JP5187663B2 - Insulated calorimeter - Google Patents

Description

  The present invention relates to an adiabatic calorimeter for measuring the heat capacities of various substances and measuring the specific heat of the substances.

  Conventionally, various calorimeters are used to measure the specific heat of various substances.

  Conventionally, as means for measuring the specific heat of a substance, in a vacuum chamber, a first sample cell in which a sample to be measured is sealed, and an empty second sample cell substantially identical to the first sample cell, Heating from the outside by a heat source, detecting the temperatures of the first sample cell, the second sample cell, and the heat source and integrating them in time, and the temperatures of the first sample cell and the second sample cell are the same. It is known that the specific heat of the sample to be measured is calculated based on the temperature of the heat source at each hour of time (see Patent Document 1).

  Also, a specific heat measuring device that drops a heated sample into a measurement container and obtains the specific heat of the sample from the temperature rise of the measurement container, and includes a heating container that contains the sample and a heater that heats the heating container And a measurement unit provided with a measurement container into which a heated sample is introduced and a heat insulating material surrounding the measurement container, and a shaking means for shaking the measurement unit after the sample is introduced into the measurement container. A characteristic sample-throwing type specific heat measuring apparatus is known (see Patent Document 2).

  Furthermore, it is an adiabatic light calorimeter that irradiates the sample with light and measures the temperature rise of the sample due to the irradiation, and maintains the ambient temperature and the sample temperature at the same temperature during and before the irradiation of the light. A featured adiabatic light calorimeter is known (see Patent Document 3).

JP 2002-156345 A Japanese Patent Laying-Open No. 2005-221402 JP 2005-003633 A

  As described above, there are various devices for measuring the specific heat as described above. However, in the specific heat measurement, heat leakage is likely to occur, causing an error in the specific heat measurement. An object of the present invention is to realize a configuration for preventing this heat leakage as much as possible, and to enable more accurate measurement.

  In addition, when the sample cell is incorporated into the apparatus, the heat insulation type that is easy to work, such as being able to easily work in a posture looking down from the posture that the measurer looks up, and easily confirming that the position and orientation of the sample cell are always correct, etc. An object is to realize a calorimeter.

  In order to solve the above problems, the present invention provides a vacuum vessel, a heat insulating vessel flange provided in the vacuum vessel and cooled by a low-temperature end of a refrigerator, and a heat insulating vessel detachably provided on the heat insulating vessel flange. An outer shield with an upper cover provided on the heat insulating container flange via a support in the heat insulating container, an inner shield with an upper cover provided in the outer shield, and a sample cell provided in the inner shield The inner shield is suspended from the upper part of the outer shield by a thread, and can be accessed by opening the upper cover of the outer shield, and the sample cell is measured It holds the target sample, and is inserted into the inner shield with its upper lid open, and can be suspended on the upper part of the inner shield with a thread. The adiabatic calorimeter is characterized in that the inner shield and the sample cell are controlled by a thermocouple and a heater attached to each other so that the temperature difference becomes zero.

  In order to solve the above problems, the present invention provides a vacuum vessel, a heat insulating vessel flange provided in the vacuum vessel and cooled by a low-temperature end of a refrigerator, and a heat insulating vessel detachably provided on the heat insulating vessel flange. An outer shield with an upper cover provided on the heat insulating container flange via a support in the heat insulating container, an inner shield with an upper cover provided in the outer shield, and a sample cell provided in the inner shield The inner shield is suspended from the upper part of the outer shield by a thread, and can be accessed by opening the upper cover of the outer shield, and the sample cell is measured It holds the target sample, and is inserted into the inner shield with its upper lid open, and can be suspended on the upper part of the inner shield with a thread. The outer shield, the inner shield, the inner shield upper lid, and the sample cell are provided with a first heater, a second heater, a third heater, and a fourth heater, respectively. One end and the other end of the first thermocouple are attached to the shield, respectively, the temperature difference between the outer shield and the inner shield is detected by the first thermocouple, and the outer shield is always at a constant temperature from the inner shield. The first heater is controlled so that the temperature is lower, and one end and the other end of the second thermocouple are respectively attached to the inner shield and the sample cell, and the inner shield is provided by the second thermocouple. And the second heater is controlled so that the temperature difference becomes zero. To provide the adiabatic calorimeter to.

  It is preferable that the said heat insulation container is made into temperature lower than an outer shield.

  It is preferable that a radiation shield that is cooled to a temperature between the temperature of the heat insulating container and room temperature is detachably attached so as to cover the heat insulating container in the vacuum container.

  It is preferable that the heat insulation container flange is provided on the refrigerator low temperature end.

  A third thermocouple is provided between the inner shield upper cover and the inner shield, and the third heater is controlled so that the temperature difference between the inner shield upper cover and the inner shield becomes zero. It is preferable that the inner surface surrounding the sample cell has a temperature equal to that of the sample cell by performing isothermal control of the inner shield.

According to the present invention, the following effects are produced.
(1) Since the inner shield opening faces upward, when working, it is much easier and more stable to look down than to look up. In the case of an upward opening, room lighting easily illuminates the inside of the inner shield. For this reason, it becomes possible to easily confirm that the state of the lead wire, the position and orientation of the sample cell are always correct.

(2) In order to support the entire insulated calorimeter, it is only necessary to attach a support foot directly to the vacuum vessel flange, and it is not necessary to overhang from the device like a mount required for the comparative example described later. There is no extra space occupied, neither access to the device nor work space is blocked by the feet.

(3) The vacuum vessel, the heat insulation vessel, and the radiation shield are all fixed after being placed on a flange or the like arranged at the lower part thereof. For this reason, even if the bolt and nut holding the flange are removed, the vacuum container or the like does not fall from the apparatus.

(4) According to the present invention, it has been experimentally clarified that the measurement result is influenced by the position and orientation of the sample cell. Therefore, the advantage of being able to easily confirm that it is always correct is to realize more accurate measurement. .

  The best mode for carrying out an adiabatic calorimeter according to the present invention will be described below with reference to the drawings based on the embodiments.

(principle)
First, the principle of the adiabatic calorimeter according to the present invention will be described. The heat capacity C of the substance can be determined from the following equation by measuring the temperature rise ΔT when a known heat quantity ΔQ is added. The specific heat of the substance can be determined by dividing this heat capacity by mass.
C = ΔQ / ΔT (J / K)

  However, in the measurement of heat capacity, heat leakage causes a large error. The adiabatic calorimeter according to the present invention employs a configuration for preventing this heat leakage as much as possible, and its configuration and principle will be described with reference to FIG.

  The heat insulating calorimeter 1 according to the present invention has a heat insulating container 2, and includes an inner shield 3 and an outer shield 4 surrounding the outer side of the inner shield 3 in the heat insulating container 2.

  The heat insulation container 2 is attached to the heat insulation container flange 6 cooled by the refrigerator low temperature end 5, and can maintain the inside in a high vacuum. During measurement, the inside of the heat insulating container 2 is kept at a high vacuum to eliminate convection and conduction heat transfer due to gas such as air.

  However, before starting the heat capacity measurement, heat exchange gas is sent from the gas handling device (not shown) through the gas pipe 18 into the heat insulating container 2 for precooling. This gas is exhausted by a vacuum pump after the outer shield 4, inner shield 3, sample cell 8, and the like disposed inside the heat insulating container 2 are cooled to a target temperature. Thereafter, after a sufficiently high vacuum is reached, measurement of the heat capacity is started.

  The heat insulating container flange 6 and the heat insulating container 2 are disposed in the vacuum container 7. The inside of this vacuum vessel 7 is vacuum-sucked by a vacuum pump through a vacuum suction pipe 19 and kept at a high vacuum, from room temperature due to convection and conduction heat transfer by gas such as air to the heat insulation vessel flange 6 and the heat insulation vessel 2. Prevents heat intrusion.

  A radiation shield (not shown) may be provided between the vacuum container 7 and the heat insulating container flange 6 and the heat insulating container 2 as necessary. This radiation shield is preferably cooled to a temperature between room temperature and the temperature of the insulating container flange 6. As a cooling source for the radiation shield, for example, there is a configuration in which a liquid nitrogen tank is provided, or a thermal contact with an intermediate stage of a mechanical refrigerator.

  A sample cell 8 is arranged in the inner shield 3, and a sample to be measured is stored in the sample cell 8 at the time of measurement. One end of a thermometer 9, a heater 10, and a thermocouple 11 is attached to the sample cell 8.

  A heater 12 is attached to the outer surface of the inner shield 3, and the other end of the thermocouple 11 attached to the sample cell 8 is attached to the inner surface. The temperature difference between the sample cell 8 and the inner shield 3 is detected by the thermocouple 11, and the heater 12 of the inner shield 3 is PID-controlled so that both are at the same temperature.

  Such isothermal control is performed by the thermocouple 11 attached between the inner surface of the inner shield 3 and the sample cell 8. However, in order to increase the accuracy, a separate is provided between the inner shield upper cover 13 and the inner shield 3. And the heater 15 attached to the outer surface of the inner shield upper lid 13 is subjected to PID control so that the temperature difference between the inner shield upper lid 13 and the inner shield 3 becomes zero, and the inner shield upper lid 13 and the inner shield 3 are Perform isothermal control. Thereby, all the inner surfaces surrounding the sample cell 8 have a temperature equal to that of the sample cell 8.

  By adopting such a configuration, the sample cell 8 is constantly put in a pseudo-insulation state during measurement. Here, the “pseudo adiabatic state” is obtained by constantly controlling the temperature of the sample cell 8 and the inner shield 3 surrounding the sample cell 8 to be equal to each other. That is, when the sample cell 8 and the surrounding inner shield 3 are at the same temperature, the heat outflow and inflow due to radiation and heat transfer are equal and cancel each other, so that it can be considered that there is no heat inflow / outflow.

  A heater 16 is also attached to the outer shield 4. A temperature difference from the inner shield 3 is detected by a thermocouple 17, and the heater 16 is PID controlled so that the temperature is always lower than the inner shield 3 by a certain temperature. It is made into the composition.

  The reason for keeping the outer shield 4 at a lower temperature than the inner shield 3 is to control the temperature of the inner shield 3. In order to heat the inner shield 3, the heater 11 attached to the inner shield 3 may be used. However, in order to cool the inner shield 3, a cooling source for cooling the inner shield 3 is required. This cooling source is the outer shield 4.

  If the temperature of the outer shield 4 is lower than that of the inner shield 3, the heat of the inner shield 3 moves to the outer shield 4 due to radiation and conduction due to the temperature difference, and the inner shield 3 is cooled. By repeating this heating and cooling control, the inner shield 3 can be controlled to be constant at a set temperature.

  The heat insulating container flange 6 is thermally connected directly to the refrigerator cold end 5. The heat insulating container 2 fixed to the heat insulating container flange 6 is always kept at a temperature lower than that of the outer shield 4. This is necessary for controlling the temperature of the outer shield 4 for the same reason that the temperature of the outer shield 4 is kept lower than that of the inner shield 3.

  When the sample cell 8 is placed in a pseudo-insulation state as described above by the heat insulation calorimeter 1 having the above configuration, the sample cell 8 containing the sample continues to be at a constant temperature as long as there is no new heat input.

  In measuring the heat capacity, a heat quantity ΔQ is supplied to the sample. For this purpose, the cell is heated by Joule heat of the heater 10 attached to the sample cell 8. During this heating, the shields 3 and 4 are controlled so as to maintain a specified temperature difference as the temperature of the sample cell 8 rises.

  Then, the heat capacity is calculated from the temperature difference before and after heating and the amount of heat applied to the sample cell 8, and further divided by mass to calculate the specific heat.

  The initial cooling of the outer shield 4, the inner shield 3 and the sample cell 8 arranged in the heat insulating container 2 is performed at a temperature equal to or lower than the temperature of the heat insulating container 2 as a heat exchange gas inside the heat insulating container 2 cooled by the refrigerator. Put in inert gas with boiling point. The outer shield 4, the inner shield 3, and the sample cell 8 are cooled to the same temperature as the heat insulating container 2 by gas convection and conduction.

  An embodiment of an adiabatic calorimeter according to the present invention will be described with reference to FIG.

  In the adiabatic calorimeter 20 of the embodiment, the vacuum vessel 22 is placed on the vacuum vessel flange 21, and the flange 23 formed at the lower end of the vacuum vessel 22 is placed via a seal (not shown) (vacuum vessel 22. (In order to increase the degree of vacuum inside, it is attached via a seal.) Bolts and nuts are detachably attached. The vacuum vessel 22 is evacuated by a vacuum pump (not shown) through a vacuum suction tube 22 '. A refrigerator low-temperature end 24 is provided above the vacuum vessel flange 21.

  The Peltier element refrigerator 25 is a mechanism that cools the vacuum container flange 21 and the vacuum container 22 and cools the heat insulating container flange 28 and the heat insulating container 29 disposed thereon. In this embodiment, the Peltier element refrigerator 25 is used as the refrigerator, but various types of refrigerators can be used regardless of the type. For example, cooling by a low temperature liquid reservoir, a pulse tube type refrigerator, a GM refrigerator, a Freon gas circulation refrigerator, a Peltier element refrigerator, and the like. However, when a cryogenic liquid, a pulse tube, or a GM refrigerator is employed, the refrigeration capacity is lowered because it is arranged to be used upside down.

  The water-cooled heat sink 26 and the gantry 27 in FIG. 2 are only necessary to employ the Peltier element refrigerator 25. The role of the water-cooled heat sink 26 here is to cool the high-temperature end of the refrigerator on the lower surface of the Peltier element refrigerator 25, and cooling water flows through the inside. In addition, the upper surface of the Peltier element refrigerator 25 is the refrigerator low temperature end 24, and the lower surface is the refrigerator high temperature end.

  Here, the heat insulating container flange 28 is paired with the opposing heat insulating container 29 and serves to keep the inside of the container in a high vacuum. And since it is cooled by the refrigerator low-temperature end 24 at a temperature lower than that of its internal organs, the temperature control of the outer shield 30 and the inner shield 31 is made possible. Further, at the time of initial cooling, the outer shield 30, the inner shield 31, and the sample cell 32 are cooled to the minimum temperature via the heat exchange gas introduced through the gas pipe 40 only at this time. Here, “built-in” means an outer shield, an inner shield, a sample cell, and the like, and includes a lid attached to these.

  On the water-cooled heat sink 26, a cylindrical radiation shield 33 is placed so as to cover the Peltier element refrigerator 25 and the heat insulating container flange 28, and is detachably attached to the water-cooled heat sink 26. The radiation shield 33 is not necessarily required, and is provided depending on the situation. The situation is when the temperature of the sample cell 32 and the room temperature are extremely different. In this case, the radiation shield 33 is necessary to prevent heat from entering or flowing out of the apparatus due to radiation.

  The heat insulating container 29 is placed on the heat insulating container flange 28 in the radiation shield 33, and the flange 34 formed at the lower end of the heat shield container 29 is put through a seal (through the seal to increase the degree of vacuum in the heat insulating container 29). .) Removably attached to the insulated container flange 28 with bolts and nuts.

  An outer shield 30 is fixed on the heat insulating container flange 28 in the heat insulating container 29 by a support base 35 formed of a low heat conductive material (stainless steel or the like). An outer shield upper lid 36 to which a mechanism for promoting heat transfer is attached is detachably attached to the upper end of the outer shield 30.

  In this embodiment, a plurality of parts called fingers (not shown) are attached to the upper end of the outer shield 30 along the circumference by soldering. This component is made of beryllium copper with high thermal conductivity and has a leaf spring shape. The fingers themselves are brought into close contact with the fitted outer shield upper lid 36 by the force of the spring, and heat transfer between the outer shield 30 and the outer shield upper lid 36 is improved.

  Further, an inner shield 31 is provided in the outer shield 30 so as to be suspended from the upper end of the outer shield 30 with a thread 37. An inner shield upper lid 38 is provided on the upper end of the inner shield 31 so as to be placed thereon. Here, since the inner shield 31 and the inner shield upper lid 38 perform temperature control independently of each other, in order to loosen the thermal connection, the inner shield 31 and the inner shield upper lid 38 are not fixed with screws or the like, but are merely placed on top.

  The sample cell 32 is suspended by a suspension thread 39 stretched over the inner shield 31. The suspension yarn 39 is made of a material having a low thermal conductivity (for example, nylon tex). A sample to be measured is accommodated in the sample cell 32. Here, the shape of the sample cell 32 is not limited as long as the sample cell 32 can be sealed as a container together with the heat exchange gas and can be suspended by a thread-like material such as nylon tex.

  One end of a thermometer 41, a heater 42, and a thermocouple 43 is attached to the sample cell 32. A heater 44 is attached to the outer surface of the inner shield 31, and the other end of a thermocouple 43 attached to the sample cell 32 is attached to the inner surface. The temperature difference between the sample cell 32 and the inner shield 31 is detected by a thermocouple 43, and the heater 44 of the inner shield 31 is PID-controlled so that both are at the same temperature.

  Such isothermal control is performed by a thermocouple 43 attached between the inner surface of the inner shield 31 and the sample cell 32. However, in order to increase accuracy, a separate is provided between the inner shield upper cover 38 and the inner shield 31. And the heater 46 attached to the outer surface of the inner shield upper lid 38 is subjected to PID control so that the temperature difference between the inner shield upper lid 38 and the inner shield 31 becomes zero, so that the inner shield upper lid 38 and the inner shield 31 are isothermally heated. Take control. As a result, all inner surfaces surrounding the sample cell 32 have a temperature equal to that of the sample cell 32.

  By adopting such a configuration, the sample cell 32 is constantly placed in a pseudo-insulation state during measurement. Here, the “pseudo adiabatic state” is obtained by constantly controlling the temperature of the sample cell 32 and the inner shield 31 surrounding the sample cell 32 to the same temperature. That is, if the sample cell 32 and the surrounding inner shield 31 are at the same temperature, the heat outflow and inflow due to radiation and heat transfer are equal and cancel each other, so that it can be considered that there is no heat inflow / outflow.

  A heater 47 is also attached to the outer shield 30, and a temperature difference from the inner shield 31 is detected by a thermocouple 48, and the heater 47 is PID controlled so that the temperature is always lower than the inner shield 31 by a certain temperature. It is made into the composition.

  The reason why the outer shield 30 is kept at a lower temperature than the inner shield 31 is to control the temperature of the inner shield 31. In order to heat the inner shield 31, a heater 44 attached to the inner shield 31 may be used. However, in order to cool the inner shield 31, a cooling source for cooling the inner shield 31 is required. This cooling source is the outer shield 30.

  The heat insulating container flange 28 is thermally connected directly to the refrigerator cold end 24. The heat insulating container 29 fixed to the heat insulating container flange 28 is always kept at a temperature lower than that of the outer shield 30. This is necessary to control the outer shield 30 for the same reason as keeping the temperature of the outer shield 30 lower than that of the inner shield 31.

(Function)
The effect | action in the Example of the heat insulation type calorimeter 20 which concerns on this invention which consists of the above structure is demonstrated.

  When measuring the heat capacity of the sample, the vacuum vessel 22, the radiation shield 33, and the heat insulation vessel 29 are removed and the bolts and nuts fixing them are removed. Then, the outer shield upper lid 36 is opened, and the inner shield upper lid 38 is opened, and the sample cell 32 containing the sample in advance is attached to the suspension thread 39, and the sample cell 32 is suspended.

  Then, the inner shield upper lid 38 is closed, and the outer shield upper lid 36 is closed. Further, the heat insulating container 29 is fixed to the heat insulating container flange 28, the radiation shield 33 is fixed to the water-cooled heat sink 26, and the vacuum container 22 is sequentially fixed to the vacuum container flange 21 with bolts and nuts.

  Before starting the heat capacity measurement, a heat exchange gas is sent from a gas handling device (not shown) through the gas pipe 18 into the heat insulating container 2 for precooling. This gas is exhausted by a vacuum pump after the outer shield 4, inner shield 3, sample cell 8, and the like disposed inside the heat insulating container 2 are cooled to a target temperature. Thereafter, after a sufficiently high vacuum is reached, measurement of the heat capacity is started.

  In this state, when the heat capacity is measured, a heat quantity ΔQ is supplied to the sample. For this purpose, the cell is heated by Joule heat of the heater 42 attached to the sample cell 32. During this heating, the inner shield 31 and the outer shield 30 are controlled so as to maintain a specified temperature difference as the temperature of the sample cell 32 increases.

  As a result, the sample cell 32 is placed in a pseudo-insulation state, and the sample cell 32 containing the sample remains at a constant temperature as long as there is no new heat input. Then, the heat capacity is calculated from the temperature difference before and after heating and the amount of heat applied to the sample cell 32, and further divided by mass to calculate the specific heat.

  The initial cooling of the inner shield 31 and the sample cell 32 arranged in the outer shield 30 is performed by putting a heat exchange gas in the heat insulating container 29. The heat exchange gas is exhausted after cooling is completed.

  At the time of the above measurement, according to the configuration of the heat insulating calorimeter 20 according to the present invention, the outer shield upper lid 36 is opened, the inner shield upper lid 38 is opened, and the sample cell 32 is opened. Since work such as setting is possible, work is easy.

  By the way, in the course of the research and development of the present invention, the present inventors made various prototypes other than the above-described examples and examined them in order to implement the above principle. One of them will be described below as a comparative example, but the above-described embodiment has a remarkable effect as will be described later as compared with this comparative example.

(Comparative example)
The heat insulation type calorimeter 50 which is a comparative example is demonstrated with FIG. A top plate 52 is supported on the gantry foot 51, and a vacuum vessel flange 53 is attached to the top plate 52.

  A vacuum container 54 is attached to the vacuum container flange 53 by fixing a flange 55 formed at the upper end thereof with bolts and nuts. Further, a two-stage refrigerator 56 is attached to the vacuum vessel flange 53, and a radiation shield attaching flange 58 is attached to an intermediate stage 57 of the refrigerator 56.

  In the vacuum vessel 54, the radiation shield 59 is attached to the lower surface of the radiation shield mounting flange 58 by a flange 60 formed at the upper end thereof being detachably fixed with bolts and nuts. In addition, a refrigerator low-temperature end 61 is disposed inside the radiation shield 59, and a heat-insulating container flange 62 is directly attached to the refrigerator low-temperature end 61 so as to transfer heat.

  A heat insulating container 63 is fixed to the heat insulating container flange 62 with a bolt and a nut through a seal. Further, in the heat insulating container 63, the outer shield upper cover 65 of the outer shield 64 is attached to the heat insulating container flange 62 by being suspended by a thread 66, and the outer shield 64 main body is disposed so as to cover the inner shield 67. And is detachably attached to the outer shield upper lid 65 by means such as screwing.

  The inner shield 67 has a main body suspended from the outer shield upper lid 65, and the inner shield lower lid 68 is semi-fixed with screws, wires, etc. while being supported from below. Here, “semi-fixed” means that the inner shield lower lid 68 is fixed to the inner shield 67. However, since the inner shield 67 and the inner shield lower lid 68 perform temperature control separately, thermal connection is established. Say to fix loosely so as not to strengthen.

  The sample cell 70 is suspended by a suspension thread 72 drawn from the inner shield upper portion 71. In particular, as shown in FIG. 4, the sample cell 70 is attached and detached by passing the suspension thread 72 through the hole 73 formed in the center of the upper portion 71 of the inner shield 67 and drawing it out of the inner shield 67. It is the structure which can be performed. The suspension yarn 72 is made of a material having a low thermal conductivity (for example, nylon tex).

(About features of the present invention)
The above is the configuration of the comparative example, but the technical features, effects, etc. of the heat insulating calorimeter 20 according to the present invention are clearer when the embodiment of the present invention is compared with the heat insulating calorimeter 50 of this comparative example. Therefore, in the following, the technical features, effects, etc. of the embodiment of the present invention will be described in comparison with this comparative example.

(1) Ease of work In the measurement and maintenance of the heat insulation calorimeter 20 of the present invention, for example, the work of attaching and removing the sample cell 32, the situation of the lead wire of the thermocouple, the position and orientation of the sample cell 32 Various operations such as confirmation work are performed.

  According to the heat insulation type calorimeter 20 according to the present invention, the situation inside the inner shield 31 can be easily seen. In other words, since the opening of the inner shield 31 of the above embodiment faces upward, when performing various operations, the measurement operator can take a posture to look down. As an operator, looking down is much easier and more stable than looking up.

  Further, in the case of the upward opening, the room lighting easily illuminates the inner shield 31. For this reason, it becomes possible to easily confirm that the state of the lead wire of the thermocouple attached to the sample cell 32 and the position and orientation of the sample cell 32 are always correct. As described above, according to the heat insulating calorimeter 20 according to the present invention, it is freed from the difficulty of work as in the case of the comparative example described later.

  In the heat insulation type calorimeter 50 of the comparative example, since the opening portion of the suspended inner shield 67 faces downward, the lead wire of the thermocouple in the inner shield 67 and the state of the cell (the lead wires of the thermocouple, the leads In order to confirm whether the line and the sample cell 70 are not entangled or whether the sample cell 70 is hung in a correct position at a predetermined position, etc., it is necessary to look into from below or use a mirror.

  Furthermore, if the opening of the inner shield 67 faces downward, indoor lighting does not reach the inner shield 67, so a flashlight or the like must be used. In this series of research and development, we have experimentally confirmed that the difference in the position and orientation of the sample cell has a negligible effect on the measurement results.

  The lead wires of the thermocouples of the inner shield 67 and the sample cell 70 are thin (about 0.1 mm in diameter) and long (about 30 cm) in consideration of heat conduction. In addition, a large number of about 10 lines are stored in a space that is not so wide.

  It is necessary to check this situation with an unnatural posture (or through a mirror) with inconvenient lighting, and if necessary, use tweezers etc. to arrange the thermocouple lead wires that are easily cut or entangled. . In particular, when the wire breaks, it is very difficult to manipulate and repair the soldering iron under the above situation.

(2) Space saving According to the heat insulation type calorimeter 20 according to the present invention, in order to support the heat insulation type calorimeter 20 as a whole, the support feet 49 may be directly attached to the vacuum vessel flange 21, and a comparative example described later. Therefore, it is not necessary to overhang the apparatus from the apparatus as in the case of the necessary frame, so that the laboratory space is not occupied, and the access to the apparatus and the work space are not obstructed by the support legs 49.

  In the heat insulation type calorimeter 50 of the comparative example, the top plate 52 (top flange) must be placed on the gantry foot 51 in order to suspend the entire apparatus of the heat insulation type calorimeter 50. Therefore, a plurality of gantry legs 51 are arranged outside the device. The gantry foot 51 occupies an extra space for the measurement work place and the laboratory, and the access to the apparatus and the work space are limited for the gantry foot 51.

(3) Easy installation and removal of each shield According to the heat insulating calorimeter 20 according to the present invention, the vacuum container 22, the heat insulating container flange 28, the radiation shield 33 are all disposed under the vacuum container flange 21, etc. After being placed on, it is fixed. For this reason, even if the bolt and nut holding the flange at the lower end of the vacuum vessel 22 are removed, the vacuum vessel 22 and the like do not fall from the apparatus.

  Accordingly, an auxiliary worker and a support stand are not required, and even if the work is performed alone, the bolts and the like can be removed, and then the vacuum vessel 22 and the like can be lifted and removed, thereby realizing stable and safe work.

  Regarding the outer shield 30, the outer shield 30 main body is fixed to the heat insulating container flange 28, so there is no need to remove it, and only the outer shield upper lid 36, which is very light compared to the outer shield 30 main body, may be removed. This operation is as simple as opening the bottle lid. However, the inner shield 31 is suspended from the outer shield 30 and the sample cell 32 is suspended from the inner shield 31 in order to maintain the heat insulation performance of the entire apparatus of the heat insulating calorimeter 20.

  In the heat insulation type calorimeter 50 of the comparative example, the outer shield 64, the heat insulation container 63, and the vacuum container 54 are attached to the radiation shield mounting flange 58, the heat insulation container flange 62 and the outer shield upper lid 65 that are fixed upward or suspended from the outside. It is fixed with bolts and nuts. Therefore, when removing them, it is necessary to remove the bolts and nuts while supporting the radiation shield 59 and the like with a hand or a support base.

  It is difficult and dangerous to perform such work alone without a support base or auxiliary worker. If the support fails, the vacuum vessel 54 and the like will not only drop and cause damage to the apparatus, but there is also a risk of injury to the operator.

  The inner shield lower cover 68 is light and easy considering, for example, the removal of the outer shield 64, but the inner shield lower cover 68 and the inner shield 67 body are generally connected by a thermocouple and a heater lead wire. It is common that it is the composition which has. Therefore, when the hand is slid when removing, the bottom cover is hung by the lead wire of the thermocouple or the like. This causes a problem of causing serious device damage such as disconnection.

  As described above, according to the adiabatic calorimeter 20 according to the present invention, labor can be expected to be reduced during sample replacement and maintenance as compared with the adiabatic calorimeter 50 of the comparative example, and safe and stable operation with few mistakes can be performed. In addition to having advantages, it is also possible to save space.

  As mentioned above, although the best form for implementing the heat insulation type calorimeter concerning the present invention was explained based on an example, the present invention is not limited to such an example, and is described in a claim. It goes without saying that there are various embodiments within the scope of the technical matters stated.

  The adiabatic calorimeter according to the present invention is configured as described above, and can be applied to measure the heat capacities of various substances and measure the specific heat of the substances.

It is a figure explaining the principle of the heat insulation type calorimeter concerning the present invention. It is a figure explaining the Example of the heat insulation type calorimeter which concerns on this invention. It is a figure explaining the comparative example of a heat insulation type calorimeter. It is a figure explaining a part of comparative example.

Explanation of symbols

(Figure 1)
1 Insulated calorimeter
2 Insulated container
3 Inner shield
4 Outer shield
5 Low temperature end of refrigerator
6 Insulated container flange
7 Vacuum container
8 Sample cell
9 Thermometer with sample cell
10 Heater with sample cell
11 Thermocouple attached to sample cell and inner shield
12 Heater with inner shield outer surface
13 Inner shield top cover
14 Inner shield upper lid and thermocouple attached to inner shield 15 Heater with inner shield upper lid
16 Heater with outer shield
17 Thermocouple attached to outer shield and inner shield
18 Gas pipe 19 Vacuum suction pipe (Figure 2)
20 Insulated calorimeter
21 Vacuum vessel flange
22 Vacuum container
23 Flange of vacuum vessel
24 Low temperature end of refrigerator
25 Peltier element refrigerator
26 Water-cooled heat sink
27 frame
28 Insulated container flange
29 Insulated container
30 Outer shield
31 Inner shield
33 Radiation shield
34 Flange at the bottom of an insulated container
35 Support stand
36 Outer shield upper lid
37 Inner shield suspension thread
38 Inner shield upper lid
39 Sample cell suspension thread
40 Gas pipe
41 Thermometer with sample cell
42 Heater with sample cell
43 Thermocouple attached to sample cell and inner shield
44 Heater with inner shield
45 Inner shield upper lid and thermocouple attached to inner shield 46 Heater with inner shield upper lid
48 Thermocouple attached to outer shield and inner shield
(Fig. 3, Fig. 4)
50 Insulated calorimeter
51 pedestal feet
52 Top plate
53 Vacuum vessel flange
54 Vacuum container
55 Flange of vacuum vessel
56 Two-stage refrigerator
57 Intermediate stage of refrigerator
58 Radiation shield mounting flange
59 Radiation shield
60 Radiation shield flange
61 Low temperature end of refrigerator
62 Insulated container flange
63 Insulated container
64 Outer shield
65 Outer shield upper lid
66 yarn
67 Inner shield
68 Inner shield lower lid
69 wire
70 Sample cell
71 Inner shield top
72 Suspension thread
73 Hole drilled in the upper center of the inner shield

Claims (6)

A vacuum container, a heat insulating container flange provided on the refrigerator in the vacuum container and cooled by a low temperature end of the refrigerator; a heat insulating container detachably provided on the heat insulating container flange; and the heat insulating container A heat insulation type comprising an outer shield with an upper lid provided on a support base on the heat insulating container flange, an inner shield with an upper lid provided in the outer shield, and a sample cell provided in the inner shield A calorimeter,
The inner shield, the are suspended with a thread at the top of the outer shield, inside the inner shield,-out the lid opening of the outer shield is accessible from above further open top cover of the inner shield,
The sample cell contains a sample to be measured, and is inserted into the inner shield by opening its upper lid, and can be suspended on the upper portion of the inner shield with a thread,
The adiabatic calorimeter, wherein the inner shield and the sample cell are controlled by a thermocouple and a heater attached to each other so that the temperature difference becomes zero. A vacuum container, a heat insulating container flange provided on the refrigerator in the vacuum container and cooled by a low temperature end of the refrigerator; a heat insulating container detachably provided on the heat insulating container flange; and the heat insulating container A heat insulation type comprising an outer shield with an upper lid provided on a support base on the heat insulating container flange, an inner shield with an upper lid provided in the outer shield, and a sample cell provided in the inner shield A calorimeter,
The inner shield, the are suspended with a thread at the top of the outer shield, inside the inner shield,-out the lid opening of the outer shield is accessible from above further open top cover of the inner shield,
The sample cell contains a sample to be measured, and is inserted into the inner shield by opening its upper lid, and can be suspended on the upper portion of the inner shield with a thread,
The outer shield, inner shield, inner shield upper lid and sample cell are provided with a first heater, a second heater, a third heater and a fourth heater, respectively.
One end and the other end of the first thermocouple are attached to the outer shield and the inner shield, respectively, and the temperature difference between the outer shield and the inner shield is detected by the first thermocouple, so that the outer shield is always constant. The first heater is controlled so that the temperature is lower than the inner shield ,
One end and the other end of a second thermocouple are respectively attached to the inner shield and the sample cell, and the temperature difference between the inner shield and the sample cell is detected by the second thermocouple, and the temperature difference is zero. Thus, the heat-insulating calorimeter is characterized in that the second heater is controlled.   The heat insulation type calorimeter according to claim 1 or 2, wherein the heat insulation container has a temperature lower than that of the outer shield.   The radiation shield which is in the said vacuum vessel and is cooled to the temperature between the temperature of a heat insulation container and room temperature is attached so that attachment or detachment is possible so that the said heat insulation container may be covered. Insulated calorimeter.   5. The heat insulation type calorimeter according to claim 1, wherein the heat insulation container flange is provided on the refrigerator.   A third thermocouple is provided between the inner shield upper cover and the inner shield, and the third heater is controlled so that the temperature difference between the inner shield upper cover and the inner shield becomes zero. The adiabatic calorimeter according to claim 2, wherein the inner surface of the sample cell is set to have the same temperature as the sample cell by performing isothermal control of the inner shield and the inner shield.

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