CN114932225B - Medical 3D printing nickel-titanium-based composite powder, preparation method and composite reinforced material - Google Patents
Medical 3D printing nickel-titanium-based composite powder, preparation method and composite reinforced material Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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Abstract
The invention discloses medical 3D printing nickel-titanium-based composite powder, a preparation method and a composite reinforcing material. In the preparation process, the carbon nano tube is treated by acid, so that the carbon nano tube and nickel-titanium alloy particles have an electrostatic adsorption effect, and the carbon nano tube stacking agglomeration, structural damage and sphericity reduction caused by mechanical composite powder preparation are effectively avoided; during laser 3D printing forming, the TiC ceramic reinforcement is synthesized by burning the carbon nano tube and the nickel-titanium alloy melt, so that the composite material has excellent biocompatibility and tribological property, and the service life of the medical artificial implant can be prolonged.
Description
Technical Field
The invention belongs to the field of materials, relates to a laser 3D printing powder preparation technology, and in particular relates to medical 3D printing nickel-titanium-based composite powder, a preparation method and a composite reinforced material.
Background
The nickel-titanium shape memory alloy has excellent shape memory function and superelastic effect, can automatically recover plastic deformation of the nickel-titanium shape memory alloy to an initial state before loading at a certain specific temperature, has corrosion resistance superior to medical stainless steel materials, has multiple characteristics of biocompatibility, high damping and the like, can effectively meet clinical needs, and is one of intelligent materials most widely applied in the medical field. Surgical implants made of medical nitinol have been actively used for clinical treatment, such as covered vascular stents, esophageal stents, bone anchors, and heart occluders. However, when implanted in a patient for long periods of time or even permanently, it is prone to inflammation of surrounding tissue and aseptic loosening of the prosthesis due to its poor bio-tribological properties, further resulting in reduced service life of medical devices and surgical implants.
At present, the functional requirements and structural design of medical nickel-titanium alloy implants are more complex, and most of the medical nickel-titanium alloy implants need to be customized in a personalized way by combining individual characteristics of patients, and the medical nickel-titanium alloy implants are machined after being formed by a traditional casting, forging and pressing die, so that the medical nickel-titanium alloy implants have various disadvantages of long production period, low material utilization rate, high manufacturing cost and the like. The laser 3D printing technology can convert the three-dimensional medical implant into rapid layer-by-layer accumulation in a two-dimensional plane after modeling and layering slicing in sequence, has extremely high customization degree of freedom, omits post-treatment processes such as die manufacturing, machining connection and the like, and can realize the integration of material preparation and structure forming of the precise medical instrument. Meanwhile, the recycling of raw materials is realized, so that manufacturing loss and medical cost required by customization of patients are reduced.
When the medical nickel-titanium alloy is modified by introducing the carbon nano tube, the implantation performance of the medical nickel-titanium alloy can be improved to a certain extent due to the excellent friction and biocompatibility of the carbon nano tube, and the early failure of the medical nickel-titanium alloy in the in-vivo use of a patient is avoided. When the medical carbon nano tube modified composite material is prepared by laser 3D printing in the prior art, the common technical principle is that the carbon nano tube and alloy powder are mechanically compounded by means of a ball milling mixing process, and the laser 3D printing forming is completed after the powder mixture is prepared. However, the ball milling process is very easy to cause the carbon nano tube to form clusters due to uneven dispersion under the action of Van der Waals force. The medical composite powder prepared by the method has the common phenomena of carbon nano tube structural damage, reduced sphericity of alloy particles and the like, and further forms metallurgical defects such as pores, cracks and the like in the printing process, thereby being not beneficial to improving the comprehensive performance of the medical nickel-titanium-based composite material.
Disclosure of Invention
Aiming at the problems of low bonding strength, poor adsorptivity, outstanding agglomeration effect, easy structural damage and oxidative deterioration in the preparation process and the problems of the preparation of medical nickel-titanium alloy by the existing laser 3D printing in the prior art, the invention provides a preparation method of medical 3D printing nickel-titanium-based composite powder. The powder material prepared by the method can form stable electrostatic adsorption effect with nickel-titanium alloy particles by acid treatment of the modified carbon nano tube; during laser 3D printing forming, the TiC ceramic reinforcement body is synthesized by burning the carbon nano tube and the nickel-titanium alloy, so that the composite material has excellent biocompatibility and tribological property, and the service life of the medical artificial implant can be prolonged.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the medical 3D printing nickel-titanium-based composite powder is characterized by comprising the following specific steps:
(1) Adding the multiwall carbon nanotubes into an acid solution, performing constant-temperature water bath reaction under stirring to perform chemical acidification treatment, centrifuging to remove supernatant after acidification, adding deionized water, and continuing centrifuging to remove supernatant until the pH value of the supernatant is neutral;
(2) Adding a dispersing reagent into the carbon nano tube solution subjected to acid treatment, and carrying out ultrasonic oscillation to uniformly disperse the dispersing reagent to prepare a carbon nano tube suspension;
(3) Adding medical nickel-titanium alloy powder into the carbon nano tube suspension, carrying out electromagnetic stirring and mixing, standing at constant temperature for adsorption, and sequentially filtering out dispersing agents, drying and screening to obtain the medical 3D printing nickel-titanium base composite powder.
Preferably, in the step (1), the purity of the multiwall carbon nanotubes is not lower than 98%, the tube diameter is 20-30 nm, and the length is 10-30 μm.
Preferably, in the step (1), the acid treatment solution is a sulfuric acid-nitric acid mixed solution or a sulfuric acid-hydrogen peroxide mixed solution;
further preferably, the volume ratio of sulfuric acid to nitric acid or hydrogen peroxide is 3:1-3.5:1, the concentration of sulfuric acid solution is 18.4mol/L, the concentration of nitric acid solution is 7.0mol/L, and the concentration of hydrogen peroxide solution is 9.8mol/L.
Preferably, in the step (1), the water bath temperature is 70-80 ℃, and the water bath reaction time is 10-12 h;
preferably, in the step (1), the time of each centrifugal treatment is 30-45 min, and the centrifugal rotation speed is 15000-20000 r/min.
Preferably, in the step (2), the dispersing agent is any one or more of methyl pyrrolidone, ammonium polyacrylate, cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate.
Further preferably, the concentration of the solution of methyl pyrrolidone, ammonium polyacrylate, cetyl trimethylammonium bromide and sodium dodecyl benzene sulfonate is not lower than 90% in the preparation ratio of the dispersant to the acid-treated carbon nanotubes of 100mL:1 to 120mL:1 g.
Preferably, in the step (2), the ultrasonic oscillation time is 1-2 hours.
Preferably, in the step (2), the ultrasonic vibration dispersing process is carried out in an experimental ultrasonic cleaner, the ultrasonic vibration output power is 300-400W, and the fixed frequency is 40kHz.
Preferably, in the step (3), the medical nickel-titanium alloy powder is spherical powder with the particle size of 15-105 μm, wherein the particle size of the powder suitable for the selective laser melting process is 15-53 μm, and the particle size of the powder suitable for the laser near-net forming process is 53-105 μm;
preferably, the mass fraction of the carbon nano tube in the medical 3D printing nickel-titanium-based composite powder is 0.1-1.0%.
Further preferably, the medical nickel-titanium alloy powder and the prepared medical 3D printing nickel-titanium base composite powder meet the ASTM F2063-18 Nickel-titanium shape memory alloy processing Material for medical instruments and surgical implants;
preferably, in mass percent, the medical nickel-titanium alloy powder comprises 54.5-57.0% of Ni, less than or equal to 0.05% of Fe, less than or equal to 0.04% of C, less than or equal to 0.05% of Co, less than or equal to 0.01% of Cu, less than or equal to 0.01% of Cr, less than or equal to 0.005% of H, less than or equal to 0.025% of Nb, less than or equal to 0.005% of N, less than or equal to 0.04% of O, and the balance of Ti.
Preferably, in the step (3), the electromagnetic stirring and mixing time is 30-50 min, the constant-temperature static adsorption temperature is 40-60 ℃, and the constant-temperature static adsorption time is 40-50 min.
Preferably, in the filtering, drying and screening processes of the step (3), the dispersant filtering process is performed in a vacuum suction filtration device, the vacuum drying temperature is 100-120 ℃, and the vacuum drying time is 8-12 h; the composite powder is preferably sieved to a particle size in the range of 15 to 105 μm and has a spherical surface.
The invention takes the high-temperature combustion chemical reaction between the modified carbon nano tube and the medical nickel-titanium alloy as the basis, and utilizes the interaction thermal interaction of the high-energy laser beam and the material system to lead the original composite powder material to generate the combustion chemical reaction to synthesize TiC ceramic reinforcing phase, thereby preparing the shape-combined medical nickel-titanium-based composite material so as to regulate and control the biocompatibility and tribological property of the composite reinforcing material. The combustion chemistry reaction equation involved is:
preparation principle of medical 3D printing nickel-titanium-based composite powder: unsaturated oxidation is carried out on the defect position on the surface of the multiwall carbon nano tube by utilizing concentrated acid solution to generate chemical functional groups such as carboxyl, carbonyl, hydroxyl and the like, peeling of the carbon tube is accelerated, negative charge is carried, so that electrostatic repulsive force required for maintaining stable dispersion of the carbon tube is generated, uniform dispersion and electrostatic adsorption effects are achieved on the surface of medical nickel-titanium alloy particles after van der Waals acting force is further weakened, and medical modified composite powder is prepared, wherein TiC ceramic reinforcing phase is synthesized by burning under laser induction.
The beneficial effects of the invention are as follows:
(1) In the preparation process of the medical 3D printing nickel-titanium-based composite powder, the free carboxyl and hydroxyl of negative charges on the surface of the carbon nano tube are treated by acid, so that a stable electrostatic adsorption effect can be formed on the surface of positively charged nickel-titanium alloy particles, the carbon nano tube is uniformly dispersed and electrostatically adsorbed on the surface of the nickel-titanium alloy particles, the accumulation agglomeration, structural damage and sphericity reduction caused by mechanical composite powder preparation are effectively avoided, and meanwhile, the carbon nano tube has excellent adsorption stability and laser processability;
(2) In the medical 3D printing nickel-titanium-based composite powder, the multiwall carbon nanotube material has extremely high laser absorptivity, and the rugged surface features can effectively prevent reflected laser beams from escaping, so that the laser fusion efficiency of a medical nickel-titanium alloy material system is remarkably improved, and the forming quality is improved;
(3) According to the invention, the medical 3D printing nickel-titanium-based composite powder laser printing is adopted to prepare the medical nickel-titanium-based composite reinforced material, and when the laser 3D printing is formed, the carbon nano tube and the nickel-titanium alloy melt are combusted to synthesize the TiC ceramic reinforced body, so that the composite material has excellent biocompatibility and tribological property, and the service life of the medical implant is further prolonged.
Drawings
FIG. 1 is a flow chart of a preparation process of medical 3D printing nickel-titanium based composite powder;
FIG. 2 is a surface topography of the medical 3D printed NiTi-based composite powder of example 1;
fig. 3 is a microscopic morphology diagram of the nickel-titanium-based composite reinforced material prepared by the medical 3D printing nickel-titanium-based composite powder of example 1.
Detailed Description
The invention will be described in further detail with reference to the following examples, which will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that several modifications or improvements may be made without departing from the spirit of the invention, and shall still fall within the scope of the invention.
Example 1: the preparation method of the medical 3D printing nickel-titanium-based composite powder (see figure 1) comprises the following specific steps:
(1) Adding a multiwall carbon nanotube into an acid treatment solution prepared by mixing a sulfuric acid solution and a nitric acid solution according to a volume ratio of 3:1, maintaining a constant-temperature water bath at 80 ℃ under a continuous stirring condition for reaction for 10 hours to carry out chemical acidification treatment, centrifuging in a high-speed refrigerated centrifuge for 30 minutes to remove supernatant, setting the centrifugation rotating speed to 15000r/min, adding deionized water, and repeating for a plurality of times until the pH value of the supernatant is constant at 7; wherein the purity of the multi-wall carbon nano tube is not lower than 98%, the average tube diameter is 23nm, and the average length is 15 mu m;
(2) Adding a dispersing reagent into the acid-treated carbon nano tube, and carrying out ultrasonic oscillation in an experimental ultrasonic cleaner for 2 hours until the carbon nano tube is uniformly dispersed, wherein the output power of ultrasonic oscillation is 300W and the fixed frequency is 40kHz, so as to prepare a carbon nano tube suspension; wherein the dispersing agent adopts methyl pyrrolidone solution with the concentration of 99 percent, and the ratio of the dispersing agent to the acid-treated carbon nano tube is 100 mL/1 g;
(3) Adding medical nickel-titanium alloy powder into a carbon nano tube suspension, carrying out electromagnetic stirring and mixing for 30min, standing and adsorbing for 40min at a constant temperature of 60 ℃, filtering a dispersing agent by using a vacuum suction filtration device, drying for 10h at a heating temperature of 120 ℃ in a vacuum drying box, and screening powder particles with a preferable particle size range of 15-105 mu m and a spherical surface to prepare medical 3D printing nickel-titanium-based composite powder (hereinafter called nickel-titanium-based composite powder); wherein the mass fraction of the carbon nano tube in the medical 3D printing nickel-titanium-based composite powder is 1.0%, the medical nickel-titanium alloy powder is spherical powder, the average grain diameter is 37.5 mu m, the medical 3D printing nickel-titanium-based composite powder meets the standard of ASTM F2063-18 (Nickel-titanium shape memory alloy processing Material for medical instruments and surgical implants), and the medical nickel-titanium alloy powder comprises Ni 56.23%, fe 0.01%, C0.004%, co 0.015%, cu 0.001%, cr 0.005%, H0.002%, nb 0.015%, N0.003%, O0.008% and the balance Ti in percentage by mass;
the mass content of the carbon nano tube in the nickel-titanium-based composite powder prepared in the embodiment is 1.0%, the surface morphology diagram of the nickel-titanium-based composite powder is shown in fig. 2, and as can be known from fig. 2, the composite powder has no accumulation agglomeration, no structural damage and no sphericity reduction, and the TiC ceramic reinforcing phase is synthesized by burning after laser processing;
the microstructure morphology of the nickel-titanium-based composite reinforced material synthesized by the nickel-titanium-based composite powder through the combustion chemical reaction in the embodiment is shown in fig. 3, and as can be seen from fig. 3, the composite powder generates fine granular TiC reinforced phase in situ under the action of high-energy laser.
Example 2: the preparation method of the medical 3D printing nickel-titanium-based composite powder (see figure 1) comprises the following specific steps:
(1) Adding a multi-wall carbon nanotube into an acid treatment solution prepared by mixing a sulfuric acid solution and a hydrogen peroxide solution according to a volume ratio of 3.5:1, maintaining a constant-temperature water bath at 70 ℃ under a continuous stirring condition for reacting for 12 hours to perform chemical acidification treatment, centrifuging in a high-speed refrigerated centrifuge for 45 minutes to remove supernatant, setting the centrifugation rotating speed to 20000r/min, adding deionized water, and repeating for a plurality of times until the pH value of the supernatant is constant at 7; wherein the purity of the multi-wall carbon nano tube is not lower than 98%, the average tube diameter is 25nm, and the average length is 20 mu m;
(2) Adding a dispersing reagent into the acid-treated carbon nano tube, and carrying out ultrasonic oscillation in an experimental ultrasonic cleaner for 1h to uniformly disperse, wherein the output power of ultrasonic oscillation is 400W and the fixed frequency is 40kHz, so as to prepare a carbon nano tube suspension; wherein the dispersing agent adopts a cetyl trimethyl ammonium bromide solution with the concentration of 90%, and the ratio of the dispersing agent to the acid-treated carbon nano tube is 120 mL/1 g;
(3) Adding medical nickel-titanium alloy powder into a carbon nano tube suspension, carrying out electromagnetic stirring and mixing for 50min, standing and adsorbing for 50min at a constant temperature of 40 ℃, filtering a dispersing agent by using a vacuum suction filtration device, drying for 12h at a heating temperature of 100 ℃ in a vacuum drying box, and screening powder particles with a preferable particle size range of 15-105 mu m and a spherical surface to prepare medical 3D printing nickel-titanium-based composite powder; the mass fraction of the carbon nano tube in the nickel-titanium-based composite powder is 0.1%, the medical nickel-titanium alloy powder is spherical powder, the average grain diameter is 75.5 mu m, the nickel-titanium-based composite powder meets the standard of ASTM F2063-18 (Nickel-titanium shape memory alloy processing Material for medical instruments and surgical implants), and the medical nickel-titanium alloy powder comprises, by mass, ni 54.86%, fe 0.01%, C0.025%, co 0.03%, cu 0.007%, cr 0.003%, H0.001%, nb 0.015%, N0.003%, O0.015% and the balance Ti;
the mass content of the carbon nano tube in the nickel-titanium-based composite powder prepared by the embodiment is 0.1%, the composite powder has no accumulation agglomeration, structural damage and sphericity reduction, and the TiC ceramic reinforcing phase is synthesized by burning after laser processing.
Example 3: the preparation method of the medical 3D printing nickel-titanium-based composite powder (see figure 1) comprises the following specific steps:
(1) Adding a multiwall carbon nanotube into an acid treatment solution prepared by mixing a sulfuric acid solution and a nitric acid solution according to a volume ratio of 3:1, maintaining a constant-temperature water bath at 75 ℃ under a continuous stirring condition for reacting for 11 hours to perform chemical acidification treatment, centrifuging in a high-speed refrigerated centrifuge for 35 minutes to remove supernatant, setting the centrifugation rotating speed to 18000r/min, adding deionized water, and repeating for a plurality of times until the pH value of the supernatant is constant at 7; wherein the purity of the multi-wall carbon nano tube is not lower than 98%, the average tube diameter is 25nm, and the average length is 15 mu m;
(2) Adding a dispersing reagent into the acid-treated carbon nano tube, and carrying out ultrasonic oscillation in an experimental ultrasonic cleaner for 1.5 hours to uniformly disperse, wherein the output power of ultrasonic oscillation is 350W and the fixed frequency is 40kHz, so as to prepare a carbon nano tube suspension; wherein the dispersing agent adopts ammonium polyacrylate solution with the concentration of 99 percent, and the ratio of the dispersing agent to the acid-treated carbon nano tube is 100 mL/1 g;
(3) Adding medical nickel-titanium alloy powder into suspension for electromagnetic stirring and mixing for 40min, standing at the constant temperature of 50 ℃ for adsorption for 45min, filtering out a dispersing agent by using a vacuum suction filter, drying for 8h in a vacuum drying oven at the heating temperature of 110 ℃, and screening powder particles with the preferable particle size range of 15-105 mu m and spherical surface to prepare medical 3D printing nickel-titanium-based composite powder; the mass fraction of the carbon nano tube in the nickel-titanium-based composite powder is 0.4%, the medical nickel-titanium alloy powder is spherical powder, the average grain diameter is 35.5 mu m, the nickel-titanium-based composite powder meets the standard of ASTM F2063-18 (Nickel-titanium shape memory alloy processing Material for medical instruments and surgical implants), and the medical nickel-titanium alloy powder comprises Ni 55.45%, fe 0.015%, C0.018%, co 0.035%, cu 0.001%, cr 0.007%, H0.001%, nb 0.015%, N0.002%, O0.01% and the balance Ti in percentage by mass;
the mass content of the carbon nano tube in the nickel-titanium-based composite powder prepared by the embodiment is 0.4%, the composite powder has no accumulation agglomeration, structural damage and sphericity reduction, and the TiC ceramic reinforcing phase is synthesized by burning after laser processing.
While the invention has been described in terms of specific embodiments, it is to be understood that the invention is not limited to the specific embodiments described above, but is capable of numerous modifications and adaptations within the scope of the following claims.
Claims (7)
1. The preparation method of the medical 3D printing nickel-titanium-based composite powder is characterized by comprising the following specific steps:
(1) Adding the multiwall carbon nanotubes into an acid solution, performing constant-temperature water bath reaction under stirring to perform chemical acidification treatment, centrifuging to remove supernatant after acidification, adding deionized water, and continuing centrifuging to remove supernatant until the pH value of the supernatant is neutral;
(2) Adding a dispersing agent into the acidified carbon nano tube solution, and carrying out ultrasonic oscillation to uniformly disperse the dispersing agent to prepare a carbon nano tube suspension;
(3) Adding medical nickel-titanium alloy powder into the carbon nano tube suspension, carrying out electromagnetic stirring and mixing, standing at constant temperature for adsorption, and sequentially filtering out a dispersing agent, drying and screening to obtain medical 3D printing nickel-titanium base composite powder;
in the step (1), the acid solution is sulfuric acid-nitric acid mixed solution or sulfuric acid-hydrogen peroxide mixed solution; the preparation ratio of the dispersing agent to the acid-treated carbon nano tube is 100mL:1 g-120 mL:1g;
in the step (2), the dispersing agent is one or more of methyl pyrrolidone, ammonium polyacrylate, hexadecyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate;
in the step (3), electromagnetic stirring and mixing are carried out for 30-50 min;
the constant-temperature standing adsorption temperature is 40-60 ℃, and the constant-temperature standing adsorption time is 40-50 min.
2. The method for preparing the medical 3D printing nickel-titanium-based composite powder according to claim 1, wherein the method comprises the following steps: in the step (1), the purity of the multiwall carbon nanotubes is not lower than 98%, the tube diameter is 20-30 nm, and the length is 10-30 μm.
3. The method for preparing the medical 3D printing nickel-titanium-based composite powder according to claim 1, wherein the method comprises the following steps: in the step (1), the water bath temperature is 70-80 ℃, and the water bath reaction time is 10-12 h;
the time of each centrifugal treatment is 30-45 min, and the centrifugal rotating speed is 15000-20000 r/min.
4. The method for preparing the medical 3D printing nickel-titanium-based composite powder according to claim 1, wherein the method comprises the following steps: in the step (3), the medical nickel-titanium alloy powder is spherical powder with the particle size of 15-105 mu m;
the mass fraction of the carbon nano tube in the obtained medical 3D printing nickel-titanium-based composite powder is 0.1-1.0%.
5. The method for preparing the medical 3D printing nickel-titanium-based composite powder according to claim 4, which is characterized in that: the medical nickel-titanium alloy powder comprises, by mass, 54.5-57.0% of Ni, less than or equal to 0.05% of Fe, less than or equal to 0.04% of C, less than or equal to 0.05% of Co, less than or equal to 0.01% of Cu, less than or equal to 0.01% of Cr, less than or equal to 0.005% of H, less than or equal to 0.025% of Nb, less than or equal to 0.005% of N, less than or equal to 0.04% of O, and the balance of Ti.
6. The medical 3D prints nickel titanium base composite powder, its characterized in that: a preparation method according to any one of claims 1 to 5.
7. A nickel titanium based composite reinforcement material, characterized in that: the medical 3D printing nickel-titanium-based composite powder according to claim 6 is obtained through laser 3D printing.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053550A1 (en) * | 2000-01-20 | 2001-07-26 | Nankai University | Composite hydrogen storage material of hydrogen storage alloy/carbon nanotube and producing method thereof |
| CN101372330A (en) * | 2008-10-08 | 2009-02-25 | 长沙理工大学 | Method for coating carbon nano-tube with metal doped zinc oxide nano-particle |
| KR20090124199A (en) * | 2008-05-29 | 2009-12-03 | 연세대학교 산학협력단 | Method for synthesizing transition metal oxide and carbon nanotube composites by using microwave-polyol process |
| KR20120129270A (en) * | 2011-05-19 | 2012-11-28 | 전북대학교산학협력단 | Method for treating surface of dental implant and dental implant treated by the same |
| KR20130120114A (en) * | 2012-04-25 | 2013-11-04 | 서강대학교산학협력단 | Magnetic inorganic composite, preparing method of the same, and uses the same |
| CN112008087A (en) * | 2020-08-30 | 2020-12-01 | 中南大学 | Method for improving comprehensive performance of carbon nano material reinforced nickel-based high-temperature alloy |
| CN112723339A (en) * | 2020-12-11 | 2021-04-30 | 深圳市德方纳米科技股份有限公司 | Array type doped multi-walled carbon nanotube, preparation method thereof and electrode material |
| CN113426996A (en) * | 2021-06-11 | 2021-09-24 | 武汉大学 | Shape memory alloy based composite intelligent material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102133634B (en) * | 2010-01-22 | 2015-08-26 | 清华大学 | The preparation method of carbon nano tube metal powder mix and metallic composite |
| JP7017562B2 (en) * | 2016-05-13 | 2022-02-08 | マントル インク | Sinterable metal paste for use in additive manufacturing |
| CN108754266B (en) * | 2018-06-29 | 2019-06-28 | 南通朝旭环保科技有限公司 | A kind of metallic composite |
-
2022
- 2022-03-09 CN CN202210221752.5A patent/CN114932225B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053550A1 (en) * | 2000-01-20 | 2001-07-26 | Nankai University | Composite hydrogen storage material of hydrogen storage alloy/carbon nanotube and producing method thereof |
| KR20090124199A (en) * | 2008-05-29 | 2009-12-03 | 연세대학교 산학협력단 | Method for synthesizing transition metal oxide and carbon nanotube composites by using microwave-polyol process |
| CN101372330A (en) * | 2008-10-08 | 2009-02-25 | 长沙理工大学 | Method for coating carbon nano-tube with metal doped zinc oxide nano-particle |
| KR20120129270A (en) * | 2011-05-19 | 2012-11-28 | 전북대학교산학협력단 | Method for treating surface of dental implant and dental implant treated by the same |
| KR20130120114A (en) * | 2012-04-25 | 2013-11-04 | 서강대학교산학협력단 | Magnetic inorganic composite, preparing method of the same, and uses the same |
| CN112008087A (en) * | 2020-08-30 | 2020-12-01 | 中南大学 | Method for improving comprehensive performance of carbon nano material reinforced nickel-based high-temperature alloy |
| CN112723339A (en) * | 2020-12-11 | 2021-04-30 | 深圳市德方纳米科技股份有限公司 | Array type doped multi-walled carbon nanotube, preparation method thereof and electrode material |
| CN113426996A (en) * | 2021-06-11 | 2021-09-24 | 武汉大学 | Shape memory alloy based composite intelligent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 重氮盐静电自组装的研究与应用;刘志达等;化工科技;第21卷(第02期);第57-60页 * |
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