Analysis system and analysis method

Abstract

To provide an analysis system and an analysis method capable of setting a sample under an atmosphere with a reduced residual moisture content without using a glove box with high airtightness.SOLUTION: The analyzing system 100 includes a sample holder 10 that holds a sample to be analyzed, an airtight part 20 that has an opening (lower opening side 23a) and accommodates the sample holder 10 therein through the opening, and a flexible and visible light-transmissive surrounding part 30 that separates the sample holder 10 and the opening of the airtight part 20 from the outside. The airtight part 20 is capable of state transition between an accommodation state in which the sample holding part 10 is accommodated therein and the opening is airtightly closed with respect to the inside of the surrounding part 30 and a non-accommodation state in which the sample holding part 10 is located outside the airtight part 20, and the cooling part is disposed inside the surrounding part 30 and outside the airtight part 20 at least when the airtight part 20 is in the non-accommodation state.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present disclosure relates to an analysis system and an analysis method. [Background technology]

[0002] In recent years, demand for rechargeable batteries, which are used in electric vehicles aimed at decarbonization and as emergency power sources in the event of a disaster, has been rapidly increasing. Many advanced materials, such as battery materials, undergo chemical reactions in the presence of oxygen and moisture, making it increasingly important to analyze the thermophysical properties that occur when such materials are cooled or heated, as well as the gas components that are generated from the materials. In addition, to accurately analyze the latest battery materials, it is necessary to carry out the analysis in an atmosphere with as little residual moisture as possible.

[0003] Given this background, in the latest analysis of battery materials, samples are prepared in a special atmosphere, for example, inside a glove box, and then analysis is performed using techniques such as introducing the sample into the analytical instrument in a sealed state in a special container to prevent the sample from being exposed to the atmosphere when introduced into the analytical instrument, or by installing the analytical instrument inside the glove box.

[0004] For example, in Patent Document 1, a sample is sampled onto a sample holder in a glove box (airtight chamber), and then the sample holder is moved into the sample chamber to perform thermal analysis, thereby making it possible to control the atmosphere around the sample before and after measurement.

[0005] Furthermore, in Patent Document 2, after a sample is sampled in a dedicated sample container inside a glove box, the sample container is sealed with indium or gallium, making it possible to take the sample outside the glove box and analyze it while maintaining a state where it is not exposed to the atmosphere.

[0006] Furthermore, Patent Document 3 discloses an airtight measurement box for placing a sample to be measured by a measuring device inside, which includes a housing having a connecting portion for connecting to a glove box and a sample stage on which the sample is loaded, and when connected to the glove box, the inside of the housing and the inside of the glove box become airtight. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 2964140 [Patent Document 2] Patent No. 5302932 [Patent Document 3] Patent No. 7323892 Summary of the Invention [Problem to be solved by the invention]

[0008] Incidentally, the glove boxes envisioned for use in Patent Documents 1 to 3 are expensive because they are airtight enough to evacuate the interior, and generally require high running costs because they require a constant supply of purge gas. Furthermore, in Patent Documents 1 and 3, the equipment must be modified to connect to the glove box, making it difficult to perform the above-mentioned analysis using ordinary equipment, and there is room for improvement in these respects.

[0009] In view of the above, an object of the present disclosure is to provide an analytical system and an analytical method that enable a sample to be set in an atmosphere with reduced residual moisture without using an airtight glove box. [Means for solving the problem]

[0010] In order to solve the above problems, the analysis system according to the present disclosure includes: [1] a sample holder for holding a sample to be analyzed; an airtight part having an opening and accommodating the sample holder therein through the opening; a flexible and visible light transmissive enclosure that separates the sample holder and the opening of the airtight section from the outside; Equipped with the airtight portion is capable of transitioning between a contained state in which the sample holder is contained therein and the opening is airtightly closed from the inside of the surrounding portion, and a non-contained state in which the sample holder is positioned outside the airtight portion, A cooling unit is disposed inside the enclosure unit and outside the airtight unit at least when the airtight unit is in the unenclosed state.

[0011] In addition, the analysis system according to the present disclosure includes: [2] In the configuration [1] above, it is preferable that the inside of the airtight portion can be evacuated or purged with a vacuum gas after the opening is airtightly closed to the inside of the enclosure portion.

[0012] In addition, the analysis system according to the present disclosure includes: [3] In the configuration of [1] or [2] above, it is preferable that the cooling section be a cooling head of a refrigerator, a Peltier element, or another cooling device, disposed inside the enclosure and outside the airtight section.

[0013] In addition, the analysis system according to the present disclosure includes: [4] In the configuration described in any one of [1] to [3] above, it is preferable that a coolant container containing a liquid coolant is arranged as the cooling section inside the enclosing section and outside the airtight section.

[0014] In addition, the analysis system according to the present disclosure includes: [5] In the above configuration [4], it is preferable that the inside of the coolant container communicates with the outside through an enclosure opening provided in the enclosure.

[0015] In addition, the analysis system according to the present disclosure includes: [6] In the configuration of [1] or [2] above, it is preferable that a cooling coil, into which a liquid coolant is supplied, is arranged as the cooling section inside the enclosure section and outside the airtight section.

[0016] In addition, the analysis system according to the present disclosure includes: [7] In the above configuration [6], it is preferable that the liquid coolant supplied into the cooling coil is supplied from the outside through an enclosure opening provided in the enclosure and is discharged to the outside.

[0017] In addition, the analysis system according to the present disclosure includes: [8] In the above configuration [7], it is preferable that the discharged liquid coolant is heated and then introduced into the enclosure as a purge gas.

[0018] In addition, the analysis system according to the present disclosure includes: [9] In the configuration of [1] or [2] above, it is preferable that a liquid coolant introduced from the outside through an enclosure opening provided in the enclosure is stored inside the enclosure and outside the airtight portion as the cooling portion.

[0019] In addition, the analysis system according to the present disclosure includes:

[10] In the above configuration [9], it is preferable that the liquid coolant introduced from the outside is contained in a coolant container arranged inside the enclosure and outside the airtight part.

[0020] In addition, the analysis system according to the present disclosure includes:

[11] In any of the above configurations [1] to

[10] , it is preferable that the surrounding portion has an operation protrusion that protrudes inward.

[0021] In addition, the analysis system according to the present disclosure includes:

[12] In any of the above configurations [1] to

[11] , it is preferable that the enclosure is provided with an exhaust portion for exhausting gas to the outside.

[0022] In addition, the analysis system according to the present disclosure includes:

[13] In any of the configurations [1] to

[12] above, it is preferable that the airtight portion has a cylindrical airtight tube that houses the sample holding portion inside, and a metallic fitting cylindrical portion that is fixed to the end of the airtight tube and forms the opening, and that the fitting cylindrical portion fits into an opening of a closed space facing the inside of the surrounding portion, thereby airtightly closing the opening from the inside of the surrounding portion.

[0023] In order to solve the above problems, the analytical method according to the present disclosure includes:

[14] a sample holder for holding a sample to be analyzed; an airtight part having an opening and accommodating the sample holder therein through the opening; a flexible and visible light transmissive enclosure that separates the sample holder and the opening of the airtight section from the outside; An analysis method using an analysis system comprising: transitioning the airtight portion to an unaccommodated state in which the sample holder is positioned outside the airtight portion; activating a cooling unit provided outside the airtight unit; transitioning the airtight portion to a storage state in which the sample holder is stored therein and the opening is airtightly closed from the inside of the enclosure portion; The present invention is characterized by comprising: [Effects of the Invention]

[0024] According to the present disclosure, it is possible to provide an analytical system and an analytical method that enable a sample to be set in an atmosphere with reduced residual moisture content without using a highly airtight and expensive glove box. [Brief explanation of the drawings]

[0025] [Figure 1A] FIG. 2 is a diagram showing the configuration of a mechanical part of the analysis system according to the first embodiment of the present disclosure (unhoused position). [Figure 1B] FIG. 2 is a diagram showing the configuration (storage position) of a mechanical part of the analysis system according to the first embodiment of the present disclosure. [Figure 2] FIG. 2 is a block diagram showing the configuration of a control system of the analysis system according to the first embodiment of the present disclosure. [Figure 3] 1 is a flowchart showing the procedure for carrying out an analysis method according to a first embodiment of the present disclosure. [Figure 4] FIG. 10 is a diagram showing the configuration of a mechanical part of an analysis system according to a second embodiment of the present disclosure. [Figure 5] 10 is a flowchart showing the procedure for carrying out an analysis method according to a second embodiment of the present disclosure. [Figure 6] FIG. 10 is a diagram showing the configuration of a mechanical part of an analysis system according to a third embodiment of the present disclosure. [Figure 7] FIG. 11 is a block diagram showing the configuration of a control system of an analysis system according to a third embodiment of the present disclosure. [Figure 8] 10 is a flowchart showing the procedure for carrying out an analysis method according to a third embodiment of the present disclosure. [Figure 9] FIG. 10 is a diagram showing the configuration of a mechanical part of an analysis system according to a fourth embodiment of the present disclosure. [Figure 10] FIG. 10 is a block diagram showing the configuration of a control system of an analysis system according to a fourth embodiment of the present disclosure. [Figure 11] 10 is a flowchart showing the procedure for carrying out an analysis method according to a fourth embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0026] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings.

[0027] 1A is a diagram showing the configuration of an analysis system 100 according to a first embodiment of the present disclosure. The analysis system 100 according to this embodiment includes a sample holder 10 that holds a sample to be analyzed, an airtight section 20 that has an opening (lower opening 23a) and accommodates the sample holder 10 therein, a film-like enclosure 30 that is transparent to visible light and separates the sample holder 10 and the opening (lower opening 23a) of the airtight section 20 from the outside, and a base section 40 that supports the sample holder 10, a measurement section 15 (described later), and the like. The enclosure 30 is flexible enough to easily deform while maintaining airtightness between it and the outside when the airtight section 20 is moved.

[0028] 1A, the airtight part 20 has a structure in which a cylindrical airtight tube 21 made of alumina, quartz, or the like and having one tapered end (upper end) is integrated with a flange member 29 made of a metal such as stainless steel and attached to the other end (lower end) of the airtight tube 21 using an adhesive or the like. The flange member 29 has a fitting cylindrical part 29a that forms a lower opening 23a. A heating part 22 is disposed radially outside the airtight tube 21, is integrated with the airtight part 20 by a fixing means, or the like, and is movable up and down together with the airtight tube 21.

[0029] In the present specification, claims, abstract, and drawings, the up-down direction is based on the state in which the analysis system 100 is placed on a horizontal surface, with the side where the airtight section 20 is located being the top and the side where the base section 40 is located being the bottom. Furthermore, the front is the left side in FIG. 1A where the operation panel 42 operated by the operator is provided, and the rear is the opposite side to the front (the right side in FIG. 1A). Furthermore, the left-right direction is the direction perpendicular to the plane of the paper in FIG. 1A. Furthermore, the "outside" refers to the space outside the analysis system 100.

[0030] In this embodiment, the analysis system 100 is described as including a thermogravimeter / differential scanning calorimeter (TG / DSC), but is not limited to this. The analysis system 100 can be any analysis system 100 that has a sample holder 10 for placing a sample and an airtight section 20 for keeping the periphery of the sample airtight. In addition to the thermogravimeter / differential scanning calorimeter (TG / DSC), the analysis system 100 may also be equipped with other thermal analysis devices, such as a thermogravimeter / differential thermal analyzer (TG / DTA), a thermomechanical analyzer (TMA), or a dynamic mechanical analyzer (DMA). The analysis system 100 may also include an analysis device other than a thermal analysis device, such as a scanning electron microscope (SEM), a gas chromatograph (GC) equipped with an accessory device for sample introduction, a GC-MS or GC / TOF-MS that combines a gas chromatograph equipped with the accessory device and a mass spectrometer (MS), a time-of-flight secondary ion mass spectrometry (TOF-SIMS), an X-ray diffractometer (XRD), or an X-ray photoelectron spectrometry (XPS).

[0031] In this embodiment, the analysis system 100 includes a second gas supply unit 47 for introducing a purge gas (an inert gas such as nitrogen, with a dew point temperature of approximately −70° C. or lower) from the second gas supply unit 47 to the internal space 24 of the airtight unit 20 in FIGS. 1A and 1B and the airtight space 41 a of the base unit 40 via a mass flow controller (MFC) 47 a. A sample may be placed in the airtight unit 20, the airtight unit 20 may be moved to a storage position (see FIG. 1B ) described below, and the airtight unit 20 may be kept airtightly closed (stored state) while the purge gas from the second gas supply unit 47 continues to flow, and measurement, analysis, etc. of the sample in the airtight unit 20 may be performed. Alternatively, a vacuum may be created by a pump 48 via a valve 48 a attached to the base unit 40. Furthermore, after evacuation, valve 48a may be closed and a purge gas (an inert gas such as nitrogen, with a dew point temperature of approximately -70°C or lower) may be introduced into the chamber via mass flow controller (MFC) 47a, thereby performing so-called vacuum gas replacement. Note that in this specification, "evacuation" refers to lowering the internal pressure to approximately 100 Pa or lower.

[0032] The sample holder 10 holds the sample and is connected to a balance 13 (weight measurement unit) (see Figure 2) of the measurement unit 15 located below, allowing changes in the weight of the sample to be measured. The measurement unit 15 also has a temperature sensor 10a (see Figure 2) that measures the temperature of the sample. An operator places the sample in a sample container 11 and places it in the sample holder 10. Note that the system may be configured so that the sample container 11 in the sample tray is automatically placed in the sample holder 10 by an autosampler.

[0033] The material of the sample container 11 can be selected from alumina, platinum, platinum-rhodium alloy, quartz glass, aluminum, magnesium oxide (MgO), yttrium oxide (Y2O3), gold (Au), silver (Ag), graphite, boron nitride (BN), molybdenum (MO), and zirconium oxide (ZrO2), taking into consideration the measurement temperature conditions, etc.

[0034] The temperature sensor 10a may be, for example, a thermocouple made by joining a platinum-rhodium alloy (PtRh) and platinum (Pt).

[0035] Furthermore, the system control unit 101 uses the balance unit 13 to measure the change in weight of the sample.

[0036] Details of other TG-DSC configurations are disclosed in Japanese Patent No. 5933653 and the like, so detailed explanation of the TG-DSC configuration will be omitted.

[0037] The balance unit 13 is appropriately installed in an airtight space 41a inside the base unit 40. The base unit 40 includes a base housing 41 with the airtight space 41a provided inside, an operation panel 42 that an operator operates to input various information and operate the device when using the analysis system 100, and a work base 45 having a substantially rectangular shape in a plan view that is provided above the base housing 41 via a fixed cylinder 43. An O-ring 43a is appropriately disposed inside the fixed cylinder 43 that forms the base opening 45a, and when the airtight unit 20 is moved downward, the engagement cylinder 29a engages with the O-ring 43a, so that the internal space 24 of the airtight unit 20, including the sample holder 10, and the airtight space 41a are all airtight.

[0038] A base opening 45a (opening) communicating with the airtight space 41a (closed space) is provided at approximately the center of the surface of the work base 45. As will be described later, after the operator sets the sample container 11 containing the sample in the sample holder 10 when the dew point has sufficiently dropped, the airtight part 20 is moved downward by the movement mechanism 27 (see FIG. 2) so that the fitting tube 29a provided at the bottom of the airtight part 20 fits into the base opening 45a on the base part 40 side. As a result, the internal space 24 of the airtight part 20 and the airtight space 41a of the base part 40 are sealed from the outside and the inner space of the enclosure part 30 and maintained in an airtight state in a housing state (housing position) (see FIG. 1B) in which the sample holder 10 is housed therein. In this storage position, the internal space 24 of the airtight portion 20 and the airtight space portion 41a of the base portion 40 are hermetically sealed not only from the outside of the analysis system 100, but also from the internal space of the enclosure portion 30 and the space outside the airtight portion 20 and the base portion 40.

[0039] The dew point temperature in the inner space of the enclosure 30 may be measured with a dew point meter, or may be controlled by the installation time of the cooling unit 90 and the supply time of the purge gas, etc. Also, the dew point temperature, oxygen concentration, etc. may be controlled by mass spectrometry via the capillary tube 26.

[0040] 1A, the airtight part 20 includes an airtight tube 21 made of alumina, quartz, or the like, having a capped cylindrical shape with a tapered upper end, and a flange member 29 airtightly integrated with the lower end of the airtight tube 21. The flange member 29 is formed of a metal material such as stainless steel, and includes a fitting cylindrical portion 29a hanging down from the lower end of the airtight tube 21 and a flange portion 29b extending radially outward from the upper end of the fitting cylindrical portion 29a. The airtight tube 21 is fixed by adhesive or the like to a notch provided at a corner where the fitting cylindrical portion 29a and the flange portion 29b are connected. The inside of the fitting cylindrical portion 29a forms a lower opening 23a that communicates the internal space 24 with the outside of the airtight part 20. As described above, by fitting the outer surface of the fitting tubular portion 29a to the inner surface of the base opening 45a on the base portion 40 side via the O-ring 43a, the internal space 24 of the airtight portion 20 and the airtight space 41a of the base portion 40 are sealed from the outside and the inside of the surrounding portion 30, and are thereby connected in an airtight manner. The dew point and oxygen concentration in the atmosphere are important in the analysis of advanced materials such as battery materials. By evacuating the airtight space 41a with a pump 48 (see FIG. 2) while the internal space 24 of the airtight portion 20 and the airtight space 41a of the base portion 40 are kept airtight from the outside and the inside of the surrounding portion 30, unnecessary gases such as oxygen can be removed from the internal space 24 of the airtight portion 20 and the airtight space 41a of the base portion 40 in addition to removing moisture with the cooling unit 90 described below.

[0041] The pump 48 may be, for example, a rotary pump, a dry pump, or a turbomolecular pump. By evacuating the airtight space 41a with a rotary pump, a dry pump, or a turbomolecular pump, the dew point in the internal space 24 of the airtight part 20 and the airtight space 41a can be lowered and gases that interfere with sample analysis, such as oxygen, can be removed. The dew point temperature in the airtight part 20 is preferably -40°C or lower, more preferably -60°C or lower, and most preferably -80°C or lower. Measurements can be performed in this state using an instrument that performs measurements while maintaining a vacuum inside the airtight part 20 (such as an SEM or TOF-SIMS).

[0042] On the other hand, in thermal analysis such as TG, after evacuation, so-called vacuum gas replacement is performed using an inert gas introduced from the second gas supply unit 47 via the mass flow controller 47a, making it possible to perform measurements with the oxygen concentration around the sample also reduced.

[0043] The upper portion of the airtight tube 21 has a reduced diameter, and is provided with an upper opening 25 for inserting a capillary tube 26. Gas generated from the sample during thermal analysis can be introduced to a mass spectrometer via the capillary tube 26 and subjected to mass spectrometry (also referred to as "MS") measurement to identify the gas. However, without being limited to this embodiment, the gas generated from the sample during thermal analysis may be introduced to a gas chromatograph-mass spectrometer (GC / MS) or a Fourier transform infrared spectrometer (FT-IR) instead of a mass spectrometer.

[0044] In this embodiment, the enclosure 30 is constructed using a so-called glove bag, which is flexible and transparent to visible light. It includes a film-like transparent synthetic resin cover 31 and an operation projection 32 protruding inward from the cover 31. The operation projection 32 is shaped like a glove, allowing a human hand to be inserted into the cover 31 to perform operations such as placing a sample from a sample tray into a sample container 11. Alternatively, the operation projection 32 may be omitted, allowing the operator to handle samples through the cover 31. It is also preferable to attach a small sample pass bag 38 (see FIGS. 1A and 1B) to the cover 31 for introducing samples from the outside. The sample pass bag 38 may have an openable / closable function, such as a zipper-like function (external zipper 38a and internal zipper 38b), on both the cover 31 side and the external side. After inserting a sample through the external zipper 38a, the external zipper 38a may be closed, and then the internal zipper 38b on the cover 31 side may be opened to introduce the sample into the enclosure 30.

[0045] The cover body 31 of the enclosure 30 has flexibility (flexibility) that allows it to follow the vertical movement of the airtight section 20. The cover body 31 is made of a transparent or translucent material that transmits visible light so that the inside of the enclosure 30 can be seen from the outside. Examples of materials that can be used for the cover body 31 include polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC).

[0046] 1A, the cover body 31 is provided with an upper cover opening 35 for connecting the interior of the enclosure 30 to the interior of the airtight part 20. The cover body 31 also has a lower cover opening 36 for connecting the interior of the enclosure 30 to the airtight space 41a of the base part 40.

[0047] 1A, with the fitting cylindrical portion 29a on the airtight portion 20 side inserted into the cover upper opening 35, the cover upper fixing screw 37a is threadedly engaged with the female thread portion provided on the flange portion 29b of the flange member 29. With this configuration, the upper part of the cover body 31 is fixed to the underside of the flange portion 29b. Similarly, with the fixing cylindrical portion 43 on the base portion 40 side inserted into the cover lower opening 36, the cover lower fixing screw 37b is threadedly engaged with the female thread portion provided on the radially outer side of the fixing cylindrical portion 43 on the upper wall of the base housing 41. With this configuration, the lower part of the cover body 31 is fixed to the upper wall of the base housing 41.

[0048] In this embodiment, the airtight portion 20 is configured such that the airtight tube 21 and the flange member 29 are fixed by adhesive or the like, but this is not limited to this configuration, and the functions of the airtight tube 21 and the flange member 29 may be realized by an integrally formed member.

[0049] 1A, a small-diameter side opening 34b is provided on the side of the cover body 31, and a purge gas is supplied from an external first gas supply unit 55 through a gas introduction pipe 50 inserted into the side opening 34b. The purge gas is, for example, dry nitrogen gas, argon gas, helium gas, or the like.

[0050] A cooling head 91 of a cooling unit 90 is disposed inside the enclosure 30 and outside the airtight section 20 on the work base 45. The cooling head 91 cools the inside of the enclosure 30 by heat exchange inside the enclosure 30 with a refrigerant supplied from a refrigerator 91b via a refrigerant tube 91a. As shown in FIG. 1A, the cooling head 91 is covered with a mesh cover 92 to prevent workers from directly touching the cooling head 91. In addition, a drain tube 93 and a stop valve 93a for controlling the flow of the discharged water are provided below the cooling head 91. These drain tubes 93 are used to discharge water produced by condensation of water vapor contained in the air inside the enclosure 30 cooled by the cooling head 91.

[0051] The refrigerator 91b constituting the cooling unit 90 can be a general refrigerator that removes heat from the surroundings by vaporizing a refrigerant in the cooling head 91, or various types of refrigerators can be used, such as a Stirling refrigerator, a Gifford-McMahon (GM) refrigerator, or a pulse tube refrigerator.

[0052] In this embodiment, for example, a cooling head 91 capable of cooling down to -90°C is disposed inside the enclosure 30 and outside the airtight section 20, so that water vapor contained in the air around the cooling head 91 condenses on the outer surface of the cooling head 91. Subsequently, water vapor contained in the air inside the enclosure 30 gradually gathers at the cooling head 91 and condenses. Furthermore, at the same time that the cooling head 91 condenses the water vapor inside the enclosure 30, dry nitrogen gas with a dew-point temperature of -70°C or lower is introduced into the enclosure 30 from the first gas supply unit 55 through the gas introduction pipe 50. With this configuration, the dew-point temperature inside the enclosure 30 can be lowered to -70°C or lower in about one minute.

[0053] In this embodiment, the cooling head 91 capable of cooling down to −90°C is disposed inside the enclosure 30 as the cooling unit. However, this is not limited to this embodiment. The minimum temperature of the cooling head 91 may be appropriately selected from, for example, −90°C to −40°C depending on the dew point temperature required inside the enclosure 30. Furthermore, instead of the combination of the refrigerator 91b and the cooling head 91, a Peltier element, one side of which is cooled by applying electricity, may be disposed inside the enclosure 30 as the cooling unit. When a Peltier element is disposed as the cooling unit, for example, the cooling surface of the Peltier element may be oriented upward, and the heat dissipation surface may be attached to a heat dissipation fin attached to the work base 45. Instead of the cooling head 91 or the Peltier element, any other cooling device capable of cooling the inside of the enclosure 30 to a predetermined dew point temperature by supplying energy may be disposed as the cooling unit.

[0054] In this embodiment, the gas supply from the first gas supply unit 55 is performed by the system control unit 101 controlling the gas supply valve of the first gas supply unit 55, but this is not limiting and the gas supply may be performed by an operator manually operating the gas supply valve. Note that, in order to perform gas purging of the airtight space 41a, it is desirable to simultaneously perform gas purging from the second gas supply unit 47 via the mass flow controller 47a.

[0055] Each process in the system control unit 101 can be realized as software processing by, for example, causing a predetermined program stored in a storage unit or the like to be executed by a CPU (Central Processing Unit) or DSP (Digital Signal Processor) included in the system control unit 101. However, this is not limiting, and each process may be configured to be realized as hardware processing by, for example, an ASIC (Application Specific Integrated Circuit), a PLD (Programmable Logic Device), or an FPGA (Field Programmable Gate Array).

[0056] The storage unit that stores the predetermined program includes a readable storage medium, and the storage medium may be a rewritable and programmable ROM such as an EPROM, an EEPROM, or a flash memory, or another tangible storage medium such as a magnetic disk storage medium that can store information, or any combination thereof. The storage unit may be provided within the system control unit 101, or may be a storage medium in an external storage device that can be connected to the system control unit 101.

[0057] Next, the procedure for carrying out the analysis method according to this embodiment using the analysis system 100 having the above configuration will be described with reference to FIG. 3 and other figures.

[0058] First, before carrying out the analysis method according to this embodiment, an operator (1) attaches the enclosure 30 to the airtight part 20 and the base part 40, and (2) places the cooling head 91 of the cooling unit 90 inside the enclosure 30 and outside the airtight part 20 so that it does not interfere with the airtight part 20 even when in the "storage position." Although the above steps (1) and (2) are prerequisites for carrying out the analysis method according to this embodiment, they are not steps that are carried out every time the analysis method is carried out, and therefore are not included in the procedure for carrying out the analysis method described below.

[0059] To attach the surrounding part 30, with the fitting cylindrical part 29a on the airtight part 20 side passed through the cover upper opening 35, the upper cover fixing screw 37a with a washer is threadedly engaged with the female threaded part provided on the radially outer side of the fitting cylindrical part 29a in the flange part 29b of the flange member 29, thereby fixing the upper part of the cover body 31 to the lower part of the airtight part 20. Furthermore, with the fixing cylindrical part 43 on the base part 40 side inserted into the cover lower opening 36, the lower cover fixing screw 37b with a washer is threadedly engaged with the female threaded part provided on the radially outer side of the fixing cylindrical part 43 on the upper wall of the base housing 41, thereby fixing the lower part of the cover body 31 to the upper wall of the base housing 41.

[0060] Furthermore, one end of a gas introduction pipe 50 is inserted into the side opening 34 b of the cover body 31 to prepare for gas supply into the enclosure 30 .

[0061] "The cooling head 91 is disposed at a position outside the airtight portion 20" means that the cooling head 91 is disposed so as to be located outside the airtight portion 20 in a plan view. The cooling head 91 is disposed at a position that does not interfere with an operator's operation of supplying a sample to the sample holder 10. In FIG. 1A, the cooling head 91 is disposed at a position offset from the sample holder 10 in the left-right direction (perpendicular to the plane of the paper in FIG. 1A) so as not to interfere with an operator's operation of supplying a sample to the sample holder 10. The cooling head 91 is disposed so as to be located inside the enclosure portion 30.

[0062] When carrying out the analysis method according to this embodiment, first, an operator operates the operation panel 42 or executes a control program, which causes the system control unit 101 to open the gas supply valve and supply purge gas from the first gas supply unit 55 into the enclosure 30 via the gas inlet pipe 50 (step S101 in FIG. 3). The purge gas may be nitrogen gas controlled to have a low dew point (e.g., a dew point temperature of −70° C.), or it may be argon gas, helium gas, or the like. The supply of purge gas may be performed by the system control unit 101 controlling the gas supply valve of the first gas supply unit 55, or the operator may directly operate the gas supply valve.

[0063] Next, by operating the operation panel 42 or the like, the airtight part 20 is moved by the movement mechanism 27 to the top dead center position (non-contained position) as shown in FIG. 1A to set it in the non-contained state (step S102 in FIG. 3).

[0064] Next, when an operator operates the operation panel 42 or executes a control program, the system control unit 101 activates the refrigerator 91b to condense the water vapor inside the enclosure 30 and lower the dew-point temperature inside the enclosure 30 to an appropriate dew-point temperature (step S103 in FIG. 3). By introducing the purge gas into the enclosure 30 in step S101 and operating the cooling unit in step S103, the dew-point temperature of the space inside the enclosure 30 (the space inside the enclosure 30, the internal space 24 of the airtight unit 20, and the airtight space 41a of the base 40) can be lowered to −70° C. or below.

[0065] Next, the operator introduces the sample into the enclosure 30 through the sample pass bag 38 (step S104 in FIG. 3). When placing the sample into the enclosure 30, first, with the inner chuck 38b closed, the outer chuck 38a is opened, the sample is placed into the sample pass bag 38, and then the outer chuck 38a is closed. Next, only the inner chuck 38b is opened, and the sample in the sample pass bag 38 is introduced into the enclosure 30.

[0066] Next, the operator places his / her hand inside the operation convex portion 32 (glove) of the enclosure portion 30, picks up the sample container 11 containing the sample over the operation convex portion 32, and places it on the sample holder 10 (step S105 in FIG. 3). Note that the sample container 11 containing the sample in the sample tray may be automatically placed on the sample holder 10 by an autosampler.

[0067] Next, the operator operates the operation panel 42 or executes a control program, which causes the system control unit 101 to move the airtight unit 20 using the movement mechanism 27 to a height position (accommodated position) where the fitting cylindrical portion 29a fits inside the base opening 45a, thereby setting the airtight unit 20 in an accommodated state (see FIG. 1B) (step S106 in FIG. 3). By moving the airtight unit 20 to the accommodated state (state transition), the sample holder 10 is accommodated in the airtight unit 20, and the fitting cylindrical portion 29a fits into the O-ring 43a on the inner surface of the base opening 45a, thereby sealing and closing the lower opening 23a (opening) of the airtight unit 20 and the base opening 45a of the base unit 40 in an airtight state from the outside and the inside of the enclosure 30. At this point, the dew-point temperatures in the internal space 24 of the airtight unit 20 and the airtight space portion 41a of the base unit 40 are maintained at approximately −70°C or below.

[0068] Next, when an operator operates the operation panel 42 or executes a control program, the system control unit 101 controls the mass flow controller (MFC) 47a and the valve 48a to maintain the interior space 24 of the airtight unit 20 and the airtight space 41a of the base unit 40 in an appropriate state (step S107 in FIG. 3). Here, maintaining an appropriate state may mean, for example, keeping the airtight unit 20 and the airtight space 41a in an airtight closed state (accommodated state) and continuing to flow purge gas from the second gas supply unit 47 via the mass flow controller (MFC) 47a. Alternatively, the airtight unit 20 and the airtight space 41a may be evacuated by the pump 48 via the valve 48a provided on the base unit 40. Furthermore, after evacuation, valve 48a may be closed and a purge gas (an inert gas such as nitrogen, with a dew point temperature of approximately −70°C or lower) may be introduced from second gas supply unit 47 into internal space 24 of airtight unit 20 and airtight space 41a of base unit 40, thereby performing so-called vacuum gas replacement. By maintaining the internal space 24 of airtight unit 20 and airtight space 41a of base unit 40 in an appropriate state while maintaining airtightness from the outside and the inside of enclosure 30, oxygen and the like can be removed from the internal space 24 of airtight unit 20 and airtight space 41a of base unit 40 in addition to removing moisture with cooling unit 90. This allows for a reduction in the dew point temperature and oxygen concentration in the atmosphere, which are important for analyzing advanced materials such as battery materials.

[0069] Next, the operator operates the operation panel 42 or executes the control program, and the system control unit 101 heats the heating unit 22 of the airtight unit 20 to analyze the sample in the internal space 24 (step S108 in FIG. 3). In the analysis system 100 according to this embodiment, the system control unit 101 calculates the sample temperature T S The change in the sample weight, etc. are measured.

[0070] Next, by the operator operating the operation panel 42 or executing the control program, the system control unit 101 stops the evacuation of the airtight unit 20 if it is being evacuated after the analysis is completed, and moves the airtight unit 20 to the non-container position to set it in an uncontained state (step S109 in FIG. 3). The operator again inserts his hand into the operation convex portion 32 of the enclosure 30 to remove the sample from the sample holder 10 (step S110 in FIG. 3). Furthermore, the operator removes the analyzed sample from the sample pass bag 38, if necessary. If the operator wishes to continue analyzing the sample (if "Yes" is selected in step S111 in FIG. 3), steps S105 to S110 in FIG. 3 are performed again.

[0071] Although the analysis system 100 has been described above as a TG / DSC, the present invention is not limited to this. The analysis system 100 may be, for example, a system for performing thermal analysis other than TG / DSC, or may be a system for analyzing samples other than thermal analysis, such as an SEM. When the analysis system 100 functions as an SEM, the sample may be placed in the sample holder 10 in an atmosphere with a low dew point temperature inside the enclosure 30 to prevent the sample from absorbing moisture, and then the airtight portion 20 may be evacuated while the sample is housed to protect the filament that emits the electron beam. In this case, the airtight space 41a of the base 40 may not be provided.

[0072] The analysis system 100 according to this embodiment is suitable for applications in which a sample is set in the sample holder 10 so as not to be exposed to moisture, and then analyzed in a vacuum environment in the airtight part 20, or after vacuum gas replacement, but is not limited to this. It can also be used for applications in which a sample is set in the sample holder 10 so as not to be exposed to moisture, and then analyzed in the airtight part 20 without evacuating.

[0073] As described above, this embodiment of the present invention provides an analytical system 100 including a sample holder 10 for holding a sample to be analyzed, an airtight portion 20 having an opening (lower opening 23a) and housing the sample holder 10 therein, and a flexible, visible-light-transmitting enclosure 30 that separates the sample holder 10 and the opening of the airtight portion 20 from the outside. The airtight portion 20 can transition between a housing state in which the sample holder 10 is housed and the opening is airtightly closed from the inside of the enclosure 30, and an unhoused state in which the sample holder 10 is located outside the airtight portion 20. At least when the airtight portion 20 is in the unhoused state, a cooling unit is disposed inside the enclosure 30 and outside the airtight portion 20. This configuration allows the dew point temperature of the atmosphere when the sample is set to the sample holder to be reduced in a short time without the need for an expensive, airtight glove box. Therefore, analysis of advanced battery materials and the like can be performed in an atmosphere with minimal residual moisture.

[0074] Furthermore, in this embodiment, the inside of the airtight part 20 is configured so that it can be evacuated or vacuum-gas substituted after the opening (lower opening 23a) is airtightly closed to the inside of the surrounding part 30. By adopting such a configuration, analysis of the latest battery materials and the like can be performed in an atmosphere in which the amount of remaining water has been reduced to the utmost and unnecessary gases such as oxygen have also been reduced to the utmost.

[0075] Furthermore, in this embodiment, a cooling unit such as the cooling head 91 of the refrigerator 91b, a Peltier element, or another cooling device is arranged inside the enclosure 30 and outside the airtight unit 20. By adopting such a configuration, the cooling unit that condenses water vapor in the air inside the enclosure 30 to lower the dew point temperature can be operated safely and stably.

[0076] In this embodiment, the enclosure 30 is configured to have an inwardly protruding operation protrusion 32. By adopting such a configuration, an operator can insert his or her hand into the operation protrusion 32 to perform operations, thereby improving the efficiency of operations such as setting a sample.

[0077] Furthermore, in this embodiment, the airtight part 20 includes a cylindrical airtight tube 21 that accommodates the sample holder 10 therein, and a metallic fitting cylinder 29a that is fixed to the end of the airtight tube 21 and forms an opening (lower opening 23a). The fitting cylinder 29a is configured to fit into an opening (base opening 45a) of a closed space (airtight space 41a) facing the inside of the enclosure 30, thereby airtightly closing the opening (lower opening 23a) from the inside of the enclosure 30. By adopting such a configuration, the interior of the airtight part 20 can be airtightly closed from the outside and the inside of the enclosure 30 simply by moving the fitting cylinder 29a of the airtight part 20 so that it fits into the base opening 45a. Furthermore, by making the fitting cylinder 29a that constitutes the seal part out of metal, the durability of the seal part can be increased.

[0078] Furthermore, this embodiment is an analytical method using an analytical system 100 including a sample holder 10 for holding a sample to be analyzed, an airtight portion 20 having an opening (lower opening 23a) and accommodating the sample holder 10 therein through the opening, and a flexible, visible-light-transmitting enclosure 30 that separates the sample holder 10 and the opening of the airtight portion 20 from the outside. The method includes the steps of: transitioning the airtight portion 20 to a non-accommodated state in which the sample holder 10 is positioned outside the airtight portion 20; activating a cooling unit provided outside the airtight portion 20; and transitioning the airtight portion 20 to a accommodated state in which the sample holder 10 is accommodated therein and the opening is airtightly closed from the inside of the enclosure 30. By employing such a configuration, the dew point temperature of the atmosphere when setting the sample can be reduced to −70° C. or below in a short time (approximately within one minute) without using an expensive, highly airtight glove box. Therefore, analysis of the latest battery materials and the like can be carried out in an atmosphere with the amount of residual moisture reduced to the utmost.

[0079] Next, an analysis system 200 according to a second embodiment of the present disclosure will be described. This second embodiment is similar in configuration to the first embodiment, except that, compared to the first embodiment, a coolant container 60 containing a liquid coolant (such as liquefied nitrogen) is placed on a work base 45 instead of the cooling head 91 of the cooling unit 90. Here, the differences from the first embodiment will be mainly described.

[0080] As shown in FIG. 4 , a small-diameter side opening 34b is provided on the side of the cover body 31, and a purge gas is supplied from a first gas supply unit 55 through a gas inlet pipe 50 inserted into the side opening 34b. The purge gas may be, for example, dry nitrogen gas, argon gas, or helium gas. The purge gas supplied through the gas inlet pipe 50 may be nitrogen gas that is vaporized from liquefied nitrogen contained in a coolant container 60 (described later) and discharged to the outside through an opening 62, and supplied as the purge gas into the cover body 31 through the gas inlet pipe 50. In this case, the purge gas supplied into the cover body 31 of the enclosure 30 may be discharged to the outside through one or more discharge units provided in the cover body 31.

[0081] A coolant container 60 containing a coolant is provided inside the enclosure 30 and outside the airtight portion 20 on the work base 45. The coolant container 60 has a body 61 that contains liquefied nitrogen as the coolant, and an opening 62 that connects the inside of the body 61 to the outside. The coolant container 60 contains liquefied nitrogen at least when the airtight portion 20 is in an uncontained state (uncontained position).

[0082] The mouth 62 of the coolant container 60 protrudes to the outside through a mouth support opening 34a provided at the top of the cover body 31 of the enclosure 30. A portion of the liquefied nitrogen contained in the body 61 of the coolant container 60 vaporizes and is discharged to the outside through the mouth 62. This allows the nitrogen gas vaporized inside the coolant container 60 to quickly escape to the outside of the enclosure 30, preventing the pressure inside the enclosure 30 from increasing excessively.

[0083] In this embodiment, the coolant container 60 is made of a material with high thermal conductivity, such as copper or aluminum. The coolant container 60 may be made of stainless steel, which has relatively high thermal conductivity and corrosion resistance, or other metal materials depending on the purpose. With this configuration, the inner surface of the body 61 is cooled to -150 to -196°C by liquefied nitrogen, and the outer surface of the body 61 is also cooled. As the outer surface of the body 61 is cooled, water vapor contained in the air surrounding the body 61 condenses on the outer surface of the body 61. Subsequently, water vapor contained in the air within the enclosure 30 gradually collects and condenses on the body 61 of the coolant container 60. At the same time that the liquefied nitrogen condenses the water vapor within the enclosure 30, dry nitrogen gas with a dew point temperature of -70°C or lower is introduced into the enclosure 30 from the first gas supply unit 55 through the gas introduction pipe 50. With this configuration, the dew point temperature within the enclosure 30 can be lowered to -70°C or lower in approximately one minute.

[0084] In this embodiment, liquefied nitrogen is contained in the coolant container 60 as a coolant, but this is not limited to this form, and depending on the dew point temperature required within the enclosure 30, dry ice + ethanol or ice + sodium chloride may also be contained as a coolant other than liquefied nitrogen.

[0085] In this embodiment, similarly to the first embodiment, a sample may be supplied from the outside and removed to the outside via the sample pass bag 38. Alternatively, a sample may be supplied from the outside and removed to the outside via an opening that can be closed with a hook-and-loop fastener or a zipper (fastener) provided on the cover body 31. This also applies to the third and subsequent embodiments.

[0086] The control system of the analysis system 200 according to this embodiment has a configuration in which the refrigerator 91b and the stop valve 93a of the cooling unit 90 are removed from the configuration of FIG. 2, and therefore further illustration is omitted.

[0087] Next, the procedure for carrying out the analysis method according to this embodiment using the analysis system 200 having the above configuration will be described with reference to FIG. 5 and other figures.

[0088] First, before carrying out the analysis method according to this embodiment, an operator (1) attaches the enclosure 30 to the airtight part 20 and the base part 40, and (2) places the coolant container 60 inside the enclosure 30 and outside the airtight part 20 so that it does not interfere with the airtight part 20 even when in the "storage position." Although steps (1) and (2) above are prerequisites for carrying out the analysis method according to this embodiment, they are not steps that are carried out each time the analysis method is carried out, and therefore are not included in the procedure for carrying out the analysis method described below. Furthermore, because step (1) above is similar to the procedure in the first embodiment, a description thereof will be omitted here.

[0089] "The coolant container 60 is disposed at a position outside the airtight portion 20" means, as in the first embodiment, that the coolant container 60 is disposed so as to be located outside the airtight portion 20 in a plan view. This also applies to the third and subsequent embodiments. The coolant container 60 is disposed at a position that does not interfere with an operator's operation of supplying a sample to the sample holder 10. In Figure 4, the coolant container 60 is disposed at a position offset from the sample holder 10 in the left-right direction (perpendicular to the plane of the paper in Figure 4) so ​​as not to interfere with an operator's operation of supplying a sample to the sample holder 10. The coolant container 60 is disposed so as to be located inside the enclosure portion 30.

[0090] The operator supplies a coolant such as liquefied nitrogen into the coolant container 60 and activates the cooling unit, condensing the water vapor in the enclosure 30 and lowering the dew point temperature inside the enclosure 30 to an appropriate dew point temperature (step S203 in FIG. 5). By introducing purge gas into the enclosure 30 in step S201 and activating the cooling unit in step S203 (supplying a coolant such as liquefied nitrogen into the coolant container 60), the dew point temperature of the space inside the enclosure 30 (the space inside the enclosure 30, the internal space 24 of the airtight portion 20, and the airtight space 41a of the base portion 40) can be lowered to -70°C or below.

[0091] In FIG. 5, the steps other than step S203 (steps S201 to S202 and steps S204 to S211) are similar to steps S101 to S102 and steps S104 to S111 in the first embodiment, and therefore further explanation will be omitted here.

[0092] As described above, in this embodiment, the coolant container 60 containing a liquid coolant is arranged as a cooling unit inside the enclosure 30 and outside the airtight unit 20. By adopting such a configuration, it is possible to easily realize an atmosphere in which the amount of residual moisture is reduced to the minimum by simply arranging a container containing a coolant on the work base 45.

[0093] Furthermore, in this embodiment, the interior of the coolant container 60 is configured to communicate with the outside through the enclosure opening (mouth support opening 34a) provided in the enclosure 30. By adopting such a configuration, it is possible to prevent the coolant that is heated and vaporized when condensing the moisture inside the enclosure 30 from excessively increasing the pressure inside the enclosure 30, making it easier to ensure the safety of the system.

[0094] Next, an analysis system 300 according to a third embodiment of the present disclosure will be described. This third embodiment is similar in configuration to the second embodiment except that, compared to the second embodiment, a cooling coil 71 into which a liquid coolant is supplied is disposed instead of the coolant container 60, and nitrogen gas discharged from the cooling coil 71 and heated by a heater 74 is supplied into the enclosure 30 instead of supplying purge gas from the first gas supply unit 55 into the enclosure 30. Here, the differences from the second embodiment will be mainly described.

[0095] As shown in FIGS. 6 and 7 , the cooling coil system 70 includes a cooling coil 71, a coolant supply unit 77 and a coolant inlet pipe 72 that supply liquid coolant (such as liquefied nitrogen) to the inside of the cooling coil 71, a coolant outlet pipe 73 that discharges the coolant from the cooling coil 71, a heater 74 that heats the coolant in the coolant outlet pipe 73, and a gas inlet pipe 75 that introduces the heated, vaporized coolant into the enclosure 30. The cooling coil 71 is made of a material such as copper or aluminum, which has high thermal conductivity. Alternatively, the cooling coil 71 may be made of a metal such as stainless steel, which has relatively high thermal conductivity and is resistant to corrosion. In this embodiment, the coolant outlet pipe 73, the heater 74, and the gas inlet pipe 75 are disposed outside the base housing 41 of the base unit 40.

[0096] The cooling coil 71 is disposed on the work base 45 at a position inside the enclosure 30 and outside the airtight part 20 in a plan view. The cooling coil 71 is disposed offset forward and left-right (perpendicular to the plane of the paper in FIG. 6) relative to the airtight part 20 in a plan view. A coolant introduction pipe 72 that supplies coolant to the cooling coil 71 passes through a coolant introduction opening 34c provided at the top of the cover body 31 of the enclosure 30 and penetrates from the inside to the outside of the enclosure 30.

[0097] In addition, a coolant discharge pipe 73 that leads the coolant discharged from the cooling coil 71 to the outside passes through a coolant discharge opening 34d provided at the bottom of the cover body 31 of the enclosure 30 and penetrates the inside and outside of the enclosure 30.

[0098] The coolant is supplied into the cooling coil 71 from a coolant supply unit 77 equipped with a liquefied nitrogen container or the like through a coolant inlet pipe 72. The coolant is supplied into the cooling coil 71 via the coolant inlet pipe 72 when the system control unit 101 opens the coolant supply valve in response to an operator operating the operation panel 42 or executing a control program. Instead of the above configuration, the coolant may be supplied into the cooling coil 71 by the operator manually opening the coolant supply valve.

[0099] The liquefied nitrogen cools the inner surface of the cooling coil 71 to a temperature between -150 and -196°C, and also cools the outer surface of the cooling coil 71. As the outer surface of the cooling coil 71 cools, water vapor contained in the air surrounding the cooling coil 71 condenses on its outer surface. Subsequently, water vapor contained in the air within the enclosure 30 gradually gathers and condenses on the cooling coil 71. At the same time that the liquefied nitrogen condenses the water vapor within the enclosure 30, the coolant (liquefied nitrogen) discharged from the cooling coil 71 is heated by a heater 74 and introduced into the enclosure 30 through a gas inlet pipe 75 as dry nitrogen gas. This configuration allows the dew point temperature within the enclosure 30 to drop to -70°C or below in just about one minute. As shown in FIG. 6, the gas inlet pipe 75 penetrates the interior and exterior of the enclosure 30 through a side opening 34b provided on the side of the cover body 31 of the enclosure 30.

[0100] In this embodiment, as shown in FIG. 6 , dry nitrogen gas heated by a heater 74 is introduced into the enclosure 30 as a purge gas through a gas inlet pipe 75. The introduced purge gas is then discharged to the outside from an outlet provided in the cover body 31. The outlet may be, for example, an outlet valve attached to the cover body 31 that controls the discharge from an outlet provided in the cover body 31. The amount of purge gas discharged from the outlet may also be controlled by a flow meter or the like. The outlet may also be one or more small-diameter holes provided in the cover body 31. This configuration makes it possible to prevent an excessive increase in pressure within the enclosure 30 when the coolant, which is heated and vaporized during condensation of moisture within the enclosure 30, is reintroduced into the enclosure 30 as a purge gas, thereby making it easier to ensure system safety.

[0101] In this embodiment, compared to the second embodiment, the amount of liquefied nitrogen supplied can be increased because liquefied nitrogen can be continuously supplied into the cooling coil 71 through the coolant introduction pipe 72. This allows the water vapor in the surrounding portion 30 to be efficiently condensed, and the dew point temperature in the surrounding portion 30 to be quickly lowered.

[0102] In this embodiment, the liquefied nitrogen discharged from the cooling coil 71 is heated and introduced as a purge gas through the gas inlet pipe 75 into the enclosed section 30, but this is not limited to this configuration. When argon gas or helium gas other than nitrogen gas is used as the purge gas, the argon gas or helium gas may be introduced into the enclosed section 30 from the first gas supply unit 55 (see FIG. 4) through the gas inlet pipe 50 in a system separate from the cooling coil 71, as in the second embodiment. In this case, it is preferable that the liquefied nitrogen discharged from the cooling coil 71 through the coolant discharge pipe 73 is not used as a purge gas but is reused, for example, as liquefied nitrogen.

[0103] Next, the procedure for carrying out the analysis method according to this embodiment using the analysis system 300 having the above configuration will be described with reference to FIG. 8 and other figures.

[0104] First, before carrying out the analysis method according to this embodiment, an operator (1) attaches the enclosure 30 to the airtight part 20 and the base part 40, and (2) places the cooling coil 71 inside the enclosure 30 and outside the airtight part 20 so that it does not interfere with the airtight part 20 even when in the "storage position." Although steps (1) and (2) above are prerequisites for carrying out the analysis method according to this embodiment, they are not steps that are carried out each time the analysis method is carried out, and therefore are not included in the procedure for carrying out the analysis method described below. Furthermore, because step (1) above is similar to the procedure in the first embodiment, a description thereof will be omitted here.

[0105] The cooling coil 71 is placed in a position that does not interfere with the operator's operation of supplying a sample to the sample holder 10. In Figure 6, the cooling coil 71 is placed in a position offset in the left-right direction (perpendicular to the plane of the paper in Figure 6) from the sample holder 10 so as not to interfere with the operator's operation of supplying a sample to the sample holder 10. The cooling coil 71 is placed so as to be located inside the enclosure 30.

[0106] The operator supplies a coolant such as liquefied nitrogen into the cooling coil 71 to operate the cooling unit, condensing the water vapor in the enclosure 30 and lowering the dew-point temperature inside the enclosure 30 to an appropriate dew-point temperature (step S303 in FIG. 8 ). Furthermore, by operating the cooling unit in step S303 (supplying and circulating a coolant such as liquefied nitrogen into the cooling coil 71), the coolant discharged from the cooling coil 71 is heated by the heater 74 and introduced into the enclosure 30 through the gas inlet pipe 75 as dry nitrogen gas or the like. With this configuration, in addition to condensing the water vapor inside the enclosure 30, dry gas is supplied into the enclosure 30, so that the dew-point temperature of the space inside the enclosure 30 (the space inside the enclosure 30, the interior space 24 of the airtight unit 20, and the airtight space 41a of the base 40) can be lowered to −70° C. or below.

[0107] 8, the steps other than S303 (step S302 and steps S304 to S311) are similar to step S102 and steps S104 to S111 in the first embodiment, and therefore further description thereof will be omitted here. Also, in this embodiment, instead of step S101 in the first embodiment (supplying purge gas from first gas supply unit 55 into enclosure 30), the coolant supplied to cooling coil 71 in step 303 is heated by heater 74 via coolant discharge pipe 73 to become dry gas, which is then supplied into enclosure 30 from gas inlet pipe 75.

[0108] As described above, in this embodiment, the cooling coil 71, into which liquid coolant is supplied, is arranged as a cooling unit inside the surrounding portion 30 and outside the airtight portion 20. By adopting such a configuration, the surface area of ​​the cooling unit can be increased compared to when the coolant container 60 is arranged inside the surrounding portion 30, and therefore the water vapor inside the surrounding portion 30 can be efficiently condensed to lower the dew point temperature.

[0109] Furthermore, in this embodiment, the liquid coolant supplied into the cooling coil 71 is configured to be supplied from the outside through an enclosure opening (coolant inlet opening 34c) provided in the enclosure 30 and to be discharged to the outside through an enclosure opening (coolant outlet opening 34d). By adopting such a configuration, compared to the second embodiment, it is possible to continuously supply liquefied nitrogen into the cooling coil 71 through the coolant inlet pipe 72, thereby increasing the amount of liquefied nitrogen supplied. Therefore, water vapor in the enclosure 30 can be efficiently condensed, and the dew point temperature inside the enclosure 30 can be quickly lowered.

[0110] In addition, in this embodiment, the discharged liquid coolant is heated and then introduced as purge gas into the enclosure 30. By adopting such a configuration, two systems, coolant and purge gas, can be supplied simply by providing the coolant supply unit 77 that introduces the coolant, thereby simplifying the system.

[0111] In this embodiment, the enclosure 30 is configured to have an exhaust section for exhausting gas to the outside. By adopting such a configuration, it is possible to prevent the coolant that is heated and vaporized when condensing the moisture inside the enclosure 30 from excessively increasing the pressure inside the enclosure 30, making it easier to ensure the safety of the system.

[0112] Next, an analysis system 400 according to a fourth embodiment of the present disclosure will be described. This fourth embodiment is similar in configuration to the second embodiment, except that, compared to the second embodiment, a coolant container 80 without a mouth is provided instead of the coolant container 60, and liquefied nitrogen is continuously supplied into the coolant container 80 from a coolant supply unit 87. Here, the differences from the second embodiment will be mainly described.

[0113] 9, the coolant container 80 has a cylindrical container body 81 with a bottom, and at the top of the enclosure 30, a coolant inlet pipe 82 that supplies liquefied nitrogen into the container body 81 passes through the coolant inlet opening 34c and penetrates the front and back of the cover body 31. In this embodiment, the coolant container 80 is made of a material with high thermal conductivity such as copper or aluminum. The coolant container 80 may also be made of a metal with relatively high thermal conductivity and corrosion resistance such as stainless steel.

[0114] The coolant container 80 is disposed on the work base 45 at a position inside the enclosure 30 and outside the airtight part 20 in a plan view. The coolant container 80 is disposed offset forward and to the left and right (directions perpendicular to the plane of the paper in FIG. 9) relative to the airtight part 20 in a plan view.

[0115] Furthermore, the liquefied nitrogen supplied to the coolant container 80 is heated and vaporized as it condenses the water vapor within the enclosure 30, and functions as a purge gas within the enclosure 30. Therefore, in this embodiment, there is no need for the gas inlet pipes 50 and 75 for introducing a purge gas into the enclosure 30 as in the second and third embodiments, and the liquefied nitrogen supplied to lower the dew point temperature functions as a purge gas as is.

[0116] Furthermore, in this embodiment, the liquefied nitrogen contained in the coolant container 80 vaporizes to become purge gas, so there is no need for the heater 74 that heats the liquefied nitrogen as in the third embodiment. In other words, the control system that constitutes the analysis system 400 according to this embodiment is configured such that the heater 74 is removed from the configuration shown in Fig. 7, and a coolant supply unit 87 that supplies liquefied nitrogen to the coolant inlet pipe 82 is used instead of the coolant supply unit 77 that constitutes the cooling coil system 70 (see Fig. 10).

[0117] When the system control unit 101 opens the coolant supply valve by operating the operation panel 42 by an operator or by executing a control program, the coolant is supplied from the coolant supply unit 87 into the coolant container 80 via the coolant introduction pipe 82. Instead of the above configuration, the coolant may be supplied into the coolant container 80 by the operator manually opening the coolant supply valve.

[0118] The liquefied nitrogen cools the inner surface of the coolant container 80 to -150 to -196°C, and also cools the outer surface of the coolant container 80. As the inner and outer surfaces of the coolant container 80 are cooled, water vapor contained in the air surrounding the coolant container 80 condenses on the inner and outer surfaces of the coolant container 80. Subsequently, water vapor contained in the air within the enclosure 30 gradually collects and condenses in the coolant container 80. The liquefied nitrogen contained within the coolant container 80 gradually vaporizes into dry nitrogen gas, which is introduced into the enclosure 30 as a purge gas. This configuration allows the dew point temperature within the enclosure 30 to be lowered to -70°C or below in just about one minute. As in the second embodiment, a configuration may be adopted in which a purge gas is further supplied into the enclosure 30 from the first gas supply unit 55.

[0119] In this embodiment, as described above, the liquefied nitrogen in the coolant container 80 is vaporized and introduced into the enclosure 30 as purge gas. The introduced purge gas is then configured to be discharged to the outside from an exhaust port provided in the cover body 31. With this configuration, when the coolant that is heated and vaporized when condensing the moisture in the enclosure 30 is introduced into the enclosure 30 as purge gas, it is possible to prevent the pressure inside the enclosure 30 from increasing excessively, making it easier to ensure the safety of the system.

[0120] In this embodiment, compared to the second embodiment, the amount of liquefied nitrogen supplied into the coolant container 80 can be increased by continuously supplying liquefied nitrogen through the coolant introduction pipe 82. Therefore, the water vapor in the enclosure 30 can be efficiently condensed, and the dew point temperature in the enclosure 30 can be quickly lowered.

[0121] Next, the procedure for carrying out the analysis method according to this embodiment using the analysis system 400 having the above configuration will be described with reference to FIG. 11 and other figures.

[0122] First, before carrying out the analysis method according to this embodiment, an operator (1) attaches the enclosure 30 to the airtight part 20 and the base part 40, and (2) places the coolant container 80 inside the enclosure 30 and outside the airtight part 20 so that it does not interfere with the airtight part 20 even when in the "storage position." Although steps (1) and (2) above are prerequisites for carrying out the analysis method according to this embodiment, they are not steps that are carried out each time the analysis method is carried out, and therefore are not included in the procedure for carrying out the analysis method described below. Furthermore, because step (1) above is similar to the procedure in the first embodiment, a description thereof will be omitted here.

[0123] The coolant container 80 is placed in a position that does not interfere with an operator's operation of supplying a sample to the sample holder 10. In Figure 9, the coolant container 80 is placed in a position offset from the sample holder 10 in the left-right direction (perpendicular to the plane of the paper in Figure 9) so as not to interfere with an operator's operation of supplying a sample to the sample holder 10. The coolant container 80 is placed so as to be located inside the enclosure 30.

[0124] The operator operates the cooling unit by supplying a coolant such as liquefied nitrogen from the coolant supply unit 87 into the coolant container 80 via the coolant introduction pipe 82, condensing the water vapor in the enclosure 30 and lowering the dew-point temperature in the enclosure 30 to an appropriate dew-point temperature (step S403 in FIG. 11 ). Furthermore, by operating the cooling unit in step S403 (supplying a coolant such as liquefied nitrogen into the coolant container 80), the coolant vaporized from the coolant container 80 is introduced into the enclosure 30 as dry nitrogen gas or the like. With this configuration, the water vapor in the enclosure 30 is condensed and dry gas is supplied into the enclosure 30, so that the dew-point temperature in the space within the enclosure 30 (the inside of the enclosure 30, the internal space 24 of the airtight unit 20, and the airtight space 41a of the base 40) can be lowered to −70° C. or below.

[0125] 11, the steps other than S403 (step S402 and steps S404 to S411) are similar to step S102 and steps S104 to S111 in the first embodiment, and therefore further description thereof will be omitted here. Also, in this embodiment, instead of step S101 in the first embodiment (supplying purge gas from the first gas supply unit 55 into the enclosure 30), the coolant supplied to the coolant container 80 in step S403 is evaporated into dry gas, which is then supplied into the enclosure 30.

[0126] As described above, in this embodiment, a cooling section is configured so that liquid coolant introduced from the outside through the enclosure opening (coolant inlet opening 34c) provided in the enclosure 30 is stored inside the enclosure 30 and outside the airtight section 20. By adopting such a configuration, compared to the second embodiment, liquefied nitrogen can be continuously supplied into the coolant container 80 through the coolant inlet pipe 82, thereby increasing the amount of liquefied nitrogen supplied. Therefore, water vapor inside the enclosure 30 can be efficiently condensed, and the dew point temperature inside the enclosure 30 can be quickly lowered.

[0127] Furthermore, in this embodiment, the liquid coolant introduced from the outside is stored in a coolant container 80 arranged inside the enclosure 30 and outside the airtight portion 20. By adopting this configuration, the liquefied nitrogen supplied to the coolant container 80 is heated and vaporized as it condenses the water vapor inside the enclosure 30, and functions as a purge gas inside the enclosure 30. Therefore, in this embodiment, there is no need for the gas inlet pipes 50 and 75 for introducing a purge gas into the enclosure 30 as in the second and third embodiments, and the liquefied nitrogen supplied to lower the dew point temperature can function as a purge gas as it is.

[0128] Although the present disclosure has been described based on the drawings and examples, it should be noted that those skilled in the art can easily make various modifications or alterations based on the present disclosure. Therefore, it should be noted that these modifications and alterations are included in the scope of the present invention. For example, the functions included in each component, step, etc. can be rearranged so as not to be logically inconsistent, and multiple components and steps can be combined or divided into one.

[0129] For example, in the first to fourth embodiments, the system control unit 101 that controls the analysis systems 100 to 400 as a whole is configured to control each functional unit, but this is not limited to this. For example, each functional unit may be controlled by an operator directly and manually operating it.

[0130] Although the first to fourth embodiments have been described using examples of platinum and platinum-rhodium thermocouples as the temperature sensor 10a, the present invention is not limited to this. The thermocouple may be made of, for example, tungsten and tungsten-rhenium alloy, iridium and iridium-rhodium alloy, chromel and constantan, chromel and alumel, or platinum.

[0131] In the first to fourth embodiments, the base 40 is configured to have the airtight space 41a, but this is not limiting. For example, if TG is not performed and there is no need to provide the balance unit 13, etc., the airtight space 41a may not be provided in the base 40.

[0132] In the first to fourth embodiments, the state transition between the accommodated state and the unaccommodated state is achieved by moving the airtight portion 20 in the vertical direction, but the present invention is not limited to this. The accommodated state may be achieved by moving the sample holder 10 into the airtight portion 20 and closing the lower opening 23 a (opening), and the unaccommodated state may be achieved by moving the sample holder 10 out of the airtight portion 20 and opening the lower opening 23 a (opening).

[0133] Furthermore, in the third and fourth embodiments, the purge gas inside the cover body 31 is gradually discharged through a discharge portion such as a discharge valve or a plurality of small-diameter holes provided in the cover body 31, but this is not limited to this. Instead of providing the cover body 31 with a discharge valve or a plurality of small-diameter holes, the purge gas may be gradually discharged, for example, from a gap between the cover body 31 and the flange member 29, or a gap between the cover body 31 and the base housing 41, or the like. [Explanation of symbols]

[0134] 10 Sample holder 10a temperature sensor 11 Sample container 13 Balance section (weight measurement section) 15 Measuring part 20 Airtight section 21 Airtight Tube 22 Heating section 23a Lower opening (opening) 24 Interior Space 25 Top opening 26 Capillary Tube 27 Moving mechanism 29 Flange member 29a Fitting cylinder part 29b Flange part 30 Encirclement 31 Cover body 32 Operation convex part 34a Mouth support opening 34b Side opening 34c Coolant inlet opening (enclosure opening) 34d Coolant discharge opening (enclosure opening) 35 Cover top opening 36 Cover bottom opening 37a Upper cover fixing screw 37b Lower cover fixing screw 38 Sample pass bag 38a outer zipper 38b Inner zipper 40 Base 41 Base housing 41a Airtight space (closed space) 42 Operation Panel 43 Fixed tube part 43a O-ring 45 Work Base 45a Base opening (opening) 47 Second gas supply section 47a Mass Flow Controller 48 Pump 48a valve 50 Gas introduction pipe 55 First gas supply section 60 Coolant container (cooling section) 61 Torso 62 Mouth 70 Cooling coil system 71 Cooling coil (cooling section) 72 Coolant introduction pipe 73 Coolant discharge pipe 74 Heater 75 Gas inlet pipe 77 Coolant supply unit 80 Coolant container (cooling section) 81 Container body 82 Coolant introduction pipe 87 Coolant supply unit 90 Cooling Unit 91 Cooling head (cooling section) 91a Refrigerant tube 91b Freezer 92 Mesh Cover 93 Drain tube 93a Stop valve 100, 200, 300, 400 Analysis System 101 System control unit

Claims

1. a sample holder for holding a sample to be analyzed; an airtight part having an opening and accommodating the sample holder therein through the opening; a flexible and visible light transmissive enclosure that separates the sample holder and the opening of the airtight section from the outside; Equipped with the airtight portion is capable of transitioning between a contained state in which the sample holder is contained therein and the opening is airtightly closed from the inside of the surrounding portion, and a non-contained state in which the sample holder is positioned outside the airtight portion, An analytical system, wherein a cooling unit is arranged inside the enclosure and outside the airtight unit at least when the airtight unit is in the uncontained state.

2. The analytical system according to claim 1 , wherein the inside of the airtight part can be evacuated or evacuated and gas replaced after the opening is airtightly closed to the inside of the enclosure part.

3. 3. The analysis system according to claim 1, wherein the cooling section is provided inside the enclosure and outside the airtight section, and the cooling section is a cooling head of a refrigerator, a Peltier element, or another cooling device.

4. 3. The analytical system according to claim 1, wherein a coolant container containing a liquid coolant is disposed as the cooling section inside the enclosure section and outside the airtight section.

5. 5. The analytical system according to claim 4, wherein the interior of the coolant container is in communication with the outside through an enclosure opening provided in the enclosure.

6. 3. The analytical system according to claim 1, wherein the cooling unit is a cooling coil, the interior of which is supplied with a liquid coolant, and the cooling coil is disposed inside the enclosure and outside the airtight unit.

7. 7. The analytical system according to claim 6, wherein the liquid coolant supplied into the cooling coil is supplied from the outside through an enclosure opening provided in the enclosure and is discharged to the outside.

8. 8. The analytical system of claim 7, wherein the discharged liquid coolant is heated and then introduced into the enclosure as a purge gas.

9. The analytical system according to claim 1 or 2, wherein a liquid coolant introduced from the outside through an enclosure opening provided in the enclosure is stored inside the enclosure and outside the airtight portion as the cooling portion.

10. 10. The analytical system according to claim 9, wherein the liquid coolant introduced from outside is contained in a coolant container arranged inside the enclosure and outside the airtight part.

11. The analysis system according to claim 1 or 2, wherein the enclosure has an operation convex portion that protrudes inward.

12. 3. The analytical system according to claim 1, wherein the enclosure is provided with an exhaust section for exhausting gas to the outside.

13. 3. The analysis system according to claim 1, wherein the airtight portion includes a cylindrical airtight tube that houses the sample holding portion therein, and a metallic fitting cylindrical portion that is fixed to an end of the airtight tube and forms the opening, and the fitting cylindrical portion fits into an opening of a closed space facing the inside of the enclosure portion, thereby airtightly closing the opening from the inside of the enclosure portion.

14. a sample holder for holding a sample to be analyzed; an airtight part having an opening and accommodating the sample holder therein through the opening; a flexible and visible light transmissive enclosure that separates the sample holder and the opening of the airtight section from the outside; An analysis method using an analysis system comprising: transitioning the airtight portion to an unaccommodated state in which the sample holder is positioned outside the airtight portion; activating a cooling unit provided outside the airtight unit; transitioning the airtight portion to a storage state in which the sample holder is stored therein and the opening is airtightly closed from the inside of the enclosure portion; Analytical methods, including:

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