WO2019009136A1 - 金属粉末、及びその製造方法 - Google Patents

金属粉末、及びその製造方法 Download PDF

Info

Publication number
WO2019009136A1
WO2019009136A1 PCT/JP2018/024121 JP2018024121W WO2019009136A1 WO 2019009136 A1 WO2019009136 A1 WO 2019009136A1 JP 2018024121 W JP2018024121 W JP 2018024121W WO 2019009136 A1 WO2019009136 A1 WO 2019009136A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal powder
gas
metal
particles
diameter
Prior art date
Application number
PCT/JP2018/024121
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
広介 六角
友則 宇野
浅井　剛
Original Assignee
東邦チタニウム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東邦チタニウム株式会社 filed Critical 東邦チタニウム株式会社
Priority to JP2018561747A priority Critical patent/JP6553313B2/ja
Priority to KR1020207002838A priority patent/KR102278500B1/ko
Priority to CN201880042882.4A priority patent/CN110799285B/zh
Publication of WO2019009136A1 publication Critical patent/WO2019009136A1/ja

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • 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
    • B22F2203/00—Controlling
    • B22F2203/11—Controlling temperature, temperature profile

Definitions

  • One aspect of the present invention relates to a metal powder suitable for conductive paste applications used for electronic parts and the like, for example, conductive paste applications for internal electrodes of multilayer ceramic capacitors, and a method for producing the same.
  • the number of electronic components tends to increase as portable information terminals represented by smartphones and tablet terminals become multifunctional and sophisticated. For this reason, in order to mount on the main board of a limited area, the miniaturization and capacity increase of the ceramic capacitor mounted on the board are required.
  • the metal powder used for the internal electrode is an ultrafine powder having an average particle diameter of primary particles of 300 nm or less, 200 nm or less, and even 100 nm or less.
  • the problem that the capacitance of the capacitor is reduced becomes remarkable. This is because the dispersibility of the small particle size metal powder used for the thin layer electrode in the paste is poor, and a region in which the filling rate of the metal powder is low is generated in the electrode, and the shrinkage at the time of firing is large in that region It is considered that the volume of the electrode is reduced as a result of the generation of a large number of voids in the electrode layer.
  • Patent Document 1 sulfur is contained in nickel powder, and among sulfur present on the surface of nickel particles, sulfur present as sulfate ion and sulfur present as sulfide ion A nickel powder is disclosed that has improved sintering characteristics and dispersibility by defining its molar ratio.
  • Patent Document 2 discloses a nickel powder in which the residual magnetization is reduced by adding a nonmagnetic metal element to nickel to make the a-axis length of the nickel crystal within a specific range, thereby suppressing aggregation.
  • one aspect of the present invention aims to provide a metal powder suitable for the conductive paste of the inner electrode, which can improve the capacity reduction of the capacitor due to the thinning of the inner electrode of the laminated ceramic capacitor.
  • the present inventors have intensively studied to solve the above problems, and the proportion of particles of a specific shape in the metal powder is determined by the behavior of the metal powder, in particular, the dispersibility, the sintering start temperature, and the like. It has been found that the filling rate and the like are greatly affected, and one aspect of the present invention has been completed.
  • the aspect ratio is 1.2 or more, the degree of circularity is 0.675 or less, and the major diameter is 50% the number of metal powders
  • the metal powder is characterized in that the proportion of connected particles that are three or more times in the metal powder is 500 ppm or less on a number basis.
  • the dispersibility of the metal particles in the electrode paste can be improved by setting the ratio of the connected particles having the above shape to 500 ppm or less, and the filling rate of the metal powder in the electrode Can be raised.
  • FIG. 2 is a view showing a metal powder production apparatus used in Example 1; It is a SEM image of the dry nickel powder obtained in Example 1.
  • the metal powder is an aggregate of metal particles, and as a metal constituting the metal particles, silicon, copper, nickel, silver, molybdenum, iron, chromium, tungsten, tantalum, Cobalt, rhenium, platinum, palladium and the like, and alloys thereof can be mentioned.
  • nickel, molybdenum, silver, tungsten, copper, platinum, palladium and their alloys are particularly preferable.
  • nickel, copper, silver and their alloys are most preferred.
  • These metal powders are suitably used as paste fillers, particularly fillers for conductive pastes.
  • the upper and lower limits of the number 50% diameter of the metal powder are not particularly limited, but for example, it is preferably 400 nm or less from the use as a filler of the conductive paste for internal electrodes of multilayer ceramic capacitors
  • the thickness is more preferably 300 nm or less, still more preferably 200 nm or less, and most preferably 100 nm or less. Further, from the viewpoint of the production cost of the metal powder and the ignitability, it is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 25 nm or more, and most preferably 50 nm or more.
  • the number 50% diameter means the diameter of the particle
  • the number 50% diameter of metal powder take a picture of metal powder with a scanning electron microscope, measure the particle size of about 1,000 metal particles from the picture using image analysis software, and obtain the metal The number 50% diameter can be calculated from the particle size distribution of the powder.
  • the "particle size” is the diameter of the smallest circle circumscribed to the projected image obtained by the image analysis of the metal particles.
  • the metal powder may include secondary particles in which primary particles are aggregated, in addition to independent primary particles without aggregation.
  • “connected particles” are secondary particles remaining in the metal powder even after being crushed by a known crusher such as, for example, a jet mill, and typically, It means secondary particles in which primary particles are fused to each other.
  • particles having low sphericity also referred to as sphericity
  • connected particles having an elongated shape exceeding a specific reference length in which a plurality of primary particles are connected in a line It has been found that the proportion of the metal powder significantly affects the behavior of the metal powder in the paste, such as the sintering start temperature and the filling rate.
  • connected particles are, for convenience, “connected particles” in particles of a metal powder taken with a scanning electron microscope, in which “aspect ratio” is 1. 2 or more, refers to connected particles that are metal particles having a “roundness” of 0.675 or less and a “major axis” of three or more times the number 50% diameter of the metal powder.
  • the “long diameter” is the length of the long side of the rectangle having the smallest area circumscribed to the projected image of the metal particle
  • the “aspect ratio” is the length of the long side of the rectangle being the short side. Divided by
  • Circularity is a value calculated
  • Circularity (4 ⁇ ⁇ [projected area of metal particles]) / [projected perimeter of metal particles] 2 (1)
  • the circularity is 1, the projected image of the particle is a true circle, and the three-dimensional shape of the particle can be expected to be close to a true sphere.
  • the degree of circularity approaches 0, the three-dimensional shape of the taken image has many irregularities, which can be expected to be a complicated shape.
  • the proportion of "connected particles” in the metal powder was determined by taking a picture of the metal powder with a scanning electron microscope and using image analysis software from about 40,000 pieces of metal particles taken in the picture.
  • the number ratio obtained by measuring the number of metal particles having a circularity of 0.65 or less and a major diameter of 3 times or more of the number 50% diameter of the metal powder (hereinafter referred to as “connected particles” It is sometimes expressed as "rate”.
  • the proportion of connected particles contained in the metal powder is preferably 500 ppm or less, and more preferably 300 ppm or less, on a number basis.
  • the proportion of the connecting particles is in this range, it is possible to improve the dispersibility of the metal powder in the electrode paste and to obtain the effect of increasing the filling rate of the metal powder in the electrode.
  • the above effects can be obtained even if the metal powder is ultrafine powder with a number 50% diameter of 400 nm or less, 300 nm or less, 200 nm or less, and 100 nm or less. Therefore, by using this metal powder as a filler of the conductive paste for internal electrodes, it is possible to prevent a decrease in capacity of the capacitor due to a defect of the electrode.
  • the ratio (crystallite diameter / number 50% diameter) of the crystallite diameter of the metal powder to the number 50% diameter of the metal powder is preferably 0.50 or more, more preferably 0.55. It is more preferable that it is more than.
  • the metal powder having a connected particle ratio of 500 ppm or less when the ratio of the crystallite diameter to the number 50% diameter is 0.50 or more, the sintering characteristics of the metal powder, particularly the smoothness of the sintered coating film is further improved can do.
  • crystallite diameter of a metal powder calculates
  • Crystallite diameter (0.9 ⁇ [X-ray wavelength]) / ([peak half width] ⁇ cos [diffraction angle])
  • the crystallite diameter of the Ni powder is determined from the half value width of the diffraction peak of the (111) plane, the (200) plane, and the (220) plane.
  • the metal powder can include coarse particles.
  • the coarse particles are spherical or substantially spherical particles having an aspect ratio of less than 1.2 or a circularity of more than 0.675, and a metal whose major axis is at least three times the number 50% diameter of the metal powder. It means particles. That is, the coarse particles are primary particles or secondary particles having a large major diameter and a near spherical shape like the connected particles although the aspect ratio or the degree of circularity does not satisfy the requirements of the connected particles.
  • the proportion of coarse particles contained in the metal powder is preferably 15 ppm or less on a number basis, and more preferably 5 ppm or less.
  • the electrode layer can be smoothed when used as a conductive paste filler of the internal electrode of the multilayer ceramic capacitor, It is possible to prevent a defect such as a short circuit between them.
  • the ratio of "coarse particles" in the metal powder was determined by taking a picture of the metal powder with a scanning electron microscope and using image analysis software from about 60,000 pieces of metal particles taken in the picture. Number ratio obtained by measuring the number of metal particles less than 1.2 or having a circularity of 0.675 or more and having a major axis of at least three times the number 50% diameter of metal powder (hereinafter referred to as “coarse particle percentage It may be written as ".
  • the metal powder according to an aspect of the present invention can be produced, for example, by a known method such as a gas phase method or a liquid phase method.
  • gas phase reduction methods such as vapor phase reduction method in which metal powder is produced by contacting metal halide gas with reducing gas, or spray pyrolysis method in which pyrolyzable metal compounds are sprayed and pyrolyzed are It is easy to control the particle size of the produced metal fine powder, and spherical particles can be produced efficiently. For this reason, it is easy to control the number of 50% diameter of the metal powder, the connected particle ratio and the coarse particle ratio to be in the suitable range.
  • a vapor phase reduction method will be described as one embodiment of a particularly preferable method for producing a metal powder.
  • the gas phase reduction method In the gas phase reduction method, the gas of vaporized metal halide is reacted with a reducing gas such as hydrogen.
  • a reducing gas such as hydrogen.
  • the gas phase reduction method is a more preferable method of producing a metal powder from the viewpoint of being able to precisely control the particle size of the metal powder to be produced, and further to prevent the generation of coarse particles.
  • a known method can be used as a method of obtaining a metal halide gas in the vapor phase reduction method.
  • a solid metal halide such as anhydrous cobalt chloride is heated, sublimated and transported to a reduction part by an inert gas.
  • a method can be adopted in which a halogen gas is brought into contact with a solid metal as a raw material to continuously generate a metal halide gas.
  • halogen gas is brought into contact with solid metal as raw material to continuously generate metal halide gas, and this metal It is preferable to introduce the halide gas directly to the reduction unit.
  • FIG. 1 An example of the apparatus which manufactures a metal powder by a gaseous-phase reduction method is shown in FIG.
  • the reactor containing the reduction reaction zone c has a bottomed cylindrical shape, and a metal halide gas nozzle a is attached to one end of the reactor, whereby metal halide gas and A mixed gas with an inert gas is supplied.
  • the reducing gas nozzle b is attached to the same end in the said reaction apparatus.
  • the metal halide is reduced in the reduction reaction area c by the reducing gas supplied from the reducing gas nozzle b into the reactor, whereby the metal powder d is generated (reduction reaction step).
  • a cooling gas nozzle e is attached to the other end of the reactor, and the metal powder d generated by the cooling gas supplied from the cooling gas nozzle e into the reactor is rapidly cooled to prevent aggregation of the metal particles.
  • the recovery pipe f is attached to the reactor, and the metal powder d is sent to the recovery device through the recovery pipe f.
  • Metal halide gas As metal halide gas, silicon chloride (III) gas, silicon (IV) chloride gas, copper (I) chloride gas, copper (II) chloride gas, nickel chloride gas, silver chloride gas, molybdenum chloride gas (III) gas Molybdenum (V) gas, iron (II) gas, iron (III) gas, chromium (III) gas, chromium (VI) gas, tungsten (II) gas, tungsten (III) gas, Tungsten (IV) gas, tungsten (V) gas, tungsten (VI) gas, tantalum (III) gas, tantalum (V) gas, cobalt chloride gas, rhenium (III) gas, rhenium chloride (IV ) Gas, and rhenium chloride (V) gas, platinum fluoride (VI) gas, palladium fluoride (II) gas and mixtures thereof Gas and the like. Most preferably, they are nickel chloride gas, copper (I) chloride gas, copper
  • the metal halide gas can be generated by reacting a solid metal charged in a chlorination furnace (not shown) with a halogen gas.
  • the temperature in the chlorination furnace is a temperature at which the raw material metal is halogenated, and may be equal to or lower than the melting point of the raw material metal.
  • the temperature should be 800 ° C. or higher to sufficiently proceed the reaction, and be 1483 ° C. or lower, which is the melting point of nickel, considering the reaction rate and the durability of the chlorination furnace.
  • a range of 900 ° C. to 1200 ° C. is preferred.
  • the partial pressure of the metal halide gas by appropriately diluting the generated metal halide gas with an inert gas such as helium, argon, neon and nitrogen.
  • an inert gas such as helium, argon, neon and nitrogen.
  • the amount of metal halide gas generated is adjusted by adjusting the amount of halogen gas supplied in the halogenation furnace, and the amount of mixing is adjusted by adjusting the amount of inert gas supplied to the generated metal halide gas.
  • the partial pressure of the metal halide gas in the gas (in other words, the mol% concentration of the metal halide gas in the mixed gas) is adjusted.
  • the partial pressure of the metal halide gas when the partial pressure of the metal halide gas is high, the particle size of the metal powder formed is large, and as the partial pressure is reduced, the particle size decreases, the metal powder formed by the partial pressure of the metal halide gas Particle size distribution can be controlled. While being able to set arbitrarily the quality of the metal powder produced
  • the partial pressure of the metal halide gas in the mixed gas of the metal halide gas and the inert gas is set to 1.0 when the total pressure of the mixed gas is 1.0.
  • metal halide gas may also include the meaning of "metal halide gas containing an inert gas (that is, mixed gas)".
  • the reducing gas for reducing the metal halide gas includes hydrogen gas, hydrogen sulfide gas, ammonia gas, carbon monoxide gas, methane gas, and a mixed gas thereof. Particularly preferred are hydrogen gas, hydrogen sulfide gas, ammonia gas, and mixed gas thereof.
  • hydrogen gas When hydrogen sulfide gas is contained in the reducing gas, metal particles in the obtained metal powder may contain sulfur as a component.
  • the supply amount of the reducing gas supplied from the reducing gas nozzle b into the reactor is limited, and is limited
  • the “reduction reaction area” is an area that occupies a part in the reactor, and is located in the vicinity of the tip of the metal halide gas nozzle a, and the generation of metal particles by the reaction of the metal halide gas and the reducing gas is performed It is an area.
  • the “reduction reaction area” is also an area including at least a point at which the metal halide gas supplied into the reactor starts to contact with the reducing gas, and a point at which metal particles begin to be generated, In such a case, a bright flame similar to a combustion flame emitted by gaseous fuel such as hydrocarbon is generated by black body radiation.
  • the metal generated in the reduction reaction region forms a nucleus, and passes through the reduction reaction region while growing the nucleus.
  • the average temperature in the reduction reaction zone is set to a temperature at which the supplied metal halide gas can be rapidly reduced.
  • the average temperature of the reduction reaction zone c shown in FIG. 1 is usually 900 to 2,000 ° C., preferably 1,000 to 1,800 ° C., more preferably Is 1,200-1,600.degree.
  • the temperature of the metal particles is about 100 to 600 ° C. higher than the atmospheric temperature (average temperature) in the reduction reaction zone by the heat of reaction of the metal halide gas.
  • This “maximum temperature” may cause variations in the metal particles formed in the reduction reaction zone.
  • the atmospheric temperature in the reduction reaction region is different depending on the place, the “highest reachable temperature” reached by the metal particles is different depending on the position where the metal particles are generated. If the variation in the maximum temperature reached is large, coupled particles and coarse particles are likely to be generated.
  • variation with the highest achieved temperature by the heat of reaction which a metal particle emits is 80 degrees C or less, and it is more preferable that it is 50 degrees C or less. If the variation in the maximum temperature reached at the time of particle formation is large, coarse particles are likely to be generated in places where the temperature is higher than the ambient temperature, and fine particles that cause connected particles in locations where the temperature is lower than the ambient temperature Is easy to generate.
  • the connected particle rate is reduced to 500 ppm or less by setting the width of the highest attainable temperature at which particles are generated, that is, the difference between the highest value and the lowest value of the highest reachable temperature, to less than 80 ° C. And the coarse particle rate can be reduced to 15 ppm or less.
  • Each of the metal particles having reached the “maximum reached temperature” is then discharged from the reduction reaction zone and cooled.
  • the temperature change at the time of particle generation in the reduction reaction region of the reactor can be determined by calculation by fluid simulation.
  • fluid simulation software (manufactured by ANSYS, Inc., trade name ANSYS CFX) is used to create a simulation model including a reducing portion, divided into hexahedral meshes about 2 mm apart, gas flow rate and temperature, And calculation is performed by giving the wall surface temperature of the device as the boundary condition.
  • the k- ⁇ model is used for the turbulent flow model and the vortex dissipation model is used for the reaction model.
  • heating means for example, microwave heating device, electric heater
  • microwave heating device for example, microwave heating device, electric heater
  • electric heater The method of heating uniformly by laser heating, a gas burner, or these combination etc.
  • the gas containing the metal powder generated in the above reduction reaction zone flows out of the reduction reaction zone, contacts with the cooling gas, and mixes. Thereby, the metal powder is rapidly cooled to a temperature of 400 ° C. or less (cooling step). It is possible to further suppress that the particles of the metal powder are joined together to be connected particles by rapid cooling.
  • the above-mentioned cooling gas is an inert gas, and nitrogen gas, helium gas, argon gas, neon gas, hydrogen gas and their mixed gas may be mentioned.
  • the temperature of the cooling gas is usually 0 to 100 ° C., preferably 0 to 50 ° C., more preferably 0 to 30 ° C.
  • the flow rate of the cooling gas is 50 to 300 times the flow rate of the metal powder per hour. Thereby, the cooling rate for cooling the metal powder can be made faster than 10,000 ° C./sec, and the connected particle rate can be reduced.
  • the metal powder obtained by the above method preferably removes residual metal halide (washing step).
  • the method of removing the metal halide is not particularly limited.
  • the volatile metal halide can be vaporized and removed by maintaining the temperature at a high temperature below the sintering temperature of the metal powder in a reduced pressure environment.
  • the metal powder is preferably washed by using an aqueous carbonic acid solution adjusted to a pH range of 4.0 to 6.5 as a washing solution. Unreacted metal halide gas can be suitably removed.
  • the metal powder can be deaggregated by replacing the cleaning solution containing the metal powder with pure water or removing the carbonic acid by heating, and the metal powder can be redispersed. Therefore, the content of connecting particles can be further suitably reduced.
  • the metal powder slurry is dried (drying step).
  • the drying method is not particularly limited, and known methods can be used. Specific examples thereof include flash drying, heating and drying, vacuum drying, etc., in which the catalyst is brought into contact with a high temperature gas for drying. Among these, air flow drying is preferable because it can suppress aggregation of particles.
  • the metal powder may break up the aggregation of particles generated by the drying (grinding process).
  • the method for breaking up the aggregation of the metal powder is not particularly limited, and known methods can be used. As a specific example, a jet mill, a bead mill, etc. which make particles collide with each other by a high pressure gas flow can be mentioned.
  • a jet mill, a bead mill, etc. which make particles collide with each other by a high pressure gas flow can be mentioned.
  • Adjustment is necessary. That is, it is preferable to adjust the number of times the metal powder is passed through the crusher so that the ratio of the crystallite diameter to the number 50% diameter of the metal powder is maintained at 0.5 or more.
  • the metal powder according to one aspect can be suitably produced by the production method described above.
  • the invention of this application does not exclude the aspect which reduces the ratio of the connection particle
  • Example 1 The apparatus shown in FIG. 2 was heated to an atmosphere temperature of 1,100 ° C. by an electric heater, and a mixed gas of nickel chloride gas and nitrogen gas was introduced from the metal halide gas nozzle a.
  • the partial pressure of the nickel chloride gas was 0.037, assuming that the total pressure of the mixed gas was 1.0.
  • hydrogen gas was introduced into the reactor from the reducing gas nozzle b, and nickel chloride gas was reduced in the reactor to obtain a metal powder (nickel powder) d.
  • the nickel powder produced by the heat of reaction is heated to about 1,400 ° C., and the gas flow containing the produced nickel powder is gaseous fuel such as hydrocarbon by black body radiation of the nickel powder. It was observed as a luminous flame resembling a burning flame.
  • the wall surface around the region where this luminous flame is generated (that is, the reduction reaction region c) is heated with a microwave heating device g at a frequency of 2.45 GHz and an output of 4.9 kW to bring nickel chloride gas and hydrogen gas into contact. Temperature variations in the area were reduced.
  • a microwave heating device g at a frequency of 2.45 GHz and an output of 4.9 kW to bring nickel chloride gas and hydrogen gas into contact. Temperature variations in the area were reduced.
  • the dispersion of the highest attainable temperature of nickel particles at the time of particle formation is determined using fluid simulation software (ANSYS, Inc., product name ANSYS CFX)
  • the range of the highest reachable temperature at the time of particle generation is the largest It was 40 ° C.
  • a simulation model including a reducing portion was prepared, divided into hexahedral meshes of about 2 mm intervals, and calculation was performed with the flow rate of the gas, the temperature of the gas, and the wall temperature of the apparatus as boundary conditions.
  • the k- ⁇ model was used for the turbulent flow model, and the vortex dissipation model was used for the reaction model.
  • the produced metal powder (nickel powder) d is mixed with nitrogen gas of 25 ° C. introduced from the two cooling gas nozzles e, cooled to 400 ° C. or less, and led to a bag filter (not shown) by a recovery pipe f The nickel powder was separated and collected.
  • the recovered nickel powder is dispersed and precipitated five times in water (in the washing solution) whose pH and temperature are properly controlled. After removing the remaining nickel chloride, the water content is 0.5 with a flash dryer. The drying process was performed so that it became% or less. Furthermore, disintegration by a jet mill was performed for one pass. The obtained nickel powder is apply
  • Example 2 In the reactor in the same manner as in Example 1, except that the partial pressure of nickel chloride gas in the mixed gas of nickel chloride gas and nitrogen gas is 0.15, and the output of the microwave heating device is 2.8 kW. The nickel chloride gas was reduced to produce a nickel powder. The temperature difference in the region where the nickel particles are formed was 45 ° C. at maximum.
  • Example 3 The reaction was performed in the same manner as in Example 1, except that the partial pressure of nickel chloride gas in the mixed gas of nickel chloride gas and nitrogen gas was 0.29, and the output of the microwave heating device was 3.2 kW. The nickel chloride gas was reduced to produce a nickel powder. The maximum temperature range of the nickel particles at particle formation was at most 65 ° C.
  • Comparative Example 1 A nickel powder was produced in the same manner as in Example 1 except that the output of the microwave heating device g was changed to 0.
  • the maximum temperature range of the nickel particles at the time of particle formation was 84 ° C. at the maximum.
  • Comparative Example 2 A nickel powder was produced in the same manner as in Example 2 except that the output of the microwave heating device g was changed to 0 and crushing by a jet mill was performed in three passes. The maximum temperature range of the nickel particles at particle formation was 95 ° C. at the maximum.
  • Comparative Example 3 A nickel powder was produced in the same manner as in Example 3 except that the output of the microwave heating device g was changed to 0 and the partial pressure of nickel chloride gas was changed to 0.33.
  • the maximum temperature range of the nickel particles at the time of particle formation was 90 ° C. at the maximum.
  • the dispersibility to a solvent, the sintering characteristic, the filling rate, and the smoothness of the coating film were evaluated by the following methods.
  • connection Particle Rate Photograph a picture of metallic nickel powder with a scanning electron microscope (product name JSM-7800F, manufactured by Nippon Denshi Co., Ltd.), and use the image analysis software (product name: MacView 4.0, product name, manufactured by Mountech Co., Ltd.) from the photograph.
  • the number of connected particles with an aspect ratio of 1.2 or more and a circularity of 0.675 or less among about 40,000 particles, the major axis of which is at least three times the number 50% of the number determined above was calculated.
  • the length of the long side of the rectangle having the smallest area circumscribed to the metal particle projection image is taken as the long diameter
  • the value of (long side length ⁇ short side length) is taken as the aspect ratio.
  • the value of (4 ⁇ ⁇ [projected area of metal particle]) / [projected circumferential length of metal particle] 2 is taken as the degree of circularity.
  • the measurement conditions were such that the accelerating voltage of the X-ray tube was 45 kV and the current value was 40 mA, and the wavelength of the X-ray was Cu-K ⁇ .
  • the incident side of the X-ray was 0.04 radian for the solar slit, 15 mm for the mask, 1/2 ° for the divergence slit, and 1 ° for the antiscatter slit.
  • the detector side had a solar slit of 0.04 radian and a scattering prevention slit of 5.5 mm.
  • the scan rate was 0.04 ° / s.
  • Dispersibility 100ml of 5wt% aqueous solution of polycarboxylic acid dispersant was added to 0.5g of nickel powder and dispersed for 60 seconds with an output of 600W and an amplitude width of 30 ⁇ m using an ultrasonic dispersator (brand name GSD600AT, manufactured by Ginsen Co., Ltd.) did. After dispersion, suction filtration is performed at a suction pressure of 0.1 MPa using a membrane filter (pore diameter: 1 ⁇ m, filter diameter: 25 mm) (manufactured by GE Healthcare Bio-Sciences Co., Ltd., trade name Nucripore membrane). The aggregation behavior of the nickel powder was evaluated as shown in Table 1.
  • the filling rate of the fired body was determined from the shrinkage rate when heated to 700 ° C. by the formula (density of fired body ⁇ ⁇ bulk density of nickel), and was evaluated as shown in Table 3. As the filling rate is higher, shrinkage due to firing when applied to the electrode is less likely to occur.
  • a nickel coating on a quartz plate is heated in an atmosphere of 1.5 volume% hydrogen-nitrogen reducing gas at a heating rate of 5 ° C. using an electric furnace (trade name SLT-2035 D, manufactured by Motoyama Co., Ltd.) The temperature was raised under the conditions of 1 / minute, and firing was performed at 1,000 ° C. for 1 hour.
  • the surface roughness (Sz: maximum height; height between the highest peak and the deepest valley) of the fired coating is measured with a digital microscope (trade name VHX-1000, manufactured by Keyence Corporation), The smoothness was evaluated as (Sz value / number of 50% diameter of nickel powder) as shown in Table 4.
  • Table 5 shows the 50% diameter, linked particle ratio, crystallite diameter, and coarse particle ratio of nickel powder of Examples and Comparative Examples in Table 5, and evaluation of dispersibility, sintering characteristics, filling ratio, and smoothness of coating film. The results are shown in Table 6.
  • Example 1 no coarse particle was found in the photographed particles, so the evaluation result was set to be less than the detection limit.
  • the nickel powder of Example 1 has the same number of 50% diameter as that of Comparative Example 1, the percentage of connected particles and the ratio of coarse particles are low. It can be seen that the dispersibility, the sintering characteristics, the filling rate and the smoothness of the fired coating film are excellent.
  • the nickel powder of Example 2 has the same number of 50% diameter as that of Comparative Example 2, the crystallite diameter is large and the number of connected particles is small, so the dispersibility, sintering characteristics and filling rate Is excellent.
  • the metal powder of the present invention has excellent dispersibility, sintering characteristics, filling rate and smoothness of the fired coating film in the manufacturing process of the multilayer ceramic capacitor, and as a result, the generation of voids in the electrode layer is suppressed. It has been proved to be effective for preventing the decrease in capacity of the capacitor.
  • the present invention can be suitably used as a metal powder for the conductive paste of the internal electrode of a laminated ceramic capacitor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Non-Insulated Conductors (AREA)
PCT/JP2018/024121 2017-07-05 2018-06-26 金属粉末、及びその製造方法 WO2019009136A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018561747A JP6553313B2 (ja) 2017-07-05 2018-06-26 金属粉末、及びその製造方法
KR1020207002838A KR102278500B1 (ko) 2017-07-05 2018-06-26 금속 분말 및 그 제조 방법
CN201880042882.4A CN110799285B (zh) 2017-07-05 2018-06-26 金属粉末及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017132246 2017-07-05
JP2017-132246 2017-07-05

Publications (1)

Publication Number Publication Date
WO2019009136A1 true WO2019009136A1 (ja) 2019-01-10

Family

ID=64950848

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/024121 WO2019009136A1 (ja) 2017-07-05 2018-06-26 金属粉末、及びその製造方法

Country Status (5)

Country Link
JP (2) JP6553313B2 (zh)
KR (1) KR102278500B1 (zh)
CN (1) CN110799285B (zh)
TW (1) TWI690381B (zh)
WO (1) WO2019009136A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020180329A (ja) * 2019-04-24 2020-11-05 東邦チタニウム株式会社 銅粉体の製造方法
JP2020180328A (ja) * 2019-04-24 2020-11-05 東邦チタニウム株式会社 銅粉体の製造方法
JP2021080549A (ja) * 2019-11-22 2021-05-27 東邦チタニウム株式会社 銅粉体とその製造方法
JP2021088757A (ja) * 2020-09-18 2021-06-10 東邦チタニウム株式会社 銅粉体およびその製造方法
JP7490528B2 (ja) 2020-01-10 2024-05-27 東邦チタニウム株式会社 銅粉体
JP7498604B2 (ja) 2020-06-26 2024-06-12 東邦チタニウム株式会社 銅粉の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012046666A1 (ja) * 2010-10-06 2012-04-12 旭硝子株式会社 導電性銅粒子および導電性銅粒子の製造方法、導電体形成用組成物、ならびに導電体付き基材
JP2014019599A (ja) * 2012-07-17 2014-02-03 Japan Health Sciences Foundation 高分散性ナノマテリアルの調製方法
WO2015156080A1 (ja) * 2014-04-08 2015-10-15 東邦チタニウム株式会社 ニッケル粉末

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101014158B1 (ko) * 2002-08-28 2011-02-14 도호 티타늄 가부시키가이샤 금속 니켈 분말 및 그 제조 방법
JP4324109B2 (ja) * 2002-09-30 2009-09-02 東邦チタニウム株式会社 金属粉末の製造方法および製造装置
CN100372639C (zh) * 2004-07-08 2008-03-05 三井化学株式会社 氮化铝粉末及其制造方法和用途
JP4942333B2 (ja) * 2005-11-29 2012-05-30 住友金属鉱山株式会社 ニッケル粉およびその製造方法、ならびに該ニッケル粉を用いたポリマーｐｔｃ素子
JP2009079239A (ja) * 2007-09-25 2009-04-16 Sumitomo Electric Ind Ltd ニッケル粉末、またはニッケルを主成分とする合金粉末およびその製造方法、導電性ペースト、並びに積層セラミックコンデンサ
JP2010043345A (ja) * 2008-08-18 2010-02-25 Sumitomo Electric Ind Ltd ニッケル粉末またはニッケルを主成分とする合金粉末およびその製造方法、導電性ペースト、並びに積層セラミックコンデンサ
JP5526856B2 (ja) * 2010-02-23 2014-06-18 住友金属鉱山株式会社 ニッケル粉末およびその製造方法
JP5768322B2 (ja) * 2010-03-19 2015-08-26 住友金属鉱山株式会社 ニッケル微粉及びその製造方法
TWI597112B (zh) * 2012-04-06 2017-09-01 東邦鈦股份有限公司 金屬鎳粉末及金屬鎳粉末之製造方法
JP2014070255A (ja) * 2012-09-28 2014-04-21 Fujifilm Corp 金属平板粒子分散液とその製造方法および熱線遮蔽材
KR101689491B1 (ko) 2012-11-20 2016-12-23 제이에프이미네라르 가부시키가이샤 니켈 분말, 도전 페이스트 및 적층 세라믹 전자 부품
JP6135935B2 (ja) * 2014-03-28 2017-05-31 住友金属鉱山株式会社 湿式ニッケル粉末の製造方法
JP6717289B2 (ja) * 2015-02-27 2020-07-01 日立化成株式会社 銅含有粒子、導体形成組成物、導体の製造方法、導体及び装置
WO2017056741A1 (ja) * 2015-09-29 2017-04-06 東邦チタニウム株式会社 ニッケル粉及びニッケルペースト
JP6172413B1 (ja) * 2015-10-19 2017-08-02 住友金属鉱山株式会社 ニッケル粉末の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012046666A1 (ja) * 2010-10-06 2012-04-12 旭硝子株式会社 導電性銅粒子および導電性銅粒子の製造方法、導電体形成用組成物、ならびに導電体付き基材
JP2014019599A (ja) * 2012-07-17 2014-02-03 Japan Health Sciences Foundation 高分散性ナノマテリアルの調製方法
WO2015156080A1 (ja) * 2014-04-08 2015-10-15 東邦チタニウム株式会社 ニッケル粉末

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020180329A (ja) * 2019-04-24 2020-11-05 東邦チタニウム株式会社 銅粉体の製造方法
JP2020180328A (ja) * 2019-04-24 2020-11-05 東邦チタニウム株式会社 銅粉体の製造方法
JP2021080549A (ja) * 2019-11-22 2021-05-27 東邦チタニウム株式会社 銅粉体とその製造方法
JP7490528B2 (ja) 2020-01-10 2024-05-27 東邦チタニウム株式会社 銅粉体
JP7498604B2 (ja) 2020-06-26 2024-06-12 東邦チタニウム株式会社 銅粉の製造方法
JP2021088757A (ja) * 2020-09-18 2021-06-10 東邦チタニウム株式会社 銅粉体およびその製造方法
JP7448446B2 (ja) 2020-09-18 2024-03-12 東邦チタニウム株式会社 銅粉体

Also Published As

Publication number Publication date
TWI690381B (zh) 2020-04-11
JPWO2019009136A1 (ja) 2019-07-04
TW201906675A (zh) 2019-02-16
JP6553313B2 (ja) 2019-07-31
JP7080856B2 (ja) 2022-06-06
CN110799285B (zh) 2022-04-29
CN110799285A (zh) 2020-02-14
JP2019173179A (ja) 2019-10-10
KR102278500B1 (ko) 2021-07-15
KR20200023442A (ko) 2020-03-04

Similar Documents

Publication Publication Date Title
JP6553313B2 (ja) 金属粉末、及びその製造方法
TWI580800B (zh) 銅粉
TWI778997B (zh) 銅粉、該銅粉的製造方法、使用該銅粉之導電性糊、及使用該導電性糊之導電性膜的製造方法
TWI638051B (zh) 鎳粉末
TWI803486B (zh) 銅粒子及其製造方法
TWI716526B (zh) 鎳粉末
JP2006210214A (ja) 導電ペースト用金属粉および導電ペースト
TW201509820A (zh) 氧化亞銅微粒子之製造方法及氧化亞銅微粒子和導體膜的製造方法
JP2020111477A (ja) 球状ＡｌＮ粒子の製造方法、及び、球状ＡｌＮ粒子
JP6425367B1 (ja) ニッケル粉及びニッケルペースト
TW201936933A (zh) 銀微粒子之製造方法及銀微粒子
JP6016729B2 (ja) 金属粉末の製造方法及び製造装置
JP7390198B2 (ja) ガラス粒子、それを用いた導電性組成物及びガラス粒子の製造方法
JP4540364B2 (ja) ニッケル粉末、並びにそれを用いた導電ペースト及び積層セラミックコンデンサ
JP7498604B2 (ja) 銅粉の製造方法
JP2022083703A (ja) 銅粉の製造方法
JP7448446B2 (ja) 銅粉体
WO2020158685A1 (ja) Ｓｎ粒子、それを用いた導電性組成物及びＳｎ粒子の製造方法
CN117043111A (zh) 钛酸钡系粉末及其制造方法、以及密封材料用填料

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018561747

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18828537

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207002838

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18828537

Country of ref document: EP

Kind code of ref document: A1