Method for measuring distribution state of Zr element in Al-Zr alloy system and application thereof

Abstract

According to the method for measuring the distribution state of the Zr element in the Al-Zr alloy system and the application of the method, after the aluminum-zirconium alloy sample is subjected to dehydration treatment, the first alloy phase in the aluminum-zirconium alloy sample is separated through the separation liquid A, and the second alloy phase particles are prepared; dissolving the second alloy phase particles by using a dissolving solution B to prepare a second alloy phase solution, and dissolving the same amount of an aluminum-zirconium alloy sample by using a dissolving solution C to prepare an aluminum-zirconium alloy solution; finally, the content of the Zr element in the second alloy phase solution and the content of the Zr element in the aluminum-zirconium alloy solution are measured through the inductively coupled plasma emission spectrometer, quantitative measurement of Zr element distribution in the Al-Zr alloy system is achieved, the Zr element distribution of the whole area can be accurately measured, the detection sensitivity of the low-concentration Zr element is improved, and the detection cost is reduced. The method effectively distinguishes the Zr element content in different phases, reduces the dissolution error of the nanoscale phase, and has the advantages of simplicity in operation, good reproducibility, low implementation cost and convenience in popularization and implementation.

Description

Technical Field

[0001] The present application belongs to the technical field of aluminum alloy preparation, and specifically relates to a method for measuring the distribution state of the Zr element in an Al-Zr alloy system and its application. Background Art

[0002] In the existing technology, aluminum alloy materials play a key role in the fields of power transmission, aerospace, etc. Among them, Zr, as an important alloying element, has a significant effect on improving the thermal stability and mechanical properties of materials. In the Al-Zr alloy system, Zr can be dissolved in the aluminum matrix or dispersed and precipitated in the form of Al3Zr intermetallic compounds. Studies have shown that the content ratio of these two existence states directly affects the comprehensive properties of the alloy: when Zr is dissolved in the matrix, although it can produce a solid solution strengthening effect, it will significantly reduce the electrical conductivity of the material; when Zr forms a nanoscale Al3Zr phase, it can maintain a high electrical conductivity while improving the heat resistance and creep resistance of the alloy. Therefore, accurately determining the quantitative distribution state of Zr in the two phases is of great guiding significance for optimizing the design of aluminum alloy materials.

[0003] However, current techniques for measuring the phase distribution of Zr in Al-Zr alloys still have significant limitations. Among existing analytical methods, transmission electron microscopy (TEM) can qualitatively observe the morphological distribution of the Al3Zr phase, but cannot achieve quantitative analysis of Zr across the entire region. X-ray diffraction (XRD) can indirectly estimate the content of precipitated phases, but its sensitivity is insufficient for detecting low concentrations of Zr and it cannot distinguish between Zr content in the aluminum matrix solid solution and in the precipitated phase. Furthermore, studies have shown that traditional chemical phase analysis methods can produce significant dissolution errors when dealing with nanoscale Al3Zr phases, causing measurement results to deviate from actual values.

[0004] These technical defects seriously restrict the research and development 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 during the research and development of aluminum alloys. When optimizing the alloy composition, only trial and error methods can be adopted, which greatly increases the research and development costs and time cycle. In particular, when developing highly conductive and heat-resistant aluminum alloys, how to balance the distribution ratio of Zr elements in the matrix solid solution and precipitation phase still lacks reliable data support. Therefore, it is urgent to develop a measurement method that can accurately distinguish and quantitatively determine the distribution of Zr elements in different phases in order to break through the current technical bottleneck of optimizing the performance of aluminum alloy materials. Summary of the Invention

[0005] In order to solve the technical problems in the existing technology that the phase distribution measurement technology of Zr element in Al-Zr alloy still has obvious defects, such as the inability to achieve quantitative statistics of Zr elements in the entire area, insufficient detection sensitivity of low-concentration Zr elements, inability to distinguish the difference in Zr element content in the solid solution and precipitation phase of the aluminum matrix, and obvious dissolution errors in the traditional chemical phase analysis method when processing nano-scale Al3Zr phase, this application proposes a method for measuring the distribution state of Zr element in Al-Zr alloy system.

[0006] In order to solve the technical problem raised in this application, this application also provides an application of a method for measuring the distribution state of the Zr element in an Al-Zr alloy system.

[0007] In order to solve the technical problem raised in this application, this application also provides a method for preparing an Al-Zr series heat-resistant aluminum alloy.

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

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

[0010] Step 102. The aluminum-zirconium alloy sample obtained in step 101 and the dehydrating agent are sequentially added to a reactor, and the mixture is reacted for 15-25 minutes at room temperature and with magnetic stirring at 100-200 rpm to complete the dehydration of the aluminum-zirconium alloy sample.

[0011] Step 103. The aluminum-zirconium alloy sample and separated liquid A after the dehydration treatment in step 102 are sequentially added to a reaction kettle. The mixture is reacted for 15-30 minutes at 200°C-280°C and 50-100 rpm with magnetic stirring to dissolve the first alloy phase in the aluminum-zirconium alloy sample. The reaction system is then filtered, washed, and dried to obtain second alloy phase particles.

[0012] Step 104. The second alloy phase particles separated in step 103 and the dissolving solution B are sequentially added into a stirring kettle and stirred until the second alloy phase particles are completely dissolved, thereby obtaining a second alloy phase solution.

[0013] Step 105. Place an equal amount of the target aluminum-zirconium alloy sample and dissolving solution C in step 101 into a stirring vessel and stir until the target aluminum-zirconium alloy sample is completely dissolved, thereby obtaining an aluminum-zirconium alloy solution.

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

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

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

[0017] Illustratively, the median particle sizes of the target aluminum-zirconium alloy samples to be tested are 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, and 1 μm.

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

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

[0020] In some possible embodiments, 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 of benzyl alcohol, phenylethyl alcohol, n-butanol, isoamyl alcohol, anisole, o-phthalic alcohol, phenylpropyl alcohol, and α-methylphenylethyl alcohol, or a combination of more than one.

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

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

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

[0024] In some possible embodiments, the dissolving solution B in step 104 is prepared by mixing hydrogen fluoride and nitric acid in a volume ratio of 1:2;

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

[0026] In order to solve the technical problem raised in this application, this application also provides an application of a method for measuring the distribution state of the Zr element in an Al-Zr alloy system, and the Zr element content measured by the method is used to quantitatively evaluate the distribution of the Zr element in the aluminum-zirconium alloy.

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

[0028] In order to solve the technical problem raised in this application, this application also provides a method for preparing an aluminum alloy, which comprises the following steps:

[0029] Step 201. Prepare materials

[0030] According to the target alloy ratio shown in Table 1, high-purity aluminum ingot, Al-Zr master alloy, high-purity iron powder and Al-Si master alloy were sequentially placed into an alumina crucible for later use;

[0031] Step 202. Melting

[0032] The alumina crucible in step 201 is transferred to a vacuum arc furnace and smelted at 780° C. to 820° C. for 2 to 3 hours to obtain a first Al-Zr melt;

[0033] Step 203. Ultrasonic treatment

[0034] 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 19 kHz to 21 kHz, and the ultrasonic vibration amplitude of the ultrasonic vibration probe is 35 μm to 70 μm. 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 35 μm, 38 μm, 45 μm, 48 μm, 55 μm, 58 μm, 65 μm, or 70 μm.

[0036] Step 204. Casting

[0037] The second Al-Zr melt prepared in step 203 is cast into a prefabricated mold and cooled to form a rough Al-Zr heat-resistant aluminum alloy. The ingot specifications obtained by the second Al-Zr melt casting are as follows: 10×10×2 mm 3 or 15×15×2mm 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 heat treated until the electrical conductivity of the crude Al-Zr heat-resistant aluminum alloy is within a preset electrical conductivity range. The heat treatment is completed to obtain a finished Al-Zr heat-resistant aluminum alloy product.

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

[0041] Step 301: Transfer the crude Al-Zr heat-resistant aluminum alloy to a heat treatment furnace and keep it at 400°C;

[0042] Step 302. After each 5-hour heat treatment, the crude Al-Zr heat-resistant aluminum alloy is removed from the heat treatment furnace and its conductivity is measured using a conductivity meter.

[0043] Step 303: Repeat the above steps. When the measured electrical conductivity reaches 60% IACS-70% IACS, the heat treatment is completed, and the Al-Zr heat-resistant aluminum alloy product is obtained.

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

[0045] The present application provides a method for measuring the distribution state of Zr elements in an Al-Zr alloy system and its application. The method comprises the following steps: dehydrating an aluminum-zirconium alloy sample, separating a first alloy phase in the aluminum-zirconium alloy sample using a separation liquid A to prepare second alloy phase particles, dissolving the second alloy phase particles using a dissolving liquid B to prepare a second alloy phase solution, and then dissolving an equal amount of the aluminum-zirconium alloy sample using a dissolving liquid C to prepare an aluminum-zirconium alloy solution. Finally, an inductively coupled plasma emission spectrometer is used to respectively measure the Zr element content in the second alloy phase solution and the Zr element content in the aluminum-zirconium alloy solution, thereby achieving quantitative measurement of the Zr element distribution in the Al-Zr alloy system. The method can accurately measure the Zr element distribution in the entire region, improve the detection sensitivity of low-concentration Zr elements, effectively distinguish the Zr element content in different phases, and reduce nanoscale phase dissolution errors. The method has the advantages of simple operation, good reproducibility, low implementation cost, high raw material utilization, and easy promotion and implementation. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for describing the embodiments.

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

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

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

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

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

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

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

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

[0055] Figure 5 is a size distribution diagram of Al3Zr compounds in the Al-Zr series heat-resistant aluminum alloy samples prepared in step 101 in Examples 1-3 of the present application and Comparative Example 1;

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

[0057] (b) is a size distribution diagram of Al3Zr compounds in the Al-Zr series heat-resistant aluminum alloy sample prepared in step 101 in Example 1 of the present application;

[0058] (c) is a size distribution diagram of Al3Zr compounds in the Al-Zr series heat-resistant aluminum alloy sample prepared in step 101 in Example 2 of 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 in Example 3 of the present application;

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

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

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

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

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

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

[0066] Figure 8 is an SEM image of the second alloy phase particles (Al3Zr compound) separated in step 103 in Examples 1-3 of the present application and Comparative Example 1;

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

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

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

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

[0071] Figure 9This is a graph showing the distribution of Zr element content in the Al-Zr series heat-resistant aluminum alloy samples in step 101 in Examples 1-3 of the present application and Comparative Example 1. DETAILED DESCRIPTION

[0072] Combined with Figure 1-9 The following Examples 1-3 and Comparative Example 1 further illustrate the present technical solution. Example 1

[0073] (1) The method for preparing the aluminum alloy comprises the following steps:

[0074] Step 201. Prepare materials

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

[0076] Step 202. Melting

[0077] The alumina crucible in step 201 is transferred to a vacuum arc furnace and smelted at 780° C. for 2 hours to obtain a 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 19 kHz, and the ultrasonic vibration amplitude of the ultrasonic vibration probe is 38 μm. After the ultrasonic vibration treatment is completed, a second Al-Zr melt is obtained.

[0080] Step 204. Casting

[0081] The second Al-Zr melt prepared in step 203 is cast into a prefabricated mold and cooled to form a rough Al-Zr heat-resistant aluminum alloy. The ingot specifications obtained by the second Al-Zr melt casting are as follows: 10×10×2 mm 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 a preset electrical conductivity range. The heat treatment is completed to obtain a finished Al-Zr heat-resistant aluminum alloy product.

[0084] (2) The heat treatment of crude Al-Zr series 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 keep it at 400°C;

[0086] Step 302. After each 5-hour heat treatment, the crude Al-Zr heat-resistant aluminum alloy is removed from the heat treatment furnace and its conductivity is measured using a conductivity meter.

[0087] Step 303: Repeat the above steps. When the measured electrical 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 elements in an Al-Zr alloy system includes 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. The aluminum-zirconium alloy sample obtained in step 101 and phenol are added to a reactor in a mass ratio of 1:1.5, and the reaction is carried out at room temperature and magnetic stirring at 100 rpm for 15 minutes to complete the dehydration treatment of the aluminum-zirconium alloy sample.

[0091] Step 103. The aluminum-zirconium alloy sample dehydrated in step 102 and benzyl alcohol are sequentially added to a reactor in a mass ratio of 1:1.5. The mixture is reacted at 250° C. and 50 rpm with magnetic stirring for 15 minutes to dissolve the first alloy phase in the aluminum-zirconium alloy sample. The reaction system is then filtered, washed, and dried to obtain second alloy phase particles.

[0092] Step 104. Add the second alloy phase particles separated in step 103 and dissolving solution B in a mass ratio of 1:5 into a stirring kettle, and stir until the second alloy phase particles are completely dissolved to obtain a second alloy phase solution;

[0093] Solution B was prepared 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 to be tested and dissolving solution C in step 101 at a mass ratio of 1:20 and put them into a stirring kettle, and stir until the target aluminum-zirconium alloy sample to be tested is completely dissolved, thereby obtaining an aluminum-zirconium alloy solution;

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

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

[0097] (1) The method for preparing the aluminum alloy comprises the following steps:

[0098] Step 201. Prepare materials

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

[0100] Step 202. Melting

[0101] The alumina crucible in step 201 is transferred to a vacuum arc furnace and smelted at 800° C. for 3 hours to obtain a 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 20 kHz, and the ultrasonic vibration amplitude of the ultrasonic vibration probe is 48 μm. After the ultrasonic vibration treatment is completed, a second Al-Zr melt is obtained.

[0104] Step 204. Casting

[0105] The second Al-Zr melt prepared in step 203 is cast into a prefabricated mold and cooled to form a rough Al-Zr heat-resistant aluminum alloy. The ingot specifications obtained by the second Al-Zr melt casting are as follows: 10×10×2 mm 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 a preset electrical conductivity range. The heat treatment is completed to obtain a finished Al-Zr heat-resistant aluminum alloy product.

[0108] (2) The heat treatment of crude Al-Zr series 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 keep it at 400°C;

[0110] Step 302. After each 5-hour heat treatment, the crude Al-Zr heat-resistant aluminum alloy is removed from the heat treatment furnace and its conductivity is measured using a conductivity meter.

[0111] Step 303: Repeat the above steps. When the measured electrical 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. The aluminum-zirconium alloy sample obtained in step 101 and phenol are added to a reactor in a mass ratio of 1:2, and the reaction is carried out at room temperature and 150 rpm magnetic stirring for 20 minutes to complete the dehydration treatment of the aluminum-zirconium alloy sample;

[0115] Step 103. The aluminum-zirconium alloy sample dehydrated in step 102 and benzyl alcohol are added to a reactor in a mass ratio of 1:2. The mixture is reacted at 250° C. and 80 rpm with magnetic stirring for 20 minutes to dissolve the first alloy phase in the aluminum-zirconium alloy sample. The reaction system is then filtered, washed, and dried to obtain second alloy phase particles.

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

[0117] Solution B was prepared 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 to be tested and dissolving solution C in step 101 at a mass ratio of 1:23 and put them into a stirring kettle, stirring until the target aluminum-zirconium alloy sample to be tested is completely dissolved, thereby obtaining an aluminum-zirconium alloy solution;

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

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

[0121] (1) The method for preparing the aluminum alloy comprises the following steps:

[0122] Step 201. Prepare materials

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

[0124] Step 202. Melting

[0125] The alumina crucible in step 201 is transferred to a vacuum arc furnace and smelted at 820° C. for 3 hours to obtain a 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 21 kHz, and the ultrasonic vibration amplitude of the ultrasonic vibration probe is 58 μm. After the ultrasonic vibration treatment is completed, a second Al-Zr melt is obtained.

[0128] Step 204. Casting

[0129] The second Al-Zr melt prepared in step 203 is cast into a prefabricated mold and cooled to form a rough Al-Zr heat-resistant aluminum alloy. The ingot specifications obtained by the second Al-Zr melt casting are as follows: 10×10×2 mm 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 a preset electrical conductivity range. The heat treatment is completed to obtain a finished Al-Zr heat-resistant aluminum alloy product.

[0132] (2) The heat treatment of crude Al-Zr series 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 keep it at 400°C;

[0134] Step 302. After each 5-hour heat treatment, the crude Al-Zr heat-resistant aluminum alloy is removed from the heat treatment furnace and its conductivity is measured using a conductivity meter.

[0135] Step 303: Repeat the above steps. When the measured electrical 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. The aluminum-zirconium alloy sample obtained in step 101 and phenol are added to the reactor in a mass ratio of 1:2.5, and the reaction is carried out at room temperature and 200 rpm magnetic stirring for 25 minutes to complete the dehydration treatment of the aluminum-zirconium alloy sample;

[0139] Step 103. The aluminum-zirconium alloy sample dehydrated in step 102 and benzyl alcohol are sequentially added to a reactor in a mass ratio of 1:2.5. The mixture is reacted at 250° C. and 100 rpm with magnetic stirring for 30 minutes to dissolve the first alloy phase in the aluminum-zirconium alloy sample. The reaction system is then filtered, washed, and dried to obtain second alloy phase particles.

[0140] Step 104. Add the second alloy phase particles separated in step 103 and dissolving solution B in a mass ratio of 1:10 into a stirring kettle, and stir until the second alloy phase particles are completely dissolved to obtain a second alloy phase solution;

[0141] Solution B was prepared 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 to be tested and dissolving solution C in step 101 at a mass ratio of 1:25 and put them into a stirring kettle, stirring until the target aluminum-zirconium alloy sample to be tested is completely dissolved, thereby obtaining an aluminum-zirconium alloy solution;

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

[0144] Step 106. The second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 are respectively transferred to an inductively coupled plasma emission spectrometer, and the Zr content in the two solutions is measured respectively. The measured Zr content in the second alloy phase solution is defined as a, the measured Zr content in the aluminum-zirconium alloy solution is defined as b, and the Zr content in the first alloy phase is defined as ba.

[0145] Comparative Example 1

[0146] (1) The method for preparing the aluminum alloy comprises the following steps:

[0147] Step 201. Prepare materials

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

[0149] Step 202. Melting

[0150] The alumina crucible in step 201 is transferred to a vacuum arc furnace and smelted at 780° C. to 820° C. for 2 to 3 hours to obtain a first Al-Zr melt;

[0151] Step 203. Casting

[0152] The first Al-Zr melt prepared in step 202 is cast into a prefabricated mold and cooled to form a rough Al-Zr heat-resistant aluminum alloy. The ingot specifications obtained by casting the second Al-Zr melt are 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 a preset electrical conductivity range. The heat treatment is completed to obtain a finished Al-Zr heat-resistant aluminum alloy product.

[0155] (2) The heat treatment of crude Al-Zr series 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 keep it at 400°C;

[0157] Step 302. After each 5-hour heat treatment, the crude Al-Zr heat-resistant aluminum alloy is removed from the heat treatment furnace and its conductivity is measured using a conductivity meter.

[0158] Step 303: Repeat the above steps. When the measured electrical 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. The aluminum-zirconium alloy sample obtained in step 101 and phenol are added to the reactor in a mass ratio of 1:2.5, and the reaction is carried out at room temperature and 200 rpm magnetic stirring for 25 minutes to complete the dehydration treatment of the aluminum-zirconium alloy sample;

[0162] Step 103. The aluminum-zirconium alloy sample dehydrated in step 102 and benzyl alcohol are sequentially added to a reactor in a mass ratio of 1:2.5. The mixture is reacted at 250° C. and 100 rpm with magnetic stirring for 30 minutes to dissolve the first alloy phase in the aluminum-zirconium alloy sample. The reaction system is then filtered, washed, and dried to obtain second alloy phase particles.

[0163] Step 104. Add the second alloy phase particles separated in step 103 and dissolving solution B in a mass ratio of 1:10 into a stirring kettle, and stir until the second alloy phase particles are completely dissolved to obtain a second alloy phase solution;

[0164] Solution B was prepared 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 to be tested and dissolving solution C in step 101 at a mass ratio of 1:25 and put them into a stirring kettle, stirring until the target aluminum-zirconium alloy sample to be tested is completely dissolved, thereby obtaining an aluminum-zirconium alloy solution;

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

[0167] Step 106. The second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 are respectively transferred to an inductively coupled plasma emission spectrometer, and the Zr content in the two solutions is measured respectively. The measured Zr content in the second alloy phase solution is defined as a, the measured Zr content in the aluminum-zirconium alloy solution is defined as b, and the Zr content in the first alloy phase is defined as ba.

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

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

[0170]

[0171] Table 2 Zr element content distribution in aluminum-zirconium alloys in 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: Observe the second alloy phase particles prepared in step 103 using a scanning electron microscope (SEM);

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

[0176] like Figure 3 As shown, specifically, by covering a total area of ​​about 1mm 2 The Al3Zr compound sample was analyzed, focusing on its particle number density, aspect ratio, and average size. Ten SEM images at 100x magnification were randomly collected to calculate the number density of the Al3Zr compound particles. 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 size specifications are 15×15×2mm respectively 3The conductivity of the finished Al-Zr heat-resistant aluminum alloy sample changes with heat treatment time during heat treatment. The conductivity of the finished Al-Zr heat-resistant aluminum alloy is expressed as a percentage of the International Annealed Copper Standard Conductivity (IACS) conductivity. The test results are as follows: Figure 4-9 And shown in Table 3.

[0180] Table 3 Trend of conductivity change with heat treatment time in test 2

[0181]

[0182] Depend on Figure 4-Figure 9 As can be seen from the test results in Table 2-Table 3, Figure 4-Figure 7 The SEM microstructure (two-dimensional morphology), size distribution, aspect ratio distribution, average size and number density statistics of Al3Zr compounds under different ultrasonic intensities are shown. Without ultrasonic treatment, the morphology of Al3Zr compounds is relatively coarse, such as Figure 4 (a) After 38µm ultrasonic treatment, the Al3Zr compound morphology is needle-like, as shown in Figure 4 As shown in (b). As the ultrasonic intensity increases to 48µm, the needle-like Al3Zr compound is changed into a rod-like shape, as shown in Figure 4 As shown in (c). When the ultrasonic intensity continues to increase to 58µm, the Al3Zr compound becomes more rounded. Figure 5 As shown in the figure, without ultrasonic treatment, the size distribution of Al3Zr compounds is between 15µm and 70µm, but when the ultrasonic intensity is 38µm and 48µm, the size of Al3Zr compounds decreases significantly. When the ultrasonic intensity is further increased 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. The results clearly showed that with the increase of ultrasonic intensity, Al3Zr compounds were modified into a more rounded morphology. Figure 4 ,Although the size distribution of Al3Zr compounds is similar after no ultrasonic treatment and 58µm ultrasonic treatment, ultrasonic treatment significantly reduces the aspect ratio of Al3Zr compounds, i.e., more rounded Al3Zr. Figure 7 The average size and number density distribution of Al3Zr compounds under different ultrasonic intensities are shown. First, since the ultrasonic vibration probe is preheated to 800℃, the treatment temperature of the first Al-Zr melt is 790℃ (slightly lower than the precipitation temperature of Al3Zr compounds) and then casting is performed. Therefore, at this temperature, regardless of whether ultrasonic treatment is performed or not, the number of Al3Zr compounds is at a relatively low level. However, even so, Figure 7It can be seen that ultrasound still significantly promotes the formation of Al3Zr compounds at this temperature; as for the average size, after 38µm ultrasonic treatment, the average size of Al3Zr compounds first decreases significantly, and then with the increase of ultrasonic intensity, the size of Al3Zr compounds increases significantly.

[0183] Figure 8 The three-dimensional morphology of the Al3Zr compound after chemical separation: Without ultrasonic treatment, the three-dimensional morphology of the Al3Zr compound is a plate with a certain thickness (less than 1µm). It should be noted that the edges of these Al3Zr compound plates are very sharp; when 38µm ultrasonic treatment is introduced, the thickness of the Al3Zr compound plate increases and the edge sharpness decreases; as the ultrasonic intensity increases to 48µm and 58µm, the Al3Zr compound plate not only continues to increase in thickness, but is gradually modified into a more rounded morphology. The above results are consistent with Figure 4 In summary, ultrasonic treatment is conducive to the formation of Al3Zr compounds, and the Zr element distribution test results in Table 2 further confirm this conclusion.

[0184] Figure 9 The Zr content distribution measurement results are revealed. The red dashed line represents the Zr content distribution of the Al-0.4%Zr alloy at thermodynamic equilibrium (75% of the Zr is distributed in the Al3Zr alloy phase). As the ultrasonic intensity increases from 0 to 38µm and 48µm, the Zr content in the Al3Zr alloy phase significantly increases from less than 35% to approximately 55%. As the ultrasonic intensity further increases to 58µm, although the Zr content in the Al3Zr alloy phase decreases, it is still significantly higher than that under the condition without ultrasonic treatment. Table 3 shows the conductivity test results. As the ultrasonic intensity increases from 0 to 38µm and 48µm, the conductivity significantly increases from approximately 50% IACS to approximately 60% IACS, and the heat treatment time is significantly reduced. In summary, ultrasound has the effect of promoting 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] The present invention provides a method for measuring the distribution state of Zr in an Al-Zr alloy system. The method comprises the following steps: dehydrating an aluminum-zirconium alloy sample, separating a first alloy phase in the aluminum-zirconium alloy sample using a separation liquid A to prepare second alloy phase particles, dissolving the second alloy phase particles using a dissolving liquid B to prepare a second alloy phase solution, then dissolving an equal amount of the aluminum-zirconium alloy sample using a dissolving liquid C to prepare an aluminum-zirconium alloy solution, and finally using an inductively coupled plasma emission spectrometer to respectively measure the Zr content in the second alloy phase solution and the Zr content in the aluminum-zirconium alloy solution. This method achieves quantitative measurement of the Zr element distribution in the Al-Zr alloy system. The method can accurately measure the Zr element distribution in the entire region, improve the detection sensitivity of low-concentration Zr elements, effectively distinguish the Zr element content in different phases, reduce nanoscale phase dissolution errors, and quantitatively analyze the effect of the distribution of Zr elements in Al3Zr compounds on the electrical conductivity of the aluminum-zirconium alloy. This method facilitates optimization of the processing technology of the aluminum-zirconium alloy during production, reduces the heat treatment time of the aluminum-zirconium alloy, and provides directional guidance and reference for the mass production of aluminum-zirconium alloys.

[0186] Combined with the proposed method for measuring the distribution of Zr in an Al-Zr alloy system, ultrasonic treatment promotes the incorporation of Zr into the Al3Zr compound. This is reflected in the three-dimensional morphology of the Al3Zr compound, where thin, sharp-edged Al3Zr plates become thicker and their edges smoother under ultrasonic treatment. Specifically, the Al3Zr compound formation process is diffusion-controlled. In Al-Zr alloy systems, Al3Zr compound growth is governed by the mass transfer of Zr in the liquid metal. Because the Zr concentration in the liquid phase is extremely low, and the stoichiometric ratio of the Al3Zr compound requires the simultaneous attachment of three atoms of Al and one atom of Zr to the crystal surface, Zr diffusion becomes the limiting step in crystal growth. In the absence of external disturbances, a thick diffusion boundary layer forms near the crystal surface, leading to slow, diffusion-restricted growth, resulting in a thin, flake-like morphology extending along the {001} crystal plane. By introducing ultrasonic treatment, the collapse of cavitation bubbles generates directional microjets that act on the large, flat surfaces of the Al3Zr compound crystal. The local convection induced by the microjet significantly weakens the thickness of the diffusion boundary layer, thereby improving the transport efficiency of Zr. As a result, the crystal growth rate accelerates with the enhanced mass transfer, especially in the direction of the originally slow-growing {001} crystal plane, resulting in a transformation of the crystal from a thin flake to a thick block. In addition, the microjet simultaneously induces local heating and partial dissolution of the Al3Zr compound particles in the cavitation zone. These thermodynamic processes further promote crystal edge rounding and crystal reconstruction, specifically manifested as blunting of crystal edges and rounding of the contours. In summary, the ultrasound-induced microjet not only enhances the mass transfer efficiency of Zr in liquid metal, but also achieves the regulation of the thickness and morphology of the Al3Zr compound crystals through the coupled heat / dissolution effect, thereby optimizing the production process of aluminum-zirconium alloy, reducing the heat treatment time of aluminum-zirconium alloy, and facilitating the mass production of aluminum-zirconium alloy.

[0187] The embodiments provided by the present invention are described in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only intended to help understand the method and core concept of the present invention. It should be noted that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection 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: The following steps are involved: Step 101. Obtain a target aluminum-zirconium alloy sample to be tested; Step 102. The aluminum-zirconium alloy sample obtained in step 101 and the dehydrating agent are sequentially added to a reactor, and the mixture is reacted for 15-25 minutes at room temperature and with magnetic stirring at 100-200 rpm to complete the dehydration of the aluminum-zirconium alloy sample. Step 103. The aluminum-zirconium alloy sample and separated liquid A after the dehydration treatment in step 102 are sequentially added to a reaction kettle. The mixture is reacted for 15-30 minutes at 200°C-280°C and 50-100 rpm with magnetic stirring to dissolve the first alloy phase in the aluminum-zirconium alloy sample. The reaction system is then filtered, washed, and dried to obtain second alloy phase particles. Step 104. The second alloy phase particles separated in step 103 and the dissolving solution B are sequentially added into a stirring kettle and stirred until the second alloy phase particles are completely dissolved, thereby obtaining a second alloy phase solution. Step 105. Place an equal amount of the target aluminum-zirconium alloy sample and dissolving solution C in step 101 into a stirring vessel and stir until the target aluminum-zirconium alloy sample is completely dissolved, thereby obtaining an aluminum-zirconium alloy solution. Step 106. The second alloy phase solution prepared in step 104 and the aluminum-zirconium alloy solution prepared in step 105 are respectively transferred to an inductively coupled plasma emission spectrometer, and the Zr content in the two solutions is measured respectively. The measured Zr content in the second alloy phase solution is defined as a, the measured Zr content in the aluminum-zirconium alloy solution is defined as b, and the Zr content in the first alloy phase is defined 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: In step 101, the target aluminum-zirconium alloy sample to be tested is composed of Zr, Fe, Si, the remainder Al, and other inevitable 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 in a granular form, and the particle size of the target aluminum-zirconium alloy sample to be tested is in the range of 0.5 μm to 1 μm.

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 be tested and 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 of anhydrous phenol, o-cresol, m-cresol, p-cresol, p-chlorophenol, catechol, methyl catechol, and pentachlorophenol, or a mixture of more than one of them.

6. 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 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 of benzyl alcohol, phenylethyl alcohol, n-butanol, isoamyl alcohol, anisole, o-phthalic alcohol, phenylpropyl alcohol, and α-methylphenylethyl alcohol, or a combination of more than one of them.

7. The method for measuring the distribution state of Zr element in an Al-Zr alloy system according to claim 1, characterized in that: The mass ratio of the aluminum-zirconium alloy sample after dehydration treatment and the separation liquid A in step 103 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 dissolving solution B is 1:(5-10); In step 105 , the mass ratio of the target aluminum-zirconium alloy sample to be tested and the dissolving 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, the dissolving solution B is prepared by mixing hydrogen fluoride and nitric acid in a volume ratio of 1:2; In step 105 , the dissolving solution C is obtained by mixing hydrogen fluoride and nitric acid in a volume ratio of 1:

1.

10. Application of the method for measuring the distribution state of Zr element in an Al-Zr alloy system according to any one of claims 1 to 9, characterized in that: The Zr element content measured by the method is used to quantitatively evaluate the distribution of the Zr element in the aluminum-zirconium alloy.

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