JP5850211B1 - X-ray diffraction apparatus and X-ray diffraction measurement method - Google Patents

Abstract

An X-ray diffractometer (1) according to an aspect of the present invention includes a measurement unit (2) that measures an X-ray diffraction intensity profile of a test sample (16), a test sample (16), and a measurement unit (2). A distance measuring unit (9) for measuring a separation distance (Z) between the two and a data processing unit (10) for correcting the X-ray diffraction intensity profile. The measurement unit (2) performs one-dimensional detection or two-dimensional detection of an X-ray irradiation unit (3) that irradiates the test sample (16) with X-rays and a plurality of diffraction X-rays from the test sample (16). An X-ray detection unit (6) and a housing (8) in which the X-ray irradiation unit (3) and the X-ray detection unit (6) are fixedly disposed relative to the reference surface (17). The data processing unit (10) calculates the displacement (ΔZ) of the test sample (16) based on the separation distance (Z), and measures the test sample (16) according to the calculated displacement (ΔZ). The true X-ray diffraction angle (2θ) at the point is calculated, and the X-ray diffraction intensity profile is corrected based on the calculated true X-ray diffraction angle (2θ).

Description

  The present invention relates to an X-ray diffraction apparatus and an X-ray diffraction measurement method for measuring an X-ray diffraction intensity profile of a substance constituting a test sample.

  The X-ray diffraction method determines the crystal structure, amount, crystal lattice spacing, strain, stress, crystal orientation of the substance constituting the test sample from the angle, intensity, width, etc. of the X-ray diffraction peak irradiated to the test sample. Many useful information such as properties and crystallinity can be obtained. For this reason, the X-ray diffraction method is widely used in various fields for evaluating characteristics when various types of processing are performed on a test sample.

  In general, X-ray diffraction measurement of a test sample using the X-ray diffraction method is performed by collecting a part of a sample from a product such as a steel strip after manufacture or during manufacture as a test sample and using the collected test sample. It takes place outside or offline. However, when X-ray diffraction measurement of a test sample is performed off-line, it is difficult to control the manufacturing conditions by immediately reflecting the obtained X-ray diffraction measurement results on the manufacturing conditions of the product being manufactured. On the other hand, when controlling the manufacturing conditions of the product being manufactured, it is desirable to immediately reflect the X-ray diffraction measurement result capable of acquiring a lot of useful information on the test sample in the manufacturing conditions as described above. For this reason, a technique for performing X-ray diffraction measurement of a test sample within a product production line, that is, online is important.

  In addition, as a conventional technique related to online X-ray diffraction measurement, for example, online X which measures an X-ray diffraction intensity by fixing an incident X-ray source and an X-ray detector so as to have a specific X-ray diffraction angle. A line diffraction device has been proposed (see Patent Documents 1 to 8 or Non-Patent Document 1). Further, an online X-ray diffraction apparatus and method for measuring an X-ray diffraction intensity profile of a test sample and calculating a diffraction peak angle, an integrated intensity, a half width, and the like have been proposed (see Patent Documents 9 to 15). Among on-line X-ray diffractometers that measure X-ray diffraction intensity profiles, as disclosed in Patent Document 9, white X-rays are used as incident X-rays, and energy dispersive detectors are used as X-ray detectors. There is an on-line X-ray diffractometer using Further, as disclosed in Patent Document 10, there is an online X-ray diffraction apparatus using a one-dimensional detector as an X-ray detector.

Japanese Patent No. 2542906 Japanese Patent No. 2707865 Japanese Examined Patent Publication No. 56-12314 Japanese Patent No. 2534834 JP-A-9-33455 Japanese Patent No. 3034801 Japanese Examined Patent Publication No. 6-68472 Japanese Patent Publication No. 6-90154 Japanese Patent No. 3817812 Japanese Patent No. 3217843 JP-A-52-21887 JP-A-6-25894 JP-A-7-276235 JP2012-163392A Japanese Patent No. 2810225

"Kawasaki Steel Technical Report" 1986 Vol.18 No.2 p.31

  As described above, according to the X-ray diffraction method, various information including the crystal structure of the substance constituting the test sample, the amount of the constituent substance, the stress, and the crystal orientation are obtained from the measured X-ray diffraction intensity profile. Can be obtained. However, in the conventional techniques described in Patent Documents 1 to 8 or Non-Patent Document 1, since the X-ray diffraction intensity at a specific X-ray diffraction angle is measured, the amount and thickness of the substance constituting the test sample In addition, the information obtained from the X-ray diffraction intensity is limited, and there is a possibility that information required by the test sample cannot be obtained.

  In addition, when measuring the X-ray diffraction intensity profile of the test sample online, not only can the X-ray diffraction intensity profile in the angle range of interest be measured quickly, but also X-rays at the time of measuring the X-ray diffraction intensity profile. It is required to suppress diffraction angle errors. However, in the prior art described in Patent Documents 9 to 15, the X-ray diffraction intensity profile is accompanied by changes in the thickness and shape of the test sample, or vibrations of the test sample and the installation stand during traveling (during transport). Since the distance between the measurement unit and the test sample changes, and this causes an error in the X-ray diffraction angle of the test sample, the X-ray diffraction intensity profile of the test sample is measured. There is a problem that accuracy decreases.

  In particular, Example 1 of Patent Document 9 describes an online X-ray diffractometer that measures an X-ray diffraction intensity profile of a test sample by rotating and scanning an X-ray source and an X-ray detector. This on-line X-ray diffractometer has a problem that no countermeasure is taken against an error in the X-ray diffraction angle caused by a change in the distance between the X-ray diffraction intensity measurement unit and the test sample. Further, in order to measure the X-ray diffraction intensity profile of the test sample, the X-ray source and the X-ray detector need to be constantly repeatedly rotated at high speed, so that the X-ray source and the X-ray detector are rotated at high speed. There is a problem that not only an error occurs in the X-ray diffraction angle of the test sample due to vibration caused by driving, but also the mechanical durability of the rotary drive unit for rotary scanning is lowered.

  Further, as described in Example 5 of Patent Document 9, an on-line X-ray diffractometer using parallel beam-like white X-rays as incident X-rays and an energy dispersive detector as a diffracted X-ray detector is used. Has a problem that the characteristic X-rays excited from the test sample affect the shape of the X-ray diffraction intensity profile. Further, since the angular resolution is not so high, there is also a problem that it is difficult to distinguish and separate diffraction peaks when several diffraction peaks are close to each other.

  On the other hand, in the prior art described in Patent Document 10, an incident X-ray source that irradiates a test sample with parallel beam X-rays and a one-dimensional detector that detects diffracted X-rays from the test sample are detected. A measurement device that is placed on both the front and back sides of the sample and measures the height relative to the average position of the test sample is placed on one side of the test sample. Based on the output data of these one-dimensional detectors and measurement devices The X-ray diffraction angle is corrected. However, in Patent Document 10, there is no specific description regarding correction of the X-ray diffraction angle, and in addition, a measuring apparatus necessary for correcting the X-ray diffraction angle is arranged only on one side of the test sample. Therefore, there is a problem that the error of the X-ray diffraction angle due to the change in the thickness and shape of the test sample cannot be sufficiently corrected.

  The present invention has been made in view of the above circumstances, and is an X-ray diffraction apparatus and an X-ray diffraction measurement method capable of measuring an X-ray diffraction intensity profile of a test sample on-line quickly and with high accuracy. The purpose is to provide.

In order to solve the above-described problems and achieve the object, an X-ray diffraction apparatus according to the present invention includes an X-ray irradiation unit that irradiates a measurement point of a test sample with X-rays, and the X-ray is the test sample. An X-ray detector that measures one or two-dimensionally a plurality of diffracted X-rays diffracted by the measurement points to measure an X-ray diffraction intensity profile of the test sample; a reference position of the test sample; A measurement unit having a housing in which the X-ray irradiation unit and the X-ray detection unit are fixedly disposed relative to a reference plane, and a separation between the measurement point of the test sample and the measurement unit A difference ΔZ in the thickness direction of the test sample is a difference between a distance measuring unit that measures the distance, a reference separation distance between the measurement unit and the reference plane, and the separation distance measured by the distance measurement unit. And the calculated displacement ΔZ and the X-ray X-ray incident angle α from the irradiation unit to the measurement point of the test sample, distance R from the reference measurement point in the reference plane to the X-ray detection unit, and from the reference measurement point to the X-ray detection unit The true X-ray diffraction angle 2θ at the measurement point of the test sample is calculated by using the apparent diffraction X-ray emission angle Θ _ex and the following formula (1), and the calculated true X And a data processing unit for correcting the X-ray diffraction intensity profile based on the line diffraction angle 2θ.

In the X-ray diffractometer according to the present invention, in the above invention, the data processing unit includes the X-ray incident angle α, the apparent diffracted X-ray emission angle Θ _ex, and the following mathematical formula (2): The apparent X-ray diffraction angle 2Θ at the reference measurement point is calculated, and the calculated apparent X-ray diffraction angle 2Θ and the thickness direction displacement ΔZ of the test sample are shown below. The true X-ray diffraction angle 2θ is calculated by using Equation (3).
_{2Θ = Θ ex + α ··· (} 2)
2θ = 2Θ + a × ΔZ + b (3)
Where a and b are constants

  In the X-ray diffractometer according to the present invention, in the above invention, a plurality of the distance measuring units are arranged along a plurality of measurement points of the test sample, and the plurality of the distance measuring units are the test sample. The distance between each of the plurality of measurement points of the sample and the measurement unit is measured.

The X-ray diffraction measurement method according to the present invention includes an X-ray irradiation unit that irradiates a measurement point of a test sample with X-rays, and a plurality of diffractions in which the X-ray is diffracted by the measurement point of the test sample. An X-ray detection unit that detects X-rays one-dimensionally or two-dimensionally, and the X-ray irradiation unit and the X-ray detection unit are fixedly arranged relative to a reference plane that is a reference position of the test sample. A measurement unit having a housing, and measuring an X-ray diffraction intensity profile of the test sample, and using a distance measuring unit to determine a separation distance between the measurement point of the test sample and the measurement unit A difference between a measurement step to be measured, a reference separation distance between the measurement unit and the reference plane and the separation distance measured by the distance measurement unit is calculated as a displacement ΔZ in the thickness direction of the test sample. The calculated displacement ΔZ and the X-ray irradiation X-ray incidence angle α from the reference point to the measurement point of the test sample, distance R from the reference measurement point in the reference plane to the X-ray detection unit, and from the reference measurement point to the X-ray detection unit An X-ray diffraction angle calculation step of calculating a true X-ray diffraction angle 2θ at the measurement point of the test sample by using the apparent diffraction X-ray emission angle Θ _ex and the following equation (4): A correction step of correcting the X-ray diffraction intensity profile based on the true X-ray diffraction angle 2θ calculated by the X-ray diffraction angle calculation step.

In the X-ray diffraction measurement method according to the present invention, in the above invention, the X-ray diffraction angle calculation step includes the X-ray incident angle α, the apparent diffraction X-ray emission angle Θ _ex, and By using the mathematical formula (5), the apparent X-ray diffraction angle 2Θ at the reference measurement point is calculated, the calculated apparent X-ray diffraction angle 2Θ, and the displacement ΔZ in the thickness direction of the test sample, The true X-ray diffraction angle 2θ is calculated by using the following formula (6).
2Θ = Θ _ex + α (5)
2θ = 2Θ + a × ΔZ + b (6)
Where a and b are constants

  Further, in the X-ray diffraction measurement method according to the present invention, in the above invention, the measurement step uses the plurality of distance measuring units arranged along a plurality of measurement points of the sample to be tested. The distance between each of the plurality of measurement points of the sample and the measurement unit is measured.

  According to the present invention, there is an effect that an X-ray diffraction intensity profile of a test sample can be measured on-line quickly and with high accuracy.

FIG. 1 is a schematic diagram showing a configuration example of an X-ray diffraction apparatus according to an embodiment of the present invention. FIG. 2 is a diagram for explaining the calculation principle of the X-ray diffraction angle in the embodiment of the present invention. FIG. 3 is a diagram illustrating the relationship of the true X-ray diffraction angle with respect to the displacement of the test sample in the embodiment of the present invention. FIG. 4 is a flowchart showing an example of the X-ray diffraction measurement method according to the embodiment of the present invention. FIG. 5 is a diagram showing an example of components in steel of the test sample in this example. FIG. 6 is a schematic cross-sectional view showing the configuration of the plated layer of the galvannealed steel strip in this example. FIG. 7 is a diagram showing X-ray diffraction intensity profile measurement results at each measurement point of the alloyed hot-dip galvanized steel strip in this example.

  Exemplary embodiments of an X-ray diffraction apparatus and an X-ray diffraction measurement method according to the present invention will be described below in detail with reference to the accompanying drawings. Note that the present invention is not limited to the embodiment.

(X-ray diffractometer)
First, an X-ray diffraction apparatus according to an embodiment of the present invention will be described. FIG. 1 is a schematic diagram showing a configuration example of an X-ray diffraction apparatus according to an embodiment of the present invention. The X-ray diffractometer 1 according to the present embodiment is an on-line X-ray diffractometer that performs X-ray diffraction measurement using a product such as a steel plate as a test sample 16 in a production line. As shown in FIG. A measurement unit 2 that measures the X-ray diffraction intensity profile of the sample 16 and a distance measurement unit 9 that measures the separation distance between the measurement unit 2 and the test sample 16 are provided. The X-ray diffractometer 1 includes a data processing unit 10 that performs various data processing relating to X-ray diffraction measurement, an input unit 11 that inputs various information, and an output unit 12 that outputs information such as X-ray diffraction measurement results. , A storage unit 13 that stores information such as X-ray diffraction measurement results, and a control unit 14 that controls each component of the X-ray diffraction apparatus 1.

  The measurement unit 2 is a unit that performs X-ray diffraction measurement of the test sample 16. As shown in FIG. 1, the measurement unit 2 includes an X-ray irradiation unit 3 that irradiates a test sample 16 with X-rays 18 a and an X-ray detection unit 6 that detects a plurality of diffraction X-rays 18 b from the test sample 16. A Kβ filter 7 that removes Kβ rays from the plurality of diffracted X-rays 18 b incident on the X-ray detection unit 6, and a housing 8 that houses the X-ray irradiation unit 3, the X-ray detection unit 6, and the Kβ filter 7. Is provided.

  The X-ray irradiation unit 3 irradiates the measurement point of the test sample 16 with X-rays 18a, and includes an X-ray source 4 and an X-ray parallel beam converting device 5 as shown in FIG. The X-ray source 4 is configured using various X-ray tubes or radiation light sources, and the X-ray 18a having a wavelength band capable of obtaining a desired X-ray diffraction intensity profile of the test sample 16 is converted into the test sample 16. The light is emitted toward the measurement point. The X-ray parallel beam forming device 5 is configured using a solar slit, a collimator, a multilayer mirror, or the like, and is provided at the X-ray exit of the X-ray source 4. The X-ray parallel beam converting device 5 converts the X-ray 18a generated and emitted by the X-ray source 4 into a parallel beam. The parallelization of the X-ray 18a by the X-ray parallel beam converting device 5 is necessary to suppress the decrease in the angular resolution of the X-ray diffraction intensity profile caused by the expansion of the X-ray beam. The X-ray 18a is converted into a parallel beam by the X-ray parallel beam forming device 5, and then enters the measurement point of the test sample 16 as shown in FIG.

  As described above, the measurement point of the test sample 16 irradiated with the X-ray 18a coincides with the reference measurement point O in the reference plane 17 in FIG. The reference surface 17 is a fixed surface that serves as a reference position in the thickness direction of the test sample 16 (hereinafter, abbreviated as the thickness direction as appropriate). The reference measurement point O is detected when the surface of the test sample 16 (hereinafter referred to as the test surface) including the measurement point irradiated with the X-ray 18a from the X-ray irradiation unit 3 coincides with the reference surface 17. This is a fixed point in the reference surface 17 that coincides with the measurement point of the sample 16. The test sample 16 is sequentially transported by a transport device (not shown) on the production line so that the test surface and the reference surface 17 are substantially coincident. The thickness direction of the test sample 16 is a direction perpendicular to the width direction and the transport direction of the test sample 16 (hereinafter, the width direction and the transport direction are abbreviated as necessary). The conveyance direction of the test sample 16 is a direction perpendicular to the paper surface of FIG.

  The X-ray detection unit 6 performs one-dimensional detection or two-dimensional detection of a plurality of diffracted X-rays 18b obtained by diffracting the X-rays 18a from the X-ray irradiation unit 3 by the measurement points of the test sample 16, The X-ray diffraction intensity profile of the sample 16 is measured. Specifically, the X-ray detection unit 6 is configured using a one-dimensional detector or a two-dimensional detector having a plurality of X-ray detection elements arranged one-dimensionally or two-dimensionally, and has a plurality of X-ray detection surfaces. Are fixedly arranged in such a manner as to face the measurement point side of the test sample 16. The X-ray detection unit 6 performs one-dimensional detection or two-dimensional detection of a plurality of diffracted X-rays 18 b emitted from a measurement point of the test sample 16 within a predetermined angle range at a time. Thereby, the X-ray detection part 6 measures the X-ray diffraction intensity profile of the measurement point of the test sample 16 at a time within a predetermined X-ray diffraction angle range. Each time, the X-ray detection unit 6 transmits the measured X-ray diffraction intensity profile to the data processing unit 10. In addition, as the one-dimensional detector or the two-dimensional detector constituting the X-ray detection unit 6, for example, a semiconductor detector having excellent sensitivity and response to signals and angular resolution and excellent maintainability is used. Is desirable.

  As shown in FIG. 1, the Kβ filter 7 is fixedly arranged on the X-ray detection surface side of the X-ray detection unit 6, and a plurality of diffraction X rays emitted from the measurement point of the test sample 16 toward the X-ray detection unit 6. The Kβ line on line 18b is removed. That is, the plurality of diffracted X-rays 18 b are incident on the plurality of X-ray detection elements of the X-ray detection unit 6 after the Kβ rays are removed by the Kβ filter 7.

  The housing 8 accommodates the X-ray irradiation unit 3, the X-ray detection unit 6, the Kβ filter 7, and the like described above, and is relatively X with respect to the reference surface 17 serving as the reference position of the test sample 16. The beam irradiation unit 3 and the X-ray detection unit 6 are fixedly arranged. Specifically, as shown in FIG. 1, the casing 8 maintains a state in which the X-ray irradiation unit 3 and the X-ray detection unit 6 are fixedly disposed therein, and the test sample 16 from the reference surface 17. Is supported by a support mechanism (not shown) or the like so as to be separated by a predetermined distance in the thickness direction. In this state, the housing 8 is configured such that the relative position and X-ray irradiation direction of the X-ray irradiation unit 3 with respect to the reference surface 17, and the relative position and X-ray detection surface direction of the X-ray detection unit 6 with respect to the reference surface 17. And fix. As a result, the X-ray irradiation unit 3 and the X-ray detection unit 6 inside the housing 8 are fixed in an arrangement state in which a desired X-ray diffraction intensity profile of the test sample 16 can be measured.

That is, the X-ray 18 a emitted from the X-ray irradiation unit 3 inside the housing 8 forms a predetermined X-ray incident angle α with respect to the reference surface 17 and specifically the reference measurement point O (specifically, the test sample 16 Incident at the measurement point. The X-ray 18a incident on the measurement point of the test sample 16 is diffracted at an X-ray diffraction angle 2θ. A plurality of diffracted X-rays 18b formed by diffracting the X-ray 18a by the test sample 16 form a diffraction X-ray emission angle θ _ex with respect to the test surface of the test sample 16, and the measurement points of the test sample 16 are measured. To the X-ray detector 6 inside the housing 8. The plurality of diffracted X-rays 18 b are detected by the X-ray detection unit 6 after passing through the Kβ filter 7 fixedly arranged on the X-ray detection surface side of the X-ray detection unit 6 inside the housing 8.

  The distance measuring unit 9 measures a separation distance between the measurement point of the test sample 16 and the measurement unit 2 (hereinafter referred to as a test sample distance). Specifically, as shown in FIG. 1, the distance measuring unit 9 is fixed to the inner wall of the housing 8 so as to face the reference measurement point O in the reference surface 17 through the housing 8 of the measurement unit 2. Be placed. The distance measuring unit 9 measures the separation distance between the test surface of the test sample 16 and the housing 8 sequentially conveyed along the reference surface 17 in a non-contact manner as the test sample distance Z, and each time the measurement is performed. The measured specimen distance Z is transmitted to the data processing unit 10. Such a distance measuring unit 9 may be a non-contact type distance meter that transmits and receives ultrasonic waves or optical signals to and from the test surface of the test sample 16 to measure the test sample distance Z. The laser distance meter measures the sample distance Z in a non-contact manner by transmitting and receiving laser light to the test surface of the test sample 16 from the viewpoint of high distance measurement accuracy and excellent responsiveness. It is desirable.

  The data processing unit 10 corrects the X-ray diffraction intensity profile of the test sample 16 in accordance with the change in the position of the test sample 16 in the thickness direction. Specifically, the data processing unit 10 acquires the distance between the measurement unit 2 and the measurement point of the test sample 16, that is, the test sample distance Z from the distance measurement unit 9. Further, the data processing unit 10 has a preset separation distance (hereinafter referred to as a reference separation distance) between the reference surface 17 and the measurement unit 2 (specifically, the housing 8). The data processing unit 10 calculates the difference between the set reference separation distance and the test sample distance Z measured by the distance measurement unit 9 as the displacement ΔZ in the thickness direction of the test sample 16. The data processing unit 10 calculates the true X-ray diffraction angle 2θ at the measurement point of the test sample 16 corresponding to the calculated displacement ΔZ. On the other hand, the data processing unit 10 acquires the X-ray diffraction intensity profile at the measurement point of the test sample 16 from the X-ray detection unit 6. The data processing unit 10 corrects the X-ray diffraction intensity profile from the X-ray detection unit 6 based on the true X-ray diffraction angle 2θ calculated as described above.

  The input unit 11 is configured using an input device such as an input key or a mouse, and inputs various types of information to the control unit 14 in accordance with an input operation by the worker. For example, as information input to the control unit 14 by the input unit 11, information instructing measurement start or measurement end of the X-ray diffraction intensity profile of the test sample 16 by the measurement unit 2, measurement time of the X-ray diffraction intensity profile The information to instruct | indicate, the information etc. which instruct | indicate with respect to the control part 14 etc. are mentioned.

  The output unit 12 outputs various information such as an X-ray diffraction intensity profile after correction by the data processing unit 10 and input information by the input unit 11 based on the control of the control unit 14. Such an output unit 12 may be a display device that displays the above-described various types of information, a printer that prints the above-described various types of information on a print medium such as paper, or a combination thereof. It may be.

  The storage unit 13 stores information instructed to be stored by the control unit 14, reads information instructed to be read out by the control unit 14 from the stored information, and transmits the information to the control unit 14. For example, the storage unit 13 stores and accumulates the X-ray diffraction intensity profile corrected by the data processing unit 10 described above in association with the measurement point of the test sample 16 based on the control of the control unit 14.

  The control unit 14 controls each component of the X-ray diffraction apparatus 1 and controls input / output of signals between these components. Specifically, the control unit 14 measures the measurement timing (start timing or end timing) of the X-ray diffraction intensity profile of the test sample 16 by the measurement unit 2 or the measurement time based on the input information from the input unit 11 or the like. To control. At this time, the control unit 14 controls the irradiation timing or irradiation time of the X-ray 18 a that the X-ray source 4 of the X-ray irradiation unit 3 irradiates the measurement point of the test sample 16. Further, the control unit 14 controls the distance measuring unit 9 so as to measure the test sample distance Z for each measurement point of the test sample 16.

  The control unit 14 also measures the measurement point of the test sample 16 whose X-ray diffraction intensity profile is measured by the measurement unit 2 and the measurement point of the test sample 16 whose measurement sample distance Z is measured by the distance measurement unit 9. The X-ray diffraction intensity profile transmitted from the X-ray detection unit 6 to the data processing unit 10 and the test sample distance Z transmitted from the distance measurement unit 9 to the data processing unit 10 are matched with each other. To control. Based on this control, the data processing unit 10 associates the X-ray diffraction intensity profile from the X-ray detection unit 6 with the test sample distance Z from the distance measurement unit 9 for each measurement point of the test sample 16. On the other hand, the control unit 14 performs operation control of the output unit 12 that outputs the corrected X-ray diffraction intensity profile and operation control of the storage unit 13 that stores and stores the corrected X-ray diffraction intensity profile.

  Although not particularly shown in FIG. 1, the X-ray diffraction apparatus 1 having the above-described configuration is accompanied by various power sources for operating the respective components such as the measurement unit 2 and the data processing unit 10. The X-ray diffractometer 1 includes a cooling device for cooling each component such as the X-ray source 4 as necessary, a thermostat for keeping the temperature of each component constant, and a measurement unit 2. A purge device or a pressure control device for controlling the atmosphere inside the housing 8 may be attached.

(Calculation principle of X-ray diffraction angle)
Next, the calculation principle of the true X-ray diffraction angle 2θ at the measurement point of the sample 16 to be measured for the X-ray diffraction intensity profile will be described. In the X-ray diffraction apparatus 1 shown in FIG. 1, the X-ray irradiation unit 3 irradiates the measurement point of the sample 16 with X-rays 18a, and the X-ray detection unit 6 includes a plurality of measurement points from the measurement point. The diffracted X-ray 18b is detected one-dimensionally or two-dimensionally, and the X-ray diffraction intensity profile at this measurement point is measured. At this time, the test sample 16 is moved in the thickness direction of the test sample 16, that is, the test sample 16 due to vibration accompanying the travel (conveyance) of the test sample 16, a change in the thickness or shape of the test sample 16, and the like. The position changes in the vertical direction of the surface. With this change in position, the test surface of the test sample 16 is displaced in the thickness direction of the test sample 16 from the above-described reference surface 17 (see FIG. 1), and as a result, is measured by the X-ray detector 6. An error occurs in the X-ray diffraction angle of the X-ray diffraction intensity profile. Therefore, in order to realize high-accuracy measurement of the X-ray diffraction intensity profile, it is necessary to correct the X-ray diffraction angle error that occurs in this way.

FIG. 2 is a diagram for explaining the calculation principle of the X-ray diffraction angle in the embodiment of the present invention. In FIG. 2, the point light source A corresponds to the X-ray source 4 of the X-ray irradiation unit 3. The X-ray detection element B represents a plurality of X-ray detection elements in the X-ray detection unit 6. When the test sample 16 is not displaced in the thickness direction with respect to the reference surface 17, that is, when the test surface of the test sample 16 matches the reference surface 17, the measurement point of the test sample 16 is the reference point. It coincides with the reference measurement point O in the surface 17. The X-ray generated in the point light source A reaches this measurement point (= reference measurement point O) and is diffracted. As a diffracted X-ray, the reference measurement point 17 forms a diffraction X-ray emission angle Θ _ex with respect to the reference measurement point. The light exits from O (see broken line arrow in FIG. 2). The diffracted X-ray emitted from the reference measurement point O reaches the X-ray detection element B, and the X-ray diffraction intensity is measured by the X-ray detection element B.

  On the other hand, as shown in FIG. 2, when the test surface of the test sample 16 is displaced in the thickness direction from the reference surface 17, the measurement point O ′ of the test sample 16 is the test sample from the reference surface 17. The position shifts from the reference measurement point O in accordance with 16 displacements ΔZ. The X-rays generated in the point light source A reach this measurement point O ′ and are diffracted, and as diffracted X-rays, the diffraction X-ray emission angle θ with respect to the test surface of the test sample 16. _exAnd exit from the measurement point O '(see solid line arrow in FIG. 2). The diffracted X-ray emitted from the measurement point O ′ reaches the X-ray detection element B, and the X-ray diffraction intensity is measured by the X-ray detection element B. At this time, the true diffraction X-ray emission angle θ of the diffraction X-ray in the test sample 16_exAnd the apparent diffraction X-ray exit angle Θ of the diffraction X-ray at the reference plane 17 described above_exAn angle shift occurs between the two. This angular deviation is an error factor of the X-ray diffraction angle when measuring the X-ray diffraction intensity.

As described above, when the test surface of the test sample 16 is displaced from the reference surface 17 in the thickness direction, the true diffraction X-ray emission angle θ _{ex at} the measurement point O ′ of the test sample 16 after the displacement and the reference The relationship between the apparent diffraction X-ray emission angle Θ _{ex at} the reference measurement point O in the surface 17 is the distance in the thickness direction and the width direction between the measurement point O ′ of the test sample 16 and the X-ray detection element B. Can be expressed by the following formula (7). As shown in FIG. 2, the displacement ΔZ is the distance that the test surface of the test sample 16 is displaced from the reference surface 17 in the thickness direction. The distance R is a distance from the reference measurement point O in the reference plane 17 to the X-ray detection element B corresponding to the X-ray detection unit 6 (hereinafter referred to as a distance between OBs as appropriate). The X-ray incident angle α is an incident angle of X-rays irradiated from the point light source A corresponding to the X-ray source 4 of the X-ray irradiation unit 3 to the measurement point O ′ of the test sample 16. This X-ray incident angle α is the same value as the X-ray incident angle irradiated from the point light source A to the reference measurement point O.

Further, the true X-ray diffraction angle 2θ at the measurement point O ′ of the test sample 16 after the displacement uses the X-ray incident angle α and the true diffraction X-ray emission angle θ _{ex at the} measurement point O ′, It can be represented by the following formula (8).
2θ = α + θ _ex (8)

  Based on Equations (7) and (8) described above, the true X-ray diffraction angle 2θ at the measurement point O ′ of the test sample 16 after displacement can be expressed by Equation (9) below.

In equation (9), the distance R from the reference measurement point O to the X-ray detection element B, the X-ray incident angle α, and the apparent diffraction X-ray emission angle Θ _{ex at the} reference measurement point O are the X shown in FIG. This is a known design value determined by fixing the relative arrangement of the beam irradiation unit 3 and the X-ray detection unit 6 with respect to the reference plane 17. Therefore, if the displacement ΔZ is determined based on the measurement result of the distance measuring unit 9 (see FIG. 1), the true X-ray diffraction angle 2θ can be calculated based on the formula (9).

In the embodiment of the present invention, the above-mentioned known distance R, X-ray incident angle α, and apparent diffracted X-ray exit angle Θ _ex are stored in advance in the data processing unit 10 of the X-ray diffractometer 1 shown in FIG. Is set. As described above, the data processing unit 10 determines the difference between the reference separation distance between the measurement unit 2 and the reference surface 17 and the test sample distance Z measured by the distance measurement unit 9 as the thickness of the test sample 16. It is calculated as the displacement ΔZ in the vertical direction. Subsequently, the data processing unit 10 calculates the calculated displacement ΔZ, the X-ray incident angle α from the X-ray irradiation unit 3 to the measurement point O ′ of the test sample 16, and the X-ray from the reference measurement point O in the reference surface 17. By using the distance R to the detection unit 6, the apparent diffraction X-ray emission angle Θ _ex from the reference measurement point O to the X-ray detection unit 6, and the above-described equation (9), the measurement of the test sample 16 is performed. The true X-ray diffraction angle 2θ at the point O ′ is calculated. Further, the data processing unit 10 calculates the X-ray diffraction intensity profile at the measurement point O ′ of the test sample 16 measured by the X-ray detection unit 6 based on the true X-ray diffraction angle 2θ calculated as described above. To correct.

On the other hand, when the distance R between OBs shown in FIG. 2 is 200 [mm], the X-ray incident angle α is 45 [°], and the apparent diffraction X-ray emission angle Θ _ex is 60 [°], As a result of calculating the relationship of the true X-ray diffraction angle 2θ with respect to the displacement ΔZ of the test sample 16 based on the above formula (9), there is a predetermined correlation between the displacement ΔZ and the true X-ray diffraction angle 2θ. It was seen. In the correlation between the displacement ΔZ and the true X-ray diffraction angle 2θ, the apparent X-ray diffraction angle 2Θ of the diffracted X-ray at the reference measurement point O in the reference surface 17 can be expressed by the following formula (10). .
_{2Θ = Θ ex + α ··· (} 10)
That is, when the X-ray incident angle α is 45 [°] and the apparent diffraction X-ray emission angle Θ _ex is 60 [°], the apparent X-ray diffraction angle 2Θ is 105 [°].

FIG. 3 is a diagram illustrating the relationship of the true X-ray diffraction angle with respect to the displacement of the test sample in the embodiment of the present invention. As shown in FIG. 3, when the displacement ΔZ of the test sample 16 is smaller than the distance R between OBs (see FIG. 2), the true X-ray diffraction angle when the apparent X-ray diffraction angle 2Θ is constant. 2θ changes substantially linearly with respect to the change in displacement ΔZ. When such a correlation between the displacement ΔZ and the true X-ray diffraction angle 2θ holds, the true X-ray diffraction angle 2θ uses the displacement ΔZ and the apparent X-ray diffraction angle 2Θ, and is expressed by the following formula (11). Can be represented.
2θ = 2Θ + a × ΔZ + b (11)
However, in Formula (11), a and b are arbitrary constants.

As described above, when the displacement ΔZ of the test sample 16 is smaller than the distance R between the OBs, the data processing unit 10 (see FIG. 1) determines the X-ray incident angle α and the apparent diffracted X-ray emission angle Θ _ex. And the apparent X-ray diffraction angle 2Θ at the reference measurement point O is calculated by using the above-described formula (10). Subsequently, the data processing unit 10 uses the calculated apparent X-ray diffraction angle 2Θ, the displacement ΔZ in the thickness direction of the sample 16 to be tested, and the above formula (11) to obtain true X-ray diffraction. The angle 2θ is calculated. Further, the data processing unit 10 calculates the X-ray diffraction intensity profile at the measurement point O ′ of the test sample 16 measured by the X-ray detection unit 6 based on the true X-ray diffraction angle 2θ thus calculated. to correct.

Note that the data processing unit 10 determines that the displacement ΔZ of the test sample 16 is the case where the distance R between OBs, the X-ray incident angle α, and the apparent diffracted X-ray emission angle Θ _ex are other than the numerical values described above. If the distance is small relative to the distance R between the OBs, the true X-ray diffraction angle 2θ can be calculated in accordance with the displacement ΔZ based on the above-described equations (10) and (11).

(X-ray diffraction measurement method)
Next, an X-ray diffraction measurement method according to an embodiment of the present invention will be described. FIG. 4 is a flowchart showing an example of the X-ray diffraction measurement method according to the embodiment of the present invention. In the X-ray diffraction measurement method according to the present embodiment, the X-ray diffraction apparatus 1 shown in FIG. 1 performs each process of steps S101 to S105 shown in FIG. 4 for each measurement point of the sample 16 to be sequentially conveyed. Do step.

  That is, as shown in FIG. 4, the X-ray diffraction apparatus 1 first measures the X-ray diffraction intensity profile of the test sample 16 and the test sample distance Z between the measurement unit 2 and the test sample 16. (Step S101). In step S101, the X-ray diffractometer 1 uses the measurement unit 2 to irradiate the measurement point of the test sample 16 with the X-ray 18a, and outputs a plurality of diffractions emitted from the measurement point to a predetermined X-ray diffraction angle range. The X-ray 18b is detected, and thereby the X-ray diffraction intensity profile at this measurement point is measured. Further, the X-ray diffraction apparatus 1 uses the distance measuring unit 9 to measure the separation distance between the measurement point of the test sample 16 and the measurement unit 2, that is, the test sample distance Z.

  Specifically, as shown in FIG. 1, the measurement unit 2 includes an X-ray irradiation unit 3 having an X-ray source 4 and an X-ray parallel beam forming device 5, and an X-ray 18 a is a measurement point of the test sample 16. X-ray detector 6 for detecting a plurality of diffracted X-rays 18b diffracted by the K, a Kβ filter 7 for removing Kβ rays from the plurality of diffracted X-rays 18b, and a reference surface 17 serving as a reference position for the sample 16 to be examined. The X-ray irradiation unit 3, the X-ray detection unit 6, and the housing 8 on which the Kβ filter 7 is fixedly disposed. The X-ray irradiation unit 3 converts X-rays 18 a in a wavelength band that can obtain a desired X-ray diffraction intensity profile of the test sample 16 into parallel beams and irradiates the measurement point of the test sample 16. The Kβ filter 7 removes the Kβ rays of the plurality of diffraction X-rays 18b from the measurement point irradiated with the X-rays 18a. The X-ray detection unit 6 performs one-dimensional detection or two-dimensional detection of the plurality of diffraction X-rays 18b after the Kβ ray is removed by the Kβ filter 7, thereby obtaining an X-ray diffraction intensity profile at the measurement point of the test sample 16. Measure at once. The X-ray detection unit 6 transmits the measured X-ray diffraction intensity profile to the data processing unit 10 every time the X-ray diffraction intensity profile at the measurement point is measured in this way.

  In parallel with the above-described measurement of the X-ray diffraction intensity profile, the distance measuring unit 9 of the X-ray diffraction apparatus 1 measures the measurement point of the test sample 16 by transmitting and receiving laser light with respect to the test surface of the test sample 16. A test sample distance Z between the measuring unit 2 and the measuring unit 2 is measured. At this time, the distance measuring unit 9 measures the separation distance between the casing 8 of the measurement unit 2 and the test surface of the test sample 16 as the test sample distance Z. Each time, the distance measuring unit 9 transmits the measured specimen distance Z to the data processing unit 10.

After executing step S101 described above, the X-ray diffraction apparatus 1 calculates the true X-ray diffraction angle 2θ at the measurement point of the test sample 16 in response to the change in the position of the test sample 16 in the thickness direction ( Step S102). In step S <b> 102, the data processing unit 10 has already acquired the measurement result of the test sample distance Z in step S <b> 101 from the distance measurement unit 9. The data processing unit 10 determines the difference between the reference separation distance between the measurement unit 2 and the reference surface 17 and the test sample distance Z measured by the distance measurement unit 9 in step S101 as the thickness of the test sample 16. Calculated as a displacement ΔZ in the direction. Next, the data processing unit 10 calculates the displacement ΔZ calculated as described above, the X-ray incident angle α from the X-ray irradiation unit 3 to the measurement point of the test sample 16, and the reference measurement point O in the reference plane 17. By using the distance R to the X-ray detector 6, the apparent diffraction X-ray emission angle Θ _ex from the reference measurement point O to the X-ray detector 6, and the above-described equation (9), the test sample 16 The true X-ray diffraction angle 2θ at the measurement point is calculated.

  Next, the X-ray diffraction apparatus 1 corrects the X-ray diffraction intensity profile at the measurement point of the test sample 16 based on the true X-ray diffraction angle 2θ calculated at step S102 (step S103). In step S103, the data processing unit 10 has already acquired the measurement result of the X-ray diffraction intensity profile in step S101 from the X-ray detection unit 6 of the measurement unit 2. The data processing unit 10 calculates the X-ray diffraction angle of the X-ray diffraction intensity profile measured by the X-ray detection unit 6 in step S101, that is, the apparent X-ray diffraction angle 2Θ based on the above-described equation (9). The true X-ray diffraction angle 2θ is corrected. Thereby, the data processing unit 10 corrects the error of the X-ray diffraction angle of the X-ray diffraction intensity profile in step S101.

  Next, the X-ray diffractometer 1 stores and outputs the X-ray diffraction intensity profile corrected in step S103 (step S104). In step S <b> 104, the control unit 14 controls the storage unit 13 to store the X-ray diffraction intensity profile corrected by the data processing unit 10 in association with the measurement point of the test sample 16. The storage unit 13 stores the X-ray diffraction intensity profile corrected by the data processing unit 10 for each measurement point of the test sample 16 based on the control of the control unit 14. In parallel with this, the control unit 14 controls the output unit 12 so as to output each piece of information indicating the X-ray diffraction intensity profile corrected by the data processing unit 10 and the measurement point of the test sample 16. Based on the control of the control unit 14, the output unit 12 displays each piece of information on a screen or prints it on a print medium such as paper. Alternatively, the output unit 12 performs screen display and print output of these pieces of information.

  Thereafter, the X-ray diffractometer 1 determines whether or not to end the measurement of the X-ray diffraction intensity profile for the test sample 16 (step S105). In step S <b> 105, when the set measurement time has elapsed from the start of measurement of the test sample 16, the control unit 14 completes the measurement of the X-ray diffraction intensity profile for all measurement points set on the test sample 16. Alternatively, when the end of the measurement of the X-ray diffraction intensity profile is instructed by the input information of the input unit 11, it is determined that the measurement of the X-ray diffraction intensity profile for the test sample 16 is completed. When the measurement of the X-ray diffraction intensity profile for the test sample 16 is completed (step S105, Yes), the X-ray diffraction apparatus 1 ends this process. If the measurement of the X-ray diffraction intensity profile for the test sample 16 has not been completed (No at Step S105), the X-ray diffraction apparatus 1 returns to Step S101 described above, and appropriately performs the processing steps after Step S101. repeat.

On the other hand, in the above-described step S102, when the distance R between the OBs shown in FIG. 2 is smaller than the displacement ΔZ of the test sample 16, the data processing unit 10 performs the above-described mathematical expressions (10) and (11). Based on the above, the true X-ray diffraction angle 2θ may be calculated. At this time, the data processing unit 10 uses the X-ray incident angle α, the apparent diffracted X-ray emission angle Θ _ex, and the above-described equation (10), so that the apparent measurement point O at the reference measurement point O in the reference plane 17 is obtained. X-ray diffraction angle 2Θ is calculated. Subsequently, the data processing unit 10 uses the calculated apparent X-ray diffraction angle 2Θ, the displacement ΔZ in the thickness direction of the test sample 16 in step S102, and the above-described equation (11), thereby The true X-ray diffraction angle 2θ at the measurement point of the specimen 16 is calculated.

  Further, in the subsequent step S103, the data processing unit 10 calculates the X-ray diffraction angle of the X-ray diffraction intensity profile from the X-ray detection unit 6, that is, the apparent X-ray diffraction angle 2Θ, using the above-described formula (10) and formula The true X-ray diffraction angle 2θ calculated based on (11) is corrected. Thereby, the data processing unit 10 corrects the error of the X-ray diffraction angle of the X-ray diffraction intensity profile.

(Example)
Next, examples of the present invention will be described. In this example, the X-ray diffraction apparatus 1 shown in FIG. 1 was applied to a continuous GA steel strip production line for producing an alloyed hot-dip galvanized steel strip (hereinafter referred to as GA steel strip).

Specifically, in a continuous GA steel strip production line, the line speed of the steel strip to be treated is constant at 100 [mpm], has the components shown in FIG. 5 and has a thickness (specifically, a steel strip is formed). The steel strip to be treated having a steel sheet thickness of 1.0 [mm] is subjected to hot dip galvanizing alloying treatment (plating adhesion amount: 42.0 to 48.48) by controlling the plating adhesion amount and the alloying temperature. 0 [g / m ² ], Fe concentration: 7.2 to 15.2 [wt%]). In the continuous GA steel strip production line, the X-ray diffractometer 1 shown in FIG. 1 is installed on a line region where the steel strip temperature becomes 100 [° C.] or less. The X-ray diffraction intensity profile of the GA steel strip as the test sample 16 was measured online. At this time, the X-ray diffractometer 1 is fixedly installed at the center of the continuous GA steel strip production line, and the X-ray diffraction intensity profile is measured at the central portion in the width direction of the GA steel strip that is sequentially conveyed. Measurements were made. The measurement time of the X-ray diffraction intensity profile of the GA steel strip by the X-ray diffractometer 1 was set to 30 [seconds].

FIG. 6 is a schematic cross-sectional view showing the configuration of the plating layer of the GA steel strip in this example. In the plated layer 20 of the GA steel strip as the test sample 16 shown in FIG. 6, the Fe concentration increases from the GA steel strip surface toward the base steel plate 24 due to thermal diffusion of Fe from the base steel plate 24. In such a plated layer 20 of the GA steel strip, as shown in FIG. 6, the ζ phase (FeZn ₁₃ ) 21 and the δ ₁ phase (FeZn _7-10 ) 22 from the GA steel strip surface toward the base steel plate 24 side. , Γ phase and Γ ₁ phase (Fe ₃ Zn ₁₀ and Fe ₁₁ Zn ₄₀ , hereinafter, Γ phase and Γ ₁ phase are simply referred to as Γ phase) 23 are formed. These alloy phases change their abundance with the progress of alloying of the plating layer 20. This is because, as the alloying of the plating layer 20 progresses, Fe diffuses from the base steel plate 24, so that the metallic zinc, that is, the η phase (not shown) disappears, and the ζ phase 21, the δ ₁ phase 22, and the Γ phase 23. This is because these are sequentially generated and grown.

On the other hand, in this embodiment, the X-ray diffraction apparatus 1 installed in the continuous GA steel strip production line uses a Cr tube for the X-ray source 4 (see FIG. 1) and a collimator (X The X-ray 18a was converted into a parallel beam by the line parallel beam forming device 5), and the traveling GA steel strip (test sample 16) was irradiated with the X-ray 18a. Further, in the X-ray diffraction apparatus 1 in this example, a semiconductor one-dimensional detector was used as the X-ray detector 6 and a laser rangefinder was used as the distance measurement unit 9. In such an X-ray diffractometer 1, the incident angle (X-ray incident angle α) of the X-ray 18a with respect to the GA steel strip as the test sample 16 was 65 [°]. The emission angle of the diffracted X-ray 18b (apparent diffracted X-ray emission angle Θ _ex shown in FIG. 2) reaching the center of the light receiving surface of the one-dimensional detector from the reference measurement point O (see FIGS. 1 and 2) of the reference surface 17 is 65 [°]. A distance R (see FIG. 2) from the reference measurement point O to the center of the light receiving surface of the one-dimensional detector was 250 [mm].

  Further, the displacement ΔZ in the thickness direction of the GA steel strip was calculated based on the measurement result by the attached laser distance meter, and the standard deviation of the calculated displacement ΔZ was 40 [μm] or less. From this, the cause of the displacement ΔZ of the GA steel strip is mainly the change in the thickness (steel plate thickness) of the GA steel strip to be passed. For this reason, in this embodiment, the average value of each displacement ΔZ based on the distance measurement results sequentially obtained by the laser distance meter during the measurement time of the X-ray diffraction intensity profile is calculated, and the average value of the calculated displacement ΔZ is calculated. Used to correct the X-ray diffraction angle.

Furthermore, in this example, the measurement point of the X-ray diffraction intensity profile by the X-ray diffractometer 1 is calculated based on the line speed of the GA steel strip as the test sample 16 and the length of the GA steel strip. An alloyed hot-dip galvanized steel piece (hereinafter referred to as GA steel piece) was collected from the GA steel strip portion at substantially the same position. For each of the three GA steel pieces corresponding to the measurement points P ₁ , P ₂ and P ₃ of the GA steel strip, the non-target surface of the X-ray diffraction intensity profile measurement is completely sealed, and a small amount of hexamethylenetetramine is added. Each of these three GA steel pieces was immersed in the added aqueous hydrochloric acid solution. As a result, the plating layers of these three GA steel pieces (for example, the plating layer 20 shown in FIG. 6) are dissolved, the weight difference (GASH 0401) of the GA steel pieces before and after dissolution is calculated, and the solution after dissolution is further added. ICP emission spectroscopic analysis was performed to calculate the coating amount of GA steel pieces and the Fe concentration during plating.

As a result, the plating adhesion amount and the Fe concentration at the measurement point P ₁ of the GA steel strip were 42.0 [g / m ² ] and 7.2 [wt%], respectively. The plating adhesion amount and Fe concentration at the measurement point P ₂ of the GA steel strip were 46.0 [g / m ² ] and 11.4 [wt%], respectively. The plating adhesion amount and Fe concentration at the measurement point P ₃ of the GA steel strip were 48.0 [g / m ² ] and 15.2 [wt%], respectively.

FIG. 7 is a diagram showing the X-ray diffraction intensity profile measurement result at each measurement point of the GA steel strip in the present example. 7, correlation line L1 shows the X-ray diffraction intensity profile measured on-line measurement point P ₁ of the GA steel strip. Correlation line L2 shows the X-ray diffraction intensity profile measured on-line measurement point P ₂ of the GA steel strip. Correlation line L3, for measuring point P ₃ of the GA steel strip showing the X-ray diffraction intensity profile measured online. As shown in FIG. 7, the X-ray diffraction angle indicating the peak of the X-ray diffraction intensity of the alloy phase (hereinafter referred to as the diffraction peak angle) )) Immediately. Therefore, various information based on the measurement result of the X-ray diffraction intensity profile shown in FIG. 7 can be quickly fed back to the control of the GA steel strip production conditions.

For example, from the measurement result of the X-ray diffraction intensity profile shown in FIG. 7, the peak of the X-ray diffraction intensity of the ζ phase decreases with the increase of the Fe concentration during plating, and the X-ray diffraction intensity of the δ ₁ phase It can be seen that the peak increases and the diffraction peak angle of the δ ₁ phase shifts to the high angle side, and that the peak of the X-ray diffraction intensity of the Γ phase increases. From these relationships, it is possible to read a phenomenon in which the ζ phase disappears with alloying, and the δ ₁ phase and the Γ phase are sequentially generated and grown. It can also be read from the shift of the diffraction peak angle of the δ ₁ phase shown in FIG. 7 that Fe is dissolved in the δ ₁ phase and the crystal lattice spacing is reduced. Based on the above results, the GA steel strip can be manufactured at a higher yield by controlling the manufacturing conditions of the GA steel strip so as to obtain an alloy phase structure having desired physical characteristics.

  Therefore, if the X-ray diffraction intensity profile of the test sample 16 is measured online using the X-ray diffraction apparatus 1 according to the embodiment of the present invention, the physical characteristics of the test sample 16 being manufactured can be quickly known. be able to. Since it is possible to quickly feed back the physical characteristics obtained in this way to the control of the manufacturing conditions of the test sample 16, the product can be manufactured with a higher yield.

  As described above, in the embodiment of the present invention, the X-ray irradiation unit and the X-ray detection unit that are fixedly arranged relative to the reference plane serving as the reference position of the test sample are included in the housing. A measurement unit is used to irradiate a measurement point of a test sample with X-rays and to detect a plurality of diffracted X-rays diffracted from the measurement point to a predetermined angle range in a one-dimensional or two-dimensional manner. The X-ray diffraction intensity profile of the sample is measured, and the test sample distance between the measurement point of the test sample and the measurement unit is measured using the distance measuring unit. Further, the displacement in the thickness direction of the test sample is calculated based on the test sample distance measured by the distance measuring unit, the calculated displacement, and the X-ray incident angle to the measurement point of the test sample, Using the distance from the reference measurement point in the reference plane to the X-ray detector and the apparent diffracted X-ray emission angle at the reference measurement point as appropriate, Equation (9) or Equation (10) and Equation (11) described above are used. Based on this, the true X-ray diffraction angle at the measurement point of the test sample is calculated, and the X-ray diffraction intensity profile at the measurement point of the test sample is corrected based on the calculated true X-ray diffraction angle. Yes.

  Therefore, an X-ray diffraction intensity profile and X-ray detection can be performed with an X-ray diffraction intensity profile capable of obtaining desired information including the crystal structure of the substance constituting the test sample, the amount of constituent substances, stress, and crystal orientation. Measurement can be performed online at one time without rotating the part. In addition to this, it is possible to sufficiently correct errors in the X-ray diffraction angle caused by changes in the thickness and shape of the test sample, or vibrations of the test sample and the installation platform during travel. The X-ray diffraction angle can be reflected in the measurement result of the X-ray diffraction intensity profile of the test sample. From the above, it is possible to efficiently measure the X-ray diffraction intensity profile in the angle range of interest, and to reduce the X-ray diffraction angle error in the X-ray diffraction intensity profile as much as possible. As a result, a desired X-ray diffraction intensity profile of the test sample can be measured quickly and with high accuracy on-line.

  In the embodiment of the present invention, an X-ray irradiation unit that irradiates the measurement point of the test sample with X-rays, and an X-ray detection unit that detects a plurality of diffraction X-rays diffracted by the measurement point of the test sample; Are fixedly arranged relative to the reference plane. For this reason, when measuring the X-ray diffraction intensity profile of the test sample, the mechanical load on the measurement unit (specifically, the X-ray irradiation unit and the X-ray detection unit) can be reduced as much as possible. As a result, since the reduction in the mechanical life of the measurement unit can be suppressed, an X-ray diffractometer with excellent mechanical durability can be realized.

  Furthermore, in the embodiment of the present invention, by providing a plurality of distance measuring units 9 in the X-ray diffractometer 1, the distance between the test sample 16 and the measurement unit 2 for each of the plurality of measurement points in the test sample 16. Can be measured. In this case, a plurality of distance measuring units 9 are arranged along a plurality of measurement points of the test sample 16. The plurality of distance measuring units 9 respectively measure the separation distance (test sample distance Z) between the plurality of measurement points of the test sample 16 and the measurement unit 2. Thus, by measuring the test sample distance Z for each measurement point of the test sample 16 using the plurality of distance measuring units 9, the displacement ΔZ in the thickness direction of the test sample 16 with respect to the reference surface 17 is measured. It is possible to measure with high accuracy every time. Therefore, the displacement ΔZ of the measurement point of the test sample 16 can be obtained with high accuracy according to the situation of each measurement point such as the thickness and shape of the test sample 16 and the influence of vibration. Thereby, the precision of the X-ray diffraction angle for every measurement point can be raised, As a result, the improvement of the measurement precision of the X-ray diffraction intensity profile in a some measurement point can be promoted. In addition, when the thickness and shape of the test sample 16 are different for each measurement point, the influence of vibration, and the like, it is desirable to arrange the plurality of distance measurement units 9 corresponding to all the measurement points.

  In the above-described embodiment, the measurement of the X-ray diffraction intensity profile of the test sample and the measurement of the test sample distance are performed in parallel, but the present invention is not limited to this. In the present invention, the measurement of the X-ray diffraction intensity profile of the test sample may be performed before or after the measurement of the test sample distance.

  In the above-described embodiment, the X-ray diffraction intensity profile of the sample to be sequentially conveyed is measured, but the present invention is not limited to this. In the present invention, the measurement of the X-ray diffraction intensity profile may be performed on the test sample in a stopped state or may be performed on the test sample in a running state. Alternatively, the X-ray diffraction intensity profile of the test sample on the sample stage may be measured by moving the sample stage on which the test sample is placed relative to the measurement unit. And the X-ray diffraction intensity profile of the test sample may be measured by moving the measurement unit relative to the test sample. In this case, the X-ray diffraction intensity profile can be measured at an arbitrary position within the test surface of the test sample.

  Furthermore, although steel products, such as GA steel strip, were used as the test sample in the above-described embodiment, the present invention is not limited to this. The test sample whose X-ray diffraction intensity profile is measured by the X-ray diffractometer and the X-ray diffraction measurement method according to the present invention may be various steel materials such as GA steel plate, or an iron alloy other than steel. It may be a metal other than an iron alloy such as copper or aluminum. Further, the present invention can also be applied to other materials exhibiting crystallinity, such as ceramic materials, semiconductor materials, and resin materials. That is, in the present invention, the material of the test sample may be any of steel, iron alloys other than steel, metals other than iron alloys, ceramic materials, semiconductor materials, resin materials, etc. The type (for example, strength and composition) is not particularly limited.

  Further, the present invention is not limited by the above-described embodiments and examples, and the present invention includes a configuration in which the above-described constituent elements are appropriately combined. In addition, other embodiments, examples, operational techniques, and the like made by those skilled in the art based on the above-described embodiments are all included in the scope of the present invention.

  As described above, the X-ray diffractometer and the X-ray diffraction measurement method according to the present invention are useful for measuring the X-ray diffraction intensity profile of the substance constituting the test sample, and in particular, the X-ray diffraction of the test sample. It is suitable for measuring the intensity profile quickly and with high accuracy online.

DESCRIPTION OF SYMBOLS 1 X-ray diffractometer 2 Measurement unit 3 X-ray irradiation part 4 X-ray source 5 X-ray parallel beam apparatus 6 X-ray detection part 7 K (beta) filter 8 Case 9 Distance measurement part 10 Data processing part 11 Input part 12 Output part Reference Signs List 13 Storage Unit 14 Control Unit 16 Test Sample 17 Reference Surface 20 Plating Layer 21 Zeta Phase 22 δ ₁ Phase 23 Γ Phase 24 Base Steel Plate A Point Light Source B X-ray Detection Element L1 to L3 Correlation Line O Reference Measurement Point O ′, P ₁ ~P ₃ measuring points

Claims (6)

An X-ray irradiator that irradiates a measurement point of the test sample with X-rays, and a plurality of diffracted X-rays formed by diffracting the X-rays by the measurement point of the test sample are detected in one or two dimensions to detect An X-ray detection unit that measures an X-ray diffraction intensity profile of a test sample, and the X-ray irradiation unit and the X-ray detection unit are fixedly disposed relative to a reference plane that is a reference position of the test sample. A measuring unit having a housing
A distance measurement unit for measuring a separation distance between the measurement point of the test sample and the measurement unit;
A difference between a reference separation distance between the measurement unit and the reference surface and the separation distance measured by the distance measurement unit is calculated as a displacement ΔZ in the thickness direction of the test sample, and the calculated displacement ΔZ An X-ray incident angle α from the X-ray irradiation unit to the measurement point of the test sample, a distance R from the reference measurement point in the reference plane to the X-ray detection unit, and the reference measurement point The true X-ray diffraction angle 2θ at the measurement point of the test sample is calculated by using the apparent diffraction X-ray emission angle Θ _ex to the X-ray detection unit and the following formula (1). A data processing unit for correcting the X-ray diffraction intensity profile based on the true X-ray diffraction angle 2θ,
An X-ray diffraction apparatus comprising:

The data processing unit uses the X-ray incident angle α, the apparent diffracted X-ray emission angle Θ _ex, and the following equation (2) to obtain an apparent X-ray diffraction angle at the reference measurement point. 2Θ is calculated, and the true X-ray diffraction angle is calculated by using the calculated apparent X-ray diffraction angle 2Θ, the displacement ΔZ in the thickness direction of the test sample, and the following equation (3). The X-ray diffractometer according to claim 1, wherein 2θ is calculated.
_{2Θ = Θ ex + α ··· (} 2)
2θ = 2Θ + a × ΔZ + b (3)
Where a and b are constants A plurality of the distance measuring units are arranged along a plurality of measurement points of the test sample,
The X-ray diffractometer according to claim 1, wherein the plurality of distance measuring units respectively measure the distances between the plurality of measurement points of the test sample and the measurement unit. An X-ray irradiator that irradiates a measurement point of the test sample with X-rays, and an X-ray that detects one-dimensionally or two-dimensionally a plurality of diffracted X-rays formed by diffracting the X-ray by the measurement point of the test sample Using the measurement unit having a detection unit and a housing in which the X-ray irradiation unit and the X-ray detection unit are fixedly arranged relative to a reference plane serving as a reference position of the test sample, A measurement step of measuring an X-ray diffraction intensity profile of the sample and measuring a separation distance between the measurement point of the test sample and the measurement unit using a distance measurement unit;
A difference between a reference separation distance between the measurement unit and the reference surface and the separation distance measured by the distance measurement unit is calculated as a displacement ΔZ in the thickness direction of the test sample, and the calculated displacement ΔZ An X-ray incident angle α from the X-ray irradiation unit to the measurement point of the test sample, a distance R from the reference measurement point in the reference plane to the X-ray detection unit, and the reference measurement point X-ray for calculating the true X-ray diffraction angle 2θ at the measurement point of the test sample by using the apparent diffraction X-ray emission angle Θ _ex to the X-ray detection unit and the following equation (4) Diffraction angle calculation step;
A correction step of correcting the X-ray diffraction intensity profile based on the true X-ray diffraction angle 2θ calculated by the X-ray diffraction angle calculation step;
An X-ray diffraction measurement method comprising:

The X-ray diffraction angle calculation step uses the X-ray incident angle α, the apparent diffraction X-ray emission angle Θ _ex, and the following equation (5) to obtain an apparent X at the reference measurement point. The true X-ray diffraction angle 2Θ is calculated, and the calculated true X-ray diffraction angle 2Θ, the displacement ΔZ in the thickness direction of the test sample, and the following formula (6) are used. The X-ray diffraction measurement method according to claim 4, wherein the line diffraction angle 2θ is calculated.
2Θ = Θ _ex + α (5)
2θ = 2Θ + a × ΔZ + b (6)
Where a and b are constants   The measurement step uses a plurality of the distance measurement units arranged along a plurality of measurement points of the test sample, and determines a separation distance between each of the plurality of measurement points of the test sample and the measurement unit. 6. The X-ray diffraction measurement method according to claim 4, wherein each measurement is performed.

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