CN101949046B - Preparation method of carbonate hydroxyapatite/carbon nano tube composite coating material - Google Patents
Preparation method of carbonate hydroxyapatite/carbon nano tube composite coating material Download PDFInfo
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- CN101949046B CN101949046B CN2010102876869A CN201010287686A CN101949046B CN 101949046 B CN101949046 B CN 101949046B CN 2010102876869 A CN2010102876869 A CN 2010102876869A CN 201010287686 A CN201010287686 A CN 201010287686A CN 101949046 B CN101949046 B CN 101949046B
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Abstract
The invention relates to the fields of electrochemistry and materials and discloses a method for preparing a carbonate hydroxyapatite/carbon nano tube composite coating, which mainly comprises the following two steps: (1) depositing calcium carbonate powder or calcium carbonate-containing powder and carbon nano tubes on the surface of a metal matrix to obtain a calcium carbonate powder/carbon nano tube coating by electrophoretic deposition; and (2) treating the calcium carbonate powder/carbon nano tube coating with a phosphoric acid buffer solution, and converting the treated solution into the carbonate hydroxyapatite/carbon nano tube composite coating. The method is executed at normal temperature and pressure, has the advantages of simple process, low equipment investment and the like, and is suitable for preparing implants of various complicated shapes. The obtained composite coating has the fine bioactivity of the carbonate hydroxyapatite, and also can give full play to the favorable mechanical properties of the carbon nano tubes and the metal matrix.
Description
Technical field
The present invention relates to electrochemistry, ceramic and biomaterial for medical purpose technical field, disclose a kind of carbonate type hydroxylapatite/carbon nanotube composite coating material and preparation method thereof.
Background technology
Carbonate type Win 40350 is the main inorganic composition of sclerous tissueses such as human body bone volume, tooth, owing to have excellent biological compatibility, biological activity, have no side effect, do not have advantage such as immunoreation.The human body osteocyte can directly form Chemical bond on phosphatic rock, and bonding strength is high, good stability, has been widely used in substitute material for human hard tissues and repair materials.Yet; There are shortcomings such as fracture toughness property is low, Young's modulus is high, fragility is big in carbonate type Win 40350; Can only be applied in that alveolar ridge increases, non-bearing materials such as the replacement of ear ossiculum and maxillofacial bone reparation, be difficult to be applied to the load bone material, therefore need strengthen toughness reinforcing to phosphatic rock.
The approach that improves the mechanical property of carbonate type hydroxyl apatite bioceramic mainly comprises following two kinds: strongtheners such as carbon nanotube, thomel are added in (1) in biological ceramics, the physical strength of the matrix material that obtains thus can with people's bone photo ratio.Carbon nanotube (CNTs) is a kind of structured material of excellent performance, not only has satisfactory stability property, and has minimum yardstick and excellent mechanical property.Theoretical Calculation shows the Young's modulus of CNTs up to 5TPa, and intensity is about 100 times of steel, therefore is widely used as strengthening and toughening material.
The CNTs/ hydroxyapatite composite material mainly adopts mechanical blending method (patent CN 1440948A) at present, obtains composite powder to CNTs and Win 40350 mechanically mixing, colds pressing then or cold isostatic compaction.Though this method technology is simple, the bonding force of CNTs and Win 40350 a little less than.The method that Sun Kangning etc. (patent CN 1958517A) have invented a kind of Win 40350 enveloped carbon nanometer tube is dispersed in CNTs in the ionic calcium soln earlier, drips phosphate anion solution then, and reaction in generates the CNTs/ hydroxyapatite complex powder.Zhao Naiqin etc. (patent CN 101156961A) adopt the vapour deposition reaction in to prepare carbon nanometer tube/hydroxyapatite complex powder.What above-mentioned technology obtained all is the CNTs/ hydroxyapatite complex powder, also needs follow-up further machine-shaping could be used as hard tissue substituting material.(2) pure titanium, titanium alloy, stainless steel, tantalum, vitallium etc. have excellent mechanical property, are that active ingredient deposits to metal or alloy surface formation activated coating with carbonate type Win 40350, and its mechanical property and bone are complementary.The domestic method of preparation bioactive coating comprises plasma spraying, electrodip process, electrophoretic deposition and biomimetic method etc.Plasma spraying (Plasma-Spraying) is to prepare one of the most widely used technology of hydroxyapatite coating layer (patent CN 101250681A, 101250682A) at present both at home and abroad.This method can obtain comparatively suitable coating thickness and higher anchoring strength of coating (tensile strength 15～25MPa).Yet the higher part of hydroxyl phosphatic rock that causes of service temperature can resolve into solubility fusion phase, and the back coating that implants is seriously dissolved, thereby has reduced coating and metallic matrix, and the bonding strength between implant and the osseous tissue.Adopt the hydroxyapatite coating layer of plasma spraying preparation need carry out aftertreatment, to improve the percent crystallinity (patent CN 1483480A, CN1254031A) of Bond Strength of Coating and Win 40350.Electrochemical deposition method causes investigator's extensive concern (patent CN 1587442A) because of advantages such as temperature of reaction are gentle, simple to operate, controllability is strong, with low cost; But its disadvantage is that coating and basal body binding force are poor, and tension test finds that surface of fracture all occurs in the interface between coating and the substrate.There is the more weak shortcoming of bonding strength equally in electrophoretic deposition, must be through subsequent handlings such as bakingout process (patent CN 1834306A).Biomimetic method is exactly the mineralising mechanism of simulating nature circle physiology phosphatic rock, in being similar to tissue, deposits the method for phosphatic rock in the aqueous solution of envrionment conditions naturally.Advantages such as the bio-ceramic coating (patent CN 101249280A, 101244294A) that adopts biomimetic method to prepare has biocompatibility and synosteosis excellent property, temperature of reaction is gentle, technology is simple, easy to operate, cost; But sedimentation velocity is slower, coating and basal body binding force a little less than.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing carbonate type hydroxylapatite/carbon nanotube compound coating.
Present method is carried out at normal temperatures and pressures, mainly comprises following two steps: (1) deposits to metal base surface with electrophoretic deposition with calcium carbonate powders or the powder and the carbon nanotube that contain lime carbonate, obtains calcium carbonate powders/carbon nanotube coating; (2) calcium carbonate powders/carbon nanotube coating changes into carbonate type hydroxylapatite/carbon nanotube compound coating after phosphate buffer solution is handled.
Concrete technical scheme is that a kind of preparation method of carbonate type hydroxylapatite/carbon nanotube composite coating material comprises the steps:
(1) in dispersion medium, adds: A. calcium carbonate powders, or biological mineral matter powder calciferous, B. carbon nanotube; Sonic oscillation disperses 0.5～2hr, forms stable suspension, and lime carbonate concentration is 3～10g/L, and carbon nanotube concentration is 0.05～0.3g/L; And add acid, and example hydrochloric acid, sulfuric acid or nitric acid, making wherein, Sorensen value is 0.001～0.005M; Dispersion medium is nonconducting organic solvent, is preferably alcohols, more preferably absolute ethyl alcohol;
(2) be negative electrode with the metallic matrix, platinized platinum or graphite are anode, place the resulting suspension-s of step (1), and electrophoretic deposition 20～120s under 30～120 V/cm strength of electric field, agitation condition obtains lime carbonate/carbon nanotube compound coating;
(3) with step (2) gained lime carbonate/carbon nanotube compound coating, in 20～50 ℃ phosphate buffer solution, soaked 1～12 day, obtain carbonate type hydroxylapatite/carbon nanotube compound coating; Phosphate radical, dihydrogen phosphate and hydrogen phosphate are contained in described phosphate buffer solution pH=4.0 ~ 12, and total concn is 0.05～0.50 mol/L.
Described calcium carbonate powders is selected from calcite, aragonite, vaterite or unformed carbonic acid calcium; Biological mineral matter powder calciferous is selected from shell powder, coral powder, tortoise bone powder or fish-bone powder.The particle diameter of above-mentioned calcium carbonate powders or biological mineral matter powder calciferous is 0.02～10 μ m.
Described metallic matrix can be selected medical pure titanium, titanium alloy, stainless steel, tantalum or vitallium for use.The pretreatment technology of metallic matrix is before electrophoretic deposition: metallic matrix polishing back is cleaned, at H
3PO
4Soak 5～20min in the mixing solutions of/HF, the surface forms one deck oxide compound; Cleaning-drying again.Described H
3PO
4In the mixing solutions of/HF, H
3PO
4Concentration be 0.5 ~ 5.0 mol/L, the mass content of HF is 0.5 ~ 5%.
Described phosphoric acid buffer is prepared with soluble phosphate, and soluble phosphate is selected from one or more in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate, dibasic, sodium phosphate, potassium primary phosphate, potassium hydrogenphosphate, potassiumphosphate, primary ammonium phosphate, ammonium phosphate or the Secondary ammonium phosphate.
Adopt the carbonate type hydroxylapatite/carbon nanotube compound coating of the present invention's preparation, detect through ESEM, coat-thickness is even; The carbonate type Win 40350 that generates is structure in the form of sheets, and interconnects.Show that through X-ray diffraction, Fourier infrared spectrum, X-ray energy spectrometer detection the phosphatic rock that obtains is B-type carbonate type Win 40350, the Ca/P mol ratio is 1.3 ~ 1.67.The carbonate type Win 40350 in the coating and the content of carbon nanotube depend primarily on the mass ratio of lime carbonate and carbon nanotube in the suspension-s.
The present invention is a matrix with medical metal or alloy; Adopt electrophoretic deposition-chemical immersion two-step approach to prepare carbonate type hydroxylapatite/carbon nanotube compound coating; The good biological activity of carbonate type Win 40350 not only can be utilized, the excellent mechanical performances of carbon nanotube and metallic matrix can also be given full play to.
Advantage of the present invention is following: the preparation of (1) carbonate type hydroxylapatite/carbon nanotube compound coating is all carried out under low-temperature atmosphere-pressure, need be to coating thermal treatment, so there are not thermal stresses in coating and basal body interface; (2) it is active that carbonate type hydroxylapatite/carbon nanotube compound coating has good external biological, after simulated body fluid soaks 1 day, just forms one deck class bone type phosphatic rock at coatingsurface; (3) coat-thickness is even, and is high with substrate combinating strength; (4) production technique is simple, and facility investment is few, is suitable for the implant of various complicated shapes.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 gained carbonate type hydroxylapatite/carbon nanotube compound coating
Fig. 2 is the SEM figure of embodiment 1 gained carbonate type hydroxylapatite/carbon nanotube compound coating.
Embodiment
embodiment 1.
1. metallic matrix pre-treatment: with the medical pure titanium is matrix, cuts into the block that xsect is 15mm * 15mm, adopts abrasive paper for metallograph to be polished down to and observes no obvious cut under the opticmicroscope, and clean up with acetone and zero(ppm) water; Then at 1.0 mol/L H
3PO
4Soak 20 min in the mixing solutions of-1.5 wt% HF; Clean dry 24h under 60 ℃ in baking oven at last with zero(ppm) water.
2. the preparation of suspension-s: in the absolute ethyl alcohol of 250ml, add the unformed carbonic acid calcium powder of 1.225 g (particle diameter 4～5um) and 0.025 g carbon nanotube; Ultra-sonic oscillation 1.0 h; Form steady suspension, drip 1.0 mol/L hydrochloric acid, 0.5 ml before the electrophoresis.
3. electrophoretic deposition: with the medical pure titanium that obtains through step 1 is negative electrode, and graphite is anode, places above-mentioned suspension-s, and control strength of electric field is at 90 V/cm, and 60 s obtain lime carbonate/carbon nanotube coating at the mechanical stirring electrophoretic deposition.Take out coating, seasoning under the room temperature.
4. the configuration of phosphate buffer solution: SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate, dibasic are dissolved in the zero(ppm) water, are made into pH=7.4, phosphorus acid ion concentration is the phosphate buffer solution of 0.2 mol/L.
5. the preparation of compound coating:, under 37 ℃, in the phosphate buffer solution that obtains through step 4, soaked 3 days through lime carbonate/carbon nanotube coating that step 3 obtains, obtain carbonate type hydroxylapatite/carbon nanotube compound coating.Take out coating, dry under the room temperature.
6. test: the XRD of resulting carbonate type hydroxylapatite/carbon nanotube compound coating and SEM figure are as depicted in figs. 1 and 2 respectively.
Forming a layer thickness between coating and the metallic matrix is the amorphous titanium oxide of about 2.0 μ m.The about 30 μ m of carbonate type hydroxylapatite/carbon nanotube compound coating thickness, Ca/P mol ratio 1.5.The mass content of carbon nanotube in compound coating is 2.0%.
The simulated body fluid immersion test shows that carbonate type hydroxylapatite/carbon nanotube has good external biological activity, soaks just to form one deck class bone type phosphatic rock after 1 day on the surface.
1. metallic matrix pre-treatment: with medical titanium alloy Ti6Al4V is matrix, cuts into the block that xsect is 15mm * 15mm, adopts abrasive paper for metallograph to be polished down to and observes no obvious cut under the opticmicroscope, and clean up with acetone and zero(ppm) water; Then at 2.0 mol/L H
3PO
4Soak 5 min in the mixing solutions of-0.5 wt% HF; Clean dry 24h under 60 ℃ in baking oven at last with zero(ppm) water.
2. the preparation of suspension-s: in the ethanol solution of 250ml, add 2.25 g shell powders (particle diameter 0.1～2 μ m; Calcium carbonate content is 98%) and 0.25 g carbon nanotube; Ultra-sonic oscillation are disperseed 2.0 h, form steady suspension, drip 1.0 mol/L hydrochloric acid, 0.5 ml before the electrophoresis.
3. electrophoretic deposition: with the medical titanium alloy Ti6Al4V that obtains through step 1 is negative electrode; Graphite is anode; Place above-mentioned suspension-s, control strength of electric field is at 60 V/cm, and electrophoretic deposition 40 s obtain lime carbonate/carbon nanotube coating under mechanical stirring or magnetic agitation.Take out coating, seasoning under the room temperature.
4. phosphate buffer solution preparation: potassium primary phosphate and potassium hydrogenphosphate are dissolved in the zero(ppm) water, are made into pH=9.0, the phosphoric acid salt total concn is the phosphate buffer solution of 0.25 mol/L.
5. the preparation of compound coating:, under 50 ℃, in the phosphate buffer solution that obtains through step 4, soaked 1 day through lime carbonate/carbon nanotube coating that step 3 obtains, obtain carbonate type hydroxylapatite/carbon nanotube compound coating.Take out coating, dry under the room temperature.
6. test: forming a layer thickness between coating and the matrix is the amorphous titanium oxide of about 0.8 μ m.The about 20 μ m of carbonate type hydroxylapatite/carbon nanotube compound coating thickness, the Ca/P mol ratio is 1.3.The mass content of carbon nanotube in compound coating is 10.0%.
The simulated body fluid immersion test shows that carbonate type hydroxylapatite/carbon nanotube has good external biological activity, soaks just to form one deck class bone type phosphatic rock after 1 day on the surface.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a carbonate type hydroxylapatite/carbon nanotube composite coating material is characterized in that, comprises the steps:
(1) in dispersion medium, add:
A. calcium carbonate powders, or biological mineral matter powder calciferous,
B. carbon nanotube,
Sonic oscillation disperses 0.5～2h, forms stable suspension, and lime carbonate concentration is 3～10g/L, and carbon nanotube concentration is 0.05～0.3g/L; And add acid, making wherein, Sorensen value is 0.001～0.005M; Described dispersion medium is nonconducting organic solvent;
(2) be negative electrode with the metallic matrix, platinized platinum or graphite are anode, place the resulting suspension-s of step (1), and electrophoretic deposition 20～120s under 30～120 V/cm strength of electric field, agitation condition obtains lime carbonate/carbon nanotube compound coating;
(3) with step (2) gained lime carbonate/carbon nanotube compound coating, in 20～50 ℃ phosphate buffer solution, soaked 1～12 day, obtain carbonate type hydroxylapatite/carbon nanotube compound coating; Phosphate radical, dihydrogen phosphate and hydrogen phosphate are contained in described phosphate buffer solution pH=4.0 ~ 12, and total concn is 0.05～0.50 mol/L.
2. the preparation method of the said carbonate type of claim 1 hydroxylapatite/carbon nanotube composite coating material is characterized in that, the acid described in the step (1) is hydrochloric acid, sulfuric acid or nitric acid.
3. the preparation method of the said carbonate type of claim 1 hydroxylapatite/carbon nanotube composite coating material is characterized in that, the dispersion medium described in the step (1) is an alcohols.
4. the preparation method of claim 1 or 3 said carbonate type hydroxylapatite/carbon nanotube composite coating materials is characterized in that described dispersion medium is an absolute ethyl alcohol.
5. the preparation method of the said carbonate type of claim 1 hydroxylapatite/carbon nanotube composite coating material is characterized in that, the calcium carbonate powders described in the step (1) is selected from calcite, aragonite, vaterite or unformed carbonic acid calcium; Biological mineral matter powder calciferous is selected from shell powder, coral powder, tortoise bone powder or fish-bone powder.
6. the preparation method of claim 1 or 5 said carbonate type hydroxylapatite/carbon nanotube composite coating materials is characterized in that, the particle diameter of described calcium carbonate powders or biological mineral matter powder calciferous is 0.02～10 μ m.
7. the preparation method of the said carbonate type of claim 1 hydroxylapatite/carbon nanotube composite coating material is characterized in that, described metallic matrix is medical pure titanium, titanium alloy, stainless steel, tantalum or vitallium.
8. the preparation method of the said carbonate type of claim 1 hydroxylapatite/carbon nanotube composite coating material is characterized in that, before electrophoretic deposition, metallic matrix is carried out pre-treatment, and technology comprises: metallic matrix polishing back is cleaned, at H
3PO
4Soak 5～20min in the mixing solutions of/HF, the surface forms one deck oxide compound; Cleaning-drying again.
9. the preparation method of the said carbonate type of claim 8 hydroxylapatite/carbon nanotube composite coating material is characterized in that described H
3PO
4In the mixing solutions of/HF, H
3PO
4Concentration be 0.5 ~ 5.0 mol/L, the mass content of HF is 0.5 ~ 5%.
10. the preparation method of the said carbonate type of claim 1 hydroxylapatite/carbon nanotube composite coating material; It is characterized in that; Described phosphoric acid buffer is prepared with soluble phosphate, and soluble phosphate is selected from one or more in SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate, dibasic, sodium phosphate, potassium primary phosphate, potassium hydrogenphosphate, potassiumphosphate, primary ammonium phosphate, ammonium phosphate or the Secondary ammonium phosphate.
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| CN102260863B (en) * | 2011-05-05 | 2013-05-01 | 陕西科技大学 | Preparation method of silicon-containing hydroxyapatite coating of carbon/carbon composite material |
| US11859080B2 (en) | 2018-02-22 | 2024-01-02 | Yeda Research And Development Co. Ltd. | Hydroxyapatite based composites and films thereof |
| CN108675281B (en) * | 2018-03-30 | 2020-10-09 | 西南交通大学 | Carbon nanotube-based composite material with both conductivity and magnetism and preparation method thereof |
| CN108570697A (en) * | 2018-04-26 | 2018-09-25 | 大同新成新材料股份有限公司 | A kind of Brush Plating composite technology |
| US11433422B2 (en) | 2018-12-17 | 2022-09-06 | King Fahd University Of Petroleum And Minerals | Polyethylene-CNT-hydroxyapatite coated materials |
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| CN1772969A (en) * | 2005-10-28 | 2006-05-17 | 厦门大学 | Process for producing nan-hydroxyl kietyoite/carbon nano-pipe compound coating |
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| CN1772969A (en) * | 2005-10-28 | 2006-05-17 | 厦门大学 | Process for producing nan-hydroxyl kietyoite/carbon nano-pipe compound coating |
Non-Patent Citations (1)
| Title |
|---|
| Yaping Guo等.Fabrication of hydroxycarbonate apatite coatings with hierarchically porous structures.《Acta Biomaterialia》.2007,第4卷334-342页. * |
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