CN1299778C - Medical surface bioactive ceramic material and its prepn - Google Patents
Medical surface bioactive ceramic material and its prepn Download PDFInfo
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- CN1299778C CN1299778C CNB2004100524380A CN200410052438A CN1299778C CN 1299778 C CN1299778 C CN 1299778C CN B2004100524380 A CNB2004100524380 A CN B2004100524380A CN 200410052438 A CN200410052438 A CN 200410052438A CN 1299778 C CN1299778 C CN 1299778C
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- ceramic material
- coating
- calcium
- phosphorus
- bioactive ceramic
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Abstract
The present invention relates to a medical surface bioactive ceramic material and a preparation method thereof. The preparation method of the medical surface bioactive ceramic material comprises the following steps: solution comprising phosphorus or calcium or sol comprising phosphorus or calcium is coated on the surface of pre-burnt porous ceramic or pre-burnt microcrystalline glass; a sintering process is carried out under high temperature; a sintering product is put in atmosphere comprising carbon and steam, and a heat treatment is carried out under the temperature of 300 DEG C to 1200 DEG C. The prepared medical surface bioactive ceramic material has the advantages of good bioactivity, high mechanical strength, firm surface bioactivity layer and basal body combination, etc.
Description
Technical field
The present invention relates to medical bio active material field, specifically be meant a kind ofly to be used for sclerous tissueses such as joint, root of the tooth, bones and organ is repaired, the preparation method of consolidation and alternate medical surface bioactive ceramic material.
Background technology
Medical biological ceramic material is divided into biologically inert, biological activity two big classes, and bio-inert ceramic materials mainly refers to mechanical property and the good ceramic materials of biocompatibility such as aluminium oxide, zirconium oxide, silicon nitride, carborundum and carbonaceous material; Biological active ceramic material mainly refers to the hydroxyapatite to be representative, good biocompatibility, can stimulate or induce the osseous tissue growth and can form the synosteotic ceramic material that contains phosphorus calcium with osseous tissue that bioactive ceramics can be divided into degradable type and non-degradable type according to the degradation speed in organism again.Bio-inert ceramic can not produce chemical bond with osseous tissue, can only be surrounded by fibrous connective tissue, its with osseous tissue combine and to the promotion of osseous tissue growth not as bioactive ceramics, the mechanical property of bioactive ceramics and chemical stability are then not as bio-inert ceramic.Therefore, in order to make full use of the advantage of this two classes ceramic material, various compound bioceramices have just occurred, can prepare mechanical property better and have certain bioactive ceramic material by the raw material of biological activity and bio-inert ceramic materials is mixed, apply bioactive ceramics on the surface of bio-inert ceramic materials by distinct methods and can prepare biological activity and all reasonable bioceramic of mechanical property.Hydroxyapatite, decomposes and irreversible dehydroxylation process takes place at 1350 ℃ of hydroxyapatite just than dehydroxylation more quickly 800 ℃ of beginnings.And in general, the firing temperature of bio-inert ceramic is all than higher, with bioactive ceramics compound after, under higher firing temperature, hydroxyl is lost, bioactive ceramics destructurized, biological activity reduces, thus the combining of influence and osseous tissue.
Apatite mineral mainly is non-stoichiometric phosphorite crystal in human body natural's bone, and oligo-element such as CO are arranged
3 2-, Na
+And F
-Plasma enters in the apatite crystalline grain in the mode of replacing, and topmost substitute is CO
3 2-, the about 5-8% of its mass percent in the bone mineral.The existence of carbonate has and helps the physiological need that bone should have certain stability may normally be absorbed again.Carbonated hydroxyapatite (Hydroxy-carbonate-apatite is called for short HCA) has the The Nomenclature Composition and Structure of Complexes very similar to the natural bone inorganic constituents, and excellent biological compatibility is arranged, and is one of the most promising bone alternate material.And many studies show that, carbonated hydroxyapatite has better biocompatibility than hydroxyapatite, but because its mechanical property is relatively poor, bending strength and fracture toughness index all are lower than the human body compact bone, thereby have limited its use at the heavier position of body burden.In addition, carbonate at high temperature is easy to decompose and breaks away from, and adopts common ceramic preparation, is difficult to obtain containing the ceramic material of carbonic acid hydroxyapatite.At present, as the coating of biomaterial, generally be that the low temperature mineralising generates carbonated hydroxyapatite in oversaturated solution, itself and high base strength are very low.
Titanium alloy is the biomedical metal material that biocompatibility is better, specific strength is high, elastic modelling quantity is lower.In recent years, be that the bioactivity coatings composite study of matrix and application have obtained progress preferably with the titanium alloy.The bioactivity coatings of titanium alloy surface is generally with plasma spray coating process preparation, also the report of method preparations such as other hot-spraying technique such as useful flame-spraying and differential arc oxidation, low temperature mineralising.The weak point of sclerous tissues's implant of this kind surface bioactive is that Bond Strength of Coating is on the low side, and along with the prolongation of implant into body time, coating shedding causes the incident of failure to increase gradually.Because titanium alloy can not be high temperature resistant, with the titanium alloy coating of matrix preparation, can not at high temperature heat-treat, based on mechanical inlay resultant force, do not have the strong chemical bond combination between coating and the titanium alloy substrate, thereby bond strength is not high.
Summary of the invention
The present invention is directed to the existing existing above-mentioned deficiency of medical surface bioactive material, from the angle of its biology of comprehensive raising and mechanical property, the preparation method of the medical surface bioactive ceramic material that provide that a kind of biologically active is good, mechanical strength is high, surface bioactive layer and matrix bond is firm.
The present invention also aims to provide the medical surface bioactive ceramic material of described method preparation.
Medical surface bioactive ceramic material of the present invention and preparation method thereof, be that the solution of calcic phosphorus or colloidal sol are coated in porous ceramics or devitrified glass surface through pre-burning, sintering at high temperature again, place the atmosphere of carbon containing and steam then, heat-treat at 300 ℃-1200 ℃.
The inventive method comprises the steps: in more detail
(1) with the pottery of molding or devitrified glass matrix 700-1300 ℃ of following pre-burning;
(2) being mixed with calcium/phosphorus mol ratio with the chemical compound of calcium, phosphorus is 1.2: 1-1.8: 1 solution or colloidal sol;
(3) solution that step (2) is obtained or colloidal sol cover the billet surface formation coating that step (1) obtains, and dry back is at 800-1800 ℃ of sintering;
(4) material that obtains of step (3) places and contains steam and CO or contain steam and CO
2Atmosphere in, handle down at 300-1200 ℃.
In the step (3), can cover the billet surface that step (1) obtains by solution or the colloidal sol that vaccum pulp absorbing, gunite, coating or dipping obtain step (2), to form the coating of one deck calcic, phosphorus substance, wherein part calcium, phosphorus substance will be inhaled in the pore of matrix, make matrix and coating in conjunction with firmly, reach the purpose that improves anchoring strength of coating;
After step (1) pre-burning formation contained pore and the base substrate of certain intensity is arranged, this base substrate can be cold worked into required shape;
The chemical compound of the calcium described in the step (2) is meant can be water-soluble or other solvent or the calcium containing compound that can decompose in water or other solvent, for example Ca (NO
3)
2, Ca (OH)
2, CaCO
3, CaCl
2, Ca (OC
2H
5)
2Deng.
The chemical compound of phosphorus is meant can be water-soluble or other solvent or the phosphorus-containing compound that can decompose in water or other solvent, for example (NH
4)
2HPO
4, H
3PO
4, K
2HPO
4, Na
2HPO
4, (CH
3O)
3PO
4Deng.
The chemical compound of calcium and phosphorus dissolved respectively or hydrolysis in solvent after, by ammonia regulate contain calcium solution pH value to 10-12, then stir and suitable temperature under dropping contain solution or the colloidal sol that calcium solution can obtain calcic phosphorus.
Can impel material surface to generate carbonated hydroxyapatite and other podolite after step (4) is handled, make medical surface bioactive ceramic material of the present invention.
The present invention compared with prior art has following advantage and effect:
1. because the pore of coating material by the pre-burning matrix entered into matrix inside, and coating is very firm with combining of matrix, material has very excellent mechanical property.
2. coating layer thickness and pattern are easy to control.The number of times of the solution by adjusting calcic, phosphorus and the concentration of colloidal sol and vaccum pulp absorbing, gunite, coating or dipping can obtain the coating of different-thickness and different surfaces pattern.
There is the material of calcium phosphorous compound coating containing steam and CO or CO on agglomerating surface
2Atmosphere in heat treatment, the hydroxyapatite that is difficult in the high-temperature sintering process exist is generated, and makes carbonate enter into coating, generate the high carbonated hydroxyapatite of biological activity and other podolite.
4. overcome the matrix that other coating production (as thermal spraying, low temperature mineralising etc.) causes and coating adhesive strength is low, the shortcoming that comes off easily behind the implant into body.In addition, the thermal expansion coefficient difference of pottery and devitrified glass matrix and face coat is less, and the internal stress of coating and matrix is less after the high-temperature calcination.
The specific embodiment
Embodiment 1
The first step adopts Ca (NO
3)
24H
2O and H
3PO
4Be raw material, press calcium-phosphorus ratio configuration in 1.2: 1 aqueous solution.
Second step will be cold worked into required shape through the alumina substrate of 700 ℃ of pre-burnings, after cleaning and the drying, place Dewar bottle to be evacuated to 10
-3MPa, the solution that feeds first step preparation then is in this Dewar bottle.
The 3rd step was taken out alumina substrate, and is dry down at 120 ℃.
The 4th step will be through the alumina substrate of the 3rd step processing, twice of second step of repetition and the 3rd step.
The 5th step burnt till the matrix of handling through the 4th step and obtains the surface for containing the material of calcium phosphorous compound coating under 800 ℃.Programming rate when burning till is 10 ℃/minute., under 1600 ℃ of temperature, be incubated 2h, cool to room temperature then with the furnace.
The 6th step had the material of calcium phosphorous compound coating to place quartz tube furnace in agglomerating surface, fed the N that contains 10% (v/v) steam and 2% (v/v) CO in quartz tube furnace
2Gas is warming up to 300 ℃ with 10 ℃/minute speed, at 300 ℃ of insulation 20h, cools to room temperature then with the furnace.
Through X-ray diffraction and infrared spectrum measurement, the surface has generated carbonated hydroxyapatite.Stretching experiment shows that coating and high base strength are greater than 70MPa.
Embodiment 2
The first step adopts Ca (NO
3)
24H
2O and H
3PO
4Be raw material, press calcium-phosphorus ratio configuration in 1.6: 1 aqueous solution.
Second step is with H
3PO
4Solution is added drop-wise to Ca (NO with suitable speed
3)
2In the solution, regulating pH value with ammonia is 10-12, places 50 ℃ of waters bath with thermostatic control to stir 60min., ageing 24h under the room temperature, and reuse distilled water wash, centrifugal, filtration, dry under 100 ℃ of temperature.
The 3rd step drying sample pre-burning under 900 ℃ of temperature reduces it and burns till contraction.
Sample after the 4th step pre-burning is to expect: ball: water=1: 0.8: 0.5 ball milling 30min.
The 5th step alumina substrate pre-burning under 900 ℃ of temperature is used distilled water wash, drying after the cold working.
The 6th step was immersed in alumina substrate in the slip of the 4th step gained, treated to take out after the surface adsorption skim coating, at air drying, again at 1600 ℃ of temperature lower calcinations.
The 7th step repeated the 6th repeatedly and goes on foot four to five times, up to the coating that obtains adequate thickness.
Coating material CO under 1000 ℃ of temperature that the 8th step handled through the 7th step
2With heat treatment 6h in the steam atmosphere, programming rate is 10 ℃/min.
Through X-ray diffraction and infrared spectrum measurement, the surface has generated carbonated hydroxyapatite.Stretching experiment shows that coating and high base strength are greater than 70MPa.
Embodiment 3
The first step adopts Ca (NO
3)
24H
2O and H
3PO
4Be raw material, respectively dispose 1.5mol/LCa (NO at 1.8: 1 by calcium-phosphorus ratio
3)
2With 1.1mol/L H
3PO
4Aqueous solution.
Second step is with H
3PO
4Solution is added drop-wise to Ca (NO with suitable speed
3)
2In the solution, regulating pH value with ammonia is 10-12, places 50 ℃ of waters bath with thermostatic control to stir 60min, ageing 24h under the room temperature.
The 3rd step will be cold worked into required shape through the silicon nitride ceramics matrix of 1300 ℃ of air pressure presintering, and after cleaning and the drying, the calcic phosphorus colloidal sol that second step was made evenly is coated on the silicon nitride ceramics surface, then 120 ℃ of dryings.
The 4th step repeated the 3rd and goes on foot two to three times, up to the coating that obtains adequate thickness.
The 5th step burnt till the matrix of handling through the 4th step and obtains the surface for containing the material of calcium phosphorous compound coating under 1800 ℃.Programming rate when burning till is 10 ℃/minute, is incubated 4h under 1800 ℃ of temperature, cools to room temperature then with the furnace.
The 6th step had the material of calcium phosphorous compound coating to place quartz tube furnace in agglomerating surface, fed the N that contains 15% (v/v) steam and 4% (v/v) CO in quartz tube furnace
2Gas is warming up to 1200 ℃ with 10 ℃/minute speed, at 1200 ℃ of insulation 5h, cools to room temperature then with the furnace.
Through X-ray diffraction and infrared spectrum measurement, the surface has generated carbonated hydroxyapatite.Stretching experiment shows that coating and high base strength are greater than 70MPa.
Claims (2)
1, a kind of preparation method of medical surface bioactive ceramic material is characterized in that comprising the steps:
(1) with the pottery of molding 700-1300 ℃ of following pre-burning;
(2) being mixed with calcium/phosphorus mol ratio with the chemical compound of calcium, phosphorus is 1.2: 1-1.8: 1 solution or colloidal sol;
(3) solution that step (2) is obtained or colloidal sol cover the billet surface formation coating that step (1) obtains, and dry back is at 800-1800 ℃ of sintering;
(4) material that obtains of step (3) places and contains steam and CO or contain steam and CO
2Atmosphere in, handle down at 300-1200 ℃.
2, the preparation method of medical surface bioactive ceramic material according to claim 1 is characterized in that in step (3), and vaccum pulp absorbing, gunite, coating or impregnation method are adopted in described covering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100524380A CN1299778C (en) | 2004-11-30 | 2004-11-30 | Medical surface bioactive ceramic material and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100524380A CN1299778C (en) | 2004-11-30 | 2004-11-30 | Medical surface bioactive ceramic material and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1636945A CN1636945A (en) | 2005-07-13 |
| CN1299778C true CN1299778C (en) | 2007-02-14 |
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ID=34846138
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|---|---|---|---|
| CNB2004100524380A Expired - Fee Related CN1299778C (en) | 2004-11-30 | 2004-11-30 | Medical surface bioactive ceramic material and its prepn |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367643B (en) * | 2008-09-24 | 2011-04-27 | 福州大学 | Novel absorbent charcoal functional ceramic and method of manufacturing the same |
| CN102850079A (en) * | 2012-09-10 | 2013-01-02 | 四川大学 | Porous bio-ceramic with surface constructed by using calcium phosphate nano-particles, and preparation method thereof |
| CN104876642B (en) * | 2015-05-11 | 2017-03-22 | 贵州大学 | Surface treatment method for improving performance of piezoelectric ceramic |
| CN106222723B (en) * | 2016-08-17 | 2018-08-31 | 高孝雪 | A kind of implant composite biological coatings and its preparation process |
| CN112919888B (en) * | 2021-03-26 | 2022-06-14 | 华南理工大学 | Alumina ceramic with HA-coated surface and preparation method thereof |
| CN113548890B (en) * | 2021-07-31 | 2023-03-24 | 华南理工大学 | Modified zirconia ceramic with high bioactivity and high mechanical strength and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03187987A (en) * | 1989-12-14 | 1991-08-15 | Inax Corp | Artificial ivory |
| JPH04144984A (en) * | 1990-10-03 | 1992-05-19 | Agency Of Ind Science & Technol | Apatite-coated composite material and production thereof |
| JP3187987B2 (en) * | 1992-11-18 | 2001-07-16 | 亨 山本 | Sustained release fiber material and method for producing the same |
| CN1486751A (en) * | 2003-08-08 | 2004-04-07 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
-
2004
- 2004-11-30 CN CNB2004100524380A patent/CN1299778C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03187987A (en) * | 1989-12-14 | 1991-08-15 | Inax Corp | Artificial ivory |
| JPH04144984A (en) * | 1990-10-03 | 1992-05-19 | Agency Of Ind Science & Technol | Apatite-coated composite material and production thereof |
| JP3187987B2 (en) * | 1992-11-18 | 2001-07-16 | 亨 山本 | Sustained release fiber material and method for producing the same |
| CN1486751A (en) * | 2003-08-08 | 2004-04-07 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
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| Publication number | Publication date |
|---|---|
| CN1636945A (en) | 2005-07-13 |
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Granted publication date: 20070214 Termination date: 20101130 |