CN117161388B - Low-oxygen-content titanium alloy powder and preparation method thereof - Google Patents
Low-oxygen-content titanium alloy powder and preparation method thereof Download PDFInfo
- Publication number
- CN117161388B CN117161388B CN202311457818.1A CN202311457818A CN117161388B CN 117161388 B CN117161388 B CN 117161388B CN 202311457818 A CN202311457818 A CN 202311457818A CN 117161388 B CN117161388 B CN 117161388B
- Authority
- CN
- China
- Prior art keywords
- alloy powder
- titanium alloy
- powder
- titanium
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000843 powder Substances 0.000 title claims abstract description 172
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000001301 oxygen Substances 0.000 claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 62
- -1 titanium hydride Chemical compound 0.000 claims abstract description 57
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 57
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 28
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 40
- 229910052719 titanium Inorganic materials 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 22
- 230000035699 permeability Effects 0.000 claims description 19
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000011946 reduction process Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The application relates to the technical field of 3D printing, and particularly discloses low-oxygen-content titanium alloy powder and a preparation method thereof. The preparation method of the low-oxygen-content titanium alloy powder comprises the following steps: carrying out hydrogen absorption grinding treatment on the titanium alloy waste powder to obtain titanium hydride alloy powder, adding magnesium powder into the titanium hydride alloy powder, carrying out heat preservation reaction for 70-90h under the conditions that the temperature is 680-700 ℃ and the vacuum degree is 0.5-0.6Pa, and then carrying out spheroidization crushing to obtain titanium alloy powder with low oxygen content; wherein the weight ratio of the magnesium powder to the titanium hydride alloy powder is 1 (10-12). The oxygen content of the titanium alloy powder prepared by the preparation method is lower than 1300ppm, the requirement of the titanium alloy powder for 3D printing on the oxygen content is met, the titanium alloy powder can be continuously applied to the 3D printing technology, and the material cost of the titanium alloy powder for 3D printing is greatly reduced.
Description
Technical Field
The application relates to the technical field of 3D printing, in particular to a low-oxygen-content spheroidal titanium alloy powder and a preparation method thereof.
Background
3D printing, also called additive manufacturing, belongs to one of rapid prototyping technologies, and is based on digital model files, and an object is constructed by applying powdery metal or plastic and other bondable materials in a layer-by-layer printing mode. Titanium and titanium alloy are important metals developed in the middle of the twentieth century, and titanium alloy powder has the characteristics of low density, high strength, corrosion resistance, no magnetism and the like, and is a key raw material of 3D printing technology.
Currently, titanium alloy powder for 3D printing on the market is mostly manufactured by a rotating electrode method, wherein a titanium alloy electrode rod is used as a consumable electrode, electrons or ion current is received under a high-speed rotating state, the end of the consumable electrode is fused into liquid, the liquid is thrown out under the action of centrifugal force to form fine liquid drops, and the fine liquid drops are solidified into spherical titanium alloy powder particles under the action of surface tension. The titanium alloy powder prepared by the method has the advantages of high sphericity, high smoothness, no agglomeration phenomenon, good fluidity, high densification degree of printed products and the like, and the preparation method generally adopts inert gas for protection, does not need crucible smelting, effectively avoids the introduction of impurities, and has higher purity.
However, since the particle size range of the titanium alloy powder produced by the rotary electrode method is usually between 0 and 250 μm, only the titanium alloy powder having a particle size distribution of between 20 and 63 μm can be used in 3D printing, which makes the material cost of the titanium alloy powder for 3D printing always high. Therefore, in order to reduce the material cost of the titanium alloy powder for 3D printing, it is necessary to recycle the titanium alloy waste powder having a particle diameter of more than 63 μm. However, the recycling of the titanium alloy waste powder (for example, the secondary atomization of the titanium alloy waste powder at a high temperature by adopting a plasma method) by using the existing method generally increases the oxygen content of the titanium alloy waste powder by 300-500ppm, so that the oxygen content of the recycled titanium alloy powder reaches 1300-1800ppm, the oxygen content requirement of the titanium alloy powder for 3D printing (less than 1300 ppm) can not be met, and the titanium alloy waste powder can not be continuously applied to the 3D printing technology.
Disclosure of Invention
In order to solve the problems, the application provides titanium alloy powder with low oxygen content and a preparation method thereof.
In a first aspect, the present application provides a method for preparing a low oxygen content titanium alloy powder, which adopts the following technical scheme:
a method for preparing low oxygen content titanium alloy powder, comprising the following steps:
carrying out hydrogen absorption grinding treatment on the titanium alloy waste powder to obtain titanium hydride alloy powder, adding magnesium powder into the titanium hydride alloy powder, carrying out heat preservation reaction for 70-90h under the conditions that the temperature is 680-700 ℃ and the vacuum degree is 0.5-0.6Pa, and then carrying out crushing spheroidization to obtain low-oxygen-content titanium alloy powder; wherein the weight ratio of the magnesium powder to the titanium hydride alloy powder is 1 (10-12).
By adopting the technical scheme, the method utilizes the reversible characteristics of titanium and hydrogen, firstly prepares titanium alloy waste powder with the particle size larger than 63 mu m by hydrogen absorption treatment, then carries out dehydrogenation treatment on the titanium alloy powder, carries out oxygen reduction process by taking magnesium powder as a reducing agent while carrying out dehydrogenation treatment, and then carries out crushing and spheroidizing, so that the oxygen content of the recovered titanium alloy powder is lower than 1300ppm, the requirement of the titanium alloy powder for 3D printing on the oxygen content is met, the method can be continuously applied to 3D printing technology, and the material cost of the titanium alloy powder for 3D printing is greatly reduced.
Preferably, the magnesium powder is filled into the porous titanium tube and then added into the titanium hydride alloy powder.
Through adopting above-mentioned technical scheme, this application utilizes the magnesium powder steam that overflows in the hole of distributing on the porous titanium pipe to carry out oxygen reduction to dehydrogenated titanium powder for magnesium powder and titanium hydride alloy powder need not directly contact, show the difficult degree of follow-up separation magnesium powder, improved production efficiency, reduced manufacturing cost. In addition, as the chemical property of titanium is relatively active, the titanium is easy to react with other metals at high temperature, so that the titanium filter tube is used for loading magnesium powder, and the possibility of introducing impurities can be reduced.
Preferably, the air permeability of the porous titanium tube is 0.8-2L/cm 2 ·min·pa。
Through adopting above-mentioned technical scheme, the air permeability of porous titanium pipe has been optimized to this application for magnesium powder steam can fully contact with the titanium powder after the dehydrogenation, has improved the sufficiency of magnesium powder steam to titanium powder oxygen reduction process, thereby has reduced the oxygen content of the titanium alloy powder after retrieving.
Preferably, the pore diameter of the porous titanium tube is 0.1-10 mu m, and the particle diameter of the magnesium powder is 10-20 mu m.
By adopting the technical scheme, the pore diameter of the porous titanium tube and the particle size of the magnesium powder are limited, the possibility that the magnesium powder overflows from the pores on the surface of the porous titanium tube is reduced, and the purity of the recycled titanium alloy powder is improved.
Preferably, the hydrogen absorption treatment comprises a hydrogen absorption process and a grinding process, wherein the hydrogen absorption process specifically comprises the following steps: and (3) carrying out hydrogen absorption on the titanium alloy waste powder under the conditions that the temperature is 550-560 ℃ and the pressure is 0.03-0.05MPa, and stopping hydrogen absorption when the weight of the titanium alloy waste powder is increased by at least 3.2%.
Preferably, the particle size of the titanium alloy waste powder is 63-250 mu m.
Preferably, the grinding process specifically comprises the following steps: grinding and spheroidizing the waste titanium alloy powder after hydrogen absorption under the condition that the pressure of inert gas is maintained at 530-550KPa, and obtaining the hydrogenated titanium alloy powder with the particle size of 20-63 mu m under the condition that the rotating speed is 4500-5000 r/min.
By adopting the technical scheme, the titanium in the titanium alloy waste powder with the particle size of 63-250 mu m is fully and completely converted into titanium hydride through hydrogen absorption, and then the titanium is ground to 20-63 mu m, at the moment, the oxygen content in the titanium hydride alloy powder is less than 1800ppm, the nitrogen content is less than 200ppm, and the hydrogen content is less than 32000ppm.
Preferably, the crushing and spheroidizing specifically comprises: under the condition that the inert gas is maintained at 600-650MPa, the titanium alloy powder after dehydrogenation reduction is spheroidized and crushed under the condition that the rotating speed is 5500-6000 r/min.
By adopting the technical scheme, the titanium alloy powder subjected to dehydrogenation reduction is subjected to secondary spheroidization crushing to obtain the spheroidal titanium alloy powder, and the spheroidal titanium alloy powder can be directly used in 3D printing.
In a second aspect, the present application provides a low oxygen titanium alloy powder produced by the above-described production method.
Preferably, the oxygen content of the low oxygen content titanium alloy powder is less than 1300ppm.
Through adopting above-mentioned technical scheme, the low oxygen content titanium alloy powder that this application made has lower oxygen content, and its oxygen content is less than 1300ppm, satisfies 3D and prints with titanium alloy powder to the requirement of oxygen content, can directly be applied to 3D and print, has reduced 3D and has printed with titanium alloy powder's material cost.
In summary, the present application has the following beneficial technical effects:
1. the titanium alloy powder prepared by the preparation method has the oxygen content of less than 1300ppm, the nitrogen content of less than 200ppm and the hydrogen content of less than 200ppm, meets the requirement of the titanium alloy powder for 3D printing on the oxygen content, and can be directly applied to 3D printing;
2. the preparation method of the titanium alloy powder realizes the aim of recycling the titanium alloy waste powder with the particle size larger than 63 mu m, and greatly reduces the material cost of the titanium alloy powder for 3D printing;
3. the preparation method has the advantages of simple steps, easy operation, lower raw material cost and suitability for large-scale industrial production.
Detailed Description
The present application is described in further detail below in connection with examples, comparative examples and application examples.
The titanium alloy waste powder is titanium alloy spherical powder with the particle size of 63-250 mu m prepared by using a titanium alloy electrode rod as a consumable electrode through a rotary electrode method, and has the oxygen content of less than 700ppm, the nitrogen content of less than 100ppm and the hydrogen content of less than 100ppm;
the size of the porous titanium tube is phi 70mm multiplied by phi 50mm multiplied by 300mm, and the aperture is 0.1-10 mu m;
the purity of the magnesium powder is more than 99.9 percent, and the grain diameter is 10-20 mu m.
Examples 1.1.1 to 1.1.3
A method for preparing low oxygen content titanium alloy powder, comprising the following steps:
(1) Placing the titanium alloy waste powder with the particle size of 63-250 mu m into a hydrogen absorption furnace, absorbing hydrogen at the temperature of 550 ℃ and the pressure of 0.03-0.05MPa, and stopping absorbing hydrogen when the weight of the titanium alloy waste powder is increased by at least 3.2%;
(2) Putting the product obtained in the step (1) into an air flow mill, and grinding at a grinding chamber pressure of 530KPa and a grinding speed of 80kg/h under the protection of argon gas at a rotating speed of 4500r/min to obtain titanium hydride alloy powder with a particle size of 20-63 mu m;
(3) Filling magnesium powder into the material with air permeability of 0.5L/cm 2 In a porous titanium tube of min pa, and co-operating with the titanium hydride alloy powder obtained in step (2)Placing the mixture into a dehydrogenation furnace, carrying out heat preservation reaction for 70 hours under the conditions of 680 ℃ and 0.5Pa of vacuum degree, and then carrying out secondary spheroidizing crushing under the protection of argon gas at the speed of 5500r/min and the pressure of 600MPa, wherein the speed is 80kg/h, so as to obtain low-oxygen-content titanium alloy powder;
wherein examples 1.1.1-1.1.3 differ in that: the weight ratio of magnesium powder to titanium hydride alloy powder is different, specifically,
in example 1.1.1, the weight ratio of magnesium powder to titanium hydride alloy powder is 1:10, wherein the magnesium powder is 10kg, and the titanium hydride alloy powder is 100kg;
in example 1.1.2, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:11, wherein the magnesium powder was 9.09kg and the titanium hydride alloy powder was 100kg;
in example 1.1.3, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:12, wherein the magnesium powder was 8.33kg and the titanium hydride alloy powder was 100kg.
Examples 1.2.1 to 1.2.3
A method for preparing low oxygen content titanium alloy powder, comprising the following steps:
(1) Placing the titanium alloy waste powder with the particle size of 63-250 mu m into a hydrogen absorption furnace, absorbing hydrogen at the temperature of 555 ℃ and the pressure of 0.03-0.05MPa, and stopping absorbing hydrogen when the weight of the titanium alloy waste powder is increased by at least 3.2%;
(2) Putting the product obtained in the step (1) into an air flow mill, and grinding at a speed of 4700r/min and a grinding chamber pressure of 540KPa under the protection of argon gas, wherein the grinding speed is 100kg/h, so as to obtain titanium hydride alloy powder with a particle size of 20-63 mu m;
(3) Filling magnesium powder into the material with air permeability of 0.5L/cm 2 Placing the titanium alloy powder and the titanium alloy powder obtained in the step (2) into a dehydrogenation furnace together, carrying out heat preservation reaction for 80 hours under the conditions that the temperature is 690 ℃ and the vacuum degree is 0.55Pa, and then carrying out secondary spheroidization crushing under the protection of argon at the speed of 5700r/min and the pressure of 630MPa, wherein the speed is 100kg/h, so as to obtain the low-oxygen-content titanium alloy powder;
wherein examples 1.2.1-1.2.3 differ in that: the weight ratio of magnesium powder to titanium hydride alloy powder is different, specifically,
in example 1.2.1, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:10, wherein the magnesium powder was 10kg and the titanium hydride alloy powder was 100kg;
in example 1.2.2, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:11, wherein the magnesium powder was 9.09kg and the titanium hydride alloy powder was 100kg;
in example 1.2.3, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:12, wherein the magnesium powder was 8.33kg and the titanium hydride alloy powder was 100kg.
Examples 1.3.1 to 1.3.3
A method for preparing low oxygen content titanium alloy powder, comprising the following steps:
(1) Placing the titanium alloy waste powder with the particle size of 63-250 mu m into a hydrogen absorption furnace, absorbing hydrogen at the temperature of 560 ℃ and the pressure of 0.03-0.05MPa, and stopping absorbing hydrogen when the weight of the titanium alloy waste powder is increased by at least 3.2%;
(2) Putting the product obtained in the step (1) into an air flow mill, and grinding at a speed of 5000r/min and a grinding chamber pressure of 550KPa under the protection of argon, wherein the grinding speed is 120kg/h, so as to obtain titanium hydride alloy powder with a particle size of 20-63 mu m;
(3) Filling magnesium powder into the material with air permeability of 0.5L/cm 2 Placing the titanium alloy powder and the titanium alloy powder obtained in the step (2) into a dehydrogenation furnace together in a porous titanium tube with the temperature of min Pa, and carrying out heat preservation reaction for 90 hours under the condition that the temperature is 700 ℃ and the vacuum degree is 0.6Pa to obtain titanium alloy powder with low oxygen content;
wherein examples 1.3.1-1.3.3 differ in that: the weight ratio of magnesium powder to titanium hydride alloy powder is different, specifically,
in example 1.3.1, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:10, wherein the magnesium powder was 10kg and the titanium hydride alloy powder was 100kg;
in example 1.3.2, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:11, wherein the magnesium powder was 9.09kg and the titanium hydride alloy powder was 100kg;
in example 1.3.3, the weight ratio of magnesium powder to titanium hydride alloy powder was 1:12, wherein the magnesium powder was 8.33kg and the titanium hydride alloy powder was 100kg.
Examples 2.1.1 to 2.1.3
A method for preparing low oxygen content titanium alloy powder, which is different from examples 1.1.1-1.1.3 in that: the air permeability of the porous titanium tube in the step (3) is 0.8-2L/cm 2 Min pa, wherein,
in example 2.1.1, the porous titanium tube had an air permeability of 0.8L/cm 2 ·min·pa；
In example 2.1.2, the porous titanium tube had an air permeability of 1.4L/cm 2 ·min·pa；
In example 2.1.3, the porous titanium tube had an air permeability of 2L/cm 2 ·min·pa。
Examples 2.2.1 to 2.2.3
A method for preparing low oxygen content titanium alloy powder, which is different from examples 1.2.1-1.2.3 in that: the air permeability of the porous titanium tube in the step (3) is 0.8-2L/cm 2 Min pa, wherein,
in example 2.2.1, the porous titanium tube had an air permeability of 0.8L/cm 2 ·min·pa；
Example 2.2.2 the porous titanium tube had an air permeability of 1.4L/cm 2 ·min·pa；
In example 2.2.3, the porous titanium tube had an air permeability of 2L/cm 2 ·min·pa。
Examples 2.3.1 to 2.3.3
A method for preparing low oxygen content titanium alloy powder, which is different from examples 1.3.1-1.3.3 in that: the air permeability of the porous titanium tube in the step (3) is 0.8-2L/cm 2 Min pa, wherein,
in example 2.3.1, the porous titanium tube had an air permeability of 0.8L/cm 2 ·min·pa；
In example 2.3.2, the porous titanium tube had an air permeability of 1.4L/cm 2 ·min·pa；
In example 2.3.3, the porous titanium tube had an air permeability of 2L/cm 2 ·min·pa。
Comparative examples 1.1.1 to 1.1.3
The differences from examples 1.1.1 to 1.1.3 are: in the step (3), the porous titanium tube filled with magnesium powder is not added into the dehydrogenation furnace, and only the titanium hydride alloy powder obtained in the step (2) is put into the dehydrogenation furnace, and the rest steps are the same as those of the examples 1.1.1-1.1.3.
Comparative examples 1.2.1 to 1.2.3
The differences from examples 1.2.1-1.2.3 are: in the step (3), the porous titanium tube filled with magnesium powder is not added into the dehydrogenation furnace, and only the titanium hydride alloy powder obtained in the step (2) is put into the dehydrogenation furnace, and the rest steps are the same as those of the examples 1.2.1-1.2.3.
Comparative examples 1.3.1 to 1.3.3
The differences from examples 1.3.1-1.3.3 are: in the step (3), the porous titanium tube filled with magnesium powder is not added into the dehydrogenation furnace, and only the titanium hydride alloy powder obtained in the step (2) is put into the dehydrogenation furnace, and the rest steps are the same as those of the examples 1.3.1-1.3.3.
Comparative examples 2.1.1 to 2.1.3
The differences from examples 1.1.1 to 1.1.3 are: in the step (3), aluminum powder is used for replacing magnesium powder by equal amount to be filled into the porous titanium tube, and the rest steps are the same as those of the embodiment 1.1.1-1.1.3.
Comparative examples 2.2.1 to 2.2.3
The differences from examples 1.2.1-1.2.3 are: in the step (3), aluminum powder is used for replacing magnesium powder by equal amount to be filled into the porous titanium tube, and the rest steps are the same as those of the embodiment 1.2.1-1.2.3.
Comparative examples 2.3.1 to 2.3.3
The differences from examples 1.3.1-1.3.3 are: in the step (3), aluminum powder is used for replacing magnesium powder by equal amount to be filled into the porous titanium tube, and the rest steps are the same as those of the embodiment 1.3.1-1.3.3.
Comparative examples 3.1.1 to 3.1.3
The differences from examples 1.1.1 to 1.1.3 are: in the step (3), the weight ratio of magnesium powder to titanium hydride alloy powder is 1:20, and the rest steps are the same as those of the embodiment 1.1.1-1.1.3; wherein,
in comparative example 3.1.1, 5kg of magnesium powder and 100kg of titanium hydride alloy powder;
in comparative example 3.1.2, 5kg of magnesium powder and 100kg of titanium hydride alloy powder;
in comparative example 3.1.3, 5kg of magnesium powder and 100kg of titanium hydride alloy powder were used.
Comparative examples 3.2.1 to 3.2.3
The differences from examples 1.2.1-1.2.3 are: in the step (3), the weight ratio of magnesium powder to titanium hydride alloy powder is 1:15, and the rest steps are the same as those of the embodiment 1.2.1-1.2.3; wherein,
comparative example 3.2.1, magnesium powder was 6.67kg and titanium hydride alloy powder was 100kg;
comparative example 3.2.2, magnesium powder 6.67kg, titanium hydride alloy powder 100kg;
in comparative example 3.2.3, 6.67kg of magnesium powder and 100kg of titanium hydride alloy powder were used.
Comparative examples 3.3.1 to 3.3.3
The differences from examples 1.3.1-1.3.3 are: in the step (3), the weight ratio of magnesium powder to titanium hydride alloy powder is 1:18, and the rest steps are the same as those of the embodiment 1.3.1-1.3.3; wherein,
comparative example 3.3.1, 5.56kg of magnesium powder and 100kg of titanium hydride alloy powder;
comparative example 3.3.2, 5.56kg of magnesium powder and 100kg of titanium hydride alloy powder;
in comparative example 3.3.3, 5.56kg of magnesium powder and 100kg of titanium hydride alloy powder were used.
Comparative examples 4.1.1 to 4.1.3
The differences from examples 1.1.1 to 1.1.3 are: in the step (3), the reaction time was 60 hours, and the rest of the steps were the same as in examples 1.1.1 to 1.1.3.
Comparative examples 4.2.1 to 4.2.3
The differences from examples 1.2.1-1.2.3 are: in the step (3), the reaction time was 90.5 hours, and the rest of the steps were the same as in examples 1.2.1 to 1.2.3.
Comparative examples 4.3.1 to 4.3.3
The differences from examples 1.3.1-1.3.3 are: in the step (3), the reaction time was 91 hours, and the rest of the steps were the same as in examples 1.3.1 to 1.3.3.
Performance detection
The low oxygen content titanium alloy powders prepared in examples 1-2 and comparative examples 1-4 were subjected to elemental analysis using an oxygen-nitrogen-hydrogen analyzer, respectively, and their corresponding oxygen content, nitrogen content and hydrogen content were recorded in table 1.
Table 1 table of performance test data
| Project | Oxygen content (ppm) | Nitrogen content (ppm) | Hydrogen content (ppm) |
| Example 1.1.1 | 935 | 185 | 171 |
| Example 1.1.2 | 928 | 183 | 168 |
| Example 1.1.3 | 921 | 180 | 165 |
| Example 1.2.1 | 933 | 179 | 165 |
| Example 1.2.2 | 925 | 178 | 163 |
| Example 1.2.3 | 919 | 175 | 160 |
| Example 1.3.1 | 934 | 182 | 168 |
| Example 1.3.2 | 926 | 180 | 166 |
| Example 1.3.3 | 919 | 178 | 164 |
| Example 2.1.1 | 925 | 181 | 170 |
| Example 2.1.2 | 917 | 180 | 166 |
| Example 2.1.3 | 911 | 176 | 163 |
| Example 2.2.1 | 921 | 175 | 164 |
| Example 2.2.2 | 915 | 174 | 162 |
| Example 2.2.3 | 908 | 171 | 158 |
| Example 2.3.1 | 923 | 177 | 166 |
| Example 2.3.2 | 917 | 175 | 164 |
| Example 2.3.3 | 910 | 174 | 161 |
| Comparative example 1.1.1 | 2730 | 185 | 170 |
| Comparative example 1.1.2 | 2725 | 182 | 168 |
| Comparative example 1.1.3 | 2718 | 180 | 166 |
| Comparative example 1.2.1 | 2727 | 178 | 165 |
| Comparative example 1.2.2 | 2721 | 178 | 163 |
| Comparative example 1.2.3 | 2715 | 176 | 160 |
| Comparative example 1.3.1 | 2728 | 182 | 169 |
| Comparative example 1.3.2 | 2723 | 180 | 165 |
| Comparative example 1.3.3 | 2715 | 178 | 163 |
| Comparative example 2.1.1 | 1352 | 185 | 170 |
| Comparative example 2.1.2 | 1347 | 183 | 168 |
| Comparative example 2.1.3 | 1340 | 180 | 166 |
| Comparative example 2.2.1 | 1349 | 179 | 165 |
| Comparative example 2.2.2 | 1344 | 178 | 162 |
| Comparative example 2.2.3 | 1337 | 175 | 160 |
| Comparative example 2.3.1 | 1351 | 182 | 169 |
| Comparative example 2.3.2 | 1345 | 180 | 166 |
| Comparative example 2.3.3 | 1339 | 178 | 164 |
| Comparative example 3.1.1 | 1229 | 186 | 171 |
| Comparative example 3.1.2 | 1224 | 182 | 168 |
| Comparative example 3.1.3 | 1220 | 180 | 165 |
| Comparative example 3.2.1 | 1226 | 179 | 165 |
| Comparative example 3.2.2 | 1221 | 178 | 163 |
| Comparative example 3.2.3 | 1218 | 174 | 160 |
| Comparative example 3.3.1 | 1228 | 182 | 168 |
| Comparative example 3.3.2 | 1222 | 180 | 166 |
| Comparative example 3.3.3 | 1219 | 178 | 164 |
| Comparative example 4.1.1 | 1209 | 205 | 337 |
| Comparative example 4.1.2 | 1204 | 203 | 334 |
| Comparative example 4.1.3 | 1198 | 200 | 330 |
| Comparative example 4.2.1 | 931 | 179 | 164 |
| Comparative example 4.2.2 | 924 | 178 | 163 |
| Comparative example 4.2.3 | 918 | 175 | 160 |
| Comparative example 4.3.1 | 931 | 182 | 164 |
| Comparative example 4.3.2 | 925 | 180 | 163 |
| Comparative example 4.3.3 | 918 | 178 | 160 |
As can be seen from Table 1, the recovered titanium alloy powder prepared in the embodiment of the application has the oxygen content of less than 1300ppm, the nitrogen content of less than 200ppm and the hydrogen content of less than 200ppm, and experimental data show that the method for recovering the titanium alloy waste powder with the particle size of 63-250 mu m does not increase the oxygen content of the titanium alloy waste powder, and the recovered titanium alloy powder still has lower oxygen content and meets the requirement of the titanium alloy powder for 3D printing on the oxygen content.
As can be seen from the data of each group of the examples 2 and 1, the porous titanium tube has further controlled air permeability, so that more magnesium powder steam can overflow from the porous titanium tube, the sufficiency of the magnesium powder steam for the oxygen reduction process of the titanium powder is improved, and the oxygen content of the recovered titanium alloy powder is further reduced.
Comparative example 1 is different from example 1 in that only the titanium hydride alloy powder was subjected to the dehydrogenation treatment without using magnesium powder for the oxygen reduction process, and as can be seen from table 1, the recovered titanium alloy powder obtained in comparative example 1 has an oxygen content of 2715 to 2730ppm, which is significantly higher than that of example 1, and experimental data shows that the oxygen content in the titanium alloy powder can be significantly reduced by using magnesium powder for the oxygen reduction process while the dehydrogenation process is performed.
Comparative example 2 is different from example 1 in that the titanium alloy powder was subjected to the oxygen reduction process using aluminum powder instead of magnesium powder, and as can be seen from table 1, the recovered titanium alloy powder obtained in comparative example 2 has an oxygen content of 1337-1352ppm, which is significantly higher than that of example 1, and experimental data shows that the magnesium powder has a more remarkable oxygen reduction effect on the titanium alloy powder, and the oxygen content in the obtained titanium alloy powder is lower.
Comparative example 3 is different from example 1 in that the weight ratio of magnesium powder to titanium hydride alloy powder is not within the scope of the present application, and as can be seen from table 1, the oxygen content of the recovered titanium alloy powder obtained in comparative example 3 is 1218-1229ppm, which is significantly higher than that of example 1, and experimental data shows that the oxygen content of the recovered titanium alloy powder can be reduced by controlling the weight ratio of magnesium powder to titanium hydride alloy powder.
Comparative example 4 differs from example 1 in that the incubation time in step (3) is different, wherein comparative example 4.1 differs from example 1.1 in that the incubation time is shortened, and as can be seen from table 1, the oxygen content of the recovered titanium alloy powder obtained in comparative example 4.1 is 1198-1209ppm, which is significantly higher than that in example 1.1, and experimental data shows that too short incubation time affects the sufficient progress of the oxygen reduction of magnesium powder, thereby making the oxygen content in the recovered titanium alloy powder higher; comparative examples 4.2 to 4.3 are different from examples 1.2 to 1.3 in that the incubation time is slightly prolonged, and as can be seen from table 1, the oxygen content of the recovered titanium alloy powder obtained in comparative examples 4.2 to 4.3 is 918 to 931ppm, which is almost the same as that in examples 1.2 to 1.3, and experimental data indicate that the incubation time is prolonged again on the basis of the present application, and the oxygen content in the titanium alloy powder cannot be reduced continuously, but the production energy consumption is increased, and the production cost is increased.
The embodiments of the present invention are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (8)
1. A method for preparing low-oxygen-content titanium alloy powder, which is characterized by comprising the following steps:
carrying out hydrogen absorption grinding treatment on the titanium alloy waste powder to obtain titanium hydride alloy powder, adding magnesium powder into the titanium hydride alloy powder, carrying out heat preservation reaction for 70-90h under the conditions that the temperature is 680-700 ℃ and the vacuum degree is 0.5-0.6Pa, and then carrying out crushing spheroidization to obtain low-oxygen-content titanium alloy powder; wherein, the weight ratio of the magnesium powder to the titanium hydride alloy powder is 1 (10-12);
firstly filling the magnesium powder into a porous titanium tube, and then adding the magnesium powder into titanium hydride alloy powder;
the air permeability of the porous titanium tube is 0.8-2L/cm 2 ·min·pa。
2. The method for preparing the low-oxygen-content titanium alloy powder according to claim 1, wherein: the pore diameter of the porous titanium tube is 0.1-10 mu m, and the particle diameter of the magnesium powder is 10-20 mu m.
3. The method for preparing low-oxygen-content titanium alloy powder according to claim 1, wherein the hydrogen-absorbing grinding treatment comprises a hydrogen-absorbing process and a grinding process, wherein the hydrogen-absorbing process is specifically as follows: and (3) carrying out hydrogen absorption on the titanium alloy waste powder under the conditions that the temperature is 550-560 ℃ and the pressure is 0.03-0.05MPa, and stopping hydrogen absorption when the weight of the titanium alloy waste powder is increased by at least 3.2%.
4. A method for preparing a low oxygen content titanium alloy powder according to claim 3, wherein: the particle size of the titanium alloy waste powder is 63-250 mu m.
5. A method for preparing a low oxygen content titanium alloy powder according to claim 3, wherein the grinding process is specifically: grinding and spheroidizing the waste titanium alloy powder after hydrogen absorption under the condition that the pressure of inert gas is maintained at 530-550KPa, and obtaining the hydrogenated titanium alloy powder with the particle size of 20-63 mu m under the condition that the rotating speed is 4500-5000 r/min.
6. The method for preparing low-oxygen-content titanium alloy powder according to claim 1, wherein the crushing and spheroidizing is specifically: under the condition that the inert gas is maintained at 600-650MPa, the titanium alloy powder after dehydrogenation reduction is spheroidized and crushed under the condition that the rotating speed is 5500-6000 r/min.
7. A low oxygen content titanium alloy powder produced by the production method of the low oxygen content titanium alloy powder as claimed in any one of claims 1 to 6.
8. The low oxygen titanium alloy powder of claim 7, wherein: the oxygen content of the low oxygen content titanium alloy powder is less than 1300ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311457818.1A CN117161388B (en) | 2023-11-04 | 2023-11-04 | Low-oxygen-content titanium alloy powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311457818.1A CN117161388B (en) | 2023-11-04 | 2023-11-04 | Low-oxygen-content titanium alloy powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117161388A CN117161388A (en) | 2023-12-05 |
| CN117161388B true CN117161388B (en) | 2024-01-12 |
Family
ID=88930367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311457818.1A Active CN117161388B (en) | 2023-11-04 | 2023-11-04 | Low-oxygen-content titanium alloy powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117161388B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525956A (en) * | 2014-12-16 | 2015-04-22 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing hydrogenated titanium alloy powder |
| CN109202090A (en) * | 2018-10-23 | 2019-01-15 | 朝阳金达钛业股份有限公司 | A kind of production method of hypoxemia hydrogenation dehydrogenation titanium powder |
| CN115026292A (en) * | 2022-04-26 | 2022-09-09 | 北京科技大学 | Titanium powder for 3D printing and preparation method and device thereof |
| CN115971502A (en) * | 2021-10-15 | 2023-04-18 | 安徽中体新材料科技有限公司 | Method for preparing 3D printing titanium alloy powder through rotary atomization of induction electrode and titanium alloy powder |
| CN116463568A (en) * | 2023-04-07 | 2023-07-21 | 浙江泰能新材料有限公司 | Titanium waste recycling method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9067264B2 (en) * | 2012-05-24 | 2015-06-30 | Vladimir S. Moxson | Method of manufacturing pure titanium hydride powder and alloyed titanium hydride powders by combined hydrogen-magnesium reduction of metal halides |
-
2023
- 2023-11-04 CN CN202311457818.1A patent/CN117161388B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525956A (en) * | 2014-12-16 | 2015-04-22 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing hydrogenated titanium alloy powder |
| CN109202090A (en) * | 2018-10-23 | 2019-01-15 | 朝阳金达钛业股份有限公司 | A kind of production method of hypoxemia hydrogenation dehydrogenation titanium powder |
| CN115971502A (en) * | 2021-10-15 | 2023-04-18 | 安徽中体新材料科技有限公司 | Method for preparing 3D printing titanium alloy powder through rotary atomization of induction electrode and titanium alloy powder |
| CN115026292A (en) * | 2022-04-26 | 2022-09-09 | 北京科技大学 | Titanium powder for 3D printing and preparation method and device thereof |
| CN116463568A (en) * | 2023-04-07 | 2023-07-21 | 浙江泰能新材料有限公司 | Titanium waste recycling method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117161388A (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108907210B (en) | Method for preparing solid spherical metal powder for additive manufacturing | |
| CN108080649B (en) | Method for preparing superfine iron powder by low-temperature hydrocarbon duplex reduction | |
| US20170008082A1 (en) | Metal powder for 3D printers and preparation method for metal powder | |
| CN104772473A (en) | Preparation method of fine-particle spherical titanium powder for three-dimensional (3D) printing | |
| WO2011082596A1 (en) | Short-flow preparation method for fine spherical titanium powder | |
| WO2020019402A1 (en) | Oxide dispersion-strengthened iron-based alloy powder and characterization method therefor | |
| CN106216705A (en) | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder | |
| CN101061252A (en) | Sputtering target for production of metallic glass film and process for producing the same | |
| CN104209526A (en) | Preparation method for micro-fine spherical titanium alloy powder | |
| US20200246875A1 (en) | Method for preparing vanadium and vanadium alloy powder from vanadium-containing materials through shortened process | |
| JP2023500975A (en) | Method for producing aluminum-containing alloy powder and its use, and alloy ribbon | |
| CN112548109B (en) | Preparation method of spherical powder of high-strength titanium alloy for additive manufacturing | |
| CN109014182A (en) | Increasing material manufacturing 7000 line aluminium alloy powder and preparation method thereof | |
| CN113579237B (en) | Preparation method for reducing apparent density of copper-tin alloy powder | |
| WO2015124094A1 (en) | Method for preparing tantalum powder for high-reliability, high specific capacity electrolytic capacitor | |
| JPS6289803A (en) | Powdery particle for fine granular hard alloy and its production | |
| CN109128207B (en) | Superfine titanium powder and preparation method thereof | |
| CN108274011B (en) | Preparation method of metal powder with bimodal distribution suitable for 3D printing | |
| CN117161388B (en) | Low-oxygen-content titanium alloy powder and preparation method thereof | |
| WO2008022495A1 (en) | Method for preparing nanometer metal powder | |
| CN106623952A (en) | Preparation method of titanium or titanium alloy powder with micro-hydrogenated surface | |
| CN109694969B (en) | Pre-alloyed powder, TiCN-based metal ceramic composite material added with pre-alloyed powder and preparation method of TiCN-based metal ceramic composite material | |
| CN110014161B (en) | Method for preparing spherical tungsten-based powder | |
| CN111036931A (en) | Tungsten-cobalt alloy powder and preparation method thereof | |
| CN111922330B (en) | Metal tungsten powder for laser additive manufacturing of tungsten product, tungsten product and preparation method of tungsten product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |