WO2012169258A1 - Method for producing molybdenum granulated powder and molybdenum granulated powder - Google Patents

Method for producing molybdenum granulated powder and molybdenum granulated powder Download PDF

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WO2012169258A1
WO2012169258A1 PCT/JP2012/057355 JP2012057355W WO2012169258A1 WO 2012169258 A1 WO2012169258 A1 WO 2012169258A1 JP 2012057355 W JP2012057355 W JP 2012057355W WO 2012169258 A1 WO2012169258 A1 WO 2012169258A1
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molybdenum
granulated powder
powder
producing
average particle
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PCT/JP2012/057355
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French (fr)
Japanese (ja)
Inventor
山口　悟
勉 森岡
斉 青山
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株式会社東芝
東芝マテリアル株式会社
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Publication of WO2012169258A1 publication Critical patent/WO2012169258A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • 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

Definitions

  • the present invention relates to a method for producing molybdenum granulated powder and molybdenum granulated powder.
  • Molybdenum (Mo) is used in various fields as a heat resistant material because it has a high melting point of 2620 ° C.
  • it is used for thermal spraying materials, sintering furnace plate materials, electrode parts, magnetron stems, sputtering targets, and the like.
  • the material for thermal spraying is a material supplied by Mo powder or Mo rod.
  • the plate material may be manufactured by sintering, or may be manufactured by combining rolling and forging.
  • electrode parts and the like may be manufactured by processing a plate material, drawing a wire by wire drawing, or manufacturing by a sintering method.
  • Mo powder or Mo molten metal will be used as an initial raw material.
  • Mo molten metal is used by a method in which raw materials are melted and cast into a desired shape.
  • the method using molten Mo is a method in which the molten metal is poured into a mold, and is a relatively simple method that can be processed into a large shape.
  • Patent Document 1 discloses a sintered electrode for a cold cathode tube having a U-shaped cross section (cup shape).
  • Patent Document 1 a cup-shaped electrode having a diameter of about 1 to 2 mm is manufactured using a sintering method.
  • a sintering method When producing a sintered compact by a sintering method, a granulation process, a formation process, a degreasing process, a sintering process, etc. are implemented with respect to Mo powder.
  • the conventional sintering methods have been advanced mainly by improving the degreasing process and the sintering process.
  • paragraph [0027] of Patent Document 1 it is disclosed that the degreasing step is performed in a wet hydrogen atmosphere while the sintering step is performed in a hydrogen atmosphere. Thereby, the sinterability is improved and the yield is improved.
  • Patent Document 2 of International Publication WO2011 / 004887A1 discloses a method for producing high-purity molybdenum powder having an average particle size of 0.5 to 100 ⁇ m.
  • Patent Document 2 discloses a molybdenum powder in which the proportion of primary particles is 50% or more.
  • the improvement regarding Mo raw material powder, a degreasing process, and a sintering process was performed. However, even if the improvement is advanced, the product yield has not necessarily reached 100%. Such a phenomenon also occurred in the same way for a Mo sintered body using Mo powder to which cobalt or the like was added.
  • the inventors have investigated the reason why the yield of products using Mo powder as an initial raw material is not improved. As a result, it was found that the size, density, fluidity, etc. of the granulated powder were dissolved and dissolved, but if they were large, the filling density and supply amount in the molding process were varied and dissolved, causing the product yield to decrease. . In addition, when Mo granulated powder is used as the thermal spray powder, the amount of supply to the thermal spray flame (supply speed) varies and dissolves, resulting in problems such as unstable properties as the thermal spray film. As a result of pursuing this cause, it was found that there was a cause that the management according to the average particle size of the intended granulated powder was not performed in the granulation step.
  • the present invention is for solving such problems, and realizes stabilization of the quality of Mo products (powder or sintered body) and improvement of yield, and enables molybdenum granulated powder to be efficiently produced with high yield. It aims at providing the manufacturing method of the molybdenum granulated powder which can be manufactured.
  • the method for producing molybdenum granulated powder according to the present invention includes a step of injecting an organic solvent into a container, a step of adding polyvinyl butyral as a binder to the organic solvent, and stirring the organic solvent while stirring the tin component and cobalt.
  • a sieving step of passing a sieve having a mesh diameter 2 to 3 times the average particle size B of the granulated powder with respect to the granulated powder after completion of the granulating step by the spray dryer.
  • the average particle diameter B of the molybdenum granulated powder is preferably 20 to 150 ⁇ m.
  • the rotational speed A of the rotating plate of the spray dryer is preferably 5000 to 16000 rpm.
  • an organic solvent is ethanol.
  • the content (addition amount) of the cobalt component is preferably in the range of 50 to 500 mass ppm (wtppm) in terms of cobalt elemental element.
  • the content of the tin component is in the range of 50 to 500 ppm by mass in terms of tin element. Moreover, it is preferable to add both a tin component and a cobalt component.
  • the volume of the binder is preferably 3 to 20 parts by volume.
  • the apparent density of the resulting molybdenum granulated powder is preferably 1.3 to 3.0 g / cc.
  • the molybdenum-containing solution preferably has an organic solvent amount of 0.2 to 1 liter when the molybdenum powder amount is 100 parts by mass.
  • the spray dryer preferably dries the molybdenum granulated powder while supplying hot air at 100 to 300 ° C. Moreover, it is preferable that the spray drier carries out the drying of the molybdenum granulated powder in a reduced-pressure atmosphere below atmospheric pressure. Moreover, it is preferable that the fluidity
  • the molybdenum granulated powder according to the present invention is characterized by containing at least one of a tin component and a cobalt component and having an apparent density of 1.3 to 3.0 g / cc.
  • the average particle diameter of the molybdenum granulated powder is preferably 20 to 150 ⁇ m. Further, when the total amount of molybdenum powder is 100 parts by volume, the volume of the binder is preferably 3 to 20 parts by volume. Further, the fluidity of the molybdenum granulated powder is preferably 50 sec / 50 g or less.
  • the method for producing a molybdenum granulated powder in the granulation step, while stirring an organic solvent, a molybdenum powder and a binder to which a tin component or / and a cobalt component are added are supplied, and the intended granulation is further performed. Since the ratio of the average particle size of the powder and the rotation speed of the rotating plate of the spray dryer is controlled within a predetermined range, it is possible to produce molybdenum granulated powder with excellent average particle size, apparent density and fluidity. it can.
  • a method for producing molybdenum granulated powder according to an embodiment of the present invention includes a step of injecting an organic solvent into a container, a step of adding polyvinyl butyral as a binder to the organic solvent, and stirring the organic solvent while tin is used.
  • a step of preparing a molybdenum-containing solution by introducing molybdenum powder having an average particle diameter of 1 to 10 ⁇ m to which at least one of a component and a cobalt component is added, and rotation of a rotating plate of a spray dryer for dispersing the molybdenum-containing solution
  • the molybdenum-containing solution is put into a spray dryer in which A / B is in the range of 50 to 700.
  • FIG. 1 shows an example of a process for preparing a molybdenum-containing solution.
  • reference numeral 1 is a container (a container for preparing a molybdenum-containing solution)
  • 2 is an organic solvent
  • 3 is a molybdenum powder (a molybdenum powder to which a tin component or a cobalt component is added)
  • 4 is a binder.
  • 5 is an organic solvent to be recharged as necessary
  • 6 is a molybdenum-containing solution.
  • the organic solvent 2 is injected into the container 1.
  • alcohol or the like is used.
  • the alcohol ethanol (ethyl alcohol: C 2 H 5 OH) is preferable.
  • Ethyl alcohol is preferable because it easily dissolves a binder (polyvinyl butyral) described later.
  • a step of adding the binder 4 to the organic solvent 2 is performed.
  • Polyvinyl butyral (PVB) is used as the material of the binder.
  • Polyvinyl butyral is well soluble in organic solvents, especially ethanol.
  • a binder stirring an organic solvent.
  • a step of preparing a molybdenum-containing solution 6 is performed by adding molybdenum powder 3 having an average particle diameter of 1 to 10 ⁇ m while stirring organic solvent 2.
  • the average particle size of the molybdenum powder 3 is the average particle size of the primary particle size.
  • the value obtained by the FSSS method Fischer method is defined as the average particle size.
  • the average particle diameter of the molybdenum powder 3 is 1 to 10 ⁇ m, and more preferably 2 to 5 ⁇ m. Further, when a large amount of molybdenum powder is added at once, the molybdenum powder tends to aggregate more than necessary, so it is preferable to add a small amount, for example, 0.5 to 2 kg.
  • the molybdenum powder after confirming that the entire amount of the binder is dissolved in the organic solvent. If the binder is added in the state of powder, it can be discriminated with the naked eye whether or not it is dissolved.
  • the organic solvent (ethanol) before adding the molybdenum powder becomes translucent. In order to easily determine whether or not the binder is completely dissolved in the organic solvent (ethanol), it is preferable to add the molybdenum powder after the binder is added.
  • the volume of the binder is 3 to 20 parts by volume. It is preferable that The binder serves as an adhesive that bonds the molybdenum powders together when forming the molybdenum granulated powder. Therefore, when the total amount of molybdenum powder is 100 parts by volume, if the amount of binder added is less than 3 parts by volume, the amount of binder becomes too small, and uniform granulated powder may not be obtained.
  • the added amount of the binder is 3 to 20 parts by volume with respect to 100 parts by volume of the molybdenum powder, and more preferably 5 to 15 parts by volume.
  • the molybdenum-containing solution preferably has an organic solvent amount of 0.2 to 1 liter when the molybdenum powder amount is 100 parts by mass.
  • the spray dryer is charged in a molybdenum-containing solution.
  • the amount of the organic solvent is less than 0.2 liters with respect to 100 parts by mass of the molybdenum powder, the amount of the organic solvent is too small, the viscosity of the molybdenum-containing solution increases, and it can be stably supplied to the spray dryer. Have difficulty.
  • the amount of the organic solvent exceeds 1 liter, the amount of the organic solvent becomes excessive, and it is difficult to stably supply the organic solvent.
  • a stable supply method can also be adopted by supplying it with stirring.
  • the supply of the molybdenum-containing solution to the spray dryer can be mechanized and automated.
  • ethanol since ethanol has a relatively low boiling point of 78.3 ° C., ethanol may evaporate and the amount of solvent may change greatly when a binder and molybdenum powder are added and mixed.
  • the amount of organic solvent is mixed with the binder and molybdenum powder at 30 to 60% of the final amount, and then the remaining organic
  • a method of adjusting the blending ratio between molybdenum powder and the amount of organic solvent by additionally adding a solvent amount of 70 to 40% can also be employed.
  • a method of adding the organic solvent is also effective.
  • the molybdenum powder of the present invention is a molybdenum powder to which at least one of a tin component and a cobalt component is added.
  • a tin component or the cobalt component compounds such as simple elements, oxides, and complex oxides can be used.
  • the content (addition amount) of the tin component is preferably in the range of 50 to 500 ppm by mass in terms of the tin (Sn) element alone.
  • the content (addition amount) of the cobalt component is preferably in the range of 50 to 500 ppm by mass in terms of cobalt (Co) element alone.
  • the tin component or the cobalt component when the tin component or the cobalt component is less than 50 ppm by mass in terms of a simple metal element, the effect of addition is small.
  • the addition of a tin component or a cobalt component increases the recrystallization temperature and increases the high-temperature strength as compared with high-purity molybdenum.
  • Secondary workability such as a drawing process to a wire, improves.
  • Secondary processing includes wire bending processing, wire bending processing, plate material (plate material made of Mo sintered body) rolling processing, bending processing, punching processing, and the like. Further, the wire characteristics can improve non-sag, high-temperature vibration resistance, and blackening resistance.
  • ammonium dimolybdate (NH 4 ) 2 ⁇ Mo 2 O 7 )
  • Mo oxide ammonium dimolybdate
  • tin chloride and / or cobalt chloride is added so as to be 50 to 500 mass ppm in terms of a metal simple substance.
  • pure water is added, kneaded, heated to 100 to 140 ° C. with stirring and dried to obtain a molybdenum component-added molybdenum oxide powder.
  • the molybdenum component-added molybdenum oxide powder can be heated and reduced at 1000 to 1200 ° C. for 2 to 5 hours in a hydrogen atmosphere to obtain a molybdenum powder to which the tin component and / or cobalt component is added. .
  • the purity of the molybdenum powder to which the tin component or cobalt component is added is not particularly limited, but the sum of Mo and tin or / and cobalt may be 99% by mass or more, and further 99.9% by mass or more. preferable.
  • Main impurities of the molybdenum powder include Fe (iron), Al (aluminum), Ca (calcium), Mg (magnesium), and Si (silicon). Other impurities include Ni (nickel), Na (sodium), K (potassium), Pb (lead), Bi (bismuth), Cd (cadmium), Cu (copper), and Mn (manganese). It is done.
  • the measurement of the purity of molybdenum is Fe (iron), Al (aluminum), Ca (calcium), Mg (magnesium), Si (silicon), Ni (nickel), Na (sodium), K (potassium), Pb (lead). ), Bi (bismuth), Cd (cadmium), Cu (copper), and Mn (manganese) are subtracted from 100% by mass.
  • Fe iron
  • Al aluminum
  • Ca calcium
  • Mg manganesium
  • Si silicon
  • Ni nickel
  • Na sodium
  • K potassium
  • Pb lead
  • Bi Bismuth
  • Cd cadmium
  • Cu copper
  • Mn manganesese
  • gas components such as oxygen, are mentioned as impurities other than the said metal impurity. While the amount of oxygen is 7% by mass or less
  • FIG. 2 shows an example of a granulation process using a spray dryer.
  • reference numeral 1 is a container containing a molybdenum-containing solution
  • 6 is a molybdenum-containing solution
  • 7 is an inlet for a molybdenum-containing aqueous solution
  • 8 is a rotating plate
  • 9 is a molybdenum granulated powder.
  • Reference numeral 10 denotes an outer wall of the spray dryer
  • reference numeral 11 denotes a molybdenum granulated powder collection container.
  • the molybdenum-containing solution 6 adjusted in the above process is poured into the charging port 7.
  • the input amount (input speed) to the input port 7 is preferably 10 to 80 cc / min.
  • the input speed is less than 10 cc / min, the input amount is too small and the mass productivity is deteriorated.
  • the input speed exceeds 80 cc / min, the input amount becomes excessive, and the characteristics of the resulting granulated powder vary.
  • the charged molybdenum-containing solution 6 is supplied onto the rotating plate 8.
  • the rotating plate 8 rotates at a constant rotational speed.
  • the molybdenum-containing solution 6 is supplied to the rotating rotating plate, it is repelled by a certain amount to form spherical molybdenum granulated powder 9 by surface tension.
  • the molybdenum granulated powder 9 falls along the outer wall 10 of the spray dryer and is collected in a molybdenum granulated powder collection container 11.
  • the average particle diameter of the molybdenum granulated powder is highly related to the rotation speed of the rotating plate 8 of the spray dryer.
  • the present invention is characterized in that A / B is controlled in the range of 50 to 700 when the rotational speed of the rotating plate 8 is A (rpm) and the average particle diameter of the granulated powder is B ( ⁇ m). It is what.
  • a / B is controlled in the range of 50 to 700 when the rotational speed of the rotating plate 8 is A (rpm) and the average particle diameter of the granulated powder is B ( ⁇ m). It is what.
  • the molybdenum-containing solution 6 is supplied to the rotating plate 8, the molybdenum-containing solution 6 is repelled on the rotating plate by a certain amount, and the repelled molybdenum-containing solution 6 becomes spherical molybdenum granulated powder 9 due to surface tension.
  • uniform granulated powder can be manufactured also from having added the binder.
  • a / B which is the value of the above ratio is less than 50, the rotation speed of the rotating plate is insufficient with respect to the average particle diameter of the intended granulated powder, and therefore the average particle diameter B of the intended granulated powder. Cannot be obtained. Moreover, when A / B is less than 50, it becomes a granulated powder having a larger average particle diameter than the average particle diameter B of the intended granulated powder. On the other hand, when A / B exceeds 700, the rotation speed of the rotating plate is too high with respect to the average particle diameter of the intended granulated powder, and thus the average particle diameter B of the intended granulated powder cannot be obtained.
  • a / B exceeds 700, it becomes a small average particle diameter with respect to the average particle diameter B of the intended granulated powder.
  • a / B in the range of 50 to 700, a granulated powder having an average particle diameter in the range of ⁇ 50% with respect to the average particle diameter B of the intended granulated powder can be obtained.
  • the average particle size B of the intended granulated powder is 50 ⁇ m
  • the average particle diameter of granulated powder uses an enlarged photograph, and makes the maximum diameter of the granulated powder reflected there the particle diameter, and the average value of 100 granulated powder is the average particle diameter of the granulated powder.
  • the average particle size B of the granulated powder is preferably 20 to 150 ⁇ m. If the average particle diameter of the granulated powder is in the range of 20 to 150 ⁇ m, it can be applied to various applications.
  • the rotation speed A of the rotary plate 8 of the spray dryer is preferably 5000 to 16000 rpm. When the rotational speed A is in the range of 5000 to 16000 rpm, the molybdenum-containing solution is efficiently repelled on the rotating plate, and a granulated powder having a target average particle diameter is easily obtained.
  • the spray dryer preferably dries the molybdenum granulated powder while supplying hot air at 100 to 300 ° C.
  • hot air having a temperature of 100 to 300 ° C.
  • the organic solvent in the granulated powder can be evaporated and the binding force between the molybdenum powders by the binder can be enhanced.
  • molybdenum granulated powder having a target average particle diameter can be produced.
  • Hot air is supplied into the outer wall 10 of the spray dryer from a hot air supply port (not shown) and exhausted from an exhaust port (not shown).
  • the spray dryer performs drying of the molybdenum granulated powder in a reduced-pressure atmosphere of atmospheric pressure or lower.
  • a reduced-pressure atmosphere of atmospheric pressure or lower By setting the inside of the outer wall 10 of the spray dryer to a reduced-pressure atmosphere of atmospheric pressure or less, the organic solvent in the granulated powder can be easily evaporated.
  • the rotation speed of the rotating plate of the spray dryer is adjusted in accordance with the average particle diameter of the granulated powder, ⁇ A granulated powder having an average particle size in the range of 50% can be obtained efficiently.
  • the apparent density of the resulting molybdenum granulated powder is preferably 1.3 to 3.0 g / cc.
  • the average particle diameter of the molybdenum granulated powder is measured using an enlarged photograph. If it is this measuring method, the average particle diameter on an external appearance can be judged.
  • the abundance ratio of the molybdenum powder partially varies. Arise. Variation in the existence ratio leads to variation in the product. For example, when granulated powder is used as a thermal spraying powder, if there are granulated powders with significantly different densities, the amount of molybdenum powder charged into the thermal flame flame will vary, resulting in variations in the thermal sprayed Mo film. Cause. Moreover, when producing a sintered compact, the variation in the amount of molybdenum inserted into the molding die occurs, and the pores in the sintered compact may become larger than necessary.
  • the apparent density is less than 1.3 g / cc, the amount of molybdenum in the molybdenum granulated powder is too small, which causes a variation in quality in the subsequent commercialization.
  • the apparent density exceeds 3.0 g / cc, the molybdenum powder is tightly packed, so that it is difficult to stably manufacture with a spray dryer.
  • the apparent density is measured according to a measurement method based on JIS-Z-2504.
  • liquidity of the obtained molybdenum granulated powder is 50 sec / 50g or less. This fluidity measurement is also carried out by a measurement method based on JIS-Z-2504.
  • the fluidity is an index indicating how smoothly and quickly the granulated powder moves (flows).
  • the fluidity is good (fluidity 50 sec / 50 g or less)
  • the filling and filling of the molding die can be smoothly and rapidly performed when commercialized.
  • the granulated powder has good handleability.
  • liquidity is good means that the shape of granulated powder is close to a sphere.
  • the aspect ratio is 1.5 or less.
  • FIG. 3 shows an example of molybdenum granulated powder.
  • 3 is a molybdenum powder
  • 9 is a molybdenum granulated powder
  • L1 is a short diameter of the molybdenum granulated powder
  • L2 is a long diameter.
  • the aspect ratio is obtained from the formula “major axis L2 / minor axis L1”.
  • An aspect ratio of 1.0 indicates a state close to a true sphere.
  • the molybdenum granulated powder excellent in average particle diameter, apparent density, and fluidity
  • a process for controlling the average particle diameter of the molybdenum granulated powder, especially the particle size distribution it has a mesh diameter 2 to 3 times the average particle diameter B of the granulated powder after completion of the granulation process by a spray dryer.
  • a method of further carrying out a sieving step through a sieve is also preferred. By carrying out this sieving step, excessive granulated powder can be removed. As a result, the average particle diameter can be further controlled.
  • this sieving step is effective because it can remove excessive granulated powder.
  • molybdenum granulated powder having excellent average particle diameter, apparent density, and fluidity can be efficiently produced with a high yield. Therefore, the granulated powder according to each product can be manufactured with a good yield.
  • Applications of this granulated powder include thermal spraying powder, raw powders of various sintered bodies, and the like.
  • the use of molybdenum granulated powder with excellent average particle diameter, apparent density and fluidity ensures uniform filling in the mold.
  • the density of the sintered body can be stabilized.
  • the yield can be further improved by changing the average particle size according to the shape of the molding die. For example, in a sintered body having a thickness of 1 mm or less, the average particle diameter of the granulated powder is set to about 50 ⁇ m, whereas in a sintered body having a thickness of about 5 mm, the average particle diameter of the granulated powder is set to about 100 ⁇ m. As a result, it is possible to efficiently fill the molding die. Moreover, since the high temperature characteristic is excellent, the workability at the time of processing into a wire is also improved.
  • Example 2 (Examples 1 to 5 and Comparative Examples 1 and 2) A molybdenum powder added with a tin component and / or a cobalt component shown in Table 1, and polyvinyl butyral (PVB) powder and ethanol were prepared as binders. First, ethanol was poured into a stainless steel container, and while stirring at room temperature, polyvinyl butyral powder was added, and all the added polyvinyl butyral powder was dissolved. When all the polyvinyl butyral powder was dissolved, it was confirmed that the solution was a translucent solution. Thereafter, a total of 40 kg of molybdenum powder was added in an amount of 1-2 kg.
  • Examples 1 to 5 were molybdenum-containing solutions using polyvinyl alcohol powder as a binder. The conditions for the preparation steps of the molybdenum-containing solution so far are shown in Tables 1 and 2 below.
  • the average particle diameter, aspect ratio, apparent density, fluidity and product yield of the granulated molybdenum powders obtained by the production methods of Examples 1A-5B and Comparative Examples 1-2 were investigated.
  • the average particle size was obtained by extracting 100 arbitrary particles of the obtained molybdenum granulated powder, taking an enlarged photograph, obtaining the maximum diameter reflected therein, and taking the average value of 100 particles as the average particle size.
  • the aspect ratio used the same enlarged photograph, calculated
  • the apparent density and fluidity were measured according to a measuring method based on JIS-Z-2504.
  • the product yield was calculated from the ratio of the amount of molybdenum powder charged to 40 kg and the total amount of recovered molybdenum granulated powder ((total amount of granulated powder / 40 kg) ⁇ 100%). The measurement results are shown in Table 4 below.
  • the molybdenum granulated powder added with the tin component and / or the cobalt component, produced by the method for producing the molybdenum granulated powder according to each example has a target average particle size.
  • the deviation with respect to the diameter B was small, and the aspect ratio, the apparent density, and the fluidity were excellent.
  • this is an efficient manufacturing method with a high yield.
  • Comparative Example 1 and Comparative Example 2 where A / B is outside the specified range in the present invention both parameters showed a deteriorated characteristic.

Abstract

This method for producing a molybdenum granulated powder is characterized by comprising: a step in which an organic solvent is injected into a container; a step in which polyvinyl butyral is added to the organic solvent as a binder; a step in which a solution containing molybdenum is prepared by loading molybdenum powder with an average particle size of 1 to 10 μm, to which a tin component and/or a cobalt component has been added, while stirring the organic solvent; and a step in which the solution containing molybdenum is loaded in a spray dryer in which, when the rotation speed of a rotator of the spray dryer in which the solution containing molybdenum is to be dispersed is regarded as A (rpm), and the average particle size of the granulated powder is regarded as B (μm), A/B ranges from 50 to 700, and the solution containing molybdenum is dispersed and dried to prepare the molybdenum granulated powder. The abovementioned method enables a molybdenum granulated powder having the intended average particle size, and containing a tin component and/or a cobalt component, to be efficiently produced at a high yield.

Description

モリブデン造粒粉の製造方法およびモリブデン造粒粉Method for producing molybdenum granulated powder and molybdenum granulated powder
　本発明は、モリブデン造粒粉の製造方法およびモリブデン造粒粉に関する。 The present invention relates to a method for producing molybdenum granulated powder and molybdenum granulated powder.
　モリブデン（Ｍｏ）は、融点が２６２０℃と高いことから耐熱材料として様々な分野に用いられている。例えば、溶射用材料、焼結炉用板材、電極部品、マグネトロン用ステム、スパッタリングターゲットなどに使用されている。溶射用材料は、Ｍｏ粉末やＭｏロッドで供給される材料である。また、板材は、焼結で製造する場合や、圧延と鍛造とを組合せて製造する場合がある。また、電極部品などは板材を加工する場合、線引き加工してワイヤ加工される場合や焼結法によって製造される場合がある。
　このようにＭｏを使用する場合、（１）Ｍｏを粉末のまま使用する方法、（２）Ｍｏを焼結した焼結体として使用する方法、（３）圧延、鍛造、鋳造などにより板状に加工して使用する方法、（４）線引き加工してワイヤとして使用する方法などが挙げられる。いずれの使用方法であっても、Ｍｏ粉末かＭｏ溶湯を初期原料として用いることになる。Ｍｏ溶湯は、原材料を溶解し鋳造して目的の形状に加工する方法で使用される。Ｍｏ溶湯を使用する方法は、金型に溶湯を流し込む方法であるため、比較的単純で、かつ大きな形状に加工することができる方法である。一方、Ｍｏは前述の通り、高融点金属であるため、Ｍｏ溶湯を厳格に管理するためには、耐熱性が高い大型設備が必要である。また、Ｍｏ溶湯を鋳型に流し込む方法であるため、複雑な形状には対応できない欠点がある。
　このため、Ｍｏ粉末を焼結してＭｏ焼結体として使用することが行われている。焼結法であれば、金型にＭｏ粉末を充填することにより、複雑な形状を有する製品も作製可能である。例えば、特許第４１５７３６９号公報（特許文献１）では、断面がコの字状（カップ形状）の冷陰極管用焼結電極が開示されている。特許文献１では焼結法を用いて直径が１～２ｍｍ程度のカップ形状の電極を作製している。
　焼結法により、焼結体を作製する場合、Ｍｏ粉末に対して、造粒工程、成形工程、脱脂工程、焼結工程などが実施される。これまでの焼結法では、脱脂工程や焼結工程の改良を中心として、進められてきた。特許文献１の［００２７］段落では、脱脂工程をウエット水素雰囲気中で実施する一方、焼結工程を水素雰囲気中で実施することが開示されている。これにより焼結性が改善され、歩留りの向上が図られている。
　また、国際公開ＷＯ２０１１／００４８８７Ａ１のパンフレット（特許文献２）では、平均粒径が０．５～１００μｍである高純度モリブデン粉末の製造方法が開示されている。特許文献２では、１次粒子の割合が５０％以上であるモリブデン粉末が開示されている。
　これまでのＭｏ焼結法においては、Ｍｏ原料粉末、脱脂工程および焼結工程に関しての改良が行われていた。しかしながら、その改良を進めても製品歩留りは必ずしも１００％には到達できていない。このような現象は、コバルト等を添加したＭｏ粉末を使用したＭｏ焼結体に関しても同様に生起していた。 Molybdenum (Mo) is used in various fields as a heat resistant material because it has a high melting point of 2620 ° C. For example, it is used for thermal spraying materials, sintering furnace plate materials, electrode parts, magnetron stems, sputtering targets, and the like. The material for thermal spraying is a material supplied by Mo powder or Mo rod. Further, the plate material may be manufactured by sintering, or may be manufactured by combining rolling and forging. Further, electrode parts and the like may be manufactured by processing a plate material, drawing a wire by wire drawing, or manufacturing by a sintering method.
Thus, when using Mo, (1) The method of using Mo as a powder, (2) The method of using Mo as a sintered compact, (3) It is plate-like by rolling, forging, casting, etc. A method of processing and using (4) a method of drawing and using as a wire, and the like. Even if it is any usage method, Mo powder or Mo molten metal will be used as an initial raw material. Mo molten metal is used by a method in which raw materials are melted and cast into a desired shape. The method using molten Mo is a method in which the molten metal is poured into a mold, and is a relatively simple method that can be processed into a large shape. On the other hand, since Mo is a high melting point metal as described above, large equipment with high heat resistance is required to strictly manage the molten Mo. Moreover, since it is the method of pouring molten Mo into a casting_mold | template, there exists a fault which cannot respond to a complicated shape.
For this reason, Mo powder is sintered and used as a Mo sintered body. If it is a sintering method, the product which has a complicated shape is also producible by filling Mo powder into a metal mold | die. For example, Japanese Patent No. 4157369 (Patent Document 1) discloses a sintered electrode for a cold cathode tube having a U-shaped cross section (cup shape). In Patent Document 1, a cup-shaped electrode having a diameter of about 1 to 2 mm is manufactured using a sintering method.
When producing a sintered compact by a sintering method, a granulation process, a formation process, a degreasing process, a sintering process, etc. are implemented with respect to Mo powder. The conventional sintering methods have been advanced mainly by improving the degreasing process and the sintering process. In paragraph [0027] of Patent Document 1, it is disclosed that the degreasing step is performed in a wet hydrogen atmosphere while the sintering step is performed in a hydrogen atmosphere. Thereby, the sinterability is improved and the yield is improved.
Further, a pamphlet (Patent Document 2) of International Publication WO2011 / 004887A1 discloses a method for producing high-purity molybdenum powder having an average particle size of 0.5 to 100 μm. Patent Document 2 discloses a molybdenum powder in which the proportion of primary particles is 50% or more.
In the conventional Mo sintering method, the improvement regarding Mo raw material powder, a degreasing process, and a sintering process was performed. However, even if the improvement is advanced, the product yield has not necessarily reached 100%. Such a phenomenon also occurred in the same way for a Mo sintered body using Mo powder to which cobalt or the like was added.
特許第４１５７３６９号公報Japanese Patent No. 4157369 国際公開ＷＯ２０１１／００４８８７Ａ１のパンフレットPamphlet of International Publication WO2011 / 004887A1
　本発明者らは、Ｍｏ粉末を初期原料として使用した製品の歩留りが向上しない原因を追究した。その結果、造粒粉のサイズ、密度、流動性などのばらつき溶解したが大きなると、成形工程での充填密度や供給量にばらつき溶解したを生じ、製品歩留りが低下する原因となることが判明した。また、溶射粉としてＭｏ造粒粉を使用する場合には、溶射フレーム炎への供給量（供給速度）にばらつき溶解したが生じ、溶射膜としての特性が安定しないなどの問題が生じていた。この原因を追及したところ、造粒工程において目的とする造粒粉の平均粒径に応じた管理がなされていないことに原因があることを見出した。
　本発明は、このような問題を解決するためのものであり、Ｍｏ製品（粉末または焼結体）の品質の安定化や歩留りの向上を実現し、モリブデン造粒粉を高い歩留りで効率的に製造できるモリブデン造粒粉の製造方法を提供することを目的とするものである。 The inventors have investigated the reason why the yield of products using Mo powder as an initial raw material is not improved. As a result, it was found that the size, density, fluidity, etc. of the granulated powder were dissolved and dissolved, but if they were large, the filling density and supply amount in the molding process were varied and dissolved, causing the product yield to decrease. . In addition, when Mo granulated powder is used as the thermal spray powder, the amount of supply to the thermal spray flame (supply speed) varies and dissolves, resulting in problems such as unstable properties as the thermal spray film. As a result of pursuing this cause, it was found that there was a cause that the management according to the average particle size of the intended granulated powder was not performed in the granulation step.
The present invention is for solving such problems, and realizes stabilization of the quality of Mo products (powder or sintered body) and improvement of yield, and enables molybdenum granulated powder to be efficiently produced with high yield. It aims at providing the manufacturing method of the molybdenum granulated powder which can be manufactured.
　本発明に係るモリブデン造粒粉の製造方法は、容器に有機溶媒を注入する工程と、上記有機溶媒にバインダーとしてのポリビニルブチラールを添加する工程と、上記有機溶媒を攪拌しながら、スズ成分およびコバルト成分の少なくとも１種を添加した平均粒径が１～１０μｍであるモリブデン粉末を投入することによりモリブデン含有溶液を調製する工程と、上記モリブデン含有溶液を分散するスプレードライヤーの回転板の回転数をＡ（ｒｐｍ）とし、モリブデン造粒粉の平均粒径をＢ（μｍ）としたときに、Ａ／Ｂが５０～７００の範囲であるスプレードライヤーにモリブデン含有溶液を投入し、上記モリブデン含有溶液を分散すると共に乾燥してモリブデン造粒粉を調製する工程と、を有することを特徴とするものである。
　また、前記スプレードライヤーによる造粒工程完了後の造粒粉に対して、造粒粉の平均粒径Ｂの２～３倍のメッシュ径を有する篩を通す篩分け工程をさらに実施することが好ましい。また、モリブデン造粒粉の平均粒径Ｂが２０～１５０μｍであることが好ましい。また、スプレードライヤーの回転板の回転数Ａが５０００～１６０００ｒｐｍであることが好ましい。また、有機溶媒がエタノールであることが好ましい。
　また、コバルト成分の含有量（添加量）が、コバルト元素単体換算で５０～５００質量ｐｐｍ(ｗｔｐｐｍ)の範囲であることが好ましい。また、スズ成分の含有量が、スズ元素単体換算で５０～５００質量ｐｐｍの範囲であることが好ましい。また、スズ成分およびコバルト成分を共に添加することが好ましい。
　また、投入するモリブデン粉末の合計量を１００体積部にしたときに、バインダーの体積を３～２０体積部とすることが好ましい。また、得られるモリブデン造粒粉の見掛け密度が１．３～３．０ｇ／ｃｃであることが好ましい。また、モリブデン含有溶液は、モリブデン粉末量を１００質量部としたときに、有機溶媒量が０．２～１リットルであることが好ましい。
　また、スプレードライヤーは、１００～３００℃の熱風を供給しながらモリブデン造粒粉の乾燥を実施することが好ましい。また、スプレードライヤーは、大気圧以下の減圧雰囲気でモリブデン造粒粉の乾燥を実施することが好ましい。また、得られたモリブデン造粒粉の流動性が５０ｓｅｃ／５０ｇ以下であることが好ましい。
　また、本発明に係るモリブデン造粒粉は、スズ成分およびコバルト成分の少なくとも１種を含み、見掛け密度が１．３～３．０ｇ／ｃｃであることを特徴とするものである。
　また、モリブデン造粒粉の平均粒径が２０～１５０μｍであることが好ましい。また、モリブデン粉末の合計量を１００体積部にしたとき、バインダーの体積が３～２０体積部であることが好ましい。また、モリブデン造粒粉の流動性が５０ｓｅｃ／５０ｇ以下であることが好ましい。 The method for producing molybdenum granulated powder according to the present invention includes a step of injecting an organic solvent into a container, a step of adding polyvinyl butyral as a binder to the organic solvent, and stirring the organic solvent while stirring the tin component and cobalt. A step of preparing a molybdenum-containing solution by adding molybdenum powder having an average particle size of 1 to 10 μm to which at least one of the components has been added, and the number of revolutions of a rotating plate of a spray dryer for dispersing the molybdenum-containing solution are (Rpm) and when the average particle diameter of the molybdenum granulated powder is B (μm), the molybdenum-containing solution is put into a spray dryer having an A / B in the range of 50 to 700, and the molybdenum-containing solution is dispersed. And drying to prepare molybdenum granulated powder.
Further, it is preferable to further carry out a sieving step of passing a sieve having a mesh diameter 2 to 3 times the average particle size B of the granulated powder with respect to the granulated powder after completion of the granulating step by the spray dryer. . The average particle diameter B of the molybdenum granulated powder is preferably 20 to 150 μm. Further, the rotational speed A of the rotating plate of the spray dryer is preferably 5000 to 16000 rpm. Moreover, it is preferable that an organic solvent is ethanol.
Further, the content (addition amount) of the cobalt component is preferably in the range of 50 to 500 mass ppm (wtppm) in terms of cobalt elemental element. Further, it is preferable that the content of the tin component is in the range of 50 to 500 ppm by mass in terms of tin element. Moreover, it is preferable to add both a tin component and a cobalt component.
In addition, when the total amount of molybdenum powder to be added is 100 parts by volume, the volume of the binder is preferably 3 to 20 parts by volume. The apparent density of the resulting molybdenum granulated powder is preferably 1.3 to 3.0 g / cc. The molybdenum-containing solution preferably has an organic solvent amount of 0.2 to 1 liter when the molybdenum powder amount is 100 parts by mass.
The spray dryer preferably dries the molybdenum granulated powder while supplying hot air at 100 to 300 ° C. Moreover, it is preferable that the spray drier carries out the drying of the molybdenum granulated powder in a reduced-pressure atmosphere below atmospheric pressure. Moreover, it is preferable that the fluidity | liquidity of the obtained molybdenum granulated powder is 50 sec / 50g or less.
The molybdenum granulated powder according to the present invention is characterized by containing at least one of a tin component and a cobalt component and having an apparent density of 1.3 to 3.0 g / cc.
The average particle diameter of the molybdenum granulated powder is preferably 20 to 150 μm. Further, when the total amount of molybdenum powder is 100 parts by volume, the volume of the binder is preferably 3 to 20 parts by volume. Further, the fluidity of the molybdenum granulated powder is preferably 50 sec / 50 g or less.
　本発明に係るモリブデン造粒粉の製造方法によれば、造粒工程において、有機溶媒を攪拌しながら、スズ成分または／およびコバルト成分を添加したモリブデン粉末およびバインダーを供給し、さらに目的とする造粒粉の平均粒径とスプレードライヤーの回転板の回転速度との比を所定範囲に制御しているために、平均粒径、見掛け密度および流動性が優れたモリブデン造粒粉を製造することができる。 According to the method for producing a molybdenum granulated powder according to the present invention, in the granulation step, while stirring an organic solvent, a molybdenum powder and a binder to which a tin component or / and a cobalt component are added are supplied, and the intended granulation is further performed. Since the ratio of the average particle size of the powder and the rotation speed of the rotating plate of the spray dryer is controlled within a predetermined range, it is possible to produce molybdenum granulated powder with excellent average particle size, apparent density and fluidity. it can.
本発明方法で使用するモリブデン含有溶液を調製する工程の一例を示す断面図である。It is sectional drawing which shows an example of the process of preparing the molybdenum containing solution used with this invention method. 本発明方法で使用するスプレードライヤーにモリブデン含有溶液を投入する工程の一例を示す断面図である。It is sectional drawing which shows an example of the process of throwing a molybdenum containing solution into the spray dryer used by the method of this invention. 本発明に係るモリブデン造粒粉の形状例を示す正面図である。It is a front view which shows the example of a shape of the molybdenum granulated powder which concerns on this invention.
　本発明の実施形態に係るモリブデン造粒粉の製造方法は、容器に有機溶媒を注入する工程と、上記有機溶媒にバインダーとしてのポリビニルブチラールを添加する工程と、上記有機溶媒を攪拌しながら、スズ成分およびコバルト成分の少なくとも１種を添加した平均粒径が１～１０μｍであるモリブデン粉末を投入することによりモリブデン含有溶液を調製する工程と、上記モリブデン含有溶液を分散するスプレードライヤーの回転板の回転数をＡ（ｒｐｍ）とし、モリブデン造粒粉の平均粒径をＢ（μｍ）としたときに、Ａ／Ｂが５０～７００の範囲であるスプレードライヤーにモリブデン含有溶液を投入し、上記モリブデン含有溶液を分散すると共に乾燥してモリブデン造粒粉を調製する工程と、を有することを特徴とするものである。
　図１に、モリブデン含有溶液を調製する工程の一例を示す。図中、符号１は容器（モリブデン含有溶液を調製するための容器）であり、２は有機溶媒であり、３はモリブデン粉末（スズ成分またはコバルト成分を添加したモリブデン粉末）であり、４はバインダーであり、５は必要に応じて再度投入する有機溶媒であり、６はモリブデン含有溶液である。
　まず、容器１に有機溶媒２を注入する。この有機溶媒は、アルコールなどが使用される。アルコールとしては、エタノール（エチルアルコール：Ｃ２Ｈ５ＯＨ）が好適である。エチルアルコールは、後述するバインダー（ポリビニルブチラール）を溶解し易いので好ましい。
　また、容器１に有機溶媒を注入した後に、必要に応じ５０℃以下に加熱する工程を実施してもよい。５０℃を超えた加熱は有機溶媒が蒸発し過ぎてしまうので好ましくない。５０℃以下の加熱であれば、バインダーを効率的に溶解することができる。 A method for producing molybdenum granulated powder according to an embodiment of the present invention includes a step of injecting an organic solvent into a container, a step of adding polyvinyl butyral as a binder to the organic solvent, and stirring the organic solvent while tin is used. A step of preparing a molybdenum-containing solution by introducing molybdenum powder having an average particle diameter of 1 to 10 μm to which at least one of a component and a cobalt component is added, and rotation of a rotating plate of a spray dryer for dispersing the molybdenum-containing solution When the number is A (rpm) and the average particle diameter of the molybdenum granulated powder is B (μm), the molybdenum-containing solution is put into a spray dryer in which A / B is in the range of 50 to 700. And preparing a molybdenum granulated powder by dispersing and drying the solution.
FIG. 1 shows an example of a process for preparing a molybdenum-containing solution. In the figure, reference numeral 1 is a container (a container for preparing a molybdenum-containing solution), 2 is an organic solvent, 3 is a molybdenum powder (a molybdenum powder to which a tin component or a cobalt component is added), and 4 is a binder. 5 is an organic solvent to be recharged as necessary, and 6 is a molybdenum-containing solution.
First, the organic solvent 2 is injected into the container 1. As this organic solvent, alcohol or the like is used. As the alcohol, ethanol (ethyl alcohol: C 2 H 5 OH) is preferable. Ethyl alcohol is preferable because it easily dissolves a binder (polyvinyl butyral) described later.
Moreover, after inject | pouring the organic solvent into the container 1, you may implement the process heated to 50 degrees C or less as needed. Heating above 50 ° C. is not preferable because the organic solvent evaporates too much. If it is a heating of 50 degrees C or less, a binder can be melt | dissolved efficiently.
　次に、有機溶媒２にバインダー４を添加する工程を実施する。バインダーの材質は、ポリビニルブチラール（ＰＶＢ：ｐｏｌｙｖｉｎｙｌ　ｂｕｔｙｒａｌ）を用いる。ポリビニルブチラールは、有機溶媒、特にエタノールによく溶解する。また、均一に有機溶媒に溶け込ませるには、有機溶媒を攪拌しながらバインダーを添加することが好ましい。
　次に、有機溶媒２を攪拌しながら平均粒径１～１０μｍのモリブデン粉末３を投入することにより、モリブデン含有溶液６を調製する工程を実施する。モリブデン粉末３の平均粒径とは一次粒径の平均粒径である。ここではＦＳＳＳ法（フィッシャー法）により求めた値を平均粒径とする。平均粒径が１μｍ未満では、Ｍｏ粉が過小であり、製造することが困難であり、コストアップの要因となる。
　一方、平均粒径が１０μｍを超えると、一次粒径が過大になり、造粒粉の特性を安定化させることが困難となる。そのため、モリブデン粉末３の平均粒径は１～１０μｍとされるが、さらには２～５μｍが好ましい。また、モリブデン粉末を、一度に大量に投入すると、モリブデン粉末が必要以上に凝集し易いので少量ずつ、例えば０．５～２ｋｇずつ投入することが好ましい。 Next, a step of adding the binder 4 to the organic solvent 2 is performed. Polyvinyl butyral (PVB) is used as the material of the binder. Polyvinyl butyral is well soluble in organic solvents, especially ethanol. Moreover, in order to make it melt | dissolve in an organic solvent uniformly, it is preferable to add a binder, stirring an organic solvent.
Next, a step of preparing a molybdenum-containing solution 6 is performed by adding molybdenum powder 3 having an average particle diameter of 1 to 10 μm while stirring organic solvent 2. The average particle size of the molybdenum powder 3 is the average particle size of the primary particle size. Here, the value obtained by the FSSS method (Fischer method) is defined as the average particle size. If the average particle size is less than 1 μm, the Mo powder is too small and difficult to manufacture, which increases the cost.
On the other hand, when the average particle size exceeds 10 μm, the primary particle size becomes excessive, and it becomes difficult to stabilize the characteristics of the granulated powder. Therefore, the average particle diameter of the molybdenum powder 3 is 1 to 10 μm, and more preferably 2 to 5 μm. Further, when a large amount of molybdenum powder is added at once, the molybdenum powder tends to aggregate more than necessary, so it is preferable to add a small amount, for example, 0.5 to 2 kg.
　また、バインダーの全量が有機溶媒に溶解したことを確認してから、モリブデン粉末を添加することが好ましい。バインダーを粉末の状態で添加すれば、溶解したか否かが肉眼で判別できる。なお、バインダーとしてポリビニルブチラール粉末を使用したとき、ポリビニルブチラール粉末が有機溶媒（エタノール）に完全に溶解すると、モリブデン粉末を添加する前の有機溶媒（エタノール）が半透明になる。バインダーが有機溶媒（エタノール）に完全に溶解したか否かを判定し易くするためにも、バインダーを添加した後に、モリブデン粉末を添加する順番であることが好ましい。
　有機溶媒２に、モリブデン粉末３、バインダー４を添加して、モリブデン含有溶液６を調製するに際し、投入するモリブデン粉末の合計量を１００体積部にしたときに、バインダーの体積を３～２０体積部とすることが好ましい。バインダーはモリブデン造粒粉を形成する際に、モリブデン粉末同士を接着する接着剤の役割を果たす。
　そのため、モリブデン粉末の合計量を１００体積部としたときに、バインダーの添加量が３体積部未満ではバインダー量が過少となり、均一な造粒粉が得られない恐れがある。また、バインダーの添加量が２０体積部を超えて大きいと、モリブデン粉末同士の隙間にバインダーが入りすぎて、密度のばらつき溶解したが大きな造粒粉となってしまう。そのため、バインダーの添加量はモリブデン粉末１００体積部に対し、３～２０体積部とされるが、さらには５～１５体積部であることが好ましい。 Further, it is preferable to add the molybdenum powder after confirming that the entire amount of the binder is dissolved in the organic solvent. If the binder is added in the state of powder, it can be discriminated with the naked eye whether or not it is dissolved. When polyvinyl butyral powder is used as the binder, when the polyvinyl butyral powder is completely dissolved in the organic solvent (ethanol), the organic solvent (ethanol) before adding the molybdenum powder becomes translucent. In order to easily determine whether or not the binder is completely dissolved in the organic solvent (ethanol), it is preferable to add the molybdenum powder after the binder is added.
In preparing the molybdenum-containing solution 6 by adding the molybdenum powder 3 and the binder 4 to the organic solvent 2, when the total amount of the molybdenum powder to be added is 100 parts by volume, the volume of the binder is 3 to 20 parts by volume. It is preferable that The binder serves as an adhesive that bonds the molybdenum powders together when forming the molybdenum granulated powder.
Therefore, when the total amount of molybdenum powder is 100 parts by volume, if the amount of binder added is less than 3 parts by volume, the amount of binder becomes too small, and uniform granulated powder may not be obtained. On the other hand, if the added amount of the binder is larger than 20 parts by volume, the binder enters too much into the gap between the molybdenum powders, resulting in a large granulated powder although the dispersion of the density varies and dissolves. Therefore, the added amount of the binder is 3 to 20 parts by volume with respect to 100 parts by volume of the molybdenum powder, and more preferably 5 to 15 parts by volume.
　また、モリブデン含有溶液は、モリブデン粉末量を１００質量部としたときに、有機溶媒量が０．２～１リットルであることが好ましい。スプレードライヤーには、モリブデン含有溶液の状態で投入される。このとき、モリブデン粉末量１００質量部に対し、有機溶媒量が０．２リットル未満では有機溶媒の量が過少であり、モリブデン含有溶液の粘性が上昇し、スプレードライヤーに安定的に供給することが困難である。また、有機溶媒量が１リットルを超えると有機溶媒の量が過多となり、安定供給し難い。なお、有機溶媒量が多いときは、攪拌しながら供給することにより、安定供給する方法も採用できる。このスプレードライヤーへのモリブデン含有溶液の供給は、機械化して自動化することも可能である。
　また、必要に応じて、有機溶媒５を追加投入してもよい。例えば、エタノールは沸点が７８．３℃と比較的に低いため、バインダーおよびモリブデン粉末を投入し混合している段階でエタノールが蒸発して溶媒量が大きく変化してしまう恐れもある。また、容器１として、容積が２０リットル以上である大型の容器を使用する場合には、まず有機溶媒量を最終的な量の３０～６０％でバインダーおよびモリブデン粉末と混合した後、残りの有機溶媒量７０～４０％を追加投入してモリブデン粉末と有機溶媒量との配合比を調整する方法も採用可能である。バインダーが有機溶媒に完全に溶解したかを目視により確認し易くするためにも、有機溶媒を追加投入する方法は有効である。 The molybdenum-containing solution preferably has an organic solvent amount of 0.2 to 1 liter when the molybdenum powder amount is 100 parts by mass. The spray dryer is charged in a molybdenum-containing solution. At this time, if the amount of the organic solvent is less than 0.2 liters with respect to 100 parts by mass of the molybdenum powder, the amount of the organic solvent is too small, the viscosity of the molybdenum-containing solution increases, and it can be stably supplied to the spray dryer. Have difficulty. On the other hand, when the amount of the organic solvent exceeds 1 liter, the amount of the organic solvent becomes excessive, and it is difficult to stably supply the organic solvent. When the amount of the organic solvent is large, a stable supply method can also be adopted by supplying it with stirring. The supply of the molybdenum-containing solution to the spray dryer can be mechanized and automated.
Moreover, you may add the organic solvent 5 further as needed. For example, since ethanol has a relatively low boiling point of 78.3 ° C., ethanol may evaporate and the amount of solvent may change greatly when a binder and molybdenum powder are added and mixed. When a large container having a volume of 20 liters or more is used as the container 1, first, the amount of organic solvent is mixed with the binder and molybdenum powder at 30 to 60% of the final amount, and then the remaining organic A method of adjusting the blending ratio between molybdenum powder and the amount of organic solvent by additionally adding a solvent amount of 70 to 40% can also be employed. In order to make it easy to visually confirm whether the binder is completely dissolved in the organic solvent, a method of adding the organic solvent is also effective.
　また、本発明のモリブデン粉末は、スズ成分およびコバルト成分の少なくとも１種を添加したモリブデン粉末である。スズ成分またはコバルト成分としては、それぞれ単体元素、酸化物、複合酸化物などの化合物が使用できる。
　また、スズ成分の含有量（添加量）は、スズ（Ｓｎ）元素単体換算で５０～５００質量ｐｐｍの範囲であることが好ましい。また、コバルト成分の含有量（添加量）は、コバルト（Ｃｏ）元素単体換算で５０～５００質量ｐｐｍの範囲であることが好ましい。また、上記スズ成分とコバルト成分とは、両方とも添加することが好ましい。
　また、スズ成分またはコバルト成分は、金属元素単体換算で５０質量ｐｐｍ未満では添加の効果が小さい一方、５００質量ｐｐｍを超えると、却って特性が低下する。
　また、スズ成分またはコバルト成分の添加により、高純度モリブデンと比較して、再結晶温度が高くなり、高温強度が高くなる。また、再結晶熱処理後に延性が向上することから、ワイヤへの線引き加工などの二次加工性が向上する。二次加工は、ワイヤへの線引き加工の他に、ワイヤの折り曲げ加工、板材（Ｍｏ焼結体からなる板材）の圧延加工、曲げ加工や打ち抜き加工などが挙げられる。また、ワイヤの特性としては、ノンサグ性、高温耐振性、耐黒化性の向上も図ることができる。
　また、スズ成分またはコバルト成分を添加したモリブデン粉末の製造方法は特に限定されるものではないが、次の方法が例示される。
　まず、モリブデン粉末の原料として、アンモニウムダイモリブデート（（ＮＨ４）２・Ｍｏ２Ｏ７））を用意し、水素気流中において６００～７５０℃で加熱し、Ｍｏ酸化物を得る。このＭｏ酸化物に塩化スズまたは／および塩化コバルトをそれぞれ金属単体換算で５０～５００質量ｐｐｍになるように添加する。このとき純水を加え、混練して、攪拌しながら１００～１４０℃に加熱して乾燥し、スズ成分または／およびコバルト成分添加モリブデン酸化物粉末とする。スズ成分または／およびコバルト成分添加モリブデン酸化物粉末を水素雰囲気中において、１０００～１２００℃で２～５時間加熱、還元して、スズ成分または／およびコバルト成分を添加したモリブデン粉末を得ることができる。 The molybdenum powder of the present invention is a molybdenum powder to which at least one of a tin component and a cobalt component is added. As the tin component or the cobalt component, compounds such as simple elements, oxides, and complex oxides can be used.
Further, the content (addition amount) of the tin component is preferably in the range of 50 to 500 ppm by mass in terms of the tin (Sn) element alone. Further, the content (addition amount) of the cobalt component is preferably in the range of 50 to 500 ppm by mass in terms of cobalt (Co) element alone. Moreover, it is preferable to add both the tin component and the cobalt component.
In addition, when the tin component or the cobalt component is less than 50 ppm by mass in terms of a simple metal element, the effect of addition is small.
In addition, the addition of a tin component or a cobalt component increases the recrystallization temperature and increases the high-temperature strength as compared with high-purity molybdenum. Moreover, since ductility improves after recrystallization heat processing, secondary workability, such as a drawing process to a wire, improves. Secondary processing includes wire bending processing, wire bending processing, plate material (plate material made of Mo sintered body) rolling processing, bending processing, punching processing, and the like. Further, the wire characteristics can improve non-sag, high-temperature vibration resistance, and blackening resistance.
Moreover, although the manufacturing method of the molybdenum powder which added the tin component or the cobalt component is not specifically limited, the following method is illustrated.
First, ammonium dimolybdate ((NH 4 ) 2 · Mo 2 O 7 )) is prepared as a raw material for molybdenum powder, and heated at 600 to 750 ° C. in a hydrogen stream to obtain Mo oxide. To this Mo oxide, tin chloride and / or cobalt chloride is added so as to be 50 to 500 mass ppm in terms of a metal simple substance. At this time, pure water is added, kneaded, heated to 100 to 140 ° C. with stirring and dried to obtain a molybdenum component-added molybdenum oxide powder. The molybdenum component-added molybdenum oxide powder can be heated and reduced at 1000 to 1200 ° C. for 2 to 5 hours in a hydrogen atmosphere to obtain a molybdenum powder to which the tin component and / or cobalt component is added. .
　スズ成分またはコバルト成分を添加したモリブデン粉末の純度に関しては特に限定されるものではないが、Ｍｏとスズまたは／およびコバルトの合計が９９質量％以上、さらには９９．９％質量以上であることが好ましい。
　モリブデン粉末の主な不純物は、Ｆｅ（鉄）、Ａｌ（アルミニウム）、Ｃａ（カルシウム）、Ｍｇ（マグネシウム）、Ｓｉ（ケイ素）が挙げられる。また、これ以外の不純物としては、Ｎｉ（ニッケル）、Ｎａ（ナトリウム）、Ｋ（カリウム）、Ｐｂ（鉛）、Ｂｉ（ビスマス）、Ｃｄ（カドミウム）、Ｃｕ（銅）、Ｍｎ（マンガン）が挙げられる。
　モリブデンの純度の測定は、Ｆｅ（鉄）、Ａｌ（アルミニウム）、Ｃａ（カルシウム）、Ｍｇ（マグネシウム）、Ｓｉ（ケイ素）、Ｎｉ（ニッケル）、Ｎａ（ナトリウム）、Ｋ（カリウム）、Ｐｂ（鉛）、Ｂｉ（ビスマス）、Ｃｄ（カドミウム）、Ｃｕ（銅）、Ｍｎ（マンガン）の合計量を１００質量％から差し引いて求めるものとする。
　また、それぞれの不純物量としては、Ｆｅ（鉄）は１０質量ｐｐｍ以下、Ａｌ（アルミニウム）は５０質量ｐｐｍ以下、Ｃａ（カルシウム）は３０質量ｐｐｍ以下、Ｍｇ（マグネシウム）は２０質量ｐｐｍ以下、Ｓｉ（ケイ素）は５０質量ｐｐｍ以下、Ｎｉ（ニッケル）は５０質量ｐｐｍ以下、Ｎａ（ナトリウム）は１０質量ｐｐｍ以下、Ｋ（カリウム）は２０質量ｐｐｍ以下、Ｐｂ（鉛）は７０質量ｐｐｍ以下、Ｂｉ（ビスマス）は７０質量ｐｐｍ以下、Ｃｄ（カドミウム）は７０質量ｐｐｍ以下、Ｃｕ（銅）は７０質量ｐｐｍ以下、Ｍｎ（マンガン）は２０質量ｐｐｍ以下であることが好ましい。
　また、上記金属不純物以外の不純物として酸素などのガス成分が挙げられる。酸素量は７質量％以下とする一方、窒素量は７質量％以下であることが好ましい。 The purity of the molybdenum powder to which the tin component or cobalt component is added is not particularly limited, but the sum of Mo and tin or / and cobalt may be 99% by mass or more, and further 99.9% by mass or more. preferable.
Main impurities of the molybdenum powder include Fe (iron), Al (aluminum), Ca (calcium), Mg (magnesium), and Si (silicon). Other impurities include Ni (nickel), Na (sodium), K (potassium), Pb (lead), Bi (bismuth), Cd (cadmium), Cu (copper), and Mn (manganese). It is done.
The measurement of the purity of molybdenum is Fe (iron), Al (aluminum), Ca (calcium), Mg (magnesium), Si (silicon), Ni (nickel), Na (sodium), K (potassium), Pb (lead). ), Bi (bismuth), Cd (cadmium), Cu (copper), and Mn (manganese) are subtracted from 100% by mass.
Moreover, as each impurity amount, Fe (iron) is 10 mass ppm or less, Al (aluminum) is 50 mass ppm or less, Ca (calcium) is 30 mass ppm or less, Mg (magnesium) is 20 mass ppm or less, Si (Silicon) is 50 mass ppm or less, Ni (nickel) is 50 mass ppm or less, Na (sodium) is 10 mass ppm or less, K (potassium) is 20 mass ppm or less, Pb (lead) is 70 mass ppm or less, Bi (Bismuth) is preferably 70 ppm by mass or less, Cd (cadmium) is 70 ppm by mass or less, Cu (copper) is 70 ppm by mass or less, and Mn (manganese) is preferably 20 ppm by mass or less.
Moreover, gas components, such as oxygen, are mentioned as impurities other than the said metal impurity. While the amount of oxygen is 7% by mass or less, the amount of nitrogen is preferably 7% by mass or less.
　次に、得られたモリブデン含有溶液６をスプレードライヤーに投入し造粒する工程を実施する。図２にスプレードライヤーによる造粒工程の一例を示す。図中、符号１はモリブデン含有溶液を入れた容器であり、６はモリブデン含有溶液であり、７はモリブデン含有水溶液の投入口であり、８は回転板であり、９はモリブデン造粒粉であり、１０はスプレードライヤーの外壁であり、１１はモリブデン造粒粉の回収容器である。
　前記工程にて調整されたモリブデン含有溶液６を投入口７に流し込む。投入口７への投入量（投入速度）は、１０～８０ｃｃ／分が好ましい。投入速度が１０ｃｃ／分未満では、投入量が過少であり、量産性が悪化する。一方、投入速度が８０ｃｃ／分を超えると、投入量が過多となり、得られる造粒粉の特性にばらつきが生じる。 Next, the obtained molybdenum-containing solution 6 is put into a spray dryer and granulated. FIG. 2 shows an example of a granulation process using a spray dryer. In the figure, reference numeral 1 is a container containing a molybdenum-containing solution, 6 is a molybdenum-containing solution, 7 is an inlet for a molybdenum-containing aqueous solution, 8 is a rotating plate, and 9 is a molybdenum granulated powder. Reference numeral 10 denotes an outer wall of the spray dryer, and reference numeral 11 denotes a molybdenum granulated powder collection container.
The molybdenum-containing solution 6 adjusted in the above process is poured into the charging port 7. The input amount (input speed) to the input port 7 is preferably 10 to 80 cc / min. When the input speed is less than 10 cc / min, the input amount is too small and the mass productivity is deteriorated. On the other hand, when the input speed exceeds 80 cc / min, the input amount becomes excessive, and the characteristics of the resulting granulated powder vary.
　次に、投入されたモリブデン含有溶液６は回転板８上に供給される。回転板８は一定の回転数で回転している。回転している回転板にモリブデン含有溶液６が供給されると、一定量ずつ弾かれ表面張力により、球状のモリブデン造粒粉９が形成される。モリブデン造粒粉９はスプレードライヤーの外壁１０に沿って落下し、モリブデン造粒粉の回収容器１１に回収される。
　モリブデン造粒粉の平均粒径は、スプレードライヤーの回転板８の回転速度との関連性が高い。そこで本発明では、回転板８の回転速度をＡ（ｒｐｍ）とし、造粒粉の平均粒径をＢ（μｍ）としたときに、Ａ／Ｂを５０～７００の範囲に制御することを特徴とするものである。モリブデン含有溶液６を回転板８に供給したとき、回転板に一定量ずつ弾かれ、弾かれたモリブデン含有溶液６は表面張力により球状のモリブデン造粒粉９になる。また、バインダーを添加していることからも均一な造粒粉を製造することができる。 Next, the charged molybdenum-containing solution 6 is supplied onto the rotating plate 8. The rotating plate 8 rotates at a constant rotational speed. When the molybdenum-containing solution 6 is supplied to the rotating rotating plate, it is repelled by a certain amount to form spherical molybdenum granulated powder 9 by surface tension. The molybdenum granulated powder 9 falls along the outer wall 10 of the spray dryer and is collected in a molybdenum granulated powder collection container 11.
The average particle diameter of the molybdenum granulated powder is highly related to the rotation speed of the rotating plate 8 of the spray dryer. Therefore, the present invention is characterized in that A / B is controlled in the range of 50 to 700 when the rotational speed of the rotating plate 8 is A (rpm) and the average particle diameter of the granulated powder is B (μm). It is what. When the molybdenum-containing solution 6 is supplied to the rotating plate 8, the molybdenum-containing solution 6 is repelled on the rotating plate by a certain amount, and the repelled molybdenum-containing solution 6 becomes spherical molybdenum granulated powder 9 due to surface tension. Moreover, uniform granulated powder can be manufactured also from having added the binder.
　上記比の値であるＡ／Ｂが５０未満では、目的とする造粒粉の平均粒径に対して回転板の回転速度が不足しているため、目的とする造粒粉の平均粒径Ｂが得られない。また、Ａ／Ｂが５０未満の場合は、目的とする造粒粉の平均粒径Ｂに対して大きな平均粒径を有する造粒粉となる。
　一方、Ａ／Ｂが７００を超えると、目的とする造粒粉の平均粒径に対して回転板の回転速度が速すぎるため、目的とする造粒粉の平均粒径Ｂが得られない。また、Ａ／Ｂが７００を超えると目的とする造粒粉の平均粒径Ｂに対して、小さな平均粒径となる。
　Ａ／Ｂを５０～７００の範囲に制御することにより、目的とする造粒粉の平均粒径Ｂに対して±５０％の範囲の平均粒径を有する造粒粉が得られる。例えば、目的とする造粒粉の平均粒径Ｂを５０μｍとしたとき、±５０％の値は５０×０．５＝２５μｍであるから、平均粒径が２５～７５μｍの造粒粉が得られることを意味している。なお、造粒粉の平均粒径は拡大写真を使って、そこに写る造粒粉の最大径を粒径とし、造粒粉１００粒の平均値を造粒粉の平均粒径とする。 When A / B which is the value of the above ratio is less than 50, the rotation speed of the rotating plate is insufficient with respect to the average particle diameter of the intended granulated powder, and therefore the average particle diameter B of the intended granulated powder. Cannot be obtained. Moreover, when A / B is less than 50, it becomes a granulated powder having a larger average particle diameter than the average particle diameter B of the intended granulated powder.
On the other hand, when A / B exceeds 700, the rotation speed of the rotating plate is too high with respect to the average particle diameter of the intended granulated powder, and thus the average particle diameter B of the intended granulated powder cannot be obtained. Moreover, when A / B exceeds 700, it becomes a small average particle diameter with respect to the average particle diameter B of the intended granulated powder.
By controlling A / B in the range of 50 to 700, a granulated powder having an average particle diameter in the range of ± 50% with respect to the average particle diameter B of the intended granulated powder can be obtained. For example, when the average particle size B of the intended granulated powder is 50 μm, the value of ± 50% is 50 × 0.5 = 25 μm, so that a granulated powder having an average particle size of 25 to 75 μm is obtained. It means that. In addition, the average particle diameter of granulated powder uses an enlarged photograph, and makes the maximum diameter of the granulated powder reflected there the particle diameter, and the average value of 100 granulated powder is the average particle diameter of the granulated powder.
　また、造粒粉の平均粒径Ｂは、２０～１５０μｍであることが好ましい。造粒粉の平均粒径が２０～１５０μｍの範囲であれば、様々な用途に適用できる。また、スプレードライヤーの回転板８の回転数Ａは５０００～１６０００ｒｐｍであることが好ましい。上記回転数Ａが５０００～１６０００ｒｐｍの範囲であれば、モリブデン含有溶液が回転板上で効率的に弾かれ、目的とする平均粒径を有する造粒粉が得やすい。 The average particle size B of the granulated powder is preferably 20 to 150 μm. If the average particle diameter of the granulated powder is in the range of 20 to 150 μm, it can be applied to various applications. The rotation speed A of the rotary plate 8 of the spray dryer is preferably 5000 to 16000 rpm. When the rotational speed A is in the range of 5000 to 16000 rpm, the molybdenum-containing solution is efficiently repelled on the rotating plate, and a granulated powder having a target average particle diameter is easily obtained.
　また、スプレードライヤーは、１００～３００℃の熱風を供給しながらモリブデン造粒粉の乾燥を実施することが好ましい。スプレードライヤーの外壁内に温度が１００～３００℃の熱風を供給することにより、造粒粉中の有機溶媒を蒸発させ、バインダーによるモリブデン粉末同士の結合力を強化することができる。
　その結果、目的とする平均粒径を有するモリブデン造粒粉を製造することができる。熱風は図示しない熱風供給口からスプレードライヤーの外壁１０内に供給され、図示しない排気口から排気される。熱風を供給口から排気口に排気しながら供給することにより、常に新鮮な熱風を供給することにより造粒粉から蒸発した水分が他の造粒粉に取り込まれることを防止できる。なお、熱風の供給温度が１００℃未満では有機溶媒分の蒸発速度が遅い一方、３００℃を超えると有機溶媒が瞬間的に蒸発し過ぎて造粒粉の粒径のばらつきが発生する原因となる。 The spray dryer preferably dries the molybdenum granulated powder while supplying hot air at 100 to 300 ° C. By supplying hot air having a temperature of 100 to 300 ° C. into the outer wall of the spray dryer, the organic solvent in the granulated powder can be evaporated and the binding force between the molybdenum powders by the binder can be enhanced.
As a result, molybdenum granulated powder having a target average particle diameter can be produced. Hot air is supplied into the outer wall 10 of the spray dryer from a hot air supply port (not shown) and exhausted from an exhaust port (not shown). By supplying hot air while exhausting it from the supply port to the exhaust port, it is possible to prevent moisture evaporated from the granulated powder from being taken into other granulated powder by always supplying fresh hot air. In addition, when the supply temperature of hot air is less than 100 ° C., the evaporation rate of the organic solvent is slow. On the other hand, when it exceeds 300 ° C., the organic solvent instantaneously evaporates and causes variation in the particle size of the granulated powder. .
　また、スプレードライヤーは大気圧以下の減圧雰囲気でモリブデン造粒粉の乾燥を実施することが好ましい。スプレードライヤーの外壁１０内を大気圧以下の減圧雰囲気とすることにより、造粒粉中の有機溶媒を蒸発し易くすることができる。なお、減圧雰囲気は、大気圧（１ａｔｍ＝１．０１×１０５Ｐａ）から１００～５００Ｐａ低い減圧雰囲気であることが好ましい。１００Ｐａ未満では減圧雰囲気とする効果が十分でない。一方、５００Ｐａを超えると、減圧雰囲気を制御する負担が大きくなりコストアップの要因となる。 Moreover, it is preferable that the spray dryer performs drying of the molybdenum granulated powder in a reduced-pressure atmosphere of atmospheric pressure or lower. By setting the inside of the outer wall 10 of the spray dryer to a reduced-pressure atmosphere of atmospheric pressure or less, the organic solvent in the granulated powder can be easily evaporated. The reduced-pressure atmosphere is preferably a reduced-pressure atmosphere that is 100 to 500 Pa lower than atmospheric pressure (1 atm = 1.01 × 10 5 Pa). If the pressure is less than 100 Pa, the effect of reducing the pressure is not sufficient. On the other hand, if it exceeds 500 Pa, the burden of controlling the reduced-pressure atmosphere increases and causes an increase in cost.
　本発明に係るモリブデン造粒粉の製造方法によれば、造粒粉の平均粒径に合わせてスプレードライヤーの回転板の回転速度を調整しているために、目的とする平均粒径に対し±５０％の範囲の平均粒径を有する造粒粉を効率的に得ることができる。
　また、得られるモリブデン造粒粉の見かけ密度が１．３～３．０ｇ／ｃｃであることが好ましい。前述のように本発明ではモリブデン造粒粉の平均粒径は拡大写真を使用して測定している。この測定方法であれば、外観上の平均粒径は判断できる。
　しかしながら、造粒粉の内部に空隙が多く密度が小さな造粒粉が存在すると、その後の製品（溶射用粉末や焼結体）に使用するときに、部分的にモリブデン粉末の存在比率にばらつきが生じる。存在比率のばらつきは、製品のばらつきに繋がる。例えば、造粒粉を溶射用粉末として使用する場合、密度が大きく異なる造粒粉が存在すると、溶射フレーム炎に投入されるモリブデン粉末量にばらつきが生じ、結果として溶射Ｍｏ膜のばらつきが発生する原因となる。また、焼結体を作製する場合は、成形金型に挿入されるモリブデン量のばらつきが生じ、焼結体中のポアが必要以上に大きくなる恐れがある。 According to the method for producing molybdenum granulated powder according to the present invention, since the rotation speed of the rotating plate of the spray dryer is adjusted in accordance with the average particle diameter of the granulated powder, ± A granulated powder having an average particle size in the range of 50% can be obtained efficiently.
The apparent density of the resulting molybdenum granulated powder is preferably 1.3 to 3.0 g / cc. As described above, in the present invention, the average particle diameter of the molybdenum granulated powder is measured using an enlarged photograph. If it is this measuring method, the average particle diameter on an external appearance can be judged.
However, if granulated powder with many voids and low density is present inside the granulated powder, when it is used for subsequent products (spraying powder or sintered body), the abundance ratio of the molybdenum powder partially varies. Arise. Variation in the existence ratio leads to variation in the product. For example, when granulated powder is used as a thermal spraying powder, if there are granulated powders with significantly different densities, the amount of molybdenum powder charged into the thermal flame flame will vary, resulting in variations in the thermal sprayed Mo film. Cause. Moreover, when producing a sintered compact, the variation in the amount of molybdenum inserted into the molding die occurs, and the pores in the sintered compact may become larger than necessary.
　見掛け密度が１．３ｇ／ｃｃ未満であると、モリブデン造粒粉中のモリブデン量が過少であり、その後の製品化における品質のばらつきが発生する原因となる。一方、見掛け密度が３．０ｇ／ｃｃを超えて過大になると、モリブデン粉末がぎっしり詰まった状態であるため、スプレードライヤーで安定的に製造することが困難になる。見掛け密度の測定方法は、ＪＩＳ－Ｚ－２５０４に準拠した測定方法に従うものとする。
　また、得られたモリブデン造粒粉の流動性が５０ｓｅｃ／５０ｇ以下であることが好ましい。この流動性の測定も、ＪＩＳ－Ｚ－２５０４に準拠した測定方法で実施するものとする。ここで流動性とは、造粒粉がどれだけ円滑迅速に移動する（流れる）かを示す指標である。流動性が良い（流動性５０ｓｅｃ／５０ｇ以下）と、製品化する際の成形金型への供給充填が円滑迅速に行えるのである。つまりは、取扱い性が良好な造粒粉であると言える。
　また、流動性が良いということは造粒粉の形状が球体に近いことを意味している。造粒粉が球体に近いとは、アスペクト比が１．５以下を示すものとする。図３にモリブデン造粒粉の一例を示す。図中、３はモリブデン粉末であり、９はモリブデン造粒粉であり、Ｌ１はモリブデン造粒粉の短径であり、Ｌ２は長径である。アスペクト比は「長径Ｌ２／短径Ｌ１」の算式から求める。アスペクト比が１．０であるとは真球に近い状態であることを示す。 When the apparent density is less than 1.3 g / cc, the amount of molybdenum in the molybdenum granulated powder is too small, which causes a variation in quality in the subsequent commercialization. On the other hand, when the apparent density exceeds 3.0 g / cc, the molybdenum powder is tightly packed, so that it is difficult to stably manufacture with a spray dryer. The apparent density is measured according to a measurement method based on JIS-Z-2504.
Moreover, it is preferable that the fluidity | liquidity of the obtained molybdenum granulated powder is 50 sec / 50g or less. This fluidity measurement is also carried out by a measurement method based on JIS-Z-2504. Here, the fluidity is an index indicating how smoothly and quickly the granulated powder moves (flows). When the fluidity is good (fluidity 50 sec / 50 g or less), the filling and filling of the molding die can be smoothly and rapidly performed when commercialized. In other words, it can be said that the granulated powder has good handleability.
Moreover, that fluidity | liquidity is good means that the shape of granulated powder is close to a sphere. When the granulated powder is close to a sphere, the aspect ratio is 1.5 or less. FIG. 3 shows an example of molybdenum granulated powder. In the figure, 3 is a molybdenum powder, 9 is a molybdenum granulated powder, L1 is a short diameter of the molybdenum granulated powder, and L2 is a long diameter. The aspect ratio is obtained from the formula “major axis L2 / minor axis L1”. An aspect ratio of 1.0 indicates a state close to a true sphere.
　このように本発明に係るモリブデン造粒粉の製造方法によれば、平均粒径、見かけ密度、流動性が優れたモリブデン造粒粉を歩留り良く効率的に製造することができる。
　また、モリブデン造粒粉の平均粒径、特に粒度分布の制御工程として、スプレードライヤーによる造粒工程完了後の造粒粉に対して、その平均粒径Ｂの２～３倍のメッシュ径を有する篩を通す篩分け工程をさらに実施する方法も好ましい。この篩分け工程を実施することにより、過大な造粒粉を除去することができる。これにより、さらに平均粒径の制御が可能となる。また、この篩分け工程により、過小な造粒粉を除去することもでき有効である。 Thus, according to the manufacturing method of the molybdenum granulated powder which concerns on this invention, the molybdenum granulated powder excellent in average particle diameter, apparent density, and fluidity | liquidity can be efficiently manufactured with a sufficient yield.
In addition, as a process for controlling the average particle diameter of the molybdenum granulated powder, especially the particle size distribution, it has a mesh diameter 2 to 3 times the average particle diameter B of the granulated powder after completion of the granulation process by a spray dryer. A method of further carrying out a sieving step through a sieve is also preferred. By carrying out this sieving step, excessive granulated powder can be removed. As a result, the average particle diameter can be further controlled. In addition, this sieving step is effective because it can remove excessive granulated powder.
　以上のように本発明に係るモリブデン造粒粉の製造方法によれば、平均粒径、見かけ密度、流動性が優れたモリブデン造粒粉を歩留り良く効率的に製造することができる。そのため、各製品に応じた造粒粉を歩留り良く製造することができる。
　この造粒粉の用途としては、溶射用粉末、各種焼結体の原料粉などが挙げられる。溶射用粉末として、平均粒径、見掛け密度および流動性が優れたモリブデン造粒粉を使用することにより、溶射フレーム炎への供給量を安定化させることができる。その結果、溶射膜の品質を均質なものとすることができる。また、各種焼結体の原料粉末としてモリブデン造粒粉を使用する場合、平均粒径、見掛け密度および流動性が優れたモリブデン造粒粉を使用することにより、成形金型への充填量を均質化できる。その結果、焼結体の密度などを安定化させることができる。特に、成形金型の形状に応じて、平均粒径を変更することにより、さらに歩留りの向上を図ることができる。例えば、厚さが１ｍｍ以下の焼結体では、造粒粉の平均粒径を５０μｍ程度とする一方、厚さが５ｍｍ程度の焼結体では、造粒粉の平均粒径を１００μｍ程度にすることにより、成形金型への充填を効率よく実施することができる。また、高温特性が優れていることから、ワイヤへ加工する際の加工性も向上する。 As described above, according to the method for producing molybdenum granulated powder according to the present invention, molybdenum granulated powder having excellent average particle diameter, apparent density, and fluidity can be efficiently produced with a high yield. Therefore, the granulated powder according to each product can be manufactured with a good yield.
Applications of this granulated powder include thermal spraying powder, raw powders of various sintered bodies, and the like. By using molybdenum granulated powder having excellent average particle diameter, apparent density and fluidity as the thermal spraying powder, the supply amount to the thermal spray flame can be stabilized. As a result, the quality of the sprayed film can be made uniform. In addition, when using molybdenum granulated powder as a raw material powder for various sintered bodies, the use of molybdenum granulated powder with excellent average particle diameter, apparent density and fluidity ensures uniform filling in the mold. Can be As a result, the density of the sintered body can be stabilized. In particular, the yield can be further improved by changing the average particle size according to the shape of the molding die. For example, in a sintered body having a thickness of 1 mm or less, the average particle diameter of the granulated powder is set to about 50 μm, whereas in a sintered body having a thickness of about 5 mm, the average particle diameter of the granulated powder is set to about 100 μm. As a result, it is possible to efficiently fill the molding die. Moreover, since the high temperature characteristic is excellent, the workability at the time of processing into a wire is also improved.
（実施例）
（実施例１～５および比較例１～２）
　表１に示すスズ成分および／またはコバルト成分を添加したモリブデン粉末と、バインダーとしてポリビニルブチラール（ＰＶＢ）粉末およびエタノールを用意した。まずステンレス製容器に、エタノールを注入し、常温で攪拌しながら、ポリビニルブチラール粉末を添加し、添加したポリビニルブチラール粉末を全て溶解させた。ポリビニルブチラール粉末が全て溶解したときは、半透明の溶液となっていることが確認できた。その後、モリブデン粉末を１～２ｋｇずつ、合計４０ｋｇ投入した。モリブデン粉末の攪拌に際して、エタノールが蒸発して不足する分は、必要に応じてエタノールを追加投入した。バインダーとしてポリビニルアルコール粉末を使用したモリブデン含有溶液を実施例１～５とした。
　ここまでのモリブデン含有溶液の調製工程の条件を下記表１，２に示す。 (Example)
(Examples 1 to 5 and Comparative Examples 1 and 2)
A molybdenum powder added with a tin component and / or a cobalt component shown in Table 1, and polyvinyl butyral (PVB) powder and ethanol were prepared as binders. First, ethanol was poured into a stainless steel container, and while stirring at room temperature, polyvinyl butyral powder was added, and all the added polyvinyl butyral powder was dissolved. When all the polyvinyl butyral powder was dissolved, it was confirmed that the solution was a translucent solution. Thereafter, a total of 40 kg of molybdenum powder was added in an amount of 1-2 kg. When the molybdenum powder was agitated, ethanol was additionally added as needed for the shortage of ethanol evaporation. Examples 1 to 5 were molybdenum-containing solutions using polyvinyl alcohol powder as a binder.
The conditions for the preparation steps of the molybdenum-containing solution so far are shown in Tables 1 and 2 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　次に、上記のように調製した実施例１～５に係る各モリブデン含有溶液を使用して、スプレードライヤーによる造粒工程を実施した。スプレードライヤーによる造粒工程の条件を下記表３に示す。 Next, using each of the molybdenum-containing solutions according to Examples 1 to 5 prepared as described above, a granulation step using a spray dryer was performed. The conditions of the granulation process with a spray dryer are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１Ａ～５Ｂおよび比較例１～２の製造方法によって得られたモリブデン造粒粉の平均粒径、アスペクト比、見掛け密度、流動性および製品歩留りを調査した。
　なお、平均粒径は得られたモリブデン造粒粉の任意の１００粒を抜き出し、拡大写真を撮り、そこに写る最大径を求め１００粒の平均値を平均粒径とした。また、アスペクト比は同様の拡大写真を使用して、短径Ｌ１および長径Ｌ２を求め、それぞれのＬ２／Ｌ１の平均値をアスペクト比とした。また、見かけ密度および流動性は、ＪＩＳ－Ｚ－２５０４に準拠する測定方法に従って測定した。また、製品歩留りは、投入したモリブデン粉末４０ｋｇ量と、回収したモリブデン造粒粉の合計量との比「（造粒粉の合計量／４０ｋｇ）×１００％」から算出した。
　それらの測定結果を下記表４に示す。 The average particle diameter, aspect ratio, apparent density, fluidity and product yield of the granulated molybdenum powders obtained by the production methods of Examples 1A-5B and Comparative Examples 1-2 were investigated.
The average particle size was obtained by extracting 100 arbitrary particles of the obtained molybdenum granulated powder, taking an enlarged photograph, obtaining the maximum diameter reflected therein, and taking the average value of 100 particles as the average particle size. Moreover, the aspect ratio used the same enlarged photograph, calculated | required the minor axis L1 and the major axis L2, and made each average value of L2 / L1 the aspect ratio. The apparent density and fluidity were measured according to a measuring method based on JIS-Z-2504. The product yield was calculated from the ratio of the amount of molybdenum powder charged to 40 kg and the total amount of recovered molybdenum granulated powder ((total amount of granulated powder / 40 kg) × 100%).
The measurement results are shown in Table 4 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記表４に示す結果から明らかなように、各実施例に係るモリブデン造粒粉の製造方法により製造された、スズ成分および／またはコバルト成分を添加したモリブデン造粒粉は、目的とする平均粒径Ｂに対するずれが小さく、アスペクト比、見掛け密度および流動性が優れていた。また、歩留りも高く効率の良い製造方法であると言える。それに対し、Ａ／Ｂが本発明での規定範囲外である比較例１および比較例２では、いずれのパラメータも悪化した特性を示した。 As is apparent from the results shown in Table 4 above, the molybdenum granulated powder added with the tin component and / or the cobalt component, produced by the method for producing the molybdenum granulated powder according to each example, has a target average particle size. The deviation with respect to the diameter B was small, and the aspect ratio, the apparent density, and the fluidity were excellent. In addition, it can be said that this is an efficient manufacturing method with a high yield. On the other hand, in Comparative Example 1 and Comparative Example 2 where A / B is outside the specified range in the present invention, both parameters showed a deteriorated characteristic.
１…容器（モリブデン含有溶液を調製するための容器）
２…有機溶媒（エチルアルコール等）
３…モリブデン粉末（スズ成分またはコバルト成分を添加したモリブデン粉末）
４…バインダー
５…必要に応じて再度投入する有機溶媒
６…モリブデン含有溶液
７…モリブデン含有溶液の投入口
８…回転板
９…モリブデン造粒粉
１０…スプレードライヤーの外壁
１１…モリブデン造粒粉の回収容器 1 ... container (container for preparing molybdenum-containing solution)
2… Organic solvent (ethyl alcohol, etc.)
3 ... Molybdenum powder (molybdenum powder with tin or cobalt added)
4 ... Binder 5 ... Organic solvent 6 to be added again as required 6 ... Molybdenum-containing solution 7 ... Molybdenum-containing solution inlet 8 ... Rotary plate 9 ... Molybdenum granulated powder 10 ... Outer wall 11 of spray dryer ... Molybdenum granulated powder Collection container

Claims (18)

  1. 　容器に有機溶媒を注入する工程と、
    　上記有機溶媒にバインダーとしてのポリビニルブチラールを添加する工程と、
    　上記有機溶媒を攪拌しながら、スズ成分およびコバルト成分の少なくとも１種を添加した平均粒径が１～１０μｍであるモリブデン粉末を投入することによりモリブデン含有溶液を調製する工程と、
    　上記モリブデン含有溶液を分散するスプレードライヤーの回転板の回転数をＡ（ｒｐｍ）とし、モリブデン造粒粉の平均粒径をＢ（μｍ）としたときに、Ａ／Ｂが５０～７００の範囲であるスプレードライヤーにモリブデン含有溶液を投入し、上記モリブデン含有溶液を分散すると共に乾燥してモリブデン造粒粉を調製する工程と、
    　を有することを特徴とするモリブデン造粒粉の製造方法。     Injecting an organic solvent into the container;
    Adding polyvinyl butyral as a binder to the organic solvent;
    Preparing a molybdenum-containing solution by adding molybdenum powder having an average particle diameter of 1 to 10 μm to which at least one of a tin component and a cobalt component is added while stirring the organic solvent;
    A / B is in the range of 50 to 700, where A (rpm) is the rotational speed of the rotating plate of the spray dryer for dispersing the molybdenum-containing solution and B (μm) is the average particle diameter of the molybdenum granulated powder. Adding a molybdenum-containing solution to a spray dryer, dispersing the molybdenum-containing solution and drying to prepare molybdenum granulated powder; and
    A method for producing molybdenum granulated powder, comprising:
  2. 前記スプレードライヤーによる造粒工程完了後のモリブデン造粒粉に対して、その平均粒径Ｂの２～３倍のメッシュ径を有する篩を通す篩分け工程をさらに実施することを特徴とする請求項１記載のモリブデン造粒粉の製造方法。 The molybdenum granulated powder after completion of the granulation step by the spray dryer is further subjected to a sieving step of passing through a sieve having a mesh diameter 2 to 3 times the average particle size B. A method for producing the molybdenum granulated powder according to 1.
  3. 前記モリブデン造粒粉の平均粒径Ｂが２０～１５０μｍであることを特徴とする請求項１または請求項２に記載のモリブデン造粒粉の製造方法。 3. The method for producing a molybdenum granulated powder according to claim 1, wherein the average particle diameter B of the molybdenum granulated powder is 20 to 150 μm.
  4. 前記スプレードライヤーの回転板の回転数Ａが５０００～１６０００ｒｐｍであることを特徴とする請求項１または請求項３に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to claim 1 or 3, wherein the rotational speed A of the rotating plate of the spray dryer is 5000 to 16000 rpm.
  5. 前記有機溶媒がエタノールであることを特徴とする請求項１乃至請求項４のいずれか１項に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to any one of claims 1 to 4, wherein the organic solvent is ethanol.
  6. 前記コバルト成分の含有量が、コバルト元素単体換算で５０～５００質量ｐｐｍの範囲であることを特徴とする請求項１乃至請求項５のいずれか１項に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to any one of claims 1 to 5, wherein a content of the cobalt component is in a range of 50 to 500 ppm by mass in terms of a cobalt element simple substance.
  7. 前記スズ成分の含有量が、スズ元素単体換算で５０～５００質量ｐｐｍの範囲であることを特徴とする請求項１乃至請求項６のいずれか１項に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to any one of claims 1 to 6, wherein the content of the tin component is in the range of 50 to 500 ppm by mass in terms of a simple element of tin.
  8. 前記スズ成分およびコバルト成分を共に添加することを特徴とする請求項１乃至請求項７のいずれか１項に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to any one of claims 1 to 7, wherein both the tin component and the cobalt component are added.
  9. 前記投入するモリブデン粉末の合計量を１００体積部にしたときに、バインダーの体積を３～２０体積部とすることを特徴とする請求項１乃至請求項８のいずれか１項に記載のモリブデン造粒粉の製造方法。 The molybdenum structure according to any one of claims 1 to 8, wherein the volume of the binder is 3 to 20 parts by volume when the total amount of the molybdenum powder to be added is 100 parts by volume. A method for producing grain flour.
  10. 得られるモリブデン造粒粉の見掛け密度が１．３～３．０ｇ／ｃｃであることを特徴とする請求項１乃至請求項９のいずれか１項に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to any one of claims 1 to 9, wherein an apparent density of the obtained molybdenum granulated powder is 1.3 to 3.0 g / cc.
  11. 前記モリブデン含有溶液は、モリブデン粉末量を１００質量部としたとき、有機溶媒量が０．２～１リットルであることを特徴とする請求項１乃至請求項１０のいずれか１項に記載のモリブデン造粒粉の製造方法。 The molybdenum according to any one of claims 1 to 10, wherein the molybdenum-containing solution has an organic solvent amount of 0.2 to 1 liter when a molybdenum powder amount is 100 parts by mass. A method for producing granulated powder.
  12. 前記スプレードライヤーは、１００～３００℃の熱風を供給しながらモリブデン造粒粉の乾燥を実施することを特徴とする請求項１乃至請求項１１のいずれか１項に記載のモリブデン造粒粉の製造方法。 The molybdenum granulated powder production according to any one of claims 1 to 11, wherein the spray dryer dries the molybdenum granulated powder while supplying hot air of 100 to 300 ° C. Method.
  13. 前記スプレードライヤーは大気圧以下の減圧雰囲気でモリブデン造粒粉の乾燥を実施することを特徴とする請求項１乃至請求項１２のいずれか１項に記載のモリブデン造粒粉の製造方法。 The method for producing a molybdenum granulated powder according to any one of claims 1 to 12, wherein the spray dryer dries the molybdenum granulated powder in a reduced-pressure atmosphere of atmospheric pressure or less.
  14. 得られたモリブデン造粒粉の流動性が５０ｓｅｃ／５０ｇ以下であることを特徴とする請求項１乃至請求項１３のいずれか１項に記載のモリブデン造粒粉の製造方法。 The fluidity of the obtained molybdenum granulated powder is 50 sec / 50 g or less, The manufacturing method of the molybdenum granulated powder of any one of Claim 1 thru | or 13 characterized by the above-mentioned.
  15. スズ成分およびコバルト成分の少なくとも１種を含み、見掛け密度が１．３～３．０ｇ／ｃｃであることを特徴とするモリブデン造粒粉。 A molybdenum granulated powder comprising at least one of a tin component and a cobalt component, and an apparent density of 1.3 to 3.0 g / cc.
  16. 前記モリブデン造粒粉の平均粒径が２０～１５０μｍであること特徴とする請求項１５に記載のモリブデン造粒粉。 The molybdenum granulated powder according to claim 15, wherein the average particle diameter of the molybdenum granulated powder is 20 to 150 µm.
  17. 前記モリブデン粉末の合計量を１００体積部にしたときに、バインダーの体積が３～２０体積部であることを特徴とする請求項１５または請求項１６に記載のモリブデン造粒粉。 The molybdenum granulated powder according to claim 15 or 16, wherein the volume of the binder is 3 to 20 parts by volume when the total amount of the molybdenum powder is 100 parts by volume.
  18. 　前記モリブデン造粒粉の流動性が５０ｓｅｃ／５０ｇ以下であることを特徴とする請求項１５乃至請求項１７のいずれか１項に記載のモリブデン造粒粉。 The molybdenum granulated powder according to any one of claims 15 to 17, wherein the fluidity of the molybdenum granulated powder is 50 sec / 50 g or less.
PCT/JP2012/057355 2011-06-08 2012-03-22 Method for producing molybdenum granulated powder and molybdenum granulated powder WO2012169258A1 (en)

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JPS57157447A (en) * 1981-03-24 1982-09-29 Toshiba Corp Rotary anode for x-ray tube
JPS62192556A (en) * 1986-02-18 1987-08-24 Tokyo Tungsten Co Ltd Printing wire for dot printer
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