Endogenous toughness phase Zr-based amorphous composite material with high yield strength and tensile plasticity and preparation method thereof
By designing a Be-free Zr-based amorphous composite material and employing a rapid cooling process, the problem of brittle fracture at room temperature in Zr-based amorphous alloys was solved, achieving a combination of high yield strength and tensile plasticity, making it suitable for various applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-03
- Publication Date
- 2026-03-17
AI Technical Summary
Existing Zr-based amorphous alloys exhibit highly concentrated plastic deformation at room temperature within localized shear bands, leading to brittle fracture. Furthermore, the use of Be element limits their application prospects in fields such as biomedicine and consumer products, making it difficult to obtain ideal endogenous dual-phase microstructures under conventional conditions.
By designing a Be-free Zr-based amorphous composite material, the body-centered cubic structure was controlled by elements such as Zr, Nb, Ti, and Ta to form an endogenous dendritic phase and an amorphous matrix phase rich in icosahedral short-range ordered structure. Combined with a rapid cooling process, an endogenous Zr-based amorphous composite material with both high yield strength and tensile plasticity was prepared.
It achieves a combination of high yield strength and tensile plasticity, the material is safe and environmentally friendly, suitable for a variety of corrosive environments, has good process repeatability and high glass-forming ability, and is suitable for harsh environments such as marine and chemical industries.
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Figure CN121674860A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of metallic materials and their preparation, specifically relating to an endogenous toughness phase Zr-based amorphous composite material with both high yield strength and tensile plasticity and its preparation method. Background Technology
[0002] Bulk amorphous alloys (BMGs), lacking the typical defects of traditional crystalline materials such as grain boundaries and dislocations, exhibit high strength, high hardness, high elastic limit, and excellent corrosion resistance, making them promising candidates for engineering materials. However, at room temperature, the plastic deformation of amorphous alloys is highly concentrated in localized shear bands, leading to brittle fracture on a macroscopic scale with almost no noticeable plasticity. This inherent drawback severely limits the engineering applications of bulk amorphous alloys as structural materials.
[0003] To improve the plasticity of amorphous alloys, researchers have developed amorphous composite materials, mainly categorized into "external" and "endogenous" types. External amorphous composites, by introducing an external second phase (such as whiskers, fibers, or particles) to hinder shear band propagation, can improve toughness to some extent, but suffer from problems such as poor wettability between the added crystalline phase and the amorphous matrix phase, poor interfacial bonding, complex processing, and susceptibility to impurity introduction. In contrast, endogenous amorphous composites, through the in-situ precipitation of a crystalline phase from the amorphous matrix during rapid cooling, achieve good interfacial bonding and stress transfer between the two phases, thus more effectively promoting shear band proliferation and inducing work hardening, significantly improving the toughness and plasticity of the material.
[0004] Currently, high-performance endogenous Zr-based amorphous composites largely rely on the addition of Be to promote in-situ precipitation and regulate the two-phase structure. However, Be is toxic, imposing stringent requirements on production operations and material recycling, and limiting its application prospects in biomedicine, consumer goods, and other fields. Although Be-free systems offer better environmental compatibility and cost advantages, their microstructure is extremely sensitive to composition design, cooling rate, and preparation process, making it difficult to obtain an ideal endogenous two-phase structure under conventional conditions, often resulting in a trade-off between strength and plasticity.
[0005] Therefore, developing an endogenous Zr-based amorphous composite material that does not depend on Be, has both high yield strength and significant room temperature tensile plasticity, and possesses good process repeatability has become a key problem that urgently needs to be solved in this technical field. Summary of the Invention
[0006] This invention addresses the technological limitations and the urgent need for high-performance amorphous composite materials by providing an endogenous Zr-based amorphous composite material with both high yield strength and tensile plasticity, along with its preparation method. Starting with Zr-based amorphous alloy systems rich in icosahedral short-range ordered structures, and considering the relationship between the content of icosahedral ordered structures and system stability, a concept for rapidly and efficiently designing Be-free endogenous Zr-based amorphous composite materials is proposed. Furthermore, by improving the process and controlling the alloying elements such as Zr, Nb, Ti, and Ta, which stabilize the body-centered cubic (bcc) phase, a Be-free endogenous Zr-based amorphous composite material with high yield strength, tensile plasticity, and a single bcc solid solution phase is developed, overcoming the challenge of amorphous alloys lacking room-temperature plasticity, especially tensile properties.
[0007] The technical solution of this invention is: This invention discloses an endogenous toughness-based Zr-based amorphous composite material that possesses both high yield strength and tensile plasticity. The atomic percentage expression for this amorphous composite material is: Zr a M b Cu c Ni d Al e M is at least one of Nb, Ta, or Ti, and each component satisfies the following ranges: 60≤a≤80, 5≤b≤12, 2≤c≤14, 1≤d≤12, 4≤e≤8, a+b+c+d+e=100; the amorphous composite material includes an endogenous dendritic phase and an amorphous matrix phase, wherein the endogenous dendritic phase is a body-centered cubic solid solution phase, and the amorphous matrix phase is rich in icosahedral short-range ordered structures.
[0008] Furthermore, in the aforementioned Zr-based amorphous composite material with both high yield strength and tensile plasticity, the endogenous dendritic phase is enriched with Zr and M elements and depleted with Cu, Ni and Al elements, and each component satisfies: 70≤a≤80, 8≤b≤12, 2≤c≤8, 1≤d≤6, 4≤e≤6, a+b+c+d+e=100.
[0009] Furthermore, in the aforementioned Zr-based amorphous composite material with both high yield strength and tensile plasticity, the amorphous matrix phase is rich in Zr, Cu, Ni and Al elements, and poor in M element, and each component satisfies: 60≤a≤70, 5≤b≤8, 8≤c≤14, 6≤d≤12, 6≤e≤8, and a+b+c+d+e=100.
[0010] Furthermore, in the aforementioned Zr-based amorphous composite material possessing both high yield strength and tensile plasticity, the composition of the amorphous composite material is selected from any of the following atomic percentages: Zr 70.5 Nb 7.5 Cu8Ni6Al8, Zr70.5 Nb 5.5 Ti2Cu8Ni6Al8 or Zr 70.5 Nb 5.5 Ta2Cu8Ni6Al8.
[0011] Furthermore, the aforementioned Zr-based amorphous composite material, which possesses both high yield strength and tensile plasticity, exhibits high glass-forming ability, and its atomic percentage expression is: Zr 63 Nb5Cu 13.5 Ni 10.5 Al8.
[0012] This invention also discloses a method for preparing the above-mentioned endogenous Zr-based amorphous composite material with both high yield strength and tensile plasticity, comprising the following steps: Step 1: According to the alloy composition, convert the atomic percentage to the mass percentage and weigh the ingredients; Step 2: Clean and dry the weighed high-purity raw materials to reduce the introduction of impurities and ensure that the mass error of each raw material does not exceed ±0.005g; Step 3: Place the raw material block into the crucible of the vacuum melting furnace. First, melt the high melting point binary ZrM master alloy. Repeat mechanical turning and electromagnetic stirring to ensure uniform composition. Then, vacuum melt the master alloy and the remaining raw materials. Adjust the process current to achieve uniform melting of the alloy. Repeat mechanical turning and electromagnetic stirring multiple times to obtain a uniform master alloy ingot. Step 4: The homogeneous molten master alloy ingot is remelted, flipped and cast, mechanically cut and heat-treated to obtain the target amorphous composite material with endogenous dendritic phase and amorphous matrix phase. Among them, flipping and casting yields 10mm diameter rods, which are mechanically cut into 5mm~7mm diameter rods. The high-temperature solution treatment temperature is 880℃~1000℃, and the holding time is 6.5min~7.5min. Then, the sample is rapidly cooled by water quenching. Samples are taken from the edge positions of the treated sample where there are no obvious defects and cracks, and the microstructure and mechanical properties are characterized.
[0013] Furthermore, in the above-mentioned preparation method of the endogenous toughness phase Zr-based amorphous composite material with both high yield strength and tensile plasticity, the raw material Zr used in step 2 is of nuclear grade purity, and the purity of the other alloying elements is not less than 99.99 wt.%.
[0014] Furthermore, in the above-mentioned method for preparing the Zr-based amorphous composite material with both high yield strength and tensile plasticity, in step 3, the vacuum melting furnace uses a water-cooled copper crucible; the melting current is 400~600A, the melting time is 10~30min, and the melting is repeated 3~4 times.
[0015] Furthermore, in the preparation method of the above-mentioned Zr-based amorphous composite material with both high yield strength and tensile plasticity, in step 4 of the inverted casting step, a copper mold is used for rapid cooling to obtain a cast sample; the melting current is 400~600A, and after the master alloy is completely melted, it is immediately cast into a copper mold to obtain a rod-shaped sample.
[0016] Advantages and beneficial effects of the present invention: 1. Excellent mechanical properties: Through precise composition design and process control, the prepared amorphous composite material maintains high yield strength (1200–1400 MPa) while achieving considerable room temperature tensile plasticity (0.4%–1.5%), successfully overcoming the bottleneck problem of brittle fracture in traditional amorphous alloys.
[0017] 2. Free of Be, environmentally friendly and low cost: Completely avoids the use of toxic Be, making the material safer and more environmentally friendly, suitable for a wider range of applications; at the same time, it uses common metal elements such as Zr, Nb, Cu, Ni, and Al, making the raw material cost low and conducive to industrial promotion.
[0018] 3. Controllable microstructure and excellent interfacial bonding: By controlling the content of elements such as Zr, Nb, Ta, and Ti, a high-content icosahedral ordered structure is generated, increasing the distortion energy and causing the system to become unstable, inducing the formation of an endogenous dendritic phase with a single bcc structure. The large structural difference between the dendritic phase and the icosahedron allows the two to reach a state of equilibrium coexistence. During rapid cooling, the dendritic phase is formed and precipitated from the amorphous matrix to obtain an endogenous amorphous composite material.
[0019] 4. Simple and highly reproducible preparation process: By considering methods such as selecting low-cost raw materials and using Zr-based amorphous alloys for melting, preparation, mechanical cutting, and secondary hot working to control the microstructure, high-performance endogenous Zr-based amorphous composite materials can be rapidly screened and prepared, overcoming the current challenges of complex design and processes that plague endogenous amorphous composite materials; the use of vacuum melting combined with subsequent hot working (such as solution treatment + water quenching) provides a clear process flow and a wide parameter window, making it easy to prepare composite materials with uniform structure and stable performance, and possessing strong engineering potential.
[0020] 5. High glass-forming ability and strong compositional tunability: providing features such as Zr 63 Nb5Cu 13.5 Ni 10.5 Al8 and other high amorphous forming ability components provide ideal matrix phase candidates for subsequent composite material design. The composition system is flexible and can adapt to a variety of performance requirements.
[0021] 6. Excellent corrosion resistance: Since it does not contain Be and is mainly composed of Zr and Nb, the material exhibits excellent corrosion resistance in a variety of corrosive media and is suitable for harsh environments such as marine and chemical industries. Attached Figure Description
[0022] Figure 1 Zr ingot prepared in Example 1 70.5 Nb 7.5 Microstructure of Cu8Ni6Al8 (at.%) amorphous composite material; Figure 2 Zr ingot prepared in Example 1 70.5 Nb 7.5 XRD pattern of Cu8Ni6Al8 (at.%) amorphous composite material; Figure 3 The ingot prepared in Example 1 and the Zr with a diameter of 5 mm 70.5 Nb 7.5 DSC curves of Cu8Ni6Al8 (at.%) amorphous composite material; Figure 4 Zr prepared in Example 1 after heat treatment and water quenching 70.5 Nb 7.5 Microstructure of Cu8Ni6Al8 (at.%) amorphous composite material; Figure 5 Zr prepared in Example 1 after heat treatment and water quenching 70.5 Nb 7.5 Room temperature tensile stress-strain curves of Cu8Ni6Al8 (at.%) amorphous composite material; Figure 6 Zr prepared in Example 2, after heat treatment and water quenching, exhibits a high glass-forming ability. 63 Nb5Cu 13.5 Ni 10.5 XRD pattern of Al8 (at.%) amorphous alloy; Figure 7 Zr prepared in Example 2, after heat treatment and water quenching, exhibits a high glass-forming ability. 63 Nb5Cu 13.5 Ni 10.5 DSC curves of Al8 (at.%) amorphous alloy; Figure 8 Zr prepared in Example 3 after heat treatment and water quenching 70.5 Nb 5.5 Room temperature tensile stress-strain curves of Ti2Cu8Ni6Al8 (at.%) amorphous composite material; Figure 9 Zr prepared in Example 4 after heat treatment and water quenching 70.5 Nb 5.5 Microstructure of Ta2Cu8Ni6Al8 (at.%) amorphous composite material; Figure 10 Zr prepared in Example 4 after heat treatment and water quenching 70.5 Nb 5.5 XRD pattern of Ta2Cu8Ni6Al8 (at.%) amorphous composite material; Figure 11 Zr prepared in Example 4 after heat treatment and water quenching 70.5 Nb 5.5 DSC curves of Ta2Cu8Ni6Al8 (at.%) amorphous composite material; Figure 12 Zr prepared in Example 4 after heat treatment and water quenching 70.5 Nb 5.5 Room temperature tensile stress-strain curves of Ta2Cu8Ni6Al8 (at.%) amorphous composite material. Detailed Implementation
[0023] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be used to limit the scope of the present invention.
[0024] Example 1 This embodiment relates to an endogenous toughness-retaining Zr-based amorphous composite material, Zr, which combines high yield strength and tensile plasticity. 70.5 Nb 7.5 Cu8Ni6Al8, its preparation method includes the following steps: Step (1): According to the alloy composition, convert the atomic percentage to the mass percentage Zr:Nb:Cu:Ni:Al=78.4:8.5:6.2:4.3:2.6 Weigh high-purity raw materials that have been polished, cleaned and dried for preparation; Step (2): Under a high-purity argon atmosphere, high-melting-point Zr and Nb raw materials are first melted in a water-cooled copper crucible in a vacuum electric arc furnace as a binary master alloy. Then, the master alloy and the remaining Cu, Ni, and Al raw materials are placed back into the water-cooled copper crucible and melted again to obtain the master alloy ingot. The two-step melting process parameters are as follows: vacuum degree ≤ 3.5 × 10⁻⁶ -3 Using parameters such as Pa, melting current (400A~600A), alloy ingot flipping times 4~7 times, and melting time of 2~5 minutes per melting, an endogenous Zr-based amorphous composite material ingot with uniform chemical composition is produced. Step (3): Cast the master alloy ingot under a vacuum degree ≤3.5×10 -3Remelt under the conditions of Pa, with melting power supply (400~600A) and melting time (10-15min). After the alloy melts and the molten pool stabilizes, turn it over and cast it into rod-shaped samples of different diameters such as 5mm and 10mm. Step (4): The surface of the rod-shaped sample obtained in step (3) is further polished and then subjected to solid solution treatment at 1000℃ for 7.5 min. Then, it is rapidly cooled by water quenching to finally obtain a high-performance endogenous tough phase amorphous composite material sample.
[0025] Depend on Figure 1 It can be seen that the microstructure of the master alloy ingot in this embodiment is uniformly distributed, the precipitated phase is a typical matured as-cast dendritic structure, and the contrast between the dendritic phase and the matrix phase is obvious. The low cooling rate of the ingot leads to a large number of as-cast defects. Figure 2 The XRD pattern shows that the as-cast Zr in this embodiment 70.5 Nb 7.5 The Cu8Ni6Al8 (at.%) amorphous composite material exhibits a relatively complex phase composition at room temperature. Figure 3 The DSC curves of the ingot and the 5mm diameter cast rod sample show that a glass-like transition and a near-crystallization thermodynamic behavior exist in the low-temperature range, indicating the presence of an amorphous phase in the matrix. This also indicates that the composition of this amorphous phase is close to the deep eutectic point, and its high-temperature melting behavior is characterized by sharp melting peaks. Some characteristics of this amorphous phase will be further analyzed in Example 2. Figure 4 It can be seen that the as-cast defects of the hot-working and water-quenched samples are significantly reduced, the dendrites exhibit a mature state, and the bcc crystal structure is still maintained. Figure 5 The room temperature tensile results show that under the conditions of hot working and rapid water quenching, obvious yielding and tensile plasticity began to appear in this embodiment, with the yield strength reaching 1220 MPa and the tensile plasticity increasing to 0.6%.
[0026] Example 2 This embodiment relates to a basic amorphous composite material based on an endogenous toughness phase Zr, which combines high yield strength and tensile plasticity, and has the composition Zr. 63 Nb5Cu 13.5 Ni 10.5 Al8, the matrix of this amorphous composite material is amorphous and has high glass-forming ability. Its preparation steps are similar to steps (1) to (3) in Example 1, wherein the melting current is adjusted to 400~500A. The difference between this example and Example 1 is that the amorphous alloy in this example contains a high content of icosahedral order, which can serve as a guide for the development and preparation of high glass-forming ability Be-free Zr-based amorphous alloys.
[0027] Depend on Figure 6The XRD pattern shows that the as-cast 5mm rod-shaped sample of this embodiment exhibits typical amorphous diffuse peak characteristics, without obvious sharp diffraction peaks of crystalline phases. This indicates that the microstructure of this embodiment remains a single amorphous state at room temperature. Figure 7 The DSC curves show that this embodiment exhibits obvious glass transition and crystallization phenomena, while possessing a low melting temperature, indicating that the alloy composition of this embodiment is near the eutectic point. The combination of these factors suggests that the interdendritic matrix structure can be screened as a candidate amorphous alloy with high glass-forming ability. Based on this, it can be used as a matrix phase to composite with the crystalline phase, thereby designing and preparing a Be-free, endogenous Zr-based amorphous composite material.
[0028] Example 3 The difference between this embodiment and Embodiment 1 is that: in this embodiment, an appropriate amount of Ti element is added to adjust the alloy composition to Zr. 70.5 Nb 5.5 Ti2Cu8Ni6Al8 (at.%), other preparation methods are the same as in Example 1.
[0029] Depend on Figure 8 The room temperature tensile results show that, compared with the brittle fracture of amorphous alloys under static tension, after hot working and water quenching rapid cooling treatment, obvious yielding phenomenon and tensile plasticity began to appear in this embodiment. Compared with Example 1, the yield strength increased to 1300MPa, but the tensile plasticity decreased slightly to 0.4%.
[0030] Example 4 The difference between this embodiment and Embodiment 1 is that: in this embodiment, an appropriate amount of Ta element is added to adjust the alloy composition to Zr. 70.5 Nb 5.5 Ta2Cu8Ni6Al8(at.%).
[0031] Depend on Figure 9 It can be seen that the as-cast Zr in this embodiment 70.5 Nb 5.5 The Ta2Cu8Ni6Al8 (at.%) microstructure is uniformly distributed, with the precipitated phase exhibiting a typical matured as-cast dendritic structure. A significant difference in light and dark contrast exists between the dendritic and matrix phases. Under relatively high cooling rates, the as-cast 4mm rod-shaped sample showed no obvious structural defects. Figure 10 The XRD pattern shows that the as-cast Zr in this embodiment 70.5 Nb 5.5 The Ta2Cu8Ni6Al8 (at.%) amorphous composite material exhibits a single bcc crystal structure at room temperature. Figure 11 The DSC curve of a 4mm diameter cast rod-shaped sample shows obvious thermodynamic behavior of glass transition and crystallization in the low-temperature range. Combined with... Figure 10This demonstrates the presence of an amorphous phase in the matrix. Referring to the analysis of Example 2, this amorphous phase has a composition close to the deep eutectic point and possesses high glass-forming ability and icosahedral order. Figure 12 The room temperature tensile results show that this embodiment exhibits significant yielding and tensile plasticity. Compared with Examples 1 and 3, the yield strength increases to 1350 MPa, while the tensile plasticity increases to 1.5%. Matters not covered in this invention are common knowledge.
[0032] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.
Claims
1. An intrinsically tough Zr-based amorphous composite material with high yield strength and tensile ductility, characterized in that, The atomic percentage expression of the amorphous composite material is Zr a M b Cu c Ni d Al e , wherein M is at least one of Nb, Ta or Ti, and each component satisfies the following ranges: 60≤a≤80, 5≤b≤12, 2≤c≤14, 1≤d≤12, 4≤e≤8, a+b+c+d+e=100; the amorphous composite material comprises an endogenous dendrite phase and an amorphous matrix phase, the endogenous dendrite phase is a body-centered cubic structure solid solution phase, and the amorphous matrix phase is rich in icosahedral short-range ordered structure.
2. The intrinsically tough Zr-based bulk metallic glass composite material with high yield strength and tensile ductility of claim 1, wherein The endogenous dendrite phase is rich in Zr and M elements, poor in Cu, Ni and Al elements, and each component satisfies: 70≤a≤80, 8≤b≤12, 2≤c≤8, 1≤d≤6, 4≤e≤6, and a+b+c+d+e=100.
3. The intrinsically tough Zr-based bulk metallic glass composite material with high yield strength and tensile ductility of claim 1, wherein The amorphous matrix phase is rich in Zr, Cu, Ni and Al elements, poor in M elements, and each component satisfies: 60≤a≤70, 5≤b≤8, 8≤c≤14, 6≤d≤12, 6≤e≤8, and a+b+c+d+e=100.
4. The intrinsically tough Zr-based bulk metallic glass composite material with high yield strength and tensile ductility of claim 1, wherein The amorphous composite has a composition selected from any of the following atomic percentage compositions: Zr 70.5 Nb 7.5 Cu8Ni6Al8, Zr 70.5 Nb 5.5 Ti2Cu8Ni6Al8, or Zr 70.5 Nb 5.5 Ta2Cu8Ni6Al8.
5. The intrinsically tough Zr-based bulk metallic glass composite material with high yield strength and tensile ductility of claim 1, wherein The matrix amorphous of the amorphous composite has high glass forming ability, which is expressed in atomic percentage as Zr 63 Nb5Cu 13.5 Ni 10.5 Al8.
6. A method for preparing the Zr-based amorphous composite material with high yield strength and tensile ductility and intrinsic toughness phase according to any one of claims 1-5, characterized in that, The method comprises the following steps: Step 1: according to the alloy composition, convert the atomic percentage into mass percentage to weigh the ingredients; Step 2: wash and dry the weighed high-purity raw materials to reduce the introduction of impurity elements and ensure that the mass error of each raw material is not more than ±0.005g; Step 3: put the raw material blocks into the crucible of a vacuum melting furnace, first melt the high-melting-point binary ZrM intermediate alloy, repeatedly mechanically turn over with electromagnetic stirring to ensure uniform composition, then vacuum melt the intermediate alloy and the remaining raw materials, realize uniform melting of the alloy by adjusting the process current, and repeatedly mechanically turn over and electromagnetic stir to obtain a uniform master alloy ingot; Step 4: re-melt, turn over and cast, mechanically cut and heat treat the uniformly melted master alloy ingot to obtain the target amorphous composite material with endogenous dendrite phase and amorphous matrix phase; wherein the turn over and casting obtains a 10mm diameter rod, which is mechanically cut into a 5mm-7mm diameter rod; the high-temperature solid solution treatment is at a temperature of 880-1000℃ for 6.5-7.5min, followed by water quenching for rapid cooling.
7. The method of producing an intrinsically tough Zr-based amorphous composite material with high yield strength and tensile ductility according to claim 6, characterized in that, The raw material Zr used in step 2 is nuclear grade purity, and the purity of the remaining alloy elements is not less than 99.99 wt.%.
8. The method of claim 6, wherein the method is characterized by: In step 3, the vacuum melting furnace adopts a water-cooled copper crucible; the melting current is 400-600A, the melting time is 10-30min, and the repeated melting is 3-4 times.
9. The method of making an intrinsically tough Zr-based amorphous composite material with high yield strength and tensile ductility according to claim 6, characterized in that, In the step of step 4 turn over and cast, a copper mold is used for rapid cooling to obtain a as-cast sample; the melting current is 400-600A, the melting time is 5-15min, and the rod-shaped sample is obtained by pouring into the copper mold immediately after the master alloy is completely melted.