CN108705092B - 3D printing in-situ rare earth doped titanium-based composite material active bone implant and forming method - Google Patents

3D printing in-situ rare earth doped titanium-based composite material active bone implant and forming method Download PDF

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CN108705092B
CN108705092B CN201810620394.9A CN201810620394A CN108705092B CN 108705092 B CN108705092 B CN 108705092B CN 201810620394 A CN201810620394 A CN 201810620394A CN 108705092 B CN108705092 B CN 108705092B
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rare earth
powder
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bone implant
printing
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CN108705092A (en
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夏木建
林岳宾
刘爱辉
李年莲
丁红燕
丁钲炜
陈中
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Huaiyin Institute of Technology
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Abstract

The invention discloses a 3D printing in-situ rare earth doped titanium-based composite material active bone implant, which comprises in-situ rare earth Re2O3In-situ rare earth doped titanium-based composite material formed by in-situ TiB ceramic phase and hydroxyapatite ceramic phase. The preparation method comprises the following steps: b is to be2O3Ball-milling and mixing the powder and the rare earth Re powder by adopting a high-energy ball-milling process protected by inert gas to obtain B2O3A Re mixed powder; weighing B2O3The method comprises the following steps of (1) obtaining titanium alloy composite material powder by adopting/Re mixed powder, hydroxyapatite powder, special spherical titanium alloy powder for 3D printing and a low-energy ball milling process under the auxiliary protection of inert gas; in-situ rare earth Re is formed by laser 3D printing under argon atmosphere2O3In-situ TiB ceramic and hydroxyapatite ceramic reinforced titanium-based composite material active bone implant. The method improves the service performance of the titanium alloy bone implant by in-situ doping of the rare earth, and can realize the precise manufacture of the high-performance complex-structure titanium alloy active bone implant.

Description

3D printing in-situ rare earth doped titanium-based composite material active bone implant and forming method
Technical Field
The invention belongs to the field of medical instrument manufacturing, relates to a novel titanium alloy active bone implant and a forming method, and particularly relates to a 3D printing in-situ rare earth doping reinforced titanium-based composite active bone implant and a forming method.
Background
In recent years, the repair and replacement of bone tissue defects are rapidly increased due to the increasing of human tissue loss or dysfunction caused by the aging of social population, traffic accidents and the like in China. Compared with medical metal materials such as stainless steel, cobalt-chromium alloy and the like, the titanium alloy has the advantages of better mechanical property, good corrosion resistance, excellent biocompatibility and the like, and becomes an ideal metal material for clinically applied artificial bone implants. The ideal biomedical implant material has good biomechanical compatibility, namely the strength and the density of the implant material are close to those of self tissues, meanwhile, the implant material has good biocompatibility, has no rejection reaction with the original tissues, has excellent bioactivity, and can promote and induce the attachment and the growth of new bones. However, titanium alloy is an inert material, the bioactivity of titanium alloy is not ideal enough, the growth of new bone and the differentiation of osteoblast cannot be promoted, and the titanium alloy and human bone tissue are only mechanically embedded and connected, and the growth of human defect bone tissue cannot be induced. The hydroxyapatite is the main component of human skeleton, has good biocompatibility and activity, can be combined with human bone tissue and induce the growth and formation of new bone, and is an ideal hard tissue substitute material. The titanium/hydroxyapatite composite material prepared by the Wang moon et al through powder sintering can obviously improve the bioactivity of the titanium alloy bone implant.
However, hydroxyapatite is unstable at high temperature and has poor sintering property with titanium alloy powder, resulting in a decrease in fracture toughness and strength, and thus being limitedMaking its application in bearing site bone replacement. The rare earth oxide can be used as the core of nucleation because the tiny solid particles can increase the solidification and nucleation rate and enhance the effect of refining grains, thereby being widely used for improving and enhancing the mechanical property of hydroxyapatite materials. In the prior art, rare earth oxide is mainly added into hydroxyapatite and a composite material coating thereof by a direct addition method so as to improve the performance of titanium alloy and hydroxyapatite. For example, Zhang Asia et al found a small amount of Y2O3The stability of the hydroxyapatite structure can be increased. Liu bin etc. to transform Y2O3、CeO2、La2O3And the rare earth oxide is directly added into the hydroxyapatite coating to obtain good biological activity and osteogenic property. Therefore, the rare earth oxide can improve the forming performance of the hydroxyapatite and enhance the biological activity of the hydroxyapatite, and is a good reinforcing agent.
At present, the prior direct addition method has the following defects: (1) because the rare earth oxide belongs to a ceramic material, the rare earth oxide is difficult to promote to form a good metallurgical bonding interface with matrix titanium alloy and hydroxyapatite, so that the mechanical property of the rare earth oxide is reduced; (2) the space structure of the titanium alloy artificial bone implant is greatly different due to the age, sex and disease condition difference of patients, meanwhile, the space structure of the artificial bone implant is very complex, especially for hip joints, knee joints and the like, and the traditional process method is difficult to realize the precise manufacture of the rare earth reinforced titanium alloy active implant.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a 3D printing in-situ rare earth doping reinforced titanium-based composite active bone implant and a forming method of the 3D printing in-situ rare earth doping reinforced titanium-based composite active bone implant, aiming at the problems of the existing rare earth reinforced artificial titanium alloy active implant.
The laser 3D printing method is a manufacturing mode of channel-by-channel and layer-by-layer based on the principle of additive manufacturing, can disperse a complex structural member into a series of thin two-dimensional sections (the thickness is usually less than 100 mu m), and realizes the precise manufacturing. Compared with the traditional process method, the laser 3D printing has the characteristics of intellectualization, no modeling and flexible manufacturing, the utilization rate of materials is improved, the follow-up complex post-processing process is not needed, and the manufacturing period is short. The process method provides an effective way for the precise manufacture of the titanium alloy artificial bone implant with a complex structure.
The technical scheme is as follows: the 3D printing in-situ rare earth doped titanium-based composite active bone implant comprises in-situ rare earth Re2O3In-situ rare earth doped titanium-based composite material formed by in-situ TiB ceramic phase and hydroxyapatite ceramic phase. The implant is in-situ rare earth Re2O3An in-situ TiB ceramic phase and a hydroxyapatite ceramic phase.
Preferably, the in-situ rare earth Re2O3And in-situ TiB ceramic phase passing through B2O3The powder, the Re powder and the special spherical titanium alloy powder for 3D printing are subjected to 2Ti + B treatment under the action of a high-energy laser beam of 250-450J/m2O3+2Re→2TiB+Re2O3Formed by in situ reaction.
The invention relates to a forming method of a 3D printing in-situ rare earth doped titanium-based composite active bone implant, which comprises the following steps:
(1) mixing a certain mass ratio of B2O3Ball-milling and mixing the powder and the rare earth Re powder by adopting a high-energy ball-milling process under the protection of argon and at the rotating speed of 250-400 rpm to obtain metallurgically bonded B2O3A Re mixed powder;
(2) weighing B in a certain mass ratio2O3The preparation method comprises the following steps of (1) obtaining titanium alloy composite material powder with good fluidity by adopting a ball-free wet low-energy ball milling process with the rotation speed of 50-150 rpm under the auxiliary protection of argon gas, wherein the ball-free wet low-energy ball milling process is used for the/Re mixed powder, the hydroxyapatite powder and the special spherical titanium alloy powder for 3D printing;
(3) forming in-situ rare earth Re by utilizing a laser 3D printing process in a high-purity argon environment2O3The titanium-based composite material active bone implant reinforced by the in-situ TiB ceramic phase and the hydroxyapatite ceramic phase.
Among them, in the above step (1), it is preferable to useB2O3The purity of the powder is better than 99.5%, the particle size is 1-30 mu m, the purity of the rare earth Re powder is better than 99.0%, the particle size is 1-30 mu m, and the rare earth Re is one of Nd, Ce and La;
further, B is2O3The mass ratio of the powder to the rare earth Re powder is 1: 2-1: 5.
Preferably, in the step (2), the spherical titanium alloy is pure Ti, Ti-Ni, Ti-Zr or Ti-Al;
further, B is2O3The mass ratio of the/Re mixed powder to the hydroxyapatite powder to the spherical titanium alloy powder special for 3D printing is 5:1: 20-2: 1: 500.
Further, in the step (3), the laser 3D printing forming process conditions are preferably: under the action of a high-energy laser beam with the laser energy density of 250-450J/m, a partition scanning mode is adopted, and the size of each partition is 1 multiplied by 1-8 multiplied by 8mm2The stacking fault increment is 30-45 degrees.
The invention principle is as follows: the forming method of the 3D printing in-situ rare earth doping titanium-based composite material active bone implant takes the improvement of the interface characteristic of hydroxyapatite and rare earth oxide in the artificial titanium alloy active bone implant and the precise manufacture of the artificial titanium alloy active bone implant with a functional complex structure as a foothold, and is based on the rapid non-equilibrium melting/solidification characteristic of multi-field coupling of laser 3D printing, high-energy laser and titanium alloy/B2O3In-situ reaction thermodynamic conditions among rare earth elements, a precise forming geometric structure is more complex, and the active bone implant is provided with an in-situ rare earth doped titanium-based composite material.
Has the advantages that: compared with the prior art, the invention has the beneficial effects that:
(1) the 3D-printed in-situ rare earth-doped titanium-based composite active bone implant disclosed by the invention has the characteristic that the bioactivity of hydroxyapatite can be remarkably improved based on rare earth oxide according to high-energy laser and titanium alloy/B2O3In-situ reaction thermodynamic conditions among rare earth elements, a laser 3D printing technology is adopted to form a rare earth oxide/hydroxyapatite interface with metallurgical bonding characteristics, and comprehensive clothes of the titanium alloy active bone implant are obviously enhancedService performance; on the other hand, the rare earth oxide generated in situ provides nucleation particles for the solidification of the titanium-based composite material, further refines the solidification tissue of the titanium-based composite material, and effectively improves the comprehensive mechanical property of the active bone implant of the titanium-based composite material.
(2) The 3D printing in-situ rare earth doped titanium-based composite active bone implant is based on 2Ti + B2O3+2Re→2TiB+Re2O3The TiB ceramic phase formed by the in-situ reaction also has a good strengthening function, and can effectively improve the mechanical property of the titanium-based composite material active bone implant; meanwhile, the rapid nonequilibrium melting/solidification characteristic of laser 3D printing multi-field coupling is easy to cause large temperature gradient, high solidification speed and the like in the forming process of the titanium-based composite material, so that the solidification structure is fine, and the fine grain strengthening effect is obvious.
(3) The forming method provided by the invention is based on the forming performance and the biological activity of the hydroxyapatite, the biological characteristics of the rare earth oxide and 2Ti + B2O3+2Re→2TiB+Re2O3In-situ reaction thermodynamic conditions and non-equilibrium forming characteristics of laser 3D printing multi-field coupling are adopted, the active bone implant made of the in-situ rare earth doped titanium-based composite material is formed by utilizing a laser 3D printing technology, and the integrated manufacturing of the artificial titanium alloy active bone implant with the high-performance complex structure is realized.
Drawings
Fig. 1 is a microstructure topography of the 3D printed in situ rare earth doped titanium matrix composite active bone implant prepared in example 1.
Fig. 2 is a graph of the room temperature tensile strength of the 3D printed in-situ rare earth doped titanium-based composite active bone implant prepared in example 2.
Fig. 3 is a fracture morphology diagram of the 3D-printed in-situ rare earth-doped titanium-based composite active bone implant prepared in example 3.
Fig. 4 is a graph of fracture toughness of the 3D-printed in-situ rare earth-doped titanium-based composite active bone implant prepared in examples 4 to 6.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The invention relates to an active bone implant made of in-situ rare earth doped titanium-based composite material through 3D printing, which is an in-situ rare earth Re2O3Phase, in-situ TiB ceramic phase and hydroxyapatite ceramic phase reinforced active titanium alloy matrix; wherein, in-situ rare earth Re2O3Phase and in situ TiB ceramic phase passing through B2O3The powder, the Re powder and the special spherical titanium alloy powder for 3D printing are synthesized in situ under the action of high-energy laser beams.
The invention is based on the forming performance and the biological activity of the hydroxyapatite, the biological characteristics of the rare earth oxide, 2Ti + B2O3+2Re→2TiB+Re2O3In-situ reaction thermodynamic conditions and non-equilibrium forming characteristics of laser 3D printing multi-field coupling, by means of a laser 3D printing technology, an in-situ rare earth doped titanium-based composite material active bone implant with a metallurgical bonding characteristic, a rare earth oxide/hydroxyapatite interface, tissue refinement and a complex structure is formed, and the comprehensive service performance of the titanium alloy active bone implant can be remarkably improved.
The following examples all use commercially available B2O3The purity of the powder is better than 99.5%, the particle size is 1-30 mu m, the purity of the rare earth Re powder is better than 99.0%, the particle size is 1-30 mu m, and hydroxyapatite powder is used as an experimental raw material.
Example 1
(1) B with the mass ratio of 1:22O3Ball-milling and mixing the powder and the rare earth Nd powder by adopting a high-energy ball-milling process with the rotation speed of 250rpm under the protection of argon gas to obtain B with metallurgical bonding2O3a/Nd mixed powder;
(2) weighing B with the mass ratio of 5:1:202O3The preparation method comprises the following steps of (1) obtaining titanium alloy composite material powder with good fluidity by adopting a ball-free wet low-energy ball milling process with the rotation speed of 50rpm under the auxiliary protection of argon gas, wherein the ball-free wet low-energy ball milling process comprises the following steps of mixing Nd mixed powder, hydroxyapatite powder and special spherical pure Ti powder for 3D printing;
(3) under the protection of high-purity argon, a laser 3D printing process is utilized, and the partition size is set to be 1 multiplied by 1mm2The stacking fault increment is 30 degrees, and the 3D printing in-situ rare earth in-situ doping is formed by adopting the laser energy density of 250J/mA hybrid reinforced titanium-based composite active bone implant.
FIG. 1 is a microstructure topography of a 3D printed in situ rare earth doped titanium matrix composite active bone implant made in example 1, from which Nd can be found2O3The rare earth oxide phase, the hydroxyapatite phase and the titanium alloy matrix have good interface bonding without obvious gaps and cracks, and meanwhile, the small-size white point-shaped particles are TiB ceramic phase and are uniformly dispersed on the titanium alloy bone implant matrix.
Example 2
A 3D printed in situ rare earth in situ doped reinforced titanium matrix composite active bone implant made with reference to the forming method of example 1, except that: in the step (1) of the embodiment, the rotation speed of the high-energy ball mill is adjusted to 300 rpm; in the step (2), the ball-free wet low-energy rotating speed is set to be 100rpm, and B2O3The mass ratio of the/Nd mixed powder to the hydroxyapatite powder to the spherical pure Ti powder special for 3D printing is set to be 3:1: 25; adjusting the size of the laser scanning subarea in the step (3) to be 4 multiplied by 4mm2The laser fluence was adjusted to 300J/m.
Fig. 2 is a graph of the tensile strength at room temperature of the 3D-printed in-situ rare earth-doped titanium-based composite active bone implant prepared in example 2, and it can be found that the strength of the rare earth-doped titanium-based composite active bone implant reaches 1102.50MPa, and the elongation reaches 19.04%, which indicates that the strength and the plasticity of the active bone implant are both significantly improved and are much higher than the strength (860.10MPa) and the elongation (8.05%) of the existing Ti/HA composite.
Example 3
A 3D printed in situ rare earth in situ doped reinforced titanium matrix composite active bone implant made with reference to the forming method of example 2, except that: in this example, in step (1), the rare earth element was Ce and B2O3Adjusting the mass ratio of the powder to the rare earth Ce powder to be 1:3, and adjusting the rotating speed of the high-energy ball mill to be 400 rpm; setting the titanium alloy in the step (2) as a Ti-Ni alloy; adjusting the size of the laser scanning subarea in the step (3) to be 5 multiplied by 5mm2The stacking fault increment was 35 °.
Fig. 3 is a fracture morphology diagram of the 3D-printed in-situ rare earth-doped titanium-based composite active bone implant prepared in example 3, and it is obvious that tensile fracture morphologies are all tough-fossilized, which indicates that the in-situ rare earth oxide and TiB ceramic phase significantly improve the mechanical properties of the hydroxyapatite/titanium alloy composite.
Example 4
A 3D printed in situ rare earth in situ doped reinforced titanium matrix composite active bone implant made with reference to the forming method of example 3, except that: this example, step (1) was carried out by selecting La as the rare earth element and B as the rare earth element2O3The mass ratio of the powder to the rare earth La powder is adjusted to 1: 5; setting the ball-free wet low-energy rotating speed to be 150rpm in the step (2), setting the titanium alloy to be Ti-Zr alloy, and setting B2O3The mass ratio of the/La mixed powder to the hydroxyapatite powder to the spherical Ti-Zr alloy powder special for 3D printing is set to be 5:1: 20.
Example 5
A 3D printed in situ rare earth in situ doped reinforced titanium matrix composite active bone implant made with reference to the forming method of example 4, except that: in the step (1) of the embodiment, the high-energy ball milling speed is adjusted to 350 rpm; setting the ball-free wet low-energy rotating speed to be 120rpm in the step (2), selecting the rare earth element to be Nd, and setting B in the step (2)2O3The mass ratio of the/Nd mixed powder to the hydroxyapatite powder to the spherical Ti-Zr alloy powder special for 3D printing is set to be 3:1: 250; adjusting the size of the laser scanning subarea in the step (3) to 8 multiplied by 8mm2。
Example 6
A 3D printed in situ rare earth in situ doped reinforced titanium matrix composite active bone implant made with reference to the forming method of example 5, except that: in the step (1) of this example, the titanium alloy was set to be a Ti-Al alloy; in the step (2), B is added2O3The mass ratio of the Re mixed powder to the hydroxyapatite powder to the spherical titanium alloy powder special for 3D printing is adjusted to be 2:1: 500; and (4) setting the increment of the laser scanning stacking fault in the step (3) to be 45 degrees, and setting the laser energy density to be 450J/m.
FIG. 4 is a graph of fracture toughness of the 3D-printed in-situ rare earth-doped titanium-based composite active bone implant prepared in examples 4 to 6, and it can be found that the fracture toughness is 6.62MPa respectively/m2、8.15MPa/m2And 9.98MPa/m2The fracture toughness (3.5 MPa/m) of the composite material is obviously higher than that of the existing Ti/HA composite material2) Therefore, the 3D printing in-situ rare earth doped titanium-based composite active bone implant provided by the invention can obviously improve the metallurgical characteristics of the composite interface and can also improve the comprehensive mechanical properties of the implant, such as strength, toughness and the like.

Claims (9)

1. A3D printed in-situ rare earth doped titanium-based composite active bone implant is characterized in that the implant comprises in-situ rare earth Re2O3In-situ rare earth doped titanium-based composite material formed by in-situ TiB ceramic phase and hydroxyapatite ceramic phase, and in-situ rare earth Re2O3And in-situ TiB ceramic phase passing through B2O3The powder, the Re powder and the special spherical titanium alloy powder for 3D printing are synthesized in situ under the action of a high-energy laser beam with the laser energy density of 250-450J/m, and the forming method of the 3D printing in-situ rare earth doped titanium-based composite material active bone implant comprises the following steps:
(1) mixing B in a certain weight ratio2O3Ball-milling and mixing the powder and the rare earth Re powder by adopting a high-energy ball-milling process with the rotation speed of 250-400 rpm under the protection of argon gas to obtain B with metallurgical bonding2O3A Re mixed powder;
(2) weighing B in a certain mass ratio2O3The preparation method comprises the following steps of (1) obtaining titanium alloy composite material powder by adopting a ball-free wet low-energy ball milling process with the rotation speed of 50-150 rpm under the auxiliary protection of argon gas, wherein the ball-free wet low-energy ball milling process comprises the steps of mixing Re mixed powder, hydroxyapatite powder and special spherical titanium alloy powder for 3D printing;
(3) under the environment of high-purity argon, titanium alloy composite material powder is formed by utilizing a laser 3D printing process to obtain in-situ rare earth Re2O3The titanium-based composite material active bone implant reinforced by the in-situ TiB ceramic phase and the hydroxyapatite ceramic phase.
2. The method for forming the 3D printed in situ rare earth doped titanium matrix composite active bone implant according to claim 1, comprising the steps of:
(1) mixing B in a certain weight ratio2O3Ball-milling and mixing the powder and the rare earth Re powder by adopting a high-energy ball-milling process with the rotation speed of 250-400 rpm under the protection of argon gas to obtain B with metallurgical bonding2O3A Re mixed powder;
(2) weighing B in a certain mass ratio2O3The preparation method comprises the following steps of (1) obtaining titanium alloy composite material powder by adopting a ball-free wet low-energy ball milling process with the rotation speed of 50-150 rpm under the auxiliary protection of argon gas, wherein the ball-free wet low-energy ball milling process comprises the steps of mixing Re mixed powder, hydroxyapatite powder and special spherical titanium alloy powder for 3D printing;
(3) under the environment of high-purity argon, titanium alloy composite material powder is formed by utilizing a laser 3D printing process to obtain in-situ rare earth Re2O3The titanium-based composite material active bone implant reinforced by the in-situ TiB ceramic phase and the hydroxyapatite ceramic phase.
3. The method for forming an in situ rare earth doped titanium matrix composite active bone implant according to claim 2, wherein in step (1), B is2O3The purity of the powder is better than 99.5%, and the particle size is 1-30 μm.
4. The forming method for the 3D printing in-situ rare earth doped titanium-based composite active bone implant according to the claim 2, characterized in that in the step (1), the purity of the rare earth Re powder is better than 99.0%, and the particle size is 1-30 μm.
5. The method for forming the 3D printed in-situ rare earth doped titanium-based composite active bone implant according to claim 2, wherein in the step (1), the rare earth Re is one of Nd, Ce and La.
6. The method for forming an in situ rare earth doped titanium matrix composite active bone implant according to claim 2, wherein in step (1), B is2O3Powder and rare earth Re powderThe weight ratio of the powder is 1: 2-1: 5.
7. The method for forming an in situ rare earth doped titanium matrix composite active bone implant according to claim 2, wherein in step (2), the spherical titanium alloy is one of pure Ti, Ti-Ni, Ti-Zr or Ti-Al.
8. The method for forming an in situ rare earth doped titanium matrix composite active bone implant according to claim 2, wherein in step (2), B is2O3The mass ratio of the/Re mixed powder to the hydroxyapatite powder to the spherical titanium alloy powder special for 3D printing is 5:1: 20-2: 1: 500.
9. The forming method of the 3D printing in-situ rare earth doped titanium-based composite active bone implant according to claim 2, wherein in the step (3), the laser 3D printing forming process adopts a partition scanning mode under the action of a high-energy laser beam with the laser energy density of 250-450J/m, and the partition size is 1 x 1-8 x 8mm2The stacking fault increment is 30-45 degrees.
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