WO2004065328A1 - Bioaktive keramische kompositmaterialien und verfahren zu deren herstellung - Google Patents
Bioaktive keramische kompositmaterialien und verfahren zu deren herstellung Download PDFInfo
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- WO2004065328A1 WO2004065328A1 PCT/EP2004/000209 EP2004000209W WO2004065328A1 WO 2004065328 A1 WO2004065328 A1 WO 2004065328A1 EP 2004000209 W EP2004000209 W EP 2004000209W WO 2004065328 A1 WO2004065328 A1 WO 2004065328A1
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- composite material
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/005—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing gelatineous or gel forming binders, e.g. gelatineous Al(OH)3, sol-gel binders
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped 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 aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
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- 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
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- 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
-
- 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
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
- C04B2235/5224—Alumina or aluminates
Definitions
- the invention relates to ceramic composite materials, in particular bioactive ceramic composite materials, processes for their production and applications of the composite materials.
- biocomposite materials offer numerous new potential advantageous applications, e.g. B. for the production of biocompatible surfaces in medical technology, for biocatalysis, biogenesis and for novel drug delivery systems.
- sol-gel systems should be the homogeneous embedding of biomolecules in ceramic materials, since these are cheaper, more stable and more malleable than sol-gel matrices, and 'moreover. an established manufacturing technology is available. So far, however, one obstacle has been the need to solidify classic ceramic moldings by means of a sintering process at high temperatures, for example above 600 ° C. Since all organic matter is destroyed at these temperatures, it has so far not been possible to embed biomolecules or living cells in conventional ceramic materials.
- DE 100 65 138 describes the production of porous ceramic molded parts, deviating from the classic process at low temperatures. This process uses a special composition of a ceramic suspension which is subjected to a freeze-drying process which is controlled in a certain way. In the method known from DE 100 65 138, however, embedding of biomaterials could not be considered, since after the drying process to solidify the ceramic molded parts, a damaging effect on biomaterials before additional treatment with acids or alkalis was necessary. The additional treatment is used for leaching, which leads to solidification.
- biomolecules or microorganisms have so far only been added to ceramic materials as auxiliaries (pore-forming substances), which result in a controlled porosity of the ceramic during the sintering process, e.g. for artificial bone materials (GB 2 365 423) or other functional ceramics (US 5 683 664, EP 631 998).
- the object of the invention is to provide improved ceramic composite materials which contain at least one biomaterial, the composite materials being intended to avoid the disadvantages of conventional composite materials.
- the object of the invention is in particular to provide composite materials with an improved degree of immobilization for the at least one biomaterial and an increased viability and / or effectiveness of the biomaterial.
- Composite materials according to the invention are also said to be producible with an expanded range of medium pore sizes and to be usable for new applications.
- Another object of the invention is to provide improved processes for producing such composite materials, which are characterized in particular by a process procedure which is gentle on the biomaterial.
- a 'first basic idea of the invention is to further develop the effect a ceramic composite material that is formed on the basis of a ceramic substrate material that in the • substrate material at least one biological material and at least a solidifying material are embedded homogeneously, wherein the solidifying material connected to each other, from inorganic nanoparticles formed from a nanoparticulate sol.
- a nanoparticulate, gel-forming and cross-linking hardening material is used.
- a homogeneous embedding of the biomaterial in the composite material means a high degree of immobilization and thus a high stability and long-term effectiveness of the composite material.
- the solidification material contained in the composite material enables the use of a procedure for ceramic solidification at low temperatures that is gentle on the biomaterial.
- the bioactive ceramic composite material according to the invention consisting of a ceramic substrate and homogeneously distributed therein, e.g. living cells, can be produced at such low temperatures that there is no denaturation of the cell material during the solidification process.
- the invention ensures such a high viability of the embedded cells that a use of the biocomposite z. B. is possible as a biocatalyst or biofilter for the purification of polluted wastewater.
- the invention is based in particular on a modification of the method known from DE 100 65 138 in such a way that the use according to the invention of the nanoparticulate strengthening material is based on conventional use of acids for leaching, which leads to solidification, can be dispensed with. Surprisingly, it has been shown that the method according to the invention enables the composite to solidify at room temperature or at lower temperatures.
- the ceramic composites according to the invention are preferably produced by solidifying known ceramic slips consisting of aqueous dispersions of aluminum oxide or aluminum silicate powders or fibers.
- aqueous dispersions of aluminum oxide or aluminum silicate powders or fibers.
- fiber material is particularly advantageous since it allows the production of mechanically particularly stable moldings at room temperature.
- aqueous dispersions means that aqueous cell dispersions can also be admixed without problems.
- Nanosoles with an average particle diameter below 200 nm are preferably used for this.
- the solidifying nanosols consist of nanoparticulate oxides of elements from the II. To V. main or subgroup of the periodic table or their mixtures in water or an aqueous-organic solvent.
- nanosoles of Si0 2 , A1 2 0 3 , Zr0 2 , Ti0 2 , B0 3 , ZnO, CaO, P 2 0s or mixtures thereof can be used, which are obtained, for example, by acidic or alkaline hydrolysis of the corresponding metal alkoxides.
- R is an organic alkyl or aryl radical which contains A ino, hydroxy, E May contain poxy or alkoxy groups or is substituted by halogens.
- R ' is an alkyl radical, preferably having 1 to 16 carbon atoms.
- This modification allows, for example, the mechanical and surface properties of the composites to be specifically adapted to the desired application.
- the proportion of the solidification material in the composite can be up to 70 percent by weight, depending on the desired degree of consolidation.
- the inventive method for the production of bioactive ceramic composite materials allows the effective immobilization of a wide range of different biomaterials, especially the use of living organisms such as. B. bacteria, fungi, • algae and protozoa. Multicellular animal and vegetable cell networks can be immobilized accordingly.
- the proportion of living cells can advantageously be up to 30% by weight, based on the dried biocomposite.
- the method is alternatively suitable for the immobilization of dead cells, cell components, enzymes and other proteins, biopolymers and other bioactive molecular substances.
- the addition of special additives can be advantageous to increase the utility value properties of the bioactive ceramic composite materials.
- Glycerol or other polyols and / or nutrients can be added.
- the dispersibility of the slip components can be improved by adding water-soluble polymers such as polyvinyl alcohol or polyacrylic acid, and the mechanical stability of the bioactive ceramic composite materials can be increased by polar interactions of the inorganic oxide matrix.
- the proportion of the additives can advantageously be up to 30% by weight, based on the dry biocomposite.
- Freezecasting is a shaping process in which the mixture of a ceramic powder and the solidifying nanosol is frozen in a freezer or a nitrogen bath, the sol irreversibly getting into the Gel phase converts and thus encloses the ceramic grains and cross-linked.
- the crystallized water is removed either by thawing and evaporation or (in the case of conventional freeze drying) by sublimation.
- the freezecasting process is advantageously characterized by a homogeneous structure and good dimensional stability of the molded body and by a low shrinkage in drying. freezing, which means that little reworking is required.
- the shaping according to (3a) can be carried out at temperatures below freezing point of water that preserve the viability of biomaterials. It can be particularly advantageous if the freezecasting is carried out at temperatures down to -80 ° C and the possible freeze drying at temperatures down to -40 ° C.
- the so-called green body is removed from the metal mold in the frozen state and freeze-dried.
- the green body is dried in air or in vacuo at room temperature.
- Composite materials of this type can therefore be used in the form of a shaped body or a membrane as a biocatalyst or biofilter for the purification of polluted wastewater. Due to their good mechanical stability, shredded molded parts are advantageous as column filling material in bioreactors.
- bioactive ceramic composite materials according to the invention offer new possibilities for production Porous ceramics with a defined uniform pore size by producing ceramic materials with a pore structure by thermal decomposition of the biological components at temperatures of at least 500 ° C, which corresponds to the shape and amount of the immobilized biocomponent (see Example 3).
- spherical yeast spores which leave true-to-shape pores when volatilized during sintering, due to their easy accessibility and their almost monodisperse size distribution. It has been observed that various biological components act like an organic binder and are solid at temperatures of at least 70 ° C form shrink-free green bodies. This allows the proportion of nanoparticulate solidifying agents for the production of bioactive ceramic composite materials to be drastically reduced.
- bioactive ceramic composite materials according to the invention can thus be summarized in the following points: for the first time, living cells can be immobilized in a ceramic molded body which are bioactive ceramic composite materials in a homogeneous distribution and high biological activity while maintaining viability Mouldable as required according to the requirements of the specific application and show a high mechanical stability, the porosity of the composites and thus their biological activity and reactivity can be controlled within wide limits due to the nature of the composition and production technology.
- the process is universally applicable, different microorganisms and cell systems can be converted into a composite by the process according to the invention, numerous applications as a biocatalyst or biofilter are possible, and The thermal removal of the biocomponent offers new possibilities for the production of porous ceramics.
- Bacillus sphaericus cells Bacillus sphaericus cells, corresponding spores (which were obtained from the cells by reduced food supply and addition of manganese salts), and normal baker's yeast cells (Saccharomyces cerevisxae) were used as cell material.
- the slip had the following composition:
- Nyacol 1440 (Akzo Nobel Chemicals Wort) as a nanoparticulate solidification material
- Table 1 Number of live Bacillus sphaericus cells and spores (CFU) after storage at 4 ° C. (determined by cultivation test)
- Table 3 Biological activity of 100 mg biocomposite compared to the corresponding amount of non-immobilized cells (using standard microbiological tests)
- Enzymes formed by the cells reduce resazurin (blue) to ressorufin (pink) 3) biocatalytic conversion of glucose
- Example 2 Immobilization of Saccharomyces cerevisiae hex room temperature and air drying
- the slip had the following composition: 20.5% by weight of Al 2 O 3 fibers
- the Nyacol is neutralized with HC1.
- the dry yeast is suspended in approx. 1/3 of the Nyacol.
- the A10 3 fibers and powder are mixed with the remaining Nyacol and then the Nyacol-yeast mixture is added.
- a pasty mass is formed in which the yeast cells are distributed homogeneously.
- the slip is spread out as a layer with a thickness of approx. 0.5 cm, compressed at a pressure of 1.5 kN and air-dried.
- the pourability can be improved by adding water or, if necessary, increasing the proportion of Nyacol.
- the plates were then sawn into cubes and tested for their biological effectiveness.
- Table 4 Number of living Saccharomyces cerevisiae cells and their biological activity in 100 mg biocomposite compared with the corresponding amount of non-immobilized cells (using standard microbiological tests)
- An aqueous slurry of 40 g of Al 2 0 3 powder, 45g Al0 3 fibers and 5 g of Nyacol 1440 is added as a premix, and dried in a suspension with 10 g of Bacillus spaerlcus.
- the suspension is poured into a mold and dried at 70 ° C. After drying, there is a solid green body that remains true to shape.
- the green body can be sintered up to 1400 ° C, for example, so that a highly porous, non-shrinking ceramic is created.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Zoology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Bioinformatics & Cheminformatics (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- Physics & Mathematics (AREA)
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- Dispersion Chemistry (AREA)
- Thermal Sciences (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/540,936 US20060148633A1 (en) | 2003-01-17 | 2004-01-14 | Bioactive ceramic composite materials and methods for the production thereof |
EP04701933A EP1587771A1 (de) | 2003-01-17 | 2004-01-14 | Bioaktive keramische kompositmaterialien und verfahren zu deren herstellung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10301669A DE10301669A1 (de) | 2003-01-17 | 2003-01-17 | Bioaktive keramische Kompositmaterialien und Verfahren zu deren Herstellung |
DE1031669.4 | 2003-01-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004065328A1 true WO2004065328A1 (de) | 2004-08-05 |
Family
ID=32602665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/000209 WO2004065328A1 (de) | 2003-01-17 | 2004-01-14 | Bioaktive keramische kompositmaterialien und verfahren zu deren herstellung |
Country Status (4)
Country | Link |
---|---|
US (1) | US20060148633A1 (de) |
EP (1) | EP1587771A1 (de) |
DE (1) | DE10301669A1 (de) |
WO (1) | WO2004065328A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2082999A1 (de) * | 2008-01-23 | 2009-07-29 | Technische Universiteit Delft | Mittel zur Selbstheilung von zementartigen Materialien und Strukturen und Verfahren zu seiner Herstellung |
DE102009037768A1 (de) | 2009-08-17 | 2011-02-24 | Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. | Bioaktives Kompositmaterial |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006031212B3 (de) * | 2006-07-03 | 2007-09-20 | Igv Institut Für Getreideverarbeitung Gmbh | In vivo Extraktion von Sekundärmetaboliten aus Mikroalgen |
JP5582944B2 (ja) * | 2009-09-28 | 2014-09-03 | 京セラ株式会社 | 配線基板、積層板及び積層シート |
JP6433490B2 (ja) * | 2013-06-24 | 2018-12-05 | デルシテク オサケ ユキチュア | シリカハイドロゲルコンポジット |
CN103922784B (zh) * | 2014-03-25 | 2015-07-29 | 西安理工大学 | 微生物发酵低温成型制备多孔陶瓷的方法 |
WO2020263116A1 (ru) * | 2019-06-28 | 2020-12-30 | Общество С Ограниченной Ответственностью "Наноком" | Теплозащитный и теплоизоляционный волокнистый керамический материал "наноксилен" и способ его получения |
CN112456835A (zh) * | 2020-12-21 | 2021-03-09 | 吴江永盛混凝土有限公司 | 生态混凝土添加剂及生态混凝土 |
Citations (4)
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GB1267685A (en) * | 1968-08-02 | 1972-03-22 | Unilever Ltd | Preparation of enzymatically active substances |
US4752459A (en) * | 1985-04-09 | 1988-06-21 | Perrer Duncan S | Preparation of porous bodies |
US5824526A (en) * | 1990-01-23 | 1998-10-20 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem, Israel | Doped sol-gel glasses for obtaining chemical interactions |
US6180378B1 (en) * | 1999-01-29 | 2001-01-30 | The United States Of America As Represented By The Secretary Of Agriculture | Immobilization of bioactive protein in phyllosilicates |
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US4148689A (en) * | 1976-05-14 | 1979-04-10 | Sanraku-Ocean Co., Ltd. | Immobilization of microorganisms in a hydrophilic complex gel |
JPS60120987A (ja) * | 1983-12-05 | 1985-06-28 | Kikkoman Corp | 固定化された微生物菌体もしくは酵素の製法 |
CA2077890A1 (en) * | 1991-01-11 | 1992-07-12 | Roger L. Sowerby | Trithianes and phosphorus acid and/or thiophosphorus acid derivatives |
US5200334A (en) * | 1991-08-13 | 1993-04-06 | The Regents Of The University Of California | Sol-gel encapsulated enzyme |
JPH0710640A (ja) * | 1993-06-25 | 1995-01-13 | Teruo Higa | 機能性セラミックスの製造法 |
US5739020A (en) * | 1995-01-10 | 1998-04-14 | Pope; Edward J. A. | Encapsulation of animal and microbial cells in an inorganic gel prepared from an organosilicon |
US5693513A (en) * | 1995-01-10 | 1997-12-02 | Pope; Edward J. A. | Encapsulation of living tissue cells in an organosilicon |
US6696258B1 (en) * | 1998-01-20 | 2004-02-24 | Drexel University | Mesoporous materials and methods of making the same |
US20020115742A1 (en) * | 2001-02-22 | 2002-08-22 | Trieu Hai H. | Bioactive nanocomposites and methods for their use |
-
2003
- 2003-01-17 DE DE10301669A patent/DE10301669A1/de not_active Ceased
-
2004
- 2004-01-14 US US10/540,936 patent/US20060148633A1/en not_active Abandoned
- 2004-01-14 WO PCT/EP2004/000209 patent/WO2004065328A1/de active Search and Examination
- 2004-01-14 EP EP04701933A patent/EP1587771A1/de not_active Ceased
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1267685A (en) * | 1968-08-02 | 1972-03-22 | Unilever Ltd | Preparation of enzymatically active substances |
US4752459A (en) * | 1985-04-09 | 1988-06-21 | Perrer Duncan S | Preparation of porous bodies |
US5824526A (en) * | 1990-01-23 | 1998-10-20 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem, Israel | Doped sol-gel glasses for obtaining chemical interactions |
US6180378B1 (en) * | 1999-01-29 | 2001-01-30 | The United States Of America As Represented By The Secretary Of Agriculture | Immobilization of bioactive protein in phyllosilicates |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2082999A1 (de) * | 2008-01-23 | 2009-07-29 | Technische Universiteit Delft | Mittel zur Selbstheilung von zementartigen Materialien und Strukturen und Verfahren zu seiner Herstellung |
WO2009093898A1 (en) * | 2008-01-23 | 2009-07-30 | Technische Universiteit Delft | Healing agent in cement-based materials and structures, and process for its preparation |
US8460458B2 (en) | 2008-01-23 | 2013-06-11 | Technische Universiteit Delft | Healing agent in cement-based materials and structures, and process for its preparation |
DE102009037768A1 (de) | 2009-08-17 | 2011-02-24 | Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. | Bioaktives Kompositmaterial |
Also Published As
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EP1587771A1 (de) | 2005-10-26 |
US20060148633A1 (en) | 2006-07-06 |
DE10301669A1 (de) | 2004-07-29 |
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