CN101010752B - Electroconductive nickel paste - Google Patents
Electroconductive nickel paste Download PDFInfo
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- CN101010752B CN101010752B CN2005800290747A CN200580029074A CN101010752B CN 101010752 B CN101010752 B CN 101010752B CN 2005800290747 A CN2005800290747 A CN 2005800290747A CN 200580029074 A CN200580029074 A CN 200580029074A CN 101010752 B CN101010752 B CN 101010752B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 272
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 137
- 239000000919 ceramic Substances 0.000 claims abstract description 153
- 239000000843 powder Substances 0.000 claims abstract description 137
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 45
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims description 28
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 33
- 238000005245 sintering Methods 0.000 abstract description 25
- 230000002401 inhibitory effect Effects 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000003985 ceramic capacitor Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 238000003475 lamination Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229910052692 Dysprosium Inorganic materials 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000002788 crimping Methods 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- 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
- H01G4/01—Form of self-supporting 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
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Ceramic Capacitors (AREA)
- Conductive Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
An electroconductive nickel paste containing a nickel powder, a ceramic powder and an organic vehicle, wherein the ceramic powder has nickel and/or a nickel compound and a rare earth element compound being present on the surface and/or in a surface layer. The use of the electroconductive nickel paste for the formation of inner electrodes (3, 4) improves the intimacy (wetness) of the ceramic powder contained in the electroconductive nickel paste with nickel, which results in preventing the ceramic powder from being discharged from the inner electrodes (3, 4) until the temperature region of sintering of the ceramic layer (2) and thus in the duration of satisfactory effect for the inhibition of sintering. Accordingly, of electroconductive nickel pastes containing a ceramic powder for the exhibition of sintering inhibiting effect, the above nickel paste exhibits the sintering inhibiting effect with higher reliability.
Description
Technical field
The present invention relates to electroconductive nickel paste, relate in particular to the electroconductive nickel paste of the internal electrode that is used to form multilayer ceramic electronic component.
Background technology
The such multilayer ceramic electronic component of multi-layer ceramic capacitor possesses article body, the structure of a plurality of ceramic layers that this article body has had lamination.In the inside of article body,, and be formed with inner conductor along the specific interface between ceramic layer for example in order to form electrostatic capacitance or inductance etc. or to carry out electric distribution.
In order to obtain described article body, and carry out following operation: prepare a plurality of ceramic green tablets, after utilizing printing to form on the specific ceramic green tablet to become the conductive paste of inner conductor film, with the overlapping and crimping of a plurality of ceramic green tablets, obtain giving birth to laminated body, and burn till this life laminated body.Powder such as for example nickel as conductive compositions, copper, silver-palladium alloy are scattered in organic vehicle, make being used to form the conductive paste that becomes the conductive paste of described inner conductor film thus.
For the miniaturization of multilayer ceramic electronic component and high performance, the especially progress of the high capacitanceization of multi-layer ceramic capacitor, need the thickness of attenuate internal electrode as far as possible, and increase the lamination number of per unit volume.For thickness that can the attenuate internal electrode, the physical size that reduces the employed conductive metal particles of powder of conductive paste as far as possible is effective.
But if reduce particle size, then sintering begins temperature decline, therefore, the coverage rate of internal electrode (coverage: the lining rate) descend, or sometimes because the action of the contraction that sintering caused between internal electrode and pottery is poor, and produce delamination.Thereby expectation is used to suppress the technology of the sintering of the conductive metal powder that conductive paste comprises.
Suppress technology as described sintering, have pair conductive paste to add the technology (for example, with reference to patent documentation 1 and 2) of ceramic component.
In patent documentation 1, put down in writing and contained the such metallic particles of nickel particle for example and the conductive paste of dielectric ceramics particle.In addition, in specific execution mode, put down in writing and make the dielectric ceramics particle be adsorbed in the lip-deep situation of metallic particles.
On the other hand, in patent documentation 2, the conductive paste that contains the nickel composite conductor that nickel and titanate one is changed into graininess and obtain is disclosed.In addition, in specific execution mode, put down in writing and titanate is adhered on the surface of nickel particle and incorporate situation perhaps, mixes and incorporate situation nickel and titanate.In addition, disclose for situation granule spraying plating such as nickel and titanate be integrated and suitable.
But, when using patent documentation 1 described conductive paste to form the conductive film that is used for internal electrode, in the operation of burning till living laminated body, if the such metallic particles of nickel particle in the conductive paste begins sintering, then electrode or conductive paste film spray to the ceramic layer side dielectric ceramics particle internally easily, its result, in the sintering temperature zone of ceramic layer, lose sometimes that the dielectric ceramics particle produces, the sintering of internal electrode is suppressed effect.
On the other hand, when using patent documentation 2 described conductive pastes to form the conductive paste film that is used for internal electrode, also lose sintering sometimes and suppress effect, maybe can't obtain sufficient sintering and suppress effect.That is, when making titanate adhere on the surface of nickel particle, cause the phenomenon identical sometimes, lose sintering and suppress effect with the situation of patent documentation 1.When nickel and titanate are mixed, still cling easily between the nickel particle, suppress effect thereby can't obtain sufficient sintering.In addition, for nickel and titanate is integrated, when being suitable for plasma spray coating, the reaction time of plasma spray coating is in a flash, and the reaction of nickel and titanate is insufficient, therefore when reduced nickel, nickel and titanate are peeled off easily, also suffer from the problem identical with patent documentation 1 thus.
Thus, with the internal electrode thin layer time,, do not solve problems such as the decline of coverage rate of described internal electrode or delamination fully at the sintering that too becomes the conductive paste of internal electrode film that burns till of the living laminated body that is used for multilayer ceramic electronic component.
Patent documentation 1: the spy opens clear 57-30308 communique
Patent documentation 2: the spy opens the 2000-232032 communique
Summary of the invention
The object of the present invention is to provide a kind of electroconductive nickel paste that can make the decline and the more difficult generation of delamination problems of so-called coverage rate.
The invention provides a kind of electroconductive nickel paste that comprises nickel by powder, ceramic powders and organic vehicle, in order to solve the technical problem, it is characterized in that,, use on its surface and/or there is the ceramic powders of nickel and/or nickel compound in superficial layer as ceramic powders.
In the present invention, ceramic powders can have nickel and/or nickel compound in its surface attachment, also can nickel compound be arranged in its superficial layer diffusion.Under the former situation, when nickel compound is adhered to, this nickel compound preferably nickel hydroxide or nickel oxide or they both.In addition, in the latter case, nickel compound is nickel oxide preferably.
In addition, in electroconductive nickel paste of the present invention, the amount of nickel and/or nickel compound is 5～100 molar part preferably with respect to ceramic powders 100 molar part.
Electroconductive nickel paste of the present invention preferably not only exists nickel and/or nickel compound at the surface and/or the superficial layer of ceramic powders, and also has rare-earth element compound.
Under the situation of described preferred implementation, preferred ceramic powders 100 molar part relatively of the amount of nickel and/or nickel compound are 1～100 molar part.On the other hand, preferred ceramic powders 100 molar part relatively of the amount of rare-earth element compound are 0.01～10 molar part.
In electroconductive nickel paste of the present invention, the particle diameter of ceramic powders is preferably below the 50nm.
(effect of invention)
According to the present invention as can be known, the nickel that ceramic powders can pass through on its surface and/or superficial layer exists and/or the effect of nickel compound, and nickel has good fused property (wetability) relatively.Therefore, in sintering process, ceramic powders is difficult for from becoming the electroconductive nickel paste film ejection of internal electrode.Its result, ceramic powders can fully remain in the internal electrode until for example as the temperature more than 900 ℃ in the sintering temperature zone of dielectric ceramics, thus the effect that can bring into play the sintering that suppresses internal electrode is until described such high-temperature area.And even thus with the internal electrode thin layerization, the continuity that constitutes the electrically conductive film of internal electrode also improves, thereby can improve coverage rate.In addition, also can make delamination be difficult for producing.
When on the surface of ceramic powders and/or superficial layer when also having rare-earth element compound, more can bring into play described such effect significantly.This is because rare-earth element compound has makes nickel and/or nickel compound be deposited in the surface of ceramic powders and/or the effect on the superficial layer.
In electroconductive nickel paste of the present invention, if surface and/or the nickel of superficial layer existence and/or relative ceramic powders 100 molar part of amount of nickel compound at ceramic powders, be selected as 5～100 molar part, perhaps, on the surface of ceramic powders and/or superficial layer when having rare-earth element compound, relative ceramic powders 100 molar part of the amount of nickel and/or nickel compound are selected as 1～100 molar part, then can realize described such effect more reliably.
When on the surface of ceramic powders and/or superficial layer when having rare-earth element compound, if relative ceramic powders 100 molar part of amount of rare-earth element compound, be selected as 0.01～10 molar part, then can realize described such effect more reliably, and can prevent from reliably to use this electroconductive nickel paste and the deterioration in characteristics of the ceramic electronic components that constitutes.
In electroconductive nickel paste of the present invention,, can prevent that then ceramic powders from becoming the thin layerization of internal electrode and the obstacle that coverage rate improves if the particle diameter of ceramic powders is below the 50nm.
Description of drawings
Fig. 1 is the profile of the multi-layer ceramic capacitor 1 of a diagrammatic example of representing the multilayer ceramic electronic component that constitutes as using electroconductive nickel paste of the present invention.
Among the figure: the 1-multi-layer ceramic capacitor; The 2-ceramic layer; 3,4-internal electrode; The 5-article body; 6,7-outer electrode.
Embodiment
Fig. 1 is the profile of the multi-layer ceramic capacitor 1 of a diagrammatic example of representing the multilayer ceramic electronic component that constitutes as using electroconductive nickel paste of the present invention.
Multi-layer ceramic capacitor 1 possesses article body 5, described article body 5 has the laminated construction that is made of a plurality of ceramic layers 2 of lamination and internal electrode 3 and 4, described ceramic layer 2 is made of dielectric ceramics, and described internal electrode 3,4 is along the specific interface of 2 of ceramic layers and form.Each end in article body 5 is formed with outer electrode 6 and 7 respectively.Outer electrode 6 and 7 is electrically connected with internal electrode 3 and 4 respectively, internal electrode 3 that is electrically connected with an outer electrode 6 and the internal electrode 4 alternately configuration on stack direction that is electrically connected with another outer electrode 7.
In order to make such multi-layer ceramic capacitor 1, implement following operation.
At first, prepare to become the ceramic green tablet of ceramic layer 2, and prepare to be used to form the electroconductive nickel paste of internal electrode 3 and 4.
Then, utilization is printed and is given electroconductive nickel paste on the ceramic green tablet, thus, becomes the electroconductive nickel paste film of internal electrode 3 and 4.
Then, a plurality of ceramic green tablets of lamination and crimping, and implement as required to cut off operation, obtain becoming the living laminated body of article body 5 thus.
Then, burn till living laminated body, thus, obtain the article body 5 of sintering.And, if form outer electrode 6 and 7, then finish multi-layer ceramic capacitor 1 at the both ends of article body 5.
As mentioned above, be used to form the electroconductive nickel paste that becomes the electroconductive nickel paste of internal electrode 3 and 4 film comprise nickel by powder, on its surface and/or superficial layer have ceramic powders and organic vehicle of nickel and/or nickel compound.
If use such electroconductive nickel paste, then owing to surface and/or superficial layer at ceramic powders exist nickel and/or nickel compound, and make with the fused property (wetability) of nickel good, thereby in described firing process, can make ceramic powders be difficult for electrode 3 and 4 ejections internally.Therefore, ceramic powders remains in internal electrode 3 and 4 until as for example more than 900 ℃ of the sintering temperature zone of ceramic layer 2, and the effect that can keep the sintering that suppresses internal electrode 3 and 4 thus is until such high-temperature area.Even its result with internal electrode 3 and 4 thin layerizations, also can improve the continuity of the conducting film that constitutes internal electrode 3 and 4, thereby improves coverage rate.
The ceramic powders that described electroconductive nickel paste comprised can have nickel and/or nickel compound in its surface attachment, also can nickel compound be arranged in its superficial layer diffusion.As described in the former, when being attached to ceramic powders surperficial, nickel compound is nickel hydroxide and/or nickel oxide preferably.In addition, as described in the latter, when making nickel compound be spread in the superficial layer of ceramic powders, nickel compound is nickel oxide preferably.
In addition, in the electroconductive nickel paste that uses, when relative ceramic powders 100 molar part of the amount of nickel and/or nickel compound are 5～100 molar part, can bring into play described effect more reliably.
Described on the surface and/or superficial layer exist the ceramic powders of nickel and/or nickel compound for example can followingly to obtain.
Promptly, making is scattered in the water ceramic powders and the slurry that obtains, in this slurry, drop into nickel salt solution and aqueous alkali, make nickel hydroxide be attached to the surface of ceramic powders, then, this ceramic powders is implemented heat treatment and pulverization process, thus, can access described on the surface and/or superficial layer have the ceramic powders of nickel and/or nickel compound.
The temperature that is endowed in described heat treatment is preferably more than 500 ℃ and below 1000 ℃.If in this scope, then especially the thin layerization of internal electrode and the raising of coverage rate had effect.Also have, when heat-treating atmosphere was reproducibility, part or all of nickel compound was reduced, and necessarily there is the nickel metal in its result at the surface and/or the superficial layer of ceramic powders.
Ceramic powders preferably not only exists nickel and/or nickel compound on its surface and/or its superficial layer, and also has rare-earth element compound.As rare-earth element compound, can use at least a in each compound of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.Because rare-earth element compound is present in the surface and/or the superficial layer of ceramic powders, the effect that therefore can keep the sintering that suppresses internal electrode 3 and 4 is until high-temperature area more.This is because the rare earth element effect makes on the easier surface that resides in ceramic powders of nickel and/or nickel compound or in the superficial layer.
So, make nickel and/or nickel compound and rare-earth element compound be attached to ceramic powders, then, this ceramic powders is implemented heat treatment and pulverization process, can access on the surface thus and/or superficial layer not only exists nickel and/or nickel compound and also has the ceramic powders of rare-earth element compound.
As making nickel and/or nickel compound and rare-earth element compound be attached to the method for ceramic powders, following method is for example arranged: manufacture and ceramic powders is scattered in the water and the slurry that obtains, in this slurry, drop into solution and the aqueous alkali that comprises nickel salt and rare earth element salt, thus, make nickel hydroxide and rare earth element hydroxide be attached to ceramic powders.Put down in writing the concrete example of this method among the embodiment 2 described later.
As making nickel and/or nickel compound and rare-earth element compound be attached to the method for ceramic powders, following method is arranged: the organic fatty acid salt solution of preparing to comprise nickel and rare earth element, ceramic powders is scattered in the water its input and in the slurry that obtains, fully after the dispersion treatment, make the organic solution volatilization, thereby make the soap that contains nickel and rare earth element be attached to ceramic powders.Get example more specifically if enumerate this method, then as described below.
At first, for example prepare the soap of octyl group hydrochlorate as Dy and Ni.Then, 50g is scattered in the 500cc acetone as the barium titanate powder of ceramic powders, and fully stirs, make slurry thus.Then, this slurry is dropped into that weighing in advance makes its adhesion amount that becomes expectation and is dissolved in Dy and Ni octyl group hydrochlorate in the acetone, and stirred 30 minutes, thus, make the octyl group hydrochlorate fused fully mutually with slurry.Then, to the suitable rotary evaporator of the mixture of octyl group hydrochlorate and slurry, make the acetone volatilization.Thus, can access the barium titanate powder that Dy and Ni octyl group hydrochlorate adhere to.
Under the above-described situation that makes the ceramic powders that rare-earth element compound adheres to, heat treated temperature afterwards is also preferably more than 500 ℃ and below 1000 ℃.
The particle diameter of the ceramic powders that electroconductive nickel paste of the present invention comprised is preferably below the 50nm.Because if surpass 50nm, then hinder the effects such as raising of the coverage rate of the thin layerization of internal electrode and internal electrode.
In addition, the particle diameter of the nickel by powder that electroconductive nickel paste of the present invention comprised is preferably below the 0.2 μ m.This be because, by the particle diameter of selection nickel by powder like this, can be with reduced thickness to the 0.25 μ m～0.3 μ m of electroconductive nickel paste film, its result, easier thin layerization of carrying out internal electrode.
Also have, in this case specification, " particle diameter " of so-called various powder be meant, with scanning electron microscope (SEM) photo mensuration, the particle diameter of 1000 objects is carried out arithmetic average and the mean value obtained.
Then, in order to confirm effect of the present invention, the experimental example of implementing is described.
1. experimental example 1
As the ceramic powders that electroconductive nickel paste contained, prepare the ceramic powders of the various test portions shown in the table 1.
[table 1]
| The examination item number | The ceramic powders kind | Nickel becomes component (molar part) | Heat treatment temperature (℃) | Heat treatment time (time) | The existence form of nickel composition/exist position (time) | Internal electrode coverage rate (%) | Internal electrode thickness (μ m) |
| 1 | BaTiO 3 | 5 | 1000 | 3 | Oxide/superficial layer | 60 | 0.6 |
| 2 | BaTiO 3 | 20 | - | - | Hydroxide/surface | 60 | 0.58 |
| 3 | BaTiO 3 | 20 | 1000 | 0.5 | Oxide/surface | 60 | 0.58 |
| 4 | BaTiO 3 | 20 | 100 | 3 | Hydroxide/surface | 60 | 0.6 |
| 5 | BaTiO 3 | 20 | 500 | 3 | Hydroxide/surface+superficial layer | 60 | 0.56 |
| 6 | BaTiO 3 | 20 | 1000 | 3 | Oxide/superficial layer | 60 | 0.58 |
| 7 | BaTiO 3 | 20 | 1200 | 3 | Oxide/superficial layer | 60 | 0.64 |
| 8 | BaTiO 3 | 20 | 1000 | 10 | Oxide/superficial layer | 60 | 0.62 |
| 9 | BaTiO 3 | 50 | 1000 | 3 | Oxide/surface+superficial layer | 62 | 0.58 |
| 10 | BaTiO 3 | 100 | 1000 | 3 | Oxide/surface+superficial layer | 64 | 0.56 |
| 11 | BaTiO 3 | 20 | 1000 | 3 | Oxide/superficial layer | 60 | 0.58 |
| 12 | BaTiO 3 | 20 | 1000 | 0.5 | Metal/superficial layer | 60 | 0.6 |
| 13 | BaZrO 3 | 20 | 1000 | 3 | Oxide/superficial layer | 60 | 0.6 |
| 14 | Al 2O 3 | 20 | 1000 | 3 | Oxide/superficial layer | 60 | 0.6 |
| 15 | BaTiO 3 | 1 | 1000 | 3 | Oxide/superficial layer | 55 | 0.66 |
| 16 | BaTiO 3 | 150 | 1000 | 3 | Oxide/surface+superficial layer | 55 | 0.6 |
| 17 | BaTiO 3 | 0 | - | - | - | 45 | 0.8 |
In table 1, " ceramic powders kind " expression constitutes the composition of the pottery of employed ceramic powders." nickel becomes component " is illustrated in the surface of ceramic powders and/or the mol ratios nickel composition, relative ceramic powders 100 molar part of superficial layer existence.
At first, the ceramic powders of the particle diameter 30nm of the composition shown in " the ceramic powders kind " with table 1 is scattered in the water and makes slurry.Then, in slurry respectively with 10cm
3/ minute the speed input nickel chloride is dissolved in the water and the solution that obtains and with dissolution of sodium hydroxide in water and the solution that obtains mixes them simultaneously, cause neutralization reaction, thus, make nickel hydroxide be attached to the surface of ceramic powders.
The input of the described aqueous solution makes its slaking 10～30 minutes after finishing, and then, with the supernatant several of pure water displacement reaction liquid, and cleans powder.And then, behind acetone displacement moisture, powder was kept dry about 2 hours with the drying machine that is set at 80 ℃ of temperature.
In this stage, investigate the surface of ceramic powders by the composition analysis device (EDX) that utilizes transmission electron microscope (TEM) and be attached to its energy dispersion type X line beam split carrying out work, results verification has nickel hydroxide in the surface attachment of ceramic powders.Also have, though utilize EDX to be estimated as nickel hydroxide, but for example be BaTiO in " ceramic powders kind "
3The time, also have the position detect Ba or Ti, but this be because analyzed area also with BaTiO
3Powder is relevant, therefore in this stage, and nickel and BaTiO
3Powder does not react.In addition, detect Cu slightly, but this is used for fixing the Cu net of ceramic powders when coming comfortable tem observation.
Also have, the test portion 17 shown in the table 1 is comparative examples, as ceramic powders, has used on the surface or there is not the BaTiO of nickel composition in superficial layer
3Powder.Thereby, test portion 17 is not carried out adhering to of described nickel hydroxide and handle or heat treatment described later.
In addition, test portion 2 uses the ceramic powders that is attached with dried nickel hydroxide as mentioned above, but also for it is carried out following heat treatment.
Except described test portion 2 and 17, with regard to test portion 1 and 3～16, the ceramic powders that dried nickel hydroxide is as mentioned above adhered to reaches the temperature and time that " heat treatment time " represented respectively with " heat treatment temperature " of table 1, heat-treats in atmosphere.
Also have, with regard to test portion 12, after this heat treatment, with the temperature of ceramic powders, at oxygen partial pressure (PO with 800 ℃
2) [MPa] become log (PO
2Carry out heat treatment in 3 hours in the reducing atmosphere of)=-16.
Then, with regard to having implemented heat treated test portion 1 and 3～16 as mentioned above, after heat treatment, carry out 12 hours pulverization process with ball mill.
" form " of " the existence hurdle of nickel composition " expression nickel composition of table 1 reaches " having the position ".
With regard to " form " of nickel composition, what " oxide " was represented is nickel oxide, and what " hydroxide " was represented is nickel hydroxide, and what " metal " was represented is nickel.Also have, " form " of these nickel compositions inferred according to heat treatment temperature and the balance oxygen partial pressure corresponding with it, therefore, for example, when in atmosphere, heat-treating with 100 ℃ temperature, certainly can be estimated as according to the balance oxygen partial pressure becomes oxide, therefore is expressed as in table 1 " oxide ".
With regard to nickel composition " having the position ", be to pass through tem observation, and confirmed to be attached to the surface of ceramic powders or reaction and solid solution (diffusion) have a position, the surface of ceramic powders is represented to be attached in the position that exists that is expressed as " surface ", and the position that exists that is expressed as " superficial layer " represents that solid solution (diffusion) is in the superficial layer of ceramic powders.
Then, prepare the nickel by powder of particle diameter 0.15 μ m, the ceramic powders of each test portion shown in this nickel by powder and the table 1 is mixed into 90: 10 weight ratio.On the other hand, preparation is mixed into vinyl fiber prime system adhesive and terpinol organic vehicle of 10: 90 weight ratio, described powder composition, this organic vehicle and terpinol be mixed into 50: 40: 10 weight ratio, and utilize 3 roller mills to carry out dispersing and mixing carefully and handle, thus, obtain the electroconductive nickel paste of each good test portion of dispersity.
On the other hand, to BaTiO as known composition
3The powder of the irreducibility dielectric ceramic composition of system, adding polyvinyl butyral resin is organic solvents such as adhesive and ethanol, utilizes ball mill to carry out wet mixed, makes the ceramic green tablet.Then, utilization is scraped the skill in using a kitchen knife in cookery this ceramic green tablet is configured as sheet, thereby obtains the ceramic green tablet of thickness 5.0 μ m.
Then, utilize screen printing on the ceramic green tablet, to print the electroconductive nickel paste of described each test portion, become the electroconductive nickel paste film of internal electrode.At this moment, by adjusting the thickness of web plate pattern, the thickness of electroconductive nickel paste film is formed 0.5 μ m.
Then, the a plurality of ceramic green tablets of lamination and crimping, make thus and be formed with 10 layers of lamination member that becomes the electroconductive nickel paste film of internal electrode, with the size of this lamination cutting of members for regulation, obtain becoming the living laminated body of the article body of multi-layer ceramic capacitor, and it is burnt till with 1150 ℃ temperature in reducing atmosphere, obtain the article body of sintering thus.
With regard to the article body of each test portion of so obtaining, measure the coverage rate of internal electrode and the thickness of internal electrode respectively.Its result is shown in table 1 " internal electrode coverage rate " and reaches in each hurdle of " internal electrode thickness ".
With reference to table 1, according to test portion 1～16 as can be known, even the thin thickness of internal electrode also can access high coverage rate.Especially, according to nickel become component be 5～100 molar part test portion 11～14 as can be known, the raising effect of the thin layerization of internal electrode and coverage rate is higher.
In addition, relatively test portion 1～11 and test portion 12 no matter the nickel composition that exists at the surface and/or the superficial layer of ceramic powders is nickel compound, or metallic nickel, can both be brought into play substantially the same effect as can be known in the raising of the thin layerization of internal electrode and coverage rate.
In addition, relatively test portion 1～12, test portion 13 and test portion 14 as can be known, irrelevant with the composition of ceramic powders, in the raising of the thin layerization of internal electrode and coverage rate, substantially the same effect is arranged all.
On the other hand, according to test portion 17 as can be known, because there are not the nickel composition in the surface or the superficial layer of ceramic powders, so the thickness of internal electrode is thick, and coverage rate is also low.
2. embodiment 2
As the ceramic powders that electroconductive nickel paste contained, prepare the ceramic powders of each test portion shown in the table 2.
[table 2]
| The examination item number | Ceramic powders | Nickel becomes component (molar part) | Rare earth element | Heat treatment temperature (℃) | Heat treatment time (time) | Heat-treating atmosphere | The existence form of nickel composition/exist position | The existence form of terres rares composition/exist position | Internal electrode coverage rate (%) | Internal electrode thickness (μ m) | ||
| Kind | Particle diameter (nm) | Kind | Become component (molar part) | |||||||||
| 21 | BaTiO 3 | 50 | - | - | - | 1000 | Air | 5 | - | - | 55 | 0.7 |
| 22 | BaTiO 3 | 50 | 0.5 | Y | 1 | 1000 | |
5 | Oxide/superficial layer | Oxide/superficial layer | 58 | 0.85 |
| 23 | BaTiO 3 | 50 | 1 | Y | 1 | 1000 | |
5 | Oxide/superficial layer | Oxide/superficial layer | 70 | 0.38 |
| 24 | BaTiO 3 | 50 | 5 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 72 | 0.36 |
| 25 | BaTiO 3 | 50 | 20 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 74 | 0.34 |
| 26 | BaTiO 3 | 50 | 100 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 76 | 0.32 |
| 27 | BaTiO 3 | 50 | 20 | Dy | 0.005 | 1000 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 62 | 0.6 |
| 28 | BaTiO 3 | 50 | 20 | Dy | 0.01 | 1000 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 74 | 0.34 |
| 29 | BaTiO 3 | 50 | 20 | Dy | 0.05 | 1000 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 76 | 0.32 |
| 30 | BaTiO 3 | 50 | 20 | Dy | 10 | 1000 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 80 | 0.3 |
| 31 | BaTiO 3 | 50 | 20 | Dy | 1 | 300 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 60 | 0.6 |
| 32 | BaTiO 3 | 50 | 20 | Dy | 1 | 500 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 74 | 0.34 |
| 33 | BaTiO 3 | 50 | 20 | Dy | 1 | 1000 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 74 | 0.34 |
| 34 | BaTiO 3 | 50 | 20 | Dy | 1 | 1200 | N 2 | 5 | Oxide/superficial layer | Oxide/superficial layer | 60 | 0.6 |
| 35 | BaTiO 3 | 10 | 20 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 74 | 0.34 |
| 36 | BaTiO 3 | 50 | 20 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 74 | 0.34 |
| 37 | BaTiO 3 | 70 | 20 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 60 | 0.58 |
| 38 | BaTiO 3 | 50 | 20 | Dy | 0.05 | 1000 →500 | N 2 →N 2+H 2 | 5 | Metal/surface+superficial layer | Oxide/superficial layer | 70 | 0.38 |
| 39 | BaTiO 3 | 50 | 20 | Dy | 0.05 | 1000 →500 | N 2 →N 2+H 2 | 5 | Metal/surface+superficial layer | Oxide/superficial layer | 70 | 0.38 |
| 40 | Ba(Ti 0.9Zr 0.1)O 3 | 50 | 20 | Y | 1 | 1000 | Air | 5 | Oxide/superficial layer | Oxide/superficial layer | 70 | 0.38 |
| 41 | BaTiO 3 | 50 | 20 | - | - | 1000 | Air | 5 | Oxide/superficial layer | - | 60 | 0.6 |
" kind " expression in " ceramic component " of table 2 constitutes the composition of the pottery of employed ceramic powders, with the particle diameter of the employed ceramic powders of " particle diameter " expression." nickel becomes component " expression is present in the surface of ceramic powders and/or the mol ratios nickel composition, relative ceramic powders 100 molar part of superficial layer." kind " in " rare earth element " expression is present in the kind of the rare earth element that rare-earth element compound comprised of the surface of ceramic powders and/or superficial layer, with " one-tenth component " expression rare-earth element compound, the mol ratios of ceramic powders 100 molar part relatively.
At first, make the ceramic powders 50g of composition shown in " ceramic powders " with table 2 and particle diameter be scattered in 1 liter of pure water, and fully stir, make slurry thus.
On the other hand, prepare to have dissolved the muriatic aqueous solution, and the sodium hydrate aqueous solution of nickel chloride and rare earth element.At this, with regard to the former dissolving with regard to the muriatic aqueous solution of nickel chloride and rare earth element, the nickel chloride that comprises the molar part shown in " nickel becomes component " that relative ceramic powders 100 molar part have table 2, and, comprise the chloride of the rare earth element shown in " kind " of " rare earth element " of table 2 with the molar part shown in the congruent amount.With regard to the latter's sodium hydrate aqueous solution, ceramic powders 100 molar part comprise the NaOH of 0.1 molar part relatively.
Then, fully stir described slurry, simultaneously in slurry with 10cm
3/ minute the speed input dissolved the muriatic aqueous solution and the sodium hydrate aqueous solution of nickel chloride and rare earth element, simultaneously they are mixed, cause neutralization reaction, thus, make nickel hydroxide and rare earth element hydroxide be attached to the surface of ceramic powders.Also have, at this moment, for the input amount that makes the muriatic aqueous solution that dissolved nickel chloride and rare earth element and sodium hydrate aqueous solution mutually with amount, adjust the nickel chloride in the former aqueous solution and the muriatic concentration of rare earth element.
After the input of the described aqueous solution finished, slaking 10～30 minutes then, with the supernatant several of pure water displacement reaction liquid, and was cleaned powder.And then, behind acetone displacement moisture, powder is remained on wherein dry about 2 hours with the baking oven that is set at 80 ℃ of temperature.
The powder of having implemented each test portion of above processing is heat-treated with the condition shown in " heat treatment temperature " of table 2, each hurdle that " heat-treating atmosphere " reaches " heat treatment time ".Also have, with regard to test portion 38 and 39, at N
2After carrying out 2 hours heat treatment with 1000 ℃ temperature in the atmosphere, at 0.1%H
2+ N
2Atmosphere in carry out 3 hours heat treatment with 500 ℃ temperature.
Then, with ball mill the powder of each test portion is carried out 12 hours pulverization process.
Each hurdle that " existence of nickel composition " of table 2 reaches " existence of terres rares composition " with the meaning identical with the situation on the corresponding hurdle of table 1 represent respectively " form " of nickel composition reach " having the position ", and " form " of rare earth element composition reach " having the position ".
Then, use the ceramic powders of each test portion shown in the table 2, the situation identical operations of enforcement and embodiment 1 obtains electroconductive nickel paste thus.
On the other hand, via with the situation identical operations of embodiment 1, make the ceramic green tablet of thickness 5.0 μ m, then, on the ceramic green tablet, form the electroconductive nickel paste film of the thickness 0.5 μ m that the electroconductive nickel paste by each test portion constitutes, then, implement the cut-out operation of the lamination of a plurality of ceramic green tablets and crimping process, lamination piece successively, and the living laminated body that is fired into, obtain the article body of sintering thus.
With regard to the article body of each test portion of so obtaining,, measure the coverage rate of internal electrode and the thickness of internal electrode respectively by the method identical with the situation of embodiment 1.Its result is shown in table 2 " internal electrode coverage rate " respectively and reaches in each hurdle of " internal electrode thickness ".
In table 2, between test portion 21～26, nickel becomes the component difference.Thereby, if between test portion 21～26, compare, then can hold and depend on that nickel becomes the size of the different effect of component.That is, become component to be in the test portion 21～26 in the scope of 1～100 molar part at nickel, with nickel become to give short measure 1 molar part test portion 21 and 22 more as can be known, the coverage rate of internal electrode improves, and has realized the thin layerization of internal electrode.
Between test portion 27～30, as the one-tenth component difference of the Dy of rare earth element.Thereby, if between test portion 27～30, compare, then can hold and depend on that rare earth element becomes the size of the different effect of component.That is, according to rare earth element become component be in the scope of 0.01～10 molar part test portion 28～30 as can be known, with the test portion 27 of less than 0.01 molar part relatively, the internal electrode coverage rate improves, and has realized the thin layerization of internal electrode.
Also have, though table 2 do not represent, but be 15 molar part and more for a long time, produce following unfavorable condition: the permittivity temperature characterisitic of the multi-layer ceramic capacitor that obtains does not satisfy the B characteristic of JIS specification at one-tenth component as the Dy of rare earth element.By this situation and described situation as can be known, the one-tenth component of rare earth element preferably is in the scope of 0.01～10 molar part.
Between test portion 31～34, the heat treatment temperature difference.Thereby, if between test portion 31～34, compare, then can find the preferable range of heat treatment temperature.That is, in the test portion 32 and 33 in heat treatment temperature is in 500～1000 ℃ scope, on internal electrode coverage rate and internal electrode thickness, can access good especially result.In heat treatment temperature is 300 ℃ and in the lower test portion 31, insufficient diffusion of carrying out nickel, and carry out the reduction of nickel in the low temperature zone, and this is considered to obtain the reason of abundant effect of the thin layerization of the raising of internal electrode coverage rate and internal electrode.On the other hand, be 1200 ℃ and in the higher test portion 34, too carry out the grain growth in heat treatment temperature, can't obtain the particulate dielectric, therefore can't obtain the abundant effect of the thin layerization of the raising of internal electrode coverage rate and internal electrode.
Between test portion 35～37, the particle diameter difference of ceramic powders.Thereby, if between test portion 35～37, compare, then can hold the size of the different effect of the particle diameter that depends on ceramic powders.Promptly can know, particle diameter at ceramic powders is respectively in the test portion 35 and 36 of 10nm and 50nm, can access the bigger effect of the thin layerization of the raising of internal electrode coverage rate and internal electrode, but be 70nm and in the bigger test portion 37, these effects are smaller at the particle diameter of ceramic powders.
Test portion 38 and 39 and other test portion relatively, different on following point: as in heat treatment stages, to have carried out reduction and handled.Relatively these test portions 38 and 39 and other test portion as can be known, handle even increased reduction, also can access and the substantially the same effect of situation of not implementing such reduction processing.Also have, the purpose that reduction is handled is, fully is not spread in unnecessary nickel compound in the ceramic powders by reduction in advance, suppresses to follow the contraction of the internal electrode that the nickel compound when burning till shrinks.
In test portion 40, as ceramic powders, do not use barium titanate, be replaced into Zr and material that the material that obtains constitutes and used by a part with Ti.Relatively even this test portion 40 and other test portion as ceramic powders, do not use barium titanate as can be known, are replaced into Zr and material that the material that obtains constitutes and used by the part with Ti, can access substantially the same effect yet.
In test portion 41, do not comprise the rare earth element composition.This test portion 41 and only contain test portion different on this point 25,29,30,33 and 36 as can be known relatively at rare earth element, by containing of rare-earth element compound, can further improve the effect of the thin layerization of internal electrode coverage rate and internal electrode.
Claims (9)
1. an electroconductive nickel paste is characterized in that, comprise nickel by powder, on its surface and/or superficial layer have ceramic powders and organic vehicle of nickel and/or nickel compound, wherein, described ceramic powders has described nickel and/or nickel compound in its surface attachment.
2. an electroconductive nickel paste is characterized in that, comprise nickel by powder, on its surface and/or superficial layer have ceramic powders and organic vehicle of nickel and/or nickel compound, wherein, described ceramic powders has described nickel compound in its superficial layer diffusion.
3. electroconductive nickel paste as claimed in claim 1, wherein, described nickel compound is nickel hydroxide and/or nickel oxide.
4. electroconductive nickel paste as claimed in claim 2, wherein, described nickel compound is a nickel oxide.
5. electroconductive nickel paste as claimed in claim 1 or 2, wherein, with respect to described ceramic powders 100 molar part, the amount of described nickel and/or nickel compound is 5～100 molar part.
6. wherein, also there is rare-earth element compound in electroconductive nickel paste as claimed in claim 1 or 2 at the surface and/or the superficial layer of described ceramic powders.
7. electroconductive nickel paste as claimed in claim 6, wherein, with respect to described ceramic powders 100 molar part, the amount of described nickel and/or nickel compound is 1～100 molar part.
8. electroconductive nickel paste as claimed in claim 6, wherein, with respect to described ceramic powders 100 molar part, the amount of described rare-earth element compound is 0.01～10 molar part.
9. electroconductive nickel paste as claimed in claim 1 or 2, wherein, the particle diameter of described ceramic powders is below the 50nm.
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|---|---|---|---|
| JP249591/2004 | 2004-08-30 | ||
| JP2004249591 | 2004-08-30 | ||
| PCT/JP2005/014630 WO2006025201A1 (en) | 2004-08-30 | 2005-08-10 | Electroconductive nickel paste |
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| CN101010752A CN101010752A (en) | 2007-08-01 |
| CN101010752B true CN101010752B (en) | 2010-12-22 |
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| JP5870625B2 (en) | 2011-02-28 | 2016-03-01 | Tdk株式会社 | Electrode sintered body, laminated electronic component, internal electrode paste, method for producing electrode sintered body, method for producing laminated electronic component |
| JP6470228B2 (en) * | 2016-05-24 | 2019-02-13 | 太陽誘電株式会社 | Multilayer ceramic capacitor |
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| JP2003115416A (en) * | 2001-10-05 | 2003-04-18 | Murata Mfg Co Ltd | Conductive paste, method of manufacturing laminated ceramic electronic component, and laminated ceramic electronic component |
| JP2003281939A (en) * | 2002-03-26 | 2003-10-03 | Murata Mfg Co Ltd | Electrically conductive paste and laminated ceramic electronic component |
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