JP2013242249A - Magnetic susceptibility measurement specimen container and magnetic susceptibility measurement method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a magnetic susceptibility measurement specimen container capable of appropriately holding a specimen while suppressing generation of contamination or chemical change, having excellent airtight property even with a simple configuration, being superior in processability, low-temperature strength and durability to heat cycle, and capable of measuring magnetic susceptibility in high precision even at a high frequency region.SOLUTION: A magnetic susceptibility measurement specimen container 1 includes: a cylindrical specimen loading main body 2; and a rod-like movable plug 3 that presses a measurement specimen s while being inserted into and screwed inside the specimen loading main body. A screw thread or screw grooves g1, g2 for screwing the rod-like movable plug to the specimen loading main body are arranged at least part of an internal surface of the specimen loading main body and an external surface of the rod-like movable plug, and the specimen loading main body and the rod-like movable plug is made of at least a kind of resin selected from polyimide resin, polyamide-imide resin and a mixed resin of the polyimide resin and the polyamide-imide resin.

Description

  The present invention relates to a magnetic susceptibility measurement sample container and a magnetic susceptibility measurement method.

  A sensor using a superconducting quantum interference device (SQUID) is a high-sensitivity magnetometer (magnetic sensor) that uses the quantum interference effect of a superconductor, and is one hundred millionth of the geomagnetism (one picotesla). ) The following magnetic field changes can be detected. Furthermore, when an ultrasensitive magnetic force reduction system is used, a magnetic field change of 1 trillionth (1 ppt) or less of the geomagnetism can be detected (for example, patents). Reference 1 (Japanese Unexamined Patent Publication No. 2011-112490)).

  As described above, since a sensor using SQUID has high detection sensitivity, recently, in addition to the fields of metal materials and conductive composite materials, in the fields of inorganic materials, organic materials, living organisms, foods, etc., nondestructive inspection It is widely used for the purpose.

  Measurement of magnetic susceptibility and the like in a measurement apparatus using SQUID (hereinafter also referred to as “SQUID measurement apparatus”) is generally performed in a state where a measurement sample is fixed inside a cylindrical measurement tube. It is.

  For example, first, a cylindrical tube made of a non-magnetic material and free of magnetic impurities such as pigment is prepared as a measurement tube. A cylindrical hollow portion is provided inside the tube, and is designed so that a measurement sample can be accommodated in the hollow portion. Next, the measurement sample is formed to have a diameter equal to the inner diameter of the tube, inserted into the tube, and both ends of the tube are sealed with sealing members. Next, a rod is attached to one of the sealing members, and the measuring tube is inserted into the measuring chamber of the SQUID measuring device from the upper part of the device, so that the measuring tube is installed and the magnetic susceptibility and the like are measured.

  For example, first, as a measurement tube, a pair of a cylindrical inner tube and a cylindrical outer tube, each made of a non-magnetic material and not containing a magnetic impurity such as a pigment, are prepared. A cylindrical hollow portion is provided in each of the inner tube and the outer tube, and the inner diameter of the outer tube (the outer diameter of the hollow portion provided in the outer tube) is the outer diameter of the inner tube. And is designed to accommodate the inner tube inside.

  When fixing the measurement sample using the measurement tube, first, after inserting the measurement sample into the inner tube and fixing with a sealing wax or the like, the inner tube is inserted into the hollow portion of the outer tube and sealed. The both ends of the outer tube into which the inner tube is inserted are sealed with a sealing member. Next, a rod is attached to one of the sealing members, and the measuring tube is inserted into the measuring chamber of the SQUID measuring device from the upper part of the device, so that the measuring tube is installed and the magnetic susceptibility and the like are measured.

JP 2011-112490 A

However, in the measurement tube, the measurement sample may be contaminated by sealing wax or adhesive used to fix the measurement sample. In addition, in the sample fixing method as described above, Airtightness is low, and depending on the measurement sample, it may react with oxygen or moisture in the air. Furthermore, when measuring magnetic susceptibility, etc., using a SQUID measurement device, the measurement temperature is usually changed from 4K to 300K. However, if the sample is in the form of particles, it loses shape during measurement due to thermal expansion and contraction or thermal expansion. Or move within the inner container.
In the SQUID measuring apparatus, since the contamination or shape change of the measurement sample greatly affects the analysis result, a measuring apparatus that eliminates these influences is required.

  In order to solve the above technical problems, as a sample container for susceptibility measurement, a sample is fixed and shaped by sequentially packing rod-like members and rod-like spacers from both ends into a cylindrical tube in which a sample is arranged. It is conceivable to use a material (pressure cell) that suppresses the occurrence of collapse and is further hermetically sealed by bolting both ends via O-rings or the like to improve hermeticity.

  However, the pressure cell increases the number of parts to improve the fixation and airtightness of the sample, and the structure is easily complicated, making it difficult to produce easily. Is difficult.

In addition, sample containers for SQUID measuring devices are usually quartz glass, hard glass, SiO ₂ —MgO—Al ₂ O ₃ ceramics, zirconia inorganic materials, polymer materials such as polypropylene and polycarbonate, oxygen-free Metal materials such as copper and beryllium-copper alloys are used, but the inorganic materials and polymer materials have low processability, low-temperature strength, durability against heat cycles, etc. Since the generated current or magnetic field tends to flow near the surface of the member as the frequency increases, a so-called skin effect is produced, so that it is difficult to measure the magnetic susceptibility in the high frequency region.

  Under such circumstances, the present invention can suitably hold a sample while suppressing the occurrence of contamination and chemical change, and has excellent sealing properties even with a simple structure, processability, and low-temperature strength. And a magnetic susceptibility measurement sample container capable of measuring magnetic susceptibility with high accuracy even in a high frequency region, and also providing a magnetic susceptibility measurement method using the sample container. It is the purpose.

  In order to solve the above technical problem, the present inventors have conducted intensive studies and found that a cylindrical sample filling main body and a rod-shaped member that is screwed into the sample filling main body and pressed into the sample filling main body are pressed. A thread for screwing the rod-shaped movable plug into the sample-filling main body at least a part of the inner surface of the sample-filling main body and the outer surface of the rod-shaped movable plug; A sample for measuring magnetic susceptibility, each having a thread groove, and wherein the sample filling main body and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin, and mixed resin of polyimide resin and polyamideimide resin It has been found that it can be solved by the container, and the present invention has been completed based on this finding.

That is, the present invention
(1) It has a cylindrical sample filling main body, and a rod-shaped movable stopper that is screwed into the sample filling main body while being screwed and presses the measurement sample,
At least a part of the inner surface of the sample filling main body and the outer surface of the rod-shaped movable stopper is provided with a thread or a screw groove for screwing the rod-shaped movable stopper into the sample filling main body, respectively.
The sample filling main body and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin, and mixed resin of polyimide resin and polyamideimide resin,
(2) The cylindrical sample filling main body includes an annular member and a bottom member that is screwed while being inserted into the annular member;
Magnetization according to (1) above, wherein at least a part of the inner surface of the annular member and the outer surface of the bottom member are provided with threads or screw grooves for screwing the bottom member into the annular member, respectively. Rate measurement sample container,
(3) A magnetic susceptibility measurement method comprising measuring the magnetic susceptibility with a sensor using a superconducting quantum interference device, using the magnetic susceptibility measurement sample container according to (1) or (2) above,
Is to provide.

  According to the present invention, it is possible to suitably hold a sample while suppressing the occurrence of contamination and chemical change, and even with a simple structure, it has excellent hermeticity, and is excellent in workability, low temperature strength and heat cycle. In addition to providing a sample container for susceptibility measurement that is excellent in durability and capable of measuring magnetic susceptibility with high accuracy even in a high-frequency region, it is possible to provide a susceptibility measurement method using the sample container.

It is sectional drawing which shows one example of a sample container for magnetic susceptibility measurement concerning this invention. It is sectional drawing which shows one example of a sample container for magnetic susceptibility measurement concerning this invention. It is a figure which shows the magnetic susceptibility measurement chart obtained in the Example of this invention. It is a figure which shows the magnetic susceptibility measurement chart obtained in the Example of this invention. It is a figure explaining the sealing method of the sample in the comparative example of this invention. It is a figure which shows the magnetic susceptibility measurement chart obtained by the comparative example of this invention.

First, the sample container for measuring magnetic susceptibility of the present invention will be described.
The sample container for susceptibility measurement of the present invention has a cylindrical sample filling main body, and a rod-shaped movable stopper that is screwed while being inserted into the sample filling main body and presses the measurement sample. At least a part of the inner surface of the sample filling main body and the outer surface of the rod-shaped movable stopper is provided with a thread or a screw groove for screwing the rod-shaped movable stopper into the sample filling main body, The main body for sample filling and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin, and mixed resin of polyimide resin and polyamideimide resin.

  Hereinafter, the sample container for measuring magnetic susceptibility of the present invention will be described with reference to the drawings as appropriate.

FIG. 1 is a cross-sectional view showing an embodiment of a sample container for measuring magnetic susceptibility according to the present invention.
A sample container 1 for susceptibility measurement shown in FIG. 1 includes a cylindrical sample filling main body 2 and a rod-shaped movable plug 3 that is screwed while being inserted into the sample filling main body and presses the measurement sample s. Threads or screw grooves for screwing the rod-shaped movable plug 3 into the sample-filling main body 2 at least partially on the inner surface of the sample-filling main body 2 and the outer surface of the rod-shaped movable plug 3 g1 and g2 are respectively provided.

In the magnetic susceptibility measurement sample container of the present invention, the sample filling main body 2 takes a cylindrical shape (cylindrical shape).
In the sample container for measuring magnetic susceptibility of the present invention, the sample filling main body preferably has an inner diameter of the cylindrical portion of 0.1 to 10 mm, more preferably 0.3 to 0.8 mm, and 0.3 What is -0.75mm is still more preferable.
In the sample container for measuring magnetic susceptibility of the present invention, the sample filling main body preferably has a cylindrical portion having a thickness (outer diameter-inner diameter) of 0.01 to 3.0 mm, preferably 0.01 to 2.0 mm. What is more preferable is that of 0.01 to 1.0 mm.
In the sample container for measuring magnetic susceptibility of the present invention, the sample filling main body preferably has a total length of 10 to 50 mm, more preferably 10 to 40 mm, and even more preferably 10 to 30 mm.

  In the sample container for susceptibility measurement of the present invention, when the inner diameter, thickness and total length of the sample filling body are within the above ranges, a predetermined pressing force can be easily applied to the measurement sample. Generation | occurrence | production of shape loss etc. can be suppressed and it can hold | maintain suitably.

In the sample container for measuring magnetic susceptibility of the present invention, the rod-shaped movable plug 3 is screwed into the sample filling main body 2 while being inserted thereinto to press the measurement sample s.
In the sample container for susceptibility measurement of the present invention, the shape of the rod-shaped movable stopper is not particularly limited, but is inserted into and screwed into the sample filling main body, so that at least the sample filling main body is inserted, The part to be screwed has a cylindrical shape (round bar shape) having an outer diameter corresponding to the inner diameter of the main body for sample filling.

  In the sample container for measuring magnetic susceptibility of the present invention, the rod-shaped movable stopper preferably has a total length of 10 to 50 mm, more preferably 10 to 40 mm, and still more preferably 10 to 30 mm.

In the sample container for measuring magnetic susceptibility of the present invention, as shown in FIG. 1, at least a part of the inner surface of the sample filling main body 2 and the outer surface of the rod-shaped movable stopper 3 are formed on the sample filling main body. Screw threads or screw grooves g1 and g2 for screwing the movable stoppers are provided.
In the sample container for susceptibility measurement of the present invention, the screw thread or the screw groove is provided on at least a part of the inner surface of the sample filling main body and the outer surface of the rod-shaped movable stopper, respectively. The range of the inner surface of the main body for sample filling provided and the outer surface of the rod-shaped movable stopper can be appropriately determined according to the pressing force to be applied to the measurement sample.

In the sample container for measuring magnetic susceptibility of the present invention, the sample filling main body 2 and the rod-shaped movable stopper 3 are screwed together by the screw threads or the screw grooves g1 and g2.
In the sample container for measuring magnetic susceptibility of the present invention, the rod-shaped movable stopper 3 is inserted into the sample filling main body 2 and screwed to press the measurement sample s, thereby suppressing the deformation of the measurement sample s. However, the magnetic susceptibility can be measured in a suitably held state.

  In the sample container for susceptibility measurement of the present invention, the sample filling main body 2 includes an annular member 21 and a bottom member 22 that is screwed into the annular member 21 while being inserted into the annular member 21 as shown in FIG. And at least a part of the inner surface of the annular member 21 and the outer surface of the bottom member 22 are provided with threads or screw grooves g4 and g3 for screwing the bottom member 22 into the annular member 21, respectively. It may be a thing.

  The range of the inner surface of the annular member 21 and the outer surface of the bottom member 22 where the screw threads or the thread grooves g4 and g3 are provided can be appropriately determined according to the pressing force to be applied to the measurement sample.

  In the sample container for susceptibility measurement of the present invention, the sample filling main body 2 comprises the annular member 21 and the bottom member 22 as described above, so that the sample container for susceptibility measurement that can be manufactured more inexpensively and easily. Can be provided.

  The sample container for measuring magnetic susceptibility of the present invention has a simple structure in which a rod-shaped movable stopper is inserted into a sample filling main body and screwed to fix the measurement sample, so that the measurement sample s can be easily inserted. Can be fixed.

  In addition, since the sample container for measuring magnetic susceptibility of the present invention is to fix the measurement sample by screwing the main body for sample filling and the rod-shaped movable stopper, it is sealed when fixing the measurement sample in the container. It is not necessary to use an adhesive or an adhesive, so that the occurrence of contamination on the sample can be suppressed.

  In the sample container for susceptibility measurement of the present invention, the sample filling main body and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin, and mixed resin of polyimide resin and polyamideimide resin.

In the sample container for measuring magnetic susceptibility of the present invention, the polyimide resin is not particularly limited as long as it is a so-called aromatic polyimide in which an aromatic compound is directly linked by an imide bond, and a known resin can be used.
Examples thereof include thermosetting polyimides such as condensation-type polyimides, bismaleide resins, terminal nadic acid resins, and acetylene resins, thermosetting polyimides, thermoplastic polyimides, and the like. Furthermore, “VESPEL”, “KAPTON”, “PYRALIN”, “NR-150”, “NR-150A2”, “NR-150B2” (all trade names, manufactured by DuPont), “Upilex”, “Upimol”, “Iupimol S” (Brand name, manufactured by Ube Industries, Ltd.), “KERIMID” (Brand name, manufactured by Rhone-Poulenc), “COMPIMIDE” (Brand name, manufactured by Boot), “TI Polymer” (Product) Name, manufactured by Toray Industries, Inc.), “Imidaroy” (trade name, manufactured by Toshiba Chemical Co., Ltd.), “BT resin” (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), “Polymerization of Monomer Reactants” (hereinafter “PMR”) ”-15”, “PMR-11”, “LARC-160” (both are trade names, NASA Lew s), “THERMID” (trade name, manufactured by Hughes Air Craft), “LARC-TPI”, “NEW-TPI” (all trade names, manufactured by Mitsui Chemicals, Inc.), “ULTEM” (trade name, GE Commercially available polyimides such as those manufactured by Kogyo Co., Ltd. can be used, and one or more selected from these polyimides can be appropriately selected and used. In consideration of workability and low-temperature strength, “TI polymer (TI 3000 series)” is preferable as the polyimide.

In the sample container for measuring magnetic susceptibility of the present invention, as the polyamideimide resin, aromatic tricarboxylic acid anhydride and diisocyanate, or aromatic tricarboxylic acid anhydride and diamine, or aromatic tricarboxylic acid anhydride halide and diamine are contained in a solvent. If it superposed | polymerized by (1), it will not restrict | limit in particular, A well-known thing can be used.
For example, “TI polymer (TI 5000 series)” (trade name, manufactured by Toray Industries, Inc.), “Torlon” (trade name, manufactured by Amoco Japan Limited) and the like can be used. In consideration of physical properties such as strength, creep resistance, and abrasion resistance, or moldability, “TI polymer (TI 5000 series)” (trade name, manufactured by Toray Industries, Inc.) is desirable.

In the sample container for measuring magnetic susceptibility of the present invention, examples of the polyimide resin and the polyamideimide resin constituting the mixed resin include the same ones as described above.
In the sample container for measuring magnetic susceptibility of the present invention, the polyimide resin and the polyamideimide resin contain 1 to 99% by mass of polyimide resin and 99 to 1% by mass of polyamideimide resin (however, polyimide resin and polyamideimide). The total resin is 100% by mass), the polyimide resin is 10 to 90% by mass, and the polyamide-imide resin is 90 to 10% by mass (however, the total of the polyimide resin and the polyamide-imide resin is 100% by mass). The thing to contain can be mentioned.

In the sample container for susceptibility measurement of the present invention, the total length of the sample container 1 for susceptibility measurement in the state where the rod-shaped movable stopper 3 is inserted into the sample filling main body 2 and screwed is 20 to 100 mm. Is more preferable, and it is more preferable that it is 20-80 mm, and it is further more preferable that it is 20-60 mm.
When the total length of the sample container 1 for susceptibility measurement is within the above range, it can be suitably used for a commercially available susceptibility measuring apparatus, particularly a sensor using a superconducting quantum interference element.

When fixing the sample to the magnetic susceptibility measurement sample container of the present invention, for example, as shown in FIG. 1, after inserting the sample s into the sample filling body 2, the rod-shaped movable stopper 2 is inserted from above, By screwing, the sample s can be pressed and the sample s can be fixed in the sample filling main body 2.
For example, as shown in FIG. 2, after inserting the sample s into the annular member 21, the rod-shaped movable stopper 2 is inserted and screwed from the top, and the bottom member 22 is inserted and screwed from the bottom. By doing so, the sample s can be sandwiched and pressed to fix the sample s in the sample filling main body 2.
The form of the sample s is preferably a powder or a lump.

  The sample container for susceptibility measurement of the present invention can be suitably used as a sample container for susceptibility measurement using a SQUID measurement device.

  In the sample container for susceptibility measurement of the present invention, the sample filling main body and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin and a mixed resin of polyimide resin and polyamideimide resin, Since these resins have self-lubricating properties, even a simple structure by screwing between the sample filling main body and the rod-shaped movable stopper has high sealing properties and suitably holds the measurement sample. be able to.

  Further, since the sample container for measuring magnetic susceptibility of the present invention has excellent hermeticity, even a measurement sample that easily reacts with oxygen or moisture in the air reacts with oxygen or moisture. The magnetic susceptibility can be easily measured with suppression.

  Furthermore, in the sample container for measuring magnetic susceptibility of the present invention, the sample filling main body and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin, and mixed resin of polyimide resin and polyamideimide resin. Because it is excellent in durability against low temperature strength and heat cycle, it can accurately measure the magnetic susceptibility even after repeated use, and it does not cause skin effect. It can be measured accurately.

Next, the magnetic susceptibility measuring method of the present invention will be described.
The magnetic susceptibility measuring method of the present invention is characterized in that the magnetic susceptibility is measured by a sensor using a superconducting quantum interference device using the magnetic susceptibility measurement sample container of the present invention.

  In the magnetic susceptibility measuring method of the present invention, details of the magnetic susceptibility measurement sample container are as described above.

In the magnetic susceptibility measurement method of the present invention, a sensor using a superconducting quantum interference device can be a known sensor, such as MPMS2 manufactured by Quantum Design.
In the magnetic susceptibility measuring method of the present invention, the measurement conditions for measuring the magnetic susceptibility are not particularly limited, and can be appropriately selected.

  Since the magnetic susceptibility measurement method of the present invention uses the magnetic susceptibility measurement sample container of the present invention, the magnetic susceptibility can be measured with high accuracy.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all by the following examples.

Example 1
Using a polyamideimide resin TI 5013 (trade name) manufactured by Toyo Plastic Seiko Co., Ltd., a sample filling main body 2 having an annular member 21 and a bottom member 22 and a rod-shaped movable stopper 3 having the shape shown in FIG. A sample container 1 having this was produced.
The annular member 21 is a circular tube having an inner diameter of 6.0 mm, an outer diameter of 8.0 mm, and an overall length of 21.0 mm, and a screw thread for screwing the rod-shaped movable plug 3 and the bottom member 22 to the inner side surface, respectively. Screw grooves g2 and g4 are provided.
The bottom member 22 has a total length of 8.0 mm, and a screw thread or a screw groove g3 for insertion and screwing into the annular member 21 is provided on the upper side surface thereof. The overall length is 22.0 mm, and a screw thread or a thread groove g1 for insertion and screwing into the sample filling main body 2 is provided on the lower side surface thereof.

<Measurement Example 1-1>
(Preparation of measurement sample)
The inside of a 1 liter three-necked flask equipped with a stirrer and a dropping funnel was sufficiently replaced with nitrogen, and then 200 ml of n-heptane and 0.5 mol of di-n-butyl phthalate were added, while keeping the temperature at 40 ° C. Stir.
Next, 0.5 mol of titanium tetrachloride was collected in a dropping funnel under a nitrogen atmosphere, and this was dropped into the flask over 1 hour while keeping the temperature at 40 ° C. with stirring, and then reacted at 40 ° C. for 2 hours. After completion of the reaction, the product was washed with n-heptane until free titanium disappeared, and then dried under reduced pressure to obtain a powdery complex (A).

  Next, a stainless steel ball having a diameter of 25 mm was introduced into a stainless steel vibration mill having a sufficient internal volume of 1 L, which had been sufficiently replaced with nitrogen gas, so that the ball / pot ratio (volume ratio) was 0.8. Next, 30 g of anhydrous magnesium chloride and 10 g of the complex (A) were added, and co-grinding was performed at room temperature for 20 hours.

  Thereafter, the entire contents of the pot were transferred to a flask equipped with a stirrer in which the contents of the pot were sufficiently substituted, thoroughly washed with n-heptane until free Ti components disappeared, and then dried under reduced pressure to obtain a measurement sample s. It was. Since the measurement sample X is a substance that reacts with oxygen and moisture in the air, it was stored in a glove box sufficiently substituted with nitrogen.

(Measurement condition)
In a glove box set in advance in a nitrogen atmosphere, 120 mg of the measurement sample s is filled in the annular portion 21 constituting the sample container 1, and then the rod-shaped movable stopper 3 is inserted from the top and the bottom member 22 is inserted from the bottom. The measurement sample s was sandwiched and pressed by screwing and fixed.
Next, the sample container 1 filled with the measurement sample s is taken out from the glove box, a measuring rod is attached to the upper end, and the rod is placed on the upper side, and is inserted into the measuring chamber of the SQUID measuring apparatus (manufactured by Quantum Design, model number MPMS2). After setting, the magnetic susceptibility was measured under the following measurement conditions. The measurement chart obtained at this time is shown in FIG.
Measuring apparatus: Superconducting quantum interference element magnetization measuring apparatus (manufactured by Quantum Design, model number MPMS2)
Magnetic field (superconducting magnet): 0 to 1 Tesla Temperature range: 4 Kelvin (K) to 300 Kelvin (K)
Measurement algorithm: Interactive Reg

<Measurement Example 1-2>
The measurement of the magnetic susceptibility was repeated 50 times in the same manner as in Measurement Example 1-1. Also in the 50th measurement, the measurement result of the magnetic susceptibility similar to FIG. 3 was obtained.
Further, after completion of the 50th measurement, the sample container 1 taken out was visually confirmed, but no deformation or cracking was observed.

(Example 2)
2 except that polyimide resin TI 3000 (trade name) manufactured by Toyo Plastic Seiko Co., Ltd. was used instead of polyamide imide resin TI 5013 (trade name) manufactured by Toyo Plastic Seiko Co., Ltd. The sample container 1 having the sample filling body 2 including the annular portion 21 and the bottom portion 22 and the rod-shaped movable stopper 3 having the shape shown in FIG. 1 was produced, and the magnetic susceptibility was measured in the same manner as in Example 1. The results are shown in FIG.

(Comparative Example 1)
As a sample container for measuring magnetic susceptibility, as shown in FIG. 5A, a cylindrical polyethylene straw h (diameter 6 mm, length 200 mm) having a form in which both ends are opened was prepared. The cylindrical polyethylene straw h does not contain magnetic impurities.

In a glove box set in advance under a nitrogen atmosphere, about 100 mg of the measurement sample s prepared in Example 1 was mixed with paraffin and sealing wax, and then formed into a cylindrical shape having a diameter of 6 mm and a height of 6 mm. As shown in FIG. 5A, a measurement sample m was prepared.
Next, as shown in FIG. 5B, the cylindrical measurement sample m was inserted into the straw h so that the upper surface and the bottom surface thereof were parallel to the longitudinal direction of the polyethylene straw h.
Both ends of the polyethylene straw h were sealed with sealing wax, and then taken out from the glove box.
Instead of using the sample container 1 filled with the measurement sample s, the magnetic susceptibility was measured in the same manner as in Measurement Example 1-1 except that the polyethylene straw h in which the measurement sample m was enclosed was used. A measurement chart is shown in FIG.
As shown in FIG. 6, in Comparative Example 1, it can be seen that the spectral line is distorted because the sample moves between the measurement temperatures of 200K to 250K.

(Comparative Example 2)
An annular member 21 and a bottom having the shape shown in FIG. 2 in the same manner as in Example 1 except that polypropylene (PP) was used instead of Toyo Plastic Seiko Co., Ltd. polyamideimide resin TI 5013 (trade name). A sample container 1 having a sample filling body 2 made of a material 22 and a rod-shaped movable stopper 3 was prepared, and 116 mg of the measurement sample s prepared in Example 1 was filled in the sample container.
The sample container 1 is cooled from 300K to 4K over 60 minutes, maintained at 4K for 10 minutes, and then subjected to a heat cycle test in which the temperature is increased from 4K to 300K over 360 minutes. The presence or absence of was confirmed visually.
When the above heat cycle test is repeated, it is confirmed that the sample container 1 taken out after the fifth test is cracked in the sample filling main body 2, the rod-shaped movable stopper 3, and the screwed portion. I was able to.

From the results of Example 1 and Example 2, the sample container for measuring magnetic susceptibility according to the present invention easily collects a powdery measurement sample without using a secondary material such as sealing wax or paraffin. It can be seen that the magnetic susceptibility can be measured easily and accurately without being deformed in the sample during measurement.
In addition, even after repeated measurements, the sample holder was neither deformed nor damaged, indicating that it is excellent in low-temperature strength and heat cycle durability. Further, since no distortion or abnormal peak occurred in the spectral line even after repeated measurement, it was found that the hermeticity of the sample container was high and the internal airtightness was maintained.

  On the other hand, from the results of Comparative Example 1 and Comparative Example 2, in the conventional sample container, the measurement sample moves during the measurement of the magnetic susceptibility, or the sample holder breaks when the temperature changes. It turns out that measurement of magnetic susceptibility is difficult.

  According to the present invention, it is possible to suitably hold a sample while suppressing the occurrence of contamination and chemical change, and even with a simple structure, it has excellent hermeticity, and is excellent in workability, low temperature strength and heat cycle. In addition to providing a sample container for susceptibility measurement that is excellent in durability and capable of measuring magnetic susceptibility with high accuracy even in a high-frequency region, it is possible to provide a susceptibility measurement method using the sample container.

Claims (3)

A cylindrical sample-filling main body, and a rod-shaped movable stopper that is screwed into the sample-filling main body while being screwed and presses the measurement sample;
At least a part of the inner surface of the sample filling main body and the outer surface of the rod-shaped movable stopper is provided with a thread or a screw groove for screwing the rod-shaped movable stopper into the sample filling main body, respectively.
The sample container for magnetic susceptibility measurement characterized in that the main body for sample filling and the rod-shaped movable stopper are made of at least one resin selected from polyimide resin, polyamideimide resin, and mixed resin of polyimide resin and polyamideimide resin. The cylindrical sample filling main body comprises an annular member and a bottom member that is screwed while being inserted into the inside of the annular member,
2. The magnetic susceptibility according to claim 1, wherein at least a part of an inner surface of the annular member and an outer surface of the bottom member are provided with a thread or a screw groove for screwing the bottom member into the annular member. Sample container for measurement.   A magnetic susceptibility measuring method, wherein the magnetic susceptibility is measured by a sensor using a superconducting quantum interference device, using the magnetic susceptibility measurement sample container according to claim 1.