CN1278996C - Process for preparing inorganic material with porous structure and product therefor - Google Patents
Process for preparing inorganic material with porous structure and product therefor Download PDFInfo
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- CN1278996C CN1278996C CN 200410021801 CN200410021801A CN1278996C CN 1278996 C CN1278996 C CN 1278996C CN 200410021801 CN200410021801 CN 200410021801 CN 200410021801 A CN200410021801 A CN 200410021801A CN 1278996 C CN1278996 C CN 1278996C
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Abstract
The present invention discloses a process for preparing an inorganic material with a porous structure and a product thereof, which comprises the following steps: in chitin slurry with high content of inorganic powder, dimethyl acetamide is used as solvent, solid particles with 1 to 10 times of the volume of the slurry and the sizes of 50 to 5000 mu m which are dissolved in water rather than dimethyl acetamide solvent are added as pore-making agents, uniformly mixed and moved to a mould; under the action of water molecules, the mould is placed under a hydrous environment, generates in situ gelation for forming; then water-soluble solvent and the pore-making agents are removed by sufficient water cleaning to obtain a crude chitin foamed blank with high content of inorganic powder; the crude blank is baked and sintered to obtain an inorganic material product with a porous structure. The present invention has the advantages of simple manufacturing process and convenient operation. The sizes of prepared materials and the products thereof are unrestricted, porous forms and structures are easy to control. The prepared materials and the products thereof have the advantages of high porosity, good pore penetration, good mechanical property, high mechanical strength and little content of trace elements. The present invention is particularly suitable for the preparation of biological material products.
Description
Technical field
The present invention relates to the preparation method of vesicular structure inorganic materials and goods thereof.
Background technology
Because the three-dimensional porous structure of vesicular structure inorganic materials uniqueness makes it to have light weight, characteristics such as density is low, specific surface is big, low heat conductivity, the porous inorganic material of the open-celled structure of perforation also has hypertonicity; Therefore, the vesicular structure inorganic materials is widely used in refractory materials, filtering material, catalyst bracket, bone substitution material etc.Vesicular structure inorganic materials for example porous structure ceramic generally obtains by drilling and powder sintering process, and its method mainly contains following several:
Method one, with ceramic mud and meet after heat the pore forming material that decomposes such as hydrogen peroxide take place mixes, pore forming material is decomposed produces gas, solidified mud takes place simultaneously, and bubble is fixed up, acquisition has the first base of vesicular structure.With after calcining process obtains to have the pottery of certain vesicular structure.The advantage of this method is that technology is simple, and shortcoming is that foaming process is difficult to accurate control, and void distribution is inhomogeneous, and its macroscopical connectivity is poor, based on the storage pore.
Method two, ceramic powder mixed and suppress with particles such as solid particulate such as polyvinyl butyral acetal, starch, wax, naphthalene, polystyrene and polymethylmethacrylates embark on journey; roast is removed solid particulate at a certain temperature subsequently; thereby just staying hole in the base, obtaining to have the pottery of certain vesicular structure again through calcining process.The advantage of this method is that technology is simple, and hole can accurately be controlled and be evenly distributed, and shortcoming is that vesicular structure macroscopic view connectivity is poor, based on the storage pore.
Methods such as method three, employing infiltration, vapour deposition and EFI are coated with are with ceramic mud or ceramic powder coated polymer such as Polyurethane three dimensional network bubble foam, drying, pyrolysis and sintering process are removed polymeric web bubble foam and are made ceramic particle generation densification reaction, thereby obtain having the three-dimensional similar and connect porous structure ceramic, and netted pottery to polymeric web bubble foam.The advantage of this method is that the hole connectivity is good, and porosity height, vesicular structure are easy to control, and shortcoming is that complex process, mechanical strength are not high.
It is that the hydrogel IQF that will be loaded with ceramic powder is separated that method four, freeze-drying prepare porous ceramics, and crystalline is iced through produce hole after the lyophilize in gel, can obtain porous structure ceramic through sintering process.The advantage of this method is that technology is simple, and shortcoming is that the space in the vesicular structure has directivity.
It is the porous ceramics preparation method based on new curing mechanism that developed recently gets up that method five, gel method are used to prepare porous ceramics, can be divided into chemical gel method and high-molecular gel method.The chemical gel method is to be cast in the organic monomer of mud by wherein in the mould under the linking agent effect, and in-situ cross-linked gelation, and is fixed foam to solid state transformation by liquid state, forms the goods form of ultimate demand; High-molecular gel casting method is by after the polymeric sol cast that contains inorganic powder gelatinizing-in-situ taking place under proper condition, simultaneously foam being fixed and moulding.The polymer foam that contains ceramic powder of moulding promptly obtains porous structure ceramic through follow-up after comprising the art breading of calcining again.
The most critical factor that the chemical gel legal system is equipped with porous ceramics is that can to form the control and the foamy of the selection of gel organic monomer and gelation reaction stable.The organic monomer solvent is called the non-aqueous solution gel method if adopt organic solvent.When making water, then be called the aqueous gel method as the solvent of organic monomer.The organic monomer that uses the earliest in this method mainly is an acrylamide; Because the danger of acrylamide, developed a series of organic supramolecular instead of propylene acid amides as gelling, they mainly comprise acrylic amine, methacrylic acid, Methacrylamide and n-methylolacrylamide etc., adopt methylene bisacrylamide as linking agent.Before cross linked gelization, can inject or add methods such as perforating agent by mechanical foaming or gas, in ceramic mud, introduce bubble, and be fixed up by gelation process by tensio-active agent is stable, final sintering process obtains porous structure ceramic.The defective of chemical gel method mainly is: need to add dispersion agent, initiator, catalyzer and linking agent etc.; Easily introduce other impurity; It is complicated to relate to technologies such as foaming, bubble stabilizes and gelation be fixing; And find after different gel organic monomers add, green body strength is also had in various degree influence after deliberation.
In the chemical gel method, also can adopt the carrier of other monomer as ceramic powder.For example, with ceramic mud and isocyanate-terminated polyoxyethylene hybrid reaction, or the direct hydrophilic crosslinked polyurethane foam that contains ceramic powder that generates, or the generation of expanding under the effect of pore forming material contains the hydrophilic crosslinked polyurethane foam of ceramic powder, form vesicular structure base just through curing process, with removing urethane, after sintering process obtains porous structure ceramic after the roast process heat is separated.The advantage of this method is that network skeleton is a solid state, the netted pottery of preparation has physical strength preferably with the netted ceramic phase ratio of method three, shortcoming is that foaming technology is complicated, be difficult to prepare the wide aperture hole, the melting process before the polyurethane foam pyrolysis at high temperature makes vesicular structure subside easily.
The high-molecular gel method mainly utilizes specific macromolecular solution that the Thermogelling process at high temperature takes place at present, makes after the slurry casting that is loaded with inorganic powder in-situ solidifying to take place and moulding.This family macromolecule mainly comprises agar, methylcellulose gum, carrageenin, gelatin and starch etc.The main difficulty high temperature gel process that this method runs into is complicated, loaded down with trivial details to the operation control of temperature; And when product size was big, the heat transmission was inhomogeneous, and the performance of goods and quality reduce, and had limited the size of product size.
The purpose of this invention is to provide a kind of method for preparing vesicular structure inorganic materials and goods thereof, this kind preparation method technology is simple, easy to operate; The vesicular structure inorganic materials of preparation and the size of goods thereof are unrestricted, and the hole shape structure is easy to control, the porosity height, and the hole connectivity is good; The mechanical property of material and goods thereof is good, the mechanical strength height; Micronutrient levels is few, is suitable for the trace element demanding various goods of limiting the quantity of are particularly useful for the preparation of biologic material products.
The present invention prepares the method for vesicular structure inorganic materials, comprises the steps:
(1) dimethylacetamide solvent that contains 4%～8% (weight) lithium chloride that is used to dissolve chitin by the inorganic powder of the chitin of 3 parts of weight, 4.5～300 parts of weight and 100～1000 parts of weight is mixed with inorganic powder/chitin mud;
(2) with granular size be the water-soluble of 50～5000 μ m but be insoluble to the sugar grain of dimethylacetamide solvent or salt particle or granule of polyvinyl alcohol as perforating agent, make the mixture of perforating agent and mud by 1～10 to 1 volume ratio uniform mixing with inorganic powder/chitin mud;
(3) rapidly mixture is transferred in the mould, gelatinizing-in-situ takes place and excipient with being placed on the chitin that makes in the moisture time-sharing environment in the mixture under the water molecules effect, in water, fully clean and remove water miscible solvent and perforating agent, obtain containing the chitin foam of inorganic powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is under 250～500 ℃ of temperature with the chitin foam, and chitin is removed in roast pyrolysis in 1～5 hour; Under hot conditions, carry out sintering subsequently and make vesicular structure skeleton and the abundant densification of hole wall, promptly make the vesicular structure inorganic materials.
The present invention prepares the method for vesicular structure inorganic materials goods, comprises the steps:
(1) dimethylacetamide solvent that contains 4%～8% (weight) lithium chloride that is used to dissolve chitin by the inorganic powder of the chitin of 3 parts of weight, 4.5～300 parts of weight and 100～1000 parts of weight is mixed with inorganic powder/chitin mud;
(2) with granular size be the water-soluble of 50～5000 μ m but be insoluble to the sugar grain of dimethylacetamide solvent or salt particle or granule of polyvinyl alcohol as perforating agent, make the mixture of perforating agent and mud by 1～10 to 1 volume ratio uniform mixing with inorganic powder/chitin mud;
(3) rapidly mixture is transferred in the mould of the required form of particular product, gelatinizing-in-situ takes place and excipient with being placed on the chitin that makes in the moisture time-sharing environment in the mixture under the water molecules effect, in water, fully clean and remove water miscible solvent and perforating agent, obtain containing the chitin foam of the specific modality of inorganic powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is under 250～500 ℃ of temperature with the chitin foam of specific modality, and chitin is removed in roast pyrolysis in 1～5 hour; Under hot conditions, carry out sintering subsequently and make vesicular structure skeleton and the abundant densification of hole wall, promptly make vesicular structure inorganic materials goods.
Inorganic powder in above-mentioned (1) step is biological ceramic powder, and the specific modality of mould is the form of human body particular anatomy dummy or the form of artificial eye tire or cutipunctor spare in (3) step; It is porous bio-ceramic goods and porous ceramics, artificial eye tire or the cutipunctor spare that the human body particular anatomy is repaired and replaced that be used for that requires form that the vesicular structure that makes does not have mechanical goods.
Inorganic powder in above-mentioned (1) step is the metal-powder of human implantable tissue, and the specific modality of mould is the form of human body particular anatomy dummy or the form of artificial eye tire or cutipunctor spare in (3) step; It is metal implant goods and metal artificial eye tire or the cutipunctor spare that the human body particular anatomy is repaired and replaced that be used for that requires form that the vesicular structure that makes does not have mechanical goods.
Above-mentioned human body particular anatomy is the skeletal sites that skull, saddle nose, jawbone, backbone and other position need be repaired.
Inorganic powder in above-mentioned (1) step is ceramic powder or metal-powder, and the specific modality of mould is the porous filter form in (3) step; The vesicular structure that makes does not have mechanical goods and is pottery or metal porous strainer.
The form of above-mentioned mould is cylinder, cylinder or discoideus, and it is cylinder, cylinder or discoideus pottery or metal porous strainer that the vesicular structure that makes does not have mechanical goods.
Compared with prior art, the invention has the advantages that: the rapid gelation process of (1) original position need not add linking agent, do not need to be heating and curing and inorganic powder is dispersed in the chitin foam framework; Its foundry processing is simple, processing ease; (2) pore-forming material not only can be easily by the water-soluble integrity that goes out to keep simultaneously vesicular structure, and the form by pore-forming material and ratio etc. are easy to control the vesicular structure of inorganic materials goods; (3) the chitin foam that contains inorganic powder shrinks with the stripping of pore-forming material, makes the inorganic powder of adhesion more tightly packed each other, and made porous foam density is even, mechanical strength good, the suitable porous article that further is machined into complicated form; (4) after the follow-up sintering art breading is removed a spot of chitin, the abundant densification of the skeleton of porous inorganic material, prepared porous inorganic material has high mechanical strength; (5) because melting process does not appear in chitin in pyroprocess, the vesicular structure in the first base of porous foam can not subside in whole calcination process, and vesicular structure is indeformable; (6) this method need not add linking agent etc., and the micronutrient levels of introducing is few, is suitable for preparation to the trace element demanding various goods of limiting the quantity of, as the application in technical field of biological material.
Vesicular structure inorganic materials and goods thereof that the present invention makes, its pore size are 5～3000 μ m; Porosity is 10～98%; Vesicular structure is sealing or connects form.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment one
(1) gets the hydroxyapatite powder of 4.5 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 4% lithium chloride of 100 parts of weight, after treating that hydroxyapatite powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, about continuously stirring 3 days, above-mentioned chitin is dissolved fully, form hydroxyapatite powder homodisperse and stable mud;
(2) the sugar grain of granular size 5000 μ m and above-mentioned mud are uniformly mixed to form sugared the mixture with mud by 10: 1 volume ratio;
(3) rapidly above-mentioned mixture is transferred in the mould, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove whole water-soluble substanceses and comprise solvent and perforating agent etc., obtain the chitin foam of hydroxyl apatite powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is that the chitin foam of hydroxyl apatite powder is removed chitin in the pyrolysis in 1 hour of 500 ℃ of roasts, and 1250 ℃ of sintering obtained the hydroxyapatite porous ceramic film material with the stove cooling after 2 hours in air subsequently.
The sugar grain that this example adopts be common table sugar grain, and the table sugar grain is water-soluble and be insoluble to dimethyl acetyl, its wide material sources, and it is easy to draw materials.
Embodiment two
(1) takes by weighing the silicon carbide powder of 4.5 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 5% lithium chloride of 1000 parts of weight, after treating that silicon carbide powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, after fully stirring is dissolved chitin fully, form silicon carbide powder homodisperse and stable mud;
(2) granule of polyvinyl alcohol of granular size 500 μ m (it is perforating agent that this example adopts granule of polyvinyl alcohol) and above-mentioned mud are uniformly mixed to form the mixture of granule of polyvinyl alcohol and mud by 8: 1 volume ratio;
(3) rapidly above-mentioned mixture is transferred in the mould, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove whole water-soluble substanceses and comprise solvent and perforating agent etc., obtain the chitin foam of silicon carbide-containing powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base be the silicon carbide-containing powder the chitin foam in a vacuum the pyrolysis in 4 hours of 300 ℃ of roasts remove chitin, 1500-1600 ℃ of sintering is after 2 hours in a vacuum subsequently, cooling promptly obtains required porous silicon carbide material.
Embodiment three
(1) takes by weighing biphasic calcium phosphate (tricalcium phosphate/hydroxyapatite) powder of 40 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 7% lithium chloride of 500 parts of weight, after treating that biphasic calcium phosphate (tricalcium phosphate/hydroxyapatite) powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, after fully stirring is dissolved chitin fully, form biphasic calcium phosphate (tricalcium phosphate/hydroxyapatite) powder homodisperse and stable mud;
(2) the sugar grain of granular size 200 μ m and above-mentioned mud are uniformly mixed to form sugared the mixture with mud by 9: 1 volume ratio;
(3) rapidly above-mentioned mixture is transferred in the mould, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove whole water-soluble substanceses and comprise solvent and perforating agent etc., obtain containing the chitin foam of biphasic calcium phosphate powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base promptly contain the biphasic calcium phosphate powder the chitin foam in a vacuum the pyrolysis in 4 hours of 300 ℃ of roasts remove chitin, 1200-1300 ℃ of sintering is after 2 hours in a vacuum subsequently, cooling promptly obtains required porous biphasic calcium phosphate bioceramic material.
Mould among the embodiment one, two, three does not require specific form (shape), the form that the porous inorganic material that makes also has no special requirements.If this material should adopt various machining process again need manufacture concrete goods the time, manufactures the goods (product) of specified shape and structure.
Embodiment four
(1) takes by weighing the tricalcium phosphate powder of 300 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 8% lithium chloride of 1000 parts of weight, after treating that tricalcium phosphate powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, about continuously stirring 3 days, chitin is dissolved fully, form tricalcium phosphate powder homodisperse and stable mud;
(2) the salt particle (being sodium chloride particle) with granular size 50 μ m evenly mixes the mixture that forms salt particle and mud by 1: 1 part volume ratio with above-mentioned mud;
(3) rapidly above-mentioned mixture being transferred to saddle nose repairs in the mould of form, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove water miscible solvent (N,N-DIMETHYLACETAMIDE) and perforating agent (salt particle) etc., obtain the chitin foam of phosphoric acid three calcium powders after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is that the chitin foam of phosphoric acid three calcium powders is removed chitin in the pyrolysis in 5 hours of 250 ℃ of roasts, and 1200～1300 ℃ of sintering obtained tricalcium phosphate porous bio-ceramic saddle nose goods with the stove cooling after 2 hours in air subsequently.These goods can be used for the reparation of human body saddle nose.
This example adopts the salt particle to make perforating agent, also can adopt other water-soluble and be insoluble to the solid salt particle of N,N-DIMETHYLACETAMIDE in the enforcement.
Mould form in this example changes the form of other position dummy of skull, jawbone, backbone or human body into.Then can make other position dummy goods of tricalcium phosphate porous bio-ceramic skull, jawbone, backbone or human body.
Embodiment five
(1) takes by weighing the aluminium sesquioxide powder of 57 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 5% lithium chloride of 200 parts of weight, after treating that the aluminium sesquioxide powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, after fully stirring is dissolved chitin fully, form aluminium sesquioxide powder homodisperse and stable mud;
(2) granule of polyvinyl alcohol and the above-mentioned mud of granular size 3000 μ m is uniformly mixed to form granule of polyvinyl alcohol and mud by 3: 1 volume ratio mixture;
(3) rapidly above-mentioned mixture is transferred in the mould of eyeball form, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove whole water-soluble substanceses and comprise solvent and perforating agent etc., obtain the chitin foam of trioxygen-containingization two aluminium powder forms after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is that the chitin foam of trioxygen-containingization two aluminium powder forms is removed chitin in the pyrolysis in 3 hours of 400 ℃ of roasts, subsequently 1600 ℃ of sintering after 2 hours in air; Cooling rate with 3 ℃ of per minutes cools to 1200 ℃, promptly obtains aluminium sesquioxide porous ceramics artificial eye tire goods with the stove cooling again.
This example adopts granule of polyvinyl alcohol to make perforating agent, and granule of polyvinyl alcohol is water-soluble and be insoluble to N,N-DIMETHYLACETAMIDE, meets the requirement of the present invention to perforating agent.
Embodiment six
(1) takes by weighing the metal titanium powder of 200 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 6% lithium chloride of 600 parts of weight, after treating that the metal titanium powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, after fully stirring is dissolved chitin fully, form metal titanium powder homodisperse and stable mud;
(2) the sugar grain of granular size 1000 μ m and above-mentioned mud are uniformly mixed to form sugared the mixture with mud by 5: 1 volume ratio;
(3) rapidly above-mentioned mixture is transferred in the mould of specific cutipunctor spare form, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove whole water-soluble substanceses and comprise solvent and perforating agent etc., obtain the chitin foam of containing metal ti powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base be the containing metal ti powder the chitin foam in a vacuum the pyrolysis in 1 hour of 250 ℃ of roasts remove chitin, 1600 ℃ of sintering after 2 hours in a vacuum subsequently cool to 1200 ℃ with the cooling rate of 3 ℃ of per minutes and promptly obtain required porous metal titanium cutipunctor spare with the stove cooling again.
Embodiment seven
(1) takes by weighing the alumina powder of 12 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that contains 8% lithium chloride of 1000 parts of weight, after treating that alumina powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, after fully stirring is dissolved chitin fully, form alumina powder homodisperse and stable mud;
(2) the sugar grain of granular size 2000 μ m and above-mentioned mud are uniformly mixed to form sugared the mixture with mud by 1: 1 volume ratio;
(3) rapidly above-mentioned mixture is transferred in cylinder or the discoideus mould, make mixing mud under the water molecules effect, gelatinizing-in-situ take place and excipient in the moisture time-sharing environment with being placed on, in water, fully clean and remove whole water-soluble substanceses and comprise solvent and perforating agent etc., obtain the chitin foam of salic powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base be salic powder the chitin foam in a vacuum the pyrolysis in 5 hours of 500 ℃ of roasts remove chitin, 1500-1600 ℃ of sintering after 2 hours in a vacuum subsequently cools to 1200 ℃ with the cooling rate of 3 ℃ of per minutes and promptly obtains required aluminum oxide porous cylinder or discoideus strainer with the stove cooling again.This strainer can be used for the purification of high-temperature metal melt, the filtration of vehicle exhaust flue dust.
Change alumina powder into strainer that Zirconium oxide powder also can make same purposes.
The form of mould changes various other required strainer forms (shape and structure) in this example, simultaneously material is changed into other inorganic materials, promptly can be made into the specific desired shape of various porous inorganic materials and structure, adapts to the strainer of various uses.(component is SiO to change porcelain sand into as inorganic powder
2, Al
2O
3, Fe
2O
5, CaO, MgO etc.), at 1200-1600 ℃ of following sintering, can make and be used for purification of water quality, as handle the porous ceramic filter of various industrial sewages, city tap-water, municipal effluent, pure water and soft water etc.Inorganic powder adopts metallic nickel 1300-1600 ℃ of following vacuum sintering, can make and be used for pharmacy, monosodium glutamate, enzyme engineering, brewage etc. the fermentation industry sterile air is filtered, also be used for the metallic nickel strainer that the high-purity gas of precision optical machinery instrument, space technology, nuclear technique and electronic industry purifies.Inorganic powder adopts metallic copper 1300-1600 ℃ of following vacuum sintering, can make the metallic copper strainer that is used for the vehicle exhaust filtrating smoke dust.Inorganic powder adopts calcium phosphate ceramic at 1200-1300 ℃ of following sintering, can make the filter tip that is used for cigarette filter, and the strainer that is used for albumen purification and water purification etc.
Obviously, mould form of the present invention changes, vesicular structure article shape that makes and the then corresponding change of structure; If the mould form does not have particular requirement, what then produce is porous structure material, and this material is made various goods again after mechanical workout.
Vesicular structure inorganic materials and goods thereof that the present invention makes, its pore size are 50～3000 μ m; Porosity is 10～98%; Vesicular structure is sealing or connects form.Can be widely used in various bone substitution materials and goods, filtering material and goods etc.
The various inorganic materials goods that the present invention makes generally can directly use, but for accuracy requirement height, baroque goods, then can produce satisfactory product for use by further mechanical workout.
Inorganic powder in preparation method's pilot process of the present invention/chitin mud, the more specifically process and the precaution of its preparation, the preparation that a kind of high-molecular gel system in " 03135763.6 " number patent application that can apply on September 5th, 2003 referring to the applicant prepares (chitin) mud that is used for excipient in the pilot process; These two intermediates are identical.Certainly, the inorganic powder/chitin mud that also can adopt other prior art to be mixed with to meet requirement component of the present invention and proportioning is for using.
Inorganic (chitin) mud powder among the present invention refers to all sintered inorganic powders, and they can be: 1, metal and powdered alloy, for example nickel, copper, aluminium and alloy thereof etc.; 2, oxide powder, for example zirconium white, titanium dioxide and aluminium sesquioxide etc.; 3, carbide powder, for example silicon carbide and norbide etc.; 4, bioactivity glass and calcium phosphate series ceramic powder etc.The sintering process condition is decided on the kind of inorganic powder; general sintering rate (intensification) is in 50～200 ℃ of scopes per hour; firing temperature is in 800～2000 ℃; sintering atmosphere can adopt air; also protective atmosphere such as oxygen, hydrogen, rare gas element and similar gas, or adopt vacuum condition.
The sugar grain that perforating agent among the present invention uses except the foregoing description, salt particle, the granule of polyvinyl alcohol, can also be that other is water-soluble and be insoluble to the various solid particulates of N,N-DIMETHYLACETAMIDE.
Claims (7)
1, a kind of method for preparing the vesicular structure inorganic materials, form by following steps successively:
(1) dimethylacetamide solvent that contains 4%～8% (weight) lithium chloride that is used to dissolve chitin by the inorganic powder of the chitin of 3 parts of weight, 4.5～300 parts of weight and 100～1000 parts of weight is mixed with inorganic powder/chitin mud;
(2) with granular size be the water-soluble of 50～5000 μ m but be insoluble to the sugar grain of dimethylacetamide solvent or salt particle or granule of polyvinyl alcohol as perforating agent, make the mixture of perforating agent and mud by 1～10 to 1 volume ratio uniform mixing with inorganic powder/chitin mud;
(3) rapidly mixture is transferred in the mould, gelatinizing-in-situ takes place and excipient with being placed on the chitin that makes in the moisture time-sharing environment in the mixture under the water molecules effect, in water, fully clean and remove water miscible solvent and perforating agent, obtain containing the chitin foam of inorganic powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is under 250～500 ℃ of temperature with the chitin foam, and chitin is removed in roast pyrolysis in 1～5 hour; Under hot conditions, carry out sintering subsequently and make vesicular structure skeleton and the abundant densification of hole wall, promptly make the vesicular structure inorganic materials.
2, a kind of method for preparing vesicular structure inorganic materials goods, form by following steps successively:
(1) dimethylacetamide solvent that contains 4%～8% (weight) lithium chloride that is used to dissolve chitin by the inorganic powder of the chitin of 3 parts of weight, 4.5～300 parts of weight and 100～1000 parts of weight is mixed with inorganic powder/chitin mud;
(2) with granular size be the water-soluble of 50～5000 μ m but be insoluble to the sugar grain of dimethylacetamide solvent or salt particle or granule of polyvinyl alcohol as perforating agent, make the mixture of perforating agent and mud by 1～10 to 1 volume ratio uniform mixing with inorganic powder/chitin mud;
(3) rapidly mixture is transferred in the mould of the required form of particular product, gelatinizing-in-situ takes place and excipient with being placed on the chitin that makes in the moisture time-sharing environment in the mixture under the water molecules effect, in water, fully clean and remove water miscible solvent and perforating agent, obtain containing the chitin foam of the specific modality of inorganic powder after the drying art breading, as the first base that utilizes for subsequent technique;
(4) just base is under 250～500 ℃ of temperature with the chitin foam of specific modality, and chitin is removed in roast pyrolysis in 1～5 hour; Under hot conditions, carry out sintering subsequently and make vesicular structure skeleton and the abundant densification of hole wall, promptly make vesicular structure inorganic materials goods.
3, preparation vesicular structure inorganic materials article process according to claim 2, it is characterized in that: the inorganic powder in described (1) step is biological ceramic powder, and the specific modality of mould is the form of human body particular anatomy dummy or the form of artificial eye tire or cutipunctor spare in (3) step; It is porous bio-ceramic goods and porous ceramics, artificial eye tire or the cutipunctor spare that the human body particular anatomy is repaired and replaced that be used for that requires form that the vesicular structure that makes does not have mechanical goods.
4, preparation vesicular structure inorganic materials article process according to claim 2, it is characterized in that: the inorganic powder in described (1) step is the metal-powder of human implantable tissue, and the specific modality of mould is the form of human body particular anatomy dummy or the form of artificial eye tire or cutipunctor spare in (3) step; It is metal implant goods and metal artificial eye tire or the cutipunctor spare that the human body particular anatomy is repaired and replaced that be used for that requires form that the vesicular structure that makes does not have mechanical goods.
5, according to claim 3 or 4 described preparation vesicular structure inorganic materials article process, it is characterized in that: described human body particular anatomy is the skeletal sites that skull, saddle nose, jawbone, backbone and other position need be repaired.
6, preparation vesicular structure inorganic materials article process according to claim 2 is characterized in that: the inorganic powder in described (1) step is ceramic powder or metal-powder, and the specific modality of mould is the porous filter form in (3) step; The vesicular structure that makes does not have mechanical goods and is pottery or metal porous strainer.
7, preparation vesicular structure inorganic materials article process according to claim 6, it is characterized in that: the form of described mould is a cylinder or discoideus, it is cylinder or discoideus pottery or metal porous strainer that the vesicular structure that makes does not have mechanical goods.
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| CN 200410021801 CN1278996C (en) | 2004-02-13 | 2004-02-13 | Process for preparing inorganic material with porous structure and product therefor |
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| CN 200410021801 CN1278996C (en) | 2004-02-13 | 2004-02-13 | Process for preparing inorganic material with porous structure and product therefor |
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| CN104396279B (en) * | 2012-03-05 | 2017-04-12 | 无线电广播技术研究所有限公司 | Sound generator, sound generation device, and electronic device |
| CN103878371B (en) * | 2014-04-18 | 2015-11-11 | 益阳市菲美特新材料有限公司 | One is composite porous and preparation method thereof |
| CN104230369B (en) * | 2014-08-25 | 2016-05-25 | 合肥工业大学 | A kind of high porosity ceramic with honeycomb and preparation method thereof |
| CN104888280B (en) * | 2015-05-06 | 2018-08-17 | 西南交通大学 | Hole wall surface has the preparation method of the osseous tissue engineering stephanoporate holder of micro- canal structure |
| CN111109253A (en) * | 2019-12-20 | 2020-05-08 | 蚌埠市鑫晟新材料科技有限公司 | Preparation method of antibacterial material for papermaking |
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