CN111467577B - Medical metal bone implant material - Google Patents
Medical metal bone implant material Download PDFInfo
- Publication number
- CN111467577B CN111467577B CN202010318690.0A CN202010318690A CN111467577B CN 111467577 B CN111467577 B CN 111467577B CN 202010318690 A CN202010318690 A CN 202010318690A CN 111467577 B CN111467577 B CN 111467577B
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- Prior art keywords
- tantalum
- hydroxyapatite
- follows
- parameters
- spraying
- Prior art date
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Classifications
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The invention provides a preparation method of a medical metal bone implant material, which obtains a Ta2O 5/hydroxyapatite material of a tantalum/nanometer pore canal array by pretreatment, sand blasting, anodic oxidation, flame spraying and roasting, wherein the porosity of the material is 80-85%, the compressive strength is 150-1700Mpa, the coating binding force is high at 15-19Mpa, and the biocompatibility is excellent.
Description
Technical Field
The invention relates to a preparation method of a medical metal bone implant material, belonging to the technical field of medical metal bone implant materials.
Technical Field
21426a biomedical material has excellent mechanical properties, easy processability and stability, and thus is widely used in clinical medicine field. However, the material is directly contacted with human tissues, so that the material has higher requirements on the design, preparation and surface modification of the material, and can meet the physical and chemical properties and excellent biocompatibility which are different from those of common materials. The selection criteria for biomedical materials are that they cause minimal biological reactions in the body and are able to meet the basic functional requirements of the tissue being replaced or repaired. Therefore, the biomedical metal material must meet the following basic requirements of (1) nontoxicity, wherein the metal simple substances which are considered to be basically nontoxic at present mainly comprise Ga, in, sn, ti, zr, mo, W, au, ta and Pt; (2) is resistant to physical corrosion. The human body fluid contains organic acid, alkali metal or alkali metal plus or minus metal, and under the action of protein, enzyme and cells, metal materials are easy to corrode in human bodies, corrosion products of the metal materials can be metal ions, oxides, even more complex metal complexes and the like, and the products can contact adjacent tissues and even permeate into normal tissues or the whole biological system to influence and stimulate normal tissues, possibly cause adverse biological reactions including abnormal growth, skillful deformation, allergy or inflammation, infection and the like of the normal tissues and even induce canceration; (3) the metal material has excellent biocompatibility, because the composition of the metal material is greatly different from the weaving of a human body, the metal material often has no biological activity, and because of the relatively stable chemical performance of the metal material, the metal material has certain biological compatibility; (4) excellent mechanical properties: medical metal materials are often used as stressed devices in human bodies, such as artificial joints, fracture internal fixation steel plates, dental implants and the like. The stress state of the parts is usually very severe, and the materials are required to have excellent mechanical properties, and (5) the workability and the applicability are easy. The material is required to have good workability and to be able to be processed into various shapes suitable for the implantation site, thereby reducing the processing cost.
At present, the metal materials widely applied in clinic mainly comprise non-cast steel, cobalt-based alloy, magnesium alloy and titanium alloy. Among them, iron metal and its alloys are most widely used in the clinical medicine field due to their superior chemical stability, corrosion resistance and good biocompatibility.
Tantalum (Ta) has attracted considerable attention as a "biophilic" metal in the last decade. The atomic number of tantalum was 73 and was found 1802 by the swedish chemist Ekeberg from tantalum ore. Similar to other eutectic metals, tantalum has a higher hardness (6.5 mohs) and better ductility. However, it has a relatively high melting point (2980 oC), thus limiting its manufacturing process. Tantalum is naturally oxidized in atmospheric environment, a Ta2O5 film is inevitably formed on the surface of the tantalum, a tantalum metal matrix can be protected, the tantalum metal matrix can keep very stable chemical properties in a human body fluid environment, the tantalum metal matrix has extremely strong corrosion resistance, and except hydrofluoric acid, sulfur trioxide and alkali, the tantalum metal matrix can resist corrosion of almost all inorganic acids and organic acids, so that the tantalum metal matrix has extremely good biocompatibility and is an ideal bone implant material. According to the results of the clinical early-stage biomechanical evaluation, the porous tantalum metal implant nail can provide mechanical support for subchondral bone tissues with bone defects, and the elasticity and the tensity of the femoral head are similar to those of the implant bone graft. In addition, tantalum wire or foil can be used to suture nerves, muscle, blood vessels, etc. When the tantalum is used on the surface of the blood vessel stent, the antithrombotic property of the blood vessel stent can be obviously improved, and the blood vessel metal stent of the tantalum metal is commercialized at present and widely applied to the treatment of blood vessel diseases.
CN 107998445A discloses a surface modified porous tantalum biomaterial and a preparation method thereof, wherein an electrochemical anodic oxidation technology is adopted to modify the surface of a tantalum sheet, so as to prepare a porous tantalum pentoxide layer with a micro-nano scale three-dimensional through porous structure, the pore size is controllable, the arrangement and connectivity of pores are good, a hydroxyapatite layer is further constructed on the surface of an oxide layer, protein absorption, cell diffusion and proliferation are significantly enhanced, biocompatibility and osteoconductivity are improved, a microenvironment beneficial to cell growth is generated, adhesion, proliferation, differentiation and mineralization of primary osteoblasts of human beings are promoted, bone tissue is promoted to grow into porous tantalum to form a unique bone-implant interface, the stability and functions of the implant in the bone tissue are significantly enhanced, the bone integration of the bone-implant interface is accelerated, the stability of the implant in the bone tissue is significantly enhanced, and the porous tantalum biomaterial has high corrosion resistance and bright application prospect, but the method has obvious defects that the binding force, compressive strength and biocompatibility of a coating and a base material are still to be improved.
CN109989089A discloses a micro-nano structure tantalum-based coating for promoting in-vitro osteogenesis and differentiation and a preparation method thereof, a method combining a vacuum plasma spraying method and an anodic oxidation technology is adopted, the plasma spraying tantalum coating has a micron porous structure, a substrate with the plasma spraying tantalum coating is used as an anode to carry out primary anodic oxidation and secondary anodic oxidation, a nano tube is prepared on the surface of the tantalum coating, and a micro-nano multilevel structure is obtained, namely the anode oxidation method is adopted to prepare the micro-nano multilevel structure coating on the surface of the vacuum plasma spraying tantalum coating. The tantalum-based coating with the micro-nano multilevel structure has excellent bone differentiation promoting performance. The invention can prepare the surface of the nano structure without changing the rough porous structure of the plasma spraying coating, thereby greatly improving the cell response speed and the osseointegration performance. The metal Ta used for obtaining Ta2O5 by anodic oxidation is a porous tantalum structure obtained by vacuum plasma spraying, namely, the tantalum coating with the porous structure obtained by vacuum plasma spraying is adopted for anodic oxidation. After the anodic oxidation, a target coating can be obtained without a subsequent heat treatment step, namely the tantalum-based coating with the micro-nano multilevel structure can be obtained at one time, but the biocompatibility of the tantalum coating is far inferior to that of hydroxyapatite and needs to be improved.
CN109825793 a 20190531 provides a medical biological coating material for improving corrosion resistance, biological activity and antibacterial property of a titanium alloy implant material and a preparation method thereof. The method comprises the following steps:
(1) Polishing the surface of the titanium alloy;
(2) Oxidizing the surface of the titanium alloy to construct a nano oxide layer;
(3) The Ta and Ta-Cu-Zn composite coating is prepared by adopting a plasma spraying technology and respectively taking Ta powder or Ta powder, cu powder and Zn powder as raw materials through spraying, and is mainly used for solving the problems of corrosion resistance and antibacterial property, but the mechanical property of the material is insufficient.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a medical metal bone implant material, which is tantalum or tantalum alloy/nanopore array Ta from inside to outside 2 O 5 Hydroxyapatite, wherein the porosity of the material is 80-85%, the compressive strength is 150-1700Mpa, the binding force of a coating is high at 15-19Mpa, and the material is obtained by sequentially carrying out (1) pretreatment on tantalum or a tantalum alloy; (2) sand blasting treatment; (3) anodizing to form a nanopore array; (4) Preparing hydroxyapatite powder and flame spraying the hydroxyapatite powder; and (5) roasting and cooling to obtain the catalyst.
Further, the pretreatment process parameters in the step (1) are as follows: 20 to 25g/L sodium carbonate and 2 to 3gMixed water solution of sodium phosphate 10-15g/L, water glass 1-2g/L, sodium dodecyl sulfate at 65-70 deg.c o And C, soaking for 5-6min, then ultrasonically cleaning for 20min by using ethanol, cleaning by using deionized water, and drying at 20-30 ℃ by using nitrogen.
Further, the sand blasting in the step (2) is dry sand blasting corundum, and the parameters are as follows: the hardness is 340-420HV, the sand size is 0.5-1.5mm, the sand blasting air pressure is 0.03-0.25, and the time is 15-20s.
Further, the anodization parameters in the step (3) are as follows: the electrolyte is aqueous solution of sulfuric acid, hydrofluoric acid, NH4F and glycol, wherein 20-30ml of sulfuric acid, 10-15ml of 48% hydrofluoric acid, 30-40ml of deionized water, 0.5-1% of NH4F and 5-10ml of glycol are used in percentage by weight.
Further, the anodic oxidation electrolysis parameters are as follows: voltage of 10-20V, time of 10-20min, and temperature of 23-25 o C, the counter electrode is a Pt electrode, the distance between the two electrodes is 2-4cm, and the obtained nano-pore array parameters are as follows: the inner aperture is 40-50nm, the outer aperture is 100-120, the wall thickness is 30-40nm, and the length of the pore canal array is 10-15 μm.
Further, the process for preparing hydroxyapatite in step (4) is as follows: (1) Weighing Ca (NO) 3 ) 2 . 4H 2 Placing the O in a beaker, pouring a proper amount of deionized water, and stirring to dissolve; (2) Weighing (NH 4) 2 HPO 4 Placing the mixture in a beaker, pouring a proper amount of deionized water, and stirring and dissolving the mixture; (3) Adding Ca (NO) in step (1) 3 ) 2 . 4H 2 Dropwise adding an ammonia solution into the O; (4) (NH) of step (2) is dropwise added by a titration method 4 ) 2 HPO 4 Adding the aqueous solution into the solution obtained in the step (3), and dropwise adding for 1.5h to obtain a precipitate; (5) Filtering, washing and drying the precipitate to 500 o C, roasting for 1.5 h-grinding to obtain hydroxyapatite powder.
Further, the flame spraying parameters prepared in the step (4) are as follows: the distance between the flame spraying port and the surface of the substrate is 90-100mm, the spraying power is 30-50KW, the combustion-supporting gas is oxygen, the combustible gas is acetylene, and the temperature of the jet flame flow is 2800-3000 o C, spraying thickness of 15-20 μm.
Further, the roasting parameters in the step (5) are as follows: directly placing the Ta2O 5/hydroxyapatite of the tantalum/nano pore canal array obtained in the step (4) in a muffle furnace at 650 DEG C o Keeping the temperature for 1h, and slowly cooling the furnace to room temperature.
Explanation about the above preparation process:
(1) Regarding the choice of substrate, the substrate selected for the present invention is not stainless steel, not titanium, not niobium, and is based primarily on the following considerations: tantalum is biologically inert and thus is difficult to form a strong bond with human bone tissue, but tantalum hydroxyl (Ta-OH) formed at the end of tantalum metal has a significant effect on the improvement of biological activity, thus contributing to the induction of the deposition of hydroxyapatite. And under the environment of human body simulated body fluid, through the porous tantalum surface of alkali treatment and heat treatment, the amorphous tantalum hydrogel surface layer can form a hydroxyapatite layer within a week, and the deposited hydroxyapatite can enable the combination between the porous tantalum and the host bone to be tighter, thereby being beneficial to realizing long-term stable osseointegration. Importantly, the porous tantalum has pores similar to human bone tissues, is beneficial to rapid vascularization and bone tissue ingrowth, the pores are suitable for bone cell ingrowth, and the communication size among the pores can influence the bone conduction performance more easily.
(2) Regarding the pretreatment: the main purpose of the pretreatment is to remove oil, the invention adopts alkaline solution for degreasing, which can saponify the vegetable oil and the animal oil on the surface of the substrate to generate soap dissolved in water and remove the soap, and the pretreatment solution and parameters of the invention are as follows: 20 to 25g/L sodium carbonate, 2 to 3g/L sodium phosphate, 10 to 15g/L water glass and 1 to 2g/L sodium dodecyl sulfate, and the temperature is 65 to 70 o C, soaking for 5-6min, then ultrasonically cleaning for 20min by using ethanol, cleaning by using deionized water, drying at 20-30 ℃ by using nitrogen, wherein the alkali of sodium carbonate is weaker than that of sodium hydroxide, the sodium carbonate has a certain saponification ability, has a buffer effect on the pH value of the solution, has lower corrosivity on metal and irritation on skin than that of sodium hydroxide, is low in price, is often used as main salt in degreasing solution, has a weak alkaline sodium phosphate, has a certain saponification ability and a buffer effect on the pH value,can complex metal ions in water to soften water, and is an emulsifier with high solubility and good washability. After alkaline degreasing, ultrasonic cleaning is carried out for 20min by using ethanol, and cleaning is carried out by using deionized water, so that pollutants remained on the surface of a workpiece after degreasing can be effectively removed, and nitrogen purging is used for preventing oxide from being formed.
(3) Sand blasting: the sand blasting parameters are the hardness of 340-420HV, the sand size is 0.5-1.5mm, the sand blasting air pressure is 0.03-0.25, and the time is 15-20s, wherein the hardness, the size, the pressure and the time are critical to the effect of removing an oxide film and forming a rough surface on the surface of the substrate, and as shown in the comparison between the attached drawing 1 and the attached drawing 2, the surface roughness of the tantalum substrate is obviously improved after the sand blasting, and the improvement of the roughness can effectively improve the bonding strength between the substrate and the coating layer.
(4) Anodic oxidation: the electrolyte is aqueous solution of sulfuric acid, hydrofluoric acid, NH4F and ethylene glycol, wherein the sulfuric acid accounts for 20-30ml, the hydrofluoric acid accounts for 48% 10-15ml, the deionized water accounts for 30-40ml, the concentration of the NH4F accounts for 0.5-1%, the ethylene glycol accounts for 5-10ml, and the anodic oxidation electrolysis parameters are as follows: voltage of 10-20V, time of 10-20min, temperature of 23-25 o C, the counter electrode is a Pt electrode, the distance between the two electrodes is 2-4cm, (a) about the electrolyte: sulfuric acid and hydrofluoric acid are used as main mixed acid of the electrolyte, fluorine ions are closely related to the size of a nanopore array, when the concentration of the fluorine ions is low, such as the concentration is less than 0.5wt%, only a compact tantalum oxide film can be generated after metal tantalum is anodized, when the concentration of the fluorine ions is higher than 2wt%, an oxide layer is difficult to precipitate, a formed fluorine tantalum complex can damage the generation and dissolution processes in the anodization process, in addition, ethylene glycol is used as an organic solvent, the conductivity of the electrolyte is mainly improved, and the effective voltage of an electrode can be reduced at the same time due to the voltage drop caused by resistance. As the anodization time increases, the reaction product formation changes the conductivity of the electrolyte, thus producing nanotube arrays of greater length and diameter. (b) with respect to the parameters: the nanotube array prepared by anodic oxidation is usually produced under the condition of constant voltage, generally the required voltage range in aqueous solution is 1-30V, the voltage range of organic solution is 5-150V, and the concentration of ions is. Typically, during growth, the diameter of the nanotubesThe electric field strength F = U/d, where d is the thickness of the nanotube array, is positively correlated to the applied oxidation voltage, such as at a constant voltage U. As the reaction proceeds, d gradually increases. Generally, the ion reactivity in the electrolyte is affected by the reaction temperature, and when the temperature is lowered, the dissolution reaction rate of the oxide layer caused by fluorine ions is lowered, and the pitting action on the oxide barrier layer is also weakened. The lower the temperature, the longer the length of the nanotube array produced and the thicker the tube wall. When the temperature rises, the resistance of the electrolyte is reduced, the interface reaction speed is accelerated, the formation speed of the oxide layer is increased, the chemical dissolution of the electrolyte to the nanotube array is enhanced, and the local breakdown is easier to occur in a short time.
The parameters of the nanopore array shown in the attached figures 3 and 4 are obtained by adjusting the composition ratio of the electrolyte and the technological parameters of anodic oxidation: the inner aperture is 40-50nm, the outer aperture is 100-120, the wall thickness is 30-40nm, the length of the pore array is 10-15 μm, and the result of XRD figure 5 shows that the oxide film is tantalum pentoxide and has perfect crystal form.
(5) For the preparation of hydroxyapatite powder: (1) Weighing Ca (NO) 3 ) 2 . 4H 2 Placing the O in a beaker, pouring a proper amount of deionized water, and stirring to dissolve; (2) Weighing (NH 4) 2 HPO 4 Placing the mixture in a beaker, pouring a proper amount of deionized water, and stirring and dissolving the mixture; (3) Adding Ca (NO) in step (1) 3 ) 2 . 4H 2 Dropwise adding an ammonia solution into the O; (4) (NH) of step (2) is added dropwise by titration 4 ) 2 HPO 4 Adding the aqueous solution into the solution obtained in the step (3), and dropwise adding for 1.5h to obtain a precipitate; (5) Filtering, washing and drying the precipitate to 500 o C roasting for 1.5 h-grinding to obtain hydroxyapatite powder, and then properly grinding to obtain the particle size.
The reaction formula of the preparation process is as follows:
the chemical precipitation method has low requirement on preparation conditions, the reaction process is easy to control, the cost is low, the prepared hydroxyapatite particles are fine and can reach the nanometer size, salt containing calcium ions and phosphate ions forms a solution, a certain additive is added, the pH value and the reaction temperature are adjusted, and the precipitate generated at the moment is filtered, dried and calcined, so that the high-purity nanometer hydroxyapatite powder is prepared. The method for preparing the hydroxyapatite by the precipitation method mainly adopts a homogeneous precipitation method, because the precipitation process is a dynamic process and is also unbalanced, if the concentration increase process of a reaction solution in the precipitation process is controlled to slowly increase, the precipitation can uniformly appear at each position of the whole solution, and the obtained hydroxyapatite has high crystallinity, few lattice defects, stable calcium-phosphorus ratio and stable quality.
(6) Regarding flame spraying: the distance between the flame spraying port and the surface of the substrate is 90-100mm, the spraying power is 30-50KW, the combustion-supporting gas is oxygen, the combustible gas is acetylene, and the temperature of the jet flame flow is 2800-3000 o C, spraying the material to a thickness of 15-20 μm; (a) spray power: in the spraying process, the flame flow temperature is directly influenced by the spraying power, so that the melting degree of the hydroxyapatite powder is controlled, the spraying power is changed, the number of particles to be melted is different from that of semi-melted particles, the particles are sputtered onto a substrate, and the microscopic morphology and the composition of a non-matter phase of the coating are also different. Within a certain range, the melting degree of the powder particles can be increased along with the increase of the spraying power, so that the binding force between the coating and the substrate is enhanced. However, too high power may affect the mechanical and biological properties of the coating; (b) spraying distance: the spraying distance refers to the flight distance from the powder body to the surface of the substrate before the powder body is sprayed out of the nozzle after being melted by the plasma flame flow, and the spraying distance directly influences the cooling time of the molten particles because the molten particles are cooled in the flight process. The cooling time is short when the distance is short, and the particles can be melted and sputtered on the surface of the substrate completely to form a complete melting and flattening state; however, the matrix is easily heated to a large extent, so that stress is generated, and the spraying quality is influenced; if the spraying distance is too long, the molten particles are cooled and solidified before being sputtered onto the surface of the substrate to form spherical particles which cannot be flattened and are easy to crack, andresulting in a low bonding force of the coating to the substrate.
(7) Roasting: the roasting is mainly used for reducing the stress of the coating and the matrix and improving the crystallinity of the hydroxyapatite, such as removing volatile impurities, chemically bonded and physically adsorbed moisture, gas, organic matters and the like in the raw materials, thereby improving the purity of the raw materials. The raw material particles are densified and crystallized to grow, so that the shrinkage in the sintering process can be reduced later. As shown in fig. 6, it can be seen that the diffraction peak position of the hydroxyapatite prepared by the chemical method before and after calcination is substantially consistent with the standard characteristic diffraction peak (JCPDS, and the figure does not show the characteristic peaks of other substances, which indicates that the sample is hydroxyapatite crystals with higher purity).
The scheme of the invention has the following beneficial effects:
according to the invention, the Ta2O 5/hydroxyapatite material of the tantalum/nano pore array is obtained through pretreatment, sand blasting, anodic oxidation, flame spraying and roasting molding, the porosity of the material is 80-85%, the compressive strength is 150-1700Mpa, the coating binding force is high (15-19 Mpa), and the biocompatibility is excellent; the anodic oxidation pore passage is suitable, so that the coating of the hydroxyapatite layer on the surface of the anodic oxidation pore passage at the later stage is facilitated, the cell diffusion and proliferation are facilitated, and the biocompatibility is improved.
Drawings
FIG. 1 is an SEM image of a pretreated tantalum substrate according to the present invention.
FIG. 2 is an SEM image of a tantalum substrate treated by grit blasting according to the present invention.
FIG. 3 is an SEM image of cross-sectional thickness of the anodized well array.
FIG. 4 is an SEM image of an anodized pore channel array.
FIG. 5 is an XRD pattern of the anodized tantalum oxide film of the invention.
FIG. 6 is XRD patterns of hydroxyapatite before and after calcination.
Fig. 7 is an SEM image of hydroxyapatite before firing according to the present invention.
Fig. 8 is an SEM image of hydroxyapatite after firing according to the present invention.
Fig. 9 is an SEM image of hydroxyapatite after firing according to the present invention.
FIG. 10 is a fluorescent microscope photograph of the MC3T 3-e 1 culture according to the present invention.
Detailed Description
Example 1
A medical metal bone implant material is prepared by sequentially carrying out (1) pretreatment on tantalum or tantalum alloy; (2) sand blasting treatment; (3) anodizing to form a nanopore array; (4) Preparing hydroxyapatite powder, and flame spraying the hydroxyapatite powder; and (5) roasting and cooling to obtain the catalyst.
The pretreatment process parameters in the step (1) are as follows: a mixed water solution of 20g/L sodium carbonate, 2g/L sodium phosphate, 10g/L water glass and 1g/L sodium dodecyl sulfate, the temperature is 65-7 DEG o C, soaking for 5min, then ultrasonically cleaning for 20min by using ethanol, cleaning by using deionized water, and cleaning for 20min o And C, drying by nitrogen.
The sand blasting in the step (2) is dry-blasting corundum sand, and the parameters are as follows: hardness 340HV, sand size 0.5mm, blasting air pressure 0.05MPa, time 15s.
The anodic oxidation parameters in step (3) are as follows: the electrolyte is aqueous solution of sulfuric acid, hydrofluoric acid, NH4F and glycol, wherein the concentration of 98 wt.% sulfuric acid is 20ml, the concentration of 48% hydrofluoric acid is 10ml, the concentration of deionized water is 30ml, the concentration of NH4F is 0.5%, and the concentration of glycol is 5ml.
The anodic oxidation electrolysis parameters are as follows: voltage 10V, time 10min, temperature 23 o And C, the counter electrode is a Pt electrode, and the distance between the two electrodes is 2cm.
The process for preparing the hydroxyapatite in the step (4) is as follows: (1) Weighing Ca (NO) 3 ) 2 . 4H 2 Placing O in a beaker, pouring a proper amount of deionized waterStirring and dissolving; (2) Weighing (NH 4) 2 HPO 4 Placing the mixture in a beaker, pouring a proper amount of deionized water, and stirring and dissolving the mixture; (3) Introduction of Ca (NO) into step (1) 3 ) 2 . 4H 2 Dropwise adding an ammonia solution into the O; (4) (NH) of step (2) is added dropwise by titration 4 ) 2 HPO 4 Adding the aqueous solution into the solution obtained in the step (3), and dropwise adding for 1.5h to obtain a precipitate; (5) Filtering, washing and drying the precipitate to 500 o C roasting for 1.5 h-grinding to obtain hydroxyapatite powder.
The flame spraying parameters prepared in the step (4) are as follows: the distance between the flame spraying port and the surface of the substrate is 90mm, the spraying power is 30KW, the combustion-supporting gas is oxygen, the combustible gas is acetylene, and the temperature of the jet flame flow is 2800 o C, jetting thickness 15 μm.
The roasting parameters in the step (5) are as follows: directly placing the Ta2O 5/hydroxyapatite of the tantalum/nano pore canal array obtained in the step (4) in a muffle furnace at 650 DEG C o Keeping the temperature for 1h at the temperature, and slowly cooling the furnace to room temperature.
Example 2
A medical metal bone implant material is prepared by sequentially carrying out (1) pretreatment on tantalum or tantalum alloy; (2) sand blasting treatment; (3) anodizing to form a nanopore array; (4) Preparing hydroxyapatite powder, and flame spraying the hydroxyapatite powder; and (5) roasting and cooling to obtain the catalyst.
The pretreatment process parameters in the step (1) are as follows: a mixed aqueous solution of 23g/L sodium carbonate, 2.5g/L sodium phosphate, 12.5g/L water glass and 1.5g/L sodium dodecyl sulfate at a temperature of 67.5 o C, soaking for 5.5min, then ultrasonically cleaning for 20min by using ethanol, cleaning by using deionized water, and cleaning for 25 min o And C, drying by nitrogen.
The sand blasting in the step (2) is dry-blasting corundum sand, and the parameters are as follows: the hardness is 370HV, the sand size is 0.1mm, the sand blasting air pressure is 0.15MPa, and the time is 17.5s.
The anodic oxidation parameters in step (3) are as follows: the electrolyte is aqueous solution of sulfuric acid, hydrofluoric acid, NH4F and ethylene glycol, wherein the weight of the electrolyte is 25ml of sulfuric acid with the weight of 98 percent and 12.5ml of hydrofluoric acid with the weight of 48 percent35ml of deionized water, 0.75% of NH4F and 7.5ml of ethylene glycol. The anodic oxidation electrolysis parameters are as follows: voltage 15V, time 15min, temperature 24 o And C, the counter electrode is a Pt electrode, and the distance between the two electrodes is 3cm.
The process for preparing the hydroxyapatite in the step (4) is as follows: (1) Weighing Ca (NO) 3 ) 2 . 4H 2 Placing the O in a beaker, pouring a proper amount of deionized water, and stirring to dissolve; (2) Weighing (NH 4) 2 HPO 4 Placing the mixture in a beaker, pouring a proper amount of deionized water, and stirring and dissolving the mixture; (3) Adding Ca (NO) in step (1) 3 ) 2 . 4H 2 Dropwise adding an ammonia solution into the O; (4) (NH) of step (2) is dropwise added by a titration method 4 ) 2 HPO 4 Adding the aqueous solution into the solution obtained in the step (3), and dropwise adding for 1.5h to obtain a precipitate; (5) Filtering, washing and drying the precipitate to 500 o C, roasting for 1.5 h-grinding to obtain hydroxyapatite powder.
The flame spraying parameters prepared in the step (4) are as follows: the distance between the flame spraying port and the surface of the substrate is 95mm, the spraying power is 40KW, the combustion-supporting gas is oxygen, the combustible gas is acetylene, and the temperature of the jet flame flow is 2900 o C, the spraying thickness is 17.5 mu m.
The roasting parameters in the step (5) are as follows: directly placing the Ta2O 5/hydroxyapatite of the tantalum/nano pore canal array obtained in the step (4) in a muffle furnace at 650 DEG C o Keeping the temperature for 1h at the temperature, and slowly cooling the furnace to room temperature.
Example 3
A medical metal bone implant material is prepared by sequentially carrying out (1) pretreatment on tantalum or tantalum alloy; (2) sand blasting treatment; (3) anodizing to form a nanopore array; (4) Preparing hydroxyapatite powder, and flame spraying the hydroxyapatite powder; and (5) roasting and cooling to obtain the catalyst.
The pretreatment process parameters in the step (1) are as follows: mixed water solution of 25g/L sodium carbonate, 3g/L sodium phosphate, 15g/L water glass and 2g/L sodium dodecyl sulfate at 70 deg.c o C, soaking for 6min, then ultrasonically cleaning for 20min by using ethanol, cleaning by using deionized water, and cleaning for 30 min o And C, drying by nitrogen.
The sand blasting in the step (2) is dry-blasting corundum sand, and the parameters are as follows: hardness 420HV, grit size 1.5mm, blast air pressure 0.25, time 20s.
The anodic oxidation parameters in step (3) are as follows: the electrolyte is aqueous solution of sulfuric acid, hydrofluoric acid, NH4F and glycol, wherein the sulfuric acid accounts for 30ml, the hydrofluoric acid accounts for 48% 15ml, the deionized water accounts for 30-40ml, the concentration of the NH4F accounts for 1%, and the glycol accounts for 10ml. The anodic oxidation electrolysis parameters are as follows: voltage 20V, time 20min, temperature 25 o And C, the counter electrode is a Pt electrode, and the distance between the two electrodes is 2-4cm.
The process for preparing the hydroxyapatite in the step (4) is as follows: (1) Weighing Ca (NO) 3 ) 2 . 4H 2 Placing the O in a beaker, pouring a proper amount of deionized water, and stirring to dissolve; (2) Weighing (NH 4) 2 HPO 4 Placing the mixture into a beaker, pouring a proper amount of deionized water, and stirring and dissolving the deionized water; (3) Introduction of Ca (NO) into step (1) 3 ) 2 . 4H 2 Dropwise adding an ammonia solution into the O; (4) (NH) of step (2) is added dropwise by titration 4 ) 2 HPO 4 Adding the aqueous solution into the solution obtained in the step (3), and dropwise adding for 1.5h to obtain a precipitate; (5) Filtering, washing and drying the precipitate to 500 o C, roasting for 1.5 h-grinding to obtain hydroxyapatite powder.
The flame spraying parameters prepared in the step (4) are as follows: the distance between the flame spraying port and the surface of the substrate is 100mm, the spraying power is 50KW, the combustion-supporting gas is oxygen, the combustible gas is acetylene, and the temperature of the jet flame flow is 3000 o C, the jet thickness is 20 μm.
The roasting parameters in the step (5) are as follows: directly placing the Ta2O 5/hydroxyapatite of the tantalum/nano pore canal array obtained in the step (4) in a muffle furnace at 650 DEG C o Keeping the temperature for 1h at the temperature, and slowly cooling the furnace to room temperature.
From the accompanying drawings 10: differentiation of mouse embryo osteogenic precursor cells MC3T3 (MC 3T 3-e 1) A study was made on a Ta2O 5/hydroxyapatite composite medical material with a tantalum/nanopore array. Activity and adhesive Capacity of MC3T3 cells an iCMBA/HA composite was studied with a fluorescence microscopeThe surface of the material can obviously show the Ta/nano-pore array Ta of the invention 2 O 5 The hydroxyapatite medical material has extremely high biocompatibility.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (4)
1. A medical metal bone implant material is characterized in that the metal bone implant material is tantalum or tantalum alloy/nanopore array Ta from inside to outside 2 O 5 Hydroxyapatite, wherein the porosity of the material is 80-85%, the compressive strength is 150-170Mpa, and the coating bonding force is 15-19Mpa, and the material is obtained by sequentially carrying out the following steps: the method comprises the following steps of (1) pretreating tantalum or tantalum alloy; (2) sand blasting treatment; (3) anodizing to form a nanopore array; (4) Preparing hydroxyapatite powder, and flame spraying the hydroxyapatite powder; (5) roasting-cooling treatment;
the sand blasting in the step (2) is dry-blasting corundum sand, and the parameters are as follows: the hardness is 340-420HV, the sand size is 0.5-1.5mm, the sand blasting air pressure is 0.03-0.25, and the time is 15-20s;
the process for preparing the hydroxyapatite in the step (4) is as follows: (a) Weighing Ca (NO) 3 ) 2 . 4H 2 Placing the O in a beaker, pouring a proper amount of deionized water, and stirring to dissolve; (b) Weighing (NH) 4 ) 2 HPO 4 Placing the mixture into another beaker, pouring a proper amount of deionized water, and stirring and dissolving the deionized water; (c) Addition of Ca (NO) to step (a) 3 ) 2 . 4H 2 Dropwise adding an ammonia solution into the O; (d) (NH) of step (b) is added dropwise by titration 4 ) 2 HPO 4 Adding the aqueous solution into the solution obtained in the step (c), and dropwise adding for 1.5h to obtain a precipitate; (e) Filtering, washing, drying, roasting at 500 ℃ for 1.5h, and grinding the precipitate to obtain hydroxyapatite powder;
the parameters of the flame spraying hydroxyapatite in the step (4) are as follows: the distance between the flame spraying port and the surface of the substrate is 90-100mm, the spraying power is 30-50kW, the combustion-supporting gas is oxygen, the combustible gas is acetylene, the temperature of the spraying flame stream is 2800-3000 ℃, and the spraying thickness is 15-20 mu m;
the roasting parameters in the step (5) are as follows: subjecting the tantalum or tantalum alloy/nanopore array Ta obtained in the step (4) to Ta 2 O 5 Directly placing hydroxyapatite into a muffle furnace, keeping the temperature at 650 ℃ for 1h, and slowly cooling the furnace to room temperature.
2. The medical metal bone implant material according to claim 1, wherein the solution and process parameters used in the pretreatment of the step (1) are as follows: 20-25g/L sodium carbonate, 2-3g/L sodium phosphate, 10-15g/L water glass and 1-2g/L sodium dodecyl sulfate, soaking at 65-70 deg.C for 5-6min, ultrasonic cleaning with ethanol for 20min, cleaning with deionized water, and drying with 20-30 deg.C nitrogen.
3. The medical metal bone implant material as set forth in claim 1, wherein the step (3) of anodizing with the electrolyte and the electrolysis parameters are as follows: the electrolyte is sulfuric acid, hydrofluoric acid, NH 4 F. Mixed aqueous solution of ethylene glycol, consisting of 20-30mL of 98 wt.% sulfuric acid, 10-15mL of 48% hydrofluoric acid, 30-40mL of deionized water, NH 4 The concentration of F is 0.5-1%, and the glycol is 5-10mL.
4. The medical metal bone implant material according to claim 3, wherein the anodic oxidation electrolysis parameters are: voltage is 10-20V, time is 10-20min, temperature is 23-25 ℃, counter electrode is Pt electrode, distance between two electrodes is 2-4cm, obtained nano pore array parameters are as follows: the inner aperture is 40-50nm, the outer aperture is 100-120nm, the wall thickness is 30-40nm, and the length of the pore array is 10-15 μm.
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