JP3890412B2 - Sample container for X-ray diffraction measurement - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a sample container for X-ray diffraction measurement that contains a sample for X-ray diffraction measurement.
[0002]
[Prior art]
X-ray diffraction measurement is performed by irradiating a sample with characteristic X-rays (CuKα rays, MoKα rays, etc.) emitted from an X-ray source, and capturing X-rays diffracted from the sample with a detector or a film negative. This is performed by performing measurement processing or optical processing and then displaying measurement results as numerical values, graphs, images, etc., and is used for structural analysis of crystals constituting an object. As X-rays used at the laboratory level, 12 kW or 18 kW for rotary anti-cathode type devices and 3 kW or less for tube type devices are commercially available.
[0003]
Conventionally, most of the knowledge we have obtained through X-ray diffraction measurement is based on the premise that the temperature and pressure surrounding various sample materials are almost unchanged. However, measuring samples in a heated (cooled) or pressurized (decompressed) state is indispensable for obtaining knowledge about the phase and structural transformation of various substances, and the measurement needs in such an environment Is growing.
[0004]
For this reason, the structure which can perform an X-ray-diffraction measurement in the state which heated the accommodated sample is proposed (for example, patent documents 1-3). The sample heating apparatus disclosed in Patent Document 1 includes a sample chamber in which a window portion that transmits X-rays is formed on a ceiling surface, and a flat sample mounting provided in the sample chamber and facing the window portion. And a heating chamber on which a placement surface is formed, and the window portion of the sample chamber is configured by disposing an X-ray permeable film in an elongated opening. The sample storage containers disclosed in Patent Documents 2 and 3 have a configuration in which a sample furnace body for heating a sample is surrounded by a casing, and a window portion through which X-rays pass is formed in the casing.
[0005]
[Patent Document 1]
JP-A-8-15183 (page 3-4, FIG. 1)
[0006]
[Patent Document 2]
Japanese Patent Laid-Open No. 9-166527 (page 3-4, FIG. 1)
[0007]
[Patent Document 3]
JP-A-9-166529 (page 3-4, FIG. 1)
[0008]
[Problems to be solved by the invention]
In the above-described conventional configuration, the window portion of the sample chamber or the casing needs to be formed of a material having little X-ray absorption. Therefore, Patent Document 1 exemplifies beryllium foil. Beryllium has stability to the atmosphere and is excellent in workability and mechanical strength.
[0009]
However, beryllium, on the other hand, has the properties of poor toughness and large thermal strain associated with temperature changes. For this reason, in order to reduce the influence of heat in the vicinity of the mounting portion of the window portion, a cooling mechanism for the wall surface of the sample chamber or the casing is required, and a certain interval or more is provided between the heating container or the sample furnace body and the window portion. Therefore, there is a problem that the configuration becomes complicated and large.
[0010]
In addition, when the sample chamber or casing is enlarged and the internal volume is increased, when the sample is measured under a high pressure condition, the standard as a pressure vessel must be satisfied, and there is a problem that troubles such as inspection become troublesome. there were. That is, according to the "High Pressure Gas Safety Law" and "Occupational Safety and Health Law", "Construction Order", "Boiler and Pressure Vessel Safety Regulations", etc., the container is subject to restrictions on the place of use, and due to its internal volume and maximum operating pressure, Type 1 pressure vessel (further subdivided into type 1 pressure vessel and small pressure vessel), type 2 pressure vessel, container or non-applicable. Assuming that the maximum operating pressure is P (kgf / cm ² ) and the container volume is V (m ³ ), when the product PV value is 0.01 or less, the product is not subject to the laws and regulations based on the Industrial Safety and Health Act. In order to measure a sample under high-pressure conditions, it is preferable to make the container volume as small as possible.
[0011]
The present invention has been made in view of the above circumstances, and an object thereof is to provide a sample container for X-ray diffraction measurement that enables X-ray diffraction measurement of a sample in a wide range of temperatures and pressures.
[0012]
[Means for Solving the Problems]
The object of the present invention is a sample container for X-ray diffraction measurement which contains a sample to be subjected to X-ray diffraction measurement, and is configured to be hermetically sealed by an upper lid and a bottom lid, and a cylindrical body capable of accommodating a sample therein And a supply part capable of supplying pressure gas to the inside of the fuselage, and the fuselage is formed of an X-ray transmitting material over the entire circumference, and is inserted into the fuselage in a state where flat surfaces are in close contact with each other. A pair of possible sample holders, wherein the pair of sample holders are formed of an X-ray transmitting material, and at least one of the flat surfaces is filled with a sample groove, and the pressure is applied to the container groove This is achieved by a sample container for X-ray diffraction measurement in which a communication groove for causing the above is formed .
[0013]
Alternatively, the object of the present invention is a sample container for X-ray diffraction measurement that contains a sample to be subjected to X-ray diffraction measurement, and is configured to be hermetically sealed by an upper lid and a bottom lid, and has a cylindrical shape that can accommodate a sample inside And a supply part capable of supplying pressure gas to the inside of the fuselage, and the fuselage is formed of an X-ray transmitting material over the entire circumference, and the inner wall surface of the fuselage when inserted into the fuselage A sample holder having a slidable flat surface, the sample holder being made of an X-ray transmitting material, a storage groove filled with the sample in the flat surface, and a pressure in the storage groove This is achieved by a sample container for X-ray diffraction measurement in which a communication groove for causing the above is formed.
[0015]
In the sample container for X-ray diffraction measurement described above, the container volume is preferably 0.1 to 3 × 10 ⁴ mm ³ .
[0016]
The X-ray transmissive material is preferably beryllium.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, actual forms of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a side view showing a schematic configuration of a sample container for X-ray diffraction measurement according to an embodiment of the present invention. As shown in the figure, the sample container 1 is configured such that both ends of a cylindrical body 2 can be sealed with an upper lid 4 and a bottom lid 6 via a gasket (not shown). One of the upper lid 4 or the bottom lid 6 does not necessarily need to be detachable from the body 2 and may be integrated.
[0018]
A supply part 4a for supplying a pressure gas such as hydrogen gas is provided at the center of the upper lid 4, and this supply part 4a is connected to a pressure gas supply source (not shown) via an introduction pipe 52. The fitting member 50 is fitted in an airtight state via an O-ring or the like. In addition, when rotating the sample container 1 at the time of X-ray diffraction measurement, it is preferable to couple the attachment member 50 and the introduction tube 52 so as to be relatively rotatable by a rotary joint or the like.
[0019]
A pair of sample holders 8 and 10 having semicircular side surfaces are detachably inserted into the body 2. On the lower surface of one of the sample holders 8, a convex portion 8 b that engages with a positioning concave portion formed in the bottom lid 6 is provided, and the rotation of the sample holders 8 and 10 inside the body 2 is prevented. ing. The rotation prevention mechanism can also be configured by a step or a groove formed on the inner peripheral surface of the body 2.
[0020]
The pair of sample holders 8 and 10 have flat surfaces 8a and 10a formed so as to be in close contact with each other. As shown in FIGS. 1 and 2, the flat surface 8 a of one sample holder 8 is formed with a storage groove 12 filled with a sample and a communication groove 14 for applying pressure to the storage groove 12. Has been. The width and depth of the communication groove 14 are preferably smaller than the width and depth of the receiving groove 12, respectively, but are not particularly limited, and may be the same as the width and depth of the receiving groove 12, respectively.
[0021]
In the sample container 1, the body 2 and the pair of sample holders 8 and 10 are made of an X-ray transmitting material. As the X-ray transmitting material, a material having a small mass attenuation coefficient (also referred to as a mass absorption coefficient) indicating the degree of attenuation when X-rays pass through the material is preferable, and its mechanical characteristics, measurement conditions, and reaction with the sample. It can be used in consideration of the properties and gas atmosphere. Specific examples include beryllium, boron nitride, lithium boride and the like, and beryllium is particularly preferably used.
[0022]
If the body 2 is excessively thick, the transmitted X-rays are attenuated. Therefore, the thickness may be appropriately determined in consideration of the material, the maximum use pressure, and the like. For example, when the outer diameter of the body 2 made of beryllium is 10 mm and the design pressure at room temperature is 100 MPa, the thickness of the body 2 may be about 1 mm.
[0023]
When X-ray diffraction measurement is performed using the sample container 1 having the above configuration, first, the sample is filled into the receiving groove 12 of one sample holder 8, and the flat surface 8a is flattened with the other sample holder 10. After the surface 10 a is brought into close contact, the sample holders 8 and 10 are inserted into the body 2. Then, both ends of the body 2 are sealed with the upper lid 4 and the bottom lid 6, set on the mounting surface of the measuring device (for example, the upper surface of the θ turntable), and the attachment member 50 is connected to the supply unit 4 a of the upper lid 4. . In order to prevent displacement between the sample container 1 and the mounting surface 60, it is preferable to provide an engagement key (not shown) between the lower surface of the bottom lid 6 and the mounting surface 60. Moreover, you may make it cover the circumference | surroundings of the sample container 1 with protection plates, such as stainless steel, in the range which does not have trouble with the passage of the X-ray mentioned later and experiment work.
[0024]
When performing X-ray diffraction measurement under pressure using the sample container 1, first, the valve opening of a pressure gas supply source (not shown) is adjusted and set to a desired pressure. Thereafter, X-ray diffraction measurement can be performed by the Guinier camera method (reflection method and transmission method), the diffractometer method, the Laue method, and the like, as in the past. In these methods, X-rays are incident on the sample and then diffracted, reflected, transmitted or scattered, and the intensity of the diffracted X-rays is converted into a numerical signal by a detector (such as a scintillation counter) and recognized as the diffraction intensity. The Alternatively, it is recorded as light shading by a high-sensitivity film, and the light shading is digitized as optical information by a film scanner or the like and recognized as diffraction intensity. After the measurement is completed, the valve of the pressure gas supply source (not shown) is closed and decompressed, and then the upper lid 4 and the bottom lid 6 are removed from the body 2 and the sample holders 8 and 10 are pushed out to exchange the sample. be able to.
[0025]
When the sample container 1 is pressurized or depressurized, heat is generated by the Joule-Thomson effect. Further, depending on the combination of the sample and the introduced gas, reaction heat may be generated by the reaction between the two. In order to prevent an increase in the internal temperature of the sample container 1 due to these, means such as water cooling or air cooling may be provided as necessary.
[0026]
According to the sample container 1 according to the present embodiment, since the body 2 and the pair of sample holders 8 and 10 are formed of an X-ray transmitting material, in the case of the reflective measurement, FIG. By irradiating with characteristic X-rays as described above, it is possible to detect diffracted X-rays reflected on the flat surface of the sample S. On the other hand, in the case of transmission measurement, characteristic X-rays as shown in FIG. , The diffracted X-rays transmitted through the sample S can be detected, and both reflection-type measurement and transmission-type measurement can be handled.
[0027]
In addition, since the sample is held by the pair of sample holders 8 and 10 inserted into the body 2, the internal space of the sample container 1 can be reduced and high pressure can be easily applied to the sample. Can be easily exchanged and the inside of the container can be easily cleaned. Furthermore, when X-ray diffraction measurement is performed by the diffractometer method, the surface of the sample placed on the θ rotation table can be easily adjusted to a predetermined reference plane.
[0028]
In addition, since the internal volume of the container can be reduced compared to the conventional configuration, it is easy to exclude the application of the pressure container based on the High Pressure Gas Safety Law, and the labor required for inspections based on laws and regulations can be saved. Can do. Specifically, the container volume of the sample container 1 is preferably 0.1~3 × 10 ⁴ mm ^3, more preferably 0.1 to 50 mm ^3. If the internal volume of the body 2 is too large, the maximum operating pressure must be reduced in order for the sample container 1 to become a non-applicable product of the pressure container based on the Industrial Safety and Health Act, and measurement under high pressure becomes difficult. On the other hand, if the internal volume of the body 2 is too small, it is difficult to accommodate a sample sufficient for measurement. In addition, when using the sample holders 8 and 10 inserted into the body 2 as in this embodiment, a desired amount of sample can be obtained by appropriately setting the size of the receiving groove 12 filled with the sample. Can be measured.
[0029]
Moreover, in this embodiment, since the whole body 2 and the pair of sample holders 8 and 10 are formed of an X-ray transmitting material, they can be uniformly expanded by uniform heating, and under the heating conditions. During measurement, local stress can be prevented from occurring in the sample container 1. Examples of a method for uniformly heating the body 2 include use of a ribbon heater, a rubber heater, a jacket heater, and the like.
[0030]
As mentioned above, although one Embodiment of this invention was explained in full detail, the specific aspect of this invention is not limited to the said embodiment. For example, in this embodiment, the storage groove 12 and the communication groove 14 are formed only on one sample holder 8, but the storage groove and the communication groove are formed on both of the pair of sample holders 8 and 10. Also good.
[0031]
In the present embodiment, when only reflection measurement is performed, one of the sample holders 8 and 10 can be formed of a material other than the X-ray transmitting material. Further, when only the transmission type measurement is performed in the present embodiment, it is not always necessary to use the sample holders 8 and 10, and the body 2 may be directly filled with the sample.
[0032]
Further, in the present embodiment, the pressure resistance performance is enhanced by making the body 2 a cylindrical shape. However, when the pressure at the time of pressurization is small and the possibility of deformation of the container is low, a rectangular tube shape or the like is used. You can also. For the rectangular tube-shaped body 2, the same effect as that of the present embodiment can be obtained by inserting only one sample holder in which a housing groove and a communication groove are formed on a flat surface. That is, in this case, since the inner wall surface of the body 2 is a flat surface, the flat surface of the sample holder may be configured to slide with the inner wall surface of the body when inserted. Furthermore, even if the sample is directly filled into the body, the sample surface becomes a flat surface, so that it is possible to cope with both reflection type measurement and transmission type measurement without using a sample holder.
[0033]
In the present embodiment, the supply unit 4a of the upper lid 4 is connected to a pressure gas supply source (not shown). However, when measurement is performed under reduced pressure, a vacuum pump is connected to the supply unit 4. You can also. In the measurement under atmospheric pressure, the supply unit 4a may be sealed with a stopper or the like.
[0034]
【The invention's effect】
As apparent from the above description, according to the present invention, it is possible to provide a sample container for X-ray diffraction measurement that enables X-ray diffraction measurement of a sample in a wide range of temperatures and pressures.
[Brief description of the drawings]
FIG. 1 is a side view showing a schematic configuration of a sample container for X-ray diffraction measurement according to an embodiment of the present invention.
FIG. 2 is a plan view of one sample holder in the sample container.
FIG. 3 is a diagram schematically showing an X-ray diffraction measurement method using the sample container.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Sample container 2 Body 4 Upper cover 4a Supply part 6 Bottom cover 8, 10 Sample holder 12 Housing groove 14 Communication groove

Claims (4)

A sample container for X-ray diffraction measurement containing a sample for X-ray diffraction measurement,
It is configured to be hermetically sealed by an upper lid and a bottom lid, and includes a cylindrical body capable of accommodating a sample therein, and a supply unit capable of supplying pressure gas inside the body,
The body is formed of an X-ray transmitting material over the entire circumference,
A pair of sample holders that can be inserted into the body with the flat surfaces in close contact with each other,
The pair of sample holders are made of an X-ray transmitting material, and at least one of the flat surfaces is formed with an accommodation groove for filling the sample and a communication groove for applying pressure to the accommodation groove. A sample container for X-ray diffraction measurement. A sample container for X-ray diffraction measurement containing a sample for X-ray diffraction measurement,
It is configured to be hermetically sealed by an upper lid and a bottom lid, and includes a cylindrical body capable of accommodating a sample therein, and a supply unit capable of supplying pressure gas inside the body,
The body is formed of an X-ray transmitting material over the entire circumference,
A sample holder having a flat surface slidable with the inner wall surface of the fuselage when inserted into the fuselage, wherein the sample holder is formed of an X-ray transmitting material, and the flat surface is filled with a sample. A sample container for X-ray diffraction measurement, in which an accommodation groove formed and a communication groove for applying pressure to the accommodation groove are formed. The sample container for X-ray diffraction measurement according to claim 1, wherein the container volume is 0.1 to 3 × 10 ⁴ mm ³ . The sample container for X-ray diffraction measurement according to any one of claims 1 to 3, wherein the X-ray transmitting material is beryllium.

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