95 17.00 X

Claims (16)

What is claimed is:
1. A production method, for a ceramic structure, comprising the steps of mixing and kneading a ceramic batch material containing at least ceramic powder and water, extruding the mixture so kneaded, and drying and sintering a extrudate, wherein:
a water-insoluble liquid lubricant consisting of acyl glycerin as its main component, and/or a derivative, is added to said ceramic batch material.
2. A production method for a ceramic structure according to claim 1, wherein a viscosity of said water-insoluble liquid lubricant at 50° C. is 15 cp to 45 cp.
3. A production method for a ceramic structure according to claim 1, wherein 2.0 to 8.0 wt % (to be added) of methyl cellulose on the basis of 100 wt % of said ceramic powder is added to said ceramic bath material.
4. A production method for a ceramic structure according to claim 1, wherein said water-insoluble liquid lubricant consists of triacyl glycerin as a main component, and an addition amount of said water-insoluble liquid lubricant is at least 0.5 wt % (to be added) on the basis of 100 wt % of said ceramic powder.
5. A production method for a ceramic structure according to claim 4, wherein a main component of an aliphatic acid constituting said triacyl glycerin is an aliphatic acid having 18 carbon atoms.
6. A production method for a ceramic structure according to claim 4, wherein said triacyl glycerin has a saponification value of not greater than 200.
7. A production method for a ceramic honeycomb structure having partitions arranged in a honeycomb shape, comprising the steps of mixing and kneading a ceramic batch material containing at least ceramic powder, water, a binder, extruding the mixture so kneaded, and drying and sintering a extrudate, wherein:
a water-insoluble liquid lubricant, that is a water-insoluble liquid at a temperature of said extrusion, is added to said ceramic batch material.
8. A production method for a ceramic honeycomb structure according to claim 7, wherein a kinematic viscosity of said water-insoluble liquid lubricant at 20° C. is 30 cSt to 120 cSt.
9. A production method for a ceramic honeycomb structure according to claim 7, wherein the sum of the contents of said water and said water-insoluble liquid lubricant contained in said ceramic batch material is 18.0 to 24.5 wt % (to be contained) on the basis of 100 wt % of said ceramic batch material.
10. A production method for a ceramic honeycomb structure according to claim 7, wherein said binder is methyl cellulose, and the content of said binder is 2.0 to 8.0 wt % (to be added) on the basis of 100 wt % of said ceramic powder.
11. A production method for a ceramic honeycomb structure according to claim 7, wherein the thickness of said partition is not greater than 150 μm.
12. A production method for a ceramic honeycomb structure according to claim 7, wherein said ceramic honeycomb structure is produced by extrusion by use of a die having slits for forming said partitions, and a width of said slits is not greater than 150 μm.
13. A production method for a ceramic honeycomb structure according to claim 7, wherein said water-insoluble liquid lubricant consists of acyl glycerin, and/or a derivative, as a main component.
14. A production method for a ceramic honeycomb structure according to claim 7, wherein said water-insoluble liquid lubricant is triacyl glycerin, and the addition amount of said water-insoluble liquid lubricant is 1.0 to 8.0 wt % (to be added) on the basis of 100 wt % of said ceramic powder.
15. A production method for a ceramic honeycomb structure according to claim 14, wherein the main component of the aliphatic acid constituting said triacyl glycerin is an aliphatic acid having 18 carbon atoms.
16. A production method for a ceramic honeycomb structure according to claim 14, wherein a saponification value of said triacyl glycerin is not greater than 200.
US10/267,049 2001-10-10 2002-10-09 Production method for ceramic structure and production method for ceramic honeycom structure Abandoned US20030098530A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/654,495 US8747729B2 (en) 2001-10-10 2009-12-22 Product method for ceramic structure and production method for ceramic honeycomb structure

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001-312797 2001-10-10
JP2001312797 2001-10-10
JP2002264263A JP4161652B2 (en) 2001-10-10 2002-09-10 Method for manufacturing ceramic structure and method for manufacturing ceramic honeycomb structure
JP2002-264263 2002-09-10

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/654,495 Continuation US8747729B2 (en) 2001-10-10 2009-12-22 Product method for ceramic structure and production method for ceramic honeycomb structure

Publications (1)

Publication Number Publication Date
US20030098530A1 true US20030098530A1 (en) 2003-05-29

Family

ID=26623830

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/267,049 Abandoned US20030098530A1 (en) 2001-10-10 2002-10-09 Production method for ceramic structure and production method for ceramic honeycom structure
US12/654,495 Expired - Fee Related US8747729B2 (en) 2001-10-10 2009-12-22 Product method for ceramic structure and production method for ceramic honeycomb structure

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/654,495 Expired - Fee Related US8747729B2 (en) 2001-10-10 2009-12-22 Product method for ceramic structure and production method for ceramic honeycomb structure

Country Status (5)

Country Link
US (2) US20030098530A1 (en)
JP (1) JP4161652B2 (en)
CN (1) CN1266073C (en)
BE (1) BE1015788A5 (en)
DE (1) DE10247030A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040062828A1 (en) * 2002-09-27 2004-04-01 Denso Corporation Apparatus for extruding ceramic molding
US20040062827A1 (en) * 2002-10-01 2004-04-01 Satoru Yamaguchi Extrusion molding apparatus for ceramic molded product
US20050025849A1 (en) * 2000-06-30 2005-02-03 Denso Corporation Method and apparatus for molding ceramic sheet
US20060208397A1 (en) * 2005-03-17 2006-09-21 Ngk Insulators, Ltd. Method for manufacturing formed honeycomb structure
EP1844918A1 (en) * 2006-04-13 2007-10-17 Ibiden Co., Ltd. Extrusion-molding machine, extrusion-molding method, and method for manufacturing honeycomb structured body
US20080106009A1 (en) * 2006-02-24 2008-05-08 Ibiden Co., Ltd. Wet mixing apparatus, wet mixing method and method for manufacturing honeycomb structure
US20080119355A1 (en) * 2006-11-16 2008-05-22 Ibiden Co., Ltd. Method for manufacturing honeycomb structure
CN102515775A (en) * 2011-12-16 2012-06-27 河南东大高温节能材料有限公司 Preparation method for energy-saving honeycomb ceramic
US20120263896A1 (en) * 2009-12-02 2012-10-18 Guenthner Gerhard Extruded molded functional body made of highly thermally conductive ceramic
US20200139581A1 (en) * 2017-07-10 2020-05-07 Arlanxeo Deutschland Gmbh Extruder system with pressure regulating device
WO2021030176A1 (en) * 2019-08-14 2021-02-18 Corning Incorporated Systems and methods for reducing surface oil streaks on wet extrudate by irradiation
US10946552B2 (en) 2017-04-19 2021-03-16 Denso Corporation Evaluation method for clay and manufacturing method of extrusion molded body
US11220021B2 (en) * 2016-08-03 2022-01-11 Corning Incorporated Apparatus and methods of ceramic pre-cursor batch rheology control

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE431321T1 (en) * 2003-11-12 2009-05-15 Ibiden Co Ltd METHOD FOR PRODUCING THE CERAMIC STRUCTURE
JP2005271395A (en) * 2004-03-24 2005-10-06 Ngk Insulators Ltd Finely dividing board, vacuum soil kneading machine and method for manufacturing column-like body containing ceramic raw material
WO2008059608A1 (en) * 2006-11-16 2008-05-22 Ibiden Co., Ltd. Process for production of honeycomb structures
CN101456744B (en) * 2008-12-26 2012-05-23 山东理工大学 Method for preparing honeycomb type ceramic film
WO2014045975A1 (en) * 2012-09-20 2014-03-27 三洋化成工業株式会社 Lubricant for ceramic extrusion molding, green body composition for ceramic extrusion molding, ceramic molded article, and method for producing ceramic molded article
US10384369B2 (en) * 2012-11-30 2019-08-20 Corning Incorporated Extrusion systems and methods with temperature control
CN104942294A (en) * 2015-06-30 2015-09-30 成都易态科技有限公司 Extrusion forming method and mold for honeycomb intermetallic compound filter element
JP6507142B2 (en) * 2016-08-09 2019-04-24 日本碍子株式会社 Die for forming honeycomb structure
CN109877942A (en) * 2019-03-09 2019-06-14 益阳胜希机械设备制造有限公司 A kind of continuous extruder
US20200383946A1 (en) * 2019-05-07 2020-12-10 Aciont Inc. Lipoic acid formulations

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2694245A (en) * 1950-11-28 1954-11-16 Bendix Aviat Corp Molding of ceramics
US4364881A (en) * 1976-08-10 1982-12-21 Ngk Insulators, Ltd. Continuous extrusion method of manufacturing ceramic honeycomb structures with the aid of screw type vacuum extruding machine
US5432224A (en) * 1988-02-18 1995-07-11 Sanyo Chemical Industries, Ltd. Moldable composition, process for producing sintered body therefrom and products from same
US5578147A (en) * 1995-05-12 1996-11-26 The Boc Group, Inc. Controlled process for the heat treating of delubed material
US5935514A (en) * 1997-01-23 1999-08-10 Corning Incorporated Method for extrusion of powder mixtures using supercritical fluids
US6080345A (en) * 1997-08-08 2000-06-27 Corning Incorporated Method of forming and shaping plasticized mixtures
US6200517B1 (en) * 1998-08-04 2001-03-13 Corning Incorporated Methods for removing organics from green structures during firing
US20030146530A1 (en) * 2000-04-27 2003-08-07 Verion Inc. Zero order release and temperature-controlled microcapsules and process for the preparation thereof
US6939825B1 (en) * 1999-06-23 2005-09-06 Ibiden Co., Ltd. Carrier for catalyst and method for preparing the same

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58181763A (en) * 1982-04-19 1983-10-24 日本油脂株式会社 Manufacture of ceramic formed body
JPH0733013B2 (en) * 1988-09-20 1995-04-12 日本碍子株式会社 Method for manufacturing ceramic honeycomb structure
JPH04209747A (en) * 1990-12-04 1992-07-31 Shin Etsu Chem Co Ltd Ceramic material for single screw type extrusion forming
JPH0685873B2 (en) * 1990-12-28 1994-11-02 住友金属鉱山株式会社 Method of manufacturing honeycomb structure carrier comprising boria silica-alumina composition
DE4226276A1 (en) * 1992-08-08 1994-02-10 Didier Werke Ag Sintered ceramic filter body for removing dust from high temp. gases - contg. aluminium oxide mainly in form of mullite producing high deg. of porosity, micropore size and specified high gas permeability
JPH06329465A (en) 1993-05-20 1994-11-29 Kyocera Corp Ceramic composition for forming
JP3283346B2 (en) 1993-07-20 2002-05-20 堺化学工業株式会社 Clay composition for extrusion molding
FR2722131B1 (en) * 1994-07-08 1996-08-14 Rhone Poulenc Chimie PROCESS FOR THE PREPARATION OF AQUEOUS PUMPABLE AGRICULTURAL MIXTURES
BR9810388A (en) * 1997-08-08 2000-09-05 Corning Inc Improved process of forming and molding plasticized mixtures and the green bodies produced from them
JP3961683B2 (en) * 1998-07-07 2007-08-22 株式会社日本自動車部品総合研究所 Cordierite honeycomb structure manufacturing method and forming aid for forming honeycomb structure
JP3799241B2 (en) * 2001-03-29 2006-07-19 日本碍子株式会社 Manufacturing method of honeycomb structure
US7422719B2 (en) * 2002-10-29 2008-09-09 Corning Incorporated Process for removing oil-based components and forming ceramic bodies
JP7069711B2 (en) 2017-12-27 2022-05-18 大日本印刷株式会社 A wiring board and a semiconductor device having a wiring board

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2694245A (en) * 1950-11-28 1954-11-16 Bendix Aviat Corp Molding of ceramics
US4364881A (en) * 1976-08-10 1982-12-21 Ngk Insulators, Ltd. Continuous extrusion method of manufacturing ceramic honeycomb structures with the aid of screw type vacuum extruding machine
US5432224A (en) * 1988-02-18 1995-07-11 Sanyo Chemical Industries, Ltd. Moldable composition, process for producing sintered body therefrom and products from same
US5578147A (en) * 1995-05-12 1996-11-26 The Boc Group, Inc. Controlled process for the heat treating of delubed material
US5935514A (en) * 1997-01-23 1999-08-10 Corning Incorporated Method for extrusion of powder mixtures using supercritical fluids
US6080345A (en) * 1997-08-08 2000-06-27 Corning Incorporated Method of forming and shaping plasticized mixtures
US6200517B1 (en) * 1998-08-04 2001-03-13 Corning Incorporated Methods for removing organics from green structures during firing
US6939825B1 (en) * 1999-06-23 2005-09-06 Ibiden Co., Ltd. Carrier for catalyst and method for preparing the same
US20030146530A1 (en) * 2000-04-27 2003-08-07 Verion Inc. Zero order release and temperature-controlled microcapsules and process for the preparation thereof

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050025849A1 (en) * 2000-06-30 2005-02-03 Denso Corporation Method and apparatus for molding ceramic sheet
US7090480B2 (en) * 2000-06-30 2006-08-15 Denso Corporation Method and apparatus for molding ceramic sheet
US7101166B2 (en) * 2002-09-27 2006-09-05 Denso Corporation Apparatus for extruding ceramic molding
US20040062828A1 (en) * 2002-09-27 2004-04-01 Denso Corporation Apparatus for extruding ceramic molding
US20040062827A1 (en) * 2002-10-01 2004-04-01 Satoru Yamaguchi Extrusion molding apparatus for ceramic molded product
US7101165B2 (en) * 2002-10-01 2006-09-05 Denso Corporation Extrusion molding apparatus for ceramic molded product
US20060208397A1 (en) * 2005-03-17 2006-09-21 Ngk Insulators, Ltd. Method for manufacturing formed honeycomb structure
US20080106009A1 (en) * 2006-02-24 2008-05-08 Ibiden Co., Ltd. Wet mixing apparatus, wet mixing method and method for manufacturing honeycomb structure
US8124002B2 (en) 2006-04-13 2012-02-28 Ibiden Co., Ltd. Extrusion-molding machine, extrusion-molding method, and method for manufacturing honeycomb structured body
EP1844918A1 (en) * 2006-04-13 2007-10-17 Ibiden Co., Ltd. Extrusion-molding machine, extrusion-molding method, and method for manufacturing honeycomb structured body
US20070243283A1 (en) * 2006-04-13 2007-10-18 Ibiden Co., Ltd. Extrusion-molding machine, extrusion-molding method, and method for manufacturing honeycomb structured body
US20080119355A1 (en) * 2006-11-16 2008-05-22 Ibiden Co., Ltd. Method for manufacturing honeycomb structure
US20120263896A1 (en) * 2009-12-02 2012-10-18 Guenthner Gerhard Extruded molded functional body made of highly thermally conductive ceramic
US9394203B2 (en) * 2009-12-02 2016-07-19 Ceramtec Gmbh Extruded molded functional body made of highly thermally conductive ceramic
CN102515775A (en) * 2011-12-16 2012-06-27 河南东大高温节能材料有限公司 Preparation method for energy-saving honeycomb ceramic
US11220021B2 (en) * 2016-08-03 2022-01-11 Corning Incorporated Apparatus and methods of ceramic pre-cursor batch rheology control
US10946552B2 (en) 2017-04-19 2021-03-16 Denso Corporation Evaluation method for clay and manufacturing method of extrusion molded body
US20200139581A1 (en) * 2017-07-10 2020-05-07 Arlanxeo Deutschland Gmbh Extruder system with pressure regulating device
US11697223B2 (en) * 2017-07-10 2023-07-11 Arlanxeo Deutschland Gmbh Extruder system with pressure regulating device
WO2021030176A1 (en) * 2019-08-14 2021-02-18 Corning Incorporated Systems and methods for reducing surface oil streaks on wet extrudate by irradiation

Also Published As

Publication number Publication date
JP2003181816A (en) 2003-07-02
US20100102491A1 (en) 2010-04-29
CN1410385A (en) 2003-04-16
US8747729B2 (en) 2014-06-10
CN1266073C (en) 2006-07-26
BE1015788A5 (en) 2005-09-06
DE10247030A1 (en) 2003-05-28
JP4161652B2 (en) 2008-10-08

Similar Documents

Publication Publication Date Title
US8747729B2 (en) Product method for ceramic structure and production method for ceramic honeycomb structure
US4725467A (en) Polycrystalline, translucent sintered tubes
EP1937385B1 (en) Self lubricating binders for ceramic extrusion
JP4369041B2 (en) An improved method for preparing and shaping plasticized mixtures by low to medium shear extrusion.
JP2011519321A (en) Method for manufacturing ceramic article
JPH06316708A (en) Manufacturing extrusion die from powder
CN1241875C (en) Improved method of forming and shaping plasticized mixtures and green bodies made therefr
US20160039718A1 (en) Ceramic precursor batch composition and method of increasing ceramic precursor batch extrusion rate
CN103443049A (en) Ceramic compositions for improved extrusion
JP3227038B2 (en) Manufacturing method of ceramic structure
CN103396102B (en) A kind of preparation method of the low-expansion coefficient cordierite honeycomb ceramic based on fluid additive
CN1311724A (en) Aqueous molding compositions for powders of stainless steel, intermetallic compound and/or metal matrix composites
JP4986606B2 (en) Long hollow ceramic member and manufacturing method thereof
CN104981443B (en) T is increased using organic additive hetero atom polyalcoholStartingCeramic precursor batch composition
Davies et al. Plastic forming of alumina from coagulated suspensions
CN104364219A (en) Control of clay crystallite size for shrinkage management
JP2999699B2 (en) Method of manufacturing black pencil lead
JP4082574B2 (en) Manufacturing method of honeycomb structure
JPH0798688B2 (en) Ceramic material for extrusion molding and extrusion molding method thereof
RU2223930C2 (en) Method of preparing and molding plasticized powdered blend, powdered blend, and product obtained by this method
FI79694B (en) POLYCRYSTALLINE GENOMSKINLIGA SINTERROER.
JPH1081847A (en) Production of pencil lead
CN117585989A (en) Novel flexible high-temperature-resistant elastic sealing material and preparation method and application thereof
Janas et al. Predicting Extrudability of Batch via Torque and Capillary Rheometry
JP2008137184A (en) Extrusion molding machine of ceramic molded object and molding method using it

Legal Events

Date Code Title Description
AS Assignment

Owner name: DENSO CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:INOGUCHI, KAZUHIRO;REEL/FRAME:013485/0600

Effective date: 20021016

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION