US20130175176A1 - FLAT Ni PARTICLE, LAMINATED CERAMIC ELECTRONIC COMPONENT USING FLAT Ni PARTICLE, AND PRODUCTION METHOD FLAT Ni PARTICLE - Google Patents
FLAT Ni PARTICLE, LAMINATED CERAMIC ELECTRONIC COMPONENT USING FLAT Ni PARTICLE, AND PRODUCTION METHOD FLAT Ni PARTICLE Download PDFInfo
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- US20130175176A1 US20130175176A1 US13/782,447 US201313782447A US2013175176A1 US 20130175176 A1 US20130175176 A1 US 20130175176A1 US 201313782447 A US201313782447 A US 201313782447A US 2013175176 A1 US2013175176 A1 US 2013175176A1
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- 239000002245 particle Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000919 ceramic Substances 0.000 title abstract description 32
- 230000005484 gravity Effects 0.000 claims abstract description 5
- 238000007747 plating Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 115
- 239000000243 solution Substances 0.000 description 35
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000003985 ceramic capacitor Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 7
- 239000002003 electrode paste Substances 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 6
- 230000002950 deficient Effects 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000007847 structural defect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- 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
- H01G4/0085—Fried electrodes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a flat Ni particle, and more particularly, relates to a flat Ni particle which has a large specific surface area.
- the present invention relates to a laminated ceramic electronic component formed using the flat Ni particle.
- the present invention relates to a method for producing the flat Ni particle.
- Methods for producing a flat (flake form) metal powder such as Ni particles which have excellent mass production productivity, include a method for producing a metal powder disclosed in Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-328270).
- This method for producing a metal powder uses electroless plating, and includes the following steps:
- the production method produces a metal powder of 0.01 to 0.5 ⁇ m in thickness and 1 to 300 ⁇ m in diameter.
- Ni particles produced by the method for producing a metal powder disclosed in Patent Document 1 are flat in shape and thin.
- the internal electrodes can be reduced in layer thickness.
- the Ni particle produced by the method for producing a metal powder disclosed in Patent Document 1 has a quite smooth surface, and thus, when a binder containing this Ni particle is used to form internal electrodes of a laminated ceramic electronic component, the binder is not sufficiently released to the surroundings during the binder removal, and there is a possibility that the resulting laminated ceramic electronic component will have structural defects.
- the laminated ceramic electronic component is produced by, for example, applying a Ni paste containing the Ni particle onto surfaces of ceramic green sheets to become internal electrodes, stacking the ceramic green sheets to prepare a raw laminated body, and firing the raw laminated body. Prior to the firing, the raw laminated body is heated at a predetermined temperature to release unnecessary binder contained in the raw laminated body, that is, a binder removal step is effected.
- a binder removal step is effected.
- the flat Ni particle produced by the method for producing a metal powder disclosed in Patent Document 1 is used in the Ni paste for internal electrodes, the release of the unnecessary binder to the outside is sometimes obstructed by the Ni particle with a quite smooth surface which acts as an obstacle in the binder removal step.
- the laminated ceramic electronic component subjected to firing with remaining unnecessary binder has structural defects as a consequence of this characteristic, and has a decreased proportion of non-defective products, thus leading to a problem of insufficiency for practical use.
- the flat Ni particle preferably has a thickness of 100 nm or less, and further, more preferably of 50 nm or less. This is because when the flat Ni particle is used for internal electrodes of a laminated ceramic electronic component, the reduction of the internal electrodes in layer thickness can be promoted.
- a laminated ceramic electronic component according to the present invention is adapted to use the flat Ni particle described above for internal electrodes.
- a method for producing the flat Ni particle according to the present invention comprises the steps of: preparing (providing) a positive electrode and a negative electrode; immersing the positive electrode and the negative electrode in a Ni plating solution; applying an electric current between the positive electrode and negative electrode immersed in the Ni plating solution to form a Ni film on the surface of the negative electrode; separating the Ni film formed on the surface of the negative electrode; and grinding the separated Ni film to obtain a Ni particle, wherein the temperature of the negative electrode is adjusted to be 10° C. or more lower than the temperature of the Ni plating solution at the point of the Ni plating. It is to be noted that the temperature of the negative electrode is more preferably 20° C. or more lower than the temperature of the Ni plating solution at the point of immersing the positive electrode and the negative electrode in the Ni plating solution.
- the flat Ni particle according to the present invention has a large specific surface area, and has some degree of surface asperity. Thus, when the flat Ni particle is used for internal electrodes of a laminated ceramic electronic component, unnecessary binder can be released from gaps formed by the surface asperity during binder removal. With this result, the produced laminated ceramic electronic component can avoid structural defects.
- the laminated ceramic electronic component according to the present invention has a high proportion of non-defective products.
- the method for producing a flat Ni particle according to the present invention can produce the above-described flat Ni particle according to the present invention.
- FIG. 1 is a cross-sectional view illustrating a step for use in the production of Ni particles according to Examples 1 and 2.
- FIG. 2 is a SEM photograph showing a Ni film deposited in Example 1.
- FIG. 3 is a cross-sectional view illustrating a laminated ceramic capacitor (laminated ceramic electronic component) according to Example 3.
- FIG. 1 is a cross-sectional view illustrating one of production steps in the production of a flat Ni particle according to Example 1.
- Example 1 a plurality of Ni chips 2 were put in a titanium anode case 1 whose dimensions were 200 mm in width, 220 mm in length, and 30 mm in height for achieving a positive electrode 3 .
- a titanium plate of 100 nm in width, 200 mm in length, and 5 mm in thickness was subjected to mirror finishing to achieve a negative electrode 4 .
- a chlorinated Ni bath of NiCl.6H 2 O: 400 g/l and H 3 BO 3 : 35 g/l in composition at pH 4.2 was prepared as a Ni plating solution (electrolytic solution) 5 .
- the Ni plating solution 5 heated to 60° C. was put in a vinyl chloride tank 6 , and the positive electrode 3 and the negative electrode 4 were immersed in the Ni plating solution 5 , and arranged so as to be opposed to each other.
- the negative electrode 4 used had been kept at 40° C. in advance of being immersed. More specifically, the negative electrode 4 made 20° C. lower than the Ni plating solution 5 at the point of the immersion in the Ni plating solution 5 .
- a shield plate 7 of vinyl chloride was placed in the tank 6 so as to cover the bottom and the right and left ends of the negative electrode (titanium plate) 4 in order to make the film thickness distribution uniform.
- an electric current was applied by a power source 8 between the positive electrode 3 and the negative electrode 4 to form a Ni film on the surface of the negative electrode 4 .
- the electric current was adjusted to Dk: 30 A/dm 2 , and the electric current value was adjusted to 54 A. It is to be noted that the plating time (cumulative time) was varied in the range of 145 milliseconds to 485 milliseconds.
- FIG. 2 shows a SEM photograph of the Ni film separated and collected. From the SEM photograph, grains of deposited particles can be observed. The Ni film had almost no pinholes observed, and was a film with few defects.
- the measured specific surface area S 1 of the Ni particle was, for example, 18.9 m 2 /g in the case of 25 nm in thickness and 2.0 ⁇ m in average particle diameter. It is to be noted that the specific surface area S 1 was measured by the BET method. The thickness was also measured with a fluorescent X-ray film thickness meter. In addition, the average particle diameter was obtained by observing the Ni film through a SEM, measuring the longer diameter of each Ni particle from the photograph, and regarding this longer diameter as the length of a diagonal line in the case of assuming the planar shape to be a square.
- the ratio (S 1 /S 0 ) of the actually measured specific surface area S 1 to the theoretical specific surface area S 0 in the case of assuming the surface to be completely smooth was determined.
- the ratio (S 1 /S 0 ) was 2.05.
- Table 1 shows the ratio (S 1 /S 0 ) of the actually measured specific surface area S 1 to the theoretical specific surface area S 0 in the case of varying the plating time (cumulative time) in order to vary the thickness of the Ni particle produced and the average particle diameter.
- the first term means the area of the front and back of a flat metal particle (Ni particle)
- the second term means the area of the side thereof
- the second term has a lower contribution ratio
- the first term accounts for most of the surface area.
- the ratio between the first term and the second term is 97:3 in the case of crushing a Ni film of 25 nm in thickness into a square of 2.0 ⁇ m in diagonal size, and it is determined that the first term is a prime factor.
- the value of the specific surface area in the case of an average particle diameter on the order of several ⁇ m can be considered to represent a feature of the deposited metal film (Ni film), rather than representing a grinding state.
- the ratio (S 1 /S 0 ) of the actually measured specific surface area S 1 to the theoretical specific surface area S 0 is 1.60 at a minimum and 2.08 at a maximum, and it is determined therefrom that the flat Ni particle according to the present example has a large surface area, and has large front and back surface asperity to some extent.
- Example 2 the temperature of the negative electrode 4 in the immersion in the Ni plating solution 5 was varied between 20 and 65° C. On the other hand, the temperature of the Ni plating solution 5 was kept at a constant temperature of 60° C.
- temperature of the negative electrode 4 approaches 60° C., in such a way that the negative electrode 4 is immersed in the Ni plating solution 5 , and then heated by the Ni plating solution 5 or cooled by the Ni plating solution, while the deposition of the Ni film is completed before the temperature of the negative electrode 4 reaches 60° C. if there is a large difference in temperature between the negative electrode 4 and the Ni plating solution 5 to some extent, because of the short plating time of 1 second or less.
- Example 2 the plating time (cumulative time) in Example 2 was also varied in order to vary the thickness of the Ni film.
- the other conditions in Example 2 were set in the same way as in Example 1.
- Table 2 shows the relationship of whether or not it is possible to separate and collect respective Ni films of 25 nm, 50 nm, and 100 nm in thickness, with the difference in temperature between the negative electrode 4 and the Ni plating solution 5 .
- the mark “ ⁇ ” means a good product
- the mark “ ⁇ ” means a partially defective product
- the mark “x” means a defective product.
- the temperature of the negative electrode 4 was 10° C. lower than the temperature of the Ni plating solution 5 , it was possible to separate and collect the Ni film of 50 nm in thickness, and it was also partially possible to separate and collect the Ni film of 25 nm or less in thickness.
- the temperature of the negative electrode 4 was 20° C. lower than the temperature of the Ni plating solution 5 , it was possible to separate and collect the respective Ni films of 100 nm, 50 nm, and 25 nm in thickness.
- the temperature of the negative electrode 4 is preferably 10° C. or more lower than the temperature of the Ni plating solution 5 in order to separate and collect the Ni film of 50 nm in thickness.
- the temperature of the negative electrode 4 is preferably 20° C. or more lower than the temperature of the Ni plating solution 5 in order to separate and collect the Ni film of 25 nm in thickness.
- the reason that thinner Ni films can be separated and collected when the temperature of the negative electrode 4 is lower than the temperature of the Ni plating solution 5 can be considered as follows.
- the vicinity of the plating interface is likely to be a diffusion-controlled environment.
- the effect of facilitating the separation and collection was not produced.
- the ability to separate and collect the thin Ni films is not considered to be due to the effect of the plating solution interface.
- the temperature of the negative electrode 4 made lower than the temperature of the Ni plating solution 5 increases the strain between the deposited Ni film and the negative electrode 4 , thereby making the Ni film likely to be separated. Therefore, the increased difference in temperature between the negative electrode 4 and the Ni plating solution 5 makes it possible to separate thinner Ni films.
- Ni plating solution 5 a totally chlorinated Ni bath was used in the present example as the Ni plating solution 5 , and the Ni films deposited from this bath are large in internal stress. Although the reason thereof is not known, the selection of the bath is also considered to make an effective contribution.
- FIG. 3 is a cross-sectional view illustrating the laminated ceramic capacitor.
- This laminated ceramic capacitor has a structure of a ceramic body 9 containing barium titanate or the like as its main constituent in the shape of a rectangular parallelepiped, which has therein alternately arranged internal electrodes 10 exposed at one end surface and internal electrodes 11 exposed at the other end surface, and has an external electrode 11 formed on one end surface of the ceramic body 9 to provide electrical conduction to the internal electrodes 10 and an external electrode 13 formed on the other end surface of the ceramic body 9 to provide electrical conduction to the internal electrodes 11 .
- the flat Ni particle of 25 nm in thickness, produced in Example 1 was used as a material for the internal electrodes 10 , 11 .
- the flat Ni particle was dispersed in a resin and a solvent to create an electrode paste.
- the resin may be any type, and acrylic resins, cellulosic resins, butyral resins, alkyd resins, etc. can be used singularly or in a mixture.
- the solvent may also be any type, and glycols, terpineol, cellosolves, acetic esters, etc. can be used.
- green sheets were prepared which had a barium titanate-based ceramic dispersed in an organic binder.
- large mother green sheets were prepared from which a large number of green sheets could be obtained.
- the mother green sheets with the internal electrodes printed thereon and the mother green sheets with no internal electrodes printed thereon were stacked in a predetermined order, and subjected to pressure bonding to obtain a large unfired ceramic body including therein the electrode paste for internal electrodes.
- This large ceramic body is intended to allow a plurality of ceramic bodies to be obtained therefrom.
- the large unfired ceramic body was then cut into a plurality of unfired ceramic bodies.
- the cut unfired ceramic bodies were heated at a predetermined temperature to release unnecessary binder in the ceramic bodies to the outside surroundings (binder removal step), and subsequently subjected to firing in accordance with a predetermined profile (firing step), thereby achieving the ceramic body 9 with the internal electrodes 10 , 11 formed therein.
- the green sheets constituting the unfired ceramic bodies and the electrode paste for the internal electrodes are fired at the same time.
- the electrode paste was applied onto both ends of the ceramic body 9 , and subjected to firing to form the external electrodes 12 , 13 .
- the electrode paste may be any type, and copper alloys, silver, silver alloys, nickel, nickel alloys, etc. can be used in addition to copper.
- the laminated ceramic capacitor produced by the production method described above uses the flat Ni particle produced in Example 1 for the material of the internal electrodes.
- This Ni particle has a large specific surface area, and has large surface asperity to some extent. Therefore, during in the binder removal in the process of producing this laminated ceramic capacitor, unnecessary binder is released efficiently from gaps formed by the surface asperity to the both sides of the internal electrodes 10 , 11 . With this result, this laminated ceramic capacitor has no structural defective caused by an unnecessary binder remaining in firing.
- the Ni particle used for the internal electrodes is flat in shape and small in thickness, and thus makes a contribution to the reduction of this laminated ceramic capacitor thickness.
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- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Electrolytic Production Of Metals (AREA)
Abstract
Provided is a flat Ni particle which has a large specific surface area, permitting efficient binder removal when the flat Ni particle is used for internal electrodes of a laminated ceramic electronic component. The flat Ni particle has a thickness t (m), a specific gravity ρ (g/m3), and a radius r (m), and a specific surface area S1 (m2/g), such that the specific surface area S1 is adapted to have a relationship of 1.5×S0<S1<1.9×S0 with a theoretical specific surface area in the case of assuming a surface to be completely smooth, represented by S0=2/(ρ×t)+2√2/(ρ×r)(m2/g).
Description
- This is a divisional of application Ser. No. 13/403,136, filed Feb. 23, 2012, which is a continuation of application Serial No. PCT/JP2010/067253, filed Oct. 1, 2010, the entire contents of which are incorporated herein by reference.
- The present invention relates to a flat Ni particle, and more particularly, relates to a flat Ni particle which has a large specific surface area.
- In addition, the present invention relates to a laminated ceramic electronic component formed using the flat Ni particle.
- Furthermore, the present invention relates to a method for producing the flat Ni particle.
- Methods for producing a flat (flake form) metal powder such as Ni particles, which have excellent mass production productivity, include a method for producing a metal powder disclosed in Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-328270).
- This method for producing a metal powder uses electroless plating, and includes the following steps:
- 1) providing a mold release layer on the surface of a substrate;
- 2) providing and activating a catalyst on the surface of the mold release layer;
- 3) generating an electroless plating film through contact with an electroless plating solution;
- 4) bringing the substrate with the electroless plating film into contact with a catalyst to dissolve and remove the mold release, and thereby separate the electroless plating film from the substrate; and
- 5) grinding the separated electroless plating film to obtain a metal powder.
- The production method produces a metal powder of 0.01 to 0.5 μm in thickness and 1 to 300 μm in diameter.
- For example, Ni particles produced by the method for producing a metal powder disclosed in
Patent Document 1 are flat in shape and thin. Thus, when the Ni particles are used for internal electrodes of a laminated ceramic electronic component, the internal electrodes can be reduced in layer thickness. -
- Patent Document 1: Japanese Patent Application Laid-Open No. 2006-328270
- The Ni particle produced by the method for producing a metal powder disclosed in
Patent Document 1 has a quite smooth surface, and thus, when a binder containing this Ni particle is used to form internal electrodes of a laminated ceramic electronic component, the binder is not sufficiently released to the surroundings during the binder removal, and there is a possibility that the resulting laminated ceramic electronic component will have structural defects. - More specifically, the laminated ceramic electronic component is produced by, for example, applying a Ni paste containing the Ni particle onto surfaces of ceramic green sheets to become internal electrodes, stacking the ceramic green sheets to prepare a raw laminated body, and firing the raw laminated body. Prior to the firing, the raw laminated body is heated at a predetermined temperature to release unnecessary binder contained in the raw laminated body, that is, a binder removal step is effected. However, when the flat Ni particle produced by the method for producing a metal powder disclosed in
Patent Document 1 is used in the Ni paste for internal electrodes, the release of the unnecessary binder to the outside is sometimes obstructed by the Ni particle with a quite smooth surface which acts as an obstacle in the binder removal step. Further, the laminated ceramic electronic component subjected to firing with remaining unnecessary binder has structural defects as a consequence of this characteristic, and has a decreased proportion of non-defective products, thus leading to a problem of insufficiency for practical use. - The present invention has been achieved in order to remedy the problem of the conventional method for producing metal powder (Ni particle), and a flat Ni particle which has a thickness t (m), a specific gravity ρ (g/m3), and a radius r (m) (obtained from half the length of a diagonal line in the case of assuming the planar shape to be a square), and a specific surface area S1 (m2/g), in which the specific surface area S1 has a relationship of 1.5×S0<S1<2.1×S0, with the theoretical specific surface area when assuming the surface to be completely smooth is represented by S0 and is =2/(ρ×t)+2√2/(ρ×r)(m2/g). It is to be noted that the flat Ni particle preferably has a thickness of 100 nm or less, and further, more preferably of 50 nm or less. This is because when the flat Ni particle is used for internal electrodes of a laminated ceramic electronic component, the reduction of the internal electrodes in layer thickness can be promoted.
- In addition, a laminated ceramic electronic component according to the present invention is adapted to use the flat Ni particle described above for internal electrodes.
- In addition, a method for producing the flat Ni particle according to the present invention comprises the steps of: preparing (providing) a positive electrode and a negative electrode; immersing the positive electrode and the negative electrode in a Ni plating solution; applying an electric current between the positive electrode and negative electrode immersed in the Ni plating solution to form a Ni film on the surface of the negative electrode; separating the Ni film formed on the surface of the negative electrode; and grinding the separated Ni film to obtain a Ni particle, wherein the temperature of the negative electrode is adjusted to be 10° C. or more lower than the temperature of the Ni plating solution at the point of the Ni plating. It is to be noted that the temperature of the negative electrode is more preferably 20° C. or more lower than the temperature of the Ni plating solution at the point of immersing the positive electrode and the negative electrode in the Ni plating solution.
- The flat Ni particle according to the present invention has a large specific surface area, and has some degree of surface asperity. Thus, when the flat Ni particle is used for internal electrodes of a laminated ceramic electronic component, unnecessary binder can be released from gaps formed by the surface asperity during binder removal. With this result, the produced laminated ceramic electronic component can avoid structural defects.
- In addition, the laminated ceramic electronic component according to the present invention has a high proportion of non-defective products.
- Also, the method for producing a flat Ni particle according to the present invention can produce the above-described flat Ni particle according to the present invention.
-
FIG. 1 is a cross-sectional view illustrating a step for use in the production of Ni particles according to Examples 1 and 2. -
FIG. 2 is a SEM photograph showing a Ni film deposited in Example 1. -
FIG. 3 is a cross-sectional view illustrating a laminated ceramic capacitor (laminated ceramic electronic component) according to Example 3. - Embodiments of the present invention will be described below.
-
FIG. 1 is a cross-sectional view illustrating one of production steps in the production of a flat Ni particle according to Example 1. - In Example 1, a plurality of
Ni chips 2 were put in atitanium anode case 1 whose dimensions were 200 mm in width, 220 mm in length, and 30 mm in height for achieving apositive electrode 3. - In addition, a titanium plate of 100 nm in width, 200 mm in length, and 5 mm in thickness was subjected to mirror finishing to achieve a
negative electrode 4. - Also, a chlorinated Ni bath of NiCl.6H2O: 400 g/l and H3BO3: 35 g/l in composition at pH 4.2 was prepared as a Ni plating solution (electrolytic solution) 5.
- Then, the
Ni plating solution 5 heated to 60° C. was put in avinyl chloride tank 6, and thepositive electrode 3 and thenegative electrode 4 were immersed in theNi plating solution 5, and arranged so as to be opposed to each other. It is to be noted that thenegative electrode 4 used had been kept at 40° C. in advance of being immersed. More specifically, thenegative electrode 4 made 20° C. lower than theNi plating solution 5 at the point of the immersion in theNi plating solution 5. In addition, ashield plate 7 of vinyl chloride was placed in thetank 6 so as to cover the bottom and the right and left ends of the negative electrode (titanium plate) 4 in order to make the film thickness distribution uniform. - Next, while circulating the
Ni plating solution 5 with a pump, an electric current was applied by apower source 8 between thepositive electrode 3 and thenegative electrode 4 to form a Ni film on the surface of thenegative electrode 4. The electric current was adjusted to Dk: 30 A/dm2, and the electric current value was adjusted to 54 A. It is to be noted that the plating time (cumulative time) was varied in the range of 145 milliseconds to 485 milliseconds. - Immediately after the formation of the Ni film, the
negative electrode 4 was pulled out of thetank 6, and washed under running water to separate and collect the Ni film from thenegative electrode 4.FIG. 2 shows a SEM photograph of the Ni film separated and collected. From the SEM photograph, grains of deposited particles can be observed. The Ni film had almost no pinholes observed, and was a film with few defects. - When this Ni film was suspended in an aqueous solution and crushed by an ultrasonic homogenizer, a flat Ni particle according to the present example was obtained after a few seconds.
- The measured specific surface area S1 of the Ni particle was, for example, 18.9 m2/g in the case of 25 nm in thickness and 2.0 μm in average particle diameter. It is to be noted that the specific surface area S1 was measured by the BET method. The thickness was also measured with a fluorescent X-ray film thickness meter. In addition, the average particle diameter was obtained by observing the Ni film through a SEM, measuring the longer diameter of each Ni particle from the photograph, and regarding this longer diameter as the length of a diagonal line in the case of assuming the planar shape to be a square.
- From the thickness t (m), specific gravity ρ (g/m3), the radius r (m) of the Ni particle, the theoretical specific surface area S0 in the case of assuming the surface to be completely smooth was found, with S0 being represented by 2/(ρ×t)+2√2/(ρ×r)(m2/g). It is to be noted that the specific gravity ρ of the Ni particle was considered 8.85×106.
- Then the ratio (S1/S0) of the actually measured specific surface area S1 to the theoretical specific surface area S0 in the case of assuming the surface to be completely smooth was determined. In the case of 25 nm thickness, 2.0 μm in average particle diameter, and 18.9 m2/g in specific surface area S1 as mentioned previously, the ratio (S1/S0) was 2.05.
- Table 1 shows the ratio (S1/S0) of the actually measured specific surface area S1 to the theoretical specific surface area S0 in the case of varying the plating time (cumulative time) in order to vary the thickness of the Ni particle produced and the average particle diameter.
-
TABLE 1 Average Specific Theoretical particle Surface specific Thickness diameter area S1 surface area S2 Ratio No. (nm) (μm) (m2/g) (m2/g) (S1/S20) 1-1 25 2.0 18.9 9.2 2.05 1-2 25 1.5 19.2 9.3 2.08 1-3 35 2.1 10.6 6.6 1.60 1-4 35 1.4 12.6 6.7 1.88 1-5 50 2.3 8.3 4.7 1.78
The thickness of the Ni particle was varied in the range of 15 to 50 nm, whereas the average particle diameter was varied in the range of 1.4 to 2.3 μm, and the ratio (S1/S0) of the actually measured specific surface area S1 to the theoretical specific surface area S0 was 1.60 at a minimum and 2.08 at a maximum. - In the formula S0=2/(ρ×t)+2√2/(ρ×r)(m2/g), which represents the theoretical specific surface area S0 in the case of assuming the surface to be completely smooth, the first term (the first half section) means the area of the front and back of a flat metal particle (Ni particle), whereas the second term (the second half section) means the area of the side thereof, the second term has a lower contribution ratio, and the first term accounts for most of the surface area. For example, the ratio between the first term and the second term is 97:3 in the case of crushing a Ni film of 25 nm in thickness into a square of 2.0 μm in diagonal size, and it is determined that the first term is a prime factor. Also for this reason, the value of the specific surface area in the case of an average particle diameter on the order of several μm can be considered to represent a feature of the deposited metal film (Ni film), rather than representing a grinding state.
- Furthermore, as described above, the ratio (S1/S0) of the actually measured specific surface area S1 to the theoretical specific surface area S0 is 1.60 at a minimum and 2.08 at a maximum, and it is determined therefrom that the flat Ni particle according to the present example has a large surface area, and has large front and back surface asperity to some extent.
- In Example 2, the temperature of the
negative electrode 4 in the immersion in theNi plating solution 5 was varied between 20 and 65° C. On the other hand, the temperature of theNi plating solution 5 was kept at a constant temperature of 60° C. - It is to be noted that temperature of the
negative electrode 4 approaches 60° C., in such a way that thenegative electrode 4 is immersed in theNi plating solution 5, and then heated by theNi plating solution 5 or cooled by the Ni plating solution, while the deposition of the Ni film is completed before the temperature of thenegative electrode 4 reaches 60° C. if there is a large difference in temperature between thenegative electrode 4 and theNi plating solution 5 to some extent, because of the short plating time of 1 second or less. - In addition, the plating time (cumulative time) in Example 2 was also varied in order to vary the thickness of the Ni film. The other conditions in Example 2 were set in the same way as in Example 1.
- Table 2 shows the relationship of whether or not it is possible to separate and collect respective Ni films of 25 nm, 50 nm, and 100 nm in thickness, with the difference in temperature between the
negative electrode 4 and theNi plating solution 5. In the table, the mark “◯” means a good product, the mark “Δ” means a partially defective product, and the mark “x” means a defective product. -
TABLE 2 Whether Whether Whether Difference possible possible possible in or not to or not to or not to Tem- Tem- temperature separate separate separate perature perature (Negative and and and of of Ni electrode − collect Ni collect Ni collect Ni negative plating Ni plating film of film of film of electrode solution solution) 25 nm in 50 nm in 100 nm in No. (° C.) (° C.) (° C.) thickness thickness thickness 2-1 65 60 5 x x ○ 2-2 60 60 0 x x ○ 2-3 50 60 −10 Δ ○ ○ 2-4 40 60 −20 ○ ○ ○ 2-5 30 60 −30 ○ ○ ○ 2-6 20 60 −40 ○ ○ ○
The Table shows that when the temperature of thenegative electrode 4 was higher than or equal to the temperature of theNi plating solution 5, it was possible to separate and collect the Ni film of 100 nm in thickness, while it was not possible to separate and collect the Ni films of 50 nm or less in thickness. - When the temperature of the
negative electrode 4 was 10° C. lower than the temperature of theNi plating solution 5, it was possible to separate and collect the Ni film of 50 nm in thickness, and it was also partially possible to separate and collect the Ni film of 25 nm or less in thickness. - When the temperature of the
negative electrode 4 was 20° C. lower than the temperature of theNi plating solution 5, it was possible to separate and collect the respective Ni films of 100 nm, 50 nm, and 25 nm in thickness. - From this result, it is determined that thinner Ni films can be separated and collected when the
negative electrode 4 is cooled before the immersion in theNi plating solution 5. For example, the temperature of thenegative electrode 4 is preferably 10° C. or more lower than the temperature of theNi plating solution 5 in order to separate and collect the Ni film of 50 nm in thickness. In addition, the temperature of thenegative electrode 4 is preferably 20° C. or more lower than the temperature of theNi plating solution 5 in order to separate and collect the Ni film of 25 nm in thickness. - The reason that thinner Ni films can be separated and collected when the temperature of the
negative electrode 4 is lower than the temperature of theNi plating solution 5 can be considered as follows. When the temperature of thenegative electrode 4 is lower than the temperature of theNi plating solution 5, the vicinity of the plating interface is likely to be a diffusion-controlled environment. Even though an experiment of lowering the temperature of theNi plating solution 5 was also carried out, the effect of facilitating the separation and collection was not produced. Thus, the ability to separate and collect the thin Ni films is not considered to be due to the effect of the plating solution interface. For this reason, it is considered that the temperature of thenegative electrode 4 made lower than the temperature of theNi plating solution 5 increases the strain between the deposited Ni film and thenegative electrode 4, thereby making the Ni film likely to be separated. Therefore, the increased difference in temperature between thenegative electrode 4 and theNi plating solution 5 makes it possible to separate thinner Ni films. - In addition, a totally chlorinated Ni bath was used in the present example as the
Ni plating solution 5, and the Ni films deposited from this bath are large in internal stress. Although the reason thereof is not known, the selection of the bath is also considered to make an effective contribution. - The Ni particle of 25 nm in thickness produced in Example 1 was used for internal electrodes to produce a laminated ceramic electronic component, specifically, a laminated ceramic capacitor.
FIG. 3 is a cross-sectional view illustrating the laminated ceramic capacitor. - This laminated ceramic capacitor has a structure of a
ceramic body 9 containing barium titanate or the like as its main constituent in the shape of a rectangular parallelepiped, which has therein alternately arrangedinternal electrodes 10 exposed at one end surface andinternal electrodes 11 exposed at the other end surface, and has anexternal electrode 11 formed on one end surface of theceramic body 9 to provide electrical conduction to theinternal electrodes 10 and anexternal electrode 13 formed on the other end surface of theceramic body 9 to provide electrical conduction to theinternal electrodes 11. In the present example, the flat Ni particle of 25 nm in thickness, produced in Example 1, was used as a material for theinternal electrodes - A method for producing this laminated ceramic capacitor will be described below.
- First, the flat Ni particle was dispersed in a resin and a solvent to create an electrode paste. It is to be noted that the resin may be any type, and acrylic resins, cellulosic resins, butyral resins, alkyd resins, etc. can be used singularly or in a mixture. In addition, the solvent may also be any type, and glycols, terpineol, cellosolves, acetic esters, etc. can be used.
- Next, green sheets were prepared which had a barium titanate-based ceramic dispersed in an organic binder. In this example, large mother green sheets were prepared from which a large number of green sheets could be obtained.
- Thereafter, screen printing was used to print the electrode paste in a desirably shaped pattern for internal electrodes on the surfaces of some of the mother green sheets.
- Next, the mother green sheets with the internal electrodes printed thereon and the mother green sheets with no internal electrodes printed thereon were stacked in a predetermined order, and subjected to pressure bonding to obtain a large unfired ceramic body including therein the electrode paste for internal electrodes. This large ceramic body is intended to allow a plurality of ceramic bodies to be obtained therefrom.
- The large unfired ceramic body was then cut into a plurality of unfired ceramic bodies.
- Next, the cut unfired ceramic bodies were heated at a predetermined temperature to release unnecessary binder in the ceramic bodies to the outside surroundings (binder removal step), and subsequently subjected to firing in accordance with a predetermined profile (firing step), thereby achieving the
ceramic body 9 with theinternal electrodes - Next, a copper electrode paste was applied onto both ends of the
ceramic body 9, and subjected to firing to form theexternal electrodes - The laminated ceramic capacitor produced by the production method described above uses the flat Ni particle produced in Example 1 for the material of the internal electrodes. This Ni particle has a large specific surface area, and has large surface asperity to some extent. Therefore, during in the binder removal in the process of producing this laminated ceramic capacitor, unnecessary binder is released efficiently from gaps formed by the surface asperity to the both sides of the
internal electrodes -
-
- 1: titanium case
- 2: Ni chip
- 3: positive electrode
- 4: negative electrode
- 5: Ni plating solution
- 6: tank
- 7: shield plate
- 8: power source
- 9: ceramic body
- 10, 11: internal electrodes
- 12, 13: external electrodes
Claims (12)
1. A flat Ni particle having a thickness t (m), a specific gravity ρ (g/m3), and a radius r (m) obtained from half the length of a diagonal line in the case of assuming a planar shape to be a square, and a specific surface area S1 (m2/g), wherein the specific surface area S1 has a relationship of 1.5×S0<S1<2.1×S0 with a theoretical specific surface area S0 in the case of assuming a surface to be completely smooth represented by S0=2/(ρ×t)+2√2/(ρ×r)(m2/g), and wherein the particle has an average diameter of at least 1.4 μm.
2. The flat Ni particle according to claim 1 , wherein the specific surface area S1 has a relationship of 1.60×S0≦S1≦2.08×S0.
3. The flat Ni particle according to claim 2 , wherein the flat Ni particle has a thickness of 100 nm or less.
4. The flat Ni particle according to claim 3 , wherein the flat Ni particle has a thickness of 50 nm or less.
5. The flat Ni particle according to claim 1 , wherein the flat Ni particle has a thickness of 100 nm or less.
6. The flat Ni particle according to claim 5 , wherein the flat Ni particle has a thickness of 50 nm or less.
7. A method for producing the flat Ni particle according to claim 1 , the method comprising:
providing a positive electrode and a negative electrode;
immersing the positive electrode and the negative electrode in a Ni plating solution;
applying an electric current between the positive electrode and the negative electrode immersed in the Ni plating solution to form a Ni film on a surface of the negative electrode;
separating the Ni film formed on the surface of the negative electrode therefrom; and
grinding the separated Ni film to obtain a Ni particle, wherein the temperature of the negative electrode is at least 10° C. lower than the temperature of the Ni plating solution at the point of the Ni plating.
8. The method for producing a flat Ni particle according to claim 7 , wherein the temperature of the negative electrode is at least 20° C. lower than the temperature of the Ni plating solution at the point of the Ni plating.
9. The method for producing a flat Ni particle according to claim 8 , wherein the Ni plating solution is made by a chlorinated Ni bath.
10. The method for producing a flat Ni particle according to claim 9 , wherein the temperature of the negative electrode is at least 30° C. or more lower than the temperature of the Ni plating solution at the point of the Ni plating.
11. The method for producing a flat Ni particle according to claim 7 , wherein the Ni plating solution is made by a chlorinated Ni bath.
12. The method for producing a flat Ni particle according to claim 11 , wherein the temperature of the negative electrode is at least 30° C. or more lower than the temperature of the Ni plating solution at the point of the Ni plating.
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US13/782,447 US20130175176A1 (en) | 2009-10-05 | 2013-03-01 | FLAT Ni PARTICLE, LAMINATED CERAMIC ELECTRONIC COMPONENT USING FLAT Ni PARTICLE, AND PRODUCTION METHOD FLAT Ni PARTICLE |
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PCT/JP2010/067253 WO2011043265A1 (en) | 2009-10-05 | 2010-10-01 | FLAT Ni PARTICLE, MULTILAYER CERAMIC ELECTRONIC COMPONENT USING THE SAME, AND PRODUCTION METHOD FOR FLAT Ni PARTICLE |
US13/403,136 US8411410B2 (en) | 2009-10-05 | 2012-02-23 | Flat Ni particle, laminated ceramic electronic component using flat Ni particle, and production method flat Ni particle |
US13/782,447 US20130175176A1 (en) | 2009-10-05 | 2013-03-01 | FLAT Ni PARTICLE, LAMINATED CERAMIC ELECTRONIC COMPONENT USING FLAT Ni PARTICLE, AND PRODUCTION METHOD FLAT Ni PARTICLE |
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US13/782,447 Abandoned US20130175176A1 (en) | 2009-10-05 | 2013-03-01 | FLAT Ni PARTICLE, LAMINATED CERAMIC ELECTRONIC COMPONENT USING FLAT Ni PARTICLE, AND PRODUCTION METHOD FLAT Ni PARTICLE |
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US20150027765A1 (en) * | 2013-07-23 | 2015-01-29 | Samsung Electro-Mechanics Co., Ltd. | Nickel powder for internal electrodes, multilayer ceramic capacitor including the same, and circuit board having electronic component mounted thereon |
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US4130696A (en) * | 1976-09-09 | 1978-12-19 | Yardney Electric Corporation | Conductive diluent for pressed nickel electrodes |
JPS59193294A (en) * | 1983-03-29 | 1984-11-01 | Sumitomo Metal Mining Co Ltd | Electrolytic nickel flake and its preparation |
JP2985448B2 (en) * | 1991-12-09 | 1999-11-29 | 株式会社村田製作所 | Lamination method of ceramic green sheet |
JPH05279701A (en) * | 1992-02-06 | 1993-10-26 | Ngk Insulators Ltd | Metallic powder and its production as well as metallic molding formed by using this metallic powder and production of metallic honeycomb monolith |
US5872695A (en) * | 1997-02-26 | 1999-02-16 | International Business Machines Corporation | Integrated electronic components having conductive filled through holes |
JP3567759B2 (en) * | 1998-09-28 | 2004-09-22 | 株式会社村田製作所 | Dielectric ceramic composition and multilayer ceramic capacitor |
US7261761B2 (en) * | 2002-08-28 | 2007-08-28 | Toho Titanium Co., Ltd. | Metallic nickel powder and process for production thereof |
KR100845688B1 (en) * | 2004-11-24 | 2008-07-11 | 삼성전기주식회사 | Method for Surface treatment of Ni nano particle with Organic solution |
JP4613362B2 (en) | 2005-01-31 | 2011-01-19 | Dowaエレクトロニクス株式会社 | Metal powder for conductive paste and conductive paste |
JP2006328270A (en) * | 2005-05-27 | 2006-12-07 | Sumitomo Metal Mining Co Ltd | Metal foil for coating and method for producing the same |
US7604679B2 (en) * | 2005-11-04 | 2009-10-20 | Sumitomo Metal Mining Co., Ltd. | Fine nickel powder and process for producing the same |
JP4942333B2 (en) * | 2005-11-29 | 2012-05-30 | 住友金属鉱山株式会社 | Nickel powder, method for producing the same, and polymer PTC element using the nickel powder |
JP4914065B2 (en) * | 2005-12-21 | 2012-04-11 | 大研化学工業株式会社 | Nickel powder for multilayer ceramic capacitor electrode, electrode forming paste and multilayer ceramic capacitor |
CN101369660A (en) * | 2007-08-15 | 2009-02-18 | 德固赛(中国)投资有限公司 | Complex particle material for electrode, electrode plate and their production method |
JP4998732B2 (en) * | 2007-10-22 | 2012-08-15 | ソニーケミカル&インフォメーションデバイス株式会社 | Anisotropic conductive adhesive |
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US20150027765A1 (en) * | 2013-07-23 | 2015-01-29 | Samsung Electro-Mechanics Co., Ltd. | Nickel powder for internal electrodes, multilayer ceramic capacitor including the same, and circuit board having electronic component mounted thereon |
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JPWO2011043265A1 (en) | 2013-03-04 |
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WO2011043265A1 (en) | 2011-04-14 |
US8411410B2 (en) | 2013-04-02 |
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