CN1927411A - Rare earth-hydroxyapatite composite biologically active film and preparation method thereof - Google Patents
Rare earth-hydroxyapatite composite biologically active film and preparation method thereof Download PDFInfo
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- CN1927411A CN1927411A CN 200610122390 CN200610122390A CN1927411A CN 1927411 A CN1927411 A CN 1927411A CN 200610122390 CN200610122390 CN 200610122390 CN 200610122390 A CN200610122390 A CN 200610122390A CN 1927411 A CN1927411 A CN 1927411A
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Abstract
The invention relates to the means of active biological film on the surface of metal materials, especially the titanium radicel rare earth hydroxyapatite complex active biological film and the process for the manufacture. The differential arc oxidation technology is used in the method, the complex active biological film is generated in the surface of titanium and titanium alloy, a electrolyte solution with phosphate radical ion, calcium ion and rare earth ion is supplied; the titanium and titanium alloy is the anode and the rustless steel or the titanium is the cathode, the direct current power supply or the direct current impulsing power source is applied to differential arc oxygenize the titanium and titanium alloy; the oxidate deposit time is 3-60min; the temperature of electrolyte is not above 50DEG C. The film produced by the method which has perfect bioactivity, high conjugation, and stable chemical property can be the alternate material of several parts with heavy load to accelerate the postoperative healing, such as femur, hip joint and teeth root.
Description
Technical field
The present invention relates to method, particularly a kind of titanio rare earth-hydroxyapatite composite biologically active film that is used as femur, hip joint and root of the tooth and preparation method thereof at medical metal material surface preparation bioactive film.
Background technology
The development and application of various biomedical materials in recent years obtains develop rapidly, and wherein, metal material is used the earliest.Metallic biomaterial generally has higher intensity and toughness, is applicable to hard tissue repair and fixing.The common metal biomaterial has cobalt to annotate.But because the case hardness of titanium or titanium alloy is hanged down basic alloy, tantalum, titanium or titanium alloy etc., wherein, titanium and alloy thereof are with its superior corrosion resisting property, high specific strength, excellent biological compatibility and be suitable for characteristics such as implantation and extensively paid close attention to, but owing to wear no resistance, its application are restricted.In addition, titanium and alloy thereof all are bio-inert materials, can only and the growth bone between produce mechanical bond and can not form chemical bond, thereby be necessary titanium and alloy thereof are carried out the bioactivation modification.Prepare the bioactive ceramics rete by process for modifying surface at metal base surface and become Recent study focus and development trend.
The preparation method of Chinese patent ZL97119791.1 artificial joint with bio-active gradient coating discloses the method that a kind of metal surface prepares hydroxyapatite (Hydroxyapatite is called for short HA) coating.Because HA is the essential mineral composition of skeleton, has excellent biological compatibility, implant into body is not only safe, nontoxic, can also conduct osteogenesis, make new bone seek connections with growth along surface and internal void from HA implant and green bone junction, therefore this invention makes material both have the bond strength of metal material, has good biological activity again, induce new bone directly and implantation material surface form firm bone bonding.But this patent adopts the prepared rete of method of plasma spraying being short of to some extent aspect the surface porosity factor control, has influenced the postoperative osseous tissue speed of growing into.And single hydroxyapatite composition in the rete top layer, the postoperative healing rate is influenced to some extent.
Though rare earth element is not an essential element, but the biological effect to it studies show that, rare earth element has promotion or inhibitory action to some substance metabolism processes of body cell and the activity of enzyme, particularly some rare earth compound has facilitation to vegeto-animal growth, the focus that becomes people's research and utilize.Rare earth is effective germicide.Rare earth compound has shown its characteristics and superiority in the application aspect medical, for performance, the raising drug effect of improving medicine found new approach.Trace rare-earth element is extremely effective at aspects such as edible, health care, medical assistances.Yet conventional method is difficult to effectively rare earth element is compound among the film layer structure, contains rare earth porous hydroxyapatite rete in the titanium or titanium alloy surface preparation at present and does not see that as yet report is arranged.
Preparation at present has plasma spraying method, ion beam sputtering, sol-gel process and micro arc oxidizing compounding process method (differential arc oxidation-hydrothermal treatment consists, differential arc oxidation-electrophoretic deposition combination process, differential arc oxidation-mineralising deposition combination process etc.) in the main method of metal surface hydroxyapatite film layer.Wherein, plasma spraying method is to adopt hydroxyapatite powder, through the plasma high temperature melt, makes particle adhesion on matrix, since the heating of granule process high temperature, volatilization easily, and therefore, the thin film of formation is formed and is difficult to control.Ion beam sputtering is to prepare hydroxyapatite by ion beam sputtering, and film integral content is difficult to control.Though the chemical constituent of sol-gel process thin film easy to control and microstructure need the post processing of high annealing, influence the performance of matrix material.Micro arc oxidizing compounding process method ubiquity strengthens the complex process degree, weakens unfavorable factors such as film adhesion; For example differential arc oxidation bound water heat treatment can transform and separate out HA, but the rete bond strength has reduced by 40%; Electrophoretic deposition utilizes electric field action to make HA be deposited on the metal surface, but owing in conjunction with loose, also need follow-up sintering processes, so not only reduced film adhesion, and sintering process has weakened the biological activity of material.If above-mentioned each method can be learnt from other's strong points to offset one's weaknesses, then be expected to realize better solving bond strength, stability and the biological activity problem of rete, for utilizing rare earth compound the advantage that vegeto-animal growth has facilitation is opened up new way.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, provide a kind of and prepare good and rare earth-hydroxyapatite composite biologically active film of having no side effect of face bond strength height, good stability and biological activity and preparation method thereof at medical titanium Base Metal material list.
Above-mentioned purpose of the present invention reaches by following measure.
A kind of preparation method of rare earth-hydroxyapatite composite biologically active film, it is characterized in that: adopt differential arc oxidization technique, directly generate porous rare earth-hydroxyapatite composite biologically active film, comprise the steps and process conditions at the titanium or titanium alloy surface in situ:
A, provide a kind of electrolyte solution that includes phosphate anion and calcium ion, rare earth element ion;
B, be anode with titanium or titanium alloy in above-mentioned specific electrolyte, rustless steel or titanium are negative electrode, adopt dc source or direct current pulse power source to titanium or titanium alloy differential arc oxidation;
C, oxide deposition time are 3～60min;
D, electrolytic process electrolyte temperature are not higher than 50 ℃.
The optimum content scope of phosphate anion is 0.01～0.2mol/L in the described electrolyte, and the optimum content scope of calcium ion is 0.01～0.5mol/L, and the optimum content scope of rare earth element ion is 0.001～0.02mol/L;
The electrolyte that phosphate anion is provided is at least a in sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, sodium or sodium hexameta phosphate preferably; The electrolyte that calcium ion is provided is at least a in calcium acetate, lime nitrate, calcium oxalate or calcium chloride preferably; The electrolyte that rare earth element ion is provided is any in lanthanum acetate, Lanthanum (III) nitrate, Cerium triacetate or cerous nitrate preferably.
When adopting dc source, voltage is 200～500V; When adopting dc pulse current, voltage is 200～700V, and frequency is 50～5000Hz, and dutycycle is 5～60%.
The bioactive film of method for preparing contains rare earth element (Ce is or/and La), and there is not the interface between matrix, be porous nano crystalline texture form, rete is that Ce is or/and the phase composition of La-HA thing by hydroxyapatite and the hydroxyapatite that contains rare earth element (Ce is or/and La) mainly, concentration and process conditions control by adjusting electrolyte middle rare earth element ion make rete middle rare earth constituent content controlled.
The present invention compared with prior art has following outstanding advantage:
1, the porous composite hydroxylapatite rete that contains rare earth element of the present invention's preparation does not have the interface between this rete and matrix, with sclerotin approaching elastic modelling quantity is arranged, and good biological activity is stablized, had to bond strength height, chemical property.Rete as the medical implantation body of titanio not only has no side effect, and with the green bone strong bonded, bone is strong between bone alternate material and the osseous tissue combines, and forms interface successive, gradient and combine between implant and bone; Solved existing biofilms layer adhesion a little less than, a difficult problem such as surface activity is not high, and biocompatibility is relatively poor makes this material can be used as the substitution material that femur, hip joint and root of the tooth etc. bear big load position effectively.
2, make full use of rare earth compound vegeto-animal growth has been had the advantage of facilitation, used this substitution material can accelerate the postoperative healing.
3, because the present invention directly generates the composite hydroxylapatite bioactive film that contains rare earth element in the surface of metal titanium original position, by the concentration of phosphate anion and calcium ion, compound rare-earth element ion in the adjustment electrolyte, it is controlled that its rete middle rare earth constituent content is realized.
4, preparation technology of the present invention is simple, quick, easy and simple to handle, is easy to apply.
The specific embodiment
Embodiment 1
Use the distilled water preparation to contain sodium hexameta phosphate 0.01mol/L, sodium phosphate 0.01mol/L, calcium acetate 0.3mol/L, the solution of lanthanum acetate 0.001mol/L.With the titanium is anode, and rustless steel or titanium are negative electrode, adopts dc source to carry out differential arc oxidation.Voltage is 300～500V; Keep electrolyte temperature not to be higher than 50 ℃.Differential arc oxidation is 5min, forms the porous layer that thickness is about 23 μ m on the titanium surface; X-ray diffraction analysis shows that this rete mainly is made up of hydroxyapatite, and EDX shows that La content is 0.4% in the rete, and the rete bond strength is 43MPa, has good biological activity.
Embodiment 2
Use the distilled water preparation to contain sodium 0.15mol/L, calcium chloride 0.2mol/L, the solution of Cerium triacetate 0.003mol/L.With the titanium alloy sheet is anode, and rustless steel or titanium are negative electrode, adopts dc source to carry out differential arc oxidation.Voltage is 200～400V; Keep electrolyte temperature not to be higher than 50 ℃.Differential arc oxidation is 30min, forms the porous layer that thickness is about 29 μ m at titanium alloy surface; X-ray diffraction analysis shows that this rete mainly is made up of hydroxyapatite, and EDX shows that Ce content is 0.9% in the rete, and the rete bond strength is 43MPa, has good biological activity.
Embodiment 3
Use distilled water preparation phosphoric acid sodium dihydrogen 0.02mol/L, lime nitrate 0.2mol/L, the solution of Lanthanum (III) nitrate 0.01mol/L.With the titanium alloy sheet is anode, and rustless steel or titanium are negative electrode, adopts direct current pulse power source to carry out differential arc oxidation.Voltage is 250～450V, and frequency is 300Hz, and dutycycle is 55%; Keep electrolyte temperature at 30～50 ℃.The oxide deposition time is 60min; Form the porous layer that thickness is about 26 μ m at titanium alloy surface; X-ray diffraction analysis shows that this rete mainly is made up of hydroxyapatite, and EDX shows that rete middle rare earth La content is 1.7%, and the rete bond strength is 36MPa, has good biological activity.
Embodiment 4
Use the distilled water preparation to contain sodium hexameta phosphate 0.01mol/L, calcium oxalate 0.01mol/L, the solution of cerous nitrate 0.01mol/L.With the titanium is anode, and rustless steel or titanium are negative electrode, adopts direct current pulse power source to carry out differential arc oxidation.Voltage is 450～550V, and frequency is 50Hz, and dutycycle is 25%; Keep electrolyte temperature at 30～50 ℃, the oxide deposition time is 20min; Form the porous layer that thickness is about 27 μ m on the titanium surface; X-ray diffraction analysis shows that this rete mainly is made up of hydroxyapatite, and EDX shows that Ce content is 2.1% in the rete, and the rete bond strength is 43MPa, has good biological activity.
Embodiment 5
Use the distilled water preparation to contain sodium 0.2mol/L, dibastic sodium phosphate 0.05mol/L, calcium chloride 0.45mol/L, the solution of lanthanum acetate 0.02mol/L.With the titanium is anode, and rustless steel or titanium are negative electrode, adopts direct current pulse power source to carry out differential arc oxidation.Voltage is 550～700V, and frequency is 2000Hz, and dutycycle is 5%; Keep electrolyte temperature at 30～50 ℃, the oxide deposition time is 3min; Form the porous layer that thickness is about 39 μ m on the titanium surface; X-ray diffraction analysis shows that this rete mainly is made up of hydroxyapatite, and EDX shows that rete middle rare earth La content is 3.6%, and the rete bond strength is 36MPa, has good biological activity.
Embodiment 6
Use distilled water preparation phosphoric acid sodium dihydrogen 0.01mol/L, calcium oxalate 0.05mol/L, calcium chloride 0.10mol/L, lanthanum acetate 0.005mol/L, the solution of Cerium triacetate 0.005mol/L.With the titanium is anode, and rustless steel or titanium are negative electrode, adopts direct current pulse power source to carry out differential arc oxidation.Voltage is 550～700V, and frequency is 5000Hz, and dutycycle is 5%; Keep electrolyte temperature at 30～50 ℃, the oxide deposition time is 10min; Form the porous layer that thickness is about 41 μ m on the titanium surface; X-ray diffraction analysis shows that this rete mainly is made up of hydroxyapatite, and EDX shows that rete middle rare earth La content is 0.8%, and Ce content is 1.2%, and the rete bond strength is 34MPa, has good biological activity.
Claims (5)
1, a kind of preparation method of rare earth-hydroxyapatite composite biologically active film, it is characterized in that: adopt differential arc oxidization technique, directly generate porous rare earth-hydroxyapatite composite biologically active film, comprise the steps and process conditions at the titanium or titanium alloy surface in situ:
A, provide a kind of electrolyte solution that includes phosphate anion and calcium ion, rare earth element ion;
B, be anode with titanium or titanium alloy in above-mentioned specific electrolyte, rustless steel or titanium are negative electrode, adopt dc source or direct current pulse power source to titanium or titanium alloy differential arc oxidation;
C, oxide deposition time are 3～60min;
D, electrolytic process electrolyte temperature are not higher than 50 ℃.
2, the preparation method of a kind of rare earth-hydroxyapatite composite biologically active film according to claim 1, it is characterized in that: the content range of phosphate anion is 0.01～0.2mol/L in the described electrolyte, the content range of calcium ion is 0.01～0.5mol/L, and the content range of rare earth element ion is 0.001～0.02mol/L.
3, the preparation method of a kind of rare earth-hydroxyapatite composite biologically active film according to claim 1 and 2 is characterized in that: provide the electrolyte of phosphate anion to be selected from least a in sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, sodium or the sodium hexameta phosphate in the described electrolyte; Provide the electrolyte of calcium ion to be selected from least a in calcium acetate, lime nitrate, calcium oxalate or the calcium chloride; Provide the electrolyte of rare earth element ion to be selected from least a in lanthanum acetate, Lanthanum (III) nitrate, Cerium triacetate or the cerous nitrate.
4, the preparation method of a kind of rare earth-hydroxyapatite composite biologically active film according to claim 1 is characterized in that: when adopting dc source, voltage is 200～500V; When adopting dc pulse current, voltage is 200～700V, and frequency is 50～5000Hz, and dutycycle is 5～60%.
5, a kind of rare earth-hydroxyapatite composite biologically active film of preparation method preparation according to claim 1, it is characterized in that: this bioactive film is compounded with rare earth element; And there is not the interface between matrix, be porous nano crystalline texture form, rete is Ce by hydroxyapatite and the hydroxyapatite that contains rare earth element mainly or/and the phase composition of La-HA thing, and concentration and process conditions control by adjusting electrolyte middle rare earth element ion make the rete ree content controlled.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631705A (en) * | 2012-04-27 | 2012-08-15 | 中南大学 | Lanthanum-doped hydroxyapatite compound coating and preparation method thereof |
| CN102747403A (en) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | Method of preparing magnesium-doped hydroxyapatite/titania active film on surface of medical titanium alloy |
| CN107115564A (en) * | 2017-03-09 | 2017-09-01 | 温州医科大学附属口腔医院 | A kind of method for preparing the pure titanium implant material for carrying cerium oxide nano particle functional film layer |
| CN109205582A (en) * | 2018-10-22 | 2019-01-15 | 南昌航空大学 | A kind of method that presoma conversion prepares nano-pore hydroxyapatite |
| CN114703530A (en) * | 2022-04-28 | 2022-07-05 | 徐州工程学院 | Method for compositely constructing samarium-doped hydroxyapatite gradient coating on surface of magnesium alloy by utilizing electrophoresis/micro-arc oxidation technology |
-
2006
- 2006-09-25 CN CNB2006101223905A patent/CN100488574C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631705A (en) * | 2012-04-27 | 2012-08-15 | 中南大学 | Lanthanum-doped hydroxyapatite compound coating and preparation method thereof |
| CN102747403A (en) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | Method of preparing magnesium-doped hydroxyapatite/titania active film on surface of medical titanium alloy |
| CN102747403B (en) * | 2012-07-03 | 2014-10-29 | 淮阴工学院 | Method of preparing magnesium-doped hydroxyapatite/titania active film on surface of medical titanium alloy |
| CN107115564A (en) * | 2017-03-09 | 2017-09-01 | 温州医科大学附属口腔医院 | A kind of method for preparing the pure titanium implant material for carrying cerium oxide nano particle functional film layer |
| CN109205582A (en) * | 2018-10-22 | 2019-01-15 | 南昌航空大学 | A kind of method that presoma conversion prepares nano-pore hydroxyapatite |
| CN109205582B (en) * | 2018-10-22 | 2021-09-17 | 南昌航空大学 | Method for preparing nano-pore hydroxyapatite by precursor conversion |
| CN114703530A (en) * | 2022-04-28 | 2022-07-05 | 徐州工程学院 | Method for compositely constructing samarium-doped hydroxyapatite gradient coating on surface of magnesium alloy by utilizing electrophoresis/micro-arc oxidation technology |
| CN114703530B (en) * | 2022-04-28 | 2023-08-25 | 徐州工程学院 | Method for compositely constructing samarium-doped hydroxyapatite gradient coating on magnesium alloy surface by utilizing electrophoresis/micro-arc oxidation technology |
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