CN113862521A - Titanium-aluminum alloy based on multistage reinforcement and preparation method thereof - Google Patents

Titanium-aluminum alloy based on multistage reinforcement and preparation method thereof Download PDF

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CN113862521A
CN113862521A CN202110864652.XA CN202110864652A CN113862521A CN 113862521 A CN113862521 A CN 113862521A CN 202110864652 A CN202110864652 A CN 202110864652A CN 113862521 A CN113862521 A CN 113862521A
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titanium
reinforcement
framework
aluminum
aluminum alloy
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CN113862521B (en
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郭艳华
曹夕浩
孙中刚
戴国庆
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Nanjing Tech University
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Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/087—Coating with metal alloys or metal elements only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention provides a titanium-aluminum alloy based on multistage reinforcement, which comprises a framework reinforcement and an aluminum matrix wrapping the framework reinforcement; the aluminum matrix is aluminum or aluminum alloy, the framework reinforcement is titanium or titanium alloy with a three-dimensional net structure, and the framework reinforcement forms a framework reinforcement structure of the alloy; coating materials are wrapped on the surface of the framework reinforcement, the coating materials are a mixture formed by uniformly mixing binding agents with coating powder, and the coating powder is Nb powder; the plating layer material and the aluminum matrix form a metal intermediate phase, and the metal intermediate phase and the plating layer material form an alloy interface reinforcing structure; the framework reinforcing structure and the interface reinforcing structure realize the multi-stage reinforcement of the titanium-aluminum alloy. The invention also provides a preparation method of the titanium-aluminum alloy based on multistage reinforcement. According to the alloy, the comprehensive performance of the aluminum alloy is improved without increasing the density by a multi-stage reinforcing mode of reinforcing a skeleton structure and reinforcing an interface, and the aluminum alloy material with high material utilization rate and excellent performance is obtained.

Description

Titanium-aluminum alloy based on multistage reinforcement and preparation method thereof
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a titanium-aluminum alloy based on multistage reinforcement and a preparation method thereof.
Background
Aluminum element has rich content in the earth crust, is second to oxygen and silicon, is easy to oxidize, generates a compact passive film on the surface, has strong corrosion resistance in the media of atmosphere, water, oil and the like, is an indispensable element in life due to good heat conductivity, low density, high specific strength, corrosion resistance and other excellent performances, can form aluminum alloys with different performances by adding different elements in the aluminum and adopting different processing modes, and plays an indispensable role in production and life.
With the development of the times, the single traditional aluminum alloy is difficult to meet the requirements of production practice and life. The titanium-aluminum alloy is a light alloy with good comprehensive performance, has excellent properties of high specific strength, heat resistance, corrosion resistance and the like, and is widely applied to the fields of aerospace and the like. However, the titanium-aluminum alloy still has the problem of insufficient mechanical properties during application, and the titanium-aluminum alloy can generate intermetallic compounds such as Ti3Al、Ti3Al, TiAl, etc., Ti3Al has unstable performance and poor oxidation resistance at high temperature, and Ti3Al has poor plasticity and is difficult to machine, and the intermediate phases also cause the problems of reduced alloy performance, low oxidation resistance, difficult processing and the like, thereby limiting the application range of the alloy.
Chinese patent publication No. CN106868338A discloses an orientation-enhanced tungsten-containing high-niobium titanium-aluminum alloy, which comprises the following components: 45.0 to 48.0 percent of Al, 5.0 to 8.0 percent of Nb, 0.2 to 0.8 percent of W and the balance of Ti, the alloy not only has fine and uniform full lamellar structure, but also has an included angle of 0 degree or close to 0 degree between the direction of the lamellar structure and the direction of the directional solidification growth, and can further improve the comprehensive mechanical property.
Chinese patent publication No. CN107400803A discloses a titanium-aluminum alloy material, which is composed of a base material, a toughening phase and a reinforcing phase, wherein the base material includes the following components in parts by weight: 70-72.5 of Ti; al 25; mo 1; the toughening phase comprises the following components in parts by mass: 0.8-1.5 HfC; ta 0.5; VN 0.2-2; the reinforcing phase is graphene, the prepared mass fraction is 0-1.5, and the titanium-aluminum alloy material has higher mechanical properties.
Although the comprehensive performance of the titanium-aluminum alloy is improved to a certain extent by the improvement, the comprehensive performance of the titanium-aluminum alloy still cannot meet the requirement when higher requirements are needed, and the titanium content in the titanium-aluminum alloy is too high, so that the cost is increased to a certain extent, the material utilization rate is low, and the further application and popularization of the material are not facilitated.
Disclosure of Invention
The invention aims to provide a titanium-aluminum alloy based on multistage reinforcement, aiming at the defects of the prior art, the titanium-aluminum alloy improves the comprehensive performance of the aluminum alloy without increasing the density by a multistage reinforcement mode of framework structure reinforcement and interface reinforcement, and obtains an aluminum alloy material with high material utilization rate and excellent performance.
The invention also aims to provide a preparation method of the titanium-aluminum alloy based on multi-stage reinforcement.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a titanium-aluminum alloy based on multi-stage reinforcement comprises a framework reinforcement and an aluminum matrix wrapping the framework reinforcement;
the aluminum matrix is aluminum or aluminum alloy, the framework reinforcement is titanium or titanium alloy, the framework reinforcement is a three-dimensional net structure, and the framework reinforcement forms a framework reinforcement structure of titanium-aluminum alloy;
coating materials are wrapped on the surface of the framework reinforcement body, the coating materials are a mixture formed by uniformly mixing coating powder with a binder, and the coating powder is Nb powder; the plating layer material and the aluminum matrix form a metal intermediate phase, and the metal intermediate phase and the plating layer material form an interface reinforcing structure of the titanium-aluminum alloy;
the framework reinforcing structure and the interface reinforcing structure realize the multi-stage reinforcement of the titanium-aluminum alloy.
Preferably, the thickness of the coating material is 4-6 mm.
Preferably, the binder is a water-based binder or an organic binder having a viscosity of 1 × 106-25×106cP。
Preferably, the three-dimensional network structure is a layered honeycomb structure and is composed of an arrangement of rods or columns.
Preferably, the diameter of the rod-shaped body is 6-8mm, and the side length of the column-shaped body is 6-8 mm.
Preferably, the content of the framework reinforcement is 20-40% by mass, the content of the coating powder is 1-5% by mass, and the balance is an aluminum matrix.
The preparation method of the titanium-aluminum alloy based on multistage reinforcement specifically comprises the following steps:
adopting additive manufacturing, printing titanium or titanium alloy according to a framework structure to obtain a framework reinforcement, and simultaneously fully mixing a binder and coating powder to form a coating material;
coating a plating material on the surface of the skeleton reinforcement, and then placing the skeleton reinforcement in a heat treatment furnace, heating to raise the temperature to densify the plating;
and (3) placing the framework reinforcement wrapped with the coating material in a mould, filling matrix powder into the mould until the matrix powder completely wraps the framework, placing the mould in a sintering furnace, heating to a sintering temperature Ts under vacuum, cooling to room temperature along with the furnace after sintering is completed, and taking out to obtain the titanium-aluminum alloy.
Preferably, the adhesive isThe binder is water-based binder or organic binder with viscosity of 1 × 106-25×106cP; the plating layer powder is Nb powder.
Preferably, the thickness of the coating material is 4-6 mm.
Preferably, the matrix powder, when filled, completely encapsulates the skeleton and extends over 10 mm.
Preferably, the sintering temperature Ts satisfies formula (1):
Ts＝(0.3～0.4)Tm (1)
where Tm is the melting temperature of the matrix powder.
The invention has the beneficial effects that:
1. according to the invention, the framework structure of the composite material is reinforced by the specific titanium or titanium alloy framework reinforcement, the overall strength, corrosion resistance and oxidation resistance of the composite material are improved, the coating material is coated on the surface of the framework reinforcement, and a good-performance Nb-Al metal intermediate compound is formed between the Nb powder of the coating material and the aluminum or aluminum alloy matrix, so that the crack propagation capacity is improved, and the mechanical performance of the composite material is improved, thereby playing a role in interface reinforcement; therefore, by the reinforcing effect of the framework structure reinforcement and the reinforcing mechanism of the interface reinforcement, multi-stage reinforcement and synergistic effect are formed, and the comprehensive performance of the titanium-aluminum alloy is greatly improved.
2. According to the invention, the titanium-aluminum alloy is prepared by combining additive manufacturing and powder metallurgy, the reinforcing phase is printed by adopting an additive manufacturing method, so that the controllability of the structure of the reinforcing phase is ensured, and the framework reinforcement body of titanium or the titanium alloy reduces the use of titanium and improves the utilization rate of materials because of the hollow framework structure, and through multi-stage reinforcement, the comprehensive performance of the alloy can be improved while the density of the titanium-aluminum alloy is not increased, so that the titanium-aluminum alloy with high material utilization rate and excellent performance is obtained, and the production cost is reduced.
Drawings
FIG. 1 is a schematic representation of the structure of the skeletal reinforcement of the present invention.
FIG. 2 is a schematic representation of the structure of the skeletal reinforcement of the present invention.
Fig. 3 is a fill schematic of the present invention.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways.
The invention provides a titanium-aluminum alloy based on multistage reinforcement, which has the basic concept that a framework reinforcement is printed by adopting an additive manufacturing method so as to ensure the controllability of the structure of the reinforcement, and the titanium alloy has excellent performances such as high specific strength, corrosion resistance and the like, so that the comprehensive performance of the alloy can be improved while the density of the aluminum alloy is not increased; in order to ensure good bonding property and interface enhancement effect of an interface, a coating material is formed by mixing coating powder with a binder, the coating material is wrapped on the surface of the framework, so that a metal intermediate phase favorable for performance is generated by using coating components and an aluminum matrix, the effect of controlling the interface is achieved, finally, the surface of the framework is covered with the aluminum alloy of the matrix, and the densification of the alloy is achieved through sintering.
In a specific embodiment, the titanium-aluminum alloy comprises a framework reinforcement and an aluminum matrix wrapping the framework reinforcement; the aluminum matrix is aluminum or aluminum alloy, the framework reinforcement is titanium or titanium alloy, the framework reinforcement is a three-dimensional net structure, and the framework reinforcement forms a framework reinforcement structure of titanium-aluminum alloy.
Coating materials are wrapped on the surface of the framework reinforcement body, the coating materials are a mixture formed by uniformly mixing coating powder with a binder, and the coating powder is Nb powder; the coating material and an aluminum matrix form a metal intermediate phase, the metal intermediate phase is Nb-Al intermetallic compound, and the metal intermediate phase and the coating material form an interface reinforcing structure of the titanium-aluminum alloy.
The framework reinforcing structure and the interface reinforcing structure realize the multi-stage reinforcement of the titanium-aluminum alloy.
In other embodiments, the coating powder may be other materials, and the coating powder satisfies the following conditions: 1. avoiding the generation of titanium-aluminum intermetallic compounds such as alpha 2 phase from aluminum and titanium, thereby causing performance reduction, and avoiding the direct contact of aluminum and titanium, so that galvanic corrosion occurs; 2. can generate an intermediate layer beneficial to the performance of the matrix, such as a copper layer beneficial to heat conduction and an aluminum-zinc alloy beneficial to improving the surface corrosion resistance; 3. the matrix material or the framework reinforcement material and the coating material form a metal intermediate phase at the interface, so that the interface bonding force is improved, the matrix performance is improved, and the bonding force of the interface and the alloy strength are enhanced if Cu atoms and alpha-Ti form a solid solution.
In other embodiments, the three conditions are that the coating powder satisfies 1 and 2, or 1 and 3, and a certain degree of interface enhancement can be achieved.
The thickness of the coating material is preferably 4-6mm, it being understood that the thickness of the coating material includes, but is not limited to, the thickness that is sufficient to continuously wrap the frame without contacting the frame with the substrate.
The binder is preferably a water-based binder or an organic binder having a viscosity, and more specifically, the binder satisfies the following condition: 1. ensuring that the coating powder can adhere to the framework, does not fall off at room temperature environment, and needs certain viscosity, wherein the viscosity is preferably 1 x 106～25×106cP; 2. during the heat treatment, most or all of the binder volatilizes, so that the binder is ensured not to be greatly left, impurities are generated, and the compactness of the material is damaged.
In a preferred embodiment, the three-dimensional network structure is a layered honeycomb structure and is composed of an arrangement of rods or columns.
In a more specific embodiment, as shown in fig. 1-2, the single skeleton bodies are hexagons, the first layer is connected by hexagons to form a planar layer, the second layer is stacked on the first layer in a manner of standing hexagons, and thus, the single skeleton bodies are sequentially stacked in the above order to form a skeleton structure, and the width of the hexagons can be designed as required.
In other embodiments, the single skeleton bodies may also be square and stacked in sequence to form a layered honeycomb structure.
In other embodiments, the skeletal reinforcement may be a two-dimensional mesh structure, and the mesh structure may be laid flat and stacked to a desired height.
The diameter of the rod-shaped body is preferably 6-8mm, and the side length of the column-shaped body is preferably 6-8 mm.
In a preferred embodiment, the content of the framework reinforcement is 20-40% by mass, the content of the coating powder is 1-5% by mass, and the balance is an aluminum matrix.
As an exemplary embodiment of the present invention, the method for preparing a titanium-aluminum alloy based on multistage reinforcement specifically comprises the following steps:
the method is characterized in that additive manufacturing is adopted, titanium or titanium alloy is printed according to a framework structure to obtain a framework reinforcement, and meanwhile, a binder and plating layer powder are fully mixed to form a plating layer material.
Coating a plating material on the surface of the skeleton reinforcement, and then placing the skeleton reinforcement in a heat treatment furnace, heating to raise the temperature to densify the plating.
And (3) placing the framework reinforcement wrapped with the coating material in a mould, filling matrix powder into the mould until the matrix powder completely wraps the framework, placing the mould in a sintering furnace, heating to a sintering temperature Ts under vacuum, cooling to room temperature along with the furnace after sintering is completed, and taking out to obtain the titanium-aluminum alloy.
Preferably, the binder is a water-based binder or an organic binder having a viscosity of 1 × 106～25×106cP; the plating layer powder is Nb powder.
Preferably, the thickness of the coating material is 4-6 mm.
Preferably, the matrix powder, when filled, completely encapsulates the matrix and extends over 10mm, as shown in FIG. 3.
Preferably, the sintering temperature Ts satisfies formula (1):
Ts＝(0.3～0.4)Tm (1)
where Tm is the melting temperature of the matrix powder.
In other embodiments, the materials of the skeleton reinforcement and the matrix may be blended according to actual needs, for example, the unidirectional strength of the aluminum alloy needs to be improved, iron may be used as the skeleton, and the aluminum alloy may be filled; meanwhile, the coating material can be selected according to the actual condition, so that the multi-stage reinforcement is realized.
For better understanding, the present invention is further described below with reference to several specific examples, but the process is not limited thereto and the present disclosure is not limited thereto.
[ example 1 ]
The framework material is TC4 (30%) with the average grain diameter of 55 mu m, the matrix powder is 7056 aluminum alloy, the plating layer powder is Nb (3%), and the binder components are as follows: silane AC-66 and waterborne epoxy resin.
TC4 is printed into a two-dimensional mesh structure by adopting a selective laser melting technology, and the side length and the diameter of a single mesh are 5 mm; wherein the printing parameters are 125W of laser power, 20 μm of layer thickness, 80 μm of scanning interval and 805mm/s of scanning speed.
Slowly adding 50g of Nb powder into a solution containing ethylene glycol and Tween-20 (volume 1:1), and uniformly stirring and mixing to obtain 200mL of a mixture A; and mixing the AC-66, the methanol and the deionized water with the total volume of 300mL and the volume ratio of 1:1:3 in another beaker, continuously stirring until the solution is in a clear state, adding the mixture A and 50mL of the water-based epoxy resin in the process of continuously stirring, continuously stirring for 3-4 h to form a coating material, and spraying the coating material on the surface of the framework for 2-3 times by using a high-pressure electric spraying machine. Then the framework is placed in a drying oven for drying at the temperature of 105 ℃, then the framework is placed in a heat treatment furnace for heat preservation at the temperature of 300 ℃ for 20min, and then the framework is taken out for air cooling.
The framework is placed in a die of a vacuum sintering furnace, and matrix metal powder (7056 aluminum alloy) is filled, wherein the metal powder needs to completely wrap the framework and exceeds about 10 mm.
And (3) performing discharge plasma sintering, wherein the sintering temperature is 500 ℃, the heating rate is 100 ℃/min, the heat preservation time is 10min, the axial loading pressure is 30MPa, the loading rate is 5MPa/min, and the sample 1-1 is obtained after the sintering is finished and the furnace is cooled.
7056 aluminum alloy is widely used in aerospace, and although the surface of the aluminum alloy has a protective oxide film, the plasticity of the oxide film is lower than that of a metal matrix, so that the alloy is easy to deform by tensile stress, and a passive film is deformed to cause stress corrosion cracking, so that the alloy fails.
The surface of the composite material prepared by the embodiment is covered with a coherent reticular bone titanium alloy framework, the blunt potential of titanium is low, the critical passivation current is small, passivation is easy, and the composite material has strong passive stability, and the titanium alloy has stronger strength relative to the aluminum alloy, so that the titanium alloy framework can improve the integral strength, corrosion resistance and oxidation resistance, a TiAl intermediate phase can be prevented from being generated between Al and Ti by plating a Nb coating on the surface of the framework, and a Nb-Al intermetallic compound with excellent performance can be generated, thereby improving the matrix performance.
The same composition as in sample 1-1 (TC 4 (30%), Nb (3%), and 7056 aluminum alloy having an average particle size of 55 μm) was used, except that sample 1-2 was prepared by a conventional melting method.
The same skeletal reinforcement composite was prepared by the same ingredients as in sample 1-1 above, except that no plating material was used, resulting in sample 1-3.
The test was performed on samples 1-1, 1-2, and 1-3, respectively, with the following results:
performance of Tensile breaking strength Compressive fracture strength
Sample 1-1 724 405
Samples 1 to 2 421 273
Samples 1 to 3 668 395
From the test results, it can be seen that the mechanical properties: the multi-stage reinforced composite material (sample 1-1) > the composite material with a framework reinforced structure (sample 1-3) > the traditional composite material (sample 1-2) shows that the multi-stage reinforced composite material of the invention greatly improves the mechanical property of the alloy material through the multi-stage reinforcement cooperation of the framework reinforcement and the interface reinforcement.
By placing samples 1-1, 1-2 and 1-3 in 3.5% sodium chloride brine, it was found that some red rust was generated on the surface of samples 1-2, and more severe corrosion occurred. A large amount of white floccules are generated in the samples 1-3, a large amount of oxidation films on the contact parts are damaged, only part of the aluminum surface of the samples 1-1 is damaged by partial oxidation films to generate corrosion, most of the aluminum surface is intact due to the outer surface coating, and the corrosion resistance of the composite material is greatly improved.
[ example 2 ]
The matrix powder is 2A12 aluminum alloy powder, the cladding powder is Nb powder (5%), the binder component is phenolic resin and low viscosity alcohol, and the framework material is Ti600 (40%) with the average grain diameter of 36 mu m.
Placing Ti600 powder in a powder feeder, introducing argon gas to avoid oxidation when the powder feeder is powered on, scanning at the speed of 1200mm/s with the power of 280W, printing a skeleton structure with the thickness of 0.015mm, wherein the diameter of metal in the skeleton is 8mm, and the integral height of the skeleton is 100 mm.
Adding low-viscosity alcohol into phenolic resin, uniformly stirring to form a binder, adding 500mL of phenolic resin and 500mL of ethanol in a volume ratio of 3:1, adding 30g of Nb powder into the binder, uniformly stirring to form a coating material, immersing the framework in the coating material to wrap a layer of Nb powder on the surface of the framework, placing the framework in a heat treatment furnace, heating to 190 ℃, and preserving heat for 3 hours.
Placing the framework in a mould, filling 2A12 aluminum alloy until the framework is completely wrapped and exceeds about 10mm, placing the framework in a vacuum hot-pressing sintering furnace, sintering at 700 ℃, keeping the temperature for 3min, axially loading the pressure to 30MPa, aging the sample at 500 ℃ for 80min, performing water quenching, aging for 12h, and cooling along with the furnace after the aging is completed to obtain a sample 2-1.
The Nb layer is added between the titanium and the aluminum alloy, so that an Nb-Al intermetallic compound with good room temperature performance can be generated, cracks are generated from Nb-Al firstly, the crack propagation function is improved due to the good performance of Nb-Al, the mechanical performance of the material is improved, the titanium-aluminum alloy is prevented from generating brittle phase Ti-Al, the Ti and the Nb have good metallurgical compatibility, and the Nb has good compatibility, so that the interface strengthening effect is achieved.
Sample 2-2 was prepared with the same composition as sample 2-1 above (Ti 600 (40%) having an average particle size of 36 μm, Nb powder (5%), and balance 2A12 aluminum alloy powder) except that the conventional melting method was used.
The same skeletal reinforcement composite was prepared by the same ingredients as in sample 2-1 above, except that no plating material was used, resulting in sample 2-3.
The test was performed on sample 2-1, sample 2-2, and sample 2-3, respectively, with the following test results:
tensile Properties σb(MPa) σ0.2(MPa) δ(％)
Sample 2-1 695 577 13
Sample 2-2 420 380 11
Samples 2 to 3 624 556 11
From the test results, it can be seen that the mechanical properties: the multi-stage reinforced composite material (sample 2-1) > the composite material with a framework reinforced structure (sample 2-3) > the traditional composite material (sample 2-2) shows that the multi-stage reinforced composite material of the invention greatly improves the mechanical property of the alloy material through the multi-stage reinforcement cooperation of the framework reinforcement and the interface reinforcement.
[ example 3 ]
TC4 (20%) with the average grain diameter of 55 mu m is selected as a framework material, 3003 aluminum alloy is selected as matrix powder, Nb powder (1%) is selected as a coating component, and polyvinyl carboxyl polymer and polyvinyl alcohol are selected as binder components.
The titanium alloy powder is placed in a powder feeder, fully mixed and stirred, then laser melting deposition is carried out, the specific laser power is 125W, the layer thickness is 20 micrometers, the scanning distance is 80 micrometers, the scanning speed is 805mm/s, a metal framework is printed, the diameter of metal in the framework is 8mm, and the overall height of the framework is 100 mm.
Preparing 7 wt% of polyvinyl carboxyl polymer aqueous solution, adjusting the pH to 7 by adding sodium hydroxide, continuously stirring the solution to gel, adding polyvinyl alcohol into the solution in a volume ratio of 95:5 to form a high-viscosity binder, mixing Nb powder into the binder, wherein the mass ratio of the Nb powder is 65 wt%, and forming the plating material. Immersing the skeleton in paint to coat the skeleton surface, heating the skeleton in heat treating furnace for 400min to 850 deg.C, holding the temp for 20min, and cooling.
The framework is placed in a die of a vacuum sintering furnace, and matrix metal powder (7056 aluminum alloy) is filled, wherein the metal powder needs to completely wrap the framework and exceeds about 10 mm.
And putting the sample into a vacuum sintering furnace, vacuumizing at room temperature, heating to 600 ℃, keeping the temperature and the pressure at 80MPa for 2 hours, cooling to 200 ℃, discharging to obtain a sample 3-1.
Under the action of thermal activation energy, aluminum diffuses to the niobium layer to form Al3Nb, the plating layer prevents the matrix aluminum alloy and titanium from generating alpha 2 phase to destroy the performance of the material, and because the alloy interface can generate excellent intermediate phase and the titanium alloy is used as framework support, the crack propagation resistance is increased, the plasticity and toughness of the composite material are enhanced, and the composite material has good performance.
Sample 3-2 was prepared with the same composition as sample 3-1 (TC 4 (20%) having an average particle size of 55 μm, Nb powder (1%), and the balance of 3003 aluminum alloy) except that the conventional melting method was used.
A skeletal reinforcement composite was also prepared by the same composition as in sample 3-1 above, except that no plating material was used, to give sample 3-3.
The test results for sample 3-1, sample 3-2 and sample 3-3 were as follows:
tensile Properties σb(MPa) σ0.2(MPa) δ(％)
Sample 3-1 442 399 11
Sample 3-2 317 285 9
Samples 3 to 3 359 317 8
From the test results, it can be seen that the mechanical properties: the multi-stage reinforced composite material (sample 3-1) > the composite material with a framework reinforced structure (sample 3-3) > the traditional composite material (sample 3-2) shows that the multi-stage reinforced composite material of the invention greatly improves the mechanical property of the alloy material through the multi-stage reinforcement cooperation of the framework reinforcement and the interface reinforcement.
In conclusion, the multistage reinforced composite material disclosed by the invention forms multistage reinforcement and synergistic effect through the reinforcement effect of framework structure reinforcement and the reinforcement mechanism of interface reinforcement, reduces the use of titanium, improves the utilization rate of the material, and improves the comprehensive performance of the alloy while ensuring that the density of the aluminum alloy is not increased.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.

Claims (11)

1. The titanium-aluminum alloy based on multistage reinforcement is characterized by comprising a framework reinforcement and an aluminum matrix wrapping the framework reinforcement;
the aluminum matrix is aluminum or aluminum alloy, the framework reinforcement is titanium or titanium alloy, the framework reinforcement is a three-dimensional net structure, and the framework reinforcement forms a framework reinforcement structure of titanium-aluminum alloy;
coating materials are wrapped on the surface of the framework reinforcement body, the coating materials are a mixture formed by uniformly mixing coating powder with a binder, and the coating powder is Nb powder; the plating layer material and the aluminum matrix form a metal intermediate phase, and the metal intermediate phase and the plating layer material form an interface reinforcing structure of the titanium-aluminum alloy;
the framework reinforcing structure and the interface reinforcing structure realize the multi-stage reinforcement of the titanium-aluminum alloy.
2. The titanium-aluminum based alloy of claim 1, wherein the thickness of the plating material is 4-6 mm.
3. The titanium-aluminum-based alloy based on multistage reinforcement according to claim 1, wherein the binder is a water-based binder or an organic binder having a viscosity of 1 x 106-25×106cP。
4. The titanium-aluminum based alloy of claim 1, wherein the three-dimensional network structure is a layered honeycomb structure and is composed of an arrangement of rods or columns.
5. The titanium-aluminum based alloy of claim 1, wherein the diameter of the rod is 6-8mm and the side length of the cylinder is 6-8 mm.
6. The titanium-aluminum alloy based on multistage reinforcement according to any one of claims 1 to 5, wherein the content of the skeleton reinforcement is 20 to 40% by mass, the content of the coating powder is 1 to 5% by mass, and the balance is an aluminum matrix.
7. The preparation method of the titanium-aluminum alloy based on the multistage reinforcement as claimed in any one of claims 1 to 6, is characterized by comprising the following steps:
adopting additive manufacturing, printing titanium or titanium alloy according to a framework structure to obtain a framework reinforcement, and simultaneously fully mixing a binder and coating powder to form a coating material;
coating a plating material on the surface of the skeleton reinforcement, and then placing the skeleton reinforcement in a heat treatment furnace, heating to raise the temperature to densify the plating;
and (3) placing the framework reinforcement wrapped with the coating material in a mould, filling matrix powder into the mould until the matrix powder completely wraps the framework, placing the mould in a sintering furnace, heating to a sintering temperature Ts under vacuum, cooling to room temperature along with the furnace after sintering is completed, and taking out to obtain the titanium-aluminum alloy.
8. The method for preparing titanium-aluminum alloy based on multistage reinforcement according to claim 7, wherein the binder is water-based or organic with viscosity, and the viscosity of the binder is 1 x 106-25×106cP; the plating layer powder is Nb powder.
9. The method for preparing the titanium-aluminum alloy based on the multistage reinforcement according to claim 7, wherein the thickness of the coating material is 4-6 mm.
10. The method for preparing a titanium-aluminum alloy based on multistage reinforcement according to claim 7, wherein the matrix powder completely wraps the skeleton and exceeds 10mm when the matrix powder is filled.
11. The method for preparing a titanium-aluminum-based alloy based on multistage reinforcement according to claim 7, wherein the sintering temperature Ts satisfies formula (1):
Ts＝(0.3～0.4)Tm (1)
where Tm is the melting temperature of the matrix powder.
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