CN100357485C - Method for post treatment of plasma spraying hydroxyapatite coating - Google Patents
Method for post treatment of plasma spraying hydroxyapatite coating Download PDFInfo
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- CN100357485C CN100357485C CNB2005100210265A CN200510021026A CN100357485C CN 100357485 C CN100357485 C CN 100357485C CN B2005100210265 A CNB2005100210265 A CN B2005100210265A CN 200510021026 A CN200510021026 A CN 200510021026A CN 100357485 C CN100357485 C CN 100357485C
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Abstract
The present invention relates to a method for the post-treatment of a plasma spraying hydroxyapatite coating, which comprises the steps that a plasma spraying hydroxyapatite coating is infused in an electrolyte solution of which the negative ions are only hydroxide ions and the concentration is from 0.1 to 10 mol/l, and a constant direct current power supply is used for anodic treatment. By local high temperature generated in the course of electrochemical reaction around an anode, non-crystalline hydroxyapatite in the coating is converted to crystalline hydroxyapatite, the hydroxide ions around the anode and calcium phosphate in the coating carry out electrochemical reaction to convert the calcium phosphate to the hydroxyapatite, and thereby, the stability of the treated hydroxyapatite coating is improved. At the same time, an anodic treatment course polarizes the hydroxyapatite coating, a large number of negative charges are generated on the surface of the hydroxyapatite coating, and thereby, the bioactivity of the treated hydroxyapatite coating is improved. The post-treatment time of the plasma spraying hydroxyapatite coating of the present invention is short, operation is convenient, and the effect of implanting a coating product into a body is good.
Description
One, technical field
The present invention relates to a kind of treatment process of biomedical material, specifically, relate to a kind of post-treating method of hydroxyapatite coating layer in plasma spraying.
Two, background technology
Hydroxyapatite (HA) have with human body bone and tooth in similar chemical constitution and the crystalline structure of main mine material, it is the main inorganic composition of skeleton tissue, can form the chemical combination key with the skeleton tissue combines, be the biological active materials of a quasi-representative, so hydroxyapatite (HA) pottery is widely used in the damaged reparation of osseous tissue.But because simple hydroxylapatite ceramic mechanical property is relatively poor, its bending strength and fracture toughness property index all are lower than the human body dense bone, so be difficult to use at organism carrying position.And behind coating one deck hydroxyapatite coating layer on the titanium alloy substrate of biologically inert, just can not only be had good biological activity but also have excellent physical strength and flexible biomaterial, therefore, it has obtained extensive studies and application in sclerous tissues replacement field.The method for preparing at present hydroxyapatite coating layer is a lot, mainly contains plasma spraying method, ion beam sputtering, electrophoretic deposition, sol-gel method, bionical solution growth method or the like.In these preparation methods, plasma spraying method is the hydroxyapatite coating layer technology of preparing the most widely of research both at home and abroad at present.
Plasma spraying technology is to utilize temperature in 5000 ℃-10000 ℃ high temperature, plasma body is at short notice with the hydroxyapatite material heating and melting that applies, beat to coated metallic substance substrate with the high speed of 50-300m/s then, form firm combining with the metallic substance substrate.This technology prepares coating efficient height, and speed is fast, is easy to obtain several microns coatings to a hundreds of micron thickness, and the stress that metal base is born can transmit in coating well by the metal-ceramic interface, has overcome ceramic fragility.Plasma spraying technology can be used in production in enormous quantities in addition, and therefore the dummy of this matrix material is very fast is widely used clinically.
But, pyroprocess just because of hydroxyapatite coating layer in plasma spraying, make hydroxyapatite in the pyrolytic coating process, decompose, produce a large amount of tricalcium phosphates or other calcium phosphate salt in coating, simultaneously because the quick process of cooling in the hydroxyapatite sprayed process causes producing in the coating non-crystalline state hydroxyapatite.These phosphoric acid salt and non-crystalline state hydroxyapatite are unstable phase in vivo, therefore degrade easily under physiological environment, and the very fast disappearance of coating is ineffective after the degradation in vivo.And in certain period, guarantee hydroxyapatite coating layer stability in vivo, be realize bioactive ceramics can with the bone bonding, thereby improve the early stage stability of implant and promote the prerequisite of its permanent stability.
The method of raising hydroxyapatite coating layer in plasma spraying stability commonly used has at present:
A, heat treating method: after thermal treatment under 630 ℃ of-850 ℃ of temperature, non-crystalline state hydroxyapatite dephasign can obviously reduce in the coating with the hydroxyapatite coating layer in plasma spraying product, and the hydroxylapatite crystal degree can significantly increase in the coating.But this method can only be converted into the non-crystalline state hydroxyapatite crystalline state hydroxyapatite, phosphoric acid salt dephasigns such as tricalcium phosphate can not be transformed into the hydroxyapatite phase.
B, LASER HEAT TREATMENT: adopt pulse laser article on plasma spraying hydroxyapatite coating product to handle, significant increase can take place in the degree of crystallinity of coating prod.But this method may cause the coating prod surface to crack, and may cause hydroxyapatite that the generation tetracalcium phosphate takes place further to decompose.
C, water vapor heat treating process: it is that 125-300 ℃, pressure are that the water vapor container of 0.15-0.5MPa kept 2-6 hour that the hydroxyapatite coating layer in plasma spraying product is placed temperature, will put into drying in oven through the coating prod that saturated vapor pressure is handled again and get final product (number of patent application is 03117835.9).Steam-treated can make the non-crystalline state in the coating be converted into crystal form, can make the impurity inversion of phases in the coating become hydroxyapatite crystal simultaneously.But this method is longer to coating aftertreatment time requirement, the waste resource, and waste time and energy.
For the stability of hydroxyapatite coating layer and bioactive requirement two aspects of contradiction often.Require the hydroxyapatite coating layer activity good on the one hand, just require it to have certain degradation capability; And require hydroxyapatite coating layer to have certain stability on the other hand, just require its degraded can not be too fast.Therefore, the post-treating method of above-mentioned existing hydroxyapatite coating layer in plasma spraying is difficult to take into account the requirement to active and stable two aspects of hydroxyapatite coating layer.
Recent study finds that the biological activity of hydroxyapatite and its surface charge have direct relation.People such as Yamashita are polarized in the hydroxyapatite coating layer surface by the surface and produce a large amount of negative charges, [the Key Engineering Materials that makes the biological activity of hydroxyapatite coating layer be greatly improved, Vols.218-220 (2002), PP.199-202].But,, thereby can not satisfy the requirement of hydroxyapatite coating layer stability because the surperficial polarization method that they adopt does not improve the degree of crystallinity of hydroxyapatite coating layer.If a kind of method can be provided, make hydroxyapatite coating layer both have good biological activity implanting, have very high stability again, this task of the present invention just place.
Three, summary of the invention
At existing defective in the above-mentioned prior art method for post treatment of plasma spraying hydroxyapatite coating, purpose of the present invention is intended to propose a kind of novel method of hydroxyapatite coating layer in plasma spraying aftertreatment.The stability that hydroxyapatite coating layer after this method is handled implants not only is greatly improved; Also obviously improved the biological activity of coating simultaneously; And treatment time weak point, save energy, easy to operate.
Basic thought of the present invention is to be immersed in negative ion only in the electrolyte solution of hydroxide ion by the hydroxyapatite coating layer product, adopt the energising of constant current direct supply to carry out anodizing, the localized hyperthermia that produces in the electrochemical reaction process around the anode makes the non-crystalline state hydroxyapatite in the hydroxyapatite coating layer be converted into the crystalline state hydroxyapatite, hydroxide ion around the anode and the calcium phosphate salt generation electrochemical reaction in the hydroxyapatite coating layer make calcium phosphate salt be converted into hydroxyapatite, thereby the stability of coating prod is greatly improved; The anodizing process makes hydroxyapatite coating layer polarization, thereby coatingsurface produces a large amount of negative charges, thereby the biological activity of coating prod is improved significantly.
Purpose of the present invention realizes by the technical scheme that is made of following measure:
Method for post treatment of plasma spraying hydroxyapatite coating of the present invention comprises following processing step:
(1) at first prepares negative ion and only be the electrolyte solution of hydroxide ion, the electrolyte solution that makes is contained in the metal vessel;
(2) metal base with the hydroxyapatite coating layer product behind the plasma spraying is connected with the anode of a constant current direct supply, the negative electrode of metallic container shell with the constant current direct supply is connected, then the hydroxyapatite coating layer product is immersed in the electrolyte solution in the metal vessel, connect the constant current direct supply, make coating prod carry out anodizing under the effect of constant current direct supply, the anodizing time is 10-150 second;
(3) disconnect the constant current direct supply, take out the hydroxyapatite coating layer in plasma spraying product; At last coating prod is cleaned with clear water, dry again, get final product to such an extent that have a hydroxyapatite coating layer in plasma spraying product that high stability has high biological activity again.
In the such scheme of the present invention, negative ion is the solution that sodium hydroxide or potassium hydroxide or ammonium hydroxide or their mixture and deionized water are mixed with for the electrolyte solution of hydroxide ion only, and its hydroxide ion concentration is a 0.1-10 mol solution.
In the such scheme of the present invention, the outward current of used constant current direct supply is 15 amperes, and output voltage is a continuous adjustable voltage between the 0-200 volt.
In the such scheme of the present invention, the storing time when hydroxyapatite coating layer in plasma spraying product is after treatment dried is 1-3 hour, and storing temperature is 100-200 ℃, uses baking oven to dry.
Hydroxyapatite coating layer in plasma spraying product after such scheme of the present invention is handled detects with X-ray diffractometer, and its crystal form hydroxyapatite content can reach more than 90%; Can detect coatingsurface with the thermally stimulated current instrument has a large amount of electric charges to exist.When therefore being used for bone tissue restoration in implant into body or the animal body,, coating prod stability is greatly improved, can makes coating prod that obvious degradation did not take place in 3 months because coating mainly is made up of the crystal form hydroxyapatite; Simultaneously because coatingsurface has a large amount of negative charges, thereby coating and osseous tissue form good biological activity combination, and its shearing resistance reaches 30Mpa.
The characteristics that the present invention compared with prior art has:
1, hydroxyapatite coating layer in plasma spraying product of the present invention has improved the hydroxyapatite content and the degree of crystallinity of coating through carry out anodizing in electrolyte solution after, thereby has improved the stability that material implants greatly.
2, anodizing process of the present invention makes the hydroxyapatite coating layer polarization, and coatingsurface produces a large amount of negative charges, thereby the biological activity of coating is improved significantly.
3, treatment time weak point required for the present invention, save energy and efficient height.
4, operation is simple in the present invention, and gained coating prod cost is low.
Four, specific embodiments
The present invention is further illustrated below by embodiment, but content of the present invention is not limited only to content related among the embodiment.
Embodiment one
In deionized water, preparation concentration is 1 mol sodium hydroxide electrolyte solution, and the sodium hydroxide electrolyte solution that makes is contained in the metal vessel with dissolution of sodium hydroxide; The metal base of the hydroxyapatite coating layer that plasma spraying is made is connected with the anode of constant current direct supply, and the negative electrode of metallic container shell with the constant current direct supply is connected; Used constant current direct supply output voltage is that the 0-200 volt is adjustable continuously, outward current is 15 amperes; The hydroxyapatite coating layer product is immersed in the sodium hydroxide electrolyte solution, connect the constant current direct supply, constant current direct supply output voltage is adjusted to 60 volts, handle after 60 seconds, disconnect the constant current direct supply, take out coating prod, clean with clear water, be 150 ℃ of bakings 2 hours with baking oven in temperature again, get final product the hydroxyapatite coating layer in plasma spraying product of high stability, high biological activity.
Embodiment two
Potassium hydroxide is dissolved in deionized water, and preparation concentration is 10 mol koh electrolytic solution, and the koh electrolytic solution that makes is contained in the metal vessel; The metal base of the hydroxyapatite coating layer product that plasma spraying is made is connected with the anode of constant current direct supply, and the negative electrode of metallic container shell with the constant current direct supply is connected; Used constant current direct supply output voltage is that the 0-200 volt is adjustable continuously, outward current is 15 amperes; The hydroxyapatite coating layer product is immersed in the koh electrolytic solution, connect the constant current direct supply, constant current direct supply output voltage is adjusted to 40 volts, handle after 30 seconds, disconnect the constant current direct supply, take out coating prod, clean with clear water, be 100 ℃ of bakings 3 hours with baking oven in temperature again, get final product the hydroxyapatite coating layer in plasma spraying product of high stability, high biological activity.
Embodiment three
Ammonium hydroxide is dissolved in deionized water, and preparation concentration is 0.1 mol ammonium hydroxide electrolyte solution, and the ammonium hydroxide electrolyte solution that makes is contained in the metal vessel; The metal base of the hydroxyapatite coating layer product that plasma spraying is made is connected with the anode of constant current direct supply, and the negative electrode of metallic container shell with the constant current direct supply is connected; Used constant current direct supply output voltage is that the 0-200 volt is adjustable continuously, outward current is 15 amperes; The hydroxyapatite coating layer product is immersed in the ammonium hydroxide electrolyte solution, connect the constant current direct supply, constant current direct supply output voltage is adjusted to 150 volts, handle after 120 seconds, disconnect the constant current direct supply, take out coating prod, clean with clear water, be 200 ℃ of bakings 1 hour with baking oven in temperature again, get final product the hydroxyapatite coating layer in plasma spraying product of high stability, high biological activity.
Embodiment four
The mixture of potassium hydroxide and sodium hydroxide is dissolved in deionized water, and the preparation hydroxide ion concentration is 10 mol electrolyte solutions, and the electrolyte solution that makes is contained in the metal vessel; The metal base of the hydroxyapatite coating layer product that plasma spraying is made is connected with the anode of constant current direct supply, and the negative electrode of metallic container shell with the constant current direct supply is connected; Used constant current direct supply output voltage is that the 0-200 volt is adjustable continuously, outward current is 15 amperes; The hydroxyapatite coating layer product is immersed in the mixed electrolyte solutions of potassium hydroxide and sodium hydroxide, connect the constant current direct supply, constant current direct supply output voltage is adjusted to 40 volts, handle after 30 seconds, disconnect the constant current direct supply, take out coating prod, clean with clear water, be 100 ℃ of bakings 3 hours with baking oven in temperature again, get final product the hydroxyapatite coating layer in plasma spraying product of high stability, high biological activity.
Embodiment five
The mixture of ammonium hydroxide and sodium hydroxide is dissolved in deionized water, and the preparation hydroxide ion concentration is 1 mol electrolyte solution, and the electrolyte solution that makes is contained in the metal vessel; The metal base of the hydroxyapatite coating layer product that plasma spraying is made is connected with the anode of constant current direct supply, and the negative electrode of metallic container shell with the constant current direct supply is connected; Used constant current direct supply output voltage is that the 0-200 volt is adjustable continuously, outward current is 15 amperes; The hydroxyapatite coating layer product is immersed in the mixed electrolyte solutions of potassium hydroxide and sodium hydroxide, connect the constant current direct supply, constant current direct supply output voltage is adjusted to 60 volts, handle after 60 seconds, disconnect the constant current direct supply, take out coating prod, clean with clear water, be 100 ℃ of bakings 3 hours with baking oven in temperature again, get final product the hydroxyapatite coating layer in plasma spraying product of high stability, high biological activity.
Claims (4)
1, a kind of method for post treatment of plasma spraying hydroxyapatite coating is characterized in that, comprises following processing step:
(1) at first prepares negative ion and only be the electrolyte solution of hydroxide ion, the electrolyte solution that makes is contained in the metal vessel;
(2) metal base with the hydroxyapatite coating layer in plasma spraying product is connected with the anode of a constant current direct supply, the negative electrode of metallic container shell with the constant current direct supply is connected, then the hydroxyapatite coating layer product is immersed in the electrolyte solution in the metal vessel, connect the constant current direct supply, coating prod is handled under the effect of constant current direct supply, and the treatment time is 10-150 second;
(3) disconnect the constant current direct supply, take out the hydroxyapatite coating layer in plasma spraying product; At last coating prod is cleaned with clear water, dry again, get final product to such an extent that have a hydroxyapatite coating layer in plasma spraying product that high stability has high biological activity again.
2, in accordance with the method for claim 1, it is characterized in that, said negative ion is a sodium hydroxide for the electrolyte solution of hydroxide ion only, or potassium hydroxide, or the solution that is mixed with of ammonium hydroxide or their mixture and deionized water, its hydroxide ion concentration is a 0.1-10 mol solution.
3, in accordance with the method for claim 1, it is characterized in that the outward current of said constant current direct supply is 15 amperes, output voltage is a continuous adjustable voltage between the 0-200 volt.
According to claim 1 or 2 or 3 described methods, it is characterized in that 4, the storing time when hydroxyapatite coating layer in plasma spraying product is after treatment dried is 1-3 hour, storing temperature is 100-200 ℃, uses baking oven to dry.
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| CNB2005100210265A CN100357485C (en) | 2005-06-03 | 2005-06-03 | Method for post treatment of plasma spraying hydroxyapatite coating |
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| CNB2005100210265A CN100357485C (en) | 2005-06-03 | 2005-06-03 | Method for post treatment of plasma spraying hydroxyapatite coating |
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| CN100357485C true CN100357485C (en) | 2007-12-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184626A (en) * | 1997-11-19 | 1998-06-17 | 化南理工大学 | Method for preparing artificial joint with bio-active gradient coating |
| US20020084194A1 (en) * | 2000-12-28 | 2002-07-04 | The Board Of Regents Of The University Of Nebraska | Electrolytic deposition of coatings for prosthetic metals and alloys |
| CN1505532A (en) * | 2001-04-02 | 2004-06-16 | ˹��̩��ҽѧ�ɷݹ�˾ | Bioactive surface layer, in particular for medical implants and prostheses |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184626A (en) * | 1997-11-19 | 1998-06-17 | 化南理工大学 | Method for preparing artificial joint with bio-active gradient coating |
| US20020084194A1 (en) * | 2000-12-28 | 2002-07-04 | The Board Of Regents Of The University Of Nebraska | Electrolytic deposition of coatings for prosthetic metals and alloys |
| CN1505532A (en) * | 2001-04-02 | 2004-06-16 | ˹��̩��ҽѧ�ɷݹ�˾ | Bioactive surface layer, in particular for medical implants and prostheses |
Non-Patent Citations (2)
| Title |
|---|
| 生物活性梯度涂层中羟基磷灰石的相转变与结构稳定性 王迎军，宁成云，赵子衷，陈，楷，刘正义.硅酸盐学报，第26卷第5期 1998 * |
| 等离子喷涂羟基磷灰石涂层优化方法的研究进展 孙瑞雪，吕宇鹏，李木森.生物骨科材料与临床研究，第1卷第1期 2003 * |
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