CN107598151B - ta-containing cobalt-chromium-molybdenum alloy powder for dental 3D printing and preparation method thereof - Google Patents
ta-containing cobalt-chromium-molybdenum alloy powder for dental 3D printing and preparation method thereof Download PDFInfo
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Abstract
A dental Ta-containing 3D printing cobalt chromium molybdenum alloy powder and a preparation method thereof, wherein the chemical components of the alloy powder comprise 26.0-30.0% of Cr, 8.0-10.0% of Mo, 0.5-5.0% of Ta, 3.0-8.0% of W and the balance of Co in percentage by weight; the preparation method comprises three steps of master alloy smelting, atomization powder preparation, powder screening and drying treatment. The alloy powder provided by the invention has the advantages that the grain diameter, the sphericity and the mechanical property are ensured, the binding property, the thermal stability and the fluidity of the gold and porcelain are improved, the oxygen content is reduced, the problems of ceramic collapse and ceramic peeling of the cobalt-chromium-molybdenum-based alloy are effectively solved, and the high-quality dental restoration part is favorably obtained.
Description
Technical Field
the invention belongs to the field of dental restoration, and relates to 3D printed cobalt-chromium-molybdenum alloy powder for dentistry and a preparation method thereof.
Background
The 3D printing is a technology for constructing an object by using a digital model file as a basis and using a bondable material such as powdered metal or plastic and the like in a layer-by-layer printing mode, and has the characteristics of quick forming, short processing period and convenience for processing personalized objects and complex-shaped objects, so that the method is particularly suitable for manufacturing crowns, bridges, brackets and the like in the field of dental restoration. In order to guarantee the quality of 3D printing, 3D printing powder material requires: high purity, low oxygen content and good fluidity; high sphericity of particle shape, fine particle size and narrow distribution. For 3D printing alloy powder for dentistry, the alloy powder also has good golden porcelain binding force, corrosion resistance and high-temperature roasting resistance.
The cobalt-chromium-molybdenum alloy has good biocompatibility, excellent mechanical property and corrosion resistance, is alloy powder commonly used for 3D printing in the prior art, is used for manufacturing dental crowns, dental bridges, brackets and other repair parts (see Chinese patent application CN106725944A and Chinese patent ZL 201410197534.8), but the existing cobalt-chromium-molybdenum alloy powder has poor gold-ceramic bonding property, needs to further reduce oxygen content, and needs to further improve thermal stability and fluidity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides Ta-containing cobalt-chromium-molybdenum alloy powder for dental 3D printing and a preparation method thereof, which can improve the binding property, thermal stability and fluidity of the cobalt-chromium-molybdenum alloy powder and reduce the oxygen content while ensuring the particle size, sphericity and mechanical property of the cobalt-chromium-molybdenum alloy powder.
The technical scheme of the invention is as follows: the chemical components of the existing cobalt-chromium-molybdenum alloy powder are improved, a small amount of Ta is added, and the content of Mo is properly increased. The preparation method of the existing cobalt-chromium-molybdenum alloy powder is improved, and the improvement mainly relates to the following two aspects, namely, a cobalt-chromium-molybdenum master alloy ingot containing Ta is formed by vacuum melting and pouring, and then the cobalt-chromium-molybdenum master alloy ingot containing Ta is melted into an alloy melt to be atomized and powdered; secondly, a vacuum drying treatment procedure is added to the screened cobalt-chromium-molybdenum alloy powder containing Ta and with the grain diameter meeting the requirement.
The chemical components of the Ta-containing 3D printing cobalt chromium molybdenum alloy powder for dental use comprise, by weight, 26.0-30.0% of Cr, 8.0-10.0% of Mo, 0.5-5.0% of Ta, 3.0-8.0% of W and the balance of Co.
the chemical composition of the alloy powder can also comprise at least one of Si, Mn and Nb, and the alloy powder comprises, by weight, 0.1-2.0% of Si, 0.1-1.5% of Mn and 0.1-1.0% of Nb.
The Ta-containing 3D printing cobalt chromium molybdenum alloy powder for dental use has a matrix which is an alpha-Co solid solution (alpha phase) with a face-centered cubic structure, the content of the alpha phase is more than 80%, the Ta-Co solid solution (epsilon phase) with a small amount of close-packed hexagonal structure is contained, and the Ta-Cr molybdenum alloy powder hardly contains a needle-shaped sigma phase solid solution with a topological close-packed structure.
The invention relates to a preparation method of Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder for dentistry, which comprises the following process steps:
(1) Master alloy melting
Preparing materials according to the chemical components of the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder for dental department, adding the prepared raw materials into a vacuum induction smelting furnace, smelting into a Ta-containing cobalt-chromium-molybdenum master alloy liquid, and casting into a Ta-containing cobalt-chromium-molybdenum master alloy ingot;
(2) Atomized powder
Putting the Ta-containing cobalt-chromium-molybdenum master alloy ingot obtained in the step (1) into a smelting chamber of a vacuum atomization powder making furnace to be melted into an alloy melt, then preserving the heat of the alloy melt by a tundish of the vacuum atomization powder making furnace, then enabling the alloy melt to flow out through a flow guide pipe, crushing the alloy melt flowing out of the flow guide pipe into fine liquid drops under the impact action of atomization airflow, and enabling the fine liquid drops to freely fall and condense to form Ta-containing cobalt-chromium-molybdenum alloy powder;
(3) Powder screening and drying treatment
And (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2), screening out alloy powder with a size larger than 900 meshes and smaller than 270 meshes, and performing vacuum drying to obtain the Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder for the dental department.
In the step (1) of the method, when the raw material is smelted in the vacuum induction smelting furnace, the vacuum degree in the furnace in the refining period is higher than 1.0 multiplied by 10-2Pa; the shape of the cobalt-chromium-molybdenum master alloy ingot containing Ta is a strip shape of 20mm multiplied by 100 mm.
In the step (2) of the method, the heat preservation temperature of the alloy melt in the tundish is 1300-1500 ℃, and the heat preservation time is at least 20 min; the atomization gas flow is high-purity nitrogen or high-purity argon (the purity is 99.999%), the pressure of the atomization gas flow is 4 MPa-6 MPa, and the high-purity nitrogen is generally used because the cost of the high-purity argon is higher than that of the high-purity nitrogen.
In the step (3) of the method, the Ta-containing cobalt-chromium-molybdenum alloy powder is subjected to screening treatment by using an airflow cyclone separator or an ultrasonic vibration sieve.
In the step (3) of the method, the temperature for vacuum drying the screened alloy powder is 90-130 ℃, and the time is 1-3 h.
The powder with the particle size smaller than 900 meshes or larger than 270 meshes screened in the step (3) of the method can be pressed into a cake-shaped spindle by a powder pressing machine to be used as atomized powder, the atomized powder is called old material, and a cobalt-chromium-molybdenum master alloy ingot (called new material) prepared from the old material and raw materials such as Co, Cr, Mo, W, Ta and the like is put into a melting chamber of a vacuum atomized powder making furnace to be melted into metal melt for atomized powder making, wherein the adding amount of the old material does not exceed 30 percent of the total weight of the atomized powder each time.
The invention has the following beneficial effects:
(1) Because a small amount of Ta is added into the cobalt-chromium-molybdenum alloy powder and the content of Mo is properly increased, the thermal expansion coefficient of a 3D printed cobalt-chromium-molybdenum alloy formed part is reduced due to the synergistic effect of Ta and Mo, but the thermal expansion coefficient of the cobalt-chromium-molybdenum alloy formed part is not lower than that of a facing porcelain [ the difference value is (0-0.6) × 10 ]-6/℃]The test shows that the binding strength of the gold and the porcelain of the object formed by the cobalt-chromium-molybdenum alloy powder containing Ta through 3D printing is about 60MPa (see each embodiment), and the gold and the porcelain binding performance is improved, so that the problem of ceramic collapse and ceramic peeling of the cobalt-chromium-molybdenum base alloy is effectively solved, and the aesthetic effect of the dental prosthesis cannot be influenced by adding a small amount of Ta.
(2) The invention adopts the technical scheme that a small amount of Ta is added into the raw material of the cobalt-chromium-molybdenum alloy powder, a cobalt-chromium-molybdenum master alloy ingot containing Ta is formed by vacuum melting and pouring, and then the cobalt-chromium-molybdenum master alloy ingot containing Ta is melted into an alloy melt to be atomized for preparing powder, because Ta element can reduce the surface activity and has poor affinity with oxygen, the purity of the prepared alloy melt is better and oxidation inclusions are less due to the addition of the Ta element, the prepared cobalt-chromium-molybdenum alloy powder is reduced, the process of shrinking and balling cannot be bonded, the sphericity is high, and tests show that the oxygen content of the cobalt-chromium-molybdenum alloy powder is less than 500ppm (see each embodiment).
(3) Because the method adds the vacuum drying treatment procedure to the screened Ta-containing cobalt-chromium-molybdenum alloy powder with the grain diameter meeting the requirement, the prepared Ta-containing cobalt-chromium-molybdenum alloy powder has improved fluidity and is beneficial to powder paving in 3D printing; because the cobalt-chromium-molybdenum alloy powder contains a small amount of Ta which can obviously improve the flow property of the alloy melt, the cobalt-chromium-molybdenum alloy powder has better spreading property after laser rapid melting, the internal defect of a 3D printed part can be reduced, and the property of a formed part is improved.
(4) because the atomic radius of Ta is larger, the Ta has better solid solution strengthening effect, and meanwhile, the addition of a small amount of Ta does not influence the plasticity of the alloy, so that the object formed by 3D printing of the Ta-containing cobalt-chromium-molybdenum alloy powder has excellent comprehensive mechanical properties (shown in each embodiment), and the strength, hardness and elongation of the object can meet the requirements of dental restoration parts.
(5) Because a small amount of Ta is added into the cobalt-chromium-molybdenum alloy powder, a formed part prepared by 3D printing of the alloy powder has good thermal stability, porcelain is favorably embedded outside, and a high-quality dental restoration part is obtained.
(6) Because the atomization powder preparation process adopted by the method of the invention and the screening treatment of the Ta-containing cobalt-chromium-molybdenum alloy powder obtained by atomization powder preparation, the prepared Ta-containing cobalt-chromium-molybdenum alloy powder has fine particles (the average particle size is less than 30 mu m), narrow particle size distribution and qualified powder yield of more than 40 percent.
(7) the method of the invention presses the screened powder with a size less than 900 meshes and larger than 270 meshes into a cake-shaped spindle by a powder pressing machine to be used as part of atomized powder, and the cake-shaped spindle and the Ta-containing cobalt-chromium-molybdenum master alloy ingot are melted into a metal melt to be atomized into powder, so that the cost of the Ta-containing cobalt-chromium-molybdenum alloy powder can be reduced.
Drawings
FIG. 1 is a topographical view of Ta-containing dental 3D-printed cobalt-chromium-molybdenum alloy powder prepared in example 1.
Fig. 2 is a particle size distribution diagram of the Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 1.
FIG. 3 is an X-ray diffraction analysis of Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 1.
FIG. 4 is a topographical view of Ta-containing dental 3D-printed cobalt-chromium-molybdenum alloy powder prepared in example 2.
Fig. 5 is a particle size distribution diagram of Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 2.
FIG. 6 is an X-ray diffraction analysis of Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 2.
FIG. 7 is a topographical view of Ta-containing dental 3D-printed cobalt-chromium-molybdenum alloy powder prepared in example 3.
Fig. 8 is a particle size distribution diagram of the Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 3.
FIG. 9 is an X-ray diffraction analysis of Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 3.
FIG. 10 is a topographical view of Ta-containing dental 3D-printed cobalt-chromium-molybdenum alloy powder prepared in example 5.
Fig. 11 is a particle size distribution diagram of Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 5.
FIG. 12 is an X-ray diffraction analysis of Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 5.
Fig. 13 is a microstructure diagram of a molded part prepared by 3D printing using Ta-containing dental 3D-printed cobalt chromium molybdenum alloy powder prepared in example 5.
Detailed Description
The dental Ta-containing 3D printing cobalt chromium molybdenum alloy powder and the preparation method thereof according to the present invention will be further described by way of examples with reference to the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
In the following examples, the raw materials of Co, Cr, Mo, W, Ta, Nb, Si, and Mn were electrolytic cobalt, metallic chromium, metallic molybdenum, metallic tungsten, tantalum rod, niobium rod, metallic silicon, and metallic manganese, respectively, and were purchased from the market.
in the following examples, the test methods and reference standards for the mechanical properties, the cermet bond strength, the thermal expansion coefficient, the flowability and the apparent density of the 3D prints are described below:
(1) Mechanical properties: the tensile test was carried out with reference to the method of GB 17168-2013 "metallic materials for dental restoration and mobility": testing on an electronic universal testing machine, wherein the stretching direction is along the long axis of the test piece, the stretching speed is 1mm/min, and the data are recorded until the test piece is broken: yield strength Rp0.2(MPa), tensile Strength Rm(MPa), elongation A (%).
(2) bonding strength of gold and porcelain: and preparing a golden porcelain combination sample and testing golden porcelain combination strength according to YY0621-2008 'dental metal porcelain repair system'. The size of a 3D printing sample is (25 +/-1) mmX (3 +/-0.1) mmX (0.5 +/-0.05) mm, the decorative porcelain powder is diluted by using a VITAVMK 95 porcelain powder special liquid, slurry is symmetrically coated on the surface of the sample subjected to surface treatment such as sand blasting, porcelain baking is carried out according to a porcelain baking program recommended by a manufacturer, the decorative porcelain is polished, the sintered decorative porcelain is 8 +/-0.1 mm in length, and the thickness of the decorative porcelain is (1.1 +/-0.1) mm. When the bonding performance is tested, the distance between the two support points is 20mm, the curvature radius of the cutting edge of the pressure head is 1.0mm, and the porcelain surface of the test piece is symmetrically positioned on the reverse side of the loading surface. Applying force at a constant rate of 1mm/min, and recording the breaking force F when one end of the porcelain layer of the test piece is peeledfail. According to the formula τb＝k·FfailAnd (3) calculating the strength of the surface porcelain when the alloy is peeled off, wherein the k value is determined by the thickness and the Young modulus of the alloy.
(3) Vickers hardness: the Vickers hardness test was carried out by referring to the method of GB/T4340.1-2009 part 1 of Vickers hardness test for Metal materials, test method, and the Vickers hardness of the test pieces was measured with a Vickers hardness tester (HV-50A, Laizhou hardness tester). The load was measured at 10kgf for 15s dwell time, and the indenter used was a diamond rectangular pyramid with a dihedral angle α of 136 °. The pressure head presses a square conical indentation on the surface of the sample under the action of the test force F, the test force is removed, and the Vickers hardness value of the sample is calculated by an instrument.
(4) Heat generationCoefficient of expansion: the test method meets the requirements of GB 17168-2013 metallic materials for dental science fixation and movable restoration and alloy product registration technical review guide principles for false tooth manufacturing, and tests are carried out according to the provisions of GB/T4339-2008 determination of thermal expansion characteristic parameters of metallic materials. 3D printing of prepared samplePutting into a thermal expansion coefficient tester, heating at a rate of 5 ℃/min, and calculating the thermal expansion coefficient of the sample at 25-500 ℃.
(5) and (3) particle shape analysis: a small amount of 3D printed cobalt-chromium-molybdenum alloy powder is taken and placed under a scanning electron microscope to observe the sphericity and the surface finish of the powder.
(6) particle size and particle size analysis: a small amount of 3D printing cobalt-chromium-molybdenum alloy powder is put into a laser particle size analyzer to detect the average particle size of the powder, and D90 results are obtained.
(7) fluidity and apparent density: according to the method of GB/T1482-1984 'determination of metal powder fluidity', blocking an outlet at the bottom of a funnel, weighing 50g of a powder sample, pouring the powder sample into the funnel, starting a lower switch at the outlet of the funnel, starting timing, stopping timing immediately after the powder in the funnel finishes flowing, recording the time consumed by the powder finishes flowing completely, measuring for at least 3 times, and taking the arithmetic mean value of the time as a final result to obtain the powder fluidity; according to the method of GB 6522-1986 "determination of bulk density of alumina powder", a powder sample is poured into a funnel and flows into a standard measuring cylinder (30ml), when a sample forms a cone at the top of the standard measuring cylinder and begins to overflow, powder feeding is stopped, then a flat steel ruler is used for scraping off excessive powder along the upper edge of the standard measuring cylinder, and the powder is placed on a balance for weighing to obtain the mass of the powder. Under normal conditions, 2 samples are tested in parallel, and the arithmetic mean value is taken as the final result.
Example 1
In this example, the chemical components and the weight percentages of the elements of the Ta-containing 3D-printed cobalt-chromium-molybdenum alloy powder for dental use are as follows: 26.0% of Cr, 10.0% of Mo, 2.0% of Si, 1.5% of Mn, 5.0% of W, 1.0% of Nb, 2.0% of Ta and the balance of Co. The preparation method comprises the following process steps:
(1) Master alloy melting
Mixing the above chemical components, adding the raw materials into a vacuum induction furnace, and smelting to obtain a Ta-containing cobalt-chromium-molybdenum master alloy liquid, wherein the vacuum degree in the furnace during the refining period is higher than 1.0 × 10-2Pa, then pouring the Ta-containing cobalt-chromium-molybdenum master alloy solution into a long-strip Ta-containing cobalt-chromium-molybdenum master alloy ingot of 20mm multiplied by 100 mm;
(2) atomized powder
Putting the Ta-containing cobalt-chromium-molybdenum master alloy ingot obtained in the step (1) into a smelting chamber of a vacuum atomization powder making furnace to be molten into an alloy melt, preserving the heat of the alloy melt in a tundish of the vacuum atomization powder making furnace, and then flowing out through a flow guide pipe, wherein the heat preservation temperature of the alloy melt in the tundish is 1500 ℃, and the heat preservation time is 25 min; the alloy melt flowing out of the flow guide pipe is broken into fine liquid drops under the impact action of high-purity nitrogen (the purity is 99.999%) with the airflow pressure of 5MPa, and the fine liquid drops freely fall and are condensed to form cobalt-chromium-molybdenum alloy powder containing Ta;
(3) Powder screening and drying treatment
and (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2) by using an ultrasonic vibration screen to obtain alloy powder with the granularity of more than 900 meshes and less than 270 meshes, and drying the screened alloy powder for 2 hours in vacuum at 110 ℃ to obtain the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder for the dental department. And finally, carrying out vacuum packaging and sealing on the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder.
the morphology of the cobalt-chromium-molybdenum alloy powder containing Ta prepared in the embodiment is shown in figure 1, the X-ray diffraction analysis spectrum is shown in figure 3, the particle size distribution is shown in figure 2, as can be seen from figure 1, the sphericity of the powder particles is very high, as can be seen from figure 3, the content of the alpha phase of the powder is 84%, no sigma phase exists, as can be seen from figure 2, the average particle size of the powder is 28.022 μm, and D90 is 52.787 μm. Detecting; oxygen content 250ppm, flowability 2.28(s/50g), bulk density 4.8658g/cm3. The Ta-containing cobalt-chromium-molybdenum alloy molded part formed by 3D printing has the following properties: tensile strength of 1128MPa, yield strength of 790MPa, elongation of 12%, Vickers hardness (HV10) of 475, and thermal expansion coefficient of 13.56X 10-6K-1The golden porcelain bonding strength is 60MPa, porcelain collapse or porcelain peeling does not occur after repeated roasting, the golden porcelain bonding performance is good, and the clinical requirement of porcelain restoration can be met.
Example 2
In this example, the chemical components and the weight percentages of the elements of the Ta-containing 3D-printed cobalt-chromium-molybdenum alloy powder for dental use are as follows: 30.0% of Cr, 8.0% of Mo, 2.0% of Si, 3.0% of W, 1.0% of Nb, 0.5% of Ta and the balance of Co. The preparation method comprises the following process steps:
(1) Master alloy melting
Mixing the above chemical components, adding the raw materials into a vacuum induction furnace, and smelting to obtain a Ta-containing cobalt-chromium-molybdenum master alloy liquid, wherein the vacuum degree in the furnace during the refining period is higher than 1.0 × 10-2Pa, then pouring the Ta-containing cobalt-chromium-molybdenum master alloy solution into a long-strip Ta-containing cobalt-chromium-molybdenum master alloy ingot of 20mm multiplied by 100 mm;
(2) Atomized powder
Putting the cobalt-chromium-molybdenum master alloy ingot containing Ta obtained in the step (1) into a smelting chamber of a vacuum atomization powder making furnace to be molten into an alloy melt, preserving the heat of the alloy melt in a tundish of the vacuum atomization powder making furnace, and then flowing out through a flow guide pipe, wherein the heat preservation temperature of the alloy melt in the tundish is 1300 ℃, and the heat preservation time is 20 min; the alloy melt flowing out of the flow guide pipe is broken into fine liquid drops under the impact action of high-purity argon (the purity is 99.999%) with the airflow pressure of 5MPa, and the fine liquid drops freely fall and are condensed to form cobalt-chromium-molybdenum alloy powder containing Ta;
(3) Powder screening and drying treatment
And (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2) by using an ultrasonic vibration screen, screening out alloy powder with the particle size of more than 900 meshes and less than 270 meshes, and drying in vacuum at 130 ℃ for 1h to obtain the Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder material for the dental department. And finally, carrying out vacuum packaging and sealing on the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder material.
The Ta-containing cobalt-chromium-molybdenum alloy powder prepared by the embodiment has the morphology shown in figure 4, the X-ray diffraction analysis spectrum shown in figure 6 and the particle size distribution shown in figure 5, and as can be seen from figure 4, the sphericity of the powder particles is very highThe powder contained 85% of the α phase as seen in FIG. 6, and no σ phase, and the average particle diameter of the powder was 24.636 μm and D90 was 50.523 μm as seen in FIG. 5. The detected oxygen content is 360ppm, the fluidity is 2.50(s/50g), and the loose packed density is 4.9801g/cm3. The Ta-containing cobalt-chromium-molybdenum alloy molded part formed by 3D printing has the following properties: a tensile strength of 1252MPa, a yield strength of 823MPa, an elongation of 13%, a Vickers hardness (HV10) of 467, and a thermal expansion coefficient of 13.62X 10-6K-1the golden porcelain bonding strength is 62MPa, porcelain collapse or porcelain peeling does not occur after repeated roasting, the golden porcelain bonding performance is good, and the clinical requirement of porcelain restoration can be met.
Example 3
In this example, the chemical components and the weight percentages of the elements of the Ta-containing 3D-printed cobalt-chromium-molybdenum alloy powder for dental use are as follows: 27.0% of Cr, 10.0% of Mo, 1.0% of Mn, 8.0% of W, 0.5% of Nb, 5.0% of Ta and the balance of Co. The preparation method comprises the following process steps:
(1) Master alloy melting
Mixing the above chemical components, adding the raw materials into a vacuum induction furnace, and smelting to obtain a Ta-containing cobalt-chromium-molybdenum master alloy liquid, wherein the vacuum degree in the furnace during the refining period is higher than 1.0 × 10-2Pa, then pouring the Ta-containing cobalt-chromium-molybdenum master alloy solution into a long-strip Ta-containing cobalt-chromium-molybdenum master alloy ingot of 20mm multiplied by 100 mm;
(2) Atomized powder
Putting the cobalt-chromium-molybdenum master alloy ingot containing Ta obtained in the step (1) into a smelting chamber of a vacuum atomization powder making furnace to be molten into an alloy melt, preserving the heat of the alloy melt in a tundish of the vacuum atomization powder making furnace, and then flowing out through a flow guide pipe, wherein the heat preservation temperature of the alloy melt in the tundish is 1400 ℃, and the heat preservation time is 28 min; the alloy melt flowing out of the flow guide pipe is broken into fine liquid drops under the impact action of high-purity nitrogen (the purity is 99.999%) with the airflow pressure of 6MPa, and the fine liquid drops freely fall and are condensed to form cobalt-chromium-molybdenum alloy powder containing Ta;
(3) Powder screening and drying treatment
And (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2) by using an ultrasonic vibration screen, screening out alloy powder with the particle size of more than 900 meshes and less than 270 meshes, and drying in vacuum at 90 ℃ for 3 hours to obtain the Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder material for the dental department. And finally, carrying out vacuum packaging and sealing on the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder material.
The morphology of the cobalt-chromium-molybdenum alloy powder containing Ta prepared by the embodiment is shown in FIG. 7, the X-ray diffraction analysis spectrum is shown in FIG. 9, the particle size distribution is shown in FIG. 8, as can be seen from FIG. 7, the sphericity of the powder particles is very high, as can be seen from FIG. 9, the content of the alpha phase of the powder is 84%, the sigma phase is absent, as can be seen from FIG. 8, the average particle size of the powder is 23.372 μm, and the D90 is 43.564 μm. The oxygen content was found to be 330ppm, the flowability was 2.31(s/50g), and the bulk density was 4.8354g/cm3. The Ta-containing cobalt-chromium-molybdenum alloy molded part formed by 3D printing has the following properties: 1158MPa for tensile strength, 804MPa for yield strength, 12% for elongation, 482% for Vickers hardness (HV10), 13.58X 10 for coefficient of thermal expansion-6K-1The golden porcelain bonding strength is 61MPa, porcelain collapse or porcelain peeling does not occur after repeated roasting, the golden porcelain bonding performance is good, and the clinical requirement of porcelain restoration can be met.
Example 4
in this example, the chemical components and the weight percentages of the elements of the Ta-containing 3D-printed cobalt-chromium-molybdenum alloy powder for dental use are as follows: 27.0% of Cr, 9.0% of Mo, 6.0% of W, 4.0% of Ta and the balance of Co. The preparation method comprises the following process steps:
(1) Master alloy melting
Mixing the above chemical components, adding the raw materials into a vacuum induction furnace, and smelting to obtain a Ta-containing cobalt-chromium-molybdenum master alloy liquid, wherein the vacuum degree in the furnace during the refining period is higher than 1.0 × 10-2pa, then pouring the Ta-containing cobalt-chromium-molybdenum master alloy solution into a long-strip Ta-containing cobalt-chromium-molybdenum master alloy ingot of 20mm multiplied by 100 mm;
(2) Atomized powder
Putting the Ta-containing cobalt-chromium-molybdenum master alloy ingot obtained in the step (1) into a smelting chamber of a vacuum atomization powder making furnace to be molten into an alloy melt, preserving the heat of the alloy melt in a tundish of the vacuum atomization powder making furnace, and then flowing out through a flow guide pipe, wherein the heat preservation temperature of the alloy melt in the tundish is 1450 ℃, and the heat preservation time is 20 min; the alloy melt flowing out of the flow guide pipe is broken into fine liquid drops under the impact action of high-purity nitrogen (the purity is 99.999%) with the airflow pressure of 4MPa, and the fine liquid drops freely fall and are condensed to form cobalt-chromium-molybdenum alloy powder containing Ta;
(3) Powder screening and drying treatment
and (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2) by using an ultrasonic vibration screen, screening out alloy powder with the particle size of more than 900 meshes and less than 270 meshes, and drying in vacuum at 110 ℃ for 2h to obtain the Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder material for the dental department. And finally, carrying out vacuum packaging and sealing on the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder material.
The cobalt-chromium-molybdenum alloy powder containing Ta prepared by the embodiment has high particle sphericity, the content of alpha phase of the powder is 85% by X-ray diffraction analysis, no sigma phase exists, the average particle size is 27.343 μm by detection, and D90 is 50.187 μm; the oxygen content was 420ppm, the flowability was 4.56(s/50g), and the apparent density was 4.6842g/cm3. The Ta-containing cobalt-chromium-molybdenum alloy molded part formed by 3D printing has the following properties: a tensile strength of 1046MPa, a yield strength of 749MPa, an elongation of 15%, a Vickers hardness (HV10) of 444, and a coefficient of thermal expansion of 13.83X 10-6K-1The golden porcelain bonding strength is 59MPa, porcelain collapse or porcelain peeling does not occur after repeated roasting, the golden porcelain bonding performance is good, and the clinical requirement of porcelain restoration can be met.
Example 5
in this example, the chemical components and the weight percentages of the elements of the Ta-containing 3D-printed cobalt-chromium-molybdenum alloy powder for dental use are as follows: 27.0% of Cr, 9.3% of Mo, 1.0% of Mn, 0.7% of Si, 7.3% of W, 3.6% of Ta, 0.15% of Nb and the balance of Co. The preparation method comprises the following process steps:
(1) Preparation of novel materials
The novel material comprises the following chemical components in percentage by weight: 27.0% of Cr, 9.0% of Mo, 1.0% of Mn, 1.0% of Si, 7.0% of W, 3.0% of Ta and the balance of Co. Proportioning according to the chemical components, adding the proportioned raw materials into a vacuum induction furnace to be smelted into a cobalt-chromium-molybdenum master alloy liquid containing Ta,the vacuum degree in the furnace in the refining period should be higher than 1.0 multiplied by 10-2Pa, then pouring the Ta-containing cobalt-chromium-molybdenum master alloy solution into a long-strip Ta-containing cobalt-chromium-molybdenum master alloy ingot of 20mm multiplied by 100mm, wherein the Ta-containing cobalt-chromium-molybdenum master alloy ingot is a new material;
(2) Atomized powder
The atomized powder material consists of new material in 70 wt% and old material in 30 wt%. The new material is the Ta-containing cobalt-chromium-molybdenum master alloy ingot prepared in the step (1), and the old material is a cake-shaped spindle which is prepared by mixing and pressing Ta-containing cobalt-chromium-molybdenum alloy powder with the particle size of less than 900 meshes and larger than 270 meshes in example 3;
melting the prepared atomized powder into an alloy melt in a melting chamber of a vacuum atomization powder making furnace, preserving the heat of the alloy melt in a tundish of the vacuum atomization powder making furnace, and then flowing out through a flow guide pipe, wherein the heat preservation temperature of the alloy melt in the tundish is 1400 ℃, and the heat preservation time is 25 min; the alloy melt flowing out of the flow guide pipe is broken into fine liquid drops under the impact action of high-purity nitrogen (the purity is 99.999%) with the airflow pressure of 5MPa, and the fine liquid drops freely fall and are condensed to form cobalt-chromium-molybdenum alloy powder containing Ta;
(3) Powder screening and drying treatment
And (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2) by using an ultrasonic vibration screen, screening out alloy powder with the particle size of more than 900 meshes and less than 270 meshes, and drying in vacuum at 120 ℃ for 2h to obtain the Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder material for the dental department. And finally, carrying out vacuum packaging and sealing on the Ta-containing 3D printed cobalt-chromium-molybdenum alloy powder material.
The morphology of the cobalt-chromium-molybdenum alloy powder containing Ta prepared by the embodiment is shown in FIG. 10, the X-ray diffraction analysis spectrum is shown in FIG. 12, the particle size distribution is shown in FIG. 11, as can be seen from FIG. 10, the sphericity of the powder particles is very high, as can be seen from FIG. 12, the content of alpha phase of the powder is 85%, no sigma phase exists, as can be seen from FIG. 11, the average particle size of the powder is 28.386 μm, and D90 is 51.788 μm. The oxygen content was found to be 350ppm, the flowability was 2.44(s/50g), and the bulk density was 4.8741g/cm3. Ta-containing cobalt-chromium-molybdenum alloy molded parts formed by 3D printing, microstructureSee fig. 13, the performance is: a tensile strength of 1210MPa, a yield strength of 819MPa, an elongation of 13%, a Vickers hardness (HV10) of 474, and a coefficient of thermal expansion of 13.71X 10-6K-1The golden porcelain bonding strength is 63MPa, porcelain collapse or porcelain peeling does not occur after repeated roasting, the golden porcelain bonding performance is good, and the clinical requirement of porcelain restoration can be met.
Claims (6)
1. The Ta-containing cobalt-chromium-molybdenum alloy powder for dental 3D printing is characterized in that the chemical components of the alloy powder comprise, by weight, 26.0-30.0% of Cr, 8.0-10.0% of Mo, 0.5-5.0% of Ta, 3.0-6.0% of W and the balance of Co;
The preparation method of the Ta-containing cobalt-chromium-molybdenum alloy powder for dental 3D printing comprises the following process steps:
(1) Master alloy melting
Proportioning according to the chemical components, adding the proportioned raw materials into a vacuum induction smelting furnace to be smelted into a cobalt-chromium-molybdenum master alloy liquid containing Ta, and casting into a cobalt-chromium-molybdenum master alloy ingot containing Ta;
(2) atomized powder
Melting the cobalt-chromium-molybdenum master alloy ingot containing Ta obtained in the step (1) into an alloy melt in a melting chamber of a vacuum atomization powder making furnace, preserving the heat of the alloy melt in a tundish of the vacuum atomization powder making furnace, then enabling the alloy melt to flow out through a flow guide pipe, crushing the alloy melt flowing out of the flow guide pipe into fine liquid drops under the impact action of atomization airflow, enabling the fine liquid drops to freely fall and condense to form cobalt-chromium-molybdenum alloy powder containing Ta, wherein the heat preservation temperature of the alloy melt in the tundish is 1300-1500 ℃, and the heat preservation time is at least 20 min; the atomized gas flow is high-purity nitrogen or high-purity argon, and the pressure of the atomized gas flow is 4 MPa-6 MPa;
(3) powder screening and drying treatment
And (3) screening the Ta-containing cobalt-chromium-molybdenum alloy powder obtained in the step (2), screening out alloy powder with a size larger than 900 meshes and smaller than 270 meshes, and performing vacuum drying to obtain the Ta-containing 3D printing cobalt-chromium-molybdenum alloy powder for the dental department.
2. A Ta-containing cobalt chromium molybdenum alloy powder for dental 3D printing according to claim 1, characterized by comprising, in addition to the chemical composition of the alloy powder according to claim 1, at least one of Si, Mn, Nb, in weight percent, Si 0.1% to 2.0%, Mn 0.1% to 1.5%, Nb 0.1% to 1.0%.
3. Ta-containing cobalt chromium molybdenum alloy powder for dental 3D printing according to claim 1 or 2, characterized in that in step (1), when the raw material is melted in a vacuum induction melting furnace, the degree of vacuum in the furnace during the refining period should be higher than 1.0 x 10-2Pa; the shape of the cobalt-chromium-molybdenum master alloy ingot containing Ta is a strip shape of 20mm multiplied by 100 mm.
4. the Ta-containing cobalt-chromium-molybdenum alloy powder for dental 3D printing according to claim 1 or 2, wherein in the step (3), the Ta-containing cobalt-chromium-molybdenum alloy powder is subjected to a sieving treatment using an air cyclone or an ultrasonic vibration sieve.
5. the Ta-containing cobalt chromium molybdenum alloy powder for dental 3D printing according to claim 1 or 2, wherein in the step (3), the temperature for vacuum drying of the sieved alloy powder is 90 ℃ to 130 ℃ for 1h to 3 h.
6. the Ta-containing cobalt chromium molybdenum alloy powder for dental 3D printing according to claim 4, wherein in the step (3), the temperature for vacuum drying of the sieved alloy powder is 90 ℃ to 130 ℃ for 1h to 3 h.
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| CN108277394A (en) * | 2018-03-12 | 2018-07-13 | 王甲林 | A kind of cobalt-base alloys and preparation method thereof for fixing human bone |
| CN108705093A (en) * | 2018-06-05 | 2018-10-26 | 广东省材料与加工研究所 | A kind of cobalt chrome molybdenum tungsten alloy powder and the preparation method and application thereof |
| CN109570519A (en) * | 2019-01-31 | 2019-04-05 | 上海材料研究所 | A kind of preparation method of the CoCrMo alloy powder for 3D printing |
| CN111790913A (en) * | 2019-03-20 | 2020-10-20 | 金川集团股份有限公司 | Preparation method of medical cobalt-chromium-molybdenum alloy powder for laser 3D printing |
| CN111054915A (en) * | 2019-12-17 | 2020-04-24 | 南通金源智能技术有限公司 | 3D printing metal powder for dental fixed and movable restoration and preparation method thereof |
| CN111172432A (en) * | 2020-01-10 | 2020-05-19 | 四川大学 | High-strength high-toughness cobalt-chromium-molybdenum-tungsten alloy manufactured based on laser additive and preparation method thereof |
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| CN112159907B (en) * | 2020-10-09 | 2021-09-07 | 成都科宁达材料有限公司 | 3D printing cobalt-chromium alloy for dental porcelain restoration and preparation method thereof |
| CN114570933A (en) * | 2020-11-30 | 2022-06-03 | 中国科学院金属研究所 | Preparation method of high-molybdenum high-silicon cobalt-based hot spraying alloy powder |
| CN112553506A (en) * | 2020-12-02 | 2021-03-26 | 石家庄利德粉末材料有限责任公司 | Cobalt-chromium-molybdenum alloy powder material for injection molding and manufacturing method thereof |
| CN113020605B (en) * | 2020-12-17 | 2022-07-22 | 南京航空航天大学 | Special in-situ toughening high-performance spherical tungsten powder for laser 3D printing and preparation method thereof |
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