CN103386148B - Bone repair material containing multi-element biocover and preparation method thereof - Google Patents
Bone repair material containing multi-element biocover and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bone repair material containing a multi-element biocover. The bone repair material is of a three-layer structure, wherein an inner layer is a metallic matrix, an intermediate layer is a plasma electrolytic oxidation film, and an outer layer is the multi-element biocover. The preparation method for the material comprises the following steps: pretreating the metallic matrix; then preparing the oxidation film containing Ca and P on the surface of the metallic matrix by using a plasma electrolytic oxidation process; preparing a coating containing bone-like elements by using a Czochralski method; and finally carrying out heat treatment so as to obtain the bone repair material rich in Ca and P and containing a trace amount of the bone-like elements consisting of Mg, Mn, Na, Ce, Dy, Y and Si. According to the invention, since the plasma electrolytic oxidation film is used as the intermediate layer and the material has the multi-element biocover formed by a plurality of bone-like elements, the material has high coating interfacial bonding strength and good biological activity; moreover, biological properties of the multi-element biocover can be adjusted by controlling Czochralski process parameters and varieties and concentrations of the bone-like elements, so the material has better capability in induction of deposition of apatite.
Description
Technical field
The invention belongs to Metal Surface Modification Technique field, relate to a kind of bone renovating material, more specifically relate to one and contain tectal bone renovating material of multi-element biologic and preparation method thereof.
Background technology
Metal titanium or titanium alloy is with its high strength, high specific strength, good toughness, and low elastic modulus and good anti-corrosion wear performance and biocompatibility, become bone renovating material study hotspot.At present, titanium or titanium alloy has been widely used in artificial bone, joint sole, knochenbruch holder, intramedullary pin, Cardiac valve prosthesis, skull, operating theater instruments etc. as bone renovating material.But titanium alloy is a kind of bio-inert material after all, its bone conductibility is poor, and a little less than the combination between bone, and long-term implant into body may produce wearing and tearing or digestion of metallic ion, far can not reach bone renovating material requirement, so researcheres do a lot of work to improve the biological property of titanium alloy.The titanium alloy that surface coverage contains bioactivity coatings, can improve biological property, because osseous tissue is mainly made up of calcium, phosphor inorganic salt, also contain electric charge and the similar inorganic ions of diameter of the carbonate of calcium and some and calcium ion, and the biological coating of titanium alloy surface can be induced the hydroxyapatite deposition of class bone, thereby improve the performance of whole repair materials.Some conventional titanium alloy surface biological coating preparation methoies have: plasma spraying, chemical vapour deposition (CVD), anodic oxidation, spatial induction mineralising method, ion implantation, heat treatment etc.These methods have certain effect for improving titanium alloy bone conductibility and biocompatibility, but also exist a lot of not enough.Biological coating is prepared in plasma spraying and chemical vapour deposition (CVD), and metallic matrix belongs to mechanical bond with painting interlayer, and interface bond strength is not high, and the reaction vessel of reaction needed high temperature and airtight decompression, and coating preparation cost is high.Anodic oxidation is high to form of metal dimensional requirement, endoporus and complicated shape difficult processing, and also coating is thin, and hardness is lower.Spatial induction mineralising method can obtain the apatite coating needing, but length consuming time.Biological coating element prepared by simple heat treatment is more single, and biological property is not ideal.
In recent years, plasma electrolysis oxidation technology has attracted more and more people's attention, as the promising process for modifying surface of one, this method has many significant advantages with the coating that it forms: coating has high rigidity, high-wearing feature, heat stability and good corrosion resistance; Coating and matrix are metallurgical state, in conjunction with firm; Preparation cost is cheap, and adaptability for materials is wide etc.But adopt the biological coating weak point of bone renovating material prepared by plasma electrolysis oxidation technology to be: the contained material of coating is single, Shortcomings on biological multielement, be unfavorable for combination and the propagation of osteocyte, make the biological property of titanium alloy on the low side, be not easy to be absorbed by surrounding tissue, easily produce local segregation.
Summary of the invention
The object of the invention is to solve the problems such as the bone renovating material face coat bond strengths such as titanium alloy are not high, biological property is on the low side, provides a kind of face coat to be rich in multiple types bone element and has bone renovating material of high interface bond strength and preparation method thereof with metallic matrix.
For achieving the above object, technical scheme of the present invention is:
One contains the tectal bone renovating material of multi-element biologic, it is characterized in that material is made up of metallic matrix, plasma electrolysis oxidation film and multi-element biologic cover layer parcel from the inside to the outside successively.Wherein said metallic matrix is titanium, titanium alloy T i-Al-V or titanium alloy T i-Zr-Nb; Described plasma electrolysis oxidation film is Ca, P oxide-film; Described multi-element biologic cover layer is to contain one or more in class bone element M g, Mn, Na, Ce, Dy, Y and Si.
The shape of described metallic matrix and size are arbitrary shape and size.
The thickness of described plasma electrolysis oxidation film is 5～30 μ m.
The tectal thickness of described multi-element biologic is 0.5～1 μ m.
The preparation method that contains the tectal bone renovating material of multi-element biologic of the present invention is: first by metallic matrix pretreatment, then on plasma electrolysis oxidation method is on metal base surface, prepare the oxide-film that one deck contains Ca, P, prepare with czochralski method the coating that contains class bone element again, then finally obtain being rich in the bone renovating material of Ca, P element and micro Mg, Mn, Na, Ce, Dy, Y, Si through Overheating Treatment.Concrete preparation process is as follows:
The first step, metal base surface pretreatment.Adopt silicon carbide paper to polish to 50～2000# metal base surface, and bore at the place of keeping to the side the hole that multiple apertures are 1～5mm, aperture is preferably 2.5～3.5mm; Adopt distilled water, dehydrated alcohol or acetone to clean, preferably acetone, then naturally dries or dries up.Fixed length plain conductor in hole, wire external layer is coated high temperature resistant gum cover, preferably hard aluminum wire.
Second step: the standby oxide-film containing Ca, P of plasma electrolysis oxidation legal system.The electrolyte solution using: Ca (CH
3cOO)
2﹒ H
2o concentration 0.03～0.07mol/L, NaH
2pO
4﹒ 2H
2o concentration is 0.05～0.1mol/L, EDTA-2Na concentration 0.04-0.115mol/L, and NaOH concentration is 0.3～3mol/L.Preparation parameter: positive negative current 0.5～25A, forward voltage 200～500V, negative voltage 50～100V, pulse frequency 50～1000Hz, positive negative duty 40～60%.What obtain is 5～30 μ m containing Ca, P composite membrane thickness.
The 3rd step: the multi-element biologic cover layer that contains other class bone element on the existing Ca of containing, P plasma electrolysis oxidation film with czochralski method preparation.
First configure the solution of required introducing class bone element, optionally one or more materials in magnesium acetate, manganese acetate, Cerium triacetate, Yttrium trinitrate, acetic acid dysprosium, sodium silicate, add chelating agent citric acid (or sodium ethylene diamine tetracetate), dropping distilled water is stirred to compound and all dissolves, and be mixed with solution at 40 DEG C～100 DEG C heating 0.1～5h, wherein the concentration of citric acid (or sodium ethylene diamine tetracetate) be in solution above-mentioned various types of bone element salinity sum and 1～4 times, preferably 2～3 times.
Then lift dryly, at room temperature the metallic matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned solution, then propose colloidal sol with the speed of 0.01～20mm/s, then room temperature hangs finish-drying.Dried sample repeats to lift loft dried process again, and number of repetition is 1～20 time, and best 5～10 times, making multi-element biologic overburden cover is 0.5～1 μ m.
In this step, preparing environment is under air atmosphere.
The 4th step: sample is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 200 DEG C～500 DEG C, best 400 DEG C, programming rate is 1～30 DEG C/min.Heat treatment time is 0.5～10h, obtains multi-element biologic composite bed.
The tectal bone renovating material of multi-element biologic that contains of the present invention, owing to adopting plasma electrolysis oxidation film as intermediate layer, and have the cover layer that contains multiple types bone element (Ca, P, Mg, Mn, Na, Ce, Dy, Y, Si), can reach following effect:
(1) composite coating that contains multiple types bone component has better induction and deposition apatite ability.
(2) lift procedure parameter by control and can change the thickness of coating, or pass through to introduce kind and the concentration of class bone element, the tectal biological property of capable of regulating multi-element biologic.
(3) due to plasma electrolysis oxidation film rough surface, there is ultrafine micropore structure, lift multi-element biologic coating and the plasma electrolysis oxidation film that heat treatment obtains and there is high interface bond strength.
(4) PROCESS FOR TREATMENT cost is relatively cheap.
Brief description of the drawings
Fig. 1 is the structural representation that contains the tectal bone renovating material of multi-element biologic.
Fig. 2 is the preparation flow figure that contains the tectal bone renovating material of multi-element biologic.
Detailed description of the invention
Embodiment 1
The block matrix that is Ti-6Al-4V by material adopts the silicon carbide paper of No. 50-800 to polish successively, and then the hole that hole diameter is 2.5mm adopts dehydrated alcohol to clean and dry up.The copper conductor of fixed length 20cm in aperture, wire and matrix junction are coated high temperature resistant gum cover.Adopt the oxide-film of plasma electrolysis oxidation technology preparation containing Ca, P, Ca(CH
3cOO)
2﹒ H
2o0.07mol/L; NaH
2pO
4﹒ 2H
2o0.06mol/L; EDTA-2Na0.05mol/L, NaOH0.3mol/L, solvent is distilled water, forward current 0.5A, negative sense 0.5A; Pulse frequency 50Hz; Positive negative duty 50%, generating ceramic membrane thickness is 20 μ m.Prepare the coating containing micro Mg class bone element with czochralski method again, configure the mixed solution of magnesium acetate and citric acid, concentration ratio is 1:2, stirs, and solution is made colloidal sol 60 DEG C of heating 30min left and right.At room temperature the Ti-6Al-4V matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned colloidal sol, then propose with the speed of 0.5mm/s, then room temperature hangs finish-drying.Dried sample repeats to lift loft dried process again, and number of repetition is 5 times.Sample after above-mentioned lifting is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 400 DEG C, programming rate is 5 DEG C/min, heat treatment time is 1h, obtains multi-element biologic composite bed.Ca, the P of gained, the biological composite bed of Mg and titanium alloy interface bond strength are 38MP, present better induction and deposition hydroxyapatite ability in simulated body fluid, approximately need 5 days, and deposition are many.
Embodiment 2
The block matrix that is pure titanium by material adopts the silicon carbide paper of No. 50-2000 to polish successively, and boring aperture is 1mm, then adopts dehydrated alcohol to clean and dry up.The copper conductor of fixed length 10cm in aperture, wire external layer is coated high temperature resistant gum cover.Adopt the oxide-film of plasma electrolysis oxidation technology preparation containing Ca, P, Ca(CH
3cOO)
2﹒ H
2o0.03mol/L; NaH
2pO
4﹒ 2H
2o0.05mol/L; EDTA-2Na0.04mol/L, NaOH0.3mol/L, solvent is distilled water, forward voltage 200V, negative sense 50V; Pulse frequency 1000Hz; Positive negative duty 40%, generates ceramic membrane thickness and is about 5 μ m.Prepare the coating containing micro-Mn and Mg class bone element with czochralski method again, configure the mixed solution of magnesium acetate, manganese acetate and sodium ethylene diamine tetracetate, concentration ratio is 1:3:12, stirs, and solution is made colloidal sol 40 DEG C of heating 2h left and right.At room temperature the metallic matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned colloidal sol, then propose with the speed of 20mm/s, then room temperature hangs finish-drying.Dried sample repeats to lift loft dried process again, and number of repetition is 20 times.Sample after above-mentioned lifting is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 400 DEG C, programming rate is 2 DEG C/min, heat treatment time is 0.1h, obtains multi-element biologic composite bed.Ca, the P of gained, the biological composite bed of Mg, Mn and titanium alloy interface bond strength are 45MP, present better induction and deposition hydroxyapatite ability in simulated body fluid, approximately need 4 days, and deposition are many.
Embodiment 3
The block matrix that is pure titanium by material adopts the silicon carbide paper of No. 50-1500 to polish successively, and boring aperture is 5mm, then adopts acetone to clean and dry up.The aluminum conductor of fixed length 30cm in aperture, wire external layer is coated high temperature resistant gum cover.Adopt the oxide-film of plasma electrolysis oxidation technology preparation containing Ca, P, Ca (CH
3cOO)
2﹒ H
2o concentration 0.07mol/L, NaH
2pO
4﹒ 2H
2o concentration is 0.1mol/L, EDTA-2Na concentration 0.115mol/L, and NaOH concentration is 3mol/L.Forward voltage 500V, negative voltage 100V, pulse frequency 100Hz, positive negative duty 60%.What obtain is about 30 μ m containing Ca, P composite membrane thickness.Prepare the coating containing micro-Ce class bone element with czochralski method again, configure the mixed solution of Cerium triacetate and citric acid, concentration ratio is 1:4, stirs, and solution is made colloidal sol 80 DEG C of heating 0.5h left and right.At room temperature the metallic matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned colloidal sol, then propose with the speed of 0.3mm/s, then room temperature hangs finish-drying.Dried sample repeats to lift loft dried process again, and number of repetition is 10 times.Sample after above-mentioned lifting is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 200 DEG C, programming rate is 20 DEG C/min, heat treatment time is 10h, obtains multi-element biologic composite bed.Ca, the P of gained, the biological composite bed of Ce and titanium alloy interface bond strength are 30MP, present better induction and deposition hydroxyapatite ability in simulated body fluid, approximately need 5 days, and deposition are many.
Embodiment 4
The strip matrix that is Ti-2Al-2.5Zr by material adopts the silicon carbide paper of No. 50-1000 to polish successively, and boring aperture is 3mm, then adopts acetone clean and dry.The aluminum conductor of fixed length 25cm in aperture, wire external layer is coated high temperature resistant gum cover.Adopt the oxide-film of plasma electrolysis oxidation technology preparation containing Ca, P, Ca (CH
3cOO)
2﹒ H
2o concentration 0.06mol/L, NaH
2pO
4﹒ 2H
2o concentration is 0.07mol/L, EDTA-2Na concentration 0.1mol/L, and NaOH concentration is 1mol/L.Preparation parameter: forward current 15A, pulse frequency 50Hz, positive negative duty 40%.What obtain is about 25 μ m containing Ca, P composite membrane thickness.Prepare the coating containing micro-Si, Na class bone element with czochralski method again, configure the mixed solution of sodium silicate and sodium ethylene diamine tetracetate, concentration ratio is 1:1, stirs, and solution is made colloidal sol 40 DEG C of heating 2h left and right.At room temperature the metallic matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned colloidal sol, then propose with the speed of 1mm/s, then room temperature hangs finish-drying.Dried sample repeats to lift loft dried process again, and number of repetition is 12 times.Sample after above-mentioned lifting is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 500 DEG C, programming rate is 30 DEG C/min, heat treatment time is 0.5h, obtains multi-element biologic composite bed.Ca, the P of gained, the biological composite bed of Si, Na and titanium alloy interface bond strength are 35MP, present better induction and deposition hydroxyapatite ability in simulated body fluid, approximately need 4 days, and deposition are many.
Embodiment 5
The strip matrix that is Ti-6Al-4V by material adopts the silicon carbide paper of No. 50-500 to polish successively, and boring aperture is 2.5mm, then adopts acetone clean and dry.The aluminum conductor of fixed length 24cm in aperture, wire external layer is coated high temperature resistant gum cover.Adopt the oxide-film of plasma electrolysis oxidation technology preparation containing Ca, P, Ca (CH
3cOO)
2﹒ H
2o concentration 0.04mol/L, NaH
2pO
4﹒ 2H
2o concentration is 0.05mol/L, EDTA-2Na concentration 0.04mol/L, and NaOH concentration is 0.3mol/L.Forward voltage 350V, negative voltage 60V, pulse frequency 800Hz, positive negative duty 50%.What obtain is about 10 μ m containing Ca, P composite membrane thickness.Prepare the coating containing micro-Y class bone element with czochralski method again, configure the mixed solution of Yttrium trinitrate and citric acid, concentration ratio is 1:2, stirs, and solution is made colloidal sol 50 DEG C of heating 0.5h left and right.At room temperature the metallic matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned colloidal sol, then propose with the speed of 0.1mm/s, then room temperature suspension finish-drying, it is 1 time that sample lifts number of times.Sample after above-mentioned lifting is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 450 DEG C, programming rate is 15 DEG C/min, heat treatment time is 1.5h, obtains multi-element biologic composite bed.Ca, the P of gained, the biological composite bed of Y and titanium alloy interface bond strength are 40MP, present better induction and deposition hydroxyapatite ability in simulated body fluid, approximately need 5 days, and deposition are many.
Embodiment 6
The block matrix that is pure titanium by material is polished with the silicon carbide paper of No. 50-800 successively, and boring aperture can be 3.5mm, then adopts distilled water to clean and dry up.The copper conductor of fixed length 18cm in aperture, the coated high temperature resistant gum cover in wire outside.Adopt the oxide-film of plasma electrolysis oxidation technology preparation containing Ca, P, Ca (CH
3cOO)
2﹒ H
2o concentration 0.04mol/L, NaH
2pO
4﹒ 2H
2o concentration is 0.1mol/L, EDTA-2Na concentration 0.09mol/L, and NaOH concentration is 2mol/L.Preparation parameter: positive negative current 0.5A, pulse frequency 500Hz, positive negative duty 40%.What obtain is about 8 μ m containing Ca, P composite membrane thickness.Prepare the coating containing micro Mg and Dy class bone element with czochralski method again, configure the mixed solution of magnesium acetate, acetic acid dysprosium and citric acid, concentration ratio is 1:0.1:1.5, stirs, and solution is made colloidal sol 70 DEG C of heating 20min left and right.At room temperature the metallic matrix that contains plasma electrolysis oxidation film is immersed in above-mentioned colloidal sol, then propose with the speed of 0.6mm/s, then room temperature hangs finish-drying.Dried sample repeats to lift loft dried process again, and number of repetition is 3 times.Sample after above-mentioned lifting is heat-treated.Under air atmosphere, sample is placed in the alumina crucible in high temperature furnace, furnace temperature rising to 300 DEG C, programming rate is 8 DEG C/min, heat treatment time is 6h, obtains multi-element biologic composite bed.Ca, the P of gained, the biological composite bed of Mg, Dy and titanium alloy interface bond strength are 42MP, present better induction and deposition hydroxyapatite ability in simulated body fluid, approximately need 4 days, and deposition are many.
Claims (3)
1. a preparation method that contains multi-element biologic cover layer bone renovating material, described bone renovating material is made up of metallic matrix, plasma electrolysis oxidation film and multi-element biologic cover layer parcel from the inside to the outside successively, it is characterized in that: described preparation method comprises following four steps:
Step 1, metal base surface pretreatment: adopt successively the silicon carbide paper of 50～No. 2000 to polish metal base surface, and boring near matrix border place the hole that multiple apertures are 1～5mm; Then clean with distilled water, dehydrated alcohol or acetone and dry or dry up; In hole, fixed packet is covered with the plain conductor of high temperature resistant gum cover again;
Step 2, adopts plasma electrolysis oxidation technology on metallic matrix, to prepare the plasma electrolysis oxidation film containing Ca, P: Ca (CH in the electrolyte solution of use
3cOO)
2﹒ H
2o concentration is 0.03～0.07mol/L, NaH
2pO
4﹒ 2H
2o concentration is 0.05～0.1mol/L, and EDTA-2Na concentration is 0.04-0.115mol/L, and NaOH concentration is 0.3～3mol/L; Preparation parameter is positive negative current 0.5～25A, forward voltage 200～500V, negative voltage 50～100V, pulse frequency 50～1000Hz, positive negative duty 40～60%; Obtain the plasma electrolysis oxidation film containing Ca, P, thickness is 5～30 μ m;
Step 3, adopt czochralski method on the plasma electrolysis oxidation film that contains Ca, P, to prepare the multi-element biologic cover layer that contains class bone element: with salt and the chelating agent of class bone element, complexing agent concentration used is 1～4 times of the total amount of substance concentration sum of class bone element salt, be stirred to compound and all dissolve, and make colloidal sol at 40 DEG C～100 DEG C heating 0.1～5h; The metallic matrix that contains plasma electrolysis oxidation film is immersed in colloidal sol, then propose colloidal sol with the speed of 0.01～20mm/s, number of repetition is 1～20 time, and making multi-element biologic overburden cover is 0.5～1 μ m;
Step 4, by sample heat treatment: the tectal bone renovating material of multi-element biologic that contains that step 3 is made is placed in high temperature furnace, and furnace temperature is slowly warming up to 200 DEG C～500 DEG C with 1～30 DEG C/min speed, and the processing time is 0.5～10h.
2. the preparation method that contains the tectal bone renovating material of multi-element biologic according to claim 1, is characterized in that: the chelating agent described in step 3 is citric acid or sodium ethylene diamine tetracetate.
3. the preparation method that contains the tectal bone renovating material of multi-element biologic according to claim 1, is characterized in that: the salt of the class bone element described in step 3 is one or more in magnesium acetate, manganese acetate, Cerium triacetate, Yttrium trinitrate, acetic acid dysprosium, sodium silicate.
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| KR101953102B1 (en) * | 2017-03-21 | 2019-02-28 | 조선대학교산학협력단 | An electrolyte composition containing manganese and silicon in a plasma electrolytic oxidation process and a method for manufacturing dental implants coated by hydroxyapatite containing manganese and silicon ions using the composition |
| KR101835623B1 (en) | 2017-03-21 | 2018-03-07 | 조선대학교산학협력단 | An electrolyte composition containing magnesium and silicon in a plasma electrolytic oxidation process and a method for manufacturing dental implants coated by hydroxyapatite containing magnesium and silicon ions using the composition |
| WO2018174475A1 (en) * | 2017-03-21 | 2018-09-27 | 조선대학교산학협력단 | Electrolyte composition containing metals and silicon in plasma electrolytic oxidation process and method for manufacturing dental implants coated with hydroxyapatite and containing metal ions and silicon ions by using same composition |
| KR101835684B1 (en) | 2017-03-21 | 2018-03-07 | 조선대학교산학협력단 | An electrolyte composition containing zinc and silicon in a plasma electrolytic oxidation process and a method for manufacturing dental implants coated by hydroxyapatite containing zinc and silicon ions using the composition |
| CN110528048A (en) * | 2019-08-30 | 2019-12-03 | 广东省新材料研究所 | A kind of titanium alloy implant Bio-surface active coating and preparation method thereof |
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