CN113000833A - Ti-6Al-4V alloy spherical powder for additive manufacturing and preparation method thereof - Google Patents
Ti-6Al-4V alloy spherical powder for additive manufacturing and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 193
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 138
- 239000000956 alloy Substances 0.000 title claims abstract description 138
- 229910000883 Ti6Al4V Inorganic materials 0.000 title claims abstract description 132
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Classifications
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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
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F9/026—Spray drying of solutions or suspensions
Abstract
The preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing comprises the following steps: mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry; granulating the slurry to obtain Ti-6Al-4V alloy powder particles; degumming Ti-6Al-4V alloy powder particles at a first temperature; the degummed Ti-6Al-4V alloy powder particles and reducing metal interact in an inert atmosphere at a second temperature, and then acid washing and drying are carried out to obtain low-oxygen-content Ti-6Al-4V alloy powder particles; spheroidizing low-oxygen content Ti-6Al-4V alloy powder particles to obtain low-oxygen content Ti-6Al-4V alloy spherical powder; wherein the spheroidization rate of the low-oxygen-content Ti-6Al-4V alloy spherical powder is more than 97%, the oxygen content is not more than 1300ppm, and the granularity is 15-105 mu m.
Description
Technical Field
The application belongs to the technical field of additive manufacturing, and particularly relates to Ti-6Al-4V alloy spherical powder for additive manufacturing and a preparation method thereof.
Background
The Ti-6Al-4V alloy has the advantages of low density, high specific strength, excellent corrosion resistance and the like, is widely applied to the fields of aerospace, biomedical treatment, ship engineering and the like, and is prepared in a multi-purpose powder metallurgy mode due to poor mechanical processing performance. The metal additive manufacturing technology realizes the preparation of solid parts in a layer-by-layer printing mode, and effectively solves the problem that the Ti-6Al-4V alloy is difficult to process. At present, the mainstream techniques of metal additive manufacturing, such as laser-powder bed melting and electron beam-powder bed melting, use powder as raw material, and have strict requirements on the raw material powder. The high-performance spherical Ti-6Al-4V alloy powder with high sphericity, good fluidity, high apparent density and low impurity content is an essential important raw material for additive manufacturing technology.
At present, the preparation technology of the spherical Ti-6Al-4V alloy powder material mainly comprises an inert gas atomization method, a plasma rotating electrode method, an induction plasma spheroidization method and the like. The inert gas atomization method and the plasma rotating electrode method have some process defects, for example, the powder prepared by the inert gas atomization method has wide particle size distribution, high impurity content, satellite particles, hollow particles and the like, and the plasma rotating electrode method has low fine powder yield and high cost. The induction plasma spheroidizing has the characteristics of high temperature, high enthalpy, controllable atmosphere and the like, and the prepared spherical powder has high sphericity, low impurity content and narrow particle size distribution, and is an ideal preparation technology of the spherical powder for additive manufacturing. However, the plasma spheroidizing technology has high requirements on the morphology, oxygen content and particle size distribution of raw material powder, and the spherical powder prepared by plasma spheroidizing by using commercially available Ti-6Al-4V powder as a raw material has the problems of high oxygen content and the like.
Disclosure of Invention
In view of the above, in one aspect, embodiments of the present application disclose a method for preparing a Ti-6Al-4V alloy spherical powder for additive manufacturing, including:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry with good dispersibility;
granulating the slurry to obtain Ti-6Al-4V alloy powder particles;
degumming Ti-6Al-4V alloy powder particles at a first temperature;
the degummed Ti-6Al-4V alloy powder particles and reducing metal interact in an inert atmosphere at a second temperature to remove oxygen in the alloy powder particles, and then acid washing, filtering and drying are carried out to obtain low-oxygen content Ti-6Al-4V alloy powder particles;
spheroidizing the low-oxygen Ti-6Al-4V alloy powder particles to obtain low-oxygen Ti-6Al-4V alloy spherical powder;
wherein the spheroidization rate of the low-oxygen-content Ti-6Al-4V alloy spherical powder is more than 97%, the oxygen content is not more than 1300ppm, and the granularity is 15-105 mu m.
Some examples disclose methods of preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, the slurry having a solid content of 40-80 wt.%.
Some embodiments disclose a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, the auxiliary additive including a binder, a dispersant and water; wherein the binder is polyvinyl alcohol or polyvinyl butyral, the dispersant is polyacrylamide, the content of the binder in the slurry is 1-5 wt.%, and the content of the dispersant is 0.1-0.5 wt.%.
Some embodiments disclose a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, wherein the particle size of a raw material of the Ti-6Al-4V alloy powder is between 2 and 10 mu m.
In some embodiments, the preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing includes that slurry is sprayed and granulated in a centrifugal spray dryer, the air inlet temperature of spray drying is 180-240 ℃, the air outlet temperature is 100-160 ℃, and the rotation speed of an atomizer is 8000-13000 rpm.
Some embodiments disclose a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, wherein the first temperature is set to be 500-750 ℃, and the degumming time is set to be 2-8 hours.
Some embodiments disclose a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, wherein the second temperature is set to be 800-1300 ℃, and the action time is set to be 2-10 hours.
Some embodiments disclose a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, wherein a reducing metal comprises calcium or magnesium, and acid washing is performed by using dilute hydrochloric acid, wherein the mass ratio of the reducing metal to Ti-6Al-4V alloy powder particles is 1: 3-3: 1, the concentration of the dilute hydrochloric acid is 1-5 wt.%, the solid-liquid mass ratio of the acid washing is 1: 5-1: 15, and the acid washing time is 4-10 hours.
Some embodiments disclose a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, wherein low-oxygen content Ti-6Al-4V alloy powder particles are spheroidized in a plasma spheroidizing device, wherein the radio frequency plasma spheroidizing power is set to be 10-200 kW, the carrier gas flow is set to be 3-30L/min, and the powder feeding rate is set to be 5-200 g/min.
On the other hand, some embodiments disclose Ti-6Al-4V alloy spherical powder for additive manufacturing, wherein the spheroidization rate of the Ti-6Al-4V alloy spherical powder is more than 97%, the oxygen content is not more than 1300ppm, and the particle size is 15-105 μm.
According to the preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing, the particle size of Ti-6Al-4V powder particles prepared by a spray drying method is controllable, the particle shape is close to spherical, the powder raw materials can be conveyed in the plasma spheroidization process, and meanwhile, the spheroidization efficiency and the powder collection rate of a final product can be improved; reducing metal is used as a reducing agent to remove oxygen in the Ti-6Al-4V spherical powder, so that the impurity content of the powder is controlled, and the granulated powder particles are preliminarily shrunk and have certain bonding strength; the finally obtained Ti-6Al-4V alloy spherical powder has high nodularity, low oxygen content and controllable particle size distribution, and is completely suitable for a high-level additive manufacturing process.
Drawings
FIG. 1 SEM image of Ti-6Al-4V spherical powder prepared in example 1
Detailed Description
The word "embodiment" as used herein, is not necessarily to be construed as preferred or advantageous over other embodiments, including any embodiment illustrated as "exemplary". Performance index tests in the examples of this application, unless otherwise indicated, were performed using routine experimentation in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly employed by those of ordinary skill in the art.
The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may mean less than or equal to ± 5%, such as less than or equal to ± 2%, such as less than or equal to ± 1%, such as less than or equal to ± 0.5%, such as less than or equal to ± 0.2%, such as less than or equal to ± 0.1%, such as less than or equal to ± 0.05%. Numerical data represented or presented herein in a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of "1 to 5%" should be interpreted to include not only the explicitly recited values of 1% to 5%, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values, such as 2%, 3.5%, and 4%, and sub-ranges, such as 1% to 3%, 2% to 4%, and 3% to 5%, etc. This principle applies equally to ranges reciting only one numerical value. Moreover, such an interpretation applies regardless of the breadth of the range or the characteristics being described. The acid-washing solid-liquid mass ratio or solid-liquid ratio mentioned herein refers to the mass ratio of solid particles to hydrochloric acid solution when Ti-6Al-4V alloy powder particles are washed with hydrochloric acid, wherein solid refers to the solid mixture obtained after the alloy powder particles react with reducing metals. wt.% means mass percent.
In this document, including the claims, all conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are to be understood as being open-ended, i.e., to mean" including but not limited to. Only the conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, apparatuses, etc. known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.
On the premise of no conflict, the technical features disclosed in the embodiments of the present application may be combined arbitrarily, and the obtained technical solution belongs to the content disclosed in the embodiments of the present application.
In some embodiments, a method of preparing a Ti-6Al-4V alloy spherical powder for additive manufacturing includes:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry; wherein, the Ti-6Al-4V alloy powder raw material can be prepared by a hydrogenation dehydrogenation method or a mechanical alloying method; the obtained slurry has good dispersibility, and is beneficial to efficient granulation in the subsequent granulation process to obtain alloy powder particles with uniform particle size;
granulating the slurry to obtain Ti-6Al-4V alloy powder particles;
degumming Ti-6Al-4V alloy powder particles at a first temperature; generally, alloy powder particles are heated to a first temperature in a set heating mode, and are kept at the first temperature for a certain time to be degummed;
the degummed Ti-6Al-4V alloy powder particles and reducing metal interact in an inert atmosphere at a second temperature, and then acid washing, filtering and drying are carried out to obtain low-oxygen content Ti-6Al-4V alloy powder particles; generally, alloy powder particles and reducing metal are heated to a second temperature by a set heating mechanism according to a determined proportion, and the second temperature is kept for a set time to ensure that the reducing metal and oxygen are fully reacted; the reaction is usually carried out under the protection of an inert atmosphere to ensure that the oxygen removal reaction is completely carried out; generally, the reductive metal reacts with oxygen, so that oxygen in Ti-6Al-4V alloy powder particles can be removed, the content of oxygen in a product is reduced, and the performance of the titanium-aluminum-vanadium alloy spherical powder in additive manufacturing is improved; the acid washing can remove redundant reaction byproducts such as reducing metal, metal oxide and the like, and prevent the reducing metal from being left in the alloy powder to become impurities, which affects the application performance of the spherical alloy powder in the aspect of additive manufacturing; after the acid washing is finished, filtering and removing the washing liquid, and drying the powder particles obtained by filtering to obtain titanium-aluminum-vanadium alloy powder particles with low oxygen content;
spheroidizing low-oxygen content Ti-6Al-4V alloy powder particles to obtain low-oxygen content Ti-6Al-4V alloy spherical powder; the spheroidization process can be carried out in radio frequency plasma equipment, the radio frequency plasma equipment is usually provided with a proper high-temperature area, alloy powder particles are melted in the high-temperature area and become liquid drops, the liquid drops formed by the Ti-6Al-4V alloy powder with low oxygen content form spherical liquid drops with high sphericity under the action of the surface tension of the liquid drops, and the spherical liquid drops are rapidly condensed under the extremely high temperature gradient to form spherical particles; wherein the spheroidization rate of the low-oxygen-content Ti-6Al-4V alloy spherical powder is more than 97%, the oxygen content is not more than 1300ppm, and the granularity is 15-105 mu m.
Generally, in the slurry granulation process, the solid content, the binder content, the dispersant content, the air inlet and outlet temperature, the rotation speed of an atomizer and the like can all influence the granulation effect. The solid content, the binder content, the dispersant content, the air inlet and outlet temperature, the rotational speed of the atomizer and the like are strictly controlled in a proper range, and are mutually influenced and coordinated, so that a good granulation effect can be achieved, the spherical powder is good in shape and uniform in granularity; otherwise, the alloy powder particles obtained by granulation have the defect of not being agglomerated into a nearly spherical shape, such as broken particles, apple-shaped particles and the like. Meanwhile, the solid content, the binder content and the rotational speed of the atomizer are factors influencing the particle size of the alloy powder particles obtained by granulation, and particularly the rotational speed of the atomizer has a great influence on the particle size of the alloy powder particles.
Generally, when the solid content in the slurry is too low, the slurry is obviously layered, and when the solid content is too high, the viscosity of the slurry is too high, which is not favorable for forming spherical particles with uniform particle size and good shape. As an alternative embodiment, the slurry has a solids content of 40 to 80 wt.%.
As an alternative embodiment, the auxiliary additives include a binder, a dispersant and water; wherein, the binder is polyvinyl alcohol or polyvinyl butyral, and the dispersant is polyacrylamide. The content of the binder in the slurry is 1-5 wt.%, and the content of the dispersant is 0.1-0.5 wt.%. The dispersing agent can improve the fluidity of the slurry, and is beneficial to conveying the slurry by a peristaltic pump.
Generally, the slurry prepared by adopting the raw material powder with smaller granularity has better stability and fluidity, and the alloy powder particles obtained by utilizing the slurry for granulation have better sphericity and compactness. However, due to the particularity of the titanium alloy, the preparation of the titanium alloy powder with small granularity has high cost, great difficulty and lower industrial practicability. Therefore, as an optional embodiment, the particle size of the Ti-6Al-4V alloy powder raw material is between 2 and 10 microns, and the requirement for preparing the titanium-aluminum-vanadium spherical powder can be met. In a more preferred embodiment, the particle size of the Ti-6Al-4V alloy powder raw material is 2 to 5 μm. For example, a hydrogenation dehydrogenation process can be used to prepare titanium alloy powder with a particle size of 5 μm, and a mechanical alloying process can be used to prepare powder with a smaller particle size.
As an optional implementation mode, slurry granulation is carried out in a centrifugal spray dryer, the air inlet temperature of spray drying is 180-240 ℃, the air outlet temperature is 100-160 ℃, and the rotation speed of an atomizer is 8000-13000 rpm. In a preferred embodiment, the rotation speed of the atomizer is 9000-12000 rpm.
Generally, the degumming temperature can be determined according to the properties of the binder, if the degumming temperature is too low, the degumming time is too long, and if the degumming temperature is too high, the powder is easily oxidized, so that the requirements on equipment are high, the energy consumption is increased, and the production cost is too high. Therefore, the degumming temperature and degumming time are generally considered together on the principle of ensuring complete binder removal. As an optional implementation mode, the first temperature of degumming is set to be 500-750 ℃, and the degumming time is 2-8 h. As a preferable embodiment, the first temperature of degumming is set to 550-700 ℃, and the time of degumming is 2-4 h.
Generally, the second temperature is determined by considering the reduction temperature of the reducing metal and the sintering temperature of the alloy particle powder together. If the second temperature is too low, the reducing metal steam reducing and oxygen reducing efficiency is slow, so that the oxygen content of the powder is high, and the bonding force of the alloy powder is low; if the second temperature is too high, the second temperature is likely to cause excessive burning. As an optional implementation mode, the second temperature of the reaction between the degummed Ti-6Al-4V alloy powder particles and the reducing metal is 800-1300 ℃, and the action time is 2-10 hours. As a preferable embodiment, the second temperature is 800-1100 ℃, and the action time is 2-4 h.
As an optional embodiment, the reducing metal comprises calcium or magnesium, the oxide of calcium and magnesium can react with dilute hydrochloric acid, so dilute hydrochloric acid is adopted for acid cleaning, the amount of the reducing metal is calculated to be enough to ensure the reducing atmosphere, the mass ratio of the reducing metal to the Ti-6Al-4V alloy powder particles is 1: 3-3: 1, and the concentration of the hydrochloric acid is too high to remove calcium or magnesium, so that the concentration of the dilute hydrochloric acid is 1-5 wt.%. Generally, the lower the solid-to-liquid ratio, the more sufficient the pickling is, the better the effect is, but the more the amount of the acid used is, the more the waste is caused. Therefore, the solid-liquid mass ratio of the pickling is 1: 5-1: 15, and the pickling time is 4-10 hours to ensure that the metal oxide generated in the previous step is completely removed.
Generally, spheroidization of low-oxygen content Ti-6Al-4V alloy powder particles is carried out in plasma spheroidization equipment, the process parameter selectable range of the plasma spheroidization equipment is very wide, however, all process parameters need to be coordinated with one another to achieve a good granulating effect, and for example, the process parameters such as power, carrier gas flow, powder feeding rate and the like are controlled within a reasonable range to achieve an expected granulating effect. For example, when the powder feed rate is high and operation is performed at a high yield, the power and carrier gas flow rates are also increased accordingly. As an optional implementation mode, the spheroidizing power of the radio frequency plasma is 10-200 kW, the carrier gas flow is 3-30L/min, and the powder feeding rate is 5-200 g/min.
In some embodiments, the spheroidization rate of the Ti-6Al-4V alloy spherical powder obtained by the preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing is more than 97%, the oxygen content is not more than 1300ppm, and the particle size is 15-105 μm. The alloy powder particles in the particle size range can meet the requirement of additive manufacturing. For example, the particle size of the powder produced by melting and additive manufacturing of the laser-powder bed is required to be 15-53 μm, and the particle size of the powder produced by melting and additive manufacturing of the electron beam powder bed is required to be 53-105 μm.
The technical details are further illustrated in the following examples.
Example 1
The preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing, disclosed by the embodiment 1, comprises the following steps of:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry; the raw material of the Ti-6Al-4V alloy powder is irregular HDH Ti-6Al-4V powder, the auxiliary additive comprises adhesive polyvinyl alcohol, dispersant polyacrylamide and pure water, the solid content of the slurry is 45 wt.%, the polyvinyl alcohol content is 2.5 wt.%, the polyacrylamide content is 0.2 wt.%, the mixing is carried out in a ball mill, the rotating speed of the ball mill is 150rpm, and the ball milling time is 20 hours;
granulating the slurry to obtain Ti-6Al-4V alloy powder particles; wherein the slurry is subjected to metal spray granulation at the speed of 40ml/min, the air inlet temperature of spray drying is 210 ℃, the air outlet temperature is 110 ℃, and the rotating speed of an atomizer is 9000 rpm;
degumming Ti-6Al-4V alloy powder particles at a first temperature; heating Ti-6Al-4V alloy powder particles obtained by spray drying to a first temperature of 600 ℃ at a heating rate of 5 ℃/min for degumming, and keeping the temperature for 4 hours;
the degummed Ti-6Al-4V alloy powder particles and reducing metal interact in an inert atmosphere at a second temperature, and then acid washing and drying are carried out to obtain low-oxygen-content Ti-6Al-4V alloy powder particles; mixing the degummed Ti-6Al-4V alloy powder particles and calcium particles according to the mass ratio of 1:2, vacuumizing for three times, sealing, heating to a second temperature of 900 ℃ at a heating rate of 5 ℃/min in a vacuum furnace under the protection of argon, and preserving heat for 4 hours; then, carrying out acid washing by using dilute hydrochloric acid with the concentration of 3%, wherein the solid-liquid mass ratio is 1:6, carrying out acid washing for 10 hours, and drying to obtain Ti-6Al-4V alloy powder particles with low oxygen content, wherein the oxygen content is 1255 ppm;
spheroidizing low-oxygen content Ti-6Al-4V alloy powder particles to obtain low-oxygen content Ti-6Al-4V alloy spherical powder; wherein, the plasma spheroidizing equipment is started, the power is stabilized at 30kW, the obtained low-oxygen content Ti-6Al-4V alloy powder particles are sent into the plasma spheroidizing equipment by the powder feeder, the powder feeding speed is 60g/min, and the argon carrier gas flow is 4L/min. The spherical particles collected. FIG. 1 is a scanning electron microscope image of the low oxygen content Ti-6Al-4V alloy spherical powder obtained in example 1, wherein the spheroidization rate is 98%, the spherical powder has uniform particle size distribution, and the average particle size is 39 μm.
Example 2
The preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing, disclosed by the embodiment 2, comprises the following steps of:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry; the raw material of the Ti-6Al-4V alloy powder is irregular HDH Ti-6Al-4V powder, the auxiliary additive comprises adhesive polyvinyl alcohol, dispersant polyacrylamide and pure water, the solid content of the slurry is 50 wt.%, the polyvinyl alcohol content is 2.5 wt.%, the polyacrylamide content is 0.2 wt.%, the mixing is carried out in a ball mill, the rotating speed of the ball mill is 150rpm, and the ball milling time is 20 hours;
granulating the slurry, wherein the slurry is subjected to metal spray granulation at the speed of 40ml/min, the air inlet temperature of spray drying is 210 ℃, the air outlet temperature is 110 ℃, and the rotating speed of an atomizer is 11000rpm, so as to obtain Ti-6Al-4V alloy powder particles;
heating the Ti-6Al-4V alloy powder particles obtained by spray drying to the first temperature of 600 ℃ at the heating rate of 5 ℃/min for degumming, and preserving heat for 4 h;
mixing the degummed Ti-6Al-4V alloy powder particles and calcium particles according to the mass ratio of 1:2, vacuumizing for three times, sealing, heating to a second temperature of 900 ℃ at a heating rate of 5 ℃/min in a vacuum furnace under the protection of argon, and preserving heat for 4 hours; then, carrying out acid washing by using dilute hydrochloric acid with the concentration of 2%, wherein the solid-liquid mass ratio is 1:6, carrying out acid washing for 10 hours, and drying to obtain Ti-6Al-4V alloy powder particles with low oxygen content, wherein the oxygen content is 1269 ppm;
and (3) starting plasma spheroidizing equipment, stabilizing the power at 30kW, and conveying the obtained low-oxygen-content Ti-6Al-4V alloy powder particles into the plasma spheroidizing equipment by using a powder feeder for spheroidizing, wherein the powder feeding speed is 40g/min, and the argon carrier gas flow is 4L/min. The resulting spherical particles were collected, and the spheroidization rate was determined to be 97%, and the average particle diameter was 67 μm.
Example 3
The preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing, disclosed by the embodiment 3, comprises the following steps of:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry; the raw material of the Ti-6Al-4V alloy powder is irregular HDH Ti-6Al-4V powder, the auxiliary additive comprises adhesive polyvinyl alcohol, dispersant polyacrylamide and pure water, the solid content of the slurry is 55 wt.%, the polyvinyl alcohol content is 2.5 wt.%, the polyacrylamide content is 0.2 wt.%, the mixing is carried out in a ball mill, the rotating speed of the ball mill is 150rpm, and the ball milling time is 20 hours;
granulating the slurry, wherein the slurry is subjected to metal spray granulation at the speed of 40ml/min, the air inlet temperature of spray drying is 210 ℃, the air outlet temperature is 110 ℃, and the rotating speed of an atomizer is 11500rpm, so that Ti-6Al-4V alloy powder particles are obtained;
heating the Ti-6Al-4V alloy powder particles obtained by spray drying to the first temperature of 600 ℃ at the heating rate of 5 ℃/min for degumming, and preserving heat for 4 h;
mixing the degummed Ti-6Al-4V alloy powder particles and calcium particles according to the mass ratio of 1:2, vacuumizing for three times, sealing, heating to a second temperature of 900 ℃ at a heating rate of 5 ℃/min in a vacuum furnace under the protection of argon, and preserving heat for 4 hours; then, carrying out acid washing by using 1% dilute hydrochloric acid with the solid-liquid mass ratio of 1:6 for 10 hours, and drying to obtain Ti-6Al-4V alloy powder particles with low oxygen content, wherein the oxygen content is 1293 ppm;
and (3) starting plasma spheroidizing equipment, stabilizing the power at 45kW, and sending the obtained low-oxygen-content Ti-6Al-4V alloy powder particles into the plasma spheroidizing equipment by using a powder feeder for spheroidizing, wherein the powder feeding speed is 40g/min, and the argon carrier gas flow is 4L/min. The resulting spherical particles were collected, and the spheroidization ratio was determined to be 98% and the average particle diameter was 79 μm.
Example 4
Example 4 discloses a method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing, comprising:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry; the raw material of the Ti-6Al-4V alloy powder is irregular HDH Ti-6Al-4V powder, the auxiliary additive comprises adhesive polyvinyl alcohol, dispersant polyacrylamide and pure water, the solid content of the slurry is 60 wt.%, the polyvinyl alcohol content is 2.5 wt.%, the polyacrylamide content is 0.3 wt.%, the mixing is carried out in a ball mill, the rotating speed of the ball mill is 150rpm, and the ball milling time is 20 hours;
granulating the slurry, wherein the slurry is subjected to metal spray granulation at the speed of 40ml/min, the air inlet temperature of spray drying is 210 ℃, the air outlet temperature is 110 ℃, and the rotating speed of an atomizer is 11500rpm, so that Ti-6Al-4V alloy powder particles are obtained;
heating the Ti-6Al-4V alloy powder particles obtained by spray drying to the first temperature of 600 ℃ at the heating rate of 5 ℃/min for degumming, and preserving heat for 4 h;
mixing the degummed Ti-6Al-4V alloy powder particles and calcium particles according to the mass ratio of 1:2, vacuumizing for three times, sealing, heating to a second temperature of 900 ℃ at a heating rate of 5 ℃/min in a vacuum furnace under the protection of argon, and preserving heat for 4 hours; then, carrying out acid washing by using dilute hydrochloric acid with the concentration of 1.52 percent, carrying out acid washing for 10 hours with the solid-liquid mass ratio of 1:6, and drying to obtain low-oxygen content Ti-6Al-4V alloy powder particles, wherein the oxygen content is 1223 ppm;
and (3) starting plasma spheroidizing equipment, stabilizing the power at 30kW, and sending the obtained low-oxygen-content Ti-6Al-4V alloy powder particles into the plasma spheroidizing equipment by using a powder feeder for spheroidizing, wherein the powder feeding speed is 40g/min, and the argon carrier gas flow is 4L/min. The resulting spherical particles were collected, and the spheroidization ratio was determined to be 98% and the average particle diameter was 86 μm.
According to the preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing, the particle size of Ti-6Al-4V powder particles prepared by a spray drying method is controllable, the particle shape is close to spherical, the powder raw materials can be conveyed in the plasma spheroidization process, and meanwhile, the spheroidization efficiency and the powder collection rate of a final product can be improved; reducing metal is used as a reducing agent to remove oxygen in the Ti-6Al-4V spherical powder, so that the impurity content of the powder is controlled, and the granulated powder particles are preliminarily shrunk and have certain bonding strength; the finally obtained Ti-6Al-4V alloy spherical powder has high nodularity, low oxygen content and controllable particle size distribution, and is completely suitable for a high-level additive manufacturing process.
The technical solutions and the technical details disclosed in the embodiments of the present application are only examples to illustrate the inventive concept of the present application, and do not constitute limitations on the technical solutions of the present application, and all the inventive changes, substitutions, or combinations that are made to the technical details disclosed in the present application without creativity are the same as the inventive concept of the present application and are within the protection scope of the claims of the present application.
Claims (10)
1. The preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing is characterized by comprising the following steps:
mixing a Ti-6Al-4V alloy powder raw material with an auxiliary additive to prepare slurry with good dispersibility;
granulating the slurry to obtain Ti-6Al-4V alloy powder particles;
degumming Ti-6Al-4V alloy powder particles at a first temperature;
the degummed Ti-6Al-4V alloy powder particles and reducing metal interact in an inert atmosphere at a second temperature to remove oxygen in the alloy powder particles, and then acid washing, filtering and drying are carried out to obtain low-oxygen content Ti-6Al-4V alloy powder particles;
spheroidizing the low-oxygen Ti-6Al-4V alloy powder particles to obtain low-oxygen Ti-6Al-4V alloy spherical powder;
wherein the spheroidization rate of the low-oxygen-content Ti-6Al-4V alloy spherical powder is more than 97%, the oxygen content is not more than 1300ppm, and the granularity is 15-105 mu m.
2. The method for preparing the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the solid content of the slurry is 40-80 wt.%.
3. The method for preparing the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the auxiliary additives comprise a binder, a dispersant and water; the adhesive is polyvinyl alcohol or polyvinyl butyral, the dispersing agent is polyacrylamide, the content of the adhesive in the slurry is 1-5 wt.%, and the content of the dispersing agent is 0.1-0.5 wt.%.
4. The method for preparing the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the particle size of the raw material of the Ti-6Al-4V alloy powder is between 2 and 10 μm.
5. The preparation method of the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the slurry is subjected to spray granulation in a centrifugal spray dryer, the air inlet temperature of the spray drying is 180-240 ℃, the air outlet temperature is 100-160 ℃, and the rotation speed of an atomizer is 8000-13000 rpm.
6. The method for preparing the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the first temperature is set to 500-750 ℃, and the degumming time is set to 2-8 hours.
7. The method for preparing the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the second temperature is set to 800-1300 ℃ and the action time is set to 2-10 h.
8. The method for preparing the Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the reducing metal comprises calcium or magnesium, and acid washing is performed by using dilute hydrochloric acid, wherein the mass ratio of the reducing metal to the Ti-6Al-4V alloy powder particles is 1: 3-3: 1, the concentration of the dilute hydrochloric acid is 1-5 wt.%, the acid washing solid-liquid mass ratio is 1: 5-1: 15, and the acid washing time is 4-10 hours.
9. The method for preparing Ti-6Al-4V alloy spherical powder for additive manufacturing according to claim 1, wherein the spheroidization of the low-oxygen content Ti-6Al-4V alloy powder particles is performed in a plasma spheroidization device, wherein the radio frequency plasma spheroidization power is set to 10 to 200kW, the carrier gas flow is set to 3 to 30L/min, and the powder feeding rate is set to 5 to 200 g/min.
10. The Ti-6Al-4V alloy spherical powder for additive manufacturing is characterized by being obtained by the preparation method of any one of claims 1 to 9, wherein the spheroidization rate of the Ti-6Al-4V alloy spherical powder is more than 97%, the oxygen content is not more than 1300ppm, and the particle size is 15 to 105 μm.
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