WO1999048840A1 - Materiau ceramique poreux massif homogene - Google Patents
Materiau ceramique poreux massif homogene Download PDFInfo
- Publication number
- WO1999048840A1 WO1999048840A1 PCT/FR1999/000607 FR9900607W WO9948840A1 WO 1999048840 A1 WO1999048840 A1 WO 1999048840A1 FR 9900607 W FR9900607 W FR 9900607W WO 9948840 A1 WO9948840 A1 WO 9948840A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paste
- pore diameter
- pore
- material according
- diameter
- Prior art date
Links
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 79
- 239000000835 fiber Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 11
- 239000011707 mineral Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 5
- 239000012764 mineral filler Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007596 consolidation process Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 25
- 229910052753 mercury Inorganic materials 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000002459 porosimetry Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 239000003361 porogen Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 229940016286 microcrystalline cellulose Drugs 0.000 description 7
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 7
- 239000008108 microcrystalline cellulose Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 3
- 229940071676 hydroxypropylcellulose Drugs 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000416162 Astragalus gummifer Species 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl sulfonic acid Chemical compound 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0046—Inorganic membrane manufacture by slurry techniques, e.g. die or slip-casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0048—Fibrous materials
- C04B20/0056—Hollow or porous fibres
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0058—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity open porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/08—Patterned membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
Definitions
- the subject of the invention is a homogeneous solid porous ceramic material, with adjustable and controlled porosity and pore diameter.
- the present ceramic porous body can be used for filtration of fluids, gas separation, or for contacting fluids such as in catalytic reactions, or production of emulsion, and other applications using a porous ceramic material.
- pore diameter and porosity are also largely a function of the characteristics of the layer on which it is deposited, which does not allow variation in a very wide field.
- their baking temperature must be lower than the baking temperature of the undercoat. In some cases, this baking temperature is low and insufficient to allow optimum adhesion of the layer to the under layer.
- the manufacture of filtration membranes is a long and expensive process comprising a large number of steps; it does not allow the membrane characteristics to be adapted to the fluids to be filtered.
- the porosity of the macro-porous support is low in order to maintain sufficient mechanical strength for the use of the membrane.
- the production of a layer with a small pore diameter requires relatively low baking temperatures, temperatures which are insufficient to obtain the optimum properties of the material.
- US-P-4446024 describes a ceramic fiber, whose pore diameter is typically of the order of a tenth of a micron, and whose porosity is greater than 35%.
- the material of this patent suffers from two major drawbacks, namely a large closed porosity, which harms the filtration capacity of this porous ceramic material, and a bubble point which does not correspond to the average pore size, thus highlighting faults.
- EP-A-0657403 describes a porous ceramic material having a honeycomb structure, using a silica oligomer as a bonding agent. No porogen is used.
- DE-A-19609126 describes a porous support, the starting paste of which comprises an agent indicated as "Porentrucknet and Grunbinder”. This agent is for example cellulose or tragacanth, which is soluble in the chosen solvent (water). It is in fact the binder conventionally used in the art.
- EP-A-0778250 describes a porous support obtained by pressing, using a binder soluble in the chosen solvent (1 water).
- O-A-9423829 describes a process for manufacturing fibers, using a binder as before.
- DE-A-19618920 describes a porous ceramic fiber comprising a carbon membrane.
- the binder used is as previously conventional.
- the subject of the present invention is a homogeneous solid porous ceramic material whose average pore diameter D50 is less than 4 ⁇ m and whose closed porosity is less than 4%, preferably less than 2%.
- D50 is the volume average diameter such that 50% of the pores have a diameter less than D50.
- the volume distribution of pore diameter is monodisperse; according to this embodiment the standard deviation is less than 35%, preferably 25% of the mean diameter by volume D50.
- the material according to the invention will have a standard deviation of between 10 and 25% of the mean diameter by volume D50.
- Figures 1 and 2 show the volume distribution curve of the pore diameters for the materials of Examples 1 and 5, respectively.
- the material according to the invention has a bubble point corresponding to the pore diameter measured on said material.
- a first advantage of the present invention is to provide a homogeneous massive structure ("bul y"), that is to say having the same pore diameter over the entire thickness of the material.
- the term "solid” is intended to distinguish the present material from a thin layer; the characteristic dimension of the material is of the order of a millimeter, namely the material is on a macroscopic scale.
- the term "homogeneous” also intends to distinguish the material from a stack of successive layers which could possibly have a similar characteristic dimension.
- a second advantage of the present invention is to be able to easily adjust the key characteristics of the structure of the membranes, that is to say the pore diameter and the porosity, in a simple and rapid manner, as well as in a large range of variation without loss of mechanical resistance.
- This adaptability is obtained independently for the pore diameter and the porosity; in other words the two criteria can be adjusted independently of each other.
- This adaptability is obtained without modifying the sintering temperature of the parts obtained.
- a third advantage of the present invention is to obtain porous ceramic membranes having no structural defect.
- a fourth advantage of the present invention is the simplicity of its manufacture due to the elimination, on the one hand of the manufacture of an intermediate layer, and on the other hand, that of the end sealing.
- the present invention relates to a porous body having a homogeneous structure.
- This structure is characterized by a pore diameter and a porosity, that is to say a pore volume. These quantities are measured by mercury porosimetry.
- the pore diameter D50 of the material is for example less than 2 ⁇ m, and in general between 50 nm and 1.5 ⁇ m. This variation in diameter is controlled by the initial composition of the spinning dough. This area of variation is very wide.
- the pore volume or porosity of the material according to the invention is such that the closed porosity is less than 4%, preferably less than 2%, advantageously less than 1%.
- the open pore volume or open porosity is generally between 10 and 70%; the invention makes it possible in particular to obtain very high open porosities, such greater than 30%, for example between 40, or even 45%, and 60%. This variation in the open porosity is controlled by the initial composition of the spinning paste.
- the present invention makes it possible to obtain membranes having no defect. This characteristic is measured by the bubble point technique (see the publication by TH MELTZER et al, Bulletin of the Parenteral Drug Association, vol. 65 (4), 1971, ppl65-174). This technique makes it possible to determine the pressure necessary for a gas bubble to pass through the membrane previously saturated with a wetting liquid. A mathematical relationship links the gas pressure, the surface tension of the wetting liquid and the diameter of the through pore (Jurin's Law). The present invention makes it possible to obtain a bubble point (through pore diameter) which corresponds to the pore diameter measured on the membrane (at 10%). The invention also relates to a hollow fiber based on the material according to the invention, as well as a filtration and / or reaction module comprising such fibers.
- Another object of the present invention is the description of a manufacturing process for a porous ceramic membrane having the advantages listed above, as well as the precursor paste of said material.
- the present invention therefore also provides a process for preparing a homogeneous solid porous ceramic material, in particular a material according to the invention, comprising the following main steps:
- the precursor paste of the material comprises the mixture of an inorganic compound or filler, an organic binder, a porosity-creating or porogenic agent, a solvent, and optionally a mineral binder and / or a deflocculant suitable for this metallic compound and / or a processability agent (in general an extrusion agent).
- the mineral part of said paste consists of particles of an inorganic compound, preferably metallic, which will form after sintering the homogeneous porous network.
- the metal compound is either a non-oxide compound or a metal oxide.
- a derivative of silicon or aluminum will be chosen, and preferably silicon carbide, silicon nitride or aluminum nitride.
- the metal compound is an oxide, it will be chosen from oxides of aluminum, of silicon or of metals of groups IVA (group of titanium) or VA (group of vanadium) and preferably alumina, oxide of zirconium or titanium oxide. These oxides can be used alone or as a mixture.
- the metallic compound has, for example, an average particle diameter (measured in the sedigraph) between 0.15 and 2 ⁇ m, and preferably between 0.15 and 0.6 ⁇ m. Its content in the dough will be between 50 and 85% by mass, and preferably between 65 and 80% by mass.
- This mineral filler will preferably consist of particles whose diameters d90 and d50 are such that d90 / d50 ⁇ 3 and advantageously d90 / d50 ⁇ 2.
- the organic binder will give the paste the rheological properties necessary for extrusion and the mechanical properties necessary to obtain good cohesion of the product after extrusion.
- Said organic binder is preferably, but not necessarily, a water-soluble polymer.
- the polymer will present, for example, for a solution at 2% by mass, a viscosity measured 20 ° C. of between 4 and 10 Pa / s.
- This polymer can be chosen from celluloses and their derivatives, in particular hydroxyethyl cellulose and / or microcrystalline cellulose, but also a polyacrylic acid or a polyvinyl alcohol, etc.
- the paste will contain, for example, between 2 and 10% by mass of organic binder and preferably between 3 and 8% by mass.
- the role of the solvent is to disperse the mineral part and the binder.
- water will be chosen as the solvent; in the case where the polymer is not water-soluble, an alcohol will be chosen, for example 1 ethanol as solvent.
- concentration of the solvent will be for example between 8 and 40% by mass and preferably between 10 and 27% by mass.
- the porosity-creating or porogenic agent is characterized by a low decomposition temperature, for example less than 450 ° C., preferably less than 250 ° C. It is characterized on the other hand by the average size of the particles which compose it, size which is in relation to that of the particles of the metallic charge.
- This size is for example between 5 and 30 ⁇ m and preferably between 8 and 16 ⁇ m.
- the porogen is substantially insoluble in the chosen solvent.
- the sizes of the mineral filler particles and the blowing agent particles can vary independently of each other to a very great extent.
- spinnability paste generally between 9 and 30 bar, and preferably between 10 and 16 bar.
- a solvent-soluble deflocculant will improve the dispersion of the particles of the metal compound.
- a polyacrylic acid, a phospho-organic acid or an alkyl sulfonic acid will be chosen.
- the deflocculant content is of the order of 0.5 to 1% by mass.
- a processability agent will generally be added, an extrusion aid agent such as a polyethylene glycol.
- the content of extruding agent is of the order of 0.5 to 1% by mass.
- the mechanical resistance to bending can be modified in a conventional manner by the introduction into the composition of the paste of mineral binders which will react during sintering to increase the cohesion forces between the particles.
- the subject of the invention is finally the precursor paste as described above, namely a paste comprising, dispersed in a solvent, a mineral part or filler, an organic binder and a blowing agent.
- the dough is shaped for example and preferably by extrusion, in a conventional manner.
- the product is then dried and then sintered at a high temperature, for example between 1400 and 1750 ° C.
- Example 1 A ceramic paste is produced by mixing an alumina of average size 0.6 ⁇ m, microcrystalline cellulose as organic binder, water as solvent and a porogen constituted by particles of low density polyethylene, the average size of these particles being 15 ⁇ m.
- the d90 / d50 ratio of the powder used is 1.4.
- the composition of this paste is (in percentage by mass):
- the dough thus obtained has a filability of 10.
- This dough is extruded through a die for hollow fiber so as to form a tube of 1.5 mm outside diameter and 0.8 mm inside diameter.
- the fiber thus obtained is baked at 1450 ° C in a normal atmosphere.
- the decomposition temperature of low density polyethylene chosen is 230 ° C, it is therefore completely destroyed during sintering of the fiber.
- the fiber is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 0.6 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.08 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in the present case 13%.
- the volume distribution curve of the pore diameters is shown in Figure 1.
- a ceramic paste is produced by mixing a silica of average size 0.2 ⁇ m, a polyvinyl alcohol as organic binder, water as solvent and a pore-forming agent constituted by particles of an ethylene vinyl acetate copolymer, the the average size of these particles being 30 ⁇ m.
- the d90 / d50 ratio of the silica used is 1.5.
- the composition of this paste is (in percentage by mass):
- the paste thus obtained has a filability of 9.
- This paste is used to form a porous block of 5 cm on one side.
- This block is baked at 1530 ° C in a normal atmosphere.
- the decomposition temperature of the ethylene vinyl acetate copolymer chosen is 180 ° C., it is therefore completely destroyed during the sintering of the porous block.
- the block is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 0.4 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.1 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in this case 25%.
- a ceramic paste is produced by mixing a titanium oxide powder of average size 2 ⁇ m, a hydroxy propyl cellulose (HPC) as an organic binder, water as a solvent, a porogen constituted by particles of activated carbon whose size average is 8 ⁇ m and a polymethacrylic acid as deflocculant.
- the d90 / d50 ratio of the titanium oxide powder used is 1.7.
- the composition of this paste is (in percentage by mass)
- the paste thus obtained has a filability of 19.
- This paste is used to form a porous fiber of 1 mm in external diameter and 0.5 mm in internal diameter.
- This fiber is baked at 1400 ° C in an argon atmosphere.
- the decomposition temperature of the activated carbon is 420 ° C, it is therefore completely destroyed during the sintering of the porous fiber.
- the fiber is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 1.2 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.1 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in this case 8%.
- a ceramic paste is produced by mixing a zirconium oxide powder of average size 0.25 ⁇ m, microcrystalline cellulose as organic binder, water as solvent, a porogen constituted by sawdust from active walnut kernels, the average size is 10 ⁇ m.
- the d90 / d50 ratio of the zirconia used is 1.2.
- the composition of this paste is (in percentage by mass):
- the pulp thus obtained has a filability of 30.
- This pulp is used to form a porous fiber of 1 mm in external diameter and 0.3 mm in internal diameter.
- This fiber is baked at 1700 ° C in a normal atmosphere.
- the sawdust decomposition temperature is 350 ° C, it is therefore completely destroyed during the sintering of the porous fiber.
- the fiber is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 0.05 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.01 ⁇ m, this width corresponds to the standard deviation of the pore distribution, which in this case is 20%.
- a ceramic paste is produced by mixing a vanadium oxide powder of average size 2 ⁇ m, a polyacrylic acid (APA) as an organic binder, water as a solvent, polyethylene glycol as an extruding agent and a pore-forming agent constituted by an emulsion of fats in water, the average size of the fat globules being 26 ⁇ m.
- the d90 / d50 ratio of the vanadium oxide powder used is 1.8.
- the composition of this paste is (in percentage by mass):
- the paste thus obtained has a filability of 13.
- This paste is used to form a porous block of 12 cm on one side.
- This block is baked at 1600 ° C in a normal atmosphere.
- the decomposition temperature of the emulsion chosen is 160 ° C. It is therefore completely destroyed during the sintering of the porous block.
- the block is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 2 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.2 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in this case 10%.
- the curve of volume distribution of pore diameters is shown in Figure 2.
- the fiber is therefore free from defects.
- a ceramic paste is produced by mixing a powder of silicon nitride of average size 0.6 ⁇ m, an ethyl cellulose as organic binder, ethanol as a solvent, a pore-forming agent constituted by particles of low density polyethylene (LDPE) whose average size is 5 ⁇ m.
- LDPE low density polyethylene
- the d90 / d50 ratio of the silicon nitride powder used is 1.5.
- the composition of this paste is (in percentage by mass): - silicon nitride 80
- the paste thus obtained has a filability of 12.
- This paste is used to form a porous fiber of 1 mm of external diameter and 0.5 mm of internal diameter.
- This fiber is baked at 1750 ° C in an argon atmosphere.
- the decomposition temperature of the activated carbon is 210 ° C, it is therefore completely destroyed during the sintering of the porous fiber.
- the fiber is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 0.5 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.12 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in this case 24%. On the other hand, its pore volume is 35%. The density of the fiber is 3.15. The absolute density of the silicon nitride being 3.18, the closed porosity not available for filtration is 0.9% at most. The bubble point measurement gives a pressure of
- a ceramic paste is produced by mixing an alumina of average size 0.9 ⁇ m, a powder of titanium oxide of average size 1.3 ⁇ m, microcrystalline cellulose as organic binder, water as solvent and a porogen consisting of particles of an ethylene vinyl acetate copolymer, the average particle size being 12 ⁇ m.
- the d90 / d50 ratio of the mixture of oxide powders used is 1.8.
- the composition of this paste is (in percentage by mass):
- the paste thus obtained has a filability of 9.
- This paste is used to form a porous block of 5 cm on one side.
- This block is baked at 1500 ° C in a normal atmosphere.
- the decomposition temperature of the emulsion chosen is 150 ° C., it is therefore completely destroyed during the sintering of the porous block.
- the block is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 0.9 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.1 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in this case 11%.
- a ceramic paste is produced by mixing an alumina of average size 1.8 ⁇ m, a hydroxy ethyl cellulose (HEC) as organic binder, water as a solvent and a porogen constituted by sawdust of nuclei, the average size of these particles being 20 ⁇ m.
- HEC hydroxy ethyl cellulose
- the d90 / d50 ratio of the alumina powder used is 2.
- composition of this paste is (in percentage by mass): - alumina 63
- the paste thus obtained has a filability of 14.
- This paste is used to form a porous plate 5 cm side by 15 cm long.
- This plate is baked at 1500 ° C in a normal atmosphere.
- the decomposition temperature of the sawdust of cores chosen is 450 ° C, it is therefore completely destroyed during the sintering of the porous plate.
- the plate is characterized by mercury porosimetry. Mercury penetration only shows a single peak centered at 1.5 ⁇ m indicating a monodisperse distribution of the pores. The width at mid-height of the peak is 0.3 ⁇ m, this width corresponds to the standard deviation of the pore distribution which is in the present case 20%.
- the bubble point measurement gives a pressure of 640 mbar, i.e. a pore diameter of 1.5 ⁇ m, which corresponds to the pore diameter determined by the mercury porosimetry.
- the fiber is therefore free from defects.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Filtering Materials (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1070028T DE1070028T1 (de) | 1998-03-20 | 1999-03-17 | Poröses homogenes massives keramikmaterial |
AU28416/99A AU2841699A (en) | 1998-03-20 | 1999-03-17 | Homogeneous massive porous ceramic material |
EP99909023A EP1070028A1 (fr) | 1998-03-20 | 1999-03-17 | Materiau ceramique poreux massif homogene |
NO20004674A NO20004674L (no) | 1998-03-20 | 2000-09-19 | Homogent bulk porøst keramisk materiale |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR98/03490 | 1998-03-20 | ||
FR9803490A FR2776287B1 (fr) | 1998-03-20 | 1998-03-20 | Materiau ceramique poreux massif homogene |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1999048840A1 true WO1999048840A1 (fr) | 1999-09-30 |
WO1999048840A9 WO1999048840A9 (fr) | 2000-05-11 |
Family
ID=9524326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/000607 WO1999048840A1 (fr) | 1998-03-20 | 1999-03-17 | Materiau ceramique poreux massif homogene |
Country Status (11)
Country | Link |
---|---|
US (2) | US6573208B1 (fr) |
EP (1) | EP1070028A1 (fr) |
JP (1) | JPH11322465A (fr) |
KR (1) | KR19990078084A (fr) |
CN (1) | CN1229770A (fr) |
AU (1) | AU2841699A (fr) |
CA (1) | CA2266566A1 (fr) |
DE (1) | DE1070028T1 (fr) |
FR (1) | FR2776287B1 (fr) |
NO (1) | NO20004674L (fr) |
WO (1) | WO1999048840A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7199067B2 (en) * | 1998-03-20 | 2007-04-03 | Pall Corporation | Homogeneous bulky porous ceramic material |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2805331B1 (fr) * | 2000-02-21 | 2002-05-31 | Ceramiques Tech Soc D | Element multicanal et procede de fabrication d'un tel element |
JP4730722B2 (ja) * | 2001-03-27 | 2011-07-20 | 日本特殊陶業株式会社 | 積層型ガスセンサ素子の製造方法及び積層型ガスセンサ素子 |
US7922964B2 (en) * | 2002-08-30 | 2011-04-12 | Itn Nanovation Ag | Ceramic hollow fibers made from nanoscale powder particles |
JP2006027925A (ja) * | 2004-07-13 | 2006-02-02 | Nagoya Institute Of Technology | 湿度センサー材料、湿度センサー材料を用いた湿度センサー及び湿度センサー材料を備えた電気機器 |
JP4473693B2 (ja) * | 2004-09-28 | 2010-06-02 | 日本碍子株式会社 | ハニカムフィルタ |
CN100406122C (zh) * | 2004-10-29 | 2008-07-30 | 中国石油化工股份有限公司 | 一种重、渣油加氢处理催化剂的制备方法 |
WO2006120772A1 (fr) * | 2005-05-10 | 2006-11-16 | Koa Glass Co., Ltd | Fibre antimicrobienne et procede de production correspondant |
DE102005031856A1 (de) * | 2005-05-13 | 2006-11-16 | Atech Innovations Gmbh | Verfahren zur Herstellung von keramischen Filtern, Engobe und keramischer Filter |
ATE513071T1 (de) * | 2005-07-08 | 2011-07-15 | Univ Bath | Anorganische poröse hohlfasern |
EP1785408A1 (fr) * | 2005-11-15 | 2007-05-16 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Procédé d'élaboration de supports poreux céramiques de microstructure contrôlée |
DE102006044635B4 (de) * | 2006-09-19 | 2008-11-06 | Gkss-Forschungszentrum Geesthacht Gmbh | Gastrenn-Membran |
DE102006047928A1 (de) * | 2006-10-10 | 2008-04-17 | Robert Bosch Gmbh | Verfahren zur Herstellung mindestens einer porösen Schicht |
JP4961189B2 (ja) * | 2006-10-20 | 2012-06-27 | 株式会社ニッカトー | 多孔質アルミナ質焼結体からなる真空チャック用部材およびその製造方法 |
JP5176198B2 (ja) | 2007-02-21 | 2013-04-03 | 独立行政法人産業技術総合研究所 | マクロポーラスな連通孔を持つセラミック多孔体の製造方法 |
EP2274066B9 (fr) * | 2008-04-11 | 2020-12-09 | LiqTech International A/S | Filtre aveugle en céramique, système de filtre et procédé de filtration |
KR101161675B1 (ko) | 2009-12-31 | 2012-07-02 | 한국에너지기술연구원 | 탄화규소 중공사 및 그 제조방법 |
KR101185490B1 (ko) | 2009-12-31 | 2012-10-02 | 한국에너지기술연구원 | 무기질 중공사 및 그 제조 방법 |
US9878272B2 (en) * | 2010-05-28 | 2018-01-30 | Corning Incorporated | Porous inorganic membranes and method of manufacture |
JP5806030B2 (ja) * | 2011-07-28 | 2015-11-10 | 京セラ株式会社 | 回路基板およびこれを備える電子装置 |
CN106000123B (zh) * | 2016-05-27 | 2019-11-01 | 成都易态科技有限公司 | 多孔薄膜的制备方法 |
DE102018200969B3 (de) | 2018-01-23 | 2018-11-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung poröser anorganischer Formkörper sowie damit hergestellte Formkörper und deren Verwendung |
JP2020200230A (ja) * | 2019-06-13 | 2020-12-17 | 日本特殊陶業株式会社 | セラミックス体およびセラミックス体の製造方法 |
CN111548125A (zh) * | 2020-04-15 | 2020-08-18 | 天津大学 | 一种梯度孔多层陶瓷膜的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994023829A1 (fr) * | 1993-04-15 | 1994-10-27 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Procede pour la production de fibres ceramiques creuses, en particulier des membranes a fibres creuses pour la microfiltration, l'ultrafiltration et la separation de gaz |
EP0657403A1 (fr) * | 1993-06-14 | 1995-06-14 | Sumitomo Electric Industries, Limited | Ceramique poreuse et son procede de fabrication |
DE19618920A1 (de) * | 1995-05-10 | 1996-11-28 | Nok Corp | Verbundhohlfaser aus poröser Keramik und Verfahren zu seiner Herstellung |
EP0778250A1 (fr) * | 1995-12-06 | 1997-06-11 | Sumitomo Chemical Company, Limited | Corps inorganique poreux fritté ou compacté et son utilisation comme filtre |
DE19701751A1 (de) * | 1996-01-21 | 1997-07-24 | Klaus Rennebeck | Mikrohohlfaser aus keramischen Material, ein Verfahren zu deren Herstellung sowie deren Verwendung |
DE19609126A1 (de) * | 1996-03-08 | 1997-09-11 | Schumacher Umwelt Trenntech | Poröse Form und Verfahren zu ihrer Herstellung |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4446024A (en) | 1977-02-22 | 1984-05-01 | E. I. Du Pont De Nemours & Company | Hollow filament product |
US4203772A (en) * | 1977-04-18 | 1980-05-20 | Corning Glass Works | Porous zirconia containing ceramics |
US4222977A (en) * | 1978-05-16 | 1980-09-16 | Monsanto Company | Process to produce inorganic hollow fibers |
US4175153A (en) * | 1978-05-16 | 1979-11-20 | Monsanto Company | Inorganic anisotropic hollow fibers |
FR2431468A1 (fr) * | 1978-07-19 | 1980-02-15 | Lafarge Sa | Materiau microporeux utilisable notamment dans l'industrie ceramique |
JPS55119402A (en) * | 1979-03-07 | 1980-09-13 | Toyobo Co Ltd | Liquid separating module |
JPS5610533A (en) * | 1979-07-09 | 1981-02-03 | Kuraray Co Ltd | Polyvinyl alcohol porous membrane and production thereof |
FR2462405A1 (fr) * | 1979-08-03 | 1981-02-13 | Produits Refractaires | Procede de preparation de sialons |
DE3103751C2 (de) * | 1981-02-04 | 1983-05-19 | Schott Glaswerke, 6500 Mainz | Verfahren zur Herstellung von porösem Glas, poröser Glaskeramik und porösen keramischen Sintermassen |
FR2553758B1 (fr) * | 1983-10-25 | 1991-07-05 | Ceraver | Materiau poreux et filtre tubulaire comprenant ce materiau |
JPS60255671A (ja) * | 1984-05-29 | 1985-12-17 | イビデン株式会社 | 高強度多孔質炭化ケイ素焼結体とその製造方法 |
US4778499A (en) * | 1984-12-24 | 1988-10-18 | Ppg Industries, Inc. | Method of producing porous hollow silica-rich fibers |
JPS63270368A (ja) * | 1987-04-30 | 1988-11-08 | Okura Ind Co Ltd | セラミツクス多孔体の製造方法 |
EP0318236B1 (fr) * | 1987-11-27 | 1993-04-14 | Ecc International Limited | Matériaux minéraux poreux |
USH721H (en) * | 1988-07-05 | 1990-01-02 | The United States Of America As Represented By The Secretary Of The Air Force | Production of 10 micron diameter hollow ceramic fibers |
GB8902050D0 (en) * | 1989-01-31 | 1989-03-22 | T & N Technology Ltd | Reinforced materials |
JPH0492874A (ja) * | 1990-08-02 | 1992-03-25 | Lion Corp | 多孔質セラミックスの製造方法 |
FR2693921B1 (fr) * | 1992-07-24 | 1994-09-30 | Tech Sep | Support monolithe céramique pour membrane de filtration tangentielle. |
ATE267149T1 (de) | 1996-01-21 | 2004-06-15 | Klaus Rennebeck | Verfahren zur herstellung von mikrohohlfasern aus keramischem material |
US5766760A (en) * | 1996-09-04 | 1998-06-16 | Kimberly-Clark Worldwide, Inc. | Microporous fibers with improved properties |
JPH10100320A (ja) * | 1996-09-30 | 1998-04-21 | Mitsubishi Gas Chem Co Inc | 複合セラミックス板およびその製造法 |
DE19648270A1 (de) * | 1996-11-21 | 1998-05-28 | Basf Ag | Offenzellige poröse Sinterprodukte und Verfahren zu ihrer Herstellung |
US5922299A (en) * | 1996-11-26 | 1999-07-13 | Battelle Memorial Institute | Mesoporous-silica films, fibers, and powders by evaporation |
US6210612B1 (en) * | 1997-03-31 | 2001-04-03 | Pouvair Corporation | Method for the manufacture of porous ceramic articles |
DE69800531T2 (de) | 1997-04-09 | 2001-09-27 | Ceramiques Tech Bazet Soc D | Makroporöser Träger mit einem Porositätsgradient und Methode zu dessen Herstellung |
JP2001514152A (ja) | 1997-09-04 | 2001-09-11 | ポール・コーポレーション | 多孔質のセラミック構造体および多孔質のセラミック構造体を製造する方法 |
FR2776286B1 (fr) | 1998-03-20 | 2000-05-12 | Ceramiques Tech Soc D | Fibre ceramique poreuse multi-canal |
FR2776287B1 (fr) * | 1998-03-20 | 2000-05-12 | Ceramiques Tech Soc D | Materiau ceramique poreux massif homogene |
FR2789908B1 (fr) | 1999-02-19 | 2002-05-31 | Ceramiques Tech Soc D | Nappe d'elements de filtration, separation ou reaction, module comprenant une telle nappe et procedes de fabrication d'une telle nappe et d'un tel module |
FR2796638B1 (fr) * | 1999-07-21 | 2001-09-14 | Ceramiques Tech Et Ind S A | Structure monolithe nid d'abeilles en materiau ceramique poreux, et utilisation comme filtre a particules |
AU778651B2 (en) * | 1999-12-16 | 2004-12-16 | Isotis N.V. | Porous ceramic body |
US6399528B1 (en) * | 2000-09-01 | 2002-06-04 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Porous aluminum oxide structures and processes for their production |
-
1998
- 1998-03-20 FR FR9803490A patent/FR2776287B1/fr not_active Expired - Fee Related
-
1999
- 1999-03-17 WO PCT/FR1999/000607 patent/WO1999048840A1/fr active Application Filing
- 1999-03-17 AU AU28416/99A patent/AU2841699A/en not_active Abandoned
- 1999-03-17 EP EP99909023A patent/EP1070028A1/fr not_active Withdrawn
- 1999-03-17 DE DE1070028T patent/DE1070028T1/de active Pending
- 1999-03-19 US US09/272,156 patent/US6573208B1/en not_active Expired - Fee Related
- 1999-03-19 KR KR1019990009458A patent/KR19990078084A/ko not_active Application Discontinuation
- 1999-03-22 CN CN99103091A patent/CN1229770A/zh active Pending
- 1999-03-22 CA CA002266566A patent/CA2266566A1/fr not_active Abandoned
- 1999-03-23 JP JP11078052A patent/JPH11322465A/ja active Pending
-
2000
- 2000-09-19 NO NO20004674A patent/NO20004674L/no not_active Application Discontinuation
-
2003
- 2003-01-10 US US10/339,827 patent/US7199067B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994023829A1 (fr) * | 1993-04-15 | 1994-10-27 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Procede pour la production de fibres ceramiques creuses, en particulier des membranes a fibres creuses pour la microfiltration, l'ultrafiltration et la separation de gaz |
EP0657403A1 (fr) * | 1993-06-14 | 1995-06-14 | Sumitomo Electric Industries, Limited | Ceramique poreuse et son procede de fabrication |
DE19618920A1 (de) * | 1995-05-10 | 1996-11-28 | Nok Corp | Verbundhohlfaser aus poröser Keramik und Verfahren zu seiner Herstellung |
EP0778250A1 (fr) * | 1995-12-06 | 1997-06-11 | Sumitomo Chemical Company, Limited | Corps inorganique poreux fritté ou compacté et son utilisation comme filtre |
DE19701751A1 (de) * | 1996-01-21 | 1997-07-24 | Klaus Rennebeck | Mikrohohlfaser aus keramischen Material, ein Verfahren zu deren Herstellung sowie deren Verwendung |
DE19609126A1 (de) * | 1996-03-08 | 1997-09-11 | Schumacher Umwelt Trenntech | Poröse Form und Verfahren zu ihrer Herstellung |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7199067B2 (en) * | 1998-03-20 | 2007-04-03 | Pall Corporation | Homogeneous bulky porous ceramic material |
Also Published As
Publication number | Publication date |
---|---|
US6573208B1 (en) | 2003-06-03 |
US20030166449A1 (en) | 2003-09-04 |
AU2841699A (en) | 1999-10-18 |
CA2266566A1 (fr) | 1999-09-20 |
US7199067B2 (en) | 2007-04-03 |
JPH11322465A (ja) | 1999-11-24 |
NO20004674D0 (no) | 2000-09-19 |
FR2776287A1 (fr) | 1999-09-24 |
DE1070028T1 (de) | 2003-05-28 |
FR2776287B1 (fr) | 2000-05-12 |
CN1229770A (zh) | 1999-09-29 |
EP1070028A1 (fr) | 2001-01-24 |
WO1999048840A9 (fr) | 2000-05-11 |
NO20004674L (no) | 2000-11-08 |
KR19990078084A (ko) | 1999-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1070028A1 (fr) | Materiau ceramique poreux massif homogene | |
EP1144099B1 (fr) | Membrane comprenant un support poreux et une couche d'un tamis moleculaire et son procede de preparation | |
EP1062185B1 (fr) | Fibre ceramique poreuse multi-canal | |
JP5054460B2 (ja) | ハニカム構造体の製造方法、及び、ハニカム焼成体用原料組成物 | |
EP3233252B1 (fr) | Filtres comprenant des membranes en sic incorporant de l'azote | |
WO2003004439A1 (fr) | Procede de preparation d'une composition ceramique de faible epaisseur a deux materiaux, composition obtenue, cellule electrochimique et membrane la comprenant | |
EP0219383B1 (fr) | Utilisation de poudres frittables de carbure de silicium de granulométrie particulière dans la réalisation d'éléments de filtration en céramique poreuse, et céramiques ainsi obtenues | |
EP3558895B1 (fr) | Produits céramiques poreux de sous oxydes de titane | |
EP2114841B1 (fr) | Procédé de fabrication d'un corps poreux céramique à base de sic | |
EP3233253B1 (fr) | Filtres comprenant des membranes a base de sic appauvri en oxygene | |
FR2936512A1 (fr) | Procede de fabrication d'un materiau poreux en sic. | |
EP3471863B1 (fr) | Filtres comprenant des couches separatrices a base de beta-sic | |
EP2091890B1 (fr) | Procede d'obtention d'une structure poreuse a base de carbure de silicium et structure poreuse obtenue | |
EP1910249B1 (fr) | Procede de preparation d'une structure poreuse utilisant des agents porogenes a base de silice | |
FR2678524A1 (fr) | Membrane filtrante minerale a permeabilite amelioree, et sa preparation. | |
FR3030296A1 (fr) | Filtres a membranes composites sic-nitrure ou sic-oxynitrure | |
EP2285753A1 (fr) | Filtre ou support catalytique à base de carbure de silicium et de titanate d'aluminium | |
FR2936963A1 (fr) | Structure tri-dimensionnelle ouverte a forte resistance mecanique | |
JP2008303133A (ja) | 炭化ケイ素焼成用原料の製造方法、及び、ハニカム構造体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
AK | Designated states |
Kind code of ref document: C2 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: C2 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
COP | Corrected version of pamphlet |
Free format text: PAGE 19, CLAIMS, ADDED |
|
NENP | Non-entry into the national phase |
Ref country code: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999909023 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1999909023 Country of ref document: EP |