CN1140299C - 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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- CN1140299C CN1140299C CNB001137875A CN00113787A CN1140299C CN 1140299 C CN1140299 C CN 1140299C CN B001137875 A CNB001137875 A CN B001137875A CN 00113787 A CN00113787 A CN 00113787A CN 1140299 C CN1140299 C CN 1140299C
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Abstract
The present invention relates to a plasma spray-hydrothermal synthesis compound preparation process of a nano acicular hydroxyapatite biologic coating used for the surface bioactivity modification of a metal dental implant and a bone implant. Calcium hydrophosphate or calcium phosphate are used for initial powdery, plasma spray technology is used for preparing an initial state coating at the metal surface, and the hydrothermal synthesis of the initial state coating is carried out. The obtained coating is made of nano acicular hydroxyapatite and has the advantages of low internal stress, medium bonding strength and high purity and crystallization degree, and the configuration of the obtained coating is similar to the configuration of apatite in a 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.
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 comparatively fast, the bond strength with metal reduces big (reducing by 30% as one month) in vivo, calcium and phosphorus atoms than, especially hydroxyapatite has than big-difference in grain form and the skeleton, 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 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 powder particles 100～300 orders
Argon is as the flow 100～200bar of main gas
Hydrogen is as the flow 5～30bar of secondary gas
Powder feeding rate 50～150g/min
Arc current 300～700A
Arc voltage 70～90V
Spraying spacing 5～20cm
It is formulated by ammonia and deionized water that the initial state coating is carried out the synthetic employed solution of hydro-thermal, and the 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, combine good and hydro-thermal synthetic coating degree of crystallinity of plasma sprayed coating and melts combine and purity height, calcium and phosphorus atoms than advantages such as moderate and nanometer-size needle-like crystal particle shape attitudes, coatings prepared have dissolving slowly, low, the microcosmic configuration of internal stress is more near characteristics such as hydroxyapatite in the skeleton.
The invention will be further described below in conjunction with implementing:
With the surface through sandblast, the titanium alloy of spray titanium pearl roughening treatment and cleaning is a matrix, adopting plasma spraying is that 200 purpose calcium hydrogen phosphate powders are at the flow 150bar of argon as main gas with granularity, hydrogen is as the flow 6bar of secondary gas, 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, combination Intensity is higher than 20MPa, in the pseudo body fluid environment, soak 1 month in conjunction with strength degradation less than 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 the calcium hydrogen phosphate powder is initial powder, adopt plasma spraying technology to prepare the initial state coating in the metal surface, hydroxyapatite coating layer with plasma spraying carries out the synthetic hydroxyapatite coating layer that is converted into of hydro-thermal then, wherein, the technological parameter of the prefabricated initial state coating of plasma spraying is:
Calcium hydrogen phosphate powder particles 100～300 orders
Argon is as the flow 100～200bar of main gas
Hydrogen is as the flow 5～30bar of secondary gas
Powder feeding rate 50～150g/min
Arc current 300～700A
Arc voltage 70～90V
It is formulated by ammonia and deionized water that spraying spacing 5～20cm carries out the synthetic employed solution of hydro-thermal to the initial state coating, and the hydro-thermal synthesis process parameter is:
The pH value 7～14 of solution
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 spray titanium pearl roughening treatment and cleaning is a matrix, adopting plasma spraying is that 200 purpose calcium hydrogen phosphate powders are at the flow 150bar of argon as main gas with granularity, hydrogen is as the flow 6bar of secondary gas, 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, cleans 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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1270841A CN1270841A (en) | 2000-10-25 |
| CN1140299C true CN1140299C (en) | 2004-03-03 |
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| Application Number | Title | Priority Date | Filing Date |
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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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Families Citing this family (9)
| 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 |
| JP5248848B2 (en) * | 2007-12-11 | 2013-07-31 | 山八歯材工業株式会社 | Implant manufacturing method and artificial tooth root manufacturing method |
| 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 |
| CN103394124B (en) * | 2013-08-01 | 2015-04-01 | 上海师范大学 | Preparation method for well-aligned rodlike hydroxylapatite coating |
| 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 |
| 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 |
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2000
- 2000-04-19 CN CNB001137875A patent/CN1140299C/en not_active Expired - Fee Related
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| CN1270841A (en) | 2000-10-25 |
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