WO2005077501A1 - Method for the production of separation membranes - Google Patents
Method for the production of separation membranes Download PDFInfo
- Publication number
- WO2005077501A1 WO2005077501A1 PCT/CZ2005/000020 CZ2005000020W WO2005077501A1 WO 2005077501 A1 WO2005077501 A1 WO 2005077501A1 CZ 2005000020 W CZ2005000020 W CZ 2005000020W WO 2005077501 A1 WO2005077501 A1 WO 2005077501A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- base surface
- base
- particles
- separation
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 238000000926 separation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0004—Organic membrane manufacture by agglomeration of particles
- B01D67/00044—Organic membrane manufacture by agglomeration of particles by plasma spraying
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/122—Separate manufacturing of ultra-thin membranes
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0004—Organic membrane manufacture by agglomeration of particles
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/002—Organic membrane manufacture from melts
-
- 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
- B01D67/00414—Inorganic membrane manufacture by agglomeration of particles in the dry state by plasma spraying
-
- 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
- B01D67/0053—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/24—Use of template or surface directing agents [SDA]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/26—Spraying processes
-
- 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
- B01D71/022—Metals
-
- 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
- B01D71/025—Aluminium oxide
Definitions
- the invention relates to a method for the production of separation membranes or contactor membranes intended for the application in devices for filtration of liquids, the separation of gases and in contactor apparatuses.
- Prior art A method of manufacturing separation membranes from inorganic materials is known starting by extrusion of the input material, a powder or paste, to form a membrane semi-product to be sintered under temperatures exceeding 1000 °C. The sintering serves for hardening the material. Also a method is known where the original material is complemented with an ingredient that is removed from the membrane after its hardening by way of leaching, by phase separation or anodic oxidation, resulting in pores being created in the membrane. Leaching is frequently used when producing polymeric membranes, such as of Teflon, PVDF, polypropylene or other chemically resistant plastic materials. The disadvantage of leaching resides in the necessity of applying large volumes of chemically aggressive substances.
- asymmetric membrane is obtained that is created by a carrying layer and a separation layer.
- the removal of the membrane is facilitated by changing the temperature of the base and/or the temperature of the membrane so as to induce a . shrinkage of the base with regard to the membrane, or a dilatation of the membrane with regard to the base.
- Yet another possible procedure for easy separation of the produced membrane from the base surface consists in covering the base surface by a separation layer before introducing the stream of partially molten particles and in removing the separation layer from the base surface by dissolving, etching, evaporating of melting away after the membrane has been formed.
- Suitable materials for making a membrane by the above method are particles of ceramics, of metals or blends thereof, or of polymers.
- a core of stainless steel was used, with 83 mm diameter and 1 m length and about 1 % tapering.
- ground white alpha corundum with 20 ⁇ m grains was evenly distributed onto the core by a plasma burner.
- the applied burner having up to 200 kW power was able to deposit up to 25 kg of powder material per hour onto the core.
- the core was chilled, which allowed, along with the taper of the core, to easily pull the membrane from the core.
- a self-supporting shell of 2 mm wall thickness and 500 mm length was produced. Then it was freed from loose particles by rinsing and fixed in a testing device. The following measurement established 18 % porosity and the ability of the membrane to withstand internal pressure up to 0,6 MPa.
- This membrane of stainless steel has been created for extreme strain.
- a cylindrical steel core of 32 mm diameter and 500 mm length turned continuously around its lengthwise axis.
- the spraying was achieved manually by metallizing gun Sulzer Metco, the material was delivered in form of a wire.
- the sprayed shell of 3,5 mm thickness and 145 mm length showed a very good strength and allowed being removed by a hydraulic press. By following measurement 21 % porosity was established.
- a metallic board 6 was used as base, see Fig. 1 , with 180x80x15 mm dimensions.
- a plasma burner was used to spray ground crystalline sodium chloride with 40 ⁇ m grain that created a separation layer 3 of 0,8 mm thickness on the board 6.
- the separation layer 3 was covered by layer 2 of white alpha corundum, again using a plasma burner for spraying.
- the metallic core 5 of semi-circular section was covered on its whole perimeter, similarly as in the case of board 6 by a separation layer 4 of sodium chloride. Then the treated core 5 was accommodated by its flat side onto the treated board 6 and attached to the same. This set was again covered by layer 1 of white alpha corundum by plasma burner spraying.
- the semi-finished product illustrated in Fig. 1 was thus produced.
Abstract
The separation membranes according to the invention are made by depositing partially molten particles of the membrane material carried by gas stream onto a base surface, said particles creating a porous layer on the base surface after having cooled down. The base surface can serve as a carrying layer of the membrane, or the membrane can be created as a self-supporting structure to be separated from the base surfice.
Description
Method for the production of separation membranes
Technical field The invention relates to a method for the production of separation membranes or contactor membranes intended for the application in devices for filtration of liquids, the separation of gases and in contactor apparatuses.
Prior art A method of manufacturing separation membranes from inorganic materials is known starting by extrusion of the input material, a powder or paste, to form a membrane semi-product to be sintered under temperatures exceeding 1000 °C. The sintering serves for hardening the material. Also a method is known where the original material is complemented with an ingredient that is removed from the membrane after its hardening by way of leaching, by phase separation or anodic oxidation, resulting in pores being created in the membrane. Leaching is frequently used when producing polymeric membranes, such as of Teflon, PVDF, polypropylene or other chemically resistant plastic materials. The disadvantage of leaching resides in the necessity of applying large volumes of chemically aggressive substances. The result of these known technologies are membranes in the shape of plates, capillaries, or tubes, or possibly modules made of them. The disadvantage of membranes manufactured in this way resides in their low resistance to substantial mechanic strain and in high power requirements for their production. The embodiments specified on the patent application PCT/CZ2004/000055 describe the production of separation membranes of polysialates: Calcinated kaolin, water glass and sodium hydroxide are blended to form a liquid paste that can be either cast in a mould or extruded to a desirable shape and then it gets hardened under ambient temperature. The sialate membranes are characterized by higher strengths than sintered membranes, however, for some purposes their strength is insufficient, especially in cases requiring wall thickness that should not exceed 3 mm. It is the aim of the present invention, accordingly, to propose a technology enabling low cost production of high strength membranes.
Summary of the invention The mentioned task is solved by a method of making separation membranes characterized in that a base surface is covered by partially molten particles of membrane material carried by gas stream, said particles creating a porous layer on the base surface after having cooled down. The porosity of membranes produced by this method is determined by the type of material used, the particle size, the extent of their melting and their kinetic energy upon impinging. Adjusting these input parameters allows to create membranes for various applications. When producing a membrane that need not be self-supporting, the partially molten material particles of the membrane are introduced onto a carrying porous or perforated base surface and allowed to adhere to the same. Thus so-called asymmetric membrane is obtained that is created by a carrying layer and a separation layer. For the production of a self-supporting membrane that should be separated from the base surface the removal of the membrane is facilitated by changing the temperature of the base and/or the temperature of the membrane so as to induce a . shrinkage of the base with regard to the membrane, or a dilatation of the membrane with regard to the base. Yet another possible procedure for easy separation of the produced membrane from the base surface consists in covering the base surface by a separation layer before introducing the stream of partially molten particles and in removing the separation layer from the base surface by dissolving, etching, evaporating of melting away after the membrane has been formed. Suitable materials for making a membrane by the above method are particles of ceramics, of metals or blends thereof, or of polymers.
Brief description of the drawing The invention is more closely explained by the drawing where the figure illustrates a separation membrane of rather complicated shape created on a planar base surface using a core.
Detailed description of invention embodiments
Example 1
As the base surface a core of stainless steel was used, with 83 mm diameter and 1 m length and about 1 % tapering. After having treated the surface by sanding, ground white alpha corundum with 20 μm grains was evenly distributed onto the core by a plasma burner. The applied burner having up to 200 kW power was able to deposit up to 25 kg of powder material per hour onto the core. After the deposition of the corundum layer the core was chilled, which allowed, along with the taper of the core, to easily pull the membrane from the core. A self-supporting shell of 2 mm wall thickness and 500 mm length was produced. Then it was freed from loose particles by rinsing and fixed in a testing device. The following measurement established 18 % porosity and the ability of the membrane to withstand internal pressure up to 0,6 MPa.
Example 2
This membrane of stainless steel has been created for extreme strain. A cylindrical steel core of 32 mm diameter and 500 mm length turned continuously around its lengthwise axis. The spraying was achieved manually by metallizing gun Sulzer Metco, the material was delivered in form of a wire. The sprayed shell of 3,5 mm thickness and 145 mm length showed a very good strength and allowed being removed by a hydraulic press. By following measurement 21 % porosity was established.
Example 3
A metallic board 6 was used as base, see Fig. 1 , with 180x80x15 mm dimensions. A plasma burner was used to spray ground crystalline sodium chloride with 40 μm grain that created a separation layer 3 of 0,8 mm thickness on the board 6. The separation layer 3 was covered by layer 2 of white alpha corundum, again using a plasma burner for spraying. The metallic core 5 of semi-circular section was covered on its whole perimeter, similarly as in the case of board 6 by a separation layer 4 of sodium chloride. Then the treated core 5 was accommodated by its flat side onto the treated board 6 and
attached to the same. This set was again covered by layer 1 of white alpha corundum by plasma burner spraying. The semi-finished product illustrated in Fig. 1 was thus produced. After having cooled down the semi-product was immersed into a water bath where both salty separation layers 3, 4 dissolved and the rigidly attached corundum layers 1, 2 was thus separated form board 6 and core 5. The cleaned membrane was fixed in a testing device that determined 13 % porosity.
Claims
1. Method for the production of separation membranes characterized in that a base surface is covered with partially molten particles of membrane material carried by gas stream, said particles creating a porous layer on the base surface after having cooled down.
2. Method according to claim 1 , characterized in that the partially molten particles of membrane material are introduced onto a carrying porous or perforated base surface and allowed to adhere to said surface.
3. Method according to claim 1 , characterized in that for separating the membrane from the base surface the temperature of the base and/or the temperature of the membrane is modified so as to induce a shrinkage of the base with regard to the membrane, or the dilatation of the membrane with regard to the base.
4. Method according to claim 1 , characterized in that prior to the introduction of the stream of partially molten particles a separation layer is deposited on the base surface and after the creation of the membrane said membrane is separated from the base surface by dissolution, by etching, evaporation, or melting of the separation layer.
5. Method according to claims 1 to 4, characterized in that particles of ceramics, metal or their blends or of a polymer are deposited onto the base surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CZ2004242A CZ2004242A3 (en) | 2004-02-16 | 2004-02-16 | Method for preparing membranes from inorganic materials or heat-resistant polymers by flame spraying |
| CZPV2004-242 | 2004-02-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005077501A1 true WO2005077501A1 (en) | 2005-08-25 |
Family
ID=34853200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CZ2005/000020 WO2005077501A1 (en) | 2004-02-16 | 2005-02-16 | Method for the production of separation membranes |
Country Status (2)
| Country | Link |
|---|---|
| CZ (1) | CZ2004242A3 (en) |
| WO (1) | WO2005077501A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007026045A1 (en) * | 2005-08-30 | 2007-03-08 | Valtion Teknillinen Tutkimuskeskus | A method for spray forming a metal component and a spray formed metal component |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2745141A (en) * | 1952-11-24 | 1956-05-15 | Joseph B Brennan | Continuous method of making porous strip material |
| EP0203577A2 (en) * | 1985-05-31 | 1986-12-03 | The Dow Chemical Company | Novel fluoropolymer solutions |
| US5071457A (en) * | 1985-11-25 | 1991-12-10 | Industrial Filter & Pump Mfg. Co. | Composite for filtering hot gas and method of its manufacture |
| WO1998020181A1 (en) * | 1996-11-06 | 1998-05-14 | Molten Metal Technology, Inc. | Process for plasma spraying ceramic residues |
| DE10023456A1 (en) * | 1999-07-29 | 2001-02-01 | Creavis Tech & Innovation Gmbh | Mesotubes and nanotubes |
| DE10123635A1 (en) * | 2001-02-14 | 2002-09-05 | Mok Hau | High-performance nano-filtration membrane and filter production, comprises plasma coating closely-sized particles of different substances for subsequent selective removal |
-
2004
- 2004-02-16 CZ CZ2004242A patent/CZ2004242A3/en unknown
-
2005
- 2005-02-16 WO PCT/CZ2005/000020 patent/WO2005077501A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2745141A (en) * | 1952-11-24 | 1956-05-15 | Joseph B Brennan | Continuous method of making porous strip material |
| EP0203577A2 (en) * | 1985-05-31 | 1986-12-03 | The Dow Chemical Company | Novel fluoropolymer solutions |
| US5071457A (en) * | 1985-11-25 | 1991-12-10 | Industrial Filter & Pump Mfg. Co. | Composite for filtering hot gas and method of its manufacture |
| WO1998020181A1 (en) * | 1996-11-06 | 1998-05-14 | Molten Metal Technology, Inc. | Process for plasma spraying ceramic residues |
| DE10023456A1 (en) * | 1999-07-29 | 2001-02-01 | Creavis Tech & Innovation Gmbh | Mesotubes and nanotubes |
| DE10123635A1 (en) * | 2001-02-14 | 2002-09-05 | Mok Hau | High-performance nano-filtration membrane and filter production, comprises plasma coating closely-sized particles of different substances for subsequent selective removal |
Non-Patent Citations (1)
| Title |
|---|
| D'ANGELO C ET AL: "RELIABLE COATINGS VIA PLASMA ARC SPRAYING", ADVANCED MATERIALS & PROCESSES, AMERICA SOCIETY FOR METALS. METALS PARK, OHIO, US, vol. 134, no. 6, 1 December 1988 (1988-12-01), pages 41 - 44, XP000022716, ISSN: 0882-7958 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007026045A1 (en) * | 2005-08-30 | 2007-03-08 | Valtion Teknillinen Tutkimuskeskus | A method for spray forming a metal component and a spray formed metal component |
| US8511366B2 (en) | 2005-08-30 | 2013-08-20 | Valtion Teknillinen Tutkimuskeskus | Method for spray forming a metal component and a spray formed metal component |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ2004242A3 (en) | 2005-10-12 |
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