CN113289057B - Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant - Google Patents

Abstract

The invention provides a tantalum-coated orthopaedic implant material, a preparation method thereof, and an orthopaedic implant. The tantalum-coated orthopaedic implant material includes a matrix layer, a transition layer, a tantalum coating and a tantalum surface functional layer that are stacked in sequence, the matrix layer is titanium or a titanium alloy, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating is porous structure. On the one hand, the tantalum-coated orthopaedic implant material of the present application improves the bonding force between the tantalum coating and the transition layer; A microenvironment conducive to cell growth, which in turn promotes the growth of bone tissue into the porous tantalum coating to form a unique bone-implant interface, significantly enhancing the stability and function of tantalum-coated orthopedic implants in bone tissue, accelerating The osseointegration of the bone-implant interface is achieved. In addition, the orthopaedic implant of the present application has low production cost and low potential harm of non-tantalum materials.

Description

Tantalum-coated orthopaedic implant material and preparation method thereof, and orthopaedic implant

technical field

The invention relates to the technical field of orthopedic implants, in particular to a tantalum-coated orthopedic implant material, a preparation method thereof, and an orthopedic implant.

Background technique

Tantalum has good corrosion resistance, and the degree of ionization of tantalum in the in vivo environment is extremely low, thus showing extremely low cytotoxicity. good clinical effect.

Invention patent CN109261958 proposes a preparation method of medical porous titanium or titanium alloy material coated with tantalum coating, but the technology is coated with a dense tantalum coating on the surface of porous titanium alloy, so that it can be implanted There are no pores for bone ingrowth in the back of the human body, which makes it difficult for bone tissue to grow into the tantalum coating.

In addition, Zimmer’s tantalum trabecular bone implants are processed by chemical vapor deposition technology, which has many process steps and high technical difficulties; in addition, due to the high melting point of tantalum, it is difficult to process by traditional powder metallurgy methods; 3D Printing metal tantalum has high raw material and processing costs, especially the high specific gravity of tantalum causes the high weight of the implant of the same specification, and is prone to problems such as subsidence after implantation.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a tantalum-coated orthopaedic implant material, a preparation method thereof, and an orthopaedic implant, so as to solve the problem that bone tissue is difficult to grow into the tantalum-coated orthopaedic implant in the prior art.

In order to achieve the above object, according to one aspect of the present invention, there is provided a tantalum-coated orthopaedic implant material, comprising a matrix layer, a transition layer, a tantalum coating and a tantalum surface functional layer stacked in sequence, and the matrix layer is titanium or For titanium alloys, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating has a porous structure.

Further, the pore size of the tantalum coating is 10-30 μm, preferably the porosity of the tantalum coating is 30-80%, and the thickness of the tantalum coating is preferably 30-60 μm.

Further, the thickness of the transition layer is 90-180 μm.

Further, the above-mentioned tantalum surface functional layer is nano-filament calcium tantalate, preferably the diameter of the nano-filament calcium tantalate is 20-35 nm, and preferably the length of the nano-filament calcium tantalate is less than or equal to 500 nm.

Further, the above-mentioned titanium alloy is selected from any one of Ti-6Al-4V, Ti-6Al-17Nb, Ti-13Nb-13Zr, and Ti-5Zr-3Mo-15Nb.

Further, the above transition layer is pure titanium or Ti-6Al-4V.

According to another aspect of the present invention, there is provided a tantalum-coated orthopaedic implant comprising the above-mentioned tantalum-coated orthopaedic implant material, and the tantalum-coated orthopaedic implant is an acetabular cup, an acetabular patch, and a femoral stem. any of the .

According to another aspect of the present invention, a preparation method of the above-mentioned tantalum-coated orthopaedic implant material is provided, the preparation method comprising sequentially forming a transition layer, a tantalum coating and a tantalum surface functional layer on the base layer, and the tantalum coating is The forming process includes spraying tantalum particles on the transition layer by means of laser cladding to form a tantalum coating, wherein the power of the laser cladding is less than or equal to 8.0KW.

Further, the above preparation method includes: step S1, spraying titanium powder or titanium alloy particles on the base layer to form a transition layer; step S2, using a laser cladding method to spray tantalum particles on the transition layer to form a tantalum coating; Step S3, hydrothermally reacting the tantalum coating with a calcium salt and a strong alkali solution to obtain a tantalum-coated orthopaedic implant material.

Further, the sphericity of the tantalum particles is 0.6-1, preferably the average particle size of the tantalum particles is 5-40 μm, and/or the D50 of the tantalum particles is 20-30 μm.

Further, the power of the above-mentioned laser cladding is 4.0-8.0KW, the diameter of the spot of the laser cladding is preferably 20-25mm, the beam scanning speed of the laser cladding is preferably 100-180mm/min, and the flow rate is preferably 8-12L/min. min inert gas or nitrogen to protect the laser cladding process.

Further, in the above step S1, it is preferable that the average particle diameter of the titanium powder or the titanium alloy particle is independently 70 to 100 μm.

Further, the above-mentioned preparation method further includes: performing surface pretreatment on the base layer, preferably the process of surface pretreatment includes: performing grinding treatment on the base layer in turn to obtain a ground base layer; Sandblasting to obtain a matrix layer after sandblasting; acid etching the matrix layer after sandblasting, preferably the average particle size of the alumina particles is 350-500 μm, and the pressure of the sandblasting treatment is preferably 0.8-1.2MPa, preferably sandblasting The treatment time is 45 to 90s; preferably, the mixed acid of V(H ₂ O): V (sulfuric acid): V (hydrochloric acid)=20:8:4 is used for acid etching treatment, and the mass concentration of H ₂ SO ₄ in the sulfuric acid is 40-50%, the mass concentration of HCl in the hydrochloric acid is 30-40%, and the time of the acid etching treatment is preferably 90-120s.

By applying the technical solution of the present invention, the tantalum-coated orthopaedic implant material of the present application forms a transition layer between the base layer and the tantalum coating, thereby reducing the thermal stress between the tantalum coating and the base layer, The bonding force between the tantalum coating and the transition layer is improved; on the other hand, the porous structure of the tantalum coating provides space for the ingrowth of the bone tissue, which enhances the ingrowth of the bone, thereby improving the biocompatibility and the biocompatibility of the tantalum coating. Osteoconductivity, creating a microenvironment conducive to cell growth, which in turn promotes the growth of bone tissue into the porous tantalum coating to form a unique bone-implant interface, significantly enhancing the stability of tantalum-coated orthopedic implants in bone tissue performance and function, accelerated the osseointegration of the bone-implant interface, and in addition, the tantalum coating of the present application improved the osseointegration of its bone-implant interface only through the improvement of the tantalum coating structure, and by introducing Compared with the method for pretreating the tantalum coating by the non-tantalum material, the orthopaedic implant of the present application has lower production cost, less potential harm of the non-tantalum material, and has a better application prospect.

Description of drawings

The accompanying drawings forming a part of the present application are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the attached image:

Fig. 1 shows the scanning electron microscope photograph of the tantalum-coated acetabular cup provided in Example 1;

Fig. 2 shows the micro-nano structure diagram of the surface functional layer of the tantalum-coated acetabular cup provided in Example 1;

Figure 3 shows a cross-sectional view of the acetabular cup orthopaedic implant provided in Example 1; and

FIG. 4 shows a partial enlarged view at A of the cross-sectional view of FIG. 3 .

Wherein, the above-mentioned drawings include the following reference signs:

1. Base layer; 2. Acid etching layer; 3. Transition layer; 4. Tantalum coating.

Detailed ways

It should be noted that the embodiments in the present application and the features of the embodiments may be combined with each other in the case of no conflict. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

As analyzed in the background art, there are problems in the prior art that the tantalum-coated orthopaedic implant is difficult to manufacture, the manufacturing cost of the tantalum-coated orthopaedic implant is high, and in particular, it is difficult for bone tissue to grow into the tantalum-coated orthopaedic implant. In order to solve the problem that the bone tissue is difficult to grow into the tantalum-coated orthopaedic implant, the present invention provides a tantalum-coated orthopaedic implant material, a preparation method thereof, and an orthopaedic implant.

In a typical embodiment of the present application, a tantalum-coated orthopaedic implant material is provided, comprising a matrix layer, a transition layer, a tantalum coating and a tantalum surface functional layer stacked in sequence, and the matrix layer is titanium or For titanium alloys, the melting point of the transition layer is lower than that of tantalum, and the tantalum coating has a porous structure.

On the one hand, the tantalum-coated orthopaedic implant material of the present application forms a transition layer between the base layer and the tantalum coating, thereby reducing the thermal stress between the tantalum coating and the base layer, and improving the relationship between the tantalum coating and the transition layer. On the other hand, the porous structure of the tantalum coating provides space for the ingrowth of bone tissue, which enhances the ingrowth of the bone, thereby improving the biocompatibility and osteoconductivity of the tantalum coating. The microenvironment for cell growth, which in turn promotes the growth of bone tissue into the porous tantalum coating to form a unique bone-implant interface, which significantly enhances the stability and function of tantalum-coated orthopedic implants in bone tissue, and accelerates bone growth. - Osseointegration of the implant interface, in addition, the tantalum coating of the present application improves the osseointegration of its bone-implant interface only through the improvement of the tantalum coating structure, which is in contrast to the tantalum coating by introducing non-tantalum substances Compared with the method of pretreatment, the orthopaedic implant of the present application has low production cost, less potential harm of non-tantalum substances, and has better application prospects.

In an embodiment of the present application, the pore size of the tantalum coating is 10-30 μm, preferably the coating porosity of the tantalum coating is 30-80%, and the thickness of the tantalum coating is preferably 30-60 μm.

The tantalum coating with the above-mentioned pore size and porosity has more pores and larger specific surface area, which is more conducive to the ingrowth of bone tissue, and the preferred thickness of the tantalum coating helps to provide tantalum-coated orthopedic implants as much as possible The space for the tantalum-coated orthopedic implant to accommodate bone tissue is improved, and the stability and biocompatibility of the tantalum-coated orthopaedic implant in vivo are improved.

In an embodiment of the present application, the thickness of the transition layer is 90-180 μm.

On the one hand, the transition layer of the above thickness helps to bond as many tantalum particles as possible, and on the other hand, it is not easy to fall off from the base layer.

In order to further improve the biocompatibility of tantalum-coated orthopaedic implant materials, preferably the above-mentioned tantalum surface functional layer is nano-filament calcium tantalate, preferably the diameter of nano-filament calcium tantalate is 20-35nm, preferably nano-filament tantalum The length of calcium acid is ≤500nm.

In order to further improve the bonding strength of the tantalum-coated orthopaedic implant material, preferably the above-mentioned titanium alloy is selected from any one of Ti-6Al-4V, Ti-6Al-17Nb, Ti-13Nb-13Zr, Ti-5Zr-3Mo-15Nb. kind.

In order to better reduce the thermal stress between the tantalum coating and the base layer, the transition layer is preferably pure titanium or Ti-6Al-4V.

In a typical embodiment of the present application, there is provided a tantalum-coated orthopaedic implant comprising the aforementioned tantalum-coated orthopaedic implant material, and the tantalum-coated orthopaedic implant is an acetabular cup, an acetabular Either block or femoral stem.

The tantalum-coated orthopaedic implant material of the present application is beneficial to promote the growth of bone tissue into the porous tantalum coating to form a unique bone-implant interface, significantly enhancing the stability of the tantalum-coated orthopaedic implant in the bone tissue and Function, accelerates the osseointegration of the bone-implant interface, and has high corrosion resistance. The tantalum-coated orthopaedic implant material is used to prepare tantalum-coated orthopaedic implants with a certain structure, such as acetabular cups, acetabular replacement parts. Blocks or femoral stems, etc., can greatly improve the safety and effectiveness of orthopaedic implants in vivo and increase their service life.

When the orthopaedic implant is an acetabular cup, preferably the effective spherical outer diameter of the acetabular cup is 36-72 mm, preferably the acetabular height of the acetabular cup is 22-50 mm, and preferably the porosity of the tantalum coating is 30-30 mm 80%.

优选股骨柄的CT值为100～280mm，优选钽涂层的孔隙率为30～80％。When the orthopaedic implant is a femoral stem, the diameter of the stem body of the femoral stem is preferably

Preferably, the CT value of the femoral stem is 100-280 mm, and the porosity of the tantalum coating is preferably 30-80%.

In another typical embodiment of the present application, a preparation method of a tantalum-coated orthopaedic implant material is provided, the preparation method comprising sequentially forming a transition layer, a tantalum coating and a tantalum surface functional layer on a base layer, The formation process of the tantalum coating includes spraying the tantalum particles on the transition layer by means of laser cladding to form the tantalum coating, wherein the power of the laser cladding is less than or equal to 8.0KW.

The above technology combines traditional spraying technology and laser cladding technology, creatively uses laser cladding to melt the transition layer, and controls the laser cladding power to melt the transition layer, while the tantalum particles do not melt or partially melt, Thus, the tantalum particles are bonded on the molten titanium transition layer, on the one hand, the formation of the interstitial phase between tantalum and titanium is avoided, and the problem of high melting point of tantalum metal and difficulty in melting and spraying is solved. On the other hand, the formed tantalum coating has a porous structure, thereby providing space for the ingrowth of bone tissue, enhancing bone ingrowth, thereby improving the biocompatibility and osteoconductivity of the tantalum coating, resulting in favorable cell growth. It promotes the growth of bone tissue into the porous tantalum coating to form a unique bone-implant interface, significantly enhances the stability and function of orthopaedic implants in bone tissue, and accelerates the bone-implant interface. At the same time, through the hydrothermal reaction of tantalum coating with calcium salt and strong alkali solution, a tantalum-coated orthopaedic implant material with a tantalum surface functional layer is obtained, thereby further improving the tantalum-coated orthopaedic implant material. comprehensive performance. In addition, the above-mentioned preparation process is simple and the cost is low.

In order to further improve the preparation efficiency of the above transition layer, tantalum coating and tantalum surface functional layer, preferably the above preparation method includes: step S1, spraying titanium powder or titanium alloy particles on the base layer to form a transition layer; step S2, using a laser The cladding method sprays tantalum particles on the transition layer to form a tantalum coating; in step S3, hydrothermally reacts the tantalum coating with a calcium salt and a strong alkali solution to obtain a tantalum-coated orthopaedic implant material.

In order to improve the efficiency of the hydrothermal reaction of the above-mentioned step S3 of the present application, preferably the process of the above-mentioned hydrothermal reaction includes: immersing the material obtained in the step S2 in 0.2 mol/L calcium dihydrogen phosphate and 5 mol/L sodium hydroxide solution The hydrothermal reaction was continued for 24 hours at a temperature of 80 °C, and finally deionized water was ultrasonically cleaned to obtain a tantalum surface functional layer composed of nano-filament calcium carbonate. Of course, those skilled in the art can also perform the above-mentioned hydrothermal reaction with reference to the prior art, which is not repeated here.

In order to increase the porosity of the tantalum coating as much as possible, the sphericity of the tantalum particles is preferably 0.6-1, the average particle size of the tantalum particles is preferably 5-40 μm, and/or the D50 of the tantalum particles is 20-30 μm. Wherein, the tantalum particles with the above particle size can be obtained by sieving.

In an embodiment of the present application, the power of the above-mentioned laser cladding is 4.0-8.0KW, preferably the spot diameter of the laser cladding is 20-25mm, and the beam scanning speed of the laser cladding is preferably 100-180mm/min, preferably The laser cladding process is protected by an inert gas with a flow rate of 8-12 L/min. Preferably, the inert gas is nitrogen or argon. Considering the cost, nitrogen is further selected.

The above laser cladding conditions can control the transition layer to form a molten state as much as possible, while the tantalum particles are not melted or partially melted, so as to improve the adhesion stability of the porous tantalum coating as much as possible, and make the tantalum particles as much as possible. Low homogeneous adhesion to the molten transition layer, thereby enriching the porosity of the tantalum coating as much as possible.

In order that the obtained transition layer can reduce the thermal stress between the base layer and the tantalum coating layer as much as possible, preferably in step S1, the average particle size of the titanium powder or titanium alloy particles is independently 70-100 μm.

In an embodiment of the present application, the above preparation method further includes: performing surface pretreatment on the base layer, preferably, the process of surface pretreatment includes: sequentially grinding the base layer to obtain a ground base layer; using alumina particles Carry out sandblasting treatment on the base layer after grinding to obtain the base layer after sandblasting; carry out acid etching treatment on the base layer after sandblasting, preferably the average particle size of the alumina particles is 350-500 μm, and the pressure of the sandblasting treatment is preferably 0.8 ～1.2MPa, preferably the sandblasting time is 45～90s; it is preferable to use the mixed acid of V(H ₂ O): V (sulfuric acid): V (hydrochloric acid)=20:8:4 for acid etching treatment, H in the sulfuric acid The mass concentration of ₂ SO ₄ is 40-50%, the mass concentration of HCl in the hydrochloric acid is 30-40%, and the time of the acid etching treatment is preferably 90-120 s.

The above-mentioned pretreatment is beneficial to improve the surface roughness of the base layer of the present application, thereby facilitating the sandblasting treatment, in order to further improve the efficiency of the acid etching treatment. Preferably, the titanium alloy substrate is sanded with 200-mesh and 800-mesh sandpaper for 3 minutes, and then sanded with 1200-mesh sandpaper for 5 minutes; ultrasonically cleaned in acetone solution for 5-8 minutes; then ultrasonically cleaned with purified water for 5 minutes, and then dried for use. Of course, those skilled in the art can also adjust the specific conditions of the grinding process as needed, which will not be repeated here. The composition of the mixed acid and the time of the acid etching treatment are beneficial to control the degree of the acid etching treatment, thereby ensuring the roughness of the base layer and improving the bonding strength between the base layer and the transition layer.

The beneficial effects of the present application will be described below with reference to specific embodiments and comparative examples.

Example 1

The acetabular cup of Ti-6Al-4V was treated with tantalum coating, the effective spherical outer diameter of the acetabular cup was 52 mm, and the height of the acetabulum was 44 mm.

Surface pretreatment of the outer surface of the acetabular cup: the outer surface of the acetabular cup was sanded with 200-grit and 800-grit sandpaper for 3 min, and then polished with 1200-grit sandpaper for 5 min; and ultrasonically cleaned in acetone solution for 6 min; Ultrasonic cleaning with water for 5 min, and then blowing dry to obtain the polished base layer; sandblasting the polished acetabular cup base layer with alumina particles to obtain the sandblasted acetabular cup base layer; The cup base layer is acid-etched, the average particle size of alumina particles is 400 μm, the pressure of sandblasting is 1MPa, and the time of sandblasting is 60s; V(H ₂ O): V (sulfuric acid): V (hydrochloric acid) )=20:8:4 mixed acid for acid etching to obtain an acid etching layer, the mass concentration of _H2SO4 in sulfuric _acid is 50%, the mass concentration of HCl in hydrochloric acid is 36%, and the time for acid etching treatment is 100s .

The acid-etched acetabular cup is thermally sprayed with titanium powder to obtain a transition layer. The average particle size of the titanium powder selected for thermal spraying is 80 μm, and the thickness of the transition layer after thermal spraying is 110 μm.

Laser cladding tantalum coating on the acetabular cup after thermal spraying of titanium powder: the sphericity of tantalum particles is 0.8, and the average particle size of spherical tantalum particles is 28 μm (D50 of tantalum particles is 25 μm). The power of laser cladding is 5KW, the spot diameter is 22mm, the beam scanning speed of laser cladding is 110mm/min, and the process of laser cladding is protected by nitrogen gas with a flow rate of 9L/min, and the thickness of the tantalum coating is 40μm, An acetabular cup tantalum coating with a pore size of 16 μm and a porosity of 60%, the scanning electron microscope photograph of the tantalum coating of the acetabular cup is shown in FIG. 1 .

At a temperature of 80 °C, the acetabular cup tantalum coating was immersed in 0.2 mol/L calcium dihydrogen phosphate and 5 mol/L sodium hydroxide solution for 24 hours of hydrothermal reaction, and finally deionized water was used. Ultrasonic cleaning obtains the acetabular cup orthopaedic implant with the surface functional layer of nano-filament calcium tantalate (the diameter of this nano-filament calcium tantalate is 25 nm, and the length is 450 nm), and the micro-nano structure of this surface functional layer is such as: As shown in the scanning electron microscope photo of FIG. 2 , the sectional view of the acetabular cup orthopaedic implant is shown in FIG. 3 . It can be seen from FIG. 3 that the acetabular cup orthopaedic implant includes a base layer 1 , an acid etching layer 2 and a transition layer 3 , Tantalum coating 4, wherein the structure of the nano-filament calcium tantalate distributed in the tantalum coating 4 is a micro-nano structure, which needs to be observed under an electron microscope (as shown in Figure 2). As shown in FIG. 4 , it can be clearly seen from FIG. 4 that the tantalum coating has a porous structure.

Example 2

The difference between Example 2 and Example 1 is that,

The sphericity of the tantalum particles was 0.6, and the final acetabular cup orthopedic implant was obtained.

Example 3

The difference between Example 3 and Example 1 is that,

The tantalum particles have a sphericity of 1, and the final acetabular cup orthopaedic implant is obtained.

Example 4

The difference between Example 4 and Example 1 is that,

The sphericity of the tantalum particles was 0.5, and the final acetabular cup orthopedic implant was obtained.

Example 5

The difference between Example 5 and Example 1 is that,

The average particle size of the tantalum particles is 5 μm, and the D50 of the tantalum particles is 6 μm, and finally the acetabular cup orthopaedic implant is obtained.

Example 6

The difference between Example 6 and Example 1 is that,

The average particle size of the tantalum particles is 40 μm, and the D50 of the tantalum particles is 35 μm, and finally the acetabular cup orthopaedic implant is obtained.

Example 7

The difference between Example 7 and Example 1 is that,

The D50 of the tantalum particles is 20 μm, and the average particle size of the tantalum particles is 22 μm, and finally the acetabular cup orthopaedic implant is obtained.

Example 8

The difference between Example 8 and Example 1 is that,

The D50 of the tantalum particles is 30 μm, and the average particle size of the tantalum particles is 35 μm, and finally the acetabular cup orthopaedic implant is obtained.

Example 9

The difference between Example 9 and Example 1 is that,

The D50 of the tantalum particles is 15 μm, and the average particle size of the tantalum particles is 20 μm, and finally the acetabular cup orthopaedic implant is obtained.

Example 10

The difference between Example 10 and Example 1 is that,

The D50 of the tantalum particles is 35 μm, and the average particle size of the tantalum particles is 40 μm, and finally the acetabular cup orthopaedic implant is obtained.

Example 11

The difference between Example 11 and Example 1 is that,

The power of laser cladding is 4.0KW, the spot diameter of laser cladding is 20mm, the beam scanning speed of laser cladding is 100mm/min, and the process of laser cladding is protected by inert gas or nitrogen with a flow rate of 8L/min. The average particle size of the alumina particles is 350 μm, the pressure of sand blasting is 0.8 MPa, and the time of sand blasting is 45 s; finally, an acetabular cup orthopaedic implant is obtained.

Example 12

The difference between Example 12 and Example 1 is that,

The power of laser cladding is 8.0KW, the spot diameter of laser cladding is 25mm, the beam scanning speed of laser cladding is 180mm/min, and the process of laser cladding is protected by inert gas or nitrogen with a flow rate of 12L/min. The average particle size of the alumina particles is 500 μm, the pressure of sand blasting is 1.2 MPa, and the time of sand blasting is 90 s; finally, an acetabular cup orthopaedic implant is obtained.

Example 13

The difference between Example 13 and Example 1 is that,

The average particle size of the titanium powder selected for thermal spraying is 70 μm, and the acetabular cup orthopaedic implant is finally obtained.

Example 14

The difference between Example 14 and Example 1 is that,

The average particle size of the titanium powder selected for thermal spraying is 100 μm, and the acetabular cup orthopaedic implant is finally obtained.

Example 15

The difference between Example 15 and Example 1 is that,

The average particle size of the titanium powder selected for thermal spraying is 60 μm, and the acetabular cup orthopaedic implant is finally obtained.

Example 16

The difference between Example 16 and Example 1 is that,

The average particle size of the titanium powder selected for thermal spraying is 110 μm, and the acetabular cup orthopaedic implant is finally obtained.

Example 17

The difference between Example 17 and Example 1 is that,

The matrix layer is Ti-5Zr-3Mo-15Nb, and finally the acetabular cup orthopaedic implant is obtained.

Example 18

The difference between Example 18 and Example 1 is that the selected titanium alloy material is Ti-5Zr-3Mo-15Nb, and the product is a femoral stem.

股骨柄的CT值为160mm。The Ti-5Zr-3Mo-15Nb femoral stem is treated with tantalum coating, and the stem diameter of the femoral stem is

The CT value of the femoral stem was 160 mm.

Surface pretreatment on the outer surface of the femoral stem: the outer surface of the femoral stem was sanded with 200-mesh, 800-mesh sandpaper for 3 minutes, then 1200-grit sandpaper for 5 minutes; and ultrasonically cleaned in acetone solution for 6 minutes; then ultrasonicated with pure water Wash for 5 minutes, and then blow dry to obtain the ground base layer; use alumina particles to sandblast the ground femoral stem base layer to obtain the sandblasted femoral stem base layer; Acid etching treatment, the average particle size of alumina particles is 400μm, the pressure of sandblasting treatment is 1MPa, and the time of sandblasting treatment is 60s; V (H ₂ O): V (sulfuric acid): V (hydrochloric acid) = 20: 8:4 mixed acid is subjected to acid etching treatment to obtain an acid etching layer, the mass concentration of _H2SO4 in sulfuric _acid is 50%, the mass concentration of HCl in hydrochloric acid is 36%, and the acid etching treatment time is 100s.

The titanium powder was thermally sprayed on the acid-etched femoral stem to obtain a transition layer. The average particle size of the titanium powder selected for thermal spraying was 80 μm, and the thickness of the transition layer after thermal spraying was 110 μm.

Laser cladding tantalum coating on the femoral stem after thermal spraying of titanium powder: the sphericity of tantalum particles is 0.8, and the average particle size of spherical tantalum particles is 28 μm (D50 of tantalum particles is 25 μm). The power of laser cladding is 5KW, the spot diameter is 22mm, the beam scanning speed of laser cladding is 110mm/min, and the process of laser cladding is protected by nitrogen gas with a flow rate of 9L/min, and the thickness of the tantalum coating is 40μm, Femoral stem tantalum coating with a pore size of 16 μm and a porosity of 60%.

At a temperature of 80 °C, the tantalum coating of the femoral stem was immersed in 0.2 mol/L calcium dihydrogen phosphate and 5 mol/L sodium hydroxide solution for 24 hours of hydrothermal reaction, and finally deionized water was used. Ultrasonic cleaning was performed to obtain a femoral stem orthopaedic implant with a surface functional layer of nano-filament calcium tantalate (the nano-filament calcium tantalate has a diameter of 25 nm and a length of 450 nm).

Comparative Example 1

The difference between Comparative Example 1 and Example 1 is that,

The power of laser cladding is 8.5KW, and finally the acetabular cup orthopaedic implant is obtained.

According to YY/T 0988.14-2016, the pore sizes of the tantalum coatings of the orthopaedic implants obtained in the above-mentioned Examples 1 to 18 and Comparative Example 1 were tested respectively, and the above-mentioned Examples 1 to 18 and Comparative Example 1 were obtained by scanning electron microscopy. The coating porosity, the thickness of the tantalum coating and the thickness of the transition layer of the tantalum coating of the orthopedic implants, and the test results are listed in Table 1.

Table 1

As can be seen from the above Table 1, compared with the examples, the acetabular cup orthopaedic implant obtained in Comparative Example 1 is easy to fall off from the bone tissue, thereby shortening the service life of the acetabular cup orthopaedic implant.

From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects:

On the one hand, the tantalum-coated orthopaedic implant material of the present application forms a transition layer between the base layer and the tantalum coating, thereby reducing the thermal stress between the tantalum coating and the base layer, and improving the relationship between the tantalum coating and the transition layer. On the other hand, the porous structure of the tantalum coating provides space for the ingrowth of bone tissue, which enhances the ingrowth of the bone, thereby improving the biocompatibility and osteoconductivity of the tantalum coating. The microenvironment for cell growth, which in turn promotes the growth of bone tissue into the porous tantalum coating to form a unique bone-implant interface, which significantly enhances the stability and function of tantalum-coated orthopedic implants in bone tissue, and accelerates bone growth. - Osseointegration of the implant interface, in addition, the tantalum coating of the present application improves the osseointegration of its bone-implant interface only through the improvement of the tantalum coating structure, which is in contrast to the tantalum coating by introducing non-tantalum substances Compared with the method of pretreatment, the orthopaedic implant of the present application has low production cost, less potential harm of non-tantalum substances, and has better application prospects.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (20)

1. a tantalum coating orthopaedic implant material, comprising a matrix layer, a transition layer, a tantalum coating and a tantalum surface functional layer stacked successively, it is characterized in that, the formation process of the described tantalum coating comprises adopting laser cladding. The method sprays tantalum particles on the transition layer, the base layer is titanium or a titanium alloy, the melting point of the transition layer is lower than the melting point of tantalum, the tantalum coating has a porous structure, and the pore diameter of the tantalum coating is The size is 10-30 μm, the coating porosity of the tantalum coating is 30-80%; the thickness of the transition layer is 90-180 μm, and the sphericity of the tantalum particles in the tantalum coating is 0.6-1, so the thickness of the transition layer is 90-180 μm. The average particle size of the tantalum particles is 5-40 μm, and the D50 of the tantalum particles is 20-30 μm. 2 . The tantalum-coated orthopaedic implant material according to claim 1 , wherein the thickness of the tantalum coating is 30-60 μm. 3 . 3. The tantalum-coated orthopaedic implant material according to claim 1 or 2, wherein the tantalum surface functional layer is nano-filament calcium tantalate. 4 . The tantalum-coated orthopaedic implant material according to claim 3 , wherein the nano-filament calcium tantalate has a diameter of 20-35 nm. 5 . 5 . The tantalum-coated orthopaedic implant material according to claim 4 , wherein the length of the nano-filament calcium tantalate is less than or equal to 500 nm. 6 . 6. The tantalum-coated orthopaedic implant material according to claim 1, wherein the titanium alloy is selected from the group consisting of Ti-6Al-4V, Ti-6Al-17Nb, Ti-13Nb-13Zr, Ti-5Zr-3Mo Any of -15Nb. 7 . The tantalum-coated orthopaedic implant material according to claim 1 , wherein the transition layer is pure titanium or Ti-6Al-4V. 8 . 8. A tantalum-coated orthopaedic implant comprising the tantalum-coated orthopaedic implant material according to any one of claims 1 to 7, wherein the tantalum-coated orthopaedic implant is an acetabular cup, Either acetabular patch or femoral stem. 9. A preparation method of the tantalum-coated orthopaedic implant material according to any one of claims 1 to 7, the preparation method comprising sequentially forming a transition layer, a tantalum coating and a tantalum surface functional layer on the base layer, wherein It is characterized in that, the formation process of the tantalum coating includes using a laser cladding method to spray tantalum particles on the transition layer to form a tantalum coating, wherein the power of the laser cladding is less than or equal to 8.0KW, so The sphericity of the tantalum particles is 0.6-1, the average particle size of the tantalum particles is 5-40 μm, and the D50 of the tantalum particles is 20-30 μm. 10. preparation method according to claim 9, is characterized in that, described preparation method comprises: Step S1, spraying titanium powder or titanium alloy particles on the base layer to form the transition layer; Step S2, using the laser cladding method to spray tantalum particles on the transition layer to form the tantalum coating; Step S3, hydrothermally react the tantalum coating with a calcium salt and a strong alkali solution to obtain the tantalum-coated orthopaedic implant material. 11. The preparation method according to claim 9 or 10, wherein the power of the laser cladding is 4.0-8.0 KW. 12 . The preparation method according to claim 11 , wherein the diameter of the light spot of the laser cladding is 20-25 mm. 13 . 13 . The preparation method according to claim 12 , wherein the beam scanning speed of the laser cladding is 100-180 mm/min. 14 . 14 . The preparation method according to claim 13 , wherein the laser cladding process is protected by using an inert gas or nitrogen with a flow rate of 8 to 12 L/min. 15 . 15 . The preparation method according to claim 10 , wherein, in the step S1 , the average particle size of the titanium powder or the titanium alloy particles is independently 70 to 100 μm. 16 . 16. preparation method according to claim 9 or 10, is characterized in that, described preparation method also comprises: Surface pretreatment is performed on the base layer. 17. The preparation method according to claim 16, wherein the process of the surface pretreatment comprises: Carrying out grinding treatment on the base layer in turn to obtain a ground base layer; Sandblasting is performed on the ground base layer by using alumina particles to obtain a sandblasted base layer; Acid etching is performed on the sandblasted base layer, and the average particle size of the alumina particles is 350-500 μm. 18. The preparation method according to claim 17, wherein the pressure of the sandblasting treatment is 0.8-1.2 MPa. 19. preparation method according to claim 18, is characterized in that, the time of described sandblasting is 45～90s; Adopt the mixed acid that volume ratio is H ₂ O:sulfuric acid:hydrochloric acid=20:8:4 to carry out the process. In the acid etching treatment, the mass concentration of H ₂ SO ₄ in the sulfuric acid is 40-50%, and the mass concentration of HCl in the hydrochloric acid is 30-40%. 20 . The preparation method according to claim 19 , wherein the time of the acid etching treatment is 90 to 120 s. 21 .

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