CN100553691C - The preparation method of composite coating material containing hydroxyapatite embedded in titanium oxide nanotube array - Google Patents
The preparation method of composite coating material containing hydroxyapatite embedded in titanium oxide nanotube array Download PDFInfo
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- CN100553691C CN100553691C CNB2007100859284A CN200710085928A CN100553691C CN 100553691 C CN100553691 C CN 100553691C CN B2007100859284 A CNB2007100859284 A CN B2007100859284A CN 200710085928 A CN200710085928 A CN 200710085928A CN 100553691 C CN100553691 C CN 100553691C
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Abstract
The present invention relates to the preparation method that a kind of hydroxyapatite embeds the composite coating material of titania nanotube array, its objective is the preparation method that a kind of active coating material is provided.It is characterized in that: as anode, electrolytic oxidation is prepared the titania nanotube array template with titanium or titanium alloy substrate; Make Ca (NO
3)
24H
2O alcoholic solution and P
2O
5Alcoholic solution stirs after dropping mixes and promptly gets hydroxyapatite colloidal sols; Hydroxyapatite is embedded in the titania nanotube array with the nano wire form, after heat treatment obtains the composite coating material of biologically active.Characteristics of the present invention are that hydroxyapatite gos deep into titanium or titanium alloy substrate inside, avoided existing technology hydroxyapatite coating layer and matrix to exist macroscopic interface to cause the low shortcoming of bond strength, hot strength, fracture toughness to matrix can not produce the essence influence, and the porous on surface, the difference of implant and flexible bone modulus be can reduce, the reparation or the replacement of diverse bone types can be used for.
Description
Technical field
The present invention relates to the preparation method that a kind of hydroxyapatite embeds the composite coating material of titania nanotube array, belong to the bone reparing biological material technology of preparing.
Background technology
Titanium and alloy thereof rely on good biocompatibility and mechanical property, become the preferred material that bone is repaired.Titanium and alloy thereof belong to bio-inert material, and biological activity is relatively poor, and behind the implant into body, the allosome as the host exists all the time, and loosening, distortion takes place easily, causes implant to lose efficacy.Utilize process for modifying surface to give biological activity, can make new bone directly be deposited on titanium alloy surface and form synostosis, and not have the intermediate interlayer of fiber sheath.The bioactive materials of usefulness is a bioactivity glass the earliest, finds that afterwards hydroxyapatite (Hydroxyapatite is called for short HA) is a kind of better bioactive materials.On structure, natural bone itself is exactly into the natural composite material of bone fibres and hydroxyapatite formation.Therefore, apply hydroxyapatite coating layer at titanium alloy surface, the good mechanical property of the existing titanium alloy of composite that obtains like this has the good biocompatibility and the biological activity of hydroxyl apatite bioceramic again, becomes one of research focus of biomaterial.Technology at titanium alloy surface coating hydroxyapatite coating layer mainly contains tens kinds of methods such as plasma spraying method, ion beam sputtering, magnetron sputtering method, laser cladding, electrodeposition process, electrophoresis method, sol-gel process at present.Because the serious mismatch of thermal coefficient of expansion between hydroxyapatite and titanium or the titanium alloy, have macroscopic interface between coating and matrix, along with the prolongation of the time of implantation, bond strength descends, the incident that coating shedding causes implant to lose efficacy increases year by year, some hospital even abandon using.Therefore, the interface bond strength of raising coating and matrix is the key issue of present hydroxyapatite coating layer investigation of materials under the prerequisite that guarantees coating biology activity and stability.
In recent years, the research for preparing titania nanotube array by the titanium anodic oxidation is just becoming the focus of current research, (J Mater Res 2001 such as Dawei Gong, 16 (12): 3331) reported to be electrolyte, prepared titania nanotube array in the titanio surface by electrochemistry anodic oxidation with HF.R.Beranek etc. (Electrochemical and Solid State Letters, 2003,6 (3): B 12) is at HF/H subsequently
2SO
4In, Gopal K.Mor (J Mater Res 2003,18 (11): 2588) in the HF/HAc medium, (J Mater Res, 2005,20 (1): such as Qingyun Cai 230) at NH
4In F/ citric acid or the sulfate medium, adopt similar method, also prepare orderly, the highdensity titania nanotube array of compound with regular structure, can realize controlled preparation titanium oxide nanotubes yardstick and pattern by the regulation voltage parameter in the titanio surface.Macak etc. (Electrochim.Acta, 2006,52:1258) in the dimethyl sulfoxine of fluoride ion or ethylene glycol medium, prepare the titania nanotube array of high length-diameter ratio.
Because the isoelectric point, IP of titanium oxide is low, the surface is electronegative, in simulated body fluid, can adsorb the calcium ion in the body fluid, phosphate anion and calcium ion codeposition then, apatite heterogeneous nucleation and crystalline growth, form class apatite at Titanium or titanium alloy-based surface, show excellent biological compatibility.The titanium oxide that Wang Zhen etc. (CN1769527A) have the surface nano-tube array structure has been induced the generation of hydroxyapatite coating layer in simulated body fluid behind the alkali heat treatment.Though this coating is successfully applied to the surface modification of medical metal with nanostructured, there is the low shortcoming of bond strength equally in coating, has limited its application clinically.
Summary of the invention
At above-mentioned situation, the purpose of this invention is to provide the preparation method of the high active coating material of a kind of bond strength, it is characterized in that: as anode, electrolytic oxidation is prepared the titania nanotube array template with titanium or titanium alloy substrate; Be solvent with ethanol respectively, make Ca (NO
3)
24H
2O alcoholic solution and P
2O
5Alcoholic solution stirs after dropping mixes and promptly gets hydroxyapatite colloidal sols; Utilize action of centrifugal force, hydroxyapatite is embedded in the titania nanotube array with the nano wire form, after heat treatment obtain the composite coating material of biologically active.Specifically comprise the steps:
1) preparation of titania nanotube array template: with titanium or titanium alloy ti6al4v matrix as anode, rustless steel or platinized platinum are as negative electrode, in 0.1～0.5wt%HF electrolyte, with voltage oxidation 20～120min of 10～30V, take out, with the distilled water cleaning and with 100 ℃ of oven dry.
2) preparation of hydroxyapatite colloidal sols: preparation 0.4～1.2mol/L Ca (NO
3)
24H
2O alcoholic solution and 0.12～0.36mol/L P
2O
5Alcoholic solution is got the Ca (NO of equal volume
3)
24H
2O alcoholic solution and P
2O
5Alcoholic solution, and with Ca (NO
3)
24H
2The O alcoholic solution is added drop-wise to P
2O
5Stir in the alcoholic solution and promptly get hydroxyapatite colloidal sols.
3) centrifugal filling: hydroxyapatite colloidal sols is placed centrifuge tube, anodised titania nanotube array template is placed the bottom of centrifuge tube, nano-tube array faces up, pour hydroxyapatite colloidal sols into and flooded height more than 2 times, with the centrifugal 20～40min of the speed of 4000～10000rpm.Take out sample, with ethanol ultrasonic cleaning titanio surface.
4) heat treatment: titanium after the ultrasonic cleaning or titanium alloy are placed the temperature control chamber type electric resistance furnace, rise to 400～600 ℃ of insulations 2～4 hours, furnace cooling then with the heating rate of 1～5 ℃/min.
The matrix titanium, titanium oxide nanotubes and the hydroxyapatite nano line composite coating material that adopt such scheme to obtain have following characteristics: 1. hydroxyapatite gos deep into titanium or titanium alloy substrate inside, the shortcoming of having avoided existing technology hydroxyapatite coating layer and matrix to exist macroscopic interface to cause bond strength to descend; 2. the thinner thickness of hydroxyapatite nano linear array, can be controlled in 10～100um, hot strength, fracture toughness to matrix can not produce the essence influence, and the porous on surface, can reduce the difference of implant and flexible bone modulus, help the growth of osteocyte and sending of nutrition, integrate thereby obtain the physiology bone.3. the hydroxyapatite in the nano-wire array utilizes its bone conduction effect, in bootable new bone is grown into the hole along the titanium oxide tube wall, can improve implant and new bone formation synostosis effectively; 4. because the hydroxyapatite nano linear array is grown along the c direction of principal axis of titanium oxide template, this structure is consistent with the hydroxyapatite structure in the biological bone, for the biological bone of more furtheing investigate biologically active provides a kind of new theoretical model and synthetic method; 5. can in the hydroxyapatite colloidal sols gel, introduce bioactive molecule (as enzyme, protein, medicine etc.), and be embedded in the nanotubes of titanium oxide, can further improve the biological activity of material, and can be used as the carrier of medicament slow release, this is the legal unexistent advantage of general physisorphtion and covalent bond; 6. the titanium oxide of anodic oxidation generation can stop the release of titanium ion in the matrix, improves the corrosion resistance of matrix.
Accompanying drawing and description of drawings
Fig. 1 is the centrifugal filling sketch map of the present invention.
Fig. 2 obtains titania nanotube array template surface microscopic appearance figure in the specific embodiment of the invention 1 through anodic oxidation.
Fig. 3 is the surface microscopic topographic figure that obtains sample in the specific embodiment of the invention 1 behind the centrifugal filling hydroxyapatite colloidal sols.
Among Fig. 1,1 is centrifuge tube; 2 is hydroxyapatite colloidal sols; 3 is titania nanotube array; 4 is titanium or titanium alloy substrate.
The specific embodiment
With pure titanium is matrix, the surface through abrasive paper for metallograph polishing, clean, the oven dry back is as anode, is negative electrode with the platinized platinum, is electrolyte with 0.5wt%HF solution, behind 10V voltage anodic oxidation 20min, take out, with the distilled water cleaning and 100 ℃ of oven dry.Shown in Figure 2 in the microscopic appearance of titanio surface such as the Figure of description, visible titanio surface forms the titania nanotube array of one deck marshalling, pattern homogeneous, the about 15nm of thickness of pipe wall, the about 100nm of caliber, the about 150nm of tube pitch among the figure.
Take by weighing 9.446 gram Ca (NO
3)
24H
2O is dissolved in and obtains Ca solution in the 100ml dehydrated alcohol, and concentration is 0.4mol/L; Take by weighing 1.704 gram P
2O
5Be dissolved in and obtain P solution in the 100ml dehydrated alcohol, concentration is 0.12mol/L; The Ca drips of solution is added to stir in the P solution promptly gets hydroxyapatite colloidal sols.
Hydroxyapatite colloidal sols at room temperature behind the ageing 30min, is poured in the centrifuge tube, and anodised pure titanio body is placed centrifuge tube, its laying method as shown in Figure 1, with the centrifugal 20min of the speed of 4000rpm.Take out sample, with ethanol ultrasonic cleaning titanio surface.Then matrix is placed the temperature control chamber type electric resistance furnace, rise to 400 ℃ of insulations 4 hours with the heating rate of 1 ℃/min, furnace cooling promptly obtains the composite coating material that hydroxyapatite embeds titania nanotube array.The microscopic appearance of material surface as shown in Figure 3, most titanium oxide nanotubes is all filled by hydroxyapatite, only stays the vestige of some mouths of pipe.By energy dispersive spectrometry (EDS) the titanium oxide nanotubes bottom is analyzed, result's demonstration contains calcium and P elements, and the ratio of atom number is 1.65, proves that hydroxyapatite is filled in the pipe.
Embodiment 2
With the titanium alloy ti6al4v is matrix, and the surface as anode, is a negative electrode with the stainless steel substrates after abrasive paper for metallograph polishing, cleaning, oven dry, with 0.1wt%HF solution is electrolyte, behind 30V voltage anodic oxidation 120min, take out, with the distilled water cleaning and 100 ℃ of oven dry.
Take by weighing 28.338 gram Ca (NO
3)
24H
2O is dissolved in and obtains Ca solution in the 100ml dehydrated alcohol, and concentration is 1.2mol/L; Take by weighing 5.112 gram P
2O
5Be dissolved in and obtain P solution in the 100ml dehydrated alcohol, concentration is 0.36mol/L; The Ca drips of solution is added to stir in the P solution promptly gets hydroxyapatite colloidal sols.
Hydroxyapatite colloidal sols at room temperature behind the ageing 30min, is poured in the centrifuge tube, anodised titanium alloy ti6al4v matrix is placed centrifuge tube, with the centrifugal 40min of the speed of 10000rpm.Take out sample, with ethanol ultrasonic cleaning titanio surface.Then matrix is placed the temperature control chamber type electric resistance furnace, rise to 600 ℃ of insulations 2 hours with the heating rate of 5 ℃/min, furnace cooling promptly obtains the composite coating material that hydroxyapatite embeds titania nanotube array.
Claims (6)
1. a hydroxyapatite embeds the preparation method of the composite coating material of titania nanotube array, it is characterized in that:
I, with titanium or titanium alloy substrate as anode, electrolytic oxidation is prepared the titania nanotube array template;
II, be solvent with ethanol respectively, make Ca (NO
3)
24H
2O alcoholic solution and P
2O
5Alcoholic solution stirs after dropping mixes and promptly gets hydroxyapatite colloidal sols;
III, utilize action of centrifugal force, hydroxyapatite is embedded in the titania nanotube array with the nano wire form, after heat treatment obtain the composite coating material of biologically active.
2. the preparation method of composite coating material according to claim 1 is characterized in that the Ca (NO for preparing
3)
24H
2O alcoholic solution and P
2O
5The concentration of alcoholic solution is respectively 0.4～1.2mol/L and 0.12～0.36mol/L.
3. the preparation method of composite coating material according to claim 1 is characterized in that described dropping mixing is meant the Ca (NO that gets equal volume
3)
24H
2O alcoholic solution and P
2O
5Alcoholic solution, and with Ca (NO
3)
24H
2The O alcoholic solution is added drop-wise to P
2O
5In the alcoholic solution.
4. the preparation method of composite coating material according to claim 1, the titania nanotube array of anodic oxidation preparation, it is characterized in that with pure titanium or titanium alloy ti6al4v matrix as anode, rustless steel or platinized platinum are as negative electrode, in 0.1～0.5wt%HF electrolyte, with voltage anodic oxidation 20～120min of 10～30V.
5. the preparation method of composite coating material according to claim 1, it is characterized in that described when utilizing action of centrifugal force, anodised titania nanotube array template is placed the bottom of centrifuge tube, nano-tube array faces up, pour hydroxyapatite colloidal sols into and flooded height more than 2 times, with the centrifugal 20～40min of the speed of 4000～10000rpm, take out sample, with ethanol ultrasonic cleaning titanio surface.
6. the preparation method of composite coating material according to claim 1, it is characterized in that described heat treatment is meant places the temperature control chamber type electric resistance furnace with titanium after the centrifugal filling or titanium alloy substrate, heating rate with 1～5 ℃/min rises to 400～600 ℃ of insulations 2～4 hours, furnace cooling then.
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| CN103285426A (en) * | 2012-02-23 | 2013-09-11 | 湖南迈迪科新材有限公司 | Hydroxyapatite embedded titanium dioxide nano tube composite coating and preparation method thereof |
| CN103834979B (en) * | 2014-03-14 | 2016-04-06 | 河北工业大学 | The preparation method of calcium phosphorus silver nanotube array is carried on a kind of medical titanium surface |
| CN108070900B (en) * | 2017-12-15 | 2020-07-31 | 太原理工大学 | Preparation method for in-situ formation of hexagonal flaky apatite coating on surface of titanium-based nanotube |
| CN108324995A (en) * | 2018-02-11 | 2018-07-27 | 福建工程学院 | The preparation method of the ultrasonic three-dimensional porous biological support of particle embedded technology surface modification |
| CN113663130A (en) * | 2020-05-13 | 2021-11-19 | 脉通医疗科技(嘉兴)有限公司 | Artificial blood vessel and preparation method thereof |
| CN114949374B (en) * | 2022-05-24 | 2023-06-13 | 安徽大学 | Antibacterial bone-promoting difunctional titanium metal orthopedic implant and preparation method thereof |
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