JP3027074B2 - X-ray diffraction dynamic measurement device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an X-ray diffraction dynamic measurement apparatus, and more particularly to a change in the crystal structure of various materials such as metals, ceramics, and magnetic materials which is changed by heat treatment, mechanical treatment, chemical reaction, and the like. The present invention relates to an X-ray diffraction dynamic measurement device capable of sequentially and dynamically measuring a process.

[0002]

2. Description of the Related Art Conventionally, it is indispensable to analyze a change in crystal structure caused by a manufacturing process such as heat treatment, mechanical treatment, or chemical reaction in designing a material. For example, in the case of alloyed hot-dip galvanized steel sheets used in large quantities in automobile bodies and building materials, in order to improve plating adhesion, slidability, press workability, etc., a brittle η-
Reduces the Zn phase and Γ phase, it is necessary to control the alloying reaction to be a plating layer of [delta] ₁ main phase. Further, in order to enhance the magnetic properties of the hard ferrite magnet, generation of Z-type magnetoplumbite (M ₂ Sr ₃ Fe ₂₄ O ₄₁ ) and hematite (Fe ₂ O ₃ ) is suppressed, and M-type magnetoplumbite (MFe ₁₂ It must be manufactured under sintering conditions such that O ₁₉ ) is the main phase.

In order to measure the change in the crystal structure that occurs during such a manufacturing process, conventionally, a method of extracting a sample during the process, immediately freezing the reaction, and then performing X-ray diffraction is most commonly used. there were. That is, conventionally used X-ray diffractometers include those based on the Guinier method, such as a Guinier camera having a concentrated beam optical system and an oblique incidence Guinier camera having a quasi-parallel beam optical system, or a Debye-Scherrer camera. Hereinafter, each configuration will be briefly described.

First, in the case of a Guinier camera using a concentrated beam optical system, an incident X-ray 2 generated by an X-ray source 1 is converted into a monochromatic X-ray 2a by a curved crystal monochromator 3 as shown in FIG.
To monochromatic incident on the sample S through the focal point F _1. Then, X-ray diffraction occurs on the sample S in accordance with the crystal structure thereof, and is diffracted on the focal point circumference 5 called a Roland circle having a radius r from the center point C of the Guinier camera 4 like F ₁ ′, F ₂ ′,. The X-ray 2b is focused. An X-ray diffraction pattern is detected by setting the film-shaped X-ray detector 6 along the focal circumference 5 and performing time exposure.

As shown in FIG. 6, the film X-ray film 6 of the film X-ray detector 6 is exposed at diffraction X-ray focal points F ₁ ′, F ₂ ′,. X-ray diffraction patterns P ₁ , P ₂ . The pattern P _1, P ₂ ... position L _1, L ₂ ... is the diffraction angle 2 [Theta] ₁ of, 2 [Theta] ₂
.. And a function of the radius r of the Guinier camera, the diffraction angle 2θ can be obtained by measuring the positions L ₁ , L ₂ ... Of this pattern, and the crystal lattice spacing d _hkl is determined from the Bragg condition. The crystal structure is known.

In the case of an oblique incidence Guinier camera of a quasi-parallel beam optical system, as shown in FIG. 7, an incident solar slit (or collimator) 7 attached to an X-ray source 1 and a flat crystal monochromator 3a enter an incident X-ray. 2 is made parallel and monochromatic, this monochromatic X-ray 2a is incident on the sample S at a low angle, and the diffraction pattern is detected by the film X-ray detector 6 of the Guinier camera 4. The feature of this oblique incidence Guinier camera is that the position where X-ray diffraction occurs is relatively shallower than that of the above-mentioned Guinier camera of the concentrated beam optical system, so that the sensitivity of X-ray diffraction on the sample surface is improved. It is suitable for measuring a chemical reaction on a surface.

In the case of a Debye-Scherrer camera,
As shown in FIG. 8, the incident X-rays 2 converged by the collimator 8
Is incident on the cylindrical sample S, and the diffracted X-rays 2b spreading conically from the center of the sample are detected by the film X-ray detector 6 of the cylindrical or semi-cylindrical Debye-Scherrer camera 9. This Debye-Scherrer camera 9 can use the Guinier camera 4 shown in FIG. 5 as it is, but by using two of them in a cylindrical shape, the X-ray diffraction is ± 180.
° Since detection can be performed from almost all directions, sensitivity and accuracy can be improved. Note that this optical system is suitable for measuring a minute area of a sample or a structural change of a wire-shaped sample.

[0008]

However, in the case of using any of the above-mentioned various types of X-ray diffractometers, the number of sampling samples required for analysis is increased when the experimental conditions such as the material composition and the rate of temperature rise increase. Not only does it significantly increase, for example,
When the reaction time is as short as several seconds to several tens of seconds as in the Zn-Fe alloying reaction, it was difficult to freeze the reaction accurately even by rapid cooling such as quenching. In addition, although a sintered sample may be crushed by quenching treatment, this method can be applied only to a solid sample having a long reaction time.

In addition to the above, a high-temperature X-ray diffractometer having a sample heating furnace mounted on a conventional X-ray diffractometer using a scintillation detector has been put to practical use, and is used for observation of phase transformation by heat treatment. However, in this apparatus, a measurement deviation corresponding to the angular scanning time of the scintillation detector occurs from the start to the end of one X-ray diffraction pattern in one X-ray diffraction pattern. It could not be applied to short time samples.

In order to compensate for this drawback, a cylindrical continuous high-temperature camera equipped with a film feed mechanism has been put into practical use instead of a scintillation detector. Since the time must be set to 10 minutes to several hours, there is a problem that it is not possible to perform measurement following a fast reaction phenomenon such as alloying of zinc plating.

Furthermore, since the X-ray film has a small dynamic range, even if the blackened pattern exposed on the film is quantitatively read by a photometer, it has a high resolution pattern having a peak intensity ratio as measured by a scintillation detector. Therefore, it was impossible to identify a complex peak such as a Zn-Fe intermetallic compound generated during the galvanizing alloying reaction.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art.
Instant diffraction X while giving mechanical processing, chemical reaction, etc.
An object of the present invention is to provide an X-ray diffraction dynamic measurement device capable of capturing a change in an X-ray diffraction pattern over time by detecting a line and dynamically tracking a change in a crystal structure.

[0013]

SUMMARY OF THE INVENTION The present invention provides a film-shaped X-ray detector which comprises an X-ray source, an incident monochromator comprising a curved crystal, and a Guinier camera, and which diffracts X-rays generated by irradiating a sample with a concentrated beam. in X Senkai OriSo location detecting in, provided with a sample processing device for processing the sample, the film-like X-ray detector together are semi-cylindrical, the automatic film feeding mechanism for sending the film a certain distance, An X-ray diffraction dynamic measurement device is provided with a reading device having an image processing function of pixel-integrating an X-ray diffraction pattern in a film feeding direction.

[0014] Incidentally, the X Senkai OriSo location is diffracted X-rays generated by irradiating a擬平line beam is configured to sample from the incident monochromator and Guinier camera comprising a X-ray source and the Soller slit or collimator and the flat plate crystals X-ray film
Detected by the detector擬平line beam X Senkai OriSo location or X-ray source and the collimator and a cylindrical or semi-cylindrical film is composed of a shaped X-ray detector Debye-Scherrer camera provided with the by X-ray beam on the sample, X-rays generated by irradiating
In Irumu shaped X-ray detector may be an X Senkai OriSo location you detected.

It is preferable that a stimulable luminous body is used as the film of the film X-ray detector, and that the pixels be integrated in the film feed direction.

[0016]

According to the present invention, by adding a sample processing apparatus and an automatic film feed mechanism to a Guinier camera or a Debye-Scherrer camera, an X-ray diffraction pattern can be instantaneously and continuously applied while heat treatment or mechanical processing is applied to the sample. , It is possible to dynamically measure the state of structural change occurring in the process of heat treatment, mechanical treatment, chemical reaction, and the like of various materials such as metals, ceramics, and magnetic materials.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the X-ray diffraction dynamic measuring apparatus according to the present invention will be described below in detail with reference to the drawings. FIG. 1 shows an embodiment of a Guinier camera having a concentrated beam optical system according to the present invention. In FIG. 1, the same elements as those of the conventional example in FIG.

As shown in FIG. 1, a sample processing chamber 10 is provided in a conventional apparatus comprising an X-ray source 1, an incident monochromator 3, and a Guinier camera 4. The film X-ray detector 6 has a semi-cylindrical shape, and the built-in film can be automatically fed by an automatic film feed mechanism 11. The sample processing chamber 10 and the automatic film feed mechanism 11 are controlled by a sample processing control device 12, respectively.

In the sample processing chamber 10, a sample S under measurement is subjected to heat treatment such as heating or cooling, or mechanical treatment such as tension or compression, based on a command from the sample processing controller 12.
Further, various controls such as a chemical reaction such as a corrosion reaction in a solution are performed as necessary. That is, when the sample S is first heated, the sample processing chamber 10 itself is used as a heating furnace to seal the X-ray path to the outside. When the sample S is a sample of a conductor such as a metal, it is preferable to use an electric heating furnace, and when the sample S is a sample to which electric current cannot be applied such as ceramics, it is preferable to use an infrared heating furnace.

The heating atmosphere at this time can be selected depending on the purpose, such as air, argon, nitrogen, and vacuum. However, in order to minimize the decrease in intensity due to absorption of X-rays in the X-ray path, A vacuum is most desirable. In addition,
Beryllium foil with low X-ray absorption is optimal for the sealing material of the heating furnace. However, even if a light element metal foil such as aluminum or a metal foil used as a Kβ filter for incident X-rays is used, the X-ray intensity due to the heating furnace wall can be improved. Can be reduced.
Further, when cooling the sample S, an argon gas or a nitrogen gas is used as necessary.

When a tensile treatment is performed on the sample S, the sample S is gripped by a chuck as in a conventional tensile tester.
Using a hydraulic cylinder or the like, a tensile force is applied to the paper in the horizontal or vertical direction. In the case of performing the compression process, the compression process may be performed by a hydraulic cylinder or the like, contrary to the tension process. If a higher pressure is required, a quadrangular pyramid-shaped diamond compressor may be used. When performing the tension processing or the compression processing, the X-ray path of the sample processing chamber 10 is opened.

Next, the film X-ray detector 6 will be described. The conventional X-ray film is used to detect the diffracted X-rays 2b, and the X-ray diffraction pattern P _{1 shown in FIG.} , P ₂ ... Can be measured by using a photometer or an image analyzer provided in the circumferential direction of the camera. Furthermore, in order to realize the dynamic measurement which is the object of the present invention, it is important to obtain an X-ray diffraction pattern having a high S / N ratio in a short time, and therefore, a photosensitivity having a high sensitivity and a high dynamic range is obtained. It is most desirable to use a light emitter.

Here, to supplement this stimulable luminescent material, a part of the X-ray energy is accumulated inside by the irradiation of X-rays, and then it is accumulated when irradiated with excitation light such as He-Ne laser. It emits stimulated emission light in accordance with the amount of energy, and is also called a stimulable luminous body (see, for example, JP-A-3-180835). By using a dedicated reading device having an image processing function and performing integration of n pixels in the black line direction of the blackened X-ray diffraction patterns P ₁ , P ₂ ... Shown in FIG. This is improved to n times the measured value at the actual detection time. For example, by performing integration for 50 pixels, it is possible to measure an X-ray diffraction pattern with a high S / N ratio in a detection time of about 1 second even with X-rays of about 18 kW.

FIG. 2 shows an example of a film cassette for loading an X-ray film or a stimulable luminous body. The film cassette body 13 has a semi-cylindrical shape along the curvature of the Guinier camera 4, and It comprises three parts: a side film cassette 14, an X-ray exposure window 15 of the camera, and a receiving side film cassette 16. The feed-side film cassette 14 and the receiving-side film cassette 16 are best made of a stainless steel plate on which a lead plate is stuck to prevent exposure to illumination light or scattered X-rays. Further, as the material of the X-ray exposure window 15 of the camera, it is preferable to use a beryllium foil or the like having a light shielding effect and a small X-ray absorption coefficient.

Here, the exposure of the diffracted X-rays and the film feeding will be described. First, an X-ray film or a stimulable luminous body is loaded into the film cassette 14 on the sending side, and the exposure time and the feeding length (necessary for the integration). Set the number of pixels) and the number of frames (number of measurements). Thereafter, only the film is guided by the film guide 17 in the direction of arrow A by the automatic film feed mechanism 11 and is sent out to the X-ray exposure window 15,
Immediately after exposure for a predetermined time, the receiving film cassette 16
Is sent to the next frame. This is repeated for the set number of measurements, and a series of dynamic X-ray diffraction measurements is completed.
If the automatic film feed mechanism 11 is controlled simultaneously by the sample processing controller 12, X-ray diffraction measurement linked to the history of the sample S can be performed, which is more preferable.

FIG. 3 shows an embodiment of an oblique incidence Guinier camera having a quasi-parallel beam optical system according to the present invention. As in the Guinier camera having a concentrated beam optical system shown in FIG. Automatic feed mechanism 11
And a sample processing controller 12 are provided, and the X-ray diffraction pattern is measured by the same control. FIG. 4 shows an embodiment of the Debye-Scherrer camera according to the present invention. The Debye-Scherrer camera 9 is constituted by combining the semi-cylindrical film-shaped X-ray detector 6 as it is or in a cylindrical shape. As with the Guinier camera having the concentrated beam optical system, a sample processing chamber 10, an automatic film feed mechanism 11, and a sample processing control device 12 are provided, and the X-ray diffraction pattern is measured by the same control.

[0027]

As described above, according to the present invention,
By selecting an X-ray camera according to the sample shape,
Even if the number of peaks in the diffraction pattern is large, an X-ray diffraction pattern with high intensity and high resolution, an X-ray diffraction pattern with high intensity from the sample surface layer, and an X-ray diffraction pattern with high intensity from a small area can be instantaneously and continuously measured. It is possible to dynamically measure the state of structural change occurring in the process of heat treatment, mechanical treatment, chemical reaction, etc. of various materials such as metals, ceramics, and magnetic materials irrespective of the sample shape.

[Brief description of the drawings]

FIG. 1 is a schematic diagram schematically showing an embodiment of a Guinier camera having a concentrated beam optical system according to the present invention.

FIG. 2 is a perspective view showing an example of a film cassette.

FIG. 3 is a schematic view schematically showing an embodiment of an oblique incidence Guinier camera having a quasi-parallel beam optical system according to the present invention.

FIG. 4 is a schematic diagram schematically showing an embodiment of the Debye-Scherrer camera of the present invention.

FIG. 5 is a schematic diagram schematically showing a conventional example of a Guinier camera having a concentrated beam optical system.

FIG. 6 is a plan view schematically showing an X-ray diffraction pattern exposed by a belt-shaped X-ray film.

FIG. 7 is a schematic diagram schematically showing a conventional example of an oblique incidence Guinier camera having a quasi-parallel beam optical system.

FIG. 8 is a schematic diagram schematically showing a conventional example of a Debye-Scherrer camera.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 X-ray source 2 Incident X-ray 2a Monochromatic X-ray 2b Diffracted X-ray 3 Curved crystal monochromator 3a Plate crystal monochromator 4 Guinier camera 5 Focal circumference 6 Film X-ray detector 7 Incident solar slit (or collimator) 8 Collimator 9 Debye-Scherrer camera 10 Sample processing chamber 11 Automatic film feed mechanism 12 Sample processing controller 13 Film cassette body 14 Feeding film cassette 15 X-ray exposure window 16 Receiving film cassette S Sample

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-196554 (JP, A) JP-A-58-35446 (JP, A) JP-A-1-202649 (JP, A) 5766 (JP, B1) Jigyo 34-3418 (JP, Y1) Jigyo 44-30793 (JP, Y1) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 23/20-23 / 207

Claims (5)

(57) [Claims] 1. A X Senkai OriSo for detecting the diffracted X-rays generated by irradiating a focused beam is configured to sample from the X-ray source and the incident monochromator and Guinier camera comprising a curved crystal filmy X-ray detector A film processing X-ray detector having a semi-cylindrical shape, an automatic film feeding mechanism for feeding the film at a constant distance, and an X-ray diffraction pattern in the film feeding direction. An X-ray diffraction dynamic measurement device, comprising: a reading device having an image processing function of integrating pixels. 2. An X- ray source, a solar slit or a collimator, an incident monochromator made of a flat crystal, and a Guinier camera, which are generated by irradiating a sample with a quasi-parallel beam.
X-ray diffraction to detect diffracted X-rays that a film-like X-ray detector
In equipment, Bei the sample processing device for processing the sample
If the film-shaped X-ray detector is formed into a semi-cylindrical shape,
In addition, an automatic film feed mechanism that feeds the film at a fixed distance
Pixel integration of the X-ray diffraction pattern in the film feed direction
That a reading device with an image processing function
X-ray diffraction dynamic measuring device according to symptoms. 3. An apparatus comprising an X- ray source, a collimator, and a Debye-Scherrer camera, which is generated by irradiating a sample with an X-ray beam.
X-ray diffraction using a film X-ray detector to detect diffracted X-rays
A sample processing device for processing the sample.
For example, with the film-like X-ray detector is a cylindrical or semi-cylindrical film-shaped X-ray detector, the film-
Automatic film feed mechanism for feeding a fixed distance and the film feed direction
Equipped with an image processing function that integrates X-ray diffraction patterns into pixels
An X-ray diffraction dynamic measurement device provided with a reading device. 4. The sample processing apparatus according to claim 1, wherein the sample processing apparatus has at least one of a heat treatment for heating / cooling, a mechanical treatment for tension / compression, and a chemical reaction. 4. The X-ray diffraction dynamic measurement device according to 2 or 3. 5. The X-ray detector according to claim 1, wherein a stimulable luminous body is used for the film of the film-shaped X-ray detector, and pixels are integrated in a film feed direction.
X-ray diffraction dynamic measurement device.