CN100496622C - Strontium containing hydroxyapatite biologically active film and preparation method thereof - Google Patents

Strontium containing hydroxyapatite biologically active film and preparation method thereof Download PDF

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CN100496622C
CN100496622C CNB2006101223712A CN200610122371A CN100496622C CN 100496622 C CN100496622 C CN 100496622C CN B2006101223712 A CNB2006101223712 A CN B2006101223712A CN 200610122371 A CN200610122371 A CN 200610122371A CN 100496622 C CN100496622 C CN 100496622C
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strontium
titanium
hydroxyapatite
calcium
ion
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CN1927410A (en
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王迎军
黄勇
宁成云
南开辉
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention relates to the means of active biological film, especially the titanium radicel porous nanometer Strontium hydroxyapatite active biological film and the Process for the manufacture. The differential arc oxidation technology is used in the method, the film is generated in the surface of titanium and titanium alloy, a electrolyte solution with phosphate radical ion, calcium ion and Strontium 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 time is 3-60min; the temperature of electrolyte is not above 50DEG C. There is no interface between the porous hydroxyapatite containing Strontium film produced by the invention and the basal body, the modulus of elasticity is approximate with the sclerotin, the porous hydroxyapatite containing Strontium film produced by the invention which has perfect bioactivity can be the alternate material of several parts with heavy load, such as femur, hip joint and teeth root.

Description

Strontium containing hydroxyapatite biologically active film and preparation method thereof
Technical field
The present invention relates to method, particularly a kind of titanio porous nano strontium containing hydroxyapatite 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 method for plasma spraying, and prepared rete is being short of aspect the surface porosity factor control to some extent, 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.
Discover that strontium is a kind of trace element that exists in the human body, the content in bone accounts for 0.01% of its weight, and all the accumulating among the skeleton more than 99% of the strontium that contains in the human body (Sr), calcium (Ca).Sr and Ca all belong to alkaline-earth metal, have many similar character.The Sr that exists with ionic forms 2+Sharing and Ca 2+Identical physiology route finally is deposited in the mineralising structure of bone.Studies show that, strontium has the special pharmacological effect of the following aspects: at first, aspect the mineralising and reconstruction of skeleton lesion, the strontium of low dosage helps to increase the quality and the volume of bone, does not find as yet that at present it produces adverse influence to mineralising pattern and mineral chemistry composition; Secondly, aspect bone metabolism, under the continuous supply conditions in the external world, the content of strontium in bone is different different because of anatomical location in the body, and finds that strontium can exchange with the small amount of calcium on phosphorite crystal surface in the bone; Its three, aspect bone conductibility, after the someone has compared the glass ion cement of different strontium contents, find that the highest group of LG125 of strontium content has best bone conductibility; Its four, aspect treatment osteoporosis disease, strontium has also been brought into play significant curative effect.Part calcium in the Sr displacement apatite and the strontium containing hydroxyapatite that obtains, not only have than the better histocompatibility of pure ha, bone conductibility even have to a certain extent bone inducibility, also change its dissolution kinetics, improved biological degradability.Therefore, if strontium can be mixed in the hydroxyapatite film layer, obtain strontium containing hydroxyapatite apatite rete, both can keep the plurality of advantages of former rete, can give full play to strontium again or contain the above-mentioned good pharmacological properties and the biology performance of saamite.Yet, because the diameter of strontium ion is greater than calcium ion, adopt conventional process to be difficult to strontium atom is incorporated among the apatite rete, and strontium/calcium constituent is than wayward in the rete, therefore containing strontium porous hydroxyapatite rete in the titanium or titanium alloy surface preparation at present still belongs to blank.
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.
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 strontium containing hydroxyapatite 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 strontium containing hydroxyapatite biologically active film is characterized in that: adopt differential arc oxidization technique, directly contain strontium porous hydroxyapatite bioactive film in the generation of titanium or titanium alloy surface in situ, comprise the steps and process conditions:
A, provide a kind of electrolyte solution that includes phosphate anion and calcium ion, strontium 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 strontium ion is 0.01~0.5mol/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 strontium ion is provided is at least a in strontium acetate, strontium nitrate, strontium oxalate or strontium chloride preferably.
When adopting dc source, voltage is 200~500V; When adopting direct current pulse power source, voltage is 200~700V, and frequency is 50~5000Hz, and dutycycle is 5~60%.
The bioactive film of method for preparing, and do not have the interface between matrix, being porous nano crystalline texture form, mainly by hydroxyapatite (HA) and the phase composition of strontium containing hydroxyapatite (Sr-HA) thing, wherein the chemical expression of strontium containing hydroxyapatite is Ca to rete 10-XSr X(PO 4) 6(OH) 20<X in the formula≤10, by the concentration and the process conditions control of phosphate anion and calcium ion, strontium ion in the adjustment electrolyte, make strontium in the rete/calcium content than controlled i.e. strontium/calcium ion concentration in rising electrolyte in 0.5~80% scope, strontium in the rete/corresponding increase of calcium constituent ratio.
The present invention compared with prior art has following outstanding advantage:
1, the porous hydroxyapatite rete of the special pharmacological effect that the contains strontium element of the present invention's preparation, there is not the interface between this rete and matrix, with sclerotin approaching elastic modelling quantity is arranged, bond strength height, chemical property are stablized, and have good biological activity and certain pharmacological action.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, because the present invention directly generates strontium containing hydroxyapatite biologically active film in the surface of metal titanium original position, by the concentration of phosphate anion and calcium ion, strontium ion in the adjustment electrolyte, it is controlled that strontium in its rete/calcium constituent ratio is realized in 0.5~80% scope.
3, 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 0.01mol/L, calcium acetate 0.45mol/L, the solution of strontium chloride 0.01mol/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 20 μ m on the titanium surface; X-ray diffraction analysis shows that mainly (wherein the strontium containing hydroxyapatite chemical formula is Ca to this rete by hydroxyapatite and strontium containing hydroxyapatite 10-XSr X(PO 4) 6(OH) 2, 0<X in the formula≤3) form, EDS shows that strontium/calcium constituent ratio is 0.6% in the rete, 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 strontium acetate 0.05mol/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 33 μ m on the titanium surface; X-ray diffraction analysis shows that this rete is mainly by hydroxyapatite and strontium containing hydroxyapatite Ca 10-XSr X(PO 4) 6(OH) 2(X is between 4~6 in the formula) are formed, and EDS shows that strontium/calcium constituent ratio is 9.6% in the rete, and bond strength is 37MPa, has good biological activity.
Embodiment 3
Use distilled water preparation phosphoric acid sodium dihydrogen 0.02mol/L, lime nitrate 0.2mol/L, strontium acetate 0.05mol/L, the solution of strontium oxalate 0.05mol/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 28 μ m on the titanium surface; X-ray diffraction analysis shows that this rete is mainly by hydroxyapatite and strontium containing hydroxyapatite Ca 10-XSr X(PO 4) 6(OH) 2(X is between 4~6 in the formula) are formed, and EDS shows that strontium/calcium constituent ratio is 26.3% in the rete, and the rete bond strength is 33MPa, has good biological activity.
Embodiment 4
Use the distilled water preparation to contain sodium hexameta phosphate 0.01mol/L, calcium oxalate 0.05mol/L, the solution of strontium nitrate 0.05mol/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 is mainly by hydroxyapatite and strontium containing hydroxyapatite Ca 10-XSr X(PO 4) 6(OH) 2(X is between 6~8 in the formula) are formed, and EDS shows that strontium/calcium constituent ratio is 43.7% in the rete, and the rete bond strength is 35MPa, has good biological activity.
Embodiment 5
Use distilled water preparation phosphoric acid hydrogen sodium 0.05mol/L, calcium acetate 0.05mol/L, the solution of strontium oxalate 0.1mol/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 4000Hz, 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 is mainly by hydroxyapatite and strontium containing hydroxyapatite Ca 10-XSr X(PO 4) 6(OH) 2(X is between 6~8 in the formula) are formed, and EDS shows that strontium/calcium constituent ratio is 68.6% in the rete, and the rete bond strength is 26MPa, has good biological activity.
Embodiment 6
Use the distilled water preparation to contain sodium 0.2mol/L, calcium acetate 0.1mol/L, lime nitrate 0.1mol/L, the solution of strontium oxalate 0.5mol/L.With the titanium alloy is anode, and rustless steel or titanium are negative electrode, adopts direct current pulse power source to carry out differential arc oxidation.Voltage is 350~450V, and frequency is 500Hz, and dutycycle is 30%; Keep electrolyte temperature at 30~50 ℃, the oxide deposition time is 15min; Form the porous layer that thickness is about 32 μ m on the titanium surface; X-ray diffraction analysis shows that this rete is mainly by hydroxyapatite and strontium containing hydroxyapatite Ca 10-XSr X(PO 4) 6(OH) 2(X is between 7~10 in the formula) are formed, and EDS shows that strontium/calcium constituent ratio is 79.4% in the rete, and the rete bond strength is 21MPa, has good biological activity.

Claims (3)

1, a kind of preparation method of strontium containing hydroxyapatite biologically active film is characterized in that: adopt differential arc oxidization technique, directly contain strontium porous hydroxyapatite bioactive film in the generation of titanium or titanium alloy surface in situ, comprise the steps and process conditions:
A, provide a kind of electrolyte solution that includes phosphate anion and calcium ion, strontium ion;
B, be anode with titanium or titanium alloy in above-mentioned electrolyte solution, 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 solution temperature are not higher than 50 ℃;
The content range of phosphate anion is 0.01~0.2mol/L in the described electrolyte solution, and the content range of calcium ion is 0.01~0.5mol/L, and the content range of strontium ion is 0.01~0.5mol/L;
Described dc source voltage is 200~500V; Described dc pulse current voltage is 200~700V, and frequency is 50~5000Hz, and dutycycle is 5~60%.
2, the preparation method of a kind of strontium containing hydroxyapatite biologically active film according to claim 1 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 solution; 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 strontium ion to be selected from least a in strontium acetate, strontium nitrate, strontium oxalate or the strontium chloride.
3, a kind of strontium containing hydroxyapatite biologically active film of preparation method preparation according to claim 1, it is characterized in that: do not have the interface between this bioactive film and matrix, be porous nano crystalline texture form, mainly by hydroxyapatite and the phase composition of strontium containing hydroxyapatite thing, wherein the chemical expression of strontium containing hydroxyapatite is Ca to rete 10-XSr X(PO 4) 6(OH) 20<X in the formula<10, concentration and process conditions control by phosphate anion and calcium ion, strontium ion in the adjustment electrolyte solution, make strontium in the rete/calcium content than controlled in 0.5~80% scope, promptly strontium/calcium ion concentration raises in electrolyte solution, strontium in the rete/corresponding increase of calcium constituent ratio.
CNB2006101223712A 2006-09-25 2006-09-25 Strontium containing hydroxyapatite biologically active film and preparation method thereof Expired - Fee Related CN100496622C (en)

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