CN115240896A - Nickel alloy powder, conductive paste and multilayer ceramic capacitor - Google Patents
Nickel alloy powder, conductive paste and multilayer ceramic capacitor Download PDFInfo
- Publication number
- CN115240896A CN115240896A CN202210815730.1A CN202210815730A CN115240896A CN 115240896 A CN115240896 A CN 115240896A CN 202210815730 A CN202210815730 A CN 202210815730A CN 115240896 A CN115240896 A CN 115240896A
- Authority
- CN
- China
- Prior art keywords
- alloy powder
- nickel alloy
- nickel
- powder
- oxygen group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 115
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 98
- 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 122
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 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
- 229910052798 chalcogen Inorganic materials 0.000 claims description 10
- 150000001787 chalcogens Chemical class 0.000 claims description 10
- 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
- 150000001786 chalcogen compounds Chemical class 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
- 239000006185 dispersion Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 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
- 238000010344 co-firing Methods 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000012071 phase Substances 0.000 description 15
- 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
- 238000000034 method Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction 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
- 239000013078 crystal Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 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
- 238000005054 agglomeration Methods 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
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 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
- 230000008859 change 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
- 238000007790 scraping Methods 0.000 description 2
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 2
- 238000001757 thermogravimetry curve Methods 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
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 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
- 238000001514 detection method Methods 0.000 description 1
- 239000007772 electrode material Substances 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
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 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
- 239000012299 nitrogen atmosphere Substances 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
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 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
- 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
- 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
- 239000012808 vapor phase Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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 a 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 in percentage by mass; the surface of the nickel alloy powder has an oxygen group element compound film containing Ni a X b 、Ni c (XH) d 、Ni e C f X g And H 2 And (4) X. The elements which form a strengthening phase with the nickel are added into the nickel alloy powder, so that the initial sintering temperature of the nickel powder is effectively improved(ii) a The added second main group elements effectively improve the stability of the nickel powder, so that the use effect and the service life of the nickel powder are improved; the added oxygen group element forms an oxygen group element compound film on the surface of the nickel powder, plays a good role in protecting the added elements in the nickel powder, and improves the co-firing property and the mutual bonding degree of the nickel powder, the glass powder and the dielectric ceramic material in the conductive paste.
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
The metal conductive powder and glass medium adhesive or other additives are uniformly mixed and dispersed in an organic carrier to prepare conductive paste, the conductive paste and dielectric layers are alternately and repeatedly laminated by a printing process, and the multilayer ceramic capacitor is prepared by firing and forming at high temperature.
Conventionally, precious metals such as palladium, silver, and platinum have been used in many cases as internal electrode materials of multilayer ceramic capacitors, but palladium or silver-palladium is oxidized and expanded during firing to cause problems such as delamination and cracking, and base metals such as nickel have been used as main conductive powders in conductive pastes in view of resource saving.
As the number of laminated layers of the multilayer ceramic capacitor is increased (more than 100 layers), the thickness of each layer is thinner (less than 3 microns), and the particle size of the nickel powder used is smaller (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 be stretched well at high temperature, so that the nickel powder is excessively sintered, and phenomena such as nickel aggregation, particle growth, and discontinuity of conductors occur, which not only causes a problem of increase of resistance value, but also causes problems such as fracture and deformation.
The change of the morphology of the nickel powder surface by conventional physical methods and the improvement of the nickel powder dispersibility by fluid dispersion have not been able to meet the demand for high performance multilayer ceramic capacitors. The nickel alloy powder obtained by adding more than one of vanadium, chromium, zirconium, niobium, molybdenum, tantalum and tungsten into the nickel powder can improve the initial sintering temperature of the conductive paste. However, these elements are liable to react with the ceramic material of the dielectric layer, and adversely affect the conductivity of the electrode of the multilayer ceramic capacitor.
Therefore, how to effectively improve the performance of nickel powders for multilayer ceramic capacitors has become a technical problem to be solved in the art.
Disclosure of Invention
An object of the present invention is to provide a novel technical solution of a nickel alloy powder that effectively improves the properties of nickel powder for a multilayer ceramic capacitor.
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 in percentage by mass;
the surface of the nickel alloy powder has an chalcogen compound film comprising Ni a X b 、Ni c (XH) d 、Ni e C f X g And H 2 X, and Ni a X b 、Ni c (XH) d 、Ni e C f X g The ratio of the sum of the atomic concentrations of the oxygen group elements to the total atomic concentration of the oxygen group elements in the nickel alloy powder is more than 70 percent, and H 2 The ratio of the concentration of oxygen group element atoms in X to the total concentration of oxygen group element atoms in the nickel alloy powder is more than 0 and less than or equal to 30 percent, wherein X is oxygen group element, and the value ranges of a, b, c, d, e, f and g are all 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 the atomic concentrations of the oxygen group elements in the nickel alloy powder from outside to inside within 5nm of the thickness to the total atomic concentration of the oxygen group elements in the nickel alloy powder is greater than 50%.
Optionally, ni a X b 、Ni c (XH) d The ratio of the sum of the atomic concentrations of the oxygen group elements to the total atomic concentration of the oxygen group elements in the nickel alloy powder is more than 40 percent.
Optionally, 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 size d of the nickel alloy powder is 10 to 100nm, the number of particles of the nickel alloy powder, the number of which is larger than 4d, in the view of the preset scanning electron microscope imaging range is less than or equal to 100;
when the average particle size d of the nickel alloy powder is 101-200 nm, the number of particles of which the observed particle size d1 is larger than 4d in the view field of the preset scanning electron microscope imaging range is less than or equal to 50;
when the average particle diameter d of the nickel alloy powder is 201-1000 nm, the number of particles of which the observed particle diameter d1 is larger than 4d in the view field of the preset scanning electron microscope imaging range is less than or equal to 25.
Optionally, the dispersion degree of the observed particle diameter d1 of the nickel alloy powder in the view field of the preset scanning electron microscope imaging range is represented by a range 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 of the conductive paste of the present invention.
The elements which form a strengthening phase with nickel are added into the nickel alloy powder, so that the initial sintering temperature of the nickel powder is effectively improved; the added second main group elements effectively improve the stability of the nickel powder, so that the use effect and the service life of the nickel powder are improved; the added oxygen group element forms an oxygen group element compound film on the surface of the nickel powder, plays a good role in protecting the added elements in the nickel powder, and improves the co-firing property and the mutual bonding degree of the nickel powder, the glass powder and the dielectric ceramic material in the conductive paste.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, 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 graph comparing the dispersibility tests of example 1 and comparative example 1.
Figure 2 is a TGA profile of example 3.
Fig. 3 is a TGA plot 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, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those 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 particular value should be construed as exemplary only and not as limiting. Thus, other examples of the 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 in percentage by mass. The average particle diameter d of the nickel alloy powder in terms of BET specific surface area may be 10 to 1000nm. The second main group element may be at least one of beryllium, magnesium, calcium, strontium, and barium. The chalcogen may be at least one of oxygen, sulfur, selenium and tellurium.
The surface of the nickel alloy powder has an oxygen group element compound film containing Ni a X b 、Ni c (XH) d 、Ni e C f X g And H 2 X, and Ni a X b 、Ni c (XH) d 、Ni e C f X g The ratio of the sum of the atomic concentrations of the oxygen family elements in the nickel alloy powder to the total atomic concentration of the oxygen family elements in the nickel alloy powder is more than 70 percent, H 2 The ratio of the concentration of the oxygen group element atoms in X to the total concentration of the oxygen group element atoms in the nickel alloy powder is more than 0 and less than or equal to 30 percent. X is an oxygen group element, and the value ranges of a, b, c, d, e, f and g are all 1-3. a. The specific values of b, c, d, e, f and g are determined by the valence of each component 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 elements which form a strengthening phase with nickel are added into the nickel alloy powder, so that the initial sintering temperature of the nickel powder is effectively improved; the added second main group elements effectively improve the stability of the nickel powder, so that the use effect and the service life of the nickel powder are improved; the added oxygen group element forms an oxygen group element compound film on the surface of the nickel powder, plays a good role in protecting the added elements in the nickel powder, and improves the co-firing property and the mutual bonding degree of the nickel powder, the 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 the atomic concentrations of the chalcogen element in the 5nm thickness from the outside to the inside of the nickel alloy powder to the total atomic concentration of the chalcogen element in the nickel alloy powder is greater than 50%. The definition in this embodiment is advantageous in avoiding the problem of instability of the nickel alloy crystal due to excessive concentration of chalcogen in the region other than the 5nm surface layer of the nickel alloy powder.
In one embodiment of the nickel alloy powder of the present invention, ni a X b 、Ni c (XH) d Atomic concentration of oxygen group element(s)The ratio of the sum to the total oxygen group element atomic concentration in the nickel alloy powder is more than 40%. Ni a X b 、Ni c (XH) d (particularly Ni) a X b ) Is beneficial to better combining the nickel alloy powder with a slurry system.
In one embodiment of the nickel alloy powder of the present invention, the morphology of the nickel alloy powder is flake, spherical or spheroidal.
The invention also provides conductive paste comprising 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 number of particles of which the observed particle diameter d1 is larger than 4d in the view field of the preset scanning electron microscope imaging range is less than or equal to 100; when the average particle diameter d of the nickel alloy powder is 101-200 nm, the number of particles of which the observed particle diameter d1 is larger than 4d in the view field of the preset scanning electron microscope imaging range is less than or equal to 50; when the average particle diameter d of the nickel alloy powder is 201-1000 nm, the number of particles of which the observed particle diameter d1 is larger than 4d in the view field of the preset scanning electron microscope imaging range is less than or equal to 25. The FOV in this embodiment may be, for example, 10 views of 100d 75d randomly selected within the scope of SEM imaging. The particle size distribution of the nickel alloy powder in the embodiment can effectively improve the uniformity and stability of the slurry.
Taking a nickel alloy powder with the particle size of 300nm as an example, in 10 SEM pictures with the proportion of 4 at random and the length of the visual field of 30 μm, the particle number of the nickel alloy powder meeting the condition that d1 is greater than 1.2 μm is not more than 25 in total through software analysis counting or manual statistics, and the requirement of the invention can be met.
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 within the field of view of the preset scanning electron microscope imaging range is represented by the range of the polar difference R, and R = Max (d 1) -Min (d 1), wherein R: d >2, d is the average particle diameter of the nickel alloy powder. The FOV in this embodiment may be, for example, 10 60d 45d FOVs randomly selected within the scope of SEM imaging. 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 an electrode formed by the conductive paste of the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified, the materials and reagents used are commercially available unless otherwise specified, and the equipment used in the experiments 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 phase evaporation and condensation method, the added elements forming a strengthening phase with nickel and the second main group elements are evaporated simultaneously with nickel in the same high-temperature evaporator, and form an oxygen group element compound film on the surface of the nickel alloy powder by a chemical method along with the nucleation, growth, crystallization and solidification of nickel vapor (for example, the oxygen group element and the nickel alloy powder are mixed under the high-temperature condition, so that the oxygen group element compound film can be formed on the surface of the nickel alloy powder).
Example 1
The nickel alloy powder of the present example had an average particle diameter of 385nm in terms of specific surface area measured by the BET method; wherein, the added elements forming the strengthening phase with the 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, is used for strengthening alloy grain boundary and improving the use effect of alloy powder, and the weight content of the added calcium is controlled to be 0.015 percent; 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. Surface element analysis by XPS shows that the oxygen group elements in the nickel alloy powder are mainly NiO and Ni (OH) 2 C-O (Compound Ni formed) e C f X g )、NiS、H 2 O and H 2 S exists in the form of NiO, ni (OH) 2 The sum of the atomic concentrations of oxygen group elements of C-O and NiS accounts for 93% of the total atomic concentration of oxygen group elements, and H 2 O、H 2 The sum of the atomic concentrations of the chalcogen elements of S accounts for 7% of the total atomic concentration of the chalcogen elements.
Comparative example 1
The nickel powder of comparative example 1 was prepared by the same procedure as in example 1, except that the element forming a strengthening phase with nickel and the second main group element were not added, and no chalcogen compound film was formed on the surface. The nickel powder had an average particle diameter of 365nm in terms of specific surface area measured by the BET method.
The nickel alloy powder prepared in example 1 and the nickel powder in comparative example 1 were exposed to 60% humidity air at room temperature, and after 24 hours, 15 days and 30 days, samples were taken, and the powder was stirred in alcohol under the same conditions and then subjected to a slurry scraping test to determine the occurrence of soft agglomeration. As shown in fig. 1, after 24 hours, the powder scratch tests of example 1 and comparative example 1 showed similar dispersibility, and no obvious agglomeration occurred; after 15 days, the dispersibility difference of powder scraping tests of the embodiment 1 and the comparative example 1 is larger, the nickel alloy powder of the embodiment 1 still keeps better dispersibility, and the nickel powder of the comparative example 1 has obvious agglomeration; after 30 days, the nickel alloy powder of example 1 slightly aggregated, and the powder aggregation of comparative example 1 was more serious than the detection result of 15 days, and larger aggregates began to appear. As can be seen from the examination, 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 the present example had an average particle diameter of 977nm in terms of specific surface area as 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, is used for strengthening alloy grain boundary and improving the use effect of alloy powder, and the weight content of the added magnesium is controlled 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. Surface element analysis by XPS shows that the oxygen group elements in the nickel alloy powder are mainly NiO and Ni (OH) 2 、C-O、NiSe 2 And H 2 O, etc., wherein NiO, ni (OH) 2 、C-O、NiSe 2 The sum of the atomic concentrations of the oxygen group elements accounts for 96 percent of the total atomic concentration of the oxygen group elements, H 2 The sum of the atomic concentrations of the oxygen group elements of O accounts for 3% of the total atomic concentration of the oxygen group elements.
Comparative example 2
The procedure for preparing the nickel powder of comparative example 2 was the same as in example 2, except that the element forming the strengthening phase with nickel and the second main group element were not added, and no chalcogen compound film was formed on the surface. The nickel powder thus obtained had an average particle diameter of 946nm in terms of specific surface area as measured by the BET method.
The nickel alloy powder prepared in example 2 and the nickel powder of comparative example 2 were prepared into a conductive paste, and a multilayer ceramic capacitor was prepared using the conductive paste. The yield (defective products with short circuit caused by warp deformation) of the multilayer ceramic capacitors prepared by the sample is counted, each thousand ceramic capacitors are taken as one group, and the number of the defective products in the three groups is counted, so that as shown in table 1, the nickel alloy powder in the embodiment 2 is added, the co-firing property and the bonding degree with the dielectric ceramic are improved, and the warp defective product rate of the prepared capacitors is reduced.
TABLE 1
Example 3
The nickel alloy powder of the present example had an average particle diameter of 95nm in terms of specific surface area measured by the BET method; wherein, the added elements which form a strengthening phase with the 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, is used for strengthening alloy crystal boundary and improving the use effect of alloy powder, and the weight content of the added barium is controlled 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. Surface element analysis by XPS shows that the oxygen group elements in the nickel alloy powder are mainly NiO and Ni (OH) 2 C-O and H 2 O, etc., wherein NiO, ni (OH) 2 The sum of the atomic concentrations of the oxygen group elements is 41% of the total atomic concentration of the oxygen group elements, the atomic concentration of the oxygen group elements of C-O is 31% of the total atomic concentration of the oxygen group elements, and H is 2 The sum of the atomic concentrations of the oxygen group elements of O accounts for 27% of the total atomic concentration of the oxygen group elements.
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 no film of the chalcogen compound was formed on the surface. The nickel powder thus obtained had an average particle diameter of 89nm in terms of specific surface area measured by the BET method.
The nickel alloy powder of example 3 and the nickel powder of comparative example 3 were tested for sintering by TMA (thermo-mechanical analysis). The powder was formed into a block sample with a length, width and height of 4 x 2, and the block was heated at a heating rate of 10 ℃/min under a nitrogen atmosphere while the shrinkage of the block height was measured. From the initial deformation temperature obtained from the obtained TMA chart, it was found that the nickel alloy powder of example 3 had an increased initial sintering temperature of 18.5 ℃.
The weight change of the powder was measured in an oxygen atmosphere during heating by TGA (thermal weight loss) to confirm the initial oxidation temperature. From fig. 2, it can be seen that the initial oxidation temperature of the nickel alloy powder prepared in example 3 is 411 deg.c, and from fig. 3, the initial oxidation temperature of the nickel powder prepared in comparative example 3 is 389 deg.c, i.e., the initial oxidation temperature of the nickel alloy powder in example 3 is raised by 22 deg.c compared to the nickel powder in comparative example 3.
Example 4
The nickel alloy powder of the present example had an average particle diameter of 16nm in terms of specific surface area measured by the BET method; wherein, the added elements which form a strengthening phase with the 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, is used for strengthening alloy crystal boundary and improving the use effect of alloy powder, and the weight content of the added beryllium is controlled 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 is carried out by XPS, the oxygen group elements in the nickel alloy powder are mainly NiO and Ni (OH) 2 C-O, wherein NiO, ni (OH) 2 The sum of the atomic concentrations of the chalcogen elements in the total atomic concentration of the chalcogen elements is 67%.
Example 5
The nickel alloy powder of the present example had an average particle diameter of 694nm in terms of specific surface area measured by the BET method; it is composed ofIn the method, 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, is used for strengthening alloy crystal boundary and improving the use effect of alloy powder, and the weight content of the added strontium is controlled to be 0.017 percent; the added oxygen group element is oxygen, and the weight content of the oxygen element is controlled to be 0.109 percent. Surface element analysis by XPS shows that the oxygen group elements in the nickel alloy powder are mainly NiO and Ni (OH) 2 C-O and H 2 O, etc., wherein NiO, ni (OH) 2 The sum of the atomic concentrations of the oxygen group elements in (1) to (21.3) of the oxygen group elements in (3) to (3) of C-O to (3) of the total atomic concentration of the oxygen group elements in (3) 2 The sum of the atomic concentrations of the oxygen group elements of O accounts for 0.6 percent of the total atomic concentration of the oxygen group elements.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present 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)
1. A nickel alloy powder is characterized by comprising 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 in percentage by mass;
the surface of the nickel alloy powder has an chalcogen compound film comprising Ni a X b 、Ni c (XH) d 、Ni e C f X g And H 2 X, and Ni a X b 、Ni c (XH) d 、Ni e C f X g The ratio of the sum of the atomic concentrations of the oxygen group elements in the nickel alloy powder to the total atomic concentration of the oxygen group elements in the nickel alloy powder is more than 70 percent, and H 2 The ratio of the concentration of oxygen group element atoms in X to the concentration of total oxygen group element atoms in the nickel alloy powder is greater than 0 and less30% or less, wherein X is oxygen group element, and a, b, c, d, e, f, g all have the value range of 1-3.
2. The nickel alloy powder of claim 1, wherein the element that forms a strengthening phase with nickel comprises at least one of aluminum, silicon, titanium, zirconium, hafnium, vanadium, niobium, and tantalum.
3. The nickel alloy powder according to claim 1, wherein a ratio of a sum of atomic concentrations of the chalcogen element in a thickness of 5nm from the outside to the inside of the nickel alloy powder to a total atomic concentration of the chalcogen element in the nickel alloy powder is more than 50%.
4. The nickel alloy powder according to claim 1, wherein Ni is Ni a X b 、Ni c (XH) d The ratio of the sum of the atomic concentrations of the oxygen group elements to the total atomic concentration of the oxygen group elements in the nickel alloy powder is more than 40 percent.
5. The nickel alloy powder according to claim 1, wherein the morphology of the nickel alloy powder is flake, spherical or spheroidal.
6. An electrically conductive paste comprising the nickel alloy powder according to any one of claims 1 to 5.
7. The conductive paste according to claim 6, wherein when the average particle diameter d of the nickel alloy powder is 10-100 nm, the number of particles of which the observed particle diameter d1 is greater than 4d in the view field of a preset scanning electron microscope imaging range is less than or equal to 100;
when the average particle size d of the nickel alloy powder is 101-200 nm, the number of particles of which the observed particle size d1 is larger than 4d in the view of the preset scanning electron microscope imaging range is less than or equal to 50;
when the average particle size d of the nickel alloy powder is 201-1000 nm, the number of particles of which the observed particle size d1 is larger than 4d in the view field of the preset scanning electron microscope imaging range is less than or equal to 25.
8. The conductive paste according to claim 6, wherein the degree of dispersion of the observed particle diameter d1 of the nickel alloy powder within the view field of a preset scanning electron microscope imaging range is represented by the range R, and R = Max (d 1) -Min (d 1), wherein R: d >2,d is the average particle diameter of the nickel alloy powder.
9. A multilayer ceramic capacitor comprising an electrode formed of the conductive paste as claimed in any one of claims 6 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210815730.1A CN115240896A (en) | 2022-07-11 | 2022-07-11 | Nickel alloy powder, conductive paste and multilayer ceramic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210815730.1A CN115240896A (en) | 2022-07-11 | 2022-07-11 | Nickel alloy powder, conductive paste and multilayer ceramic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115240896A true CN115240896A (en) | 2022-10-25 |
Family
ID=83673798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210815730.1A Pending CN115240896A (en) | 2022-07-11 | 2022-07-11 | Nickel alloy powder, conductive paste and multilayer ceramic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115240896A (en) |
Citations (7)
| 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 |
| CN1979694A (en) * | 2005-12-07 | 2007-06-13 | 昭荣化学工业株式会社 | Nickel powder, conductive paste, and multilayer electronic component using same |
| CN101264523A (en) * | 2007-03-12 | 2008-09-17 | 昭荣化学工业株式会社 | Nickel powder, method for manufacturing same, conductor paste, and multilayer ceramic electronic component using same |
| CN101808767A (en) * | 2007-09-25 | 2010-08-18 | 住友电气工业株式会社 | Nickel powder or alloy powder having nickel as main component, method for manufacturing the powder, conductive paste and laminated ceramic capacitor |
| CN106735279A (en) * | 2016-11-30 | 2017-05-31 | 江永斌 | The device of the continuous volume production high-purity Nano-class metallic of 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 |
| 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 |
-
2022
- 2022-07-11 CN CN202210815730.1A patent/CN115240896A/en active Pending
Patent Citations (8)
| 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 |
| CN1979694A (en) * | 2005-12-07 | 2007-06-13 | 昭荣化学工业株式会社 | Nickel powder, conductive paste, and multilayer electronic component using same |
| 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 |
| CN101264523A (en) * | 2007-03-12 | 2008-09-17 | 昭荣化学工业株式会社 | Nickel powder, method for manufacturing same, conductor paste, and multilayer ceramic electronic component using same |
| CN101808767A (en) * | 2007-09-25 | 2010-08-18 | 住友电气工业株式会社 | Nickel powder or alloy powder having nickel as main component, method for manufacturing the powder, conductive paste and laminated ceramic capacitor |
| CN106735279A (en) * | 2016-11-30 | 2017-05-31 | 江永斌 | The device of the continuous volume production high-purity Nano-class metallic of 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 |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5952040A (en) | Passive electronic components from nano-precision engineered materials | |
| JP3644235B2 (en) | Multilayer ceramic electronic components | |
| JP2014160791A (en) | Multilayer ceramic electronic part | |
| WO1998018741A9 (en) | Passive electronic components prepared from suspensions of nanoscale ceramic powders | |
| US9287043B2 (en) | Multilayer ceramic electronic component having controlled difference in continuity between internal electrodes and method of manufacturing the same | |
| WO2007040195A1 (en) | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder | |
| JP5253351B2 (en) | MULTILAYER CERAMIC ELECTRONIC COMPONENT AND METHOD FOR MANUFACTURING THE SAME, FLAT CONDUCTIVE FINE POWDER FOR MULTILAYER CERAMIC ELECTRONIC COMPONENT AND FLAT CONDUCTIVE FINE POWDER DISPERSION FOR MULTILAYER CERAMIC ELECTRONIC COMPONENT | |
| JP2022067317A (en) | Composite particle, conductive paste and electronic component | |
| TW200417435A (en) | Surface-treated ultrafine metal powder, method for producing the same, conductive metal paste of the same, and multilayer ceramic capacitor using said paste | |
| CN115240896A (en) | Nickel alloy powder, conductive paste and multilayer ceramic capacitor | |
| CN1599653A (en) | Copper alloy powder for electroconductive paste | |
| JP5590289B2 (en) | Method for producing silver paste | |
| US20230080684A1 (en) | Ceramic electronic component, method of manufacturing ceramic electronic component, and method of producing dielectric powder | |
| JP4427966B2 (en) | Multilayer ceramic electronic component and manufacturing method thereof | |
| US20120169447A1 (en) | Nanocomposite powder for inner electrode of multilayer ceramic electronic device and fabricating method thereof | |
| JP4061462B2 (en) | Composite fine particles, conductive paste and conductive film | |
| JP2007332446A (en) | Nickel particle with dielectric particle and method of producing the nickel particle with dielectric particle | |
| JP5942791B2 (en) | Method for producing nickel powder | |
| JP6575411B2 (en) | Dielectric thin film element | |
| JP3542079B2 (en) | Nickel powder and conductive paste | |
| JP6799931B2 (en) | Nickel fine particle-containing composition and its manufacturing method, internal electrodes and laminated ceramic capacitors | |
| JP2004183027A (en) | Method for manufacturing nickel powder, nickel powder, electroconductive paste, and multilayered ceramic electronic component | |
| JP2002275509A (en) | Method for manufacturing metal powder, metal powder, conductive paste which uses the same and multilayer ceramic electronic parts which use the same | |
| JP4441951B2 (en) | Multilayer ceramic electronic components | |
| TWI829834B (en) | Silver paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |