阅读说明：本技术 一种陶瓷颗粒增强Ti-Ta基骨植入复合材料及其制备方法 (Ceramic particle reinforced Ti-Ta-based bone implantation composite material and preparation method thereof ) 是由 刘守法 肖传军 张丽娟 于 2021-09-09 设计创作，主要内容包括：本发明公开了一种陶瓷颗粒增强Ti-Ta基骨植入复合材料及其制备方法,该方法包含：将碳化二钼或二硼化钛与钛粉、钽粉和羰基镍粉混合,与分散剂和磨球制成浆料,混合,分离磨球,干燥浆料,压制成型；在真空条件下烧结,先将炉温以10℃/min由室温升至600℃后并保温30min,再以10℃/min升温至1250～1300℃并保温60min,最后以-20℃/min降温至室温；于封闭高压设备中保持温度850～940℃,通过惰性气体保持压力90～140MPa,随炉冷却至265℃后出炉；于900～1200℃保温后水淬火,在450～700℃下保温后空冷。本发明的复合材料中元素的均匀性、耐腐蚀性和材料强度均得到提高。(The invention discloses a ceramic particle reinforced Ti-Ta based bone implantation composite material and a preparation method thereof, wherein the method comprises the following steps: mixing dimolybdenum carbide or titanium diboride with titanium powder, tantalum powder and nickel carbonyl powder, preparing slurry with a dispersant and a grinding ball, mixing, separating the grinding ball, drying the slurry, and performing compression molding; sintering under a vacuum condition, namely, firstly heating the furnace temperature to 600 ℃ from room temperature at the speed of 10 ℃/min, then preserving the heat for 30min, then heating to 1250-1300 ℃ at the speed of 10 ℃/min, preserving the heat for 60min, and finally cooling to room temperature at the speed of-20 ℃/min; keeping the temperature at 850-940 ℃ in closed high-pressure equipment, keeping the pressure at 90-140 MPa by using inert gas, cooling to 265 ℃ along with the furnace, and discharging; and (3) performing water quenching after the temperature is kept at 900-1200 ℃, and performing air cooling after the temperature is kept at 450-700 ℃. The uniformity, the corrosion resistance and the material strength of elements in the composite material are all improved.)

1. A method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite, the method comprising:

and (2) mixing the following components in a mass ratio of 84-88: 8: 4-8: 1-5 parts of dimolybdenum carbide or titanium diboride, titanium powder, tantalum powder and nickel carbonyl powder are uniformly mixed, and the mixed powder, a dispersing agent and a grinding ball are mixed according to a mass ratio of 1:1:1, preparing slurry, mixing at a temperature of between 5 ℃ below zero and 2 ℃ below zero, separating the slurry from grinding balls after the completion of the mixing, drying the slurry, and performing compression molding under the pressure of 180 to 240 MPa;

at 10^-3～10^-2Sintering under Pa vacuum degree, heating furnace temperature from room temperature to 600 deg.C at a heating rate of 10 deg.C/min, maintaining for 30min, and sintering at high temperatureHeating to 1250-1300 ℃ at the speed of 10 ℃/min, preserving the heat for 60min, and finally cooling to room temperature at the speed of-20 ℃/min;

placing the sintered material in a closed high-pressure device, keeping the temperature at 850-940 ℃, keeping the pressure at 90-140 MPa through inert gas, keeping for 2 hours, cooling to 265 ℃ along with the furnace, and discharging; and then, carrying out heat preservation on the material at 900-1200 ℃ for 40min, then carrying out water quenching, then carrying out heat preservation at 450-700 ℃ for 5h, and then carrying out air cooling to obtain the ceramic particle reinforced Ti-Ta based bone implantation composite material.

2. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite material according to claim 1, wherein the pressure maintaining time is 5min when the composite material is press-molded at 180 to 240 MPa.

3. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite material according to claim 1, wherein the dimolybdenum carbide or titanium diboride is mixed with titanium powder, tantalum powder and nickel carbonyl powder in an ultrasonic manner, and the ultrasonic frequency is 35 Hz.

4. The method of claim 1, wherein the dispersant is octadecanoic acid.

5. The method of claim 1, wherein the grinding balls are zirconia balls.

6. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite according to claim 1, wherein the mixing time at-5 to-2 ℃ is 24 hours.

7. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite according to claim 1, wherein the temperature at which the slurry is dried is 72 ℃.

8. A ceramic particle reinforced Ti-Ta based bone implant composite prepared according to the method of any one of claims 1 to 7.

Technical Field

The invention relates to a bone implantation composite material, in particular to a ceramic particle reinforced Ti-Ta based bone implantation composite material and a preparation method thereof.

Background

The titanium alloy material for bone implantation mainly comprises alpha type and beta type, wherein the alpha type is Ti-6AL-4V alloy, the beta type is Ti-5AL-2.5Fe and Ti-6AL-7Nb alloy, the alpha type and the beta type are applied to bone implantation, but V and Al elements contained in the alloy are harmful to human bodies, V is used as a beta phase and is a stable alloy element, the cost is high, the cytotoxicity is high, and the Al element easily causes senile dementia after being existed in the human bodies for a long time. From the medical application point of view, the most important criteria for bone implant alloys are not only the non-toxicity, corrosion resistance and cost of the alloy elements. Therefore, it is important to develop a titanium alloy free from harmful elements such as Al.

Among the bone-implanted titanium alloys without harmful elements such as V and Al, Ti-Ta alloy is one of the most promising alloys. The excellent biocompatibility and corrosion resistance of pure titanium and pure tantalum have been widely accepted by many medical researchers, and compared to pure Ta, Ti-Ta alloys are lighter and cheaper, and are superior materials to replace Ta. Among the currently used bone implant materials, the Ti — Ta alloy has the lowest young's modulus and strength comparable to that of the cobalt-based alloy.

In the powder metallurgy of Ti-Ta alloys, sintering the mixed Ti and Ta powders does not fully guarantee the homogeneity of the alloy despite the high sintering temperatures used (from 1200 to 1500 ℃). Therefore, Ti-Ta powder is not fully diffused in the sintering process, so that Ti-rich and Ta-rich areas in the alloy are alternately distributed, and the problem of uneven element distribution can be effectively solved by utilizing an initial mechanical alloying method and then sintering at the temperature lower than the melting point of titanium. In the process of preparing the titanium alloy through powder metallurgy, the porosity (the porosity is 5-20%) can be controlled by adjusting powder components and sintering parameters, so that the Ti-Ta alloy with low elastic modulus is obtained, and is suitable for bone implant, but the strength and the fatigue resistance of the alloy surface are reduced, and even harmful substances in the chemical treatment process remain in pores, so that the problem of obtaining the Ti-Ta alloy with proper pores, high bending strength and good corrosion resistance is a great problem.

Disclosure of Invention

The invention aims to provide a ceramic particle reinforced Ti-Ta based bone implantation composite material and a preparation method thereof.

In order to achieve the above objects, the present invention provides a method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite, the method comprising: and (2) mixing the following components in a mass ratio of 84-88: 8: 4-8: 1-5 parts of dimolybdenum carbide or titanium diboride, titanium powder, tantalum powder and nickel carbonyl powder are uniformly mixed, and the mixed powder, a dispersing agent and a grinding ball are mixed according to a mass ratio of 1:1:1, preparing slurry, mixing at a temperature of between 5 ℃ below zero and 2 ℃ below zero, separating the slurry from grinding balls after the completion of the mixing, drying the slurry, and performing compression molding under the pressure of 180 to 240 MPa; at 10^-3～10^-2Sintering under the Pa vacuum degree, firstly heating the furnace temperature from room temperature to 600 ℃ at the heating rate of 10 ℃/min, then preserving the heat for 30min, then heating to 1250-1300 ℃ at the heating rate of 10 ℃/min, preserving the heat for 60min, and finally cooling to the room temperature at the speed of-20 ℃/min; placing the sintered material in a closed high-pressure device, keeping the temperature at 850-940 ℃, keeping the pressure at 90-140 MPa through inert gas, keeping for 2 hours, cooling to 265 ℃ along with the furnace, and discharging; and then, carrying out heat preservation on the material at 900-1200 ℃ for 40min, then carrying out water quenching, then carrying out heat preservation at 450-700 ℃ for 5h, and then carrying out air cooling to obtain the ceramic particle reinforced Ti-Ta based bone implantation composite material.

Preferably, the pressure maintaining time is 5min when the material is pressed and formed under 180-240 MPa.

Preferably, the dimolybdenum carbide or titanium diboride is mixed with titanium powder, tantalum powder and nickel carbonyl powder in an ultrasonic mode, and the ultrasonic frequency is 35 Hz.

Preferably, the dispersant is octadecanoic acid.

Preferably, the grinding balls are zirconia balls.

Preferably, the mixing time is 24 hours at-5 to-2 ℃.

Preferably, the temperature at which the slurry is dried is 72 ℃.

The invention also aims to provide a ceramic particle reinforced Ti-Ta based bone implant composite material prepared by the method.

The ceramic particle reinforced Ti-Ta based bone implantation composite material and the preparation method thereof have the following advantages:

the ceramic particle reinforced Ti-Ta based bone implantation composite material is prepared by mixing ceramic particles Mo₂C or TiB₂The Ti-Ta alloy is used as reinforcing particles and added into the Ti-Ta alloy, so that the uniformity, the corrosion resistance and the material strength of elements in the composite material are improved. Wherein added Mo₂The C particles are distributed in the matrix material in a criss-cross mode, so that the crack expansion in the material can be effectively hindered, and the bending strength of the material can be favorably improved. Added Mo₂The wetting property between the C particles and the matrix is strong, the swelling phenomenon of the material can be eliminated, and the uniformity of particle distribution is improved. Ta and Mo are beneficial to alloy to generate a passivation layer, and the corrosion resistance of the material is also improved.

Drawings

FIG. 1 is a schematic diagram of sintering temperatures for various embodiments of the present invention.

Fig. 2 is the EDS element distribution test results of the composite material of example 1 of the present invention.

Fig. 3 is the EDS elemental distribution test results for the composite of example 4 of the invention.

FIG. 4 is a polarization impedance for various embodiments of the present invention.

FIG. 5 is a graph of the flexural strength of composite materials prepared in various examples of the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A ceramic particle reinforced Ti-Ta based bone implantation composite material is prepared by the following steps:

(1) titanium powder (average particle size of 35 microns) with the purity of 95%, tantalum powder (average particle size of 10 microns), nickel carbonyl powder (average particle size of 10 microns) and molybdenum carbide (average particle size of 6 microns) are mixed together to prepare mixed powder, the mass of the mixed powder is 84g, 8g, 4g and 1g respectively, the mixed powder is subjected to ultrasonic treatment by an ultrasonic cleaning machine and is convenient to mix uniformly, the treatment frequency is 35Hz, and the treatment time is 43 min. Stearic acid and zirconia balls are respectively used as a dispersing agent and a grinding ball, and the mixed powder, stearic acid and the grinding ball are prepared into slurry according to the mass ratio of 1:1: 1.

(2) And (2) completely putting the slurry prepared in the step (1) into a three-dimensional space rotary mixer for mixing for 24 hours at the mixing temperature of-2 ℃. And after the powder mixing is finished, pouring the slurry out, separating the slurry from the grinding balls, placing the slurry in a drying oven at 72 ℃ for baking for 24 hours to remove the octadecanoic acid dispersing agent in the slurry, and carrying out press forming on the dried powder under the pressure of 180MPa for 5 minutes.

(3) Firing the pressed green body in a vacuum sintering furnace at 10 deg.C to reduce the adverse effects of harmful components such as nitrogen, oxygen and water in the atmosphere on the workpiece^-2And sintering under Pa vacuum degree, wherein the sintering temperature is shown in figure 1, the furnace temperature is firstly increased from 25 ℃ to 600 ℃ at the heating rate of 10 ℃/min and then is kept for 30min, then is increased to 1250 ℃ at the heating rate of 10 ℃/min and is kept for 60min, and finally is reduced to 25 ℃ at the room temperature at the speed of-20 ℃/min.

(4) And (4) putting the material prepared in the step (3) into a closed high-pressure device, keeping the temperature at 850 ℃, keeping the pressure at 90MPa through inert gas, keeping for 2 hours, cooling to 265 ℃ along with the furnace, and discharging.

(5) And (3) putting the material prepared in the step (4) into a furnace at 900 ℃ for heat preservation for 40min, then carrying out water quenching, then carrying out heat preservation at 450 ℃ for 5h, and then carrying out air cooling to obtain the ceramic particle reinforced Ti-Ta based bone implantation composite material.

Example 2

A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 1, except that:

in the step (1), the mass of the titanium powder, the mass of the tantalum powder, the mass of the nickel carbonyl powder and the mass of the molybdenum carbide are respectively 86g, 8g, 6g and 3 g;

in the step (2), the mixing temperature of the slurry is-3 ℃; the pressure for carrying out press forming on the dried powder is 210MPa, and the pressure maintaining time is 5 min;

in step (3), at 10^-3Sintering under Pa vacuum degree, wherein the sintering temperature is shown in figure 1, the furnace temperature is firstly increased from 25 ℃ to 600 ℃ at the heating rate of 10 ℃/min and then is kept for 30min, then is increased to 1275 ℃ at the heating rate of 10 ℃/min and is kept for 60min, and finally is reduced to 25 ℃ at the temperature of-20 ℃/min;

in the step (4), the temperature is maintained at 900 ℃, and the pressure is maintained at 120 MPa;

in the step (5), the material is put into 1100 ℃ for heat preservation for 40min, then water quenching is carried out, and then heat preservation is carried out for 5h at 600 ℃ and then air cooling is carried out.

Example 3

A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 1, except that:

in the step (1), the mass of the titanium powder, the mass of the tantalum powder, the mass of the nickel carbonyl powder and the mass of the molybdenum carbide are respectively 88g, 8g and 5 g;

in the step (2), the mixing temperature of the slurry is-5 ℃; the pressure for press forming the dried powder is 240 MPa;

in step (3), at 10^-3Sintering under Pa vacuum degree, wherein the sintering temperature is shown in figure 1, the furnace temperature is firstly increased from 25 ℃ to 600 ℃ at the heating rate of 10 ℃/min and then is kept for 30min, then is increased to 1300 ℃ at the heating rate of 10 ℃/min and is kept for 60min, and finally is reduced to 25 ℃ at the room temperature at the speed of-20 ℃/min;

in the step (4), keeping the temperature at 940 ℃ and the pressure at 140 MPa;

in the step (5), the material is subjected to heat preservation at 1200 ℃ and then water quenching, and then is subjected to heat preservation at 700 ℃ and then air cooling.

Example 4

A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 1, except that: titanium diboride (average particle size 10 μm) was substituted for dimolybdenum carbide.

Example 5

A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 2, except that: titanium diboride (average particle size 10 μm) was substituted for dimolybdenum carbide.

Example 6

A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 3, except that: titanium diboride (average particle size 10 μm) was substituted for dimolybdenum carbide.

Uniformity test of elemental distribution for example 1 and example 4

EDS element distribution tests are carried out on the samples prepared in the example 1 and the example 4, and the test results are shown in a figure 2 and a figure 3, wherein in the example 1, C is converted from molybdenum carbide and is distributed in a material in a fine particle shape, other elements are uniformly distributed, and the structure has no obvious pores; in example 4, B is converted from titanium diboride, and the elements are uniformly distributed without obvious pores in the structure.

Corrosion resistance testing of examples 1-6

The corrosion resistance of the material is tested by adopting a dynamic potential polarization experimental method, the test specification refers to ASTM G59-97, the electrolyte is 0.5mol/L sulfuric acid aqueous solution, the auxiliary electrode is platinum, Ag/AgCl is a reference electrode, and the area of a corrosion test sample is 0.8cm²。

The polarization resistance of each example is shown in FIG. 4, where the polarization resistance is the greatest and the corrosion resistance is the best in example 3, followed by example 6, surface Mo₂C and TiB₂The addition of (2) is beneficial to improving the corrosion resistance of the composite material.

Flexural Strength testing of examples 1-6

The bending strength test adopts a three-point bending strength experimental method for measurement, the measurement specification refers to ASTM B528-2016, the loading rate is 2mm/min, the width, the height and the length of a tested sample are respectively 5.5mm, 6mm and 200mm, and the span of two supporting points below the test sample is 25.4 mm.

The bending strength calculation formula is as follows:

TRS＝(3×P×L)/(2×T²×W)

wherein P is the measured breaking load (N), L is the span (mm) of two fulcrums under the sample, T is the height (mm) of the sample, and W is the width (mm) of the sample.

As shown in FIG. 5, for the flexural strength of the composite materials prepared in the respective examples, it can be seen that Mo was contained in examples 1, 2 and 3₂The content of C particles is increased in sequence, the bending strength is also increased, and Mo is shown₂The addition of the C particles can effectively prevent the crack from expanding, thereby improving the bending strength of the material. TiB in example 4, example 5 and example 6₂The particle content increases in turn when TiB₂The particles are enlarged to a certain degree, and the bending strength of the material is improved.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.