CN117444197A - Sulfide coated modified nickel powder material by gas phase co-evaporation method and preparation method thereof - Google Patents
Sulfide coated modified nickel powder material by gas phase co-evaporation method and preparation method thereof Download PDFInfo
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- CN117444197A CN117444197A CN202311403573.4A CN202311403573A CN117444197A CN 117444197 A CN117444197 A CN 117444197A CN 202311403573 A CN202311403573 A CN 202311403573A CN 117444197 A CN117444197 A CN 117444197A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000010549 co-Evaporation Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 115
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000013077 target material Substances 0.000 claims description 9
- 239000012798 spherical particle Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 2
- 239000012467 final product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 238000002161 passivation Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000004891 communication Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 19
- 210000002381 plasma Anatomy 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- GNTJFIMIXKRWEL-UHFFFAOYSA-N [S].[Ni]=O Chemical group [S].[Ni]=O GNTJFIMIXKRWEL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfide modified nickel powder Chemical class 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
Abstract
A sulfide coated modified nickel powder material by a gas phase co-evaporation method and a preparation method thereof belong to the technical field of material preparation. The nickel powder particles are of a spherical core/shell structure, the core is Ni particles, the shell is a NiS layer coated on the Ni particles and an outermost ultrathin passivation layer, the S content is 100-1500 ppm, and the thickness of the coating layer is 2-10 nm. The thermal plasma is used as an evaporation heat source, micron-sized nickel and sulfur powder are mixed to be used as a raw material target, and a gas phase co-evaporation method is adopted for in-situ co-evaporation to synthesize the nickel sulfide coated modified nickel powder material. The sulfur content in the raw materials is controlled to regulate and control the sulfur component, the sulfide coating structure and the thickness of the sulfide coating structure in the powder product, so that the special requirements of the MLCC inner electrode on the metal powder material are met. The invention realizes the control of the microstructure, the size and the distribution of powder particles through the technological parameters such as raw material proportion, gas phase, temperature field, heat source power and the like; the method has simple process, low production cost and mass production, and is suitable for the wide demands of important fields such as electronic communication, aerospace, medical equipment and the like for metal powder materials.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a sulfide coated modified metal powder material by a gas phase co-evaporation method and a preparation method thereof, which are used as an inner electrode material of a low-volume shrinkage multilayer ceramic capacitor (Multilayer Ceramic Capacitor, MLCC).
Background
The MLCC, which is one of the most widely used electronic components in integrated circuits, has the characteristics of small size, large specific volume, high efficiency, good reliability, low equivalent resistance, and the like, and has been widely used in important fields such as automotive electronics, aerospace military industry, medical equipment, and the like. The raw materials for preparing the MLCC comprise dielectric ceramic powder, internal electrode conductive paste and end electrode conductive paste, wherein the main materials of the electrode paste comprise metal powder, glass phase and organic carrier, and the superfine metal powder is used as the main component of the electrode paste to determine the electrode performance. Early MLCCs were noble metal palladium or palladium-silver alloy with higher cost. With the continuous expansion of the market scale of MLCC products, in order to reduce the production and use cost, slurry preparation is started in the middle 90 th century to prepare base metallization, the inner electrode adopts nickel to replace palladium, the end electrode adopts copper to replace silver and the like, and the cost of various electronic materials is greatly reduced on the basis of maintaining the performance. BME-MLCC (base metal electrode plate type multilayer ceramic capacitor) has now accounted for more than 90% of the total MLCC.
As a main functional phase of the MLCC internal electrode paste, the internal electrode metal powder should have the following characteristics: (1) high melting point (above 1000deg.C), sintering at 1400 deg.C without oxidation, melting, volatilization and loss (MLCC mainly adopts BaTiO) 3 The ceramic is used as a medium and needs to be sintered at about 950-1300 ℃ so as to keep the continuity of the metal slurry layer after sintering and film forming. (2) Low electron mobility to prevent diffusion into the dielectric while sintering with the ceramic dielectric, and diffusion tolerance to the dielectric is such that the dielectric does not react with the dielectric while the dielectric properties of the dielectric are not affected. (3) High purity to ensure good electrical conductivity. (4) The spherical or spheroidic particles have good morphology, good dispersibility and uniform size distribution. The spherical metal powder with uniform particle size can ensure the uniformity of the conductive paste, so that metal particles are in good contact after sintering, and meanwhile, the defect that large particles penetrate through a dielectric layer to cause a non-laminated structure can be avoided. (5) The tap density is large enough to resist shrinkage during sinteringThe stronger the capability, the more suitable as the inner electrode slurry material.
The nickel powder has the characteristics of low cost, high conductivity, small electric mobility, good corrosion resistance and heat resistance to solder and higher sintering temperature, and is the most used internal electrode material of the MLCC at present. The method for preparing nickel powder mainly comprises three steps: (1) the hydration hypochondriac reduction method is to reduce nickel ions by utilizing reducing substances such as hydration hypochondriac, sodium borohydride, potassium borohydride and the like to obtain metal nickel powder. The method relates to more sensitive reaction parameters, has poor batch stability and is difficult for mass industrialized production. (2) The physical thermal evaporation method is to evaporate the nickel material by using high-energy heat sources such as plasma or laser, and the like, and obtain nickel metal powder in a low-temperature chamber. The method is convenient for industrialized mass production, but has higher equipment cost, and the prepared nickel powder has wider particle size distribution and generally needs to be subjected to particle size classification treatment. (3) The polyol reduction method mainly utilizes the polyol to reduce nickel hydroxide to obtain nano nickel, the process of the method is still immature, nickel powder particles are not uniform, meanwhile, the viscosity of a polyol system is high, and the separation of nickel powder and polyol is difficult.
At present, nickel powder faces two main problems in the application of electrodes in MLCCC: firstly, in the preparation process of the MLCC, heating evaporation treatment is required to be carried out in the atmospheric environment at the temperature of 250-400 ℃ to remove organic residual components, and at the moment, oxidation phenomenon is easy to occur on metal nickel powder in electrode slurry so as to influence the conductivity of the MLCC; secondly, the shrinkage rate of nickel powder is higher than that of ceramic dielectric materials in the high-temperature (usually 1200 ℃ and above) sintering process, which may lead to the deformation of electrode layers and dielectric layers caused by stress, and even cracking or stripping phenomena occur in severe cases, which is a main source of failure rate in the current MLCC production.
At present, the method for improving the usability of the nickel powder mainly comprises the steps of carrying out surface coating treatment on the nickel powder, and forming a protective coating layer to effectively improve the oxidation resistance and shrinkage performance of the powder, and simultaneously ensure that the nickel powder maintains good conductivity in the use process. Patent CN112872349A discloses a nano nickel powder with a core-shell structure, the diameter of the nickel powder is 10nm-600nm, the thickness of the protective layer is 0.5nm-6nm, the protective layer is a nickel-sulfur-oxygen protective layer, the nickel-sulfur-oxygen protective layer comprises nickel sulfide, nickel oxide, nickel hydroxide, basic nickel carbonate, carbon dioxide and water, the nickel powder of the nickel powder has high sphericity, complete crystal structure and good dispersibility, and the sintering temperature and shrinkage rate are improved to a certain extent compared with those of the nickel powder. However, the preparation process is complicated and the production cost is high; the preparation of the nickel powder surface coating layer is complex and contains impurities; the nickel powder has a wide size distribution.
Disclosure of Invention
The invention provides sulfide modified nickel powder for an MLCC inner electrode, which has similar volume shrinkage rate with a ceramic dielectric layer during sintering, and a preparation method thereof, in order to solve the technical problem that the shrinkage rate of the nickel powder of the inner electrode layer is higher than that of the ceramic dielectric material during sintering in the existing MLCC preparation process. Specifically, after uniformly mixing a micron-sized nickel powder raw material and a sublimed sulfur powder raw material, the mixture is used as a conductive target material to be evaporated in direct-current arc plasma to in-situ synthesize the nickel sulfide coated metal nickel powder material with set components. The invention has the advantages of simple preparation method, low production cost, high powder purity, low volume shrinkage, good sintering performance and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the gas phase co-evaporation sulfide coating modified nickel powder material has a spherical core/shell structure, wherein the core is Ni particles, and the shell is a NiS coating layer coated on the nickel particles and a thin oxide layer formed on the outermost surface of the nickel powder due to passivation. According to the nickel sulfide coated modified nickel powder material, elemental sulfur powder is doped into raw materials, the proportion of corresponding raw material components is determined, the preparation process parameters are modulated, and the microstructure, particle size and distribution of powder particle cores/shells can be regulated and controlled.
The spherical particle size of the nickel sulfide coated modified nickel powder material is between 10 and 200nm, the thickness of the NiS coating layer is between 2 and 10nm, and the S content is between 500 and 1500 ppm.
The nickel sulfide coated modified nickel powder material has high sphericity, high crystallinity and high purity, and the nickel sulfide coated on the surface of the nickel powder forms stable chemical bonding between sulfur and nickel components, so that the high temperature resistance of the nickel powder is further improved, high temperature cracking and stripping phenomena are not easy to occur, and the high temperature sintering performance is greatly improved; a thin oxide layer is formed on the outermost surface of the nickel powder through passivation, so that the oxidation resistance and dispersibility of the nickel powder are improved to a certain extent.
The preparation method takes thermal plasma as an evaporation source, and the micron-sized nickel powder and sulfur powder are uniformly mixed to serve as a raw material target material, and the multi-component raw materials are subjected to in-situ co-evaporation to finally synthesize the nickel sulfide coated modified nickel powder material. The sulfur content in the raw material target material is controlled to regulate and control the sulfur component, the sulfide coating layer structure and the thickness thereof in the powder product, and finally, the special requirements of the MLCC inner electrode on the metal powder material are met. The method specifically comprises the following steps:
first, raw materials and mass ratio
The method adopts automatic control direct current arc plasma powder production equipment, a cathode uses a high-temperature-resistant metal alloy bar or a graphite bar, and an anode uses a raw material target material formed by mixing micron-sized nickel powder and sublimed sulfur powder. The nickel and sulfur raw materials with fixed proportion are weighed and mechanically and evenly mixed, the mixed raw material target is pressed into a material target with fixed size by a hydraulic press, the material target is placed on an anode bearing crucible in a furnace body, and the interval between a cathode bar at the upper end of the crucible and the anode material target is 10-30 mm.
The micron-sized nickel powder is micron-sized coarse nickel powder (more than micron size); the sublimed sulfur powder is micron-sized sulfur powder (the size above micron); the mass ratio of Ni to S in the raw material target material is in the range of 500:1-2000:1.
Secondly, synthesizing powder by adopting a gas phase co-evaporation method
The whole production equipment connected in series comprises an evaporation chamber, a condensation chamber, a powder trapping chamber and an airflow circulation system, and the vacuum degree is pumped to 10 -3 And after Pa, introducing working gas with certain pressure. And (3) switching on a plasma power supply, igniting an electric arc between the cathode and the anode, generating a large amount of thermal plasmas under the action of current, evaporating the material mixed target material, and forming a nickel sulfide coated modified nickel powder product.
The working gas is one or more of nitrogen, argon, hydrogen and ammonia; the gas pressure is in the range of 30 to 100 kPa; the working current is in the range of 90-1000A.
Thirdly, in-situ passivation and collection of powder
The co-evaporation process is continuously carried out, after a sufficient amount of powder products are formed, a plasma power supply is turned off, powder in the cavity is kept stand for a certain time (1-2 h) to settle and stabilize, and a small amount of air is introduced into the cavity to passivate the surface of the powder. After passivation (6-12 h), the powder product was finally collected in a trap chamber.
The application of the nickel sulfide coated modified nickel powder material is used for the MLCC inner electrode metal powder material used in the integrated circuits in the fields of automobile electronics, aerospace military industry, medical equipment and the like, compared with the existing MLCC inner electrode metal powder, the high-temperature sintering performance of the MLCC inner electrode metal powder material is obviously improved, the cracking or stripping phenomenon caused by stress of an electrode layer and a dielectric layer due to the fact that the shrinkage rate of nickel powder is higher than that of a ceramic medium in the preparation process of the MLCC can be reduced, and the production failure rate of the MLCC is obviously reduced.
The principle of the invention is as follows:
the basic process for preparing the powder material by the physical vapor phase evaporation method comprises the following steps: and a high-temperature heat source (thermal plasma, high-energy laser, resistance heating, electromagnetic induction heating and the like) is adopted to evaporate the target material and form a gas phase state. When the gaseous concentration of one of the constituent elements reaches a supersaturated state and approaches the melting point temperature, nucleation centers begin to appear, solid-phase crystal nuclei are formed and gradually grow into particles. During the nucleation process, single material crystal nucleus or multiple material crystal nuclei can appear, and the phase composition of the powder product is finally determined; during the growth of the crystal nuclei, the gas phase concentration, the ambient temperature and the temperature field conditions thereof affect the size and distribution of the particle products and the microstructure of the particles determined by the composition of various substances. In the invention, micron-sized nickel powder and sublimed sulfur powder raw materials are used as raw materials, the raw materials are evaporated and decomposed under the condition of high-temperature nitrogen plasma or hydrogen plasma, a high-temperature gas phase state composed of Ni, S, O, N, H atoms, ions and electrons is formed in a central region of the plasma, and the processes of inter-element combination (combination), nucleation and crystal nucleus growth, solid phase precipitation, particle surface recrystallization, particle growth, formation of a core/shell structure and the like are generated along with the diffusion and migration of atoms (main component elements Ni and S) from a high-temperature region to a low-temperature region. The metal element Ni and the nonmetal element S used in the invention have the advantages that as the melting point of Ni is obviously higher than that of S and nickel-sulfur compounds, when high-concentration Ni and S steam reach a Ni melting point temperature range at first in a low-temperature zone, the Ni element in a dilute oxygen environment is nucleated and grown in a single state to form a core composition of particles; along with the Ni core and S steam reaching the low temperature range, i.e. the melting point temperature range of nickel sulfide, S element gathers and diffuses on the surface of the Ni core, combines with the surface Ni element to form a nickel sulfide coating layer, and prevents the Ni particles from further growing and growing. The key points of the invention are as follows: the method comprises the steps of adopting a physical evaporation means of a thermal plasma heat source to co-evaporate a sulfur-containing target, wherein the mass ratio of S in the target is used as a key element for controlling the sulfur content of powder, the preferred range is 1000:1-2000:1, and the nickel sulfide coated modified nickel powder is synthesized in one step in situ, and the concentration of a growth substance, the growth rate, the microstructure of a product, the size of powder particles and the distribution of the powder are regulated and controlled by adjusting preparation process parameters and condensation conditions.
The beneficial effects of the invention are as follows:
1) The invention provides a preparation method for in-situ synthesis of nickel sulfide coated modified nickel powder by a physical vapor co-evaporation method, which has the advantages of large-scale production, environmental friendliness, high raw material utilization rate, easy regulation and control of powder microstructure and size, good particle dispersibility and the like.
2) The surface of the nickel powder forms a coating layer formed by nickel-sulfur chemical bonds, and the outermost surface of the nickel powder forms a thin oxide layer due to passivation, so that under the combined action of nickel-oxygen and nickel-sulfur chemical bonds, the high temperature resistance and sintering performance of the modified nickel powder are obviously improved.
3) The preparation method provides a wide technical approach for surface modification of the metal powder, has simple process, strong universality, strong adjustability and low preparation cost, and can meet the special requirements of multiple fields such as microelectronics, automobiles, communication, aerospace and military industry on the metal powder material.
Drawings
Fig. 1 is a TEM image (fig. a) of the NiS coated modified Ni powder particles (example 3), and a corresponding elemental scan image, wherein fig. b is a Ni elemental scan image of the modified Ni powder (example 3), fig. c is an S elemental scan image of the modified Ni powder (example 3), and fig. d is an O elemental scan image of the modified Ni powder (example 3);
FIG. 2 is an X-ray diffraction pattern of pure Ni powder (comparative example 1) and NiS-modified Ni powder (examples 1 to 4);
FIG. 3 is an XPS plot of NiS coated modified Ni powder particles (example 3), wherein plot a is the Ni fine spectrum of the modified Ni powder (example 3), plot b is the S fine spectrum of the modified Ni powder (example 3), and plot c is the O fine spectrum of the modified Ni powder (example 3);
FIG. 4 is a graph showing the relationship between sulfur content in the target material and the corresponding powder product (examples 1 to 4);
FIG. 5 is a pure Ni powder (comparative), commercial BaTiO 3 Powder, and NiS modified Ni powder (examples 1-4, fig. 5 a-5 d), volume shrinkage curves in the range of 50-1200 ℃; wherein FIG. a is a graph of modified Ni powder (example 1) versus pure Ni powder, commercially available BaTiO 3 Powder volume shrinkage curve, panel b, for modified Ni powder (example 2) versus pure Ni powder, commercial BaTiO 3 Powder volume shrinkage curve, panel c, for modified Ni powder (example 3) versus pure Ni powder, commercial BaTiO 3 A volumetric shrinkage curve of the powder; FIG. d shows the modified Ni powder (example 4) and pure Ni powder, commercially available BaTiO 3 Volumetric shrinkage curve of the powder.
Detailed Description
The above-described aspects of the invention will be described in further detail with reference to the following embodiments, but the scope of the invention is not limited to the following examples:
comparative example:
1. for comparison with sulfide coated modified nickel powder, pure Ni powder was prepared. Weighing 50g of micron-sized coarse nickel powder, pressing into blocks, placing the blocks on an anode copper target in a direct current arc plasma working chamber, taking a graphite rod as a cathode, and measuring the diameter of the graphite rod4mm long and 100mm long. Evacuating the working chamber to 1X 10 -3 Pa, nitrogen was introduced to 80kPa. Wherein the purity of the nitrogen is 99.99 percent;
2. starting a circulating cooling system, starting an arc power supply, adjusting the arc current to 120A, and starting an arc for 20min at the working voltage of 30-45V;
3. and (3) turning off the power supply, and collecting a powder sample from the trapping chamber after stabilizing for 12 hours, wherein the powder sample is used as a pure Ni powder comparison sample and is marked as S0.
4. As shown in fig. 2, the XRD diffractogram of the pure Ni powder (comparative).
5. As shown in FIG. 3, XPS spectrum (bottom curve) of pure Ni powder (comparative example) shows that Ni and NiO peaks appear on the surface of the fine Ni spectrum, and no S peak appears.
6. As shown in FIG. 5, the volume shrinkage curve (black curve) of the pure Ni powder in the range of 50-1200 ℃ is shown as shrinkage starting at 647 ℃ and continuously accelerating shrinkage in the subsequent temperature rising process, the final volume shrinkage reaches-14.9%, and the volume shrinkage variation is obviously larger than that of BaTiO 3 And (5) powder.
Example 1:
1. the method comprises the steps of mixing micron-sized coarse nickel powder with sublimed sulfur powder according to a weight ratio of 500:1 (wherein the quality of nickel powder is controlled to be 50 g) are uniformly mixed and pressed into blocks, the blocks are placed on an anode copper target in a direct current arc plasma working chamber, a graphite rod is used as a cathode, the interval between the cathode rod at the upper end of a crucible and the anode material target is 20mm, wherein the diameter of the graphite rod is as follows4mm long and 100mm long. Evacuating the working chamber to 1X 10 -3 Pa, introducing nitrogen atmosphere into the working chamber, and controlling the air pressure to 80kPa. Wherein the purity of the nitrogen is 99.99 percent;
2. starting a circulating cooling system and a power supply, adjusting the arc current to 120A, and igniting an arc for 20min at the working voltage of 30-45V;
3. stopping arc, and charging into the reaction chamber for about 1×10 after 2 hr 3 Pa, a trace amount of air, and passivating nickel powder. Continuous stabilizationAfter 10 hours, a sample of nickel sulfide coated modified nickel powder, designated sample S1, was collected from the trap chamber.
4. As shown in FIG. 2, the X-ray diffraction pattern of sample S1 (example 1) showed that the main phase was Ni and that no Ni/S compound diffraction peak was present.
5. As shown in fig. 4, the raw material ratio of sample S1 (example 1) was Ni: s=500:1, the S content in the raw material was 0.2wt.%, and the S content in the corresponding powder product was 0.338wt.%, as measured by a carbon sulfur analyzer. In the raw material evaporation process, since the melting point of Ni is significantly higher than that of S, the evaporation rate of S is higher than that of Ni in co-evaporation, resulting in a higher concentration of S in the gas phase than that of Ni, and the S content in the powder is higher than that in the raw material.
6. As shown in fig. 5 (a), the volume shrinkage curve of sample S1 (example 1) in the range of 50 to 1200 ℃ exhibited slow shrinkage before 960 ℃, at which stage shrinkage performance was somewhat better than that of pure Ni powder; but starts to be converted into abrupt expansion when the temperature reaches 960 ℃, and finally the volume shrinkage reaches +9.1 percent, and finally the BaTiO is adopted 3 The difference of the powder shrinkage rate of-4.2 percent reaches 13.3 percent, which is higher than that of pure Ni powder and BaTiO 3 The powder shrinkage difference was 10.7%. Taken together, sample S1 (example 1) had somewhat poorer volume shrinkage performance than pure Ni powder in the range of 50-1200 ℃, presumably due to the excessively high S content.
Example 2:
1. the method comprises the steps of mixing micron-sized coarse nickel powder with sublimed sulfur powder according to a weight ratio of 1000:1 (wherein the quality of nickel powder is controlled to be 50 g) are uniformly mixed and pressed into blocks, the blocks are placed on an anode copper target in a direct current arc plasma working chamber, a graphite rod is used as a cathode, a gap between a cathode rod at the upper end of a crucible and an anode material target is 10mm, wherein the diameter of the graphite rod is as follows4mm long and 100mm long. Evacuating the working chamber to 1X 10 -3 Pa, introducing nitrogen atmosphere into the working chamber, and controlling the air pressure to 80kPa. Wherein the purity of the nitrogen is 99.99 percent;
2. starting a circulating cooling system and a power supply, adjusting the arc current to 120A, and igniting an arc for 20min at the working voltage of 30-45V;
3. stopping arc, and charging into the reaction chamber for about 1×10 after 2 hr 3 And (5) Pa trace air passivation treatment of nickel powder. After 10 hours of continuous stabilization, a sample of nickel sulfide coated modified nickel powder, designated sample S2, was collected from the trap chamber.
4. As shown in FIG. 2, the X-ray diffraction pattern of sample S2 (example 2) showed that the main phase was Ni and that no Ni/S compound diffraction peak was present.
5. As shown in fig. 4, the raw material ratio of the sample S2 is Ni: s=1000:1, the S content in the raw material is 0.1wt.%, and the S content in the corresponding powder product measured by the carbon-sulfur analyzer is 0.156wt.%.
6. As shown in fig. 5 (b), the volume shrinkage curve of sample S2 (example 2) in the range of 50 to 1200 ℃ exhibited shrinkage before 905 ℃, but the shrinkage performance at this stage was also somewhat inferior to that of pure Ni powder; at 905 deg.C, the material begins to expand quickly to reach final volume shrinkage of +7.2% and to reach BaTiO 3 The difference of the powder shrinkage rate of-4.2 percent reaches 11.4 percent, which is higher than that of pure Ni powder and BaTiO 3 The powder shrinkage difference was 10.7%. Taken together, sample S2 (example 2) had comparable volume shrinkage performance to pure Ni powder over the range of 50-1200 ℃.
Example 3:
1. mixing micron-sized coarse nickel powder with sublimed sulfur powder raw materials according to a weight ratio of 1500:1 (wherein the quality of nickel powder is controlled to be 50 g) are uniformly mixed and pressed into blocks, the blocks are placed on an anode copper target in a direct current arc plasma working chamber, a graphite rod is used as a cathode, a spacing between a cathode rod at the upper end of a crucible and the anode material target is 30mm, wherein the diameter of the graphite rod is as follows4mm long and 100mm long. Evacuating the working chamber to 1X 10 -3 Pa, introducing nitrogen atmosphere into the working chamber, and controlling the air pressure to 80kPa. Wherein the purity of the nitrogen is 99.99 percent;
2. starting a circulating cooling system and a power supply, adjusting the arc current to 120A, and igniting an arc for 15min at the working voltage of 30-45V;
3. stopping arc, and charging into the reaction chamber for about 1×10 after 1.5 hr 3 And (5) Pa trace air passivation treatment of nickel powder. After a sustained stabilization period of 6 hours, a sample of nickel sulfide coated modified nickel powder, designated sample S3, was collected from the trap chamber.
4. As shown in fig. 1, a TEM image (fig. a) of a sample S3 (example 3) and corresponding component scans (fig. a, b, c) show that the S element is uniformly distributed on the surface of the powder particles, so as to realize sulfide coating of the modified Ni particles.
5. As shown in FIG. 2, the X-ray diffraction pattern of sample S3 (example 3) showed that the main phase was Ni and that no Ni/S compound diffraction peak was present.
6. As shown in FIG. 3, the XPS spectrum of sample S3 (example 3) shows the Ni, niO and NiS peaks on the surface, and the S fine spectrum shows the obvious NiS peaks. Indicating that the surface of the modified nickel powder particle realizes a NiS coating layer.
7. As shown in fig. 4, the raw material ratio of sample S3 (example 3) was Ni: s=1500:1, the S content in the raw material was 0.067wt.%, and the S content in the corresponding powder product was 0.84wt.%, as measured by a carbon sulfur analyzer.
8. As shown in FIG. 5 (c), the volume shrinkage curve of sample S3 (example 3) in the range of 50 to 1200℃is shown to start shrinkage at 695℃with a certain improvement over the pure Ni powder sample S0 (comparative example). The obvious difference is that the shrinkage curve of sample S3 after 695 ℃ becomes very gentle, the shrinkage rate drops significantly, significantly lower than that of pure Ni powder sample S0 (comparative). At the same time, sample S3 (example 3) also showed a slight volume expansion after reaching 1000℃and eventually a volume shrinkage of-0.7% at 1200 ℃. The results show that sample S3 of modified Ni powder (example 3) starts sintering shrinkage at 695 ℃ to the end of sintering, and that sample S3 and BaTiO throughout the sintering process 3 The volume shrinkage curve of the powder has good matching degree, is obviously superior to that of pure Ni powder (comparative example), and shows excellent sintering shrinkage performance.
Example 4:
1. mixing micron-sized coarse nickel powder with sublimed sulfur powder as raw material according to weight ratioThe weight ratio is 2000:1 (wherein the quality of nickel powder is controlled to be 50 g) are uniformly mixed and pressed into blocks, the blocks are placed on an anode copper target in a direct current arc plasma working chamber, a graphite rod is used as a cathode, the interval between the cathode rod at the upper end of a crucible and the anode material target is 20mm, wherein the diameter of the graphite rod is as follows4mm long and 100mm long. Evacuating the working chamber to 1X 10 -3 Pa, introducing nitrogen atmosphere into the working chamber, and controlling the air pressure to 80kPa. Wherein the purity of the nitrogen is 99.99 percent;
2. starting a circulating cooling system and a power supply, adjusting the arc current to 120A, and igniting an arc for 10min at the working voltage of 30-45V;
3. stopping arc, and charging into the reaction chamber for about 1×10 after 1 hr 3 And (5) Pa trace air passivation treatment of nickel powder. After 6 hours of continuous stabilization, a sample of nickel sulfide coated modified nickel powder, designated sample S4, was collected from the trap chamber.
4. As shown in FIG. 2, the X-ray diffraction pattern of sample S4 (example 4) showed that the main phase was Ni and that no Ni/S compound diffraction peak was present.
5. As shown in fig. 4, the raw material ratio of sample S4 (example 4) was Ni: s=2000:1, the S content in the raw material was 0.05wt.%, and the S content in the corresponding powder product was 0.073wt.%, as measured by a carbon sulfur analyzer.
6. As shown in FIG. 5 (d), the volume shrinkage curve of sample S4 (example 4) in the range of 50 to 1200℃exhibited slow shrinkage before 1000℃at which the shrinkage rate was significantly lower than that of pure Ni powder, compared with BaTiO 3 The volumetric shrinkage curve of the powder matches well. Very slow expansion occurs between 1000 ℃ and 1130 ℃, a faster volume expansion occurs after 1130 ℃, and finally the volume shrinkage is +2.5% at 1200 ℃. The results show that the sintering curve of modified Ni powder sample S4 (example 4) was compared with BaTiO before 1130 DEG C 3 The powder has good volume shrinkage curve matching degree, and is expanded to BaTiO after 1130 DEG C 3 The volume shrinkage curve of the powder is deviated to a certain extent, but finally the powder is matched with BaTiO 3 The difference of the powder shrinkage rate of-4.2% is 6.7%, which is lower than that of pure Ni powderWith BaTiO 3 The powder shrinkage difference was 10.7%. Taken together, sample S4 (example 4) exhibited superior sintering shrinkage performance over pure Ni powder with volume shrinkage performance in the range of 50-1200 ℃.
The optimum range of the S-doped amount of the sulfide-coated modified Ni powder was determined by comparing the volume shrinkage properties of the samples of examples 1 to 4 and comparative example 1. The results show that samples S3 and S4 were equipped with BaTiO 3 Good matching degree of volume shrinkage, volume shrinkage of samples S1 and S2 and BaTiO 3 The matching degree is poor. The S content of the nickel sulfide coated modified nickel powder disclosed by the invention is preferably in the range of 500-1500 ppm.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The sulfide coated modified nickel powder material is characterized in that the nickel sulfide coated modified nickel powder material has a spherical core/shell structure, wherein the core is Ni particles, and the shell is a NiS coating layer coated on the nickel particles and an oxide layer formed by passivating the outermost surface of the NiS coating layer.
2. The gas phase co-evaporation method sulfide coating modified nickel powder material according to claim 1, wherein the spherical particle size of the nickel sulfide coating modified nickel powder material is between 10 and 200nm, the thickness of the NiS coating layer is between 2 and 10nm, and the S content is between 500 and 1500 ppm.
3. The method for preparing the sulfide coated modified nickel powder material by the gas phase co-evaporation method according to claim 1 or 2, which is characterized in that the preparation method uses thermal plasma as an evaporation source, micron-sized nickel powder and sulfur powder are uniformly mixed and then used as raw material targets, the gas phase co-evaporation method is adopted to co-evaporate the mixed raw material targets in situ, a nickel sulfide coated modified nickel powder product is formed, and finally the powder surface is passivated by air, so that the final product is obtained.
4. The method for preparing the sulfide coated modified nickel powder material by the gas phase co-evaporation method according to claim 3, wherein the sulfur content in the raw material target material is controlled to regulate and control the sulfur component, the sulfide coating structure and the thickness of the sulfide coating layer in the powder product, so that the special requirements of the inner electrode of the MLCC on the metal powder material are finally met.
5. The method for preparing the sulfide coated modified nickel powder material by the gas phase co-evaporation method according to claim 3, wherein the mass ratio of the micron-sized nickel powder to the sulfur powder in the raw material target is in the range of 500:1-2000:1.
6. The method for preparing a sulfide coated modified nickel powder material by a gas phase co-evaporation method according to claim 3, wherein the sulfur powder is micron-sized sublimed sulfur powder.
7. The use of the gas-phase co-evaporation sulfide coated modified nickel powder material according to claim 1 or 2 as an electrode metal powder material in an MLCC.
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