Method for measuring distribution state of zirconium element in al-zr alloy system and application thereof

Abstract

This application provides a method for measuring the Zr element distribution in an Al-Zr alloy system and its application. After dehydrating an aluminum-zirconium alloy sample, the first alloy phase is separated using separation solution A to prepare second alloy phase particles. These particles are then dissolved using solution B to prepare a second alloy phase solution. An equal volume of the aluminum-zirconium alloy sample is then dissolved using solution C to prepare an aluminum-zirconium alloy solution. Finally, inductively coupled plasma atomic emission spectrometry (ICP-AES) is used to measure the Zr content in both the second alloy phase solution and the aluminum-zirconium alloy solution, achieving quantitative measurement of the Zr element distribution in the Al-Zr alloy system. This method can accurately measure the Zr element distribution across the entire region, improve the detection sensitivity for low-concentration Zr, effectively distinguish the Zr content in different phases, and reduce nanoscale phase dissolution errors. It has the advantages of simple operation, good reproducibility, low implementation cost, and ease of widespread implementation.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of aluminum alloy preparation, and particularly relates to a method for measuring the distribution state of Zr elements in an Al-Zr alloy system and application thereof. BACKGROUND

[0002] In the prior art, aluminum alloy materials play a key role in the fields of power transmission, aerospace, etc. Zr elements, as important alloying elements, have a significant effect on improving the thermal stability and mechanical properties of materials. In the Al-Zr alloy system, Zr elements can be either solid-solved in the aluminum matrix or dispersedly precipitated in the form of Al3Zr intermetallic compounds. Research shows that the content ratio of the two existing states directly affects the comprehensive performance of the alloy: when Zr elements are solid-solved in the matrix, although solid-solution strengthening effect can be produced, the electrical conductivity of the material is significantly reduced; and when Zr elements form nanoscale Al3Zr phases, the thermal resistance and creep resistance of the alloy can be improved while maintaining high electrical conductivity. Therefore, accurate measurement of the quantitative distribution state of Zr elements in the two phases has important guiding significance for optimizing the design of aluminum alloy materials.

[0003] However, the current phase distribution measurement technology of Zr elements in Al-Zr alloys still has obvious defects. In the existing analysis method, although the transmission electron microscope (TEM) can qualitatively observe the morphology distribution of Al3Zr phases, it cannot realize quantitative statistics of Zr elements in the whole region; the X-ray diffraction (XRD) technology can indirectly calculate the content of precipitated phases, but the detection sensitivity of low-concentration Zr elements is insufficient, and it cannot distinguish the difference in Zr content between the solid-solution of the aluminum matrix and the precipitated phase. Further research shows that the traditional chemical phase analysis method will produce obvious dissolution error when dealing with nanoscale Al3Zr phases, resulting in deviation of the measurement results from the actual values.

[0004] These technical defects seriously restrict the research and development process of high-performance aluminum alloys. Due to the lack of accurate phase distribution data, it is difficult to establish an accurate composition-structure-performance relationship model in the research and development process of aluminum alloys, and only trial-and-error method can be used in the optimization of alloy composition, which greatly increases the research and development cost and time cycle. Especially in the development of high-conductivity heat-resistant aluminum alloys, how to balance the distribution ratio of Zr elements in the matrix solid solution and the precipitated phase still lacks reliable data support. Therefore, it is urgent to develop a measurement method that can accurately distinguish and quantitatively measure the distribution of Zr elements in different phases, so as to break through the technical bottleneck of the performance optimization of current aluminum alloy materials. SUMMARY

[0005] The application aims at solving the technical problems that the measurement technology of phase distribution of Zr element in Al-Zr alloy still has obvious defects in the prior art, quantitative statistics of Zr element in the whole area cannot be realized, the detection sensitivity of low-concentration Zr element is insufficient, the content difference of Zr element in the solid solution and precipitated phase of the aluminum matrix cannot be distinguished, and the traditional chemical phase analysis method will produce obvious dissolution error when processing nanoscale Al3Zr phase, and proposes a measurement method of Zr element distribution state in Al-Zr alloy system.

[0006] In order to solve the technical problems proposed in the application, the application further provides an application of the measurement method of Zr element distribution state in Al-Zr alloy system.

[0007] In order to solve the technical problems proposed in the application, the application further provides a preparation method of Al-Zr heat-resistant aluminum alloy.

[0008] The application adopts the following scheme, a measurement method of Zr element distribution state in Al-Zr alloy system, comprising the following steps:

[0009] Step 101. Obtain a target aluminum-zirconium alloy sample to be measured;

[0010] Step 102. The aluminum-zirconium alloy sample obtained in step 101 and the dehydrating agent are sequentially added into the reaction kettle, under the condition of room temperature and 100 rpm-200 rpm magnetic stirring, after reaction for 15 min-25 min, the dehydration treatment of the aluminum-zirconium alloy sample is completed;

[0011] Step 103. The aluminum-zirconium alloy sample after dehydration treatment in step 102 and separation liquid A are sequentially added into the reaction kettle, under the condition of 200℃-280℃ and 50 rpm-100 rpm magnetic stirring, after reaction for 15 min-30 min, the first alloy phase in the aluminum-zirconium alloy sample is dissolved, then the reaction system is sequentially filtered, washed and dried to obtain the second alloy phase particles;

[0012] Step 104. The second alloy phase particles separated in step 103 and the dissolving liquid B are sequentially put into the stirring kettle, after stirring until the second alloy phase particles are completely dissolved, the second alloy phase solution is obtained;

[0013] Step 105. An equal amount of target aluminum-zirconium alloy sample to be measured in step 101 and dissolving liquid C are put into the stirring kettle, after stirring until the target aluminum-zirconium alloy sample to be measured is completely dissolved, the aluminum-zirconium alloy solution is obtained;

[0014] Step 106. The second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 are transferred into an inductively coupled plasma emission spectrometer respectively, the content of Zr element in the two solutions is measured respectively, the content of Zr element in the second alloy phase solution is defined as a, the content of Zr element in the aluminum-zirconium alloy solution is defined as b, and the content of Zr element in the first alloy phase is b-a.

[0015] In some possible embodiments, the target aluminum-zirconium alloy sample to be measured in step 101 is composed of Zr, Fe, Si, the balance of Al and inevitable other impurity elements.

[0016] In some possible embodiments, the target aluminum-zirconium alloy sample to be measured in step 101 is in a granular form, and the particle size of the target aluminum-zirconium alloy sample to be measured ranges from 0.5 μm to 1 μm.

[0017] Illustratively, the median particle size of the target aluminum-zirconium alloy sample to be measured is 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm.

[0018] In some possible embodiments, the mass ratio of the target aluminum-zirconium alloy sample to be measured to the dehydrating agent in step 102 is 1: (1.5-2.5).

[0019] In some possible embodiments, the dehydrating agent in step 102 is selected from any one or a mixture of more than one of anhydrous phenol, o-cresol, m-cresol, p-cresol, p-chlorophenol, o-diphenol, methyl o-diphenol and pentachlorophenol.

[0020] In some possible embodiments, the first alloy phase in step 103 is an aluminum matrix phase, the second alloy phase is an Al3Zr phase, and the separation liquid A is selected from any one or a combination of more than one of benzyl alcohol, phenethyl alcohol, n-butyl alcohol, isoamyl alcohol, benzyl ether, o-phenylenedimethyl alcohol, phenylpropyl alcohol and α-methyl phenethyl alcohol.

[0021] In some possible embodiments, the mass ratio of the dehydrated aluminum-zirconium alloy sample to the separation liquid A in step 103 is 1: (1.5-2.5).

[0022] In some possible embodiments, the mass ratio of the second alloy phase particles to the dissolution liquid B in step 104 is 1: (5-10).

[0023] In step 105, the mass ratio of the target aluminum-zirconium alloy sample to be measured to the dissolution liquid C is 1: (20-25).

[0024] In some possible embodiments, the dissolution liquid B in step 104 is obtained by mixing hydrogen fluoride and nitric acid in a volume ratio of 1:2.

[0025] The dissolving solution C in step 105 is obtained by mixing hydrogen fluoride and nitric acid at a volume ratio of 1:1.

[0026] In order to solve the technical problems proposed in the present application, the present application further provides an application of a method for measuring the distribution state of Zr elements in an Al-Zr alloy system. The Zr element content measured by the method is used for quantitative evaluation of the distribution of Zr elements in the aluminum-zirconium alloy.

[0027] In order to solve the technical problems proposed in the present application, the present application further provides an aluminum alloy, which consists of the following components in mass percentage: Zr 0.2wt%-0.6wt%, Fe 0.01wt%-0.1wt%, Si 0.01wt%-0.15wt%, the balance of Al, and inevitable other impurity elements, and the total content of inevitable other impurity elements is less than or equal to 0.01wt%.

[0028] In order to solve the technical problems proposed in the present application, the present application further provides a preparation method of an aluminum alloy, which comprises the following steps:

[0029] Step 201. Preparation of materials

[0030] According to the target alloy ratio shown in Table 1, high-purity aluminum ingots, Al-Zr master alloys, high-purity iron powder, and Al-Si master alloys are sequentially put into alumina crucibles for standby;

[0031] Step 202. Melting

[0032] The alumina crucible in step 201 is transferred to a vacuum arc furnace, and after holding and melting at 780-820℃ for 2-3h, a first Al-Zr melt is obtained;

[0033] Step 203. Ultrasonic treatment

[0034] After the first Al-Zr melt prepared in step 202 is cooled to 730℃, an ultrasonic vibration probe preheated to 800℃ is inserted into the first Al-Zr melt to apply ultrasonic vibration. The ultrasonic vibration frequency of the ultrasonic vibration probe is 19-21kHz, and the ultrasonic vibration amplitude of the ultrasonic vibration probe is 35-70μm. After the ultrasonic vibration treatment is completed, a second Al-Zr melt is obtained;

[0035] Illustratively, the ultrasonic vibration amplitude of the ultrasonic vibration probe is 35μm, 38μm, 45μm, 48μm, 55μm, 58μm, 65μm, or 70μm.

[0036] Step 204. Casting

[0037] casting the second Al-Zr melt prepared in step 203 into a preform mold and cooling to form a crude Al-Zr heat-resistant aluminum alloy, the size of the ingot obtained by casting the second Al-Zr melt is as follows: 10x10x2mm 3 or 15x15x2mm 3 ;

[0038] Step 205. Heat treatment

[0039] The crude Al-Zr heat-resistant aluminum alloy prepared in step 204 is transferred to a heat treatment furnace, and the heat treatment is carried out until the electrical conductivity of the crude Al-Zr heat-resistant aluminum alloy is within the preset electrical conductivity range, and the heat treatment is completed, thereby obtaining the finished Al-Zr heat-resistant aluminum alloy.

[0040] (2) The heat treatment of the crude Al-Zr heat-resistant aluminum alloy includes the following steps:

[0041] Step 301. The crude Al-Zr heat-resistant aluminum alloy is transferred to a heat treatment furnace and heat treated at 400℃;

[0042] Step 302. After heat treatment for 5h, the crude Al-Zr heat-resistant aluminum alloy is taken out of the heat treatment furnace and its electrical conductivity is measured with an electrical conductivity meter;

[0043] Step 303. Repeat the above steps, and when the measured electrical conductivity reaches 60%IACS-70%IACS, the heat treatment is completed, thereby obtaining the finished Al-Zr heat-resistant aluminum alloy.

[0044] Compared with the prior art, the present application has the following beneficial effects:

[0045] The application provides a method for measuring the distribution state of Zr elements in an Al-Zr alloy system and an application thereof. After dehydration treatment of an aluminum-zirconium alloy sample, a first alloy phase in the aluminum-zirconium alloy sample is separated by using a separation liquid A, second alloy phase particles are prepared, the second alloy phase particles are dissolved by using a dissolving liquid B to prepare a second alloy phase solution, an equal amount of aluminum-zirconium alloy sample is dissolved by using a dissolving liquid C to prepare an aluminum-zirconium alloy solution, and finally, the content of Zr elements in the second alloy phase solution and the content of Zr elements in the aluminum-zirconium alloy solution are measured by using an inductively coupled plasma emission spectrometer, so that quantitative measurement of the distribution of Zr elements in the Al-Zr alloy system is realized. The method can accurately measure the distribution of Zr elements in the whole region, improve the detection sensitivity of low-concentration Zr elements, effectively distinguish the content of Zr elements in different phases, reduce the dissolution error of nanoscale phases, has the advantages of simple operation, good reproducibility, low implementation cost, high raw material utilization rate, and easy popularization and implementation. BRIEF DESCRIPTION OF DRAWINGS

[0046] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiment description will be briefly introduced.

[0047] Figure 1 is a preparation process schematic diagram of an Al-Zr heat-resistant aluminum alloy according to the present application;

[0048] Figure 2 is a binary alloy phase diagram of an Al-Zr heat-resistant aluminum alloy according to the present application;

[0049] Figure 3 is a schematic diagram of the morphology structure of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy according to the present application;

[0050] Figure 4 is an SEM image of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiments 1-3 and Comparative Example 1 according to the present application;

[0051] (a) is an SEM image of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Comparative Example 1 according to the present application;

[0052] (b) is an SEM image of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiment 1 according to the present application;

[0053] (c) is an SEM image of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiment 2 according to the present application;

[0054] (d) is an SEM image of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiment 3 according to the present application;

[0055] Figure 5 is a size distribution diagram of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiments 1-3 and Comparative Example 1 according to the present application;

[0056] (a) is a size distribution diagram of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Comparative Example 1 according to the present application;

[0057] (b) is a size distribution diagram of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiment 1 according to the present application;

[0058] (c) is a size distribution diagram of an Al3Zr compound in an Al-Zr heat-resistant aluminum alloy sample prepared in step 101 in Embodiment 2 according to the present application;

[0059] (d) is a size distribution diagram of Al3Zr compounds in the Al-Zr heat-resistant aluminum alloy sample prepared in step 101 of Example 3 of this application;

[0060] Figure 6 This is an aspect ratio distribution diagram of Al3Zr compounds in the Al-Zr heat-resistant aluminum alloy samples prepared in step 101 of Examples 1-3 and Comparative Example 1 of this application;

[0061] (a) is a diagram showing the aspect ratio distribution of Al3Zr compounds in the Al-Zr heat-resistant aluminum alloy sample prepared in step 101 of Comparative Example 1 of this application;

[0062] (b) is a diagram showing the aspect ratio distribution of Al3Zr compounds in the Al-Zr-based heat-resistant aluminum alloy sample prepared in step 101 of Example 1 of this application;

[0063] (c) is a diagram showing the aspect ratio distribution of Al3Zr compounds in the Al-Zr heat-resistant aluminum alloy sample prepared in step 101 of Example 2 of this application;

[0064] (d) is the aspect ratio distribution of Al3Zr compounds in the Al-Zr heat-resistant aluminum alloy sample prepared in step 101 of Example 3 of this application;

[0065] Figure 7 This is a diagram showing the average size and number density distribution of Al3Zr compounds in the Al-Zr heat-resistant aluminum alloy samples prepared in step 101 of Examples 1-3 and Comparative Example 1 of this application;

[0066] Figure 8 These are SEM images of the second alloy phase particles (Al3Zr compound) separated in step 103 of Examples 1-3 and Comparative Example 1 of this application;

[0067] (a) is a SEM image of the second alloy phase particles (Al3Zr compound) separated in step 103 of Comparative Example 1 of this application;

[0068] (b) is a SEM image of the second alloy phase particles (Al3Zr compound) separated in step 103 of Example 1 of this application;

[0069] (c) is a SEM image of the second alloy phase particles (Al3Zr compound) separated in step 103 of Example 2 of this application;

[0070] (d) is a SEM image of the second alloy phase particles (Al3Zr compound) separated in step 103 of Example 3 of this application;

[0071] Figure 9This is a graph showing the measurement results of the Zr element content distribution in the Al-Zr heat-resistant aluminum alloy samples in step 101 of Examples 1-3 and Comparative Example 1 of this application. Detailed Implementation

[0072] Combination such as Figures 1-9 The following Examples 1-3 and Comparative Example 1 further illustrate this technical solution. Example 1

[0073] (1) The preparation method of aluminum alloy includes the following steps:

[0074] Step 201. Material preparation

[0075] According to the target alloy ratio shown in Table 1, high-purity aluminum ingots, Al-Zr master alloy, high-purity iron powder and Al-Si master alloy were sequentially added into an alumina crucible for later use.

[0076] Step 202. Smelting

[0077] The alumina crucible from step 201 is transferred to a vacuum arc furnace and melted at 780°C for 2 hours to obtain the first Al-Zr melt.

[0078] Step 203. Ultrasonic treatment

[0079] After the first Al-Zr melt prepared in step 202 is cooled to 730°C, an ultrasonic vibration probe preheated to 800°C is inserted into the first Al-Zr melt to apply ultrasonic vibration. The ultrasonic vibration frequency of the ultrasonic vibration probe is 19kHz and the ultrasonic vibration amplitude is 38μm. After the ultrasonic vibration treatment is completed, the second Al-Zr melt is obtained.

[0080] Step 204. Casting

[0081] The second Al-Zr melt prepared in step 203 is poured into a pre-made mold and cooled to form a crude Al-Zr heat-resistant aluminum alloy. The ingot size obtained from the casting of the second Al-Zr melt is as follows: 10×10×2mm. 3 Or 15×15×2mm 3 ;

[0082] Step 205. Heat Treatment

[0083] The crude Al-Zr heat-resistant aluminum alloy prepared in step 204 is transferred to a heat treatment furnace and heat-treated until the electrical conductivity of the crude Al-Zr heat-resistant aluminum alloy is within the preset electrical conductivity range. The heat treatment is then completed, and the finished Al-Zr heat-resistant aluminum alloy is obtained.

[0084] (2) The heat treatment of crude Al-Zr heat-resistant aluminum alloy includes the following steps:

[0085] Step 301. Transfer the crude Al-Zr heat-resistant aluminum alloy to a heat treatment furnace and hold it at 400°C;

[0086] Step 302. After each heat treatment of 5 hours, the crude Al-Zr heat-resistant aluminum alloy is taken out of the heat treatment furnace and its conductivity is measured with a conductivity meter.

[0087] Step 303. Repeat the above steps. When the measured conductivity reaches 60% IACS, the heat treatment is completed, and the Al-Zr heat-resistant aluminum alloy product is obtained.

[0088] (3) A method for measuring the distribution state of Zr element in an Al-Zr alloy system, comprising the following steps:

[0089] Step 101. Use a drilling machine (model: E-Value DP-375V) to drill the Al-Zr heat-resistant aluminum alloy product prepared in step 303 to obtain an Al-Zr heat-resistant aluminum alloy sample with a median particle size of 0.5 μm;

[0090] Step 102. Add the aluminum-zirconium alloy sample obtained in step 101 and phenol to the reaction vessel in a mass ratio of 1:1.5. After reacting for 15 minutes at room temperature and with magnetic stirring at 100 rpm, the dehydration treatment of the aluminum-zirconium alloy sample is completed.

[0091] Step 103. Add the dehydrated aluminum-zirconium alloy sample from step 102 and benzyl alcohol to the reaction vessel in a mass ratio of 1:1.5. After reacting for 15 minutes at 250°C and 50 rpm with magnetic stirring, dissolve the first alloy phase in the aluminum-zirconium alloy sample. Then, filter, wash and dry the reaction system to obtain the second alloy phase particles.

[0092] Step 104. Add the second alloy phase particles obtained in step 103 and the solution B into the stirred tank in a mass ratio of 1:5. Stir until the second alloy phase particles are completely dissolved to obtain the second alloy phase solution.

[0093] Solution B was obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:2;

[0094] Step 105. Take an equal amount of the target aluminum-zirconium alloy sample and the solution C from Step 101 and put them into a stirring vessel at a mass ratio of 1:20. Stir until the target aluminum-zirconium alloy sample is completely dissolved to obtain the aluminum-zirconium alloy solution.

[0095] The solution C is obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:1;

[0096] Step 106. Transfer the second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 to an inductively coupled plasma atomic emission spectrometer, respectively, and measure the Zr content in the two solutions. Define the Zr content in the second alloy phase solution as a, the Zr content in the aluminum-zirconium alloy solution as b, and the Zr content in the first alloy phase as ba. Example 2

[0097] (1) The preparation method of aluminum alloy includes the following steps:

[0098] Step 201. Material preparation

[0099] According to the target alloy ratio shown in Table 1, high-purity aluminum ingots, Al-Zr master alloy, high-purity iron powder and Al-Si master alloy were sequentially added into an alumina crucible for later use.

[0100] Step 202. Smelting

[0101] The alumina crucible from step 201 is transferred to a vacuum arc furnace and melted at 800°C for 3 hours to obtain the first Al-Zr melt.

[0102] Step 203. Ultrasonic treatment

[0103] After the first Al-Zr melt prepared in step 202 is cooled to 730°C, an ultrasonic vibration probe preheated to 800°C is inserted into the first Al-Zr melt to apply ultrasonic vibration. The ultrasonic vibration frequency of the ultrasonic vibration probe is 20kHz and the ultrasonic vibration amplitude is 48μm. After the ultrasonic vibration treatment is completed, the second Al-Zr melt is obtained.

[0104] Step 204. Casting

[0105] The second Al-Zr melt prepared in step 203 is poured into a pre-made mold and cooled to form a crude Al-Zr heat-resistant aluminum alloy. The ingot size obtained from the casting of the second Al-Zr melt is as follows: 10×10×2mm. 3 Or 15×15×2mm 3 ;

[0106] Step 205. Heat Treatment

[0107] The crude Al-Zr heat-resistant aluminum alloy prepared in step 204 is transferred to a heat treatment furnace and heat-treated until the electrical conductivity of the crude Al-Zr heat-resistant aluminum alloy is within the preset electrical conductivity range. The heat treatment is then completed, and the finished Al-Zr heat-resistant aluminum alloy is obtained.

[0108] (2) The heat treatment of crude Al-Zr heat-resistant aluminum alloy includes the following steps:

[0109] Step 301. Transfer the crude Al-Zr heat-resistant aluminum alloy to a heat treatment furnace and hold it at 400°C;

[0110] Step 302. After each heat treatment of 5 hours, the crude Al-Zr heat-resistant aluminum alloy is taken out of the heat treatment furnace and its conductivity is measured with a conductivity meter.

[0111] Step 303. Repeat the above steps. When the measured conductivity reaches 60% IACS, the heat treatment is completed, and the Al-Zr heat-resistant aluminum alloy product is obtained.

[0112] (3) A method for measuring the distribution state of Zr element in an Al-Zr alloy system, comprising the following steps:

[0113] Step 101. Use a drilling machine (model: E-Value DP-375V) to drill the Al-Zr heat-resistant aluminum alloy product prepared in step 303 to obtain an Al-Zr heat-resistant aluminum alloy sample with a median particle size of 0.7 μm;

[0114] Step 102. Add the aluminum-zirconium alloy sample obtained in step 101 and phenol to the reaction vessel in a mass ratio of 1:2. After reacting for 20 minutes at room temperature and with magnetic stirring at 150 rpm, the dehydration treatment of the aluminum-zirconium alloy sample is completed.

[0115] Step 103. Add the dehydrated aluminum-zirconium alloy sample from step 102 and benzyl alcohol to the reaction vessel in a mass ratio of 1:2. After reacting for 20 minutes at 250°C and 80 rpm with magnetic stirring, dissolve the first alloy phase in the aluminum-zirconium alloy sample. Then, filter, wash, and dry the reaction system to obtain the second alloy phase particles.

[0116] Step 104. Add the second alloy phase particles obtained in step 103 and the solution B into the stirred tank in a mass ratio of 1:7, and stir until the second alloy phase particles are completely dissolved to obtain the second alloy phase solution.

[0117] Solution B was obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:2;

[0118] Step 105. Take an equal amount of the target aluminum-zirconium alloy sample and the solution C from Step 101 and put them into a stirring vessel at a mass ratio of 1:23. Stir until the target aluminum-zirconium alloy sample is completely dissolved to obtain the aluminum-zirconium alloy solution.

[0119] The solution C is obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:1;

[0120] Step 106. Transfer the second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 to an inductively coupled plasma atomic emission spectrometer, respectively, and measure the Zr content in the two solutions. Define the Zr content in the second alloy phase solution as a, the Zr content in the aluminum-zirconium alloy solution as b, and the Zr content in the first alloy phase as ba. Example 3

[0121] (1) The preparation method of aluminum alloy includes the following steps:

[0122] Step 201. Material preparation

[0123] According to the target alloy ratio shown in Table 1, high-purity aluminum ingots, Al-Zr master alloy, high-purity iron powder and Al-Si master alloy were sequentially added into an alumina crucible for later use.

[0124] Step 202. Smelting

[0125] The alumina crucible from step 201 is transferred to a vacuum arc furnace and melted at 820°C for 3 hours to obtain the first Al-Zr melt.

[0126] Step 203. Ultrasonic treatment

[0127] After the first Al-Zr melt prepared in step 202 is cooled to 730°C, an ultrasonic vibration probe preheated to 800°C is inserted into the first Al-Zr melt to apply ultrasonic vibration. The ultrasonic vibration frequency of the ultrasonic vibration probe is 21kHz and the ultrasonic vibration amplitude is 58μm. After the ultrasonic vibration treatment is completed, the second Al-Zr melt is obtained.

[0128] Step 204. Casting

[0129] The second Al-Zr melt prepared in step 203 is poured into a pre-made mold and cooled to form a crude Al-Zr heat-resistant aluminum alloy. The ingot size obtained from the casting of the second Al-Zr melt is as follows: 10×10×2mm. 3 Or 15×15×2mm 3 ;

[0130] Step 205. Heat Treatment

[0131] The crude Al-Zr heat-resistant aluminum alloy prepared in step 204 is transferred to a heat treatment furnace and heat-treated until the electrical conductivity of the crude Al-Zr heat-resistant aluminum alloy is within the preset electrical conductivity range. The heat treatment is then completed, and the finished Al-Zr heat-resistant aluminum alloy is obtained.

[0132] (2) The heat treatment of crude Al-Zr heat-resistant aluminum alloy includes the following steps:

[0133] Step 301. Transfer the crude Al-Zr heat-resistant aluminum alloy to a heat treatment furnace and hold it at 400°C;

[0134] Step 302. After each heat treatment of 5 hours, the crude Al-Zr heat-resistant aluminum alloy is taken out of the heat treatment furnace and its conductivity is measured with a conductivity meter.

[0135] Step 303. Repeat the above steps. When the measured conductivity reaches 60% IACS, the heat treatment is completed, and the Al-Zr heat-resistant aluminum alloy product is obtained.

[0136] (3) A method for measuring the distribution state of Zr element in an Al-Zr alloy system, comprising the following steps:

[0137] Step 101. Use a drilling machine (model: E-Value DP-375V) to drill the Al-Zr heat-resistant aluminum alloy product prepared in step 303 to obtain an Al-Zr heat-resistant aluminum alloy sample with a median particle size of 1 μm.

[0138] Step 102. Add the aluminum-zirconium alloy sample obtained in step 101 and phenol to the reaction vessel in a mass ratio of 1:2.5. After reacting for 25 minutes at room temperature and with magnetic stirring at 200 rpm, the dehydration treatment of the aluminum-zirconium alloy sample is completed.

[0139] Step 103. Add the dehydrated aluminum-zirconium alloy sample from step 102 and benzyl alcohol to the reaction vessel in a mass ratio of 1:2.5. After reacting for 30 minutes at 250°C and 100 rpm with magnetic stirring, dissolve the first alloy phase in the aluminum-zirconium alloy sample. Then, filter, wash and dry the reaction system to obtain the second alloy phase particles.

[0140] Step 104. Add the second alloy phase particles obtained in step 103 and the solution B into the stirred tank in a mass ratio of 1:10. Stir until the second alloy phase particles are completely dissolved to obtain the second alloy phase solution.

[0141] Solution B was obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:2;

[0142] Step 105. Take an equal amount of the target aluminum-zirconium alloy sample and the solution C from Step 101 and put them into a stirring vessel at a mass ratio of 1:25. Stir until the target aluminum-zirconium alloy sample is completely dissolved to obtain the aluminum-zirconium alloy solution.

[0143] The solution C is obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:1;

[0144] Step 106. Transfer the second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 to an inductively coupled plasma atomic emission spectrometer, respectively, and measure the Zr content in the two solutions. Define the Zr content in the second alloy phase solution as a, the Zr content in the aluminum-zirconium alloy solution as b, and the Zr content in the first alloy phase as ba.

[0145] Comparative Example 1

[0146] (1) The preparation method of aluminum alloy includes the following steps:

[0147] Step 201. Material preparation

[0148] According to the target alloy ratio shown in Table 1, high-purity aluminum ingots, Al-Zr master alloy, high-purity iron powder and Al-Si master alloy were sequentially added into an alumina crucible for later use.

[0149] Step 202. Smelting

[0150] The alumina crucible from step 201 is transferred to a vacuum electric arc furnace and smelted at 780℃-820℃ for 2-3 hours to obtain the first Al-Zr melt.

[0151] Step 203. Casting

[0152] The first Al-Zr melt prepared in step 202 is poured into a pre-made mold and cooled to form a crude Al-Zr heat-resistant aluminum alloy. The ingot size obtained by casting the second Al-Zr melt is as follows: 10×10×2mm. 3 Or 15×15×2mm 3 ;

[0153] Step 205. Heat Treatment

[0154] The crude Al-Zr heat-resistant aluminum alloy prepared in step 204 is transferred to a heat treatment furnace and heat-treated until the electrical conductivity of the crude Al-Zr heat-resistant aluminum alloy is within the preset electrical conductivity range. The heat treatment is then completed, and the finished Al-Zr heat-resistant aluminum alloy is obtained.

[0155] (2) The heat treatment of crude Al-Zr heat-resistant aluminum alloy includes the following steps:

[0156] Step 301. Transfer the crude Al-Zr heat-resistant aluminum alloy to a heat treatment furnace and hold it at 400°C;

[0157] Step 302. After each heat treatment of 5 hours, the crude Al-Zr heat-resistant aluminum alloy is taken out of the heat treatment furnace and its conductivity is measured with a conductivity meter.

[0158] Step 303. Repeat the above steps. When the measured conductivity reaches 60% IACS, the heat treatment is completed, and the Al-Zr heat-resistant aluminum alloy product is obtained.

[0159] (3) A method for measuring the distribution state of Zr element in an Al-Zr alloy system, comprising the following steps:

[0160] Step 101. Use a drilling machine (model: E-Value DP-375V) to drill the Al-Zr heat-resistant aluminum alloy product prepared in step 303 to obtain an Al-Zr heat-resistant aluminum alloy sample with a median particle size of 1 μm.

[0161] Step 102. Add the aluminum-zirconium alloy sample obtained in step 101 and phenol to the reaction vessel in a mass ratio of 1:2.5. After reacting for 25 minutes at room temperature and with magnetic stirring at 200 rpm, the dehydration treatment of the aluminum-zirconium alloy sample is completed.

[0162] Step 103. Add the dehydrated aluminum-zirconium alloy sample from step 102 and benzyl alcohol to the reaction vessel in a mass ratio of 1:2.5. After reacting for 30 minutes at 250°C and 100 rpm with magnetic stirring, dissolve the first alloy phase in the aluminum-zirconium alloy sample. Then, filter, wash and dry the reaction system to obtain the second alloy phase particles.

[0163] Step 104. Add the second alloy phase particles obtained in step 103 and the solution B into the stirred tank in a mass ratio of 1:10. Stir until the second alloy phase particles are completely dissolved to obtain the second alloy phase solution.

[0164] Solution B was obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:2;

[0165] Step 105. Take an equal amount of the target aluminum-zirconium alloy sample and the solution C from Step 101 and put them into a stirring vessel at a mass ratio of 1:25. Stir until the target aluminum-zirconium alloy sample is completely dissolved to obtain the aluminum-zirconium alloy solution.

[0166] The solution C is obtained by mixing hydrogen fluoride (50 wt%) and nitric acid (65 wt%) in a volume ratio of 1:1;

[0167] Step 106. Transfer the second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 to an inductively coupled plasma atomic emission spectrometer, respectively, and measure the Zr content in the two solutions. Define the Zr content in the second alloy phase solution as a, the Zr content in the aluminum-zirconium alloy solution as b, and the Zr content in the first alloy phase as ba.

[0168] The Zr element distribution in the aluminum-zirconium alloys of Examples 1-3 and Comparative Example 1 is shown in Table 2 below.

[0169] Table 1 Alloy composition table for Examples 1-3 and Comparative Example 1

[0170]

[0171] Table 2. Zr content distribution in aluminum-zirconium alloys of Examples 1-3 and Comparative Example 1

[0172]

[0173] The Al-Zr heat-resistant aluminum alloy products prepared in Examples 1-3 and Comparative Example 1 were subjected to the following tests:

[0174] Test 1: The second alloy phase particles prepared in step 103 were observed using a scanning electron microscope (SEM);

[0175] The Al-Zr heat-resistant aluminum alloy samples prepared in step 101 were observed using a scanning electron microscope (SEM).

[0176] like Figure 3 As shown, specifically, by measuring the total coverage area of ​​approximately 1mm 2 The Al3Zr compound samples were analyzed, focusing on their particle number density, aspect ratio, and average size. Ten SEM images were randomly acquired at 100x magnification, and the particle number density of the Al3Zr compound was calculated. Subsequently, the magnification was increased to 500x, and further SEM images were taken. To determine the aspect ratio and average size of the particles, ImageJ software was used to perform calculations based on formulas (1) and (2), respectively.

[0177] Formula (1): ;

[0178] Formula (2): .

[0179] Test 2: The dimensions are 15×15×2mm respectively. 3The change in electrical conductivity of Al-Zr-based heat-resistant aluminum alloy samples with heat treatment time during heat treatment is presented. The electrical conductivity of the Al-Zr-based heat-resistant aluminum alloy samples is expressed as a percentage relative to the International Standard for Annealed Copper (IACS) conductivity. The test results are as follows: Figures 4-9 And as shown in Table 3.

[0180] Table 3. Trend of conductivity with heat treatment time in Test 2

[0181]

[0182] Depend on Figures 4-9 As can be seen from the test results in Tables 2 and 3, Figures 4-7 The SEM microstructure (two-dimensional morphology), size distribution, aspect ratio distribution, average size, and number density statistics of Al3Zr compounds under different ultrasonic treatment intensities are presented. Without ultrasonic treatment, the Al3Zr compounds exhibit a relatively coarse morphology, such as... Figure 4 As shown in (a), after being treated with ultrasound at 38 µm, the Al3Zr compound exhibits a needle-like morphology, as shown in [the image]. Figure 4 As shown in (b), as the ultrasonic intensity increased to 48 µm, the needle-like Al3Zr compound was transformed into a rod-like shape, as... Figure 4 As shown in (c), when the ultrasonic intensity continued to increase to 58 µm, the Al3Zr compound became more rounded. Figure 5 As shown, without ultrasonic treatment, the size distribution of Al3Zr compounds ranges from 15µm to 70µm. However, when the ultrasonic intensity is 38µm and 48µm, the size of Al3Zr compounds decreases significantly. When the ultrasonic intensity continues to increase to 58µm, the size distribution of Al3Zr compounds is similar to that without ultrasonic treatment. Figure 6 The aspect ratio distribution of Al3Zr compounds under different ultrasonic intensities was revealed. This result clearly shows that as the ultrasonic intensity increases, the Al3Zr compounds are modified into more rounded morphologies. (Comparison) Figure 4 Although the size distribution of Al3Zr compounds was similar after treatment with ultrasound and after treatment with 58µm ultrasound, treatment with ultrasound significantly reduced the aspect ratio of Al3Zr compounds, resulting in more rounded Al3Zr. Figure 7 The average size and number density distribution of Al3Zr compounds under different ultrasonic intensities are shown. First, the ultrasonic probe was preheated to 800°C, at which point the processing temperature of the first Al-Zr melt was 790°C (slightly below the precipitation temperature of Al3Zr compounds), followed by casting. Therefore, at this temperature, the number of Al3Zr compounds remained relatively low regardless of whether ultrasonic treatment was performed. However, even so, the... Figure 7It can be seen that ultrasound still significantly promotes the formation of Al3Zr compounds at this temperature; regarding the average size, after treatment with 38µm ultrasound, the average size of Al3Zr compounds first decreases significantly, and then increases significantly with the increase of ultrasound intensity.

[0183] Figure 8 The three-dimensional morphology of the Al3Zr compound after chemical separation is shown below: Without ultrasonic treatment, the Al3Zr compound exhibits a plate-like morphology with a certain thickness (less than 1 µm). It is noteworthy that these Al3Zr plates have very sharp edges. When 38 µm ultrasonic treatment is introduced, the thickness of the Al3Zr plate increases, and the edge sharpness decreases. With increasing ultrasonic intensity to 48 µm and 58 µm, the Al3Zr plate, in addition to continuing to increase in thickness, is gradually modified into a more rounded morphology. The results described above are consistent with... Figure 4 The morphology of the tissues under two-dimensional SEM images was consistent. In summary, ultrasonic treatment facilitates the formation of Al3Zr compounds, and the Zr elemental distribution test results in Table 2 further confirm this conclusion.

[0184] Figure 9 The results of Zr content distribution measurements were revealed. The red dashed line represents the Zr content distribution of the Al-0.4%Zr alloy under thermodynamic equilibrium (75% of Zr is distributed in the Al3Zr alloy phase): As the ultrasonic intensity increased from 0 to 38µm and 48µm, the Zr content in the Al3Zr alloy phase significantly increased from less than 35% to approximately 55%. With a further increase in ultrasonic intensity to 58µm, although the Zr content in the Al3Zr alloy phase decreased, it was still significantly higher than under conditions without ultrasonic treatment. Table 3 shows the conductivity test results. As the ultrasonic intensity increased from 0 to 38µm and 48µm, the conductivity significantly increased from approximately 50% IACS to approximately 60% IACS, and the heat treatment time decreased significantly. In summary, ultrasound promotes the distribution of Zr in the Al3Zr compound, and this effect increases with increasing ultrasonic intensity; correspondingly, the alloy conductivity is positively correlated with the distribution of Zr in the Al3Zr compound.

[0185] This invention provides a method for measuring the Zr element distribution in an Al-Zr alloy system. After dehydrating an aluminum-zirconium alloy sample, the first alloy phase is separated using separation solution A to prepare second alloy phase particles. These particles are then dissolved using solution B to prepare a second alloy phase solution. An equal volume of the aluminum-zirconium alloy sample is then dissolved using solution C to prepare an aluminum-zirconium alloy solution. Finally, inductively coupled plasma atomic emission spectrometry (ICP-AES) is used to measure the Zr content in both the second alloy phase solution and the aluminum-zirconium alloy solution. This method enables quantitative measurement of the Zr element distribution in the Al-Zr alloy system. It can accurately measure the Zr element distribution across the entire region, improve the detection sensitivity for low-concentration Zr, effectively distinguish the Zr content in different phases, reduce nanoscale phase dissolution errors, and quantitatively analyze the impact of Zr distribution in Al3Zr compounds on the electrical conductivity of aluminum-zirconium alloys. This facilitates optimization of the aluminum-zirconium alloy processing technology during production, reduces heat treatment time, and provides guidance and reference for the mass production of aluminum-zirconium alloys.

[0186] Based on the measurement method for Zr element distribution in the Al-Zr alloy system proposed in this application, it is known that ultrasonic treatment promotes the incorporation of more Zr into the Al3Zr compound. In terms of the three-dimensional morphology of the Al3Zr compound, this is reflected in the increased thickness and smoother edges of thin Al3Zr compound plates with sharp edges under ultrasonic treatment. Specifically, the formation process of the Al3Zr compound is diffusion-controlled. In the Al-Zr alloy system, the growth of the Al3Zr compound is controlled by the mass transfer of Zr in the liquid metal. Since the Zr concentration in the liquid phase is extremely low, and the stoichiometry of the Al3Zr compound requires three atoms of Al and one atom of Zr to simultaneously adhere to the crystal surface, Zr diffusion becomes the limiting step in crystal growth. Without external disturbance, a relatively thick diffusion boundary layer forms near the crystal surface, causing the crystal to grow slowly mainly through confined diffusion, forming a thin, sheet-like morphology extending along the {001} crystal plane. By introducing ultrasonic treatment, the collapse of cavitation bubbles generates directional microjet streams that act on the large planar surface of the Al3Zr compound crystal. The localized convection induced by microjets significantly weakens the diffusion boundary layer thickness, thereby improving Zr transport efficiency. Consequently, the crystal growth rate accelerates with enhanced mass transfer, particularly along the previously slow-growing {001} crystal plane, leading to a transformation from lamellar to bulk crystals. Furthermore, in the cavitation region, the microjets simultaneously induce localized heating and partial dissolution of Al3Zr compound particles. These thermodynamic processes further promote crystal edge rounding and crystal reconstruction, specifically manifested as blunted crystal edges and rounded contours. In summary, ultrasound-induced microjets not only enhance the mass transfer efficiency of Zr in liquid metals but also achieve control over the thickness and morphology of Al3Zr compound crystals through coupled thermal / dissolution effects. This optimizes the production process of aluminum-zirconium alloys, reduces heat treatment time, and facilitates mass production.

[0187] The embodiments provided by the present invention have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of the present invention. The descriptions of the embodiments above are merely for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A method for measuring the distribution state of Zr element in an Al-Zr alloy system, characterized in that, Includes the following steps: Step 101. Obtain the target aluminum-zirconium alloy sample to be tested; Step 102. Add the aluminum-zirconium alloy sample obtained in step 101 and the dehydrating agent to the reaction vessel in sequence. Under the conditions of room temperature and magnetic stirring at 100 rpm-200 rpm, react for 15 min-25 min to complete the dehydration treatment of the aluminum-zirconium alloy sample. Step 103. Add the dehydrated aluminum-zirconium alloy sample and separation liquid A from step 102 into the reaction vessel in sequence. Under the conditions of 200℃-280℃ and magnetic stirring at 50rpm-100rpm, react for 15min-30min to dissolve the first alloy phase in the aluminum-zirconium alloy sample. Then, filter, wash and dry the reaction system in sequence to obtain the second alloy phase particles. Step 104. The second alloy phase particles separated in step 103 and the solution B are sequentially added into a stirred tank and stirred until the second alloy phase particles are completely dissolved to obtain the second alloy phase solution. Step 105. Take an equal amount of the target aluminum-zirconium alloy sample and the solution C from step 101 and put them into a stirring vessel. Stir until the target aluminum-zirconium alloy sample is completely dissolved to obtain the aluminum-zirconium alloy solution. Step 106. Transfer the second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 to an inductively coupled plasma atomic emission spectrometer, respectively, and measure the Zr content in the two solutions. Define the Zr content in the second alloy phase solution as a, the Zr content in the aluminum-zirconium alloy solution as b, and the Zr content in the first alloy phase as ba.

2. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, The target aluminum-zirconium alloy sample to be tested in step 101 consists of Zr, Fe, Si, balance Al, and other unavoidable impurity elements.

3. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, In step 101, the target aluminum-zirconium alloy sample to be tested is granular, and the particle size range of the target aluminum-zirconium alloy sample to be tested is 0.5μm-1μm.

4. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, In step 102, the mass ratio of the target aluminum-zirconium alloy sample to the dehydrating agent is 1:(1.5-2.5).

5. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, In step 102, the dehydrating agent is selected from any one or a mixture of one or more of anhydrous phenol, o-cresol, m-cresol, p-cresol, p-chlorophenol, catechol, methyl catechol, and pentachlorophenol.

6. The method for measuring the Zr element distribution state in an Al-Zr alloy system according to claim 1, characterized in that, In step 103, the first alloy phase is an aluminum matrix phase, the second alloy phase is an Al3Zr phase, and the separation liquid A is selected from any one or more of benzyl alcohol, phenethyl alcohol, n-butanol, isoamyl alcohol, anisole, o-phenylenediethanol, phenylpropanol, and α-methylphenylethanol.

7. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, In step 103, the mass ratio of the dehydrated aluminum-zirconium alloy sample to the separation liquid A is 1:(1.5-2.5).

8. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, In step 104, the mass ratio of the second alloy phase particles to the solution B is 1:(5-10). In step 105, the mass ratio of the target aluminum-zirconium alloy sample to the solution C is 1:(20-25).

9. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that, In step 104, solution B is obtained by mixing hydrogen fluoride and nitric acid in a volume ratio of 1:2; In step 105, solution C is obtained by mixing hydrogen fluoride and nitric acid in a volume ratio of 1:

1.

10. The application of the method for measuring the Zr element distribution state in an Al-Zr alloy system according to any one of claims 1-9, characterized in that, The distribution of Zr in aluminum-zirconium alloys is quantitatively evaluated using the Zr content measured by the aforementioned method.

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