A multi-principal element alloy foil and preparation method thereof

Abstract

The present invention discloses a multi-principal alloy foil and a preparation method thereof. The multi-principal alloy foil is denoted by atomic number ratio as Zr x Ti y Nb z M w , wherein M is at most one of Al, Cr, Si, and B, and the 42%≤x≤55%, 36%≤y≤40%, 18%≤z≤20%, 0≤w≤5%, and x+y+z+w=100%. The thickness of the multi-principal element alloy foil is 0.05~0.15mm. The multi-principal element alloy foil developed by the present invention is a Zr‑Ti‑Nb‑M series metal multi-principal element alloy system, which is designed through the synergistic driving performance of multiple dominant elements and has excellent comprehensive mechanical properties and unique physical and chemical properties. The multi-principal element alloy foil described in the present invention has excellent cold rolling forming ability, and the hot-rolled plate can be directly formed into foil through multiple cold rolling passes. No annealing treatment is required during the cold rolling process, and the total deformation of cold rolling is 97%~99%.

Description

Technical Field

[0001] The present invention belongs to the technical field of alloy materials, and in particular relates to a multi-principal-element alloy foil and a preparation method thereof. Background Art

[0002] Different from the single dominant element design concept of traditional alloys, multi-principal element alloys are a new type of material developed based on "chemical disorder" at the atomic scale. They usually contain three or more dominant elements and belong to the category of medium-entropy and high-entropy alloys. They have been proven to have many excellent properties that are superior to traditional alloys, such as high strength, good high-temperature stability, good corrosion resistance and radiation resistance, and have shown great development potential in aerospace, electronics, energy and other fields.

[0003] In the application process of multi-principal alloys, in order to meet the application requirements of various components and structural parts, they are usually prepared into plates, strips, and foils, such as resistance alloy foils. However, multi-principal alloys are a type of high-concentration solid solution alloys, which generally have high intrinsic strength, large deformation resistance, and limited plasticity. This poses a great challenge to the preparation of multi-principal alloy plates, strips, and foils. In addition, due to the complexity of the constituent elements of multi-principal alloy blocks, their thermal processing window is relatively narrow, resulting in a long deformation processing process flow that is time-consuming and labor-intensive, which further hinders the industrial application and development of new multi-principal alloy foils. Summary of the Invention

[0004] In response to the problems existing in the prior art, the present invention provides a multi-principal element alloy foil and a preparation method thereof, which specifically includes the following contents:

[0005] A multi-principal alloy foil, wherein the multi-principal alloy foil is Zr x Ti y Nb z M w , wherein M is at most one of Al, Cr, Si, and B, 42%≤ x ≤55%, 36%≤ y ≤40%, 18%≤ z ≤ 0%, 0 ≤w≤5%, and x + y + z + w=100%.

[0006] Preferably, the thickness of the multi-principal element alloy foil is 0.05 to 0.15 mm.

[0007] A method for preparing a multi-principal element alloy foil comprises the following steps:

[0008] (1) Melting: The raw materials of Zr, Ti, Nb and M are prepared according to the atomic percentage of Zr 42% to 55%, Ti 36% to 40%, Nb 18% to 20%, and M0 to 5%, wherein M is at most one of Al, Cr, Si and B, and then melted to obtain a multi-principal element alloy ingot;

[0009] (2) Primary machining: The multi-principal alloy ingot is subjected to a primary machining process to remove the surface oxide scale and obtain a primary machined ingot;

[0010] (3) Hot forging: The once machined ingot is reforged by hot forging to obtain a rolled slab;

[0011] (4) Secondary machining: The rolled slab is subjected to secondary machining and milling treatment to obtain a secondary machined slab;

[0012] (5) Hot rolling: The secondary machined slab is subjected to multiple hot rolling passes to obtain a hot rolled slab with uniform thickness and flatness;

[0013] (6) Cold rolling: The hot-rolled slab is subjected to multiple cold rolling passes to obtain a cold-rolled sheet;

[0014] (7) Finish rolling: The cold rolled sheet is subjected to a single finish rolling to correct the thickness and obtain a finished rolled foil;

[0015] (8) Annealing: Annealing the finished rolled foil to obtain a finished multi-element alloy foil.

[0016] Preferably, the smelting method in step (1) is magnetic levitation vacuum induction melting, and the smelting is carried out under the protection of high-purity nitrogen.

[0017] Preferably, in step (3), the hot forging is performed at a heating temperature range of 700-900°C, a holding time of 90-120 min, a final forging temperature range of 550-750°C, and air cooling of the rolled slab after hot forging.

[0018] Preferably, the hot rolling in step (5) is carried out at a temperature range of 650-850°C, with a holding time of 40-60 min, a reduction of 10%-30% per pass, and air cooling of the hot-rolled slab after hot rolling.

[0019] Preferably, in step (6), the cold rolling is performed with a total reduction of 97% to 99%, a reduction of 15% to 20% per pass, and no annealing is required during the multi-pass cold rolling process.

[0020] Preferably, in step (7), the finishing rolling: the pressing amount ranges from 5% to 10%.

[0021] Preferably, the annealing method in step (8) is: vacuum heat treatment of the finished rolled foil at a temperature range of 500-700 °C for 10-20 min, followed by furnace cooling.

[0022] Preferably, the diameter Φ of the ingot obtained in step (1) is 80-150 mm; the thickness of the surface oxide scale removed in step (2) is 0.5-1 mm; the thickness of the rolled slab obtained in step (3) is 30-50 mm; the thickness of the hot-rolled slab obtained in step (5) is 6-10 mm; and the thickness of the finished rolled foil obtained in step (7) is 0.05 mm-0.15 mm.

[0023] Beneficial effects of the present invention:

[0024] (1) The multi-principal element alloy foil developed in this invention is a Zr-Ti-Nb-M alloy system. Through the synergistic drive of multiple dominant elements, it exhibits excellent comprehensive mechanical properties and unique physical and chemical properties. Unlike traditional alloy foils containing only a single dominant element, the multi-principal element alloy foil developed in this invention represents a completely new category of alloy foil. The development of multi-principal element alloy foils can provide new candidate materials for foil design and application.

[0025] (2) The present invention proposes a novel multi-principal alloy foil and a method for preparing the same. The multi-principal alloy foil (Zr-Ti-Nb-M series multi-principal alloy foil) can have a thickness of 0.05 to 0.15 mm. Furthermore, the multi-principal alloy foil of the present invention has excellent cold-rolling formability. Hot-rolled sheet metal can be directly formed into foil through multiple cold-rolling passes. Annealing is not required during the cold-rolling process, and the total cold-rolling deformation is 97% to 99%.

[0026] (3) The thickness of the multi-principal element alloy foil disclosed in the present invention is controllable, and the processing and preparation process has the characteristics of simple process, low energy consumption and low cost. The foil preparation method in the present invention is simple to operate, safe and reliable, and the elements contained are non-toxic and harmless and easy to obtain, with good safety and economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The multi-principal alloy Zr prepared in Example 1 of the present invention 43 Ti 37 Nb 20 Block photos;

[0028] Figure 2 The multi-principal alloy Zr prepared in Example 1 of the present invention 43 Ti 37 Nb 20 Photo of foil;

[0029] Figure 3 The multi-principal alloy Zr prepared in Example 1 of the present invention 43 Ti 37 Nb 20 Phase structure characterization results;

[0030] Figure 4 Zr prepared in Example 2 of the present invention 43 Ti 37 Nb 17 Photo of Cr3 multi-principal alloy foil;

[0031] Figure 5 Zr prepared in Example 3 of the present invention 43 Ti 37 Nb 18 Photo of Al2 multi-principal element bulk alloy;

[0032] Figure 6 Zr prepared in Example 3 of the present invention 43 Ti 37 Nb 18 Photo of Al2 multi-principal alloy foil. Implementation Method

[0033] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The embodiments shown below do not limit the invention as described in the claims. In addition, the entire contents of the structures shown in the following embodiments are not limited to those necessary for the solution of the invention as described in the claims.

[0034] A multi-principal alloy foil is designated by atomic ratio as ZrxTiyNbzMw, where M is at most one of Al, Cr, Si, and B, 42%≤x≤55%, 36%≤y≤40%, 18%≤z≤20%, 0≤w≤5%, and x+y+z+w=100%. The thickness of the multi-principal alloy foil is 0.05 to 0.15 mm. Specifically, x can be 42%, 44%, 46%, 48%, 50%, 52%, 54%, 55%, etc.; y can be 36%, 37%, 38%, 39%, 40%, etc.; z can be 18%, 19%, 20%, etc.; and w can be 0, 1%, 2%, 3%, 4%, etc.

[0035] A method for preparing a multi-principal element alloy foil comprises the following steps:

[0036] (1) Melting: Zr, Ti, Nb, and M raw materials are prepared according to the atomic percentage of Zr 42% to 55% (for example, 42%, 44%, 46%, 48%, 50%, 52%, 54%, and 55%), Ti 36% to 40% (for example, 36%, 37%, 38%, 39%, and 40%), Nb 18% to 20% (for example, 18%, 19%, and 20%), and M 0 to 5%, wherein M is at most one of Al, Cr, Si, and B, and then subjected to magnetic levitation vacuum induction melting. The melting is carried out under the protection of high-purity nitrogen to obtain a multi-principal alloy ingot, and the ingot has a diameter Φ of 80 to 150 mm (for example, 85 mm, 90 mm, 100 mm, 110 mm, 120 mm, and 140 mm, etc.);

[0037] (2) Primary machining: The multi-principal alloy ingot is subjected to a primary machining process to remove the surface oxide scale. The thickness of the surface oxide scale removed is 0.5-1 mm, and a primary machining ingot is obtained.

[0038] (3) Hot forging: The once machined ingot is reforged by hot forging process, the heating temperature range is 700~900℃ (for example, 720℃, 750℃, 780℃, 800℃, 850℃, 880℃, etc.), the holding time is 90~120 min (for example, 92min, 95min, 98min, 100min, 105min, 110min, 115min, etc.), the final forging temperature range is 550~750℃ (for example, 580℃, 600℃, 620℃, 650℃, 680℃, 690℃, etc.), and the rolled slab is air-cooled after hot forging to obtain a rolled slab with a thickness of 30~50 mm (for example, 32mm, 35mm, 38mm, 40mm, 42mm, 45mm, etc.);

[0039] (4) Secondary machining: The rolled slab is subjected to secondary machining and milling treatment to obtain a secondary machined slab;

[0040] (5) Hot rolling: The secondary machined slab is subjected to multiple hot rolling passes, with a temperature range of 650-850°C (e.g., 680°C, 700°C, 720°C, 750°C, 780°C, 800°C, etc.), a holding time of 40-60 min (e.g., 42 min, 45 min, 48 min, 50 min, 52 min, 55 min, 58 min, etc.), and a reduction of 10%-30% (e.g., 12%, 15%, 18%, 20%, 22%, 25%, 28%, etc.) per pass. After hot rolling, the hot rolled slab is air cooled to obtain a uniform and flat hot rolled slab with a thickness of 6-10 mm (e.g., 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, etc.);

[0041] (6) Cold rolling: The hot-rolled slab is subjected to multiple cold rolling passes with a total reduction of 97% to 99% (e.g., 97%, 97.5%, 98%, 98.5%, 99%, etc.), and a reduction of 15% to 20% (e.g., 15%, 16%, 17%, 18%, 19%, 20%, etc.) per pass. No annealing treatment is required during the multiple cold rolling process to obtain a cold-rolled sheet;

[0042] (7) Finish rolling: The cold-rolled sheet is subjected to a single finish rolling to correct the thickness. The pressing amount ranges from 5% to 10% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, etc.), and a finish-rolled foil with a thickness of 0.05 mm to 0.15 mm (e.g., 0.06 mm, 0.08 mm, 0.10 mm, 0.12 mm, 0.14 mm, etc.) is obtained.

[0043] (8) Annealing: The finished rolled foil is annealed. The annealing method is as follows: the finished rolled foil is subjected to vacuum heat treatment at a temperature range of 500-700°C (e.g., 520°C, 550°C, 580°C, 600°C, 650°C, 680°C, etc.), and the heat preservation time is 10-20 min (e.g., 12 min, 14 min, 16 min, 18 min, 19 min, etc.), and then cooled in the furnace to obtain a finished multi-principal element alloy foil.

[0044] Example 1

[0045] A multi-principal alloy foil Zr 43 Ti 37 Nb 20 The composition (atomic percentage) includes: Zr 43%, Ti 37%, Nb 20%, and the thickness of the multi-principal element alloy foil is 0.09 mm.

[0046] The method for preparing the multi-principal element alloy foil described in this embodiment includes the following steps:

[0047] (1) Using Zr, Ti, and Nb metal elements with a purity of not less than 99.5 wt% as raw materials, prepare a total weight of 5 kg of raw materials according to the above atomic percentages, and clean the raw materials;

[0048] (2) Put the prepared raw materials into the induction melting furnace, and then evacuate the chamber. When the pressure in the chamber is less than 1×10 -2 After Pa, high-purity argon gas is filled in for protection. After the metal raw materials are fully melted, the alloy melt is cast into the mold to obtain a multi-principal alloy ingot.

[0049] (3) The surface oxide scale of the alloy ingot is removed by machining. The thickness of the oxide scale removed is 0.7 mm. The alloy ingot is milled. After machining, the alloy ingot is as follows: Figure 1 shown.

[0050] (4) Place the milled alloy ingot into a heat treatment furnace and heat it at 850°C for 90 minutes.

[0051] (5) The alloy ingot was forged three times by hot forging with a total deformation of 85% and a final forging temperature of 600 °C. It was forged into a slab with a thickness of about 30 mm. The alloy billet after forging was air-cooled to room temperature.

[0052] (6) After air cooling, the blank is machined and milled to remove the surface oxide scale.

[0053] (7) The milled thick plate is placed in a heat treatment furnace for heating at a temperature of 650°C for 50 minutes.

[0054] (8) The heated alloy billet is subjected to multiple hot rolling passes, with a deformation of 30% in each pass and a reduction of 15% in the last pass. The thickness of the slab after hot rolling is 10 mm.

[0055] (9) The hot-pressed slab was subjected to multiple cold rolling passes, with a total cold rolling deformation of 99%, a reduction of 15% in each pass, and a thickness of 0.1 mm.

[0056] (10) The final correction cold rolling deformation of the foil is 10%, and the thickness of the foil after final rolling is 0.09 mm. The obtained multi-principal element foil is as follows Figure 2 shown.

[0057] (11) The alloy foil was vacuum annealed at 550 °C for 15 min and then cooled in the furnace.

[0058] (12) The phase structure of the obtained multi-principal element alloy foil is a body-centered cubic structure, such as Figure 3 As shown in the figure, the yield strength of the obtained multi-principal element alloy foil is greater than 650 MPa.

[0059] Example 2

[0060] A multi-principal alloy foil Zr 43 Ti 37 Nb 17 Cr3, its composition (atomic percentage) is: Zr 43%, Ti 37%, Nb17%, Cr 3%, and the thickness of the multi-principal element alloy foil is 0.1 mm.

[0061] The method for preparing the multi-principal element alloy foil described in this embodiment comprises the following steps:

[0062] (1) Using Zr, Ti, and Nb metal elements with a purity of not less than 99.5 wt% as raw materials, prepare a total weight of 5 kg of raw materials according to the above atomic percentages, and clean the raw materials;

[0063] (2) Put the prepared raw materials into the induction melting furnace and then evacuate the chamber. When the vacuum degree in the chamber is lower than 1×10 -2 After Pa, high-purity argon gas is filled in for protection. After the metal raw materials are fully melted, the alloy melt is cast into the mold to obtain a multi-principal alloy ingot.

[0064] (3) The surface oxide scale of the alloy ingot is removed by machining, the thickness of the removed oxide scale is 0.7 mm, and the alloy ingot is milled.

[0065] (4) Place the milled alloy ingot into a heat treatment furnace and heat it at 870 °C for 90 min.

[0066] (5) The alloy ingot was forged three times by hot forging with a total deformation of 85% and a final forging temperature of 700 °C. It was forged into a slab with a thickness of about 30 mm. The alloy billet after forging was air-cooled to room temperature.

[0067] (6) After air cooling, the blank is machined and milled to remove the surface oxide scale.

[0068] (7) The milled thick plate is placed in a heat treatment furnace for heating at 700 °C for 50 minutes.

[0069] (8) The heated alloy billet is subjected to multiple hot rolling passes, with a deformation of 25% in each pass and a reduction of 15% in the last pass. The thickness of the slab after hot rolling is 10 mm.

[0070] (9) The hot-pressed slab was subjected to multiple cold rolling passes, with a total cold rolling deformation of 99%, a reduction of 15% in each pass, and a thickness of 0.11 mm.

[0071] (10) The final correction cold rolling deformation of the foil is 9.1%, and the thickness of the foil after final rolling is 0.1 mm. The obtained multi-principal element foil is as follows Figure 4 shown.

[0072] Example 3

[0073] A multi-principal alloy foil Zr 43 Ti 37 Nb 18 Al2, its composition (atomic percentage) is: Zr 43%, Ti 37%, Nb18%, Al 2%, and the thickness of the multi-principal element alloy foil is 0.15 mm.

[0074] The method for preparing the multi-principal element alloy foil of the present invention comprises the following steps:

[0075] (1) Using Zr, Ti, Nb, and Al metal elements with a purity of not less than 99.5 wt% as raw materials, preparing a total weight of kg of raw materials according to the above atomic percentages, and washing the raw materials;

[0076] (2) The prepared raw materials are placed in an induction melting furnace, and then vacuumed. When the pressure in the cavity is less than 1×10-2Pa, high-purity argon is filled in for protection. After the metal raw materials are fully melted, the alloy melt is cast into a mold to obtain a multi-principal alloy ingot.

[0077] (3) The surface oxide scale of the ingot is removed by machining to a thickness of 0.7 mm, and the alloy ingot is milled. The prepared alloy block is as follows Figure 5 shown.

[0078] (4) The milled alloy ingot is placed in a heat treatment furnace and heated at 800 °C for 90 min.

[0079] (5) The alloy ingot was forged three times by hot forging with a total deformation of 85% and a final forging temperature of 700 °C. It was forged into a slab with a thickness of about 30 mm. The alloy billet after forging was air-cooled to room temperature.

[0080] (6) After air cooling, the blank is machined and milled to remove the surface oxide scale.

[0081] (7) The milled thick plate is placed in a heat treatment furnace for heating at 650 °C for 50 min.

[0082] (8) The heated alloy billet is subjected to multiple passes of hot rolling, with a deformation of 20% in each pass and a reduction of 15% in the last pass. The thickness of the slab after hot rolling is 10 mm.

[0083] (9) The hot-pressed slab was subjected to multiple cold rolling passes, with a total cold rolling deformation of 99%, a reduction of 15% per pass, and a thickness range of 0.16 mm.

[0084] (10) The final correction cold rolling deformation of the foil is 6.3%, and the thickness of the foil after final rolling is 0.15 mm. The obtained multi-principal element foil is as follows Figure 6 shown.

[0085] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a multi-principal element alloy foil, characterized in that: The following steps are involved: (1) Melting: Zr, Ti, Nb, and M raw materials are prepared according to the atomic percentage of Zr 42% to 55%, Ti 36% to 40%, Nb 18% to 20%, and M 0% to 5%. The multi-principal element alloy foil is recorded as ZrxTiyNbzMw according to the atomic ratio, where x+y+z+w=100%, wherein M is at most one of Al, Cr, Si, and B. Then, the material is melted to obtain a multi-principal element alloy ingot. (2) Primary machining: The multi-principal alloy ingot is subjected to a primary machining process to remove the surface oxide scale to obtain a primary machined ingot; (3) Hot forging: The once machined ingot is reforged by hot forging to obtain a rolled slab; (4) Secondary machining: The rolled slab is subjected to secondary machining and milling treatment to obtain a secondary machined slab; (5) Hot rolling: The secondary machined slab is subjected to multiple hot rolling passes to obtain a hot-rolled slab with uniform thickness and flatness; the temperature range is 650-850°C, the holding time is 40-60 minutes, the reduction per pass is 10%-30%, and the hot-rolled slab is air-cooled after hot rolling; (6) Cold rolling: The hot-rolled slab is subjected to multiple cold rolling passes to obtain a cold-rolled sheet; the total reduction is 97% to 99%, and the reduction per pass is 15% to 20%. Annealing is not required during the multiple cold rolling process; (7) Finish rolling: The cold-rolled sheet is subjected to a single finish rolling to correct the thickness and obtain a finished foil; (8) Annealing: The finished rolled foil is annealed to obtain a finished multi-principal alloy foil. The thickness of the multi-principal alloy foil is 0.05 to 0.15 mm.

2. The method for preparing a multi-principal element alloy foil according to claim 1, characterized in that: The smelting method in step (1) is magnetic levitation vacuum induction melting, and the smelting is carried out under the protection of high-purity nitrogen.

3. The method for preparing a multi-principal element alloy foil according to claim 1, characterized in that: The hot forging in step (3) includes: a heating temperature range of 700-900°C, a holding time of 90-120 minutes, a final forging temperature range of 550-750°C, and air cooling of the rolled slab after hot forging.

4. The method for preparing a multi-principal element alloy foil according to claim 1, characterized in that: In step (7), the finishing rolling is performed with a pressing amount ranging from 5% to 10%.

5. The method for preparing a multi-principal component alloy foil according to claim 1, characterized in that: The annealing method in step (8) is as follows: vacuum heat treatment is performed on the finished rolled foil at a temperature range of 500 to 700° C. for 10 to 20 minutes, followed by furnace cooling.

6. The method for preparing a multi-principal component alloy foil according to any one of claims 1 to 5, characterized in that: The diameter Φ of the ingot obtained in step (1) is 80 to 150 mm; the thickness of the surface oxide scale removed in step (2) is 0.5 to 1 mm; the thickness of the rolled slab obtained in step (3) is 30 to 50 mm; the thickness of the hot-rolled slab obtained in step (5) is 6 to 10 mm; and the thickness of the finished rolled foil obtained in step (7) is 0.05 to 0.15 mm.

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