CN111394604A - Application of composite reinforcement body with annular structure in nickel-based composite material - Google Patents
Application of composite reinforcement body with annular structure in nickel-based composite material Download PDFInfo
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Abstract
The invention discloses an application of a composite reinforcement with an annular structure in a nickel-based composite material, wherein the composite reinforcement can be mixed with nickel powder to prepare the nickel-based composite material, the composite reinforcement has an annular structure, the annular structure consists of a mesoporous nano titanium oxide hollow sphere, a magnesium oxide nano sheet which grows perpendicular to the mesoporous nano titanium oxide hollow sphere and nano silicon oxide at the outermost layer, and the mass ratio of the mesoporous nano titanium oxide hollow sphere to the magnesium oxide nano sheet is 3: (1-2): 5; the outer diameter of the composite reinforcement body with the annular structure is 300 +/-5 nm, and the inner diameter of the composite reinforcement body is 60 +/-5 nm. The invention also discloses a specific application method of the composite reinforcement in a nickel-based composite material. The invention overcomes the problems of poor infiltration of the metal matrix and the reinforcement, uneven dispersion of the reinforcement, and particularly difficult compounding of the nano-scale reinforcement and the metal matrix, and the prepared composite material has good mechanical property, good interface bonding property of the reinforcement and the metal matrix, simple preparation process and effectively reduced preparation cost.
Description
Technical Field
The invention relates to the field of composite material preparation, in particular to application of a composite reinforcement body with an annular structure in a nickel-based composite material.
Background
The metal matrix composite material has the advantages of high specific strength, high specific modulus, good thermal expansion coefficient, good wear resistance and the like, and is widely applied to the industrial fields of aviation, kantian, automobiles and the like. For metal matrix composites, the bonding properties of the reinforcement and the metal matrix, as well as the amount, size, shape, etc. of the reinforcement, all have a significant impact on the properties of the composite. For the classification of metal matrix composites, they can be classified according to the type of reinforcement: (1) the particle reinforced composite material is characterized in that dispersed reinforced phase exists in a particle form, the particle diameter and the particle distance of the dispersed reinforced phase are larger and are generally larger than 1 mu m; (2) the layered composite material is characterized in that the strength of the composite layered composite material which is formed by adding the repeatedly arranged high-strength and high-modulus lamellar reinforcements into a metal matrix with better toughness and formability is closer to the performance of large-size reinforcements, and is greatly different from the performance of whisker or fiber small-size reinforcements. Since the dimension of the reinforcement sheet in two dimensions corresponds to the size of the structural member, defects in the reinforcement may become the core of cracks of the same length as the structural member. Because the strength of the sheet reinforcement is not as high as the fiber reinforcement, the strength of the laminate structural composite is limited. (3) The one-dimensional reinforcement in the metal matrix composite can be divided into long fibers, short fibers and whiskers according to the length of the one-dimensional reinforcement. Long fibers, also called continuous fibers, which reinforce the metal matrix in such a way that the composite material reinforced by the latter exhibits a marked anisotropic character, can be present as single fibers, as two-dimensional fabrics, whose mechanical properties in the direction of the plane of the fabric are different from those perpendicular to the plane, and as three-dimensional fabrics, whose properties are substantially isotropic. The continuous reinforced metal matrix composite material is a composite material prepared by using high-performance fibers as a matrix and using metal or alloy of the high-performance fibers and the metal as the matrix. The fibers bear load, and the addition of the fibers not only greatly changes the mechanical property of the material, but also improves the temperature resistance. The short fibers and the whiskers are dispersed in the metal matrix randomly and uniformly, so that the short fibers are isotropic macroscopically, and under special conditions, the short fibers can be directionally arranged, such as can be achieved by carrying out secondary processing on the material. When a ductile metal matrix is reinforced with high strength brittle fibers, the yield and plastic flow of the matrix are the primary characteristics of the composite's performance, but the fibers have a considerable effect on the reinforcement of the composite's elastic modulus.
According to the matrix, the metal matrix composite mainly comprises aluminum matrix, magnesium matrix, copper matrix, nickel matrix, titanium matrix and other composite materials. . Due to the significant demands in the field of aircraft engines and gas turbines, the manufacture of high temperature resistant components of large size and complex construction has attracted considerable attention. The nickel-based composite material is expected to become a candidate material for the large-size complex structural component due to the excellent performances of the nickel-based composite material in the aspects of high-temperature mechanics, creep resistance and the like. The nickel-based composite material is manufactured by using nickel and nickel alloy as a matrix. However, the problems of manufacturing process, reliability and the like are not solved, so that a satisfactory result is not obtained for the preparation of the nickel-based composite material.
A patent (CN200710061689.9, application date: 2017.4.10) discloses a carbon fiber reinforced nickel-based composite material and a preparation method thereof, relating to a metal-based composite material. The metal matrix composite prepared by the prior art is not suitable for parts such as steam turbines used at high temperature. The composite material comprises the following components in percentage by volume: carbon fiber: 30-35%, copper: 6-8%, nickel: 57-64%. The process comprises the following steps: pretreating carbon fiber, electrodepositing copper, cleaning, neutralizing, electrodepositing nickel, forming electrodeposited nickel, cleaning and drying blank, cutting the blank, putting the cut blank into a die, carrying out vacuum hot pressing, and cooling along with a furnace. The Cf/Ni composite material prepared by the three-step electrodeposition method not only can meet the use requirements of the blades of the gas turbine engine, but also has the advantages of good high-temperature strength, high elastic modulus, low density, high melting point, creep resistance and the like. The patent (CN201810762498.3, application date: 2018.7.12) discloses a nickel-based composite material with 3D net-shaped distribution of nano ceramic particles and a preparation method thereof, wherein nickel or nickel alloy powder and nano particles are subjected to ball milling together, and then the nickel composite material is obtained by technologies such as hot-pressing sintering or discharge plasma sintering. The reinforcing phase distribution of the composite material is a unique 3D network structure, the nano reinforcing phase is gathered at a grain boundary microscopically, and forms a network shape in a macroscopic space, so that the uniform distribution of a reinforcing body is not pursued, and the excellent strength and plasticity can be still maintained. The method has the advantages of simple process, low energy consumption, short time consumption and easy regulation and control of material performance by adjusting the reinforcing phase. However, the dispersibility of the reinforcement in the matrix is poor, so that the performance of the composite material is easily uneven, and the toughness is greatly reduced. The patent (CN200910091602.1) discloses a method for synthesizing a TiCx particle reinforced nickel-based composite material by in-situ reaction, belonging to the field of composite materials. The preparation process comprises the following steps: preparation of mixed powder: the powder material consists of Ti, C, Al, Fe and Mo, wherein the weight ratio of Al powder: 8-12 wt.%, Fe powder: 12-15 wt.%, Mo powder: 3-5 wt.%, graphite C powder: 8-12 wt.%, and the balance of Ti powder, wherein the ratio of the weight of the Ti powder to the weight of the C powder in the powder needs to satisfy the relationship of (5-6.7) to 1; preparing a powder chip: rolling the Ni foil into a cylinder with the diameter of 16-25mm, and filling mixed powder obtained after ball milling and mixing into the cylinder; smelting and casting process: and preparing the TiCx/Ni composite material by using a vacuum intermediate frequency induction smelting furnace. Has the advantages that the TiCx/Ni composite material with the volume fraction of TiCx of 20-40 percent is prepared; the density is close to 100%, and the high-temperature strength and hardness are obviously higher than those of the conventional nickel-based high-temperature alloy. But the method has larger reaction energy consumption and increases the preparation cost of the composite material.
Disclosure of Invention
The invention provides the application of the composite reinforcement with the annular structure in the nickel-based composite material, which solves the problems that the nickel-based composite material in the prior art is high in preparation cost, the reinforcement in the composite material is difficult to disperse uniformly and the compatibility with a metal matrix is poor, so that the performance of the composite material is poor.
In order to better solve the technical problems, the invention adopts the following technical scheme:
the application of the composite reinforcement body with the annular structure in the nickel-based composite material is characterized in that the composite reinforcement body can be mixed with nickel powder to prepare the nickel-based composite material, the composite reinforcement body has the annular structure, the annular structure is composed of mesoporous nano titanium oxide hollow spheres, magnesium oxide nanosheets growing perpendicular to the mesoporous nano titanium oxide hollow spheres and outermost layer of nano silicon oxide, and the mass ratio of the mesoporous nano titanium oxide hollow spheres to the magnesium oxide nanosheets is 3: (1-2): 5; the outer diameter of the composite reinforcement body with the annular structure is 300 +/-5 nm, and the inner diameter of the composite reinforcement body is 60 +/-5 nm.
In order to better solve the technical problems, the invention also provides an application process of the composite reinforcement body with the annular structure in the nickel-based composite material, which comprises the following specific steps:
(1) mixing a styrene monomer, N-methylene bisacrylamide and ethanol, adding the mixture into a three-neck flask with a condensation pipe, adding azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 10 to 20 hours at 60 to 70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing, placing in a reaction kettle, sealing, reacting at 150 ℃ for 7-11h, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by using deionized water and ethanol in sequence, drying, treating the dried solid in a muffle furnace at 500 ℃ in a nitrogen atmosphere for 1h, and treating at 800 ℃ in an air atmosphere for 1h to prepare the mesoporous nano titanium oxide hollow spheres;
(3) dispersing the prepared mesoporous nano titanium oxide hollow spheres in deionized water, simultaneously adding methylene bisacrylamide, stirring and dispersing uniformly, dissolving magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 5-10 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; dispersing a composite reinforcement precursor in deionized water, mixing with silica sol, adding into a three-neck flask, introducing nitrogen at 150 ℃, stirring and refluxing for 8-15h, cooling to room temperature after the reaction is finished, washing a solid obtained by filtering a reaction liquid, drying, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2h under the protection of inert gas to obtain a composite reinforcement;
(5) and (2) grinding and uniformly mixing nickel powder and the prepared composite reinforcement, placing the mixture in a cold pressing die, performing pre-pressing treatment and demolding to obtain a blank, and placing the prepared blank in a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering treatment to obtain the nickel-based composite material.
Preferably, in the step (1), the mass ratio of the styrene monomer, the N, N-methylene bisacrylamide, and the azobisisobutyronitrile is 2: (0.011-0.014): 0.25.
preferably, in the step (2), the molar ratio of tetrabutyl titanate, polystyrene microspheres and hydrochloric acid is 1: 035:0.01.
Preferably, in the step (3), the mass ratio of the mesoporous nano titanium oxide hollow spheres to the methylene bisacrylamide is 2: 0.0033.
In the above-mentioned means, preferably, in the step (3), the molar ratio of the magnesium chloride hexahydrate to the ammonium chloride is 1 (0.5 to 1).
Preferably, in the step (4), the molar ratio of the ethyl orthosilicate to the ethanol to the hydrochloric acid is 1:5: 0.03.
Preferably, in the step (5), the mass ratio of the nickel powder to the composite reinforcement is 1: (1-2).
Preferably, in the step (5), the pressure of the preliminary press treatment is 25MPa, and the dwell time is 20 min.
As a preferable aspect of the above technical means, in the step (5), specific conditions of the vacuum hot press sintering treatment are as follows: starting a vacuum pump, vacuumizing to 0.2-0.5Pa, starting a pressure pump, pressurizing to 40MPa, starting a furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished.
Compared with the prior art, the invention has the following beneficial effects:
in the prior art, the mechanical property of the prepared composite material is often difficult to meet the requirements of modern technological development because the interface bonding property of the reinforcement and the metal matrix is poor or the reinforcement is not uniformly dispersed in the metal matrix. In order to improve the interface bonding performance of the reinforcement and a metal matrix, the invention firstly takes a self-made crosslinked polystyrene microsphere as a template to prepare a mesoporous nano titanium oxide hollow sphere which has good dispersibility, a mesoporous structure on the surface, a large specific surface area and high strength, and in order to improve the dispersion uniformity of the mesoporous nano titanium oxide hollow sphere in the metal matrix, the invention grows a magnesium oxide nanosheet on the surface in situ, the magnesium oxide nanosheet is vertically dispersed on the surface of the mesoporous nano titanium oxide hollow sphere to improve the interface performance of the mesoporous nano titanium oxide hollow sphere and the metal matrix, and finally the surface of the magnesium oxide nanosheet is coated with a layer of nano silicon oxide to prepare the composite reinforcement with an annular structure, and the composite reinforcement has the advantages of high strength, good wear resistance, good heat conductivity and good size stability.
The nickel-based composite material is prepared by mixing and sintering the prepared composite reinforcement with the annular structure and the nickel powder, the composite reinforcement is uniformly dispersed in the nickel-based composite material, and interface layers with certain structures can be formed on the surfaces of nickel grains and at crystal boundaries, so that the reinforcement effect is achieved, and the hardness of the composite material is improved. The composite reinforcement prepared by the invention has few defects, and the composite reinforcement can form an interconnected annular structure in a metal matrix, so that the stress transmission is facilitated, the toughness of the composite material is improved, and the heat-conducting property of the nickel-based composite material is not obviously influenced.
Detailed Description
In order to better understand the present invention, the following examples further illustrate the invention, the examples are only used for explaining the invention, not to constitute any limitation of the invention.
Example 1
(1) Mixing 2g of styrene monomer, 0.011g of N, N-methylene-bisacrylamide and 50ml of ethanol, adding the mixture into a three-neck flask with a condensation pipe, adding 0.25g of azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 10h at 60-70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving 1mol of tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing to obtain a reaction solution, placing the reaction solution in a reaction kettle, sealing, reacting for 7 hours at 150 ℃, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by deionized water and ethanol in sequence, drying, placing the dried solid in a muffle furnace, treating for 1 hour at 500 ℃ in a nitrogen atmosphere, and treating for 1 hour at 800 ℃ in an air atmosphere to obtain mesoporous nano titanium oxide hollow spheres;
(3) dispersing the 2g of the prepared mesoporous nano titanium oxide hollow spheres in deionized water, adding 0.0033g of methylene bisacrylamide, stirring and uniformly dispersing, dissolving 1mol of magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 5 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, and washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; the method comprises the following steps of (1) keeping the molar ratio of ethyl orthosilicate to ethanol to hydrochloric acid at 1:5:0.03, dispersing a composite reinforcement precursor in deionized water, mixing the precursor with silica sol, adding the mixture into a three-neck flask, introducing nitrogen at 150 ℃, stirring, refluxing and reacting for 8 hours, cooling to room temperature after the reaction is finished, washing a solid obtained after reaction liquid is filtered, drying, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2 hours under the protection of inert gas to obtain a composite reinforcement;
(5) nickel powder and the composite reinforcement prepared by the method are mixed according to the mass ratio of 1: 1, placing the mixture in a cold pressing die after grinding and uniformly mixing, carrying out pre-pressing treatment for 20min under the pressure of 25MPa, demolding to obtain a blank, placing the prepared blank in a vacuum hot-pressing sintering furnace, firstly starting a vacuum pump, vacuumizing to 0.2-0.5Pa, then starting a pressure pump, pressurizing to 40MPa, finally starting the furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished to obtain the nickel-based composite material.
Example 2
(1) Mixing 2g of styrene monomer, 0.014g of N, N-methylene bisacrylamide and 50ml of ethanol, adding the mixture into a three-neck flask with a condenser tube, adding 0.25g of azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 20h at 60-70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving 1mol of tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing to obtain a reaction solution, placing the reaction solution in a reaction kettle, sealing, reacting for 11 hours at 150 ℃, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by deionized water and ethanol in sequence, drying, placing the dried solid in a muffle furnace, treating for 1 hour at 500 ℃ in a nitrogen atmosphere, and treating for 1 hour at 800 ℃ in an air atmosphere to obtain mesoporous nano titanium oxide hollow spheres;
(3) dispersing the 2g of the prepared mesoporous nano titanium oxide hollow spheres in deionized water, adding 0.0033g of methylene bisacrylamide, stirring and uniformly dispersing, dissolving 1mol of magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 10 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, and washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; the method comprises the following steps of (1) keeping the molar ratio of ethyl orthosilicate to ethanol to hydrochloric acid at 1:5:0.03, dispersing a composite reinforcement precursor in deionized water, mixing the precursor with silica sol, adding the mixture into a three-neck flask, introducing nitrogen at 150 ℃, stirring, refluxing and reacting for 15 hours, cooling to room temperature after the reaction is finished, washing a solid obtained after reaction liquid is filtered, drying, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2 hours under the protection of inert gas to obtain a composite reinforcement;
(5) nickel powder and the composite reinforcement prepared by the method are mixed according to the mass ratio of 1: 2, placing the mixture in a cold pressing die after grinding and uniformly mixing, carrying out pre-pressing treatment for 20min under the pressure of 25MPa, demolding to obtain a blank, placing the prepared blank in a vacuum hot-pressing sintering furnace, firstly starting a vacuum pump, vacuumizing to 0.2-0.5Pa, then starting a pressure pump, pressurizing to 40MPa, finally starting the furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished to obtain the nickel-based composite material.
Example 3
(1) Mixing 2g of styrene monomer, 0.012g of N, N-methylene-bisacrylamide and 50ml of ethanol, adding the mixture into a three-neck flask with a condenser tube, adding 0.25g of azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 12h at 60-70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving 1mol of tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing to obtain a reaction solution, placing the reaction solution in a reaction kettle, sealing, reacting for 8 hours at 150 ℃, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by deionized water and ethanol in sequence, drying, placing the dried solid in a muffle furnace, treating for 1 hour at 500 ℃ of nitrogen, and treating for 1 hour at 800 ℃ of air to obtain mesoporous nano titanium oxide hollow spheres;
(3) dispersing the 2g of the prepared mesoporous nano titanium oxide hollow spheres in deionized water, adding 0.0033g of methylene bisacrylamide, stirring and uniformly dispersing, dissolving 1mol of magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 6 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, and washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; the method comprises the following steps of (1) keeping the molar ratio of ethyl orthosilicate to ethanol to hydrochloric acid at 1:5:0.03, dispersing a composite reinforcement precursor in deionized water, mixing the precursor with silica sol, adding the mixture into a three-neck flask, introducing nitrogen at 150 ℃, stirring, refluxing and reacting for 10 hours, cooling to room temperature after the reaction is finished, washing a solid obtained after reaction liquid is filtered, drying, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2 hours under the protection of inert gas to obtain a composite reinforcement;
(5) nickel powder and the composite reinforcement prepared by the method are mixed according to the mass ratio of 1: 1, placing the mixture in a cold pressing die after grinding and uniformly mixing, carrying out pre-pressing treatment for 20min under the pressure of 25MPa, demolding to obtain a blank, placing the prepared blank in a vacuum hot-pressing sintering furnace, firstly starting a vacuum pump, vacuumizing to 0.2-0.5Pa, then starting a pressure pump, pressurizing to 40MPa, finally starting the furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished to obtain the nickel-based composite material.
Example 4
(1) Mixing 2g of styrene monomer, 0.013g of N, N-methylene bisacrylamide and 50ml of ethanol, adding the mixture into a three-neck flask with a condenser pipe, adding 0.25g of azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 15h at 60-70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving 1mol of tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing to obtain a reaction solution, placing the reaction solution in a reaction kettle, sealing, reacting at 150 ℃ for 9 hours, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by deionized water and ethanol in sequence, drying, placing the dried solid in a muffle furnace, treating at 500 ℃ for 1 hour in a nitrogen atmosphere, and treating at 800 ℃ for 1 hour in an air atmosphere to obtain mesoporous nano titanium oxide hollow spheres;
(3) dispersing the 2g of the prepared mesoporous nano titanium oxide hollow spheres in deionized water, adding 0.0033g of methylene bisacrylamide, stirring and uniformly dispersing, dissolving 1mol of magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 7 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, and washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; the method comprises the following steps of (1) keeping the molar ratio of ethyl orthosilicate to ethanol to hydrochloric acid at 1:5:0.03, dispersing a composite reinforcement precursor in deionized water, mixing the precursor with silica sol, adding the mixture into a three-neck flask, introducing nitrogen at 150 ℃, stirring, refluxing and reacting for 12 hours, cooling to room temperature after the reaction is finished, washing and drying solid obtained after reaction liquid is filtered, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2 hours under the protection of inert gas to obtain a composite reinforcement;
(5) nickel powder and the composite reinforcement prepared by the method are mixed according to the mass ratio of 1: grinding and uniformly mixing the materials according to the proportion of 1.5, placing the materials in a cold pressing die, carrying out pre-pressing treatment for 20min under the pressure of 25MPa, demolding to obtain a blank, placing the prepared blank in a vacuum hot-pressing sintering furnace, firstly starting a vacuum pump, vacuumizing to 0.2-0.5Pa, then starting a pressure pump, pressurizing to 40MPa, finally starting the furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished to obtain the nickel-based composite material.
Example 5
(1) Mixing 2g of styrene monomer, 0.014g of N, N-methylene bisacrylamide and 50ml of ethanol, adding the mixture into a three-neck flask with a condenser tube, adding 0.25g of azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 18h at 60-70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving 1mol of tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing to obtain a reaction solution, placing the reaction solution in a reaction kettle, sealing, reacting for 10 hours at 150 ℃, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by deionized water and ethanol in sequence, drying, placing the dried solid in a muffle furnace, treating for 1 hour at 500 ℃ of nitrogen, and treating for 1 hour at 800 ℃ of air to obtain mesoporous nano titanium oxide hollow spheres;
(3) dispersing the 2g of the prepared mesoporous nano titanium oxide hollow spheres in deionized water, adding 0.0033g of methylene bisacrylamide, stirring and uniformly dispersing, dissolving 1mol of magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 8 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, and washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; the method comprises the following steps of (1) keeping the molar ratio of ethyl orthosilicate to ethanol to hydrochloric acid at 1:5:0.03, dispersing a composite reinforcement precursor in deionized water, mixing the precursor with silica sol, adding the mixture into a three-neck flask, introducing nitrogen at 150 ℃, stirring, refluxing and reacting for 14 hours, cooling to room temperature after the reaction is finished, washing and drying solid obtained after reaction liquid is filtered, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2 hours under the protection of inert gas to obtain a composite reinforcement;
(5) nickel powder and the composite reinforcement prepared by the method are mixed according to the mass ratio of 1: 2, placing the mixture in a cold pressing die after grinding and uniformly mixing, carrying out pre-pressing treatment for 20min under the pressure of 25MPa, demolding to obtain a blank, placing the prepared blank in a vacuum hot-pressing sintering furnace, firstly starting a vacuum pump, vacuumizing to 0.2-0.5Pa, then starting a pressure pump, pressurizing to 40MPa, finally starting the furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished to obtain the nickel-based composite material.
Comparative example
The amount of the reinforcing material, namely, the granular nano-silica, added to the nickel-based composite material was the same as that used in example 5.
And (3) performance testing:
the microhardness of the sample is measured by adopting a TMV-1S model digital display micro Vickers hardness meter, the load is 200g, the loading time is 15S, and the hardness value is taken as the average value of 7 times of tests. The thermal conductivity of the composite material is measured by a laser pulse method thermal conductivity coefficient measuring instrument which is self-developed by Shanghai silicate research institute of Chinese academy of sciences. The sample size is phi 10.2 +/-0.2 mm, the thickness is 2.5 +/-0.2 mm, and the test environment is inert atmosphere. The tensile strength of the composite material was tested according to GB/T1447-2005 using a BTC-T1-FR020TN.A50 model Universal Material testing machine from ZWICK corporation, with a specimen thickness of 2mm and a tensile rate of 0.1 mm/min. The abrasion loss of the sample under the conditions of the sliding speed of 9mm/s, the load of 5N and the amplitude of 5mm is measured by adopting a UMT-2 multifunctional friction abrasion tester.
The performance tests of the nickel-based composite materials prepared in the present invention and comparative example are shown in the following table.
| Vickers hardness, MPa | Tensile strength, MPa | Amount of abrasion, mg | Thermal conductivity, W/m.k | |
| Example 1 | 165 | 513.5 | 0.012 | 83.5 |
| Example 2 | 169 | 515.2 | 0.015 | 85.5 |
| Example 3 | 165 | 513.8 | 0.013 | 83.9 |
| Example 4 | 167 | 514.9 | 0.015 | 84.2 |
| Example 5 | 168 | 515.3 | 0.014 | 84.5 |
| Comparative example | 133 | 321.9 | 0.67 | 63.3 |
From the test results, the composite reinforcement prepared by the invention can better improve the heat-conducting property, the wear-resisting property and the mechanical property of the nickel-based composite material.
Although specific embodiments of the invention have been described, many other forms and modifications of the invention will be apparent to those skilled in the art. It is to be understood that the appended claims and this invention generally cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims (10)
1. The application of the composite reinforcement body with the annular structure in the nickel-based composite material is characterized in that: the composite reinforcement can be mixed with nickel powder to prepare a nickel-based composite material, the composite reinforcement has an annular structure, the annular structure is composed of mesoporous nano titanium oxide hollow spheres, magnesium oxide nano sheets vertical to the mesoporous nano titanium oxide hollow spheres and outermost nano silicon oxide, and the mass ratio of the mesoporous nano titanium oxide hollow spheres to the magnesium oxide nano sheets to the outermost nano silicon oxide is 3: (1-2): 5; the outer diameter of the composite reinforcement body with the annular structure is 300 +/-5 nm, and the inner diameter of the composite reinforcement body is 60 +/-5 nm.
2. The application of the annular-structure composite reinforcement in the nickel-based composite material is characterized in that the application method comprises the following steps:
(1) mixing a styrene monomer, N-methylene bisacrylamide and ethanol, adding the mixture into a three-neck flask with a condensation pipe, adding azobisisobutyronitrile, stirring and mixing the mixture for 30min at 1000rpm, introducing nitrogen, and reacting the mixture for 10 to 20 hours at 60 to 70 ℃ to obtain polystyrene microsphere emulsion;
(2) dissolving tetrabutyl titanate in ethanol, adding the prepared polystyrene microsphere emulsion, mixing and stirring uniformly, then adding 0.35 mol/L hydrochloric acid solution, stirring and mixing, placing in a reaction kettle, sealing, reacting at 150 ℃ for 7-11h, cooling to room temperature after the reaction is finished, filtering the reaction solution, washing the obtained solid by using deionized water and ethanol in sequence, drying, treating the dried solid in a muffle furnace at 500 ℃ in a nitrogen atmosphere for 1h, and treating at 800 ℃ in an air atmosphere for 1h to prepare the mesoporous nano titanium oxide hollow spheres;
(3) dispersing the prepared mesoporous nano titanium oxide hollow spheres in deionized water, simultaneously adding methylene bisacrylamide, stirring and dispersing uniformly, dissolving magnesium chloride hexahydrate in the deionized water to prepare a magnesium ion solution, adding the magnesium ion solution into the dispersion liquid of the mesoporous nano titanium oxide hollow spheres, stirring and mixing, adding an ammonium chloride solution with the mass concentration of 20% to prepare a reaction liquid, then placing the reaction liquid in a reaction kettle, sealing, reacting at 120 ℃ for 5-10 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing and drying the solid in sequence to prepare a composite reinforcement precursor;
(4) dissolving ethyl orthosilicate in ethanol, then dropwise adding a hydrochloric acid solution while violently stirring to prepare silicasol; dispersing a composite reinforcement precursor in deionized water, mixing with silica sol, adding into a three-neck flask, introducing nitrogen at 150 ℃, stirring and refluxing for 8-15h, cooling to room temperature after the reaction is finished, washing and drying solid obtained by filtering reaction liquid, placing the dried solid in a muffle furnace, and calcining at 1000 ℃ for 2h under the protection of inert gas to obtain a composite reinforcement;
(5) and (2) grinding and uniformly mixing nickel powder and the prepared composite reinforcement, placing the mixture in a cold pressing die, performing pre-pressing treatment and demolding to obtain a blank, and placing the prepared blank in a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering treatment to obtain the nickel-based composite material.
3. The use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (1), the mass ratio of the styrene monomer to the N, N-methylene bisacrylamide to the azobisisobutyronitrile is 2: (0.011-0.014): 0.25.
4. the use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (2), the molar ratio of tetrabutyl titanate, polystyrene microspheres and hydrochloric acid is 1: 035:0.01.
5. The use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (3), the mass ratio of the mesoporous nano titanium oxide hollow spheres to the methylene bisacrylamide is 2: 0.0033.
6. The use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (3), the molar ratio of the magnesium chloride hexahydrate to the ammonium chloride is 1 (0.5-1).
7. The use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (4), the molar ratio of the ethyl orthosilicate to the ethanol to the hydrochloric acid is 1:5: 0.03.
8. The use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (5), the mass ratio of the nickel powder to the composite reinforcement is 1: (1-2).
9. The use of the annular composite reinforcement of claim 2 in a nickel-based composite material, wherein: in the step (5), the pressure of the pre-pressing treatment is 25MPa, and the pressure maintaining time is 20 min.
10. The application of the annular-structure composite reinforcement body in the nickel-based composite material according to claim 2, wherein in the step (5), the specific conditions of the vacuum hot-pressing sintering process are as follows: starting a vacuum pump, vacuumizing to 0.2-0.5Pa, starting a pressure pump, pressurizing to 40MPa, starting a furnace, heating to 500 ℃, carrying out heat preservation and pressure maintaining treatment for 50min, and cooling to room temperature along with the furnace after the treatment is finished.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004277804A (en) * | 2003-03-14 | 2004-10-07 | Hitachi Metals Ltd | Nickel material |
| CN103803643A (en) * | 2014-03-03 | 2014-05-21 | 福州大学 | Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof |
| WO2014142089A1 (en) * | 2013-03-12 | 2014-09-18 | 株式会社東北テクノアーチ | HEAT-RESISTANT Ni-BASED ALLOY AND METHOD FOR MANUFACTURING SAME |
| CN105817269A (en) * | 2016-05-06 | 2016-08-03 | 扬州大学 | Preparation method of carbonized polyaniline/titanium dioxide composite photocatalyst |
| CN109825899A (en) * | 2019-03-05 | 2019-05-31 | 山东大学 | A kind of method that electrostatic spinning directly prepares mesoporous silicon Magnesium coumpoud oxide fiber |
-
2020
- 2020-04-03 CN CN202010257012.8A patent/CN111394604A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004277804A (en) * | 2003-03-14 | 2004-10-07 | Hitachi Metals Ltd | Nickel material |
| WO2014142089A1 (en) * | 2013-03-12 | 2014-09-18 | 株式会社東北テクノアーチ | HEAT-RESISTANT Ni-BASED ALLOY AND METHOD FOR MANUFACTURING SAME |
| CN103803643A (en) * | 2014-03-03 | 2014-05-21 | 福州大学 | Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof |
| CN105817269A (en) * | 2016-05-06 | 2016-08-03 | 扬州大学 | Preparation method of carbonized polyaniline/titanium dioxide composite photocatalyst |
| CN109825899A (en) * | 2019-03-05 | 2019-05-31 | 山东大学 | A kind of method that electrostatic spinning directly prepares mesoporous silicon Magnesium coumpoud oxide fiber |
Non-Patent Citations (1)
| Title |
|---|
| 匡达: "《石墨烯/镍基复合材料的制备和性能研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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