CN1270841A - Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting - Google Patents
Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting Download PDFInfo
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- CN1270841A CN1270841A CN 00113787 CN00113787A CN1270841A CN 1270841 A CN1270841 A CN 1270841A CN 00113787 CN00113787 CN 00113787 CN 00113787 A CN00113787 A CN 00113787A CN 1270841 A CN1270841 A CN 1270841A
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Abstract
The present invention relates to a plasma jet-hydrothermal synthesis compounding process of preparing nanometer-level needle-shaped hydroxyl apatite biological painting for biological surface modification of metal tooth and bone implant. By using calcium biphosphate or calcium phosphate as initial material, an initial painting is prepared on the surface of metal through plasma jet process and is hydrothermally synthesized to obtain nanometer-level needle-shaped hydroxyl apatite painting with low internal stress, moderate bond strength, high purity, high crystallinity an configuation similar to that of apatite in bone.
Description
The present invention relates to metal tooth implant and bone implant surface bioactive modification hydroxyl apatite biological painting preparation technology, specifically, relating to a kind of is the synthetic compound preparation technology of plasma spraying-hydro-thermal of initial powder with calcium hydrogen phosphate or calcium phosphate.
Metals such as titanium alloy are the usual materials that uses of tooth implant and load bone implant, have good obdurability, but lack biological activity, in early days can not be longer with bone formation chemical bond and healing time in implantation; Hydroxyapatite has excellent biological compatibility and biological activity, can promote the growth of bone and shorten healing time, but its obdurability is relatively poor.Biomedical engineering circle reaches common understanding, surface-coated have the composite metal of hydroxyapatite coating layer be have concurrently mechanics and biology combination property implant.The hydroxyl apatite biological painting of clinical practice both at home and abroad adopts plasma spraying preparation technology more at present, promptly is on metal (as titanium or titanium alloy) surface, to form hydroxyapatite coating layer with the initial spraying of powdery row material of hydroxyapatite.Its shortcoming is that used initial powder---the hydroxyapatite price is expensive partially, and waste is also bigger in the production; It is harmful mutually that coatings prepared contains lyotropic phase and calcium oxide such as amorphous state hydroxyapatite, tricalcium phosphate and tetracalcium phosphate, the coating internal stress is bigger and easy to crack, dissolving is very fast, bond strength with metal reduces big (reducing by 30% as one month) in vivo, calcium and phosphorus atoms ratio, especially in grain form and the skeleton there be than big-difference hydroxyapatite, causes the coating miopragia.
The objective of the invention is to overcome the shortcoming of above-mentioned existing technology, a kind of compound preparation technology of nanometer needle-like hydroxyl apatite biological painting is proposed, it is cheap to have initial powder, and coatings prepared has degree of crystallinity and purity height, dissolving is slow, internal stress is low, bond strength is moderate, microcosmic configuration (calcium with phosphorus atoms than moderate, nanometer-size needle-like crystal particle shape attitude) is more near characteristics such as hydroxyapatite in the skeleton.
Technology of the present invention is: with calcium hydrogen phosphate or calcium phosphate is initial powder, adopts plasma spraying technology to prepare the initial state coating in the metal surface, and initial state is coated with to be placed on carries out in the autoclave that hydro-thermal is synthetic to make it change into nanometer needle-like hydroxyapatite coating layer.Wherein, the technological parameter of plasma spraying initial state coating is:
Calcium hydrogen phosphate or calcium phosphate powder particles 100～300 orders
Main gas (argon) flow 100～200bar
Secondary gas (hydrogen) flow 5～30bar
Powder feeding rate 50～150g/min
Arc current 300～700A
Arc voltage 70～90V
Spraying spacing 5～20cm hydro-thermal synthesis process parameter is:
PH value of aqueous solution 7～14
100～300 ℃ of synthesis temperatures
Synthesis pressure 0.5～10MPa
Generated time 2～15 hours
Above-mentioned technology is initial powder with cheap calcium hydrogen phosphate or calcium phosphate, combine plasma sprayed coating and melts combine good and hydro-thermal synthetic coating degree of crystallinity and purity height, calcium and phosphorus atoms are than advantages such as moderate and nanometer-size needle-like crystal particle shape attitudes, it is slow that coatings prepared has dissolving, internal stress is low, and the microcosmic configuration is more near characteristics such as hydroxyapatite in the skeleton.
The invention will be further described below in conjunction with embodiment:
With the surface through sandblast, the titanium alloy of roughening treatment such as spray titanium pearl and cleaning is a matrix, adopting plasma spraying is that 200 purpose calcium hydrogen phosphate powders are at main gas (argon) flow 150bar with granularity, secondary gas (hydrogen) flow 6bar, powder feeding rate 50g/min, arc current 400A, prefabricated thickness is 200 μ m initial state coatings under the condition of spraying spacing 10cm, initial state is coated with is placed in the autoclave, add deionized water and be 12 back sealings with the pH value that ammonia is adjusted water, through 200 ℃, take out the synthetic back of 3 hours hydro-thermal, clean with deionized water and dehydrated alcohol, and oven dry got final product in 4 hours in 80 ℃ drying baker.
The present invention has following advantage than existing hydroxyapatite coating layer in plasma spraying technology:
1, coating phase free from foreign meter, degree of crystallinity height (more than 95%), crystallization crystal grain are nanoscale Needle-like hydroxyapatite, calcium and phosphorus atoms are than adjustable between 1.5～1.67.
Even 2 in thicker situation (such as 200 μ m), the coating internal stress is lower than 30Mpa, Bond strength is higher than 20MPa, in the pseudo body fluid environment, soak 1 month little in conjunction with strength degradation In 10%, structural stability is good.
3, in animal body remarkable in conjunction with effect with early stage (such as one month) of bone.
Claims (2)
1, the compound preparation technology of hydro-thermal synthesis of nano hydroxyl apatite biological painting, it is characterized in that, with non-hydroxyl floats such as calcium hydrogen phosphate or calcium phosphate is initial powder, adopt plasma spraying technology to prepare the initial state coating in the metal surface, it is synthetic to be converted into hydroxyapatite coating layer then the non-hydroxyl apatite initial state coating of plasma spraying to be carried out hydro-thermal, wherein, the technological parameter of plasma spraying initial state coating is:
Calcium hydrogen phosphate or calcium phosphate powder particles 100～300 orders
Main gas (argon) flow 100～200bar
Secondary gas (hydrogen) flow 5～30bar
Powder feeding rate 50～150g/min
Arc current 300～700A
Arc voltage 70～90V
Spraying spacing 5～20cm hydro-thermal synthesis process parameter is:
PH value of aqueous solution 7～14
100～300 ℃ of synthesis temperatures
Synthesis pressure 0.5～10MPa
Generated time 2～15 hours
2, technology according to claim 1, it is characterized in that, with the surface through sandblast, the titanium alloy of roughening treatment such as spray titanium pearl and cleaning is a matrix, adopting plasma spraying is that 200 purpose calcium hydrogen phosphate or calcium phosphate powder are at main gas (argon) flow 150bar with granularity, secondary gas (hydrogen) flow 6bar, powder feeding rate 50g/min, arc current 400A, prefabricated thickness is 200 μ m initial state coatings under the condition of spraying spacing 10cm, initial state is coated with is placed in the autoclave, add deionized water and be 12 back sealings with the pH value that ammonia is adjusted water, through 200 ℃, take out the synthetic back of 3 hours hydro-thermal, clean with deionized water and dehydrated alcohol, and oven dry got final product in 4 hours in 80 ℃ drying baker.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001137875A CN1140299C (en) | 2000-04-19 | 2000-04-19 | Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001137875A CN1140299C (en) | 2000-04-19 | 2000-04-19 | Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1270841A true CN1270841A (en) | 2000-10-25 |
| CN1140299C CN1140299C (en) | 2004-03-03 |
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| CNB001137875A Expired - Fee Related CN1140299C (en) | 2000-04-19 | 2000-04-19 | Composite hydrothermal synthesis process for preparing nanometer-level hydroxyl apatite biological painting |
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| CN (1) | CN1140299C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293144C (en) * | 2004-07-28 | 2007-01-03 | 上海师范大学 | Inorganic-organic hybridization material of dendritic polymer of hydroxy calcium phosphate/polyamide-amine |
| BG65595B1 (en) * | 2002-11-04 | 2009-02-27 | Лиляна ПРАМАТАРОВА | Method for growing of hydroxyapatite layers by a system materializing the laser-solution-substrate interaction |
| CN101888815A (en) * | 2007-12-11 | 2010-11-17 | 山八齿材工业株式会社 | The manufacture method of implant and artificial dental root |
| CN101905033A (en) * | 2010-07-27 | 2010-12-08 | 中国人民解放军第二军医大学 | Medicament microcapsule composite calcium deficiency calcium phosphate bone cement and use, preparation method and application thereof |
| CN103394124A (en) * | 2013-08-01 | 2013-11-20 | 上海师范大学 | Well-aligned rodlike hydroxylapatite coating and preparation method thereof |
| CN104225674A (en) * | 2014-08-28 | 2014-12-24 | 北京航空航天大学 | Preparation method for fluid shear stress-mediated hydroxyapatite |
| CN105641741A (en) * | 2014-11-10 | 2016-06-08 | 中国科学院上海硅酸盐研究所 | HA (Hydroxyapatite) coating with high degree of crystallinity and nano-structure and preparation method of HA coating |
| CN106620852A (en) * | 2016-10-09 | 2017-05-10 | 江苏科技大学 | Method for preparing dicalicium phosphate anhydrous (DCPA) bioceramic coating on surface of pure titanium |
| CN108079369A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院上海硅酸盐研究所 | Silicate cement bracket with surface nano-structure and its preparation method and application |
-
2000
- 2000-04-19 CN CNB001137875A patent/CN1140299C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BG65595B1 (en) * | 2002-11-04 | 2009-02-27 | Лиляна ПРАМАТАРОВА | Method for growing of hydroxyapatite layers by a system materializing the laser-solution-substrate interaction |
| CN1293144C (en) * | 2004-07-28 | 2007-01-03 | 上海师范大学 | Inorganic-organic hybridization material of dendritic polymer of hydroxy calcium phosphate/polyamide-amine |
| CN101888815B (en) * | 2007-12-11 | 2013-12-04 | 山八齿材工业株式会社 | Method of manufacturing implant and method of manufacturing artificial dental root |
| CN101888815A (en) * | 2007-12-11 | 2010-11-17 | 山八齿材工业株式会社 | The manufacture method of implant and artificial dental root |
| CN101905033B (en) * | 2010-07-27 | 2014-04-02 | 中国人民解放军第二军医大学 | Medicament microcapsule composite calcium deficiency calcium phosphate bone cement and use, preparation method and application thereof |
| CN101905033A (en) * | 2010-07-27 | 2010-12-08 | 中国人民解放军第二军医大学 | Medicament microcapsule composite calcium deficiency calcium phosphate bone cement and use, preparation method and application thereof |
| CN103394124A (en) * | 2013-08-01 | 2013-11-20 | 上海师范大学 | Well-aligned rodlike hydroxylapatite coating and preparation method thereof |
| CN104225674A (en) * | 2014-08-28 | 2014-12-24 | 北京航空航天大学 | Preparation method for fluid shear stress-mediated hydroxyapatite |
| CN104225674B (en) * | 2014-08-28 | 2016-07-06 | 北京航空航天大学 | A kind of preparation method of the hydroxyapatite of hydrodynamic shear mediation |
| CN105641741A (en) * | 2014-11-10 | 2016-06-08 | 中国科学院上海硅酸盐研究所 | HA (Hydroxyapatite) coating with high degree of crystallinity and nano-structure and preparation method of HA coating |
| CN106620852A (en) * | 2016-10-09 | 2017-05-10 | 江苏科技大学 | Method for preparing dicalicium phosphate anhydrous (DCPA) bioceramic coating on surface of pure titanium |
| CN108079369A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院上海硅酸盐研究所 | Silicate cement bracket with surface nano-structure and its preparation method and application |
| CN108079369B (en) * | 2016-11-21 | 2021-01-12 | 中国科学院上海硅酸盐研究所 | Portland bone cement scaffold with surface nano structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1140299C (en) | 2004-03-03 |
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