Anti-oxidation zero-coherence scattering alloy with BCC structure and preparation method of anti-oxidation zero-coherence scattering alloy

Abstract

The invention relates to the field of neutron scattering experiment materials, and provides a neutron diffraction peak-free anti-oxidation zero-coherence scattering alloy material with a single-phase BCC structure and suitable for a high-temperature neutron scattering experiment and a preparation method of the neutron diffraction peak-free anti-oxidation zero-coherence scattering alloy material. The alloy contains 37.07% of Ti, 59.95% of Ta and 2.98% of Al, the theoretical melting point is 1867 DEG C, no neutron diffraction peak exists, and the alloy can be used for preparing a sample containing container and a neutron beam window. The TiTaAl alloy has no neutron diffraction peak in an X-ray and neutron diffraction pattern, data interference can be avoided, and the quality of experimental data is improved. The TiZr alloy keeps high strength and high plasticity at a high temperature, and is suitable for a high-temperature experiment environment of 800 DEG C or above. After the material is oxidized for 80 hours in an atmospheric environment of 1000 DEG C, the oxidation weight gain is only 43mg / cm < 2 >, the oxidation resistance is excellent, and the reusability and economical efficiency of the material are improved; according to the method, accurate component control and efficient manufacturing are achieved by optimizing the steps of burdening, smelting, alloying, homogenizing treatment, forging and the like, the problems that an existing process is inaccurate in component control, low in efficiency, high in cost and the like are solved, and the product quality and the production efficiency are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of neutron scattering experimental materials, and in particular to a BCC structured, oxidation-resistant zero-coherence scattering alloy and a preparation method thereof. The alloy material can be used to prepare sample holding containers and neutron beam windows in neutron scattering experiments to meet the material performance requirements of high-temperature in-situ experiments. Background Art

[0002] Neutron scattering experiments, as an important tool for studying the microstructure and dynamic properties of matter, have broad applications in fields such as materials science, physics, and chemistry. In this experiment, the test samples come in a variety of forms, including solid, liquid, and powder, and require specialized sample containers placed in the test neutron beam. During the experiment, the neutron beam passes through the container containing the sample, interacting with it and acquiring neutron scattering data to analyze the sample's microstructure and dynamic properties.

[0003] However, the scattering signal from the sample container itself can significantly hinder data analysis, severely impacting data quality. Furthermore, the sample environment plays an increasingly important role in in-situ neutron testing. The complex structures and metal components within the sample environment further exacerbate the impact of external signals on neutron scattering data. To obtain high-quality neutron scattering data, neutron scattering experiments require strict control of the scattering background to prevent various background signal sources from impacting neutron scattering data quality.

[0004] At present, metallic vanadium, TiZr, and VNi alloys are generally used internationally as sample containers. However, existing materials have obvious limitations in high-temperature experimental environments. Metallic vanadium will undergo obvious embrittlement at temperatures exceeding 1200°C, and will also undergo rapid and catastrophic oxidation reactions at temperatures above 675°C, which seriously restricts its reusability and economy. Although TiZr zero-coherence scattering alloy has certain application potential, its melting point is only 1550°C. When the temperature exceeds 750°C, it will soften and undergo a recrystallization process, which greatly limits the application potential of this material under high-temperature experimental conditions. In addition, the existing VNi alloy also has oxidation and embrittlement problems at temperatures above 675°C, which makes it difficult to meet the needs of high-temperature neutron scattering experiments.

[0005] Currently, no suitable zero-coherent scattering alloy material is available internationally for high-temperature experimental environments above 800°C. Existing alloy manufacturing processes suffer from inaccurate composition control, low production efficiency, and high costs, making it difficult to produce alloys that meet the requirements of high-temperature neutron scattering experiments. Summary of the Invention

[0006] Based on the above problems, the present invention aims to develop a BCC structure (i.e., body-centered cubic structure) and oxidation-resistant zero-coherence scattering alloy with no neutron diffraction peaks, and a preparation method thereof, so as to improve the data quality and experimental efficiency of neutron scattering experiments.

[0007] The technical solution adopted by the present invention is: a BCC structure, oxidation-resistant zero coherent scattering alloy, the chemical composition of the alloy is as follows by weight: Ti37.07%, Ta59.95%, Al2.98%, and the rest are unavoidable impurities, and the theoretical melting point of the alloy is 1867 ° C, and there is no neutron diffraction peak.

[0008] The alloy was oxidized at 1000℃ for 2 hours, and the oxidation weight gain was not obvious; after oxidizing for 80 hours, the oxidation weight gain was only 43mg / cm 2 , showing excellent antioxidant properties.

[0009] The raw materials for preparing the alloy include bulk elemental Ti with a purity better than 99.99%, elemental Ta with a purity better than 99.99%, and elemental Al with a purity better than 99.999%.

[0010] The alloy raw materials need to be cleaned with 10% HCl solution before batching to remove the surface oxide layer.

[0011] A method for preparing a diffraction peak-free, oxidation-resistant, zero-coherence scattering alloy for high-temperature neutron scattering comprises the following steps:

[0012] Step 1, Proportioning: Prepare alloy raw materials with a ratio of 37.07Ti:59.95Ta:2.98Al (wt%) by mixing Ti with a purity better than 99.99%, Ta with a purity better than 99.99%, and Al with a purity better than 99.999%, and then clean the surface oxide layer with 10% HCl solution;

[0013] Step 2: Melting: Using vacuum suspension melting, first put Ti / Ta into the furnace for pre-melting at a melting power of 209kW for 5 minutes, then slowly reduce the power to the minimum, cool for 1 hour, and then take out of the furnace to obtain a TiTa alloy ingot;

[0014] Step 3: Alloying: The TiTa alloy ingot prepared in step 2 and the pure aluminum ingredient are placed in a furnace for smelting. The smelting powers are 235kW, 220kW, and 200kW, respectively. The smelting and refining time for each smelting and refining is 10 minutes, and the cooling time is 1 hour, to prepare kilogram-grade alloy ingots with uniform composition.

[0015] Step 4: Homogenization: Place the alloy ingot in a high-temperature furnace at 1000°C-1400°C for more than 24 hours of vacuum annealing (vacuum degree better than 5*10-3Pa) or annealing under Ar gas protection for homogenization;

[0016] Step 5: Forging: Forge the homogenized bar at a temperature above 1000°C to obtain bars or plates of ideal size.

[0017] In step 2, the vacuum degree during the smelting process is better than 5*10-3Pa or more.

[0018] In step 3, cooling treatment is performed after each smelting, and the cooling time is 1 hour.

[0019] In step 4, the homogenization treatment is performed by vacuum annealing or annealing under Ar gas protection.

[0020] The alloy exhibits excellent high strength and high plasticity at high temperatures.

[0021] The diffraction peak-free, oxidation-resistant zero-coherence scattering alloy for high-temperature neutron scattering or its preparation method is suitable for the manufacture of sample containers and neutron beam windows in neutron scattering experiments, and can effectively improve the data quality and experimental efficiency of neutron scattering experiments.

[0022] The beneficial effects of the present invention are as follows: the TiTaAl alloy of the present invention has no neutron diffraction peak in the neutron diffraction pattern, which can effectively avoid interference with neutron scattering data, significantly improve the data quality of neutron scattering experiments, and provide reliable guarantees for accurate analysis of sample microstructure and dynamic characteristics; the alloy of the present invention has a theoretical melting point of 1867°C, which is significantly improved compared with the existing TiZr alloy (melting point 1550°C), and can still maintain high strength and high plasticity at high temperatures, and can be stably used in high-temperature experimental environments above 800°C, meeting the mechanical performance requirements of high-temperature neutron scattering experiments for sample containers and neutron beam windows; after oxidation in an atmospheric environment at 1000°C for 80 hours, the oxidation weight gain of the TiTaAl alloy is only 43 mg / cm 2 , while V and VNi alloys undergo severe oxidation under these conditions. The alloy of the present invention exhibits excellent oxidation resistance, improves the material's reusability and affordability, and reduces experimental costs. By optimizing the batching, smelting, alloying, homogenization, and forging steps, the present invention achieves precise alloy composition control and an efficient manufacturing process, improving product quality and production efficiency. It addresses the problems of inaccurate composition control, low production efficiency, and high costs associated with existing alloy manufacturing processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The figure is a relationship diagram between the calculated Pandat phase diagram and the theoretical melting point of the TiTaAl alloy of the present invention;

[0024] Figure 2 The X-ray diffraction pattern of the TiTaAl alloy of the present invention has a typical BCC structure;

[0025] Figure 3 The neutron diffraction spectrum of the TiTaAl alloy of the present invention has no neutron diffraction peak;

[0026] Figure 4 It is the oxidation performance test result of the TiTaAl alloy of the present invention;

[0027] Figure 5 1 is a comparison chart of the mechanical properties of the TiTaAl alloy in the embodiment of the present invention and the current zero coherent scattering alloy;

[0028] Figure 6 Schematic diagram of high-temperature mechanical properties of TiTaAl alloy compared with TiZr alloy in an embodiment of the present invention; DETAILED DESCRIPTION

[0029] The following describes the specific implementation of the present invention in detail through specific embodiments in conjunction with the accompanying drawings:

[0030] like Figure 1-6 As shown, a diffraction peak-free, oxidation-resistant, zero-coherence scattering alloy for high-temperature neutron scattering is suitable for the manufacture of sample containers and neutron beam windows in neutron scattering experiments, and can effectively improve the data quality and experimental efficiency of neutron scattering experiments. It exhibits excellent high strength and high plasticity at high temperatures. The chemical composition of the alloy is as follows, by weight percentage: Ti 37.07%, Ta 59.95%, Al 2.98%, with the remainder being unavoidable impurities. The alloy has a theoretical melting point of 1867°C and no neutron diffraction peak.

[0031] The alloy was oxidized at 1000℃ for 2 hours, and the oxidation weight gain was not obvious; after oxidizing for 80 hours, the oxidation weight gain was only 43mg / cm 2 , showing excellent antioxidant properties.

[0032] The raw materials for preparing the alloy include bulk elemental Ti with a purity better than 99.99%, elemental Ta with a purity better than 99.99%, and elemental Al with a purity better than 99.999%.

[0033] The alloy raw materials need to be cleaned with 10% HCl solution before batching to remove the surface oxide layer.

[0034] A method for preparing a diffraction peak-free, oxidation-resistant, zero-coherence scattering alloy for high-temperature neutron scattering comprises the following steps:

[0035] Step 1, Proportioning: Prepare alloy raw materials with a ratio of 37.07Ti:59.95Ta:2.98Al (wt%) by mixing Ti with a purity better than 99.99%, Ta with a purity better than 99.99%, and Al with a purity better than 99.999%, and then clean the surface oxide layer with 10% HCl solution;

[0036] Step 2: Melting: Using vacuum suspension melting, first put Ti / Ta into the furnace for pre-melting at a melting power of 209kW for 5 minutes, then slowly reduce the power to the minimum, cool for 1 hour, and then take out of the furnace to obtain a TiTa alloy ingot;

[0037] Step 3: Alloying: The TiTa alloy ingot prepared in step 2 and the pure aluminum ingredient are placed in a furnace for smelting. The smelting powers are 235kW, 220kW, and 200kW, respectively. The smelting and refining time for each smelting and refining is 10 minutes, and the cooling time is 1 hour, to prepare kilogram-grade alloy ingots with uniform composition.

[0038] Step 4: Homogenization: Place the alloy ingot in a high-temperature furnace at 1000°C-1400°C for more than 24 hours of vacuum annealing (vacuum degree better than 5*10-3Pa) or annealing under Ar gas protection for homogenization;

[0039] Step 5: Forging: Forge the homogenized bar at a temperature above 1000°C to obtain bars or plates of ideal size.

[0040] In step 2, the vacuum degree during the smelting process is better than 5*10-3Pa or more.

[0041] In step 3, cooling treatment is performed after each smelting, and the cooling time is 1 hour.

[0042] In step 4, the homogenization treatment is performed by vacuum annealing or annealing under Ar gas protection.

[0043] Example 1

[0044] Step 1: Ingredients

[0045] The raw materials used were Ti (bulk element) with a purity better than 99.99%, Ta (element element) with a purity better than 99.99%, and Al (element element) with a purity better than 99.999%, in a ratio of 37.07 Ti: 59.95 Ta: 2.98 Al (wt%). The raw materials were washed in a 10% HCl solution to remove the surface oxide layer and ensure the purity of the raw materials.

[0046] Step 2: Melting

[0047] Using vacuum levitation melting technology, Ti and Ta are first placed in a melting furnace for pre-melting. The melting power is set at 209 kW for 5 minutes. The power is then slowly reduced to the minimum, maintaining a vacuum level better than 5×10-3 Pa. The ingot is then removed from the furnace after cooling for 1 hour to obtain a TiTa alloy ingot.

[0048] Step 3: Alloying

[0049] The TiTa alloy ingot obtained in step 2 was placed in a melting furnace along with the pure aluminum batch and smelted three times. The first smelting power was 235kW, the second smelting power was 220kW, and the third smelting power was reduced to 200kW. Each smelting and refining time was 10 minutes, and the cooling time was 1 hour to ensure uniform alloy composition. Finally, a kilogram-level TiTaAl alloy ingot was produced.

[0050] Step 4: Homogenization

[0051] The alloy ingot is placed in a high-temperature furnace and subjected to vacuum annealing treatment (vacuum degree better than 5×10-3Pa) at 1000℃-1400℃ for more than 24 hours, or annealing treatment is performed under Ar gas protection to achieve homogenization of the alloy.

[0052] Step 5: Forging

[0053] The homogenized alloy bars are forged at a temperature above 1000°C, and bars or plates of ideal size are obtained by controlling the forging process parameters.

[0054] Compared with the TiZr alloy in the prior art, the TiTaAl alloy prepared in this embodiment has no obvious oxidation weight gain after oxidation at 1000℃ for 2 hours; after oxidation for 80 hours, the oxidation weight gain is only 43mg / cm 2 , showing excellent oxidation resistance. At the same time, the theoretical melting point of TiTaAl alloy is 1867℃, which is significantly higher than the 1550℃ of TiZr alloy, and it can still maintain high strength and high plasticity at high temperatures.

[0055] Example 2

[0056] Step 1: Ingredients

[0057] Similar to Example 1, raw materials were selected according to the ratio of 37.07Ti:59.95Ta:2.98Al (wt%) and cleaned.

[0058] Steps 2 to 5: smelting, alloying, homogenizing and forging.

[0059] Steps 2 to 5 are exactly the same as those in Example 1. High-quality TiTaAl alloy rods or plates are prepared through precise melting, alloying, homogenization and forging processes.

[0060] The TiTaAl alloy prepared in this example exhibits excellent mechanical properties. Its yield strength is significantly higher than that of TiZr alloys over the temperature range from room temperature to 800°C. In particular, at 800°C, the yield strength of the TiTaAl alloy remains high, while the yield strength of the TiZr alloy drops significantly due to softening. Furthermore, the TiTaAl alloy exhibits excellent plasticity, meeting the stringent requirements for sample containers and neutron beam windows in high-temperature neutron scattering experiments.

[0061] In the embodiment, TiZr alloy and VNi alloy in the prior art are selected as comparative examples. Under the same high-temperature neutron scattering experimental conditions, TiZr alloy softens when the temperature exceeds 750°C and is accompanied by the occurrence of recrystallization process, which seriously affects its high-temperature mechanical properties. VNi alloy will undergo rapid and catastrophic oxidation reaction when the temperature is higher than 675°C, resulting in a sharp decline in material properties. In contrast, the TiTaAl alloy of the present invention can still maintain excellent mechanical properties and oxidation resistance under high-temperature experimental environments above 800°C, and has significant technical advantages.

[0062] In summary, the TiTaAl alloy of the present invention achieves a perfect combination of high strength, high plasticity, and excellent oxidation resistance through precise alloy composition control and efficient manufacturing process, providing an ideal sample container and neutron beam window material for high-temperature neutron scattering experiments.

Claims

1. A BCC structured, oxidation-resistant zero coherent scattering alloy, characterized by: The chemical composition of the alloy is as follows by weight: Ti 36.5-37.5%, Ta 59.5-60.5%, Al 2.7-3.1%, with the remainder being unavoidable impurities. The alloy has a theoretical melting point of 1867° C., a single-phase BCC structure, and no neutron diffraction peak.

2. The BCC structured, oxidation-resistant zero-coherent scattering alloy according to claim 1, characterized in that: The alloy was oxidized at 1000℃ for 2 hours, and the oxidation weight gain was not obvious; after oxidizing for 80 hours, the oxidation weight gain was only 43mg / cm 2 , showing excellent antioxidant properties.

3. The BCC structured, oxidation-resistant zero coherent scattering alloy according to claim 1 or 2, characterized in that: The raw materials for preparing the alloy include bulk elemental Ti with a purity better than 99.99%, elemental Ta with a purity better than 99.99%, and elemental Al with a purity better than 99.999%.

4. The anti-oxidation zero-coherence scattering alloy with no diffraction peak for high-temperature neutron scattering according to claim 3, characterized in that: The alloy raw materials need to be cleaned with 10% HCl solution before batching to remove the surface oxide layer.

5. A method for preparing a BCC structured, oxidation-resistant zero coherent scattering alloy, characterized by: The following steps are involved: Step 1: Proportioning: Prepare alloy raw materials with a ratio of 37.07Ti:59.95Ta:2.98Al (wt%) using bulk elemental Ti with a purity better than 99.99%, elemental Ta with a purity better than 99.99%, and elemental Al with a purity better than 99.999%. The alloy raw materials are then washed with a 10% HCl solution to remove the surface oxide layer. Step 2: Melting: Using vacuum suspension melting, first put Ti / Ta into the furnace for pre-melting at a melting power of 209kW for 5 minutes, then slowly reduce the power to the minimum, cool for 1 hour, and then take out of the furnace to obtain a TiTa alloy ingot; Step 3: Alloying: The TiTa alloy ingot prepared in step 2 and the pure aluminum ingredient are placed in a furnace for smelting. The smelting powers are 235kW, 220kW, and 200kW, respectively. The smelting and refining time for each smelting and refining is 10 minutes, and the cooling time is 1 hour, to prepare kilogram-grade alloy ingots with uniform composition. Step 4: Homogenization: Place the alloy ingot in a high-temperature furnace at 1000°C-1400°C for more than 24 hours in a vacuum annealing process (vacuum degree better than 5*10-3 Pa) or annealing under Ar gas protection for homogenization; Step 5: Forging: Forge the homogenized bar at a temperature above 1000°C to obtain bars or plates of ideal size.

6. The method for preparing a BCC structured, oxidation-resistant zero coherent scattering alloy according to claim 5, characterized in that: In step 2, the vacuum degree during the smelting process is better than 5*10-3 Pa or above.

7. The method for preparing a BCC structured, oxidation-resistant zero coherent scattering alloy according to claim 5, characterized in that: In step three, cooling treatment is performed after each smelting, and the cooling time is 1 hour.

8. The method for preparing a BCC structured, oxidation-resistant zero coherent scattering alloy according to claim 5, characterized in that: In step 4, the homogenization treatment is performed by vacuum annealing or annealing under Ar gas protection.

9. The method for preparing a BCC structured, oxidation-resistant zero coherent scattering alloy according to claim 5, characterized in that: The alloy exhibits excellent high strength and high plasticity at high temperatures.

10. The oxidation-resistant zero-coherence scattering alloy with no diffraction peak for high-temperature neutron scattering or the preparation method thereof according to any one of claims 1 to 9, characterized in that: The alloy or the preparation method is suitable for manufacturing sample holding containers and neutron beam windows in neutron scattering experiments, and can effectively improve the data quality and experimental efficiency of the neutron scattering experiments.

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