Porous titanium boride alloy / hydroxyapatite fluoride composite material, preparation and application thereof

Abstract

The application belongs to the field of ceramic materials, and particularly relates to a preparation method of a porous titanium boride alloy / hydroxyapatite fluoride composite material. 10 (PO4)6OH 2‑2x F 2x Wherein, x is 0.1-0.6; in the mixture, the weight ratio of TC4, TiB2 and FHA is 86-94:3-7:3-7; the sintering temperature is 1000-1100 DEG C. The application also includes the composite material prepared by the preparation method and the application of the composite material in oral implant materials. The preparation method can realize synergy, improve the strength and biological activity of the material based on the combination of components, proportions and sintering processes.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of ceramic materials, and particularly relates to the field of biologic implant ceramic materials. BACKGROUND

[0002] Pure titanium and titanium alloy have high mechanical strength, good corrosion resistance and biocompatibility, and have been widely used in the field of oral repair and bone repair. However, the elastic modulus of pure titanium and titanium alloy is much higher than that of cortical bone, which will cause stress shielding to the surrounding bone tissue when used as an implant, resulting in bone resorption. In addition, the surface of pure titanium and titanium alloy does not have bioactivity, and it is difficult to form a chemical bond with bone tissue with high strength and stable chemical properties, which leads to insufficient stability of the implant and repair failure in clinical use. Therefore, since the 1960s, composite implant materials based on titanium and titanium alloy materials have gradually become popular. Among them, coating hydroxyapatite (HA) and tricalcium phosphate (TCP) and other ceramic materials similar to the composition of teeth on the surface of titanium-based materials can significantly improve the bioactivity of the implant. However, this field still faces three major problems: first, the bonding strength between the coating and the titanium alloy substrate is low, and the coating is easy to fall off; second, the coating method has limited effect on reducing the elastic modulus of the implant, and cannot effectively inhibit bone resorption; third, HA has insufficient thermal stability and is easy to decompose during high-temperature processing.

[0003] To overcome the above problems, powder forming method for preparing titanium alloy / HA composite materials has gradually become the focus of researchers. The implant product prepared by powder forming method has uniform composition distribution, which overcomes the application limitations caused by low surface strength of the coating. In addition, the addition of HA powder not only improves the bioactivity of the implant, but also improves the porosity of the implant, effectively reducing the elastic modulus of the implant.

[0004] However, even if titanium alloy / HA composite materials prepared by sintering technology are used, there are still the following problems: first, during the sintering process, the high temperature leads to the decomposition of HA, resulting in insufficient bioactivity; second, due to the mismatch of the thermal expansion coefficient between titanium alloy which is a metal material and HA which is a ceramic material, the mechanical properties are affected. Third, although the addition of HA can reduce the elastic modulus to a certain extent, the elastic modulus of this kind of composite material is still high for patients with poor bone quality. SUMMARY

[0005] In view of the problems of the existing implant material, such as the unsatisfactory strength, the unsatisfactory stimulation reproduction performance of osteoblasts, etc., the first object of the present application is to provide a preparation method of porous titanium boride alloy / hydroxyapatite fluoride composite material, aiming at improving the strength and the stimulation effect of osteoblasts of the prepared porous titanium boride alloy / hydroxyapatite fluoride composite material, and improving the elastic modulus regulation range.

[0006] The second object of the present application is to provide the porous titanium boride alloy / hydroxyapatite fluoride composite material prepared by the preparation method.

[0007] The third object of the present application is to provide the application of the porous titanium boride alloy / hydroxyapatite fluoride composite material in the preparation of body implant materials, such as oral implant materials.

[0008] A preparation method of porous titanium boride alloy / hydroxyapatite fluoride composite material, which comprises the following steps:

[0009] The chemical formula of FHA is Ca 10 (PO4)6OH 2-2x F 2x Wherein, x is 0.1-0.6.

[0010] The weight ratio of TC4, TiB2 and FHA in the mixture is 86-94:3-7:3-7.

[0011] The sintering temperature is 1000-1100 DEG C.

[0012] The present application innovatively adopts the synergistic composite raw material of TC4, TiB2 and FHA for sintering treatment, and further cooperates the mixture component ratio, the F substitution amount of FHA and the sintering temperature, so that the synergistic effect can be achieved, the strength of the prepared material can be improved, the stimulation reproduction ability of osteoblasts can be improved, and the elastic modulus regulation range can be effectively improved, so that it can adapt to the implantation needs of patients with different bone characteristics, especially patients with relatively weak bone quality.

[0013] In the present application, the combination of FHA and the F substitution amount is synergistically combined with TC4 and TiB2, which is one of the keys to improve the strength and the stimulation ability of osteoblasts.

[0014] In the present application, the FHA is prepared by a precipitation method, and the steps are as follows:

[0015] A solution containing a calcium source and a F source is obtained; and a solution containing a phosphorus source is obtained; the solution B is added dropwise into the solution A, and precipitation is carried out; the molar ratio of Ca / F in the solution A is 1:0.05-0.2, preferably 1:0.05-0.15, and further preferably 1:0.09-0.11; and the molar ratio of Ca in the solution A and P in the solution B is 1.50-2.00:1, preferably 1.67-1.70:1.

[0016] The calcium source can be at least one of calcium nitrate and calcium chloride.

[0017] The F source can be at least one of ammonium fluoride, sodium fluoride and potassium fluoride.

[0018] The phosphorus source can be at least one of ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.

[0019] Preferably, the temperature in the precipitation reaction stage is 20-70℃.

[0020] Preferably, ammonia is used to adjust the pH to 9.5-11 during the precipitation reaction.

[0021] The FHA has a particle size of ≤250nm (further can be 190-240nm), a thermal decomposition temperature of ≥1050℃, and a F substitution amount of 10-60%, further can be 30-40%.

[0022] The FHA has a chemical formula of Ca 10 (PO4)6OH 2-2x F 2x The x is the substitution amount of F, and preferably, the x is 0.1-0.6, further preferably 0.3-0.4. It is found that, under the preferred F substitution amount, the strength, biological activity and other comprehensive properties of the prepared material can be further improved unexpectedly in combination with other components and the calcination process.

[0023] In the present application, the weight ratio of TC4, TiB2 and FHA is 88-92:4-6:4-6; preferably 90:5:5. Under the preferred ratio, the comprehensive properties of the prepared material can be further improved, for example, the material can have good biological activity under the premise of strength.

[0024] In the present application, the TC4 can be a commercial product, or can be obtained by using the existing method, and the D50 can be 10-50μm.

[0025] In the present application, the TiB2 can be a commercial product, and the average particle size can be 100-300nm,

[0026] In the present application, the components can be mixed to meet the sintering requirements by using the known method.

[0027] For example, the components can be mixed to form the mixture, or the mixture can be obtained by means of adhesive complex molding.

[0028] The adhesive can be a component with adhesive properties in the industry, for example, at least one of stearic acid, zinc stearate, and liquid paraffin.

[0029] The amount of the adhesive is not particularly limited, for example, it can be 1-5% of the total weight of TC4, TiB2, and FHA.

[0030] In the present application, the porous titanium boride alloy / hydroxyapatite fluoride composite material with microporous structure, excellent strength, and osteoblast stimulating performance can be obtained by the preparation method. On the basis of the innovation, the further preferred scheme of the present application is that a pore-forming agent is further added to the mixture. The present application researches and finds that, under the joint innovation of TC4, TiB2, and FHA, and further in cooperation with the use of the pore-forming agent, a composite material with more optimal strength, osteoblast stimulating performance, and wider elastic modulus can be obtained, which has a hierarchical pore structure of micropores, mesopores, and macropores.

[0031] In the present application, the pore-forming agent is at least one of urea, ammonium carbonate, ammonium bicarbonate, and starch.

[0032] In the present application, the amount of the pore-forming agent is 1-5% of the total weight of TC4, TiB2, and FHA.

[0033] In the present application, the components are mixed, ball milled, and compression molded to obtain the mixture.

[0034] In the present application, the mixing method is acoustic resonance pre-mixing.

[0035] For example, in the present application, the TC4, TiB2, and FHA powders are pre-mixed by acoustic resonance to obtain a mixture, the adhesive is ball milled to obtain a ball mill, the pore-forming agent is mixed into the ball mill by means of an acoustic resonance mixer, then the green body is obtained by compression molding, the green body is subjected to water bath and calcination to remove the pore-forming agent and the adhesive, and microwave sintering is carried out in an inert atmosphere to obtain the porous titanium boride alloy / hydroxyapatite fluoride composite material.

[0036] In the present application, before sintering, a pre-sintering step is allowed. The pre-sintering temperature is, for example, 300-450℃.

[0037] Preferably, the sintering temperature is 1030-1070 DEG C, and further preferably 1040-1060 DEG C. The present application research shows that, on the basis of TC4, TiB2, FHA components and proportion synergy, further cooperating with the sintering temperature control at 1040-1060 DEG C, the occurrence of the material can be further improved, which is helpful to further improve the strength, biological activity and other comprehensive performance of the material.

[0038] In the present application, the sintering process is carried out under the assistance of microwave.

[0039] The power of the microwave is 300-1400 W.

[0040] The sintering time is 15-60 min.

[0041] In the present application, the sintering process is carried out in a protective atmosphere, for example, at least one of nitrogen and inert gas.

[0042] The present application also provides a porous titanium boride alloy / fluorinated hydroxyapatite composite material prepared by the preparation method.

[0043] The present application also provides an application of the porous titanium boride alloy / fluorinated hydroxyapatite composite material prepared by the preparation method, which is used to prepare a biological implant material.

[0044] Preferably, the implant material is an implant material, and preferably an oral implant material.

[0045] Beneficial effects

[0046] The present application innovatively uses TC4, TiB2 and FHA to carry out sintering treatment, and further cooperates with the joint of the mixture component proportion, the F substitution amount of FHA and the sintering temperature, so that the strength of the prepared material can be improved, the stimulation and proliferation ability of the osteoblasts can be improved, and the regulation range of the elastic modulus can be effectively improved, so that it can adapt to the implanting needs of different bone structures.

[0047] The present application also innovatively adds a pore-forming agent, and through the joint control of the preparation conditions, a hierarchical pore can be obtained, and the composite material with excellent strength, biological activity and excellent elastic modulus controllable range can be obtained. DETAILED DESCRIPTION

[0048] Figure 1XRD diffractograms of FHA with different F substitution (Step 1 of Examples 1-2) (The percentage in the figure refers to the theoretical addition ratio of F, for example, the 100% group refers to a Ca / F ratio of 1:0.2 (Comparative Example B of Example 2); the 75% group refers to a Ca / F ratio of 1:0.15 (Example 2B); the 50% group refers to a Ca / F ratio of 1:0.1 (Example 1); the 25% group refers to a Ca / F ratio of 1:0.05 (Example 2A); and the 0% group refers to a Ca / F ratio of 1:0 (Comparative Example A of Example 2).

[0049] Figure 2 XRD diffractograms of the composites finally prepared in Examples 1-2 (The 100% group in the figure refers to Comparative Example B in Comparative Example 2; the 75% group refers to Example 2B; the 50% group refers to Example 1; the 25% group refers to Example 2A; and the 0% group refers to Comparative Example A in Example 2.)

[0050] Figure 3 SEM images of the composites finally prepared in Examples 1-2 (The 100% group in the figure refers to Comparative Example B in Comparative Example 2; the 75% group refers to Example 2B; the 50% group refers to Example 1; the 25% group refers to Example 2A; and the 0% group refers to Comparative Example A in Example 2; wherein A: α-Ti, B: β-Ti, C: TiB2, D: TiB, and E: HA+β-TCP.)

[0051] Figure 4 SEM-EDS analysis of the composite prepared in Example 1

[0052] Figure 5 Compressive strength, compressive modulus and Vickers microhardness of the composites of Examples 1-2 with different FHA substitution (The 100% group in the figure refers to Comparative Example B in Comparative Example 2; the 75% group refers to Example 2B; the 50% group refers to Example 1; the 25% group refers to Example 2A; and the 0% group refers to Comparative Example A in Example 2.)

[0053] Figure 6 Water contact angle of the composites of Examples 1-2 with different FHA substitution (The 100% group in the figure refers to Comparative Example B in Comparative Example 2; the 75% group refers to Example 2B; the 50% group refers to Example 1; the 25% group refers to Example 2A; and the 0% group refers to Comparative Example A in Example 2.)

[0054] Figure 7 SEM images of the surface deposits of the composite of Example 1 after 14 days of immersion in SBF (TC4 / TiB (Comparative Example B of Example 3) and TC4 / TiB / HA (Comparative Example A of Example 2) composites are used as controls)

[0055] Figure 8SEM images of cells grown on the surface of the composite material with 50% FHA substitution (Example 1 composite material) for 24 hours and alizarin red staining images of cells grown for 14 days (with TC4 / TiB / HA (Example 2 Comparative Group A) composite material as a control) DETAILED DESCRIPTION

[0057] The application will be further described in connection with the following detailed description and examples. It should be understood that the examples described are merely examples of part of the application and are not intended to limit the application in any way. The application encompasses all alternatives, modifications and variations falling within the scope of the application based on the examples described herein.

[0058] The application provides a porous titanium boride alloy / hydroxyfluorapatite composite material with a microporous structure (also referred to as TC4 / TiB / FHA in the application), which is prepared by the following steps: mixing TC4 powder, TiB2 powder and FHA by acoustic resonance to obtain a mixture, adding a binder to ball mill the mixture to obtain a ball mill material, mixing a pore-forming agent into the ball mill material by an acoustic resonance mixer, and then pressing the mixture to obtain a green body, removing the pore-forming agent and the binder from the green body by water bath and calcination, and performing microwave sintering under an inert atmosphere to obtain the porous titanium boride alloy / hydroxyfluorapatite composite material.

[0059] The application also provides a porous titanium boride alloy / hydroxyfluorapatite composite material with a hierarchical porous structure, which is prepared by the following steps: mixing TC4 powder, TiB2 powder, FHA and a pore-forming agent by acoustic resonance to obtain a mixture, adding a binder to ball mill the mixture to obtain a ball mill material, mixing a pore-forming agent into the ball mill material by an acoustic resonance mixer, and then pressing the mixture to obtain a green body, removing the pore-forming agent and the binder from the green body by water bath and calcination, and performing microwave sintering under an inert atmosphere to obtain the porous titanium boride alloy / hydroxyfluorapatite composite material.

[0060] In the application, the FHA (Ca 10 (PO4)6OH 2-2x F 2x is prepared by a precipitation method, and the solutions used are A liquid (a mixed solution of calcium nitrate and ammonium fluoride, wherein the molar ratio of Ca / F is 1:0.05-0.2) and B liquid (diammonium hydrogen phosphate solution). B liquid is added dropwise into A liquid, the reaction process is heated in a water bath to make the solution temperature be 20-70°C, ammonia water is used to adjust the pH to be 9.5-11, the molar ratio of Ca / P in the suspension after the reaction is 1.50-2.00, the suspension is aged at room temperature for 6-24 hours, and then washed, filtered and dried, and the substitution amount is detected by an ion selective electrode method.

[0061] Preferably, the molar ratio of Ca / F in the A solution is 1:0.1, and the actual substitution of the prepared FHA is 34%, and the average particle size is 210 nm.

[0062] Further preferably, the molar ratio of Ca / F in the A solution is 1:0.1, and the actual substitution of the prepared FHA is 34%, and the average particle size is 210 nm.

[0063] The raw material composition of TC4, TiB2 and FHA is as follows: TC4: 86%-94%, TiB2: 3%-7%, and FHA: 3%-7%. Preferably, TC4: 88%-92%, TiB2: 4-6%, and FHA: 4%-6%. Further preferably, TC4: 90%, TiB2: 5%, and FHA: 5%.

[0064] The average particle size of the TC4 powder is 10-50 μm, the average particle size of the TiB2 powder is 250 nm, the average particle size of the FHA powder is 190-240 nm, and the particle size range of the urea powder is 74-125 μm. Further, the average particle size of the TC4 powder is 17 μm, the average particle size of the TiB2 powder is 250 nm, and the average particle size of the FHA powder is 210 nm. In the preferred particle size ratio, the material can obtain the best density.

[0065] The mixed acceleration is 10-100 g (g refers to the acceleration of gravity), and the time can be 600-1800 s.

[0066] The parameters of the ball milling are as follows: the ball-to-material ratio is 5-15:1, the ball milling time is 10-30 hours, and the rotation speed is 150-250 r / min.

[0067] The pressure of the pressing forming is 500-1000 MPa, and the pressure holding time is 15-60 s. Further, the pressure of the pressing forming is 800-1000 MPa, and the pressure holding time is 30-60 s.

[0068] Preferably, the temperature of the water bath removal of the pore-forming agent is 30-50 °C, and the time is 20-40 h.

[0069] Preferably, the process of the calcination removal of the binder is carried out in a protective atmosphere, the temperature is 300-400 °C, the time is 1.5-3 h, and the heating speed is 1-5 °C / min.

[0070] In actual operation, the green body of the pressed cylinder is put into a high-temperature calcining furnace to make the stearic acid slowly and fully volatilize.

[0071] Further preferably, the binder removal process is carried out in an argon atmosphere.

[0072] Preferably, the microwave sintering temperature is 1000-1100℃.

[0073] Further preferably, the microwave sintering temperature is 1050℃.

[0074] Preferably, the microwave sintering time is 15-60min.

[0075] Further preferably, the microwave sintering time is 30min.

[0076] Preferably, the inert atmosphere is an argon atmosphere. The inventors have found that the atmosphere has a great influence on the material, and the use of an argon atmosphere can ensure the performance of the obtained material.

[0077] The application of the porous titanium boride alloy / fluo-hydroxyapatite composite material as an oral implant material.

[0078] Osteoblast stimulation study:

[0079] The composite material is immersed in a human body simulation body fluid (SBF), and the PH value of the SBF solution is measured at 0, 2, 4, 6, 8, 10, 12, and 14 days of the experiment, respectively, and the Ca and P ion concentrations in the solution are detected by ICP. After the immersion is completed, the sample is taken out, washed, dried, and gold sprayed, and the morphology change and element composition of the sample surface after immersion are detected by SEM-EDS. The influence of the composite material on the cell osteogenic and mineralization ability is detected by ALP (alkaline phosphatase) activity analysis method and alizarin red staining method, and the optical density values of the stained samples after 7 days and 14 days of cell culture are used for quantification.

[0080] The following are specific embodiments:

[0081] Example 1:

[0082] Step (1): Preparation of FHA:

[0083] Preparation of A solution (calcium nitrate, ammonium fluoride mixed solution, the mole ratio of Ca / F is 1:0.1) and B solution (diammonium hydrogen phosphate solution). B solution is added dropwise into A solution, the solution temperature is heated to 60-65°C in water bath during the reaction process, the pH is adjusted to 9.9-10.1 with ammonia water, the mole ratio of Ca / P in the suspension after reaction is 5:3, the sample is aged at room temperature for 24 hours, then washed, filtered and dried. According to the element proportion of the reactants, the theoretical F substitution amount of the FHA is 50% (marked as 50% group in the figure), but F does not participate in the reaction completely, the actual F substitution amount is 34% (that is, x=0.34). The average particle size is 210 nm.

[0084] Step (2):

[0085] A certain amount of TC4 (average particle size 17 μm), TiB2 (average particle size 250 nm) and the above FHA powder are pre-mixed by acoustic resonance at a mass ratio of 90% TC4 + 5% TiB2 + 5% FHA (also referred to as mixed raw materials), the acceleration is 50 g, and the mixing time is 300 s. After pre-mixing, 3% stearic acid (based on the weight of the mixed raw materials of TC4, TiB2 and FHA) is added as a binder. The above powders are sequentially placed into a vacuum ball mill jar, and grinding balls are added in an amount of 10:1 ball-to-material ratio. The ball mill jar is sealed, evacuated, and filled with argon gas for protection. The ball mill jar is placed in a planetary ball mill and ball milled for 12 hours at a speed of 200 r / min. After ball milling, the powder is taken out in a vacuum glove box, pressed into a small cylindrical green body with a specification of Φ8 mm x 10 mm using a precision servo hydraulic press at a pressure of 900 MPa for 45 s.

[0086] Step (3):

[0087] The pressed cylindrical green body is placed in a high-temperature calcination tube furnace for binder removal, with a heating rate of 3°C / min, slowly rising to 380°C, and maintaining for 2 h under high-purity argon gas atmosphere to allow the stearic acid to volatilize slowly. Microwave sintering process is used for preparation, with a sintering temperature of 1050°C, a sintering time of 30 min, and a high-purity Ar sintering atmosphere. After cooling to room temperature, the sample is subjected to mechanical property evaluation (including compressive strength, hardness, bulk density, elastic modulus, porosity, contact angle, etc.). The effects of the composite material on cell osteogenesis and mineralization are detected by ALP activity analysis and alizarin red staining, and the optical density values after 7 days and 14 days of cell culture are used for quantification.

[0088] The prepared porous titanium boride alloy / hydroxyapatite fluoride composite implant material has a compressive strength of 397.7 MPa, a hardness of 385.3 HV, a bulk density of 3.86 g / cm 3, elastic modulus of 10.65 GPa, porosity of 9.75%, and contact angle of 38.8°. The degradation and absorption of Ca and P ions and the change of pH can be detected during the 14-day immersion. The sample immersed for 7 days can be observed to have a complete coating of apatite on the surface of the sample, forming a uniform coating, and the coating can be observed to be significantly thickened after 14 days of immersion, proving that the composite has excellent bioactivity. The optical density values measured by ALP activity analysis and alizarin red staining are 0.463 and 0.285, respectively, which are significantly better than those of the TC4 titanium alloy (optical density values are 0.145 and 0.051, respectively) in the control group, and have the function of promoting osteoblast differentiation.

[0089] Example 2

[0090] Compared with Example 1, the only difference is that the amount of F in A liquid in step (1) is changed to regulate the molar ratio of Ca / F, and the experimental groups are as follows:

[0091] Group A (labeled as 25% group): the molar ratio of Ca / F in A liquid in step (1) is 1:0.05. According to the element ratio of the reactants, the theoretical F substitution amount of the FHA is 25%, but F does not participate in the reaction completely, and the actual F substitution amount is 17%. The average particle size is 200 nm.

[0092] Group B (labeled as 75% group): the molar ratio of Ca / F in A liquid in step (1) is 1:0.15. According to the element ratio of the reactants, the theoretical F substitution amount of the FHA is 75%, but F does not participate in the reaction completely, and the actual F substitution amount is 51%. The average particle size is 240 nm.

[0093] Comparative group A (labeled as 0% group): HA is used instead of FHA, that is, there is no F source in A liquid, and the substitution amount is 0. The average particle size is 240 nm.

[0094] Comparative group B (labeled as 100% group): the molar ratio of Ca / F in A liquid in step (1) is 1:0.2. According to the element ratio of the reactants, the theoretical F substitution amount of the FHA is 100%, but F does not participate in the reaction completely, and the actual F substitution amount is 72%. The average particle size is 380 nm.

[0095] The test is carried out according to the method of Example 1, and the results are as follows:

[0096] Group A:

[0097] The compressive strength of the prepared porous titanium boride alloy / hydroxyfluorapatite stone composite implant material is 397.6 MPa, the hardness is 375.3 HV, and the bulk density is 3.85 g / cm 3, the elastic modulus is 10.60 GPa, the porosity is 9.83%, and the contact angle is 48.9°. The optical density values measured by ALP activity analysis and alizarin red staining are 0.352 and 0.156, respectively.

[0098] Group B:

[0099] The prepared porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material has a compressive strength of 365.5 MPa, a hardness of 324.7 HV, a bulk density of 3.84 g / cm 3 , the elastic modulus is 9.68 GPa, the porosity is 9.96%, and the contact angle is 37.8°. The optical density values measured by ALP activity analysis and alizarin red staining are 0.376 and 0.221, respectively.

[0100] Comparative group A group:

[0101] The prepared porous TC4 / TiB / HA stone composite implant material has a compressive strength of 286.0 MPa, a hardness of 267.3 HV, a bulk density of 3.78 g / cm 3 , the elastic modulus is 8.43 GPa, the porosity is 10.32%, and the contact angle is 56.6°. During the 14-day immersion process of the sample, degradation and absorption of Ca and P ions, as well as changes in pH, can be detected. After 14 days of immersion, it can be observed that the deposits exist only in part of the area and do not cover the entire surface, indicating that the biological activity of the composite material is limited. The optical density values measured by ALP activity analysis and alizarin red staining are 0.295 and 0.108, respectively, which are lower than those of groups A and B.

[0102] Comparative group B group:

[0103] The prepared porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material has a compressive strength of 304.1 MPa, a hardness of 302.0 HV, a bulk density of 3.79 g / cm 3 , the elastic modulus is 10.25 GPa, the porosity is 10.25%, and the contact angle is 36.2°. During the 14-day immersion process of the sample, degradation and absorption of Ca and P ions, as well as changes in pH, can be detected. After 14 days of immersion, it can be observed that the deposits exist only in part of the area and do not cover the entire surface, indicating that the biological activity of the composite material is limited. The optical density values measured by ALP activity analysis and alizarin red staining are 0.295 and 0.108, respectively, which are lower than those of groups A and B.

[0104] Example 3

[0105] Compared with Example 1, the only difference is that the composition and proportion of the mixed raw materials in step (2) are changed, and the total amount of raw materials is the same. The experimental groups are as follows:

[0106] Group A: In the mixed raw materials, the weight ratio of TC4, TiB2 and FHA is 94:3:3;

[0107] Group B: In the mixed raw materials, the weight ratio of TC4, TiB2 and FHA is 86:7:7;

[0108] Comparative Group A: In the mixed raw materials, the mixed raw materials contain 95% TC4+5% FHA, and lack of TiB2;

[0109] Comparative Group B: In the mixed raw materials, the mixed raw materials contain 95% TC4+5% TiB2, and lack of FHA; other operations and parameters are the same as Example 1;

[0110] The test is carried out according to the method of Example 1, and the results are respectively:

[0111] Group A:

[0112] The prepared porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material has a compressive strength of 560.5 MPa, a hardness of 361.2 HV, a bulk density of 3.95 g / cm 3 , an elastic modulus of 10.83 GPa, a porosity of 5.45%, and a contact angle of 53.0°. During the 14-day immersion process, the degradation and absorption of Ca and P ions, and the change of pH can be detected. After 14 days of immersion, a thin layer of apatite is observed on the surface of the sample, indicating that the composite material has preliminary bioactivity.

[0113] Group B:

[0114] The prepared porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material has a compressive strength of 233.5 MPa, a hardness of 357.5 HV, a bulk density of 3.54 g / cm 3 , an elastic modulus of 9.20 GPa, a porosity of 12.45%, and a contact angle of 32.5°. During the 14-day immersion process, the degradation and absorption of Ca and P ions, and the change of pH can be detected. After 14 days of immersion, a thick layer of apatite is observed on the surface of the sample, indicating that the composite material has good bioactivity.

[0115] Comparative Group A:

[0116] The prepared porous TC4 / FHA composite implant material has a compressive strength of 82.6 MPa, a hardness of 195 HV, and a bulk density of 3.69 g / cm 3, the elastic modulus is 3.36 GPa, the porosity is 11.33%, and the contact angle is 40.5°. The sample of this ratio contains macroscopic defects, even with cracking phenomenon, and the mechanical properties are poor. This is due to the significant difference in thermal expansion coefficient between TC4 and FHA.

[0117] Comparative group B:

[0118] According to the method of Example 1, the bioactivity test results show that after the SBF simulation immersion experiment, the pH value and Ca, P ion concentration of the solution do not change significantly, and SEM-EDS detection of the sample surface after immersion does not generate new substances, indicating that the composite material does not have bioactivity.

[0119] Example 4

[0120] Compared with Example 1, the difference is only that the sintering temperature of step (3) is changed, respectively:

[0121] A: sintering temperature is 1000℃;

[0122] B: sintering temperature is 1100℃;

[0123] Comparative group A: sintering temperature is 950℃

[0124] Group A:

[0125] The compressive strength of the porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material prepared is 235.2 MPa, the hardness is 285.4 HV, the bulk density is 3.79 g / cm 3 , the elastic modulus is 7.85 GPa, the porosity is 11.25%, and the contact angle is 33.1°. The sample surface sintering effect is good under scanning electron microscope, but there is a small part of the sample center with obvious poor density, and there is an obvious boundary between the two different densities, which is caused by the insufficient microwave power due to the lower set temperature and the difficulty of penetrating to the inside of the sample. During the 14-day immersion process, the degradation and absorption of Ca and P ions, as well as the change of pH can be detected. After 14 days of immersion, a thick layer of apatite can be observed on the surface of the sample, indicating that the composite material has good bioactivity.

[0126] Group B:

[0127] The compressive strength of the porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material prepared is 435.5 MPa, the hardness is 392.6 HV, the bulk density is 3.91 g / cm 3, the elastic modulus is 11.27 GPa, the porosity is 9.46%, and the contact angle is 53.2°. The mechanical properties are good under this ratio, but the SBF simulation body fluid immersion experiment shows that the solution PH value and Ca, P ion concentration change is small, the SEM-EDS detection generates a layer of calcareous on the surface of the sample after immersion, and it has not been completely converted into apatite, which shows that the sample has preliminary biological activity, but it is limited.

[0128] Comparative group A:

[0129] The compressive strength of the prepared porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material is only 98.5 MPa, the hardness is 184.2 HV, the bulk density is 3.74 g / cm 3 , the elastic modulus is 4.35 GPa, the porosity is 11.95%, and the contact angle is 23.0°. Scanning electron microscopy shows that the sample has very poor density, which is caused by insufficient sintering temperature.

[0130] Example 5 - hierarchical pore scheme

[0131] Compared with Example 1, the only difference is that in step (2), a pore-forming agent is added, and the difference in step (2) is:

[0132] A certain amount of TC4 (average particle size 17 μm), TiB2 (average particle size 250 nm), and the above FHA powder are pre-mixed by acoustic resonance at a mass ratio of 90% TC4 + 5% TiB2 + 5% FHA (also referred to as mixed raw materials), with an acceleration of 50 g and a mixing time of 300 s. After pre-mixing, 3% stearic acid (based on the weight of the mixed raw materials of TC4, TiB2, and FHA) is added as a binder. The above powders are sequentially placed into a vacuum ball mill jar, and grinding balls are added in an amount of 10:1 ball-to-material ratio. The ball mill jar is sealed and evacuated, and argon gas is filled for protection. The ball mill jar is placed in a planetary ball mill for 12 hours at a speed of 200 r / min. After ball milling, the powder is taken out in a vacuum glove box, and the removed powder is preliminarily mixed with 5% urea (74-125 μm) and then transferred to an acoustic resonance mixer for mixing at an acceleration of 50 g for 1200 s. A precision servo hydraulic press is used for briquetting at a pressure of 900 MPa for 45 s, and a small cylindrical green body with a specification of Φ8 mm x 10 mm is obtained. The pore-forming agent is removed in a water bath at a temperature of 40°C for 30 h.

[0133] Other processes are the same as in Example 1.

[0134] The compressive strength of the porous titanium boride alloy / hydroxyapatite fluoride stone composite implant material prepared in this example is 120.2 MPa, the hardness is 270.3 HV, and the bulk density is 3.26 g / cm 3, the elastic modulus is 2.93 GPa, the porosity is 26.65%, and the contact angle is 20.5°.

[0135] Example 6 - hierarchical pore scheme

[0136] Compared with Example 1, the only difference is that in step (2), a pore-forming agent is added, and the step (2) of the difference is:

[0137] A certain amount of TC4 (average particle size 17 μm), TiB2 (average particle size 250 nm), and the above-mentioned FHA powder are taken, and the sound resonance premixing is carried out according to the mass ratio of 90% TC4 + 5% TiB2 + 5% FHA (also referred to as mixed raw materials). The acceleration is 50 g, and the mixing time is 300 s. After pre-mixing, 3% stearic acid (based on the weight of the mixed raw materials of TC4, TiB2 and FHA) is added as a binder. The above powders are sequentially placed into a vacuum ball mill jar, and grinding balls are sequentially added according to the ball-to-material ratio of 10:1. The ball mill jar is sealed and vacuumized, and then filled with argon gas for protection. It is placed in a planetary ball mill for ball milling for 12 hours at a speed of 200 r / min. After ball milling, the powder is taken in a vacuum glove box, and the taken powder is preliminarily mixed with 1% urea (74-125 μm) and then transferred to a sound resonance mixer for mixing at an acceleration of 50 g for 1200 s. A precision servo hydraulic press is used for briquetting, the pressure is 900 MPa, and the pressure maintaining time is 45 s. A small cylindrical green body with a specification of Φ8 mm x 10 mm is prepared. The pore-forming agent is removed by water bath, the temperature is 40°C, and the time is 30 h.

[0138] Other processes are the same as in Example 1. The compressive strength of the porous titanium boride alloy / hydroxyapatite fluoride composite implant material prepared in this case is 236.9 MPa, the hardness is 325.8 HV, the bulk density is 3.77 g / cm 3 , the elastic modulus is 7.12 GPa, the porosity is 15.17%, and the contact angle is 24.7°.

Claims

1. A method for producing a porous titanium boride alloy / hydroxyapatite fluoride composite material, characterized by: The mixed material containing TC4, TiB2 and FHA is sintered to obtain; The chemical formula of FHA is Ca 10 (PO4)6OH 2-2x F 2x wherein x is 0.1-0.6; The weight ratio of TC4, TiB2 and FHA in the mixed material is 86-94:3-7:3-7. The sintering temperature is 1000-1100 ℃.

2. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 1, wherein: The FHA is prepared by a precipitation method, and the steps are as follows: A solution A containing a calcium source and an F source is obtained, and a solution B containing a phosphorus source is obtained; the solution B is added dropwise into the solution A to perform precipitation; the molar ratio of Ca / F in the solution A is 1:0.05-0.2; the molar ratio of Ca in the solution A to P in the solution B is 1.50-2.00:

1.

3. The method of making a porous titanium boride alloy / fluoridated hydroxyapatite composite material of claim 2, wherein: The calcium source is at least one of calcium nitrate and calcium chloride.

4. The method of making a porous titanium boride alloy / fluoridated hydroxyapatite composite material of claim 2, wherein: The F source is at least one of ammonium fluoride, sodium fluoride and potassium fluoride.

5. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 2, wherein: The phosphorus source is at least one of ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.

6. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 2, wherein: The molar ratio of Ca / F is 1:0.05-0.

15.

7. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 2, wherein: The molar ratio of Ca in the solution A to P in the solution B is 1.67-1.70:

1.

8. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 2, wherein: The temperature in the precipitation reaction stage is 20-70 ℃.

9. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 2, wherein: Ammonia water is used to adjust the pH to 9.5-11 during the precipitation reaction process.

10. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 1, wherein: The weight ratio of TC4, TiB2 and FHA is 88-93:4-6:4-6.

11. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 10, wherein: The weight ratio of TC4, TiB2 and FHA is 90:5:

5.

12. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 1, wherein: The mixed material further contains a binder.

13. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 12, wherein: The binder is at least one of stearic acid, zinc stearate and liquid paraffin.

14. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 12, wherein: The binder accounts for 1-5% of the total weight of TC4, TiB2 and FHA.

15. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to any one of claims 1 to 14, wherein: The mixed material further contains a pore-forming agent.

16. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 15, wherein: The pore-forming agent is at least one of urea, ammonium carbonate, ammonium bicarbonate and starch.

17. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 15, wherein: The pore-forming agent accounts for 1-5% of the total weight of TC4, TiB2 and FHA.

18. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 15, wherein: Each component is mixed, ball-milled and press-formed to obtain the mixed material.

19. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 18, wherein: The mixing mode is acoustic resonance pre-mixing.

20. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 1, wherein: The sintering process is performed under microwave assistance.

21. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 1, wherein: The sintering temperature is 1030-1070 ℃.

22. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 21, wherein: The sintering temperature is 1040-1060 ℃.

23. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material of claim 20, wherein: The power of the microwave is 300-1400 W.

24. The method of making a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 1, wherein: The sintering time is 15-60 min.

25. A porous titanium boride alloy / hydroxyapatite fluoride composite material prepared by the preparation method of any one of claims 1-24.

26. Use of a porous titanium boride alloy / hydroxyapatite fluoride composite material produced by the production method according to any one of claims 1 to 24, characterized in that The porous titanium boride alloy / hydroxyapatite fluoride composite material is prepared into a biological implant material.

27. Use of a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 26, wherein The implant material is an implant material.

28. Use of a porous titanium boride alloy / hydroxyapatite fluoride composite material according to claim 27, characterized in that The implant material is an oral implant material.

Images