Method for rapid testing and analysis of corrosion resistance of zirconium alloy based on H ion implantation

Abstract

The present application relates to a method for rapid testing and analysis of corrosion resistance of zirconium alloy based on H ion implantation, and belongs to the technical field of material performance testing and analysis. The method comprises the following steps: preparing a TEM thin film sample of zirconium alloy; performing in-situ H ion implantation and collecting in-situ TEM images at multiple cumulative implantation amount nodes; obtaining the hydride volume ratio generated according to each image; fitting the evolution relationship between the hydride volume ratio and the cumulative implantation H concentration, extracting key parameters and establishing a rapid evaluation index, and realizing the corrosion resistance ranking of multiple screened zirconium alloy samples. The present application can realize rapid analysis and evaluation of the corrosion resistance of zirconium alloy and rapid pre-screening, and is suitable for composition optimization, preparation process optimization and corrosion hydrogen absorption behavior evaluation of zirconium alloy materials.

Description

Technical Field

[0001] This invention relates to the technical field of material performance testing and analysis, specifically to a rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H-ion implantation. Background Technology

[0002] Zirconium metal and its alloys possess low thermal neutron absorption cross-sections, good corrosion resistance, and favorable overall service performance, making them widely used as fuel cladding materials for nuclear reactors such as pressurized water reactors and boiling water reactors. When zirconium alloys operate in high-temperature, high-pressure water environments, they undergo oxidation and hydrogen absorption; hydrogen entering the matrix further migrates and may form hydrides. Hydride formation alters the local microstructure and mechanical response of the material; therefore, the corrosion and hydrogen absorption behavior of zirconium alloys has always been a key issue in the safety assessment of nuclear cladding materials.

[0003] Currently, the evaluation of the corrosion resistance of zirconium alloys mainly relies on high-temperature, high-pressure water corrosion tests or autoclave corrosion tests. While these methods can reflect relatively realistic service environments, they typically involve long experimental cycles, often requiring months or even longer. Sample preparation, corrosion treatment, and subsequent characterization procedures are also quite cumbersome, hindering rapid cross-sectional comparisons and high-throughput pre-screening among multiple candidate zirconium alloys. Especially in the alloy composition optimization and initial selection of new materials, relying entirely on real corrosion tests will significantly limit material development efficiency.

[0004] On the other hand, existing corrosion assessments are typically based on final-state results such as post-corrosion cross-sectional morphology, oxide film thickness, local microstructure, and hydrogen content. While these characterization results reflect the final state after corrosion, they often fail to directly provide continuous dynamic information on the initiation, growth, and stabilization of hydrides, and also struggle to establish a correlation between microstructure changes and hydrogen introduction within the same region. Therefore, relying solely on final-state characterization can easily overlook differences among different zirconium alloys in early hydrogen absorption sensitivity, hydride nucleation lag, and subsequent growth rates, thus limiting a deeper understanding of the sources of material corrosion resistance differences. Furthermore, when screening materials, if only single final-state information is available without continuously tracking the structural evolution process, both screening speed and accuracy will be affected. Summary of the Invention

[0005] The purpose of this invention is to provide a rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H ion implantation, in order to solve the problems that the existing evaluation of the corrosion resistance of zirconium alloys mainly relies on high-temperature and high-pressure water corrosion tests, which have long experimental cycles, cumbersome sample processing and subsequent characterization procedures, difficulty in directly obtaining continuous dynamic evolution information of hydrides, and are not conducive to rapid cross-sectional comparison of multiple candidate samples.

[0006] This invention enables rapid comparison of the hydrogenation behavior of different zirconium alloys under laboratory conditions, obtains dynamic microscopic information on hydride formation and evolution, extracts kinetic characteristic parameters reflecting the differences in corrosion resistance of materials, and achieves rapid and effective screening of corrosion-resistant zirconium alloys.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H-ion implantation includes the following steps:

[0009] S1. Prepare zirconium alloy as a TEM thin film sample, select at least one in-situ observation area, and confirm the substrate state of the in-situ observation area before injection.

[0010] S2. Perform in-situ H ion implantation on the in-situ observation area, and acquire TEM images of the in-situ observation area at multiple cumulative H concentration nodes;

[0011] S3. Based on each of the images, identify the hydrides in at least a portion of the in-situ observation area and obtain the hydride volume ratio;

[0012] S4. Fit the evolution relationship between the hydride volume ratio and the cumulative injected H concentration to extract the initial hydride formation concentration parameter. Characteristic diffusion-propellant concentration parameters and saturated volume ratio ;

[0013] S5. For multiple zirconium alloys, based on the above... , and Establish a rapid evaluation index According to the above The corrosion resistance of the various zirconium alloys was ranked, among which...

[0014] ,

[0015] , and In the plurality of zirconium alloys respectively , and The maximum value, , and These are the weighting coefficients, and .

[0016] in, Used to characterize the minimum H concentration required for the identifiable formation of hydrides; Used to characterize the degree of lag in the progression of hydride volume ratio from initial formation to rapid growth stage; Used to characterize the final degree of hydrogenation achievable by a sample under continuous H ion implantation conditions. For the same implantation conditions, The larger the value, the less likely the sample is to form hydrides at low concentrations; The larger the value, the slower the increase in hydride volume ratio; The lower the value, the smaller the total volume of hydride formed in the final sample.

[0017] Optionally, in step S1, the thickness of the thin film sample is 100~150 nm.

[0018] Optionally, in step S1, the pre-implantation substrate state confirmation includes confirming that the thin film sample is in an initial state without identifiable hydrides by at least one of TEM morphology observation, selected area electron diffraction, and Raman characterization.

[0019] Optionally, in step S2, the in-situ H ion implantation conditions are determined based on the thickness of the thin film sample and the implantation distribution of H in the zirconium alloy.

[0020] Optionally, the SRIM program is used to calculate the range distribution of H ions in the thin film sample, and the H ion implantation energy is determined based on the range distribution, so that the H implantation peak is located within the thickness range of the in-situ observation area.

[0021] Optionally, in step S3, the major axis length, minor axis length, and number of the identified hydrides are statistically analyzed to obtain the hydride number density and average volume, and then the hydride volume ratio is calculated, wherein the hydride volume ratio is the volume fraction of hydrides per unit area.

[0022] Furthermore, within the in-situ observation area of ​​each image, the same statistical region is selected, and the major axis length, minor axis length, and number of hydrides within the statistical region are statistically analyzed to determine the hydride number density. :

[0023] ,

[0024] in, To count the number of hydrides in the region, To calculate the area, The thickness of the statistical region; approximating a single hydride as a rotating ellipsoid, the volume fraction of hydride per unit volume within the statistical region. for:

[0025]

[0026] in, The mean major axis length of the hydride. The mean minor axis length of the hydride. The average volume of the hydride.

[0027] Optionally, in step S4, the fitted expression is:

[0028] ,

[0029] in, The cumulative H concentration injected.

[0030] Furthermore, multiple in-situ observation areas are selected for the thin film sample, and the average hydride volume ratio of the multiple in-situ observation areas is taken to obtain the average hydride volume ratio, which is then used for fitting.

[0031] Optionally, in step S5, the plurality of zirconium alloys differ in at least one variable among composition, microstructure, preparation process, and heat treatment state; the rapid evaluation index The size of the sample is positively correlated with its corrosion resistance.

[0032] The beneficial effects of this invention are as follows:

[0033] 1) It can analyze and pre-screen the corrosion resistance of different zirconium alloys in a short time, significantly shortening the evaluation cycle required by traditional high temperature and high pressure water corrosion tests; it can quantitatively compare the hydrogenation resistance of different samples, improving the material screening efficiency.

[0034] 2) It can obtain continuous dynamic microscopic information on hydride formation and evolution during in-situ H ion implantation, rather than relying solely on post-corrosion final state characterization, thus effectively improving reliability;

[0035] 3) The method is highly feasible and easy to repeat;

[0036] 4) It can be used for the optimization of zirconium alloy material composition, the optimization of preparation process, the pre-evaluation of corrosion resistance, and the study of related corrosion and hydrogen absorption mechanisms. Attached Figure Description

[0037] Figure 1 This is a schematic flowchart of an embodiment of a rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H-ion implantation.

[0038] Figure 2 Figure 1 shows the results of confirming the matrix state of the sample before injection in Example 1. Among them, (a) is a transmission electron microscope image of a representative sample before injection, (b) is a selected area electron diffraction pattern of the corresponding region, and (c) is a Raman spectrum of the sample before injection.

[0039] Figure 3The figure shows the SRIM calculation results of H ions in the zirconium alloy thin film sample in Example 1, which shows the concentration distribution of H ions in the thickness direction of the sample, the position of the injection peak, and the average deposition concentration within the sample thickness range.

[0040] Figure 4 This is an in-situ microstructure evolution diagram of the representative sample in Example 1 under different cumulative injection volume conditions.

[0041] Figure 5 The graph shows the statistical results of hydrides in samples #6, #7 and #8 in Example 1. Among them, (a) is the statistical result of the change of the long axis length of hydrides with the cumulative injection amount, (b) is the statistical result of the change of the short axis length of hydrides with the cumulative injection amount, and (c) is the statistical result of the change of the number density of hydrides with the cumulative injection amount.

[0042] Figure 6 The figure shows the fitting results of hydride volume ratio and diffusion control for samples #6, #7 and #8 in Example 1, illustrating the experimental data and fitting curves of hydride volume ratio as a function of H ion implantation.

[0043] Figure 7 The diagram shows the structural verification results of the representative sample after injection in Example 1; where (a) is the selected area electron diffraction pattern of the corresponding region of the sample after injection, and (b) is the Raman spectrum of the sample after injection.

[0044] Figure 8 These are actual corrosion results of samples #6, #7 and #8 in Example 1; where (a)~(c) are cross-sectional morphology diagrams of samples #6, #7 and #8 after actual corrosion, respectively, and (d) is the statistical result diagram of the corresponding oxide film thickness. Detailed Implementation

[0045] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. These embodiments are for illustrative purposes only and do not constitute a limitation on the scope of protection of the present invention.

[0046] This embodiment utilizes in-situ H-ion implantation on zirconium metal or zirconium alloy thin film samples to obtain dynamic microscopic information on hydride formation and evolution, extract hydrogenation kinetic characteristic parameters, and combine this with real corrosion results to analyze, rapidly compare, and screen the corrosion resistance of different zirconium alloys. This method is applicable to the pre-evaluation of corrosion resistance, material composition optimization, and related corrosion and hydrogen absorption mechanism studies of zirconium alloys used for nuclear fuel cladding.

[0047] For details, please refer to Figure 1 The rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H ion implantation in this embodiment includes the following steps:

[0048] S1. Prepare thin film samples of zirconium alloys to be screened into thin films suitable for in-situ observation by transmission electron microscopy; select in-situ observation areas before ion implantation, and confirm that there are no obvious hydride features in the sample matrix by transmission electron microscopy, selected area electron diffraction and Raman characterization.

[0049] S2. Determine the H ion implantation parameters based on the sample thickness and the H implantation distribution in the zirconium alloy; set the implantation temperature, filler rate, and multiple cumulative implantation amount nodes to ensure the implantation peak is within the thickness range of the in-situ observation area, and that the cumulative implantation amount covers the entire process of hydride development from absence, initial formation, continuous growth, to stabilization. At multiple cumulative implantation amount nodes, perform continuous microstructural observation and image acquisition in the in-situ observation area, recording the evolution of hydride development from absence to initial formation, continuous growth, and stabilization.

[0050] S3. Measure the major axis length, minor axis length, and number of hydrides under each cumulative injection condition, and calculate the hydride number density. Further, based on the average size and number density of hydrides, calculate the volume ratio of hydrides in a unit volume of sample. Selected area electron diffraction and Raman characterization can be performed on representative samples after injection to verify that the anomalous contrast characteristics observed in situ correspond to hydrides.

[0051] S4. Using the cumulative injected H concentration as the independent variable and the hydride volume ratio as the dependent variable, a diffusion-controlled fitting model was used to fit the hydride evolution process, and the initial hydride formation concentration parameter was extracted. Characteristic diffusion-propellant concentration parameters and saturated volume ratio .

[0052] S5, based on the above , and Establish a rapid evaluation index to rank the corrosion resistance of the samples to be screened.

[0053] The zirconium alloys to be screened are zirconium metal, Zr-2, Zr-4, Nb-containing zirconium alloys, Cr-containing zirconium alloys, Sn-containing zirconium alloys, or zirconium alloys containing at least two of the elements Sn, Fe, Cr, and Nb. The samples to be screened may differ in at least one variable: composition, microstructure, preparation process, or heat treatment state. For example, they may be zirconium alloy samples with the same nominal composition but different preparation processes.

[0054] The thin film sample was a φ=3 mm circular sample, which was obtained by mechanical thinning and double-spray electrolytic thinning. In order to reduce the influence of surface hydrides or local abnormal structures introduced during the sample preparation process on the subsequent observation results, the sample was further cleaned by PIPS after double spraying.

[0055] In step S1, multiple in-situ observation areas are selected in each zirconium alloy sample, preferably no less than three, and more preferably four; the thickness of the in-situ observation areas is relatively uniform, preferably 100~150 nm as measured by CBED. Preferably, the in-situ observation areas are photographed under

[0001] positive band axis conditions. Confirmation of the matrix state before sample implantation includes at least two of the following: transmission electron microscopy morphology observation, selected area electron diffraction, and Raman characterization. In particular, when no obvious hydride features are observed in the sample matrix before implantation, and the diffraction results correspond to the diffraction characteristics of the zirconium matrix and no obvious hydride characteristic peaks appear in the Raman spectrum, it can be determined that the sample is in an initial state without obvious hydrides before ion implantation.

[0056] In step S2, the SRIM program is used to calculate the range distribution of H ions in the zirconium alloy thin film sample, and the implantation energy is determined based on the sample thickness and implantation distribution. Preferably, the H ion implantation energy ensures that the H implantation peak is located within the thickness range of the in-situ observation area. The cumulative implantation amount is calculated using the cumulative implanted H concentration. Characterization can be expressed in appm; when the injection rate is constant, the cumulative injection volume corresponds one-to-one with the ion implantation time. Specifically, the cumulative injected H concentration covers the entire process of hydride formation from absence, initial formation, rapid growth to stabilization. After each preset cumulative injection volume node is reached, the corresponding in-situ observation area's microstructure image is recorded; preferably, repeated positioning of the same area is used for image acquisition to ensure the comparability of images under different cumulative injection volume conditions.

[0057] In step S3, a statistical region is selected for each in-situ observation area, and the major axis length of the hydride is measured one by one. and minor axis length And the average major axis length was calculated respectively. and average minor axis length At the same time, the total number of hydrides in this area will be counted. Combined with the area of ​​the statistical region and actual thickness Calculate the number density of hydrides ( The selected statistical regions are the same for images at different cumulative injection volume nodes. Approximating a single hydride as a rotating ellipsoid, the volume fraction of hydride per unit volume of sample within the statistical region is... It can be represented as:

[0058]

[0059] in, Characterizes the volume fraction of hydrides in a unit volume of sample. This represents the average volume of hydride. For each sample, under the same cumulative injection volume, the statistical results (i.e., the volume fraction of hydride per unit volume of sample) for selected statistical regions across multiple in-situ observation areas are used. The average value is taken as the average hydride volume ratio of the sample at that cumulative injection amount. In particular, local areas with significant changes in edge thickness, heavy contamination, or difficulty in distinguishing hydrides from other abnormal contrasts are not included in the statistics to reduce the impact of statistical errors on the results.

[0060] In step S4, the evolution of the hydride volume ratio as a function of the cumulative injected H concentration is fitted using the following diffusion control fitting expression:

[0061]

[0062] in, To accumulate the H concentration, The initial concentration parameter for hydride formation. For characteristic diffusion-propellant concentration parameters, This is the saturated volume ratio.

[0063] In step S5, the initial hydride formation concentration is selected. Characteristic diffusion-propellant concentration and saturated volume ratio As a key parameter for evaluating the hydrogenation resistance of different samples, a rapid evaluation index was established. The evaluation index is expressed as:

[0064]

[0065] in, , and Let be the weight coefficient, and satisfy... In particular, the evaluation index The larger the value, the stronger the sample's resistance to hydrogenation and the better its expected corrosion resistance.

[0066] When the evaluation objective focuses more on short-term corrosion effects and It can take a larger value within its range, especially during the early formation of hydrides. A larger value can be taken within its range; when more emphasis is placed on the diffusion and growth rate after hydride formation, A larger value can be taken within its range. When the focus is more on the final hydride accumulation after long-term corrosion, It can take a larger value within its range.

[0067] For example, when the focus is more on the final hydride accumulation after long-term corrosion, Take a value of 0.1 to 0.2. Take a value of 0.2~0.4. Take a value of 0.4 to 0.7.

[0068] Selected area electron diffraction and Raman characterization were performed on representative samples after implantation. When additional diffraction features appeared in the diffraction results of the corresponding region after implantation in addition to the diffraction spots of the zirconium matrix, and hydride characteristic peaks that did not appear before implantation appeared in the Raman spectrum, it can be confirmed that the abnormal contrast features observed and used for statistical analysis during in-situ H ion implantation correspond to hydrides.

[0069] Further real corrosion experiments were conducted on the samples to be screened, and the cross-sectional morphology after corrosion was characterized and statistically analyzed. The real corrosion results were compared with the rapid screening and ranking results obtained based on the evaluation index to verify the effectiveness. The real corrosion characterization results include, but are not limited to, at least one of the following: average oxide film thickness, interface smoothness, crack characteristics, pore characteristics, porosity characteristics, and dense layer thickness.

[0070] Using the above-mentioned detection and analysis methods, the evaluation index of multiple samples is ranked; the relative corrosion resistance of the samples is evaluated based on the ranking results, which enables rapid screening.

[0071] Example 1

[0072] Three zirconium alloy samples were selected as screening materials, designated as #6, #7 and #8 respectively. Their nominal composition was Zr-1.3Sn-0.23Fe-0.12Cr, and the content of each element was expressed as a mass percentage (wt.%). The three samples corresponded to three different preparation processes.

[0073] S11. In this embodiment, the above three zirconium alloys are processed into φ=3 mm circular samples, and after mechanical thinning, transmission electron microscope (TEM) thin film samples are prepared by double-jet electrolytic thinning. In order to further reduce the influence of surface hydrides introduced by the double-jet process on the subsequent observation results, the samples are cleaned by PIPS after double-jet.

[0074] S12. Before in-situ H ion implantation, in-situ observation areas were selected and the matrix condition was confirmed under a transmission electron microscope. In this embodiment, four in-situ observation areas were selected in each zirconium alloy sample. The thickness of the selected areas was relatively uniform as measured by CBED, with a thickness of approximately 120 ± 10 nm.

[0075] S13, such as Figure 2 As shown in (a), taking sample #7 as an example, no obvious hydride characteristics were observed in the sample matrix before injection. The thickness within the region was uniform, without impurities, corrosion contamination, or obvious stress striations. Figure 2As shown in (b), the diffraction spots in this region correspond to the zirconium matrix diffraction characteristics along the

[0001] positive band axis. Figure 2 As shown in (c), no obvious hydride characteristic peaks appeared in the Raman spectrum; only a substrate signal was observed. These results indicate that the sample was in an initial state without obvious hydrides before ion implantation.

[0076] S21. Before in-situ H ion implantation, the implantation parameters are first determined based on the sample thickness and the H implantation distribution in the zirconium alloy. In this embodiment, the SRIM program is used to calculate the range distribution of H ions in the zirconium alloy thin film sample. The ex-situ threshold energy (Ed) of Zr, Fe, and Cr elements used in the simulation calculation is 40 eV, and the Ed of Sn element is 20 eV.

[0077] S22, Calculation results are as follows Figure 3 As shown, under the condition of H ion energy of 10 keV, the peak of incident H concentration is located at a depth of 80.0 nm, when the cumulative implantation amount is 1.0 × 10⁻⁶. 16 H + / cm 2 The peak concentration was approximately 5.48 at.% (5.48 × 10⁻⁶). 4 (appm), the injection peak is located within the sample thickness range. Combined with the aforementioned in-situ observation region thickness of approximately 120±10 nm, when the zirconium alloy sample passes through 1.0×10... 16 H + / cm 2 After implantation, the average deposition concentration of H atoms in the 0–120 nm thickness range is 3.28 at.% (3.28 × 10⁻⁶). 4 appm).

[0078] S23. In this embodiment, the in-situ H ion implantation temperature is set to room temperature, and the injection rate is 1.93 × 10⁻⁶. 13 H + ·cm -2 ·s -1 The corresponding deposition rate is 63.50 appm·s. -1 To obtain a continuous process of hydride formation and evolution, 10 cumulative implantation nodes were set during ion implantation, with a maximum cumulative implantation volume of 1 × 10⁻⁶. 17 H + / cm 2 The corresponding cumulative H concentrations were 3.28 × 10⁻⁶. 5 appm.

[0079] S31. In-situ H ion implantation experiments were conducted on samples #6, #7, and #8 under the same conditions. Continuous microstructure observation and image acquisition were performed on pre-selected in-situ observation areas for each sample at different cumulative implantation levels. Four in-situ observation areas were selected for each zirconium alloy sample during CBED thickness measurement, and bright-field images were preferably obtained under the

[0001] positive band axis conditions.

[0080] S32. After reaching each preset cumulative injection volume node, record the microscopic structure image of the corresponding region for subsequent hydride identification, quantity density statistics, and kinetic parameter extraction. For example... Figure 4 As shown, taking sample #7 as an example, the in-situ microstructure evolution process under different cumulative injection amounts is presented, where (a) is the cumulative injection amount of 1×10 15 H + / cm 2 The TEM image of the matrix shows that at this time, only a few weakly contrasting dot-like features appear in the sample matrix, and the number of hydrides is small and has not yet formed a clear continuous distribution; (b) and (c) correspond to a cumulative implantation amount of 5×10 15 H + / cm 2 and 1×10 16 H + / cm 2 In-situ images at time 10 show that as the H ion implantation rate increases, more punctate and short rod-shaped abnormal contrasts gradually appear in the region, the number of hydrides increases significantly, and local areas begin to show aggregated distribution; (d) shows the cumulative implantation rate of 4×10 16 H + / cm 2 At this point, the number of hydrides further increases, and some hydrides come into contact and merge, forming a large irregular contrast region; after continuing to increase the cumulative injection amount, (e) and (f) correspond to 8×10 16 H + / cm 2 and 1×10 17 H + / cm 2 The distribution and size of hydrides within the region further evolved, with larger clusters becoming more pronounced. However, the rate of increase in the number of newly added hydrides decreased, exhibiting a slowdown in growth and a gradual approach to saturation. These results indicate that the formation and evolution of hydrides in the sample exhibit distinct stage-specific characteristics during in-situ H ion implantation.

[0081] S41. Statistical analysis was performed on the identifiable hydrides in samples #6, #7, and #8. During the statistical analysis, the major axis length, minor axis length, and number of hydrides were measured based on four pre-selected in-situ observation areas in each sample under each cumulative injection volume condition. Local areas with significant changes in edge thickness, heavy contamination, or difficulty in distinguishing hydrides from other abnormal contrasts were not included in the statistical scope.

[0082] S42. For each selected statistical region in the in-situ observation area, measure the major axis length of the hydride one by one. and minor axis length And the average major axis length is calculated respectively. and average minor axis length At the same time, the total number of hydrides in this area will be counted. Combined with the area of ​​the statistical region and actual thickness Calculate the number density of hydrides ( ).

[0083] S43. Furthermore, to comprehensively characterize the formation and growth behavior of hydrides in different samples, this embodiment uses the hydride volume ratio as a subsequent fitting parameter. Approximating a single hydride as a rotating ellipsoid, its average volume... It can be represented as:

[0084]

[0085] Then the volume fraction of hydride in a unit volume of sample within the statistical region. It can be represented as:

[0086]

[0087] For each sample, under the same cumulative injection volume, the average of the statistical results of the four in-situ observation areas is taken as the average hydride volume ratio of the sample under the same cumulative injection volume.

[0088] S44, such as Figure 5As shown, the statistical results of hydride number density and volume ratio changes with cumulative injection amount in samples #6, #7, and #8 are presented. With increasing cumulative injection amount, the hydride number density and volume ratio in all three samples gradually increase and eventually stabilize. However, significant differences exist among the samples in terms of the cumulative injection amount at which hydrides first appear, the growth rate, and the final stable level. Specifically, sample #7 shows identifiable hydrides at a relatively low cumulative injection amount, indicating its greater sensitivity to H ion injection. Sample #6 exhibits the fastest volume ratio growth and the highest saturation value, indicating a higher rate of hydride formation and growth. In contrast, hydrides appear later in sample #8, with a slower volume ratio growth and a lower saturation value, indicating lower hydride sensitivity under the same conditions.

[0089] S51. To further quantitatively characterize the differences in hydrogenation behavior among different samples during H ion implantation, this embodiment uses a diffusion control model based on Fick's second law to fit the evolution of the hydride volume ratio. Under the condition of a fixed observation area thickness, the hydride volume ratio is considered as a characterizing factor of the local hydrogenation degree, and its expression can be written as:

[0090]

[0091] S52, where, To accumulate the H concentration, This is the initial concentration parameter for hydride formation, used to characterize the minimum H concentration required for identifiable formation of hydrides. The characteristic diffusion-propellant concentration parameter is used to characterize the degree of lag in the propagation of hydride volume ratio from the initial formation to the rapid growth stage. The saturated volume ratio is used to characterize the final degree of hydrogenation that a sample can achieve under continuous H ion implantation conditions.

[0092] S53, such as Figure 6 As shown, the fitting results for the hydride volume ratios of samples #6, #7, and #8 are presented; the corresponding fitting parameters are listed in Table 1.

[0093] Table 1

[0094]

[0095] The fitting results show that sample #6... The highest value indicates that the total integral of hydrides formed in the later stages of injection is the largest; Sample #7 The lowest concentration indicates that it begins to form hydrides at relatively low H concentrations; sample #8 has a higher concentration. and the lowest This indicates that hydride formation is somewhat delayed during the low injection stage, and the final hydride accumulation level is the lowest. (Summary) , and The three parameters show that sample #8 exhibits the lowest final hydrogenation degree and the highest initial formation concentration, followed by sample #7, while sample #6 has a relatively higher degree of hydrogenation.

[0096] S61. After completing in-situ H ion implantation, post-implantation characterization is performed on representative samples. Preferably, sample #7 is selected as the representative sample from three samples #6, #7, and #8, and its cumulative implantation amount is 1×10⁻⁶. 17 H + / cm 2 The state under the given conditions was characterized by selected area electron diffraction and Raman spectroscopy.

[0097] S62, such as Figure 7 As shown in (a), the selected area electron diffraction results of the corresponding region after implantation show additional diffraction spots besides the diffraction spots of the zirconium matrix. These spots, after calibration, can be attributed to the zirconium hydride phase, indicating that a new phase structure distinct from the α-Zr matrix was formed in the sample after implantation. Figure 7 As shown in (b), a 780 cm⁻¹ pattern appeared in the Raman spectrum of the sample after injection. -1 and 1180 cm -1 The characteristic peaks near the implanted H ion were observed, while no corresponding signal was present before implantation. These results indicate that the anomalous contrast characteristics observed and used for statistical analysis during in-situ H ion implantation can be attributed to hydride formation, thus validating the reliability of the aforementioned hydride statistical and diffusion equation fitting analysis.

[0098] S63. Based on the aforementioned fitting results, this embodiment selects the initial hydride formation concentration. Characteristic diffusion-propellant concentration and saturated volume ratio As a key parameter for evaluating the hydrogenation resistance of different samples, this embodiment further establishes a rapid evaluation index to comprehensively compare the corrosion resistance of samples #6, #7, and #8. Preferably, after normalizing the above key parameters, they are combined in a weighted manner, and the evaluation index can be expressed as:

[0099]

[0100] in, , and Let be the weight coefficient, and satisfy... In this embodiment, more attention is paid to the hydrogenation situation after long-term corrosion; therefore, the weighting coefficient is: Take 0.15, Take 0.25, Let it be 0.60. In the above expression, the evaluation index... The larger the value, the stronger the sample's resistance to hydrogenation and the better its expected corrosion resistance.

[0101] Based on the fitting parameters in Table 1, the evaluation indices for samples #6, #7, and #8 are 0.039, 0.408, and 0.668, respectively. Sample #8 has the highest evaluation index, indicating lower hydrogenation sensitivity and stronger hydrogenation inhibition under in-situ H ion implantation conditions; sample #7 is next; and sample #6 has the lowest evaluation index, indicating a greater susceptibility to hydride formation and accumulation. Therefore, the rapid screening ranking of the three samples is: #8 > #7 > #6, with higher rankings indicating better corrosion resistance.

[0102] To verify the effectiveness of the rapid screening and ranking results obtained based on the evaluation index, real corrosion experiments were further conducted on samples #6, #7, and #8, and the cross-sectional morphology after corrosion was characterized and statistically analyzed. The real corrosion results are as follows: Figure 8 As shown, the corresponding statistical results are listed in Table 2.

[0103] Table 2

[0104]

[0105] like Figure 8 As shown in (a) to (c), all three samples, #6, #7, and #8, formed oxide layers after 300 days of actual corrosion. However, there were significant differences among the samples in terms of oxide film thickness and interface smoothness. Among them, the oxide film of sample #8 was relatively thin, the oxide layer / substrate interface was relatively smooth, and the oxide layer continuity was good; the corrosion degree of sample #7 was moderate; while the oxide film of sample #6 was thicker, and the interface undulations were more obvious, indicating that its corrosion resistance under actual corrosion conditions was relatively poor.

[0106] According to the statistical results in Table 2, the average oxide film thicknesses of samples #6, #7, and #8 are 10.11±0.9 μm, 8.48±0.6 μm, and 5.78±0.5 μm, respectively. A comprehensive comparison shows that the corrosion resistance of the three samples after actual corrosion is ranked as follows: #8>#7>#6, with the earlier samples indicating superior corrosion resistance.

[0107] Comparing the actual corrosion ranking results with the rapid screening ranking results obtained based on the evaluation index, it can be seen that the two have a consistent size pattern and are ranked in the same order. This indicates that the evaluation index established based on the hydride statistical results obtained from in-situ H ion implantation and the fitting parameters can effectively reflect the differences in corrosion resistance of different samples under real corrosion conditions.

[0108] By combining in-situ H ion implantation, hydride statistics, diffusion control fitting, and evaluation index analysis, the corrosion resistance of different zirconium alloy samples can be rapidly screened in a short time. The screening results are consistent with the actual corrosion test results, demonstrating feasibility and effectiveness.

[0109] The above embodiments are only used to further illustrate the rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H ion implantation of the present invention. However, the present invention is not limited to the embodiments. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the technical solution of the present invention.

Claims

1. A rapid testing and analysis method for the corrosion resistance of zirconium alloys based on H ion implantation, characterized in that, Includes the following steps: S1. Prepare zirconium alloy as a TEM thin film sample, select at least one in-situ observation area, and confirm the substrate state of the in-situ observation area before injection. S2. Perform in-situ H ion implantation on the in-situ observation area, and acquire TEM images of the in-situ observation area at multiple cumulative H concentration nodes; S3. Based on each of the images, identify the hydrides in at least a portion of the in-situ observation area and obtain the hydride volume ratio; S4. Fit the evolution relationship between the hydride volume ratio and the cumulative injected H concentration to extract the initial hydride formation concentration parameter. Characteristic diffusion-propellant concentration parameters and saturated volume ratio ; S5. For multiple zirconium alloys, based on the above... , and Establish a rapid evaluation index According to the above The corrosion resistance of the various zirconium alloys was ranked, among which... ， , and In the plurality of zirconium alloys respectively , and The maximum value, , and These are the weighting coefficients, and .

2. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 1, characterized in that: In step S1, the thickness of the thin film sample is 100~150 nm.

3. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 1, characterized in that: In step S1, the pre-implantation substrate state confirmation includes confirming that the thin film sample is in an initial state without identifiable hydrides by at least one of TEM morphology observation, selected area electron diffraction, and Raman characterization.

4. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 1, characterized in that: In step S2, the in-situ H ion implantation conditions are determined based on the thickness of the thin film sample and the implantation distribution of H in the zirconium alloy.

5. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 4, characterized in that: The range distribution of H ions in the thin film sample was calculated using the SRIM program, and the H ion implantation energy was determined based on the range distribution so that the H implantation peak was located within the thickness range of the in-situ observation area.

6. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 1, characterized in that: In step S3, the major axis length, minor axis length, and number of the identified hydrides are statistically analyzed to obtain the hydride number density and average volume, and then the hydride volume ratio is calculated, wherein the hydride volume ratio is the volume fraction of hydrides per unit area.

7. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 6, characterized in that: Within the in-situ observation area of ​​each of the images, the same statistical region is selected, and the major axis length, minor axis length, and number of hydrides within the statistical region are statistically analyzed. The hydride number density is then determined. : ， in, To count the number of hydrides in the region, To calculate the area of ​​the region, The thickness of the statistical region; approximating a single hydride as a rotating ellipsoid, the volume fraction of hydride per unit volume within the statistical region. for: ， in, The mean major axis length of the hydride. The mean minor axis length of the hydride. The average volume of the hydride.

8. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 7, characterized in that: In step S4, the fitted expression is: ， in, The cumulative H concentration injected.

9. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 8, characterized in that: Multiple in-situ observation areas were selected for the thin film sample. The average hydride volume ratio of the multiple in-situ observation areas was obtained by averaging the average hydride volume ratio, and the average hydride volume ratio was used for fitting.

10. The rapid testing and analysis method for corrosion resistance of zirconium alloys based on H-ion implantation according to claim 1, characterized in that: In step S5, the multiple zirconium alloys differ in at least one variable among composition, microstructure, preparation process, and heat treatment state; the rapid evaluation index The size of the sample is positively correlated with its corrosion resistance.

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