JP2001041828A - Temperature measuring device and measuring method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable measuring more accurately temperature change due to heat of a sample to be measured. SOLUTION: Metal (conductive member for measurement) 58c and a printed coil 59 for measurement are arranged at prescribed positions via a quartz cell 56 for measurement which has a high thermal resistance. The temperature change caused by the change of state of the sample which is accommodated in the quartz cell 56 is measured by using an eddy current generated in the metal 58c. Thereby temperature change due to heat of a plurality of samples can be measured more accurately. As a result, a desired sample can be more quickly selected out of the plurality of samples to be measured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a temperature measuring apparatus and a measuring method using the same, and more particularly, to a method of measuring a temperature change or a resistance change of a plurality of samples with good responsiveness and more accurately. The present invention relates to a temperature measurement device and a measurement method using the same.

[0002]

2. Description of the Related Art As one of new techniques for synthesizing a sample (substance), there is a technique called "combinatorial synthesis technique". The “combinatorial synthesis method” is, as the name implies, a method of synthesizing many samples (substances) at a time and searching for a desired sample. This is a technique devised for the development of new drugs that have subtle differences such as those that affect bioactivity.

[0003] The "combinatorial synthesis technique" is also applied to the search for superconducting materials and the like. FIG. 1 shows an example of a “combinatorial synthesis method” of an inorganic material. In the example of FIG. 1, the first to fourth laminated films 2 to 5 are formed on the substrate 1 by vapor deposition or sputtering, and a sample (substance) is synthesized.

A plurality of evaporation sources or sputtering
Different samples (substances) one after another using a ring target
When deposition is performed on a predetermined area on the substrate 1,
By covering with a mask and removing the mask, each layer
Multilayer films with different combinations of materials are formed separately.
You. Generally, if a two-divided mask is used, two steps are required in P steps.
^PDifferent types of laminated films can be produced. Also, substrate 1
By controlling the thickness of the laminated film deposited on the
The composition ratio of the constituent materials can also be changed. Generated product
The layer film is subjected to a heat treatment after the film formation to finish the film uniformly.

In the example shown in FIG. 1, a sample A is
A sample B is deposited on the second laminated film 3, a sample C is deposited on the third laminated film 4, and a sample D is deposited on the fourth laminated film 5. , A sample BD is generated, and a sample ABCD is generated in the region 8.

Consider a case in which a sample having the largest amount of gas (for example, methane gas) adsorbed therein is searched from among the generated samples. As a method of measuring the gas adsorption amount of the sample, a method of calculating the gas adsorption amount based on the decrease amount of the pressure in the container (hereinafter, referred to as a first measurement method) and a method of measuring the increase amount of the sample weight (Hereinafter referred to as a second measurement method) has been established.

FIG. 2 is a diagram for explaining the first measuring method. In the first measurement method, first, a gas 13 (for example, methane gas or the like) is sealed in the container 11. In this state, the pressure in the container 11 is measured by the pressure gauge 14. Next, the evaluation sample 12 is placed in the container 11. In this state, the pressure in the container 11 is measured again by the pressure gauge 14, and the evaluation sample 1 is determined based on the amount of decrease in the pressure in the container 11.
The amount of adsorption of the gas 13 to 2 is calculated.

FIG. 3 is a diagram for explaining the second measuring method. In the second measuring method, first, the weight of the evaluation sample 22 in the container 21 is measured by the weighing scale 23.
Next, the gas 24 (for example, methane gas or the like) is placed in the container 21.
, And after a predetermined time has passed, the evaluation sample 2
2 is measured by the weighing scale 23. Then, based on the increase in the weight of the evaluation sample 22, the amount of adsorption of the gas 24 to the evaluation sample 22 is calculated.

As a method of measuring the gas adsorption amount of a sample,
In addition to the first and second measurement methods, for example, there is a method of measuring the heat of gas adsorption of a sample. As an apparatus used for measuring the heat of gas adsorption of a sample, there is, for example, a gas adsorption heat measuring apparatus disclosed in Japanese Patent Application Laid-Open No. 50-15595.

FIG. 4 shows this gas adsorption heat measuring apparatus. The constant temperature body 31 is made of, for example, a metal block, and a gas storage container 32 for temporarily storing a gas 39 and a reference sample container 33 for containing a reference sample are provided in a hole 31 a of the constant temperature body. , A measurement sample container 34 for containing a measurement sample 36, semiconductor thermoelectric elements 37 and 38 for detecting heat and converting the detected heat to voltage, and a glass tube 4.
0 is arranged. The hole 31a of the constant temperature body is
Sealed.

Next, a method of measuring the heat of gas adsorption will be described with reference to FIG. First, the measurement sample container 34
The valves B ₁ , B ₂ and B ₄ are opened without putting the reference sample in the reference sample container 33 and the valve B _3.
With the closed, the vacuum pump 43 is operated to evacuate the gas storage container 32, the reference sample container 33, the measurement sample container 34, and the glass tube 40.

Thereafter, the valve B ₄ is closed and the vacuum pump 4
3 was stopped, further closing the valve B _1, opening the valve B ₃ while opening the valve B _2, by supplying the gas 39 from the gas supply tank 42 to the gas container 32, a gas container 32
Gas 39 is temporarily stored inside.

Next, the valves B ₂ and B ₃ are closed, and the valve B
Open ₁ to supply gas 39 in gas storage container 32 to reference sample container 33 and measurement sample container 34. At this time, since the reference sample container 33 and the measurement sample container 34 are in a vacuum state, the gas 39 is sucked from the gas storage container 32 having a high pressure.

[0014] measured from the time you open the valve B ₁ sample 36
Gas adsorption begins, generating heat. The generated heat is converted into a voltage by the thermoelectric elements 37 and 38 and output from the detection terminals 45 and 46. Then, a temperature difference (ΔT) -time curve is created from a difference (ΔV) between the voltage V ₁ output from the detection terminal 45 and the voltage V ₂ output from the detection terminal 46, and the created temperature difference-time curve Is used to calculate the heat of gas adsorption.

[0015]

However, in the first and second measurement methods described above, detailed physical properties can be measured. However, since a single measurement time is long, when a plurality of samples exist. However, there is a problem that the measurement time is further increased.

Further, in the above-mentioned gas adsorption heat measuring apparatus, since the thermoelectric element is brought into direct contact with the sample container, if the sample does not have a certain heat capacity, the escape of heat to the thermoelectric element becomes large, and accurate There was a problem that it was not possible to measure a large thermal change.

Further, in the above-mentioned gas adsorption heat measuring apparatus,
Since the thermoelectric element is directly in contact with the sample container, an error occurs in the measurement depending on the degree of contact of the thermoelectric element, and there has been a problem that the heat of gas adsorption cannot be measured accurately.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a temperature measuring device and a measuring method using the same, which are capable of measuring the temperature change of a plurality of samples due to heat in a shorter time and more accurately. It is in.

[0019]

In order to achieve the above object, one aspect of the present invention is to store a measurement sample and a conductive member for measurement in a measurement container having a high thermal resistance. An electric current is applied to a measuring coil provided outside the container. This allows
A change in magnetic flux occurs in the measurement coil, and an eddy current is generated in the measurement conductive member. For example, since the resistance value of the conductive member for measurement changes according to the heat generated by the change in the state of the measurement sample, the magnitude of the eddy current also changes according to the calorific value of the measurement sample. The change of the eddy current flowing through the measuring coil at this time is detected. As a result, the escape of heat from the measurement sample can be reduced, and a temperature change due to heat generation of the measurement sample can be measured more accurately.

In order to achieve the above object, a temperature measuring apparatus according to the present invention comprises a measuring container having a high thermal resistance for accommodating a measuring sample and a measuring conductive member in which an eddy current is generated. A measuring coil that is provided outside the container and in the vicinity of the measuring conductive member and that generates a predetermined magnetic field.

According to the present invention, the escape of heat to the measuring coil can be reduced, and the temperature change and the resistance change due to the heat generation due to the change in the state of the measurement sample can be measured more accurately.

In order to achieve the above object, a temperature measuring apparatus according to the present invention comprises: a measuring container for storing a conductive measuring sample having a high thermal resistance; A measurement coil provided in the vicinity of the sample and generating a predetermined magnetic field.

According to the present invention, a change in temperature and a change in resistance due to a change in the state of the conductive measurement sample can be more accurately measured through a change in eddy current generated in the measurement sample.

In order to achieve the above object, a temperature measuring apparatus according to the present invention comprises a reference container having a high thermal resistance for accommodating a reference conductive member in which an eddy current is generated, and a reference container outside the reference container. There is provided in the vicinity of the reference conductive member,
A reference coil for generating a predetermined magnetic field, wherein a temperature of the measurement sample is measured by a differential component of signals output from the measurement coil and the reference coil.

According to the present invention, a temperature change due to heat generation accompanying a change in the state of a measurement sample is determined by using a differential signal.
It can measure more accurately.

In order to achieve the above object, the temperature measuring apparatus of the present invention is characterized in that there are a plurality of sets of the measuring container and the measuring coil.

According to the present invention, a temperature change or a resistance change due to heat of a plurality of measurement samples due to heat can be measured more efficiently.

In order to achieve the above object, a temperature measuring apparatus according to the present invention comprises a plurality of cells for accommodating a sample and a conductive member in which an eddy current is generated. And a sensor array provided outside the cell of the storage section and at a position corresponding to the cell and formed with a plurality of measurement coils for generating a predetermined magnetic field.

According to the present invention, a change in temperature and a change in resistance due to heat generation due to a change in the state of a plurality of measurement samples can be measured more efficiently.

In order to achieve the above object, a temperature measuring apparatus according to the present invention comprises: a storage section having a plurality of cells for storing a conductive sample; And a sensor array provided at a position corresponding to the cell and formed with a plurality of measurement coils for generating a predetermined magnetic field.

According to the present invention, a temperature change and a resistance change due to a state change of a plurality of conductive samples can be measured more efficiently through a change in eddy current generated in the measurement sample.

To achieve the above object, the method for measuring the amount of heat of adsorption and desorption according to the present invention comprises placing the sample in an atmosphere in which a substance is adsorbed or desorbed on the sample by using any one of the above temperature measuring devices. And measuring a temperature change caused by the substance being adsorbed or desorbed on the sample by the measurement coil.

According to the present invention, a temperature change caused by the adsorption or desorption of a substance on a sample can be measured more accurately.

In order to achieve the above object, a method for measuring the transition calorimetry according to the present invention comprises heating the sample using any one of the temperature measuring devices described above and causing the sample to undergo a transition (chemical change).
The temperature change due to this is measured by the measuring coil.

According to the present invention, a temperature change accompanying a transition (chemical change) of a sample can be measured more accurately.

In order to achieve the above object, according to the reaction calorimetry method of the present invention, the sample is reacted with a predetermined substance using any one of the above temperature measuring devices, and the sample undergoes a chemical change. The temperature change associated with the measurement is measured by the measurement coil.

According to the present invention, a temperature change caused by a chemical change of a sample can be measured more accurately.

In order to achieve the above object, a method for measuring the phase transition calorimetry according to the present invention comprises the steps of: The change is measured by the measurement coil.

According to the present invention, a temperature change caused by a phase transition of a sample can be measured more accurately.

In order to achieve the above object, a resistance measuring method according to the present invention is characterized in that the conductivity measuring sample is pressurized by using the temperature measuring device, and the conductivity measuring sample undergoes a phase transition. The resistance change is measured by the measurement coil.

According to the present invention, it is possible to more accurately measure a resistance change caused by a phase transition of a conductive measurement sample.

In order to achieve the above object, another temperature measuring apparatus according to the present invention comprises a sample forming member having a high thermal resistance and having a plurality of regions where catalysts or samples are grown separated from each other; And a measurement coil, which is provided on the opposite side of the growth region and in the vicinity of the sample forming member and generates a predetermined magnetic field.

According to the present invention, it is possible to more accurately and efficiently measure a temperature change and a resistance change due to heat generation accompanying a change in the state of a plurality of samples.

In order to achieve the above object, a method for measuring the amount of heat of adsorption and desorption according to the present invention comprises forming a catalytic metal layer on the plurality of regions by using the temperature measuring device, and forming the catalytic metal layer on the catalytic metal layer. Growing a sample having a corresponding composition, placing the sample in an atmosphere in which a substance is adsorbed or desorbed on the sample, and measuring a temperature change caused by the adsorption or desorption of the substance on the sample by the measurement coil. It is characterized by.

According to the present invention, a temperature change caused by the adsorption or desorption of a substance on a sample can be measured more accurately and efficiently.

In order to achieve the above object, a resistance measuring method according to the present invention comprises the steps of: growing a conductive sample on the plurality of regions by using the temperature measuring device; The resistance change caused by the phase transition of the conductive sample is measured by the measurement coil.

According to the present invention, it is possible to more accurately and efficiently measure a resistance change caused by a phase transition of a conductive sample.

[0048]

Embodiments of the present invention will be described below with reference to the drawings. However, such embodiments do not limit the technical scope of the present invention.

FIG. 5 shows a configuration of an embodiment of a temperature measuring apparatus to which the present invention is applied. In the example of FIG. 5, the temperature change when the water vapor 54b is adsorbed on the measurement sample (coconut shell activated carbon) 57 or the reference sample 61 and the temperature change when the water vapor 54b is desorbed from the measurement sample (coconut shell activated carbon) 57 or the reference sample 61 are shown. Measure the temperature change.

For example, a quartz cell container 56 for measurement is attached to a member 51 a inside a container 51 made of an acrylic resin via a printed coil 59. Further, a quartz cell container 60 for reference is attached to the member 51 a via a printed coil 63.

The structure of the quartz cell container 56 for measurement and the quartz cell container 60 for reference will be described with reference to FIG.
FIG. 6A shows the structure of a reference quartz cell container 60, and FIG.
(B) shows the structure of the quartz cell container 56 for measurement.
Metal (aluminum) 62a and 62b are coated on the inner side surface of the reference quartz cell container 60, and metal (aluminum) 62c is coated as a conductive material on the lower surface inside the reference quartz cell container 60. Have been. The reference sample 61 or nothing is appropriately introduced into the reference quartz cell container 60. In this example,
Nothing is introduced. A print coil 63 for detecting a temperature change of the reference sample 61 is disposed at a lower portion outside the quartz cell container 60 for reference.

On the other hand, metals (aluminum) 58a and 58b are coated on the inner side surface of the quartz cell container 56 for measurement, and metal (aluminum) 58a is coated on the lower surface inside the quartz cell container 56 for measurement as a conductive material. Aluminum) 58c. A measurement sample 57 (for example, coconut shell activated carbon) is introduced into the quartz cell container 56 for measurement. A measurement sample 57 is provided at the lower portion outside the quartz cell container 56 for measurement.
A print coil 59 for detecting a change in temperature of the print coil is disposed.

Returning to FIG. 5, a reference print coil output signal I ₃ is output from the detection terminal 68, and a measurement print coil output signal I ₄ is output from the detection terminal 69.
The container 53 stores water 54a for supplying the water vapor 54b to the container 51. The stainless tube 55 is
A valve B _{6 to a} valve B ₈ are provided at a predetermined position of the stainless steel pipe 55, which is a passage for supplying the steam 54 b from the container 3 to the container 51.

Next, the reason why water vapor is used as a gas will be described below. For example, when a gas is introduced into the container 51 and the inside of the container 51 is changed from a vacuum state to an atmospheric pressure state, the temperature of the atmosphere in the container 51 increases due to adiabatic compression. In this case, it is difficult to distinguish between a temperature rise due to adiabatic compression and a temperature rise due to heat of adsorption.

By the way, the vapor pressure of water vapor is determined by the temperature, and is 2660 to 3990 at room temperature (30 ° C.).
It has only a vapor pressure of Pa. Therefore, when steam is introduced into the container 51, the temperature rise due to adiabatic compression can be suppressed lower than that of other gases, and the temperature change due to the heat of adsorption can be measured more accurately. In addition, since the amount of water vapor adsorbed on a sample is larger than that of a gas such as the atmosphere and the amount of generated heat of adsorption is large, it is easy to detect a temperature change due to heat of adsorption. In general, a sample having a large amount of adsorbed water vapor is judged to have a high utility value as an adsorbent.

Next, a method for measuring the heat of adsorption and desorption of water vapor in the temperature measuring device of FIG. 5 will be described. First,
The valves B ₆ and B ₈ are opened, and the container 5 is opened by the vacuum pump 52.
The 1 was evacuated, outputs a measurement printed coil output signal I ₄ is the measuring printed coil 59 is confirmed to stabilize. Then, the measurement print coil output signal I ₄
When is stabilized, the valves B ₆ and B ₈ are closed, and the evacuation by the vacuum pump 52 ends.

Next, the valves B ₆ and B ₇ are opened, and steam 5
4b is introduced into the container 51 from the container 53 via the glass tube 55. Adsorption of water vapor is started from the time when the water vapor 54b is introduced into the container 51. When the measurement print coil output signal I ₄ becomes stable, the valves B ₆ and B ₇ are closed, and the introduction of the water vapor 54b is terminated.

Next, the valves B ₆ and B ₈ are opened, and the evacuation of the vessel 51 is started by the vacuum pump 52. At this point, the desorption of steam starts. When the measurement print coil output signal I ₄ is stabilized, the valves B ₆ and B ₈ are closed, the evacuation by the vacuum pump 52 is stopped, and the temperature measurement ends.

FIG. 7 shows the measurement results obtained by the above-described measurement method. FIG. 7 shows a print coil 5 for measurement when coconut shell activated carbon is used as the measurement sample 57 (when there is an adsorbent).
9 shows an example of the output characteristic of No. 9. For evaluation of measurement accuracy, a thermocouple (not shown) is brought into contact with the measurement sample 57 to detect the internal temperature of the measurement sample 57. The vertical axis of FIG. 7 represents normalized temperature data, and the horizontal axis of FIG. 7 represents time. In the figure, a curve C ₁ shows the output characteristics of the thermocouple, and a curve C ₂ shows the output characteristics of the measurement print coil 59.

During the evacuation time T ₁ , the container 51 is evacuated by the vacuum pump 52. Then, in the subsequent steam introduction time T ₂ , the steam 5
4b is being introduced. That is, the adsorption of the water vapor 54b is performed. At the water vapor introduction time T ₂ , the temperature of the measurement sample 57, which is the adsorbent, is rapidly rising because the water vapor 54b is adsorbed to generate heat of adsorption. However, since the heat of adsorption is gradually released, the temperature decreases and eventually becomes constant.

During the evacuation time T ₃ , evacuation is performed by the vacuum pump 52 after the introduction of the water vapor 54b. That is, the desorption of the steam 54b is performed. In evacuation time T _3, the temperature is rapidly lowered by heat of desorption of water vapor 54b. Thereafter, the heat of desorption is gradually released, the temperature has become equivalent to when stabilized with water vapor introduction time T _2.

As shown in FIG. 7, the output curve C ₂ of the measurement print coil 59 is delayed by a delay time T _D1 from the output curve C ₁ of the thermocouple at the rising edge, and the output of the thermocouple at the falling edge. although later than the curve C ₁ only delay time T _D2, shows a very good agreement with the output curve C ₁ thermocouple. Therefore, according to FIG.
It is understood that the heat of adsorption and the heat of desorption of the water vapor 54b can be accurately measured using the measurement print coil 59.

FIG. 8 shows an example of the output characteristics of the thermocouple and the measurement print coil 59 when there is no measurement sample 57 (when there is no adsorbent). The thermocouple here is
The internal temperature of the quartz cell for measurement 56 is detected. The vertical axis of FIG. 8 represents normalized temperature data, and the horizontal axis of FIG. 8 represents time. In the figure, a curve C ₃ represents the output characteristics of the thermocouple, and a curve C ₄
Indicates the output characteristics of the print coil 59 for measurement.

At the steam introduction time T ₄ , the steam 54 b is introduced into the vessel 51, and the temperature slightly increases due to adiabatic compression. As shown in FIG. 8, the output curve C ₄ of the measuring printed coil 59 is in very good agreement with the output curve C ₃ thermocouples. Therefore, it is possible to accurately measure the temperature rise due to adiabatic compression by using the measurement print coil 59.

Since the temperature change due to the heat of adsorption and the temperature change due to the adiabatic compression can be distinguished to some extent from the output characteristics shown in FIGS.
Can be said to be very reliable.

Next, the principle of measuring the above-mentioned temperature change due to the heat of adsorption by the measurement print coil 59 will be described with reference to FIG. FIG. 9 is a diagram for explaining the principle of temperature measurement using eddy current in the present embodiment. Measurement sample and metal not shown (conductive member for measurement)
The reference numeral 58c and the measurement print coil 59 are arranged at predetermined positions via a measurement quartz cell 56 having a high thermal resistance. The measurement print coil 59 includes a high-frequency power source 7.
1 and the resistor 72 are connected to form a drive circuit.
The detection signal amplifier 73 amplifies and outputs a signal detected at both ends of the resistor 72.

Now, when a high-frequency excitation current i flows from the high-frequency power supply 71 to the measurement print coil 59, an alternating magnetic flux f is generated. This change in the magnetic flux f generates an eddy current i _e the metal 58c provided in close proximity to the measuring printed coil 59. Flux f _s is generated by the eddy currents i _e.
Flux f _s that have occurred by eddy currents i _e generates a current i _s in measuring the printed coil 59.

Incidentally, the metal (conductive member for measurement) 58c
The magnitude of the eddy currents i _e which is generated, the magnitude and degree of change in the magnetic flux f through the metal 58c, and depends on the resistance of the metal 58c. The magnitude of the magnetic flux f passing through the metal (conductive member for measurement) 58c depends on the magnitude of the exciting current i applied to the print coil 59 for measurement, the size of the gap between the print coil 59 for measurement and the metal 58c, and the like. I do. Also,
The resistance value of the metal (conductive member for measurement) 58c changes depending on the temperature of the metal 58c that changes with the temperature change of the sample in the quartz cell 56 (not shown).

Therefore, the metal (conductive member for measurement) 58c
Generated eddy current i_eIs the magnitude of the magnetic flux passing through the metal 58c.
If the magnitude of f is constant, it depends on the temperature of the metal 58c.
Eddy current i_eCaused by
Magnetic flux f_sAnd this magnetic flux f_sBy measurement for print carp
Current i generated in_sAlso depends on the temperature of the metal 58c
Will change. Therefore, the measurement print coil 5
Output current i flowing through 9 _sBy measuring the change in
Temperature change of metal 58c due to the change of temperature
You.

Further, since the contactless heat is transmitted through the high thermal resistance, the heat change due to the sample does not leak to the print coil 59 for measuring the temperature, and the heat change can be accurately measured. In addition, since the measuring conductive member 58c only needs to generate an eddy current, the heat capacity can be reduced.

Next, the use of the temperature measuring device shown in FIG. 5 will be described. The temperature measuring device shown in FIG. 5 is used not only for measuring a temperature change due to heat of adsorption and desorption but also for measuring a temperature change due to heat of transition, heat of reaction, heat of phase transition, and the like. The heat of transition is the heat generated when heat is applied to a sample to cause transition. The heat of reaction is the heat generated when a sample is reacted with a predetermined substance to cause a chemical change. The phase transition heat is heat generated when pressure is applied to a sample and the structure of the sample changes (phase transition).

In the temperature measuring apparatus shown in FIG. 5, a metal (aluminum) 58c is provided in the quartz cell 56 for measurement. However, if the measurement sample 57 is conductive, the metal (aluminum) 58c is required. Not done. As an application of the temperature measuring device when the conductivity measurement sample is used, for example, measurement of a resistance change due to a phase transition of the sample can be considered. That is,
When pressure is applied to the conductivity measurement sample to cause a phase transition,
The resistance of the conductivity measurement sample itself changes. This resistance change can be measured by the print coil 59.

Next, a description will be given, with reference to FIG. 10, of an array-like storage section 81 and a sensor array 82 capable of simultaneously measuring temperature changes of a plurality of samples due to heat. FIG. 10 shows an example of the structure of the array-shaped storage section 81 and the sensor array 82. The array-shaped storage section 81 is made of a material having a high thermal resistance such as quartz, for example, and has nine cells (cells 81a to 81i) formed therein as concave storage sections. One of the nine cells is used for reference. The structure of each cell is, for example, cell 8
As shown in FIG. 1c, it is a concave rectangular parallelepiped, and a metal body 83c is arranged below it. A sample is stored in each cell.

In the sensor array 82, print coils 82a to 82i for measuring a temperature change due to heat are formed on the array. The positions of the print coils 82a to 82i on the sensor array 82 correspond to the positions of the cells 81a to 81i of the array-shaped storage unit 81, respectively. Alternatively, they are mounted in close proximity.

The principle of the temperature measurement is as described with reference to FIGS. 5, 6, and 9. Although the temperature measuring device shown in FIG. 5 can measure only the temperature change of one sample, as shown in FIG. 10, a plurality of cells and a printed coil are formed in the array-shaped storage portion 81 and the sensor array 82. By doing so, it becomes possible to measure temperature changes of a plurality of samples at the same time.

In the example shown in FIG. 10, the cells and the print coils are arranged in a grid pattern, but may be arranged at any other position. Further, in the example of FIG. 10, nine cells and print coils are formed, but of course, other numbers can be formed. Further, in the example of FIG. 10, a metal body is provided in each cell. However, as described above, if the sample is conductive, the metal body 83c does not need to be provided.

Next, the print coil shown in FIGS. 6 and 10 will be described in more detail. 11A and 11B show the structure of the print coil 82a, FIG. 11A is a plan view, and FIG. 11B is a cross-sectional view taken along line A ₀ -A ₁ in FIG. . Print coil 82a of FIG.
Is formed on one surface of the insulating substrate 97 by using a multilayer printed wiring technique. Further, a holding member (insulating layer) 98 having a predetermined thickness is formed on the other surface of the insulating substrate 97.

For the insulating substrate 97, an insulating substrate material such as a phenol resin, a xylene resin, a urea resin, a melamine resin, a polyester resin, an alkyd resin, an epoxy resin, and a silicon resin is used.

A printed coil 82a is formed on the surface of the insulating substrate 97 by using a printed wiring board manufacturing technique. The print coil 82a is formed by, for example, attaching a thin copper foil or the like made of a conductive material to the surface of the insulating substrate 97 to form a conductive layer, and etching the conductive layer into a predetermined pattern. Alternatively, the conductive layer can be formed by plating a conductive metal or the like. Further, the print coil 82a can be directly formed by screen printing using a conductive metal paste.

The printed coil 82a is connected to the insulating substrate 97
, A winding 91 formed on one surface, a pad 93-1, a pad 92-2, and a pad 93-3, and a lead wire 92 formed on the other surface. Pads 94-1 and 94-2 are formed at both ends of the lead wire 92. The pad 93-2 and the pad 94-1 are connected via a plating layer 95-1 formed on the wall surface of the through hole 96-1. Similarly, pad 93-3 and pad 94
-2 is connected via a plating layer 95-2 formed on the wall surface of the through hole 96-2.

By forming the print coils 82a shown in FIG. 11 on a plurality of arrays, the sensor array 82 of FIG. 10 can be formed.

Next, the structure of the array-shaped storage section 81 will be described in more detail with reference to FIG. FIG. 12 shows the structure of the array-shaped storage section 81, and FIG.
2 (A) is a perspective view, and FIG. 12 (B) is x in FIG. 12 (A).
Shows a cross-sectional view taken at ₁ -x _2-wire.

The array-shaped storage section 81 is formed of a quartz substrate, and has a cell 81 having a concave storage section therein.
a to 81i are formed. The structure of each cell is, for example, a concave shape on a quartz substrate 81 as shown in a cell 81b, and a metal body 102b, which is a conductive material generating an eddy current, is provided below the cell. Then, different samples are stored inside each cell. At least one of the cells 81a to 81i is used as a reference cell. Thus, by arranging a plurality of cells in an array, it is possible to simultaneously measure a temperature change accompanying a change in a state of a plurality of samples. As a result, a plurality of samples can be efficiently evaluated.

FIG. 13 is a diagram in which a portion corresponding to the array-shaped storage portion 81 in FIG. 10 is replaced with another structure. FIG.
3 (A) is a perspective view, and FIG. 13 (B) is x in FIG. 13 (A).
Shows a cross-sectional view taken at ₃ -x ₄ wire. In the example of FIG.
Nine catalytic metal layers 112 are formed on each cell of the quartz substrate 111 having high thermal resistance in which lattice-like grooves are formed and cell regions on the array are formed, and correspond to each catalytic metal layer. A sample (eg, carbon) 113 having a composition is grown. As a result, the pair of the catalyst metal layer 112 and the sample 113 are separately provided on the quartz substrate 111.
Then, by attaching the sensor array 82 shown in FIG. 10 to the lower part of the quartz substrate 111, it is possible to measure a temperature change accompanying a change in the state of the sample.

As the catalyst of the catalyst metal layer 112, for example, iron, cobalt, nickel is used, and a combination thereof may be used. However, there are catalysts other than iron, cobalt and nickel, and of course, substances other than these may be used. On each catalyst metal layer 112, a sample (carbon) 113 having a different pore structure such as columnar (fiber), graphite-like, or amorphous is grown. The pore structure of the growing sample 113 corresponds to the catalytic metal layer 112, respectively.

Next, a method for growing the catalyst metal layer 112 will be described. The catalyst metal layer 112 is formed by sputtering, vapor deposition, screen printing, CVD (chemical vapor deposition), PVD
(Physical vapor deposition). When a multi-component catalyst is formed by these methods, a predetermined heat treatment is performed after laminating a single component film. Thereby, a uniform multi-component catalyst metal layer is formed. In addition, heat treatment may be performed in the process of film formation so that the catalytic metal layer becomes uniform. The region where the catalyst is formed is defined by a mask or lift-off after film formation.

Next, a method of growing the sample (carbon) 113 will be described. The carbon 113 is grown by a thermal CVD method, a plasma CVD method, or the like. The case where the thermal CVD method is used will be described. First, the quartz substrate 11 on which the catalyst metal layer 112 was formed
1 is placed in a reaction vessel, and gas (methane / hydrogen) is introduced into the reaction vessel. Next, the reaction vessel is heated to a predetermined temperature (700 ° C.) by a heater and reacted for a predetermined time (1 hour). As a result, hollow carbon fibers 113 grow on the catalyst metal layer 112. However, carbon fibers having different diameters and lengths are formed by the catalyst. In the thermal CVD method described above,
Although the methane gas is used as the introduction gas, a hydrocarbon gas or the like may be used instead.

FIG. 13 shows an example of a quartz substrate 11 having a high thermal resistance.
1, a lattice-shaped groove is formed to separate a region where a sample is to be grown later. Then, a plurality of types of samples can be formed on the conductive material in each growth region according to the above-described combinatorial synthesis method. By providing the sensor array 82 shown in FIG. 10 in the vicinity of or in contact with the quartz substrate 111, it is possible to simultaneously measure a temperature change accompanying a change in the state of the sample.

In the example shown in FIG. 13, the sample is grown on the catalyst metal layer. However, when a conductive sample is used, the conductive sample is directly grown without growing the catalyst metal layer. It is also possible to generate an eddy current by itself and measure a temperature change accompanying a state change.

FIG. 14 shows a configuration in which a portion corresponding to the array-shaped storage section 81 shown in FIG. Figure 14 (A) is a perspective view, FIG. 14 (B) shows a sectional view in x ₅ -x ₆ line in FIG. 14 (A).
As shown in FIG. 14A, nine quartz cells 121 (quartz cells 121a to 121i) are arranged. The structure of each quartz cell is, for example, concave as shown in the quartz cell 121b, and a metal body 122b, which is a conductive material, is provided below the quartz cell 121b. Different samples are stored inside each cell. At least one of the quartz cells 121a to 121i is used as a reference quartz cell.

By providing the sensor array 82 shown in FIG. 10 near or in contact with the lower side of the above-mentioned quartz cells 121a to 121i, it is possible to simultaneously measure the temperature change accompanying the state change of a plurality of samples. it can. As a result, a plurality of samples can be efficiently evaluated.

In the example of FIG. 14, a metal body is provided in each quartz cell. However, if the sample to be stored is conductive, it is not necessary to provide a metal body.

[0093]

As described above, according to the present invention, a measurement sample and a conductive member for measurement are accommodated in a plurality of measurement containers having high thermal resistance, and the measurement sample and the conductive member are provided outside the measurement container. Since a plurality of measurement coils are provided near the conductive member,
Temperature changes of a plurality of measurement samples due to heat can be measured more accurately. As a result, a desired sample can be quickly selected from a plurality of measurement samples.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a combinatorial synthesis method.

FIG. 2 is a diagram for explaining a first measurement method of a gas adsorption amount.

FIG. 3 is a diagram for explaining a second method of measuring the gas adsorption amount.

FIG. 4 is a view for explaining a conventional gas adsorption heat measuring device.

FIG. 5 is a diagram for explaining a temperature measuring device to which the present invention is applied.

6 is a diagram for explaining the structure of a reference quartz cell container 60 and a measurement quartz cell container 56 of FIG.

FIG. 7 is a diagram showing output characteristics of the print coil 59 when an adsorbent is present.

FIG. 8 is a diagram showing output characteristics of the print coil 59 when there is no adsorbent.

FIG. 9 is a diagram for explaining the principle of temperature measurement by a print coil 59;

FIG. 10 is a diagram for explaining the structure of an array-shaped storage section 81 and a sensor array 82;

11 is a diagram for explaining a structure of a print coil 82a in FIG.

FIG. 12 is a view for explaining a structure of an array-shaped storage section 81 of FIG. 10;

FIG. 13 is a diagram for explaining a case where a catalyst metal layer and a sample are grown on a quartz substrate 111.

FIG. 14 is a diagram for explaining a case where a portion corresponding to the array-shaped storage section 81 in FIG. 10 is configured by individual quartz cells 121.

[Explanation of symbols]

 51 Container 52 Vacuum Pump 53 Container 54b Water Vapor 56 Measurement Quartz Cell 57 Measurement Sample 58 Metal 59 Measurement Print Coil 60 Reference Quartz Cell 61 Reference Sample 62 Metal 63 Reference Print Coil 81 Array Housing 82 Sensor Array

Claims (14)

[Claims] 1. A measuring container having a high thermal resistance for accommodating a measuring sample and a measuring conductive member in which an eddy current is generated, and outside the measuring container and near the measuring conductive member. And a measuring coil for generating a predetermined magnetic field. 2. A container having a high thermal resistance for accommodating a conductive measurement sample, and a measurement container which is provided outside the measurement container and near the conductivity measurement sample and generates a predetermined magnetic field. A temperature measuring device comprising: a coil; 3. A reference container having a high thermal resistance for accommodating a reference conductive member in which an eddy current is generated, provided outside the reference container and near the reference conductive member, 2. The apparatus according to claim 1, further comprising: a reference coil for generating a predetermined magnetic field, wherein a temperature of the measurement sample is measured by a differential component of a signal output from the measurement coil and the reference coil. The temperature measuring device according to item 1. 4. The apparatus according to claim 1, wherein a plurality of sets of said measuring container and said measuring coil are provided.
The temperature measuring device according to item 1. 5. A storage section having a high thermal resistance, in which a plurality of cells for storing a sample and a conductive member in which an eddy current is generated are provided, and the cell is provided outside of the storage section. And a sensor array provided with a plurality of measurement coils for generating a predetermined magnetic field. 6. A storage section having a high thermal resistance, in which a plurality of cells for storing a conductive sample are formed, and provided outside the cells of the storage section at positions corresponding to the cells, And a sensor array in which a plurality of measurement coils for generating the magnetic field are formed. 7. The method according to claim 1, wherein the sample is placed in an atmosphere in which a substance is adsorbed or desorbed on the sample, and the substance is adsorbed or desorbed on the sample. A method for measuring the amount of heat of adsorption and desorption, wherein a temperature change accompanying the measurement is measured by the measurement coil. 8. The temperature measuring device according to claim 1, wherein the sample is heated, and a temperature change caused by the transition of the sample is measured by the measuring coil. Transition calorimetry method. 9. The measurement coil according to claim 1, wherein the sample is caused to react with a predetermined substance and a temperature change caused by a chemical change of the sample is measured. A reaction calorimetric method characterized by measuring the reaction calorimetry. 10. The temperature measurement apparatus according to claim 1, wherein the sample is pressurized, and a temperature change associated with the phase transition of the sample is measured by the measurement coil. Phase transition calorimetry method. 11. The conductive measurement sample is pressurized by using the temperature measuring device according to claim 2 or 6, and a resistance change caused by a phase transition of the conductive measurement sample is measured by the measurement coil. A method for measuring resistance. 12. A sample forming member having a high thermal resistance having a plurality of regions where a catalyst or a sample is grown at a distance, and an opposite side of the sample forming member to the growth region and in the vicinity of the sample forming member. And a measuring coil for generating a predetermined magnetic field. 13. A catalyst metal layer is formed on the plurality of regions by using the temperature measurement device according to claim 12, and a sample having a corresponding composition is grown on the catalyst metal layer. A method for measuring the amount of heat of adsorption and desorption, wherein the sample is placed in an atmosphere for adsorption or desorption, and a temperature change caused by the adsorption or desorption of the substance to or from the sample is measured by the measurement coil. 14. The method according to claim 12, wherein a conductive sample is grown on the plurality of regions, the conductive sample is pressurized, and a resistance caused by a phase transition of the conductive sample is generated. A resistance measuring method, wherein the change is measured by the measuring coil.