CN111014706A - Cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing and preparation method thereof - Google Patents
Cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing and preparation method thereof Download PDFInfo
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- CN111014706A CN111014706A CN201911051809.6A CN201911051809A CN111014706A CN 111014706 A CN111014706 A CN 111014706A CN 201911051809 A CN201911051809 A CN 201911051809A CN 111014706 A CN111014706 A CN 111014706A
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/0003—Making bridge-work, inlays, implants or the like
- A61C13/0006—Production methods
- A61C13/0019—Production methods using three dimensional printing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/08—Artificial teeth; Making same
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
Abstract
The invention discloses a preparation method of cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing, which comprises the following components in percentage by weight: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent, and the balance being impurities. The invention also discloses a preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing. The powder prepared by the method has the advantages of high sphericity, good fluidity, no satellite powder, high apparent density, smooth powder surface and concentrated particle size distribution, and is suitable for 3D printing technologies such as SLM (selective laser melting) and the like, and the prepared 3D printing formed part has low linear expansion coefficient, high golden ceramic bonding strength and high residual ceramic AFAP (atomic fluorescence plating).
Description
Technical Field
The invention relates to the field of preparation of 3D printing materials, in particular to cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing and a preparation method thereof.
Background
The 3D printing is a sophisticated technology developed by relying on multiple subjects such as information technology, precision machinery, material science and the like, also called as a "rapid prototyping" technology or an "additive manufacturing" technology, and materials are layered, "printed" and superimposed mainly through a three-dimensional design drawing created by a computer, and finally integrally formed. In recent years, with the increasing demand for precision in various industries, 3D printing technology has rapidly developed, and has become a hot spot of current research. 3D printing has the advantages of low cost, high speed and high precision, and is widely applied to the fields of aerospace, industrial design, biomedicine and the like. In the traditional pharmaceutical industry market, biological products produced in batches in factories cannot meet the requirements of patients, particularly, the differences among individuals such as human bones and false teeth are large, the structures are complex, and the traditional production mode cannot be met, so that the 3D printing technology with the advantages of personalized customization, high precision, small batch and the like is promoted to be developed in the medical field. Currently, 3D printing has been applied in the fields of dentistry, orthopedics, and the like.
The denture manufactured by the 3D printing technology is almost the same as the metal denture manufactured by the traditional casting method in mechanical property, but is better than the metal denture manufactured by the casting method in certain properties such as density, golden porcelain combination property, wear resistance, corrosion resistance and the like. Meanwhile, compared with the traditional casting technology, the 3D printing technology has the advantages of high efficiency, material saving, high fitting degree with a patient and the like, and has a very wide application prospect in the aspect of false tooth manufacturing.
After the false tooth is manufactured, the false tooth also needs to be subjected to digital porcelain baking. Namely, the surface of the false tooth is coated with porcelain powder which has the color similar to the color of the human tooth and can not react with other teeth, the porcelain powder and the false tooth are combined together by sintering in a porcelain oven, and the porcelain tooth is obtained after cooling. In the porcelain baking process, if the defects such as air bubbles or holes exist in the false tooth raw material, broken porcelain or porcelain body cracking can be caused. Meanwhile, the thermal expansion coefficient difference between the denture raw material and the porcelain layer is too large, and the residual stress can also cause porcelain collapse or porcelain body cracking during cooling. The false tooth manufactured by the traditional casting method has the defects that air bubbles or impurities and the like are easily generated inside, so that the porcelain breaking phenomenon is frequent in the porcelain baking process. At present, the powder for 3D printing on the market is mostly prepared by a vacuum gas atomization method, when the powder is prepared by the method, a gasification dehydrogenation process is needed, the powder is easy to adhere to form satellite powder, and a large amount of hydrogen and oxygen elements easily form hollow powder or shrinkage cavities and other defects in the powder, so that the comprehensive performances of the powder such as flowability, apparent density, sphericity, aspect ratio, smooth surface and the like are influenced. Meanwhile, the traditional cobalt-chromium-molybdenum alloy powder lacks standardization and serialization specifications in properties such as particle size distribution, apparent density and fluidity, so that the 3D printing formed part has poor performance, and further popularization and application in the field of biological medical treatment are influenced.
Disclosure of Invention
The invention aims to provide cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing, which solves the problem that powder adhesion is easily caused when the powder for 3D printing is prepared by a vacuum gas atomization method in the prior art.
The invention also aims to provide a preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing.
The technical scheme adopted by the invention is that the technical problem is solved by the invention mainly through the following technical scheme: the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing comprises the following components in percentage by weight: co: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent, and the balance being impurities.
The technical scheme of the invention also comprises a preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing, which comprises the following steps:
step 1, smelting: taking the percentage content as Co: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent and the balance of impurities, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and processing the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar;
step 2, vacuum pressure maintaining gas protection: transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, vacuumizing the whole equipment and filling inert gases such as argon and helium;
step 3, atomizing and condensing: the water circulation system and the atomization function are started, and the power supply of the plasma generator is switched on, namely, the plasma gun is ignited. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar, adjusting the distance between a plasma gun and the end face of the bar, heating the end face of the rotating bar to melt the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber;
and 4, collecting: forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, and enabling the metal powder to flow out of a discharge port at the lower end of the atomizing chamber, wherein the metal powder is collected in a collector with argon gas with the purity of more than or equal to 99.99 percent in advance;
step 5, grading: introducing the powder in the collector into three-dimensional vibrating mesh holes with the aperture of 45 mu m and the aperture of 53 mu m and horizontal and vertical directions at the flow rate of 60kg/h, so as to classify the metal powder according to the particle size, wherein the same grade is below 45 mu m and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm;
step 6, proportioning: and (3) proportioning the classified metal powder according to the proportion that the particle size is less than 45 mu m and accounts for 45-55 percent, and the particle size is 45-53 mu m and accounts for 45-55 percent to obtain the cobalt-chromium-tungsten-molybdenum alloy powder.
The vacuum degree in step 2 is controlled at 5X 10-5And introducing inert gases such as argon and helium as atomizing gases within Pa, so that the problem of powder oxidation in the preparation process is avoided.
And 3, the axial rotating speed of the bar is 28000-35000 r/min.
And 3, the distance between the plasma gun and the end face of the bar is 1.5-3.0 mm, and the moving speed of the bar is 65-75 mm/min.
And 4, introducing the powder into a three-dimensional vibrating mesh, passing through 53 microns firstly and then passing through 45 microns, setting the amplitude to be 1.25-1.55 mm, and setting the vibration frequency to be 50 Hz.
And 5, proportioning according to the particle size, and controlling the proportioning time to be completed within 1-2 h.
In conclusion, the invention has the following beneficial effects:
the invention aims to overcome the defects of the prior art, and provides cobalt-chromium-tungsten-molybdenum alloy powder for dental 3D printing, which has the characteristics of high sphericity, high apparent density, good fluidity and the like, the false tooth prepared by the method after 3D printing is high in density, low in thermal expansion coefficient and strong in corrosion resistance, is not easy to break porcelain in the subsequent porcelain baking process, and has good golden porcelain bonding performance, so that the popularization and application in the field of biological medical treatment are facilitated; the preparation method provided by the invention is convenient to operate and moderate in cost, and can ensure the batch production and use of the cobalt-chromium-tungsten-molybdenum alloy powder.
(1) The cobalt-chromium-tungsten-molybdenum alloy powder is formed after liquid drops are condensed, and has the advantages that the sphericity of the powder can reach more than 95%, the aspect ratio is not more than 2, and no air hole exists in the powder, which is different from the forming modes of gas atomization and the like on the market at present. Meanwhile, the atomization condensation process is in a vacuum and inert gas protection state, and the inert gas is introduced into the collector in advance, so that the conditions of inclusion, oxidation and the like cannot be introduced into the product.
(2) The cobalt-chromium-tungsten-molybdenum alloy powder prepared by the method has the advantages of high sphericity, good fluidity, no satellite powder, high apparent density, smooth powder surface and concentrated particle size distribution, and is suitable for 3D printing technologies such as SLM (selective laser melting) and the like. Meanwhile, the 3D printing technology is scanning layer by layer, each layer of powder can be uniformly distributed by combining the advantages of high powder flowability and smooth surface according to scanning paths in different directions, gaps among the powder are filled with powder with finer particle size, the laser energy enables each layer of powder to be fully melted, bubbles and holes are not easily generated due to high scanning speed and high temperature among the layers, and finally the density of a 3D printed part can reach more than 96%.
(3) The weight percentage of cobalt (Co) in the powder prepared by the invention is within the range of 60-78%, and the weight percentage of chromium (Cr) is within the range of 20-30%, so that the powder formed part has better wear resistance and corrosion resistance. The tungsten (W) accounts for 3.0-7.0% by weight, so that the 3D printed denture workpiece has good toughness, and the golden porcelain combination property can reach more than 30MPa, and the subsequent porcelain baking is easy. The weight percentage of harmful substances of human body such as beryllium (Be), cadmium (Cd) and nickel (Ni) is respectively less than or equal to 0.02 percent, less than or equal to 0.02 percent and less than or equal to 0.1 percent, which meets the requirements of chemical components in the GB17168 metallic materials for dentistry fixation and movable restoration standard. Meanwhile, the 3D printed denture workpiece has good biocompatibility, reduces the problems of periodontitis and the like caused by interaction of the denture workpiece and gingiva, and is favorable for popularization and application of the powder prepared by the method in the field of biological medical treatment.
(4) The preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder sequentially comprises 6 steps of smelting, vacuum pressure maintaining gas protection, atomization and condensation, collection, classification and proportioning, and has the advantages of simple whole process, convenient operation and low manufacturing cost. Meanwhile, the particle size of the prepared powder is controlled during the steps of collection and classification, and the quality requirement of the product is ensured.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing comprises the following components in percentage by weight: co: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent, and the balance being impurities.
A preparation method of cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing comprises the following steps:
step 1, smelting: taking the percentage content as Co: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent and the balance of impurities, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and processing the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar;
step 2, vacuum pressure maintaining gas protection: transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, vacuumizing the whole equipment and filling inert gases such as argon and helium;
step 3, atomizing and condensing: the water circulation system and the atomization function are started, and the power supply of the plasma generator is switched on, namely, the plasma gun is ignited. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar, adjusting the distance between a plasma gun and the end face of the bar, heating the end face of the rotating bar to melt the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber;
and 4, collecting: forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, and enabling the metal powder to flow out of a discharge port at the lower end of the atomizing chamber, wherein the metal powder is collected in a collector with argon gas with the purity of more than or equal to 99.99 percent in advance;
step 5, grading: introducing the powder in the collector into three-dimensional vibrating mesh holes with the aperture of 45 mu m and the aperture of 53 mu m and horizontal and vertical directions at the flow rate of 60kg/h, so as to classify the metal powder according to the particle size, wherein the same grade is below 45 mu m and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm;
step 6, proportioning: and (3) proportioning the classified metal powder according to the proportion that the particle size is less than 45 mu m and accounts for 45-55 percent, and the particle size is 45-53 mu m and accounts for 45-55 percent to obtain the cobalt-chromium-tungsten-molybdenum alloy powder.
The vacuum degree in step 2 is controlled at 5X 10-5And introducing inert gases such as argon and helium as atomizing gases within Pa, so that the problem of powder oxidation in the preparation process is avoided.
And 3, the axial rotating speed of the bar is 28000-35000 r/min.
And 3, the distance between the plasma gun and the end face of the bar is 1.5-3.0 mm, and the moving speed of the bar is 65-75 mm/min.
And 4, introducing the powder into a three-dimensional vibrating mesh, passing through 53 microns firstly and then passing through 45 microns, setting the amplitude to be 1.25-1.55 mm, and setting the vibration frequency to be 50 Hz.
And 5, proportioning according to the particle size, and controlling the proportioning time to be completed within 1-2 h.
In order to make the obtained product of the invention accurate, uniform and strict in performance characterization, in the invention, the sampling and detection of the powder and the printed product are carried out according to the following standard method:
GB17168-2013 metallic materials for dental science fixation and movable repair
GB/T1479.1-2011 determination of bulk Density of Metal powders part 1: funnel law
GB/T1480-2012 Dry sieving method for determining particle size composition of Metal powders
GB/T1482-
GB/T5314-2011 powder sampling method for powder metallurgy
YY 0621.1-2016 section 1 of dental suitability test: metal-ceramic system
Example 1:
the method comprises the following specific steps: step 1, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and treating the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar, wherein the alloy material comprises the following components in percentage by weight: 63.9%, Cr:24.7％，W：5.4％，Mo：5.0％，Si：1.0％， Be：＜0.7×10-5％，Cd：＜1.7×10-5％，Ni：＜7.7×10-5percent, the balance being impurities; step 2, transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, and vacuumizing the whole equipment to 5 multiplied by 10-5Filling inert gases such as argon and helium into the reactor within Pa; and 3, starting the water circulation system and the atomization function, and switching on a power supply of the plasma generator to ignite the plasma gun. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar to 28000r/min, adjusting the distance between a plasma gun and the end face of the bar to 1.5mm, heating the end face of the rotating bar at the moving speed of 65mm/min, melting the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber; step 4, forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, and enabling the metal powder to flow out of a discharge hole in the lower end of the atomizing chamber, wherein the metal powder is collected in a collector with the purity of more than or equal to 99.99% argon gas introduced in advance; and step 5, introducing the powder in the collector into a three-dimensional vibrating mesh with a pore size of 53 microns and horizontal and vertical directions at a flow rate of 60kg/h, and then introducing into a three-dimensional vibrating mesh with a pore size of 45 microns and horizontal and vertical directions, wherein the amplitude is set to be 1.25mm, and the vibration frequency is 50 Hz. Grading the metal powder according to the particle size, wherein the particle size below 45 mu m is the same grade and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm; and 6, mixing the classified metal powder with the grain size of less than 45 microns accounting for 45-55 percent and the grain size of 45-53 microns accounting for 45-55 percent, controlling the mixing time within 1 hour, and finally obtaining the cobalt-chromium-tungsten-molybdenum alloy powder which is used as the final cobalt-chromium-tungsten-molybdenum alloy powder for dental 3D printing.
The cobalt-chromium-tungsten-molybdenum alloy powder prepared by the embodiment comprises the following components in percentage by weight: 63.9%, Cr: 24.7%, W: 5.4%, Mo: 5.0%, Si: 1.0%, Be: < 0.7X 10-5％，Cd：＜1.7×10-5％，Ni：＜7.7×10-5Percent, the balance being impurities. According to standard test method, the powder has a particle size of 45 μm or less36.35 percent of the powder with the particle size of 45-53 mu m, 60.94 percent of the powder with the particle size of more than or equal to 53 mu m, and 2.71 percent of the powder with the particle size of more than or equal to 53 mu m; the sphericity is 95.85%; an aspect ratio of 1.04; the comprehensive physical properties are excellent.
Example 2:
the method comprises the following specific steps: step 1, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and treating the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar, wherein the alloy material comprises the following components in percentage by weight: 62.3%, Cr: 26.0%, W: 5.9%, Mo: 5.1%, Si: 0.82%, Be: < 0.6X 10-5％，Cd：＜1.6×10-5％，Ni：＜7.4×10-5Percent, the balance being impurities; step 2, transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, and vacuumizing the whole equipment to 5 multiplied by 10-5Filling inert gases such as argon and helium into the reactor within Pa; and 3, starting the water circulation system and the atomization function, and switching on a power supply of the plasma generator to ignite the plasma gun. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar to 35000r/min, adjusting the distance between a plasma gun and the end face of the bar to 2.5mm, heating the end face of the rotating bar at a moving speed of 75mm/min, melting the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber; step 4, forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, and enabling the metal powder to flow out of a discharge hole in the lower end of the atomizing chamber, wherein the metal powder is collected in a collector with the purity of more than or equal to 99.99% argon gas introduced in advance; and step 5, introducing the powder in the collector into a three-dimensional vibrating mesh with a pore size of 53 microns and horizontal and vertical directions at a flow rate of 60kg/h, and then introducing into a three-dimensional vibrating mesh with a pore size of 45 microns and horizontal and vertical directions, wherein the amplitude is set to be 1.55mm, and the vibration frequency is 50 Hz. Grading the metal powder according to the particle size, wherein the particle size below 45 mu m is the same grade and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm; step 6, the classified metal powder accounts for 45 percent according to the grain diameter of less than 45 mu m55 percent, the grain diameter is 45-53 mu m and accounts for 45-55 percent, the proportioning time is controlled within 2 hours, and finally the cobalt-chromium-tungsten-molybdenum alloy powder is obtained and used as the final cobalt-chromium-tungsten-molybdenum alloy powder for dental 3D printing.
The cobalt-chromium-tungsten-molybdenum alloy powder prepared by the embodiment comprises the following components in percentage by weight: 62.3%, Cr: 26.0%, W: 5.9%, Mo: 5.1%, Si: 0.82%, Be: < 0.6X 10-5％，Cd：＜1.6×10-5％，Ni：＜7.4×10-5Percent, the balance being impurities. According to a standard test method, 40.21 percent of powder with the particle size of less than or equal to 45 mu m, 57.29 percent of powder with the particle size of 45-53 mu m and 2.50 percent of powder with the particle size of more than or equal to 53 mu m; the sphericity is 95.87%; an aspect ratio of 1.04; the comprehensive physical properties are excellent.
Example 3:
the method comprises the following specific steps: step 1, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and treating the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar, wherein the alloy material comprises the following components in percentage by weight: 63.5%, Cr: 27.4%, W: 5.4%, Mo: 5.0%, Si: 0.83%, Be: < 0.5X 10-5％，Cd：＜1.3×10-5％，Ni：＜6.5×10-5Percent, the balance being impurities; step 2, transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, and vacuumizing the whole equipment to 5 multiplied by 10-5Filling inert gases such as argon and helium into the reactor within Pa; and 3, starting the water circulation system and the atomization function, and switching on a power supply of the plasma generator to ignite the plasma gun. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar to 30000r/min, adjusting the distance between a plasma gun and the end face of the bar to 2.0mm, heating the end face of the rotating bar, wherein the moving speed of the bar is 73mm/min, melting the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber; step 4, forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, enabling the metal powder to flow out of a discharge hole at the lower end of the atomizing chamber, and collecting the metal powder in a collector with argon gas with purity not less than 99.99 percent introduced in advanceCollecting; and step 5, introducing the powder in the collector into a three-dimensional vibrating mesh with a pore size of 53 microns and horizontal and vertical directions at a flow rate of 60kg/h, and then introducing into a three-dimensional vibrating mesh with a pore size of 45 microns and horizontal and vertical directions, wherein the amplitude is set to be 1.30mm, and the vibration frequency is 50 Hz. Grading the metal powder according to the particle size, wherein the particle size below 45 mu m is the same grade and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm; step 6, grading the metal powder according to the particle size<45-55% of the powder with the particle size of 45-53 microns and 45-55% of the powder with the particle size of 45-53 microns are proportioned, the proportioning time is controlled within 1.5h, and finally the cobalt-chromium-tungsten-molybdenum alloy powder is obtained and is used as the final cobalt-chromium-tungsten-molybdenum alloy powder for dental 3D printing.
The cobalt-chromium-tungsten-molybdenum alloy powder prepared by the embodiment comprises the following components in percentage by weight: 63.5%, Cr: 27.4%, W: 5.4%, Mo: 5.0%, Si: 0.83%, Be: < 0.5X 10-5％，Cd：＜1.3×10-5％，Ni：＜6.5×10-5Percent, the balance being impurities. According to a standard test method, 38.73% of powder with the particle size of less than or equal to 45 mu m, 59.29% of powder with the particle size of 45-53 mu m and 1.98% of powder with the particle size of more than or equal to 53 mu m; the sphericity is 94.67%; the aspect ratio is 1.09; the comprehensive physical properties are excellent.
Example 4:
the method comprises the following specific steps: step 1, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and treating the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar, wherein the alloy material comprises the following components in percentage by weight: 65.5%, Cr: 23.6%, W: 5.6%, Mo: 4.9%, Si: 0.77%, Be: < 0.6X 10-5％，Cd：＜1.4×10-5％，Ni：＜5.3×10-5Percent, the balance being impurities; step 2, transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, and vacuumizing the whole equipment to 5 multiplied by 10-5Filling inert gases such as argon and helium into the reactor within Pa; step 3 starting the water circulation systemThe atomization function is integrated, and the power supply of the plasma generator is switched on, namely, the plasma gun is ignited. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar to 32000r/min, adjusting the distance between a plasma gun and the end face of the bar to 3.0mm, heating the end face of the rotating bar, wherein the moving speed of the bar is 70mm/min, melting the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber; step 4, forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, and enabling the metal powder to flow out of a discharge hole in the lower end of the atomizing chamber, wherein the metal powder is collected in a collector with the purity of more than or equal to 99.99% argon gas introduced in advance; and step 5, introducing the powder in the collector into a three-dimensional vibrating mesh with a pore size of 53 microns and horizontal and vertical directions at a flow rate of 60kg/h, and then introducing into a three-dimensional vibrating mesh with a pore size of 45 microns and horizontal and vertical directions, wherein the amplitude is set to be 1.40mm, and the vibration frequency is 50 Hz. Grading the metal powder according to the particle size, wherein the particle size below 45 mu m is the same grade and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm; and 6, mixing the classified metal powder with the grain size of less than 45 microns accounting for 45-55 percent and the grain size of 45-53 microns accounting for 45-55 percent, controlling the mixing time within 1 hour, and finally obtaining the cobalt-chromium-tungsten-molybdenum alloy powder which is used as the final cobalt-chromium-tungsten-molybdenum alloy powder for dental 3D printing.
The cobalt-chromium-tungsten-molybdenum alloy powder prepared by the embodiment comprises the following components in percentage by weight: 65.5%, Cr: 23.6%, W: 5.6%, Mo: 4.9%, Si: 0.77%, Be:<0.6×10-5％，Cd：<1.4×10-5％，Ni：<5.3×10-5percent, the balance being impurities. According to a standard test method, 33.98 percent of powder with the particle size of less than or equal to 45 mu m, 63.11 percent of powder with the particle size of 45-53 mu m and 2.91 percent of powder with the particle size of more than or equal to 53 mu m; the sphericity is 95.48%; the aspect ratio is 1.08; the comprehensive physical properties are excellent.
Application example 1:
the cobalt chromium tungsten molybdenum alloy powder prepared in each example was taken, a sample piece was printed by using a 3D printing apparatus, and the sample piece prepared by a conventional lost wax casting method was used as a comparative example. Wherein the 3D printing parameters are specifically: the laser power is 160W, the scanning speed is 1300mm/s, the printing space is 0.06mm, the spot diameter is 0.05mm, and the powder spreading thickness is 0.03 mm.
The parts obtained in each of the examples and comparative examples were processed into a 5X 26mm long strip having a cross-sectional area of not more than 30mm2The coefficient of linear expansion is tested according to the method in the GB17168-2013 standard, and the specific results are as follows:
TABLE 1 results of coefficient of linear expansion test
Application example 2:
the cobalt chromium tungsten molybdenum alloy powder prepared in each example was taken, a 3D printing apparatus was used to print a sample piece, and a sample piece prepared by a conventional lost wax casting method was used as a comparative example, wherein 3D printing parameters were consistent with application example 1.
The parts prepared in the examples and the comparative examples are processed into long strips of (25 +/-1) mmX (3.0 +/-0.1) mmX (0.5 +/-0.05) mm, the gold-ceramic bonding strength is tested by a three-point bending method according to YY 0621.1-2016 standard, and the area fraction AFAP of the residual ceramic with cracked ceramic is tested after the test, and the specific results are as follows:
TABLE 2 golden porcelain bond Strength test results
TABLE 3 AFAP test results for residual porcelain
As can be seen from tables 2 and 3, the cobalt-chromium-tungsten-molybdenum alloy powder prepared in the embodiments of the present invention has better performance than the cobalt-chromium-tungsten-molybdenum alloy powder prepared in the embodiments of the present invention by the test of the gold-ceramic bonding strength and the residual ceramic compared with the conventional lost-wax casting method. The tests show that the false tooth processed by 3D printing with the powder prepared by the invention can be smoothly combined with porcelain powder, has good adhesion and is not easy to break and fall off.
Claims (7)
1. The cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing is characterized by comprising the following components in percentage by weight: co: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent, and the balance being impurities.
2. A preparation method of cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing is characterized by comprising the following steps:
step 1, smelting: taking the percentage content as Co: 60-78%, Cr: 20-30%, W: 3.0-7.0%, Mo: 2.0-6.0%, Si: less than or equal to 1.0%, Be: less than or equal to 0.02 percent, Cd: less than or equal to 0.02 percent, Ni: less than or equal to 0.1 percent and the balance of impurities, adding metal cobalt, chromium, tungsten, molybdenum and silicon into a vacuum induction furnace for smelting, removing surface oxide skin, putting the furnace into vacuum consumable remelting to obtain a cobalt-chromium-tungsten-molybdenum alloy ingot, and processing the ingot to obtain a cobalt-chromium-tungsten-molybdenum alloy bar;
step 2, vacuum pressure maintaining gas protection: transferring the cobalt-chromium-tungsten-molybdenum alloy bar into a feeding chamber of plasma rotating electrode atomization equipment, vacuumizing the whole equipment and filling inert gases such as argon and helium;
step 3, atomizing and condensing: the water circulation system and the atomization function are started, and the power supply of the plasma generator is switched on, namely, the plasma gun is ignited. Axially rotating a cobalt-chromium-tungsten-molybdenum alloy bar, adjusting the distance between a plasma gun and the end face of the bar, heating the end face of the rotating bar to melt the bar, throwing away metal droplets by virtue of centrifugal force generated by the rotation of the bar, and cooling and solidifying the bar in an atomizing chamber;
and 4, collecting: forming metal powder from the liquid drops cooled and solidified in the atomizing chamber, and enabling the metal powder to flow out of a discharge port at the lower end of the atomizing chamber, wherein the metal powder is collected in a collector with argon gas with the purity of more than or equal to 99.99 percent in advance;
step 5, grading: introducing the powder in the collector into three-dimensional vibrating mesh holes with the aperture of 45 mu m and the aperture of 53 mu m and horizontal and vertical directions at the flow rate of 60kg/h, so as to classify the metal powder according to the particle size, wherein the same grade is below 45 mu m and is recorded as < 45 mu m; the particle size is more than 45 μm and less than 53 μm, and the particle size is the same grade and is marked as 45-53 μm; the particle size is above 53 μm, and is recorded as > 53 μm;
step 6, proportioning: and (3) proportioning the classified metal powder according to the proportion that the particle size is less than 45 mu m and accounts for 45-55 percent, and the particle size is 45-53 mu m and accounts for 45-55 percent to obtain the cobalt-chromium-tungsten-molybdenum alloy powder.
3. The method for preparing the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing according to claim 2, wherein the degree of vacuum pumping in the step 2 is controlled to be 5 x 10-5And introducing inert gases such as argon and helium as atomizing gases within Pa, so that the problem of powder oxidation in the preparation process is avoided.
4. The preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing according to claim 2, wherein the axial rotating speed of the rod in the step 3 is 28000-35000 r/min.
5. The preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing according to claim 2, wherein the distance between the plasma gun and the end face of the bar in the step 3 is 1.5-3.0 mm, and the moving speed of the bar is 65-75 mm/min.
6. The preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing according to claim 2, wherein in the step 4, the powder is introduced into a three-dimensional vibrating mesh, passes through 53 μm and then passes through 45 μm, the amplitude is set to be 1.25-1.55 mm, and the vibration frequency is 50 Hz.
7. The preparation method of the cobalt-chromium-tungsten-molybdenum alloy powder for biomedical 3D printing according to claim 2, wherein the step 5 is carried out according to the particle size, and the matching time is ensured to be controlled within 1-2 h.
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