Preparation method of high-toughness amorphous composite material

Abstract

The application provides a preparation method of high-toughness amorphous composite material, comprising the following steps: S01, preparing a base amorphous material: selecting a zirconium-based amorphous material, and preparing an amorphous alloy according to the chemical composition of the amorphous material; S02, preparing a second-phase amorphous material: according to the composition of the base amorphous material, selecting the chemical composition of a precipitated phase in the base amorphous material to prepare a second-phase amorphous material; S03, preparing a toughening phase alloy: according to the composition of the base amorphous material, selecting the chemical composition of a non-precipitated phase in the base amorphous material, and pressing the toughening phase alloy by using a powder metallurgy process; and S04, hot-pressing the base amorphous material, the toughening phase alloy and the second-phase amorphous material in a mold to prepare the high-toughness amorphous composite material. The application aims to provide a method for preparing high-toughness amorphous composite material, and aims to solve the technical problem that amorphous alloys cannot be applied in the field with high mechanical performance requirements in the prior art.

Description

Technical Field

[0001] This invention belongs to the field of amorphous composite material processing technology, specifically relating to a method for preparing a high-toughness amorphous composite material. Background Technology

[0002] As the application fields of bulk amorphous materials gradually expand, more and more industries are trying to apply amorphous alloys to their respective fields. However, the fracture brittleness exhibited by bulk amorphous materials after molding limits their application in some industries with higher requirements. If the room temperature brittleness of amorphous base materials can be improved, thereby enhancing their toughness, the application of bulk amorphous materials in the field of engineering materials will be greatly expanded.

[0003] In the prior art, many technical solutions have been proposed to improve the mechanical properties of amorphous alloy materials. For example, Chinese patent CN 109434118A proposes mixing and ball-milling amorphous powder with other metal powders for application in additive manufacturing. Another example is Chinese patent CN 104878328A, which proposes pre-forming TiZr-based amorphous materials and their second-phase alloys, then impregnating and bonding them into a composite material. However, the aforementioned prior art solutions are difficult to industrialize due to high processing costs and limitations on the amorphous composition. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing high-toughness amorphous composite materials, aiming to solve the technical problem that amorphous alloys cannot be applied in fields with high mechanical performance requirements in the prior art.

[0005] To address the issue of improving the mechanical properties of amorphous alloys, existing technologies fall into two main categories. One approach involves improving the amorphous alloy material itself, specifically adjusting its chemical composition to enhance the material's inherent properties. The other approach involves selecting a suitable amorphous system, determining its amorphous composition, and then combining it with compatible toughening materials to create composite materials with superior mechanical properties. While the former approach, focusing on improving the material itself, can fundamentally improve the properties, it is difficult to develop amorphous alloy formulations with both good mechanical properties and excellent formability due to the inherent characteristics of amorphous materials. Furthermore, developing new material systems is extremely costly. The latter approach, utilizing amorphous materials with known formability and mechanical properties for composite material processing, facilitates the rapid development of materials directly applicable to industrial production. This invention adopts the latter approach, utilizing known amorphous alloys with good formability and mechanical properties, combined with toughening materials, to further increase the toughness of the amorphous material.

[0006] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows: This invention provides a method for preparing a high-toughness amorphous composite material, comprising the following steps: S01, refining the matrix amorphous material: selecting zirconium-based amorphous material and refining the amorphous alloy according to the amorphous chemical composition; S02, Pre-formed second-phase amorphous material: Based on the composition of the matrix amorphous material, the chemical composition of the precipitated phase in the matrix amorphous material is selected and refined into a second-phase amorphous material; S03, Pre-formed toughening phase alloy: Based on the composition of the matrix amorphous material, the chemical composition of the non-precipitated phase in the matrix amorphous material is selected, and the toughening phase alloy is pressed into a toughening phase alloy using powder metallurgy process; S04, the matrix amorphous material, the toughening phase alloy, and the second phase amorphous material are placed in a mold and hot-pressed to produce a high-toughness amorphous composite material; The three components are arranged in the mold as follows: one toughening phase alloy is placed on each side of the amorphous matrix, and one second phase amorphous alloy is placed on the other side of each toughening phase alloy.

[0007] In the technical solution of this invention, a suitable matrix amorphous material is first prepared, with zirconium-based amorphous material selected as having excellent forming ability and mechanical properties. Next, based on the composition of the matrix amorphous material, a suitable precipitate phase composition is selected to refine the second-phase amorphous material. The selection principles for the second-phase amorphous material include: selecting the main component of the precipitate phase in the matrix amorphous material, and ensuring that the atomic percentage of the main component is approximately the same. Then, based on the composition of the matrix amorphous material, a suitable toughening material is selected. The selection principles for the toughening material include: selecting the chemical composition of the non-precipitate phase in the matrix amorphous material. After the toughening material is processed into a toughening phase alloy using powder metallurgy, the matrix amorphous material, the toughening phase alloy, and the second-phase amorphous material are stacked in a "sandwich" manner with the matrix amorphous material as the center. Finally, hot pressing is used to form the composite material body.

[0008] Preferably, the chemical composition of the amorphous matrix is ​​Zr. 55 Al 15 Cu 12 Ni 7.5 Ti5Nb5Y 0.5 Zr 55 Al 16 Cu 12 Ni 6.5 Ti5Nb5Y 0.5 Zr 56 Al 13 Cu 10 Ni 10 Ti5Nb5Y1, Zr 58 Al 15 Cu 10 One of Ni6Ti5Nb5Y1. The numbers after the matrix amorphous elements above represent the atomic percentage of each element. In this invention, a zirconium-based amorphous material with a forming capability greater than 6 mm and excellent forming performance is selected.

[0009] Preferably, the second amorphous phase is Al. 35 Cu 32 Zr 31 Y2, Al 34 Cu 32 Zr 32 Y2, Al 34 Cu 34 Zr 31 Y1, Al 33 Cu 33 Zr 33 One of Y1. The numbers after the above-mentioned second-phase amorphous elements represent the atomic percentage of each element. In this invention, AlCuZr is preferred as the main component of the second-phase amorphous material, and element Y is an additive. The role of the second-phase amorphous material in the composite material is, on the one hand, similar to the function of an encapsulating material, firmly wrapping the toughening phase alloy between the matrix amorphous materials; on the other hand, the second-phase amorphous material also serves as the outer surface of the composite material, requiring certain strength and hardness, and also compensating for the matrix amorphous properties through the toughening phase alloy.

[0010] Preferably, the toughening phase alloy is an Al-Zr alloy, with an atomic ratio of Al to Zr of (3~5):1. The Al-Zr alloy is chosen as the toughening phase in this invention because, on the one hand, it exhibits good plasticity and excellent fusion performance with the second amorphous phase, and can achieve good bonding with the amorphous phases on both sides during a phase-compatible hot pressing process. On the other hand, the Al content is crucial during the melting of zirconium-based amorphous phases, as Al is easily lost during the melting process. Often, after melting a batch of alloy, the Al content in the master alloy ingot is lower than the Al content in the initial feed. Analysis shows that the loss of Al equivalent in the alloy is due to the fact that, as the melting temperature increases, the first melting Al reacts with Zr to form a high-melting-point compound Al3Zr2 (~1600℃). However, due to the limitation of the melting temperature (<1400℃), the high-melting-point compound Al3Zr2 cannot continue to melt into the alloy, resulting in a loss of Al equivalent in the alloy. Therefore, the Al-Zr alloy used as the toughening phase in this invention not only plays a toughening role, but also effectively compensates for the chemical composition of the amorphous matrix.

[0011] Furthermore, in this invention, a toughening phase alloy is formed by pressing using powder metallurgy. The toughening phase alloy formed by this process naturally has a certain porosity. During the hot pressing of the composite material, its porosity can effectively improve the degree of integration with the matrix amorphous and the second phase amorphous, thereby improving the bonding performance between the layers of the composite material.

[0012] The selection of materials in the technical solution of this invention has the following advantages: (1) The chemical composition of the second-phase amorphous phase is not limited to being completely identical to the precipitated phase in the matrix amorphous phase. This invention uses zirconium-based amorphous phases, so the selection of the second-phase amorphous phase can refer to the molding properties of existing zirconium-based amorphous phases to select amorphous components compatible with the matrix amorphous phase. In short, the second-phase amorphous phase is a zirconium-based amorphous phase with fewer component types than the matrix amorphous phase, but is closely related to the precipitated phase of the matrix amorphous phase. In actual industrial production, the equipment and molds for prefabricating the second-phase amorphous phase are similar to those for the matrix amorphous phase, or only require modification of the mold core, greatly improving the efficiency of industrial production of this composite material.

[0013] (2) The selection of non-precipitated phase chemical composition in the matrix amorphous alloy can avoid excessive crystallization during composite hot pressing, or the formation of weak crystallization points or crystallization bands that affect mechanical properties.

[0014] Preferably, the matrix amorphous material, the toughening phase alloy, and the second phase amorphous material are all in sheet form and are placed in a mold for hot pressing according to a set placement method. Sheet-shaped materials are more conducive to hot pressing bonding.

[0015] Preferably, the hot pressing temperature is 680~950℃, and the hot pressing process is under constant pressure conditions, with a pressure of 8~16MPa. The process in this invention is suitable for thin-walled parts; therefore, the desired process effect can be achieved by pressing under constant pressure within the temperature range near the melting point of zirconium-based amorphous materials.

[0016] Preferably, in order to make the composite material bonding surface tighter, the thickness of the toughening phase alloy is 5-15% of the matrix amorphous material, and the thickness of the second phase amorphous material is 10-20% of the matrix amorphous material.

[0017] The pressing of the composite material is preferably carried out in a vacuum environment. Preferably, the matrix amorphous material, the toughening phase alloy, and the second phase amorphous material are placed in the mold according to the set position, and the mold is evacuated to a vacuum degree of less than 0.1 Pa in the cavity. Then, it is heated to the set hot pressing temperature and constant pressure pressing is performed at the same time. The holding time is 1 to 10 minutes. After the holding time is completed, the obtained composite material is cooled with inert gas so that the composite material drops to room temperature within 3 seconds.

[0018] Preferably, the method of the present invention is more applicable to thin-walled parts, wherein the thickness of the amorphous matrix is ​​1~20mm, the thickness of the toughening phase alloy is 5~10% of the amorphous matrix, and the thickness of the second amorphous phase is 10~15% of the amorphous matrix.

[0019] Preferably, ultrasonic treatment can be performed during the hot pressing process, and the frequency of the ultrasonic vibration is 10. 6 ~10 10 Hz. Ultrasound is beneficial for improving the bonding force between layers.

[0020] The method for preparing high-toughness amorphous composite materials provided in this invention utilizes known amorphous alloys with good forming ability and mechanical properties, along with toughening materials, to further increase the toughness of amorphous materials and solve the technical problem that amorphous alloys cannot be applied in fields with high mechanical performance requirements in the prior art. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the structure of the high-toughness amorphous composite material in an embodiment of the present invention; Explanation of icon numbers: 101, 105, Second phase amorphous; 102, 104, First toughening phase amorphous; 103, Matrix amorphous. Detailed Implementation

[0022] To make the objectives, technical solutions, and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. The embodiments described below are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art in conjunction with the embodiments of the present invention without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed; where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0023] In the description of this invention, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0024] In the description of this invention, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0025] It should be understood that the weights of the relevant components mentioned in the embodiments of this invention can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this invention is within the scope of this invention. Specifically, the weights mentioned in the embodiments of this invention can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg. Example

[0026] This embodiment provides a method for preparing a high-toughness amorphous composite material, the steps of which are detailed below.

[0027] S01, Refining the matrix amorphous: Select zirconium-based amorphous materials and refine the amorphous alloy according to the amorphous chemical composition.

[0028] In this embodiment, the amorphous matrix with the chemical composition of Zr is selected. 55 Al 15 Cu 12 Ni 7.5 Ti5Nb5Y 0.5 The number after each element represents the atomic percentage of that element. The atomic percentage is converted to a mass percentage, and then the elemental raw material is weighed according to the mass percentage. In this embodiment of the invention, a test vacuum arc melting furnace is used for smelting. The maximum smelting capacity of a single amorphous material in the test furnace is 200g.

[0029] After mixing the elements, they are placed into a crucible in a melting furnace. The furnace cavity is closed, a vacuum is drawn, and an electric arc is turned on for melting. The melting is repeated three times until the molten liquid is uniform. Then, it is poured into a copper mold to form a sheet material with a thickness of 10 mm, a length of 100 mm, and a width of 15 mm.

[0030] S02, Pre-fabricated second-phase amorphous material: Based on the composition of the matrix amorphous material, Al is selected as the second-phase amorphous material. 35 Cu 32 Zr 31 Y2. The number after the element is the atomic percentage of each element. Convert the atomic percentage to the mass percentage, and then weigh the elemental raw material according to the mass percentage. Similarly, use a vacuum arc melting furnace to melt the second-phase amorphous material into a sheet material with a thickness of 1.2 mm, a length of 100 mm, and a width of 15 mm.

[0031] S03, Pre-formed toughening phase alloy: Based on the amorphous composition of the matrix, Al3Zr is selected as the toughening phase alloy. The numbers after the elements represent the atomic percentages of each element. The atomic percentages are converted to mass percentages, and then the powder raw materials are weighed according to the mass percentages. The toughening phase alloy sheets are pressed using powder metallurgy technology, with a thickness of 0.8 mm, a length of 100 mm, a width of 15 mm, and a density greater than 98%.

[0032] The above-mentioned powder metallurgy process includes: mixing Al powder and Zr powder according to a mass ratio; adding 0.5 wt% organic binder to the total mass of the powder raw materials and mixing again; pressing the mixture from the previous step into a green compact (forming pressure of 650 MPa); sintering the green compact in a non-oxidizing atmosphere, followed by sandblasting to remove burrs; and shaping using a jig to meet the flatness requirements. The powder metallurgy process in this embodiment can also employ other compatible processes from the prior art, or supplement or reduce individual process steps according to actual needs. The raw materials used in the powder metallurgy process are all commercially available products; as long as they meet the usage requirements, they are acceptable and will not be elaborated upon here.

[0033] S04, the matrix non-crystalline material, toughened phase non-crystalline material, and second-phase non-crystalline material prepared in the above steps are placed in a mold. The mold is evacuated until the vacuum level inside the cavity is below 0.1 Pa, and then hot pressing is performed. The hot pressing temperature is 930~950℃, the pressure is constant at 15MPa, and the holding time is 8min. After the holding time is completed, the composite material is cooled using argon gas, allowing the composite material to drop to room temperature within 3 seconds.

[0034] The placement of the three components in the mold is shown in the attached figure. Figure 1 As shown, a toughening phase alloy 102 and 104 are placed on each side of the matrix amorphous 103, and a second phase amorphous 101 and 105 are placed on the other side of each toughening phase alloy. The matrix amorphous 103, toughening phase alloys 102 and 104, and second phase amorphous 101 and 105 are stacked in a "sandwich" manner with the matrix amorphous as the center, and finally formed by hot pressing to form the composite material body.

[0035] In this embodiment, a horizontal stacking and left-right pressing method is used, as shown in the attached figure. In other embodiments, a vertical stacking and vertical pressing method may also be used.

[0036] In this embodiment, a single-layer stacking method is used on both sides of the amorphous matrix for toughening. In other embodiments, a multi-layer stacking method can also be used, and the parameters of the processing technology (such as hot pressing pressure and holding time) can be adaptively adjusted.

[0037] Example 2 In this embodiment, the process flow is the same as in Example 1, except that the chemical composition of the amorphous matrix is ​​Zr. 55 Al 16 Cu 12 Ni 6.5 Ti5Nb5Y 0.5 The chemical composition of the second amorphous phase is Al. 34 Cu 32 Zr 32 Y2, the toughening phase alloy is Al 3.5Zr.

[0038] Example 3 In this embodiment, the process flow is the same as in Example 1, except that the chemical composition of the amorphous matrix is ​​Zr. 56 Al 13 Cu 10 Ni 10 Ti5Nb5Y1, the second-phase amorphous chemical composition is Al 34 Cu 34 Zr 31 Y1, the toughening phase alloy is Al4Zr.

[0039] Example 4 In this embodiment, the process flow is the same as in Example 1, except that the chemical composition of the amorphous matrix is ​​Zr. 58 Al 15 Cu 10 Ni6Ti5Nb5Y1, the second-phase amorphous chemical composition is Al 33 Cu 33 Zr 33 Y1, the toughening phase alloy is Al5Zr.

[0040] Example 5 In this embodiment, the process flow is the same as in Embodiment 1, except that ultrasonic treatment is incorporated into the hot pressing process, and the frequency of the ultrasonic vibration is 10. 10 Hz. Ultrasonic processing can reduce the holding time of hot pressing to a certain extent and promote the bonding of composite layers.

[0041] The mechanical properties of the amorphous composite materials prepared in Examples 1-5 were tested according to GB / T7732-2008 "Metallic Materials - Surface Crack Tensile Specimens Test Method". The fracture toughness values ​​obtained were all greater than 100 MPa·m. 1 / 2 It can be used as an engineering material.

[0042] As can be seen from the above embodiments, the preparation method of high-toughness amorphous composite material provided in this invention utilizes amorphous alloys with known good forming ability and mechanical properties, along with toughening materials, to further increase the toughness of amorphous materials and solve the technical problem that amorphous alloys cannot be applied in fields with high mechanical performance requirements in the prior art.

[0043] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A method for preparing a high-toughness amorphous composite material, characterized in that, Includes the following steps, S01, Refining the matrix amorphous material: Selecting zirconium-based amorphous materials, and refining the amorphous alloy according to the amorphous chemical composition; the chemical composition of the matrix amorphous material is Zr. 55 Al 15 Cu 12 Ni 7.5 Ti5Nb5Y 0.5 Zr 55 Al 16 Cu 12 Ni 6.5 Ti5Nb5Y 0.5 Zr 56 Al 13 Cu 10 Ni 10 Ti5Nb5Y1, Zr 58 Al 15 Cu 10 One of Ni6Ti5Nb5Y1; S02, Pre-fabricated second-phase amorphous material: Based on the composition of the matrix amorphous material, the chemical composition of the precipitated phase in the matrix amorphous material is selected and refined to form a second-phase amorphous material; the second-phase amorphous material is Al. 35 Cu 32 Zr 31 Y2, Al 34 Cu 32 Zr 32 Y2, Al 34 Cu 34 Zr 31 Y1, Al 33 Cu 33 Zr 33 One of Y1; S03, Pre-formed toughening phase alloy: Based on the composition of the amorphous matrix, the chemical composition of the non-precipitated phase in the amorphous matrix is ​​selected, and the toughening phase alloy is pressed into a toughening phase alloy using powder metallurgy; the toughening phase alloy is an Al-Zr alloy, and the atomic ratio of Al to Zr is (3~5):

1. S04, the matrix amorphous material, the toughening phase alloy, and the second phase amorphous material are placed in a mold and hot-pressed to produce a high-toughness amorphous composite material; The three components are arranged in the mold as follows: one toughening phase alloy is placed on each side of the amorphous matrix, and one second phase amorphous alloy is placed on the other side of each toughening phase alloy.

2. The method for preparing the high-toughness amorphous composite material according to claim 1, characterized in that, The matrix amorphous material, the toughening phase alloy, and the second phase amorphous material are all in sheet form and are placed in a mold for hot pressing according to a set placement method.

3. The method for preparing the high-toughness amorphous composite material according to claim 2, characterized in that, The hot pressing temperature is 680~950℃, and the hot pressing process is under constant pressure conditions with a pressure of 8~16MPa.

4. The method for preparing the high-toughness amorphous composite material according to claim 2, characterized in that, The thickness of the toughening phase alloy is 5-15% of the matrix amorphous material, and the thickness of the second phase amorphous material is 10-20% of the matrix amorphous material.

5. The method for preparing the high-toughness amorphous composite material according to claim 1, characterized in that, After placing the matrix amorphous material, the toughening phase alloy, and the second phase amorphous material in the mold according to the set positions, the mold is evacuated until the vacuum degree inside the cavity is lower than 0.1 Pa. Then, it is heated to the set hot pressing temperature and constant pressure pressing is performed at the same time. The holding time is 1 to 10 minutes. After the holding time is completed, the obtained composite material is cooled with inert gas so that the composite material drops to room temperature within 3 seconds.

6. The method for preparing the high-toughness amorphous composite material according to claim 5, characterized in that, The thickness of the amorphous matrix is ​​1-20 mm, the thickness of the toughening phase alloy is 5-10% of the amorphous matrix, and the thickness of the second amorphous phase is 10-15% of the amorphous matrix.

7. The method for preparing the high-toughness amorphous composite material according to claim 6, characterized in that, Ultrasonic treatment can be performed during the hot pressing process, with the ultrasonic vibration frequency being 10. 6 ~10 10 Hz.

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