JP2008304455A - Measuring method of permeability - Google Patents
Measuring method of permeability Download PDFInfo
- Publication number
- JP2008304455A JP2008304455A JP2008118436A JP2008118436A JP2008304455A JP 2008304455 A JP2008304455 A JP 2008304455A JP 2008118436 A JP2008118436 A JP 2008118436A JP 2008118436 A JP2008118436 A JP 2008118436A JP 2008304455 A JP2008304455 A JP 2008304455A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- permeability
- sample
- cell
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
本発明は、試料の透過度の測定方法に関する。詳しくは、吸着剤を用いることにより試料のガスの透過度を測定する方法に関する。 The present invention relates to a method for measuring the transmittance of a sample. Specifically, the present invention relates to a method for measuring gas permeability of a sample by using an adsorbent.
試料の透過度を測定する方法については多くの方法が知られており、特許文献１には、測定しようとする膜状の試料の一方にガスを接し、他方に質量分析装置を有する真空容器を接することで種々のガスの透過度を測定する方法が開示されている。この方法は優れた方法であり、容易に比較的透過度の低い試料の評価をすることができる。また、常温では液体で存在するガスの透過度を測定する方法として、特許文献２には、質量分析装置を有する真空容器に試料で覆われた液体を有するガス室を導入することでガス化した液の透過度を測定する方法が開示されている。この方法は、試料とかガスを変更する度に真空容器の真空を破る必要がない優れた方法である。 Many methods are known for measuring the permeability of a sample, and Patent Document 1 discloses a vacuum vessel having a gas in contact with one of the film-like samples to be measured and a mass spectrometer on the other. A method for measuring the permeability of various gases by contact is disclosed. This method is an excellent method, and a sample having a relatively low transmittance can be easily evaluated. In addition, as a method for measuring the permeability of a gas existing in liquid at normal temperature, Patent Document 2 gasifies by introducing a gas chamber having a liquid covered with a sample into a vacuum container having a mass spectrometer. A method for measuring the permeability of a liquid is disclosed. This method is an excellent method in which it is not necessary to break the vacuum of the vacuum vessel every time the sample or gas is changed.
最近、種々の用途にガスバリヤー性に優れた材料が要求されており、高分子化合物の膜の表面に種々の加工を施した極めてガスの透過度の低い試料の透過度を測定する必要が益々高まっている。特に材料の使用条件下での透過度の測定が重要となっているが、前述の方法は何れも一方が真空条件での測定となっており、使用条件下での透過度の測定とは言えない。また、長時間の測定に際しては高価な装置を長時間占有することになり好ましくない。
本発明の目的は、透過度の低い試料の透過度を測定することができる簡便な方法を提供することにある。 An object of the present invention is to provide a simple method capable of measuring the transmittance of a sample having a low transmittance.
本発明者は、上記課題を解決する為に、鋭意検討したところ、特定の方法を用いることで上記問題が解決できることを見出して本発明を完成した。 The present inventor has intensively studied in order to solve the above problems, and has found that the above problems can be solved by using a specific method, and has completed the present invention.
即ち本発明は、ガスの濃度を一定の値に制御した容器の中にガスの吸着剤を試料によって封入したセルを設置し、一定時間放置した後、吸着剤に吸着したガスの量を質量分析計により測定することにより、試料を介して透過したガスの透過度を測定することを特徴とするガスの透過度の測定方法である。 That is, according to the present invention, a cell in which a gas adsorbent is sealed with a sample is placed in a container in which the gas concentration is controlled to a constant value, and after standing for a certain time, the amount of gas adsorbed on the adsorbent is subjected to mass spectrometry. A gas permeability measurement method characterized by measuring the permeability of a gas that has passed through a sample by measuring with a meter.
本発明の方法を実施することにより、試料の透過度を容易に知ることができ工業的に極めて有用である。特に、試料の使用条件下での条件でのガスの透過度を知ることが可能な点、および長時間な測定に際して高価な装置を占有しない点で大きな価値がある。 By carrying out the method of the present invention, the permeability of the sample can be easily known, which is extremely useful industrially. In particular, it has great value in that it can know the gas permeability under the conditions under which the sample is used and that it does not occupy an expensive device for long-time measurement.
本発明の方法が適用されるガスとしては、適当な吸着剤が存在するものであればどのようなものでも適用可能である。例えば、ガスが水蒸気であれば、種々の乾燥剤として知られるものを吸着剤として用いればよい。また、活性炭を用いれば、種々のガスを吸着することができる。また、適度な細孔径を有するゼオライトを用いると、特定のガスのみを吸着することも可能である。また、種々のガスの透過度を同時に知るため、使用するガスに合わせて種々の吸着剤を混合して用いることも可能である。 As the gas to which the method of the present invention is applied, any gas can be applied as long as an appropriate adsorbent is present. For example, if the gas is water vapor, various known desiccants may be used as the adsorbent. Moreover, if activated carbon is used, various gases can be adsorbed. In addition, when a zeolite having an appropriate pore size is used, it is possible to adsorb only a specific gas. Further, in order to know the permeability of various gases at the same time, various adsorbents can be mixed and used according to the gas used.
中でも、ガスとして水蒸気、特に重水の蒸気を用いると、種々の材料の水蒸気透過度を測定までの間に環境からの水の影響を排除して知ることができ有用である。この場合には、水分の吸着剤として用いられている種々の吸着剤が利用でき、特に、熱によって可逆的に水を吸収、脱離できるシリカゲル、塩化カルシウムなどを用いると効率的である。 Among them, when water vapor, particularly heavy water vapor is used as the gas, it is useful to know the water vapor permeability of various materials by eliminating the influence of water from the environment until measurement. In this case, various adsorbents that are used as moisture adsorbents can be used. In particular, it is efficient to use silica gel, calcium chloride or the like that can reversibly absorb and desorb water by heat.
本発明において、セルは、試料によって開口部を封じることができればどのような形状のものであっても良いが、材料は膜状に成型した試料として用いるのが通常であり、材料を膜状に成型した試料で開口部を洩れなく封じることができるように、接着剤、Ｏ−リングなどが密着できるように平坦な面を有するものが好ましい。材質としては種々のガスを吸着、透過せず、加熱などによってもガスを発生しないものが利用でき、金、白金、アルミニウム、ステンレススチールなどの金属が好ましく利用でき、ガラスも利用することができる。形状については発明の趣旨から明らかなように特定されないが、比較的短時間で透過度を精度よく分析するためガスが材料を通してセル内に入り吸着する速度が早くなるように、開口部を大きくし、吸着剤を設置する場所を比較的小さくするなど工夫も可能である。 In the present invention, the cell may have any shape as long as the opening can be sealed with the sample, but the material is usually used as a sample molded into a film, and the material is formed into a film. It is preferable to have a flat surface so that an adhesive, an O-ring and the like can be in close contact so that the opening can be sealed without omission with a molded sample. A material that does not adsorb or permeate various gases and does not generate gas even when heated can be used. Metals such as gold, platinum, aluminum, and stainless steel can be preferably used, and glass can also be used. The shape is not specified as is apparent from the gist of the invention, but the opening is enlarged so that the gas can enter the cell through the material and be adsorbed faster in order to analyze the permeability accurately in a relatively short time. Also, it is possible to devise such that the place where the adsorbent is installed is relatively small.
また、吸着剤、試料をセットしたセルは、ガスを入れる容器に入れた後、加熱脱気して吸着している不要なガスなどを充分に除去することで透過度をより正確に測定することができる。 Also, in the cell where the adsorbent and sample are set, the permeability can be measured more accurately by removing the unnecessary gas adsorbed by heating and degassing after putting it in the gas container. Can do.
試料をセットした後、容器には、測定しようとするガスを導入し一定温度に保たれた雰囲気に置くことで測定を開始できる。吸着するガスに比べて充分な量のガスを導入した場合には、一定量のガスを一度導入すれば恒温に保つだけでガス濃度を一定にすることができ、透過度の測定ができるが、必要に応じ容器中のガス濃度を測定して濃度が一定になるようにガスの導入、排出を行い必要に応じガスを循環することもできる。さらに、試料が実際に使用される条件に合わせて、ガスの組成などを変更することも可能である。 After setting the sample, the measurement can be started by introducing the gas to be measured into the container and placing it in an atmosphere kept at a constant temperature. When a sufficient amount of gas is introduced compared to the gas to be adsorbed, once a certain amount of gas is introduced, the gas concentration can be made constant just by keeping the temperature constant, and the permeability can be measured. If necessary, the gas concentration in the container is measured, and the gas is introduced and discharged so that the concentration becomes constant, and the gas can be circulated as necessary. Furthermore, it is possible to change the gas composition and the like according to the conditions under which the sample is actually used.
また、容器内の雰囲気が一定の条件になって初めて吸着剤、試料が雰囲気と接触できるように容器にセルを導入するための小さな部屋を設け、雰囲気を大きく変えないでセルを導入するような工夫も可能である。このような工夫によって、比較的透過度の大きい材料の評価も可能となる。 In addition, a small room for introducing a cell into the container is provided so that the adsorbent and the sample can come into contact with the atmosphere only when the atmosphere in the container is in a certain condition, and the cell is introduced without greatly changing the atmosphere. Devise is also possible. By such a device, it is possible to evaluate a material having a relatively high transmittance.
なお、吸着材に吸着したガスを脱着して定量する方法については周知であり、吸着材を特定の温度に加熱することができる加熱脱着する部分と、脱着したガスを定量できる質量分析部を備えた装置であれば好ましく利用でき、例えば、市販の昇温脱離質量分析装置（TDC-MS）を利用して測定することが可能である。この場合、透過度は吸着したガスの重量を、雰囲気に置いた時間×試料の面積で除することで、例えば、ｇ／ｍ2・ｈｒとして算出することができる。 The method of desorbing and quantifying the gas adsorbed on the adsorbent is well known, and includes a heat desorbing part that can heat the adsorbent to a specific temperature and a mass analyzer that can quantify the desorbed gas. For example, measurement can be performed using a commercially available thermal desorption mass spectrometer (TDC-MS). In this case, the permeability can be calculated as, for example, g / m 2 · hr by dividing the weight of the adsorbed gas by the time in the atmosphere × the area of the sample.
以下に、本発明の実施の一例について示す。 An example of the implementation of the present invention is shown below.
実施例１
直径４ｍｍの開口部を有する厚さ１ｍｍのステンレススチールで成型された内容積１５０ｍｍ3の円筒形のセルに１．０ｍｇのシリカゲルの微粉末を入れ、開口部をエポキシ系の接着剤で厚さ２０μｍのポリエチレンテレフタレートのフイルムで封じてセルを作成した。この操作はドライボックス中、乾燥窒素雰囲気下で行った。このセルをガス濃度が一定の値になるように制御できる容器に設置した。この容器は、縦横高さがすべて５０ｃｍのステンレス製容器内部に小部屋を有し、上記セルを格納できる形状を持っている。この容器に上記セルを入れ、２５０℃、１０-6ｍｍＨｇで１２時間処理し、次いで容器内の小部屋に格納した。
Example 1
1.0 mg of silica gel fine powder is put into a cylindrical cell with an internal volume of 150 mm 3 formed of 1 mm thick stainless steel having an opening with a diameter of 4 mm, and the opening is 20 μm thick with an epoxy adhesive. A cell was prepared by sealing with a polyethylene terephthalate film. This operation was performed in a dry box in a dry nitrogen atmosphere. This cell was installed in a container that can be controlled so that the gas concentration becomes a constant value. This container has a small room inside a stainless steel container whose height and width are all 50 cm, and has a shape capable of storing the cell. The cell was placed in this container, treated at 250 ° C. and 10 −6 mmHg for 12 hours, and then stored in a small chamber inside the container.
次いで、冷却後に容器内に乾燥空気を入れ４０℃に保った状態で重水の蒸気を導入して湿度８０％とした。１２時間後安定していることを確認して小部屋よりセルを取出し、さらに４０℃、湿度８０％で１２時間保持し、セルを取出し電子科学株式会社製の昇温脱離質量分析装置でセル中のシリカゲルを２５０℃に加熱して脱着する重水量を測定したところ１６０μｇであり、透過速度は１．１ｇ／ｍ2・ｈｒであった。 Next, after cooling, dry air was introduced into the container, and vapor of heavy water was introduced at a temperature of 40 ° C. to achieve a humidity of 80%. After confirming that the cell is stable after 12 hours, remove the cell from the small room, hold it at 40 ° C. and 80% humidity for 12 hours, remove the cell, and use the temperature desorption mass spectrometer manufactured by Electronic Science Co., Ltd. When the amount of heavy water desorbed by heating the silica gel inside was heated to 250 ° C., it was 160 μg, and the permeation rate was 1.1 g / m 2 · hr.
実施例２
直径４ｍｍの開口部を有する高さ７ｍｍのステンレススチールで成型された内容積８８ｍｍ3の円筒形のセルに１．０ｍｇのシリカゲルの微粉末を入れ、開口部をエポキシ系の接着剤で厚さ１００μｍのポリエチレンテレフタレートのフイルムで封じてセルを作成した。対比として、ポリエチレンテレフタレートに代え厚さ５００μｍのステンレススチールの板を用いて封じたセルも準備した。この操作はドライボックス中、乾燥窒素雰囲気下で行った。このセルをデシケータ中に重水と共にいれ、デシケータはさらに恒温槽に入れ４０℃で６時間保った。別途、温度湿度データロガーＥＬＵＳＢ−２（（株）エムケーサイエンティフィック社製）を入れて同様な操作をしてデシケータ中湿度を測定したところ、４０℃で略９０％に維持できることを確認した。６時間経過後、デシケータからセルを取出した。
Example 2
1.0 mg of silica gel fine powder is put into a cylindrical cell with an inner volume of 88 mm 3 formed of 7 mm high stainless steel having an opening with a diameter of 4 mm, and the opening is 100 μm thick with an epoxy-based adhesive. A cell was prepared by sealing with a polyethylene terephthalate film. For comparison, a cell sealed with a stainless steel plate having a thickness of 500 μm instead of polyethylene terephthalate was also prepared. This operation was performed in a dry box in a dry nitrogen atmosphere. This cell was placed in a desiccator with heavy water, and the desiccator was further placed in a thermostatic bath and kept at 40 ° C. for 6 hours. Separately, a temperature / humidity data logger ELUSB-2 (manufactured by MK Scientific Co., Ltd.) was inserted and the same operation was performed to measure the humidity in the desiccator. After 6 hours, the cell was removed from the desiccator.
フィルムや接着部に吸収されている水分の影響を避けるため、セルはシリカゲルの入った底の部分と接着剤を使用した上部とを切り離すことができるように中央部がくびれた構造をしており、上下の部分を捻ることでシリカゲルの入った部分を切り離した。電子科学株式会社製の昇温脱離質量分析装置でセル中のシリカゲルを３００℃に１０分間加熱して脱着する分子量１８の成分を測定したところ０．１９３ｍｇであり、対比のステンレスでシールしたものは０．２５７ｍｇであった。一方、分子量１９の成分はポリエチレンテレフタレートフイルムを用いたもので０．０１７０ｍｇ、対比で０．０００６ｍｇ、分子量２０の成分はポリエチレンテレフタレートを用いたもので０．００１２ｍｇ、対比で０．０００５ｍｇであった。これより透過した重水を計算すると５．５ｇ／ｍ2・ｄａｙであった。 In order to avoid the influence of moisture absorbed in the film and adhesive part, the cell has a constricted center part so that the bottom part containing silica gel and the upper part using adhesive can be separated. The part containing silica gel was cut off by twisting the upper and lower parts. A component with a molecular weight of 18 to be desorbed by heating the silica gel in the cell to 300 ° C. for 10 minutes was measured with a temperature programmed desorption mass spectrometer manufactured by Electronic Science Co., Ltd. and found to be 0.193 mg, which was sealed with a contrasting stainless steel. Was 0.257 mg. On the other hand, the component having a molecular weight of 19 was 0.0170 mg using a polyethylene terephthalate film, 0.0006 mg in comparison, and the component having a molecular weight of 20 was 0.0012 mg using polyethylene terephthalate, and 0.0005 mg in comparison. From this, the permeated heavy water was calculated to be 5.5 g / m 2 · day.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008118436A JP2008304455A (en) | 2007-05-07 | 2008-04-30 | Measuring method of permeability |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007122309 | 2007-05-07 | ||
| JP2008118436A JP2008304455A (en) | 2007-05-07 | 2008-04-30 | Measuring method of permeability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008304455A true JP2008304455A (en) | 2008-12-18 |
Family
ID=40233289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008118436A Pending JP2008304455A (en) | 2007-05-07 | 2008-04-30 | Measuring method of permeability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008304455A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010117012A1 (en) * | 2009-04-07 | 2010-10-14 | Shimada Toshihiro | Permeability evaluation device and evaluation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06241978A (en) * | 1993-02-17 | 1994-09-02 | Mitsui Toatsu Chem Inc | Gas transmittance measuring device for film |
| JP2001220518A (en) * | 2000-02-07 | 2001-08-14 | Rikuo Himeno | Inorganic curable composition |
| JP2002088219A (en) * | 2000-09-12 | 2002-03-27 | Bridgestone Corp | Gasket material and gasket for hard disk apparatus |
| JP2004168995A (en) * | 2002-09-13 | 2004-06-17 | Kao Corp | Oil and fat composition |
| JP2004219407A (en) * | 2002-12-25 | 2004-08-05 | Matsushita Electric Ind Co Ltd | Method of measuring gas permeability and apparatus for measuring gas permeability |
| JP2007090874A (en) * | 2005-08-31 | 2007-04-12 | Mitsubishi Plastics Ind Ltd | Gas barrier laminated film |
-
2008
- 2008-04-30 JP JP2008118436A patent/JP2008304455A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06241978A (en) * | 1993-02-17 | 1994-09-02 | Mitsui Toatsu Chem Inc | Gas transmittance measuring device for film |
| JP2001220518A (en) * | 2000-02-07 | 2001-08-14 | Rikuo Himeno | Inorganic curable composition |
| JP2002088219A (en) * | 2000-09-12 | 2002-03-27 | Bridgestone Corp | Gasket material and gasket for hard disk apparatus |
| JP2004168995A (en) * | 2002-09-13 | 2004-06-17 | Kao Corp | Oil and fat composition |
| JP2004219407A (en) * | 2002-12-25 | 2004-08-05 | Matsushita Electric Ind Co Ltd | Method of measuring gas permeability and apparatus for measuring gas permeability |
| JP2007090874A (en) * | 2005-08-31 | 2007-04-12 | Mitsubishi Plastics Ind Ltd | Gas barrier laminated film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010117012A1 (en) * | 2009-04-07 | 2010-10-14 | Shimada Toshihiro | Permeability evaluation device and evaluation method |
| JP4759096B2 (en) * | 2009-04-07 | 2011-08-31 | 敏宏 島田 | Permeability evaluation apparatus and evaluation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hernández-Huesca et al. | Adsorption equilibria and kinetics of CO2, CH4 and N2 in natural zeolites | |
| Epiepang et al. | Low-pressure performance evaluation of CO2, H2O and CH4 on Li-LSX as a superior adsorbent for air prepurification | |
| JP4759096B2 (en) | Permeability evaluation apparatus and evaluation method | |
| EP2233438A1 (en) | Aluminum silicate complex, and high-performance adsorbent comprising the same | |
| ES2886761T3 (en) | Adsorbent composition for argon purification | |
| Andersen et al. | Minimisation of artefact formation of dimethyl disulphide during sampling and analysis of methanethiol in air using solid sorbent materials | |
| Lee et al. | A model for the adsorption kinetics of CO2 on amine-impregnated mesoporous sorbents in the presence of water | |
| Snider et al. | Gas sorption studies on Zeolite Y membrane materials for post-combustion CO2 capture in coal-fired plants | |
| ES2906779T3 (en) | Use of molecular sieves for the decarbonation of natural gas | |
| JP2014059204A (en) | Gas sampling device | |
| JP2008304455A (en) | Measuring method of permeability | |
| CN107894472B (en) | Method for measuring hydrogen isotope mixed gas separation factor of separation material | |
| Chen et al. | Preparation of high specific surface area activated carbon fiber by high-temperature vacuum activation and its superior water vapor adsorption for air humidity control | |
| Namieśnik et al. | Water vapour removal from gaseous samples used for analytical purposes. A review | |
| ES2607284T3 (en) | Method and apparatus for the supply of dry gases | |
| JP3799446B2 (en) | Adsorption performance prediction method for porous adsorbents | |
| Ward et al. | Carbon dioxide sorption studies on magnesium oxide | |
| Fitch et al. | Investigation of the mechanism for the separation of nitrogen—oxygen mixtures on carbon molecular sieves | |
| Branton et al. | Ethyl acetate adsorption onto activated carbon | |
| CN219266187U (en) | Device for testing adsorption performance of VOCs adsorbent on higher boiling point VOCs | |
| CN211877516U (en) | Volatile organic compound adsorption device and volatile organic compound monitoring equipment | |
| Ramzy | Experimental procedure to develop the isotherm equation for moisture adsorption on Silica Gel particles | |
| Tazibet et al. | The influence of the cooling down step in the heat treatment on the stability of activated carbons hydrophobicity | |
| Rogers | Introducing water vapor into a high vacuum chamber at AEDC. | |
| Hub | Mariana VELASCO-CARRASCO, Jorge Luis AGUILAR-SANTANA 2, Saffa RIFFAT 3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110314 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120612 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120710 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120815 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130219 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130917 |