WO2005021462A1 - Verfahren zur herstellung von porösen kohlenstoffbasierten formkörpern und deren verwendung als zellkulturträger- und aufzuchtsysteme - Google Patents
Verfahren zur herstellung von porösen kohlenstoffbasierten formkörpern und deren verwendung als zellkulturträger- und aufzuchtsysteme Download PDFInfo
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- WO2005021462A1 WO2005021462A1 PCT/EP2004/000077 EP2004000077W WO2005021462A1 WO 2005021462 A1 WO2005021462 A1 WO 2005021462A1 EP 2004000077 W EP2004000077 W EP 2004000077W WO 2005021462 A1 WO2005021462 A1 WO 2005021462A1
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- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/94—Products characterised by their shape
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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
- C12N2533/00—Supports or coatings for cell culture, characterised by material
- C12N2533/10—Mineral substrates
Definitions
- the present invention relates to processes for the production of carbon-based molded articles.
- the present invention relates to methods for producing porous, carbon-based shaped articles by carbonizing organic polymer materials which are mixed with non-polymeric fillers, and then removing the fillers from the carbonized shaped article.
- the present invention relates to a method for producing porous, carbon-based shaped bodies by carbonizing organic polymer materials with polymer fillers, which are essentially completely degraded during carbonization.
- the present invention relates to a method for producing porous, carbon-based shaped bodies by carbonizing organic polymer materials, the carbon-based shaped body being partially oxidized after the carbonization to produce pores.
- the present invention relates to porous molded articles produced by one of the processes mentioned and to their use, in particular as cell culture carrier and / or cultivation systems.
- Carbon-based materials are used in mechanical engineering, vehicle construction, as well as in medical technology and process engineering.
- DE 35 28 185 describes a method for producing high-strength, high-density carbon materials from special powdered carbon-containing raw materials without the use of a binder.
- DE 198 23 507 describes processes for the production of carbon-based molded articles by carbonizing biogenic precursors from natural vegetable fibers or wood products.
- DE 100 11 013 and EP 0 543 752 describe processes for producing carbon-containing materials by carbonization or pyrolysis of foamed starting polymers such as
- No. 3,342,555 also describes a process for producing light porous carbon by carbonizing foamed polymers based on phenol aldehyde resins of the resol or novolac type.
- Another object of the present invention is to provide manufacturing processes for porous carbon-based molded articles, which enable the customized manufacture of corresponding molded articles in a variety of shapes and dimensions.
- the present invention provides methods in which porous carbon-based shaped articles are produced from organic polymer materials by carbonizing semi-finished parts, the porosity of the shaped article being produced during or after pyrolysis.
- a method for producing porous carbon-based shaped bodies comprises the following steps: Mixing organic carbon materials carbonizable with carbon with non-polymeric fillers; Producing a semi-finished molded part from the mixture; Carbonizing the semi-finished molded part in a non-oxidizing atmosphere at elevated temperature, a carbon-based molded body being obtained; Removing the fillers from the carbonized molded body with suitable solvents.
- the organic polymer materials which can be carbonized to carbon are mixed or blended with non-polymeric fillers in a first step.
- this can be done by suitable mixing processes known to the person skilled in the art, such as, for example, dry mixing of polymer pellets with filler powders or granules, mixing fillers into the polymer melt or mixing the fillers with polymer solutions or suspensions.
- Suitable non-polymeric fillers are all substances which are essentially stable under carbonization conditions and which can be removed from the carbon-based shaped body with suitable solvents after carbonization. Also suitable are non-polymeric fillers which are converted to solvent-soluble substances under carbonization conditions.
- Preferred fillers are selected from inorganic metal salts, in particular the salts of alkali and / or alkaline earth metals, preferably alkali or alkaline earth metal carbonates, sulfates, sulfites, nitrates, nitrites, phosphates, Phosphites, halides, sulfides, oxides, and mixtures of these.
- suitable fillers are selected from organic metal salts, preferably those of the alkali, alkaline earth and / or transition metals, in particular their formates, acetates, propionates, aleates, malates, oxalates, tartrates, citrates, benzoates, salicylates, phthalates, stearates, phenolates, Sulfonates, amine salts and mixtures thereof.
- organic metal salts preferably those of the alkali, alkaline earth and / or transition metals, in particular their formates, acetates, propionates, aleates, malates, oxalates, tartrates, citrates, benzoates, salicylates, phthalates, stearates, phenolates, Sulfonates, amine salts and mixtures thereof.
- Suitable solvents for removing the fillers from the carbonized shaped body are, for example, water, in particular hot water, dilute or concentrated inorganic or organic acids, alkalis and the like.
- Suitable inorganic acids in diluted or concentrated form are hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and dilute hydrofluoric acid.
- Suitable lyes are e.g. Sodium hydroxide solution, ammonia solution, carbonate solutions, but also organic amine solutions.
- Suitable organic acids are formic acid, acetic acid, trichloromethanoic acid, trifluoromethanoic acid, citric acid, tartaric acid, oxalic acid and mixtures thereof.
- the fillers can essentially or completely be removed from the carbonized shaped body, depending on the type and duration of use of the solvent. The essentially complete dissolution of the fillers is preferred.
- the fillers can be used in suitable grain sizes.
- Powders or granular fillers with average particle sizes of 3 are particularly preferred Angstroms to 2 mm, particularly preferably 1 nm to 500 ⁇ m and particularly preferably 10 nm to 100 ⁇ m.
- Suitable solvents for removing the fillers are organic solvents, such as methanol, ethanol, N-propanol, isopropanol, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene glycol, dimethoxydiglycol, Dimethyl ether, dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethylhexanediol, glycol, hexanediol, 1, 2,6-hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxydiglycol, methoxyethanol, methoxybutylene glycol, methyloxymethyl propanol, methyloxymethanol, methyl
- a method for producing porous carbon-based molded articles comprising the following steps: mixing organic polymer materials which can be carbonized with carbon and polymeric fillers; - Production of a semi-finished molded part from the mixture; - Carbonization of the semi-finished molded part in a non-oxidizing atmosphere at elevated temperature, the polymer fillers being essentially completely broken down.
- the pores in the carbon-based molded body are generated during the carbonization by incorporating polymeric fillers into the organic polymer materials to be carbonized, which are essentially completely degraded under carbonization conditions.
- Temperatures and exclusion of oxygen by means of crack-analogous processes, can be substantially completely broken down into volatile hydrocarbons such as methane, ethane and the like, which then escape from the porous carbon structure of the carbonized shaped body during the pyrolysis or carbonization.
- Suitable polymeric fillers can be selected from saturated, branched or unbranched aliphatic hydrocarbons, which homo- or can be copolymers.
- Polyolefins such as polyethylene, polypropylene, polybutene, polyisobutene, polypentene and their copolymers and mixtures are preferred.
- the polymeric fillers are mixed with the carbonizable organic polymer materials.
- This can be done according to the prior art methods known in principle to the person skilled in the art, for example mixing polymer pellets or granules, mixing polymeric fillers in melts from carbonizable organic polymer materials or suspensions or solutions of these polymer materials, coextrusion of the polymeric fillers with the carbonizable organic polymer materials and the like ,
- the carbonized can be any suitable selection of the molecular weight, the chain length and / or the degree of branching of the polymeric fillers.
- Shaped pores produced are appropriately dimensioned or varied within wide limits.
- the polymeric fillers can also be used in the form of thin fibers, which form suitably dimensioned pore channels during carbonization.
- the porosity can be adjusted by the choice of the fiber diameter and the fiber length, whereby larger fiber diameters and lengths require a larger porosity.
- the desired intermediate effects can also be achieved by suitable mixing of the fibers used, or asymmetrical porosity distributions and textures of the shaped bodies.
- This embodiment of the method according to the invention using polymer fillers as pore former is particularly suitable for porous molded articles with small pore sizes in the nano to micrometer range, in particular with pore sizes of 3 angstroms to 2 mm, particularly preferably 1 nm to 500 ⁇ m and particularly preferably 10 nm to 100 ⁇ m.
- the carbonized shaped body is after the carbonization with suitable oxidation and / or
- a method for producing porous carbon-based shaped bodies which comprises the following steps:
- a shaped body is formed by carbonization of suitable polymer materials, and after carbonization by means of suitable oxidizing agents in the carbonized
- Shaped body porosity is generated and / or increased by "burning" pores in the carbon-based shaped body by partial oxidation of the carbon. Essentially all oxidation processes and oxidizing agents suitable for the oxidation of carbon materials are suitable for producing pores in the carbon-based shaped body.
- the treatment of the carbonized shaped body is preferred in the case of elevated
- Suitable oxidizing agents for the partial oxidation in the oxidizing gas phase are air, oxygen, carbon monoxide, carbon dioxide, nitrogen oxides and similar oxidizing agents. These gaseous oxidizing agents can be mixed with inert gases such as noble gases, in particular argon, or also nitrogen, and suitable volume concentrations of the oxidizing agent can be set exactly. By reaction with these oxidizing agents, holes or pores are burned into the porous molded body by way of partial oxidation.
- the partial oxidation is preferably carried out at elevated temperatures, in particular in the range from 50 ° C. to 800 ° C.
- the partial oxidation is carried out by treating the molded body with air which may flow, at room temperature or above.
- liquid oxidizing agents can also be used, such as concentrated nitric acid, which is applied to the shaped body in a suitable manner.
- concentrated nitric acid it may be preferred to add the concentrated nitric acid
- the above-mentioned methods of creating pores can also be combined with one another according to the invention.
- the coarser pores produced from the fillers can be linked to the micro- or nanopores of the polymeric fillers to form anisiotropic pore distributions.
- the existing pores can also be expanded, linked or modified by partial oxidation.
- ORGANIC POLYMER MATERIAL In all three of the above-mentioned embodiments of the method according to the invention, such materials are used as the organic polymer material which can be carbonized to carbon and which, under carbonization conditions, i. H. at elevated temperature and in a substantially oxygen-free atmosphere, carbon materials made of amorphous, partially crystalline and / or crystalline symmetrical or asymmetrical material remain.
- unsaturated, branched aliphatic hydrocarbons in particular, branched or unbranched, crosslinked or uncrosslinked aromatic or partially aromatic hydrocarbons, and substituted derivatives thereof are suitable.
- Unsaturated hydrocarbons, especially aromatic hydrocarbons are usually built under carbonization conditions to form graphite-like cross-linked six-ring structures, which form the basic structure of the carbonized molded body.
- Saturated aliphatic and / or aromatic hydrocarbons with heteroatom components are also suitable as carbonizable organic polymer materials or in mixtures with other aliphatic or aromatic unsaturated hydrocarbons in the processes according to the invention.
- carbonizable organic polymer materials are preferably selected from: polybutadiene; Polyvinyls such as polyvinyl chloride or polyvinyl alcohol, poly (meth) acrylic acid, polyacrylic cyanoacrylate; Polyacrylonitrile, polyamide, polyester, polyurethane, polystyrene, polytetrafluoroethylene; Polymers such as collagen, albumin, gelatin, hyaluronic acid, starch, celluloses such as methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose phthalate; Casein, Dextrans, Polysaccharides, Fibrinogen, Poly (D, L-Lactide), Poly (D, L-Lactide-Co-Glycolide), Polyglycolide, Polyhydroxybutylate, Polyalkylcarbonate, Polyorthoester, Polyester, Polyhydroxyvalerinchure, Polydioxanone, Polyethyleneterephthalate, Polymala
- the carbonizable organic polymer materials can furthermore contain customary additives such as further in particular insoluble fillers, plasticizers, lubricants, flame retardants, glass, glass fibers, carbon fibers, cotton, fabrics, metal powders, metal compounds, silicon, silicon oxides, zeolites, titanium oxides, zirconium oxides, aluminum oxides, aluminosilicates, talc, Graphite, soot,
- customary additives such as further in particular insoluble fillers, plasticizers, lubricants, flame retardants, glass, glass fibers, carbon fibers, cotton, fabrics, metal powders, metal compounds, silicon, silicon oxides, zeolites, titanium oxides, zirconium oxides, aluminum oxides, aluminosilicates, talc, Graphite, soot,
- Contain clay materials, phyllosilicates and the like Contain clay materials, phyllosilicates and the like.
- fibrous materials made of cellulose, cotton, textile fabrics, glass fibers, carbon fibers and the like as polymer additives are suitable in preferred embodiments of the present invention for improving the mechanical properties of the porous moldings produced.
- the semi-finished molded parts can be produced according to the methods of the present invention by means of conventional shaping methods for polymer materials known to the person skilled in the art.
- Suitable shaping processes are casting processes, extrusion processes, pressing processes, injection molding processes, coextrusion blow molding or other customary shaping processes, for example also winding processes or strand winding processes using flat starting materials.
- Carbonization takes place in an essentially oxygen-free or oxidizer-free atmosphere.
- suitable Carbonization atmospheres are, for example, protective gas, preferably nitrogen and / or argon, noble gases, SiF 6 and mixtures of these protective gases. If necessary, these protective gas atmospheres can be used for negative or positive pressure. Carbonation in a vacuum can also be used advantageously in the processes according to the invention.
- reactive gases may be added to the inert gas atmosphere.
- Preferred reactive gases for this are non-oxidizing gases such as hydrogen, ammonia, dC 6 saturated aliphatic hydrocarbons such as methane, ethane, propane and butane, mixtures of these, and the like.
- Suitable temperatures for the carbonation step are in the range of 200 ° C to 4000 ° C or more.
- carbon-containing molded articles can be produced, the base material of which ranges in structure from amorphous to ordered crystalline graphite-like structures or mixtures of both materials.
- the atmosphere in the carbonization step of the process according to the invention is essentially free of oxygen, preferably with O 2 kept below 10 ppm, particularly preferably below 1 ppm.
- O 2 oxygen
- the carbonization step will preferably take place in a batch process in suitable furnaces, but can also take place in a continuous process
- the semi-finished parts are fed to the furnace on one side and exit again at the other end of the furnace.
- the semi-finished molded part can rest in the oven on a perforated plate, a sieve or the like, so that negative pressure can be applied through the polymer film during the pyrolysis or carbonization.
- this enables simple fixation of the implants in the furnace, and on the other hand, suction and optimal flow of inert gas through the semi-finished parts during carbonization.
- the furnace can be divided into individual segments by appropriate inert gas locks, in which one or more carbonization steps can be carried out in succession, optionally under different carbonization conditions such as different temperature levels, different inert gases or vacuum.
- Post-treatment, activation or intermediate treatment steps, such as partial oxidation, reduction or also impregnation with metal salt solutions and the like, can also optionally be carried out in corresponding segments of the furnace.
- the carbonization can be carried out in a closed furnace, which is particularly preferred if the carbonization is to be carried out in a vacuum.
- a decrease in weight of the material of approximately 5% to 95%, preferably approximately 40% to 90%, in particular 50% to 70%.
- the physical and chemical properties of the carbon-based shaped bodies or of the pores generated after the carbonization are further modified by suitable post-treatment steps and adapted to the particular intended use.
- Suitable aftertreatments are, for example, reducing or oxidative aftertreatment steps in which the porous moldings are treated with suitable reducing agents and / or oxidizing agents such as hydrogen, carbon dioxide, nitrogen oxides such as N 2 O, water vapor, oxygen, air, nitric acid and the like, and, if appropriate, mixtures of these.
- suitable reducing agents and / or oxidizing agents such as hydrogen, carbon dioxide, nitrogen oxides such as N 2 O, water vapor, oxygen, air, nitric acid and the like, and, if appropriate, mixtures of these.
- the surfaces can be coated, which can be carried out on one side or on both sides.
- Suitable coating materials can be, for example, the above-mentioned organic polymer materials, which, if appropriate, are subjected to a further carbonization or pyrolysis step in order to achieve asymmetrical textures in the shaped body.
- Coating with inorganic substances, biocompatible polymers and substances is also possible according to the invention in order to give the surfaces of the moldings the desired properties.
- the post-treatment steps may take place at elevated temperature, but below the carbonization temperature, for example from 15 ° C. to 1000 ° C., preferably 70 ° C. to 900 ° C., particularly preferably 100 ° C. to 850 ° C., particularly preferably 200 ° C.
- the porous molded articles produced according to the invention are modified reductively or oxidatively, or with a combination of these post-treatment steps at room temperature.
- the surface properties of the carbon-containing material can be made hydrophilic or hydrophobic.
- porous shaped bodies can be coated by subsequent coating, e.g. with polymer solutions, closed on one or both sides.
- This coating can optionally be carbonized again, for example to increase stability.
- the porous moldings produced according to the invention can also be subsequently equipped with biocompatible outer and / or inner surfaces by incorporating suitable additives.
- Shaped bodies modified in this way can be used, for example, as bioreactors, cell culture carrier or rearing systems, implants or as drug carriers or depots, in particular also systems which can be implanted in the body.
- drugs or enzymes for example, can be introduced into the material. can be released in a controlled manner by suitable retardation and / or selective permeation properties of applied coatings.
- the porous molded body can optionally also be subjected to a further optional process step, a so-called CVD process (Chemical Vapor Deposition, chemical vapor deposition) or CVI process (Chemical Vapor Infiltration) in order to further modify the surface or pore structure and its properties. if necessary, to superficially or completely close the pores
- the carbonized coating is treated with suitable, carbon-releasing precursor gases at high temperatures.
- Other elements can also be deposited with it, for example silicon, aluminum or titanium, in particular for producing the corresponding carbides. Such methods are known in the prior art. Appropriate pre-structuring of the shaped bodies, for example using fiber materials of different lengths and / or thicknesses, can thus
- Gradient materials are obtained which have a concentration of certain intercalation or reaction compounds, for example the metal or non-metal carbides, nitrides or borides, which is distributed asymmetrically over the volume of the shaped body. Gradient materials can thus be obtained which are symmetrical or asymmetrical, isotropic or anisotropic, have closed pores, are porous or have fiber-like guide structures or any combination thereof.
- saturated and unsaturated hydrocarbons with sufficient volatility under CVD conditions are suitable as carbon-releasing precursors.
- Examples include methane, ethane, ethylene, acetylene, linear and branched alkanes, alkenes and alkynes with carbon numbers of Ci - C 20 , aromatic hydrocarbons such as benzene, naphthalene etc., and one and multi-alkyl, alkenyl and alkynyl-substituted aromatics such as toluene, xylene, cresol, styrene etc.
- the ceramic precursor can BC1 3, NH 3, silanes such as SiH, tetraethoxysilane (TEOS), dichlorodimethylsilane (DDS), methyltrichlorosilane (MTS), Trichlorosilyl- dichloroboran (TDADB) Hexadichloromethylsilyloxid (HDMSO), A1C1 3, TiCl 3 or mixtures thereof be used.
- TEOS tetraethoxysilane
- DDS dichlorodimethylsilane
- MTS methyltrichlorosilane
- TDADB Trichlorosilyl- dichloroboran
- HDMSO Hexadichloromethylsilyloxid
- A1C1 3 TiCl 3 or mixtures thereof be used.
- pores in the carbon-containing porous shaped body can be deliberately reduced to the point where the pores are completely closed / sealed.
- sorptive properties, as well as the mechanical properties of the shaped bodies can be tailored.
- the carbon-containing porous shaped bodies can be modified, for example by oxidation, by carbide or oxycarbide formation. If the carbides are not already formed under CVD conditions, elevated temperatures may be necessary to promote carbide formation.
- the porous moldings according to the invention can additionally be coated or modified by means of sputtering processes.
- carbon, silicon or metals or metal compounds from suitable sputtering targets can be applied by methods known per se. Examples of these are Ti, Zr, Ta, W, Mo, Cr, Cu, which can be dusted into the porous shaped bodies, the corresponding carbides generally forming.
- the surface properties of the porous molded body can also be modified by means of ion implantation.
- nitride, carbonitride or oxynitride phases with embedded transition metals can be formed by implantation of nitrogen, which means the chemical resistance and mechanical
- the coating with e.g. Liquid-crystalline tar pitches can lead to asymmetrical material properties, depending on the orientation of the lattice structures during the subsequent crosslinking, carbonization or graphitization. These include the thermal expansion, the mechanical properties, the electrical conductivity, etc.
- biodegradable or resorbable polymers such as collagen, albumin, gelatin, hyaluronic acid, starch, celluloses such as methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose phthalate; Casein, dextrans, polysaccharides, fibrinogen, Poly (D, L-lactide), poly (D, L-lactide-co-glycolide), poly (glycolide), poly (hydroxybutylate), poly (alkylcarbonate), poly (orthoester), polyester, poly (hydroxyvaleric acid), polydioxanone , Poly (ethylene terephthalate), poly (malate acid), poly (tartronic acid), polyanhydrides, polyphosphazenes, poly (amino acids), and their copolymers or non-biodegradable or resorbable polymers at least partially to coat.
- biodegradable or resorbable polymers such as collagen, albumin, gelatin,
- the porous molded body can be subjected to further chemical or physical surface modifications after the carbonization and / or after any post-treatment steps that may have taken place. Cleaning steps to remove any residues and contaminants can also be provided here.
- the acids already mentioned above, in particular oxidizing acids, or solvents can be used, boiling out in acids or solvents is preferred.
- the moldings according to the invention can be adjusted in a wide range in a targeted manner by suitable choice of the starting materials and additives in their pH value and the buffer capacity in an aqueous environment.
- the pH value of shaped articles produced according to the invention in water can be in the range from pH 0 to pH 14, preferably in the range from pH 6-8 and particularly preferably at pH values from 6.5 to 7.5.
- the buffer area of molded articles produced according to the invention is preferably in the neutral to acidic range, particularly preferably in the weakly acidic range, and the buffering capacity can be up to 50 mol / liter, preferably up to 10 Mol / liter and in preferred applications is usually 0.5 to 5 mol / liter.
- the moldings which can be produced by the processes according to the invention can be produced in any two- or three-dimensional shape.
- the semi-finished molded parts made of the organic polymer materials, optionally in a mixture with polymeric or non-polymeric fillers are processed into suitable raw forms by means of suitable shaping processes, which, taking into account the dimensional shrinkage occurring during carbonization, may correspond to the final forms of the porous carbon-based shaped bodies.
- the porous moldings according to the invention can be produced in the form of tubes, round rods, plates, blocks, cuboids, cubes, solid or hollow spheres, flanges, seals, housings and the like, or else be elongated, such as circular columns, polygonal columns such as triangular columns or bars ; or plate-shaped; or also polygonal, such as tetrahedral, pyramidal, octahedral, dodecahedral, icosahedral, rhomboid, prismatic; or be spherical, such as spherical, spherical or cylindrical lenticular, or annular, honeycomb-shaped, with straight or curved channels, coiled, folded with different channel diameters and flow directions (parallel, crosswise or with any angle between the channels).
- a tube made of porous carbon-based material is produced using one of the production methods according to the invention.
- the carbonization of a hose made of natural or synthetic rubber or suitable plastics is preferred as mentioned above as carbon-containing moldings which can be carbonized to carbon and which is optionally reinforced with fiber or fabric inserts.
- Particularly preferred is the use of a textile fabric impregnated with synthetic resins in the form of a tube, which is used as a semi-finished molded part for producing a tube from porous plastic-based material according to one of the methods of the present invention.
- the hose used to produce a porous tube can be constructed in several layers, for example comprising an inner layer made of foamed plastic and an outer layer made of non-foamed plastic or vice versa.
- the application of further layers is also possible according to the invention.
- the multi-layer hose is produced by co-extrusion blow molding as a semi-finished molded part and then carbonized into a tube.
- a tube made of carbon-based material can be produced by winding a paper material impregnated or coated with polymer materials, for example on a lathe, into a tube, which is then carbonized under carbonization conditions to form a porous carbon-containing tube.
- a flat fiber fabric, channel structures or felt structures and all combinations thereof are preferably impregnated and / or coated with organic polymer materials and wound up over a suitable dome. Then carbonization is carried out with or without the dome and the dome is then removed if necessary. This makes it easy and precise Produce porous tubes that can then be treated, recompressed or sealed.
- Porous tubes produced in this way can be completely or partially sealed with organic polymers.
- fiber-reinforced hoses is also particularly preferred here, the fibers being able to be selected from textile or fabric fibers, glass fibers, carbon fibers, rock wool, polymer fibers, for example from polyacrylonitrile, nonwoven materials, nonwoven fabrics, felts, cellulose, PET fibers and any mixtures thereof Materials.
- foamed polymer materials such as polyurethane foam, polyacrylonitrile foam and the like can be molded with a further layer of dense polymer material, which are then carbonized to give moldings with regionally different porosity distributions.
- flanges can also be laminated on in the semifinished molded part, which are then essentially carbonized through with closed pores.
- full carbon module units are created with an excellent adhesive bond between fiber and matrix.
- the carbon-based moldings produced by a process according to the invention in particular carbon tubes, can be used as a tube membrane, in tube membrane reactors, in tube bundle reactors and heat exchangers and also in bioreactors.
- the moldings according to the invention can also be used as porous catalyst supports, in particular in the automotive sector or for flue gas cleaning in technical systems. Their heat resistance, chemical resistance and dimensional stability are advantageous here. Furthermore, the moldings and materials according to the invention are almost stress-free and extremely resistant to thermal shock, i.e. Even strong jumps in temperature are easily tolerated. By applying metals, in particular noble metals, and other catalytically active materials, long-term stable and highly effective catalyst supports can be produced by the processes according to the invention.
- Sheets made from flat channel structures, as well as pipe structures wound from them, are excellently suitable as insulating materials, e.g. for high temperature applications or for shielding microwaves (microwave absorbers).
- the electrical properties can be set so that e.g. High-frequency heating systems can couple their energy into the furnace area almost loss-free through these insulating materials.
- Highly oriented materials can also be set so that they are directly excited by high frequency and thus directly heated. This is also a simple process for technical production (carbonization) or for graphitization.
- Shaped bodies produced by the method according to the invention can also be used as medical implants, for example orthopedic, surgical, and / or non-orthopedic implants such as bone or joint prostheses, orthopedic plates, screws, nails, fixations and the like can be used.
- orthopedic, surgical, and / or non-orthopedic implants such as bone or joint prostheses, orthopedic plates, screws, nails, fixations and the like can be used.
- the use of the shaped bodies which can be produced according to the invention is a substrate or carrier for colonization with microorganisms and cell cultures is particularly preferred.
- TAS growth systems
- porous or non-porous, carbon-containing materials are suitable for use as carrier and rearing systems (TAS) for the cultivation of primary cell cultures.
- TAS carrier and rearing systems
- symmetrical or asymmetrical, textured carbon or ceramic-based materials and their combinations are suitable for use as TAS.
- the materials and moldings mentioned can also be used specifically as support and rearing systems for nerve tissue. It is particularly advantageous that carbon-containing materials are particularly adaptable and suitable here, in particular by simply adjusting the conductivity of the shaped bodies and applying pulse currents for the cultivation of nerve tissue.
- the materials and moldings mentioned also serve as in vitro or in vivo lead structures, so-called scaffolds, for 2- and 3-dimensional tissue growth; their specific shape makes it possible to grow parts of organs or whole organs from cell cultures.
- the TAS support or modulate the lead, tissue or organ growth from a physical point of view, in particular through adjustable provision, as a guiding structure through suitable adjustment of the porosity, through the flow channel design and the two- or three-dimensional shape. Distribution and replenishment of nutrient solution or medium at the place of consumption, as well as by supporting or promoting cell and tissue proliferation and differentiation.
- the materials and moldings or carrier systems can be 2-dimensional and 3-dimensional.
- Suitable macrostructures are, for example, tubes, in particular for the production or cultivation of natural vessels, cubic shapes, etc., as mentioned above for shaped bodies.
- the shaped bodies according to the invention and other carbon-based materials for use as TAS can be modeled natural organ forms, for example cartilaginous articular surfaces of knee, Hip, shoulder, finger joints, etc., which can then be used for growing appropriately shaped cartilage, bone skins and the like. These can then either be implanted with the grown tissue, or the cultured tissue is separated in an appropriately grown form by methods of the prior art, such as mechanical or chemical-enzymatic detachment, and then implanted.
- the moldings and materials can be used as TAS for cultivation in existing bioreactor systems, e.g. B. passive systems without continuous control technology such as Fabric plates, fabric bottles, roller bottles; but also active systems with gas supply and automatic setting of parameters (acidity, temperature), in the broadest sense reactor systems with measurement and control technology.
- existing bioreactor systems e.g. B. passive systems without continuous control technology such as Fabric plates, fabric bottles, roller bottles; but also active systems with gas supply and automatic setting of parameters (acidity, temperature), in the broadest sense reactor systems with measurement and control technology.
- the TAS according to the invention can be provided by providing suitable devices such as connections for perfusion with nutrient solutions and the Gas exchange as a reactor system are in particular also carried out modularly in corresponding row reactor systems and tissue cultures.
- TAS according to the invention can also be used as ex vivo reactor systems, e.g. extracorporeal assistance systems, or used as organ reactors, e.g. so-called liver assist systems or liver replacement systems; or also in vivo or in vitro for encapsulated islet cells, e.g. B. as an artificial Pancreas, encapsulated urothelial cells, e.g. as an artificial Kidney and the like, which are preferably implantable.
- ex vivo reactor systems e.g. extracorporeal assistance systems, or used as organ reactors, e.g. so-called liver assist systems or liver replacement systems
- organ reactors e.g. so-called liver assist systems or liver replacement systems
- encapsulated islet cells e.g. B. as an artificial Pancreas
- encapsulated urothelial cells e.g. as an artificial Kidney and the like, which are preferably implantable.
- the TAS according to the invention can be suitably modified to promote organogenesis, for example with proteoglycans, collagens, tissue-typical salts, e.g. Hydroxyapatite etc., especially with the above-mentioned biodegradable or resorbable polymers.
- the TAS according to the invention are preferably further modified by impregnation and / or adsorption of growth factors, cytokines, interferons and / or adhesion factors.
- suitable growth factors are PDGF, EGF, TGF- ⁇ , FGF, NGF, erythropoietin, TGF-ß, IGF-I and IGF-II.
- Suitable cytokines include, for example, IL-1- ⁇ and -ß, IL-2, IL-3, IL-4, IL-5, IL-6, IL-7, IL-8, IL-9, IL-10, IL -11, IL-12, IL-13.
- Suitable interferons include e.g. INF- ⁇ and -ß, INF- ⁇ .
- suitable adhesion factors are fibronectin, laminin, vitronectin, fetuin, poly-D-lysine and the like.
- the moldings according to the invention can also be used as microarray systems for, for example, drag discovery, tissue screening, tissue engineering etc.
- a glass fiber fabric made of E-CR glass (chemical-resistant modified E-glass) of 30mm width was coated / impregnated with GRP resin based on phenolic resin in a cloister on one appropriate steel mandrel laid and the cathedral removed.
- the weight was 3.6 g / cm before pyrolysis.
- the pyrolysis was carried out under nitrogen at 800 ° C. for 48 hours.
- the weight after pyrolysis was 3.0 g / cm.
- the membrane properties were measured using the bubble point test (ASTM El 294), a pore size of 500 angstroms being determined.
- Example 4 Pipe production in the winding process as given in Example 1, using a glass fiber fleece made of E-CR glass (chemical-resistant modified E-glass) of 30 mm in width, and polyacrylonitrile (PAN) nonwoven (from Freudenberg) of 30 mm in width (ratio 1: 1) and GRP resin based on phenolic resin, laid on a steel dome in a cloister. Weight 3.6g / cm before pyrolysis. Pyrolysis under nitrogen at 800 ° C for 48 hours. Weight after pyrolysis 2.0 g / cm.
- E-CR glass chemical-resistant modified E-glass
- PAN polyacrylonitrile
- Carbon-based plates made of natural fiber-reinforced, composite polymer with inorganic fillers and with a basis weight of 100 g / m 2 and 110 micrometers thickness were produced.
- This flat composite material was provided with a channel structure by a commercially available embossing machine
- a tube of 10 cm length and 40 mm diameter with a wall thickness of 6 mm wound from this material was set in a coupling test in an 8 KHz high-frequency heating device.
- the quiescent current practically did not change compared to the quiescent current and there was no significant heating of the material even after 5 minutes.
- the material produced in this way can be sawed, drilled, milled, etc. easily and precisely.
- a natural fiber-containing polymer composite with a basis weight of 100 g / m 2 and 110 ⁇ m thickness was carbonized in a nitrogen atmosphere at 800 ° C. for 48 hours, air being added towards the end in order to modify the pores. A weight loss of 50% by weight occurred.
- the resulting material has a pH of 7.4 in water and a buffer area in the weakly acidic state. Pieces of 20x40 mm, each about 60 ⁇ m thick, of this carbon material were loaded with 4 ml of nutrient solution and 1.5 ml of cell suspension in each case on conventional six-piece tissue plates.
- the cell suspension contained Hybridoma FLT 2 MAB against Shigatoxin producing cell lines, known for non-adherent, non-adhesive suspension growth.
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Abstract
Description
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Priority Applications (36)
Application Number | Priority Date | Filing Date | Title |
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DE202004006867U DE202004006867U1 (de) | 2003-07-31 | 2004-01-08 | Kohlenstoffbasierte Formkörper geeignet zur Verwendung als Zellkulturträger- und Aufzuchtsysteme |
AU2004268732A AU2004268732A1 (en) | 2003-07-31 | 2004-01-08 | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
CA002532737A CA2532737A1 (en) | 2003-07-31 | 2004-01-08 | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
MXPA06001238A MXPA06001238A (es) | 2003-07-31 | 2004-01-08 | Metodo para la produccion de cuerpos moldeados porosos basados en carbono y uso de los mismos como sistemas de soporte de cultivos celulares y sistemas de cultivo. |
JP2006521397A JP2007500663A (ja) | 2003-07-31 | 2004-01-08 | 多孔質炭素系成形体を製造するための方法、ならびに細胞培養担体システムおよび培養システムとしてのその使用 |
CN2004800215629A CN1829667B (zh) | 2003-07-31 | 2004-01-08 | 生产多孔碳基模制体的方法及其作为细胞培养载体系统和培养系统的用途 |
BRPI0413080-4A BRPI0413080A (pt) | 2003-07-31 | 2004-01-08 | processo para a preparação de artigos moldados porosos à base de carbono e uso como sistemas de suporte de cultura de células |
EP04700670A EP1658248A1 (de) | 2003-07-31 | 2004-01-08 | Verfahren zur herstellung von porösen kohlenstoffbasierten formkörpern und deren verwendung als zellkulturträger- und aufzuchtsysteme |
EA200600286A EA011114B1 (ru) | 2003-07-31 | 2004-01-08 | Способ изготовления пористых формованных тел на основе углерода и их применение |
AU2004261745A AU2004261745B2 (en) | 2003-07-31 | 2004-08-02 | Cell cultivation and breeding method |
AU2004260618A AU2004260618B2 (en) | 2003-07-31 | 2004-08-02 | Support for immobilising catalytically active units |
EP04741349A EP1648591A1 (de) | 2003-07-31 | 2004-08-02 | Trägerkörper mit immobilisierten katalytisch aktiven einheiten |
SG200805683-0A SG145702A1 (en) | 2003-07-31 | 2004-08-02 | Support for immobilising catalytically active units |
BRPI0412574-6A BRPI0412574A (pt) | 2003-07-31 | 2004-08-02 | processo para cultivo e cultura de células |
SG200805684-8A SG145703A1 (en) | 2003-07-31 | 2004-08-02 | Cell cultivation and breeding method |
KR1020067001868A KR20060054361A (ko) | 2003-07-31 | 2004-08-02 | 촉매 활성 유니트를 고정하기 위한 지지체 |
MXPA06001240A MXPA06001240A (es) | 2003-07-31 | 2004-08-02 | Cuerpo de soporte con unidades cataliticamente activas inmovilizadas. |
CA002531093A CA2531093A1 (en) | 2003-07-31 | 2004-08-02 | Support for immobilising catalytically active units |
MXPA06001239A MXPA06001239A (es) | 2003-07-31 | 2004-08-02 | Cultivo de celulas y metodo de reproduccion. |
KR1020067001869A KR20060054362A (ko) | 2003-07-31 | 2004-08-02 | 세포 배양 및 육종 방법 |
JP2006521553A JP2007500505A (ja) | 2003-07-31 | 2004-08-02 | 細胞の培養及び増殖方法 |
PCT/EP2004/008641 WO2005011844A1 (de) | 2003-07-31 | 2004-08-02 | Trägerkörper mit immobilisierten katalytisch aktiven einheiten |
NZ544944A NZ544944A (en) | 2003-07-31 | 2004-08-02 | Support for immobilising catalytically active units |
CA002532970A CA2532970A1 (en) | 2003-07-31 | 2004-08-02 | Cell cultivation and breeding method |
EA200600345A EA009716B1 (ru) | 2003-07-31 | 2004-08-02 | Способ культивирования клеток |
JP2006521552A JP2007500589A (ja) | 2003-07-31 | 2004-08-02 | 触媒活性単位を固定化するための支持体 |
NZ544945A NZ544945A (en) | 2003-07-31 | 2004-08-02 | Cell cultivation and breeding method |
BRPI0413133-9A BRPI0413133A (pt) | 2003-07-31 | 2004-08-02 | suportes com unidades cataliticamente ativas imobilizadas |
PCT/EP2004/008642 WO2005012504A1 (de) | 2003-07-31 | 2004-08-02 | Zellkultivierungs- und aufzuchtverfahren |
EA200600232A EA009017B1 (ru) | 2003-07-31 | 2004-08-02 | Носитель с иммобилизованными каталитически активными единицами |
EP04763711A EP1673443A1 (de) | 2003-07-31 | 2004-08-02 | Zellkultivierungs- und aufzuchtverfahren |
IL172851A IL172851A0 (en) | 2003-07-31 | 2005-12-27 | Support for immobilising catalytically active units |
IL173164A IL173164A0 (en) | 2003-07-31 | 2006-01-16 | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
IL173165A IL173165A0 (en) | 2003-07-31 | 2006-01-16 | Cell cultivation and breeding method |
US11/343,480 US20060159718A1 (en) | 2003-07-31 | 2006-01-30 | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
US11/343,307 US20060172417A1 (en) | 2003-07-31 | 2006-01-31 | Cell cultivation and breeding method |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10335131A DE10335131A1 (de) | 2003-07-31 | 2003-07-31 | Verfahren und Herstellung von porösen kohlenstoffbasierten Formkörpern |
DE10335131.0 | 2003-07-31 |
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US11/343,480 Continuation-In-Part US20060159718A1 (en) | 2003-07-31 | 2006-01-30 | Method for the production of porous carbon-based molded bodies, and use thereof as cell culture carrier systems and culture systems |
US11/343,307 Continuation-In-Part US20060172417A1 (en) | 2003-07-31 | 2006-01-31 | Cell cultivation and breeding method |
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WO2005021462A1 true WO2005021462A1 (de) | 2005-03-10 |
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PCT/EP2004/000077 WO2005021462A1 (de) | 2003-07-31 | 2004-01-08 | Verfahren zur herstellung von porösen kohlenstoffbasierten formkörpern und deren verwendung als zellkulturträger- und aufzuchtsysteme |
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US (1) | US20060159718A1 (de) |
EP (2) | EP1658248A1 (de) |
JP (1) | JP2007500663A (de) |
KR (1) | KR20060065660A (de) |
CN (1) | CN1829667B (de) |
AU (1) | AU2004268732A1 (de) |
BR (1) | BRPI0413080A (de) |
CA (1) | CA2532737A1 (de) |
DE (2) | DE10335131A1 (de) |
EA (1) | EA011114B1 (de) |
IL (1) | IL173164A0 (de) |
MX (1) | MXPA06001238A (de) |
SG (1) | SG154326A1 (de) |
WO (1) | WO2005021462A1 (de) |
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- 2004-01-08 EP EP08169278A patent/EP2025657A2/de not_active Withdrawn
- 2004-01-08 EA EA200600286A patent/EA011114B1/ru not_active IP Right Cessation
- 2004-01-08 WO PCT/EP2004/000077 patent/WO2005021462A1/de active Application Filing
- 2004-01-08 CA CA002532737A patent/CA2532737A1/en not_active Abandoned
- 2004-01-08 BR BRPI0413080-4A patent/BRPI0413080A/pt not_active IP Right Cessation
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1982772A1 (de) | 2003-05-16 | 2008-10-22 | Cinvention Ag | Biokompatibel beschichtete medizinische Implantate |
EP2033666A2 (de) | 2003-05-28 | 2009-03-11 | Cinvention Ag | Implantate mit funktionalisierten Kohlenstoffoberflächen |
EP2014708A1 (de) | 2005-01-13 | 2009-01-14 | Cinvention Ag | Geformter Körper aus einem Verbundstoffmaterial |
JP2009500054A (ja) * | 2005-07-01 | 2009-01-08 | シンベンション アーゲー | 網状複合材料を含む医療装置 |
Also Published As
Publication number | Publication date |
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US20060159718A1 (en) | 2006-07-20 |
CA2532737A1 (en) | 2005-03-10 |
SG154326A1 (en) | 2009-08-28 |
CN1829667A (zh) | 2006-09-06 |
MXPA06001238A (es) | 2006-04-11 |
DE202004006867U1 (de) | 2004-08-05 |
EA011114B1 (ru) | 2008-12-30 |
KR20060065660A (ko) | 2006-06-14 |
CN1829667B (zh) | 2010-04-07 |
EP2025657A2 (de) | 2009-02-18 |
EA200600286A1 (ru) | 2006-06-30 |
DE10335131A1 (de) | 2005-02-24 |
IL173164A0 (en) | 2006-06-11 |
BRPI0413080A (pt) | 2006-10-03 |
AU2004268732A1 (en) | 2005-03-10 |
EP1658248A1 (de) | 2006-05-24 |
JP2007500663A (ja) | 2007-01-18 |
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