CN112055628A - Titanium-based powder and method for producing same - Google Patents
Titanium-based powder and method for producing same Download PDFInfo
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- CN112055628A CN112055628A CN201980019823.XA CN201980019823A CN112055628A CN 112055628 A CN112055628 A CN 112055628A CN 201980019823 A CN201980019823 A CN 201980019823A CN 112055628 A CN112055628 A CN 112055628A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/023—Hydrogen absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/048—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by pulverising a quenched ribbon
Abstract
The invention provides a titanium powder with reduced pores in the titanium powder. The titanium-based powder is characterized in that the area ratio of pores obtained by dividing the cross-sectional area of the titanium-based powder by the cross-sectional area of the titanium-based powder is 0.3% or less. The method for producing titanium-based powder of the present invention is characterized by producing titanium-based powder by treating a titanium-based material containing total MgCl by a hydrogenation dehydrogenation method including a hydrogenation step, a pulverization step, and a dehydrogenation step2Has a concentration of 1.0 mass% or less and contains MgCl internally2The concentration is 0.1 mass% or less.
Description
Technical Field
The present invention relates to a titanium-based powder, and more particularly, to an unprecedented novel titanium-based powder produced by a hydrogenation dehydrogenation method (hereinafter referred to as HDH method) and a production method thereof.
Background
Conventionally, the fine pores in titanium-based powder are in the following state: there is little attention in industry, and there is little literature on the detailed study of the pore generation mechanism. In recent years, with the increasing demand for density increase of sintered bodies using titanium-based powders and the increasing demand for quality of titanium products made of titanium-based powders, there has been an increasing demand for reduction of pores in titanium-based powders.
No prior art document disclosing a technique for reducing the number of pores in titanium-based powder has been searched for. As prior art documents relating to the production of titanium-based powders, there are patent document 1 and patent document 2. In the present specification, titanium powder and titanium alloy powder are referred to as titanium-based powder.
Documents of the prior art
Patent document
Patent document 1: JP-A-5-247503;
patent document 2: JP-A No. 7-278601.
Disclosure of Invention
Problems to be solved by the invention
In order to solve the above problems, an object of the present invention is to provide a titanium-based powder in which pores in the titanium-based powder are reduced.
Means for solving the problems
In order to produce the titanium-based powder having a small number of pores, the present inventors analyzed the structure and generation mechanism of the pores in detail. As a result, it was found that the number of generated pores greatly changed by adjusting the raw material and the production method of the titanium-based powder, and as a result of analysis of the generation of pores, pores having a substantially circular (spherical) cross-sectional shape remained due to the presence (or once presence) of gas in the titanium-based powder.
According to one embodiment of the present invention, there is provided a titanium-based powder, characterized in that a pore area ratio obtained by dividing a cross-sectional area occupied by pores in a cross-section of the titanium-based powder by a cross-sectional area of the titanium-based powder is 0.3% or less.
The titanium-based powder may be HDH powder.
According to an embodiment of the present invention, there is provided a method for producing titanium-based powder by treating a titanium-based raw material by a hydrogenation and dehydrogenation method including a hydrogenation step, a pulverization step, and a dehydrogenation step, wherein the titanium-based raw material contains total MgCl2Has a concentration of 1.0 mass% or less and contains MgCl internally2The concentration is 0.1 mass% or less.
The maximum thickness of the titanium-based material may be 20mm or less.
In the grinding step, the titanium hydride-based powder may be ground to a D95 particle size of 300 μm or less.
In the hydrogenation step, the temperature of the titanium-based raw material may be adjusted to a range of 716 to 1050 ℃ and it may take 90 minutes or more to hydrogenate the titanium-based raw material.
Effects of the invention
The pore generation in the titanium-based powder is closely related to the gas. By preventing the gas from being entrained in the titanium-based powder, the amount of the titanium-based powder having pores can be greatly reduced by preventing the gas from being generated inside the titanium-based powder or by quickly removing the generated gas from the inside of the titanium-based powder.
Drawings
Fig. 1 is a diagram illustrating a method of image processing, and particularly illustrates pores included therein.
Fig. 2 is a diagram illustrating a method of image processing, and particularly illustrates open pores.
FIG. 3 is an optical micrograph of the titanium powder according to example 1.
FIG. 4 is an optical micrograph of titanium powder according to example 3.
FIG. 5 is a photograph of the titanium powder according to comparative example 2 when it was subjected to image processing in an optical microscope photograph.
Detailed Description
Currently, titanium powder is mostly produced from titanium sponge by Kroll process (magnesiothermic reduction process). In addition, waste materials can also be used as raw materials from the viewpoint of economy and resource conservation.
[ description of Kroll method ]
The Kroll process refers to a process in which titanium tetrachloride (TiCl) obtained by chlorinating titanium ore is treated with magnesium (Mg)4) A method for obtaining metallic titanium by reduction.
In the Kroll process, the reduction step (TiCl)4+2Mg→Ti+2MgCl2) MgCl produced in (1)2Coexisting with titanium sponge, MgCl is used by the separation process2Removing the titanium sponge. However, upon careful examination of the titanium sponge, MgCl was found2MgCl adhered to the surface of the titanium sponge remained without being completely removed2(surface MgCl)2) And MgCl enclosed inside the titanium sponge and isolated from the outside2(internal MgCl)2) These two MgCl types2。
MgCl remaining on the surface of the titanium sponge not sufficiently removed in the separation step2(surface MgCl)2) Can be removed by reheating under reduced pressure. On the other hand, when the titanium sponge heated under a reduced pressure was cut and examined for the inside, it was found that this method could not remove MgCl enclosed in the inside of the titanium sponge2(internal MgCl)2)。
[ description of the method for producing titanium powder by atomization ]
The methods for producing titanium powder are roughly classified into an atomization method and an HDH method. In the atomization method, a titanium raw material is melted, and then liquefied titanium in argon gas is converted into fine liquid particles, which are rapidly cooled and solidified to produce titanium powder.
The inventor of the invention has concluded through research and investigation that there are two mechanisms for generating pores in titanium powder in the atomization method. The first mechanism is the presence of MgCl within the titanium source2(internal MgCl)2) Gasification and rapid quenching of the vaporized MgCl2Is enclosed inside the particles of liquefied titanium, resulting in the generation of fine pores in the titanium powder. The second mechanism is that the particles of liquefied titanium entrain argon or gasify MgCl2The gas solidifies, resulting in the creation of pores in the titanium powder. Therefore, it was concluded that the HDH method is suitable for achieving the object of the present invention.
[ description of the method for producing titanium powder by HDH method ]
The so-called HDH process is a process for forming brittle TiH by temporarily hydrogenating a titanium feedstock2And then pulverized and dehydrogenated, thereby obtaining titanium powder. That is, this method produces titanium powder (HDH powder) through the steps of hydrogenation-pulverization-dehydrogenation-pulverization. The above-mentioned crushing step is optional, but it is preferable to perform the crushing step when producing titanium powder (HDH powder).
In this case, in the hydrogenation step, the titanium raw material is charged into a hydrogenation furnace capable of vacuum replacement, and is subjected to hydrogenation treatment at a temperature of 400 ℃ or higher in a hydrogen atmosphere, and is replaced from the hydrogen atmosphere to an argon atmosphere, thereby obtaining a titanium hydride bulk. The titanium material is hydrogen embrittled in the hydrogenation step.
The pulverization step follows. In the pulverization step, the titanium hydride bulk is mechanically pulverized into titanium hydride powder having a pulverized surface which is a mechanical fracture surface. The obtained titanium hydride powder is classified and/or sieved to remove fine powder of titanium hydride. For mechanical pulverization of titanium hydride, a pulverizing device such as a ball mill or a vibration mill may be used, and a sieve classifying device such as a circular vibration sieve or an air classifier may be used to adjust the particle diameter of titanium hydride powder.
In the dehydrogenation step, the titanium hydride powder is charged into a vessel and charged into a vacuum heating type dehydrogenation furnace, for example, at 10-3Heating the mixture to a temperature of 450 ℃ or higher in a vacuum of 0.13Pa or lower to dehydrogenate the mixture, thereby obtaining a titanium hydride powder. In addition, argon gas may be introduced, if necessary.
In the pulverization step, the temporarily sintered portion of the titanium dehydrogenation bulk temporarily sintered after the dehydrogenation step is decomposed and restored to a titanium powder shape having a pulverized surface or a pulverized surface after pulverization.
[ description of pore generation mechanism in HDH method ]
The present inventors investigated conditions in each production step of the HDH method in detail from the viewpoint of pores, and found out how to prevent the formation of pores. In the HDH method, if titanium is not melted and liquefied in each production process, argon gas in the atmosphere is not entrained and pores are not generated. The heat treatment in the HDH method may be performed at a temperature not higher than the melting point because of the two steps of hydrogenation and dehydrogenation. However, since stainless steel is generally used as a vessel in which a titanium material is put, it is not satisfactory because iron contained in stainless steel comes into contact with titanium, and when both temperatures reach a temperature equal to or higher than the eutectic temperature of iron and titanium, titanium is in a liquid state. Thus, the present inventors found that: in order to prevent the generation of pores, it is necessary to control the temperature of titanium to be equal to or lower than the eutectic temperature of iron and titanium to prevent liquefaction of titanium. That is, an important component of the present invention is to control the upper limit temperature.
For example, patent documents 1 and 2 only describe "heating to 650 ℃ in a vacuum atmosphere", and do not describe temperature control of a titanium material after introduction of hydrogen gas thereafter. Since the hydrogenation reaction for hydrogenating titanium is an exothermic reaction, hydrogen absorption is initially performed in a vacuum furnace at 650 ℃, for example, but the temperature spontaneously rises thereafter. Therefore, it is necessary to perform fine control, and for example, it is necessary to constantly observe the manner of charging the titanium material into the vessel, the amounts of hydrogen and argon charged, the charging time, and the temperatures of the respective portions, and to cool down the titanium material so as to suppress the temperature rise so that any portion including the local portion is equal to or lower than the eutectic temperature.
MgCl at atmospheric pressure2Has a boiling point of 1412 deg.C, at which MgCl is present in the titanium source2(internal MgCl)2) Will vaporize. On the other hand, titanium has a melting point of 1668 ℃, so that at 1412 ℃, titanium exists in a solid state. Internal MgCl after gasification2The volume becomes large compared to the solid state, resulting in an extremely high pressure state inside the titanium. The vaporized internal MgCl2The high-pressure state caused by the hydrogenation causes cracking of the titanium hydride which becomes brittle by the hydrogenation, so that MgCl can be discharged to the outside of the titanium hydride2。
However, in the HDH method, the vessel containing the titanium material is mostly stainless steel, and the temperature is not raised to the eutectic temperature (1085 ℃ C.) of iron and titanium or higher. The present inventors have found that MgCl which causes generation of pores can be removed while observing the limiting temperature2And a control method which has not been found so far, thereby completing the present invention. That is, the temperature of the titanium raw material is adjusted to MgCl at the lowest level2At a temperature of not less than the melting point of (714 ℃ C.) of MgCl2In the liquid phase, MgCl2Expands in volume compared to the solid state. At this timeTitanium exists in the solid state, so internal MgCl2The volume in the liquid state is larger than that in the solid state, so that an extremely high pressure state is formed inside the titanium. MgCl inside the liquid phase2The resulting high pressure conditions crack the titanium hydride, which becomes brittle upon hydrogenation. Liquid-phase MgCl exposed to the outside of titanium due to cracking2Can be vaporized by gradual evaporation. In this case, the temperature in the furnace and the heating time (temperature maintaining time) need to be controlled in consideration of the thickness of the titanium material to be hydrogenated and the hydrogenation time. For example MgCl if it evaporates before embrittlement of the titanium2As the internal pressure of titanium becomes high, titanium is easily softened at high temperature and deformed, and thus spherical pores are formed in the titanium, which is contrary to the present invention. For example, in the present invention, MgCl is present in the titanium material by taking 90 minutes or more in the range of 716 to 1050 deg.C2Evaporating from the cracks of the titanium and simultaneously realizing the hydrogenation of the titanium. In theory, the temperature of the titanium feedstock can be set at MgCl2Is within a range of from the melting point (714 ℃) of (a) to less than the eutectic temperature (1085 ℃) of iron and titanium, and temperature control can be performed more accurately by setting within the above temperature range.
In the HDH method according to the present embodiment, the temperature is controlled so as not to melt the titanium material. However, when MgCl is attached to the surface of the titanium raw material2In the process of the HDH method, MgCl is used2Gasification, in order to remove surface MgCl2Preferably, a high vacuum is applied. In the HDH method according to the present embodiment, it is important to reduce MgCl adhering to the surface with the titanium raw material2While the amount is being measured, the temperature, time, vacuum degree, argon substitution, etc. are optimized in consideration of cost.
In the hydrogenation step according to the present embodiment, MgCl present in the titanium is removed so as not to generate pores2(internal MgCl)2) The hydrogenation step is a hydrogenation step which embodies the mechanism found in the present invention. If it takes a sufficient time for embrittlement by hydrogenation, MgCl can be converted2Discharge, however, this is not industrially suitable for productivity and cost.
The results of the research survey showed that: comparison with MgCl attached to the surface of the titanium raw material2Amount of MgCl present in the titanium raw material2The amount has a greater influence on productivity and cost. Various experiments show that: total MgCl of the titanium starting material is required2The concentration is controlled to 1.0 mass% or less. And, total MgCl of the titanium raw material2The concentration is preferably controlled to 0.05% by mass or less, and more preferably controlled to 0.001% by mass or less. In particular, when MgCl is present in the interior of the titanium raw material2Concentration (internal MgCl)2Concentration) of 0.5 mass% or less, even if the titanium raw material temperature is set to MgCl in the HDH method2Is maintained for 90 minutes in a range of not less than the melting point (714 ℃) of iron and less than the eutectic temperature (1085 ℃) of titanium, and MgCl which causes generation of pores can be efficiently removed2. By reacting MgCl present in the titanium starting material2Concentration (internal MgCl)2Concentration) is 0.1 mass% or less, the effect is more clearly exhibited. In the present invention, MgCl is present in the titanium starting material2Concentration (internal MgCl)2Concentration) is preferably 0.1% by mass or less, more preferably 0.001% by mass or less.
[ method of suppressing pores in raw Material ]
In the HDH method of the present invention, titanium does not melt, and therefore, fine pores are not generated by the entrainment of argon gas or the like.
Total MgCl as raw material for titanium2The concentration of MgCl in the titanium material is controlled to 1.0 mass% or less2Concentration (internal MgCl)2Concentration) of 0.1 mass% or less, and although it is costly, a method of further refining the titanium sponge in advance and performing heat treatment again in vacuum may be used.
The maximum thickness of the titanium material may be 20mm or less, and more preferably 10mm or less. When the maximum thickness of the titanium material is 20mm or less, hydrogen is sufficiently diffused into the material during hydrogenation, and the titanium is embrittled and crack generation is accelerated.
[ Total MgCl ]2Definition of concentration]
For total MgCl2The method of measuring the concentration of (1) will be described. The chlorine concentration of the target titanium material was measured by silver nitrate titration method (JIS H1615), and the chlorine concentration value was determinedConverted to MgCl2MgCl in a concentration such that it is contained as a titanium raw material2Concentration (Total MgCl)2Concentration).
[ internal MgCl ]2Definition of concentration]
For internal MgCl2The method of measuring the concentration of (1) will be described. First, a target titanium material is subjected to a heat treatment at 750 ℃ for 1 hour under a reduced pressure environment (50pa or less) to form MgCl on the surface2And (4) dissipating. Then, the chlorine concentration of the material was measured by silver nitrate titration method (JIS H1615), and converted into MgCl based on the chlorine concentration value2Concentration of the MgCl and taking it as MgCl existing in the interior of the titanium raw material2Concentration (internal MgCl)2Concentration).
[ description of the size of titanium powder ]
In the pulverization step, the hydrogenated titanium hydride is pulverized and refined to obtain titanium hydride powder having a pulverized surface, whereby the probability that the remaining pores in the titanium hydride will break and open as starting points can be further increased. The smaller the particle diameter of the titanium hydride powder is, the higher the opening probability of the pores becomes. However, the titanium hydride powder may have a particle diameter of 300 μm or less, preferably 150 μm or less, because of industrial cost and time limitations. Here, the titanium hydride powder produced and pulverized by the HDH method may have a distribution of particle diameters, and 95% or more of the particle diameters of the entire titanium hydride powder may be equal to or less than the above value. That is, the effect is more excellent when the D95 particle size of the titanium hydride powder is 300 μm or less, preferably 150 μm or less. The lower limit of the D95 particle size is not particularly limited, and may be 70 μm or more, or 80 μm or more, for example. In the present invention, D95 indicates a particle size at which the volume-based integral distribution of the particle size distribution obtained by the laser diffraction/scattering method is 95%. Specifically, the reference value is based on JIS Z8825: 2013 for measurement.
In addition, 95% or more of the entire titanium particle diameter of the titanium powder produced and crushed by the HDH method may be 150 μm or less.
[ application to spheroidization Process ]
MgCl in the titanium powder produced by the HDH method2The residue is small. Therefore, the titanium powder produced by the HDH method of the present invention is preferable asThe titanium powder is surface-melted (for example, plasma-melted) to form a spherical surface of the crushed surface or the angular surface of the crushed surface, thereby obtaining a raw material powder of a spherical powder. Since the titanium powder produced and crushed by the HDH method has a crushed surface or a crushed surface having an uneven structure, the melting at the time of introducing plasma can be accelerated by a large surface area thereof. Further, even if the titanium powder surface is melted for spheroidizing, the generation of new micropores can be suppressed without introducing an ion gas such as argon.
As described above, the present inventors have found that: in order to suppress the generation of pores in the HDH method, the temperature, time, hydrogen injection amount, material shape, MgCl, etc. may be appropriately controlled as described above2Amount introduced (total amount and MgCl enclosed)2The amount of (b) to complete the present invention.
In the present embodiment, the description is based on titanium powder. However, even in a titanium alloy powder containing 50 mass% or less of elements such as Al and V in titanium, the temperature is controlled by the HDH method so that the raw material titanium alloy does not melt, and the same effect as that of the titanium powder can be obtained. The content of the element in titanium is preferably 20 mass% or less, and more preferably 15 mass% or less. The titanium alloy powder may also contain a plurality of elements. For example, the titanium alloy powder may be a Ti-Al-V alloy powder. In this case, the Ti-Al-V alloy powder may have an Al content of 5.5 to 7.5% by mass and a V content of 3.5 to 4.5% by mass.
[ description of the area ratio of pores in cross section ]
According to the method for producing titanium-based powder of the present embodiment, it is possible to realize: the value (cross-sectional pore area ratio) obtained by dividing the cross-sectional area of the contained pores (hereinafter referred to as internal pores) appearing on any cross-section of the titanium-based powder by the cross-sectional area of the titanium-based powder may be 0.3% or less. In the titanium-based powder produced by the present invention, the number of internal pores appearing on any cross section of the titanium-based powder is preferably 20 pores/mm per unit area2The following. The titanium powder having a cross-sectional pore area ratio of 0.3% or less means that when the titanium powder is embedded in a resin and ground, and then a cross section of 16 arbitrary sites having a size of 700 μm × 500 μm is observed at a magnification of 500 by an optical microscope, the titanium powder is observed as an image having a brightness in the range of 90 to 250 by image processingThe value obtained by dividing the cross-sectional area of the fine pores by the total cross-sectional area of the powder is 0.3% or less. The number of inner pores is the number of inner pores observed as an image having a brightness in the range of 90 to 250 by image processing at the time of the observation. In any observation, powder having a major axis of 10 μm or less was removed by image processing. In the image processing, pores that appear to be internal pores but are clearly open from the original image are excluded (fig. 1 is a photograph before the image processing, and fig. 2 is a photograph after the image processing). Even when two pores are clearly connected, one internal pore is calculated as one pore connected in the image processing. In the present invention, since the area ratio of the cross-sectional pores is 0.3% or less, the titanium powder produced by the production method according to the present invention is suitably used in a technical field (for example, an aircraft material or the like) in which pores are required to be small. On the other hand, it is found that if the cross-sectional pore area ratio exceeds 0.3%, the use thereof in this technical field is difficult.
[ example 1]
Titanium sponge was used as the titanium raw material. In the titanium starting material used, total MgCl2Concentration and internal MgCl2The concentrations were all 0.05 mass% or less, and the diameters were 1/2 inches or less.
After evacuating 300kg of the raw material to 5Pa or less, the atmosphere was heated to 650 ℃ with a heater and maintained for 120 minutes. Then, hydrogen was supplied to initiate a hydrogen storage exothermic reaction, and at the same time, heater control, argon gas introduction and cooling device operation were performed to control the temperature of the titanium raw material to 1000 ℃ or lower, and hydrogenation was performed for 120 minutes. The temperature range is 716-1000 ℃.
The bulk density of the titanium starting material during hydrogenation was 1.2g/cm3。
Thereafter, the titanium hydride block is pulverized by a pulverizer/classifier to obtain titanium hydride powder having a particle diameter of 10 to 150 μm.
After dehydrogenation treatment is performed under the condition of a vacuum heat treatment furnace, the titanium hydride block is subjected to disintegration treatment. The resulting titanium powder had a D95 particle size of 100. mu.m.
Fig. 3 shows an optical microscope photograph of the obtained titanium powder. Embedding titanium powder into resin, grinding the cross section of the sampleThen, 16 arbitrary sites of 700. mu. m.times.500. mu.m size were observed with an optical microscope at a magnification of 500. As a result of analyzing the number and area ratio of the fine pores, the number of fine pores per unit area was 20/mm2. And the pore area ratio was 0.11%.
[ example 2]
Use of Total MgCl2Scrap powder produced from a sponge titanium material having a concentration of 0.1 mass% or less as a titanium material, and MgCl as a total amount2The concentration is 0.0002 mass% or less and the maximum thickness is 7 mm. Namely, the internal MgCl of the titanium raw material2The concentration is also 0.0002 mass% or less. After evacuating 300kg of the raw material to 5Pa or less, the atmosphere was heated to 650 ℃ with a heater and maintained for 120 minutes. Then, hydrogen was supplied to initiate the exothermic reaction of hydrogen storage, and at the same time, the heater control, argon gas introduction and cooling device operation were carried out, and the temperature of the titanium raw material was controlled to 1000 ℃ or lower, and hydrogenation was carried out for 120 minutes. The temperature range is 716-1000 ℃.
The bulk density at hydrogenation was 1.2g/cm3. Thereafter, the titanium hydride block is pulverized by a pulverizer/classifier to obtain titanium hydride powder having a particle diameter of 10 to 150 μm. Then, after dehydrogenation treatment is carried out under the condition of a vacuum heat treatment furnace, the bulk of the dehydrogenated titanium is subjected to disintegration treatment. The resulting titanium powder had a D95 particle size of 100. mu.m.
The titanium powder thus obtained was embedded in a resin, the cross section of the sample was polished, and 16 arbitrary sites having a size of 700. mu. m.times.500. mu.m were observed at 500 magnifications with an optical microscope, and as a result, pores were detected at 8 pores/mm per unit area2. And the pore area ratio was 0.02%.
In example 2, the impurity iron concentration in the titanium material in the production of the titanium powder was 200 mass ppm or less, and 200 mass ppm or more and 500 mass ppm or less. In either case, the number of pores detected is 8 to 10/mm per unit area2. In either case, the pore area ratio was 0.02%. Therefore, it is considered that the content of the impurity iron has no influence, in other words, the purity of titanium has no relation with the pore generation behavior.
[ example 3]
Use of Total MgCl2A sponge titanium material having a concentration of 0.1% by mass or less and 90% Ti-6% Al-4% V (mass%) scrap powder made of an alloy of 60% Al-40% V as a raw material. Total MgCl of titanium alloy dust used as raw material2The concentration is 0.0002 mass% or less and the maximum thickness is 7 mm. Namely, MgCl inside the titanium alloy powder2The concentration is also 0.0002 mass% or less. After evacuating 300kg of the raw material to 5Pa or less, the atmosphere was heated to 650 ℃ with a heater and maintained for 120 minutes. Then, hydrogen is supplied, hydrogen storage exothermic reaction is initiated, heater control, argon gas access and cooling device operation are carried out simultaneously, the temperature of the titanium alloy scrap powder is controlled to be below 1000 ℃, and hydrogenation is carried out for 120 minutes. The temperature range is 716-1000 ℃.
The bulk density at hydrogenation was 1.2g/cm3. Thereafter, the titanium hydride block was pulverized by a pulverizer/classifier to obtain a powder having a particle size of 10 to 150 μm. Then, dehydrogenation treatment is performed under the condition of a vacuum heat treatment furnace, and the bulk of the dehydrogenated titanium is subjected to disintegration treatment. The resulting titanium powder had a D95 particle size of 100. mu.m.
The titanium alloy powder thus obtained was embedded in a resin, the cross section of the sample was polished, and 16 arbitrary sites having a size of 700. mu. m.times.500. mu.m were observed at a magnification of 500 with an optical microscope, and as a result, 9 pores/mm per unit area were detected as pores2. And the pore area ratio was 0.03%.
The titanium alloy powder obtained above was melted on the surface by a high-frequency heat induction plasma apparatus using argon gas as a plasma gas to form a spherical shape. The spheroidization conditions are shown in table 1. Fig. 4 shows an optical micrograph of the obtained titanium alloy powder. The titanium alloy powder was embedded in a resin, and 16 arbitrary portions of 700. mu. m.times.500. mu.m size in the cross section of the sample were observed with an optical microscope at a magnification of 500. As a result of analyzing the number-to-area ratio of the fine pores, the fine pores were detected to be 3 pores/mm per unit area2. And the pore area ratio was 0.01%. It was confirmed that the titanium alloy powder produced by the HDH method and disintegrated was usable as a raw material powder for the spherical powder.
[ Table 1]
[ example 4]
Use of Total MgCl2A sponge titanium material having a concentration of 0.1% by mass or less and 89% Ti-7% Al-4% V (mass%) scrap powder made of an alloy of 70% Al-40% V were used as raw materials. Total MgCl of titanium alloy dust used as raw material2The concentration is 0.0002 mass% or less and the maximum thickness is 2 mm. Namely, MgCl inside the titanium alloy powder2The concentration is also 0.0002 mass% or less. After evacuating 300kg of the raw material to 5Pa or less, the atmosphere was heated to 650 ℃ with a heater and maintained for 120 minutes. Then, hydrogen is supplied to initiate hydrogen storage exothermic reaction, and simultaneously, heater control, argon gas access and cooling device operation are carried out, the temperature of the titanium alloy scrap powder is controlled below 1000 ℃, and hydrogenation is carried out for 120 minutes. The temperature range is 716-1000 ℃.
The bulk density at hydrogenation was 1.2g/cm3. Then, the titanium hydride bulk is pulverized by a pulverizer/classifier to obtain a powder of 10 to 150 μm. Then, dehydrogenation treatment is performed under the condition of a vacuum heat treatment furnace, and the bulk of the dehydrogenated titanium is subjected to disintegration treatment. The resulting titanium powder had a D95 particle size of 100. mu.m.
The titanium alloy powder thus obtained was embedded in a resin, the cross section of the sample was polished, and 16 arbitrary sites having a size of 700. mu. m.times.500. mu.m were observed at a magnification of 500 with an optical microscope, and as a result, 9 pores/mm per unit area were detected as pores2. And the pore area ratio was 0.03%.
The results of the Ti-Al-V alloys and the dust powders of examples 3 and 4 were the same as those of the titanium dust powder of example 2. Therefore, the method for producing titanium powder according to the present embodiment is also considered to be applicable to the production of titanium alloy powder.
Comparative example 1
Using internal MgCl2Titanium powder was produced under the same conditions as in example 1 except that titanium sponge having a concentration of 0.2 mass% was used as the titanium raw material. In addition, the total MgCl of the titanium sponge2The concentration was 0.3 mass%. The obtained titanium powder was embedded in a resin, and after grinding the cross section of the sample, 16 samples of 700. mu. m.times.500. mu.m were observed at 500 magnifications with an optical microscopem is any part of the size. As a result of analyzing the number-to-area ratio of the fine pores, the fine pores were detected at 85 pores/mm per unit area2. The pore area ratio was 0.7%.
Comparative example 2
Titanium powder produced by a gas atomization method having the same particle diameter as in example 1 was purchased, embedded in a resin, and the cross section of the sample was polished, followed by observation of 16 arbitrary sites having a size of 700 μm × 500 μm with an optical microscope at a magnification of 500. As a result of analyzing the number-to-area ratio of the fine pores, the fine pores were detected to be 130 pores/mm per unit area2. The pore area ratio was 1.0% (fig. 5).
Claims (6)
1. A titanium-based powder, characterized in that the area ratio of pores obtained by dividing the cross-sectional area of the titanium-based powder by the cross-sectional area of the titanium-based powder is 0.3% or less.
2. The titanium-based powder according to claim 1, wherein the titanium-based powder is an HDH powder.
3. A method for producing a titanium-based powder, which comprises treating a titanium-based material containing total MgCl by a hydrogenation and dehydrogenation method comprising a hydrogenation step, a pulverization step and a dehydrogenation step2Has a concentration of 1.0 mass% or less and contains MgCl internally2The concentration is 0.1 mass% or less.
4. The method for producing titanium-based powder according to claim 3, wherein the maximum thickness of the titanium-based raw material is 20mm or less.
5. The method of producing titanium-based powder according to claim 3 or 4, wherein in the grinding step, the titanium hydride-based powder is ground to a D95 particle size of 300 μm or less.
6. The method of producing the titanium-based powder according to any one of claims 3 to 5, wherein in the hydrogenation step, the temperature of the titanium-based raw material is adjusted to a range of 716 ℃ to 1050 ℃ and it takes 90 minutes or more to hydrogenate the titanium-based raw material.
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| PCT/JP2019/008968 WO2019176700A1 (en) | 2018-03-16 | 2019-03-06 | Titanium powder and method for producing same |
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| JP6976415B2 (en) | 2021-12-08 |
| EP3766601A1 (en) | 2021-01-20 |
| EP3766601A4 (en) | 2021-12-01 |
| JPWO2019176700A1 (en) | 2021-03-11 |
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| TW201938810A (en) | 2019-10-01 |
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