CN1603284A - Ceramic with submicron micropore and method for preparing same - Google Patents
Ceramic with submicron micropore and method for preparing same Download PDFInfo
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- CN1603284A CN1603284A CN 200410086707 CN200410086707A CN1603284A CN 1603284 A CN1603284 A CN 1603284A CN 200410086707 CN200410086707 CN 200410086707 CN 200410086707 A CN200410086707 A CN 200410086707A CN 1603284 A CN1603284 A CN 1603284A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000919 ceramic Substances 0.000 title claims abstract description 24
- 229920002472 Starch Polymers 0.000 claims abstract description 71
- 235000019698 starch Nutrition 0.000 claims abstract description 71
- 239000008107 starch Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 21
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 238000002309 gasification Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 2
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 2
- 239000004571 lime Substances 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 230000008520 organization Effects 0.000 abstract 1
- 238000001356 surgical procedure Methods 0.000 abstract 1
- 239000003053 toxin Substances 0.000 abstract 1
- 231100000765 toxin Toxicity 0.000 abstract 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 17
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
- 230000035699 permeability Effects 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 8
- 239000011800 void material Substances 0.000 description 8
- 241000700605 Viruses Species 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000315672 SARS coronavirus Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000721 bacterilogical effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
The invention relates to a method to produce ceramics with submicron micropore, which belongs to abio-non-metallic material, surgery recovering and organization project transplanting fields. The ceramics uses water-soluble starch as micropore making medium adding water for dissolution, mixing phosphor hydroxyl lime powder and sintering. The method adopts water-soluble starch as micropore making medium, adding water to form solution and mixing the phosphor hydroxyl lime powder, the quantity of adding is 10vol.% to 80vol.% to the total solid content. Heating the mixture to decompose and gasify water-soluble starch, the ceramics with submicron micropore would be gained. The ceramics is no pollution and no toxin. The method is simple technology, low cost and convenient for popularizing.
Description
Technical field
The invention belongs to ceramic and surgical repair and organizational project graft materials field, particularly be used to prepare the manufacture method of the pottery of handling the required filtering material of the waste water and gas that contains bacterium and virus with the fine hole of submicron order.
Background technology
The main method of the preparation micropore hydroxylapatite ceramic of report has at present:
(1) by Wang Xinyu, Han Yingchao, Dai Honglian, Li Shipu is published on " Chinese biological engineering in medicine journal ", 2003, vol.22, No.3 276 ~ 278, be entitled as: the method in " preparation of the imitative bone material of porous gradient-structure hydroxyapatite and microscopic appearance observation ", this method is pressed certain mass than mixing with pore-creating media citric acid particle and hydroxyapatite raw material powder, adds less water and polyvinyl alcohol and makes binding agent, behind the compression molding, earlier, discharge the pore-creating media, again sintering at a certain temperature through the low temperature biscuiting.It is that 3～5 μ m minute apertures and a large amount of aperture are the spherical pore of 300～500 μ m that the pottery of preparing contains a small amount of aperture.
(2) by Yao Xiumin, Tan Shouhong, the east of a river is bright to be published in " functional materials and device journal " goes up (calendar year 2001, Vol.7, No.2,153 ~ 156), is entitled as: the method in " Study on Preparation of the porous hydroxyapatite of controllable aperture ".Polymethylmethacrylate (PMMA) particle after this method employing screening mixes with the hydroxy apatite powder ball milling as the pore-creating media, and oven dry aftershaping, sintering can prepare the porous hydroxyapatite pottery of pore size distribution from several microns to 200 μ m.
(3) by Yao Xiumin, Tan Shouhong, the east of a river is bright to be published in " Journal of Inorganic Materials " upward (2000, Vol.15, No.3,467～472), be entitled as the method in " preparation of porous hydroxyapatite pottery ", this method is: hydroxy apatite powder and powdered carbon ball milling mixed, and oven dry aftershaping, sintering, can make the aperture is the porous hydroxyapatite pottery of 2～200 μ m.
(4) be published in " Journal of the EuropeanCeramic Society " by O.Lyckfeldt and J.M.F.Ferreira:J. and go up (Vol.18 in 1998, p.131 ~ 140), be entitled as the method in " Processing of PorousCeramics by Starch Consolidation ".This method is: with hydroxy apatite powder with mix the post slip-casting moulding as the common starch of pore-creating media, utilize the gelatination property of starch that base substrate is solidified, carry out sintering by the temperature of setting after the drying, the air vent aperture that makes is tens of to microns up to a hundred, and the porous hydroxyapatite pottery of higher apparent porosity is arranged.
Aforesaid method all adopts the solid phase particles that can decompose in certain temperature as the pore-creating media, the diameter of the hole that forms and solid phase pore-creating particulate size are quite or greater than solid phase pore-creating particulate size, generally between 2～300 μ m, pore size distribution range is wide in the aperture, and the aperture is relatively large.Owing to reasons such as reunions, therefore general bigger the and dispersion of solid phase particles size as the pore-creating media is difficult to prepare the pottery with submicron order hole.
Summary of the invention
The objective of the invention is provides a kind of pottery with submicron order micropore and preparation method thereof for overcoming the weak point of existing procucts and technology.The present invention adopts water soluble starch to prepare the fine hole of a large amount of submicron orders as the pore-creating media.This pottery totally nontoxic is harmless, can filter or adsorb very tiny bacterium of size and virus more effectively.This method technology is simple, with low cost, easy to utilize.
A kind of pottery with submicron order micropore that the present invention proposes is characterized in that, is the pore-creating media with the water soluble starch, after being dissolved in water, forms with hydroxy apatite powder mixing moulding, sintering.
The scope of above-mentioned water soluble starch addition can be the 10vol.%～80vol.% of total solid load.
Also can be added with the common starch particle that in sintering range, can decompose in the above-mentioned mixing moulding process.
A kind of preparation method with pottery of submicron order micropore that the present invention proposes is characterized in that, may further comprise the steps:
1) adopt water soluble starch as the pore-creating media, formation solution is dissolved in water;
2) with water soluble starch solution and hydroxy apatite powder mixing moulding, the scope of described water soluble starch addition is the 10vol.%～80vol.% of total solid load;
3) make water soluble starch decompose gasification the water soluble starch of moulding and hydroxy apatite powder mixture heating up after, sintering obtains having the pottery of submicron order micropore.
The above-mentioned the 3rd) temperature rise rate of the Heating temperature in the step between 100 ℃ to 550 ℃ preferably is no more than 30 ℃/h.
The above-mentioned the 2nd) step is added in the common starch particle that can decompose in the sintering range in water soluble starch solution and ceramic powder mixing moulding process.
Principle of the present invention:
Get fine hole owing to be difficult to make a large amount of submicron orders by the method for adding decomposable solid phase particles manufacturing pore, this be because the screening of solid phase particles to reach 10 μ m following and difficult, even obtained molecule also owing to agglomeration becomes bigger coacervate, the present invention uses water soluble starch solution then can avoid the problems referred to above as the pore-creating media by discovering.Water soluble starch obtains water-fast common starch after sulfation or carboxymethylation processing, this starch is widely used in pharmacy and packaging industry, has advantage nontoxic, harmless, that output is big, price is low, is a kind of industrial raw material that conveniently is easy to get.Water soluble starch at room temperature can be water-soluble fully, forms water white solution, after mixing with powder stock, and the drying dehydration, starch is coated on the powder granule surface, and crosslinking curing takes place, with powder adhesion together.The agglutinating powder through pulverize, dry-pressing formed after, starch granules is evenly dispersed between the powder granule, through staying extremely trickle hole after degreasing, the sintering, it is much smaller that its aperture ratio adds other pore-creating solid phase particles, can reach sub-micrometer scale.
Analyze as can be known by water soluble starch being carried out thermal weight loss etc., water soluble starch in air since 250 ℃ of decomposition, and then burning, generation CO, CO
2Gas, its perfect combustion pyrolysis temperature is no more than 550 ℃.The contriver is by relatively in the normal pressure atmospheric atmosphere, and different temperature rise rate below 550 ℃ is to the moulding and the Effect on Performance of product, and obtaining rational temperature rise rate is to be no more than 30 ℃/h between 100 ℃～550 ℃.Temperature rise rate is too fast between 100 ℃～550 ℃, is unfavorable for the complete decomposition combustion of water soluble starch, and the microvoid structure of product is relatively poor, and the CO of burning generation, CO
2Gas expansion is too fast to be caused the product buckling deformation easily even subsides.Though this explanation only mentions the temperature rise rate of the amylolysis gasification in the normal pressure air atmosphere, but by heating up in vacuum environment or pressurization heats up or biscuit is fixing suppressing its craze and transfiguration, and other can keep the way of biscuit shape can further improve the upper limit of this temperature rise rate under the condition of being rapidly heated.
The pyrolysis temperature of water soluble starch generally is lower than the sintering temperature of hydroxylapatite ceramic, so the fine hole of submicron order that stays after the amylolysis gasification can dwindle even closure owing to growing up of crystal grain in follow-up sintering process.The present invention adds content to after forming the influence of number cells purpose by more different starch, and the interpolation scope that obtains water soluble starch is preferably the 10vol.%～80vol.% of total solid load.The addition of water soluble starch is during less than the 10vol.% of total solid load, and prepared hydroxylapatite ceramic grain growing is abundant, densified sintering product, and hole is less, and is mostly the disconnected hole of holding one's breath, and the void content of product is lower, ventilation property is relatively poor; The addition of water soluble starch is during greater than the 80vol.% of solid load, and prepared pottery subsides in sintering process easily, and formed product is relatively poor.
Find after the influence of the solid phase particles that the present invention further can decompose when being added on sintering in water soluble starch and hydroxy apatite powder blended process by research to the void content of product and Gas permeability, the suitable solid phase particle does not influence the formation of the fine hole of submicron order, does not influence the number of micropore substantially; And the uniform solid phase particles of size can disperse to form the pore of respective number and size in pottery after decomposing gasification, above-mentioned submicron micropore played the effect of connection, thereby reach the ceramic void content of control and the purpose of Gas permeability.This solid phase particles can be organism such as PMMA, paraffin, and common starch etc. also can be inorganicss such as powdered carbon.In various solid phase particles, common starch is preferable selection.Common starch is water insoluble, and totally nontoxic is harmless, with water soluble starch decomposition gasification character about the same is arranged, and sintering process need not to change.The even size distribution of common starch, particle shape is better, and the pore size and the starch granules of formation are suitable, and pore quantity is relevant with the addition of starch, thereby can control the void content and the Gas permeability of pottery preferably.
Though above-mentioned explanation only mentions hydroxylapatite ceramic, form mechanism as can be known from micropore of the present invention, the present invention also can be used for making other the micropore ceramics with submicron hole.
Characteristics of the present invention and technique effect
(be about 0.5 micron because the size of bacterium that is run in the daily life and virus is very little as the intestinal bacteria diameter, and SARS virus diameter 80～140 nanometers only), require the aperture of filtering material as far as possible little, could filter or adsorb bacterium and virus more effectively like this.The present invention adopts water soluble starch to prepare the hydroxylapatite ceramic that contains the fine hole of a large amount of submicron orders as the pore-creating media, can form the fine hole of submicron order effectively, helps filtering virus and bacterium.Water soluble starch does not have toxicity fully, and the product safety of preparation is harmless.The present invention adopts hydroxyapatite as raw material, and itself is also fully harmless and with body excellent biological compatibility is arranged to human body, and hydroxyapatite has adsorption (Japanese Patent JP2002053812-A number) to bacterium and virus simultaneously.
Further in order to satisfy the needs of different filtration conditions, the method of the solid phase particles that can decompose during by the interpolation sintering, especially adopt common starch as solid phase particles, the void content and the Gas permeability of the simple and effective control micropore hydroxylapatite ceramic of energy, and common starch itself is also nontoxic.
The inventive method technology is simple, and is with low cost, easy to utilize.
Embodiment
The ratio that embodiment 1 usefulness measuring tank is measured volume is 6: 4 water soluble starch (room temperature water solubleness 〉=96%, pH value 5～8, moisture≤12%, ash content≤0.5%) and hydroxy apatite powder (mean particle size is that 80 μ m, average grain size are 90nm), the addition that is water soluble starch is the 60vol.% of total solid load, with slight vibrations measuring tank the flat volume reading of powder heap is as the criterion when measuring.Water soluble starch is dissolved the colourless transparent solution that obtains fully with deionized water, with the hydroxy apatite powder ball milling be mixed and made into slurry, the slurry drying, grind, sieve after, dry-pressing formed.Compressing tablet is placed the chamber type electric resistance furnace sintering, and the temperature rise rate between 100 ℃～500 ℃ is 30 ℃/h, and the temperature rise rate between 550 ℃～1200 ℃ is 200 ℃/h, furnace cooling behind 1200 ℃ of sintering 3h.The micropore ceramics outward appearance that sinters into is regular, and by measuring diameter 8.6mm, thickness 0.7mm sample is exerted pressure pressure when the fracture as the method for valence along diametric(al), and its result is 11.5N.The apparent density of ceramic body is 2.01g/cm
3, total porosity is 36%, and the perforate void content is 20%, and Gas permeability is 0.11 * 10
-6m
2SEM observes and shows most micropore size below 1 μ m, and the aperture of the micropore that minority is communicated with also only is several microns.The pore size distribution of submicron order micropore is more concentrated, between 0.6 μ m～1 μ m.The bacteriological filtration test shows that this pottery of thickness 2.4mm can filter intestinal bacteria fully.
It is 8: 2 that embodiment 2 adopts the ratio of the volume of water soluble starch and hydroxy apatite powder, and promptly the addition of water soluble starch is the 80vol.% of total solid load.Other condition is with embodiment 1.The micropore hydroxylapatite ceramic outward appearance that obtains like this is regular, and breaking tenacity is 3.2N, and apparent density is 1.3g/cm
3, total porosity is 58%, and apparent porosity is 31%, and during less than 20ml/min, recording Gas permeability is 0.13 * 10 at gas flow
-6m
2SEM observes and shows submicron pore pattern and embodiment 1 basically identical, and quantity wants many than embodiment 1.
The ratio that embodiment 3 is measured volume is 3: 4: 3 water soluble starch, hydroxy apatite powder and a common starch (median size is 43 μ m), the addition that is water soluble starch is the 30vol.% of total solid load, and the addition of common starch is the 30vol.% of total solid load.Water soluble starch is dissolved the colourless transparent solution that obtains fully with deionized water, mix with hydroxy apatite powder and common starch ball milling, other conditions are with embodiment 1.The micropore ceramics outward appearance that obtains is regular, and breaking tenacity is 14.8N, and apparent density is 1.55g/cm
3, total porosity is 50%, and the perforate void content is 38%, and Gas permeability is 0.55 * 10
-6m
2SEM observes and shows except the micropore existence of a large amount of submicron orders, and also have a lot of micron-sized connection pores, does not wait from several microns to tens microns in the aperture.SEM observes also and confirms, the gross blow hole conducting original mutual isolated micropore, thereby improved ceramic void content and Gas permeability.
The ratio of embodiment 4 water soluble starchs, hydroxy apatite powder and common starch three's volume is 3: 5.5: 1.5, and promptly the addition of water soluble starch is the 30vol.% of total solid load, and the addition of common starch is the 15vol.% of total solid load.Other condition is with embodiment 3.The micropore hydroxylapatite ceramic outward appearance that obtains like this is regular, and breaking tenacity is 40.8N, and apparent density is 2.17g/cm
3, total porosity is 35%, and apparent porosity is 23%, and Gas permeability is 0.30 * 10
-6m
2SEM observe to show submicron pore pattern and quantity and embodiment 3 basically identicals, and the quantity of connection pore will be lacked than the product of embodiment 3.
Comparative example
Comparative example 1 mean particle size is that 80 μ m, average grain size are after the hydroxy apatite powder ball milling of 90nm, through sieve, dry-pressing formed.Compressing tablet is placed the chamber type electric resistance furnace sintering, and the temperature rise rate between 100 ℃～500 ℃ is 30 ℃/h, the 200 ℃/h of temperature rise rate between 550 ℃～1200 ℃, furnace cooling behind 1200 ℃ of sintering 3h.The micropore ceramics outward appearance that sinters into is regular, and apparent density is 2.96g/cm
3, total porosity is 5%, Gas permeability is 0.SEM observes and shows that grain growing is abundant, and tissue tight rarely has hole.
Comparative example 2 water soluble starchs are 6: 4 with the ratio of the volume of hydroxy apatite powder, and promptly the addition of water soluble starch is the 60vol.% of total solid load.Temperature rise rate between 100 ℃～550 ℃ is 60 ℃/h, and other condition is with embodiment 1.The micropore ceramics moulding that obtains like this is bad, and warpage appears in profile, and the part that has efflorescence occurs because of densified sintering product not.
Comparative example 3 conditions are with embodiment 2, and when product was measured at Gas permeability, when gas flow surpassed 20ml/min, the product air penetrability increased suddenly, showed product because the excessive internal pore structure of gaseous tension destroys.The undercapacity of proof product is to satisfy the traffic requirement of most of practical applications.
Claims (6)
1, a kind of pottery with submicron order micropore is characterized in that, is the pore-creating media with the water soluble starch, after being dissolved in water, forms with hydroxy apatite powder mixing moulding, sintering.
2, pottery as claimed in claim 1 is characterized in that, the scope of water soluble starch addition is the 10vol.%～80vol.% of total solid load.
3, pottery as claimed in claim 1 is characterized in that, also is added with the common starch particle that can decompose in sintering range in the mixing moulding process.
4, a kind of preparation method with pottery of submicron order micropore is characterized in that, may further comprise the steps:
1) adopt water soluble starch as the pore-creating media, formation solution is dissolved in water;
2) with water soluble starch solution and hydroxy apatite powder mixing moulding, the scope of described water soluble starch addition is the 10vol.%～80vol.% of total solid load;
3) make water soluble starch decompose gasification the water soluble starch of moulding and hydroxy apatite powder mixture heating up after, sintering obtains having the pottery of submicron order micropore.
5, preparation method as claimed in claim 4 is characterized in that, the described the 3rd) in the step during heating temperature rise rate of temperature between 100 ℃ to 550 ℃ be no more than 30 ℃/h.
6, preparation method as claimed in claim 4 is characterized in that, the described the 2nd) step is added in the common starch particle that can decompose in the sintering range in water soluble starch solution and ceramic powder mixing moulding process.
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| CN 200410086707 CN1251999C (en) | 2004-10-29 | 2004-10-29 | Ceramic with submicron micropore and method for preparing same |
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| CN 200410086707 CN1251999C (en) | 2004-10-29 | 2004-10-29 | Ceramic with submicron micropore and method for preparing same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967750A (en) * | 2016-05-06 | 2016-09-28 | 郑伟阳 | High-adsorptivity ceramic and preparation method thereof |
| CN111233457A (en) * | 2020-01-19 | 2020-06-05 | 陕西科技大学 | Method for preparing porous magnesium-doped HA-based composite material based on carbon fibers as pore-forming agent and reinforcement |
| CN115572177A (en) * | 2021-07-05 | 2023-01-06 | 陈月端 | Bone filler prepared from natural calcium-containing waste and preparation method thereof |
-
2004
- 2004-10-29 CN CN 200410086707 patent/CN1251999C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967750A (en) * | 2016-05-06 | 2016-09-28 | 郑伟阳 | High-adsorptivity ceramic and preparation method thereof |
| CN111233457A (en) * | 2020-01-19 | 2020-06-05 | 陕西科技大学 | Method for preparing porous magnesium-doped HA-based composite material based on carbon fibers as pore-forming agent and reinforcement |
| CN111233457B (en) * | 2020-01-19 | 2022-02-08 | 陕西科技大学 | Method for preparing porous magnesium-doped HA-based composite material based on carbon fibers as pore-forming agent and reinforcement |
| CN115572177A (en) * | 2021-07-05 | 2023-01-06 | 陈月端 | Bone filler prepared from natural calcium-containing waste and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1251999C (en) | 2006-04-19 |
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