JP2002115005A - METHOD FOR PRODUCING Ti OR Ti ALLOY POWDER USING Ti OR Ti ALLOY SCRAP AS RAW MATERIAL - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing Ti or Ti alloy powders from Ti or Ti alloy scraps without dissolving the same or without making the same into a compound. SOLUTION: In this method for producing Ti or Ti alloy powders, Ti or Ti alloy scraps is pulverized by a mechanical pulverizing method using a vibrating mill or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing Ti or Ti alloy powder which is obtained by mechanically pulverizing Ti or Ti alloy scrap using Ti or Ti alloy scrap as a raw material. Ti or Ti crushed by a mechanical crushing method using a mill or the like
The present invention relates to a method for producing an alloy powder.

[0002]

2. Description of the Related Art Ti and Ti alloys have a small specific gravity,
Because of its high strength, high toughness, and excellent corrosion resistance, it is widely used as a material for spacecraft, seawater desalination equipment, chemical equipment, automotive parts, biomaterials, sports equipment such as golf club heads, etc. It has become to. Therefore, a large amount of unprocessed material such as punching residue, machining waste (Dalai powder), plastic processing residue, etc. is generated in the manufacturing process, and a large amount of waste is generated by discarding the above products. It has become.

Conventionally, Ti or Ti scrap, such as the above-mentioned residual material and product waste, is crushed or cut by mechanical means, or crushed after being fragile by hydrogenation, and then dehydrogenated. Was melted in a vacuum or non-oxidizing atmosphere in a plasma melting furnace, arc furnace, etc., and reused, but Ti or Ti scrap was directly powdered and this powder was converted into a sintered alloy. No use had been made.

On the other hand, as a method of turning Ti or a Ti alloy into a powder, a Hunter method of reducing titanium tetrachloride with sodium to obtain a Ti powder, hydrogenating and pulverizing, and then dehydrogenating under vacuum to obtain a powder. Hydrodehydrogenation method, gas atomizing method in which Ar gas is blown into a molten stream by dissolving and dropping, plasma rotating electrode method in which raw materials are rotated at high speed, melted from the tip with a plasma torch, and molten metal is scattered and solidified into powder. However, pulverization of Ti or a Ti alloy material by a mechanical pulverization method using a vibration mill or the like has not been performed.

[0005]

An object of the present invention is to provide a method for producing Ti or Ti alloy powder from Ti or Ti alloy scrap without melting or compounding.

[0006]

In order to solve the above-mentioned problems, Ti or Ti alloy scrap is replaced with Ti or Ti alloy.
When investigating and studying a method of manufacturing alloy powder, Ti or Ti alloy scrap was said to be difficult to pulverize into a powder by a mechanical pulverization method because of its high strength and toughness, When the thickness of the Ti or Ti alloy scrap is reduced, for example, about 5 mm or less, preferably about 0.5 mm or less, width 20 mm or less, and length 5 mm or less.
If it is 0 mm or less, it can be pulverized into a powder by a mechanical pulverization method such as a vibration mill, Ti or Ti
Knowledge of the fact that, when crushing alloy scrap, after primary crushing using a lot-shaped crushing medium, secondary crushing using a ball-shaped crushing medium can be efficiently crushed to an average particle diameter of about 15 μm. I got The present invention has been made based on these findings.

That is, in the method for producing Ti or Ti alloy powder from Ti or Ti alloy scrap according to the present invention, the Ti or Ti alloy scrap is pulverized by a mechanical pulverization method using a vibration mill or the like. Further, in the method for producing Ti or Ti alloy powder from Ti or Ti alloy scrap of the present invention,
The grinding method using a vibration mill is a vibration mill, that is, a raw material, a grinding aid, and a grinding medium are put into a grinding cylinder (sometimes referred to as a mill pot, a grinding drum, or a drum) of the vibration mill, and hexane is further added. By a wet method pulverization method or a vibration mill in which pulverization is carried out in a solution, that is, a pulverization raw material, a pulverization aid,
A dry crushing method of crushing in a vacuum or a non-oxidizing atmosphere, for example, by adding a crushing medium.

In the method for producing Ti or Ti alloy powder from Ti or Ti alloy scrap according to the present invention, the Ti or Ti alloy scrap is subjected to primary grinding by a grinding method using a lot-like grinding medium in a vibration mill. ,
Secondary grinding is performed by a grinding method using a ball-shaped crushing medium in a vibration mill. In addition, according to the present invention, Ti or Ti
In the method of producing Ti or Ti alloy powder from alloy scrap, a pulverizing method using a lot-like crushing medium in the vibrating mill or a pulverizing method using a ball-like crushing medium in the vibrating mill is performed by a vibrating mill, Raw materials, grinding aids, crushing media, etc. are put into the grinding tube of the mill, and furthermore, hexane and the like are added and ground in a solution. A dry pulverization method in which a pulverization aid and a pulverization medium are added and pulverization is carried out in a vacuum or in a non-oxidizing atmosphere. In addition, after these pulverizations, classification, washing and drying as necessary are generally performed.

[0009]

The Ti or Ti alloy scrap of the present invention is
The method for producing i or Ti alloy powder is Ti or T
Since the i-alloy scrap is powdered by a mechanical pulverization method, the powder can be produced without melting or compounding, and the pulverizing operation can be performed unattended for a long time.
Powder manufacturing costs can be reduced. In addition, after the primary pulverization using a lot-shaped crushing medium by a vibration mill, and the secondary pulverization using a ball-shaped crushing medium, even if the thickness is about 5 mm, the average particle diameter can be reduced. To about 15 μm.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION A Ti or Ti alloy scrap of the present invention is a scrap having a Ti content of 50% or more, and is used for spacecraft, seawater desalination equipment, chemical equipment, electronic equipment, OA equipment, cameras, Biomaterials, automotive parts (valves, combined products), golf club heads, processing residuals such as sporting goods such as fishing equipment, and waste of the above products. These Ti or Ti alloy scraps have a thickness of about 5 mm or less, and may be used as long as they can fit into the pulverizing cylinder of the vibrating mill with a margin.
Those which are thicker than m and cannot be put into the pulverizing cylinder of the vibrating mill with sufficient margins become difficult to pulverize. Therefore, the thickness is about 5 mm or less, preferably about 0.
It is necessary to process, crush or cut such that the width is 5 mm or less, the width is 20 mm or less, and the length is 50 mm or less.

The mechanical pulverization method in the method for producing Ti or Ti alloy powder from Ti or Ti alloy scrap is a pulverization method using a vibration mill or the like. The vibration mill is used in the present invention because the kinetic energy is high and the gravitational acceleration G (impact force) becomes 4 or more necessary for pulverizing Ti or Ti alloy scrap. From the mechanism that works simultaneously,
This is because stretching and shearing work effectively on the pulverized raw material, and the crushing medium can be freely selected. The crushing medium used for the vibration mill is made of a ceramic material such as iron, special steel, alumina, or zirconia, and has a lot-like or ball-like shape.

The pulverization method using the vibration mill of the present invention includes a wet pulverization method of pulverization in a solution by a vibration mill and a dry pulverization method of pulverization in a vacuum or a non-oxidizing atmosphere by a vibration mill. Either method can be used, but a wet pulverization method is preferred from the viewpoint of easiness and certainty of preventing oxidation or ignition of Ti. Further, according to the type of the crushing medium using the crushing method using the vibration mill of the present invention, there are a method using a lot-like material and a method using a ball-like material.

In the wet method using the vibration mill of the present invention, the grinding raw material, the lot-shaped or ball-shaped crushing medium, the grinding aid, and the process until the void in the grinding cylinder of the vibration mill disappears in the grinding cylinder of the vibration mill. This is a method in which a solvent is added and crushed.
Usually, after pulverization, classification, washing and drying are performed. Grinding aids used in this method include stearic acid, calcium stearate, magnesium stearate, sodium stearate, lithium stearate, zinc stearate, chloride doptylamine, α-terbineol, dodecyl ammonium triethanolamine, ethylene glycogen, sodium carbonate Such as cyclohexane is used in a solvent.

The amount of the grinding aid used is usually 5 to 20% by weight of the raw material to be ground. Since Ti is a highly reactive material, it progresses from an agglomerated state to a solidified state in a short time, and pulverization stops. Therefore, it is necessary to add Ti in an amount of 5% by weight or more. Is saturated and the removal becomes difficult, so the amount is preferably 20% by weight or less. The solvent used in this method is cyclohexane, naphthesol, or the like.

In the dry method of pulverizing in a vacuum or in a non-oxidizing atmosphere using the vibrating mill, the pulverizing raw material, a lot-shaped or ball-shaped pulverizing medium and a pulverizing aid are usually put in a pulverizing cylinder of a vibrating mill. Is a method of pulverizing the inside of the container under a vacuum or a non-oxidizing atmosphere. Usually, after pulverization, classification, washing and drying are performed if necessary.

The grinding aid used in this method is for preventing agglomeration of the powder in the grinding, and includes stearic acid, calcium stearate, magnesium stearate, sodium stearate, lithium stearate, zinc stearate, acrylamide, ε- Examples thereof include caprolactam and colloidal silica, and a stearic acid-based one that has little effect on the subsequent steps is preferable. The amount of the grinding aid used is 5 to 20% by weight of the raw material. 5-20% by weight
The reason is the same as in the case of the wet method.

In the present invention, after the primary grinding of Ti or Ti alloy scrap by a grinding method using a lot-like crushing medium in a vibration mill, and then the secondary grinding by a grinding method using a ball-like crushing medium in a vibration mill, The primary pulverization and the secondary pulverization can be performed by a dry method, the primary pulverization and the secondary pulverization can be performed by a wet method, and the primary pulverization or the secondary pulverization is performed by a dry method, and the secondary pulverization or the secondary pulverization is performed. The primary grinding can be performed by a wet method.

Hereinafter, the present invention will be described with reference to examples.

EXAMPLES Example 1 As the primary pulverization, the dimensions of pure Ti (99% by weight of Ti) were 0.2 to 0.4 in thickness x 4.8 to 11 in width x 35 to 45 in length.
400g of pulverized raw material (machined residue) consisting of (mm)
Was placed in a grinding cylinder of a vibration mill. Next, a rod having a diameter of 25 mm and a length of 200 mm was used as a pulverizing medium, and the filling rate was 60%.
%, Stearic acid was added as a grinding aid at 5% by weight of the raw material, and then cyclohexane was injected as a solvent until the voids in the grinding cylinder disappeared. afterwards,
Grinding was performed under the following conditions: vibration frequency: 1200 cpm, amplitude: 6.5 mm, and grinding time: 15 hours.

In the secondary pulverization, a spherical crushing medium having a diameter of 12 mm is charged into a pulverizing cylinder at a filling rate of 80%, and pulverized powder of 35 mesh or less (35 mesh or less) obtained by primary pulverization is charged into the pulverizing cylinder. Was 80% by weight of the raw material for pulverization), stearic acid as a grinding aid used in the primary pulverization, and cyclohexane as a solvent were injected into the pulverizing cylinder until no voids were left.

Thereafter, the frequency: 1200 cpm, the amplitude:
It grind | pulverized on conditions of 6.5 mm and grinding | pulverization time: 30Hr. The obtained powder was washed, dried and measured for particle size. As a result, a powder having an average particle diameter of 40 μm was obtained. The particle size distribution and the like were as described in Table 1 below. The powder obtained by the pulverization was classified with a sieve of 350 mesh (44 μm) to obtain a fine powder having an average particle diameter of 14 μm.

Example 2 As the primary pulverization, the dimensions of pure Ti (99% by weight of Ti) were 0.2 to 0.4 thickness x 4.8 to 11 width x 35 to 45 length.
(Mm) and the dimensions of the Ti alloy (6Al-4V @ Ti) are 0.2 to 0.4 × thickness 3.1 to 6.1 × length 26 to 3
5 (mm) of the pulverized raw material (residue after machining) of 40
0 g was placed in the grinding cylinder of the vibration mill. Next, a rod of φ25 × length 200 (mm) is inserted as a pulverizing medium so that the filling rate becomes 60%, and stearic acid is added as a pulverizing aid in an amount of 5% by weight of the pulverizing raw material. After evacuating the air, Ar gas was introduced to change the atmosphere in the grinding cylinder to a non-oxidizing atmosphere. Then, frequency: 1200 cpm, amplitude: 8 mm, grinding time: 10H
After the pulverization, the powder was discharged into a container in a non-oxidizing atmosphere.

In the secondary pulverization, a spherical crushing medium having a diameter of 12 mm is charged into a pulverizing cylinder at a filling rate of 80%, and the pulverized powder of 60 mesh or less (60 mesh or less) obtained by the primary pulverization is charged into the pulverizing cylinder. The crushed powder was 95% by weight of the crushed raw material) and stearic acid as a crushing aid used in the primary crushing were inserted, and then the air in the crushing cylinder was exhausted with a rotary pump, and then Ar gas was introduced. The atmosphere in the pulverizing cylinder was made a non-oxidizing atmosphere.

Thereafter, the frequency: 1200 cpm, the amplitude:
It grind | pulverized on conditions of 7.5 mm and grinding | pulverization time: 20Hr. The obtained powder was washed, dried and measured for particle size. As a result, the average particle diameter was 48 μm for pure Ti and 40 μm for Ti alloy.
A μm powder was obtained. The particle size distribution and the like were as described in Table 1 below. In addition, the powder obtained by grinding is
Classified with a 50 mesh (44 μm) sieve, the average particle diameter is 17 μm for pure Ti and 12 μm for Ti alloy.
Was obtained.

[0024]

[Table 1]

According to the results shown in Table 1 and the like, in the wet method of Example 1 of the present invention, about 71% by weight (pure T
i) could be ground to an average particle size of 14 μm. This powder having an average particle diameter of 14 μm could be used as a raw material for a sintered alloy. In the dry method according to the second embodiment of the present invention, about 86% by weight of the pulverized raw material has an average particle diameter of 17 μm of pure Ti and an average particle diameter of 1 μm of Ti alloy.
It could be ground to 2 μm. The powder having an average particle diameter of 17 μm and 12 μm could be used as a raw material for a sintered alloy.

[0026]

The method of the present invention for producing Ti or Ti alloy powder from Ti or Ti alloy scrap produces Ti or Ti alloy powder that can be used for sintered alloys without melting or compounding. The effect is excellent.

Claims (6)

[Claims] 1. A method for producing Ti or Ti alloy powder, wherein Ti or Ti alloy scrap is pulverized by a mechanical pulverization method. 2. The method for producing Ti or Ti alloy powder according to claim 1, wherein the mechanical grinding method is a grinding method using a vibration mill. 3. The pulverization method using a vibration mill is a wet pulverization method in which a pulverization is performed in a solution using a vibration mill, or a dry pulverization method in which a pulverization is performed in a vacuum or a non-oxidizing atmosphere using a vibration mill. The method for producing a Ti or Ti alloy powder according to claim 2, wherein 4. A primary pulverization of Ti or Ti alloy scrap by a pulverization method using a lot-shaped pulverizing medium in a vibration mill, and then a secondary pulverization by a pulverization method using a ball-shaped pulverizing medium in a vibration mill. Characterized by Ti or T
Method for producing i-alloy powder. 5. A pulverizing method using a lot-shaped crushing medium in the vibrating mill or a pulverizing method using a ball-shaped crushing medium in the vibrating mill is a wet-type pulverizing method or pulverizing in a solution by a vibrating mill. 5. The method for producing Ti or Ti alloy powder according to claim 4, wherein the pulverization method is a dry method of crushing in a vacuum or in a non-oxidizing atmosphere. 6. The method for producing Ti or Ti alloy powder according to claim 3, wherein the pulverization method of the dry method or the pulverization method of the wet method is a pulverization method using a pulverization aid. .