CN1321947C - Prepn process of porous spherical granular inorganic material - Google Patents
Prepn process of porous spherical granular inorganic material Download PDFInfo
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- CN1321947C CN1321947C CNB2004100813997A CN200410081399A CN1321947C CN 1321947 C CN1321947 C CN 1321947C CN B2004100813997 A CNB2004100813997 A CN B2004100813997A CN 200410081399 A CN200410081399 A CN 200410081399A CN 1321947 C CN1321947 C CN 1321947C
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Abstract
The present invention discloses a preparation process of porous spherical granular inorganic material products, which comprises the following steps: chitin slurry with high inorganic powder content and dimethyl acetamide as solvent, or after a pore forming agent is added, is added into an emulsifying agent and stirred; the slurry is emulsified into sol-shaped spherical particles; by controlling the adding form and the adding amount of water, the sol-shaped spherical particles generate in-situ gelatinization for forming under the action of water molecules; after the emulsifying agent is filtered, the rest emulsifying agent, water soluble solvent and the pore forming agent are removed by sufficiently washing with water or acetone and alcohol to obtain porous spherical gel particles; the porous spherical gel particles are dried to obtain a primary blank; the primary blank is processed through roasting, mechanical shaping and sintering to obtain a product. The present invention has the advantages of simple manufacturing process, convenient operation, few introduced impurity elements, good sphericity, wide size range and narrow size distribution of the product, easy control of porous form and structure and good mechanical property. The present invention can be widely used as a human tissue repairing and stuffing materials, a tissue engineering rack material, a medicine releasing carrier, a filtering material, etc.
Description
Affiliated technical field
The present invention relates to the preparation method of porous spherical granular inorganic material.
Background technology
Because the spherical three-dimensional porous structure of vesicular structure spheroidal particle inorganic materials uniqueness makes it to have light weight, characteristics such as density is low, specific surface is big, good fluidity, have the porous inorganic material that connects open-celled structure and also have hypertonicity; Therefore, vesicular structure spheroidal particle inorganic materials is widely used in drug carrier material, filtering separation material, catalyst bracket, filling material of bone and other special purpose etc.Especially the reaction because the particle of irregular form causes inflammation behind implant into body easily influences osteoplastic speed, therefore, generally tends to use spheroidal particle with smooth surface material as the tissue defects filling.In addition, the vesicular structure of perforation helps growing into of cambium, strengthens combining between tissue and the implant, thereby reaches the reparation purpose of expectation.Vesicular structure spheroidal particle inorganic materials mainly contains following several preparation method:
Method one, rolling balling method: the inorganic powder of certain granules degree is inserted in the container of rotation, water is sprayed into by a certain percentage obtain first nuclear, again powder and water are added the rolling container simultaneously, make powder adhere to first nuclear surface and the formation porous particle base just of growing up.With after calcining process obtains to have the inorganic spheroidal particle of certain vesicular structure.The advantage of this method is that technology is simple, and particle size distribution is even, and shortcoming is that vesicular structure is wayward and the aperture is less.
Method two, crush method: the porous block inorganic materials is promptly obtained the vesicular structure particulate material through broken classification.This method advantage is that method is simple, and shortcoming is that particle form is irregular sharp-pointed many prismatics looks.，
Method three, freeze-drying: inorganic powder is mixed with the aqueous solution in proportion, then drips of solution is added in the liquid nitrogen, make the water droplet IQF that is loaded with inorganic powder be separated, crystalline ice can obtain porous structure ceramic through produce hole after the lyophilize in inorganic particle through sintering process.The advantage of this method is that technology is simple, and it is few to introduce impurity, and shortcoming is that vesicular structure is wayward, and hole has directivity, inefficiency and cost height.
Method four, the two emulsion methods of class: inorganic powder is mixed with the aqueous solution in proportion, add a certain amount of pore forming material then, behind bubbling process, add whiteruss as interior oil phase, and adopt means such as stirring that bubble and paraffin are uniformly dispersed, next above-mentioned mixed phase is joined in the whiteruss as outer oil phase, the two emulsion systems of the back formation class that is uniformly dispersed, the employing glutaraldehyde is solidified the liquid spherolite that contains inorganic powder and is promptly got spheroidal particle base just, can obtain the porous spherical particles inorganic materials through oversintering again.The advantage of this method is the particle good sphericity, and distribution of sizes is good, and granular size is controlled, but technology is complicated, and the gained hole generally is a closed pores, and wayward, and especially the use of paraffin brings inconvenience.
Method five, gelatin suspension method: inorganic powder is mixed with aqueous gelatin solution with gelatin in proportion, the gelatin solution that will contain inorganic powder adds in the emulsifying agent, under surface tension effects, be emulsified into spherical particle by mechanical stirring, clean with acetone and ethanol again and obtain spheroidal particle base just; Can obtain the porous spherical particles inorganic materials through follow-up calcining process processing.This method technology is simple, easy to operate, but pore size can not be prepared the hole greater than 6 microns by the crystal grain gap decision that sintering produces in the particle.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing porous spherical granular inorganic material, this kind preparation method technology is simple, easy to operate; The good sphericity of goods, size range is wide, and vesicular structure is the three-dimensional hole that connects, and pore size and form are easy to control, and porosity ranges is adjustable; It is few that technological process is introduced impurity element, is particularly useful for the preparation of biologic material products.
The preparation method of porous spherical granular inorganic material of the present invention comprises the steps:
(1) dimethylacetamide solvent that contains 4%～8% (weight) lithium chloride that is used to dissolve chitin by the sintered inorganic powder of the chitin of 3 parts of weight, 3～300 parts of weight and 100～1000 parts of weight is mixed with sintered inorganic powder/chitin mud;
(2) sintered inorganic powder/chitin mud of making of (1) step is joined sintered inorganic powder/chitin mud is had the liquid substance of emulsifying effect also is in the emulsifying agent, under air-tight state, stir, mud is emulsified into colloidal sol shape spheroidal particle, feed subsequently and contain the air of moisture or directly add water, make the spherical chitin colloidal sol shape particle that contains sintered inorganic powder under the water molecules effect, the gelatinizing-in-situ process take place and solidify excipient, behind the filtering emulsifying agent gel spheroidal particle abundant cleaning in water removed water miscible solvent, obtain containing the chitin spheroidal particle of sintered inorganic powder after the drying technology, as the first base that utilizes for subsequent technique;
What (3) (2) step is made contains sintered inorganic powder chitin spheroidal particle base just, and under 250～500 ℃ of temperature, chitin is removed in roast pyrolysis in 1～5 hour; Again spheroidal particle is carried out the mechanical mill shaping, sintering makes the abundant densification of spheroidal particle under the sintering temperature condition of sintered inorganic powder subsequently, promptly makes porous spherical particles inorganic materials goods.
Above-mentioned (2) are in the step, clean remove water miscible solvent after, before the drying process, also the gel spheroidal particle is fully cleaned in acetone and ethanol and removes degrease.
The porous spherical granular inorganic material that adopts above method to make, the aperture of its vesicular structure are below the 10 μ m, are micron-sized vesicular structure.
After above-mentioned (1) step is mixed with sintered inorganic powder/chitin mud, other get particle diameter be 5～500 μ m and the water-soluble but solid particulate that is insoluble to dimethylacetamide solvent as perforating agent, join the mixture that uniform mixing in the mud makes perforating agent and mud with sintered inorganic powder/chitin mud by 1～10 to 1 weight ratio; Again mixture is carried out the step in above-mentioned (2), (3) step, make porous spherical granular inorganic material.
The preparation method who also adds perforating agent in mud, the aperture of the vesicular structure of the goods that make at last is 5～500 μ m, and is identical with the particle diameter of perforating agent.
Compared with prior art, the invention has the beneficial effects as follows: (1) realizes the solid shape process of the rapid gelation of original position by control moisture, sintered inorganic powder is dispersed in the chitin spheroidal particle, and the chitin of small proportion (the chitin strength of solution is not more than 2 weight percents) the first base of sintered inorganic powder high-content particle that can form fine intensity very; (2) spherical particle size controlled amount can optionally obtain the spheroidal particle of large size scope by the different stirring velocitys and the processing parameters such as temperature of emulsifying agent; (3) perforating agent not only can be easily by the water-soluble integrity that goes out to keep simultaneously vesicular structure, and the form by perforating agent and ratio etc. are easy to control the vesicular structure of inorganic materials goods; (4) the chitin spheroidal particle that contains sintered inorganic powder shrinks with the stripping of perforating agent, make the sintered inorganic powder of adhesion more tightly packed each other, through follow-up roast and sintering process handle remove a spot of chitin and the abundant densification of sintered inorganic powder after, prepared spherical granular inorganic material has higher mechanical strength; (5) because melting process does not appear in chitin in pyroprocess, the vesicular structure in the first base of porous particle can not subside in whole calcination process, and vesicular structure is indeformable; (6) this method need not add linking agent etc., and technological process is seldom introduced impurity element, is fit to be applied to preparation to the trace element demanding various goods of limiting the quantity of, as the application in technical field of biological material.
Above-mentioned sintered inorganic powder can adopt biological ceramic powder.The goods that make like this are vesicular structure spheroidal particle biological ceramics goods, be mainly used in the human body particular anatomy: the filling reparation of skull, saddle nose, jawbone, backbone and other skeletal sites that need repair, the aspects such as carrier of filter separator, chromatograph, medicine and catalyzer.
Above-mentioned sintered inorganic powder can adopt the metal-powder of human implantable tissue.The goods that make like this are vesicular structure spheroidal particle metal products, are mainly used in the human body particular anatomy and fill reparation, efficient liquid phase chromatographic analysis, the aspects such as carrier of blood plasma perfusion matrix and catalyzer.
Above-mentioned sintered inorganic powder adopts ceramic powder or metal-powder.The goods that make like this are vesicular structure spheroidal particle stupalith goods or metal products, mainly as support of the catalyst, and strainer filter substrate, aspects such as ion-exchanger.
The porous spherical granular inorganic material that the present invention makes, its granular size are 5～5000 μ m; Porosity is 10～90%; Pore texture is abundant, and the hole dimension size is divided into three grades: micropore≤1 μ m, mesopore 1～20 μ m, macropore 〉=20 μ m; But vesicular structure can be sealing or communicating structure as required.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment one
(1) gets the hydroxyapatite powder of 15 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) rapidly above-mentioned mixture is joined in the edible oil, under air-tight state, stir, chitin mud is emulsified into spheroidal particle, after a few hours, gelatinizing-in-situ takes place and excipient down in the aerial water molecules effect of particle, then the spheroidal particle of moulding is transferred to fully to clean in the deionized-distilled water and removed whole solvents, remove degrease with acetone and ethanol again, obtain the first base of chitin spheroidal particle of hydroxyl apatite powder after the drying art breading.
(3) just base is that the chitin spheroidal particle of hydroxyl apatite powder was 500 ℃ of following roasts 1 hour, chitin is removed in pyrolysis, again spheroidal particle is carried out the mechanical mill shaping, sintering 2 hours under 1200 ℃ of conditions of box-type furnace subsequently, obtaining the aperture with the stove cooling is hydroxyapatite micrometre level vesicular structure spheroidal particle bioceramic material goods below the 10 μ m.
This example adopts edible oil as emulsifying agent, and its wide material sources are drawn materials easily.And sintered inorganic powder adopts the hydroxyl apatite bioceramic powder, finished product can be widely used in the human body particular anatomy: the filling reparation of skull, saddle nose, jawbone, backbone and other skeletal sites that need repair, the aspects such as carrier of filter separator, chromatograph, medicine and catalyzer.
Embodiment two
(1) gets the tricalcium phosphate powder of 15 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 tricalcium phosphate 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 tricalcium phosphate powder homodisperse and stable mud.
With granular size is that the sugar grain (this example adopts the sugar grain as a perforating agent) of 100 μ m joins in the above-mentioned chitin mud with the weight ratio of above-mentioned tricalcium phosphate powder by 2: 1, and fully stirs, make sugared to be dispersed in the mud after.
(2) rapidly the mixture of above-mentioned sugar grain with chitin mud joined in the whiteruss, under air-tight state, stir, the chitin mud that will contain the sugar grain is emulsified into spheroidal particle, spraying into moisture in system makes the emulsion state particle gelatinizing-in-situ take place and excipient under the water molecules effect, then the spheroidal particle of moulding is transferred in the deionized-distilled water fully to clean and removed whole water-soluble substanceses and comprise solvent and perforating agent etc., the chitin porous spherical particles that obtains phosphoric acid three calcium powders after the drying art breading is base just.
(3) just base is that the chitin porous spherical particles of phosphoric acid three calcium powders is removed chitin in the pyrolysis in 1 hour of 500 ℃ of roasts, again spheroidal particle is carried out the mechanical mill shaping, sintering obtained the tricalcium phosphate vesicular structure spheroidal particle ceramic that the aperture is 100 μ m with the stove cooling after 2 hours under 1200 ℃ of conditions of box-type furnace subsequently.
Embodiment three
(1) takes by weighing the aluminium sesquioxide powder of 15 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, fully stirring is dissolved chitin fully, forms aluminium sesquioxide powder homodisperse and stable mud;
With the granule of polyvinyl alcohol (it is perforating agent that this example adopts granule of polyvinyl alcohol) and weight ratio and the mud uniform mixing of aluminium sesquioxide powder of granular size 500 μ m, form the mixture of granule of polyvinyl alcohol and mud by 5: 1;
(2) rapid mixture with above-mentioned granule of polyvinyl alcohol and chitin mud joins in the edible oil, under air-tight state, stir, the chitin mud that will contain granule of polyvinyl alcohol is emulsified into spheroidal particle, after a few hours, gelatinizing-in-situ takes place and excipient down in the aerial water molecules effect of particle, then the spheroidal particle of moulding is transferred in the deionized-distilled water fully to clean and removed whole water-soluble substanceses and comprise solvent and perforating agent etc., adopt acetone and ethanol to clean and remove degrease, obtain the first base of chitin porous spherical particles of trioxygen-containingization two aluminium powder forms after the drying art breading;
(3) just base is that the chitin porous spherical particles of trioxygen-containingization two aluminium powder forms is removed chitin in the pyrolysis in 4 hours of 300 ℃ of roasts, again spheroidal particle is carried out the mechanical mill shaping, sintering after 2 hours under box-type furnace 1500-1600 ℃ condition subsequently, cooling rate with 3 ℃ of per minutes cools to 1200 ℃, promptly obtains the vesicular structure spheroidal particle aluminium sesquioxide ceramic that required aperture is 500 μ m with the stove cooling again.Main as support of the catalyst, strainer filter substrate, aspects such as ion-exchanger.
Embodiment four
(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 closes 7% lithium chloride of 500 parts of weight, after treating that the biphasic calcium phosphate 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 powder homodisperse and stable mud;
Salt particle and the above-mentioned biphasic calcium phosphate of granular size 100 μ m are pressed 4: 1 weight ratio and mud uniform mixing, form the mixture of salt grain and mud;
(2) rapid mixture with above-mentioned salt grain and chitin mud joins in the edible oil, under air-tight state, stir, the chitin mud of saliferous grain is emulsified into spheroidal particle, after a few hours, gelatinizing-in-situ takes place and excipient down in the aerial water molecules effect of particle, then the spheroidal particle of moulding is transferred in the distilled water fully to clean and removed whole water-soluble substanceses and comprise solvent and perforating agent etc., adopt acetone and ethanol to clean and remove degrease, obtain containing the first base of chitin porous spherical particles of biphasic calcium phosphate powder after the drying art breading;
(3) just base promptly contain the biphasic calcium phosphate powder the chitin spheroidal particle in a vacuum the pyrolysis in 4 hours of 300 ℃ of roasts remove chitin, again spheroidal particle is carried out the mechanical mill shaping, 1200-1300 ℃ of sintering promptly obtained the vesicular structure spheroidal particle biphasic calcium phosphate biological ceramics goods that required aperture is 100 μ m with the stove cooling after 2 hours in a vacuum subsequently.Be mainly used in the human body particular anatomy: the filling reparation of skull, saddle nose, jawbone, backbone and other skeletal sites that need repair, the aspects such as carrier of filter separator, chromatograph, medicine and catalyzer.
The salt grain that this example adopts is common edible salt, also can adopt other water-soluble and be insoluble to the N,N-DIMETHYLACETAMIDE solid particulate as perforating agent.
Embodiment five
(1) takes by weighing the metal titanium powder of 200 parts of weight under well-beaten condition, add in the dimethylacetamide solvent that closes 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;
With the sugar grain and weight ratio and the mud uniform mixing of above-mentioned metal titanium powder of granular size 150 μ m, form sugared the mixture with mud by 5: 1;
(2) rapidly the mixture of above-mentioned sugar grain with chitin mud joined in the edible oil, under air-tight state, stir, the chitin mud that will contain the sugar grain is emulsified into spheroidal particle, and after a few hours, the aerial water molecules effect of particle gelatinizing-in-situ takes place and excipient down; Then the spheroidal particle of moulding is transferred in the deionized-distilled water fully to clean and removed whole water-soluble substanceses and comprise solvent and perforating agent etc., adopt acetone and ethanol to clean and remove degrease, obtain the first base of chitin spheroidal particle of containing metal ti powder after the drying art breading;
(3) just base be the containing metal ti powder the chitin spheroidal particle in a vacuum the pyrolysis in 1 hour of 250 ℃ of roasts remove chitin, again spheroidal particle is carried out the mechanical mill shaping, 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 the vesicular structure spheroidal particle metal titanium goods that required aperture is 150 μ m with the stove cooling again.This routine metal titanium is the metal-powder of human implantable tissue, and spheroidal particle metal titanium goods are mainly used in the human body particular anatomy and fill reparation, efficient liquid phase chromatographic analysis, the aspects such as carrier of blood plasma perfusion matrix and catalyzer.
Embodiment six
(1) (component is SiO to take by weighing the porcelain sand of 3 parts of weight
2, Al
2O
3, Fe
2O
5CaO, MgO etc.) under well-beaten condition, add in the dimethylacetamide solvent that contains 8% lithium chloride of 1000 parts of weight, after treating that porcelain sand evenly is suspended in the solvent, the chitin that adds 3 parts of weight after fully stirring is dissolved chitin fully, forms husky powder homodisperse of porcelain and stable mud;
With the sugar grain and weight ratio and the mud uniform mixing of the husky powder of porcelain of granular size 5 μ m, form sugared the mixture with mud by 10: 1;
(2) rapidly the mixture of above-mentioned sugar grain with chitin mud joined in the edible oil, under air-tight state, stir, the chitin mud that will contain the sugar grain is emulsified into spheroidal particle, after a few hours, gelatinizing-in-situ takes place and excipient down in the aerial water molecules effect of particle, then the spheroidal particle of moulding is transferred in the deionized-distilled water fully to clean and removed whole water-soluble substanceses and comprise solvent and perforating agent etc., adopt acetone and ethanol to clean and remove degrease, obtain containing the first base of chitin spheroidal particle of porcelain sand after the drying art breading;
(3) just base promptly contain the husky powder of porcelain the chitin spheroidal particle in a vacuum the pyrolysis in 5 hours of 450 ℃ of roasts remove chitin, again spheroidal particle is carried out the mechanical mill shaping, subsequently in a vacuum at 1200-1600 ℃ of following sintering after 2 hours, cool to 1200 ℃ with the cooling rate of 3 ℃ of per minutes and promptly obtain the vesicular structure spheroidal particle titanium metal goods that required aperture is 5 μ m with the stove cooling again.Can make the strainer that is 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.
Embodiment seven
(1) takes by weighing the metallic copper powder of 300 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 the metallic copper powder evenly is suspended in the solvent, the chitin that adds 3 parts of weight, after fully stirring is dissolved chitin fully, form metallic copper powder homodisperse and stable mud;
With the sugar grain and weight ratio and the mud uniform mixing of metallic copper powder of granular size 300 μ m, form sugared the mixture with mud by 1: 1;
(2) rapidly the mixture of above-mentioned sugar grain with chitin mud joined in the edible oil, under air-tight state, stir, the chitin mud that will contain the sugar grain is emulsified into spheroidal particle, after a few hours, gelatinizing-in-situ takes place and excipient down in the aerial water molecules effect of particle, then the spheroidal particle of moulding is transferred in the deionized-distilled water fully to clean and removed whole water-soluble substanceses and comprise solvent and perforating agent etc., adopt acetone and ethanol to clean and remove degrease, obtain the first base of chitin spheroidal particle of containing metal copper powder after the drying art breading;
(3) just base be the containing metal copper powder the chitin spheroidal particle in a vacuum the pyrolysis in 2 hours of 250 ℃ of roasts remove chitin, again spheroidal particle is carried out the mechanical mill shaping, subsequently in a vacuum at 1300-1600 ℃ of following sintering after 2 hours, cool to 1300 ℃ with the cooling rate of 3 ℃ of per minutes and promptly obtain the vesicular structure spheroidal particle metallic copper goods that required aperture is 300 μ m with the stove cooling again.The metallic copper strainer that can be used as the vehicle exhaust filtrating smoke dust.
The present invention uses the sintered inorganic powder of above embodiment instead other sintered inorganic powder when implementing, promptly can be made into the vesicular structure spheroidal particle goods of various inorganic materials.As: sintered 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 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.
In a word, inorganic (chitin) mud powder among the present invention refers to all sintered inorganic powders.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.Emulsifying agent removes available edible oil, whiteruss, also can adopt other any sintered inorganic powder/chitin mud to be had the liquid substance of emulsifying effect.When stirring, can control by stirring velocity and emulsifying agent temperature etc., and realization is to the control of spherical particle size.
The porous spherical granular inorganic material that the present invention makes, its granular size are 5～5000 μ m; Porosity is 5～90%; Vesicular structure can be made into dead front type or connectivity as required, and the aperture size size is divided into three grades: micropore≤1 μ m, mesopore 1～20 μ m, macropore 〉=20 μ m.Can be widely used in various filling material of bone, tissue engineering bracket material, slow releasing carrier of medication and filtering material etc.
The various inorganic materials goods that the present invention makes generally can directly use, but for accuracy requirement height (as sphericity), then can produce satisfactory product for use by further mechanical workout.
Sintered inorganic powder/chitin mud in preparation method's interstation process of the present invention, 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.Also can adopt other prior art to be mixed with and meet the sintered inorganic powder/chitin mud of requirement component of the present invention and proportioning for using.
Claims (6)
1, a kind of method for preparing porous spherical granular inorganic material, form by following steps successively:
(1) dimethylacetamide solvent that contains 4%～8% (weight) lithium chloride that is used to dissolve chitin by the sintered inorganic powder of the chitin of 3 parts of weight, 3～300 parts of weight and 100～1000 parts of weight is mixed with sintered inorganic powder/chitin mud;
(2) sintered inorganic powder/chitin mud of making of (1) step is joined sintered inorganic powder/chitin mud is had the liquid substance of emulsifying effect also is in the emulsifying agent, under air-tight state, stir, mud is emulsified into colloidal sol shape spheroidal particle, feed subsequently and contain the air of moisture or directly add water, make the spherical chitin colloidal sol shape particle that contains sintered inorganic powder under the water molecules effect, the gelatinizing-in-situ process take place and solidify excipient, behind the filtering emulsifying agent gel spheroidal particle abundant cleaning in water removed water miscible solvent, obtain containing the chitin spheroidal particle of sintered inorganic powder after the drying technology, as the first base that utilizes for subsequent technique;
What (3) (2) step is made contains sintered inorganic powder chitin spheroidal particle base just, and under 250～500 ℃ of temperature, chitin is removed in roast pyrolysis in 1～5 hour; Again spheroidal particle is carried out the mechanical mill shaping, sintering makes the abundant densification of spheroidal particle under the sintering temperature condition of sintered inorganic powder subsequently, promptly makes porous spherical particles inorganic materials goods.
2, a kind of method for preparing porous spherical granular inorganic material according to claim 1, its feature is as follows: in described (2) step, after water miscible solvent is removed in cleaning, before the drying process, also the gel spheroidal particle is fully cleaned in acetone and ethanol and remove degrease.
3, a kind of method for preparing porous spherical granular inorganic material according to claim 1 and 2, its feature is as follows:
After described (1) step is mixed with sintered inorganic powder/chitin mud, other gets particle diameter is that 5～500 μ m and the water-soluble but solid particulate that is insoluble to dimethylacetamide solvent are as perforating agent, with sintered inorganic powder/chitin mud by 1～10 to 1 weight ratio, join the mixture that uniform mixing in the mud makes perforating agent and mud; Again mixture is carried out the step in (2), (3) step, promptly make porous spherical granular inorganic material.
4, a kind of method for preparing porous spherical granular inorganic material according to claim 1 and 2, it is characterized in that: described sintered inorganic powder is a biological ceramic powder.
5, a kind of method for preparing porous spherical granular inorganic material according to claim 1 and 2, it is characterized in that: described sintered inorganic powder is the metal-powder of human implantable tissue.
6, preparation porous spherical granular inorganic material method according to claim 1 and 2, it is characterized in that: described sintered inorganic powder is ceramic powder or metal-powder.
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| CN102846408B (en) * | 2011-06-29 | 2015-09-16 | 北京大学第三医院 | Metallic granular body for bone-grafting filling |
| CN108772052B (en) * | 2018-05-30 | 2020-12-11 | 中国科学院宁波材料技术与工程研究所 | Titanium dioxide-based porous block and preparation method and application thereof |
| TWI680149B (en) | 2018-06-07 | 2019-12-21 | 國立臺北科技大學 | Porous microsphere and method for preparing the same |
| CN108855034B (en) * | 2018-06-15 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Size-adjustable photocatalytic functional microsphere and preparation method and application thereof |
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|---|---|---|---|---|
| JPH0551465A (en) * | 1991-08-23 | 1993-03-02 | Unitika Ltd | Method for producing spherical chitin |
| US5290752A (en) * | 1984-03-16 | 1994-03-01 | Unitika Ltd. | Method for preparation of a shaped chitin body containing a physiologically active substance |
| CN1091754A (en) * | 1993-12-20 | 1994-09-07 | 屈步华 | The manufacture method of spherical chitin |
| CN1105369A (en) * | 1994-01-14 | 1995-07-19 | 屈步华 | Process for producing ultramicro chitin particles |
| CN1424441A (en) * | 2002-12-27 | 2003-06-18 | 上海士林纺织有限公司 | Production of modified chitin and viscose fiber dope mixture and its product |
-
2004
- 2004-12-06 CN CNB2004100813997A patent/CN1321947C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290752A (en) * | 1984-03-16 | 1994-03-01 | Unitika Ltd. | Method for preparation of a shaped chitin body containing a physiologically active substance |
| JPH0551465A (en) * | 1991-08-23 | 1993-03-02 | Unitika Ltd | Method for producing spherical chitin |
| CN1091754A (en) * | 1993-12-20 | 1994-09-07 | 屈步华 | The manufacture method of spherical chitin |
| CN1105369A (en) * | 1994-01-14 | 1995-07-19 | 屈步华 | Process for producing ultramicro chitin particles |
| CN1424441A (en) * | 2002-12-27 | 2003-06-18 | 上海士林纺织有限公司 | Production of modified chitin and viscose fiber dope mixture and its product |
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|---|---|
| CN1636943A (en) | 2005-07-13 |
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