WO2014080600A1 - ニッケル粉末、導電ペースト、および、積層セラミック電子部品 - Google Patents

ニッケル粉末、導電ペースト、および、積層セラミック電子部品 Download PDF

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WO2014080600A1
WO2014080600A1 PCT/JP2013/006702 JP2013006702W WO2014080600A1 WO 2014080600 A1 WO2014080600 A1 WO 2014080600A1 JP 2013006702 W JP2013006702 W JP 2013006702W WO 2014080600 A1 WO2014080600 A1 WO 2014080600A1
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nickel powder
nickel
powder
conductive paste
sample
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PCT/JP2013/006702
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English (en)
French (fr)
Japanese (ja)
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貴紀 牧瀬
健志 諸住
賀菜 恩田
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Ｊｆｅミネラル株式会社
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Priority to CN201380060360.4A priority Critical patent/CN104837580B/zh
Priority to JP2013554131A priority patent/JP6000983B2/ja
Priority to KR1020157012938A priority patent/KR101689491B1/ko
Publication of WO2014080600A1 publication Critical patent/WO2014080600A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to nickel powder, a conductive paste, and a multilayer ceramic electronic component.
  • Nickel powder is used as a material for forming internal electrodes of multilayer ceramic electronic components such as multilayer capacitors, multilayer inductors, multilayer actuators, and the like.
  • a conductive paste for internal electrodes is printed in a predetermined pattern on a dielectric ceramic green sheet such as barium titanate, and a plurality of such sheets are stacked at several tens to several hundreds of MPa.
  • a green laminate in which ceramic green sheets and internal electrode conductive paste are alternately laminated is obtained by pressure bonding. After cutting the obtained multilayer body into a predetermined shape, the ceramic green sheet and the internal electrode conductive paste are simultaneously fired at a high temperature to obtain a multilayer ceramic capacitor body.
  • a conductive paste for a terminal electrode mainly composed of a conductive powder, a dielectric material such as barium titanate and an organic solvent was applied to the end face where the internal electrode of the obtained element body was exposed, and dried. Then, a terminal electrode is formed by baking at high temperature. At this time, if a dielectric such as barium titanate is not included in the conductive paste, the nickel powder is sintered before the ceramic green sheet reaches a temperature of 1000 ° C. or higher, and the ceramic green sheet is sintered. In doing so, stress is applied to the internal electrodes, and cracks and the like occur.
  • Patent Document 2 sulfur is added to the nickel powder (Patent Document 2). Since the sulfur addition is concentrated on the surface of the nickel powder to obtain a sintering suppressing effect, the necessary amount of sulfur increases as the nickel powder becomes finer. Since it is necessary to remove sulfur before it becomes a capacitor, in the case of fine-grained nickel powder, the effort for removing sulfur only works in an increasing direction. Further, the nickel powder added with sulfur tends to lower the sintering temperature as the hydrogen concentration during firing increases.
  • HCP hexagonal close-packed
  • Patent Document 1 nickel particles produced by a liquid phase method are heated in a polyol to 150 to 380 ° C. to cause a phase transition from a face-centered cubic lattice (hereinafter also referred to as “FCC”) structure to an HCP structure.
  • FCC face-centered cubic lattice
  • Non-patent Document 1 Non-patent Document 1
  • the multilayer ceramic capacitor has ESR (equivalent series resistance) which is a resistance component due to the dielectric material and the internal electrode, and ESL (equivalent series inductance) which is an inductor component of the lead wire and the internal electrode, These components appear connected in series.
  • the capacitance component is mainly the impedance until the self-resonant frequency of the capacitor, and the impedance decreases as the frequency becomes higher, but the inductor component becomes the main impedance at the self-resonance frequency or higher, and the impedance increases as the frequency becomes higher. In order to manufacture a capacitor used in a high-frequency circuit, it is necessary to reduce the inductor component.
  • the magnetic field in the capacitor changes according to the direction of the current.
  • This change in the magnetic field is an inductor component.
  • the inductor component of the coil depends not only on the structure but also on the relative permeability of the electrode member. Since nickel is a ferromagnetic metal, the inductor component can be further reduced and the performance of the capacitor can be improved by replacing it with a material having a low relative permeability. Considering the cheapness of the metal and the low relative permeability, there is a means called a copper electrode.
  • the sintering temperature is low and it is easy to oxidize, it cannot be fired together with a dielectric having a high dielectric constant.
  • nickel having an HCP structure which is effective as a countermeasure against magnetic aggregation, returns to an FCC structure having magnetism upon sintering at 1000 ° C., and thus does not help improve the high-frequency characteristics of the capacitor.
  • the solvent component of the electrode paste remains at the time of firing the capacitor, it suddenly evaporates and bubbles are generated, causing separation between the electrode layer and the dielectric layer, thereby degrading the performance of the capacitor.
  • the nickel powder is required to have oxidation resistance during the removal of the solvent.
  • the removal of the solvent means removal of organic solvent components such as terpineol.
  • Patent Document 4 There is an example of an alloy powder with improved oxidation resistance for a multilayer ceramic capacitor (Patent Document 4). Although this patent document states that various alloys are effective for improving the oxidation resistance of copper and nickel powder, zirconium is mixed as an inevitable impurity.
  • Zirconium oxide is added to adjust the Curie temperature of barium titanate, but when zirconium is oxidized, it diffuses from the electrode into the dielectric layer and mixes, and the Curie temperature changes to obtain the prescribed dielectric properties. There is a problem that makes it impossible.
  • the present invention has been made in view of the above points, and is a nickel powder used for an internal electrode of a multilayer ceramic electronic component, which has a high sintering temperature, suppressed aggregation, and improved high-frequency characteristics.
  • the purpose is to provide.
  • nickel powder with a-axis length in a specific range by adding a non-magnetic metal element to nickel can reduce remnant magnetization and suppress aggregation, increase sintering temperature, and improve high-frequency characteristics.
  • the present invention was completed.
  • nickel powder including nickel alloy powder obtained by adding a nonmagnetic metal element to nickel is referred to as nickel powder.
  • the present invention provides the following (1) to (3).
  • Nickel powder used for an internal electrode of a multilayer ceramic electronic component the peak of a face-centered cubic lattice (FCC) structure is obtained by X-ray diffraction, and the a-axis length is 3.530 mm or more and less than 3.600 mm Nickel powder having a nickel content of 50% by mass or more.
  • nickel powder having a high sintering temperature, suppressed aggregation, and improved high frequency characteristics can be provided.
  • FIG. 1 is a schematic diagram showing an example of a PVD apparatus 1.
  • FIG. 2 is a schematic diagram showing an example of a microreactor 31.
  • FIG. It is a graph which shows the XRD pattern of nickel powder. It is a graph which expands and shows a part of XRD pattern of FIG. It is a graph which shows the relationship between the temperature and volume change rate of nickel powder. It is a graph which shows the relationship between the temperature of nickel powder of Example 6, and a volume change rate. It is a graph which shows the relationship between the frequency of nickel powder, and an impedance, (A) is the comparative example 1, (B) is Example 2.
  • FIG. 1 is a schematic diagram showing an example of a PVD apparatus 1.
  • FIG. 2 is a schematic diagram showing an example of a microreactor 31.
  • FIG. It is a graph which shows the XRD pattern of nickel powder. It is a graph which expands and shows a part of XRD pattern of FIG. It is a graph which shows the relationship between
  • the nickel powder of the present invention is a nickel powder used for an internal electrode of a multilayer ceramic electronic component, and a peak of a face-centered cubic lattice (FCC) structure is obtained by X-ray diffraction, and the a-axis length is 3.530 mm or more.
  • the nickel powder has a nickel content of less than 600% and a nickel content of 50% by mass or more.
  • the a-axis length is extended and the crystal structure is distorted to reduce magnetism.
  • the a-axis length is 3.530 mm or more. As the a-axis length increases, it becomes more difficult to form a single magnetic domain, so 3.540 mm or more is preferable.
  • the a-axis length is less than 3.600 mm, more preferably less than 3.570 mm, and even more preferably less than 3.550 mm.
  • the amount of the additive element with respect to nickel is preferably in the solid solution range. That is, the nickel content in the nickel powder of the present invention is 50% by mass or more, preferably 70 to 99.5% by mass, and more preferably 80 to 99% by mass.
  • the element added to nickel is not particularly limited as long as it is a nonmagnetic metal element.
  • titanium (Ti), zinc (Zn), tin (Sn), bismuth (Bi), yttrium (Y), a lanthanoid element, etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
  • tin is preferred because it is inexpensive and has a wide temperature range of the liquid phase from the melting point to the boiling point, so that the alloy powder can be easily produced.
  • a preferable range of the tin concentration is 0.1 to 10% by mass, more preferably 1 to 6% by mass.
  • the concentration of iron, which is an inevitable impurity is preferably less than 0.01% by mass.
  • Zr is preferably 30 ppm or less as an impurity.
  • a fine nickel powder particularly a nickel powder having a primary particle diameter of 200 nm or less, is likely to receive a stronger magnetic cohesive force and the secondary particle diameter tends to be large.
  • the nickel powder of the present invention in which the a-axis length is extended by adding an element, not only saturation magnetization but also residual magnetization is reduced, as will be described later in [Example]. For this reason, the cohesive force due to magnetism is reduced, the attractive force between particles is reduced, and the secondary particle size is reduced.
  • the nickel powder of the present invention having an extended a-axis length has an improved sintering temperature as described later in [Examples], and, for example, an effect equal to or higher than that of conventional sulfur addition can be obtained. For this reason, it is possible to reduce the amount of co-agent barium titanate mixed with the conductive paste for the sintering suppressing effect, and to form a smoother and higher quality internal electrode.
  • the conventional sintering suppression by sulfur addition if the hydrogen concentration at the time of firing is increased, the sintering temperature tends to decrease, but in the nickel powder of the present invention in which the a-axis length is increased, the hydrogen concentration is increased. Even so, the reduction range of the sintering temperature is small, and it is possible to select conditions that facilitate removal of the solvent.
  • the nickel powder of the present invention to which tin is added is compared with the pure nickel powder as will be described later in [Example].
  • the impedance increases, the amount of increase in impedance is small even when the frequency is high, and it can be used with low impedance even in a high frequency region.
  • the dielectric loss can be reduced in addition to the small increase in impedance at a high frequency as described above. In this case, heat loss at high frequencies can be suppressed, and the upper limit of usable frequencies can be widened. Since the magnetic permeability of nickel is smaller than that of nickel, the reactance of the capacitor is also reduced and the high frequency characteristics are improved. This is also true when other nonmagnetic elements are added. Thus, since the high frequency characteristics are improved, the nickel powder powder of the present invention is suitable for a high-capacitance capacitor.
  • the method for producing the nickel powder of the present invention is not particularly limited, and there are methods such as a vapor phase method and a liquid phase method, but the powder obtained by the liquid phase method has low crystallinity and is easy to sinter.
  • the gas phase method is preferred.
  • the gas phase method is roughly classified into a PVD method and a CVD method.
  • the PVD method prepares a sample made of nickel and a target metal or alloy, and evaporates the sample by heat such as direct current or alternating current arc discharge, high frequency induction plasma, microwave plasma, high frequency induction heating, or laser.
  • heat such as direct current or alternating current arc discharge, high frequency induction plasma, microwave plasma, high frequency induction heating, or laser.
  • powder is obtained by rapid cooling. Since the PVD method does not use a chemical reaction, it is easy to produce a fine powder by increasing the cooling rate.
  • FIG. 1 is a schematic diagram illustrating an example of the PVD apparatus 1.
  • the PVD apparatus 1 includes a chamber 11 for evaporating the sample 4, a heat exchanger 6 for cooling the vapor of the sample 4, and a collector 12 provided with a collection filter 7.
  • the heat exchanger The chamber 11 and the collector 12 are connected via 6.
  • a sample support 5, which is a water-cooled copper crucible, for example, is installed to support the sample 4.
  • An electrode 2 is provided inside the chamber 11.
  • the electrode 2 is disposed in the torch 13 at a position where the tip thereof is close to the sample support 5.
  • the torch 13 is water cooled by a water cooling means (not shown).
  • the gas introduced into the chamber 11 from the line 14 returns to the circulation pump 8 through the heat exchanger 6 and the collector 12, and a gas flow is formed.
  • the line 14 has a branch line 14a connected to the torch 13, and a part of the gas flowing through the line 14 is introduced into the torch 13 via the branch line 14a and discharged from the tip.
  • a chamber flow meter 10 for measuring the flow rate of the gas flow is provided in the middle of the line 14, and a torch flow meter 9 is also provided in the middle of the branch line 14 a connected to the torch 13.
  • an atmosphere that generates arc discharge in the chamber 11 (hereinafter also referred to as “arc atmosphere”) is a predetermined gas atmosphere, and the sample support 5 is connected to an anode of a DC power source (not shown).
  • the electrode 2 is connected to the cathode of the DC power source, an arc discharge is generated between the sample 4 on the sample support 5 and the tip of the electrode 2, and a transfer arc 3 is generated.
  • the supported sample 4 is forcibly evaporated to a gas phase.
  • the vapor of the sample 4 is conveyed to the gas stream and guided to the collector 12 via the heat exchanger 6. In this process, the vapor is cooled, the atoms aggregate together and a powder is obtained.
  • the powder adheres to the collection filter 7 and is collected, and the gas is separated.
  • a flat end surface flat surface is formed at the forefront of the electrode 2.
  • the PVD method is advantageous in DC arc discharge, which can increase the size of equipment and can use an inexpensive power source.
  • DC arc discharge since a sample is placed on a crucible, it is difficult to form an alloy if the vapor pressures of the mixed metals differ greatly. For this reason, it is preferable to add an element having a boiling point close to that of nickel.
  • the concentration gradient of the alloy composition in the powder can be suppressed by rapidly cooling the sample vapor. For this reason, it is preferable to use a water-cooled copper crucible and a water-cooled plasma chamber in which only one point around the arc becomes a high-temperature part, instead of using a heat-insulating crucible that increases the high-temperature part.
  • the water-cooled copper crucible and the sample melt are in contact with each other through the solidified sample, the crucible material is not mixed.
  • the CVD method is generally a method for producing metal powder by reacting raw materials such as chlorides or carbonate compounds.
  • a microreactor is used for the production of metal powder by the CVD method.
  • FIG. 2 is a schematic diagram illustrating an example of the microreactor 31.
  • the microreactor 31 is an experimental device that causes a chemical reaction in a small space, and includes an electric furnace 32, a quartz reaction tube 33, a hydrogen gas nozzle 34, and a carrier nitrogen gas nozzle 35.
  • a metal chloride is put into the sample boat 36 and set in the quartz reaction tube 33 (outside the electric furnace 32).
  • the quartz reaction tube 33 is heated to the reduction temperature by the electric furnace 32, and the sample boat 36 set in the quartz reaction tube 33 is placed in the electric furnace 32 while flowing hydrogen gas from the hydrogen gas nozzle 34 and nitrogen gas from the carrier nitrogen gas nozzle 35.
  • a metal powder is generated by pushing inward to vaporize the metal chloride (a region where the metal chloride is vaporized is also referred to as a “vaporization part”) and a hydrogen reduction reaction.
  • the reaction portion 37 extends from the tip of the hydrogen gas nozzle 34 to the outlet of the electric furnace 32, where the length of the reaction portion 37 is 1 and the inner diameter of the reaction portion 37 is d. It is thought that reduction reaction and particle growth occur.
  • Nickel powder can be produced by using nickel chloride as a raw material metal chloride, and nickel powder can be produced by using nickel chloride and other metal chlorides together.
  • metal chloride is vaporized and reduced to metal with hydrogen.
  • chloride is easier to vaporize than metal, energy efficiency is high, and powder can be produced at low cost by the CVD method.
  • the cooling gas is blown near the reaction field that is kept warm, a large amount of cooling gas is required, and the cost is greatly increased.
  • the nickel powder of the present invention can be suitably used as a material for forming internal electrodes of multilayer ceramic electronic components such as multilayer capacitors, multilayer inductors and multilayer actuators.
  • a conductive paste may be prepared using the nickel powder of the present invention, and an internal electrode may be manufactured using the prepared conductive paste.
  • the manufacturing method of an electrically conductive paste and a multilayer ceramic electronic component is not specifically limited, A conventionally well-known method can be used.
  • Nickel powder was manufactured using the PVD apparatus 1 of FIG. First, the inside of the chamber 11 was evacuated to 10 Pa or less, and when the pressure was 0.7 atm filled with argon, the nickel and the additive metal were melted together to prepare the sample 4. The sample 4 was set on the sample support 5 and the mass of the sample 4 was set to 60 g in total. Thereafter, the arc 3 was blown from the electrode 2 attached to the tip of the torch 13 toward the sample 4 and melted. In order to obtain a more uniform sample, the melted sample 4 was turned over and melted, and this operation was repeated three times. The sample 4 thus obtained was used.
  • the production conditions were such that the arc atmosphere was a mixed gas atmosphere of argon and hydrogen, and the volume ratio (argon / hydrogen) was 50/50. Further, the pressure in the chamber 11 is set to 0.7 atm, and the sample 4 is subjected to arc discharge, adjusted to have an arc current of 150 A and an arc voltage of 40 V, and the evaporated metal vapor is sufficiently obtained by the heat exchanger 6. Then, the nickel powder was collected by the collection filter 7 of the collector 12. A tungsten electrode to which 3% by mass of thorium oxide was added was used as the electrode 2 at the tip of the torch 13.
  • the gas was circulated by the circulation pump 8 with the gas flow rate measured by the torch flow meter 9 being 1 NL / min and the carrier gas flow rate being measured by the chamber flow meter 10 being 150 NL / min.
  • the collected nickel powder was subjected to gradual oxidation with a gas based on nitrogen gas. Gas was circulated at the same gas flow rate as above, and gradual oxidation was performed with oxygen 0.25% for 30 minutes, oxygen 1% for 30 minutes, oxygen 5% for 30 minutes, and oxygen 20% for 30 minutes. After the slow oxidation, the nickel powder was recovered by jetting gas from the inside to the outside of the filter 7 and dropping the powder adhering to the filter 7.
  • Nickel powder was produced using the microreactor 31 of FIG.
  • the inner diameter d of the reaction part 37 was 26 mm, and the length l of the reaction part 37 was 130 mm.
  • the quartz reaction tube 33 is heated by the electric furnace 32, the temperature of the vaporizing section for vaporizing tin chloride is 800 ° C., the temperature of the vaporizing section for vaporizing nickel chloride is 1120 ° C., and the temperature of the reaction section 37 for hydrogen reduction reaction.
  • the temperature and gas in the electric furnace 32 are maintained at 1050 ° C., the amount of nitrogen gas from the carrier nitrogen gas nozzle 35 is 6.5 NL / min, the amount of hydrogen gas from the hydrogen gas nozzle 34 is 3.0 NL / min. The amount was stabilized.
  • a sample boat 36 filled with 40 g of anhydrous nickel chloride and anhydrous tin chloride was pushed in from the outside of the electric furnace 32 to produce nickel powder. At this time, the amount of anhydrous tin chloride was 1.2 g in Example 1, 3.1 g in Examples 2 and 3, and 5.1 g in Example 4. Note that the microreactor 31 of FIG.
  • the reaction unit 37 has a structure in which carrier nitrogen gas passes through the sample boat 36 so that the vaporized nickel chloride gas and tin chloride gas are smoothly sent to the reaction unit 37.
  • the produced nickel powder was passed through a cooling pipe (not shown), collected by a filter (not shown), and collected.
  • ⁇ A-axis length > The obtained nickel powder and nickel powder were subjected to X-ray diffraction under the following conditions using an X-ray diffractometer (D8 ADVANCE, manufactured by Bruker AXS) in an atmosphere of 15 to 20 ° C., and an XRD pattern was obtained. Obtained.
  • ⁇ Tube CuK ⁇ line
  • Tube voltage 40 kV
  • Tube current 150 mA
  • Sampling interval 0.02 degrees
  • Scanning speed 4.0 degrees / min ⁇ Start angle: 20 degrees
  • End angle 100 degrees
  • FIG. 3 is a graph showing an XRD pattern of nickel powder.
  • the FCCC was calculated as sin 2 ⁇ from the value of 2 ⁇ at the peak position of the XRD pattern, and the ratio was 3: 4: 8: 11: 12.
  • the peaks of the (111) plane, (200) plane, (220) plane, (311) plane, and (222) plane were determined.
  • the a-axis length (unit: ⁇ ) was determined from the peak position near 44 degrees on the strong (111) plane.
  • the nickel powder containing 50 mass% of tin many peaks were seen and the single phase was not obtained.
  • the tin addition amount increases, a peak shift in which 2 ⁇ shifts to the lower angle side is seen, and therefore the a-axis length increases with tin addition.
  • tin was 3.536% at 2% by mass, 3.547% at 5% by mass of tin, 3.560% at 8% by mass of tin, and 3.614% at 20% by mass of tin.
  • ⁇ Sintering temperature> The obtained nickel powder and the sintering temperature (unit: ° C.) of the nickel powder were determined. Specifically, first, 0.25 mL of 10% PVA aqueous solution was added to 5 g of the obtained powder, and after drying, 0.58 g was weighed and press-shaped at 6 kN to produce a 7 mm ⁇ pellet. did. Next, the temperature of the produced pellet was increased at 10 ° C./min in a gas atmosphere of 0.12% hydrogen based on nitrogen gas or 3% hydrogen based on nitrogen gas. Thereby, the volume of a pellet shrinks gradually.
  • FIG. 5 is a graph showing the relationship between the temperature and the volume change rate of nickel powder. In the graph of FIG. 5, only a few examples of the obtained nickel powder are shown.
  • the temperature (unit: ° C.) and the volume change rate (unit:%) are plotted on a graph, and the tangent line (not shown in FIG. 5) of the temperature region before and after the volume change is drawn.
  • the temperature at the point where the two tangents intersect was determined as the sintering temperature.
  • Examples 1 to 9 in which the a-axis length is 3.530 mm or more and less than 3.600 mm are compared with Comparative Examples 1 to 4 in which the a-axis length is less than 3.530 mm. Then, in Examples 1 to 9, the residual magnetization could be reduced and the secondary particle diameter tended to be smaller than those in Comparative Examples 1 to 4. Zirconium was less than the detection limit of 10 ppm in all samples. Further, it was found that Examples 1 to 9 had higher sintering temperatures than Comparative Examples 1 to 4.
  • Nickel powder (Comparative Example 5) to which 0.2% of sulfur with a primary particle size D50 of 220 nm was added and nickel powder (Example 10) to which 5% by mass of tin with a primary particle size D50 of 230 nm was added were prepared.
  • the sintering temperature in an atmosphere of 0.12% hydrogen was 480 ° C, whereas the sintering temperature decreased to 310 ° C when hydrogen was increased to 3%.
  • FIG. 6 is a graph showing the relationship between the temperature and the volume change rate of the nickel powder powder of Example 6. As shown in the graph of FIG. 6, in the nickel powder of Example 6, the sintering temperature does not change even when the hydrogen concentration is increased from 0.12% to 3%, and the sintering temperature is decreased even at a high hydrogen concentration. It turned out that it can suppress.
  • the frequency dependence of impedance was examined for the nickel powder of Comparative Example 1 and the nickel powder of Example 2.
  • a dispersing agent KD-12, manufactured by Croda Japan Co., Ltd.
  • KD-12 was applied to the nickel powder obtained by classifying the powder obtained in Comparative Example 1 or 40 g of the unclassified nickel powder obtained in Example 2.
  • 1.44 g, 31.25 g of binder (TE-45, manufactured by Yasuhara Chemical Co.) and 27.31 g of solvent (terpineol C) were blended to obtain a conductive paste.
  • the film-shaped sample of 10 micrometers thickness was produced by baking for 10 minutes at 650 degreeC.
  • FIG. 7 is a graph showing the relationship between the frequency and impedance of nickel powder.
  • (A) is Comparative Example 1 and (B) is Example 2.
  • the increase in impedance was small even when the frequency was increased. It was found that it can be used with low impedance even in the high frequency region.
  • a multilayer ceramic capacitor was fabricated using the above conductive paste obtained using the nickel powder of Comparative Example 1 and the nickel powder of Example 2, and the multilayer evaluation was performed.
  • the dielectric is an X5R characteristic material using BT powder of 0.2 ⁇ m
  • the sheet thickness is 3 ⁇ m
  • the shape is 3225 type
  • the number of lamination is 5 layers
  • the firing temperature is 1220 ° C.
  • the hydrogen is 0.9%
  • the Wetter 35 ° C. It was.
  • dielectric loss (DF, unit:%) was measured using an LCR meter
  • insulation resistance (unit: ⁇ 10 10 ⁇ ) was measured using an insulation resistance meter.
  • five capacitors were prepared, and five measurement results were obtained. The results are shown in Table 2 below.
  • Example 2 As shown in Table 2, it was found that the dielectric loss (DF) of Example 2 could be reduced from about 3.3% in Comparative Example 1 to about 3.1%. It was also found that the insulation resistance value of Example 2 was more stable than that of Comparative Example 1. Thereby, the yield and performance of the capacitor can be stabilized. Due to the small increase in impedance at high frequency (see FIG. 7) and the small DF, heat loss at high frequency can be suppressed when using a capacitor, and the upper limit of the usable frequency can be widened. .

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PCT/JP2013/006702 2012-11-20 2013-11-14 ニッケル粉末、導電ペースト、および、積層セラミック電子部品 WO2014080600A1 (ja)

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CN201380060360.4A CN104837580B (zh) 2012-11-20 2013-11-14 镍粉末、导电膏以及层叠陶瓷电子部件
JP2013554131A JP6000983B2 (ja) 2012-11-20 2013-11-14 ニッケル粉末、導電ペースト、および、積層セラミック電子部品
KR1020157012938A KR101689491B1 (ko) 2012-11-20 2013-11-14 니켈 분말, 도전 페이스트 및 적층 세라믹 전자 부품

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200023442A (ko) 2017-07-05 2020-03-04 도호 티타늄 가부시키가이샤 금속 분말 및 그 제조 방법

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017122689A1 (ja) * 2016-01-12 2017-07-20 東邦チタニウム株式会社 ニッケル粉末
EP3360627B1 (de) * 2017-02-08 2022-01-05 Heraeus Deutschland GmbH & Co. KG Pulver zur verwendung in einem additiven fertigungsverfahren
KR102105057B1 (ko) * 2018-08-16 2020-04-27 삼성전기주식회사 적층 세라믹 전자부품
KR102140622B1 (ko) * 2018-08-23 2020-08-03 삼성전기주식회사 적층 세라믹 전자부품 및 그 제조방법
KR20190121210A (ko) 2018-10-17 2019-10-25 삼성전기주식회사 적층 세라믹 전자부품 및 그 제조방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008024961A (ja) * 2006-07-18 2008-02-07 Sumitomo Osaka Cement Co Ltd ニッケル−鉄合金ナノ粒子の製造方法およびニッケル−鉄合金ナノ粒子
JP2008081818A (ja) * 2006-09-28 2008-04-10 Sumitomo Osaka Cement Co Ltd ニッケル―鉄合金ナノ粒子の前駆体粉末の製造方法およびニッケル―鉄合金ナノ粒子の前駆体粉末、ニッケル―鉄合金ナノ粒子の製造方法およびニッケル―鉄合金ナノ粒子
JP2008179842A (ja) * 2007-01-23 2008-08-07 Sumitomo Osaka Cement Co Ltd ニッケル―鉄―亜鉛合金ナノ粒子の製造方法およびニッケル―鉄―亜鉛合金ナノ粒子、平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法および平板状ニッケル―鉄―亜鉛合金ナノ粒子
JP2008179841A (ja) * 2007-01-23 2008-08-07 Sumitomo Osaka Cement Co Ltd ニッケル―鉄―モリブデン合金ナノ粒子の製造方法およびニッケル―鉄―モリブデン合金ナノ粒子
JP2009228070A (ja) * 2008-03-24 2009-10-08 Kyocera Corp 卑金属粉末およびその製法、導体ペースト、ならびに電子部品
JP2012193418A (ja) * 2011-03-17 2012-10-11 Nippon Steel Chem Co Ltd 鉄酸化物を含有する金属複合ニッケルナノ粒子の製造方法及び鉄酸化物を含有する金属複合ニッケルナノ粒子

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100480873B1 (ko) * 1999-11-12 2005-04-07 미츠이 긴조쿠 고교 가부시키가이샤 니켈 분말 및 도전 페이스트
JP3452034B2 (ja) * 2000-07-05 2003-09-29 株式会社村田製作所 導電性ペーストおよび積層セラミック電子部品
CA2359347A1 (en) 2001-10-18 2003-04-18 Cesur Celik Laminated ceramic capacitor internal electrode material
JP4409989B2 (ja) * 2003-03-12 2010-02-03 Ｊｆｅミネラル株式会社 ニッケル基超微粉及びその製造方法
TWI243725B (en) 2003-05-27 2005-11-21 Samsung Electronics Co Ltd Method for preparing non-magnetic nickel powders
WO2005020256A1 (ja) 2003-08-22 2005-03-03 Murata Manufacturing Co., Ltd. 積層型電子部品
JP4394535B2 (ja) 2004-07-29 2010-01-06 東邦チタニウム株式会社 ニッケル粉末の製造方法
JP2007243026A (ja) * 2006-03-10 2007-09-20 Tdk Corp セラミック粉末及びこれを用いた導電ペースト、積層セラミック電子部品、その製造方法
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008024961A (ja) * 2006-07-18 2008-02-07 Sumitomo Osaka Cement Co Ltd ニッケル−鉄合金ナノ粒子の製造方法およびニッケル−鉄合金ナノ粒子
JP2008081818A (ja) * 2006-09-28 2008-04-10 Sumitomo Osaka Cement Co Ltd ニッケル―鉄合金ナノ粒子の前駆体粉末の製造方法およびニッケル―鉄合金ナノ粒子の前駆体粉末、ニッケル―鉄合金ナノ粒子の製造方法およびニッケル―鉄合金ナノ粒子
JP2008179842A (ja) * 2007-01-23 2008-08-07 Sumitomo Osaka Cement Co Ltd ニッケル―鉄―亜鉛合金ナノ粒子の製造方法およびニッケル―鉄―亜鉛合金ナノ粒子、平板状ニッケル―鉄―亜鉛合金ナノ粒子の製造方法および平板状ニッケル―鉄―亜鉛合金ナノ粒子
JP2008179841A (ja) * 2007-01-23 2008-08-07 Sumitomo Osaka Cement Co Ltd ニッケル―鉄―モリブデン合金ナノ粒子の製造方法およびニッケル―鉄―モリブデン合金ナノ粒子
JP2009228070A (ja) * 2008-03-24 2009-10-08 Kyocera Corp 卑金属粉末およびその製法、導体ペースト、ならびに電子部品
JP2012193418A (ja) * 2011-03-17 2012-10-11 Nippon Steel Chem Co Ltd 鉄酸化物を含有する金属複合ニッケルナノ粒子の製造方法及び鉄酸化物を含有する金属複合ニッケルナノ粒子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200023442A (ko) 2017-07-05 2020-03-04 도호 티타늄 가부시키가이샤 금속 분말 및 그 제조 방법

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