CN110205610B - Method for coating copper-nickel protective layer on surface of hollow microsphere - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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Abstract
The invention provides a method for coating a copper-nickel protective layer on the surface of a hollow microsphere, which comprises the steps of firstly carrying out alkali washing and surface roughening treatment on the hollow microsphere, and then carrying out Ni (NO) treatment3)2·6H2O and Cu (NO)3)2·3H2Dissolving O in a mixed solution of ethanol and deionized water, immersing the hollow microspheres subjected to roughening treatment in the mixed solution, stirring to be viscous under the condition of 50 ℃ water bath, placing in a forced air drying oven, fully drying at 100 ℃, placing the dried solid mixture in a tubular furnace, roasting in argon atmosphere to obtain CuO/NiO-coated hollow microspheres, and finally reducing by using hydrogen at 700 ℃ to obtain the hollow microspheres coated with a Cu-Ni protective layer. The method has simple process, and the obtained Cu-Ni coating layer has complete structure, uniform thickness and good combination with the surface of the hollow microsphere, can play a role in protecting the hollow microsphere/magnesium alloy composite material in the preparation process, reduces or prevents mechanical damage and interface reaction, and ensures that the hollow microsphere is kept complete.
Description
Technical Field
The invention belongs to the field of powder surface modification, relates to a method for coating a copper-nickel protective layer on the surface of a hollow microsphere, and particularly relates to a method for coating a copper-nickel protective layer on the surface of a hollow microsphere or a hollow glass microsphere, so that the wall of the hollow microsphere is strengthened and protected, and the hollow microsphere is ensured to be kept complete and not broken in the process of preparing a hollow microsphere/magnesium alloy light composite material.
Background
Ceramic particles or fiber reinforced magnesium-based composite materials are favored in the fields of aerospace, rail transit, energy and chemical engineering and the like due to the characteristics of low density, high specific stiffness and specific strength, strong damping, good size stability and the like. In recent years, cenosphere reinforced magnesium-based composite material is applied and developed, and the cenosphere is a hollow thin film with tiny sizeWall spheres with particle diameter of 10-250 μm and SiO as main component2And Al2O3The hollow glass microsphere has the characteristics of low density, high strength, good thermal stability and the like, and is mainly derived from floating beads extracted from coal ash which is a byproduct of a coal-fired thermal power plant and artificially-manufactured hollow glass microspheres. The hollow microsphere is added into the magnesium alloy as a reinforcement to keep the hollow microsphere in a complete hollow state in the preparation process of the material so as to reduce the density of the composite material, and the preparation method is a novel method for preparing the light magnesium-based composite material and mainly comprises a powder metallurgy method, a pressure casting method and a stirring casting method. However, in the preparation process of the hollow microsphere magnesium-based composite material, the wall of the hollow microsphere is broken due to mechanical damage and interface reaction with liquid magnesium alloy, so that the inside of the floating bead is filled with the magnesium alloy matrix, and the density of the composite material is not reduced or increased. The Liu Enyang and the like adopt a stirring casting method to add floating beads into a magnesium alloy melt to prepare a floating bead/AZ 91D composite material, and the result shows that in the preparation process of the composite material, the floating beads and the magnesium alloy melt undergo interfacial reaction to generate Mg2Si and MgO, the floating bead breaking filled with the matrix alloy, making the composite density higher than expected (Liu Enyang, Yan Si Rong, Zhao Yan, etc. floating bead/AZ 91D composite microstructure and performance [ J]Rare metal materials and engineering, 2017,46(11): 3298-. Rohatgi P K et al prepared a floating bead/AZ 91D composite by die casting and found that the floating beads in the composite also existed in the form of crushed microspheres with the interior of the floating beads filled with a matrix material (Rohatgi P K, Daoud A, Schultz B F, et al. Microtreatment and mechanical behavior of two casting AZ 91D-flash nonsphere composites [ J.]Applied Science and Manufacturing,2009,40(7): 883-. In order to solve the problem that the density ratio of the composite material is expected to increase due to the fact that the walls of the cenospheres are broken and the interior of the cenospheres is filled with the matrix alloy, researchers propose solutions, wherein a protective layer is coated on the surfaces of the cenospheres and used for strengthening the cenospheres and preventing the cenospheres and the magnesium alloy melt from undergoing an interface reaction in the material preparation process, so that the integrity of the cenospheres in the composite material is maintained, and the solutions are proved to be effective solutions. Braszczy ń ska M et al, using chemistryThe plating method coats a Ni-P protective layer on the surface of the fly ash floating bead, and the floating bead/AZ 91magnesium alloy composite material is prepared by a stirring casting method, and the results show that the Ni-P layer effectively prevents the floating bead wall from reacting with the matrix magnesium alloy, the floating bead has good integrity and is not broken, and the density of the composite material is effectively reduced (Braszczy ń ska M, Katarzyna N, Kamieniak J. analysis of interface between composites in AZ91magnesium alloy foam composite with Ni-P coated floating beads [ J ] with]Journal of Alloys and Compounds,2017,720: 352-. However, when the chemical plating method is used for coating the Ni-P protective layer, AgNO is required3、PdCl2And precious metal salt is used as an activator, so that the cost of raw materials is increased, the preparation steps of the chemical plating layer are complicated, the components of the chemical plating solution are complex, and meanwhile, a large amount of waste liquid generated by chemical plating is difficult to recover, so that the environmental pollution is easily caused. Therefore, an economical and effective method for coating a protective layer on the surface of the hollow microsphere is found, and the method has important significance for comprehensive utilization of the hollow microsphere and research, development and application of the light magnesium alloy composite material.
Disclosure of Invention
The invention aims to solve the problem that hollow microspheres are broken due to mechanical collision and interface reaction in the material preparation process when the hollow microspheres are used as reinforcement bodies to prepare hollow microsphere/magnesium alloy composite materials, and particularly provides a method for coating a Cu-Ni protective layer on the surfaces of the hollow microspheres, which can coat the surfaces of fly ash floating beads and hollow glass microspheres.
The method comprises the following specific steps of coating a Cu-Ni protective layer on the surface of the hollow microsphere:
(1) and (4) treating the surfaces of the hollow microspheres by alkali washing and coarsening. Firstly, putting a certain amount of cenospheres into 0.5-1mol/L NaOH solution, stirring and cleaning for 30-60min at room temperature by using a mechanical stirrer, on one hand, removing oil stains and impurities on the surfaces of the cenospheres, on the other hand, reducing the aggregation of the cenospheres by alkali washing, increasing the dispersibility of the cenospheres in a medium, then carrying out suction filtration, and repeatedly rinsing with deionized water until the pH value is 7. Adding the hollow microspheres washed by alkali into 30g/L ammonium fluoride solution, stirring for 20-50min under the condition of 50 ℃ water bath, and adding ammonium fluorideHydrofluoric acid generated by hydrolysis in hot water to SiO2The etching effect (the mechanism is shown in a reaction formula (1) and a reaction formula (2)), a plurality of tiny pits and grooves are formed on the surface of the cenosphere, the surface area of the cenosphere is increased, the adsorption of metal ions on the surface of the cenosphere and the fixation of a coating layer on the surface of the cenosphere are facilitated, in addition, the roughening treatment by utilizing ammonium fluoride can avoid the problems of perforation and fracture of the surface of the cenosphere caused by excessive reaction when directly utilizing hydrofluoric acid for roughening, finally, deionized water is used for repeatedly rinsing until the pH value is 7, and the. The surface appearance of the hollow microspheres after alkali washing and coarsening treatment is shown in figure 1.
SiO2+4HF═SiF4↑+2H2O (2)
(2) A certain amount of Ni (NO)3)2·6H2O and Cu (NO)3)2·3H2Dissolving O in mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 1:1) to keep the total concentration of metal ions in the mixed solution at 0.3-0.5mol/L, wherein Ni2+And Cu2+In a ratio of 1: 0.2-1: 5; and (2) immersing the hollow microspheres roughened by alkali washing in the step (1) into the mixed solution, wherein the solid-to-liquid ratio of the hollow microspheres to the mixed solution is 1: 25-1: 40, stirring the mixture by a mechanical stirrer at the speed of 100-:
(3) slightly grinding and scattering CuO/NiO-coated hollow microspheres in a mortar, then putting the ground microspheres into a tubular furnace, taking a mixed gas of hydrogen and high-purity argon as a reducing gas, firstly introducing high-purity argon to discharge air in the tubular furnace, and then introducing the mixed gas of hydrogen and high-purity argon at a flow rate of 30-60mL/min, wherein the volume ratio of the hydrogen to the high-purity argon is 1: 9-2: and 3, heating the tube furnace to 700 ℃ at the speed of 10 ℃/min, continuously introducing gas for reduction for 2-4h at the temperature of 700 ℃, then closing hydrogen, introducing high-purity argon at the flow rate of 50mL/min to prevent the coated copper-nickel protective layer from being oxidized at high temperature, and finally cooling to room temperature along with the furnace to obtain the hollow microspheres coated with the Cu-Ni protective layer. The reaction is as follows:
the method for coating the copper-nickel protective layer on the surface of the hollow microsphere overcomes the defects of complicated chemical plating steps, high raw material cost and the like. The obtained Cu-Ni protective layer has the advantages of complete structure, uniform thickness and simple preparation process, can provide good protection effect on the hollow microspheres, can reduce the mechanical damage of the hollow microspheres and reduce or prevent the occurrence of interface reaction in the preparation process of the hollow microsphere/magnesium alloy composite material, ensures that the hollow microspheres are kept complete, and finally achieves the purpose of reducing the density of the composite material.
Drawings
FIG. 1 is a surface topography diagram of a pulverized fuel ash floating bead after coarsening;
FIG. 2 is a surface topography diagram of fly ash floating beads coated with a Cu-Ni protective layer;
FIG. 3 is an EDS spectrum of fly ash floating beads coated with a Cu-Ni protective layer;
FIG. 4 is a surface topography of hollow glass microspheres coated with a Cu-Ni protective layer.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1:
20g of fly ash floating beads are put into 500mL of NaOH solution with the concentration of 0.5mol/L, stirred and cleaned for 60min at room temperature by a mechanical stirrer, filtered, and repeatedly rinsed by deionized water until the pH value is 7; then adding the alkali washing beads into 500mL of 30g/L ammonium fluoride solution, stirring for 20min under the condition of 50 ℃ water bath, repeatedly rinsing with deionized water until the pH value is 7, and filtering and drying. Mixing 53g Ni (NO)3)2·6H2O and 15g Cu (NO)3)2·3H2Dissolving O in 600mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 1:1), immersing the coarsened hollow microspheres in the mixed solution, stirring the mixture for 8 hours at the speed of 100r/min by using a mechanical stirrer under the condition of a water bath at 50 ℃ until the mixed solution is viscous, and then placing the mixed solution in a forced air drying oven to dry the mixed solution for 12 hours at the temperature of 100 ℃. Putting the dried solid mixture into a tubular furnace, introducing high-purity argon at the flow rate of 50mL/min, quickly heating the tubular furnace to 500 ℃, roasting for 3h, taking out, cooling in the air, slightly grinding in a mortar to break up the solid mixture, putting the tubular furnace again, introducing high-purity argon at the flow rate of 100mL/min for 5min, introducing hydrogen and high-purity argon at the flow rates of 15mL/min and 35mL/min respectively, heating the tubular furnace to 700 ℃ at the speed of 10 ℃/min, keeping the temperature for 3h after the furnace temperature is stable, finally closing the hydrogen, introducing high-purity argon at the flow rate of 50mL/min, cooling along with the furnace to room temperature, and taking out to obtain the floating bead with the surface being coated with the Cu-Ni protective layer. The surface appearance is shown in fig. 2, and it can be seen that fine particles with uniform size are tightly coated on the surface of the floating bead to form a complete, compact and uniform-thickness coating layer, the EDS spectrum is shown in fig. 3, the main peaks are Ni and Cu, and the Ni-Cu protective layer is successfully coated on the surface of the floating bead.
Example 2:
25g of hollow glass microspheres are placed into 500mL of 0.7mol/L NaOH solution by a machineStirring and cleaning the mixture for 30min at room temperature by using a stirrer, performing suction filtration, and repeatedly rinsing the mixture by using deionized water until the pH value is 7; adding alkali washing hollow glass beads into 30g/L ammonium fluoride solution, stirring for 50min under the condition of 50 ℃ water bath, repeatedly rinsing with deionized water until the pH value is 7, and performing suction filtration and drying. 50g of Ni (NO)3)2·6H2O and 40g Cu (NO)3)2·3H2Dissolving O in 800mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 1:1), immersing the coarsened hollow glass microspheres in the mixed solution, stirring for 6 hours at the speed of 300r/min by using a mechanical stirrer under the condition of 50 ℃ water bath until the mixed solution is viscous, and then placing the mixed solution in a forced air drying oven to dry for 15 hours under the condition of 100 ℃. Placing the dried solid mixture in a tubular furnace, introducing high-purity argon at the flow rate of 50mL/min, rapidly heating the tubular furnace to 600 ℃, roasting for 4h, taking out, cooling in the air, slightly grinding in a mortar to break up the solid mixture, placing the solid mixture in the tubular furnace again, introducing high-purity argon at the flow rate of 100mL/min for 5min, introducing hydrogen and high-purity argon at the flow rates of 10mL/min and 40mL/min respectively, heating the tubular furnace to 700 ℃ at the speed of 10 ℃/min, keeping the temperature for 4h after the furnace temperature is stable, finally closing the hydrogen, introducing high-purity argon at the flow rate of 50mL/min, cooling the tubular furnace to room temperature, and taking out to obtain the hollow glass microspheres with the surface coated with the Cu-Ni protective layer. The surface appearance is shown in fig. 4, and fine particles with uniform size are coated on the surface of the hollow glass microsphere.
Example 3:
putting 25g of fly ash floating beads into 700mL of NaOH solution with the concentration of 1mol/L, stirring and cleaning for 40min at room temperature by using a mechanical stirrer, performing suction filtration, and repeatedly rinsing with deionized water until the pH value is 7; adding alkali washing hollow glass beads into 30g/L ammonium fluoride solution, stirring for 30min under the condition of 50 ℃ water bath, repeatedly rinsing with deionized water until the pH value is 7, and performing suction filtration and drying. 51g of Ni (NO)3)2·6H2O and 43g Cu (NO)3)2·3H2Dissolving O in 700mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 1:1), immersing the fly ash floating beads in the mixed solution, and adding water at 50 DEG CStirring with a mechanical stirrer at 200r/min for 6 hr under bath condition until the mixture is viscous, and drying in a forced air drying oven at 100 deg.C for 20 hr. Placing the dried mixture in a tubular furnace, introducing high-purity argon at the flow rate of 50mL/min, rapidly heating the tubular furnace to 400 ℃, roasting for 5 hours, taking out, cooling in air, slightly grinding in a mortar to break up the solid mixture, placing the tubular furnace again, introducing high-purity argon at the flow rate of 100mL/min for 5 minutes, introducing hydrogen and high-purity argon at the flow rates of 20mL/min and 40mL/min respectively, heating the tubular furnace to 700 ℃ at the speed of 10 ℃/min, keeping the temperature for 2 hours after the furnace temperature is stabilized, finally closing the hydrogen, introducing high-purity argon at the flow rate of 50mL/min, cooling along with the furnace to the room temperature, and taking out. Example 3 also yielded a Cu — Ni protective layer with a dense structure and uniform thickness.
Claims (1)
1. A method for coating a copper-nickel protective layer on the surface of a hollow microsphere can coat the surfaces of fly ash floating beads and hollow glass microspheres with the copper-nickel protective layer, and is characterized in that the copper-nickel protective layer is prepared by the following steps:
(1) roughening the surface of the hollow microsphere, namely firstly putting the hollow microsphere into 0.5-1mol/L NaOH solution, stirring and cleaning for 30-60min at room temperature to remove oil stains and impurities on the surface of the hollow microsphere, then performing suction filtration, and repeatedly rinsing with deionized water until the pH value is 7; then putting the hollow microspheres subjected to suction filtration into 30g/L ammonium fluoride solution, stirring for 20-50min under the condition of 50 ℃ water bath, etching and roughening the surfaces of the hollow microspheres so as to enhance the bonding force between the surfaces of the hollow microspheres and a coating layer, finally performing suction filtration, repeatedly rinsing with deionized water until the pH value is 7, and drying for later use;
(2) mixing Ni (NO)3)2·6H2O and Cu (NO)3)2·3H2Dissolving O in a mixed solution of ethanol and deionized water at a volume ratio of 1:1, and keeping the total concentration of metal ions at 0.3-0.5mol/L, wherein Ni2+And Cu2+In a ratio of 1: 0.2-1: and 5, immersing the hollow microspheres roughened by alkali washing in the step (1) into the mixed solution, wherein the solid-to-liquid ratio of the hollow microspheres to the mixed solution is 1: 25-1: 40 in a water bath at 50 DEG CStirring with a mechanical stirrer at the speed of 100-;
(3) putting the CuO/NiO coated hollow microspheres obtained in the step (2) into a tubular furnace, firstly introducing high-purity argon to discharge air in the tubular furnace, and then introducing a mixed gas of hydrogen and high-purity argon at a flow rate of 30-60mL/min, wherein the volume ratio of the hydrogen to the high-purity argon is 1: 9-2: and 3, heating the tube furnace to 700 ℃ at the speed of 10 ℃/min, continuously introducing gas for reduction for 2-4h at the temperature, cooling to room temperature along with the furnace to obtain the hollow microspheres coated with the Cu-Ni protective layer, and introducing high-purity argon at the flow rate of 50mL/min in the cooling process to prevent the coating layer from being oxidized.
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| CN1333387A (en) * | 2001-08-07 | 2002-01-30 | 东南大学 | Method for making light tye composite hollow metal microball |
| CN102586881A (en) * | 2010-10-29 | 2012-07-18 | 北京矿冶研究总院 | Preparation method of zinc oxide whisker containing metal nickel copper |
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| JPH02305970A (en) * | 1989-05-22 | 1990-12-19 | Hitachi Chem Co Ltd | Production of hollow fine metal sphere |
| CN102071411B (en) * | 2010-08-19 | 2012-05-30 | 比亚迪股份有限公司 | Plastic product and preparation method thereof |
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| CN1333387A (en) * | 2001-08-07 | 2002-01-30 | 东南大学 | Method for making light tye composite hollow metal microball |
| CN102586881A (en) * | 2010-10-29 | 2012-07-18 | 北京矿冶研究总院 | Preparation method of zinc oxide whisker containing metal nickel copper |
| CN108203819A (en) * | 2016-12-19 | 2018-06-26 | 宜宾市翠屏区显峰建材有限公司 | A kind of silver-plated teaching test method of glass fibre |
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