JP3666831B2 - Thermal analysis and X-ray measurement equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermal analysis and X-ray measurement apparatus capable of performing both thermal analysis measurement and X-ray measurement.
[0002]
[Prior art]
Thermal analysis is the measurement of the temperature dependence of the properties of a sample when the temperature of the sample is changed. There are very many kinds of specific analysis methods. Typical examples include differential thermal analysis (DTA) and differential scanning calorimetry (DSC). Etc.
[0003]
DTA is a method in which a sample and a standard substance are heated at the same time, and the thermal change generated in the sample is known from the temperature difference that appears between them during the reaction. DSC is a method for obtaining the heat change generated in a sample as the amount of heat necessary to compensate for it. Specifically, if there is a temperature difference between the sample and the standard substance, Increase or decrease the amount of heat per unit time supplied to one side, and control the temperature so that constant temperature rise, constant cooling or isothermal state is maintained, and measure the amount of heat increased or decreased at that time To do. The DTA indirectly measures the thermal change of the sample in the form of a temperature difference. For example, the transition heat, that is, the latent heat cannot be measured, but the DSC can also measure the transition heat.
[0004]
On the other hand, X-ray measurement is to measure the properties of a sample by irradiating the sample with X-rays, detecting X-rays diffracted or reflected by the sample. There are very many kinds of specific analysis methods for this X-ray measurement, for example, X-ray diffraction measurement and X-ray reflectivity measurement.
[0005]
The X-ray diffraction measurement is a measurement for detecting X-rays diffracted by the sample, and the X-ray reflectance measurement is a measurement for detecting X-rays reflected by the sample. In general, when the incident angle of X-rays incident on the sample is large, the X-rays are often diffracted by the sample. When the X-ray incident angle is small, the X-ray is often reflected by the sample.
[0006]
Conventionally, in the industry, it has been common to perform a measurement using a dedicated measuring device for thermal analysis and to perform a measurement using a dedicated measuring device for X-ray measurement. However, although there are few examples, there is also proposed one in which both thermal analysis and X-ray measurement are performed by one measuring device. For example, as shown in FIGS. 5 and 6, a sample 53 and a standard material 54 are arranged inside a cylindrical heater 51 or 52, and both the sample 53 and the standard material 54 are heated by the heaters 51 and 52. An apparatus is known in which X-ray measurement is performed by irradiating the sample 53 with X-rays R, while thermal analysis is performed by detecting the temperatures of the sample 53 and the standard material 54 with a thermocouple 55.
[0007]
[Problems to be solved by the invention]
However, in the conventional thermal analysis and X-ray measurement apparatus as shown in FIG. 5 and FIG. 6, it was not possible to perform measurement related to a temperature of 0 ° C. or less or measurement to rapidly heat and cool the sample temperature. . Also, as shown in FIG. 5, when the heater 51 having a high height is used, there is a problem that the X-ray R cannot be incident on the sample 53 at a low angle. On the other hand, when the heater 52 having a low height as shown in FIG. 6 is used, the X-ray R can be incident on the sample 53 from a low angle, but the temperature distribution in the sample chamber H by the heater 52 is extremely high. The problem of getting worse occurs.
[0008]
The present invention has been made to solve the above-described problems, and when both the thermal analysis and the X-ray measurement are performed by one measuring device, the sample can be heated with a uniform temperature distribution, Moreover, a first object is to allow X-rays to enter the sample from a low angle.
[0009]
Further, when both the thermal analysis and the X-ray measurement are performed by a single measuring device, it is possible to perform a measurement related to a temperature of 0 ° C. or less and a measurement that rapidly heats and cools the sample temperature. This is the second purpose.
[0010]
[Means for Solving the Problems]
In order to achieve the second object, the thermal analysis and X-ray measurement apparatus according to the present invention includes a thermal analysis measurement for measuring the temperature dependence of the property of the sample when the temperature of the sample is changed, In a thermal analysis and X-ray measuring apparatus capable of performing both X-ray measurement by irradiating X-rays and detecting X-rays diffracted or reflected by the sample and measuring the properties of the sample, a block member A sample chamber formed by a concave portion of the substrate and a cover that covers the concave portion and allows X-rays to pass therethrough, a sample heating means for heating the sample disposed in the sample chamber, and a sample disposed in the sample chamber Sample cooling means for cooling the sample cooling means, the sample cooling means having a refrigerant tank formed in a cylindrical shape in the block member so as to surround the sample chamber and storing or flowing a cryogen. Features and That.
[0011]
In order to achieve the first object, in the thermal analysis and X-ray measurement apparatus according to the present invention, the sample heating means is behind the X-ray irradiation surface of the sample and is in contact with or close to the sample. It is desirable to provide a heater at the position.
[0012]
The configuration of the sample cooling means is not limited to a specific one. Desirably, a refrigerant tank is provided around the sample, and liquid nitrogen is stored in the refrigerant tank. Further, Ru can also be caused to flow through the liquid nitrogen other cryogen in the refrigerant tank.
[0013]
In the thermal analysis and X-ray measurement apparatus having a configuration in which a heater is provided on the back side of the X-ray irradiation surface of the sample and in contact with or close to the sample, a cylindrical heater having a low height as shown in FIG. 6 is used. Compared to the conventional apparatus, the sample can be heated with a uniform temperature distribution, and moreover, X-rays to the sample are compared with the conventional apparatus using a cylindrical heater having a high height as shown in FIG. The incident angle can be widened to the low angle side. That is, it is possible to simultaneously satisfy both the requirements of maintaining a wide angle measurement range in X-ray measurement and maintaining a uniform temperature distribution of the sample.
[0014]
In a thermal analysis and X-ray measurement apparatus having a structure including both a sample heating unit and a sample cooling unit, a sample heating unit is used when the sample is to be heated to a high temperature, and a sample cooling unit is used when the sample is to be 0 ° C. or lower. When it is desired to rapidly cool the sample temperature from a high temperature, both the sample heating means and the sample cooling means are used.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
(First embodiment)
FIG. 1 shows an embodiment of a thermal analysis and X-ray measurement apparatus according to the present invention. This apparatus includes a cylindrical block member 2, a concave sample chamber H formed at the center of the block member 2, an arc-shaped cover 6 that covers the upper portion of the sample chamber H in an airtight manner, and around the sample chamber H And a ring-shaped refrigerant tank 7 formed inside the block member 2 so as to surround the.
[0016]
Inside the sample chamber H, two support bars 8a and 8b are erected, and sample dishes 9a and 9b are provided at the upper ends of the support bars. The sample 3 is placed on one sample tray 9a, and the standard substance 4 is placed on the other sample tray 9b. As the standard substance 4, a material that does not change its properties even when the temperature changes, that is, a thermally stable material is used. A heater 1a is provided directly below the sample 3, that is, on the back side of the X-ray irradiation surface of the sample 3 and in contact with or close to the sample 3 in two upper and lower stages. Further, a heater 1b is also provided directly below the standard material 4 in two upper and lower stages.
[0017]
As shown in FIG. 2, the cover 6 is formed in a rectangular shape when viewed from above, and an X-ray transmission window 10 is provided at the center thereof. When the inside of the sample chamber H rises only to a relatively low temperature, for example, about 500 ° C., the cover 6 is formed of, for example, stainless steel or brass. When the sample chamber H rises to a relatively high temperature, for example, about 1500 ° C., the cover 6 is formed of alumina, for example. The X-ray transmission window 10 is formed of a material that can maintain hermeticity and can transmit X-rays, such as beryllium (Be) or nickel.
[0018]
In FIG. 1, a coolant such as liquefied nitrogen (LN ₂ ) is stored in the refrigerant tank 7. Thermocouples 5a and 5b having temperature measurement points on the bottom surface of the sample 3 and the bottom surface of the standard material 4 are stored in the support rods 8a and 8b, respectively.
[0019]
An X-ray measurement system 11 is disposed above the sample support system, and a thermal analysis system 12 is disposed below the X-ray measurement system 11. In the case of the present embodiment, the X-ray measurement system 11 is configured by a θ-θ scanning type X-ray diffraction apparatus, and the thermal analysis system 12 is configured by a differential scanning calorimetry (DSC) apparatus. More specifically, the X-ray measurement system 11 includes an X-ray source F, an X-ray counter 13, an X-ray intensity calculation circuit 14, and an X-ray diffraction recorder 15. The thermal analysis system 12 includes a T and ΔT measurement circuit 16, a calorific value compensation circuit 17, and a thermal analysis recorder 18.
[0020]
Hereinafter, the operation of the thermal analysis and X-ray measurement apparatus configured as described above will be described. The inside of the sample chamber H is cooled with a constant cooling capacity by LN ₂ in the refrigerant tank 7. At the same time, the sample 3 and the standard material 4 are heated to the same temperature by the corresponding heaters 1a and 1b. Since the heaters 1a and 1b are provided in contact with or in close proximity to the sample 3 and the standard material 4, respectively, the sample 3 and the standard material 4 are uniformly heated over their entire area to raise the temperature uniformly. The temperature rise and temperature drop state in the sample chamber H is controlled according to a program stored in advance in the heat quantity compensation circuit 17 that also serves as a temperature controller. Since the cooling means using LN ₂ is installed, the inside of the sample chamber H can be set to 0 ° C. or less, and the set high temperature can be rapidly cooled.
[0021]
As described below, the X-ray diffraction measurement by the X-ray diffraction measurement system 11 and the differential scanning calorimetry (DSC) by the thermal analysis system 12 are performed in the state where the temperature of the sample 3 and the standard substance 4 is controlled as described below.
[0022]
(X-ray diffraction measurement)
The X-ray source F scans and rotates in the vertical direction in the figure (so-called θ rotation) around the sample 3 and the X-ray counter 13 scans and rotates around the sample 3 in the opposite direction at the same speed (so-called θ rotation). Rotate. During these θ rotations, the X-ray R emitted from the X-ray source F enters the sample 3. Although not shown, if necessary, a divergence regulating slit for regulating the divergence of X-ray R on the X-ray optical path from the X-ray source F to the sample 3, a monochromator for monochromatic continuous X-rays, etc. Is disposed.
[0023]
When a known Bragg condition is satisfied between the X-ray incident on the sample 3 and the crystal lattice plane of the sample 3, the X-ray is diffracted by the sample 3. The diffracted X-ray is taken into the X-ray counter 13, converted into an electrical pulse signal and output, and the output pulse is sent to the X-ray intensity calculation circuit 14. Although not shown, if necessary, a scattered radiation blocking slit for preventing scattered X-rays from entering the X-ray counter 13 or an X-ray counter 13 between the X-ray counter 13 and the sample 3 may be provided. A light receiving slit or the like for restricting the cross-sectional shape of the diffracted X-rays to a certain size is provided.
[0024]
The X-ray intensity calculation circuit 14 calculates the X-ray intensity, that is, the number of output pulses (cps) per unit time, and sends the result to the recorder 15. The recorder 15 calculates the rotation angle of the X-ray counter 13 with respect to the incident X-ray R, that is, the diffracted X-ray intensity with respect to the 2θ angle value, and creates a known X-ray diffraction pattern. By examining this X-ray diffraction pattern, identification of substances constituting the sample 3, determination of the crystal structure, and various other analyzes are performed.
[0025]
(Differential scanning calorimetry)
The surface temperature of the sample 3 detected by the thermocouple 5 a and the surface temperature of the standard material 4 detected by the thermocouple 5 b are sent to the T and ΔT measurement circuit 16. The measurement circuit 16 measures the temperature (T) of the sample 3 and the standard material 4 and simultaneously calculates the difference (ΔT) between them. The calculation result is sent to the heat compensation circuit 17. The calorific value compensation circuit 17 adjusts the energization amount to either the sample side heater 1a or the standard material side heater 1b so that when ΔT is not 0 (zero) and ΔT = 0, Sometimes measure the amount of heat supplied. Thereby, a change in the amount of heat generated in the sample 3 is detected. The thermal analysis recorder 18 obtains the relationship between the sample temperature (T) and the change in the amount of heat generated in the sample and displays it on the graph. By examining this graph, the physical properties of the sample 3, such as the temperature dependence of the transition point and melting point, are measured.
[0026]
As described above, according to the thermal analysis and X-ray measurement apparatus of the present embodiment, two types of measurement of X-ray measurement and thermal analysis can be simultaneously performed on one sample 3.
[0027]
(Second Embodiment)
FIG. 4 shows another embodiment of the thermal analysis and X-ray measurement apparatus according to the present invention. This thermal analysis and X-ray measurement apparatus is different from the apparatus shown in FIG. 1 in that a differential thermal analysis (DTA) apparatus is used as the thermal analysis system 22 instead of the differential scanning calorimetry (DSC) apparatus. .
[0028]
This DTA apparatus has a T and ΔT measurement circuit 16, a thermal analysis recorder 18, and a temperature controller 27. The temperature controller 27 controls energization to the sample side heater 1a and the standard material side heater 1b according to a predetermined program. The thermal analysis recorder 18 obtains the relationship between the temperature difference (ΔT) between the sample 3 and the standard material 4 and the temperature change (T) of the sample 3 and displays it on the graph.
[0029]
The present invention has been described with reference to the preferred embodiments. However, the present invention is not limited to the embodiments, and various modifications can be made within the technical scope described in the claims.
For example, instead of storing LN ₂ in the refrigerant tank 7, it is possible to always pass the refrigerant tank 7 through it. As shown in FIG. 3, instead of the refrigerant tank 7, a spiral refrigerant pipe 19 as viewed from above is arranged around the sample chamber H and is introduced from the upper end suction port 20 of the refrigerant pipe 19. ₂ may be discharged from the lower end discharge port 21.
[0030]
As the thermal analysis system, any thermal analysis system other than the DSC and DTA exemplified in the above description can be applied. As the X-ray measurement system, in addition to the X-ray diffractometer exemplified in the above description, any other X-ray apparatus such as an X-ray reflectivity measurement apparatus or a fluorescent X-ray apparatus can be applied.
[0031]
【The invention's effect】
According to the thermal analysis and X-ray measurement apparatus according to the present invention, when both the thermal analysis and the X-ray measurement are performed by one measurement apparatus, the measurement relating to the temperature of 0 ° C. or lower and the sample temperature are rapidly heated. Measurements such as cooling can be performed.
[0032]
Oite thermal analysis and X-ray measuring apparatus according to the present invention, there is provided a back side of the X-ray irradiation surface of the sample that the to lever providing a heater at a position in contact with or in proximity to the sample, the sample uniform temperature distribution And X-rays can be incident on the sample from a low angle. In other words, it is possible to simultaneously satisfy the two requirements, that is, the requirement to uniformly heat the sample and the requirement to maintain a wide angle measurement range of the X-ray apparatus.
[0033]
In particular, Oite thermal analysis and X-ray measuring apparatus according to the present invention, there is provided a back side of the X-ray irradiation surface of the sample that the to lever providing a heater at a position in contact with or in proximity to the sample, uniform heating of the sample All the requirements such as expansion of the angle range of the X-ray apparatus, measurement of sample temperature below 0 ° C., and rapid heating or cooling of the sample temperature can be satisfied.
[0034]
According to the thermal analysis and X-ray measurement apparatus according to the present invention, the sample can be efficiently cooled with a simple structure.
[0035]
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an embodiment of a thermal analysis and X-ray measurement apparatus according to the present invention.
FIG. 2 is a plan view of the thermal analysis and X-ray measurement apparatus.
FIG. 3 is a cross-sectional view showing another embodiment of the thermal analysis and X-ray measurement apparatus according to the present invention.
FIG. 4 is a cross-sectional view showing still another embodiment of a thermal analysis and X-ray measurement apparatus according to the present invention.
FIG. 5 is a cross-sectional view showing an example of a conventional thermal analysis and X-ray measurement apparatus.
FIG. 6 is a cross-sectional view showing another example of a conventional thermal analysis and X-ray measurement apparatus.
[Explanation of symbols]
1a, 1b Heater 2 Block member 3 Sample 4 Reference materials 5a, 5b Thermocouple 6 Cover 7 Refrigerant tanks 8a, 8b Support rods 9a, 9b Sample pan 10 X-ray transmission window 11 X-ray measurement system 12 Thermal analysis system 13 X-ray counter 19 Refrigerant pipe 22 Thermal analysis system R X-ray H Sample chamber F X-ray source

Claims (3)

Thermal analysis measurement that measures the temperature dependence of the properties of the sample when the temperature of the sample is changed, and the properties of the sample by irradiating the sample with X-rays and detecting X-rays that are diffracted or reflected by the sample In the thermal analysis and X-ray measurement apparatus capable of performing both the X-ray measurement and the X-ray measurement,
A sample chamber formed by a recess of the block member and a cover that covers the recess and allows X-rays to pass through;
Sample heating means for heating the sample disposed in the sample chamber ;
Possess the sample cooling means for cooling the placed sample into the sample chamber,
The thermal analysis and X-ray measurement characterized in that the sample cooling means has a refrigerant tank that is formed in a cylindrical shape in the block member so as to surround the sample chamber and that stores or flows a cryogen. apparatus. 2. The thermal analysis and X-ray measurement apparatus according to claim 1, wherein the sample heating means is provided with a heater on the back side of the X-ray irradiation surface of the sample and in contact with or close to the sample. Thermal analysis and X-ray measurement equipment. In the thermal analysis and X-ray measurement apparatus according to claim 1 or 2,
A sample pan for a measurement sample disposed in the sample chamber for placing a measurement sample;
A standard substance sample pan placed in the sample chamber for placing a standard substance,
The thermal analysis and X-ray measurement apparatus characterized in that the surface of the sample pan for measurement sample and the surface of the sample pan for standard material are arranged on the same plane .

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