WO2014080600A1 - Nickel powder, conductive paste, and laminated ceramic electronic component - Google Patents

Nickel powder, conductive paste, and laminated ceramic electronic component Download PDF

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Publication number
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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Prior art keywords
nickel powder
nickel
powder
conductive paste
sample
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PCT/JP2013/006702
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French (fr)
Japanese (ja)
Inventor
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 JP2013554131A priority Critical patent/JP6000983B2/en
Priority to CN201380060360.4A priority patent/CN104837580B/en
Priority to KR1020157012938A priority patent/KR101689491B1/en
Publication of WO2014080600A1 publication Critical patent/WO2014080600A1/en

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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 OR LIGHT-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 OR LIGHT-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. .

Abstract

Provided is a nickel powder to be used in an internal electrode of a laminated ceramic electronic component, and having a high sintering temperature, exhibiting minimal condensation, and having improved high-frequency properties. Specifically, this nickel powder obtains a peak having a face-centered cubic lattice (FCC) structure as a result of x-ray diffraction, has an a-axis length of 3.530Å or more and less than 3.600Å, and contains 50 or more mass% of nickel.

Description

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Nickel powder, conductive paste, and multilayer ceramic electronic components
　本発明は、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に関する。 The present invention relates to nickel powder, a conductive paste, and a multilayer ceramic electronic component.
　ニッケル粉末は、例えば、積層コンデンサ、積層インダクタ、積層アクチュエーターなどの積層セラミック電子部品の内部電極を形成する材料として、使用されている。 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.
特開２００４－３５３０８９号公報JP 2004-353089 A 特開２００６－０３７１９５号公報JP 2006-037195 A 特許第４０８９７２６号公報Japanese Patent No. 4089726 特表２００５－５０５６９５号公報JP 2005-505695 A
　積層コンデンサを形成するためには、まず、チタン酸バリウムなどの誘電体セラミックグリーンシート上に、内部電極用導電ペーストを所定のパターンで印刷し、このシートを複数枚積み重ね数十～数百ＭＰａで圧着して、セラミックグリーンシートと内部電極用導電ペーストとが交互に積層された未焼成の積層体を得る。得られた積層体を所定の形状に切断した後、高温でセラミックグリーンシートと内部電極用導電ペーストとを同時焼成して、積層セラミックコンデンサ素体を得る。
　次いで、得られた素体における内部電極が露出する端面に、導電性粉末、チタン酸バリウム等の誘電体および有機溶媒を主成分とする端子電極用導電ペーストを、浸漬等により塗布し、乾燥した後、高温焼成することで端子電極が形成される。
　このとき、チタン酸バリウム等の誘電体を導電ペーストに含めないと、セラミックグリーンシートの焼結温度である１０００℃以上の温度に達する前に、ニッケル粉末が焼結し、セラミックグリーンシートが焼結する際に内部電極に応力がかかりクラック等が発生する。
　そこで、ニッケル粉末の焼結温度を誘電体の焼結温度に近づけるために、従来はニッケル粉末に硫黄が添加されている（特許文献２）。硫黄添加は、ニッケル粉末の表面に濃化して焼結抑制効果が得られるため、ニッケル粉末が細粒化するに従って、必要な硫黄の量も増加する。コンデンサになる前に硫黄は除く必要があるため、細粒ニッケル粉末においては硫黄除去の手間は増える方向にしか働かない。また、硫黄添加したニッケル粉末は、焼成時の水素濃度が高くなるほど焼結温度が低下する傾向がある。 In order to form a multilayer capacitor, first, 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.
Next, 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.
Therefore, in order to bring the sintering temperature of the nickel powder close to the sintering temperature of the dielectric, conventionally, 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.
　近年、積層セラミック電子部品の薄層化は著しく、コンデンサの内部電極も薄層化しており、内部電極用導電ペーストに用いられるニッケル粉末の細粒化が望まれている。
　ニッケル粉末は、細粒化すると導電ペーストにする際に強い凝集を起こしやすく、強固な二次粒子が生成してしまうため、細粒化した効果が十分に得られない。特に一次粒子径が２００ｎｍ以下のニッケル粉末は、凝集が強い。
　導電ペーストに粗大な二次粒子が残っていると内部電極どうしでショートを起こす原因となるため、凝集体をフィルターで濾過するが、これによりコストが増大し、歩留まりも悪化する。そこで、細粒化したニッケル粉末の凝集を低減することが強く求められている。
　ところで、細粒ニッケル粉末の導電ペーストを電子顕微鏡で観察すると、ひも状に連なった粒子が多数観察されることから、粒子どうしの凝集力として、磁気力が強い影響を及ぼしていることが分かる。
　磁気力を低減させる方法としては、ニッケル粒子を六方最密充填（以下、「ＨＣＰ」ともいう）構造の非磁性ニッケル相に変化させるという方法が挙げられる（特許文献１）。この方法は、液相法で製造したニッケル粒子をポリオール中で１５０～３８０℃に加熱することにより面心立方格子（以下、「ＦＣＣ」ともいう）構造からＨＣＰ構造に相転移させるものである。しかし、低温では相転移の速度が遅く、高温ではＨＣＰ構造は不安定になりやすい。細粒ニッケル粉末においては、相転移を起こすための加熱により粒子どうしが焼結してショートの原因となる粗大な粒子が生成するため好ましくない。また、ＨＣＰ構造の非磁性ニッケルは熱的に不安定な結晶構造であるため、４００℃以上に加熱すると磁性を持つＦＣＣ構造に戻ってしまう（非特許文献１）。 In recent years, multilayer ceramic electronic components have become extremely thin, and internal electrodes of capacitors have also been thinned, and it is desired to make nickel powder used for internal electrode conductive paste finer.
When nickel powder is finely divided, strong aggregation tends to occur when forming a conductive paste, and strong secondary particles are generated. Therefore, the effect of the fine particle cannot be sufficiently obtained. In particular, a nickel powder having a primary particle size of 200 nm or less has strong aggregation.
If coarse secondary particles remain in the conductive paste, it may cause a short circuit between the internal electrodes, and thus the aggregate is filtered with a filter. This increases the cost and the yield. Therefore, there is a strong demand to reduce the aggregation of the finely divided nickel powder.
By the way, when a conductive paste of fine nickel powder is observed with an electron microscope, a large number of particles connected in a string are observed, and it can be seen that the magnetic force exerts a strong influence as the cohesive force between the particles.
As a method for reducing the magnetic force, there is a method in which nickel particles are changed to a nonmagnetic nickel phase having a hexagonal close-packed (hereinafter also referred to as “HCP”) structure (Patent Document 1). In this method, 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. However, the phase transition rate is slow at low temperatures, and the HCP structure tends to become unstable at high temperatures. The fine nickel powder is not preferable because the particles are sintered by heating for causing phase transition to generate coarse particles that cause a short circuit. In addition, since nonmagnetic nickel having an HCP structure has a thermally unstable crystal structure, when it is heated to 400 ° C. or higher, it returns to a magnetic FCC structure (Non-patent Document 1).
　高容量の通信を行うためには電子回路で扱う周波数を高める必要があり、電子回路の処理速度を上げるためにも回路内で扱う周波数を高める必要がある。このような高周波信号を扱う電子回路においては、ノイズ除去用のローパスフィルターや電源周りのバイパスコンデンサなどの用途でコンデンサが用いられている。近年ではＧＨｚを超えるようなノイズの処理が求められている。ノイズの処理においてコンデンサのインピーダンスが高いと、ノイズをグラウンド側に除去しようとした際にノイズ電流が小さくなってしまうため、より高い電圧を印加する必要がある。
　積層セラミックコンデンサには、容量Ｃの他に、誘電体材料および内部電極による抵抗成分であるＥＳＲ（等価直列抵抗）、リード線および内部電極が持つインダクタ成分であるＥＳＬ（等価直列インダクタンス）があり、こうした成分が直列に繋がって現される。コンデンサの自己共振周波数までは容量成分がインピーダンスの主体であり、高周波になるに従ってインピーダンスは低下するが、自己共振周波数以上ではインダクタ成分がインピーダンスの主体となり、高周波になるほどインピーダンスは増加する。
　高周波回路に用いるコンデンサを製造するためには、インダクタ成分を低下させる必要がある。高周波電流を流すとコンデンサ内の磁場が電流の向きに応じて変化する。この磁場の変化がインダクタ成分となっている。
　このため、現在の対策としては、外部電極から内部電極の先端までの距離を短くして、コンデンサ内で磁場が打ち消しあうような構造とすることで発生する磁場の低減を図っている（特許文献３）。
　コイルのインダクタ成分については、構造だけでなく、電極部材の比透磁率にも依存する。ニッケルは強磁性の金属であるため、比透磁率が低い物質に置き換えればインダクタ成分をさらに低減でき、コンデンサの性能を上げることができる。地金の安さと比透磁率の低さを考えると銅電極という手段もあるが、焼結温度が低く酸化しやすいため高誘電率の誘電体とは一緒に焼成できない。
　また、磁気凝集の対策として効果的であるＨＣＰ構造のニッケルは、１０００℃の焼結で磁性を持つＦＣＣ構造に戻るため、コンデンサの高周波特性を改善するためには役立たない。
また、コンデンサ焼成時には電極ペーストの溶媒成分が残留していると急激に蒸発して気泡を生じさせ電極層と誘電体層の間に剥離が生じコンデンサの性能が低下してしまう。そこで焼成前に溶媒成分を揮発させる必要があるが、高温の酸化雰囲気で脱媒すると脱媒速度が増して生産性を上げる事ができる。脱媒時にニッケル粉末は耐酸化性が要求される。なお脱媒とはターピネオール等の有機溶媒成分を除去することをいう。積層セラミックコンデンサ用の耐酸化性を向上させた合金粉末という例がある（特許文献４）。この特許文献では銅およびニッケル粉末の耐酸化性向上のために各種合金が有効と述べているが、不可避不純物としてジルコニウムが混入する。酸化ジルコニウムはチタン酸バリウムのキュリー温度を調整するために添加するが、ジルコニウムが酸化する事で電極から誘電体層に拡散して混入してしまい、キュリー温度が変化して所定の誘電特性を得られなくなってしまう問題がある。
  In order to perform high-capacity communication, it is necessary to increase the frequency handled in the electronic circuit, and in order to increase the processing speed of the electronic circuit, it is necessary to increase the frequency handled in the circuit. In electronic circuits that handle such high-frequency signals, capacitors are used for applications such as low-pass filters for noise removal and bypass capacitors around power supplies. In recent years, noise processing exceeding GHz has been demanded. When the impedance of the capacitor is high in noise processing, the noise current becomes small when attempting to remove the noise to the ground side, so a higher voltage needs to be applied.
In addition to the capacitance C, 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. When a high frequency current is applied, the magnetic field in the capacitor changes according to the direction of the current. This change in the magnetic field is an inductor component.
For this reason, as a current measure, the distance from the external electrode to the tip of the internal electrode is shortened to reduce the magnetic field generated by making the magnetic field cancel each other in the capacitor (Patent Document). 3).
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. However, since the sintering temperature is low and it is easy to oxidize, it cannot be fired together with a dielectric having a high dielectric constant.
Further, 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.
In addition, if 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. Therefore, it is necessary to volatilize the solvent component before firing, but if the solvent is removed in a high-temperature oxidizing atmosphere, the removal rate can be increased and the productivity can be increased. 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. 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.
　本発明は、以上の点を鑑みてなされたものであり、積層セラミック電子部品の内部電極に用いるニッケル粉末であって、焼結温度が高く、凝集が抑制され、高周波特性が改善されたニッケル粉末を提供することを目的とする。 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.
　本発明者らは、上記目的を達成するために鋭意検討を行った。その結果、ニッケルに非磁性金属元素を添加することでａ軸長を特定範囲にしたニッケル粉末は、残留磁化が低くなり凝集を抑制できること、焼結温度を高くできること、高周波特性が改善されることを見出し、本発明を完成させた。
　なお本発明では、ニッケルに非磁性金属元素を添加したニッケル合金粉末を含めてニッケル粉末というものとする。 The present inventors have intensively studied to achieve the above object. As a result, 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.
In the present invention, nickel powder including nickel alloy powder obtained by adding a nonmagnetic metal element to nickel is referred to as nickel powder.
　すなわち、本発明は、以下の（１）～（３）を提供する。
　（１）積層セラミック電子部品の内部電極に用いるニッケル粉末であって、Ｘ線回折によって面心立方格子（ＦＣＣ）構造のピークが得られ、ａ軸長が３．５３０Å以上３．６００Å未満であり、ニッケルの含有率が５０質量％以上である、ニッケル粉末。
　（２）上記（１）に記載のニッケル粉末を用いた導電ペースト。
　（３）上記（２）に記載の導電ペーストを用いて内部電極を形成した積層セラミック電子部品。 That is, the present invention provides the following (1) to (3).
(1) 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.
(2) A conductive paste using the nickel powder described in (1) above.
(3) A multilayer ceramic electronic component in which an internal electrode is formed using the conductive paste according to (2).
　本発明によれば、焼結温度が高く、凝集が抑制され、高周波特性が改善されたニッケル粉末を提供することができる。 According to the present invention, nickel powder having a high sintering temperature, suppressed aggregation, and improved high frequency characteristics can be provided.
ＰＶＤ装置１の一例を示す模式図である。1 is a schematic diagram showing an example of a PVD apparatus 1. FIG. マイクロリアクタ３１の一例を示す模式図である。2 is a schematic diagram showing an example of a microreactor 31. FIG. ニッケル粉末のＸＲＤパターンを示すグラフである。It is a graph which shows the XRD pattern of nickel powder. 図３のＸＲＤパターンの一部を拡大して示すグラフである。It is a graph which expands and shows a part of XRD pattern of FIG. ニッケル粉末の温度と体積変化率との関係を示すグラフである。It is a graph which shows the relationship between the temperature and volume change rate of nickel powder. 実施例６のニッケル粉末の温度と体積変化率との関係を示すグラフである。It is a graph which shows the relationship between the temperature of nickel powder of Example 6, and a volume change rate. ニッケル粉末の周波数とインピーダンスとの関係を示すグラフであり、（Ａ）は比較例１、（Ｂ）は実施例２である。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.
　本発明のニッケル粉末は、積層セラミック電子部品の内部電極に用いるニッケル粉末であって、Ｘ線回折によって面心立方格子（ＦＣＣ）構造のピークが得られ、ａ軸長が３．５３０Å以上３．６００Å未満であり、ニッケルの含有率が５０質量％以上である、ニッケル粉末である。 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.
　本発明のニッケル粉末においては、ＦＣＣ構造を有するニッケルに、例えばスズ等の非磁性金属元素を添加することにより、ａ軸長を伸ばし、結晶構造を歪めることで磁性の低減を図っている。
　本発明のニッケル粉末において、ａ軸長は３．５３０Å以上とする。ａ軸長が伸びるほど単磁区が形成されにくくなることから、３．５４０Å以上が好ましい。 In the nickel powder of the present invention, by adding a nonmagnetic metal element such as tin to nickel having an FCC structure, the a-axis length is extended and the crystal structure is distorted to reduce magnetism.
In the nickel powder of the present invention, 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.
さらに、元素の添加によってａ軸長が伸びすぎると、結晶構造が熱的に不安定になり、コンデンサの焼成中に電極内にニッケル以外の異相の合金組織が析出し、異相が成長する過程で電極内の連続性が低下してしまう。また、電極の連続性が保たれたとしてもニッケルと異相との境界面では電気抵抗が増加するため好ましくない。
以上の問題を抑制する観点から、ａ軸長は、３．６００Å未満とするがより好ましくは３．５７０Å未満であり、３．５５０Å未満がさらにより好ましい。 Furthermore, if the a-axis length is too long due to the addition of elements, the crystal structure becomes thermally unstable, and an alloy structure of a different phase other than nickel is precipitated in the electrode during the firing of the capacitor, and the different phase grows. The continuity in the electrode is reduced. Further, even if the continuity of the electrode is maintained, it is not preferable because the electric resistance increases at the interface between nickel and the different phase.
From the viewpoint of suppressing the above problems, 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.
　本発明のニッケル粉末においては、ａ軸長を上記範囲とするために、ニッケルに対する添加元素の量は、固溶範囲とするのが好ましい。
　すなわち、本発明のニッケル粉末におけるニッケルの含有率は、５０質量％以上であり、７０～９９．５質量％が好ましく、８０～９９質量％がより好ましい。 In the nickel powder of the present invention, in order to make the a-axis length in the above range, 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.
　本発明のニッケル粉末において、ニッケルに添加する元素としては、非磁性金属元素であれば特に限定されず、例えば、チタン（Ｔｉ）、亜鉛（Ｚｎ）、スズ（Ｓｎ）、ビスマス（Ｂｉ）、イットリウム（Ｙ）やランタノイド元素などが挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
　これらのうち、コストが安く、かつ、融点から沸点までの液相の温度領域が広いために合金粉末を容易に製造できるという理由から、スズが好ましい。スズ濃度の好適範囲は0.1～10質量％、より好ましくは1～6質量％である。なお不可避的不純物である鉄の濃度は0.01質量％未満が好ましい。また、不純物としてZrは30ｐｐｍ以下が好ましい。 In the nickel powder of the present invention, the element added to nickel is not particularly limited as long as it is a nonmagnetic metal element. For example, 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.
Of these, 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. Further, Zr is preferably 30 ppm or less as an impurity.
　ところで、粒子を細かくすると単磁区化していくため、細かいニッケル粉末、特に一次粒子径が２００ｎｍ以下のニッケル粉末では、より強い磁気の凝集力を受けやすく、二次粒子径が大きくなりやすい。
　しかしながら、元素添加によってａ軸長が伸びた本発明のニッケル粉末においては、後述［実施例］でも説明するように、飽和磁化だけではなく残留磁化も低減する。このため、磁気による凝集力が減り、粒子どうしの引力が低減して、二次粒子径が小さくなる。 By the way, when the particles are made finer, they become single magnetic domains. Therefore, 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.
However, in 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.
　また、ａ軸長が伸びた本発明のニッケル粉末は、後述［実施例］でも説明するように、焼結温度が向上し、例えば、従来の硫黄添加と同等以上の効果が得られる。
　このため、焼結抑制効果のために導電ペーストに混ぜる共剤のチタン酸バリウムの量を低減することができ、より平滑な高品質の内部電極を形成できる。
　そして、従来の硫黄添加による焼結抑制では、焼成時における水素濃度を高くすると、焼結温度が低下する傾向にあるが、ａ軸長が伸びた本発明のニッケル粉末においては、水素濃度を高くしても、焼結温度の低下幅は小さく、より脱媒しやすい条件を選ぶことができる。 In addition, 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.
In 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.
　また、本発明のニッケル粉末を用いて導電ペーストを製造し、インピーダンスを測定すると、後述［実施例］でも説明するように、例えばスズを添加した本発明のニッケル粉末においては、純ニッケル粉末と比較して、インピーダンスは増加するものの、周波数が高くなっても、インピーダンスの増加量は小さく、高周波領域でも低インピーダンスで使うことができる。 Further, when a conductive paste is manufactured using the nickel powder of the present invention and the impedance is measured, for example, 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]. Although 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.
　また、後述［実施例］でも説明するように、本発明のニッケル粉末末を用いた場合、上記のように、高周波でのインピーダンスの上昇幅が小さいことに加え、誘電損失を低減できることから、コンデンサとした際に、高周波での発熱ロスが抑えられ、使用できる周波数の上限を広げることができる。
　なお、ニッケルの透磁率はニッケルと比べて小さくなるために、コンデンサのリアクタンスも小さくなり高周波特性が改善される。これは他の非磁性元素を添加した際にも成り立つ。
　このように、高周波特性が改善されるため、本発明のニッケル粉末末は、高容量コンデンサに好適である。 Further, as will be described later in [Example], when the nickel powder powder of the present invention is used, 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.
　本発明のニッケル粉末の製造方法としては、特に限定されず、気相法、液相法などの方法があるが、液相法で得られる粉末は、結晶性が低く、焼結しやすいことから、気相法が好ましい。気相法は、ＰＶＤ法とＣＶＤ法とに大別される。 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.
　ＰＶＤ法は、概略的には、ニッケルと対象金属または合金化した試料を用意して、試料を直流または交流アーク放電、高周波誘導プラズマ、マイクロ波プラズマ、高周波誘導加熱、レーザーなどの熱によって蒸発させ、急冷することで粉末を得る方法である。ＰＶＤ法は化学反応を用いないため、冷却速度を上げることで細かい粉末を製造することが容易である。 In general, 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. In this method, 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.
　ＰＶＤ法によるニッケル粉末の製造に用いるＰＶＤ装置の一例について、図１に基いて説明する。
　図１は、ＰＶＤ装置１の一例を示す模式図である。ＰＶＤ装置１は、試料４を蒸発させるためのチャンバ１１と、試料４の蒸気を冷却するための熱交換器６と、捕集フィルタ７が設けられた捕集器１２とを備え、熱交換器６を介して、チャンバ１１と捕集器１２とが連結されている。チャンバ１１の内部には、試料４を支持するために、例えば水冷銅るつぼである試料支持台５が設置されている。また、チャンバ１１の内部には、電極２が設置されている。電極２は、その先端が試料支持台５に近接する位置で、トーチ１３内に配置されている。トーチ１３は、図示しない水冷手段によって水冷されている。
　ＰＶＤ装置１においては、ライン１４からチャンバ１１に導入されたガスが、熱交換器６および捕集器１２を経て、循環ポンプ８に戻り、ガス気流が形成される。ライン１４は、トーチ１３に接続する分岐ライン１４ａを有し、ライン１４を流れるガスの一部は、分岐ライン１４ａを経由してトーチ１３内に導入され先端から放出される。ライン１４の途中には、ガス気流の流量を測定するためのチャンバ用流量計１０が設けられ、トーチ１３に接続する分岐ライン１４ａの途中にも、トーチ用流量計９が設けられている。
　このような構成において、チャンバ１１内でアーク放電を発生させる雰囲気（以下、「アーク雰囲気」ともいう）を所定のガス雰囲気とし、試料支持台５を直流電源（図示せず）の陽極と接続し、電極２を直流電源の陰極と接続して、試料支持台５上の試料４と電極２の先端との間でアーク放電を生じさせ、移行式アーク３を生じさせて、試料支持台５に支持された試料４を強制蒸発させて気相とする。試料４の蒸気は、ガス気流に搬送されて、熱交換器６を経由して、捕集器１２に導かれる。この過程において、蒸気は冷却され、原子どうしが互いに凝集し、粉末が得られる。捕集器１２においては、捕集フィルタ７に粉末が付着して捕集され、ガスが分離される。
　なお、電極２の最先端には、平坦な端面（平坦面）が形成されているのが好ましい。これにより、アーク３は、それほど絞られずに加速が抑制されて、試料融液は対流が減少して温度が上昇し、蒸発量が増加して回収率が向上する。 An example of a PVD apparatus used for producing nickel powder by the PVD method will be described with reference to FIG.
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. Inside the chamber 11, 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).
In the PVD apparatus 1, 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.
In such a configuration, 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. In the collector 12, the powder adheres to the collection filter 7 and is collected, and the gas is separated.
In addition, it is preferable that a flat end surface (flat surface) is formed at the forefront of the electrode 2. Thereby, the acceleration of the arc 3 is suppressed without being reduced so much, the convection of the sample melt decreases, the temperature rises, the amount of evaporation increases, and the recovery rate improves.
　ＰＶＤ法は、設備の大型化が可能で、安価な電源が利用できる直流アーク放電が有利である。直流アーク放電においては、るつぼ上に試料を置くので、混ぜ合わせた金属どうしの蒸気圧が大きく異なると合金化させることが困難である。このため沸点がニッケルと近い元素を添加するのが好ましい。また、試料蒸気を急冷することで粉末内の合金組成の濃度勾配を抑えることができる。このため、高温部が大きくなってしまう断熱るつぼを用いるのではなく、アーク周囲の一点のみが高温部となる水冷銅るつぼおよび水冷されたプラズマチャンバを用いるのが好ましい。また、水冷銅るつぼと試料融液は凝固した試料を挟んで接しているためるつぼ材が混入しないという点でも好ましい。 The PVD method is advantageous in DC arc discharge, which can increase the size of equipment and can use an inexpensive power source. In 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. Moreover, 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. Moreover, since 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.
　ＣＶＤ法は、概略的には、塩化物または炭酸化合物などの原材料を反応させて、金属粉末を製造する方法である。ＣＶＤ法による金属粉末の製造には、例えば、マイクロリアクタが用いられる。
　図２は、マイクロリアクタ３１の一例を示す模式図である。マイクロリアクタ３１は、小さな空間で化学反応させる実験装置であり、電気炉３２と、石英反応管３３と、水素ガスノズル３４と、キャリア窒素ガスノズル３５と、を有する。
　まず、試料ボート３６に金属塩化物を入れて、石英反応管３３内（電気炉３２の外側）にセットする。電気炉３２により還元温度まで石英反応管３３を加熱し、水素ガスノズル３４から水素ガス、キャリア窒素ガスノズル３５から窒素ガスを流しながら、石英反応管３３内にセットされた試料ボート３６を電気炉３２の内側に押し込み、金属塩化物を気化させ（金属塩化物を気化させる領域を「気化部」ともいう）、水素還元反応させることにより金属粉末を生成させる。
　このとき、水素ガスノズル３４の先端から電気炉３２の出口までが反応部３７であり、反応部３７の長さをｌ、反応部３７の内径をｄとした場合に、ｌ×ｄの領域で水素還元反応と粒子成長とが行われると考えられる。
　なお、生成した金属粉末については、例えば、冷却管（図示せず）内を通過させてフィルタ（図示せず）にて捕集し、回収することができる。原料の金属塩化物として塩化ニッケルを用いる事でニッケル粉末を、塩化ニッケル及び他の金属塩化物を一緒に用いる事でニッケル粉末を作製する事ができる。 The CVD method is generally a method for producing metal powder by reacting raw materials such as chlorides or carbonate compounds. For example, 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.
First, 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.
At this time, 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.
In addition, about the produced | generated metal powder, it can pass through the inside of a cooling pipe (not shown), can be collected with a filter (not shown), and can be collect | recovered. 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.
　ＣＶＤ法による製造の場合、金属塩化物を気化させ、水素により金属に還元させる。一般的に、塩化物は金属に比べ気化しやすいためエネルギー効率がよく、ＣＶＤ法により安価に粉末を製造できる。しかし、ＣＶＤ法で粒子径が１００～２００ｎｍ以下の粉末を得ようとする場合、粒成長をすぐに止めるために、反応場を出た直後の場所で冷やすことになる。したがって、保温している反応場の近くで冷却ガスを吹くことになるため、多量の冷却ガスが必要となり、コストが大きくかさむ。 In the case of production by the CVD method, metal chloride is vaporized and reduced to metal with hydrogen. In general, since chloride is easier to vaporize than metal, energy efficiency is high, and powder can be produced at low cost by the CVD method. However, when trying to obtain a powder having a particle size of 100 to 200 nm or less by the CVD method, in order to immediately stop the grain growth, it is cooled at a place immediately after leaving the reaction field. Therefore, since 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.
　本発明のニッケル粉末は、例えば、積層コンデンサ、積層インダクタ、積層アクチュエーターなどの積層セラミック電子部品の内部電極を形成する材料として、好適に用いることができる。この場合、本発明のニッケル粉末を用いて導電ペーストを作製し、作製した導電ペーストを用いて内部電極を作製すればよい。なお、導電ペーストおよび積層セラミック電子部品の製造方法は、特に限定されず、従来公知の方法を用いることができる。 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. In this case, 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. In addition, 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.
　以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
　＜ＰＶＤ法によるニッケル粉末の製造＞
　図１のＰＶＤ装置１を用いて、ニッケル粉末を製造した。
　まず、チャンバ１１内を１０Ｐａ以下まで真空引きし、アルゴンで満たし０．７気圧となったところで、ニッケルと添加金属とを一緒に溶融させ試料４を作製した。試料支持台５上に試料４をセットし、試料４の質量は合計で６０ｇとなるようにした。その後、トーチ１３の先端部に取り付けてある電極２からアーク３を試料４に向かって飛ばし、溶融させた。より均一な試料とするため、溶融させた試料４を裏返して溶融させ、この操作を３回繰り返した。このようにして得られた試料４を用いた。
　製造条件は、アーク雰囲気をアルゴンと水素との混合ガス雰囲気として、その体積比（アルゴン／水素）を５０／５０とした。また、チャンバ１１内の圧力を０．７気圧として、試料４に対してアーク放電を行い、アーク電流１５０Ａ、アーク電圧４０Ｖとなるように調整し、蒸発した金属蒸気を、熱交換器６で十分に冷却した後、捕集器１２の捕集フィルタ７で、ニッケル粉末を捕集した。トーチ１３の先端の電極２には、３質量％の酸化トリウムを添加したタングステン電極を用いた。トーチ用流量計９で測定されるガス流量を１ＮＬ／ｍｉｎとし、チャンバ用流量計１０で測定されるキャリアガスの流量を１５０ＮＬ／ｍｉｎとして、ガスを循環ポンプ８で循環させた。
　捕集したニッケル粉末は、窒素ガスをベースとしたガスで徐酸化を行った。上記と同じガス流量でガスを循環させ、酸素０．２５％で３０分、酸素１％で３０分、酸素５％で３０分、酸素２０％で３０分の徐酸化を行った。徐酸化を行った後、フィルタ７の内側から外側にガスを噴出させ、フィルタ７に付着した粉末を落とすことで、ニッケル粉末を回収した。 <Production of nickel powder by PVD method>
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.
　＜ＣＶＤ法によるニッケル粉末の製造＞
　図２のマイクロリアクタ３１を用いて、ニッケル粉末を製造した。なお、反応部３７の内径ｄを２６ｍｍ、反応部３７の長さｌを１３０ｍｍとした。
　まず、石英反応管３３を電気炉３２により加熱し、塩化スズを気化させる気化部の温度を８００℃、塩化ニッケルを気化させる気化部の温度を１１２０℃、水素還元反応させる反応部３７の温度を１０５０℃に保ち、キャリア窒素ガスノズル３５からの窒素ガスのガス量を６．５ＮＬ／ｍｉｎとし、水素ガスノズル３４からの水素ガスのガス量を３．０ＮＬ／ｍｉｎとし、電気炉３２内の温度およびガス量を安定させた。
　次に、無水塩化ニッケル４０ｇおよび無水塩化スズを充填させた試料ボート３６を電気炉３２の外側から内側に押し込み、ニッケル粉末を製造した。このとき、無水塩化スズの量は、実施例１では１．２ｇ、実施例２および３では３．１ｇ、実施例４では５．１ｇとした。なお、図２のマイクロリアクタ３１においては、気化した塩化ニッケルガスおよび塩化スズガスがスムーズに反応部３７に送られるようにするため、キャリア窒素ガスが試料ボート３６内を通過する構造とした。製造したニッケル粉末については、冷却管（図示せず）内を通過させてフィルタ（図示せず）にて捕集し、回収した。 <Manufacture of nickel powder by CVD method>
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.
First, 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.
Next, 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. 2 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軸長＞
　得られたニッケル粉末およびニッケル粉末について、１５～２０℃の雰囲気で、Ｘ線回折装置（Ｄ８ ＡＤＶＡＮＣＥ、ブルカー・エイエックスエス社製）を用いて、下記条件でＸ線回折を行ない、ＸＲＤパターンを得た。
　・管球：ＣｕＫα線
　・管電圧：４０ｋＶ
　・管電流：１５０ｍＡ
　・サンプリング間隔：０．０２度
　・スキャンスピード：４．０度／ｍｉｎ
　・開始角度：２０度
　・終了角度：１００度 <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: CuKα 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
　図３は、ニッケル粉末のＸＲＤパターンを示すグラフである。なお、図３のグラフには、得られたニッケル粉末およびニッケル粉末のうちの数例のみを挙げて示している。比較例１～４および実施例１～９のニッケル粉末については、ＸＲＤパターンのピーク位置の２θの値からsin2θを計算するとその比が３：４：８：１１：１２となる事からＦＣＣ構造の（１１１）面、（２００）面、（２２０）面、（３１１）面、（２２２）面のピークであることを判断した。また、強度の強い（１１１）面の４４度付近のピーク位置からａ軸長（単位：Å）を求めた。なお、スズを５０質量％含むニッケル粉末については、多数のピークが見られており単相が得られなかった。
　図４は、図３のＸＲＤパターンの一部を拡大して示すグラフである。（１１１）面のピークの２θの角度および測定に用いたＸ線の波長λから（１１１）面の面間隔ｄが2dsinθ=λと求められ、ＦＣＣ構造のa軸長は（１１１）面の面間隔の√3倍となる。図４に示すようにスズの添加量が増えるほど２θが低角度側に移るピークシフトが見られるのでスズ添加に伴いa軸長が伸びていくことが分かる。例えばスズ２質量％で3.536Å、スズ5質量％で3.547Å、スズ8質量％で3.560Å、スズ20質量％で3.614Åとなった。 FIG. 3 is a graph showing an XRD pattern of nickel powder. In the graph of FIG. 3, only a few examples of the obtained nickel powder and nickel powder are shown. With respect to the nickel powders of Comparative Examples 1 to 4 and Examples 1 to 9, the FCCC was calculated as sin 2 θ from the value of 2θ 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: Å) was determined from the peak position near 44 degrees on the strong (111) plane. In addition, about the nickel powder containing 50 mass% of tin, many peaks were seen and the single phase was not obtained.
FIG. 4 is an enlarged graph showing a part of the XRD pattern of FIG. From the angle of 2θ of the peak of the (111) plane and the X-ray wavelength λ used for the measurement, the plane spacing d of the (111) plane is obtained as 2dsinθ = λ, and the a-axis length of the FCC structure is the plane of the (111) plane √3 times the interval. As shown in FIG. 4, it can be seen that as the tin addition amount increases, a peak shift in which 2θ shifts to the lower angle side is seen, and therefore the a-axis length increases with tin addition. For example, 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.
　＜一次粒子径（Ｄ５０）＞
　得られたニッケル粉末およびニッケル粉末について、電子顕微鏡（ＨＩＴＡＣＨＩ Ｓ－４３００）を用いて倍率２万倍で撮影されたＳＥＭ像から、一次粒子の粒子径を測定し、平均粒子径（Ｄ５０）を求めた（単位：ｎｍ）。 <Primary particle diameter (D50)>
About the obtained nickel powder and nickel powder, the particle diameter of a primary particle is measured from the SEM image image | photographed by the magnification of 20,000 times using the electron microscope (HITACHI S-4300), and an average particle diameter (D50) is calculated | required. (Unit: nm).
　＜飽和磁化、残留磁化＞
　得られたニッケル粉末およびニッケル粉末について、試料振動型磁力計を用いて、飽和磁化および残留磁化を測定した（単位：ｅｍｕ／ｇ）。 <Saturation magnetization, residual magnetization>
The obtained nickel powder and nickel powder were measured for saturation magnetization and remanent magnetization using a sample vibration magnetometer (unit: emu / g).
　＜二次粒子径（Ｄ５０）＞
　得られたニッケル粉末およびニッケル粉末について、日機装社製のレーザー粒度測定装置（マイクロトラック）を用いて、二次粒子の粒子径を測定し、平均粒子径（Ｄ５０）を求めた（単位：ｎｍ）。 <Secondary particle diameter (D50)>
About the obtained nickel powder and nickel powder, the particle size of the secondary particles was measured using a laser particle size measuring device (Microtrack) manufactured by Nikkiso Co., Ltd., and the average particle size (D50) was determined (unit: nm). .
　＜焼結温度＞
　得られたニッケル粉末およびニッケル粉末の焼結温度（単位：℃）を求めた。具体的には、まず、得られた粉末５ｇに対して１０％ＰＶＡ水溶液０．２５ｍＬを、添加混合し、乾燥した後、０．５８ｇを量り取り、６ｋＮでプレス整形して７ｍｍφのペレットを作製した。次に、作製したペレットを、窒素ガスをベースとした水素０．１２％あるいは窒素ガスをベースとした水素３％のガス雰囲気で、１０℃／ｍｉｎで昇温させた。これにより、ペレットの体積は徐々に縮んでいく。
　図５は、ニッケル粉末の温度と体積変化率との関係を示すグラフである。なお、図５のグラフには、得られたニッケル粉末のうちの数例のみを挙げて示している。
　図５に示すように、温度（単位：℃）と体積変化率（単位：％）とをグラフに取り、体積変化が起こる前後の温度領域の接線（図５中には図示せず）を引き、２つの接線が交わる点の温度を、焼結温度として求めた。 <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 mmφ 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.
As shown in FIG. 5, 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す結果から明らかなように、ａ軸長が３．５３０Å以上３．６００Å未満である実施例１～９と、ａ軸長が３．５３０Å未満である比較例１～４とを対比すると、実施例１～９は、比較例１～４よりも、残留磁化を低減でき、二次粒子径が小さくなる傾向が見られた。なお、ジルコニウムは全試料で検出下限の１０ｐｐｍ未満であった。
　また、実施例１～９は、比較例１～４よりも、焼結温度が高くなることが分かった。
 
なお、ＰＶＤ法によってスズ２０質量％を添加したニッケル粉末を作製した所、軸長が３．６００Åを超えても「準安定状態」の単相の粉末を得る事ができた。しかし、熱履歴を受けた後の試料のスズの分布をエネルギー分散型Ｘ線分光法（ＥＤＸ）を用いて観察した所、スズの濃い領域と薄い領域の２相に分かれていた。電極ペーストを焼成する際にも同様な熱履歴がかかるので好ましくない。なお、軸長が３．６００Å以下の試料では焼結温度の測定の熱履歴で２相に分かれた試料は無かった。
　 As is clear from the results shown in Table 1, 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.

When a nickel powder to which 20% by mass of tin was added by the PVD method was produced, a “metastable state” single-phase powder could be obtained even when the axial length exceeded 3.600 mm. However, when the distribution of tin in the sample after receiving the thermal history was observed using energy dispersive X-ray spectroscopy (EDX), it was divided into two phases, a tin-rich region and a thin region. A similar heat history is also applied when firing the electrode paste, which is not preferable. In the samples with an axial length of 3.600 mm or less, there were no samples that were divided into two phases according to the thermal history of the sintering temperature measurement.
　ニッケル粉末の焼成時の水素濃度の焼結温度に与える影響を調べるために以下のような調査も行った。一次粒子径のＤ50が220nmの硫黄を0.2％添加したニッケル粉末(比較例５)と一次粒子径のＤ50が230nmのスズ５質量％添加したニッケル粉末(実施例１０)を作製し、焼結温度を比較した。スズ無添加のニッケル粉末の場合は水素0.12%雰囲気での焼結温度は480℃であったのに対して水素を3％まで増加させると焼結温度は310℃と低下した。スズを添加したニッケル粉末の場合は水素0.12％雰囲気での焼結温度は550℃であったのに対して水素3％雰囲気での焼結温度は540℃とあまり変化しなかった。
 
次に、実施例６のニッケル粉末を用いて、水素濃度を変えて、焼結温度を測定した。具体的には、上記と同様にして、ペレットを作製して焼結温度を求めたが、このとき、窒素ガスをベースとしたガス雰囲気の水素を０．１２％または３％として、焼結温度を求めた。結果を図６に示す。
　図６は、実施例６のニッケル粉末末の温度と体積変化率との関係を示すグラフである。図６のグラフに示すように、実施例６のニッケル粉末においては、水素濃度を０．１２％から３％に上げても焼結温度は変化せず、高い水素濃度でも焼結温度の低下が抑制できることが分かった。
  In order to investigate the influence of the hydrogen concentration upon sintering of the nickel powder on the sintering temperature, the following investigation was also conducted. 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. Compared. In the case of nickel powder without addition of tin, 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%. In the case of nickel powder to which tin was added, the sintering temperature in a hydrogen 0.12% atmosphere was 550 ° C., whereas the sintering temperature in a hydrogen 3% atmosphere was not much changed to 540 ° C.

Next, using the nickel powder of Example 6, the sintering temperature was measured while changing the hydrogen concentration. Specifically, pellets were produced in the same manner as described above, and the sintering temperature was determined. At this time, hydrogen in a gas atmosphere based on nitrogen gas was set to 0.12% or 3%, and the sintering temperature was determined. Asked. The results are shown in FIG.
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.
　次に、比較例１のニッケル粉末および実施例２のニッケル粉末について、インピーダンスの周波数依存性を調べた。具体的には、比較例１で得られた粉末を分級したニッケル粉末、または、実施例２で得られた未分級のニッケル粉末４０ｇに対して、分散剤（ＫＤ－１２、クローダ・ジャパン社製）１．４４ｇ、バインダ（ＴＥ－４５、ヤスハラケミカル社製）３１．２５ｇ、および、溶剤（ターピネオールＣ）２７．３１ｇを配合し、導電ペーストを得た。次に、得られた導電ペーストを、ガラス基板上に塗布した後、６５０℃で１０分焼成することにより、１０μｍ厚の膜状の試料を作製した。作製した試料について、インピーダンス測定器を用いてインピーダンス（単位：Ω）を測定し、周波数（単位：ｋＨｚ）との関係をプロットしてグラフ化した。
　図７は、ニッケル粉末の周波数とインピーダンスとの関係を示すグラフであり、（Ａ）は比較例１、（Ｂ）は実施例２である。図７のグラフに示すように、スズを添加した実施例２のニッケル粉末においては、比較例１と比べて、インピーダンスは増加しているものの、周波数が増加してもインピーダンスの増加量は小さく、高周波領域でも低インピーダンスで使うことができることが分かった。 Next, the frequency dependence of impedance was examined for the nickel powder of Comparative Example 1 and the nickel powder of Example 2. Specifically, a dispersing agent (KD-12, manufactured by Croda Japan Co., Ltd.) 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. Next, after apply | coating the obtained electrically conductive paste on a glass substrate, the film-shaped sample of 10 micrometers thickness was produced by baking for 10 minutes at 650 degreeC. About the produced sample, the impedance (unit: Ω) was measured using an impedance measuring instrument, and the relationship with the frequency (unit: kHz) was plotted and plotted.
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. As shown in the graph of FIG. 7, in the nickel powder of Example 2 to which tin was added, although the impedance was increased as compared with Comparative Example 1, 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.
　次に、比較例１のニッケル粉末および実施例２のニッケル粉末を用いて得られた上記導電ペーストを用いて、積層セラミックコンデンサを作製し、積層評価を行った。積層条件として、誘電体は０．２μｍのＢＴ粉を用いたＸ５Ｒ特性材とし、シート厚さ３μｍ、形状は３２２５タイプで積層数は５層、焼成温度１２２０℃、水素０．９％、Ｗｅｔｔｅｒ３５℃とした。
　作製した積層セラミックコンデンサについて、ＬＣＲメーターを用いて誘電損失（ＤＦ、単位：％）を測定し、絶縁抵抗計を用いて絶縁抵抗（単位：×１０１０Ω）を測定した。なお、各例ともにコンデンサを５個作製し、５個の測定結果を求めた。結果を下記第２表に示す。 Next, 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. As for the lamination conditions, the dielectric is an X5R characteristic material using BT powder of 0.2 μm, the sheet thickness is 3 μm, the shape is 3225 type, the number of lamination is 5 layers, the firing temperature is 1220 ° C., the hydrogen is 0.9%, and the Wetter is 35 ° C. It was.
With respect to the produced multilayer ceramic capacitor, dielectric loss (DF, unit:%) was measured using an LCR meter, and insulation resistance (unit: × 10 10 Ω) was measured using an insulation resistance meter. In each example, five capacitors were prepared, and five measurement results were obtained. The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表２に示すように、実施例２の誘電損失（ＤＦ）は、比較例１の約３．３％から、約３．１％に低減できたことが分かった。また、実施例２の絶縁抵抗の値は比較例１と比べて安定していることが分かった。これにより、コンデンサの歩留まりや性能を安定させることができる。
　高周波でのインピーダンスの上昇幅が小さいこと（図７参照）、ＤＦが小さいことの２点により、コンデンサとした際に、高周波での発熱ロスが抑えられ、使用できる周波数の上限を広げることができる。 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. .
　１　　ＰＶＤ装置
　２　　電極
　３　　アーク
　４　　試料
　５　　試料支持台
　６　　熱交換器
　７　　捕集用フィルタ
　８　　循環ポンプ
　９　　トーチ用流量計
１０　　チャンバ用流量計
１１　　チャンバ
１２　　捕集器
１３　　トーチ
１４　　ライン
１４ａ　分岐ライン
１５　　ライン
３１　　マイクロリアクタ
３２　　電気炉
３３　　石英反応管
３４　　水素ガスノズル
３５　　キャリア窒素ガスノズル
３６　　試料ボート
３７　　反応部
  DESCRIPTION OF SYMBOLS 1 PVD apparatus 2 Electrode 3 Arc 4 Sample 5 Sample support stand 6 Heat exchanger 7 Filter for collection 8 Circulating pump 9 Flow meter for torch 10 Flow meter for chamber 11 Chamber 12 Collector 13 Torch 14 Line 14a Branch line 15 Line 31 Microreactor 32 Electric furnace 33 Quartz reaction tube 34 Hydrogen gas nozzle 35 Carrier nitrogen gas nozzle 36 Sample boat 37 Reaction section

Claims (3)

  1. 　積層セラミック電子部品の内部電極に用いるニッケル粉末であって、
    　Ｘ線回折によって面心立方格子（ＦＣＣ）構造のピークが得られ、
    　ａ軸長が３．５３０Å以上３．６００Å未満であり、
    　ニッケルの含有率が５０質量％以上である、ニッケル粉末。     Nickel powder used for internal electrodes of multilayer ceramic electronic components,
    The peak of the face-centered cubic lattice (FCC) structure is obtained by X-ray diffraction,
    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.
  2. 　請求項１に記載のニッケル粉末を用いた導電ペースト。 A conductive paste using the nickel powder according to claim 1.
  3. 　請求項２に記載の導電ペーストを用いて内部電極を形成した積層セラミック電子部品。
          A multilayer ceramic electronic component in which an internal electrode is formed using the conductive paste according to claim 2.
PCT/JP2013/006702 2012-11-20 2013-11-14 Nickel powder, conductive paste, and laminated ceramic electronic component WO2014080600A1 (en)

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