JPH0611465A - X-ray diffraction device - Google Patents

Abstract

PURPOSE:To provide an X-ray diffraction device which effectively serves for structural analysis of mono-crystals by furnishing a cumulative phosphor and a counter. CONSTITUTION:X-rays emitted by an X-ray source 16 are passed through a collimator 21 and cast onto a specimen 28 which is mounted on a kappa goniometer 18. The diffracted X-rays from the specimen 28 are recorded in cumulative phosphor 12, 13 in the form stretching along the inner surface of a cylindrical surface and read by a read device 36. Besides the phosphor 12, 13, a scintillation counter 14 is installed in a black box 20. To make structural analysis of the specimen 28, selection may be done according to the purpose among the measurement using the phosphor 12, 13 and the measurement using the scintillation counter 14. It may also be accepted that determination of the unitary lattice of crystal is solely made through utilization of the scintillator counter 14 and that the data for structural, analysis thereafter is measured with the cumulative phosphor 12, 13.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an X-ray diffractometer for recording diffracted X-rays from a sample on a stimulable phosphor as a latent image and irradiating the stimulable phosphor with excitation light to read out the latent image. .

[0002]

2. Description of the Related Art Single crystals of high molecules such as proteins and low molecular weight X
A fully automated 4-axis diffractometer is known as a device for performing line structure analysis. This 4-axis diffractometer is capable of fully automatic structural analysis after setting the sample, and has the advantage of being easy to use even for beginners. However, since a large number of diffraction peaks are recorded as data one by one, there is a disadvantage that it takes time to obtain the data of the diffraction image. Depending on the complexity of the molecular structure, the time required can range from a few days to a month.

On the other hand, it is also practiced to utilize a stimulable phosphor for detecting the diffraction X-ray without using a counter. When this stimulable phosphor is used, data of many diffraction peaks can be recorded at one time, which is advantageous in that measurement can be completed in a short time. However, it is difficult to determine the unit cell of the crystal, and the operation of setting the sample crystal requires skill.

[0004]

[Problem to be Solved by the Invention] 4 using a counter
The axial structure diffractometer and the crystal structure analyzer utilizing the stimulable phosphor have advantages and disadvantages as described above. Therefore, it would be convenient to have an apparatus that can selectively use both of these apparatuses depending on the purpose, or can use both of them together to perform one structural analysis. Therefore, an object of the present invention is to provide an X-ray diffractometer including a stimulable phosphor and a counter, and particularly to provide an X-ray diffractometer useful for structural analysis of a single crystal. is there.

[0005]

According to a first aspect of the invention, diffracted X-rays from a sample are recorded on a stimulable phosphor as a latent image, and the stimulable light is irradiated to the stimulable phosphor to read the latent image. The X-ray diffractometer has the following features. (A) The recording surface of the stimulable phosphor is formed along the inner surface of the cylindrical surface. (B) The sample is placed on the center line of the cylindrical surface. (C) The stimulable phosphor can be moved in a direction parallel to the center line. (D) A counter tube type X-ray detector rotatable around the center line is installed on the detector mounting base. (E) The detector mounting base can be moved in a direction parallel to the center line. A scintillation counter, a proportional counter, or the like can be used as the counter tube type X-ray detector.

A second invention is the same as the first invention, wherein the sample is rotatable about three rotational axes. As a sample holding device therefor, a kappa goniometer having three axes of ω, κ (kappa), and φ, ω, χ
A full circle goniometer having three axes of (chi) and φ can be used.

According to a third aspect of the present invention, in the first aspect, the stimulable phosphor and the X-ray detector are arranged inside a common dark box.

A fourth aspect of the invention is the same as the first aspect of the invention, in which the IP holder for holding the stimulable phosphor has the following features. (F) The IP holder can hold a plurality of stimulable phosphors. (G) The IP holder can move in a direction parallel to the center line between the stimulable phosphor exposure position and the stimulable phosphor exchange position. (H) The IP holder can rotate around the center line of the IP holder at the storage phosphor exchange position.

In a fifth aspect based on the fourth aspect, when one stimulable phosphor held by the IP holder is at the exposure position, another accumulation held by the IP holder is different. When the luminescent phosphor is in the reading position and the IP holder is in the stimulable phosphor exchange position, the stimulable phosphor held in the IP holder can be erased by the erasing lamp. .

[0010]

By providing a stimulable phosphor and a counter tube type X-ray detector in one X-ray diffractometer, both can be selectively used according to the purpose. Furthermore, for example, in the case of crystal structure analysis, the unit cell of the crystal is automatically determined using a counter, and then the data for structure analysis is obtained in a short time using the stimulable phosphor. ,
It is also possible to adopt a combination of such measurement methods.

[0011]

1 is a plan view of an embodiment of the present invention, and FIG. 2 is a front view thereof. This X-ray diffractometer is used for crystal structure analysis of a single crystal sample. The sample is held by a Kappa goniometer so that it can rotate about three axes of rotation. The diffracted X-rays can be recorded by the stimulable phosphor and the scintillation counter can also detect the diffracted X-rays.

In FIG. 1, this X-ray diffractometer mainly comprises an X-ray source 16, a sample holder 18, and a diffractive X-ray recorder arranged inside a dark box 20. The X-rays emitted from the X-ray source 16 pass through the collimator 21 and are applied to the sample 28 attached to the tip of the sample holding device 18,
The diffracted X-rays from the sample 28 are recorded by the diffracted X-ray recorder in the dark box 20. The sample holding device 18 is a Kappa goniometer, which will be described later, and can rotate the sample around three rotation axes. In this embodiment, a microscope 22 for observing the X-ray irradiation position of the sample and a coolant spraying device 24 for cooling the sample to a low temperature are provided.

Inside the dark box 20, there are a diffractive X-ray recording apparatus using a stimulable phosphor and a diffractive X-ray recording apparatus using a counter. First, a diffractive X-ray recording apparatus using a storage phosphor will be described. In FIG. 2, an IP having a substantially cylindrical shape as a whole
Two stimulable phosphors 12 and 13 can be attached to the holder 26. The recording surface of the stimulable phosphors 12, 13 has a shape along the inner surface of the cylindrical surface. Stimulable phosphor 1
The sample 28 is arranged on the center line 29 (see FIG. 1) of the cylindrical surface of 2. Black paper 35 is placed on the sample side of the stimulable phosphor 12.
The black paper 35 constitutes a part of the dark box 20. The IP holder 26 is rotatably supported by two support legs 30, and the support legs 30 are fixed to a moving base 32. The moving table 32 is mounted on the rail 34,
It is movable in the axial direction of the IP holder 26. Note that FIG.
Then, the IP holder 26 and the stimulable phosphors 12 and 13 are I
It shows a cross-sectional view of the P holding body 26 taken along the center in the height direction.

An IP reader 36 is provided on the side opposite to the sample holder 18. The IP reading device 36 rotates and scans the laser light as the excitation light, and the stimulable phosphor 13
Fluorescence generated from the latent image recorded on is detected. The entire reader 36 rests on a rail 38 and can be moved in the direction of arrow 66 in FIG.

Returning to FIG. 1, the IP holder 26 can be moved from the storage phosphor exposure position shown to the storage phosphor exchange position 40 shown by the alternate long and short dash line. An erasing lamp 42 is provided in the vicinity of the stimulable phosphor exchange position 40, and the latent image can be erased by irradiating the already-read stimulable phosphor with erasing light.

FIG. 3 is a perspective view showing the principle of the Kappa goniometer constituting the sample holding device 18. This kappa goniometer has a capillary (or glass rod) 44
The sample 28 attached to the tip of the ω axis, κ (kappa) axis,
It can be rotated around the φ axis. The κ-axis makes an angle of 45 degrees with the ω-axis and rotates about the ω-axis.
The φ-axis makes an angle of 45 degrees with the κ-axis and rotates about the κ-axis. The capillary 44 rotates around the φ axis. As a result, the sample 28 at the tip of the capillary 44 is
Can be oriented in any direction while always being on the ω-axis. In the present embodiment, this kappa goniometer ω
The axis is arranged so as to coincide with the center line 29 of the cylindrical surface of the stimulable phosphor 12. By using this Kappa goniometer, the diffracted X-rays from the sample 28 can reach the stimulable phosphor without being blocked by the goniometer.

FIG. 4 is a plan view of the internal mechanism of the reading device 36. The laser light emitted from the laser generator 46 is reflected by the mirrors 48 and 50, passes through the dichroic mirror 52, is focused by the lens 54, and strikes the stimulable phosphor 13 perpendicularly. When the latent image recorded on the stimulable phosphor 13 is irradiated with the laser light, fluorescence is generated from the laser light, and the fluorescence is condensed by the lens 54 and the dichroic mirror 5 is used.
Come back to 2. This dichroic mirror 52 has wavelength selectivity such that laser light passes through and fluorescence is reflected, so that fluorescence is reflected by the dichroic mirror 52,
It passes through the filter 56 and is detected by the photomultiplier tube 57. The filter 56 is a blue filter for cutting red light. The mirrors 48, 50, the dichroic mirror 52, and the lens 54 are attached to a rotating body 58, which can rotate about a rotation axis 59. This rotation axis 59 coincides with the center line of the cylindrical surface of the stimulable phosphor 13. The laser generator 46, the filter 56, and the photomultiplier tube 57 do not rotate. When the rotating body 58 rotates, the laser light scans the surface of the stimulable phosphor 13 in the circumferential direction. Then, by moving the entire reading device 36 in the direction of the arrow 60, the entire surface of the stimulable phosphor 13 can be read.

Next, a diffraction X-ray recording apparatus using a counter will be described. In FIG. 2, an arcuate frame 62 is fixed to the moving table 32, and the scintillation counter 14 can move along the frame 62. Thereby, the scintillation counter 14 can rotate around the rotation axis, and the rotation axis coincides with the center line 29 (see FIG. 1) of the cylindrical surface of the stimulable phosphor 12. By moving the moving table 32 in the direction of the arrow 64 (see FIG. 1), the scintillation counter 14 can come to a position facing the sample 28. This position will be called a counter setting position. When the scintillation counter 14 is located at this counter setting position, the configuration is the same as that of a 4-axis X-ray diffractometer equipped with a kappa goniometer. In FIG. 2, the microscope and the coolant spraying device are omitted. The dark box 20 is shown in cross section.

Next, the method of using this X-ray diffraction apparatus will be described by taking the case of analyzing the single crystal structure of a low molecular weight sample as an example. With this diffractometer, measurement using a stimulable phosphor, measurement using a scintillation counter, and measurement combining a stimulable phosphor and a scintillation counter are possible.

First, the measurement using the stimulable phosphor will be described. In FIG. 1, the two stimulable phosphors 12 and 13 are I
It is attached to the P holder 26. The IP holder 26 is brought to the illustrated storage position of the stimulable phosphor. The sample 28 is attached to the sample holding device 18, and the microscope 22 is used to adjust the sample position so that the center of the sample 28 comes to the center of rotation of the goniometer. If necessary, the coolant spraying device 24 is used to cool the sample 28. First, the sample 28 is pivoted. This axis setting is an operation of determining the orientation of the sample 28 so that any axis or a specific axis of the crystal of the sample 28 coincides with the ω axis. Perform the following work to set up the shaft. Diffracted X-rays from the sample 28 are continuously exposed to the stimulable phosphor 12 while the sample 28 is rotated about the ω axis in an angle range of 0 to 30 degrees. When the exposure is completed, the IP holder 26 is moved to the storage phosphor exchange position 40,
This is rotated 180 degrees. Then, the IP holder 26 is returned to the exposure position. Then, the reading device 36 reads the latent image recorded on the stimulable phosphor 12. During this reading operation, the sample 28 is continuously exposed to the other stimulable phosphor 13 while rotating the sample 28 in the angular range of 30 to 60 degrees around the ω axis. When the exposure of the storage phosphor 13 and the reading of the storage phosphor 12 are completed, the IP holder 26
Is moved to the storage phosphor exchange position 40, and the read storage phosphor 12 is erased by the erase lamp 42. After that, the IP holder 26 is rotated 180 degrees and then returned to the exposure position. As a result, the erased stimulable phosphor 12 returns to the position where it can be exposed and is reused.
On the other hand, the exposed storage phosphor 13 is read by the reading device 36.
Read in. Such an operation is repeated after shifting the angular range of ω rotation by 30 degrees, and six diffraction images are recorded in a total range of 180 degrees. The orientation of the sample 28 is examined with reference to the six diffraction images, and the κ rotation and φ rotation of the sample 28 are adjusted so that the shaft is correctly oriented.

After the axis setting is completed, a diffraction image for structural analysis is measured by the Weissenberg method as follows. Sample 2
8 and the stimulable phosphor 12, a slit having an opening perpendicular to the ω axis is arranged, and while rotating the sample 28 by ω,
In synchronization with this, the IP holder 26 is moved in the direction of the arrow 64, and the diffraction image at that time is recorded on the stimulable phosphor 12. This diffracted image is read by the reading device 36 in the same manner as the above-described axis setting work. After that, the structure of the sample is analyzed based on this diffraction image.

Next, measurement using a scintillation counter will be described. The movable table 32 in FIG. 2 is moved upward in FIG. 1 to bring the scintillation counter 14 to the counter setting position. In this state, the 3-axis (ω, κ, φ) rotation of the sample by the kappa goniometer of the sample holding device 18 and the 2θ rotation of the scintillation counter 14 constitute a 4-axis diffractometer. Therefore, similarly to the conventional four-axis diffractometer, the structural analysis of the sample 28 can be performed by automatic measurement.

As described above, in this X-ray diffractometer, structural analysis using a stimulable phosphor and structural analysis using a scintillation counter can be performed by one apparatus. The measurement using the stimulable phosphor has an advantage that the measurement time is short, and the measurement using the scintillation counter has the advantage that it can be fully automated and has high measurement accuracy. Therefore, both can be used properly according to the purpose of measurement. In the measurement using the stimulable phosphor,
Diffraction images can be recorded in the range of 60 degrees up and down and the range of 60 degrees left and right from the sample. Further, in the measurement using the scintillation counter, the diffraction peak can be detected in the range of 10 degrees below and 60 degrees above the sample.

Next, a measuring method using a stimulable phosphor and a scintillation counter together will be described. First,
The unit cell of the sample 28 is determined using the scintillation counter 14. Then, based on this measurement result, the specific axis of the sample crystal is made to coincide with the ω axis. Then, this time, a diffraction image for structural analysis is recorded using the stimulable phosphor 12. In analyzing the diffraction image obtained here, since the unit cell that has already been obtained can be used, the analysis becomes easy. In this way, the unit cell can be automatically and accurately determined by the scintillation counter, and the data for the subsequent structural analysis can be obtained in a short time by using the stimulable phosphor.

[0025]

In the X-ray diffractometer of the present invention, structural analysis using a stimulable phosphor and structural analysis using a scintillation counter can be performed by one device, and both can be selected according to the purpose. Can be used for various purposes. Furthermore, it is possible to adopt a combination measurement method in which a scintillation counter is used to automatically determine the unit cell of the crystal, and thereafter, data for structural analysis is obtained in a short time using a stimulable phosphor. it can.

[Brief description of drawings]

FIG. 1 is a plan view of an embodiment of the present invention.

2 is a front view of the device of FIG. 1. FIG.

FIG. 3 is a perspective view showing the principle of a kappa goniometer.

FIG. 4 is a plan view of the internal mechanism of the storage phosphor reader.

[Explanation of symbols]

 12, 13 ... Accumulative phosphor 14 ... Scintillation counter 16 ... X-ray source 18 ... Sample holder 20 ... Dark box 26 ... IP holder 28 ... Sample 29 ... Center line of cylindrical surface of accumulative phosphor 36 ... Reader 42 … Erase lamp

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[Procedure amendment]

[Submission date] July 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

First, the measurement using the stimulable phosphor will be described. In FIG. 1, the two stimulable phosphors 12 and 13 are I
It is attached to the P holder 26. The IP holder 26 is brought to the illustrated storage position of the stimulable phosphor. The sample 28 is attached to the sample holding device 18, and the microscope 22 is used to adjust the sample position so that the center of the sample 28 comes to the center of rotation of the goniometer. If necessary, the coolant spraying device 24 is used to cool the sample 28. First, the sample 28 is pivoted. This axis setting is an operation of determining the orientation of the sample 28 so that any axis or a specific axis of the crystal of the sample 28 coincides with the ω axis. For a specific upright method
I will explain in detail later, so here,
The measurement by the Weissenberg method at that time will be described. Trial
Rotate the material 28 around the ω axis in the range of 0 to 90 degrees,
In synchronization with this, the IP holder 26 is parallel to the direction of the arrow 64.
Move and move the diffraction image at that time to the latent image on the stimulable phosphor 12.
To record as. After the exposure is completed, the IP holder 26
Move it to the storage phosphor exchange position 40, and
Rotate 0 degrees. After that, move the IP holder 26 to the exposure position.
return. Then, the reader 36 is used to display the stimulable phosphor 12.
Read the recorded latent image. During this reading process,
Start the end angle of the ω axis recorded in the storage phosphor 12 last time
As a point, the sample 28 is set in an angle range of 0 to 90 degrees around the ω axis.
The accumulated X-rays of the other X-ray are accumulated while rotating in the surrounding area.
The body 13 is exposed. Exposure of storage phosphor 13 and storage phosphor
When the reading of the optical body 12 is completed, the IP holder 26 is stored.
It was moved to the accumulative phosphor exchange position 40 and the reading was completed.
The stimulable phosphor 12 is erased by the erase lamp 42. That
After rotating the IP holder 26 180 degrees,
Return to the light position. This allows the erased storage phosphor
12 is again returned to the position where it can be exposed and is reused. one
On the other hand, the exposed storage phosphor 13 is read by the reading device 36.
Read. This kind of work can be performed by changing the angular range of ω rotation.
Repeatedly staggering them one after another, repeating a total of 180 degrees
Record the image. Note that the Laue symmetry of sample 28 is clear.
If you know the full rotation range of the ω axis required for measurement
It may be set smaller than 180 degrees described above. like this
The structure of the sample is processed by data processing of the diffraction image taken in the procedure.
Analyze.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Next, a vertical method using a stimulable phosphor will be described.
And explain. For this, method 1 using vibration photography
And method 2 using the Weissenberg method,
Then, these are used properly. Method 1 uses the IP holder 26
With the sample still stationary, rotate the sample 28 around the ω axis at 0 to 1 degree.
Performs micro-rotational vibration in the angular range and accumulates vibration diffraction images.
Recording on the optical body 12. This diffraction image is the above-mentioned Weissenberg
Read with the reading device 36 in the same way as the measurement work.
However, before starting the reading work, set the ω-axis to an appropriate angle.
Advance only once, and the next minute
A small vibration diffraction image is recorded on the stimulable phosphor 13. like this
Repeats various tasks within the angle range of 0 to 90 degrees on the ω axis
Based on several microscopic vibration diffraction images obtained,
Calculate columns. In the method 2, first, the IP holder 2
With sample 6 still, the sample 28 is rotated around the ω axis by 10 to 3
Record the diffraction image on the stimulable phosphor by rotating it by 0 degree.
It Next, keeping the rotation range of the ω-axis in the same range,
Is moved while synchronizing the IP holder 26 with the ω-axis rotation.
Double exposure of the diffraction image using the Weissenberg method
It At this time, the vibration diffraction image and the Weissenberg diffraction image are
The exposure time is changed so that they can be distinguished. Next, the ω axis
Take the same double-exposure image as before with 90 degrees forward
To do. Data processing of two double exposure images and crystal orientation matrix
To decide. Determine the crystal orientation matrix by Method 1 or Method 2.
After that, the specific axis of the crystal of sample 28 coincides with the ω axis.
And three axes of the kappa goniometer of the sample holding device 18.
Adjust the rotation of (ω, κ, φ). In addition, extremely quick
If measurements are required, use the above-mentioned steps
It is also possible to omit it and start the measurement.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

Next, a measuring method using a stimulable phosphor and a scintillation counter together will be described. First,
Using a scintillation counter 14, binding of the sample 28
Determine the crystallographic orientation matrix . Then, based on this measurement result, the specific axis of the sample crystal is made to coincide with the ω axis. afterwards,
Next, the stimulable phosphor 12 is used to record a diffraction image for structural analysis. In analyzing the diffraction image obtained here, the already-obtained crystal orientation matrix can be used, which facilitates the analysis. In this way, the crystal orientation matrix can be automatically and accurately determined by the scintillation counter, and the data for the subsequent structural analysis can be obtained in a short time by using the stimulable phosphor.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

In the X-ray diffractometer of the present invention, structural analysis using a stimulable phosphor and structural analysis using a scintillation counter can be performed by one device, and both can be selected according to the purpose. Can be used for various purposes. Furthermore, adopt a combination measurement method that automatically determines the crystal orientation matrix of the crystal using a scintillation counter, and then obtains data for structural analysis in a short time using a stimulable phosphor. You can also

Claims (5)

[Claims] 1. An X-ray diffractometer which records diffracted X-rays from a sample as a latent image on a stimulable phosphor and irradiates the stimulable phosphor with excitation light to read out the latent image. An X-ray diffractometer having. (A) The recording surface of the stimulable phosphor is formed along the inner surface of the cylindrical surface. (B) The sample is placed on the center line of the cylindrical surface. (C) The stimulable phosphor can be moved in a direction parallel to the center line. (D) A counter tube type X-ray detector rotatable around the center line is installed on the detector mounting base. (E) The detector mounting base can be moved in a direction parallel to the center line. 2. The X-ray diffraction apparatus according to claim 1, wherein the sample is rotatable about three rotation axes. 3. The stimulable phosphor and the X-ray detector are arranged inside a common dark box.
The X-ray diffractometer described. 4. The X according to claim 1, wherein the IP holder holding the stimulable phosphor has the following characteristics.
Line diffractometer. (F) The IP holder can hold a plurality of stimulable phosphors. (G) The IP holder can move in a direction parallel to the center line between the stimulable phosphor exposure position and the stimulable phosphor exchange position. (H) The IP holder can rotate around the center line of the IP holder at the storage phosphor exchange position. 5. When one stimulable phosphor held by the IP holder is at an exposure position, another stimulable phosphor held by the IP holder is at a reading position, and 5. The X-ray diffraction according to claim 4, wherein the stimulable phosphor held by the IP holder can be erased by an erasing lamp when the IP holder is at the stimulable phosphor exchange position. apparatus.