CN108220925A - A kind of method of fabricated in situ biphasic calcium phosphate nano composite material coating - Google Patents

A kind of method of fabricated in situ biphasic calcium phosphate nano composite material coating Download PDF

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CN108220925A
CN108220925A CN201611195203.6A CN201611195203A CN108220925A CN 108220925 A CN108220925 A CN 108220925A CN 201611195203 A CN201611195203 A CN 201611195203A CN 108220925 A CN108220925 A CN 108220925A
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calcium phosphate
gel
composite material
situ
fabricated
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CN108220925B (en
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邓泽贤
蔡文迪
陈玲
罗永祥
谭惠民
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Hong Kong Polytechnic University HKPU
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Hong Kong Polytechnic University HKPU
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412—Tissue-regenerating or healing or proliferative agents
    • A—HUMAN NECESSITIES
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
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Abstract

The invention discloses a kind of methods of fabricated in situ biphasic calcium phosphate nano composite material coating, include the following steps：Laser ablation and chemical etching are carried out to metallic substrate surfaces；Tetraethyl titanate is mixed into the acetic acid for being 3.5~4.5 in pH value, prepares TiO 2 sol；Calcium carbonate and calcium monohydrogen phosphate are mixed into dicalcium phosphate dihydrate solvent, prepares Calcium phosphate gel；The TiO 2 sol prepared and Calcium phosphate gel with 1: 1.5 weight ratio are mixed, and mechanical agitation and ultrasonication are carried out to mixed sols, titanium dioxide calcium phosphate nanoparticles gel is made；By gel coating in metallic substrate surfaces；The metal substrate that titanium dioxide calcium phosphate nanoparticles gel coat is coated with to surface carries out hybrid microwave heating.This method makes the biphasic calcium phosphate nano composite material coating of preparation have good bioactivity, and strong with the bonding force of metal surface, can be good at promoting bone growth and functional rehabilitation.

Description

A kind of method of fabricated in situ biphasic calcium phosphate nano composite material coating
Technical field
The present invention relates to microwave technologies and new material manufacturing technology field, double more specifically to a kind of fabricated in situ The method of calcium phosphate phase nano composite material coating.
Background technology
Biphasic calcium phosphate (Biphasic Calcium Phosphates), is made of hydroxyapatite and tricalcium phosphate, in mistake Decades is gone to attract a large amount of academic research, because its excellent biocompatibility and bioactivity can be used as artificial bone material Material.Biphasic calcium phosphate coating is widely used, bioadhesion layer including implanted equipment and for golden in adverse circumstances The protective layer of metal surface.
The conventional method for carrying out biphasic calcium phosphate coating in metal surface includes plasma spraying, ion beam sputtering, swashs Light deposition, hydrothermal synthesis and Mechano-chemical Synthesizing.However, prepare and the production equipment of these coating processes is set to usually require very Big investment and operating cost.All these conventional methods are required for high high temperature and harsh pH value condition, so as to easily Lead to the thermal decomposition of biphasic calcium phosphate and the low adhesion degree between metal surface.Therefore, industrial quarters needs one kind to gold in a hurry Metal surface carries out the high efficiency preparation method of biphasic calcium phosphate coating.
Invention content
The technical problem to be solved in the present invention is that the high cost and inefficient biphasic calcium phosphate for the prior art apply The defects of layer, provide a kind of method of the fabricated in situ biphasic calcium phosphate nano composite material coating based on microwave technology, the party Method make preparation biphasic calcium phosphate nano composite material coating have improvement bioactivity, and with the bonding force of metal surface By force, can be good at promoting bone growth and functional rehabilitation.
The technical solution adopted by the present invention to solve the technical problems is：A kind of fabricated in situ biphasic calcium phosphate nanometer is provided The method of composite coating, the described method comprises the following steps：
S1：Laser ablation and chemical etching are carried out to metallic substrate surfaces；
S2：Tetraethyl titanate is mixed into the acetic acid for being 3.5~4.5 in pH value, prepares TiO 2 sol；In two water phosphorus Calcium carbonate and calcium monohydrogen phosphate are mixed into sour hydrogen calcium solvent, prepares Calcium phosphate gel；
S3：The TiO 2 sol prepared and Calcium phosphate gel are mixed with 1: 1.5 weight ratio, and molten to mixing Glue carries out mechanical agitation and ultrasonication, and titanium dioxide-calcium phosphate nanoparticles gel is made；
S4：Titanium dioxide-calcium phosphate nanoparticles gel is carved into engraving machine by roller and is coated on metallic substrate surfaces, is formed 1~10 μm of coating.
S5：The metal substrate progress receptor that titanium dioxide-calcium phosphate nanoparticles gel coat is coated with to surface is auxiliary The hybrid microwave heating that heating and microwave heating are combined is helped, realizes titanium dioxide-calcium phosphate nanoparticles gel in Metal Substrate The fabricated in situ of plate surface.
Preferably, in step sl, the metal substrate is titanium alloy substrate.
Preferably, step S1 is further comprising the steps of：
S11, laser ablation-Room pressure with laser direct-writing machine with the frequency of 45 kHz to metallic substrate surfaces into In 1.5~3.0mm/s, laser pulse interval is 100 nanoseconds for row processing, wherein sweep speed control；
Metallic substrate surfaces are continued into infiltration in sodium hydroxide solution immediately after S12, chemical etching-laser ablation process 24 hours, and by sodium hydroxide solution temperature setting at 55~65 degrees Celsius；
S13, it is taken out, and rinsed well metallic substrate surfaces with distilled water, and taken the photograph 35~45 after infiltrating 24 hours It is dry in the environment of family name's degree.
Preferably, step S3 is further comprising the steps of：
S31：The TiO 2 sol prepared and Calcium phosphate gel are mixed with 1: 1.5 weight ratio, and to mixing Colloidal sol carries out mechanical agitation and ultrasonication, continues at least two hours to the mixed sols progress churned mechanically time；
S32：Mixed sols is placed into 7~9 hours at room temperature, titanium dioxide-calcium phosphate nanoparticles gel is made, Its viscosity is
Preferably, in step s 4, coating speed control is in 4~5mm/s；Forming 1~10 μm of titanium dioxide-phosphoric acid After calcium nano gel coat, metal substrate is placed 24 hours under ordinary room temperature.
Preferably, step S5 is further comprising the steps of：
S51：Metal substrate is fixed on the insulating oxide aluminium sheet in the aluminium oxide stove of microwave sintering device, the oxidation The inner surface of aluminium stove is coated with coat of silicon carbide as microwave susceptor；
S52：Full of nitrogen in aluminium oxide stove, and metal substrate is micro- with the rate of 35~45 degrees Celsius of heating per minute Wave is preheating to 445~455 degrees Celsius；
S53：To metal substrate with the rate microwave heating of 75~85 degrees Celsius of heating per minute to 790~810 degrees Celsius, And maintain the metal substrate be in 790~810 degrees Celsius at a temperature of 9~11 minutes, then metal substrate is allowed to drop naturally For temperature to indoor temperature, the chemical reaction that wherein microwave heating and when high temperature occur is as follows：
CaCO3+CaHPO4→β-Ca3(PO4)2[TCP]+H2O+CO2。
The beneficial effects of the present invention are this method makes the biphasic calcium phosphate nano composite material coating of preparation have more The bioactivity of improvement, and coating and the bonding force of metal surface are strong, can be good at promoting bone growth and function extensive It is multiple.
Description of the drawings
Below in conjunction with accompanying drawings and embodiments, the invention will be further described, in attached drawing：
Fig. 1 is a kind of flow chart of the method for fabricated in situ biphasic calcium phosphate nano composite material coating of the present invention；
Fig. 2 be the present invention a kind of fabricated in situ biphasic calcium phosphate nano composite material coating method in step S1 son Flow chart of steps；
Fig. 3 be the present invention a kind of fabricated in situ biphasic calcium phosphate nano composite material coating method in step S5 son Flow chart of steps；
Fig. 4 be the present invention a kind of fabricated in situ biphasic calcium phosphate nano composite material coating method in provide mixing it is micro- One embodiment schematic diagram of the microwave sintering device of Wave heating；
Fig. 5 is using the biphasic calcium phosphate nano composite material coating that scanning electron microscope is shown after method of the invention Aspect graph；
Fig. 6 is that have biphasic calcium phosphate nanocomposite using what scanning electron microscope after method of the invention was shown The titanium alloy substrate of coating is infiltrated on configuration of surface figure of the simulated body fluid after 7 days；
Fig. 7 is using coating surface after 3 days Cell culture invitros that scanning electron microscope is shown after method of the invention The osteoblast of growth.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, now control attached drawing is described in detail The specific embodiment of the present invention.
Fig. 1 is a kind of flow chart of the method for fabricated in situ biphasic calcium phosphate nano composite material coating of the present invention.Institute The method of stating includes the following steps：
S1：Laser ablation and chemical etching are carried out to metallic substrate surfaces；
S2：Tetraethyl titanate is mixed into the acetic acid for being 3.5~4.5 in pH value, prepares TiO 2 sol；In two water phosphorus Calcium carbonate is mixed into sour hydrogen calcium solvent, prepares Calcium phosphate gel；
S3：The TiO 2 sol prepared and Calcium phosphate gel are mixed with 1: 1.5 weight ratio, and molten to mixing Glue carries out mechanical agitation and ultrasonication, and titanium dioxide-calcium phosphate nanoparticles gel is made；
S4：Titanium dioxide-calcium phosphate nanoparticles gel is carved into engraving machine by roller and is coated on metallic substrate surfaces, is formed 1~10 μm of coating.
S5：The metal substrate progress receptor that titanium dioxide-calcium phosphate nanoparticles gel coat is coated with to surface is auxiliary The hybrid microwave heating that heating and microwave heating are combined is helped, realizes titanium dioxide-calcium phosphate nanoparticles gel in Metal Substrate The fabricated in situ of plate surface.
Fig. 2 be the present invention a kind of fabricated in situ biphasic calcium phosphate nano composite material coating method in step S1 son Flow chart of steps.In step sl, the metal substrate is titanium alloy substrate.The titanium alloy substrate that thickness is 1mm can be from firmly Friendly metal company is bought.Titanium alloy substrate can carry out ultrasonic wave with the mixed solution of distilled water, acetone and ethyl alcohol before use Cleaning, is then dried at room temperature.
Step S1 is further comprising the steps of：S11, laser ablation-in Room pressure are with laser direct-writing machine with 45 kHz Frequency metallic substrate surfaces are handled, wherein sweep speed control in 1.5~3.0mm/s, laser pulse interval It is 100 nanoseconds；
Metallic substrate surfaces are continued into infiltration in sodium hydroxide solution immediately after S12, chemical etching-laser ablation process 24 hours, and by sodium hydroxide solution temperature setting at 55~65 degrees Celsius；
S13, it is taken out, and rinsed well metallic substrate surfaces with distilled water, and taken the photograph 35~45 after infiltrating 24 hours It is dry in the environment of family name's degree.Analysis can be detected to the surface smoothness of titanium alloy substrate, after laser ablation process to ensure The surface of titanium alloy substrate reaches smooth requirement.
In step s 2, titanium dioxide-calcium phosphate nanoparticles gel is made by sol-gel method.Two are prepared at one In the embodiment of titanium oxide sol, 5 milliliters of tetraethyl titanate (C8H20O4Ti it) is diluted to first with 50 milliliters of absolute ethyl alcohol Mixed solution；Then with by 7.5 milliliters of acetic acid (CH3COOH) and 5 milliliters of distilled water is added to the mixed solution, is made two Titanium oxide sol.Add in nitric acid (HNO3) pH value of TiO 2 sol is maintained at 4 or so, then the colloidal sol is continued It 24 hours is vigorously stirred.In one prepares the embodiment of Calcium phosphate gel, by 0.54 gram of calcium carbonate (CaCO3) and 1.4 Gram dicalcium phosphate dihydrateIt adds in 50 milliliters of absolute ethyl alcohols under the state that is vigorously stirred, phosphorus is made Sour calcium sol.And step S3 is further comprising the steps of：
S31：The TiO 2 sol prepared and Calcium phosphate gel are mixed with 1: 1.5 weight ratio, and to mixing Colloidal sol carries out mechanical agitation and ultrasonication, continues at least two hours to the mixed sols progress churned mechanically time；
S32：Mixed sols is placed into 7~9 hours at room temperature, titanium dioxide-calcium phosphate nanoparticles gel is made, Its viscosity is 260~300mPa*S.Viscosity can be measured by digital rotational viscometer.
In step S2 and S3, during the calcium phosphate nanoparticles gel containing titanium dioxide can synthesize in situ Its degree of adhesion between titanium alloy substrate is significantly improved, makes the biphasic calcium phosphate nano composite material coating after fabricated in situ firm Admittedly be coated in titanium alloy substrate surface.
In step s 4, coating speed control is in 4~5mm/s；Forming 1~10 μm of titanium dioxide-calcium phosphate nano After granulated gel coating, metal substrate is placed 24 hours under ordinary room temperature.
Fig. 3 be the present invention a kind of fabricated in situ biphasic calcium phosphate nano composite material coating method in step S5 son Flow chart of steps.Step S5 is further comprising the steps of：
S51：Metal substrate is fixed on the insulating oxide aluminium sheet in aluminium oxide stove；
S52：Full of nitrogen in aluminium oxide stove, and metal substrate is pre- with the rate of 35~45 degrees Celsius of heating per minute Heat is to 445~455 degrees Celsius；
S53：790~810 degrees Celsius are heated to, and tie up with the rate of 75~85 degrees Celsius of heating per minute to metal substrate It holds at a temperature of the metal substrate is in 790~810 degrees Celsius 9~11 minutes, wherein the chemical reaction equation below occurred：
CaCO3+CaHPO4→β-Ca3(PO4)2[TCP]+H2O+CO2
HA (Hydroxyapatite, hydroxyapatite) and TCP (Tricalcium Phosphate, tricalcium phosphate) is to carbon Sour calcium (CaCO3) and dicalcium phosphate dihydrate (Dicalcium Phosphate Dihydrate,) carry out hot place The sintetics generated after reason.HA and TCP is two-phase biological ceramic material, and HA and TCP can be after bone implant surgeries effectively Accelerate the growth of bone.
Fig. 4 be the present invention a kind of fabricated in situ biphasic calcium phosphate nano composite material coating method in provide mixing it is micro- One embodiment schematic diagram of the microwave sintering device of Wave heating.In a preferred embodiment, to being coated with titanium dioxide-phosphoric acid The titanium alloy substrate of calcium nano gel coat carries out hybrid microwave heating, and microwave heating is in 2.45GHz, and 0.3~2.85 thousand It is carried out in watt microwave sintering device (HAMiLab-HV3000, long sand swell Thailand microwave thermal technology).Titanium alloy substrate is fixed on one absolutely On edge alumina plate, which is arranged in aluminium oxide stove.The inner wall of aluminium oxide stove is coated with silicon carbide/graphite and applies Layer, the silicon carbide/equadag coating play the role of auxiliary heating as microwave susceptor.Space in aluminium oxide stove is full of nitrogen Gas (fullness rate can reach 99.99%) is to prevent the oxidation of titanium alloy substrate.As shown in figure 4, the microwave sintering device is fixed Setting on a spinstand, is driven by turntable in rotary state, microwave is transmitted to from a fixed direction and is coated with titanium dioxide The titanium alloy substrate of titanium-calcium phosphate nanoparticles gel coat, such microwave heating cause the surface of titanium alloy substrate Can thermally equivalent, the excellent coating effect that this kind of mode of heating obtains is also demonstrated to the verification result of substrate surface later.
For measuring the temperature of titanium alloy-based plate surface, the precision of measurement can reach infrared pyrometer (Raytek, the U.S.) To in the range of 450~2250 degrees Celsius error be no more than measurement temperature value ± 0.3%.By titanium alloy substrate with per minute The rate microwave preheating of 40 degrees Celsius of heating is to 450 degrees Celsius；Again to titanium alloy substrate with the speed of 80 degrees Celsius of heating per minute Rate microwave heating maintains titanium alloy substrate 10 minutes at a temperature of 800 degrees Celsius to 800 degrees Celsius, then allows titanium alloy Substrate cools to indoor temperature naturally, completes original of the titanium dioxide-calcium phosphate nanoparticles gel in titanium alloy-based plate surface Position synthesis, forms biphasic calcium phosphate nano composite material coating.
Fig. 5 is using the biphasic calcium phosphate nano composite material coating that scanning electron microscope is shown after method of the invention Aspect graph.After fabricated in situ is completed, two-phase phosphoric acid is studied using X-ray diffractometer (XRD, Rigaku SmartLab 9kW) The crystalline phase of calcium nano composite material coating, the diffractometer can send out CuK alpha rays under conditions of 45 kilovolts and 200 milliamperes, 2 θ investigative ranges are 20~80 degrees Celsius, and sweep speed is 2 °/min.The form of coating passes through scanning electron microscope (JEOL JSM-6490 it) shows.The very thin gold of last layer can be applied on the surface of coating to increase electric conductivity.The chemical composition of coating can To be obtained by energy dispersive spectrometer to analyze.As can be seen from Figure 5 the biphasic calcium phosphate nanocomposite of fabricated in situ Coating uniform it is distributed in the surface of titanium alloy substrate, it was demonstrated that the in-situ synthetic method can make titanium dioxide-calcium phosphate receive Rice grain gel is sticked together well on the surface of titanium alloy substrate.
The adhesive strength of the biphasic calcium phosphate nano composite material coating of fabricated in situ passes through computer-controlled mechanical measurement System (MTS 810) is obtained according to ASTM C633-79 program measurements.Prepare to measure, titanium alloy substrate affixes 8mm aluminum strips With epoxy resin (3M DP460, the U.S.), pulling force is applied with the loading velocity of 1mm/min to titanium alloy substrate, until coating is broken It splits and comes off.The wetability of the titanium alloy substrate of coating and non-coating in room temperature condition by continuing lower drop distillation water droplet in substrate table Behind face 10 seconds, the contact angle for measuring water droplet and surface obtains.The measurement of angle can use the light microscope for having video camera It is obtained with image analysis system (Sindatek, Taiwan).The volume often dripped probably is 5 μ L.
Fig. 6 is that have biphasic calcium phosphate nanocomposite using what scanning electron microscope after method of the invention was shown The titanium alloy substrate of coating is infiltrated on configuration of surface figure of the simulated body fluid after 7 days.By biphasic calcium phosphate nano composite material coating Titanium alloy substrate immersion in vitro in the simulated body fluid formed with human plasma comparable ionic, so as to test two-phase phosphoric acid The external activity of the titanium alloy substrate of calcium nano composite material coating.Simulated body fluid meets the ion of human cell's external solution (ECF) Concentration, by solubilising reagent chemical substance, including sodium chloride (NaCl), sodium bicarbonate (NaHCO3), potassium chloride (KCl), phosphoric acid Hydrogen potassium trihydrate (di-potassium hydrogen phosphate trihydrate,), magnesium chloride Hexahydrate (magnesium chloride hexahydrate,), calcium chloride (CaCl2) and sodium sulphate (Na2SO4) in distilled water.Again in the trishydroxymethylaminomethane (NH that pH value is 7.4~7.52C(CH2OH)3) and hydrochloric acid (HCl) it is made in buffer.
It is 50mm by surface area2Titanium alloy substrate sample infiltrate in simulated body fluid in aseptic polyethylene pipe 7 days, The volume of simulated body fluid is 25 milliliters or so.The opening of test tube is sealed during infiltration.During the experiment, test tube is placed on In 37 degrees Celsius of warm water, simulated body fluid is replaced primary for every two days.After infiltration 7 days, titanium alloy substrate sample is from simulated body fluid In take out, cleaned with distilled water and dried at room temperature.The configuration of surface and crystalline phase of titanium alloy substrate are shown by scanning electron Micro mirror is shown.As can be seen from Figure 6 the newly deposited apatite that coating surface has fine granularity covered with one layer, this Phenomenon, which shows the titanium alloy substrate coated with biphasic calcium phosphate nano composite material coating, has enhancing and improved external life Object activity.
Fig. 7 is using coating surface after 3 days Cell culture invitros that scanning electron microscope is shown after method of the invention The osteoblast of growth.As can be seen from the figure osteoblast is securely and to be widely attached to biphasic calcium phosphate nano combined Material coating surface, this feature show coating with good Bioactivity.
The method of the present invention makes biphasic calcium phosphate nano composite material coating be coated on titanium alloy doctor uniformly and securely With the surface of implantation material.High speed and high efficiency method of this kind based on microwave technology can within the relatively short time fabricated in situ it is double For calcium phosphate phase nano composite material coating in metal surface, this method only needs the time of lasting 20 minutes, but other routine sides Method needs the time of at least one hour, and low using the cost of equipment, coating procedure and the conventional method phase of fabricated in situ The energy consumption of specific consumption is relatively fewer.Therefore this method has been compared in production efficiency with conventional method is obviously improved.Fig. 5, Fig. 6 The titanium alloy substrate tool coated with biphasic calcium phosphate nano composite material coating is also demonstrated with the scanning electron microscope diagram of Fig. 7 There is the bioactivity of improvement.
And on the contrary, conventional bioceramic nano composite material coating method require high equipment investment and operation into This, and coating procedure needs very big energy consumption.In addition, using coating obtained after conventional method because of the heat point of bioceramic Solution and metal surface poor adhesion, and the cated metallic substrate surfaces bioactivity of tool is low, it can not be well as implantation Formula bioadhesion layer and protective layer use.
The embodiment of the present invention is described above in conjunction with attached drawing, but the invention is not limited in above-mentioned specific Embodiment, above-mentioned specific embodiment is only schematical rather than restricted, those of ordinary skill in the art Under the enlightenment of the present invention, present inventive concept and scope of the claimed protection are not being departed from, can also made very much Form, these are belonged within the protection of the present invention.

Claims (6)

  1. A kind of 1. method of fabricated in situ biphasic calcium phosphate nano composite material coating, which is characterized in that the method includes with Lower step：
    S1：Laser ablation and chemical etching are carried out to metallic substrate surfaces；
    S2：Tetraethyl titanate is mixed into the acetic acid for being 3.5~4.5 in pH value, prepares TiO 2 sol；In hydrogen phosphate dihydrate Calcium carbonate and calcium monohydrogen phosphate are mixed into calcium solvent, prepares Calcium phosphate gel；
    S3：The TiO 2 sol prepared and Calcium phosphate gel are mixed with 1: 1.5 weight ratio, and to mixed sols into Titanium dioxide-calcium phosphate nanoparticles gel is made in row mechanical agitation and ultrasonication；
    S4：By titanium dioxide-calcium phosphate nanoparticles gel by roller carve engraving machine be coated on metallic substrate surfaces, formed 1~ 10 μm of coating.
    S5：The metal substrate progress microwave susceptor that titanium dioxide-calcium phosphate nanoparticles gel coat is coated with to surface adds The hybrid microwave heating that heat and microwave heating are combined, realizes titanium dioxide-calcium phosphate nanoparticles gel in metal substrate table The fabricated in situ in face.
  2. 2. the method for fabricated in situ biphasic calcium phosphate nano composite material coating according to claim 1, which is characterized in that In step sl, the metal substrate is titanium alloy substrate.
  3. 3. the method for fabricated in situ biphasic calcium phosphate nano composite material coating according to claim 1, which is characterized in that Step S1 is further comprising the steps of：
    S11, laser ablation-Room pressure with laser direct-writing machine with the frequency of 45 kHz to metallic substrate surfaces at For the control of reason, wherein sweep speed in 1.5~3.0mm/s, laser pulse interval is 100 nanoseconds；
    It is 24 small in sodium hydroxide solution that metallic substrate surfaces are continued into infiltration immediately after S12, chemical etching-laser ablation process When, and by sodium hydroxide solution temperature setting at 55~65 degrees Celsius；
    S13, it is taken out, and rinsed well metallic substrate surfaces with distilled water, and at 35~45 degrees Celsius after infiltrating 24 hours Environment in it is dry.
  4. 4. the method for fabricated in situ biphasic calcium phosphate nano composite material coating according to claim 1, which is characterized in that Step S3 is further comprising the steps of：
    S31：The TiO 2 sol prepared and Calcium phosphate gel are mixed with 1: 1.5 weight ratio, and to mixed sols Mechanical agitation and ultrasonication are carried out, at least two hours are continued to the mixed sols progress churned mechanically time；
    S32：Mixed sols is placed into 7~9 hours at room temperature, titanium dioxide-calcium phosphate nanoparticles gel is made, is glued Consistency is
  5. 5. the method for fabricated in situ biphasic calcium phosphate nano composite material coating according to claim 1, which is characterized in that In step s 4, coating speed control is in 4~5mm/s；Forming 1~10 μm of titanium dioxide-calcium phosphate nanoparticles gel After coating, metal substrate is placed 24 hours under ordinary room temperature.
  6. 6. the method for fabricated in situ biphasic calcium phosphate nano composite material coating according to claim 1, which is characterized in that Step S5 is further comprising the steps of：
    S51：Metal substrate is fixed on the insulating oxide aluminium sheet in the aluminium oxide stove of microwave sintering device, the aluminium oxide stove Inner surface be coated with coat of silicon carbide as microwave susceptor；
    S52：Full of nitrogen in aluminium oxide stove, and metal substrate is pre- with the rate microwave of 35~45 degrees Celsius of heating per minute Heat is to 445~455 degrees Celsius；
    S53：To metal substrate with the rate microwave heating of 75~85 degrees Celsius of heating per minute to 790~810 degrees Celsius, and tie up It holds at a temperature of the metal substrate is in 790~810 degrees Celsius 9~11 minutes, then metal substrate is allowed to cool to naturally The chemical reaction occurred when indoor temperature, wherein microwave heating and high temperature is as follows：
    CaCO3+CaHPO4→β-Ca3(PO4)2[TCP]+H2O+CO2。
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