JP5879567B2 - X-ray diffraction sample rocking device, X-ray diffraction device, and X-ray diffraction pattern measurement method - Google Patents

Description

The present invention relates to an X-ray diffraction sample rocking device, an X-ray diffraction device, and an X-ray diffraction pattern measurement method. In particular, the present invention is a technique for obtaining a uniform powder X-ray diffraction ring by swinging a coarse and minute powder sample under high pressure at an X-ray irradiation position.

  In an X-ray diffraction experiment under a high pressure using a very small diamond anvil cell (hereinafter referred to as DAC) sample, it is difficult to obtain a high-quality diffraction intensity profile sufficient for precise analysis due to statistical problems of particles contributing to diffraction. In particular, in a laser heating experiment under high pressure using a DAC, crystal grain growth is unavoidable, and it is extremely difficult to obtain accurate X-ray diffraction intensity data.

Non-Patent Document 1 describes a Gandolfi camera type swing. Non-Patent Document 2 and Non-Patent Document 3 explain the principle of the Gandolfi camera.
From the description of Non-Patent Documents 1, 2, and 3, we focused on the Gandolfi camera-type oscillation that can obtain uniform Debye ring from a minute and coarse sample.
However, rocking by the Gandolfi camera is X-ray diffraction of the sample under atmospheric pressure, and the sample support direction is supported at a tilt angle of 45 degrees with respect to the incident X-ray direction, and revolves while rotating. Therefore, the high pressure device cannot be rotated.

  According to the prior art, rocking only in the θ direction has been performed under high pressure. This is insufficient, and the number of diffraction points increases, but a uniform diffraction ring cannot be obtained. Even in the case of the oscillation of only ω or the oscillation of a combination of θ and ω, the number of diffraction points increases, but a uniform diffraction ring cannot be obtained.

H. H. Otto, W. et al. Hofmann, K.M. Schroder, J.A. Appl. Cryst. , 35, 13-16 (2002) Nakahirota Yoshihiro, Mineralogical Journal, 28, 117-121. 1999.01. G. Gandolfi, Miner. Petrogr. Acta, 13, 67-74 (1967) Hammersley, A.M. P. European Synchrotron Radiation Facility Internal Report 1997, ESRF97HA02T G. Malmros, Acta Chemica Scandinavia, 24, 384-396 (1970) A. C. Larson, R.A. B. V. Dreame, Los Alamos National Laboratory Report LAUR, 2004. pp86-748.

It is an object of the present invention to provide an X-ray diffraction sample rocking device, an X-ray diffraction device, and an X-ray diffraction pattern measurement method capable of obtaining a uniform diffraction ring even with a coarse and fine sample. . In particular, it is an object of the present invention to provide an X-ray diffraction sample rocking device, an X-ray diffraction device, and an X-ray diffraction pattern measurement method that can obtain a uniform diffraction ring of a coarse particle and a small sample even under high pressure. .

In view of the above circumstances, the present inventor has repeated trial and error, and in addition to the conventional oscillation of only θ, an adjustment mechanism for aligning the centers of all axes is provided to enable the alignment of ω and φ. Thus, it has been found that a uniform diffraction ring can be obtained by combined oscillation of φ, θ, and ω. In addition, a rocking mechanism that can rotate the high-pressure device (diamond anvil cell) has been developed because it can be held perpendicular to the X-rays. This rocking mechanism can hold the sample in the hollow pinhole, and can take a uniform X-ray diffraction ring while rocking the sample under atmospheric pressure. Based on these technologies, we developed a multi-axis oscillating device for high-pressure powder X diffraction by DAC and completed the present invention. To the best knowledge of the present inventor, there has been no research report on X-ray diffraction experiments with such oscillation under high pressure.
The present invention has the following configuration.

(1) A first swinging portion that can swing around a first rotating shaft in which a sample holding portion that holds an X-ray diffraction sample is parallel to the X-ray incident direction, and orthogonal to the first rotating shaft A second swinging portion swingable around the second rotating shaft, and a third swinging swingable around the third rotating shaft orthogonal to the first and second rotating shafts. An X-ray diffraction sample rocking device characterized by having a section.

(2) The X-ray diffraction sample swing according to (1), wherein a first rotation mechanism for rotating the first swinging portion around the first rotation axis by 360 degrees is attached. Moving device.
(3) The X-ray diffraction sample oscillating device according to (2), wherein a second rotating mechanism that rotates the second oscillating portion around the second rotating shaft is attached. .
(4) The X-ray diffraction sample oscillating device according to (3), wherein a third rotating mechanism that rotates the third oscillating portion around the third rotating shaft is attached. .

(5) The X-ray diffraction sample oscillating device according to (4), wherein the third oscillating portion is fixed on a table provided with a three-axis pulse motor control device.
(6) A shaft adjusting mechanism capable of independently adjusting the axial directions of the first rotating shaft, the second rotating shaft, and the third rotating shaft is provided. (5) The X-ray diffraction sample rocking device according to any one of (5).
(7) The X-ray diffraction sample rocking device according to any one of (1) to (6), wherein the sample holder is a diamond anvil cell.

(8) An X-ray diffraction apparatus comprising the X-ray diffraction sample rocking device according to any one of (1) to (7), an X-ray generation unit, and a two-dimensional X-ray detector.

(9) A method for measuring an X-ray diffraction pattern using the X-ray diffractometer according to (8), wherein the first rotating shaft and the second oscillating unit of the first oscillating unit are arranged by an axis adjustment mechanism. Adjusting the axial direction of the third rotating shaft of the second rotating shaft and the third swinging portion to be orthogonal to each other, the first swinging portion, the second swinging portion, and the third swinging portion. The X-ray diffraction sample is irradiated with X-rays generated by the X-ray generation unit while the rocking unit is swung, to the X-ray diffraction sample held by the sample holding unit of the X-ray diffraction sample rocking device. Projecting the X-rays scattered by the sample onto a two-dimensional X-ray detector, and a method for measuring an X-ray diffraction pattern.

(10) The method for measuring an X-ray diffraction pattern according to (9), wherein the first oscillating portion, the second oscillating portion, and the third oscillating portion are simultaneously oscillated.
(11) The X-ray diffraction pattern according to any one of (9) to (10), including a step of adjusting a first rotation axis of the first swinging portion in parallel with an X-ray incident direction. Measuring method.

(12) The X-ray diffraction pattern according to any one of (9) to (11), including a step of controlling the position and direction of the third oscillating unit by a three-axis pulse motor control device. Measuring method.
(13) The diamond anvil cell is used as the sample holder, and X-rays are irradiated in a state where a high pressure is applied to the X-ray diffraction sample. X in any one of (9) to (12) Measuring method of line diffraction pattern.

The X-ray diffraction sample rocking device of the present invention includes a first rocking portion that can rock around a first rotation axis in which a sample holding portion that holds an X-ray diffraction sample is parallel to the X-ray incident direction; A second swinging portion swingable around a second rotation axis orthogonal to the first rotation axis, and a third rotation axis orthogonal to the first and second rotation axes. Since the third rocking portion is configured to be rockable, the X-ray diffraction sample is moved to three axes by a rocking mechanism including the first rocking portion, the second rocking portion, and the third rocking portion. When the X-ray diffraction pattern is measured, a uniform diffraction ring can be obtained. As a result, the crystal structure factor can be refined, and the atomic position in the crystal structure can be accurately determined. It is done.

In the X-ray diffraction sample rocking device of the present invention, since the sample holder is a diamond anvil cell, the diamond anvil cell is fixed, and the diamond anvil cell is rotated to rotate the internal high-pressure X-ray diffraction. The sample can be swung in the X-ray irradiation state.

Since the X-ray diffractometer of the present invention includes the X-ray diffraction sample oscillating device described above, an X-ray generator, and a two-dimensional X-ray detector, the first oscillating unit, the second oscillating unit, A uniform diffractive ring is obtained by the rocking mechanism including the rocking part and the third rocking part. As a result, the crystal structure factor is refined, and the atomic position in the crystal structure is precisely obtained.

The X-ray diffraction pattern measurement method of the present invention is an X-ray diffraction pattern measurement method using the above-described X-ray diffraction apparatus, and the first rotating shaft of the first oscillating portion is adjusted by the axis adjustment mechanism. Adjusting the axial directions of the second rotating shaft of the second swinging portion and the third rotating shaft of the third swinging portion to be orthogonal to each other, the first swinging portion, the second swinging portion, With the rocking part and the third rocking part being swung, the X-ray diffraction sample held by the sample holding part of the X-ray diffraction sample rocking device is irradiated with the X-rays generated by the X-ray generating part. And projecting the X-rays scattered by the X-ray diffraction sample onto the two-dimensional X-ray detector, so that the first oscillating unit, the second oscillating unit, and the third oscillating unit are included. A uniform diffractive ring is obtained by a rocking mechanism consisting of moving parts, which leads to refinement of the crystal structure factor and precise determination of the atomic position in the crystal structure. That.

It is a schematic diagram which shows an example of the X-ray-diffraction apparatus which is embodiment of this invention. FIG. 2 is a plan view (a), a front view (b), and a right side view (c) of the X-ray diffraction sample rocking device shown in FIG. 1. It is a schematic diagram which shows an example of a diamond anvil cell (DAC). It is process drawing which shows an example of the manufacturing method of DAC. It is process drawing which shows an example of the manufacturing method of DAC. It is a conceptual diagram of the comparison of the presence or absence of rocking | fluctuation. It is a powder X-ray diffraction ring on an imaging plate with and without rocking. This is an evaluation of strength vs. 2θ by Rietveld analysis.

(Embodiment of the present invention)
<X-ray diffractometer>
An example of the X-ray diffraction apparatus according to the embodiment of the present invention will be described.
FIG. 1 is a schematic diagram illustrating an example of an X-ray diffraction apparatus according to an embodiment of the present invention.
As shown in FIG. 1, an X-ray diffraction apparatus 1 according to an embodiment of the present invention includes an X-ray generator 41, an X-ray diffraction sample rocking device 11, and a two-dimensional X-ray detector 51. Yes.
The sample holder 31 is irradiated with X-rays generated by the X-ray generator 41, and X-rays are scattered by the X-ray diffraction sample held by the sample holder 31, and the two-dimensional X-ray detector 51 receives X-rays. A diffraction pattern is formed.
The two-dimensional X-ray detector 51 is, for example, an imaging plate.

<X-ray diffraction sample rocking device>
Next, an example of the X-ray diffraction sample rocking device according to the embodiment of the present invention will be described.
As shown in FIG. 1, an X-ray diffraction sample rocking device 11 according to an embodiment of the present invention includes a first rocking portion 21, a second rocking portion 22, and a third rocking portion 23. I have. The sample holding part 31 is fixed to the first swing part 21.
2 is a plan view (a), a front view (b), and a right side view (c) of the X-ray diffraction sample rocking device shown in FIG.

The first oscillating portion 21 is a ring-shaped member having a sample holding portion 31 fixed at the center, and a first rotating mechanism (not shown) for rotating around the first rotating shaft 61 is attached. .
The first rotating shaft 61 is aligned with the central axis of the ring-shaped first oscillating portion 21 and is parallel to the X-ray incident direction.
In FIG. 2C, it is shown that the first swing portion 21 can rotate around the first rotation shaft 61 by φ degrees. Note that the first oscillating portion 21 can be rotated 360 degrees around the first rotation shaft 61.

The second oscillating part 22 is a member to which the first oscillating part 21 is fixed, and a second rotating mechanism (not shown) for rotating around the second rotating shaft 62 is attached.
The second oscillating portion 22 is held by the curved portion of the holding member 25 and can be oscillated around the second rotation shaft 62 in accordance with the curved shape of the curved portion.
FIG. 2B shows that the second swinging portion 22 can rotate around the second rotation shaft 62 by ω degrees.

The third oscillating portion 23 is a disk-like member to which the second oscillating portion 22 is fixed, and a third rotating mechanism (not shown) that rotates around the third rotating shaft 63 is attached. ing.
In FIG. 2A, it is shown that the third swing part 23 can rotate around the third rotation shaft 63 by θ degrees.

The 3rd rocking | swiveling part 23 is being fixed on the stand with which the 3 axis | shaft pulse motor control apparatus was equipped (illustration omitted). By controlling the three-axis pulse motor control device, the position and direction of the third swing portion 23 can be set to arbitrary values.

A shaft adjusting mechanism is provided (not shown) that can adjust the axial directions of the first rotating shaft 61, the second rotating shaft 62, and the third rotating shaft 63 independently of each other. By controlling the shaft adjusting mechanism, the axial directions of the first rotating shaft 61, the second rotating shaft 62, and the third rotating shaft 63 can be set to be orthogonal to each other.

A diamond anvil cell (DAC) can be used as the sample holder 31. By using DAC, an X-ray diffraction pattern of an X-ray diffraction sample in a high pressure state can be obtained.
If an atmospheric pressure cell is used as the sample holder 31, an X-ray diffraction pattern of an X-ray diffraction sample under atmospheric pressure can be obtained.

FIG. 3 is a schematic diagram illustrating an example of a DAC.
As shown in FIG. 3, the DAC is symmetrical and includes a pair of diamond anvils 32 a and 32 b, a single gasket 33, and an X-ray diffraction sample 34. The two diamond anvils 32a and 32b are provided above and below the X-ray diffraction sample 34, and the X-ray diffraction sample 34 can be pressurized with the X-ray diffraction sample 34 existing therebetween.
In FIG. 3, in order to display the lower diamond anvil 32a, the gasket is virtually cut and displayed.

4 and 5 are process diagrams showing an example of a DAC manufacturing method. Each process drawing is shown with the top view and sectional drawing in the BB 'line.
First, as shown in FIG. 4A, a gasket substrate 33 having a substantially square shape in plan view is prepared. For example, a rhenium gasket substrate having a thickness of 100 to 250 μm can be used.
Next, as shown in FIG. 4B, recesses 33 h and 33 i having a circular shape in plan view are formed in the center of both surfaces of the gasket substrate 33.
Next, as shown in FIG.4 (c), the through-hole 33j is formed in the center of the recessed parts 33h and 33i. For example, the diameter of the through hole 33j is 100 to 150 μm.
Next, as shown in FIG. 5A, the X-ray powder is placed inside the through-hole 33j whose one surface side is closed after the circular surface portion of one diamond anvil 32a is fitted into the recess portion 33i on one surface side. Sample 35 is loaded.

Next, as shown in FIG. 5B, a hydraulic medium made of water, alcohol or a mixture of water and alcohol is injected and mixed into the X-ray powder sample 35 by a hydraulic medium injection container 36 such as a syringe. X-ray diffraction sample 34. For example, methanol: ethanol: water = 16: 3: 1 can be used. Note that the hydraulic medium is used in the case of pressurization at room temperature.
Next, as shown in FIG. 5C, the circular surface portion of another diamond anvil 32b is fitted into the concave portion 33h on the other surface side, and the other surface side of the through hole 33j is closed.
The DAC is manufactured through the above steps.

<Measurement method of X-ray diffraction pattern>
Next, an example of a method for measuring an X-ray diffraction pattern according to an embodiment of the present invention will be described.
An X-ray diffraction pattern measuring method according to an embodiment of the present invention is an X-ray diffraction pattern measuring method using the X-ray diffractometer 1, and the first adjustment of the first oscillating portion 21 is performed by an axis adjustment mechanism. Adjusting the axial directions of the rotary shaft 61, the second rotary shaft 62 of the second swing portion 22 and the third rotary shaft 63 of the third swing portion 23 to be orthogonal to each other; X-rays generated by the X-ray generation unit 41 in a state where the oscillating unit 21, the second oscillating unit 22, and the third oscillating unit 23 are oscillated are transmitted to the X-ray diffraction sample oscillating device 11. Irradiating the X-ray diffraction sample 34 held by the sample holding unit 31 and projecting the X-rays scattered by the X-ray diffraction sample 34 to the two-dimensional X-ray detector 51.

FIG. 6 is a conceptual diagram for comparison of the presence or absence of oscillation.
As shown in FIG. 6A, when a coarse powder sample is used and it is not rocked, the X-ray diffraction pattern projected on the two-dimensional X-ray detector 51 becomes a dot-like pattern, and uniform X-ray diffraction I can't get a ring.
On the other hand, as shown in FIG. 6B, the X-ray generation unit 41 generates the first oscillating unit 21, the second oscillating unit 22, and the third oscillating unit 23 while oscillating them. By irradiating the X-ray diffraction sample 34 held by the sample holding unit 31 of the X-ray diffraction sample rocking device 11 with the X-ray diffraction sample, a uniform X-ray diffraction ring is obtained even for a coarse powder sample. be able to.
The axial directions of the first rotating shaft 61 of the first swinging portion 21, the second rotating shaft 62 of the second swinging portion 22, and the third rotating shaft 63 of the third swinging portion 23 are defined. By adjusting so as to be orthogonal to each other, the X-ray diffraction sample 34 can be largely swung.

The first swing portion 21, the second swing portion 22, and the third swing portion 23 may be swung simultaneously. As a result, a uniform X-ray diffraction ring can be obtained even for a coarse powder sample, and even if it is not oscillated, even if it is a dotted X-ray diffraction pattern, it becomes a linear X-ray diffraction pattern. can do.

It is preferable to have the process of adjusting the 1st rotating shaft 61 of the 1st rocking | swiveling part 21 in parallel with an X-ray incident direction. Accordingly, the first rotation shaft 61 of the first swing part 21, the second rotation shaft 62 of the second swing part 22, and the third rotation of the third swing part 23 are performed by the shaft adjustment mechanism. It is easy to adjust the axial directions of the shafts 63 to be orthogonal to each other.

It is preferable to have a step of controlling the position and direction of the third oscillating portion 23 by a three-axis pulse motor control device. Accordingly, the first rotation shaft 61 of the first swing part 21, the second rotation shaft 62 of the second swing part 22, and the third rotation of the third swing part 23 are performed by the shaft adjustment mechanism. It is easy to adjust the axial directions of the shafts 63 to be orthogonal to each other.

A diamond anvil cell may be used as the sample holder 31 and X-rays may be irradiated with a high pressure applied to the X-ray diffraction sample 34. Thus, by rotating the X-ray diffraction sample 34 under high pressure, a uniform X-ray diffraction ring can be obtained even with a coarse powder sample, and the X-ray diffraction pattern under high pressure can be easily measured. .

In-situ high-pressure X-ray diffraction at room temperature can be performed by, for example, Spring 8 (High Intensity Photoscience Research Center (JASPRI)) BL04B2. Monochromatic synchrotron X-rays adjusted to 38 keV are focused to a spot with a diameter of about 50 μm on the sample in the DAC, and the diffracted X-rays can be detected using an imaging plate (IP). The Debye ring recorded in the detector can be converted to intensity vs. 2θ data using the FIT2D program (Non-Patent Document 4). Non-Patent Document 4 relates to a conversion program.

The X-ray diffraction sample rocking device 11 according to the embodiment of the present invention can rock around the first rotation shaft 61 in which the sample holding unit 31 holding the X-ray diffraction sample 34 is parallel to the X-ray incident direction. The first swinging portion 21, the second swinging portion 22 swingable around the second rotating shaft 62 orthogonal to the first rotating shaft 61, and the first and second rotating shafts 61. , 62 is provided with a third oscillating portion 23 that can oscillate around a third rotating shaft 63, so that the first oscillating portion, the second oscillating portion, and the third oscillating portion are provided. The X-ray diffraction sample can be swung around three axes by a rocking mechanism comprising, and when the X-ray diffraction pattern is measured, a uniform diffraction ring is obtained. This leads to refinement, and the atomic position in the crystal structure is required precisely.

The X-ray diffraction sample rocking device 11 according to the embodiment of the present invention has a configuration in which a first rotating mechanism that rotates the first rocking portion 21 around the first rotating shaft 61 by 360 degrees is attached. The X-ray diffraction sample can be swung around the first rotation axis 61, and when the X-ray diffraction pattern is measured, a uniform diffraction ring can be obtained. As a result, the crystal structure factor can be refined. The atomic position in the crystal structure is precisely determined.

The X-ray diffraction sample rocking device 11 according to the embodiment of the present invention has a configuration in which a second rotation mechanism for rotating the second rocking portion 22 around the second rotation shaft 62 is attached. The line diffraction sample can be swung around the second rotation axis 62, and when the X-ray diffraction pattern is measured, a uniform diffraction ring is obtained, resulting in refinement of the crystal structure factor, The atomic position in the crystal structure is required precisely.

The X-ray diffraction sample rocking device 11 according to the embodiment of the present invention has a configuration in which a third rotating mechanism for rotating the third rocking portion 23 around the third rotating shaft 63 is attached. The line diffraction sample can be swung around the second rotation axis 63, and when the X-ray diffraction pattern is measured, a uniform diffraction ring is obtained. As a result, the crystal structure factor is refined, The atomic position in the crystal structure is required precisely.

The X-ray diffraction sample oscillating device 11 according to the embodiment of the present invention has a configuration in which the third oscillating portion 23 is fixed on a table provided with a three-axis pulse motor control device. Can be swung around the second rotation axis 63, and when the X-ray diffraction pattern is measured, a uniform diffraction ring is obtained. As a result, the crystal structure factor is refined, and the crystal structure Is precisely required.

An X-ray diffraction sample oscillating device 11 according to an embodiment of the present invention includes an axis adjustment mechanism that can independently adjust the axial directions of the first rotation shaft 61, the second rotation shaft 62, and the third rotation shaft 63. Therefore, the axial directions of the first rotating shaft 61, the second rotating shaft 62, and the third rotating shaft 63 can be adjusted to be orthogonal to each other, and the X-ray diffraction sample can be made as large as possible. When the X-ray diffraction pattern is measured, a uniform diffraction ring can be obtained. As a result, the crystal structure factor is refined, and the atomic position in the crystal structure is accurately determined.

The X-ray diffraction sample oscillating device 11 according to the embodiment of the present invention has a configuration in which the sample holding unit 31 is a diamond anvil cell. Therefore, by rotating the diamond anvil cell together with the diamond anvil cell fixed, A high-pressure X-ray diffraction sample can be swung in an X-ray irradiation state.

Since the X-ray diffractometer 1 according to the embodiment of the present invention includes the X-ray diffraction sample oscillating device 11, the X-ray generator 41, and the two-dimensional X-ray detector 51, the first oscillating unit The oscillating mechanism comprising the second oscillating part and the third oscillating part provides a uniform diffractive ring, which leads to the refinement of the crystal structure factor and the precise atomic position in the crystal structure. Desired.

An X-ray diffraction pattern measuring method according to an embodiment of the present invention is an X-ray diffraction pattern measuring method using the X-ray diffractometer 1, and the first adjustment of the first oscillating portion 21 is performed by an axis adjustment mechanism. Adjusting the axial directions of the rotary shaft 61, the second rotary shaft 62 of the second swing portion 22 and the third rotary shaft 63 of the third swing portion 23 to be orthogonal to each other; In the state where the first oscillating unit 21, the second oscillating unit 22, and the third oscillating unit 23 are oscillated, the X-ray generated by the X-ray generation unit 41 is oscillated by the X-ray diffraction sample. Irradiating the X-ray diffraction sample 34 held by the sample holding unit 31 of the apparatus 11 and projecting the X-rays scattered by the X-ray diffraction sample 34 to the two-dimensional X-ray detector 51, A uniform diffractive ring is obtained by the rocking mechanism including the first rocking part, the second rocking part and the third rocking part. Results, leading to refinement of the crystal structure factors, atom positions in the crystal structure is determined precisely.

Since the X-ray diffraction pattern measuring method according to the embodiment of the present invention is configured to simultaneously swing the first swinging portion 21, the second swinging portion 22, and the third swinging portion 23, it is uniform. A diffractive ring is obtained, and as a result, the crystal structure factor is refined, and the atomic position in the crystal structure is accurately determined.

Since the X-ray diffraction pattern measurement method according to the embodiment of the present invention includes a step of adjusting the first rotation shaft 61 of the first oscillating portion 21 in parallel with the X-ray incident direction, a uniform diffraction ring is provided. As a result, the crystal structure factor is refined, and the atomic position in the crystal structure is precisely determined.

Since the X-ray diffraction pattern measurement method according to the embodiment of the present invention includes a step of controlling the position and direction of the third oscillating unit by a three-axis pulse motor control device, a uniform diffraction ring can be obtained. As a result, the crystal structure factor is refined, and the atomic position in the crystal structure is precisely determined.

The X-ray diffraction pattern measurement method according to the embodiment of the present invention uses a diamond anvil cell as the sample holder 31 and irradiates X-rays with a high pressure applied to the X-ray diffraction sample 34. A uniform diffractive ring is obtained for the sample, and as a result, the crystal structure factor is refined, and the atomic position in the crystal structure is precisely determined.

The X-ray diffraction sample oscillating device, the X-ray diffraction device, and the X-ray diffraction pattern measurement method according to the embodiment of the present invention are not limited to the above-described embodiments, and are within the scope of the technical idea of the present invention. Various modifications can be made. Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.

Example 1
Hereinafter, the present invention will be described based on examples.
Example 1 is an example in which the X-ray diffraction pattern in a high-pressure state and an atmospheric pressure state was measured by changing the pressure applied to the X-ray diffraction sample.
Next, a symmetric diamond anvil cell (DAC) shown in FIG. 3 was prepared. Using a rhenium gasket having a thickness of 100 μm, holes having a diameter of 100 to 150 μm were formed.
Next, after loading the X-ray powder sample into the hole, a hydraulic medium consisting of methanol: ethanol: water = 16: 3: 1 was added to obtain an X-ray diffraction sample.
Next, a DAC was placed on the X-ray diffraction sample rocking device.
In order to obtain a result in a high pressure state, the pressure was increased from atmospheric pressure (1 atm) to 70,000 atm with a pair of diamond anvils provided between the upper and lower sides sandwiching an X-ray diffraction sample between them.
The experimental conditions are the case where no pressure is applied (Experiment No. 1 and 2), the case where pressure is applied (Experiment No. 3 and 4), the case where no pressure is applied (Experiment No. 1 and 3), and the case where the material is rocked (Experiment No. 1). .2, 4).

In-situ high-pressure X-ray diffraction experiments at room temperature were performed in Spring 8 (High Intensity Photoscience Research Center (JASPRI)) BL04B2.
Monochromatic synchrotron X-rays adjusted to 38 keV were focused to a spot with a diameter of about 50 μm on the sample in the DAC.
Diffracted X-rays were detected using an imaging plate (IP).
The Debye ring recorded on the detector was converted to intensity vs. 2θ data using the FIT2D program (Non-Patent Document 4).

  Table 1 shows Experiment No. Experimental conditions of φ, ω, and θ in 1 to 4 and detection results using an imaging plate (IP) (FIGS. 7a to 7d). Experiment No. 1 and 2 are at atmospheric pressure (1 atm). 3 and 4 are at high pressure.

In the experimental results shown in Table 1, Experiment No. In cases 1 and 3, spot-like X-ray diffraction rings were observed. On the other hand, Experiment No. In cases 2 and 4, a uniform X-ray diffraction ring was observed.
8 uses the atomic coordinates described in Non-Patent Document 5 and the analysis program GSAS described in Non-Patent Document 6, and the experiment No. It is the result of the Rietveld analysis obtained by converting the X-ray diffraction rings of 1 and 2 into data of intensity versus 2θ. Non-patent document 5 relates to the structure of Bi ₂ O ₃ and non-patent document 6 relates to a program.
As shown in FIG. R _wp = 7.1%, which is an R factor of 2 (FIG. 8 (b): with rocking) (a factor for evaluating the certainty of the structure) Compared to R _wp = 16.3% in FIG. 1 (FIG. 8A: no swing), the structure was small and the structure was refined. In FIG. 8, φ is expressed as fixed and 100 sec / turn instead of 0 and 360 degrees, respectively.

The present invention relates to an X-ray diffraction sample oscillating device, an X-ray diffraction device, and an X-ray diffraction pattern measurement method, and can be used as an X-ray diffraction device optical system. It can be used in industries.

DESCRIPTION OF SYMBOLS 1 ... X-ray diffraction apparatus, 11 ... X-ray diffraction sample rocking | fluctuation apparatus, 21 ... 1st rocking | fluctuation part, 22 ... 2nd rocking | fluctuation part, 23 ... 3rd rocking | fluctuation part, 25 ... Holding member, 31 Sample holder 32a, 32b Diamond anvil 33 Gasket (substrate) 33h 33i Recess 33j Through hole 34 X-ray diffraction sample 35 X-ray powder sample 36 Hydraulic medium injection Container, 61 ... first rotation axis, 62 ... second rotation axis, 63 ... third rotation axis.

Claims (12)

A first oscillating portion that can oscillate a diamond anvil cell holding an X-ray diffraction sample around a first rotation axis that is parallel to the X-ray incident direction and passes through a pressure axis of the diamond anvil cell. A second oscillating portion that can oscillate around a second rotation axis that is orthogonal to the first rotation axis, and a third rotation axis that is orthogonal to the first and second rotation axes. a third oscillating member swingable, to have a an X-ray diffraction sample oscillating device comprising, in the X-ray diffraction sample rocking device, on the side opposite the X-ray incident side An X-ray diffraction sample rocking device that detects X-rays .  2. The X-ray diffraction sample rocking device according to claim 1, further comprising: a first rotation mechanism that rotates the first rocking portion around the first rotation axis by 360 degrees.  The X-ray diffraction sample oscillating apparatus according to claim 2, further comprising a second rotation mechanism that rotates the second oscillating portion around the second rotation axis.  The X-ray diffraction sample oscillating apparatus according to claim 3, further comprising a third rotating mechanism that rotates the third oscillating portion around the third rotation axis.  5. The X-ray diffraction sample rocking device according to claim 4, wherein the third rocking portion is fixed on a table provided with a three-axis pulse motor control device.  6. The shaft adjusting mechanism according to claim 1, further comprising an axis adjusting mechanism capable of independently adjusting the axial directions of the first rotating shaft, the second rotating shaft, and the third rotating shaft. The X-ray diffraction sample rocking device according to claim 1. The X-ray diffraction sample rocking device according to any one of claims 1 to 6 , an X-ray generation unit, and a two-dimensional X on the opposite side of the X-ray diffraction sample rocking device to the X-ray generation unit. An X-ray diffraction apparatus comprising: a line detector. A method for measuring an X-ray diffraction pattern using the X-ray diffractometer according to claim 7 , wherein the first rotating shaft of the first oscillating portion and the second of the second oscillating portion are adjusted by an axis adjusting mechanism. A step of adjusting the axial direction of the third rotating shaft of the rotating shaft and the third swinging portion to be orthogonal to each other, at least the first swinging portion, the second swinging portion, and the third The X-ray generated by the X-ray generator is held on the sample holder of the X-ray diffraction sample oscillator while either one of the oscillating units is rocked or fixed after being rocked. Irradiating an X-ray diffraction sample and projecting the X-rays scattered by the X-ray diffraction sample onto a two-dimensional X-ray detector. 9. The X-ray diffraction pattern measurement method according to claim 8 , wherein the first oscillating portion, the second oscillating portion, and the third oscillating portion are simultaneously oscillated. The method for measuring an X-ray diffraction pattern according to any one of claims 8 to 9 , further comprising a step of adjusting a first rotation axis of the first oscillating portion in parallel with an X-ray incident direction. . The method for measuring an X-ray diffraction pattern according to any one of claims 8 to 10 , further comprising a step of controlling the position and direction of the third oscillating portion by a three-axis pulse motor control device. The X-ray diffraction pattern according to any one of claims 8 to 11 , wherein a diamond anvil cell is used as the sample holder, and X-rays are irradiated in a state where a high pressure is applied to the X-ray diffraction sample. Measuring method.