JPH076511Y2 - High temperature sample holder for X-ray diffractometer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a sample holder for an X-ray diffraction apparatus, and more particularly to a sample holder for making a sample at a high temperature for diffraction measurement.

[Prior Art] In order to perform X-ray diffraction measurement with a sample at a high temperature, the sample is attached to a sample holder dedicated to the high temperature measurement, and this sample holder is placed in a heating furnace. Then, the X-ray diffraction measurement is performed with the sample holder still in the heating furnace. A sample holder for high temperature measurement needs to have the following features.
That is, (1) When the sample expands due to the high temperature, the sample is prevented from falling off the sample holder.

(2) When the sample expands due to high temperature, the sample surface may move back and forth, and the sample surface may deviate from the focal circle (concentrated circle) of the diffractometer. As a result, the angle measurement accuracy of the diffraction pattern may be reduced. In this case, it is preferable that the sample holder be modified in some way so that the diffraction angle of the obtained diffraction pattern can be corrected.

Conventional high temperature sample holders have been devised to prevent the sample from falling off, but have not been devised to correct the diffraction angle. A specific example of a conventional high temperature sample holder is shown below.

FIG. 8 and FIG. 9 show a method of attaching a plate-shaped sample to a high temperature sample holder. In FIG. 8, on both sides of the sample holder 50, side walls 52, 5 having a U-shaped cross section are provided.
There are four. The sample plate 56 can be attached to the sample holder 50 by inserting both ends of the sample plate 56 inside the side walls 52 and 54. Both ends of the sample plate 56 are obliquely cut so as to be easily inserted into the side wall. The surface of the central portion of the sample plate 56 is arranged on the same plane as the surfaces of the side walls 52 and 54. A thermocouple 58 can be inserted inside the side wall 52. FIG. 9 shows the same sample holder 50.
An example of attaching plate-shaped samples 57 having different shapes is shown in FIG. This plate-shaped sample 57 has steps at both ends.

FIG. 10 shows how the same sample holder 50 is filled with the powder sample 60. First, the sample holder 50 is placed on the glass plate 64, and the powder sample 60 is filled between the two side walls 52 and 54. The rear surface of the sample holder 50 has many holes 66 for preventing the powder sample from falling off. The powder sample 60 is also filled into the captive prevention holes 66 and the insides of the side walls 52 and 54, and is finally filled to the same height as the surfaces of the side walls 52 and 54 on both sides. When the powder sample is filled, the jig 62 is previously inserted inside the side wall 52 in order to secure an insertion space for the thermocouple.

In summary, such a conventional sample holder has the following features. That is, (1) the plate-like sample can be prevented from falling off by devising the shape of both ends of the plate-like sample. (2) The powder sample can be prevented from falling off by filling the powder sample into the dropout prevention hole and the inside of the side wall.

[Problems to be Solved by the Invention] In the conventional sample holder described above, it is difficult to clean the sample holder when replacing the powder sample. 1000 powder samples
After being exposed to a high temperature of about ℃, it is cooled and removed from the sample holder. This high temperature often causes the powder sample to stick to the sample holder. The work of removing this is difficult, and in particular, the powder sample stuck to the inside of the U-shaped side wall cannot be easily removed.

Furthermore, the conventional sample holder does not take any measures against the deviation of the diffraction angle due to the sample surface deviating from the focal circle. If the sample does not reach a high temperature, for example, a powder sample may be mixed with a standard substance serving as an angle reference of a diffraction pattern. Then, the angular deviation of the measured diffraction pattern can be determined based on the diffraction pattern of the standard substance. However, when the temperature of the sample is high, there is a possibility that the mixed standard substance and the powder sample may chemically react with each other, and the above-described internal standard sample cannot be used. In the case of plate-shaped samples, of course, no measures have been taken against angular displacement.

The present invention has been made in view of such circumstances, and an object thereof is to facilitate cleaning of a sample holder when replacing a powder sample, and a diffraction pattern when a sample surface is out of a focal circle. An object of the present invention is to provide a high temperature sample holder for an X-ray diffractometer capable of correcting the angle.

[Means and Actions for Solving the Problems] In order to achieve the above-mentioned object, the sample holder according to the present invention has the following features. That is, a wire guide groove for guiding the sample fixing wire is formed on the reference surface of the sample holder. If the sample fixing wire is passed through the wire guide groove and the powder sample is fixed by the sample fixing wire, the powder sample can be prevented from falling off. Then, the side wall of the sample holder does not have to be U-shaped. The sample fixing wire is embedded in the surface of the powder sample, and the surface of the sample fixing wire is flush with the surface of the powder sample. Therefore, if a standard material for diffraction measurement is used as the material of the sample fixing wire, the angle of the diffraction pattern of the powder sample can be corrected based on the diffraction line from the sample fixing wire. That is, the sample fixing wire can be used as an external standard sample for angle correction.

In addition to these features, on the side of the sample holder,
Another wire guide groove for guiding the sample fixing wire may be formed at a position different from the wire guide groove on the reference surface. The other wire guide groove guides the wire for fixing the plate-shaped sample. Since the wire cannot be embedded in the plate sample, it is not preferable to form the wire guide groove on the reference surface. This is because a step is formed between the surface of the plate-shaped sample and the inner surface of the wire guide groove of the reference surface. Therefore, a wire guide groove is provided on the side surface. By providing the two types of guide grooves in this way, it becomes possible to use both the powder sample and the plate sample.

By the way, the surface of the wire for fixing the plate sample is
The sample fixing wire itself cannot be used as an external standard sample because it protrudes from the surface of the plate sample. If it is to be used as an external standard sample, it is necessary to consider in advance the distance correction of the amount of protrusion from the sample surface. It is not preferable that this distance correction is large compared to the amount of movement of the sample surface due to thermal expansion. Therefore, in addition to the above-mentioned two types of wire guide grooves, a ribbon guide groove for guiding the ribbon made of the standard substance is formed on the side surface of the sample holder at a position different from the wire guide groove on the reference surface. You can also If a very thin ribbon is used as an external standard sample, the above-mentioned distance correction can be omitted, or even a slight distance correction can be performed.

Further, the two inner wall surfaces that connect the back plate of the sample holder and the two reference planes and define the sample filling space may be formed as planes substantially perpendicular to the back plate. In this way, unlike the conventional U-shaped cross section, cleaning of the sample holder when replacing the powder sample becomes easy.

[Embodiment] Next, an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a perspective view of an embodiment of the present invention. The sample holder 10 is made by bending a platinum plate. The sample holder 10 includes a back plate 12 and two side walls 14,1.
It consists of 6 and a bottom plate 18.

The rear plate 12 is provided with a large number of drop-out preventing holes 22 for preventing the powder sample from falling off. A protrusion 20 is integrally formed at the center of the upper end of the back plate 12. The protrusion 20 is a knob for holding the sample holder 10.

Side walls 14 and 16 are provided on both sides of the back plate 12. One side wall 14
Has formed therein a space 28 extending in the vertical direction. This space 28 is for inserting a thermocouple. The front surface of the side wall 14 serves as a reference surface 24. This reference plane is arranged in a plane including the rotation axis of the sample holder and is on the focal circle of the diffractometer. The outer side surface 27 of the side wall 14 becomes the side surface of the sample holder 10. Five wire guide grooves 30 extending in the horizontal direction are formed on the reference surface 24 of the side wall 14. On the other hand, on the side surface 27 of the side wall 14, two wire guide grooves 32 extending in the horizontal direction are formed. The wire guide groove 30 of the reference surface 24 is for guiding the wire for fixing the powder sample,
The wire guide groove 32 on the side surface 27 is for guiding a wire for fixing the plate-shaped sample. It should be noted that the latter sample holder without the wire guide groove 32 may be made, and in that case, it is dedicated to the powder sample.

The other side wall 16 is formed by folding in two. Similar to the side wall 14, the side wall 16 also has five wire guide grooves 30 on its reference surface 26 and two wire guide grooves on the outer side surface thereof. The inner wall surface 25 of the side wall 16 is perpendicular to the back plate 12 and defines a filling space for the sample. The inner wall surface of the other side wall 24 is also perpendicular to the back plate.

The sample holder 10 is formed by bending a single plate shown in FIG. That is, the side wall 14 can be formed by bending the part A of this plate as shown by the chain double-dashed line. On the other hand, the side wall 16 can be formed by bending the portion B as shown by the chain double-dashed line. After that, the portion of the bottom plate 18 is bent horizontally toward you to complete the sample holder.

Next, a method of using this sample holder will be described.

FIG. 3 shows a method of attaching the powder sample 34 to the sample holder 10. First, the sample holder 10 is placed on the glass plate in the same manner as shown in FIG.
Between 6 fill powder sample 34. Powder sample 34 has reference surface 2
Fill to be higher than 4,26. Next, the front side of the sample holder 10 is pressed against the glass plate to make the surface of the powder sample 34 at the same height as the reference planes 24 and 26. Next, the platinum wire 36 for fixing the powder sample is wound around the sample holder 10. At that time, the wire guide groove 30 formed on the reference surfaces 24 and 26
Pass the platinum wire 36 through. The platinum wire 36 is screwed behind the sample holder. Then, again, the front side of the sample holder 10 is pressed against the glass plate to embed the platinum wire 36 in the powder sample 34. FIG. 5 is an enlarged view showing a partial cross section of the sample holder in the state where the filling of the powder sample is completed in this way. The outer surface of the platinum wire 36 is level with the surface of the powder sample 34.

The platinum wire 36 used has a diameter of 0.1 to 0.2 mm. The depth of the wire guide groove 30 matches the diameter of the platinum wire,
0.1 to 0.2 mm.

The sample holder 10 to which the powder sample 34 is attached is placed in a heating furnace, and X-ray diffraction measurement of the powder sample is performed in that state. As can be seen from FIG. 5, the powder sample 34 does not fall out of the sample holder 10 due to the action of the drop-out preventing hole 22 and the platinum wire 36, even if the powder sample 34 expands due to high temperature. When the diffraction pattern of the powder sample 34 is measured, the diffraction pattern of the platinum wire 36 is also measured at the same time. Since platinum is a standard substance in which the angular position of the diffraction peak is accurately determined, the angle of the measurement result can be corrected by comparing the measured platinum diffraction pattern with the standard platinum diffraction pattern. Therefore, even if the sample moves back and forth due to temperature expansion, the platinum wire also shifts back and forth at the same time, so that the angular shift of the diffraction pattern due to the forward and backward movement can be corrected by the above-described angle correction.

Next, a method of attaching a plate-shaped sample to this sample holder will be described. In FIG. 4, the plate-shaped sample 38 is fixed by two platinum wires 36. In this case, the inner surface of the platinum wire 36 is in contact with the surface of the plate-shaped sample 38, as shown in FIG. Then, the outer surface of the platinum wire 36 is
It is in a state of protruding from the surface of the plate sample 38. Therefore, the diffraction line from the platinum wire 36 cannot be the angle standard. Therefore, the two platinum wires 36 fix the upper end and the lower end of the plate-like sample 38, and the platinum wire does not exist in the central portion irradiated with the X-ray. The two platinum wires 36 are guided in the wire guide groove 32 on the side surface of the sample holder 10. If the wire guide groove for fixing the plate-shaped sample is formed on the reference surface, the wire may be disengaged from the groove due to the step between the surface of the plate-shaped sample and the inner surface of the wire guide groove.

Note that the surface of the plate-shaped sample 38 also has a reference
It should be placed on the same plane as 24 and 26. Therefore, as shown in FIG. 6, a suitable platinum spacer 40 is sandwiched between the plate sample 38 and the back plate 12. 2 in FIG.
A spacer is shown.

FIG. 7 shows a modification of this embodiment. In this modification, a ribbon guide groove 42 is added to the side wall 14 in addition to the two types of wire guide grooves 30 and 32. This ribbon guide groove 42
Is for guiding the platinum ribbon. The platinum ribbon is used by being wound around the surface of the plate sample. This platinum ribbon is not for fixing the plate sample,
Used only as an external standard for correction of diffraction angles. Since the platinum ribbon is very thin, it can be considered that the surface of the platinum ribbon and the surface of the plate-like sample are approximately on the same plane. Alternatively, the distance correction is taken into consideration by the thickness of the platinum ribbon, and then the angle correction is performed by the platinum diffraction pattern. In this case, the distance correction is so small that the angle measurement accuracy does not deteriorate so much. The platinum ribbon used has a thickness of 5 to 50 μm. It is sufficient that the depth of the ribbon guide groove 42 is about 0.1 mm. Although only one ribbon guide groove 42 is shown in FIG. 7, a plurality of ribbon guide grooves 42 may be provided if necessary. A similar ribbon guide groove is also formed on the side surface of the other side wall 16 of the sample holder.

Although platinum is used as the material of the sample holder in the above-mentioned embodiments, other materials can be used. That is, if the sample is heated up to 800 ° C, nickel can be used. 1500
Platinum is preferred up to ° C. If the heating temperature is higher than that, tungsten can be used. The sample holder made of tungsten can be used up to 2500 ° C. In any case,
A material excellent in heat resistance and chemical stability at high temperature may be selected.

Further, in the above description, platinum is taken as an example of the material of the wire and the ribbon, but other standard materials such as tungsten can be used as long as there is no problem in using at high temperature.

[Advantage of the Invention] In the sample holder according to the invention as defined in claim 1, since the wire guide groove for guiding the sample fixing wire is formed on the reference surface of the sample holder, it is convenient for attaching the powder sample. . That is, if the sample fixing wire is passed through the wire guide groove and the powder sample is fixed by the sample fixing wire, the powder sample is prevented from falling off. Then, the side wall of the sample holder does not have to be U-shaped. Further, if a standard substance for which the angle of the diffraction peak is accurately determined is used as the material of the sample fixing wire, this sample fixing wire becomes the external standard substance, and the angle of the measured diffraction pattern can be corrected.

In addition to the features of claim 1, the sample holder according to the invention of claim 2 has another wire guide groove formed on the side surface of the sample holder. The other wire guide groove guides the wire for fixing the plate-shaped sample. By providing two types of guide grooves in this way, this sample holder can be used for both powder samples and plate samples.

In addition to the features of claim 2, the sample holder according to the invention of claim 3 has a ribbon guide groove formed on a side surface of the sample holder for guiding a ribbon made of a standard substance. Accordingly, in the case of a plate-shaped sample, a ribbon having a very thin thickness can be used as the external standard sample.

In addition to the features of claim 1, the sample holder according to the invention of claim 4 has two inner wall surfaces that define the sample filling space in a plane perpendicular to the back plate. This facilitates cleaning of the sample holder when replacing a powder sample, unlike the conventional U-shaped sidewall cross section.

[Brief description of drawings]

FIG. 1 is a perspective view of an embodiment of the present invention, FIG. 2 is a perspective view showing a shape of the sample holder before a bending step, and FIG. 3 is a perspective view of a sample holder to which a powder sample is attached. FIG. 4 is a perspective view of a sample holder to which a plate-like sample is attached, FIG. 5 is a partially enlarged vertical sectional view of the sample holder in the state of FIG. 3, and FIG. 6 is a state of FIG. FIG. 7 is a partially enlarged vertical sectional view of the sample holder, FIG. 7 is a partially enlarged perspective view of a modified example of the sample holder, and FIGS. 8 to 10 are perspective views showing how to use the conventional sample holder. is there. 10 …… Sample holder 12 …… Back plate 24,26 …… Reference surface 25 …… Inner wall surface 30 …… Wire guide groove formed on the reference surface 32 …… Wire guide groove formed on the side surface 42 …… Ribbon guide groove

Claims (4)

[Scope of utility model registration request] 1. A sample holder for an X-ray diffraction apparatus having two reference planes in the same plane and a sample filling space formed between the reference planes, wherein a sample fixing wire is guided to the reference plane. A sample holder for high temperature, characterized in that a wire guide groove for forming is formed. 2. A wire guide groove for guiding the sample fixing wire is formed on a side surface of the sample holder at a position different from the wire guide groove on the reference surface. The high temperature sample holder described. 3. A ribbon guide groove for guiding a ribbon made of a standard substance is formed on a side surface of the sample holder at a position different from the wire guide groove on the reference surface. The high temperature sample holder described in 2. 4. The two inner wall surfaces connecting the back plate of the sample holder and the two reference planes to define the sample filling space are formed as planes substantially perpendicular to the back plate. The sample holder for high temperature according to claim 1, wherein the sample holder is for high temperature.