CN1255464A - Process for preparing porous ceramic material - Google Patents
Process for preparing porous ceramic material Download PDFInfo
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- CN1255464A CN1255464A CN 98125149 CN98125149A CN1255464A CN 1255464 A CN1255464 A CN 1255464A CN 98125149 CN98125149 CN 98125149 CN 98125149 A CN98125149 A CN 98125149A CN 1255464 A CN1255464 A CN 1255464A
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- ceramic material
- porous ceramic
- manufacture method
- tcp
- spongy bone
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 51
- 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 abstract description 25
- 241001465754 Metazoa Species 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 30
- 239000005416 organic matter Substances 0.000 claims description 9
- 239000001488 sodium phosphate Substances 0.000 claims description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 9
- 239000004254 Ammonium phosphate Substances 0.000 claims description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 230000029087 digestion Effects 0.000 claims 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims 1
- 229940048086 sodium pyrophosphate Drugs 0.000 claims 1
- VZWGHDYJGOMEKT-UHFFFAOYSA-J sodium pyrophosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O VZWGHDYJGOMEKT-UHFFFAOYSA-J 0.000 claims 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 206010010582 Congenital osteodystrophy Diseases 0.000 abstract 1
- 208000007652 Dysostoses Diseases 0.000 abstract 1
- 201000001324 Dysostosis Diseases 0.000 abstract 1
- 238000010009 beating Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001900 immune effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 241000283073 Equus caballus Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241000699666 Mus <mouse, genus> Species 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 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 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000001694 thigh bone Anatomy 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Materials For Medical Uses (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
A porous ceramic material such as HAP/beta-TCP, HAP/beta-TCP/SCP, beta-TCP/SCP, or beta-TCP, which can be used as filler for dysostosis is prepared from the animal's sponge bone through beating for removing organic substance, immersing in aqueous solution of phosphate, drying and sintering at temp higher than 900 deg.C.
Description
The present invention is the manufacture method that relates to stupalith, particularly about can be as the manufacture method of the porous ceramic material of bone filler.
It is the problem of the immunological rejection of organism that bone xenograft faces maximum problem now.Many researcher of past is with different processing modes, as freezing, boil or soak methods such as pharmaceutical chemicals, all can't get rid of the problem of xenogenesis bone immunological rejection effectively.People such as Mittelmeier then gave burn off in the mode of heat with the organic component that the meeting in the ox bone causes immunological rejection fully in 1988, and stayed the good inorganic composition of biological affinity.Because the inorganics in the bone is mainly oxyhydrogen-base apatite Ca10 (PO4) 6 (OH) 2 (hydroxyapatite; HAP), after organic composition is removed, remaining mineral composition will can form a solid ceramic structure by sintering as the same living embryo that forms with the powder metallurgy piezocrystallization in continuing heat-processed.And owing to take from the sponge bony site of ox, it possesses natural multi-pore structure, and porosity can reach more than 70% volume ratio.Therefore, utilizing this mode can obtain with HAP is the main natural porous ceramic material of forming.At present, it is extensive use of by the orthopaedics clinical operation, as the packing material of bone defective.
Because the inorganic composition in the sponge bone of giving birth to is mainly HAP, identical with the human skeleton composition, therefore, it will have good biological affinity in body, but, also β is because close with the composition of bone, and it will form stable flat permanent state in the bone environment, therefore, its biological activity also will lower thereupon.In recent years, existing investigator β-tricalcium phosphate (β-Ca that the molten property released is higher
3(PO
4)
2β-TCP) adds and forms the two-phase (stupalith of HAP/ β-TCP) among the HAP.Prove that through experimentation on animals this more monophasic HAP of biphase stupalith implantable bone organizational environment or β-TCP have better clinical effectiveness.
Purpose of the present invention is to provide a kind of manufacture method of porous ceramic material, and it can be in order to prepare excellent bone filler.
Another object of the present invention is to provide a kind of manufacture method of porous ceramic material, and it can obtain the porous ceramic material that different crystallization phasess are formed.
A further object of the present invention is to provide a kind of manufacture method of porous ceramic material, and it can control the crystallization phases proportion of composing of resulting porous ceramic material.
The manufacture method of porous ceramic material of the present invention, its step comprise that roughly (a) provides the spongy bone of an animal; (b) this spongy bone has been removed organic matter through heat treated; (c) spongy bone that will be somebody's turn to do through removing organic matter is soaked in the aqueous phosphatic; And (d) after drying,, and get the porous ceramic material that different crystallization phasess are formed with high temperature sintering more than 900 ℃.
According to manufacture method of the present invention, can produce the two-phase that contains HAP/ β-TCP or the three-phase porous ceramic material of HAP/ β-TCP/SCP.Even obtain the two-phase of β-TCP/SCP or the single-phase porous ceramic material of β-TCP.SCP is calcium phosphate sodium (NaCaPO
4).
The three-phase porous ceramic material of the two-phase of HAP/ β-TCP or HAP/ β-TCP/SCP, these contain the heterogeneous porous ceramic material of HAP, and the more monophasic HAP of implantable bone organizational environment or β-TCP have better clinical effectiveness.
Moreover, according to manufacture method of the present invention, and, obtain the two phase structure pottery that different ratios HAP/ β-TCP forms by the phosphatic interpolation of different concns.
For further specifying purpose of the present invention and feature, below in conjunction with embodiment the present invention is done one and introduce in detail,
The diagram simple declaration:
Fig. 1 is the spongy bone of the ox of embodiment one to ten, soaks the porous ceramic material relation of different concns sodium phosphate and gained respectively.
Fig. 2 is the spongy bone of the ox of embodiment 11 to 21, soaks the porous ceramic material relation of different concns ammonium phosphate and gained respectively.
The manufacture method of porous ceramic material of the present invention is that the spongy bone with animal is a material, and this spongy bone has been removed organic matter through heat treated, be soaked in the aqueous phosphatic then, after drying, with high temperature sintering more than 900 ℃, and get the two-phase porous ceramic material.
In the manufacture method of the present invention, the spongy bone of employed animal, so long as the spongy bone of animal gets final product, and without particular limitation.Mainly be comparatively suitable, for example can be ox, horse, pig, rabbit, mouse, chicken, duck, goose, fish etc. with the spongy bone of mammal.Its shape and size also need not limit; Generally speaking, then be cut into 0.1-10 cubic centimeter size as spongy bone with pig or ox.
Because manufacture method of the present invention is a work material with the spongy bone of animal, for preventing that the fried material internal that makes takes place produces a large amount of slight cracks in heat-processed, the organic matter that is contained in must the spongy bone with animal is removed.A lot of about the method for removing the organic matter in the animal skeleton, by this skill personage is familiar with, in method of the present invention, also there is not special restriction, as long as the organic matter in the bone can be removed.In embodiments of the invention, be to adopt methods of heating treatment, the spongy bone of animal is boiled six hours degreases that deoiled in boiling water, the ox bone behind the degrease again with step by step dehydration of alcohol it, and in 70 ℃ baking oven dry three days.The spongy bone of handling animal later places the platinum crucible High Temperature Furnaces Heating Apparatus to add the heat extraction organic composition, and its heat treated temperature rise rate is 5 ℃/min, and stops 6 hours in 800 ℃, with the organism of the spongy bone of sloughing animal fully.
In the manufacture method of the present invention, employed aqueous phosphatic, for example the alkali metal phosphate aqueous solution, alkaline earths aqueous phosphatic and phosphorous acid group salts solution such as ammonium phosphate (NH
4)
2HPO
4The aqueous solution.
Will slough organic and the spongy bone of unsintered animal is dipped in the different concns aqueous phosphatic, after drying, with high temperature sintering more than 900 ℃, and can control various porous ceramic materials.
About resultant porous ceramic material, the decision of each crystallization phases structure can be shown electron microscope (scanning electron microscope with X-ray winding analyser (XRD), infrared analysis spectrograph (FTIR) and scanning; SEM), and determine its composition and ratio,, do not giving unnecessary details one by one in this by this skill personage is familiar with.
The present invention gets nationality and helps specifying of following examples, and gets a better understanding, but claim of the present invention is not limited to these embodiment.Embodiment one
The Thigh bone of getting ox is cut into 1 cubic centimeter size with electric saw with it near the spongy bone at knee endoprosthesis place, boils six hours degreases that deoiled in boiling water, the ox bone behind the degrease again with step by step dehydration of alcohol it, and in 70 ℃ baking oven dry three days.Handle ox bone later and place the platinum crucible High Temperature Furnaces Heating Apparatus to add the heat extraction organic composition, its heat treated temperature rise rate is 5 ℃/min, and in 800 ℃ of stops 6 hours, to slough the organism in the ox bone fully.
To remove organic ox bone again, be dipped in concentration and be 0.01 not ear/liter sodium phosphate aqueous solution in 24 hours, takes out the back and inhale with filter paper and removes unnecessary sodium phosphate aqueous solution, and drying is removed moisture content in 70 ℃ baking oven.
Soak the ox bone of peroxophosphoric acid sodium water solution, through 1300 ℃ temperature sintering.Can obtain the two-phase porous ceramic material of HAP/ β-TCP.Phosphate concn that soaks and the porous ceramic material of gained relation can be referring to Fig. 1.Embodiment two to four
The step of imitative embodiment one, but change respectively with concentration be 0.02,0.03,0.04 not ear/liter sodium phosphate aqueous solution, soak and removed organic ox bone.Temperature sintering through 1300 ℃.Can obtain the two-phase porous ceramic material of HAP/ β-TCP respectively.Phosphate concn that soaks and the porous ceramic material of gained relation can be referring to Fig. 1.Embodiment five to nine
The step of imitative embodiment one, but change into respectively concentration be 0.05,0.06,0.07,0.08,0.09 not ear/liter sodium phosphate aqueous solution, soak and removed organic ox bone.Temperature sintering through 1300 ℃.Can obtain the three-phase porous ceramic material relation of HAP/ β-TCP/SCP respectively, can be referring to Fig. 1.Embodiment ten
The step of imitative embodiment one, but change into concentration be 0.01 not ear/liter sodium phosphate aqueous solution, soak and removed organic ox bone.Temperature sintering through 1300 ℃.Can obtain the two-phase porous ceramic material of β-TCP/SCP.Phosphate concn that soaks and the porous ceramic material of gained relation can be referring to Fig. 1.Embodiment 11 to 19
The step of imitative embodiment one, but change into concentration be 0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 not ear/liter ammonium phosphate solution, soak and removed organic ox bone.Temperature sintering through 1300 ℃.Can obtain the two-phase porous ceramic material of HAP/ β-TCP respectively.Phosphate concn that soaks and the porous ceramic material of gained relation can be referring to Fig. 2.Embodiment 20 to 21
The step of imitative embodiment one, but change into concentration be 0.9, and 1.0 not ear/liter ammonium phosphate solution, soak and removed organic ox bone.Temperature sintering through 1300 ℃.Can obtain the single-phase porous ceramic material of β-TCP respectively.Phosphate concn that soaks and the porous ceramic material of gained relation can be referring to Fig. 2.
By Figure 1 and Figure 2, can clearly show, according to manufacture method of the present invention, not only can produce various porous ceramic materials; And can see through the phosphoric acid salt kind and the concentration of soaking, and control resulting porous ceramic material crystallization phases kind and composition ratio.
In sum, the present invention really can the disclosed structure of mat reaching goal of the invention, tool novelty, progressive, with can supply industry applications, and be consistent with the patent of invention important document.Only, above those disclosed herein are preferred embodiment, and patent right category of the present invention is not all taken off in partial such as change or modification and come from technological thought of the present invention and be easy to the person of knowing by inference by the personage who has the knack of this skill.
Claims (12)
1, a kind of manufacture method of porous ceramic material is characterized in that, it comprises:
(a) provide the spongy bone of an animal;
(b) this spongy bone has been removed organic matter through heat treated;
(c) spongy bone that will be somebody's turn to do through removing organic matter is soaked in the aqueous phosphatic;
And
(d) after drying, with high temperature sintering more than 900 ℃, and get porous ceramic material.
2, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein the spongy bone of this animal is the spongy bone for ox.
3, the manufacture method of a kind of porous ceramic material as claimed in claim 1, it is characterized in that wherein the heat treated of step (b) is to place the boiling water digestion with the degrease that deoils spongy bone, after taking out drying, be heated to 600 ℃-800 ℃ to slough organic matter in the spongy bone.
4, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein this aqueous phosphatic is to be the alkali metal phosphate aqueous solution, the alkali earth metal phosphate aqueous solution or ammonium phosphate (NH
4)
2HPO
4The aqueous solution.
5, the manufacture method of a kind of porous ceramic material as claimed in claim 4 is characterized in that, wherein this aqueous phosphatic is to be sodium phosphate (sodiumpyrophosphate, Na
4P
2O
7.10H
2O, NP) aqueous solution.
6, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein this aqueous phosphatic is to be sodium phosphate aqueous solution, its concentration be between 0.001-0.10 not ear/liter between.
7, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein this porous ceramic material is the two-phase porous ceramic material for HAP/ β-TCP.
8, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein this porous ceramic material is the three-phase porous ceramic material for HAP/ β-TCP/SCP.
9, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein the spongy bone of step (a) is through being cut into 0.1-10 cubic centimeter size.
10, the manufacture method of a kind of porous ceramic material as claimed in claim 1, it is characterized in that, wherein the concentration of the sodium phosphate aqueous solution of step (c) be between 0.001-0.09 not ear/liter between, and the high temperature sintering temperature of step (d) is between 900-1350 ℃, and gets the two-phase porous ceramic material of HAP/ β-TCP.
11, the manufacture method of a kind of porous ceramic material as claimed in claim 1 is characterized in that, wherein this aqueous phosphatic is to be ammonium phosphate solution.
12, the manufacture method of a kind of porous ceramic material as claimed in claim 11, it is characterized in that, wherein the aqueous phosphatic of step (c) is to be ammonium phosphate solution, its concentration be between 0.005-0.8 not ear/liter between, and the high temperature sintering temperature of step (d) is between 900-1350 ℃, and gets the two-phase porous ceramic material of HAP/ β-TCP.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125149A CN1069887C (en) | 1998-11-26 | 1998-11-26 | Process for preparing porous ceramic material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125149A CN1069887C (en) | 1998-11-26 | 1998-11-26 | Process for preparing porous ceramic material |
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|---|---|
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| CN1069887C CN1069887C (en) | 2001-08-22 |
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|---|---|---|---|
| CN98125149A Expired - Fee Related CN1069887C (en) | 1998-11-26 | 1998-11-26 | Process for preparing porous ceramic material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450973C (en) * | 2003-10-07 | 2009-01-14 | 庆东塞拉泰克有限公司 | Manufacturing method of ceramic body with excellent adiabatic capacity |
| CN109095446A (en) * | 2018-08-27 | 2018-12-28 | 上海应用技术大学 | A kind of biophasic calcium phosphate ceramic material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340307C (en) * | 2004-06-03 | 2007-10-03 | 瑞安大药厂股份有限公司 | Manufacturing method of chinky ceramic skeleton filling material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049202C (en) * | 1991-07-22 | 2000-02-09 | 中南工业大学 | Process for mfg. porous ceramic materials with biological activity |
| CN1078452A (en) * | 1992-09-21 | 1993-11-17 | 同济医科大学附属同济医院 | Built-in anti-tuberculosis anti-cancer anti-inflammation slow released material |
-
1998
- 1998-11-26 CN CN98125149A patent/CN1069887C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450973C (en) * | 2003-10-07 | 2009-01-14 | 庆东塞拉泰克有限公司 | Manufacturing method of ceramic body with excellent adiabatic capacity |
| CN109095446A (en) * | 2018-08-27 | 2018-12-28 | 上海应用技术大学 | A kind of biophasic calcium phosphate ceramic material and preparation method thereof |
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|---|---|
| CN1069887C (en) | 2001-08-22 |
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