CN118563169A - Scandium-nickel composite metal material, preparation method and application thereof - Google Patents
Scandium-nickel composite metal material, preparation method and application thereof Download PDFInfo
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- CN118563169A CN118563169A CN202410683732.9A CN202410683732A CN118563169A CN 118563169 A CN118563169 A CN 118563169A CN 202410683732 A CN202410683732 A CN 202410683732A CN 118563169 A CN118563169 A CN 118563169A
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- XTOHTGPYKSWPDX-UHFFFAOYSA-N nickel scandium Chemical compound [Sc].[Ni] XTOHTGPYKSWPDX-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000007769 metal material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 11
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 57
- 239000000843 powder Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 24
- 238000009826 distribution Methods 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 150000003325 scandium Chemical class 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003985 ceramic capacitor Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 239000000956 alloy Substances 0.000 abstract description 12
- 229910045601 alloy Inorganic materials 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 7
- 229910001111 Fine metal Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002905 metal composite material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 oxalic acid compound Chemical class 0.000 description 4
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000346 scandium sulfate Inorganic materials 0.000 description 1
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 1
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- FKZFOHABAHJDIK-UHFFFAOYSA-K trichloroscandium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Sc+3] FKZFOHABAHJDIK-UHFFFAOYSA-K 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a scandium-nickel composite metal material, a preparation method and application thereof, and relates to the technical field of composite metal materials. According to the scandium-nickel composite metal material, scandium is introduced to enhance the high temperature resistance, corrosion resistance, ductility, electric conductivity and thermal conductivity of nickel powder in alloy application; the scandium-nickel precursor is prepared by adopting wet synthesis, and then the scandium-nickel composite metal material product is prepared by high-temperature roasting, so that the scandium-nickel composite metal material has smaller particle size and more uniform distribution, and the application range of the product can be further widened.
Description
Technical Field
The invention relates to the technical field of composite metal materials, in particular to a scandium-nickel composite metal material, a preparation method and application thereof.
Background
The superfine nickel powder has the advantages of small size, large specific surface area, special property of nano materials, quite large proportion of atoms in crystal boundary and surface, better performance than that of bulk materials, high-efficiency photocatalysis, high conductivity, magnetic property and the like, and has been widely used in the fields of hard alloy, catalyst, ceramic capacitor, drug transportation and the like.
In order to further improve the strength, ductility, corrosion resistance and other characteristics of nickel powder, a method for preparing metal composite powder is often adopted. The traditional manufacturing method of the metal composite powder mainly comprises the following two methods:
(1) The mechanical mixing method utilizes mechanical forces such as extrusion, impact, shearing, friction and the like to uniformly distribute the modifier on the outer surfaces of the powder particles, so that various components mutually infiltrate and diffuse to form a coating.
(2) The atomization method utilizes high-pressure gas, high-pressure liquid or high-speed rotating blades to break high-temperature and high-pressure molten metal or alloy into fine liquid drops, and then the fine liquid drops are condensed in a collector to obtain superfine metal powder, and the process does not generate chemical change.
However, the existing manufacturing method of the metal composite powder generally has the problem that the composite powder is unevenly mixed, so that more defects exist in the alloy easily, and the service life of the alloy is influenced. In addition, these two methods are relatively high in energy consumption and have certain requirements on equipment.
Therefore, there is a need to further improve the performance of nickel powder in the alloy field by improving the preparation method of the metal composite powder to prepare the metal composite powder with better uniformity.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a scandium-nickel composite metal material, a preparation method and application thereof, and aims to obtain superfine scandium-nickel metal powder with good uniformity.
The invention is realized in the following way:
In a first aspect, the invention provides a scandium-nickel composite metal material, which is a composite metal powder containing nickel element and scandium element, wherein the average grain diameter of the composite metal powder is smaller than 880nm, and the grain diameter distribution D50 is smaller than 1150nm.
In an alternative embodiment, the composite metal powder has an average particle size of 400nm to 880nm and a particle size distribution D50 of 550nm to 1150nm.
In an alternative embodiment, in the scandium-nickel composite metal material, the molar ratio of scandium element to nickel element is 1: (9-99), preferably 1: (15-20).
In a second aspect, the present invention provides a method for preparing a scandium nickel composite metal material according to any of the preceding embodiments, comprising: and preparing a scandium-nickel precursor by taking nickel salt and scandium salt as raw materials through a coprecipitation method, and roasting the scandium-nickel precursor.
In an alternative embodiment, the scandium-nickel precursor preparation process includes: mixing nickel salt, scandium salt and a solvent to obtain scandium-nickel mixed salt solution, mixing the scandium-nickel mixed salt solution with a precipitator solution and a dispersing agent, and carrying out precipitation reaction;
Preferably, after the precipitation reaction, aging for 0.5 to 12 hours, followed by solid-liquid separation and drying;
Optionally, adding scandium-nickel mixed salt solution and precipitant solution into a reactor, adding a dispersing agent in the stirring process to carry out precipitation reaction, controlling the stirring speed to be 1000-2000 rpm, and controlling the reaction time to be 5-100 min.
In an alternative embodiment, the precipitant solution is an ammonium oxalate solution;
Optionally, the adding amount of the precipitant solution is regulated to make the mole ratio of the adding amount of the precipitant to the theoretical amount be (0.25-1.00): 1;
Optionally, the mass fraction of the ammonium oxalate solution is 5% -15%.
In an alternative embodiment, the dispersant is selected from at least one of polyvinylpyrrolidone and sodium lauryl sulfate;
Alternatively, the dispersant is used in an amount to nickel in the nickel salt mass ratio of (0-10): 100.
In an alternative embodiment, in the process of roasting scandium-nickel precursor, the roasting temperature is controlled to be 400-550 ℃ and the roasting time is controlled to be 0.5-2.0 h;
Optionally, controlling the heating rate during roasting to be 2-8 ℃/min;
Optionally, the calcination is performed under an inert atmosphere.
In an alternative embodiment, washing and drying are performed after the firing is completed.
In a third aspect, the invention provides an application of the scandium nickel composite metal material according to any one of the preceding embodiments or the scandium nickel composite metal material prepared by the preparation method according to any one of the preceding embodiments in preparing a hard alloy, a catalyst or a ceramic capacitor.
The invention has the following beneficial effects: according to the scandium-nickel composite metal material, scandium is introduced to enhance the high temperature resistance, corrosion resistance, ductility, electric conductivity and thermal conductivity of nickel powder in alloy application; the scandium-nickel composite metal material has smaller particle size and more uniform distribution, and can further widen the application range of the product.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of scandium-nickel composite ultra-fine metal powder according to example 1 of the present invention;
FIG. 2 is a graph showing the particle size distribution of scandium-nickel composite ultra-fine metal powder according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a preparation method of scandium-nickel composite metal material, which comprises the following steps:
S1, preparing materials
Respectively weighing nickel salt, scandium salt, precipitant and other raw materials, and preparing into a solution for later use.
In some embodiments, a nickel salt, a scandium salt, and a solvent may be mixed to obtain a scandium-nickel mixed salt solution, the nickel salt may be nickel chloride, nickel nitrate, or the like, the scandium salt may be scandium chloride, scandium nitrate, or the like, and the solvent may be water, but is not limited thereto. The raw materials such as nickel chloride, scandium chloride and the like can be commercial industrial grade raw materials.
In order to further control the scandium-nickel molar ratio in the product, the scandium-nickel molar ratio in scandium-nickel mixed salt solution is optimized, and the molar ratio of scandium in scandium salt and nickel in nickel salt in the raw material scandium salt is 1: (9-99), preferably 1: (15-20). The scandium-nickel molar ratio is optimized to further reduce the grain size of the product, and a more uniform scandium-nickel composite metal material is obtained. Specifically, the molar ratio of scandium in the scandium salt and nickel in the nickel salt of the feedstock used may be 1:9, 1:10, 1:15, 1:19, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:99, etc.
In some embodiments, the precipitant may be ammonium oxalate, but is not limited to this, and the auxiliary material ammonium oxalate has the functions of precipitant and complexing agent at the same time in the wet synthesis process, so that hydrochloric acid generated after the reaction of nickel chloride and scandium chloride can be recycled in theory, thereby effectively reducing the production cost.
Further, the precipitant is dissolved to obtain a precipitant solution, and the solvent used may be water, but is not limited thereto. The mass fraction of the ammonium oxalate solution is 5% -15%, such as 5%, 8%, 10%, 12%, 15% and the like.
In some embodiments, a dispersing agent selected from at least one of polyvinylpyrrolidone and sodium lauryl sulfate may also be added, and the product distribution may be more uniform by incorporating polyvinylpyrrolidone.
S2, preparing scandium-nickel precursor
And (3) coprecipitating nickel salt and scandium salt in a solution system to prepare scandium-nickel precursor.
In the actual operation process, the scandium-nickel mixed salt solution, the precipitator solution and the dispersing agent are mixed, and the precipitation reaction, the aging, the solid-liquid separation and the drying are sequentially carried out, so that the scandium-nickel precursor is obtained. The scandium-nickel mixed salt solution and the precipitant solution can be added into a reactor, and a dispersing agent is added in the stirring process to carry out precipitation reaction. Compared with the mode of dripping the precipitant, the pH value is more stable by adopting a one-time mixing mode, and the particle size of the obtained product is smaller and more uniform.
The inventor regulates the dosage of the precipitant and the dispersant, and the molar ratio of the adding amount of the precipitant to the theoretical amount is (0.25-1.00): 1 by regulating the adding amount of the precipitant solution, so that the product with uniform particle size can be prepared in the range, and the effect is better when the product is used in the theoretical amount. The mass ratio of the dispersant to the nickel in the nickel salt is (0-10): 100, and the dispersant can improve the uniformity of the product more in the above range.
Specifically, the molar ratio of the precipitant addition amount to the theoretical amount may be 0.25:1, 0.30:1, 0.50:1, 0.80:1, 1.00:1, etc. The mass ratio of the dispersant to the nickel in the nickel salt may be 0:100, 1:100, 3:100, 5:100, 8:100, 10:100, etc.
In some embodiments, during the precipitation reaction, the stirring speed is controlled to be 1000rpm-2000rpm, the reaction time is controlled to be 5min-100min, and the raw materials are fully reacted by regulating the stirring speed and the reaction time of the precipitation reaction. Specifically, the precipitation reaction can be carried out at normal temperature and normal pressure, namely, the temperature and the pressure are not regulated and controlled, and the temperature can be 15-30 ℃. The stirring rate may be 1000rpm, 1200rpm, 1500rpm, 1800rpm, 2000rpm, etc., and the reaction time may be 5min, 10min, 50min, 100min, etc.
Further, the aging time is controlled to be 0.5h-12h, so that the solid sediment obtained by the reaction is fully deposited. Specifically, the aging time may be 0.5h, 1.0h, 3.0h, 5.0h, 8.0h, 10.0h, 12.0h, etc.
S3, roasting
Roasting scandium-nickel precursor, wherein the scandium-nickel precursor is oxalic acid compound, washing and drying after roasting to obtain scandium-nickel composite metal powder product.
In some embodiments, in the process of roasting scandium-nickel precursor, the temperature rising rate during roasting is controlled to be 2 ℃/min-8 ℃/min, the roasting temperature is 400 ℃ -550 ℃, the roasting time is controlled to be 0.5h-2.0h, the roasting temperature and the roasting time are controlled to be in the above ranges, and the uniformity of the particle size of the product can be further improved. Specifically, the heating rate may be 2 ℃/min, 5 ℃/min, 8 ℃/min, etc., the baking temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, etc., and the baking time may be 0.5h, 1.0h, 1.5h, 2.0h, etc.
In some embodiments, the calcination is performed under an inert atmosphere to prevent oxidation of the metal, and the specific kind of inert atmosphere is not limited, and may be nitrogen, argon, or the like.
In the preparation method of the scandium-nickel composite metal material provided by the embodiment of the invention, scandium salt is added in the wet synthesis process of the nickel powder precursor, ammonium oxalate is utilized to form a scandium-nickel precursor composite product, and then the scandium-nickel composite metal powder is obtained through roasting. Compared with the traditional method for preparing the composite metal powder, the method provided by the embodiment of the invention can effectively improve the phenomena of uneven mixing of scandium-nickel composite powder and insufficient physical properties of single nickel powder in the hard alloy field, the obtained scandium-nickel ultrafine metal powder has good uniformity, meanwhile, the scandium-nickel composite metal powder obtained by the process route provided by the embodiment of the invention has controllable granularity, the minimum granularity can reach 400nm, and the performances of the scandium-nickel composite metal powder in the alloy field, such as electric conductivity and thermal conductivity, can be further improved.
The embodiment of the invention also provides a scandium-nickel composite metal material, which is composite metal powder containing nickel element and scandium element, wherein the average grain diameter of the composite metal powder is smaller than 880nm, the grain diameter distribution D50 is smaller than 1150nm, and the scandium-nickel composite metal material provided by the embodiment of the invention has the characteristics of small grain diameter and uniform grain diameter distribution.
In some embodiments, the composite metal powder has an average particle size of 400nm to 880nm and a particle size distribution D50 of 550nm to 1150nm.
In some embodiments, the scandium-nickel composite metal material has a molar ratio of scandium element to nickel element of 1: (9-99), preferably 1: (15-20). The molar ratio of scandium element to nickel element is preferably in the above range, and the particle size of the product can be further reduced.
The scandium-nickel composite metal material provided by the embodiment of the invention has smaller particle size and more uniform particle size distribution, and can be further prepared into products such as hard alloy, catalyst or ceramic capacitor, and the like, so that the strength, ductility, corrosion resistance, welding performance and the like of a rear-end product are improved.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of scandium-nickel composite metal material, which comprises the following steps:
(1) Preparation of materials
Weighing 135.5g of industrial grade nickel chloride hexahydrate and 7.7g of industrial grade scandium chloride hexahydrate, putting into a beaker, slowly pouring water, stirring until the nickel chloride and the scandium chloride are dissolved and uniformly mixed, and fixing the volume to 300mL to obtain a mixed aqueous solution containing scandium salt and nickel salt, wherein Sc: ni=1: 19.
87.33G of analytically pure ammonium oxalate monohydrate is weighed, placed in a beaker, poured into water, and dissolved by ultrasonic oscillation to obtain an ammonium oxalate solution with the mass fraction of 10%.
(2) Preparation of scandium-nickel precursor
Mixing scandium-nickel mixed salt solution and ammonium oxalate solution in a beaker, wherein the ammonium oxalate addition amount is 100% of theoretical addition amount, stirring is started at normal temperature and normal pressure (25 ℃, standard atmospheric pressure and the same applies below), stirring speed is 1500rpm, 2g of polyvinylpyrrolidone is added into a reaction system after stirring is started for 2min, stirring is stopped after reaction for 0.5h, filtering is performed after aging for 1h, hot water (100 ℃ and the same applies below) is used for leaching, and drying is performed at 80 ℃ for 12h, so that scandium-nickel precursor is obtained. Weigh 88.52g dry weight.
(3) Roasting
Placing the dried scandium-nickel precursor in a crucible, placing the crucible in a tube furnace, vacuumizing three times by using a vacuum pump, enabling the interior of the tube furnace to be in a vacuum state (the vacuum degree is-0.1 Mpa, the same applies below), and then introducing nitrogen for 0.5h at a flow rate of 1.5L/min; and after 0.5h, the tube furnace is operated to start heating, the heating rate is 8 ℃/min, the roasting temperature is 450 ℃, the roasting time is 1.5h, and the nitrogen flow is 1.5L/min. And washing and drying after roasting to obtain scandium-nickel composite metal powder product.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 85%, and the purity of scandium-nickel composite metal powder is more than 97%; SEM and Nano Measurer observation analysis shows that the scandium-nickel composite metal powder has an average grain diameter smaller than 400nm and a uniformly dispersed spheroid morphology; the particle size distribution D50 is <0.55 μm as measured by a laser particle sizer. Table 1 shows the chemical composition of scandium-nickel composite ultra-fine metal powder according to example 1.
TABLE 1 chemical composition Table of scandium-nickel composite ultra-fine metal powder prepared in example 1
| Element(s) | Ni | Sc | Co | Ca | Mg | Cl | Fe | Cu | Al | Zn |
| Product (%) | 94.37 | 3.82 | 0 | 0.0039 | 0.002 | 0.0216 | 0 | 0 | 0 | 0 |
The scandium-nickel composite superfine metal powder has higher purity which reaches more than 98 percent.
Fig. 1 is a scanning electron microscope image of scandium-nickel composite ultra-fine metal powder obtained in example 1, and it can be seen that the metal powder has a smaller particle size, a uniform particle size, and a uniformly dispersed spherical morphology.
Fig. 2 is a graph showing the particle size distribution of scandium-nickel composite ultra-fine metal powder according to example 1, and it can be seen that the particle size distribution of the product is relatively uniform.
Example 2
Example 2 differs from example 1 only in that the molar ratio of Sc to Ni is different, sc: ni=1: 9.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 83.7%; SEM and Nano Measurer observation analysis shows that the scandium-nickel composite metal powder has an average particle diameter smaller than 470nm and a uniformly dispersed sphere-like morphology; the particle size distribution D50 is less than 0.65 μm as measured by a laser particle sizer.
Example 3
Example 3 differs from example 1 only in that the amount of ammonium oxalate added is 25% of the theoretical amount.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 22.3%; SEM and Nano Measurer observation analysis shows that the scandium-nickel composite metal powder has an average grain diameter smaller than 880nm and a uniform and dispersed square morphology; the particle size distribution D50 is less than 1.15 μm as measured by a laser particle sizer.
Example 4
Example 4 differs from example 1 only in that (1) the molar ratio of Sc to Ni is different, sc: ni=1: 99, a step of; (2) no dispersant polyvinylpyrrolidone is added.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 89.6%; SEM and Nano Measurer observation analysis shows that the scandium-nickel composite metal powder has an average particle diameter smaller than 720nm and a uniformly dispersed spheroid morphology; the particle size distribution D50 is less than 0.85 μm as measured by a laser particle sizer.
Example 5
The only main points of embodiment 5 and embodiment 1 are: (1) Step (2), replacing polyvinylpyrrolidone with equal amount of sodium dodecyl sulfate; (2) The precipitation reaction time in the step (2) is shortened, and after 2g of sodium dodecyl sulfate is added, the stirring is stopped after the reaction is carried out for 5min, and no aging is carried out.
The specific procedure of step (2) of example 5 is as follows: mixing scandium-nickel mixed salt solution and ammonium oxalate solution in a beaker, wherein the ammonium oxalate addition amount is 100% of the theoretical addition amount, stirring is started at normal temperature and normal pressure, the stirring speed is 1500rpm, 2g of sodium dodecyl sulfate is added into a reaction system after stirring is started for 2min, stirring is stopped after reaction for 5min, filtering, hot water leaching and drying at 80 ℃ for 12h, and scandium-nickel precursor is obtained.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 62.3%; the average grain diameter of scandium-nickel composite metal powder is smaller than 0.87 mu m through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder has a uniformly dispersed spherical morphology; the particle size distribution D50 is less than 1.05 μm as measured by a laser particle sizer.
Example 6
Example 6 differs from example 1 only in that: in the step (1), the molar ratio Sc in the scandium chloride nickel mixed solution is as follows: ni=1: 99.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 84.2%; SEM and Nano Measurer observation analysis shows that the scandium-nickel composite metal powder has an average particle diameter smaller than 420nm and a uniformly dispersed spheroid morphology; the particle size distribution D50 is <0.59 μm as measured by a laser particle sizer.
Example 7
Example 7 differs from example 1 only in that: in the step (1), scandium sulfate and nickel mixed solution is prepared.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 82.2%; the average grain diameter of scandium-nickel composite metal powder is smaller than 540nm through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder has a uniformly dispersed spherical morphology; the particle size distribution D50 is <0.67 μm as measured by a laser particle sizer.
Comparative example 1
The main differences from example 1 are: (1) The precipitation reaction conditions are different, and a hydrothermal kettle is adopted for reaction; (2) polyvinylpyrrolidone is not added.
Comparative example 1 the specific procedure of step (2) is as follows: mixing scandium-nickel mixed salt solution and ammonium oxalate solution in a beaker, wherein the ammonium oxalate addition is 100% of theoretical addition, stirring is started at normal temperature and normal pressure, the stirring speed is 1500rpm, pouring the mixture into a hydrothermal reaction kettle after stirring is started for 10min, placing the hydrothermal reaction kettle in an 80 ℃ oven for 4h, taking out the hydrothermal reaction kettle, placing the hydrothermal reaction kettle for cooling, opening the hydrothermal reaction kettle when the temperature is reduced to room temperature, taking out a precursor product, filtering, leaching with hot water, and drying at 80 ℃ for 12h to obtain scandium-nickel precursor.
Through ICP-MS analysis, the utilization rate of metal in the precursor synthesis process is 94.5%; the average grain diameter of scandium-nickel composite metal powder is smaller than 1.1 mu m through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder presents a uniformly dispersed sphere-like morphology; the particle size distribution D50 is <1.7 μm as measured by a laser particle sizer.
Comparative example 2
The only difference from example 1 is that: the ammonium oxalate addition amount in the step (2) is 150% of the theoretical addition amount.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 97.2%; the average grain diameter of scandium-nickel composite metal powder is 4.13 mu m through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder has uniform and dispersed spherical morphology; the particle size distribution D50 is less than 6.23 μm as measured by a laser particle sizer.
Comparative example 3
The only difference from example 4 is that: and (2) gradually dropwise adding an ammonium oxalate solution into the scandium-nickel mixed solution in a positive adding mode, wherein the flow rate of the ammonium oxalate is 10mL/min.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 85.6%; the average grain diameter of scandium-nickel composite metal powder is smaller than 2.2 mu m through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder has a uniformly dispersed spherical morphology; the particle size distribution D50 is less than 2.85 μm as measured by a laser particle sizer. The nucleation speed of the crystal is far less than the growth speed of the crystal by the positive addition mode of liquid feeding, the sphericity of the precursor is obviously improved, but the corresponding grain size is increased, and the strength, the toughness and the conductivity are reduced.
Comparative example 4
The only difference from example 6 is that: and (3) prolonging the reaction time of the step (2) to 2h.
Step (2) of comparative example 4 is specifically as follows: mixing scandium-nickel mixed salt solution and ammonium oxalate solution in a beaker, wherein the ammonium oxalate addition amount is 100% of theoretical addition amount, stirring is started at normal temperature and normal pressure, the stirring speed is 1500rpm, 2g of sodium dodecyl sulfate is added into a reaction system after stirring is started for 2min, stirring is stopped after reaction for 2h, filtering, hot water leaching and drying at 80 ℃ for 12h, and scandium-nickel precursor is obtained.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 81.4%; the average grain diameter of scandium-nickel composite metal powder is smaller than 1.8 mu m through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder presents a uniformly dispersed sphere-like morphology; the particle size distribution D50 is <2.1 μm as measured by a laser particle sizer. The precipitation reaction time is prolonged, the reaction activation energy is increased to deepen the particle agglomeration phenomenon, and the particle size is obviously increased.
Comparative example 5
The only difference from comparative example 4 is that: and (3) after the reaction in the step (2) is finished, adding an ageing step for 12 hours.
Step (2) of comparative example 5 is specifically as follows: mixing scandium-nickel mixed salt solution and ammonium oxalate solution in a beaker, wherein the ammonium oxalate addition amount is 100% of theoretical addition amount, stirring is started at normal temperature and normal pressure, the stirring speed is 1500rpm, 2g of sodium dodecyl sulfate is added into a reaction system after stirring is started for 2min, stirring is stopped after 2h of reaction, filtering is performed after 12h of aging, hot water leaching is performed, and drying is performed at 80 ℃ for 12h, so that scandium-nickel precursor is obtained. Weigh 85.43g dry weight.
Through ICP-MS analysis, the metal utilization rate in the precursor synthesis process is 82%; the average grain diameter of scandium-nickel composite metal powder is smaller than 1.87 mu m through SEM and Nano Measurer observation analysis, and the scandium-nickel composite metal powder presents a uniformly dispersed sphere-like morphology; the particle size distribution D50 is <2.23 μm as measured by a laser particle sizer. The aging time is prolonged, the scandium-nickel composite metal powder has small particle size change, and the influence is negligible.
In summary, the invention provides a scandium-nickel composite metal material, a preparation method and application thereof, which adopts wet synthesis to prepare a scandium-nickel precursor, and then carries out high-temperature roasting to prepare a scandium-nickel composite metal material product, and has the following advantages:
(1) The morphology and the grain size of the final product are determined by the precursor sediment, the grain size morphology of the precursor can be controlled by controlling the sedimentation process parameters, so that the preparation of 400nm superfine scandium-nickel composite metal powder is realized, and the effect of the product in the alloy field is further improved.
(2) The auxiliary material ammonium oxalate has the functions of a precipitator and a complexing agent in the wet synthesis process, and hydrochloric acid generated in the process can be recycled in theory, so that the production cost is effectively reduced.
(3) The product has low impurity removal cost, ni 2+、Cl- can be removed by water washing, the product and the process are less affected by TOC, and the organic matters introduced in the system can be removed by roasting, decomposing and removing.
(4) The scandium-nickel composite oxalic acid compound precursor has self-reducing property when being decomposed at high temperature under vacuum condition, so that no reducing gas or reducing agent is required to be introduced in the roasting process, and the scandium-nickel composite oxalic acid compound precursor can be self-reduced into a nickel-cobalt metal simple substance under the protective atmosphere of nitrogen or argon and the like, and is safe and environment-friendly.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The scandium-nickel composite metal material is characterized in that the scandium-nickel composite metal material is composite metal powder containing nickel element and scandium element, the average grain diameter of the composite metal powder is smaller than 880nm, and the grain diameter distribution D50 is smaller than 1150nm.
2. Scandium nickel composite metal material according to claim 1, wherein the average particle size of the composite metal powder is 400nm-880nm and the particle size distribution D50 is 550nm-1150nm.
3. Scandium nickel composite metal material according to claim 1 or 2, characterized in that the molar ratio of scandium element to nickel element in the scandium nickel composite metal material is 1: (9-99), preferably 1: (15-20).
4. A method of producing the scandium nickel composite metal material according to any of claims 1-3, comprising: and preparing a scandium-nickel precursor by taking nickel salt and scandium salt as raw materials and adopting a coprecipitation method, and roasting the scandium-nickel precursor.
5. The method of claim 4, wherein the scandium-nickel precursor preparation process comprises: mixing nickel salt, scandium salt and a solvent to obtain scandium-nickel mixed salt solution, mixing the scandium-nickel mixed salt solution with a precipitator solution and a dispersing agent, and carrying out precipitation reaction;
Preferably, after the precipitation reaction, aging for 0.5 to 12 hours, followed by solid-liquid separation and drying;
Optionally, adding the scandium-nickel mixed salt solution and the precipitator solution into a reactor, adding the dispersing agent in the stirring process for precipitation reaction, and controlling the stirring speed to be 1000-2000 rpm, wherein the reaction time is 5-100 min.
6. The method of claim 5, wherein the precipitant solution is an ammonium oxalate solution;
Optionally, the adding amount of the precipitant solution is regulated so that the molar ratio of the adding amount of the precipitant to the theoretical amount is (0.25-1.00): 1;
Optionally, the mass fraction of the ammonium oxalate solution is 5% -15%.
7. The method according to claim 5, wherein the dispersant is at least one selected from polyvinylpyrrolidone and sodium dodecyl sulfate;
Optionally, the mass ratio of the dispersant to the nickel in the nickel salt is (0-10): 100.
8. The preparation method according to claim 4, wherein in the process of roasting the scandium-nickel precursor, the roasting temperature is controlled to be 400-550 ℃ and the roasting time is controlled to be 0.5-2.0 h;
Optionally, controlling the heating rate during roasting to be 2-8 ℃/min;
Optionally, the calcination is performed under an inert atmosphere.
9. The method according to claim 8, wherein the baking is performed after the completion of the washing and drying.
10. Use of scandium-nickel composite metal material according to any of claims 1-3 or obtainable by a method according to any of claims 4-9 for the manufacture of cemented carbide, catalysts or ceramic capacitors.
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