阅读说明：本技术 一种连续金属Mo丝增强Ti/Al3Ti层状复合材料及制备方法 (Continuous metal Mo wireStrong Ti/Al3Ti laminated composite material and preparation method thereof ) 是由 姜风春 常云鹏 牛中毅 王振强 果春焕 李秀才 于 2019-09-25 设计创作，主要内容包括：本发明提供一种连续金属Mo丝增强Ti/Al_3Ti层状复合材料及制备方法,包括如下步骤：将TC_4箔、Al箔和Mo丝进行预处理；将预处理好的TC_4箔、Al箔和Mo丝按照“TC_4-Al-Mo-Al-TC_4”为一个单元叠放,最外层为TC_4箔；将叠放好的试样整体放入真空热压炉中,设置工艺参数并进行烧结。本发明制备的层状复合材料由于其特殊的叠层结构和纤维增强作用,复合材料的失效分析结果表明：Al_3Ti基体的失效为穿晶断裂,金属钼丝的脱粘、拔出等行为和韧性层Ti层对复合材料的韧性提高明显,本发明使用来源广泛的商用金属箔材,复合材料制备过程中低温、无毒、节能环保,且工艺简单易行,成本低廉,性能稳定可靠。(The invention provides a continuous metal Mo wire reinforced Ti/Al 3 The Ti layered composite material and the preparation method thereof comprise the following steps: mixing TC 4 Pretreating the foil, the Al foil and the Mo wire; pre-treated TC 4 Foil, Al foil and Mo wire according to "TC 4 ‑Al‑Mo‑Al‑TC 4 "is a unit stack with the outermost layer being TC 4 A foil; and putting the stacked sample into a vacuum hot-pressing furnace, setting process parameters and sintering. Due to the special laminated structure and the fiber reinforcement effect of the laminated composite material prepared by the invention, the failure analysis result of the composite material shows that: al (Al) 3 The failure of the Ti substrate is transgranular fracture, the behaviors of debonding and pulling out the metal molybdenum wire and the like, and the toughness of the composite material is obviously improved by the Ti layer of the toughness layer.)

1. Continuous metal Mo wire reinforced Ti/Al₃The preparation method of the Ti layered composite material is characterized by comprising the following steps:

the method comprises the following steps: mixing TC₄Pretreating the foil, the Al foil and the Mo wire;

step two: pre-treated TC₄Foil, Al foil and Mo wire according to "TC₄-Al-Mo-Al-TC₄"is a unit stack with the outermost layer being TC₄A foil;

step three: and putting the stacked sample into a vacuum hot-pressing furnace, setting process parameters and sintering.

The process parameters are specifically as follows: at 10^-3The temperature is raised to 640 ℃ within 100min under the conditions of low vacuum degree of Pa and initial pressure of 3MPa, the temperature is kept for about 20min to ensure that the sample is uniformly heated, and at the moment, although the melting point of Al is not reached, the softening phenomenon of Al can occur, so that the pressure needs to be reduced to prevent the phenomenon that the Al is extruded too much after melting, the pressure is reduced to 2MPa, and the temperature is raised to about 660 ℃ within 20 min. When the temperature reaches the melting point 660 ℃ of Al, the pressure head pressure needs to be stopped, the pressure is gradually changed from 2MPa to 0 at the moment, the pressure is gradually adjusted to 2MPa after heat preservation is carried out for 140min, and heating is stopped after heat preservation is continuously carried out for 40 min.

2. The continuous metallic Mo wire reinforced Ti/Al of claim 1₃The preparation method of the Ti layered composite material is characterized in that the pretreatment specifically comprises the following steps: original TC of sand paper polishing₄Edges and surfaces of foils, Al foils and Mo wires; cleaning and polishing TC by using ultrasonic cleaner₄Foils, Al foils, and Mo wires; soaking in acetone solution for 10 min; then soaking and cleaning TC by alcohol₄Foil, Al foil and Mo wire surface, followed byAnd (5) drying.

3. The continuous metallic Mo wire reinforced Ti/Al of claim 1 or 2₃The preparation method of the Ti layered composite material is characterized in that the Al content of the Al foil is more than or equal to 99.6%.

4. The continuous metallic Mo wire reinforced Ti/Al of claim 1 or 2₃The preparation method of the Ti layered composite material is characterized in that the Mo content in the molybdenum wire is more than or equal to 99.93 percent.

5. The continuous metallic Mo wire reinforced Ti/Al of claim 3₃The preparation method of the Ti layered composite material is characterized in that the Mo content in the molybdenum wire is more than or equal to 99.93 percent.

6. Continuous metal Mo wire reinforced Ti/Al₃The Ti laminated composite material is characterized by comprising the following chemical components: mo is more than or equal to 99.93 percent, and other elements are less than or equal to 0.07 percent;

the other elements are specifically: fe is less than or equal to 0.30, carbon is less than or equal to 0.10, nitrogen is less than or equal to 0.05, hydrogen is less than or equal to 0.015, oxygen is less than or equal to 0.20, aluminum is 5.5-6.8, vanadium is 3.5-4.5, and the balance is titanium.

Technical Field

The invention relates to a composite material and a preparation method thereof, in particular to continuous metal Mo wire reinforced Ti/Al₃A Ti laminated composite material and its preparing process, which belongs to the field of composite material, includes such technological steps as toughening fibres, reinforcing fibres and special laminated high-energy-absorbing material.

Background

With the rapid development of modern industry and the gradual change of material science and technology, a single metal or alloy cannot meet the requirements of the modern industry on the comprehensive properties of materials, and the requirements of various industries on high-performance composite materials are increasingly urgent. In the aerospace field, which has been rapidly developed in recent years, the requirements for the adopted high-temperature structural materials are stricter and more urgent. For an aviation aircraft, the total weight of the aircraft is reduced, the working temperature of an engine of the aircraft is increased, the thrust-weight ratio of the aircraft can be increased, and fuel consumed by the aircraft can be saved, so that the aircraft has better flight performance. Therefore, the requirements of the aviation material with light weight, high strength, high modulus, high temperature resistance, oxidation resistance and creep resistance make the high temperature nickel-based alloy which is generally applied to the aerospace field originally not well meet the requirements. The disadvantages that superalloys gradually exhibit have shifted their attention to composites, such as ceramic matrix composites, C/C composites, refractory metal silicide based composites, intermetallic compound based composites, and the like. In the research of novel high-temperature materials, intermetallic compound-based composite materials attract great attention.

The intermetallic compound not only has excellent physical and chemical properties, but also has a plurality of excellent properties such as high specific strength, excellent high-temperature mechanical property, oxidation resistance, high creep resistance and the like. Meanwhile, the bonding mode of the intermetallic compound is the characteristic of coexistence of metallic bond and covalent bond. The use temperature of the material can be between that of metal super alloy and ceramic, the material has higher use temperature compared with metal alloy and lower brittleness compared with ceramic, and the material is a novel high-temperature structural material developed in the 90 s of the 20 th century. The advantages of the intermetallic compound make the intermetallic compound have wide application prospect in many industrial fields such as aerospace, transportation, mechanical and chemical engineering and the like.

Despite the advantages of the intermetallic compounds, not all intermetallic compounds can be used as high-temperature structural materials, and only the intermetallic compounds with beryllide, aluminide and silicide meet the requirements of new high-temperature structural materials, and the intermetallic compounds with aluminide are the most well studied. In recent years, a large amount of research has been conducted on intermetallic compounds such as Ti-Al, Fe-Al, and Ni-Al systems at home and abroad.

Among them, the research on more and mature Ti-Al intermetallic compounds has become one of the hot spots in the research on light high temperature structural materials in recent years. The Ti-Al intermetallic compound has the advantages of low density, high specific strength, high specific modulus, high oxidation resistance and the like, so that the Ti-Al intermetallic compound becomes an ideal material for replacing high-temperature nickel-based alloy which is commonly applied to the field of aerospace. TiAl intermetallic compounds are the most studied Ti-Al intermetallic compounds at present. Compared with other intermetallic compounds, the Al with the minimum density, the highest specific strength and the best high-temperature oxidation resistance₃Ti people also proceedA great deal of research effort has been devoted to this work. However, the practical application of intermetallic compounds in engineering is limited to a great extent due to the defects of large low-temperature brittleness, poor plasticity, low fracture toughness, low fatigue toughness and the like. In order to overcome the defects, researchers have conducted a great deal of research and study experiments, and the defects of poor room temperature plasticity are overcome by adding alloy elements to perform alloying, thermo-mechanical treatment and the like to obtain fine, uniform and less-segregation alloy structures, but research proves that the method can improve Al to a certain extent₃The strength of Ti intermetallic compound improves the fracture toughness, but the problem of large brittleness cannot be effectively solved, so that Al₃The wide use of Ti intermetallics is limited. And far from reaching the level of practical application.

Because various materials in the composite material can mutually make up for deficiencies in terms of performance to generate a synergistic effect, the comprehensive performance of the composite material is superior to that of each original composition material, and thus, various different requirements can be met. People think that the problem of poor plasticity of intermetallic compounds is solved by introducing metal with good plasticity and toughness to prepare the layered composite material, namely introducing metal Ti with good mechanical property and preparing the Ti/Al with low density and high strength by utilizing the bionic design of a shell structure in the nature₃Ti intermetallic compound based layered composite material. The problem of poor room temperature plastic toughness of the composite material is improved to a great extent.

On the other hand, continuous fibers are receiving general attention because of their excellent properties exhibited by composites for reinforcement. The continuous fiber reinforcement is introduced into the composite material, so that the comprehensive performance of the composite material can be improved to a great extent. The fiber reinforcement with good performance, whether ceramic or metal fiber reinforcement, is used as a main supporting body, so that the composite material has high strength, high toughness and good high-temperature performance at the same time, the unique performance advantages of the continuous fiber reinforced composite material are shown, and the use potential is huge.

Disclosure of Invention

The invention aims to provide a continuous metal Mo wire reinforced Ti/Al wire with simple process, low cost, stable and reliable performance₃Ti layered composite material and its preparation method.

The purpose of the invention is realized as follows:

continuous metal Mo wire reinforced Ti/Al₃The preparation method of the Ti layered composite material comprises the following steps:

the method comprises the following steps: mixing TC₄Pretreating the foil, the Al foil and the Mo wire;

step two: pre-treated TC₄Foil, Al foil and Mo wire according to "TC₄-Al-Mo-Al-TC₄"is a unit stack with the outermost layer being TC₄A foil;

step three: and putting the stacked sample into a vacuum hot-pressing furnace, setting process parameters and sintering.

The process parameters are specifically as follows: at 10^-3The temperature is raised to 640 ℃ within 100min under the conditions of low vacuum degree of Pa and initial pressure of 3MPa, the temperature is kept for about 20min to ensure that the sample is uniformly heated, and at the moment, although the melting point of Al is not reached, the softening phenomenon of Al can occur, so that the pressure needs to be reduced to prevent the phenomenon that the Al is extruded too much after melting, the pressure is reduced to 2MPa, and the temperature is raised to about 660 ℃ within 20 min. When the temperature reaches the melting point 660 ℃ of Al, the pressure head pressure needs to be stopped, the pressure is gradually changed from 2MPa to 0 at the moment, the pressure is gradually adjusted to 2MPa after heat preservation is carried out for 140min, and heating is stopped after heat preservation is continuously carried out for 40 min.

The invention also includes such features:

the pretreatment specifically comprises the following steps: original TC of sand paper polishing₄Edges and surfaces of foils, Al foils and Mo wires; cleaning and polishing TC by using ultrasonic cleaner₄Foils, Al foils, and Mo wires; soaking in acetone solution for 10 min; then soaking and cleaning TC by alcohol₄The surfaces of the foil, the Al foil and the Mo wire are subjected to drying treatment;

the Al content of the Al foil is more than or equal to 99.6 percent;

the Mo content in the molybdenum wire is more than or equal to 99.93 percent;

continuous metal Mo wire reinforced Ti/Al₃The Ti laminated composite material comprises the following chemical components: mo is more than or equal to 99.93 percent, and other elements are less than or equal to 0.07 percent;

the other elements are specifically: fe is less than or equal to 0.30, carbon is less than or equal to 0.10, nitrogen is less than or equal to 0.05, hydrogen is less than or equal to 0.015, oxygen is less than or equal to 0.20, aluminum is 5.5-6.8, vanadium is 3.5-4.5, and the balance is titanium.

The innovation points of the invention are as follows:

(1) the fiber reinforced composite material applied at present does not have the structural and performance characteristics of a layered material, and the continuous Mo wire reinforced Ti/Al prepared by the method₃The Ti layered composite material has a special high energy absorption laminated structure and has excellent performance in the aspect of mechanical property.

(2) The invention adopts a vacuum hot-pressing sintering preparation method, which is a low-temperature foil metallurgy technology, can meet the reaction requirement at a lower temperature, saves energy and simultaneously can keep the performance of raw materials;

the invention can conveniently design the structure and the performance of the composite material by changing the thickness of the initial metal foil, the type of the foil, the arrangement sequence and the size of the continuous Mo wire, and optimize the performance of the composite material to prepare the high-performance structure-function integrated composite material.

Compared with the prior art, the invention has the beneficial effects that:

(1) the special technological parameters set by the invention are favorable for generating single-phase matrix Al by reaction₃Ti, and other intermetallic compounds of Ti-Al series (such as TiAl and AlTi)₃) In contrast, Al₃Ti has higher elastic modulus (215GPa) and lower density (3.3 g/cm)³) Therefore, the continuous Mo reinforced laminated composite material has the mechanical properties of low density, high strength, high modulus and the like.

(2) Due to the special laminated structure and the fiber reinforcement effect of the laminated composite material prepared by the invention, the failure analysis result of the composite material shows that: al (Al)₃The failure of the Ti matrix is transgranular fracture, the behaviors of debonding, pulling out and the like of the metal molybdenum wire and the toughness of the composite material improved obviously by the Ti layer of the toughness layer.

(3) The continuous Mo wire prepared by the invention strengthens Ti/Al₃The interface of the Ti layered composite material layer and the fiber interface form a defect-free and high-quality interface combination through metallurgical combination, and the tough metal Ti has a toughening effectWhile the addition of continuous Mo wire makes Mo-Ti/Al₃The tensile strength and the bending strength of the Ti composite material are greatly improved.

(4) The invention uses commercial metal foils (TC4 foil and aluminum foil) with wide sources, and the composite material has low temperature, no toxicity, energy saving and environmental protection in the preparation process, simple and easy process, low cost and stable and reliable performance.

Drawings

FIG. 1 is a flow diagram of composite material preparation;

FIG. 2 is a schematic view of the arrangement of metal foils; according to "TC₄-Al-Mo-Al-TC₄"is a unit stack with the outermost layer being TC₄A foil;

FIGS. 3a-b are continuous Mo filaments and Al filaments in example 1₃Scanning electron microscope photos of Ti matrix interface;

FIG. 4 shows the continuous Mo wire and Al wire in example 2₃Metallographic pictures of Ti matrix interface;

FIGS. 5a-b are continuous Mo filaments and Al filaments in example 3₃And (5) scanning electron microscope pictures of Ti matrix interfaces.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

The method successfully prepares the Mo-Ti/Al by introducing the Ti layer as the toughness layer, adding the high-performance continuous metal molybdenum wire and adopting a vacuum hot-pressing sintering mode₃A Ti layered composite material.

The invention adopts the following technical scheme: vacuum hot-pressing method for preparing continuous metal Mo wire reinforced Ti/Al₃A Ti layered composite material. The raw material used by the method is TC4 titanium alloy, and the alloy comprises the following chemical components: the balance of titanium (Ti), iron (Fe) is less than or equal to 0.30, carbon (C) is less than or equal to 0.10, nitrogen (N) is less than or equal to 0.05, hydrogen (H) is less than or equal to 0.015, oxygen (O) is less than or equal to 0.20, aluminum (Al) is 5.5-6.8, and vanadium (V) is 3.5-4.5; the Al foil is 1060 industrial pure aluminum, and the Al content is more than or equal to 99.6 percent; the molybdenum fiber adopts molybdenum wire with the mark of MO1, the element content Mo in the molybdenum fiber is more than or equal to 99.93 percent, and other elements are less than or equal to 0.07 percent. There are no other added elements.

The preparation method of the invention comprises the following steps:

using metallographic sandThe paper is prepared by polishing original foil and fiber, removing oxidation layer, cleaning foil and fiber with ultrasonic cleaner for 15-20min, soaking in acetone solution for 10min, and cleaning metal foil and fiber surface with alcohol. In order to prevent the surface of the foil from being oxidized and polluted again, the surface of the foil is dried by a blower, the foil is put into a vacuum drying box for drying, and the foil is taken out after being dried completely and is wrapped by a preservative film for later use. After drying treatment according to "TC₄-Al-Mo-Al-TC₄"is a unit stack (see figure 2), with the outermost layer being TC₄A foil. The whole stacked sample is put into a vacuum hot pressing furnace for sintering, and the flow chart is shown in attached figure 1.

The main technological parameters are as follows: at 10^-3The temperature is raised to 640 ℃ within 100min under the conditions of low vacuum degree of Pa and initial pressure of 3MPa, the temperature is kept for about 20min to ensure that the sample is uniformly heated, and at the moment, although the melting point of Al is not reached, the softening phenomenon of Al can occur, so that the pressure needs to be reduced to prevent the phenomenon that the Al is extruded too much after melting, the pressure is reduced to 2MPa, and the temperature is raised to about 660 ℃ within 20 min. When the temperature reaches the melting point 660 ℃ of Al, the pressure head pressure needs to be stopped, the pressure is gradually changed from 2MPa to 0 at the moment, the pressure is gradually adjusted to 2MPa after heat preservation is carried out for 140min, and heating is stopped after heat preservation is continuously carried out for 40 min.

The technical solutions of the present invention are described in detail by the following specific examples, it should be understood that these examples are for illustrating the present invention, but not limiting the present invention, and the present invention is simply modified on the premise of the concept of the present invention, and all of them fall into the scope of the claimed invention.