JPS59159059A - Humidity measuring cell - Google Patents
Humidity measuring cellInfo
- Publication number
- JPS59159059A JPS59159059A JP3325483A JP3325483A JPS59159059A JP S59159059 A JPS59159059 A JP S59159059A JP 3325483 A JP3325483 A JP 3325483A JP 3325483 A JP3325483 A JP 3325483A JP S59159059 A JPS59159059 A JP S59159059A
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- measuring cell
- humidity measuring
- cell
- sample
- 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.)
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Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/121—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid for determining moisture content, e.g. humidity, of the fluid
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明は湿度測定セルに関する。 さらに詳しくは、
改善された湿度応答性を有し種々の分野、例えば石油精
製工程におけるリサイクルガスあるいは塩素やフッ素化
学工業におけるプロセス監視や高圧ボンベガス中の水分
測定等の湿度測定用として有用な湿度測定セルに関する
。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field This invention relates to a humidity measuring cell. For more details,
The present invention relates to a humidity measuring cell which has improved humidity responsiveness and is useful for humidity measurement in various fields, such as process monitoring in the recycling gas or chlorine and fluorochemical industries in petroleum refining processes, moisture measurement in high pressure cylinder gas, etc.
（ロ）従来技術
従来、湿度を測定するためのセンサーは試料を導入する
管を有する湿度測定用容器内に固定され湿度測定セルと
して用いられるが、セル内壁面の接ガス部表面の化学的
活性、親水性によって、水分子が物理吸着又は化学吸着
し、湿度の濃度変化に対するセンサーの応答性を著しく
遅らせていた。 すなわち、第１図に示すように従来の
典型的な湿度測定セルは、試料導入管部（１）と試料排
出管部（２）を備えた金属、ガラスやセラミックス製の
湿度測定セル用容器（４）内に、湿度センサー（３）を
固定した購造（なお、図中（４つはセル保持器、（５）
は出力ビンを示す）からなるが、いかに湿度センサーの
応答速度が迅速であっても、試料導入管部内面や湿度セ
ンサー固定部内面等のセルの接ガス部に水分子が吸着し
易く試料が変わった場合にセル内のガス置換を遅らせて
しまい、見かけ上センサーの応答が悪く、正確な湿度測
定ができない場合がしばしばあった。 ことに試料ガス
とゼロガスとを交互にセル内に導入してその立ち上りを
測定するレート法の場合、大きな不都合を生じさせてい
た。(B) Prior Art Conventionally, a sensor for measuring humidity is fixed in a humidity measuring container having a tube for introducing a sample and used as a humidity measuring cell. Due to its hydrophilic nature, water molecules are physically or chemically adsorbed, which significantly delays the response of the sensor to changes in humidity concentration. That is, as shown in FIG. 1, a typical conventional humidity measuring cell consists of a humidity measuring cell container (made of metal, glass, or ceramics) equipped with a sample introduction pipe section (1) and a sample discharge pipe section (2). 4) with the humidity sensor (3) fixed inside (in the figure (4) is the cell holder, (5)
(indicates the output bin) However, no matter how fast the response speed of the humidity sensor is, water molecules tend to adsorb to the gas contact parts of the cell, such as the inner surface of the sample introduction tube and the inner surface of the humidity sensor fixing part, and the sample If the temperature changes, gas replacement within the cell is delayed, and the response of the sensor appears to be poor, often making it impossible to measure humidity accurately. In particular, the rate method, in which a sample gas and a zero gas are alternately introduced into a cell and the rise of the gas is measured, has caused a major inconvenience.
Ｃ→発明の目的
この発明は、水分子の吸着を抑え試料が変わった場合に
もガス置換が迅速になされそれにより湿度測定器として
の応答性を向上させた湿度測定セルを提供することを目
的とする。C→Purpose of the Invention The purpose of the present invention is to provide a humidity measuring cell that suppresses the adsorption of water molecules, allows rapid gas replacement even when the sample changes, and thereby improves the responsiveness of a humidity measuring device. shall be.
に）発明の構成
かくしてこの発明によれば、試料導入管部及び排出管部
を備え湿度センサーを内部に固定してなる湿度測定セル
において、該湿度測定セルの内壁面に、表面自由エネル
ギーが５０ ｅｒｇ ＊ｃｒｔｔ−２以下の高分子膜を
被覆形成したことを特徴とする湿度測定セルが提供され
る。B) Structure of the Invention According to the present invention, in a humidity measuring cell having a sample introduction pipe section and a discharge pipe section and a humidity sensor fixed therein, the inner wall surface of the humidity measuring cell has a surface free energy of 50 Provided is a humidity measuring cell characterized by being coated with a polymer film having an erg *crtt-2 or less.
この発明の最も特徴とする点は湿度測定セルの内壁面に
特定の高分子膜を被層形成したことである。 特定の高
分子膜としては表面自由エネルギー５０ｅｒｇ＊ｃ＊＝
”以下のものを用いる必要がある。The most distinctive feature of this invention is that a specific polymer film is formed on the inner wall surface of the humidity measuring cell. For a specific polymer film, the surface free energy is 50erg*c*=
``The following must be used.
表面自由エネルギーが５００ｒｇ−（７）−２を越える
と親水性が強くなり実質的に水分子の吸着を抑制するこ
とができず不適当である。 かようなこの発明の高分子
の具体例としてはポリエチレン、ポリメチルメタクリレ
ート、ポリエステル系樹脂、ポリウレタン系樹脂等が挙
げられ、シリコーンやテフロンのようなオルガノポリシ
ロキサン系高分子やフッ素化炭化水素系高分子等の表面
自由エネルギーが２５０ｒｇす「２以下、通常、１５〜
２５ ｅｒｇ・ロー２のものが吸着抑制効果の点で好ま
しく、被覆形成の簡便さ等からオルガノポリシロキサン
系高分子を用いるのが最も好せしい。If the surface free energy exceeds 500 rg-(7)-2, the hydrophilicity becomes too strong and the adsorption of water molecules cannot be substantially suppressed, which is inappropriate. Specific examples of such polymers of the present invention include polyethylene, polymethyl methacrylate, polyester resins, polyurethane resins, organopolysiloxane polymers such as silicone and Teflon, and fluorinated hydrocarbon polymers. The surface free energy of molecules, etc. is 250rg or less, usually 15~
25 erg/low 2 is preferable from the viewpoint of adsorption suppression effect, and it is most preferable to use an organopolysiloxane polymer from the viewpoint of ease of coating formation.
この発明の湿度測定セルに用いる容器の材質や試料導入
管部及び排出管部の構成としては当該分野で知られた種
々のものを適用することができる。Various materials known in the art can be used as the material of the container and the configuration of the sample introduction tube and the discharge tube used in the humidity measuring cell of the present invention.
前記高分子膜は、通常、少なくとも湿度測定セルの試料
導入管内壁面及び湿度センサー固定部内壁面に被覆形成
されておればよく、場合によっては試料排出管を含めセ
ル内壁面全体に被覆形成されていてもよい。 ただし、
水分の非吸着性部分（例えば、第１図におけるセル保持
器内面）にはとくに形成させなくてもよい。Usually, the polymer film only needs to be formed to coat at least the inner wall surface of the sample introduction tube and the inner wall surface of the humidity sensor fixing part of the humidity measuring cell, and in some cases, the entire inner wall surface of the cell including the sample discharge tube may be coated. Good too. however,
It is not necessary to form it on the non-moisture adsorbing portion (for example, the inner surface of the cell holder in FIG. 1).
かような高分子膜は、通常、前記高分子の有機溶媒溶液
や懸濁液を湿度測定セル用容器の内壁面にディップ又は
スプレーコーティングやプラズマ重合法によりコートし
たのち、溶媒等を除去することにより簡便に形成させる
ことができる。Such a polymer film is usually produced by coating an organic solvent solution or suspension of the polymer on the inner wall surface of a container for a humidity measurement cell by dip coating, spray coating, or plasma polymerization, and then removing the solvent, etc. It can be easily formed by
このようにして得られたこの発明のセル内に湿度センサ
ーを固定することによりこの発明の湿度測定セルが得ら
れる。The humidity measuring cell of the present invention is obtained by fixing a humidity sensor within the cell of the present invention thus obtained.
上記湿度センサーとしてはセラミック、金属酸化物等を
利用したものや、圧電素子上に蒸着によって一対の導電
性材料、例えば金や銀からなる電極を被覆形成し、さら
にこれらの電極上に予め作製された高分子電解質（例え
ば、スチレン−ジビニルベンゼン共重合体スルホン化物
、ポリスチレンスルホン化物、ポリスチレンろルホン化
物とポリビニルアルコールとの混合物、ポリビニルアル
コールトメチルセルローススルホン化物との混合物等）
を刷毛塗りやスピンナーコーティング等の手法により塗
布して造膜したものなどの従来知られた湿度センサーを
用いることができる。 しかし、感湿性能の安定性及び
応答性の点から発明者らが新たに見出し次湿度センサー
、すなわち、圧電素子上に、プラズマ重合高分子薄膜か
らなる感湿膜を薄膜電極を介して密着形成してなる湿度
センサーを用いるのが好ましい。The above-mentioned humidity sensor may be one that uses ceramics, metal oxides, etc., or a piezoelectric element that is coated with a pair of electrodes made of a conductive material, such as gold or silver, by vapor deposition, and that is further fabricated in advance on these electrodes. (e.g., styrene-divinylbenzene copolymer sulfonate, polystyrene sulfonate, mixture of polystyrene sulfonate and polyvinyl alcohol, mixture of polyvinyl alcohol and methyl cellulose sulfonate, etc.)
It is possible to use a conventionally known humidity sensor, such as a film formed by coating by brush coating, spinner coating, or the like. However, in view of the stability and responsiveness of humidity-sensing performance, the inventors discovered the following humidity sensor: a humidity-sensitive film made of a plasma-polymerized polymer thin film is closely attached to a piezoelectric element via a thin-film electrode. It is preferable to use a humidity sensor made of:
上記プラズマ重合膜を用いた湿度センサーにおける圧電
素子としては、当該分野で圧電特性を示す物質として知
られたものが種々使用可能であり、具体的には水晶発振
子、電気石、ロツシエル塩、チタン酸バリウム、酸化亜
鉛等が挙げられる。As the piezoelectric element in the humidity sensor using the above-mentioned plasma polymerized film, various materials known in the field as exhibiting piezoelectric properties can be used. Specifically, quartz crystal oscillator, tourmaline, Rothsiel salt, titanium Examples include barium acid and zinc oxide.
また、薄膜電極としては導電性材料であれば使用可能で
あり、具体的には金、銀等の腐食性の少ない金属類を蒸
着して用いるのが好適である。Moreover, any conductive material can be used as the thin film electrode, and specifically, it is preferable to use a metal such as gold or silver that is less corrosive by vapor deposition.
また、プラズマ重合高分子薄膜としてはその表層に親水
性基が導入されたものを用いるのが好ましい。 通常、
プラズマ重合により得られたポリスチレン、スチレン−
ジビニルベンゼン共重合体、スチレン−ビニルアルコー
ル共重合体等のビニル芳香族系ｉ合体やビニルアルコー
ル−メチルセルロース共重合体の薄膜（約０．０１〜１
μｍ程度）ノ表層にスルホネート基、第四級アンモニウ
ム基、ホスホネート基等の親水性基を導入したものが適
当である。Furthermore, it is preferable to use a plasma-polymerized polymer thin film having hydrophilic groups introduced into its surface layer. usually,
Polystyrene, styrene obtained by plasma polymerization
Thin films of vinyl aromatic polymers such as divinylbenzene copolymer, styrene-vinyl alcohol copolymer, and vinyl alcohol-methylcellulose copolymer (approximately 0.01 to 1
It is suitable to have a hydrophilic group such as a sulfonate group, a quaternary ammonium group, or a phosphonate group introduced into the surface layer.
なお、プラズマ重合条件としては、公知の条件を適用で
き、ことに低周波プラズマ重合により行なうことが高分
子の構造や膜の均一性の点好ましい。As the plasma polymerization conditions, known conditions can be applied, and low frequency plasma polymerization is particularly preferred from the viewpoint of polymer structure and film uniformity.
（ホ）実施例
以下、この発明の湿度測定セルの実施例を図面と共に詳
説する。(E) Examples Hereinafter, examples of the humidity measuring cell of the present invention will be explained in detail with reference to the drawings.
内径１．５問、長さ５０朋の試料導入管部（ｉ）及び試
料排出管部（２）を備えた長方体状（幅１３ｇ、奥行５
ｇ、高さ１８ｍ、下方は開０のステンレス製容器（４）
内に、シリコン樹脂液（シリコンゾルをトルエン２０重
量係に分散してなる液；商品名ベルガンスプレー、ダウ
コーニング社製）をスプレーし乾燥させることにより約
０．１〜２！！ｎＩｉのシリコーン高分子膜を内壁面に
被覆形成させ、次いで感湿センサー（３“）を固定した
セル保持器（４′）を取シ付けることによって第２図に
示すごときこの発明の湿度測定セルを得た。A rectangular parallelepiped (width 13 g, depth 5
g, 18 m high, stainless steel container with opening at the bottom (4)
By spraying a silicone resin liquid (liquid made by dispersing silicone sol in 20 parts by weight of toluene; trade name: Bergan Spray, manufactured by Dow Corning) and drying it, approximately 0.1 to 2. ! The humidity measuring cell of the present invention as shown in FIG. I got it.
なお、上記感湿センサー（３）としては、水晶振動子の
上にプラズマ重合（重合条件：圧力１朋Ｈｇ、湿度２５
℃、放電電流７ Ｑ ｍＡ 、放電電圧５００■、放電
時間９０分）にて形成したポリスチレンを常法によって
３０分間５０３（硫酸ガス）でスルホン化して、水洗し
た後、Ｎａ０Ａ’溶液でスルホン化ナトリウムにし、さ
らに水洗、乾燥して得たものを・用いた。The humidity sensor (3) is prepared by plasma polymerization (polymerization conditions: pressure 1 Hg, humidity 25
℃, discharge current 7 Q mA, discharge voltage 500 ■, discharge time 90 minutes), the polystyrene formed was sulfonated with 503 (sulfuric acid gas) for 30 minutes by a conventional method, washed with water, and then treated with sodium sulfonate with Na0A' solution. The product obtained by washing, washing with water, and drying was used.
このようにして得た湿度測定セルに試料導入管より定湿
度のガス（窒素ガス中に２０ｐｐｍの湿分含有ガス）を
流量２００πｔ／分、６０℃下で２分間流し、次いでゼ
ロガス（湿分を含有しないガス）を同条件で３分間流し
た際の応答性（Ａ）及びその逆の場合の応答性（Ｂ）を
調べた。 その結果を比較例（高分子膜を被覆形成して
いない以外同様の湿度測定セル）と共に第３図に示す。Constant humidity gas (gas containing 20 ppm of moisture in nitrogen gas) was flowed through the sample introduction tube at a flow rate of 200 πt/min at 60°C for 2 minutes through the sample introduction tube, and then zero gas (humidity The responsivity (A) when a non-containing gas) was flowed for 3 minutes under the same conditions and the responsivity (B) when vice versa were investigated. The results are shown in FIG. 3 together with a comparative example (a similar humidity measuring cell except that it was not covered with a polymer film).
なお図においてプロット○はこの発明の湿度測定セルに
よるものであり、プロット△は比較例の湿度測定セルに
よるものである。In the figure, the plot ◯ is based on the humidity measuring cell of the present invention, and the plot △ is based on the humidity measuring cell of the comparative example.
このように、この発明の湿度測定セルは、高分子膜をセ
ル内壁面に形成していない従来のものに比し、その応答
速度は上昇していることが判る。Thus, it can be seen that the response speed of the humidity measuring cell of the present invention is increased compared to the conventional one in which a polymer film is not formed on the inner wall surface of the cell.
（へ）発明の効果
以上の説明からも理解されるようにこの発明の湿度測定
セルは湿度センサーの応答性を良好に発揮させ、簡便な
構成にもかかわらず湿度測定器として優ねた応答性を示
すものであって種々の用途に有用であり、ことにステン
レス製の容器を用いた防曝用の湿度測定セルとして有利
である。(f) Effects of the Invention As can be understood from the above explanation, the humidity measuring cell of the present invention exhibits good responsiveness as a humidity sensor, and has excellent responsiveness as a humidity measuring device despite its simple configuration. It is useful for various uses, and is particularly advantageous as a humidity measuring cell for exposure protection using a stainless steel container.
また、湿度センサーとして、圧電素子上にプラズマ重合
高分子薄膜からなる感湿膜を薄膜電極を介して密着形成
したものを組合せて用いた場合、湿度センサー自体の優
れた応答性、安定性と相まって、この発明のセル構造に
よる前記効果がより発揮される。In addition, when a humidity sensor is used in combination with a piezoelectric element in which a moisture-sensitive film made of a plasma-polymerized thin film is closely formed via a thin film electrode, it is possible to combine this with the excellent responsiveness and stability of the humidity sensor itself. , the above-mentioned effects due to the cell structure of the present invention are more fully exhibited.
第１図は、従来の湿度測定セルを例示する要部断面図、
第２図は、この発明の湿度測定セル全例示する第１図相
当図、第３図は、この発明の湿度測定セルの応答性を比
較例と共に例示するグラフである。
（１）・・・試料導入管部、（２）−・・試料排出管部
、（３） （８’）・・・湿度センサー、（４）・・・
湿度測定セル用容器、（４′）・・・セル保持器、（５
）・・・出力ピン、（６）・・・高分子膜。
第３図
時間ｃ勺〕−FIG. 1 is a sectional view of main parts illustrating a conventional humidity measuring cell,
FIG. 2 is a diagram corresponding to FIG. 1 illustrating all examples of the humidity measuring cell of the present invention, and FIG. 3 is a graph illustrating the responsiveness of the humidity measuring cell of the present invention together with a comparative example. (1)...Sample introduction tube section, (2)...Sample discharge tube section, (3) (8')...Humidity sensor, (4)...
Humidity measurement cell container, (4')...Cell holder, (5
)...Output pin, (6)...Polymer membrane. Figure 3 Time C] -
Claims (1)
内部に固定してなる湿度測定セルにおりで、 該湿度測定セルの内壁面に、表面自由エネルギーが５０
ｅｒｇ−ＣＩｌｔ−２以下の高分子膜を被覆形成した
ことを特徴とする湿度測定セル。[Claims] 1. A humidity measuring cell comprising a sample introduction pipe section and a discharge pipe section and a humidity sensor fixed therein, the inner wall surface of the humidity measuring cell having a surface free energy of 50
1. A humidity measuring cell characterized by being coated with a polymer film of erg-CIlt-2 or less.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3325483A JPS59159059A (en) | 1983-02-28 | 1983-02-28 | Humidity measuring cell |
| US06/516,959 US4562725A (en) | 1982-07-31 | 1983-07-25 | Moisture sensor and a process for the production thereof |
| EP83304392A EP0100661B1 (en) | 1982-07-31 | 1983-07-29 | Moisture sensor and a process for the production thereof |
| DE8383304392T DE3375829D1 (en) | 1982-07-31 | 1983-07-29 | Moisture sensor and a process for the production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3325483A JPS59159059A (en) | 1983-02-28 | 1983-02-28 | Humidity measuring cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59159059A true JPS59159059A (en) | 1984-09-08 |
| JPH0564295B2 JPH0564295B2 (en) | 1993-09-14 |
Family
ID=12381361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3325483A Granted JPS59159059A (en) | 1982-07-31 | 1983-02-28 | Humidity measuring cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59159059A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247299A (en) * | 1978-06-19 | 1981-01-27 | Johnson Controls, Inc. | Non-conductive polar gas sensing element and detection system |
-
1983
- 1983-02-28 JP JP3325483A patent/JPS59159059A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247299A (en) * | 1978-06-19 | 1981-01-27 | Johnson Controls, Inc. | Non-conductive polar gas sensing element and detection system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0564295B2 (en) | 1993-09-14 |
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