CN101491693A - Preparation method of hydroxylapatite/titanic oxide composite biological coatings - Google Patents
Preparation method of hydroxylapatite/titanic oxide composite biological coatings Download PDFInfo
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- CN101491693A CN101491693A CNA2008101510580A CN200810151058A CN101491693A CN 101491693 A CN101491693 A CN 101491693A CN A2008101510580 A CNA2008101510580 A CN A2008101510580A CN 200810151058 A CN200810151058 A CN 200810151058A CN 101491693 A CN101491693 A CN 101491693A
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Abstract
The invention provides a method for preparing a hydroxyapatite/titanium dioxide composite bioactive coating on the surfaces of medical metals such as a titanium alloy, and the like, and belongs to the technical field of the preparation of bioactive coatings on the surface of the titanium alloy. The composite coating is prepared by preparing precursor sols of HA and TiO2 respectively, then mixing the precursor sols of the HA and the TiO2, and performing aging, coating, drying and heat treatment. The coating has high bioactivity, low cost of preparation technology, and high bonding strength with a matrix, is applicable to the preparation of surface coatings of various complicated geometric structures, and can be used for surface modification of surgical implants such as artificial hip joints and dental implants as well as orthopedic instrument products.
Description
Technical field
The present invention relates to the preparation method of medical metal surface hydroxyl apatite/titanic oxide composite biological coatings such as a kind of titanium alloy, belong to titanium alloy surface bioactivation coat preparing technology field.
Background technology
Titanium and alloy, medical stainless steel etc. are the bio-medical metal materials of extensive use, have excellent biological compatibility, good mechanical performance and corrosion resistance, but composition and tissue are completely different, bigger with sclerous tissues biomechanical property difference, as hard tissue implanting material, and be that the bone that connects of a kind of mechanical embedding is integrated between the bone, and synostosis non-chemically, cause to implant to combine relatively poorly between back and the osseous tissue, often cause to implant and lost efficacy.
Hydroxyapatite HA forms identical with the inanimate matter material of human body hard tissue (bone and tooth), can be directly after implanting and the bone formation synostosis, and interface bond strength meets or exceeds the intensity of bone and implant self between the bone, but, be not suitable for being used as the bigger hard tissue repair of carrying and substitute because simple HA crystal fragility is big, rupture strength is low.
Medical metal is carried out surface modifying method can prepare biological composite implantation material with high-performance, high reliability at its surface formation one deck HA.Composite has been avoided the active characteristics of the inanimate object of titanium and alloy, can overcome the defective of HA poor mechanical property simultaneously again.Medical metal is a metallic bond, and the HA pottery is covalent bond or ionic bond, two kinds of lattice types differences, the compatibility is poor, so good chemical bond of difficult at the interface formation of HA material and titanium alloy substrate, it is also bigger that the elastic modelling quantity of HA and titanio body, thermal coefficient of expansion differ, and this causes the still low interface peeling phenomenon that is prone to of HA coating and high base strength.
Detitanium-ore-type TiO
2Pottery has better biocompatibility, can induce the deposition of apatite and the formation of osseous tissue in vitro and in vivo, as cushion, and TiO
2Implant and living organism can be isolated effectively, and the intensity at coating and interface can be improved
[3]Researcher adopts both at home and abroad increases TiO between substrate and HA coating
2Prepare TiO as cushion or employing several different methods
2/ HA composite coating is not reducing under the active situation of coating biology, improves Bond Strength of Coating, corrosion resistance and stability.
HA/TiO
2The preparation method of composite coating has physics method, chemical method and electrochemical process.Because the difference of preparation method, the surface topography of coating, phase composition, degree of crystallinity, crystal structure etc. are all different.
The physics method is to introduce coating by spraying, sputter, coating sintering etc. on the titanium surface, preparation bioactivity coatings/titanium composite material.Wherein plasma spraying method is to study comparatively ripe, the maximum method of application now clinically, but process relates to high temperature, and bigger variation takes place for the chemical constituent of HA and crystal structure, produces the impurity phase, the degree of crystallinity reduction of HA.Electrochemical method is under conditions such as uniform temperature, concentration pH value, current/voltage is controlled to make treat that deposit fluid grows ceramic coating at titanium alloy surface.Chemical method is by alkali heat treatment, sol-gal process, spatial induction mineralising etc. chemical modification to be carried out on the titanium surface.Collosol and gel (sol-gel) method is by preparing bioactivity coatings at titanium or titanium alloy surface-coated titanium or phosphoric acid salt gel, the sol-gel method is simple to operate, cost is low, synthetic coating and matrix bond are comparatively tight, be particularly suitable for various complex geometries (position) face coat preparation in the medical apparatus and instruments (as artificial hip joint and tooth implant etc.), be widely used in the preparation bioactivity coatings in recent years.By process conditions such as control after-baking, adopt sol-gel method to prepare and have the active HA/TiO of good biological
2Composite coating.
Traditional sol-gal process will prepare HA or TiO earlier
2Be distributed to behind the powder body and prepare colloidal sol in the medium, again with other TiO
2Or HA is mixed with HA/TiO by the colloidal sol that presoma prepares
2Complex sol prepares HA/TiO through coating, sintering
2Composite coating.Because HA or TiO2 powder body are to adopt other method preparation, granule is bigger, and poor than the dispersibility for preparing colloidal sol by forerunner's salt, this causes the uniformity of coating wayward.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provide a kind of cost low, component is adjusted easily, prepares the preparation method of the hydroxyapatite/titanic oxide composite biological coatings of coating easily on each shape matrix, to improve hydroxyapatite HA and TiO
2The chemistry of two kinds of phases and physical compatibility reduce grain size and the coating and the high base strength of coating, thus prepare component purity higher, more residual hydroxy groups and the higher hydroxyapatite/titanic oxide composite biological coatings of biological activity arranged.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of hydroxyapatite/titanic oxide composite biological coatings is characterized in that preparation process is:
The preparation of step 1, hydroxyapatite colloidal sols:
(11) triethyl phosphate being joined in the dehydrated alcohol, is that 2mol/L dilutes by the triethyl phosphate molar concentration;
(12) triethyl phosphate mole 2-3.5 pure water doubly slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 24-36h, stand-by;
(13) lime nitrate is carried out the drying of 24-36h under 160 ℃-270 ℃ of temperature, airtight, to be cooled to room temperature, dried lime nitrate is mixed with the lime nitrate alcoholic solution by mole concentration 2mol/L, airtight stand-by;
(14) the lime nitrate alcoholic solution of preparation and the triethyl phosphate of hydrolysis were mixed in 5: 3 in molar ratio, adopt magnetic stirrer 3-6h, ageing 36-48h under the room temperature promptly makes hydroxyapatite colloidal sols;
Step 2, TiO
2The preparation of colloidal sol:
(21) butyl titanate and ethylene glycol monomethyl ether solution were mixed in 1: 20 in molar ratio, adopt magnetic stirrer 25min;
(22) mol ratio by ethyl acetoacetate and butyl titanate is 1: 5, adds ethyl acetoacetate again in the butyl titanate and carries out chelating, adopts magnetic stirrer 0.5-1h; Adding pH value then is the adjusting aqueous solution of nitric acid of 1-1.5, and the addition of regulating aqueous solution of nitric acid is 0.1-0.2 a times of butyl titanate volume, continues to stir 1.5-2h, and ageing 8-15h under the room temperature promptly makes TiO
2Colloidal sol;
The preparation of step 3, complex sol:
With hydroxyapatite colloidal sols in the step 1 and the TiO in the step 2
2Colloidal sol is 0.1-10 in molar ratio: 1 mixes, and adopting the magnetic stirrer time is 1.5h, and 4 ℃ of cold preservation ageings of refrigerator 15-60h promptly makes complex sol;
The preparation of step 4, composite coating:
(41) with metallic matrix treat coating surface after grinding, successively in tap water, dilute hydrochloric acid, pure water, acetone and pure water with each 10min of ultrasonic cleaner ultrasonic cleaning;
(42) metallic matrix that will be after ultrasonic cleaning immerses in the complex sol in the step 3, time of repose is 1-5min, with pulling machine metallic matrix is treated that coating surface lifts out the complex sol liquid level perpendicular to described complex sol liquid level, the speed of pulling out is 0.5-2mm/s, then the non-coating of described metallic matrix position is protected with resin;
(43) the gluing metallic matrix is placed into dry 15-30min in 60 ℃ the vacuum drying oven, removes moisture and partial solvent, remove the protection resin at the non-coating of gluing metallic matrix position then, at described non-coating position coated titanium alloy protecting coating;
(44) the heat-treatment furnace initial temperature is made as 60 ℃, the gluing metallic matrix by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 1-4 ℃/min, the speed with 3-6 ℃/min is warmed up to 750-900 ℃ again, insulation 0.5-1h; Speed with 4-7 ℃/min is cooled to room temperature with stove, promptly forms hydroxyapatite/titanic oxide composite biological coatings at metal base surface, removes the titanium alloy protective coating at the non-coating of described metallic matrix position then.
Metallic matrix described in the above-mentioned steps 4 is titanium alloy, medical stainless steel, cochrome or other medical metal.
Heat-treatment furnace is Muffle furnace or tube furnace described in the above-mentioned steps (44).
The present invention compared with prior art has the following advantages: hydroxyapatite HA and TiO among the present invention
2All lead to forerunner's salt and prepare colloidal sol, and direct compound two kinds of colloidal sols, prepared composite coating, the composition uniformity is better, HA and TiO
2The ratio of two kinds of components is adjusted easily, helps improving HA and TiO
2The chemistry of two kinds of phases and physical compatibility reduce the grain size of coating, improve coating and high base strength.Adopt Prepared by Sol Gel Method HA/TiO
2The coating ingredients purity that the composite coating cost is low, the component adjustment prepares coating, preparation easily, easily on each shape matrix is higher, more residual hydroxy groups is arranged, biological activity is higher.
Below by embodiment, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is HA/TiO of the present invention
2The structural representation of composite coating.
Fig. 2 is HA of the present invention and TiO
2Mol ratio is the SEM figure of 5,750 ℃ of insulation 0.5h.
Fig. 3 is HA of the present invention and TiO
2Mol ratio is the SEM figure of 3,800 ℃ of insulation 0.5h.
Fig. 4 is HA/TiO of the present invention
2Than being followed successively by 1/2.5,1/1,2.5/1,5/1 four layers of composite coating and pure HA coating XRD figure at 550,750 ℃ of insulation 0.5h.
The specific embodiment
Embodiment 1
Hydroxyapatite colloidal sols is the preparation of HA colloidal sol: with triethyl phosphate [(C
2H
5O)
3PO] to join in the dehydrated alcohol by the triethyl phosphate molar concentration be that 2mol/L dilutes; The pure water of 2.7 times of triethyl phosphate moles slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 24h; Lime nitrate is carried out 36 hours drying under 165 ℃ of temperature, airtight, cooling; Dried lime nitrate is pressed 2mol/L preparation lime nitrate alcoholic solution; The triethyl phosphate of lime nitrate alcoholic solution and hydrolysis was mixed in 5: 3 in molar ratio, stir 3h, ageing 40h.
TiO
2The preparation of colloidal sol: with butyl titanate and ethylene glycol monomethyl ether solution is to mix stirring at 1: 20 in molar ratio, and mixing time is 25min; Mol ratio by ethyl acetoacetate and butyl titanate is 1: 5, adds ethyl acetoacetate again and carries out chelating, adopts magnetic stirrer 0.5h; Add pH value subsequently and be 1.3 adjusting aqueous solution of nitric acid, the addition of regulating aqueous solution of nitric acid is 0.15 times of butyl titanate volume, continues to stir ageing 10h behind the 1.5h.
The preparation of complex sol: with HA colloidal sol and the TiO after the ageing
2Colloidal sol is pressed HA: TiO
2Mol ratio be mix to stir at 5: 1, mixing time is 1.5h, at last cold preservation ageing 20h in 4 ℃ in refrigerator.
The preparation of composite coating: with metallic matrix treat coating surface through pretreatment (sandblast, acid etching, polishing etc.), subsequently successively in tap water, dilute hydrochloric acid, pure water, acetone and pure water with each 10min of ultrasonic cleaner ultrasonic cleaning.Metallic matrix immerses in the complex sol, leaves standstill 2min, described metallic matrix is treated that the Surface Vertical of coating lifts out liquid level in described complex sol liquid level with pulling machine, and the speed of pulling out is 1mm/s, then the non-coating of metallic matrix position is protected with resin.Metallic matrix sample behind the gluing is placed into dry 20min in 60 ℃ the vacuum drying oven; remove moisture and partial solvent; remove the protection resin at the non-coating of metallic matrix position then; apply commercially available titanium alloy high-temperature protective coating at described non-coating position, to prevent the oxidation at high temperature of non-coating position.The heat-treatment furnace initial temperature is made as 60 ℃, the metallic matrix sample behind the gluing by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 1 ℃/min, the speed with 3 ℃/min is warmed up to 750 ℃ again, insulation 0.5h.Speed with 6 ℃/min is cooled to room temperature with stove, takes out sample.
Its surface scan photo as shown in Figure 2, the X diffraction analysis shows that this coating is mainly by HA and a small amount of calcium titanate, tricalcium phosphate, TiO
2Form.
Embodiment 2
The preparation of HA colloidal sol: with triethyl phosphate [(C
2H
5O)
3PO] to join in the dehydrated alcohol by the triethyl phosphate molar concentration be that 2mol/L dilutes; The pure water of 2.7 times of triethyl phosphate moles slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 24h; Lime nitrate is carried out the drying of 32h under 175 ℃ of temperature, airtight, cooling; Dried lime nitrate is pressed 2mol/L preparation lime nitrate alcoholic solution; The triethyl phosphate of lime nitrate alcoholic solution and hydrolysis was mixed in 5: 3 in molar ratio, stir 3h, ageing 40h.
The preparation of TiO 2 sol: with butyl titanate and ethylene glycol monomethyl ether solution is to mix at 1: 20 in molar ratio, adopts magnetic stirrer 25min; Mol ratio by ethyl acetoacetate and butyl titanate is 1: 5, adds ethyl acetoacetate again and carries out chelating, stirs 0.5h; Add pH value subsequently and be 1.0 adjusting aqueous solution of nitric acid, the addition of regulating aqueous solution of nitric acid is 0.14 times of butyl titanate volume, continues to stir ageing 12h behind the 1.5h.
The preparation of complex sol: with HA colloidal sol and the TiO after the ageing
2Colloidal sol is pressed HA: TiO
2Mol ratio be mix to stir at 3: 1, mixing time is 1.5h, at last cold preservation ageing 30h in 4 ℃ in refrigerator.
The preparation of composite coating: metallic matrix treated coating surface through pretreatment (sandblast, acid etching, polishing etc.), each 10min of ultrasonic cleaning in tap water, dilute hydrochloric acid, pure water, acetone, pure water successively subsequently.Metallic matrix is immersed in the mixed sols, leave standstill 2min, metallic matrix is treated that the Surface Vertical of coating lifts out liquid level in the colloidal sol liquid level with pulling machine, the speed of pulling out is 1mm/s, then the non-coating position of metallic matrix is protected with resin.The gluing sample is placed into dry 15min in 60 ℃ the vacuum drying oven; remove moisture and partial solvent; remove the protection resin at the non-coating of metallic matrix position then, apply commercially available titanium alloy high-temperature protective coating, to prevent the oxidation at high temperature of non-coating position at non-coating position.The heat-treatment furnace initial temperature is made as 60 ℃, the gluing sample by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 2 ℃/min, the speed with 4 ℃/min is warmed up to 800 ℃ again, insulation 0.5h.Speed with 5 ℃/min is cooled to room temperature with stove, takes out sample.
Its surface scan photo such as accompanying drawing 3, X diffraction analysis show that this coating is by TiO
2, HA and a small amount of calcium titanate, tricalcium phosphate and calcium oxide are formed.
Embodiment 3
HA colloidal sol 0 preparation 0: with triethyl phosphate [(C
2H
5O)
3PO] to join in the dehydrated alcohol by the triethyl phosphate molar concentration be that 2mol/L dilutes; The pure water of 2.7 times of triethyl phosphate moles slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 28h; Lime nitrate carries out the drying of 28h under 185 ℃, airtight, cooling; Dried lime nitrate is pressed 2mol/L preparation lime nitrate alcoholic solution; The triethyl phosphate of lime nitrate alcoholic solution and hydrolysis was mixed in 5: 3 in molar ratio, stir 3h, ageing 40h.
TiO 2 sol preparation: is to mix at 1: 20 butyl titanate and ethylene glycol monomethyl ether solution by the mole concentration ratio, adopt magnetic stirrer 25min, mol ratio by ethyl acetoacetate and butyl titanate is 1: 5 again, add ethyl acetoacetate and carry out chelating, stir 0.5h, add pH value subsequently and be 1.1 adjusting aqueous solution of nitric acid, the addition of regulating aqueous solution of nitric acid is 0.14 times of butyl titanate volume, continues to stir ageing 10h behind the 1.5h.
The preparation of complex sol: with HA colloidal sol and the TiO after the ageing
2Colloidal sol is pressed HA: TiO
2Mol ratio be mix to stir at 1: 2.5, mixing time is 1.5h, at last cold preservation ageing 40h in 4 ℃ in refrigerator.
The preparation of composite coating: metallic matrix treated coating surface through pretreatment (sandblast, acid etching, polishing etc.), each 10min of ultrasonic cleaning in tap water, dilute hydrochloric acid, pure water, acetone, pure water successively subsequently.Metallic matrix is immersed in the mixed sols, leave standstill 3min, metallic matrix is treated the Surface Vertical of coating lifts place's colloidal sol liquid level in the colloidal sol liquid level, the speed of pulling out is 1.5mm/s, then the non-coating position of metallic matrix is protected with resin.Gluing matrix sample is placed into dry 25min in 60 ℃ the vacuum drying oven; remove moisture and partial solvent; remove the protection resin at the non-coating of metallic matrix position then, apply commercially available titanium alloy high-temperature protective coating, to prevent the oxidation at high temperature of non-coating position at non-coating position.The heat-treatment furnace initial temperature is made as 60 ℃, gluing matrix sample by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 3 ℃/min, the speed with 5 ℃/min is warmed up to 750 ℃ again, insulation 1h.Speed with 4 ℃/min is cooled to room temperature with stove, takes out sample.
Its X diffraction analysis shows that this coating is by TiO
2, HA and a small amount of calcium titanate, calcium deficiency type apatite are formed.
Embodiment 4
HA colloidal sol preparation: with triethyl phosphate [(C
2H
5O)
3PO] to join in the dehydrated alcohol by the triethyl phosphate molar concentration be that 2mol/L dilutes; The pure water of 3 times of triethyl phosphate moles slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 32h; Lime nitrate is carried out the drying of 26h under 195 ℃ of temperature, airtight, cooling; Dried lime nitrate is pressed 2mol/L preparation lime nitrate alcoholic solution; The triethyl phosphate of lime nitrate alcoholic solution and hydrolysis was mixed in 5: 3 in molar ratio, adopt magnetic stirrer 3h, ageing 40h.
TiO 2 sol preparation: is to mix employing magnetic stirrer 25min at 1: 20 with butyl titanate and ethylene glycol monomethyl ether solution by the mole concentration ratio; Mol ratio by ethyl acetoacetate and butyl titanate is 1: 5 again, adds ethyl acetoacetate and carries out chelating, stirs 0.5h; Add pH value subsequently and be 1.3 adjusting aqueous solution of nitric acid, the addition of regulating aqueous solution of nitric acid is 0.16 times of butyl titanate volume, continues to stir ageing 8h behind the 1.5h.
The preparation of complex sol: with HA colloidal sol and the TiO after the ageing
2Colloidal sol is pressed HA: TiO
2Mol ratio be mix to stir at 1: 2.5, mixing time is 1.5h, at last cold preservation ageing 50h in 4 ℃ in refrigerator.
The preparation of composite coating: with metallic matrix treat coating surface through pretreatment (sandblast, acid etching, polishing etc.), subsequently successively in tap water, dilute hydrochloric acid, pure water, acetone, pure water with each 10min of ultrasonic cleaner ultrasonic cleaning.Metallic matrix is immersed in the mixed sols, leave standstill 4min, metallic matrix is treated that the Surface Vertical of coating lifts out the colloidal sol liquid level in the colloidal sol liquid level with pulling machine, the speed of pulling out is 1.5mm/s, then the non-coating position of metallic matrix is protected with resin.Gluing metallic matrix sample is placed into dry 20min in 60 ℃ the vacuum drying oven; remove moisture and partial solvent; remove the protection resin at the non-coating of metallic matrix position then, apply commercially available titanium alloy high-temperature protective coating, to prevent the oxidation at high temperature of non-coating position at non-coating position.The heat-treatment furnace initial temperature is made as 60 ℃, gluing matrix sample by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 3 ℃/min, the speed with 6 ℃/min is warmed up to 800 ℃ again, insulation 0.5h.Speed with 4 ℃/min is cooled to room temperature with stove, takes out the matrix sample.
Its X diffraction analysis shows this coating by TiO2, HA, and calcium titanate, tricalcium phosphate and calcium deficiency type apatite are formed.
Embodiment 5
HA colloidal sol preparation: with triethyl phosphate [(C
2H
5O)
3PO] to join in the dehydrated alcohol by the triethyl phosphate molar concentration be that 2mol/L dilutes; The pure water of 2.5 times of triethyl phosphate moles slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 36h; Lime nitrate is carried out the drying of 24h under 200 ℃ of temperature, airtight, cooling; Dried lime nitrate is pressed 2mol/L preparation lime nitrate alcoholic solution; The triethyl phosphate of lime nitrate alcoholic solution and hydrolysis was mixed in 5: 3 in molar ratio, stir 3h, ageing 36h.
TiO 2 sol preparation: is to mix employing magnetic stirrer 25min at 1: 20 with butyl titanate and ethylene glycol monomethyl ether solution by the mole concentration ratio; Mol ratio by ethyl acetoacetate and butyl titanate is 1: 5 again, adds ethyl acetoacetate and carries out chelating, stirs 0.5h; Add pH value subsequently and be 1.5 adjusting aqueous solution of nitric acid, the addition of regulating aqueous solution of nitric acid is 0.2 times of butyl titanate volume, continues to stir ageing 8h behind the 1.5h.
The preparation of complex sol: with HA colloidal sol and the TiO after the ageing
2Colloidal sol is pressed HA: TiO
2Mol ratio be mix to stir at 1: 2.5, mixing time is 1.5h, at last cold preservation ageing 60h in 4 ℃ in refrigerator.
The preparation of composite coating: metallic matrix treated coating surface through pretreatment (sandblast, acid etching, polishing etc.), each 10min of ultrasonic cleaning in tap water, dilute hydrochloric acid, pure water, acetone, pure water successively subsequently.Metallic matrix is immersed in the mixed sols, leave standstill 5min, metallic matrix is treated the Surface Vertical of coating lifts place's colloidal sol liquid level in the colloidal sol liquid level, the speed of pulling out is 2mm/s, then the non-coating of metallic matrix position is protected with resin.Gluing metallic matrix sample is placed into dry 30min in 60 ℃ the vacuum drying oven; remove moisture and partial solvent; remove the protection resin at the non-coating of metallic matrix position then, apply commercially available titanium alloy high-temperature protective coating, to prevent the oxidation at high temperature of non-coating position at non-coating position.The heat-treatment furnace initial temperature is made as 60 ℃, gluing matrix sample by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 3 ℃/min, the speed with 4 ℃/min is warmed up to 900 ℃ again, insulation 0.5h.Speed with 7 ℃/min is cooled to room temperature with stove, takes out the metallic matrix sample.
Its X diffraction analysis shows that this coating is by TiO
2, HA, calcium titanate, tricalcium phosphate and calcium deficiency type apatite are formed.
Claims (3)
1. the preparation method of a hydroxyapatite/titanic oxide composite biological coatings is characterized in that preparation process is:
The preparation of step 1, hydroxyapatite colloidal sols:
(11) triethyl phosphate being joined in the dehydrated alcohol, is that 2mol/L dilutes by the triethyl phosphate molar concentration;
(12) triethyl phosphate mole 2-3.5 pure water doubly slowly is added drop-wise in the above-mentioned diluent is hydrolyzed, adopt magnetic stirring apparatus strong agitation 24-36h, stand-by;
(13) lime nitrate is carried out the drying of 24-36h under 160 ℃-270 ℃ of temperature, airtight, to be cooled to room temperature, dried lime nitrate is mixed with the lime nitrate alcoholic solution by mole concentration 2mol/L, airtight stand-by;
(14) the lime nitrate alcoholic solution of preparation and the triethyl phosphate of hydrolysis were mixed in 5: 3 in molar ratio, adopt magnetic stirrer 3-6h, ageing 36-48h under the room temperature promptly makes hydroxyapatite colloidal sols;
Step 2, TiO
2The preparation of colloidal sol:
(21) butyl titanate and ethylene glycol monomethyl ether solution were mixed in 1: 20 in molar ratio, adopt magnetic stirrer 25min;
(22) mol ratio by ethyl acetoacetate and butyl titanate is 1: 5, adds ethyl acetoacetate again in the butyl titanate and carries out chelating, adopts magnetic stirrer 0.5-1h; Adding pH value then is the adjusting aqueous solution of nitric acid of 1-1.5, and the addition of regulating aqueous solution of nitric acid is 0.1-0.2 a times of butyl titanate volume, continues to stir 1.5-2h, and ageing 8-15h under the room temperature promptly makes TiO
2Colloidal sol;
The preparation of step 3, complex sol:
With hydroxyapatite colloidal sols in the step 1 and the TiO in the step 2
2Colloidal sol is 0.1-10 in molar ratio: 1 mixes, and adopting the magnetic stirrer time is 1.5h, and 4 ℃ of cold preservation ageings of refrigerator 15-60h promptly makes complex sol;
The preparation of step 4, composite coating:
(41) with metallic matrix treat coating surface after grinding, successively in tap water, dilute hydrochloric acid, pure water, acetone and pure water with each 10min of ultrasonic cleaner ultrasonic cleaning;
(42) metallic matrix that will be after ultrasonic cleaning immerses in the complex sol in the step 3, time of repose is 1-5min, with pulling machine metallic matrix is treated that coating surface lifts out the complex sol liquid level perpendicular to described complex sol liquid level, the speed of pulling out is 0.5-2mm/s, then the non-coating of described metallic matrix position is protected with resin;
(43) the gluing metallic matrix is placed into dry 15-30min in 60 ℃ the vacuum drying oven, removes moisture and partial solvent, remove the protection resin at the non-coating of gluing metallic matrix position then, at described non-coating position coated titanium alloy protecting coating;
(44) the heat-treatment furnace initial temperature is made as 60 ℃, the gluing metallic matrix by being transferred to fast in the vacuum drying oven in the heat-treatment furnace, is warmed up to 400 ℃ with the speed of 1-4 ℃/min, the speed with 3-6 ℃/min is warmed up to 750-900 ℃ again, insulation 0.5-1h; Speed with 4-7 ℃/min is cooled to room temperature with stove, promptly forms hydroxyapatite/titanic oxide composite biological coatings at metal base surface, removes the titanium alloy protective coating at the non-coating of described metallic matrix position then.
2. according to the preparation method of the described hydroxyapatite/titanic oxide composite biological coatings of claim 1, it is characterized in that heat-treatment furnace is Muffle furnace or tube furnace described in the step (44).
3. according to the preparation method of the described hydroxyapatite/titanic oxide composite biological coatings of claim 1, it is characterized in that metallic matrix described in the step 4 is titanium alloy, medical stainless steel, cochrome or other medical metal.
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