A three-dimensional visualization and kinetic calculation method for inorganic phase migration in organic-inorganic composite materials

Abstract

A three-dimensional visualization and kinetic calculation method for the migration of inorganic phases in organic-inorganic composite materials belongs to the technical field of material structure visualization and quantitative analysis. The present invention adopts a fluorescent tracer three-dimensional imaging analysis method to perform an in-situ visualization analysis of the migration process of the inorganic phase in the composite material. By counting the number of nanoparticles at different depths inside the composite material, the migration direction and migration process of the inorganic phase are analyzed. Statistical models are further used to calculate the migration amount, migration speed and direction of the inorganic phase, and the differences in inorganic phase migration under different external conditions and different polymer matrices are studied, further exploring the intrinsic connection between inorganic phase migration and composite material performance. This method realizes in-situ, non-destructive, three-dimensional quantitative analysis of the early migration process of the inorganic phase, providing an effective basis for studying the structure-activity relationship of composite materials and designing high-performance composite materials. This method is simple, sensitive, accurate, and has wide applicability and practical value.

Description

Technical Field

[0001] The present invention belongs to the technical field of material structure visualization and quantitative analysis, and specifically relates to a method for three-dimensional visualization of the migration process of inorganic phase nanoparticles in composite materials under external environmental conditions and in-situ analysis of migration dynamics. Background Art

[0002] Organic-inorganic composite materials are widely used, with the inorganic phase acting as a reinforcement to significantly enhance the composite's performance. Numerous studies have shown that organic-inorganic composites in a thermodynamically non-equilibrium state gradually transition toward a stable equilibrium state during storage, transportation, and use, leading to changes in the material's density, entropy, enthalpy, and macroscopic properties. During this transition, inorganic phase migration occurs, causing changes in the composite's structure and morphology, leading to a significant decrease in performance.

[0003] The migration of inorganic phases in composite materials has been studied. Chromatography, infrared spectroscopy, electron microscopy, gravimetric analysis, and other methods can be used to analyze the morphology, composition, and content of inorganic phases that have migrated to the surface of a material. However, these analytical processes suffer from poor accuracy, low sensitivity, and sample destruction, making it impossible to observe the migration of inorganic phases within the composite material and conduct in situ, non-destructive, and kinetic analysis. This limits the study of the microscopic migration behavior of inorganic phases and their interactions with composite materials. Therefore, developing a method to visualize the migration of inorganic phases and achieve three-dimensional, in situ tracking and real-time monitoring of the migration of inorganic phases within composite materials is key to understanding the intrinsic relationship between inorganic phase migration and the aging properties of composite materials.

[0004] The method of the present invention intends to use fluorescence identification and imaging analysis methods to perform fluorescence positioning and tracking of the inorganic phase in the composite material, and to study the migration path and migration dynamics of the inorganic phase through a three-dimensional visualization method. By imaging and quantitatively analyzing the composite material at different depths, the migration direction and migration behavior of the inorganic phase in the composite material under the external environment are observed, the migration amount and migration speed of the inorganic phase are quantitatively calculated, and the intrinsic connection between the migration of the inorganic phase and the aging of the composite material is explored. This method is non-destructive, in-situ, and accurate, and realizes three-dimensional visualization and quantitative analysis of the migration process of the inorganic phase inside the composite material. It is applicable to a variety of organic-inorganic composite materials and provides an effective basis for studying the structure-activity relationship of composite materials and designing high-performance composite materials. Summary of the Invention

[0005] After forming, organic-inorganic composite materials are in a thermodynamically non-equilibrium state. During their transition to equilibrium, they are simultaneously affected by multiple external factors, leading to inorganic phase migration and affecting the composite's properties. This invention provides a method for three-dimensional visualization and analysis of the migration dynamics of inorganic phases in composite materials.

[0006] The technical solution of the present invention is: the inorganic phase in the composite material is subjected to fluorescence positioning and three-dimensional imaging methods to obtain the dispersion of the inorganic phase in the composite material. For composite materials exposed to external stimuli for different periods of time, the distribution of the inorganic phase therein is tracked in situ, the migration direction and amount of the inorganic phase under different conditions are observed, and the migration dynamics are calculated. This method realizes the in-situ analysis of the early migration process of the inorganic phase inside the composite material through a three-dimensional fluorescence visualization analysis method, studies the key factors affecting its migration process through migration dynamics, and explores the correlation between the migration of the inorganic phase and the macroscopic properties of the composite material. This method is a non-destructive, in-situ tracing method for the migration process of the inorganic phase, which is suitable for tracking and analyzing the internal structure of a variety of organic-inorganic composite materials under different external conditions.

[0007] A method for three-dimensional visualization and migration dynamics of inorganic phase migration in an organic-inorganic composite material, characterized by comprising the following steps:

[0008] (1) Preparation of organic-inorganic composite materials and confirmation of the three-dimensional imaging analysis method of the inorganic phase

[0009] Select polymer and inorganic phase materials and construct polymer composites using methods such as hot pressing and injection molding; confirm the use of fluorescent molecular recognition strategy to fluorescently locate the inorganic phase in the composite material, and use three-dimensional laser confocal fluorescence microscopy to perform three-dimensional imaging analysis of the dyed composite material;

[0010] (2) Aging of organic-inorganic composite materials and in-situ tracking of the inorganic phase

[0011] An aging experiment is performed on the composite material constructed in step (1), and one or more conditions of different temperatures, humidity, light, oxygen, stress, etc. are used for different treatment times; a fluorescent molecular staining method is used to perform imaging analysis on the composite material before and after treatment and at different treatment times using the fluorescence recognition strategy of step (1), and the distribution of the inorganic phase in the composite material at different times is observed in the xyz three-dimensional space to analyze the migration of the inorganic phase;

[0012] (3) Statistics of inorganic phase distribution

[0013] Analyze at different depths. The depth direction is divided into n layers on average. The thickness of each layer is m microns, which is divided into 0~m microns, m microns~2m microns, 2m microns~3m microns, ... (n-1)*m microns~n*m microns. Calculate the inorganic phase distribution data of each layer. For example, take 10μm as a layer, and quantify the inorganic phase distribution data in the layers of 0~10, 10~20, 20~30, D~(D+10)μm, etc.; the corresponding inorganic phase particle content w in the i-th layer i % = N i / Nall , where N i is the number of inorganic phase particles in the i-th layer, N all is the total number of inorganic phase particles in all layers, i = 1, 2...n; obtain the change law of inorganic phase at different time and depth, and quantitatively evaluate its migration law; according to w i % Changes over time, explore the differences in changes of inorganic phase particles at different depths over time, and analyze the inorganic phase migration kinetics;

[0014] (4) Quantitative analysis of inorganic phase migration kinetics

[0015] The inorganic phase migration process was studied using statistical methods, and the migration amount of the inorganic phase in different depth layers was counted. It was assumed that the inorganic phase was evenly distributed in each layer at the beginning, and the inorganic phase content in each layer was N. Under external conditions, the number of inorganic phase particles migrating from layer i to layer i-1 was recorded as x. i , then the number of remaining particles in the i-th layer under the combined effect of migrating to the previous layer and receiving the next layer is Nx i +x i+1 , see Figure 6 , further calculate the average migration velocity of the inorganic phase in layer i: v = (the number of particles remaining in layer i at the previous moment minus the number of particles remaining in layer i at the next moment) / t, where t is the time interval between the previous and next moments. If v is a positive value, it means that the amount of particles migrating out of this layer is greater than the amount migrating in; if v is a negative value, it means that the amount of particles migrating out of this layer is less than the amount migrating in. Based on this, the migration dynamics of different inorganic phases in different polymer matrices at different times are obtained.

[0016] (5) Relationship between inorganic phase migration and composite material aging

[0017] The optical, electrical and mechanical properties of the composite materials under the above-mentioned different conditions and at different time points were tested to obtain quantitative evaluation indicators, study the correlation between the inorganic phase migration kinetics and the macroscopic properties of the composite materials, and determine the key factors and regulatory mechanisms affecting the performance of the composite materials.

[0018] The polymer material in step (1) can be a blend of one or more of polyolefins, polyesters, and polyamides, and the inorganic phase can be a variety of materials such as hydrotalcite, montmorillonite, silica, aluminum hydroxide, and magnesium hydroxide. The inorganic phase particle size ranges from 100 nm to 20 μm, and the secondary agglomerated particle size of the inorganic phase ranges from greater than 200 nm.

[0019] The various aging conditions in step (2) are as follows: temperature: the treatment can be carried out for different times at a temperature lower than the melting temperature of the polymer; humidity: a saturated salt solution steam atmosphere can be used for treatment with different humidity; light radiation intensity: a specific aging box is used to select an intensity of 0.05-2.00W / m 2 / nm for processing; in addition, stress, tension, etc. can be selectively added to change the migration process of the inorganic phase in the composite material.

[0020] In step (3), the statistics of the distribution of the inorganic phase can be performed using depth segments with different thicknesses of 0.5-50 μm for each layer with a thickness of m microns. The smaller the depth segment, the better it is for improving the accuracy of the analysis.

[0021] When calculating the migration amount in step (4), it is necessary to consider both the inorganic phase that migrates to the previous layer and the inorganic phase that receives the next layer within each layer. The combined effect of the two is reflected in the final number of particles in the layer. When calculating the average migration velocity of the inorganic phase, if v is a positive value, it means that the amount of migration out of the layer is greater than the amount of migration in; if v is a negative value, it means that the amount of migration out of the layer is less than the amount of migration in.

[0022] Step (5) can statistically analyze the migration process of nanoparticles with different particle sizes, different aspect ratios, and different morphologies in the system, thereby obtaining a correlation relationship.

[0023] The macroscopic properties of the composite material studied in step (5) may include mechanical, optical, electrical and other properties.

[0024] The present invention enables early, highly sensitive, in-situ tracer imaging of the inorganic phase migration process in organic-inorganic composite materials, visualizing the migration process of the inorganic phase within the composite material. Based on quantitative analysis data, the direction, amount, and speed of inorganic phase migration are studied. This method provides a non-destructive, three-dimensional visualization and quantitative analysis method for in-situ analysis of the inorganic phase migration process and migration behavior characteristics within the composite material. This method can be used to explore the inorganic phase migration behavior under different external conditions and different organic-inorganic compatibility conditions, providing a theoretical basis for studying the structure-activity relationship of composite materials, designing, and preparing high-performance composite materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The LDH-PP composite film was aged at 130°C for different times and stained with fluorescent molecules to obtain a three-dimensional fluorescence confocal imaging cross-section, i.e., a cross-section perpendicular to the layer (laser: 405 nm, collection range: 450-500 nm).

[0026] Figure 2 This is the imaging result analysis of LDH-PP composite film after aging at 130℃ for different times, and the percentage of LDHs particles in the total number of particles changes with depth.

[0027] Figure 3This is an analysis of the imaging results of LDH-PP composite films after aging at 130°C for different times. The percentage of LDHs particles in the total number of particles changes with time in the depth range of (A) 0-10μm, (B) 40-50μm, and (C) 110-120μm.

[0028] Figure 4 This is a graph showing the average migration rate of LDHs to the surface at different depths after the LDH-PP composite film is aged at 130°C (where x is the depth and y is the average migration rate at different depths).

[0029] Figure 5 Figure 3 is the correlation between the distribution percentage of LDH particles and the tensile properties of the composite material; (A) shows the changes in the distribution percentage of LDH particles in the range of 0-30 μm (black) and the tensile properties of the composite material (gray) at different times, and (B) shows the correlation between the distribution percentage of LDH particles and the tensile properties of the composite material.

[0030] Figure 6 This is a diagram showing the combined effect of the i-th layer migrating to the previous layer and receiving the migration of the next layer. DETAILED DESCRIPTION

[0031] The present invention will be further described below with reference to the examples, but the present invention is not limited to the following examples.

[0032] Example 1:

[0033] (1) Preparation and aging of hydrotalcite-polypropylene (LDH-PP) composite films

[0034] A 1% LDH-PP composite film was prepared by hot-pressing at 170°C. The composite film was placed in a heat aging chamber and aged at 130°C in air for 0-10 hours, ensuring that the film did not deform. After aging, it was taken out and naturally cooled at room temperature.

[0035] (2) Dyeing positioning and three-dimensional imaging tracking of LDHs nanoparticles in LDH-PP composite films

[0036] The composite films before and after aging were immersed in a boric acid-modified fluorescent molecule solution to stain and locate LDHs, and three-dimensional laser confocal fluorescence microscopy was used to perform three-dimensional imaging of the stained LDH-PP composite films. Figure 1 As shown in the figure, for the untreated composite material, the inorganic phase can basically be evenly dispersed along the depth; and after the composite material is heat-treated, the distribution of the inorganic phase is studied, and it can be found that the inorganic phase inside the material continuously migrates to the surface of the material, showing a gradient distribution trend.

[0037] (3) Quantitative analysis of the distribution of LDHs nanoparticles in LDH-PP composite films

[0038] The number of LDHs nanoparticles in the composite film at different depths was counted with 10 μm as a layer, and the content of inorganic phase particles w at different depths was calculated. D .like Figure 2 As shown in the figure, when the composite material is untreated, the number of LDHs nanoparticles per layer is about 0.1. However, after the composite film is treated, the distribution of LDHs nanoparticles changes: the number of nanoparticles on the surface is close to 0.2, while the number of particles in the interior approaches 0.

[0039] The number of nanoparticles at different depths was counted, with the depths of 0-10μm, 40-50μm, and 110-120μm being used for statistics. Figure 3 As shown in the figure, the number of particles at 0-10 μm increases with the treatment time of the composite film, reaching equilibrium around 5 hours and remaining essentially unchanged. The number of particles at 40-50 μm generally fluctuates, while the number of nanoparticles at 110-120 μm decreases with treatment time. These results indicate that LDH nanoparticles at different depths exhibit different migration behaviors under heat treatment.

[0040] (4) Quantitative analysis of the migration rate of LDHs nanoparticles in LDH-PP composite films

[0041] Calculating the average migration rate of LDHs nanoparticles using the particle migration rate formula revealed a surface migration rate of approximately 0.25 μm / h, indicating that the particles migrate toward the surface. This rate initially decreases with increasing depth, then remains constant at around 40 μm. As depth increases, the LDHs nanoparticle migration rate becomes negative, indicating that the particles migrate away from these locations. The absolute value of the migration rate increases with increasing depth. This allows for a quantitative evaluation of LDHs nanoparticles and explores the differences in inorganic phase migration rate at different depths.

[0042] The migration process of LDHs at different temperatures was further studied, and the migration rate at different temperatures was calculated. According to the Arrhenius equation, the activation energy of LDHs migration in PP can be obtained, proving the feasibility of the migration process.

[0043] (5) Correlation between LDHs nanoparticle migration and macroscopic properties of LDH-PP composite films

[0044] The changes in tensile strength of composite materials under heat treatment were studied, such as Figure 5The results show two stages: in the first stage (before 5 hours), the tensile strength of the composite material rapidly decreased from 42.39 MPa to 36.66 MPa; in the second stage (after 5 hours), the tensile strength slowly decreased and remained basically stable. This pattern is consistent with the change in the migration of inorganic phase nanoparticles. The percentage of inorganic phase particles distributed in the surface layer and the tensile properties of the composite material are linearly related, indicating that the migration of the inorganic phase directly determines the macroscopic properties of the composite material. When the inorganic phase migration rate is fast, the mechanical strength of the composite material will deteriorate severely; when the inorganic phase remains stable, the mechanical properties of the composite material are stable. This provides a foundation for the study of the migration process of composite materials and the exploration of structure-activity relationships, and provides a theoretical basis for the design of high-performance composite materials.

Claims

1. A method for three-dimensional visualization and kinetic calculation of inorganic phase migration in organic-inorganic composite materials, characterized in that: The following steps are involved: (1) Preparation of organic-inorganic composite materials and confirmation of three-dimensional imaging analysis methods for inorganic phases Select polymer and inorganic phase materials and construct polymer composite materials by hot pressing or injection molding; confirm the use of fluorescent molecular recognition strategy to fluorescently locate the inorganic phase in the composite material, and use three-dimensional laser confocal fluorescence microscopy to perform three-dimensional imaging analysis of the dyed composite material; (2) Aging of organic-inorganic composite materials and in-situ tracking of the inorganic phase An aging experiment is performed on the composite material constructed in step (1), and one or more conditions of different temperatures, humidity, light, oxygen, and stress are used for different treatment times; a fluorescent molecule recognition strategy of step (1) is used to perform a fluorescent molecule staining method to perform imaging analysis on the composite material before and after treatment and at different treatment times, and the distribution of the inorganic phase in the composite material at different times is observed in the xyz three-dimensional space to analyze the migration of the inorganic phase; (3) Statistics of inorganic phase distribution Analyze at different depths. The depth direction is divided into n layers. Each layer is m microns thick, which is divided into 0 ~ m microns, m microns ~ 2m microns, 2m microns ~ 3m microns, ... (n-1)*m microns ~ n*m microns. Calculate the inorganic phase distribution data for each layer. Corresponding to the content of inorganic phase particles in layer i w i % = N i / N all， in N i is the number of inorganic phase particles in the i-th layer, N all is the total number of inorganic phase particles in all layers, i = 1, 2...n; obtain the change pattern of inorganic phase at different time and depth, and quantitatively evaluate its migration pattern; according to w i % changes over time, explore the differences in the changes of inorganic phase particles at different depths over time, and analyze the inorganic phase migration kinetics; (4) Quantitative analysis of inorganic phase migration kinetics The inorganic phase migration process was studied using statistical methods, and the migration amount of the inorganic phase in layers of different depths was counted. It was assumed that the inorganic phase was evenly distributed in each layer at the beginning, and the inorganic phase content in each layer was N. Under external conditions, i Layer direction i ‒The number of inorganic phase particles migrating in one layer is recorded as x i , then the number of remaining particles in the i-th layer under the combined effect of migrating to the previous layer and receiving the next layer is N‒ x i + x i+1， Calculate the average migration velocity of the inorganic phase layer i v = (the number of remaining particles in the i-th layer at the previous moment minus the number of remaining particles in the i-th layer at the next moment) / t, where t is the time interval between the previous moment and the next moment; if v If it is a positive value, it means that the outflow of this layer is greater than the inflow; if v A negative value indicates that the amount of migration out of the layer is less than the amount of migration in; based on this, the migration dynamics of different inorganic phases in different polymer matrices at different times were obtained; (5) Relationship between inorganic phase migration and composite material aging The optical, electrical and mechanical properties of the composite materials under the above-mentioned different conditions and at different time points were tested to obtain quantitative evaluation indicators, study the correlation between the inorganic phase migration kinetics and the macroscopic properties of the composite materials, and determine the key factors and regulatory mechanisms affecting the performance of the composite materials.

2. A method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: The polymer material is selected from one or more blended polymers of polyolefins, polyesters and polyamides, and the inorganic phase is selected from one or more of hydrotalcite, montmorillonite, silicon dioxide, aluminum hydroxide and magnesium hydroxide.

3. A method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: The particle size of the inorganic phase ranges from 100 nm to 20 μm, and the secondary agglomerated particle size ranges from more than 200 nm.

4. A method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: The various factors and conditions of aging in step (2): temperature: treatment for different time periods below the melting temperature of the polymer; Humidity: Saturated salt solution steam atmosphere was used for different humidity treatments; Light radiation intensity: The intensity was selected in an aging box with an intensity of 0.05‒2.00 W / m 2 / nm is processed; stress is to selectively add one or two of stress and tension to change the migration process of the inorganic phase in the composite material.

5. The method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: In step (3), the statistics of the inorganic phase distribution are performed using depth segments with different thicknesses of 0.5-50 μm for each layer with a thickness of m microns. The smaller the depth segment, the better the accuracy of the analysis.

6. A method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: In step (3), when analyzing at different depths, 10 μm is taken as one layer, and the quantitative range is 0 ~ 10, 10 ~ 20, 20 ~ 30, D ~ ( D +10) μm and so on for the inorganic phase distribution data within the layer.

7. A method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: When performing migration statistics in step (4), it is necessary to consider both the inorganic phase that migrates to the previous layer and the inorganic phase that receives the next layer in each layer. The combined effect of the two is expressed as the final number of particles in this layer. When calculating the average velocity of inorganic phase migration, if v If it is a positive value, it means that the outflow of this layer is greater than the inflow; if v A negative value indicates that the outflow of this layer is less than the inflow.

8. The method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: The migration process of nanoparticles with different particle sizes, different aspect ratios, and different morphologies in the system is statistically analyzed to obtain relevant relationships.

9. The method for three-dimensional visualization and kinetic calculation of inorganic phase migration in an organic-inorganic composite material according to claim 1, characterized in that: The macroscopic properties of the composite material studied in step (5) include mechanical, optical and electrical properties.

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