CN114318258B - Al-coated AlN nanoparticles and preparation method thereof - Google Patents
Al-coated AlN nanoparticles and preparation method thereof Download PDFInfo
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- CN114318258B CN114318258B CN202011054762.1A CN202011054762A CN114318258B CN 114318258 B CN114318258 B CN 114318258B CN 202011054762 A CN202011054762 A CN 202011054762A CN 114318258 B CN114318258 B CN 114318258B
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Abstract
An Al-coated AlN nanoparticle and a preparation method thereof are disclosed, which are obtained by preparing a multilayer structure composite film consisting of a two-phase structure layer consisting of AlN and Al and an Al layer which are alternately overlapped by adopting a physical vapor deposition coating technology, wherein the two-phase structure layer adopts a reaction deposition method, and the AlN and the Al realize separation growth at high temperature by controlling the proportion of Al and N components and the temperature of a base material close to the melting point of Al to form a two-phase structure in which AlN nano columnar crystals are coated by metallic Al and are arranged in the matrix of Al. The AlN nanoparticle material which has wide shape and size change range and is coated with Al on the surface is easy to be added into molten metal and is not easy to generate particle aggregation, a composite material with uniformly dispersed nanoparticles can be obtained, and the performance of a metal matrix composite material, particularly an Al matrix composite material, is obviously improved.
Description
Technical Field
The invention relates to a technology in the field of metal-based composite nano materials, in particular to Al-coated AlN nano particles and a preparation method thereof.
Background
The performance advantage of the ceramic particle reinforced metal matrix composite material is more and more widely applied in modern industry, and when the diameter of the particles is reduced to the nanometer level, the performance of the particles is expected to be greatly improved, so that the ceramic particle reinforced metal matrix composite material becomes an important development direction of the particle reinforced metal matrix composite material at present. However, the problems of large specific surface area, surface adsorption and pollution of the nanoparticles make it very difficult to add the nanoparticles into the molten metal and to obtain uniform dispersion, which becomes a critical difficulty to be overcome in the preparation of nanoparticle-reinforced metal-based composite materials. The method for coating particles by metal in the prior art has a good effect of improving the fusion of micron-sized particles into molten metal, but is difficult to be used for nano-sized particles because most of the molten metal cannot directly wet ceramic, ceramic particles are difficult to be coated, high bonding strength cannot be obtained, and the difficulty of surface treatment and complete coverage by metal is increased due to the extremely small diameter and large amount of interfaces of the nano-particles. On the other hand, for some metals with stable oxides, such as Al, mg, ti, etc., even if full-coverage coating of ceramic particles can be achieved, new oxide films (Al) are formed on the coated surfaces 2 O 3 、MgO、TiO 2 Etc.), ask questions ofThe problem is still unsolved. Therefore, in the research and production of the present nanoparticle reinforced metal matrix composite, there is an urgent need for a nanoparticle whose surface is completely coated with metal, which not only requires the particle to have the characteristics of controllable shape, high dimensional accuracy and dimensional uniformity, but also requires the surface coated with metal not to generate a new stable oxide film, but such nanoparticle and the preparation technology thereof are still blank.
Disclosure of Invention
The invention provides an Al-coated AlN nanoparticle and a preparation method thereof, aiming at the problems that the shape and size of ceramic nanoparticles are not wide in variation range, the size precision and the size uniformity are not high, and especially the nanoparticles are difficult to be added into molten metal and obtain uniform distribution in the existing preparation technology of particle-reinforced metal-based composite materials. The AlN nano-particles in the form of the AlN/Al composite film have the advantage of being easily added into molten metal without aggregation, can obtain a metal-based composite material with uniformly dispersed nano-particles, and obviously improves the performance of the composite material, particularly the Al-based composite material.
The invention is realized by the following technical scheme:
the invention relates to a preparation method of AlN nano-particles coated with Al, which is obtained by preparing a multi-layer structure composite film consisting of two phase structure layers consisting of AlN and Al and an Al layer which are alternately overlapped by adopting a physical vapor deposition coating technology, wherein the two phase structure layers adopt a reaction deposition method, and the AlN and the Al realize separation growth at high temperature by controlling the proportion of Al and N and the temperature of a base material close to the melting point of Al to form the two phase structure layers of AlN nano-columnar crystals coated by metal Al and arranged in the base material of Al.
The two-phase structure layer is as follows: composed of an AlN nanopillar crystal phase and an Al phase which are immiscible with each other, and characterized in that the AlN nanopillar crystal is completely covered with Al.
The Al layer is deposited by adopting a non-reaction method to block the growth of AlN nano columnar crystals, and then the nano multi-layer structure composite film with the two-phase structure layer and the Al layer which are alternately overlapped is formed by repeated deposition.
The physical vapor deposition coating technology adopts physical methods such as but not limited to vacuum evaporation coating, sputtering coating and the like to enable metal to be gasified and then deposited on the surface of a solid to form a film.
The reaction deposition method comprises the following steps: adding N in the process of physical vapor deposition of metal Al 2 Gas, passing through N 2 The reaction of the gas and Al obtains partial AlN film preparation method.
The control of the proportion of the Al component and the N component refers to that: the atomic percent of N in the film is in the range of 17-35at.%, N when deposited by reaction 2 The partial pressure and flow of the gas are obtained, and N is adopted for the evaporation coating method of the reaction 2 Gas, for the reactive sputtering coating method, ar gas and N are used 2 Gas mixture of gases.
The base material is as follows: the support film includes a thin sheet of Al, ni, ti or the like as a base metal of the metal matrix composite.
The substrate temperature close to the melting point of Al is as follows: throughout the deposition of the film, the substrate is heated and maintained within the range of 600-650 ℃.
The invention relates to the Al-coated AlN nanoparticles prepared by the method, the AlN nanoparticles exist in an AlN/Al two-phase structural layer of the multilayer structure composite film, and no oxide film or other adsorbed or polluted substances exist on the surface of the coated Al.
The AlN nano-particles are in the shape of particles or needle bars with the average diameter of 10-30nm and the length of 30-1000nm, and the error of the length of the particles is less than +/-3 nm.
The length of the obtained AlN nano-particles can be controlled and changed through the thickness of the two-phase structure layer, so that the AlN nano-particles have the characteristics of wide length change range and high size precision and size uniformity. In addition, different from the coating of powder particles by metals, the Al-coated AlN nano-particles are bonded by Al and orderly arranged in an AlN/Al two-phase structure layer of the multilayer structure composite film, so that the problem that the surface of the coated Al layer of the powder particles is oxidized is solved.
The invention relates to application of the AlN nanoparticles coated with Al on the surface, and the AlN nanoparticles are used for AlN nanoparticle reinforced metal matrix composite materials, in particular to Al matrix composite materials, so that the AlN nanoparticles can be easily added into a metal melt and uniformly dispersed in a matrix, and the performance of the composite materials can be obviously improved.
Technical effects
The invention solves the problem that AlN nanoparticles with variable length and high size uniformity are difficult to obtain in the prior art, particularly the defect of complete coating of the nanoparticles is overcome, and the defect that new oxide films are generated on the surface of a coated metal, particularly the surface of Al after the powdery particles are coated so as to cause difficulty in adding and uniformly distributing the AlN nanoparticles in a metal melt is overcome, and the AlN nanoparticles are obtained by the technical means of selecting the specific proportion of Al and N components, particularly the substrate temperature close to the melting point of Al, preparing a structure layer with AlN nano columnar crystals and an Al two-phase separation growth structure layer, and blocking the AlN columnar crystals by using a metal Al layer to control the length of the needle-rod-shaped AlN. The AlN ceramic nanoparticles provided by the invention provide a large space for the metal matrix composite material to meet the requirements of the shape and size selection of the reinforcement particles. In particular, complete coating of AlN particles with Al is achieved and the Al-coated surface oxide film is eliminated. The Al-coated AlN nanoparticles have the advantages of being easy to add into a metal solution and realize uniform distribution, can effectively and obviously improve the performance of the metal-based composite material, particularly the mechanical property of the Al-based composite material, and have important value in promoting the development and application of the metal-based composite material.
Drawings
FIG. 1 is a schematic structural diagram of an Al-coated AlN nanoparticle multilayer composite film prepared according to the present invention;
in the figure: 1AlN nano-particles, 2Al matrix, 3Al layer and 4 base materials.
FIG. 2 is the observation result of the two-phase structure of the composite film from the surface direction of the film by a transmission electron microscope;
in the figure: the dark granular region is the cross section of AlN nanopillar crystals, and the light region is an Al matrix.
Detailed Description
Example 1
In this embodiment, a multi-target magnetron sputtering apparatus is adopted, and a direct current cathode controls a pure Al target, which includes the following steps:
step 1) by pumping the vacuum chamber to 10 deg.C -3 Heating the pure Al base material in the vacuum chamber after Pa is lower than Pa (keeping the temperature at 600 ℃ in the whole deposition and coating process), and depositing a 100nm Al transition layer on the Al base material by non-reactive sputtering;
step 2) filling Ar gas and keeping the pressure at 6 multiplied by 10 -1 Pa, depositing an Al layer on the Al transition layer; refilling with Ar and N 2 Mixed gas of the components and maintaining the total pressure of 6 multiplied by 10 -1 Pa, depositing a two-phase structure layer consisting of AlN and Al on the Al layer by a reactive sputtering method, and adjusting N 2 The partial pressure ratio or flow ratio of Ar to N controls the content of N in the two-phase structural layer, preferably N 2 And the partial pressure ratio of the Al layer to Ar is 1-1, the thicknesses of the Al layer and the two-phase structure layer are controlled by the deposition coating time, and the treatment is circulated until a multilayer structure composite film which is alternately overlapped is obtained.
And 3) plating a 100nm Al covering layer on the surface of the deposited multilayer structure composite film.
In this example, the thickness of the two-phase structure layer was 1000nm, the thickness of the Al layer was 10nm, and the total thickness of the multi-layer structure composite film was about 10 μm by controlling the deposition temperature and the plating time of each layer, so as to obtain the needle-like AlN nanoparticles coated with Al and bonded together as shown in fig. 1, the length of the particles was 1000nm, and the average diameter was 10nm. The observation of the two-phase structure layer of the multilayer composite film by a transmission electron microscope is shown in FIG. 2.
Example 2
In this example, compared with example 1, the substrate temperature was maintained at 625 ℃, the thickness of the two-phase structure layer was 100nm, the thickness of the Al layer was 10nm, and the total thickness of the multilayer-structure composite film was about 10 μm by controlling the deposition coating time, and cylindrical AlN nanoparticles coated with Al and bonded together were obtained, the AlN nanoparticles having an average diameter of 20nm and a length of 100nm.
Example 3
In this example, compared with example 1, the substrate temperature was maintained at 650 ℃, the thickness of the two-phase structure layer was 30nm, the thickness of the Al layer was 10nm, and the total thickness of the multilayer structure composite film was about 10 μm by controlling the deposition coating time, so as to obtain equiaxed AlN nanoparticles coated with Al and bonded together, and the average diameter and length of the AlN nanoparticles were 30nm.
In summary, the present invention obtains a two-phase structure layer with AlN columnar crystals and Al separated growth by combining AlN and Al in a specific ratio, which have a large melting point temperature difference and have wettability but are not solid-soluble with each other, especially by using the prior art blank that the substrate temperature is deposited at a temperature close to the melting point temperature of Al, and further obtains AlN nanoparticles coated with Al and having no oxide film coated on the Al surface by using a multi-layer structure composite thin film method in which only an Al-plated layer is used to block the growth of AlN columnar crystals in the two-phase structure layer, and such AlN nanoparticles also have characteristics of wide length variation range and high dimensional accuracy and dimensional uniformity.
The foregoing embodiments may be modified in many different ways by one skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and not by the preceding embodiments, and all embodiments within their scope are intended to be limited by the scope of the invention.
Claims (9)
1. A preparation method of AlN nano-particles coated with Al is characterized in that a physical vapor deposition coating technology is adopted, and a multi-layer structure composite film consisting of two-phase structure layers consisting of AlN and Al layers which are alternately overlapped is prepared, wherein the two-phase structure layers adopt a reaction deposition method, and the two phases of AlN and Al are separated and grown at a high temperature by controlling the atomic percentage content of N in the film to be within a range of 17-35 at% and controlling the substrate to be heated and always kept at the substrate temperature close to the melting point of Al, namely within a range of 600-650 ℃ in the whole process of film deposition, so that AlN nano columnar crystals are coated by metal Al and are arranged in a two-phase structure in the substrate of Al.
2. The method of claim 1, wherein the two-phase structure layer is: the two-phase structure layer is composed of an AlN nano columnar crystal phase and an Al phase which are not mutually soluble, and has the characteristic that the AlN nano columnar crystal is completely coated by Al.
3. The method of claim 1, wherein the Al layer is deposited by a non-reactive method to block the growth of AlN nanocolumnar crystals, and the deposition is repeated to form a nano multi-layered structure composite film in which two phase structure layers are alternately stacked on the Al layer.
4. The method of claim 1, wherein the physical vapor deposition coating technique is a vacuum evaporation coating and a sputtering coating, and the metal is vaporized and deposited on a solid surface to form a thin film.
5. The method of claim 1, wherein the reactive deposition method is: adding N in the process of physical vapor deposition of metal Al 2 Gas through N 2 The reaction of the gas and Al results in a thin film of partial AlN.
6. The method of claim 1, wherein said controlling is performed by reacting N during deposition 2 The partial pressure and flow of gas are obtained, and the evaporation coating method for reactionBy using N 2 Gas, for the reactive sputtering coating method, ar gas and N are used 2 Gas mixture of gases.
7. The method of producing Al-coated AlN nanoparticles, according to claim 1, wherein the substrate is: the support film includes a thin sheet of Al, ni, ti or the like as a base metal of the metal matrix composite.
8. The Al-coated AlN nanoparticle prepared by the method according to any one of claims 1 to 7, wherein the AlN nanoparticle is present in an AlN/Al two-phase structure layer of the multilayer structure composite film, and an oxide film and other adsorbed or contaminated substances are not present on the surface of the coated Al;
the AlN nano-particles are in a particle or needle-rod structure with the average diameter of 10-30nm and the length of 30-1000nm, and the error of the particle length is less than +/-3 nm.
9. Use of the Al-coated AlN nanoparticles prepared by the method according to any one of claims 1 to 7 or according to claim 8 for AlN nanoparticle-reinforced Al-based composite materials, to facilitate the addition of AlN nanoparticles to a metal melt and to achieve uniform dispersion in the matrix to significantly improve the properties of the composite materials.
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| US4943450A (en) * | 1987-01-20 | 1990-07-24 | Gte Laboratories Incorporated | Method for depositing nitride-based composite coatings by CVD |
| CN1887815A (en) * | 2006-07-20 | 2007-01-03 | 上海交通大学 | Nanometer multilayer hard AlN/SiO2 film |
| JP2011117059A (en) * | 2009-11-30 | 2011-06-16 | Takashi Harumoto | METHOD FOR PRODUCING AlN THIN FILM |
| CN109996625A (en) * | 2016-11-16 | 2019-07-09 | Hrl实验室有限责任公司 | For producing the material and method and thus obtained metal nanometer composite material of metal nanometer composite material |
| CN110042353A (en) * | 2019-04-04 | 2019-07-23 | 内蒙古科技大学 | A kind of nano-stack aluminum matrix composite and preparation method |
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2020
- 2020-09-27 CN CN202011054762.1A patent/CN114318258B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4943450A (en) * | 1987-01-20 | 1990-07-24 | Gte Laboratories Incorporated | Method for depositing nitride-based composite coatings by CVD |
| CN1887815A (en) * | 2006-07-20 | 2007-01-03 | 上海交通大学 | Nanometer multilayer hard AlN/SiO2 film |
| JP2011117059A (en) * | 2009-11-30 | 2011-06-16 | Takashi Harumoto | METHOD FOR PRODUCING AlN THIN FILM |
| CN109996625A (en) * | 2016-11-16 | 2019-07-09 | Hrl实验室有限责任公司 | For producing the material and method and thus obtained metal nanometer composite material of metal nanometer composite material |
| CN110042353A (en) * | 2019-04-04 | 2019-07-23 | 内蒙古科技大学 | A kind of nano-stack aluminum matrix composite and preparation method |
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