Method for detecting migration ability of metal elements in glass matrix

Abstract

The application provides a detection method for migration ability of metal elements in a glass matrix, and relates to the technical field of glass material structure analysis. The detection method comprises the following steps: S1, coating an inert metal layer on the surface of the glass matrix to obtain a first sample; pressing a material containing a target metal element into a second sample; S2, clamping the second sample between two first samples to obtain a laminated sample; S3, performing heat treatment on the laminated sample to obtain a sample to be detected; S4, obtaining the diffusion layer thickness and the diffusion coefficient of the target metal element in the sample to be detected, and judging the migration ability of the metal element according to the diffusion layer thickness and the diffusion coefficient. The migration ability of the target metal element in the glass matrix can be intuitively and accurately reflected by the detection method.

Description

Technical Field

[0001] This application relates to the field of glass material structure analysis technology, and more specifically, to a method for detecting the migration ability of metal elements in a glass matrix. Background Technology

[0002] Steel is highly susceptible to oxidative corrosion under high-temperature oxidizing atmospheres, resulting in severe oxidation and burn-off. This not only reduces the yield and surface quality of the steel but also leads to significant waste of resources and energy. Currently, to reduce high-temperature oxidation and burn-off in steel, a glass-based protective coating is primarily applied to the surface of the steel. During high-temperature processing, metallic elements in the steel matrix, such as iron (Fe), chromium (Cr), silicon (Si), magnesium (Mg), and aluminum (Al), can diffuse through the glass melt. These elements migrate from the steel matrix to the glass-based protective coating or form a new diffusion layer at the interface between the two. Detecting the migration ability of these metallic elements can provide a basis for optimizing and controlling the glass-based protective coating, enhancing its corrosion resistance at high temperatures. Currently, the migration ability of metallic elements is typically detected using an immersion method, which involves immersing the glass matrix in a solution containing the target metallic element and then analyzing the concentration of the metallic element in the glass matrix. This method has advantages such as simple operation and low cost, but it also has the following drawbacks: the immersion method results deviate significantly from the actual migration intensity; and the immersion method detects the migration of metal ions, not the migration ability of metal elements, which are fundamentally different. Therefore, existing detection methods cannot effectively characterize the migration ability of metal elements in glass matrices. Summary of the Invention

[0003] The main objective of this application is to provide a method for detecting the migration ability of metal elements in a glass matrix, so as to solve the problem that existing detection methods cannot effectively characterize the migration ability of metal elements in a glass matrix.

[0004] To achieve the above objectives, this application provides a method for detecting the migration ability of metal elements in a glass matrix, comprising the following steps:

[0005] S1, an inert metal layer is coated on the surface of a glass substrate to obtain a first sample; the material containing the target metal element is pressed into a second sample;

[0006] S2, the second sample is sandwiched between the two first samples to obtain a superimposed sample;

[0007] S3, heat-treat the stacked samples to obtain the sample to be tested;

[0008] S4, obtain the diffusion layer thickness and diffusion coefficient of the target metal element in the sample to be tested, and determine the migration ability of the metal element based on the diffusion layer thickness and diffusion coefficient.

[0009] Furthermore, the inert metal layer comprises at least one of Au, Pt, and Pd.

[0010] Furthermore, the thickness of the inert metal layer is 0.05 μm to 0.3 μm.

[0011] Furthermore, the target metallic element includes at least one of Fe, Cr, Si, Mg, and Al.

[0012] Furthermore, both the glass substrate and the second sample are cylindrical in shape.

[0013] Furthermore, the diameter of the glass substrate and the second sample are each independently 5-50 mm, and the height is each independently 3-30 mm.

[0014] Furthermore, the diameter of the glass substrate is 10–30 mm and the height is 10–30 mm; the diameter of the second sample is 10–30 mm and the height is 5–15 mm.

[0015] Furthermore, when both the glass substrate and the second sample are cylindrical, S1 includes: coating an inert metal layer on the bottom surface of the glass substrate to obtain a first sample; S2 includes: sandwiching the second sample between the two first samples with their bottom surfaces facing each other to obtain a stacked sample.

[0016] Furthermore, the heat treatment includes sequential heating heat treatment and holding heat treatment;

[0017] Preferably, the initial temperature of the heat treatment is 15-30℃, the final temperature is 850℃-1250℃, the holding time of the heat treatment is 20-40 minutes, and the heating rate of the heat treatment is 5℃ / min-20℃ / min.

[0018] The temperature for heat treatment is 850℃~1250℃, and the holding time is 30min~720min.

[0019] Further, S3 includes: heat-treating the stacked samples at a fixed temperature and different holding times t to obtain the sample to be tested;

[0020] S4 includes: performing cross-sectional processing on the sample to be tested to expose the cross-section, performing elemental analysis on the cross-section, obtaining the diffusion layer thickness L of the target metal element in the glass matrix at different holding times t, and obtaining L. 2-t fitting curve; obtain the slope of the fitting curve, obtain the diffusion coefficient based on the slope, and determine the migration ability of metal elements based on the diffusion coefficient.

[0021] Furthermore, the diffusion layer thickness is the vertical distance from the surface of the glass substrate to the point where the content of the target metal element in the glass substrate reaches the baseline level.

[0022] Furthermore, the glass matrix comprises the following components by mass fraction: SiO2 40%–70%, Al2O3 5%–12%, CaO 0.2%–0.7%, Fe2O3 2%–5%, K2O 2%–5%, and Na2O 5%–8%.

[0023] By applying the technical solution of this application, the diffusion path and diffusion thickness of the target metal element can be displayed more directly, and the migration ability of the target metal element under high temperature conditions can be reflected intuitively and accurately. Furthermore, by controlling the temperature and time of heat treatment, the migration law of the target metal element under different temperature and time conditions can be studied. By studying the migration law of the target metal element in the glass matrix, it can be adjusted according to actual production, achieving controllable protection, effectively improving the protective effect of glass-based protective materials on steel materials, reducing resource waste, and improving resource utilization. Detailed Implementation

[0024] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present application will now be described in detail with reference to the embodiments.

[0025] As described in the background section, existing detection methods cannot effectively characterize the migration ability of metal elements in a glass matrix. To address this technical problem, this application provides a method for detecting the migration ability of metal elements in a glass matrix, comprising the following steps:

[0026] S1, an inert metal layer is coated on the surface of a glass substrate to obtain a first sample; the material containing the target metal element is pressed into a second sample;

[0027] S2, the second sample is sandwiched between the two first samples to obtain a superimposed sample;

[0028] S3, heat-treat the stacked samples to obtain the sample to be tested;

[0029] S4, obtain the diffusion layer thickness and diffusion coefficient of the target metal element in the sample to be tested, and determine the migration ability of the metal element based on the diffusion layer thickness and diffusion coefficient.

[0030] Specifically, in step S1, an inert metal layer is uniformly coated on the surface of the glass substrate to form a first sample. The inert metal layer acts as a barrier that does not participate in chemical reactions, marking and protecting the surface of the glass substrate so that the original interface and the interface after element migration can be distinguished in subsequent detection. Simultaneously, the material containing the target metal element is pressed into a second sample. The second sample is a specimen containing the target metal element to be detected, designed to simulate the environment of interaction with the glass substrate under high-temperature conditions, thereby observing the migration process of the specific target metal element in the glass substrate. The target metal element is any element that can diffuse through the glass substrate under high-temperature conditions.

[0031] In step S2, the second sample is sandwiched between the two first samples to obtain a superimposed sample. By sandwiching the second sample between the two first samples, it can be ensured that the target metal element can only diffuse through the glass substrate during subsequent heat treatment, thereby accurately detecting and evaluating the migration ability of the target metal element.

[0032] In step S3, the stacked sample is heat-treated. Heat treatment is a crucial step in inducing the diffusion of the target metal element in the glass matrix. Heat treatment accelerates the interaction between the target metal element and the glass matrix, promoting the diffusion of the target metal element into the glass matrix. By controlling the temperature and time of the heat treatment, the actual high-temperature working environment can be simulated, and the diffusion of the target metal element can be observed.

[0033] In step S4, the diffusion layer thickness and diffusion coefficient of the target metal element in the sample to be tested are obtained. The diffusion layer thickness refers to the thickness of the portion of the sample from the surface of the glass substrate where the concentration of the target metal element changes significantly due to diffusion. The thicker the diffusion layer, the stronger the diffusion and migration ability of the target metal element in the glass substrate. The diffusion coefficient is a physical parameter describing the diffusion rate of the target metal element in the glass substrate, and its unit is usually square meters per second (m² / s). 2 / s) or centimeter squared per second (cm) 2 The larger the diffusion coefficient, the faster the diffusion rate of the target metal element, the farther the particles diffuse per unit time, and the stronger their migration ability. The migration ability of the target metal element can be comprehensively evaluated based on the diffusion layer thickness and the diffusion coefficient. The diffusion layer thickness directly reflects the size of the diffusion range of the target metal element within the glass matrix, while the diffusion coefficient provides a quantitative indicator of the diffusion rate. Combining these two parameters allows for the construction of diffusion models of the target metal element under different temperature and time conditions, thereby predicting its diffusion behavior under practical application conditions. Specifically, the diffusion layer thickness can be measured using a microscope, and the diffusion coefficient can be calculated based on the diffusion layer thickness and reaction time.

[0034] Based on the diffusion layer thickness and diffusion coefficient of the target metal element, it is possible not only to effectively evaluate and characterize the high-temperature migration ability of the target metal element in the glass matrix, but also to quantitatively evaluate and characterize the diffusion inhibition or promotion ability of the glass matrix for the target metal element, thereby scientifically characterizing the migration ability of metal elements in the glass matrix.

[0035] This application obtains the diffusion layer thickness and diffusion coefficient of the target element by coating an inert metal layer on the surface of a glass substrate and sandwiching a material containing the target metal element between two inert metal-coated glass substrates for heat treatment. This method can intuitively and accurately reflect the migration ability of metal elements under high-temperature conditions. Compared with traditional methods, it can more directly show the diffusion path and depth of the element. By controlling the temperature and time of heat treatment, the migration law of metal elements under different conditions can be studied, thereby achieving controllability of the migration and distribution of metal elements in the glass substrate. This is crucial for optimizing the high-temperature protection performance of the glass substrate, regulating the migration of metal elements, and achieving the best protection effect under different conditions. In addition, this application simplifies the sample preparation, heat treatment, and analysis steps into a series of standardized operations, making the method easy to implement, reducing the complexity of experimental operations, lowering the technical requirements for experimental personnel, and improving the repeatability of experiments and the reliability of data. By accurately measuring the diffusion layer thickness of metal elements in the glass substrate, high-temperature oxidation loss can be effectively reduced in actual production, saving metal resources, while reducing energy consumption and environmental pollution in the production process, which is in line with the concept of green manufacturing and sustainable development. Furthermore, since the target metal element is any element that can diffuse through the glass matrix under high temperature conditions, this means that the detection method of this application is not limited to specific metal elements, but is applicable to the migration detection of a variety of metal elements, providing flexibility and breadth for the performance evaluation and application selection of different types of glass-based protective materials.

[0036] In the specific implementation of this invention, the diffusion of the target metal element in the glass matrix can be observed and measured by microscopic analysis and detection technology, thereby obtaining the diffusion layer thickness and diffusion coefficient of the target metal element in the sample to be tested.

[0037] In some embodiments, the inert metal layer comprises at least one of Au, Pt, and Pd. The inert metal layer can be composed of metals such as gold (Au), platinum (Pt), and palladium (Pd), or combinations thereof. These metals are chemically stable at high temperatures and do not readily react with the glass substrate or other metallic elements. Simultaneously, these metals possess good electrical and thermal conductivity, ensuring they do not interfere with subsequent microscopic analysis and detection, and clearly characterizing the diffusion layer thickness and morphological distribution of the target metallic element. By using these metals as materials for the inert metal layer, a stable layer can be formed under high-temperature conditions, while providing clear markers for subsequent microscopic analysis and detection. Thus, when a material containing the target metallic element is sandwiched between two glass substrates coated with inert metal layers and subjected to heat treatment, the diffusion layer thickness and morphological distribution of the target metallic element can be accurately detected using microscopic analysis and detection techniques, thereby more accurately assessing the migration ability of metallic elements in the glass substrate.

[0038] In step S1, the coating can be performed using physical or chemical deposition methods such as ion sputtering, chemical vapor deposition (CVD), physical vapor deposition (PVD), or electron beam evaporation. In some embodiments, the thickness of the inert metal layer is 0.05 μm to 0.3 μm, for example, a range of 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, or any combination thereof. By controlling the thickness of the inert metal layer within the above range, it is possible to ensure that the inert metal layer remains stable during high-temperature heat treatment without affecting the normal migration of the target metal elements.

[0039] The detection method of this application is applicable to a variety of metallic elements, providing flexibility and versatility for the research and development of new glass protective coating materials. This application does not limit the specific type of the target metallic element; different metallic elements can be selected according to actual production needs. In some embodiments, the target metallic element includes at least one of Fe (iron), Cr (chromium), Si (silicon), Mg (magnesium), and Al (aluminum). These metallic elements are the main additive elements in steel materials in practical applications. By using these target metallic elements as detection objects, the interaction between steel materials and glass substrates in actual production can be simulated, providing a scientific basis for optimizing the formulation and heat treatment process of glass protective coatings to achieve effective protection of steel materials under high-temperature conditions. The detection results of different metallic elements can reveal the protective mechanism of the glass substrate against different metals, thereby guiding the selection and design of coating materials and improving their protective performance in specific applications.

[0040] The material containing the target metallic element can be a metal oxide, metal alloy, etc., containing the target metallic element. It is pressed into a shape that matches the first sample to form the second sample. The pressing process needs to ensure the uniformity and density of the material so that the metallic element can diffuse uniformly during heat treatment.

[0041] In the specific implementation of this invention, when the target metal element is Fe, the material containing the target metal element can be a substance containing iron, such as stainless steel or carbon steel, or a substance containing Fe that can migrate under high temperature conditions, or a test object made of iron compounds (such as Fe2O3 or Fe3O4) that can exist stably in a high temperature environment; when the target metal element is Cr, the material containing the target metal element can be a Cr oxide, steel, or a substance containing Cr that can migrate under high temperature conditions; when the target metal element is Si, the material containing the target metal element can be a Si oxide, steel, or a substance containing Si that can migrate under high temperature conditions; when the target metal element is Mg, the material containing the target metal element can be a Mg oxide, steel, or a substance containing Mg that can migrate under high temperature conditions; when the target metal element is Al, the material containing the target metal element can be an Al oxide, steel, or a substance containing Al that can migrate under high temperature conditions.

[0042] In the specific implementation of this invention, a mold can be used to press the glass-based protective coating material into a glass substrate with a specific shape, or a mold can be used to press a material containing the target metal element into a second sample with a specific shape. The pressing pressure is 20 MPa to 40 MPa, and the holding time is 5 min to 20 min.

[0043] In some embodiments, both the glass substrate and the second sample are cylindrical. By controlling the shapes of both the glass substrate and the second sample to be cylindrical, a relatively uniform contact interface can be provided, which facilitates the uniform migration of the target metal element in the glass substrate and avoids the influence of boundary effects. Simultaneously, cylindrical samples are easy to process into cross-sections, making it convenient to observe the migration of the target metal element using microscopic analysis and detection techniques. Furthermore, cylindrical samples are easy to press using molds during preparation, ensuring the density and shape consistency of the sample.

[0044] In some preferred embodiments, the diameters of the glass substrate and the second sample are each independently 5–50 mm, and their heights are each independently 3–30 mm. By controlling the diameters of the glass substrate and the second sample to be within the range of 5–50 mm and the heights to be 3–30 mm, the feasibility of experimental operation and the fulfillment of different research needs can be considered. This avoids the problem that smaller sizes may not provide sufficient observation area, while excessively large sizes may increase the difficulty and cost of the experiment.

[0045] The diameters of the glass substrate and the second sample are each independently 5 to 50 mm, for example, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm or any two of these ranges, and the heights are each independently 3 to 30 mm, for example, 3 mm, 5 mm, 8 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm or any two of these ranges.

[0046] In some preferred embodiments, the glass substrate has a diameter of 10–30 mm and a height of 10–30 mm; the second sample has a diameter of 10–30 mm and a height of 5–15 mm. By controlling the glass substrate and the second sample within the above-mentioned size range, a sufficiently large contact area is ensured to observe the migration of the target metal element, which also facilitates the processing in the experiment and subsequent microscopic analysis and detection.

[0047] When both the glass substrate and the second sample are cylindrical, in step S1, an inert metal layer is coated on the bottom surface of the glass substrate to obtain the first sample; step S2 includes: sandwiching the second sample between the two first samples with their bottom surfaces facing each other to obtain a stacked sample. Specifically, one bottom surface of the second sample is positioned opposite the bottom surface of one first sample, and the other bottom surface of the second sample is positioned opposite the bottom surface of another first sample, so that the second sample is sandwiched between the two first samples to form a stacked sample.

[0048] In some embodiments, the second sample is sandwiched between two first samples, and can be fixed using a high-temperature and pressure-resistant clamp or container to form a stacked sample. This ensures close contact between the two glass substrates and the second sample in the middle, promoting the migration of the target metal element. Specifically, a positioning device can be used for precise positioning. For example, one first sample is placed at the bottom of the positioning device, and then the bottom surface of the second sample is positioned above the first sample, ensuring that one bottom surface of the second sample contacts the first sample. Subsequently, another first sample is placed on top of the second sample, ensuring that the other bottom surface of the second sample contacts the first sample. Appropriate pressure or a fixing device is used to press the three samples together, ensuring close contact without deformation.

[0049] In some embodiments, the composite sample is placed in a high-temperature furnace (such as a muffle furnace) and heat-treated according to a predetermined temperature program and time. After heat treatment, the composite sample needs to be naturally cooled to room temperature to avoid the influence of rapid cooling on the migration of target metal elements. The cooled composite sample is then polished to make the surface smooth, thereby obtaining the sample to be tested. The polishing process can be carried out using a polishing machine with 200-2000 grit sandpaper.

[0050] In some embodiments, the heat treatment includes a sequential heating heat treatment and a holding heat treatment, wherein the initial temperature of the heating heat treatment is 15-30°C, the final temperature is 850°C-1250°C, the holding time of the heating heat treatment is 20-40 minutes, and the heating rate of the heating heat treatment is 5°C / min-20°C / min; the temperature of the holding heat treatment is 850°C-1250°C, and the holding time of the holding heat treatment is 30-720 minutes.

[0051] Specifically, by first subjecting the stacked samples to a high-temperature heat treatment to ensure the temperature of the high-temperature furnace (such as a muffle furnace) remains stable at a fixed temperature, it facilitates the smooth progress of subsequent heat treatment. After reaching the set temperature, the samples need to be held at that temperature for a certain period of time to allow sufficient time for the metal elements to diffuse.

[0052] In some embodiments, the heating rate of the heat treatment is 5°C / min to 20°C / min. The heating rate affects the migration rate and morphological distribution of the target metal element in the glass matrix. A slower heating rate may slow down the migration process of the metal element, but more detailed element distribution information can be obtained; while a faster heating rate accelerates the element migration, but may lead to non-uniformity of element distribution. In some preferred embodiments, the heating rate of the heat treatment is 10°C / min to 15°C / min. By controlling the heating rate within the range of 10°C / min to 15°C / min, a moderate heating rate is achieved, which ensures both rapid migration of the metal element and relatively uniform element distribution, facilitating subsequent microscopic analysis and detection.

[0053] In some embodiments, the heat treatment temperature is 850°C to 1250°C. By controlling the heat treatment temperature within the range of 850°C to 1250°C, the glass substrate begins to enter a high-temperature softening or flow state, and the diffusion kinetics of the target metal element are significantly enhanced. Higher temperatures are beneficial to the migration of the target metal element in the glass substrate, but excessively high temperatures may lead to over-softening or decomposition of the glass substrate, affecting the accuracy of the experimental results. In some preferred embodiments, the heat treatment temperature is 900°C to 1200°C. By controlling it within the range of 900°C to 1200°C, effective migration of the metal element can be ensured, while avoiding the adverse effects of excessively high temperatures on the glass substrate and the inert metal layer.

[0054] In some embodiments, the holding time for the heat treatment is 30 min to 720 min. This holding time ensures sufficient time for the target metal element to migrate and diffuse within the glass matrix. By controlling the holding time, significant element migration can be observed. However, too short a time may not achieve the required diffusion level, while too long a time may result in complete diffusion, making it difficult to distinguish between the initial location and the post-diffusion distribution. Controlling the holding time to 30 min to 720 min allows for more precise control of the metal element's diffusion depth, obtaining sufficient data to ensure the accuracy of the final results.

[0055] By controlling the heat treatment conditions described above, the migration patterns of metallic elements in a glass matrix can be precisely studied, including the diffusion rate, diffusion depth, and diffusion morphology. This further improves the accuracy and repeatability of the detection, ensuring the reliability and scientific validity of the research results.

[0056] In step S4, the microscopic analysis and detection can utilize scanning electron microscopy (SEM), electron probe microanalysis (EPMA), or X-ray photoelectron spectroscopy (XPS), etc. In some embodiments, S3 includes: heat-treating the stacked sample at a fixed temperature and different holding times t to obtain the sample to be tested; S4 includes: performing cross-sectional processing on the sample to be tested to expose the cross-section, performing elemental detection on the cross-section, and obtaining the diffusion layer thickness L of the target metal element in the glass substrate at different holding times t, obtaining L... 2 -t fitting curve; obtain the slope of the fitting curve, obtain the diffusion coefficient based on the slope, and determine the migration ability of metal elements based on the diffusion coefficient.

[0057] Specifically, after heat treatment, the diffusion path of the target metal element in the glass matrix needs to be visualized through cross-sectional processing. This involves cutting the sample into thin or semi-thin slices to expose the diffusion path. The purpose of this is to directly observe the depth and morphology of the diffusion of the target metal element in subsequent microscopic analysis, thereby obtaining accurate data on the diffusion layer thickness. During cross-sectional processing, physical or chemical damage to the sample should be minimized to ensure a smooth and clean surface for subsequent analysis.

[0058] After cross-sectional processing, microscopic analysis techniques, such as scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDS) or electron probe microanalysis (EPMA), are used to perform detailed scans of the cross-section. These techniques provide high-resolution images and chemical composition analysis, helping to determine the diffusion path of the target metal element in the glass matrix and the microstructure of the diffusion layer. Scanning images allow for direct visualization of the diffusion layer thickness and the distribution of the target metal element within it.

[0059] Following microscopic analysis, image analysis software was used to measure the thickness of the diffusion layer, a direct indicator of metal element migration. Simultaneously, quantitative analysis revealed the distribution of metal element content within the diffusion layer, specifically the concentration variations at different depths—a crucial parameter for assessing element migration capabilities.

[0060] The cross-sectional processing and elemental analysis in step S4 provide a direct and accurate assessment of the migration ability of target metal elements in the glass matrix. This is of great significance for studying and optimizing the performance of glass-based protective coatings and understanding the migration patterns of metal elements under high-temperature conditions. In practical applications, this information can guide the design of coatings and the optimization of heat treatment processes to achieve optimal high-temperature oxidation and corrosion resistance.

[0061] After obtaining data on the diffusion layer thickness and total content of the target metal element in the diffusion layer, diffusion kinetics or thermodynamics theories can be used to calculate parameters such as the diffusion coefficient or activation energy of the target metal element in the glass matrix, thereby scientifically characterizing the migration ability of the metal element. By comparing data from different glass matrices or under different heat treatment conditions, it is possible to identify which glass matrix or heat treatment condition can more effectively control the migration of metal elements, providing data support for practical applications.

[0062] Specifically, during the heat treatment process, the holding time t can be set to a series of different values, such as 30 min, 60 min, 90 min, 180 min, 360 min, 540 min, and 720 min, to observe the change in the thickness of the metal element diffusion layer over time. After the heat treatment, the sample needs to be cooled to room temperature according to a preset procedure to avoid sudden temperature changes causing additional structural changes or damage to the sample. A cross-section is then prepared on the heat-treated sample, and elemental analysis is performed on the cross-section to obtain the thickness of the metal element diffusion layer. Based on Fick's second law, the relationship between the detected diffusion layer thickness L and the holding time t is fitted to obtain L. 2-t is the fitted curve; the slope of the fitted curve can be used as the diffusion coefficient D. The diffusion coefficient D is a key parameter for measuring the migration ability of metal elements. The larger the D value, the faster the migration speed of the metal element and the stronger the migration ability.

[0063] In some embodiments, the diffusion layer thickness is the vertical distance from the surface of the glass substrate to the point where the content of the target metal element in the glass substrate reaches a baseline level. Specifically, the diffusion layer thickness refers to the vertical distance from the surface of the glass substrate until the content of the target metal element inside the glass substrate decreases to a “baseline level” consistent with its original state. Here, the “baseline level” refers to the content of the target metal element in the original glass substrate unaffected by the diffusion of the target metal element. Before heat treatment, the content of the target metal element in the glass substrate is fixed and recorded by measurement. After heat treatment, the target metal element begins to migrate from the second sample into the interior of the glass substrate, forming a diffusion layer. As the migration depth increases, the content of the target metal element gradually decreases until, at a certain depth, its content returns to the same level as the original state; this level is the “baseline level.” To accurately measure the depth of the target metal element migration, a direction perpendicular to the surface of the glass substrate needs to be determined as a measurement reference. The measurement of the diffusion layer thickness is a straight-line distance from the surface of the glass substrate along a direction perpendicular to the surface until the metal element content drops to the baseline level.

[0064] In microscopic analysis, by performing point-by-point or line-by-line chemical composition analysis on the cross-section, a concentration distribution curve of the target metal element in the glass matrix can be plotted. The diffusion layer thickness is the vertical distance between the surface and the point on the curve where the content recovers to the baseline level.

[0065] The diffusion layer thickness is a crucial parameter for evaluating the migration ability of metallic elements within a glass matrix. It reflects not only the diffusion rate and depth of the metallic element but also indirectly characterizes the glass matrix's ability to hinder or promote its migration. In optimizing glass-based protective coatings, understanding the diffusion layer thickness of the target metallic element helps determine the coating's suitability and stability, and how to adjust the coating formulation or heat treatment conditions to control metallic element migration, thereby improving the coating's protective effect and service life. By accurately measuring the diffusion layer thickness, the detection method presented in this application provides a scientific basis for the research and development of glass-based protective coatings, contributing to the design of more efficient and durable protective coatings, especially providing better protection for steel materials under high-temperature conditions, reducing resource waste, and improving product performance.

[0066] This application does not limit the specific type of glass matrix; different glass matrices with different compositions can be selected according to actual testing needs. In some embodiments, the glass matrix comprises the following components by mass fraction: SiO2 40%–70%, Al2O3 5%–12%, CaO 0.2%–0.7%, Fe2O3 2%–5%; K2O 2%–5%, Na2O 5%–8%, and other components 5%–20%.

[0067] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0068] Example 1

[0069] In this embodiment, the glass-based protective coating material comprises, by mass fraction: 65% SiO2, 8.7% Al2O3, 0.63% CaO, 3.79% Fe2O3, 4.29% K2O, 7.92% Na2O, and 9.67% other components; the material containing the target metal element is Cr2O3 powder.

[0070] The method for detecting the migration ability of metal elements in a glass matrix in this embodiment includes the following steps:

[0071] S1. Under a pressure of 30 MPa and a holding time of 15 min, the glass-based protective coating material is pressed into a cylindrical sample with a diameter of 20 mm and a height of 20 mm using the first mold to obtain a glass substrate. A uniform Au layer (thickness of 0.1 μm) is sputtered onto the bottom surface of the glass substrate using an ion sputtering instrument to obtain the first sample. The material containing the target metal element is pressed into a cylindrical sample with a diameter of 20 mm and a height of 5 mm using the second mold to obtain the second sample.

[0072] S2, the second sample is sandwiched between the two first samples with their bottom surfaces facing each other to obtain a stacked sample;

[0073] S3. Place the stacked sample in a muffle furnace and heat it for 30 minutes from room temperature (25°C) to 200°C. Then, heat it to 900°C at a rate of 10°C / min. Hold the sample at this temperature for 30 min, 60 min, 90 min, 180 min, 360 min, 540 min, and 720 min respectively. Allow the sample to cool to room temperature with the furnace after holding it for different times. Remove the sample and cold mount it. Then, use a polishing machine to polish it with sandpaper of 200 grit, 500 grit, 800 grit, 1200 grit, and 2000 grit in sequence. Finally, use polishing paste to polish the surface smooth to obtain the sample to be tested.

[0074] S4. The sample to be tested is cross-sectionally processed to expose the diffusion path of the target metal element. Electron probe microanalysis is used to analyze the cross-section of the sample to detect the diffusion layer thickness of the target metal element in the glass matrix at different holding times. Based on the diffusion layer thickness L at different holding times t, t is used as the abscissa and L is used as the ordinate. 2 The slope of the fitted curve is obtained by fitting the curve to the vertical axis, which is the diffusion coefficient.

[0075] Example 2

[0076] In this embodiment, the glass-based protective coating material comprises, by mass fraction: 64.3% SiO2, 8.79% Al2O3, 0.67% CaO, 3.86% Fe2O3, 4.27% K2O, 6.58% Na2O, and 11.53% other components. The material containing the target metal element is Cr2O3 powder.

[0077] The method for detecting the migration ability of metal elements in a glass matrix in this embodiment includes the following steps:

[0078] S1. Under a pressure of 30 MPa and a holding pressure of 15 min, the glass-based protective coating material is pressed into a cylindrical sample with a diameter of 20 mm and a height of 20 mm using the first mold to obtain a glass substrate. A uniform Pt layer (thickness of 0.2 μm) is sputtered onto the bottom surface of the glass substrate using an ion sputtering instrument to obtain the first sample. The material containing the target metal element is pressed into a cylindrical sample with a diameter of 20 mm and a height of 10 mm using the second mold to obtain the second sample.

[0079] S2, the second sample is sandwiched between the two first samples with their bottom surfaces facing each other to obtain a stacked sample;

[0080] S3. Place the stacked sample in a muffle furnace and heat it for 30 minutes from room temperature to 200°C. Then, heat it to 1000°C at a rate of 10°C / min and hold it for 30 minutes. Then, let it cool to room temperature with the furnace. Take out the sample and cold mount it. Then, use a polishing machine to polish it with sandpaper of 200 grit, 500 grit, 800 grit, 1200 grit and 2000 grit in sequence. Finally, use polishing paste to polish the surface smooth to obtain the sample to be tested.

[0081] S4. The sample to be tested is cross-sectionally processed to expose the diffusion path of the target metal element. Electron probe microanalysis is used to analyze the cross-section of the sample to detect the diffusion layer thickness of the target metal element in the glass matrix at different holding times. Based on the diffusion layer thickness L at different holding times t, t is used as the abscissa and L is used as the ordinate. 2The slope of the fitted curve is obtained by fitting the curve to the vertical axis, which is the diffusion coefficient.

[0082] Example 3

[0083] In this embodiment, the glass-based protective coating material comprises, by mass fraction: 68.5% SiO2, 9.5% Al2O3, 0.7% CaO, 4.68% Fe2O3, 3.7% K2O, 7.84% Na2O, and 5.08% other components. The material containing the target metal element is Cr2O3 powder.

[0084] The method for detecting the migration ability of metal elements in a glass matrix in this embodiment includes the following steps:

[0085] S1. Under a pressure of 30 MPa and a holding pressure of 15 min, the glass-based protective coating material is pressed into a cylindrical sample with a diameter of 20 mm and a height of 20 mm using the first mold to obtain a glass substrate. A uniform Pd layer (thickness of 0.3 μm) is sputtered onto the bottom surface of the glass substrate using an ion sputtering instrument to obtain the first sample. The material containing the target metal element is pressed into a cylindrical sample with a diameter of 20 mm and a height of 15 mm using the second mold to obtain the second sample.

[0086] S2, the second sample is sandwiched between the two first samples with their bottom surfaces facing each other to obtain a stacked sample;

[0087] S3. Place the stacked sample in a muffle furnace and heat it for 30 minutes from room temperature to 200°C. Then, heat it to 1100°C at a rate of 10°C / min and hold it for 30 minutes. Then, let it cool to room temperature with the furnace. Take out the sample and cold mount it. Then, use a polishing machine to polish it with sandpaper of 200 grit, 500 grit, 800 grit, 1200 grit and 2000 grit in sequence. Finally, use polishing paste to polish the surface smooth to obtain the sample to be tested.

[0088] S4. The sample to be tested is cross-sectionally processed to expose the diffusion path of the target metal element. Electron probe microanalysis is used to analyze the cross-section of the sample to detect the diffusion layer thickness of the target metal element in the glass matrix at different holding times. Based on the diffusion layer thickness L at different holding times t, t is used as the abscissa and L is used as the ordinate. 2 The slope of the fitted curve is obtained by fitting the curve to the vertical axis, which is the diffusion coefficient.

[0089] Example 4

[0090] In this embodiment, the glass-based protective coating material comprises, by mass fraction: 68.5% SiO2, 9.5% Al2O3, 0.7% CaO, 3.86% Fe2O3, 3.7% K2O, 6.63% Na2O, and 7.11% other components. The material containing the target metal element is Cr2O3 powder.

[0091] The method for detecting the migration ability of metal elements in a glass matrix in this embodiment includes the following steps:

[0092] S1. Under a pressure of 30 MPa and a holding pressure of 15 min, the glass-based protective coating material is pressed into a cylindrical sample with a diameter of 20 mm and a height of 20 mm using the first mold to obtain a glass substrate. A uniform Au layer (thickness of 0.05 μm) is sputtered onto the bottom surface of the glass substrate using an ion sputtering instrument to obtain the first sample. The material containing the target metal element is pressed into a cylindrical sample with a diameter of 20 mm and a height of 10 mm using the second mold to obtain the second sample.

[0093] S2, the second sample is sandwiched between the two first samples with their bottom surfaces facing each other to obtain a stacked sample;

[0094] S3. Place the stacked sample in a muffle furnace and heat it for 30 minutes from room temperature to 200°C. Then, heat it to 1200°C at a rate of 10°C / min and hold it for 30 minutes. Then, let it cool to room temperature with the furnace. Take out the sample and cold mount it. Then, use a polishing machine to polish it with sandpaper of 200 grit, 500 grit, 800 grit, 1200 grit and 2000 grit in sequence. Finally, use polishing paste to polish the surface smooth to obtain the sample to be tested.

[0095] S4. The sample to be tested is cross-sectionally processed to expose the diffusion path of the target metal element. Electron probe microanalysis is used to analyze the cross-section of the sample to detect the diffusion layer thickness of the target metal element in the glass matrix at different holding times. Based on the diffusion layer thickness L at different holding times t, t is used as the abscissa and L is used as the ordinate. 2 A curve was fitted to the ordinate, and the slope of the fitted curve was obtained, which is the diffusion coefficient. The diffusion coefficient results are shown in Table 1.

[0096] Table 1

[0097] Example 1 <![CDATA[1.63×10 -8 ]]> Example 2 <![CDATA[7.26×10 -8 ]]> Example 3 <![CDATA[2.91×10 -8 ]]> Example 4 <![CDATA[7.10×10 -8 ]]>

[0098] As shown in Table 1, the method provided by this invention can obtain the diffusion coefficient of metal elements in different glass substrates at different temperatures, and then evaluate the migration ability of metal elements based on the diffusion coefficient.

[0099] It should be noted that the terms "first," "second," etc., used in the specification and claims of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in a sequence other than those described herein.

[0100] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for detecting the migration ability of metal elements in a glass matrix, characterized in that, Includes the following steps: S1, an inert metal layer is coated on the surface of a glass substrate to obtain a first sample; the material containing the target metal element is pressed into a second sample; S2, the second sample is sandwiched between the two first samples to obtain a stacked sample; S3, the stacked sample is heat-treated to obtain the sample to be tested; S4, obtain the diffusion layer thickness and diffusion coefficient of the target metal element in the sample to be tested, and determine the migration ability of the metal element based on the diffusion layer thickness and the diffusion coefficient.

2. The detection method according to claim 1, characterized in that, The inert metal layer contains at least one of Au, Pt, and Pd.

3. The detection method according to claim 2, characterized in that, The thickness of the inert metal layer is 0.05μm to 0.3μm.

4. The detection method according to claim 1, characterized in that, The target metallic element includes at least one of Fe, Cr, Mg, and Al.

5. The detection method according to claim 1, characterized in that, Both the glass substrate and the second sample are cylindrical in shape.

6. The detection method according to claim 5, characterized in that, The diameter of the glass substrate and the second sample are each 5-50 mm, and the height is each 3-30 mm.

7. The detection method according to claim 5, characterized in that, The diameter of the glass substrate is 10-30 mm and the height is 10-30 mm; the diameter of the second sample is 10-30 mm and the height is 5-15 mm.

8. The detection method according to claim 5, characterized in that, When both the glass substrate and the second sample are cylindrical, S1 includes: coating the bottom surface of the glass substrate with the inert metal layer to obtain the first sample; S2 includes: sandwiching the second sample between the two first samples with their bottom surfaces facing each other to obtain the stacked sample.

9. The detection method according to any one of claims 1 to 8, characterized in that, The heat treatment includes sequential heating heat treatment and heat holding heat treatment; The initial temperature of the heating heat treatment is 15~30℃, the final temperature is 850℃~1250℃, the holding time of the heating heat treatment is 20min~40min, and the heating rate of the heating heat treatment is 5℃ / min~20℃ / min. The temperature of the heat treatment is 850℃~1250℃, and the heat treatment time is 30min~720min.

10. The detection method according to claim 9, characterized in that, S3 includes: heat-treating the stacked sample at a fixed temperature and different holding times t to obtain the sample to be tested; S4 includes: performing cross-sectional processing on the sample to be tested to expose the cross-section of the sample to be tested, performing elemental detection on the cross-section, and obtaining the diffusion layer thickness L of the target metal element in the glass matrix under different heat preservation times t; Get L 2 -t fitting curve; obtain the slope of the fitting curve, obtain the diffusion coefficient based on the slope, and determine the migration ability of the metal element based on the diffusion coefficient.

11. The detection method according to claim 10, characterized in that, The thickness of the diffusion layer is the vertical distance from the surface of the glass substrate to the point where the content of the target metal element in the glass substrate reaches the baseline level.

12. The detection method according to any one of claims 1 to 8, characterized in that, The glass matrix comprises the following components by mass fraction: SiO2 40%~70%, Al2O3 5%~12%, CaO 0.2%~0.7%, Fe2O3 2%~5%; K2O 2%~5%, Na2O 5%~8%.