CN115240896B - Nickel alloy powder, conductive paste and multilayer ceramic capacitor - Google Patents
Nickel alloy powder, conductive paste and multilayer ceramic capacitor Download PDFInfo
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- CN115240896B CN115240896B CN202210815730.1A CN202210815730A CN115240896B CN 115240896 B CN115240896 B CN 115240896B CN 202210815730 A CN202210815730 A CN 202210815730A CN 115240896 B CN115240896 B CN 115240896B
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- 239000000843 powder Substances 0.000 title claims abstract description 124
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 107
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 105
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 238000005728 strengthening Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims description 48
- 238000003384 imaging method Methods 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052798 chalcogen Inorganic materials 0.000 claims 5
- 150000001787 chalcogens Chemical class 0.000 claims 5
- 150000001786 chalcogen compounds Chemical class 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 8
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000004438 BET method Methods 0.000 description 8
- 230000000007 visual effect Effects 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical group [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000528 statistical test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic 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
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Powder Metallurgy (AREA)
- Ceramic Capacitors (AREA)
Abstract
The invention discloses nickel alloy powder, conductive paste and a multilayer ceramic capacitor, wherein the nickel alloy powder comprises 0.001-0.1% of elements forming a strengthening phase with nickel, 0.001-0.1% of second main group elements and 0.1-15% of oxygen group elements by mass percent; the surface of the nickel alloy powder is provided with an oxygen group element compound film, and the oxygen group element compound film comprises Ni aXb、Nic(XH)d、NieCfXg and H 2 X. The nickel alloy powder of the invention contains the elements which form the strengthening phase with nickel, so that the initial sintering temperature of the nickel powder is effectively improved; the added second main group element effectively improves the stability of the nickel powder, so that the use effect and the service life of the nickel powder are both improved; the added oxygen group element forms an oxygen group element compound film on the surface of the nickel powder, plays a better role in protecting the internal added element of the nickel powder, and improves the cofiring property and the mutual combination degree of the nickel powder, glass powder in the conductive paste and the dielectric ceramic material.
Description
Technical Field
The invention relates to the field of metal powder, in particular to nickel alloy powder, conductive paste and a multilayer ceramic capacitor.
Background
Uniformly mixing and dispersing metal conductive powder and a glass medium adhesive or other additives in an organic carrier to prepare conductive paste, alternately and repeatedly laminating the conductive paste and a dielectric layer through a printing process, and firing and forming at high temperature to obtain the multilayer ceramic capacitor.
Noble metals such as palladium, silver and platinum have been used in many cases as internal electrode materials for multilayer ceramic capacitors, but oxidation expansion during firing of palladium or silver-palladium causes problems such as delamination and cracking, and base metals such as nickel have been increasingly used as main conductive powders in conductive pastes for resource saving.
As the number of laminated layers of the multilayer ceramic capacitor increases (more than 100 layers), the thickness of each layer also increases to be thinner (less than 3 micrometers), and the particle size of the nickel powder used also decreases (10-1000 nm). As the particle size of the nickel powder becomes smaller, the sintering temperature of the nickel powder also tends to decrease. However, the sintering temperature of the dielectric layer is far higher than that of the nickel powder, and the dielectric layer and the conductive layer cannot stretch well together at high temperature, so that the nickel powder is excessively sintered, and further phenomena such as nickel aggregation, particle growth, discontinuous conductors and the like are generated, so that the resistance value is increased, and the problems such as fracture and deformation are caused.
The need for high performance multilayer ceramic capacitors has not been met by changing the morphology of the nickel powder surface by conventional physical methods and improving the dispersibility of the nickel powder by fluid dispersion. The nickel alloy powder obtained by adding more than one element of vanadium, chromium, zirconium, niobium, molybdenum, tantalum and tungsten into the nickel powder can improve the initial sintering temperature of the conductive paste. However, the above elements are liable to react with the ceramic material of the dielectric layer and adversely affect the conductivity of the multilayer ceramic capacitor electrode.
Therefore, how to effectively improve the performance of nickel powder for multilayer ceramic capacitors has become a technical problem to be solved in the art.
Disclosure of Invention
It is an object of the present invention to provide a new technical solution of nickel alloy powder which effectively improves the performance of nickel powder for multilayer ceramic capacitors.
According to a first aspect of the present invention, there is provided a nickel alloy powder.
The nickel alloy powder comprises 0.001-0.1% of elements forming a strengthening phase with nickel, 0.001-0.1% of second main group elements and 0.1-15% of oxygen group elements by mass percent;
The surface of the nickel alloy powder is provided with an oxygen group element compound film, the oxygen group element compound film comprises Ni aXb、Nic(XH)d、NieCfXg and H 2 X, the ratio of the sum of the atomic concentrations of oxygen group elements in Ni aXb、Nic(XH)d、NieCfXg to the total atomic concentration of oxygen group elements in the nickel alloy powder is more than 70%, the ratio of the atomic concentration of oxygen group elements in H 2 X to the total atomic concentration of oxygen group elements in the nickel alloy powder is more than 0 and less than or equal to 30%, wherein X is an oxygen group element, and the value range of a, b, c, d, e, f, g is 1-3.
Optionally, the element forming the strengthening phase with nickel includes at least one of aluminum, silicon, titanium, zirconium, hafnium, vanadium, niobium, and tantalum.
Optionally, the ratio of the sum of atomic concentrations of the oxygen group elements in the thickness of the nickel alloy powder from outside to inside to the total atomic concentration of the oxygen group elements in the nickel alloy powder is more than 50%.
Optionally, the ratio of the sum of atomic concentrations of the oxygen elements of Ni aXb、Nic(XH)d to the total atomic concentration of the oxygen elements in the nickel alloy powder is greater than 40%.
Optionally, the morphology of the nickel alloy powder is flaky, spherical or spheroidal.
According to a second aspect of the present invention, there is provided a conductive paste.
The conductive paste comprises the nickel alloy powder.
Optionally, when the average particle diameter d of the nickel alloy powder is 10-100 nm, the particle number of the nickel alloy powder with the observed particle diameter d1 larger than 4d in the visual field of the preset scanning electron microscope imaging range is smaller than or equal to 100;
when the average particle diameter d of the nickel alloy powder is 101-200 nm, the particle number of the nickel alloy powder with the observed particle diameter d1 larger than 4d in the visual field of a preset scanning electron microscope imaging range is smaller than or equal to 50;
when the average particle diameter d of the nickel alloy powder is 201-1000 nm, the particle number of the nickel alloy powder with the observed particle diameter d1 larger than 4d in the visual field of the preset scanning electron microscope imaging range is smaller than or equal to 25.
Optionally, the degree of dispersion of the observed particle diameter d1 of the nickel alloy powder in the field of view of the preset scanning electron microscope imaging range is represented by an extremely poor R, and r=max (d 1) -Min (d 1), wherein R: d >2, d is the average particle diameter of the nickel alloy powder.
According to a third aspect of the present invention, there is provided a multilayer ceramic capacitor.
The multilayer ceramic capacitor comprises an electrode formed by the conductive paste.
The nickel alloy powder of the invention contains the elements which form the strengthening phase with nickel, so that the initial sintering temperature of the nickel powder is effectively improved; the added second main group element effectively improves the stability of the nickel powder, so that the use effect and the service life of the nickel powder are both improved; the added oxygen group element forms an oxygen group element compound film on the surface of the nickel powder, plays a better role in protecting the internal added element of the nickel powder, and improves the cofiring property and the mutual combination degree of the nickel powder, glass powder in the conductive paste and the dielectric ceramic material.
Other features of the present invention and its advantages will become apparent from the following detailed description of exemplary embodiments of the invention, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a comparative graph of the dispersibility test of example 1 and comparative example 1.
FIG. 2 is a TGA plot of example 3.
FIG. 3 is a TGA graph of comparative example 3.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise.
The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of exemplary embodiments may have different values.
The nickel alloy powder provided by the invention comprises 0.001-0.1% of elements forming a strengthening phase with nickel, 0.001-0.1% of second main group elements and 0.1-15% of oxygen group elements by mass percent. The nickel alloy powder may have an average particle diameter d of 10 to 1000nm in terms of BET specific surface area. The second main group element may be at least one of beryllium, magnesium, calcium, strontium, and barium. The above-mentioned oxygen group element may be at least one of oxygen, sulfur, selenium and tellurium.
The surface of the nickel alloy powder is provided with an oxygen group element compound film, the oxygen group element compound film comprises Ni aXb、Nic(XH)d、NieCfXg and H 2 X, the ratio of the sum of the atomic concentrations of oxygen group elements in Ni aXb、Nic(XH)d、NieCfXg to the total atomic concentration of oxygen group elements in the nickel alloy powder is more than 70 percent, and the ratio of the atomic concentration of oxygen group elements in H 2 X to the total atomic concentration of oxygen group elements in the nickel alloy powder is more than 0 and less than or equal to 30 percent. X is an oxygen group element, and a, b, c, d, e, f, g has the value range of 1-3. a. The specific value of b, c, d, e, f, g is determined by the valence of each constituent element of the compound.
The nickel alloy powder has the characteristics of high initial oxidation temperature, good corrosion resistance, excellent cofiring property with a ceramic dielectric layer, better use effect and longer service life.
The nickel alloy powder of the invention contains the elements which form the strengthening phase with nickel, so that the initial sintering temperature of the nickel powder is effectively improved; the added second main group element effectively improves the stability of the nickel powder, so that the use effect and the service life of the nickel powder are both improved; the added oxygen group element forms an oxygen group element compound film on the surface of the nickel powder, plays a better role in protecting the internal added element of the nickel powder, and improves the cofiring property and the mutual combination degree of the nickel powder, glass powder in the conductive paste and the dielectric ceramic material.
In one embodiment of the nickel alloy powder of the present invention, the element forming the strengthening phase with nickel includes at least one of aluminum, silicon, titanium, zirconium, hafnium, vanadium, niobium, and tantalum.
In one embodiment of the nickel alloy powder of the present invention, the ratio of the sum of atomic concentrations of the oxygen group elements within a thickness of 5nm from the outside to the inside of the nickel alloy powder to the total atomic concentration of the oxygen group elements in the nickel alloy powder is greater than 50%. The limitation in this embodiment is advantageous in avoiding the problem of instability of nickel alloy crystals caused by excessive concentration of the oxygen group element in the region of the 5nm surface layer of the non-nickel alloy powder.
In one embodiment of the nickel alloy powder of the present invention, the ratio of the sum of the atomic concentrations of the oxygen group elements of Ni aXb、Nic(XH)d to the total atomic concentration of the oxygen group elements in the nickel alloy powder is greater than 40%. Ni aXb、Nic(XH)d (particularly Ni aXb) facilitates better bonding of the nickel alloy powder to the slurry system.
In one embodiment of the nickel alloy powder of the present invention, the morphology of the nickel alloy powder is lamellar, spherical or spheroidal.
The invention also provides a conductive paste which comprises the nickel alloy powder.
In one embodiment of the conductive paste, when the average particle diameter d of the nickel alloy powder is 10-100 nm, the particle number of the nickel alloy powder with the observed particle diameter d1 larger than 4d in the visual field of a preset scanning electron microscope imaging range is smaller than or equal to 100; when the average particle diameter d of the nickel alloy powder is 101-200 nm, the particle number of the nickel alloy powder with the observed particle diameter d1 larger than 4d in the visual field of the preset scanning electron microscope imaging range is smaller than or equal to 50; when the average particle diameter d of the nickel alloy powder is 201-1000 nm, the particle number of the nickel alloy powder with the observed particle diameter d1 larger than 4d in the visual field of the preset scanning electron microscope imaging range is smaller than or equal to 25. The field of view in this embodiment may be, for example, 10 100d×75d fields of view randomly selected within the scanning electron microscope imaging range. The particle size distribution of the nickel alloy powder in the embodiment can effectively improve the uniformity and stability of the slurry.
Taking 300nm nickel alloy powder as an example, in SEM pictures with random 10 pieces of 4:3 proportion and 30 μm long side of visual field, the total particle number of the nickel alloy powder meeting the condition of d1>1.2 μm is not more than 25 through software analysis counting or manual statistics, so that the requirement of the invention can be considered to be satisfied.
In one embodiment of the conductive paste of the present invention, the degree of dispersion of the observed particle diameter d1 of the nickel alloy powder in the field of view of the preset scanning electron microscope imaging range is represented by a very poor R, and r=max (d 1) -Min (d 1), where R: d >2, d is the average particle diameter of the nickel alloy powder. The field of view in this embodiment may be, for example, 10 60d×45d fields of view randomly selected within the scanning electron microscope imaging range. The particle size distribution of the nickel alloy powder in the embodiment can effectively improve the uniformity and stability of the slurry.
The invention also provides a multilayer ceramic capacitor comprising the electrode formed by the conductive paste.
The experimental procedures used in the examples below are conventional, and the materials and reagents used, unless otherwise indicated, are commercially available, and the equipment used in the experiments, unless otherwise indicated, are well known to those skilled in the art.
The nickel alloy powder in the embodiment of the invention is prepared by a physical vapor evaporation condensation method, and the added elements forming a strengthening phase with nickel and the second main group element and nickel are simultaneously evaporated in the same high-temperature evaporator, and are formed into nickel alloy powder along with nickel vapor nucleation, growth, crystallization and solidification, and an oxygen group element compound film is formed on the surface of the nickel alloy powder by a chemical method (for example, oxygen group element and nickel alloy powder are mixed under a high-temperature condition, so that an oxygen group element compound film can be formed on the surface of the nickel alloy powder).
Example 1
The nickel alloy powder of this example had an average particle diameter of 385nm in terms of specific surface area measured by the BET method; wherein the added elements forming a strengthening phase with nickel are zirconium and silicon, the weight content of the added zirconium is controlled to be 0.025 percent, and the weight content of the silicon is controlled to be 0.003 percent; the added second main group element is calcium element, which is used for strengthening alloy grain boundary, improving the use effect of alloy powder and controlling the weight content of the added calcium to be 0.015%; the added oxygen group elements are oxygen and sulfur, the weight content of the oxygen is controlled to be 1.05 percent, and the weight content of the sulfur is controlled to be 0.075 percent. The surface element analysis was performed by XPS, and the oxygen group elements in the nickel alloy powder mainly existed in the form of NiO, ni (OH) 2, C-O (the compounds Ni eCfXg)、NiS、H2 O and H 2 S were formed), wherein the ratio of the sum of the atomic concentrations of the oxygen group elements of NiO, ni (OH) 2, C-O, niS to the total atomic concentration of the oxygen group elements was 93%, and the ratio of the sum of the atomic concentrations of the oxygen group elements of H 2O、H2 S to the total atomic concentration of the oxygen group elements was 7%.
Comparative example 1
The nickel powder of comparative example 1 was prepared in the same manner as in example 1, except that the elements forming the strengthening phase with nickel and the second main group element were not added, and the oxide film was not formed on the surface. The average particle diameter of the nickel powder as measured by BET method was 365nm in terms of specific surface area.
The nickel alloy powder prepared in example 1 and the nickel powder prepared in comparative example 1 are exposed in air with the humidity of 60% at normal temperature, sampling is carried out after 24 hours, 15 days and 30 days respectively, and soft agglomeration is carried out on the powder after stirring in alcohol under the same conditions. As shown in fig. 1, after 24 hours, the powder slurry scraping test of example 1 and comparative example 1 were similar in dispersibility, and no obvious agglomeration phenomenon occurred; after 15 days, the powder scraping test of the embodiment 1 and the powder scraping test of the comparative embodiment 1 have larger dispersion difference, the nickel alloy powder of the embodiment 1 still keeps better dispersion, and the nickel powder of the comparative embodiment 1 has obvious agglomeration phenomenon; after 30 days, the nickel alloy powder of example 1 had undergone a slight agglomeration, and the powder of comparative example 1 had an increased agglomeration compared to the 15-day test, and started to appear larger agglomerates. It can be seen from the examination that the nickel alloy powder of example 1 has improved stability and service life compared to comparative example 1.
Example 2
The nickel alloy powder of this example has an average particle diameter of 977nm in terms of specific surface area measured by the BET method; wherein the added element forming a strengthening phase with nickel is aluminum, and the weight content of the added aluminum is controlled to be 0.012%; the added second main group element is magnesium element, which is used for strengthening alloy grain boundary, improving the use effect of alloy powder and controlling the weight content of the added magnesium to be 0.009%; the added oxygen group elements are oxygen and selenium, the weight content of the oxygen element is controlled to be 0.15 percent, and the weight content of the selenium element is controlled to be 0.005 percent. The surface element analysis is carried out by XPS, and the oxygen group elements in the nickel alloy powder mainly exist in the forms of NiO, ni (OH) 2、C-O、NiSe2, H 2 O and the like, wherein the sum of the atomic concentration of the oxygen group elements of NiO, ni (OH) 2、C-O、NiSe2 accounts for 96% of the atomic concentration of the total oxygen group elements, and the sum of the atomic concentration of the oxygen group elements of H 2 O accounts for 3% of the atomic concentration of the total oxygen group elements.
Comparative example 2
The nickel powder of comparative example 2 was prepared in the same manner as in example 2, except that the element forming the strengthening phase with nickel and the second main group element were not added, and the oxide film was not formed on the surface. The average particle diameter of the nickel powder as measured by BET method was 946nm in terms of specific surface area.
The nickel alloy powder prepared in example 2 and the nickel powder of comparative example 2 were made into a conductive paste, and a multilayer ceramic capacitor was made using the conductive paste. The yield (defective products of short circuit caused by warp deformation) of the multilayer ceramic capacitors prepared by the statistical test samples were counted, and the number of defective products occurring in three groups was counted for each thousand ceramic capacitors, as shown in table 1, and it was found that the nickel alloy powder of example 2 was added to improve co-firing with and bonding with dielectric ceramics, and the defective products of warp occurring in the preparation of capacitors were reduced.
TABLE 1
Example 3
The nickel alloy powder of this example has an average particle diameter of 95nm in terms of specific surface area measured by BET method; wherein the added elements forming a strengthening phase with nickel are hafnium and titanium, the weight content of the added hafnium is controlled to be 0.015 percent, and the weight content of the added titanium is controlled to be 0.001 percent; the added second main group element is barium element, which is used for strengthening alloy grain boundary, improving the use effect of alloy powder and controlling the weight content of the added barium to be 0.033%; the added oxygen group element is oxygen, and the weight content of the oxygen element is controlled to be 7.45 percent. The surface element analysis is carried out by XPS, and the oxygen group elements in the nickel alloy powder mainly exist in the forms of NiO, ni (OH) 2, C-O, H 2 O and the like, wherein the sum of the oxygen group element atomic concentrations of NiO, ni (OH) 2 accounts for 41 percent of the total oxygen group element atomic concentration, the proportion of the oxygen group element atomic concentration of C-O accounts for 31 percent of the total oxygen group element atomic concentration, and the sum of the oxygen group element atomic concentrations of H 2 O accounts for 27 percent of the total oxygen group element atomic concentration.
Comparative example 3
The nickel powder of comparative example 3 was prepared in the same manner as in example 3, except that the element forming the strengthening phase with nickel and the second main group element were not added, and the oxide film was not formed on the surface. The average particle diameter of the nickel powder as measured by BET method was 89nm in terms of specific surface area.
The nickel alloy powder of example 3 above and the nickel powder of comparative example 3 were tested for sintering by TMA (thermo mechanical analysis). The powder was prepared into a block-shaped sample having a length-width height of 4 x 2, and the sample block was heated at a heating rate of 10 c/min under nitrogen protection while measuring the shrinkage of the sample block height. The initial deformation temperature obtained from the obtained TMA chart found that the initial sintering temperature of the nickel alloy powder of example 3 was raised by 18.5 ℃ as compared with that of the nickel powder of comparative example 3.
The initial oxidation temperature was confirmed by detecting the weight change of the powder in an oxygen atmosphere during heating by TGA (thermal weight loss). The initial oxidation temperature of the nickel alloy powder prepared in example 3 was 411 deg.c as shown in fig. 2, and the initial oxidation temperature of the nickel alloy powder prepared in comparative example 3 was 389 deg.c as shown in fig. 3, that is, the initial oxidation temperature of the nickel alloy powder in example 3 was 22 deg.c higher than that of the nickel alloy powder in comparative example 3.
Example 4
The nickel alloy powder of this example has an average particle diameter of 16nm in terms of specific surface area measured by BET method; wherein, the added elements forming a strengthening phase with nickel are vanadium and tantalum, the weight content of the added vanadium is controlled to be 0.015 percent, and the weight content of the added tantalum is controlled to be 0.001 percent; the added second main group element is beryllium element, which is used for strengthening alloy grain boundary, improving the use effect of alloy powder and controlling the weight content of the added beryllium to be 0.097%; the added oxygen group element is oxygen, and the weight content of the oxygen element is controlled to be 2.76 percent. The surface element analysis was performed by XPS, and the oxygen group elements in the nickel alloy powder mainly exist in the form of NiO, ni (OH) 2, C-O, and the like, wherein the sum of the oxygen group element atomic concentrations of NiO, ni (OH) 2 accounts for 67% of the total oxygen group element atomic concentration.
Example 5
The nickel alloy powder of this example had an average particle diameter of 694nm in terms of specific surface area measured by BET method; wherein the added element forming a strengthening phase with nickel is niobium, and the weight content of the added niobium is controlled to be 0.004%; the added second main group element is strontium element, which is used for strengthening alloy grain boundary, improving the use effect of alloy powder and controlling the weight content of the added strontium to be 0.017%; the added oxygen group element is oxygen, and the weight content of the oxygen element is controlled to be 0.109 percent. The surface element analysis is carried out by XPS, and the oxygen group elements in the nickel alloy powder mainly exist in the forms of NiO, ni (OH) 2, C-O, H 2 O and the like, wherein the proportion of the sum of the atomic concentration of the oxygen group elements of NiO, ni (OH) 2 to the atomic concentration of the total oxygen group elements is 77.1 percent, the proportion of the atomic concentration of the oxygen group elements of C-O to the atomic concentration of the total oxygen group elements is 21.3 percent, and the proportion of the sum of the atomic concentration of the oxygen group elements of H 2 O to the atomic concentration of the total oxygen group elements is 0.6 percent.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (9)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214979A (en) * | 1997-10-17 | 1999-04-28 | 昭荣化学工业株式会社 | Nickel powder and preparation process thereof |
| CN100565713C (en) * | 2005-12-07 | 2009-12-02 | 昭荣化学工业株式会社 | Nickel powder, conductive paste and the multilayer electronic component that uses them |
| CN114566327A (en) * | 2021-11-11 | 2022-05-31 | 江苏博迁新材料股份有限公司 | Alloy powder production method, and alloy powder, slurry and capacitor prepared by method |
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| JP4807581B2 (en) * | 2007-03-12 | 2011-11-02 | 昭栄化学工業株式会社 | Nickel powder, method for producing the same, conductor paste, and multilayer ceramic electronic component using the same |
| JP2009079239A (en) * | 2007-09-25 | 2009-04-16 | Sumitomo Electric Ind Ltd | Nickel powder or nickel-based alloy powder and method for producing the same, conductive paste, and multilayer ceramic capacitor |
| CN106735279B (en) * | 2016-11-30 | 2020-08-28 | 江永斌 | Device for continuous mass production of high-purity nano-scale metal particles by circulating cooling |
| CN109648093A (en) * | 2018-12-18 | 2019-04-19 | 江苏博迁新材料股份有限公司 | A kind of superfine metal nickel powder surface treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1214979A (en) * | 1997-10-17 | 1999-04-28 | 昭荣化学工业株式会社 | Nickel powder and preparation process thereof |
| CN100565713C (en) * | 2005-12-07 | 2009-12-02 | 昭荣化学工业株式会社 | Nickel powder, conductive paste and the multilayer electronic component that uses them |
| CN114566327A (en) * | 2021-11-11 | 2022-05-31 | 江苏博迁新材料股份有限公司 | Alloy powder production method, and alloy powder, slurry and capacitor prepared by method |
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