Analysis method

Abstract

To provide an analysis method for obtaining in-plane data of an x-ray diffraction intensity profile.SOLUTION: An analysis method disclosed herein involves scanning an irradiation point of incident x-rays on a sample in a plane intersecting an irradiation direction of the incident x-rays, and measuring x-ray diffraction from each irradiation point so as to obtain in-plane data of an x-ray diffraction intensity profile of the sample in a state where an external force is applied to the sample.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to analytical methods. [Background technology]

[0002] Patent Document 1 discloses a method for visualizing the strain of a material using a random pattern drawn on the surface of a sample. In the method of Patent Document 1, the random pattern is photographed with a digital camera before and after a tensile test, and the amount of displacement of the random pattern is determined. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-3234 Summary of the Invention [Problem to be solved by the invention]

[0004] The method of Patent Document 1 can only analyze the amount of displacement due to deformation of the sample surface. In other words, it cannot analyze the crystal structure of a sample when an external force is applied to the sample. In other words, it does not disclose a method for acquiring X-ray diffraction intensity profile data that allows for crystal structure analysis of a sample when an external force is applied to the sample, and for acquiring the X-ray diffraction intensity profile within the sample plane. The purpose of this disclosure is to provide an analytical method for obtaining in-plane data of an X-ray diffraction intensity profile when an external force is applied to the sample. [Means for solving the problem]

[0005] The analytical method disclosed herein is an analytical method for determining in-plane data of the X-ray diffraction intensity profile of a sample by scanning the irradiation position of incident X-rays on the sample within a plane intersecting the irradiation direction of the incident X-rays while applying an external force to the sample, and measuring X-ray diffraction from each irradiation position. [Effects of the Invention]

[0006] According to the present disclosure, an analysis method for determining in-plane data of an X-ray diffraction intensity profile can be provided. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a conceptual diagram showing the positional relationship of the sample, tester, incident X-rays, and X-ray diffraction when viewed from above the X-ray diffraction apparatus. [Figure 2] FIG. 2 is a conceptual diagram showing the positional relationship between the sample and the testing machine in the X-ray diffraction device. [Figure 3] FIG. 3 is a flowchart of the analysis method in the first embodiment. [Figure 4] FIG. 4 is a flowchart of the analysis method according to the second embodiment. [Figure 5] FIG. 5 is a diagram showing the relationship between the deformation amount of the sample and time when the deformation amount of the sample is changed discretely. [Figure 6] FIG. 6 is a diagram showing the relationship between the deformation amount of the sample and time when the deformation amount of the sample is increased at a constant rate with respect to time. [Figure 7] FIG. 7 is a diagram showing an example of an X-ray diffraction intensity profile of a sample. [Figure 8] FIG. 8 is a diagram showing an example of the in-plane distribution of the index related to stress when an external force is applied to the sample. [Figure 9] FIG. 9 is a diagram showing an example of the in-plane distribution of the index related to stress when the sample is broken by an external force. [Figure 10] FIG. 10 is a diagram showing an example of the in-plane distribution of indices related to non-uniform strain or dislocations when an external force is applied to a sample. [Figure 11] FIG. 11 is a diagram showing an example of the in-plane distribution of indices related to non-uniform strain or dislocations in a state where a sample is broken by an external force. DETAILED DESCRIPTION OF THE INVENTION

[0008] [Summary of the embodiments of the present disclosure] First, an overview of the embodiment of the present disclosure will be described.

[0009] (1) The analytical method disclosed herein is an analytical method for determining in-plane data of the X-ray diffraction intensity profile of a sample by scanning the irradiation position of incident X-rays on the sample within a plane intersecting the irradiation direction of the incident X-rays while applying an external force to the sample and measuring X-ray diffraction from each irradiation position.

[0010] According to the above method, in-plane data of the X-ray diffraction intensity profile of a sample can be obtained when an external force is applied to the sample. In this disclosure, a sample refers to a specimen to be analyzed, which is a solid material having any shape. The X-ray diffraction intensity profile of a sample refers to the relationship between the X-ray intensity and the diffraction angle of the X-ray diffraction of the sample. By obtaining in-plane data of the X-ray diffraction intensity profile of the sample when an external force is applied to the sample, it is possible to analyze the in-plane distribution of an index related to the stress of the sample, or the in-plane distribution of an index related to the inhomogeneous strain or dislocation of the sample.

[0011] (2) In the above (1), the external force may have a plurality of values, and in-plane data of a plurality of X-ray diffraction intensity profiles may be obtained in the state in which each external force is applied.

[0012] It is possible to obtain in-plane data of the X-ray diffraction intensity profile of multiple samples while applying multiple external forces to the sample, which allows the analysis of indices related to the stress, inhomogeneous strain, or dislocations of the sample as their in-plane distribution.

[0013] (3) In (2) above, the external force may be changed to a plurality of values ​​by continuously or discretely changing the amount of deformation of the sample.

[0014] By continuously changing the amount of deformation of the sample, it is possible to make it easier for the state of the sample to change continuously. In other words, it is possible to make it harder for the state of the sample to change suddenly. This makes it easier to understand the state of the sample as a continuous state change. Furthermore, by discretely changing the amount of deformation of the sample, it is easier to quantitatively understand the state change of the sample in response to the change in the amount of deformation of the sample.

[0015] (4) In (2) above, the external force may be changed to a plurality of values ​​by increasing the deformation amount of the sample at a constant rate over time.

[0016] By increasing the deformation of the sample at a constant rate over time, it becomes easier to quantitatively understand the changes in the state of the sample in response to changes in the deformation. Furthermore, by measuring X-ray diffraction without setting a specific relaxation time (described below), the measurement time can be shortened.

[0017] (5) In (2) above, the external force may be varied to multiple values ​​by discretely changing the amount of deformation of the sample, and a predetermined relaxation time may be set between the time a certain amount of deformation is applied to the sample and the time the X-ray diffraction intensity profile is measured.

[0018] When the deformation amount of the sample is changed discretely, the state of the sample may gradually change after the deformation amount of the sample reaches a certain value, depending on the type and structure of the sample. By setting a predetermined relaxation time, measurement can be performed after the state of the sample has stabilized, allowing for more accurate and stable measurements.

[0019] (6) In any of the above (1) to (5), the external force applied to the sample may be any of a tensile force, a compressive force, a torsional force, and a bending force applied to the sample.

[0020] The basic properties of a sample can be determined by applying external forces such as tension, compression, torsion, or bending to the sample. These forces can be applied using a simple testing machine.

[0021] (7) In any of (1) to (6) above, the in-plane distribution of the elastic deformation state of the sample when an external force is applied to the sample and the in-plane distribution of the plastic deformation state of the sample when an external force is applied to the sample may be obtained from the in-plane data of the X-ray diffraction intensity profile of the sample.

[0022] The in-plane distribution of the elastic deformation state and the in-plane distribution of the plastic deformation state can be determined from the in-plane data of a single X-ray diffraction intensity profile. By determining the two states from the in-plane data of the same X-ray diffraction intensity profile, it is possible to understand the corresponding states in the exact same sample. If the elastic deformation state and the plastic deformation state were measured separately, the two data sets may not correspond due to the different sample states. By determining the two states from the in-plane data of a single X-ray diffraction intensity profile, it is possible to accurately determine the correspondence between the two states.

[0023] (8) In any of the above (1) to (6), the in-plane distribution of an index related to the stress of the sample when an external force is applied to the sample and the in-plane distribution of an index related to the non-uniform strain or dislocation of the sample when an external force is applied to the sample may be obtained from the in-plane data of the X-ray diffraction intensity profile of the sample.

[0024] The in-plane distribution of stress-related indices and the in-plane distribution of indices related to inhomogeneous strain or dislocations can be determined from the in-plane data of a single X-ray diffraction intensity profile. By determining the two states from the in-plane data of the same X-ray diffraction intensity profile, it is possible to understand the corresponding states of the exact same sample. If the in-plane distribution of stress-related indices and the in-plane distribution of indices related to inhomogeneous strain or dislocations were measured separately, the two data sets may not correspond due to different sample states. By determining the two states from the in-plane data of a single X-ray diffraction intensity profile, it is possible to accurately determine the correspondence between the two states.

[0025] (9) In any of the above (1) to (6), an in-plane distribution of an index relating to the thickness of the sample when an external force is applied to the sample may be obtained from in-plane data of the X-ray diffraction intensity profile of the sample.

[0026] When the in-plane data of the X-ray diffraction intensity profile of a sample includes zero-order X-ray diffraction, i.e., transmitted X-rays, the in-plane distribution of an index related to the thickness of the sample can also be determined by analyzing the in-plane data of the X-ray diffraction intensity profile.

[0027] (10) In any of the above (1) to (9), the sample may be held in a testing machine, and the testing machine may include an external force applying mechanism that applies an external force to the sample and a movable mechanism that changes the position of the sample within a plane.

[0028] By changing the irradiation position of the incident X-rays on the sample within a plane that intersects with the irradiation direction of the incident X-rays while maintaining the state in which an external force is applied to the sample, in-plane data of the X-ray diffraction intensity profile can be obtained easily and accurately.

[0029] (11) In any of the above (1) to (10), the X-ray diffraction intensity profile may be detected using a one-dimensional detector or a two-dimensional detector.

[0030] By using a one-dimensional detector, it is possible to obtain an X-ray diffraction intensity profile with high sensitivity. By using a two-dimensional detector, it is possible to obtain an X-ray diffraction intensity profile in a short time. Furthermore, by measuring in a short time, it is possible to analyze changes in the state of a sample that occur in a relatively short time.

[0031] (12) In the above (11), the X-ray diffraction intensity profile detected by the one-dimensional detector or the two-dimensional detector may include a plurality of diffraction indices.

[0032] By detecting multiple diffraction indices in the detected X-ray diffraction intensity profile, changes in the sample state can be analyzed for each diffraction index. Therefore, multiple measurement results can be obtained from a single measurement. For example, detailed information such as inhomogeneous strain and dislocation density can be analyzed by applying the classical Williamson-Hall method or a combination of the modified Williamson-Hall and modified Warren-Averbach methods based on information on multiple peak positions and widths. Multiple diffraction indices may also arise from multiple crystal structures. In this case, the phase fraction of each crystal structure can be analyzed.

[0033] (13) In any of the above (1) to (12), the incident X-rays may be X-rays obtained by synchrotron radiation.

[0034] By using high-intensity X-rays obtained from synchrotron radiation as the incident X-rays, it is possible to measure the X-ray diffraction intensity profile in a shorter time. Also, this short measurement time makes it possible to analyze changes in the state of the sample that occur over a relatively short period of time.

[0035] (14) In any of the above (1) to (13), the wavelength of the incident X-ray may include a range of 0.01 nm to 0.2 nm.

[0036] By setting the wavelength of the incident X-rays in the range of 0.01 nm to 0.2 nm, there is an advantage that the X-rays can easily penetrate even heavy metals such as a 25 μm thick copper plate.

[0037] (15) In any of the above (1) to (14), the sample may be a metal.

[0038] The analytical method of the present disclosure is suitable for analyzing changes in the state of metals.

[0039] [Details of the embodiments of the present disclosure]

[0040] Hereinafter, details of embodiments of the present disclosure will be described. In the following description, the same or corresponding elements will be given the same symbols, and the same description will not be repeated. In the crystallographic descriptions in this specification, a collective orientation is indicated by <>, and an individual plane is indicated by (). A negative crystallographic index is usually expressed by adding a "-" (bar) above the number, but in this specification, a negative crystallographic index is expressed by adding a negative sign before the number.

[0041] (First embodiment) The analysis method in the first embodiment will be described with reference to FIGS.

[0042] FIG. 1 is a conceptual diagram showing the positional relationship of a sample 10, a testing machine 20, incident X-rays 2, X-ray diffraction beams 3a and 3b, etc., when the X-ray diffraction apparatus 1 is viewed from above. However, the frame portion 23 shown in FIG. 2 is not shown. FIG. 2 is a conceptual diagram showing the positional relationship of the sample 10 and the testing machine 20 when the X-ray diffraction apparatus 1 is viewed from the X direction, which is the direction of incidence of the X-rays, as described below. In the drawing, directions are indicated by arrows X, Y, and Z. The X direction, Y direction, and Z direction are perpendicular to each other. For example, the YZ plane is a plane that includes the Y axis and the Z axis.

[0043] As shown in Figure 1, incident X-rays 2 emitted from an X-ray source 6 are irradiated along the X-axis direction onto an irradiation position 12 on a sample 10. A measurement target surface 11 of the sample 10 can be perpendicular to the incident X-rays 2. X-ray diffraction 3a occurs from the irradiation position 12 on the sample 10. The X-ray diffraction 3a is detected by a detector 4a, and the information obtained by the detector 4a is processed by a processing device 5a.

[0044] An external force is applied to the sample 10 by a testing machine 20. The testing machine 20 includes a chuck unit 21, an external force application mechanism 22, a frame unit 23, and a movable mechanism 30. The sample 10 is gripped by two chuck units 21. The chuck units 21 are connected to the external force application mechanism 22. As shown in FIG. 2, the external force application mechanism 22 is fixed to the frame unit 23. An external force can be applied to the sample 10 by operating the external force application mechanism 22. The frame unit 23 is disposed on the movable mechanism 30. The movable mechanism 30 can move the frame unit 23 within the YZ plane. This allows the position of the sample 10 to be changed within the YZ plane. These mechanisms allow the irradiation position 12 to be moved within the YZ plane while maintaining the state in which an external force is applied to the sample 10 by the testing machine 20, and X-ray diffraction 3a at each irradiation position 12 can be detected by a detector 4a.

[0045] The incident X-rays 2 are monochromatic X-rays. The X-ray source 6 includes an X-ray source, a spectrometer, a slit, and other components (not shown). An X-ray tube with a target made of copper, tungsten, molybdenum, or the like can be used as the X-ray source. Synchrotron radiation is more preferable. Compared to an X-ray tube, synchrotron radiation has high directivity and brightness. Using synchrotron radiation enables high-precision measurements in a short time. The wavelength of the incident X-rays 2 can range from 0.01 to 0.2 nm. The wavelength of the incident X-rays 2 can also range from 0.01 to 0.07 nm. A shorter wavelength of the incident X-rays has the advantage that they can easily penetrate heavy metals, such as a 25 μm-thick copper plate. A double-crystal spectrometer using a silicon (111) surface can be used as the spectrometer. The use of a spectrometer allows the incident X-rays 2 to be monochromatic. A four-quadrant slit with a tantalum blade can be used as the slit. The use of a slit allows for adjustment to an appropriate irradiation width. For example, the irradiation width of the X-ray can be set to 0.05 mm square to 1 mm square.

[0046] FIG. 1 is a diagram illustrating a configuration using a transmission X-ray diffraction method. As the X-ray diffraction method, either a transmission method or a reflection method can be used. In the case of the transmission method, X-ray diffraction 3a from the entire material located in the thickness direction 13 of the sample 10 can be obtained. Therefore, it is suitable for analyzing the strength of the sample 10.

[0047] When the transmission method is used, the intensity of the transmitted X-rays can be measured by measuring the zeroth order X-ray diffraction, i.e., the transmitted X-rays, as the X-ray diffraction 3b. A transmitted light intensity detector may be used as the detector 4b for this X-ray diffraction 3b. The information obtained by the detector 4b can be processed by the processing device 5b. The processing devices 5a and 5b may be separate devices or may be a single device.

[0048] In the case of a reflection method (not shown), X-ray diffraction 3a can be obtained from the vicinity of the surface of the sample 10. The vicinity of the surface means, for example, a range of 5 μm or less in terms of the penetration depth from the surface when X-rays with a wavelength of 0.154 nm are used with copper as the target. Therefore, this method is suitable for analyzing the surface side of the sample 10.

[0049] The X-ray intensity versus diffraction angle (2θ) can be measured for the X-ray diffraction 3a of the sample 10. In the present disclosure, the X-ray intensity versus diffraction angle (2θ) of the X-ray diffraction 3a is referred to as an X-ray diffraction intensity profile.

[0050] The X-ray diffraction intensity profile can be measured by using a detector 4a such as a scintillator to detect the X-ray intensity while moving the detector 4a along the diffraction angle (2θ). A one-dimensional detector or a two-dimensional detector can be used as the detector 4a. When a one-dimensional detector is used as the detector 4a, the X-ray diffraction intensity profile can be obtained with high sensitivity. In other words, it is possible to measure an X-ray diffraction intensity profile with a wide dynamic range. When a two-dimensional detector is used as the detector 4a, the X-ray diffraction intensity profile can be obtained at once without moving the detector 4a. Using a two-dimensional detector can shorten the measurement time.

[0051] Furthermore, by widening the detection range of the diffraction angle (2θ) of the X-ray diffractometer 3a, it is possible to obtain an X-ray diffraction intensity profile including multiple diffraction indices. By including multiple diffraction indices, it is possible to analyze multiple diffraction indices with a single measurement. This makes it possible to perform more accurate analysis.

[0052] The movable mechanism 30 is disposed on a pedestal 40. The pedestal 40 can be fixed to, for example, the floor of a laboratory (not shown). For example, a commercially available two-axis stage can be used as the movable mechanism 30.

[0053] When an external force is applied to the sample 10 using the testing machine 20, a force corresponding to the external force is also applied to the frame portion 23. The frame portion 23 of this embodiment has sufficient rigidity to withstand the force corresponding to the external force.

[0054] The external force applying mechanism 22 may be, for example, an air cylinder, a hydraulic cylinder, a servo motor, or the like. The testing machine 20 also has a load cell and a control device (not shown) that can monitor the applied force and control it to a predetermined value. The testing machine 20 also has a positioning center (not shown) that can monitor the amount of deformation, such as elongation, of the sample 10 when an applied force is applied. The testing machine 20 also uses a servo motor or the like to control the position of the chuck 21, thereby controlling the amount of deformation of the sample 10 gripped by the chuck 21 and monitoring the force at that time. The external force applying mechanism 22 is configured to apply a tensile force, a compressive force, or a torsional force to the sample 10.

[0055] The testing machine 20 shown in Figures 1 and 2 is an example that is particularly suitable for tensile and compressive forces. It is also possible to select a testing machine 20 with a configuration different from that shown in Figures 1 and 2. In that case, bending force or torsion force can be applied to the sample 10. A bending tester, a twisting tester, or the like can be used as the testing machine 20.

[0056] The sample 10 may have any shape suitable for measurement, for example, a plate shape. When the external force is a tensile force, the sample 10 may be dumbbell-shaped as shown in FIG. 2. As shown in FIG. 2, the shape of the sample 10 may include a necking region 14, which is a region with a narrow width in the Z direction, and a gripping portion 15, which is a region with a wide width in the Z direction. The thickness 13 (FIG. 1) of the sample 10 may be constant.

[0057] The measurement target surface 11 in the analysis method of the present disclosure includes the entire necking region 14 and may include a portion of the gripping portion 15. By moving the sample 10 using the movable mechanism 30 and scanning the sample 10 with the incident X-rays 2, the entire measurement target surface 11 is sequentially irradiated with the incident X-rays 2. When an external force is applied to both ends of the gripping portion 15, the stress experienced by the sample 10 is high in the necking region 14. As a result, a particularly significant change in state occurs in the necking region 14 of the sample 10. Because the necking region 14 is included in the measurement target surface 11, particularly significant changes in state of the sample 10 can be analyzed.

[0058] FIG. 3 is a flowchart of an analysis method for obtaining in-plane data of an X-ray diffraction intensity profile of the sample 10 (hereinafter, sometimes simply referred to as "profile in-plane data") in the first embodiment.

[0059] 3 is a step of holding sample 10 in testing machine 20 and applying an external force. When holding sample 10, the vicinity of both ends of gripping portion 15 may be held by two chuck portions 21. The external force applied to sample 10 is given by external force applying mechanism 22.

[0060] The external force applied to the sample 10 may be a tensile force, a compressive force, a torsional force, or a bending force. In FIG. 1, when the external force applied to the sample 10 is a tensile force or a compressive force, the external force applied to the sample 10 is in the Y direction.

[0061] The testing machine 20 is equipped with a control device (not shown) that controls the value of the external force. The value of the external force can be controlled to a specified value while being monitored by a load cell or the like provided in the testing machine 20. The amount of displacement, such as elongation or compression, of the sample 10 when stress is applied may also be monitored. Furthermore, the testing machine 20 can also control the amount of deformation of the sample 10 gripped by the chuck portion 21 by controlling the position of the chuck portion 21 using a servo motor or the like, and monitor the force at that time as the value of the external force.

[0062] 3 is a step of irradiating the irradiation position 12 of the sample 10 with incident X-rays 2. The third step (S003) in FIG. 3 is a step of obtaining the X-ray diffraction intensity profile of the sample 10 at each irradiation position 12.

[0063] As described above, incident X-rays 2 are irradiated onto irradiation position 12 of sample 10, and the generated X-ray diffraction 3a is detected by detector 4a. If detector 4a is a scintillator or the like, the X-ray intensity is detected while the scintillator or the like is moved along the diffraction angle (2θ). As a result, the X-ray diffraction intensity of X-ray diffraction 3a versus the diffraction angle (2θ) can be obtained, i.e., an X-ray diffraction intensity profile at irradiation position 12 of sample 10 can be obtained.

[0064] When a transmitted light intensity detector is arranged as detector 4b to detect X-ray diffraction 3b, which is transmitted X-rays, it is also possible to determine the distribution of thickness 13 of sample 10. It is also possible to include the X-ray intensity of X-ray diffraction 3b in the X-ray diffraction intensity profile.

[0065] The fourth step (S004) in FIG. 3 will be explained later. The fifth step (S005) in FIG. 3 is a step of moving the sample 10 to change the irradiation position 12. The incident X-rays 2 are oriented along the Z direction. The irradiation position 12 of the sample 10 is changed by moving the sample 10 within the YZ plane. The irradiation position 12 of the sample 10 is changed by using the movable mechanism 30 to move the frame unit 23, the chuck unit 21, and the external force applying mechanism 22 as a unit within the YZ plane. This changes the irradiation position 12 of the sample 10 while maintaining the external force applied to the sample 10 in the first step. As shown in FIG. 3, after the fifth step (S005), the process returns to the second step (S002), followed by the third step (S003). By repeating this process, it is possible to obtain the X-ray diffraction intensity profile of the sample 10 at each irradiation position 12 when scanning the irradiation position 12 of the sample 10 with the incident X-ray 2 within a plane intersecting the irradiation direction of the incident X-ray 2, i.e., the profile in-plane data of the sample 10. The irradiation position 12 of the sample 10 can be set within the range of the surface 11 to be measured.

[0066] The in-plane profile data of the sample 10 is a collection of multiple data points of X-ray diffraction intensity profiles. Each data point is data from two or more measurement points on the measurement target surface 11. Preferably, the data points cover the entire surface of the measurement target surface 11.

[0067] 3 is a step of determining whether or not the X-ray diffraction intensity profiles of the measurement target surface 11 of the sample 10 have been measured for all of the planned irradiation positions 12. If all have been measured, that is, if the answer is YES, the measurement is completed. If not all have been measured, that is, if the answer is NO, the measurement continues.

[0068] As described above, when an external force is applied to the sample 10, it is possible to obtain profile in-plane data of the sample 10 at each irradiation position 12 when scanning the irradiation position 12 of the sample 10 with the incident X-rays 2 within a plane intersecting the irradiation direction of the incident X-rays 2. From the profile in-plane data, it is possible to analyze the in-plane distribution of an index related to stress in the sample 10 and the in-plane distribution of an index related to non-uniform strain or dislocation in the sample 10.

[0069] (Second embodiment) Next, a second embodiment will be described. In the second embodiment, the positional relationship between the X-ray diffraction device 1, the testing machine 20, the sample 10, the incident X-ray 2, and the X-ray diffractor 3a is the same as in the first embodiment.

[0070] FIG. 4 is a flowchart of an analysis method for obtaining profile in-plane data in the second embodiment.

[0071] The first step (S001) to the fifth step (S005) in Fig. 4 are the same as the first step (S001) to the fifth step (S005) in Fig. 3. By performing the first step (S001) to the fifth step (S005) in Fig. 4, it is possible to obtain the X-ray diffraction intensity profile of sample 10 at each irradiation position 12 when irradiating position 12 of incident X-ray 2 on sample 10 is scanned within a plane intersecting the irradiation direction of incident X-ray 2, i.e., the profile in-plane data of sample 10.

[0072] When all the X-ray diffraction intensity profiles of the measurement target surface 11 of the sample 10 have been measured, the determination in the fourth step (S004) of FIG. 4 becomes YES, and the process proceeds to the sixth step (S006) of FIG.

[0073] In the second embodiment, the value of the external force is set to a plurality of different values. If it is necessary to change the value of the external force and continue the measurement, that is, if the answer is YES, the seventh step (S007) in FIG. 4 is executed.

[0074] The seventh step (S007) in Figure 4 is a step in which an external force of a different value is set to the external force applied to sample 10 in the first step (S001) to the fifth step (S005) in the previous measurement loop, and the external force is applied to sample 10.

[0075] After executing the seventh step (S007), the second step (S002) to the fifth step (S005) are repeated. This allows for obtaining profile in-plane data when the irradiation position 12 of the incident X-rays 2 on the sample 10 is scanned in a plane intersecting with the irradiation direction of the incident X-rays 2 under different applied external forces. The external force is set to a plurality of different values, and the measurement is further repeated. This allows for obtaining a plurality of profile in-plane data under each state under which a plurality of values ​​of external force are applied to the sample 10.

[0076] The in-plane profile data in each state where a plurality of external forces are applied to the sample 10 refers to the aforementioned data in which the in-plane profile data of the sample 10 exists for each of a plurality of different external force values. By using these data, it is possible to analyze changes in the in-plane distribution of the stress-related index of the sample 10, changes in the in-plane distribution of the indices related to non-uniform strain or dislocations, and the like, when the external force applied to the sample 10 is changed. For example, when a tensile force is gradually applied to the sample 10, it is possible to analyze changes in the in-plane distribution of the stress index and changes in the in-plane distribution of the indices related to non-uniform strain or dislocations with increasing tensile force.

[0077] The value of the external force can be changed continuously or discretely. For example, as a method of changing the external force to a plurality of values ​​in the seventh step (S007), the amount of deformation of the sample 10 can be continuously increased or decreased over time. Also, as a method of changing the external force to a plurality of values ​​in the seventh step (S007), the amount of deformation of the sample 10 can be changed discretely. For example, the amount of deformation of the sample 10 can be changed discretely, such as by changing the elongation value of the sample 10 relative to its initial length by 1%, 2%, or 3%. Here, the length of the sample 10 refers to the distance between the chuck portions 21 that hold the sample 10. Note that hereinafter, the amount of deformation of the sample 10 will be simply referred to as the deformation amount.

[0078] The multiple values ​​can be changed by discretely changing the amount of deformation, and a predetermined relaxation time can be set between applying a certain amount of deformation to the sample 10 and measuring the X-ray diffraction intensity profile. When the amount of deformation is discretely changed, depending on the material, structure, etc. of the sample 10, a predetermined time may be required for the sample 10 to reach a stable state. That is, a relaxation phenomenon may occur in the sample 10. In this case, a predetermined relaxation time can be set between changing the amount of deformation to a certain value and measuring the X-ray diffraction intensity profile. The predetermined relaxation time can be determined by taking into account the time it takes the sample 10 to reach a stable state. This allows for more accurate and stable measurements by measuring the X-ray diffraction intensity profile after the sample 10 has reached a stable state. Note that a predetermined relaxation time can also be set after applying a certain amount of deformation to the sample 10 and before measuring the X-ray diffraction.

[0079] 5 is a diagram showing the relationship between the amount of deformation and time when the amount of deformation is changed discretely. The horizontal axis represents time and the vertical axis represents the amount of deformation. The amount of deformation changes discretely with respect to time.

[0080] The first step (S001) is a step of maintaining the sample 10 in a state in which a deformation amount has been applied. After the sample 10 has been deformed, a predetermined relaxation time is allowed. After the relaxation time has elapsed, the second step (S002) to the fifth step (S005) are executed. The deformation amount is constant over time. After all X-ray diffraction intensity profiles of the measurement target surface 11 of the sample 10 have been measured, the sixth step (S006) and the seventh step (S007) are executed. If it is determined in the sixth step that measurement should be continued and the seventh step is executed, the deformation amount is changed to a constant value different from the previous deformation amount. After the constant deformation amount has been applied to the sample 10, a predetermined relaxation time is allowed. After the relaxation time has elapsed, the second step (S002) to the fifth step (S005) are repeatedly executed. After all X-ray diffraction intensity profiles of the measurement target surface 11 of the sample 10 have been measured, the process is repeated from the sixth step (S006).

[0081] As is clear from Figure 5, while the profile in-plane data of sample 10 is being obtained, i.e., while the second step (S002) to the fifth step (S005) are being repeatedly performed, the amount of deformation applied to sample 10 is constant.

[0082] Furthermore, the amount of deformation can be increased at a constant rate over time, rather than being changed discretely. By increasing the amount of deformation at a constant rate over time, the state of the sample 10 can be stably analyzed without requiring a predetermined relaxation time. In other words, there is no need to provide a waiting time, and the measurement time can be shortened.

[0083] FIG. 6 is a diagram showing the relationship between the deformation amount and time when the deformation amount is increased at a constant rate over time. The horizontal axis represents time, and the vertical axis represents the deformation amount. The deformation amount is increased at a constant rate over time. The first step (S001) is the step of setting the deformation amount for the sample 10. After the deformation amount for the sample 10 is set, the deformation amount is increased at a constant rate over time when performing steps 2 (S002) to 5 (S005). After all X-ray diffraction intensity profiles of the measurement target surface 11 of the sample 10 are measured, steps 6 (S006) and 7 (S007) are performed. If it is determined in step 6 that measurement should be continued and step 7 is performed, the deformation amount continues to be increased over time at the same constant rate as before. Then, steps 2 (S002) to 5 (S005) are repeatedly performed. After all X-ray diffraction intensity profiles of the measurement target surface 11 of the sample 10 are measured, the process is repeated from step 6 (S006).

[0084] 6, while the profile in-plane data of the sample 10 is being obtained, i.e., while the second step (S002) to the fifth step (S005) are being repeatedly performed, the amount of deformation applied to the sample 10 changes over time. That is, the amount of deformation applied to the sample 10 varies depending on the location on the measurement target surface 11 of the sample 10.

[0085] When the change in deformation amount with respect to time is set sufficiently small relative to the deformation amount at which fracture or the like occurs in the sample 10, it is possible to clearly analyze the state of stress in the sample 10, as well as the state of non-uniform strain and dislocation, as in the examples described below. In addition, it is possible to represent the deformation amount by the average value of the deformation amount during the second step (S002) to the fifth step (S005).

[0086] (Other embodiments) Another embodiment will now be described.

[0087] From the profile in-plane data obtained in the second embodiment, it is possible to analyze the in-plane distribution of the elastic deformation state of sample 10 when an external force is applied to sample 10, and the in-plane distribution of the plastic deformation state of sample 10 when an external force is applied to sample 10.

[0088] In the X-ray diffraction intensity profile of sample 10 at each irradiation position 12, the peak position of the diffraction angle is extracted. This peak position indicates the lattice spacing of the crystal lattice of sample 10 through Bragg's equation, and therefore indicates the state of uniform strain and stress in sample 10, i.e., the elastic deformation state of sample 10. Therefore, by extracting the in-plane distribution of peak positions from the in-plane profile data, it is possible to determine the in-plane distribution of the elastic deformation state of sample 10 when an external force is applied to sample 10.

[0089] Furthermore, the peak width is extracted from the X-ray diffraction intensity profile of the sample 10 at each irradiation position 12. The peak width is caused by variations or imperfections in the interplanar spacing of the crystal lattice of the sample 10, and indicates the state of non-uniform strain or dislocation, i.e., the plastic deformation state of the sample 10. Therefore, by extracting the in-plane distribution of the peak width from the in-plane profile data, the in-plane distribution of the plastic deformation state of the sample 10 when an external force is applied to the sample 10 can be determined. Note that, for example, FWHM (Full Width at Half Maximum) can be used as the peak width.

[0090] The in-plane distribution of these elastic and plastic deformation states can be simultaneously determined by analyzing the peak shift and peak width of a single profile in-plane data. In other words, separate measurements are not required to analyze the in-plane distribution of the elastic and plastic deformation states. This allows for more accurate determination of the in-plane distribution of the elastic and plastic deformation states when an external force is applied.

[0091] Furthermore, from the profile in-plane data obtained in the second embodiment, it is possible to obtain the in-plane distribution of indices related to stress in sample 10 when an external force is applied to sample 10, and the in-plane distribution of indices related to non-uniform strain or dislocation in sample 10 when an external force is applied to sample 10.

[0092] In the X-ray diffraction intensity profile of the sample 10 at each irradiation position 12, the peak position of the diffraction angle is extracted. The peak position indicates the interplanar spacing of the crystal lattice of the sample 10, and therefore indicates an index related to the uniform strain and stress of the sample 10. Therefore, by extracting the in-plane distribution of the peak positions from the in-plane profile data, it is possible to determine the in-plane distribution of an index related to the stress of the sample 10 when an external force is applied to the sample 10.

[0093] The peak width is extracted from the X-ray diffraction intensity profile of the sample 10 at each irradiation position 12. The peak width is caused by variations in the interplanar spacing or imperfections of the crystal lattice of the sample 10, and indicates an index related to inhomogeneous strain or dislocation. Therefore, by extracting the in-plane distribution of the peak width from the in-plane profile data, the in-plane distribution of the index related to inhomogeneous strain or dislocation of the sample 10 when an external force is applied to the sample 10 can be determined. Note that, for example, FWHM can be used as the peak width.

[0094] The in-plane distribution of these stress-related indices and the in-plane distribution of indices related to inhomogeneous strain or dislocations can be determined simultaneously by analyzing the peak shift and peak width of one profile in-plane data. In other words, separate measurements are not required to analyze the in-plane distribution of stress-related indices and the in-plane distribution of indices related to inhomogeneous strain or dislocations. This makes it possible to determine more accurate in-plane distributions of stress-related indices and indices related to inhomogeneous strain or dislocations under applied external force.

[0095] Furthermore, when the profile in-plane data obtained in the second embodiment includes zero-order X-ray diffraction 3b, i.e., transmitted X-rays, the in-plane distribution of the thickness 13 of the sample 10 when an external force is applied to the sample 10 can be obtained from the profile in-plane data obtained in the second embodiment.

[0096] In the measurement configuration shown in Figure 1, consider the case where a transmitted light intensity detector is used as detector 4b. The transmitted light intensity of the X-rays decays exponentially with respect to the product of t, which is the thickness 13 of the sample 10, and the X-ray absorption coefficient μ. If the transmittance is defined as the transmitted light intensity detected by the transmitted light intensity detector divided by the transmitted light intensity when the sample 10 is not present, then the transmittance is expressed as exp(-μt). Here, the X-ray absorption coefficient μ is a constant uniquely determined by the elements and density that make up the sample 10 and the wavelength of the incident X-rays 2. The transmittance can be calculated from the X-ray diffraction intensity profile of the sample 10, and the thickness 13 of the sample 10 can be calculated from the transmittance. Therefore, the transmittance can be calculated from the X-ray diffraction intensity profile of the sample 10 at each irradiation position 12, and the in-plane distribution of the thickness 13 of the sample 10 can be calculated from the transmittance. [Example]

[0097] An example will be described.

[0098] The X-ray diffraction apparatus 1 used was one with the configuration shown in Figures 1 and 2. Pure copper with a thickness of 0.3 mm was softened by annealing at 250°C for 1 hour. It was then laser processed into a dumbbell shape as shown in Figure 2 to create sample 10. The thickness 13 of sample 10 was 0.3 mm. The length in the Y direction of the parallel portion of the necking region 14 of sample 10 was approximately 1 mm.

[0099] A commercially available tensile tester (manufacturer: Linkam, model number: 10073B) was used as part of the testing machine 20. The sample 10 was clamped near the end of the gripping portion 15 with a chuck portion 21, and the sample 10 was placed in a tensile state using the tensile tester. The tensile tester corresponds to the chuck portion 21, external force applying mechanism 22, and frame portion 23 of the present disclosure. The tensile tester has a load cell and is capable of monitoring a predetermined tensile force. The tensile tester is also capable of setting the tensile force.

[0100] A commercially available motorized stage (manufacturer: Kozu Seiki, model numbers: YRA-071 and ZA07A-V1F) was used as the movable mechanism 30. The tensile tester described above was placed on the motorized stage. The motorized stage can move in the Y and Z directions in FIG. 2. That is, the motorized stage can move within the YZ plane in FIG. 2. The combination of the tensile tester and the motorized stage constitutes the testing machine 20 of the present disclosure.

[0101] The incident X-rays 2 were X-rays from BL16XU at the SPring-8 synchrotron radiation facility. The X-rays were monochromated using a double crystal monochromator with a silicon (111) surface. The wavelength of the X-rays was λ = 0.0335 nm. The beam size of the incident X-rays 2 was 0.2 mm square.

[0102] A two-dimensional detector (manufacturer: Dectris, model number: PILATUS 300K CdTe) was used as the detector 4a. The two-dimensional detector was placed at a position 0.459 m from the sample 10.

[0103] The analysis was performed according to the flowchart of the analysis method shown in Figure 4. The area of ​​the measurement surface 11 shown in Figure 2 was measured while applying a tensile force to the sample 10. Specifically, 31 measurements were performed in the Y direction and 15 rows in the Z direction, resulting in a total of 465 X-ray diffraction intensity profile measurements, and in-plane profile data was obtained. The 465 measurements took 270 seconds. The measurement to obtain the in-plane profile data was repeated 26 times while changing the tensile force applied to the sample 10. As shown in Figure 6, the tensile force applied to the sample 10 was increased at a constant rate over time. The deformation rate of the sample 10 was approximately 500 seconds, at a rate at which the sample 10 elongated by 1% of its initial length. The tensile force was then applied to the sample 10 until it broke. As a result, in-plane profile data was obtained under various tensile forces. The direction of the tensile force was the Y direction in Figure 1.

[0104] Figure 7 shows an example of an X-ray diffraction intensity profile measured at a certain irradiation position 12 for a certain deformation amount. The horizontal axis represents the diffraction angle (2θ) in degrees (°). Note that these angles are those when the wavelength of the incident X-ray 2 is 0.0335 nm. The vertical axis represents the intensity of the X-ray diffraction 3a. The vertical axis is a logarithmic scale. Five X-ray diffraction peaks corresponding to diffraction indices (111), (200), (220), (311), and (222) can be observed in Figure 7. Here, the peak at 2θ approximately 9.1° corresponds to (111), the peak at 2θ approximately 10.5° corresponds to (200), the peak at 2θ approximately 15.0° corresponds to (220), the peak at 2θ approximately 17.7° corresponds to (311), and the peak at 2θ approximately 18.5° corresponds to (222). In this example, the peak shift amount and peak width of the peak 50 corresponding to (311) were extracted to perform the analyses shown in Fig. 8 to Fig. 11. Note that the peak width was measured using FWHM.

[0105] Figure 8 shows the in-plane distribution of the stress index of Sample 10 when Sample 10 is stretched by approximately 14% relative to its initial length as a deformation amount. In Figure 8, the position of the peak corresponding to the diffraction index (311) was converted into a plane spacing and used as the stress index. Figure 8 shows the in-plane distribution of stress of Sample 10. The numerical value of the stress index at each point is indicated by shading. The right side of Figure 8 shows the relationship between shading and numerical value. The left-right direction in Figure 8 is the Y direction, and the up-down direction is the Z direction. The same is true for Figure 9. The tensile force on Sample 10 is in the Y direction.

[0106] The region near the outer periphery of sample 10 in Figure 8 is a region where no diffraction peaks of sample 10 could be detected. Stress is applied almost uniformly to the necking region 14 of sample 10. The value is approximately 0.1094 nm to 0.1093 nm. Compared to the necking region 14, the gripping portion 15 has a lower stress, and the stress decreases with increasing distance from the necking region 14. The value is approximately 0.1093 nm to 0.1091 nm. This is because the width of sample 10 in the Z direction is wide at gripping portion 15, dispersing the tensile force and reducing the stress applied to sample 10.

[0107] FIG. 9 shows the in-plane distribution of the index related to the stress of the sample 10 when the sample 10 of FIG. 8 is broken by applying an additional tensile force to the sample 10.

[0108] The region near the periphery of sample 10 in Figure 9 is a region where the diffraction peak of sample 10 could not be detected. Near the center of the necking region 14 of sample 10, there are vertically linear areas that are the same color as the dark color near the periphery of sample 10. This indicates that the necking region 14 of sample 10 has fractured. Furthermore, the necking region 14 of sample 10 and the gripping portion 15 are the same color. The value is approximately 0.1091 nm. This means that when sample 10 fractures, tensile force is no longer applied to sample 10, and a low, uniform stress is applied across the entire surface of sample 10. It also means that the stress is elastic deformation.

[0109] Figure 10 shows the in-plane distribution of indices related to inhomogeneous strain or dislocations in sample 10 when it is stretched by approximately 17% relative to its initial length as a deformation amount. In Figure 10, the indices related to inhomogeneous strain or dislocations are the (311) peak widths, and the FWHM is used as the peak width. Figure 10 shows the in-plane distribution of inhomogeneous strain or dislocations in sample 10.

[0110] The numerical values ​​of the indices relating to the non-uniform strain or dislocation at each point are indicated by the shading in the figure. The relationship between the shading and the numerical values ​​is shown on the right side of Figure 10. The left-right direction in Figure 10 is the Y direction, and the up-down direction is the Z direction. The same is true for Figure 11. The tensile force on sample 10 is in the Y direction.

[0111] Figure 10 shows the results obtained from the same in-plane profile data as Figure 8. Figure 8 was created by extracting peak shifts from the in-plane profile data. Figure 10 was created by extracting peak widths from the same in-plane profile data. Nearly uniform non-uniform strain or dislocations are present in the necking region 14 near the center of sample 10. On the other hand, the occurrence of non-uniform strain or dislocations is low in the gripping portion 15, and this becomes even less as one approaches the edge of sample 10. This is because the gripping portion 15 is wider, reducing the force applied to that portion, thereby reducing the resulting non-uniform strain or dislocations. Comparing Figures 8 and 10, the in-plane stress distribution and the in-plane distribution of non-uniform strain or dislocations in sample 10 tend to be similar.

[0112] Figure 11 shows the in-plane distribution of indices related to inhomogeneous strain or dislocations in Sample 10 when Sample 10 fractures due to the application of tensile force. Figure 11 shows the results obtained from the same in-plane profile data as Figure 9. That is, Figure 9 shows the results of extracting peak shifts from the in-plane profile data. Figure 11 shows the results of extracting peak widths from the same in-plane profile data.

[0113] The center of sample 10 is the same color as the outer periphery. This indicates that sample 10 has fractured. Figure 11 shows that even after sample 10 fractures, the non-uniform strain or dislocations in the necking region 14 and gripping portion 15 remain high. This non-uniform strain or dislocation occurs due to plastic deformation. This is because, once non-uniform strain or dislocations, which are plastic deformation, occur, they remain even after sample 10 fractures due to tensile force and the tensile force is no longer applied to sample 10. Furthermore, the non-uniform strain or dislocations near the fractured portion of the necking region 14 are at their highest values. This is thought to be because, at the moment of fracture, the cross-sectional area of ​​that portion decreases, further increasing the pressure and further progressing the plastic deformation, resulting in the highest non-uniform strain or dislocations in the fractured portion.

[0114] As described above, an analysis was performed to obtain in-plane profile data for a plurality of external force values ​​using the process shown in Fig. 4. As a result, in-plane profile data for sample 10 could be obtained for each state in which a plurality of external force values ​​were applied to sample 10. As shown in the analysis results of Figs. 7 to 11, the in-plane distribution of the stress-related index and the in-plane distribution of the indices related to non-uniform strain or dislocations for sample 10 could be obtained from the in-plane profile data.

[0115] The embodiments and examples disclosed herein are illustrative in all respects and should not be considered limiting. The scope of the present invention is defined by the claims rather than the above-described embodiments and examples, and it is intended to include any modifications within the scope of the claims that are equivalent to the claims.

[0116] The present disclosure includes the inventions according to the following appendices.

[0117] (Appendix 1) A step A of irradiating an irradiation position, which is a part of the surface of a sample, with incident X-rays; A step B of measuring X-ray diffraction from the irradiation position; a step C of changing the irradiation position within a plane intersecting the irradiation direction of the incident X-ray; and step D of obtaining in-plane data of the X-ray diffraction intensity profile of the sample, An analytical method, wherein the sample is held in a state in which an external force is applied in the steps A, B, and C.

[0118] (Appendix 2) The analytical method described in Appendix 1, wherein the external force is changed to a plurality of values, and step A, step B, step C, and step D are performed in each state in which the external force of the plurality of values ​​is applied to the sample, thereby obtaining in-plane data of the plurality of X-ray diffraction intensity profiles. [Explanation of symbols]

[0119] 1 X-ray diffraction equipment 2 Incident X-ray 3a X-ray diffraction 3b X-ray diffraction 4a Detector 4b Detector 5a Processing equipment 5b Processing equipment 6 X-ray source 10 Samples 11 Measurement surface 12 Irradiation position 13 Thickness 14 Necking region 15 Gripping part 20 Testing Machine 21 Chuck part 22 External force application mechanism 23 Frame section 30 Movable mechanism 40 pedestal 50 Peak

Claims

1. An analytical method for determining in-plane data of an X-ray diffraction intensity profile of a sample by scanning the irradiation position of incident X-rays on the sample within a plane intersecting the irradiation direction of the incident X-rays while applying an external force to the sample, and measuring X-ray diffraction from each of the irradiation positions.

2. The analysis method according to claim 1 , wherein the external force has a plurality of values, and a plurality of in-plane data of the X-ray diffraction intensity profile are obtained in states where the external force is applied, respectively.

3. The analytical method according to claim 2 , wherein the external force is changed to the plurality of values ​​by continuously or discretely changing the amount of deformation of the sample.

4. The analytical method according to claim 2 , wherein the external force is changed to a plurality of values ​​by increasing the deformation amount of the sample at a constant rate with respect to time.

5. 3. The analytical method according to claim 2, wherein the external force is changed to the plurality of values ​​by discretely changing the deformation amount of the sample, and a predetermined relaxation time is set between the time when a constant deformation amount of the sample is applied to the sample and the time when the X-ray diffraction intensity profile is measured.

6. 3. The analytical method according to claim 1, wherein the external force applied to the sample is any one of a tensile force, a compressive force, a torsional force, and a bending force applied to the sample.

7. From the in-plane data of the X-ray diffraction intensity profile, an in-plane distribution of an elastic deformation state of the sample when the external force is applied to the sample; and 3. The analysis method according to claim 1, further comprising: acquiring an in-plane distribution of a state of plastic deformation of the sample when the external force is applied to the sample;

8. From the in-plane data of the X-ray diffraction intensity profile, an in-plane distribution of an index related to stress of the sample in a state in which the external force is applied to the sample; 3. The analysis method according to claim 1, further comprising the step of: acquiring an in-plane distribution of an index relating to non-uniform strain or dislocation of the sample in a state in which the external force is applied to the sample;

9. From the in-plane data of the X-ray diffraction intensity profile, The analysis method according to claim 1 , further comprising the step of acquiring an in-plane distribution of the thickness of the sample in a state where the external force is applied to the sample.

10. The sample is held in a testing machine; 3. The analysis method according to claim 1, wherein the tester comprises an external force applying mechanism that applies the external force to the sample, and a moving mechanism that changes the position of the sample within the plane.

11. 3. The analytical method according to claim 1, wherein the X-ray diffraction intensity profile is detected using a one-dimensional detector or a two-dimensional detector.

12. The analysis method according to claim 11 , wherein the X-ray diffraction intensity profile detected by the one-dimensional detector or the two-dimensional detector includes a plurality of diffraction indices.

13. 3. The analytical method according to claim 1, wherein the incident X-rays are X-rays obtained by synchrotron radiation.

14. 3. The analytical method according to claim 1, wherein the wavelength of the incident X-rays is in the range of 0.01 nm to 0.2 nm.

15. The analytical method according to claim 1 or 2, wherein the sample is a metal.

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