CN105648390A - Preparation method for hydroxylapatite coating - Google Patents
Preparation method for hydroxylapatite coating Download PDFInfo
- Publication number
- CN105648390A CN105648390A CN201610027327.7A CN201610027327A CN105648390A CN 105648390 A CN105648390 A CN 105648390A CN 201610027327 A CN201610027327 A CN 201610027327A CN 105648390 A CN105648390 A CN 105648390A
- Authority
- CN
- China
- Prior art keywords
- coating layer
- preparation
- coating
- spraying
- hydroxyapatite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method for a hydroxylapatite coating. A liquid material which is a calcium salt solution precursor or hydroxylapatite suspension liquid serves as the feedstock. Plasma spraying or hypersonic flame spraying or common flame spraying thermal spraying flame flow serves as the heating means to heat liquid drops. The liquid material is injected into the flame flow through a pressure pump or a peristaltic pump, and after entering the flame flow, the liquid drops are subjected to all or a part of the processes of decomposition, evaporation, nucleation, growth, melting and acceleration and are deposited on a metallic matrix to form the coating. According to the preparation method for the hydroxylapatite coating, the defects that a hydroxylapatite coating in the plasma spraying process is prone to being decomposed, low in crystallinity, large in residual stress and the like are overcome; the flame flow is surrounded by water vapor which beneficially improves the crystallinity of the hydroxylapatite, accordingly, compared with a conventional coating method, reducing of the residual stress in the coating is facilitated through liquid material spraying, and the crystallinity of the hydroxylapatite coating is very high.
Description
Technical field
The present invention relates to engineering and material science, particularly to the preparation method of a kind of hydroxyapatite coating layer.
Background technology
Hydroxyapatite is the main inorganic composition of human body hard bone tissue, the hydroxyapatite of synthetic is essentially identical with the host inorganic mineralogical composition of skeleton tissue in chemical composition and crystal structure, being not likely to produce rejection after introducing human body, therefore hydroxy-apatite has broad prospect of application in implantation.
But along with deeply finding with clinical practice of research: conventional plasma spraying is prepared in coating procedure, due to plasma flame flow high temperature action, hydroxyapatite is decomposed the generation impurity phase such as tricalcium phosphate, tetracalcium phosphate, calcium oxide, and particle arrival matrix surface solidification cooling stage is a chilling process, coating exists a large amount of amorphous, quick heating-cooling process causes that the degree of crystallinity of coating is not enough, residual stress is excessive, and these problems still govern the application of hydroxyapatite material system.
Before the present invention makes, in existing conventional plasma spraying coating process, hydroxyapatite coating layer also exists the difficult problems such as easy decomposition, degree of crystallinity is low, residual stress is big, and the consequence that particularly degree of crystallinity is not enough is the most serious. Being dissolved rapidly by body fluid after in the Hydroxapatite implant body that degree of crystallinity is not enough, biological stability is poor. ISO13779-2 standard specifies that the degree of crystallinity of hydroxyapatite coating layer have to be larger than 45%, and conventional plasma spraying hydroxyapatite coating degree of crystallinity is difficult to meet this requirement, require over the post-processing steps such as heat treatment to improve the degree of crystallinity of coating, but this causes again degradation problem under grain growth or anchoring strength of coating, and complex process, molding cost improve.
Summary of the invention
The purpose of the present invention is that and overcomes drawbacks described above, the preparation method developing a kind of hydroxyapatite coating layer.
The technical scheme is that
A kind of preparation method of hydroxyapatite coating layer, it is as follows that it is mainly characterized by step;
(1) with liquid material, i.e. calcium salt soln presoma or hydroxyapatite suspensions, for charging;
(2) drop is heated with plasma spraying or HVAF or common flame spraying thermal spraying flame stream for heater means;
(3) by compression pump or peristaltic pump, liquid material is injected in flame stream;
(4) drop enters after flame stream, through decompositions, evaporation, nucleation, all or part of process growing up, melt and accelerate, deposits to and forms coating on metallic matrix.
Calcium salt in described step (1) is be dissolved in water or the calcium fluoride of organic solvent, calcium bromide, calcium iodide, calcium nitrate inorganic salt.
Solution presoma in described step (1) also allows for containing phosphoric acid or other composition.
Flame stream temperature in described step (2) is all more than 3000 DEG C.
The high speed of described hot flame stream, reaches tens to thousands of m/s.
The charging that drop in described step (2) is in step (1) enters flame stream with jet.
Compression pump in described step (3) or the range of flow of peristaltic pump are in mL/min level.
In described step (4), all or part of process of single drop all completes within the time of Microsecond grade.
Coating layer thickness in described step (4) is at micron order.
Advantages of the present invention and effect are in that in liquid material spraying process, and flame stream is surrounded by steam, and steam is favorably improved the degree of crystallinity of hydroxyapatite, and therefore liquid material spraying is compared to Typical spray method, and the degree of crystallinity of hydroxyapatite coating layer is high. The particle of liquid material thermal spraying is less than conventional thermal spraying, it is easy to heating, solvent can consume part of heat energy heat simultaneously, alleviates the thermal source impact on coating, advantageously reduces the residual stress in coating. Liquid material spraying hydroxyapatite coating is made up of fine particle, and the size of deposited particles only has the one thousandth of Typical spray particle to 1/10th, and coating structure is more fine, also therefore can prepare relatively thin micron order coating.
CN103031508A is a kind of plasma spraying with liquid feedstock device, and including plasma system and liquid material conveyer device, liquid material induction system includes liquid material power delivery unit, cleaning systems and liquid material injected system. For preparing the ceramic coating with nanostructured on matrix, drop deposits, after the heating of described plasma jet is accelerated, the ceramic coating forming nanostructured on the matrix.
Compared to patent CN103031508A, the target material of the present invention is hydroxyapatite, and compared to the ceramic coating of CN103031508A, the target of this patent specifically, is applied more clear and definite. This patent adopts commercial small pressure pump and peristaltic pump, it is not necessary to mechanical stirring device needed for CN103031508A, relief valve and cleaning device etc., therefore has simple in construction, reliability high. This patent is applicable not only to the solution presoma in CN103031508A, applies also for suspension; It is applicable not only to plasma spraying, is also applied for flame-spraying, HVAF and detonation flame spraying method.
CN103014801A is a kind of preparation method at titanium or titanium alloy surface electro-deposition hydroxyapatite coating layer. With pretreated titanium or titanium alloy substrate for negative electrode, with platinized titanium net for anode, the constant temperature of electroplate liquid heating to 40-80 DEG C, when magnetic agitation, constant current or constant potential mode is adopted to carry out electro-deposition, have that crystallization is careful, smooth surface is smooth and etc. feature, there is good biological activity and mechanical property.
Compared to patent CN103014801A, the technology that the present invention adopts is without heating liquid material, it is not necessary to additional anode, has the advantages that deposition velocity is fast, coating porosity is controlled.
CN103394124B is the preparation method of a kind of orderly bar-shaped hydroxyapatite coating, pretreated metallic matrix is immersed in bio-vitric precursor sol, adopt dipping-pulling method, bio-vitric presoma is deposited on metal base surface, through high-temperature calcination, matrix surface forms bio-vitric coating, forms orderly bar-shaped hydroxyapatite coating then through hydro-thermal converted in-situ.
Compared to patent CN103394124B, the present invention, without heat treatment, has the advantages that shaping speed is fast, bond strength is high.
Other concrete advantage of the present invention and effect will go on to say below.
Accompanying drawing explanation
Fig. 1 spraying process schematic diagram of the present invention.
The XRD figure spectrum schematic diagram of Fig. 2 hydroxyapatite coating layer of the present invention.
The coating schematic diagram that Fig. 3 plasma spraying+suspension of the present invention obtains.
The coating schematic diagram that Fig. 4 plasma spraying of the present invention+solution presoma obtains.
Another coating schematic diagram that Fig. 5 plasma spraying of the present invention+solution presoma obtains.
Component names corresponding to number in the figure is as follows:
Liquid tank (built-in solution or suspension) 1, feed pipe 2, compression pump (peristaltic pump) 3, thermal spraying spray gun 4, feeding syringe needle 5, suspension (solution) 6, flight granule 7, hydroxyapatite 8, tricalcium phosphate 9, tetracalcium phosphate 10, calcium oxide 11.
Detailed description of the invention
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
The technical thought of the present invention is:
The present invention is directed to the problem that hydroxyapatite is low with bond strength in metallic matrix cohesive process and degree of crystallinity is not enough, adopt liquid material heat spraying method, obtain hydroxyapatite coating layer at metal base surface. Utilize liquid material plasma spray technology while raising coating with basal body binding force, keep higher degree of crystallinity, to problems such as perishable, the disbondings that hydroxyapatite under solution or part solution human body environment causes because adhesion is inadequate and degree of crystallinity is not high.
The illustrating of the present invention is presented herein below.
Hydroxyapatite plasma spraying with liquid feedstock method provided by the invention, its step includes:
(1) material prepares: joins in solvent by the solute chosen or suspension particle, obtains solution presoma or suspension is standby.
(2) matrix prepares: spraying matrix adopts metal, the step such as including cleaning, dry, sandblasting.
(3) prepared by coating: utilizes peristaltic pump that by syringe needle press-in, liquid material is adopted spray gun, through decomposition, evaporation, nucleation, all processes grown up, melt and accelerate or partial routine, deposits on matrix.
As shown in Figure 1:
Liquid tank 1 is connected with syringe needle 5 by feed pipe 2, feed pipe 2 is inserted peristaltic pump 3 control liquid material flow and (or insert compression pump 3, control liquid tank pressure by feed pipe 2 and regulate liquid material flow, and connect liquid tank 1 and syringe needle 5 by another root feed pipe), syringe needle 5 is near thermal spraying spray gun 4 front, the center of alignment gun slot 4, radial distance is at 3-10mm, axial distance is at 1-15mm, relying on liquid material kinetic energy liquid material to be injected in flame stream, suspension (solution) 6 generates flight granule 7 through steps such as decomposition/forming core/heating/acceleration.
For at metal, as on graft materials in the applicable human bodies such as titanium alloy, thermal spraying forms the hydroxyapatite coating layer of good organization's structure.
By at least one spraying method, a kind of solution presoma or suspension liquid material are carried out spraying and obtain coating.
Heat spraying method includes but not limited to: air plasma spraying, HVAF and flame-spraying.
Solution presoma includes adopting two or more following material: calcium oxide CaO, calcium phosphate Ca3(PO4)2, calcium nitrate Ca (NO3)2, calcium hydrogen phosphate CaHPO4, phosphoric acid H3PO4, diammonium phosphate (NH4)2HPO4, trimethyl phosphate C3H9O4P��
The particle diameter of the solid granulates in suspension is between 0.05-5 ��m, it is possible to form stable suspension, or at least under the auxiliary of magnetic agitation, it is possible to form stable suspension.
The solvent of precursor solution or suspension can adopt deionized water, pure water; Or organic solvent such as ethanol, isopropanol.
Except reacting substance, solid constituent and solvent, according to forming the needs stablizing solution and suspension, it is possible to add a small amount of surfactant, such as Polyethylene Glycol etc.
In presoma, solute mass percent in a solvent is between 1-20%; Solid state component in suspension content in a solvent is between 1-25%.
Adopting external force means liquid material to be injected in spraying flame stream by syringe needle, external force means can be compression pump, it is also possible to be peristaltic pump.
Syringe needle internal diameter is between 0.1-0.5mm.
Liquid material through pervaporation, nucleation, all processes grown up, melt and accelerate or partial routine, deposits on matrix after entering flame stream.
Matrix is metal material, it is possible to is titanium alloy, can also be rustless steel or other metal material.
Certain hydroxyl apatite suspension is joined in liquid tank, as it is shown in figure 1, connect liquid tank 1 and peristaltic pump 3 by feed pipe 2, and peristaltic pump 3 and syringe needle 5. Regulating peristaltic pump rotating speed, liquid material is injected in the flame stream of plasma gun 4 with certain flow so that drop 6 in the central axis of plasma flame flow, and forms coating at the particle beam 7 formed after pervaporation-heating-accelerator on metallic matrix. Then pass through X-ray diffraction XRD figure spectrum and calculate the degree of crystallinity of coating, observe the thickness of coating by polishing section light microscopic OM photo, observed the microscopic appearance of coating by field emission scanning electron microscope FE-SEM.
With specific embodiment, the present invention is described in detail below:
Embodiment 1:
Hydroxyapatite powder by 35g particle diameter about 0.5 ��m, it is scattered in 500mL dehydrated alcohol, add a small amount of Polyethylene Glycol, stable suspension is formed after magnetic agitation, suspension is sent in flame gun flame stream with the flow of 20mL/min through the syringe needle that internal diameter is 0.24mm, is deposited in No. 45 steel matrix and forms hydroxyapatite coating layer. Spray gun is gases used for oxygen with acetylene, and spray gun translational speed is 150m/s, moves down 2mm, continuous spray 15 times every time. Observe phase structure with X-ray diffractometer, as in figure 2 it is shown, by XRD phase calibration, hydroxyapatite 8, tricalcium phosphate 9, tetracalcium phosphate 10, calcium oxide 11, hydroxyapatite 8 peak is the strongest, and content is the highest, be 75% by calculating coating degree of crystallinity.
Embodiment 2:
Hydroxyapatite powder by 50g particle diameter about 1 ��m, it is scattered in 1000mL deionized water, and add a small amount of dispersant, stable suspension is formed after magnetic agitation, suspension is sent in plasma gun flame stream with the flow of 25mL/min through the syringe needle that internal diameter is 0.26mm, is deposited on titanium alloy substrate and forms hydroxyapatite coating layer. In spraying process, spray power is 30kW, and spray gun translational speed is 200m/s, moves down 2mm, continuous spray 20 times every time. With field emission microscopy observation coating surface microstructure. As it is shown on figure 3, there is relatively low porosity, it does not have gross blow hole, coating is well combined, and coating layer thickness is 240 ��m, namely coating deposition rate be about 12 ��m/secondary. Being calculated by XRD figure spectrum, coating degree of crystallinity is 68%. This parameter is suitable for preparing the hydroxyapatite coating layer that thickness requirement is relatively thin, porosity is relatively low.
Embodiment 3
0.5M calcium nitrate, 0.3M diammonium phosphate and 0.4M ammonia spirit presoma are sent in plasma gun flame stream through the syringe needle that internal diameter is 0.22mm with the flow of 30mL/min, are deposited on stainless steel base and form hydroxyapatite coating layer.In spraying process, spray gun translational speed is 250m/s, moves down 3mm, continuous spray 20 times every time. Microstructure is observed with field emission scanning electron microscope FE-SEM. As shown in Figure 4, there is spilehole local, and porosity is moderate. By fractograph analysis, coating layer thickness is 240 ��m, namely coating deposition rate be about 12 ��m/secondary, by XRD figure spectrum calculate, coating degree of crystallinity is 70%. This parameter is suitable for preparing the hydroxyapatite coating layer that thickness requirement is relatively thin, have loose structure.
Embodiment 4:
1M calcium nitrate, 0.6M diammonium phosphate and 0.8M ammonia spirit presoma are sent in supersonic spray gun flame stream through the syringe needle that internal diameter is 0.18mm with the flow of 20mL/min, are deposited on 304 stainless steel bases and form hydroxyapatite coating layer. In spraying process, spray gun translational speed is 300m/s, moves down 2mm, continuous spray 25 times every time. Microstructure is observed with field emission scanning electron microscope FE-SEM. As it is shown in figure 5, there is obvious pore, porosity is higher. By fractograph analysis, coating layer thickness is 250 ��m, namely coating deposition rate be about 10 ��m/secondary. Being calculated by XRD figure spectrum, coating degree of crystallinity is 77%. This parameter is suitable for preparing the hydroxyapatite coating layer that thickness requirement is relatively thin, have high pore structure.
Embodiment 5:
By 1M calcium hydroxide, 0.6M phosphoric acid stirs at 40 DEG C, and dropping phosphoric acid to pH value is 9, is sent in plasma gun flame stream with the flow of 30mL/min through the syringe needle that internal diameter is 0.26mm by suspension, is deposited on titanium alloy substrate and forms hydroxyapatite coating layer. In spraying process, spray gun power is 30kW, and spray gun translational speed is 250m/s, moves down 4mm, continuous spray 25 times every time. Microstructure is observed with field emission scanning electron microscope FE-SEM and XRD. Coating is well combined, and porosity is relatively low, and there is obvious microfissure on surface, and coating layer thickness is 150 ��m, namely coating deposition rate be about 6 ��m/secondary. Being calculated by XRD figure spectrum, coating degree of crystallinity is 62%. This parameter is suitable for preparing the hydroxyapatite coating layer that thickness requirement is relatively thin, finer and close.
Instant invention overcomes the difficult problem that in conventional plasma spraying coating process, hydroxyapatite coating layer easily decomposes, degree of crystallinity is low, by solution presoma or suspension are injected thermal spraying flame stream, metallic matrix obtains porous or dense coating. The degree of crystallinity of spraying state coating, far above the 45% of ISO13779-2 standard, reaches 60-80%. It is suitable for preparing thickness requirement at 50 ��m��250 �� m-thick, hydroxyapatite coating layer that degree of crystallinity is high
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof; those of ordinary skill in the art are when can make various corresponding change and deformation according to the present invention, but these change accordingly and deformation all should belong to the scope of the claims appended by the present invention.
Claims (9)
1. the preparation method of a hydroxyapatite coating layer, it is characterised in that step is as follows;
(1) with liquid material, i.e. calcium salt soln presoma or hydroxyapatite suspensions, for charging;
(2) drop is heated with plasma spraying or HVAF or common flame spraying thermal spraying flame stream for heater means;
(3) by compression pump or peristaltic pump, liquid material is injected in flame stream;
(4) drop enters after flame stream, through decompositions, evaporation, nucleation, all or part of process growing up, melt and accelerate, deposits to and forms coating on metallic matrix.
2. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that the calcium salt in step (1) is be dissolved in water or the calcium fluoride of organic solvent, calcium bromide, calcium iodide, calcium nitrate inorganic salt.
3. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that the solution presoma in step (1) also allows for containing phosphoric acid or other composition.
4. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that the flame stream temperature in step (2) is all more than 3000 DEG C.
5. the preparation method of a kind of hydroxyapatite coating layer according to claim 4, is further characterized in that the high speed of hot flame stream, reaches tens to thousands of m/s.
6. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that the charging that the drop in step (2) is in step (1) enters flame stream with jet.
7. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that compression pump in step (3) or the range of flow of peristaltic pump are in mL/min level.
8. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that in step (4), all or part of process of single drop all completes within the time of Microsecond grade.
9. the preparation method of a kind of hydroxyapatite coating layer according to claim 1, it is characterised in that the coating layer thickness in step (4) is at micron order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610027327.7A CN105648390A (en) | 2016-01-13 | 2016-01-13 | Preparation method for hydroxylapatite coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610027327.7A CN105648390A (en) | 2016-01-13 | 2016-01-13 | Preparation method for hydroxylapatite coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105648390A true CN105648390A (en) | 2016-06-08 |
Family
ID=56486752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610027327.7A Pending CN105648390A (en) | 2016-01-13 | 2016-01-13 | Preparation method for hydroxylapatite coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105648390A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086764A (en) * | 2016-06-24 | 2016-11-09 | 扬州大学 | A kind of method forming Fluorin doped hydroxyapatite nano coating at stainless steel surfaces |
| CN106838076A (en) * | 2016-12-13 | 2017-06-13 | 杭州电子科技大学 | A kind of brake disc and manufacture method with wear-resisting hydroxyapatite coating layer |
| CN106896146A (en) * | 2017-01-05 | 2017-06-27 | 扬州大学 | A kind of coating production of zinc ferrite acetone gas sensing layer |
| CN108330427A (en) * | 2017-11-10 | 2018-07-27 | 上海工程技术大学 | A kind of high-performance ceramic coating and preparation method thereof |
| CN109182952A (en) * | 2018-09-28 | 2019-01-11 | 扬州大学 | A kind of compound soft template plasma spraying with liquid feedstock method preparing hollow micro-nano structure air-sensitive coating |
| CN109179356A (en) * | 2018-11-23 | 2019-01-11 | 广州新诚生物科技有限公司 | A kind of method that titanium or titanium alloy surface prepare hydroxyapatite coating layer |
| CN109457207A (en) * | 2018-11-22 | 2019-03-12 | 九江学院 | A kind of preparation method of hydroxylapatite-magnesium composite coating |
| CN111467577A (en) * | 2020-04-21 | 2020-07-31 | 王永芝 | Medical metal bone implant material |
| CN112194456A (en) * | 2020-10-10 | 2021-01-08 | 云南莱德福科技有限公司 | Material containing calcium hydroxy phosphate, one-step synthesis and forming method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450123A (en) * | 2003-04-28 | 2003-10-22 | 西安交通大学 | Process for preparing nano structured titanium dioxide photocatalyst coating |
| CN101250681A (en) * | 2008-03-27 | 2008-08-27 | 四川大学 | Method for suspending liquid plasma spraying preparation of hydroxyapatite bioactivity coatings |
| CN103031508A (en) * | 2011-09-30 | 2013-04-10 | 中国农业机械化科学研究院 | Liquid feedstock plasma spraying device |
| CN104947029A (en) * | 2015-06-26 | 2015-09-30 | 中国科学院宁波材料技术与工程研究所 | Method of preparing MAX phase ceramic coating by using hot spraying |
-
2016
- 2016-01-13 CN CN201610027327.7A patent/CN105648390A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450123A (en) * | 2003-04-28 | 2003-10-22 | 西安交通大学 | Process for preparing nano structured titanium dioxide photocatalyst coating |
| CN101250681A (en) * | 2008-03-27 | 2008-08-27 | 四川大学 | Method for suspending liquid plasma spraying preparation of hydroxyapatite bioactivity coatings |
| CN103031508A (en) * | 2011-09-30 | 2013-04-10 | 中国农业机械化科学研究院 | Liquid feedstock plasma spraying device |
| CN104947029A (en) * | 2015-06-26 | 2015-09-30 | 中国科学院宁波材料技术与工程研究所 | Method of preparing MAX phase ceramic coating by using hot spraying |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086764A (en) * | 2016-06-24 | 2016-11-09 | 扬州大学 | A kind of method forming Fluorin doped hydroxyapatite nano coating at stainless steel surfaces |
| CN106838076A (en) * | 2016-12-13 | 2017-06-13 | 杭州电子科技大学 | A kind of brake disc and manufacture method with wear-resisting hydroxyapatite coating layer |
| CN106896146A (en) * | 2017-01-05 | 2017-06-27 | 扬州大学 | A kind of coating production of zinc ferrite acetone gas sensing layer |
| CN106896146B (en) * | 2017-01-05 | 2019-03-01 | 扬州大学 | A kind of coating production of zinc ferrite acetone gas sensing layer |
| CN108330427A (en) * | 2017-11-10 | 2018-07-27 | 上海工程技术大学 | A kind of high-performance ceramic coating and preparation method thereof |
| CN109182952A (en) * | 2018-09-28 | 2019-01-11 | 扬州大学 | A kind of compound soft template plasma spraying with liquid feedstock method preparing hollow micro-nano structure air-sensitive coating |
| CN109182952B (en) * | 2018-09-28 | 2020-08-14 | 扬州大学 | Composite soft template liquid material plasma spraying method for preparing hollow micro-nano structure gas-sensitive coating |
| CN109457207A (en) * | 2018-11-22 | 2019-03-12 | 九江学院 | A kind of preparation method of hydroxylapatite-magnesium composite coating |
| CN109179356A (en) * | 2018-11-23 | 2019-01-11 | 广州新诚生物科技有限公司 | A kind of method that titanium or titanium alloy surface prepare hydroxyapatite coating layer |
| CN111467577A (en) * | 2020-04-21 | 2020-07-31 | 王永芝 | Medical metal bone implant material |
| CN111467577B (en) * | 2020-04-21 | 2023-01-17 | 王永芝 | Medical metal bone implant material |
| CN112194456A (en) * | 2020-10-10 | 2021-01-08 | 云南莱德福科技有限公司 | Material containing calcium hydroxy phosphate, one-step synthesis and forming method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105648390A (en) | Preparation method for hydroxylapatite coating | |
| US8877283B2 (en) | Method for preparing porous hydroxyapatite coatings by suspension plasma spraying | |
| Qiu et al. | Fabrication, characterization and evaluation of bioceramic hollow microspheres used as microcarriers for 3-D bone tissue formation in rotating bioreactors | |
| CN103751840B (en) | A kind of have bone defect repair support of the controlled low modulus of porous and preparation method thereof | |
| EP2361100B1 (en) | Article and method of surface treatment of an article | |
| Huang et al. | Hydroxyapatite coatings deposited by liquid precursor plasma spraying: controlled dense and porous microstructures and osteoblastic cell responses | |
| CN101837147A (en) | Preparation method of hydroxyapatite bioactive coating doped with trace elements | |
| CN101250681B (en) | Method for suspending liquid plasma spraying preparation of hydroxyapatite bioactivity coatings | |
| Graßmann et al. | Compositional and microstructural changes of engineered plasma‐sprayed hydroxyapatite coatings on Ti6Al4V substrates during incubation in protein‐free simulated body fluid | |
| CN101311328A (en) | Process for preparing titanium-based hydroxylapatite/titanium oxide nanotube composite coating | |
| CN108588626B (en) | Micron/nanometer multilevel structure titanium dioxide coating with excellent biocompatibility and preparation method thereof | |
| Su et al. | Effect of the hydroxyapatite particle size on the properties of sprayed coating | |
| Luo et al. | Surface modification of titanium and its alloys for biomedical application | |
| CN101250682B (en) | Injection type plasma spraying device for producing hydroxyapatite bioactivity coating | |
| CN108728844A (en) | A kind of cold spraying preparation method of medical bio coating | |
| Tang et al. | Enhanced spreading, migration and osteodifferentiation of HBMSCs on macroporous CS-Ta–A biocompatible macroporous coating for hard tissue repair | |
| Chen et al. | Phase transformation and morphology of calcium phosphate prepared by electrochemical deposition process through alkali treatment and calcination | |
| Ozeki et al. | Influence of the crystallinity of a sputtered hydroxyapatite film on its osteocompatibility | |
| CN101797399A (en) | Biomedical material with silver-ion-bearing hydroxyapatite coating and preparation method thereof | |
| CN112176272B (en) | Method for preparing hydroxyapatite coating by plasma spraying | |
| CN201195743Y (en) | Injection type plasma spraying device for producing hydroxyapatite bioactivity coating | |
| CN1243130C (en) | Composite hydrothermal and electrodepositing process to prepare hydroxyapatite/TiO2 coating | |
| CN106086764A (en) | A kind of method forming Fluorin doped hydroxyapatite nano coating at stainless steel surfaces | |
| CN109457207A (en) | A kind of preparation method of hydroxylapatite-magnesium composite coating | |
| CN103961744A (en) | Method for making simvastatin drug-containing hydroxyapatite coating on surface of pure titanium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Chao Inventor after: Zheng Bingbing Inventor after: Xu Haifeng Inventor after: Geng Xin Inventor after: Xiao Jinkun Inventor before: Zhang Chao Inventor before: Xu Haifeng Inventor before: Geng Xin Inventor before: Xiao Jinkun |
|
| CB03 | Change of inventor or designer information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160608 |
|
| RJ01 | Rejection of invention patent application after publication |