Rapid detection and analysis method for oxidation rate of active elements in alloy material

Abstract

The invention discloses a rapid detection and analysis method for the oxidation rate of active elements in an alloy material. The rapid detection and analysis method comprises the following steps: respectively preparing a to-be-detected sample containing the active elements and a background deduction sample not containing the active elements according to the same process steps; carrying out active element content quantitative detection on the to-be-detected sample; respectively detecting the oxygen content of the background deducted sample and the oxygen content of the to-be-detected sample by using oxygen content analysis equipment; and calculating the oxidation rate of the active element based on the oxygen content of the background deduction sample and the oxygen content of the to-be-detected sample. The method can be used for rapidly detecting and analyzing the oxidation rate of the active elements in the oxide dispersion strengthened platinum-based alloy material, the oxygen content of a background deduction sample and the content and the oxygen content of the active elements in a to-be-detected sample are determined, the oxidation rate of the active elements in the oxide dispersion strengthened platinum-based alloy material can be effectively analyzed, and the process can be guided to prepare the oxide dispersion strengthened platinum-based alloy material with more excellent performance and more stable performance. The invention discloses a stable oxide dispersion strengthened platinum-based material.

Description

Technical Field

[0001] This invention relates to the field of precious metal materials technology, and specifically to a rapid detection and analysis method for the oxidation rate of active elements in alloy materials. Background Technology

[0002] Platinum-based alloy dispersion-strengthened materials are widely used in high-tech fields such as glass and glass fiber, aerospace, energy and chemical industries, and electronics due to their excellent high-temperature resistance, corrosion resistance, and oxidation resistance, especially their outstanding performance in high-temperature tensile strength, high-temperature creep strength, and high-temperature creep resistance. Oxide dispersion-strengthened platinum-based materials introduce trace amounts of uniform and fine second-phase oxide particles into a platinum matrix. The particle size is typically in the micrometer or nanometer range, or both. To introduce these trace amounts of uniform and fine particles, methods such as chemical co-precipitation, internal spray oxidation, high-temperature oxidation-mechanical lamination, and special powder metallurgy are commonly used.

[0003] Of the methods mentioned above, except for chemical co-precipitation, the other processes all involve the oxidation of active elements (elements that introduce oxides) in the matrix. Whether it's high-temperature mechanical lamination, internal spray oxidation, or special powder metallurgy, the active elements in the platinum matrix need to be oxidized during processing to generate corresponding oxide particles, achieving a second-phase dispersion strengthening effect. The degree of oxidation of active elements significantly affects the performance of the finished material; poor oxidation can drastically reduce various properties of platinum-based materials. Furthermore, testing the degree of oxidation of active elements in the material at different processing times is a crucial parameter for developing dispersion-strengthened material preparation processes. For platinum-based materials used in certain fields, it's necessary to control the oxidation rate of active elements, preventing complete oxidation. Allowing active elements to oxidize slowly during use can effectively slow down the high-temperature oxidation and volatilization rate of platinum-based alloys.

[0004] Currently, the main methods for monitoring and analyzing the oxidation rate of active elements in platinum-based alloy materials include the following three:

[0005] (1) Gravimetric method

[0006] This method calculates the oxidation rate by measuring the difference in weight of the sample before and after oxidation using an analytical balance. It is simple to operate, inexpensive, and a commonly used analytical method.

[0007] (2) Chemical analysis method

[0008] The main principle of this method is as follows: The oxides formed after the oxidation of active elements in platinum-based alloy dispersion-strengthened materials are insoluble in aqua regia. The oxidation rate of the active elements is derived by measuring the content of unoxidized active elements in the matrix using ICP. Patent CN117092090 B describes a method for determining the zirconium oxidation rate in dispersion-strengthened platinum-based materials, and patent CN117929084 A describes a microwave digestion-inductively coupled plasma atomic emission spectrometry method for determining the zirconium oxidation rate in dispersion-strengthened platinum-based materials. Both methods utilize the different solubilities of zirconium and zirconium oxide in platinum-based dispersion-strengthened materials with acid. The zirconium content in the sample before oxidation is analyzed using inductively coupled plasma atomic emission spectrometry, and the oxidation rate of zirconium in the platinum-based alloy material is calculated by using the difference in zirconium content before and after oxidation.

[0009] (3) Spectroscopic analysis

[0010] Some sources indicate that spectroscopic analysis methods can be used to test the oxidation rate of metallic materials. For example, techniques such as X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) can be used to analyze the surface composition and chemical state of samples, thereby obtaining information on the oxidation rate.

[0011] However, these existing methods have the following drawbacks:

[0012] (1) Gravimetric method

[0013] This method is only applicable when the matrix contains a high content of active elements, and the sample weight changes significantly before and after oxidation, with the weight gain of the active elements after oxidation falling within the sensing range of the analytical balance. However, for platinum-based alloy dispersion-strengthened materials, the nominal amount of active elements added is generally less than or equal to 0.5 wt%, which is considered a trace element. Furthermore, when using an analytical balance for weighing, the sample size is small, and the increase in the amount of active elements added after oxidation is small, resulting in unreliable test results and low reliability.

[0014] (2) Chemical analysis method

[0015] Chemical analysis methods are complex, requiring large quantities of chemical reagents. This not only demands high technical skills from operators but also easily causes environmental pollution. Furthermore, the detection cycle is long, often taking hours or even days from sample preparation to obtaining results, making it difficult to meet the needs of rapid testing. Additionally, errors may be introduced during chemical analysis, such as incomplete sample dissolution or inaccurate titration endpoint determination, thus affecting the accuracy of the results.

[0016] In platinum-based dispersion-strengthened materials, the dispersed zirconium oxide particles are small, generally ranging from a few to a few hundred nanometers, and are relatively uniformly distributed in the matrix. However, when dissolving platinum-based alloy samples using a heating and pressurized microwave digestion method, some of the fine zirconium oxide particles will dissolve into zirconium ions and enter the solution, which will lead to distorted test results.

[0017] This method can only test oxides in the matrix that are insoluble in solutions such as hydrochloric acid, nitric acid, and aqua regia. If the dispersed phase of the platinum-based dispersion-reinforced material is hafnium oxide (HfO2), scandium oxide (Sc2O3), yttrium oxide (Y2O3), or various rare earth oxides (ReO), these oxides will dissolve in acids, and this method cannot be used for testing, thus having certain limitations.

[0018] (3) Spectroscopic analysis

[0019] The main drawback of this method is that it can only measure the surface composition and chemical state of the sample, and cannot effectively reflect the oxidation status of active elements inside the material. For platinum-based dispersion-reinforced materials, the degree of oxidation on the surface and inside the material differs significantly depending on the process used. If this method is used to test the oxidation rate, the measured oxidation rate of active elements will be distorted. For example, when platinum-based dispersion-reinforced materials are prepared using a high-temperature oxidation-mechanical stacking method, the oxidation degree of surface active elements is much greater than that of active elements inside the material.

[0020] Spectroscopic analysis equipment is typically expensive and requires high maintenance costs, limiting its widespread application in some laboratories and enterprises. Furthermore, spectroscopic analysis demands precise sample preparation; impurities, particle size, and other factors in the sample can interfere with the spectral signal, leading to inaccurate results. Additionally, for some low-abundance reactive elements, the detection sensitivity of spectroscopic analysis may be insufficient, making it difficult to accurately determine their oxidation rate.

[0021] In summary, existing methods for detecting the oxidation rate of active elements in platinum-based alloy materials have certain shortcomings in terms of detection speed, accuracy, cost, and ease of operation. There is an urgent need for a rapid, accurate, economical, and easy-to-operate detection and analysis method. Summary of the Invention

[0022] To achieve the above objectives, this invention provides a rapid detection and analysis method for the oxidation rate of active elements in alloy materials, comprising the following steps:

[0023] The test sample containing active elements and the back-subtraction sample without active elements were prepared using the same process steps.

[0024] The content of active elements in the sample to be tested was quantitatively determined.

[0025] The oxygen content of the back-subtracted sample and the oxygen content of the sample to be tested were detected using an oxygen content analysis device.

[0026] The oxidation rate of the active element is calculated based on the oxygen content of the back-subtracted sample and the oxygen content of the sample to be tested.

[0027] Preferably, the alloy material is a noble metal-based dispersion-strengthened alloy.

[0028] Preferably, the noble metal-based dispersion-strengthened alloy is a platinum-based alloy.

[0029] Preferably, the active element includes at least one of zirconium, hafnium, and rare earth elements.

[0030] Preferably, the oxygen content analysis equipment includes a pulse-heated inert gas melting-infrared absorber or a glow discharge mass spectrometer.

[0031] Preferably, the back-subtracted sample and the sample to be tested are subjected to ultrasonic cleaning before testing.

[0032] As a preferred method, the method for calculating the oxidation rate of active elements includes:

[0033] Let m1 be the total oxygen content in the sample to be tested and m2 be the total oxygen content of the sample after background subtraction.

[0034] Calculate the content of the active element being oxidized based on the oxygen content m1-m2 and the stoichiometric ratio of the chemical reaction. ;

[0035] The total content of active elements is set as follows: Based on its calculated oxidation rate:

[0036]

[0037] Preferably, the quantitative detection of the content of the active element is performed by ICP-OES or ICP-MS.

[0038] Preferably, the oxygen content detection of both the back-subtracted sample and the sample to be tested is repeated 3 to 5 times, and the average value of the detection is taken as the result.

[0039] Preferably, the back-subtracted sample can be reused for the detection and analysis of multiple batches of samples while keeping the same process steps unchanged.

[0040] The rapid detection and analysis method for the oxidation rate of active elements in alloy materials provided by this invention has the following technical advantages:

[0041] The rapid detection and analysis method for the oxidation rate of active elements in alloy materials proposed in this invention, especially for platinum-based alloy materials, overcomes the technical bottlenecks of traditional detection methods. Traditional methods suffer from cumbersome procedures, long processing times, and low accuracy. This method, however, achieves rapid and accurate detection of the oxidation rate of active elements by comparing the background sample and the sample to be tested using an oxidation content analyzer. The detection can be completed in a short time with accuracy far superior to traditional methods. This not only improves detection efficiency but also provides more reliable technical support for the quality control and performance optimization of platinum-based alloy materials.

[0042] Specifically, a rapid detection and analysis method for the oxidation rate of active elements in platinum-based alloy materials is as follows:

[0043] Before analyzing the oxygen content of oxide dispersion-reinforced platinum-based alloys, a background subtraction sample needs to be prepared according to the process steps for preparing the dispersion material. This is because different processes used to prepare platinum-based dispersion-reinforced materials will affect the oxygen content within the material itself. For example, when preparing oxide dispersion-reinforced platinum-based materials using the mechanical lamination method, a background subtraction sample without reactive elements should also be prepared using the same process steps. Similarly, when preparing platinum-based dispersion-reinforced materials using special powder metallurgy, a background subtraction sample without reactive elements should also be prepared using the same process steps. As long as the process steps and parameters for preparing the oxide remain unchanged, the background subtraction sample only needs to be prepared once for long-term use of the background subtraction value.

[0044] The oxygen content in platinum-based solids is related to factors such as the source of raw materials, the manufacturing process, and the environment. High-purity platinum has a very low oxygen content, typically a few ppm or even lower. Platinum materials used in general industrial applications have an oxygen content ranging from tens to hundreds of ppm. This oxygen content can fluctuate due to factors such as contact with air during manufacturing, absorption of oxygen under specific conditions, and other process influences. For example, if platinum is exposed to air at high temperatures for extended periods, oxygen will gradually diffuse into the platinum interior, altering its oxygen content. There is no fixed standard value for the oxygen content in solid platinum; it varies due to multiple factors, and the required oxygen content differs across different applications.

[0045] In oxide dispersion strengthened (ODS) metallic materials, reducing the oxide content is sufficient to significantly improve the material's mechanical properties and high-temperature stability; the range is generally between 0.01 wt% and 2 wt%. Excessive oxide content leads to a sharp deterioration in the material's processing and welding properties. Therefore, in platinum-based oxide dispersion strengthened materials, the content of active elements is generally between 0.01 wt% and 0.5 wt%.

[0046] Because the proportion of active elements in the matrix is ​​low during the initial design phase, and because the secondary addition of active elements during the platinum-based material melting process leads to significant differences in element loss rates due to process variations, quantitative analysis of active elements in the sample is necessary to ensure the accuracy of subsequent measurements. ICP-OES or ICP-MS is used to determine the content of active elements. The analyzed active element content values ​​are then used in subsequent calculations.

[0047] As a preferred method, standardized equipment such as pulse heating inert gas melting-infrared absorption method is used for detection, which has the advantages of high detection sensitivity, ability to detect low oxygen content, relatively simple sample pretreatment, fast analysis speed, and can generally complete a measurement within a few minutes; and accurate and reliable measurement results.

[0048] As a preferred method, ultrasonic cleaning is performed to avoid the impact of oxygen-containing impurities such as oil on the accuracy of test results. Attached Figure Description

[0049] Figure 1 This is a flowchart illustrating the rapid detection and analysis of the oxidation rate of active elements in a platinum-based alloy material according to a specific embodiment of the present invention. Detailed Implementation

[0050] This invention provides a method for detecting and analyzing the oxygen content in platinum-based alloy dispersion-strengthened materials, based on an oxygen analyzer or glow discharge mass spectrometer. The specific operating steps are as follows:

[0051] Step 1: Prepare the test sample containing the active element and the test sample with background subtraction.

[0052] Before analyzing the oxygen content of oxide dispersion-reinforced platinum-based alloys, a background subtraction sample needs to be prepared according to the process steps for preparing the dispersion material. This is because different processes used to prepare platinum-based dispersion-reinforced materials will affect the oxygen content within the material itself. For example, when preparing oxide dispersion-reinforced platinum-based materials using the mechanical lamination method, a background subtraction sample without active elements should also be prepared simultaneously using the same process steps. Similarly, when preparing platinum-based dispersion-reinforced materials using special powder metallurgy, a background subtraction sample without active elements should also be prepared using the same process steps. As long as the process steps and parameters for preparing the oxide remain unchanged, the background subtraction sample only needs to be prepared once for long-term use of the background subtraction value.

[0053] The main reason for implementing step one is that the oxygen content in platinum-based solids is related to factors such as the source of raw materials, the preparation process, and the environment. High-purity platinum has a very low oxygen content, generally a few ppm or even lower; platinum materials for general industrial use have an oxygen content of approximately tens to hundreds of ppm. This oxygen content can fluctuate due to contact with air during preparation, absorption of oxygen under specific conditions, and other process factors. For example, if platinum is in prolonged contact with air at high temperatures, oxygen will gradually diffuse into the interior of the platinum, causing changes in its oxygen content. There is no fixed standard value for the oxygen content in solid platinum; it varies due to multiple factors, and the requirements for the oxygen content of platinum differ in different application fields.

[0054] Step 2: Quantitative Detection and Analysis of Active Elements in the Sample

[0055] In oxide dispersion strengthened (ODS) metallic materials, reducing the oxide content is sufficient to significantly improve the material's mechanical properties and high-temperature stability; the range is generally between 0.01 wt% and 2 wt%. Excessive oxide content leads to a sharp deterioration in the material's processing and welding properties. Therefore, in platinum-based oxide dispersion strengthened materials, the content of active elements is generally between 0.01 wt% and 0.5 wt%.

[0056] Because the proportion of active elements in the matrix is ​​low during the initial design phase, and because the secondary addition of active elements during the platinum-based material melting process leads to significant differences in element loss rates due to process variations, quantitative analysis of active elements in the sample is necessary to ensure the accuracy of subsequent measurements. ICP-OES or ICP-MS is used to determine the content of active elements. The analyzed active element content values ​​are then used in subsequent calculations.

[0057] Step 3: Sample preparation and processing

[0058] Sample preparation: Select a representative solid platinum sample and use appropriate methods (such as cutting or trimming) to make it into small pieces of suitable size, with a mass of about 0.5 to 1.0 grams, depending on the instrument requirements.

[0059] Sample Preparation: Before testing and analyzing the oxygen content in the sample, pretreatment is necessary. Preparation method: Use acetone or ethanol solution as the cleaning solution. The ratio of acetone to deionized water is 50-70%:50-30 wt%; the ratio of pure ethanol to deionized water is 70-95 wt%. Ultrasonic cleaning time is 5-10 minutes, with the ultrasonic frequency controlled between 80 kHz and 120 kHz. After cleaning, dry the sample.

[0060] Step 4: Use an oxygen analyzer to test the oxygen content in the sample and the test sample after background subtraction.

[0061] The oxidation content in platinum-based solid samples is determined using a pulse-heated inert gas melting-infrared absorption method. The basic principle is as follows: The solid platinum sample is placed in an inert atmosphere (such as helium, argon, or nitrogen), and the sample is rapidly melted using a pulse heating device. At high temperature, the oxygen in the sample is released as carbon monoxide (CO) or carbon dioxide (CO2). The released gas enters the infrared absorption cell with the carrier gas. Since CO or CO2 absorbs infrared light of specific wavelengths, the oxygen content can be calculated by measuring the change in infrared light intensity according to the Lambert-Beer law.

[0062] Oxygen in the platinum matrix is ​​heated in a pulse furnace and reduced by graphite in a crucible at high temperature, releasing it from the metal as CO. The reaction process is as follows:

[0063]

[0064] This method has the advantages of high detection sensitivity, capable of detecting low levels of oxygen; relatively simple sample pretreatment; fast analysis speed, generally completing a measurement within a few minutes; and accurate and reliable measurement results.

[0065] Taking the pulse heating inert gas melting-infrared absorption method as an example, the specific operation steps for detecting and analyzing the oxidation rate of active elements in platinum-based alloy materials are as follows:

[0066] 1. Instrument Preparation: Check that all connections of the pulse-heated inert gas melting-infrared absorber are correct and secure, ensuring the instrument's gas and electrical circuits are functioning properly. Turn on the instrument's power switch and preheat the instrument according to the operation manual, allowing it to reach a stable operating state. Preheating time is typically 30 minutes to 1 hour. Purge the gas system with a high-purity inert gas (such as argon, with a purity generally required to be above 99.99%) to remove air and impurities. Purge time is typically 10-15 minutes. Based on the sample properties and expected oxygen content, set appropriate analytical parameters, such as pulse heating power, integration time, and carrier gas flow rate.

[0067] 2. Background subtraction sample testing: Place the prepared background subtraction sample into a graphite crucible, then place the crucible on the instrument's sample stage. Close the instrument's furnace lid, ensuring a good system seal. Start the instrument's analysis program; the instrument automatically pulses heat the sample, melting it in an inert atmosphere. Oxygen in the sample is released as carbon monoxide or carbon dioxide. The released gas enters the infrared absorption cell with the carrier gas. The infrared detector detects the absorption signal of the gas at the desired wavelength of infrared light and converts it into an electrical signal. After amplification and processing, the measured value of the oxygen content of the background subtraction sample is obtained.

[0068] 3. Testing of the sample to be tested: The operation steps and methods are the same as those for the sample with the backing removed, and will not be repeated here.

[0069] 4. Data Processing: Both the background-subtracted sample and the test sample should be measured repeatedly 3-5 times, and the average value should be taken as the determination result of the oxygen content in the sample. Based on the test results of the background-subtracted sample, the measured values ​​of the sample are corrected to obtain the true oxygen content in the sample. The relative standard deviation of the measurement results can be calculated as needed to evaluate the precision of the analysis results. Let the total oxygen content in the test sample be m1, and the total oxygen content in the background-subtracted sample be m2, then the oxygen content in the platinum-based alloy dispersion-strengthened material is (m1-m2).

[0070] Calculate the oxidation rate of the active element:

[0071] (1) Based on the data processing results in step 4 above, the oxygen content in the obtained sample is (m1-m2). The content of the active element that is oxidized (x) can be calculated according to the following reaction equation.

[0072]

[0073] but, .

[0074] (2) Oxidation rate of active elements

[0075] In the second step, the total content of active elements (before oxidation) in the platinum-based alloy material has been obtained (assuming the total content of active elements is a). From this, the oxidation rate of active elements in the platinum-based alloy material after oxidation can be calculated.

[0076]

[0077] Other active elements can also be obtained using the methods and steps described above.

[0078] Instrument Cleaning and Maintenance: After analysis, open the furnace lid, remove the crucible, clean the sample stage and furnace chamber, and remove any residual sample and impurities. Turn off the instrument's power switch and perform necessary cleaning and maintenance according to the instrument's operation manual, such as cleaning the gas path and replacing filters, to ensure the normal operation of the instrument and the accuracy of the next analysis.

[0079] The following detailed description, in conjunction with embodiments, illustrates a rapid detection and analysis method for the oxidation rate of active elements in platinum-based alloy materials provided by the present invention.

[0080] Example 1

[0081] This embodiment uses a special powder metallurgy method to prepare platinum-based dispersion-reinforced materials, a method currently widely used in China. The oxygen content in the background subtracted sample and the sample to be tested is measured using an oxygen analyzer. The specific operating steps are as follows:

[0082] Step 1: Prepare the test sample containing the active element and the test sample with background subtraction.

[0083] A special powder metallurgy preparation process was used to prepare test samples containing active elements and back-subtraction test samples, respectively. The specific preparation process was as follows: melting of Pt-based alloy materials → preparation of powder materials → powder oxidation-sintering → pressing → hot forging → rolling into plates. The active element added to the test sample containing active elements was zirconium, with a nominal addition amount of 0.30 wt%; the back-subtraction sample was pure Pt material.

[0084] Step 2: Quantitative Detection and Analysis of Active Elements in the Sample

[0085] In the preparation process of step one, after the Pt-based alloy material is melted (sample with added active elements), a sample is taken to perform quantitative analysis of the active elements. Assuming the content of the active elements is a, this value is obtained for subsequent calculations.

[0086] Step 3: Sample preparation and processing

[0087] Sample preparation: After rolling into sheet metal, representative solid platinum samples were selected and cut into appropriately sized pieces using a cutting method. In this case, three representative samples of zirconia dispersion-reinforced platinum were taken, with masses of 0.49g, 0.53g, and 0.51g, respectively; the pure Pt backing samples had masses of 0.55g, 0.52g, and 0.54g, respectively.

[0088] Sample Preparation: Before testing and analyzing the oxygen content in the sample, the sample must be pretreated. Treatment method: Acetone solution is used as the cleaning solution, with a ratio of 70% acetone to 30 wt% deionized water; ultrasonic cleaning time is 10 min, and the ultrasonic frequency is controlled at 120 kHz; the sample is dried after cleaning.

[0089] Step 4: Use an oxygen analyzer to test the oxygen content in the sample and the test sample after background subtraction.

[0090] Taking the pulse heating inert gas melting-infrared absorption method as an example, the specific operation steps for detecting and analyzing the oxidation rate of active elements in platinum-based alloy materials are as follows:

[0091] Instrument Preparation: Check that all connections of the pulse-heated inert gas melting-infrared absorber are correct and secure, ensuring the instrument's gas path and electrical circuit are functioning properly. Turn on the instrument's power switch and preheat the instrument according to the operation manual, allowing it to reach a stable operating state. The preheating time is typically 60 minutes. Purge the gas path system with high-purity inert gas to remove air and impurities. The purging time is generally 15 minutes. Based on the sample properties and expected oxygen content, set appropriate analytical parameters, such as pulse heating power, integration time, and carrier gas flow rate.

[0092] Background subtraction sample testing: Place the prepared background subtraction sample into a graphite crucible, then place the crucible on the instrument's sample stage. Close the instrument's furnace lid, ensuring a good system seal. Start the instrument's analysis program; the instrument automatically pulses heat the sample, melting it in an inert atmosphere. Oxygen in the sample is released as carbon monoxide or carbon dioxide. The released gas enters the infrared absorption cell with the carrier gas. The infrared detector detects the absorption signal of the gas to the desired wavelength of infrared light and converts it into an electrical signal. After amplification and processing, the measured value of the oxygen content of the background subtraction sample is obtained.

[0093] Testing of the sample to be tested: The operation steps and methods are the same as those for the sample with the backing removed, and will not be repeated here.

[0094] Data Processing: Both the background-subtracted sample and the test sample should be measured three times, and the average value should be taken as the determination result of the oxygen content in the sample. Based on the test results of the background-subtracted sample, the measured values ​​of the sample are corrected to obtain the true oxygen content in the sample. The relative standard deviation of the measurement results can be calculated as needed to evaluate the precision of the analytical results. Let the total oxygen content in the test sample be m1, and the total oxygen content in the background-subtracted sample be m2, then the oxygen content in the platinum-based alloy dispersion-strengthened material is (m1-m2).

[0095] Table 1. Oxygen content test values ​​of samples with background subtraction (samples prepared from special powder metallurgy).

[0096]

[0097] Table 2 Test values ​​of samples containing active elements

[0098]

[0099] 1. Calculate the oxidation rate of the active element.

[0100] ODS-Pt-1#~3# Sample:

[0101] (1) Based on the data processing results in step 4 above, the oxygen content in samples ODS-Pt-1#~3# obtained under the same oxidation time and process is m1-m2=0.096390-0.007966=0.088424. The content (x) of the oxidized active element can be calculated according to the following reaction equation.

[0102]

[0103] but, .

[0104] (2) Oxidation rate of active elements

[0105] In the second step, the total content of active elements (before oxidation) in the platinum-based alloy material has been obtained (assuming the total content of active elements is a). From this, the oxidation rate of active elements in the platinum-based alloy material after oxidation can be calculated.

[0106]

[0107] Other active elements can also be obtained using the methods and steps described above.

[0108] ODS-Pt-4#~6# Sample:

[0109] (1) Similarly, the oxygen content in the samples obtained under the same oxidation time and process for ODS-Pt-4#~6# is m1-m2=0.044470-0.007966=0.036504. The content (x) of the oxidized active element can be calculated according to the following reaction equation.

[0110]

[0111] but .

[0112] (2) Then calculate the oxidation rate of its active elements:

[0113] In the second step, the total content of active elements (before oxidation) in the platinum-based alloy material has been obtained (assuming the total content of active elements is a). Therefore, the oxidation rate of the active elements in the platinum-based alloy material after oxidation can be calculated as follows:

[0114]

[0115] ODS-Pt-7#~9# Sample:

[0116] (1) Similarly, the oxygen content in samples obtained under the same oxidation time and process for ODS-Pt-7#~9# is m1-m2=0.031782-0.007966=0.023816. The content of the active element oxidized (x) can be calculated according to the following reaction equation.

[0117]

[0118] but .

[0119] (2) Then calculate the oxidation rate of its active elements:

[0120] In the second step, the total content of active elements (before oxidation) in the platinum-based alloy material has been obtained (assuming the total content of active elements is a). Therefore, the oxidation rate of the active elements in the platinum-based alloy material after oxidation can be calculated as follows:

[0121]

[0122] ODS-Pt-10#~12# Sample:

[0123] Other patents (publication number CN 117471059 A) mention that oxygen content detection in dispersion-strengthened alloys can be achieved by using a high-power oxygen analyzer with fluxing agents to detect the oxygen content of high-melting-point substances, and a low-power oxygen analyzer to detect the oxygen content of low-melting-point substances. In the ODS-Pt-10#~12# examples, the oxygen content of the platinum matrix and zirconium oxide is detected separately by controlling the high and low power of the oxygen analyzer. However, when the power is controlled at the melting temperature of platinum diamond, the oxygen content result is between the oxygen content of the sample after background subtraction and the oxygen content of the sample containing active elements. This result cannot determine the oxygen content in the platinum matrix.

[0124] This method is insufficient for detecting the oxygen content of either the matrix or the oxide in oxide-dispersed platinum-based materials, especially when their melting points are close. The oxide is dispersed in the matrix at nanoscale, and due to the nano-effect, the physicochemical properties of powders reduced to the nanoscale differ significantly from those of bulk materials. The melting point of nanoparticles... The relationship between (r) and its particle size r can be described by the modified Gibbs-Thomson equation:

[0125]

[0126] in:

[0127] = Melting point (K) of bulk materials

[0128] = Solid-liquid interface energy (J / )

[0129] =Enthalpy of fusion (J / kg)

[0130] Solid density (kg / )

[0131] r = particle radius (m)

[0132] The melting point of bulk platinum is 1768℃, while that of bulk zirconia is 2715℃, a difference of nearly 1000℃. However, zirconia exists as nano-sized particles within platinum. As the particle size decreases, the surface energy of the particles increases, leading to greater thermodynamic instability and a decrease in the melting point. Since the melting points of bulk platinum and zirconia nanoparticles are close, it is difficult to separately detect the oxygen content of platinum and zirconia by controlling the power of an oxygen analyzer.

[0133] Instrument Cleaning and Maintenance: After analysis, open the furnace lid, remove the crucible, clean the sample stage and furnace chamber, and remove any residual sample and impurities. Turn off the instrument's power switch and perform necessary cleaning and maintenance according to the instrument's operation manual, such as cleaning the gas path and replacing filters, to ensure the normal operation of the instrument and the accuracy of the next analysis.

Claims

1. A rapid detection and analysis method for the oxidation rate of active elements in alloy materials, characterized in that, Includes the following steps: The test sample containing active elements and the back-subtraction sample without active elements were prepared using the same process steps. The content of active elements in the sample to be tested was quantitatively determined. The oxygen content of the back-subtracted sample and the oxygen content of the sample to be tested were detected using an oxygen content analysis device. The oxidation rate of the active element is calculated based on the oxygen content of the back-subtracted sample and the oxygen content of the sample to be tested.

2. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The alloy material is a noble metal-based dispersion-strengthened alloy.

3. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 2, characterized in that, The noble metal-based dispersion-strengthened alloy is a platinum-based alloy.

4. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The active element includes at least one of zirconium, hafnium, and rare earth elements.

5. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The oxygen content analysis equipment includes a pulse-heated inert gas melting-infrared absorber or a glow discharge mass spectrometer.

6. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The back-subtracted sample and the sample to be tested need to be ultrasonically cleaned before testing.

7. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1 or 4, characterized in that, Methods for calculating the oxidation rate of reactive elements include: Let m1 be the total oxygen content in the sample to be tested and m2 be the total oxygen content of the sample after background subtraction. Calculate the content of the active element being oxidized based on the oxygen content m1-m2 and the stoichiometric ratio of the chemical reaction. ; The total content of active elements is set as follows: Based on its calculated oxidation rate:

8. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The quantitative detection of the content of the active elements was performed by ICP-OES or ICP-MS.

9. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The oxygen content of both the back-subtracted sample and the sample to be tested was measured repeatedly 3 to 5 times, and the average value of the measurements was taken as the result.

10. The rapid detection and analysis method for the oxidation rate of active elements in alloy materials according to claim 1, characterized in that, The back-subtracted sample can be repeatedly used for the detection and analysis of multiple batches of samples while keeping the same process steps unchanged.

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