JPH1038797A - Trace oil detector - Google Patents
Trace oil detectorInfo
- Publication number
- JPH1038797A JPH1038797A JP18795396A JP18795396A JPH1038797A JP H1038797 A JPH1038797 A JP H1038797A JP 18795396 A JP18795396 A JP 18795396A JP 18795396 A JP18795396 A JP 18795396A JP H1038797 A JPH1038797 A JP H1038797A
- Authority
- JP
- Japan
- Prior art keywords
- light
- surface plasmon
- plasmon resonance
- oil
- lipophilic
- Prior art date
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Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水などの溶媒中に微
量に存在する油分の検知装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a device for detecting a minute amount of oil present in a solvent such as water.
【０００２】[0002]
【従来の技術】水中の微量油分の検知に関しては、浄水
場における取水中の表面油分の検知する方法として、例
えば、光反射式油膜検知法や、ＴＶカメラによる画
像監視法が、また、下水、工場排水中の油分の検知方法
として、例えば、抽出・赤外線吸収測定法、乳化・
濁度測定法、乳化・紫外線吸収測定法などの方法が従
来から知られている。2. Description of the Related Art With respect to detection of trace oil content in water, as a method for detecting surface oil content in water intake at a water purification plant, for example, a light reflection type oil film detection method, an image monitoring method using a TV camera, a sewage, Methods for detecting oil content in factory wastewater include, for example, extraction, infrared absorption measurement, emulsification,
Methods such as a turbidity measurement method and an emulsification / ultraviolet absorption measurement method have been conventionally known.
【０００３】これらの測定方法のそれぞれの概要につい
て簡単に記述すると、まず光反射式油膜検知法は、光
源にレーザやＬＥＤを用いて光線を水面上にあて、反射
した光の反射率が増大することを利用して、油膜を検知
するものである。ＴＶカメラによる画像監視法は、照
明装置によって水面を照らし、ＴＶカメラでこの水面を
撮影し、得られた画像を２値化し、油膜の反射率が水よ
りも大きいことを利用して、油膜を検知する方法であ
る。抽出・赤外線吸収測定法は、四塩化炭素などの抽
出溶媒に油分を抽出し、赤外線分析計で吸収スペクトル
を測定して、油分濃度を測定する方法である。乳化・
濁度測定法、および乳化・紫外線吸収測定法は、乳化
剤で油分を乳化させ、乳化した成分を濁度計、およびＵ
Ｖ計でそれぞれの測定をして、油分濃度を測定する方法
である。これら各種の測定方法を利用した装置もそれぞ
れ実用化されている。[0003] The outline of each of these measurement methods is briefly described. First, in the light reflection type oil film detection method, a light beam is applied to a water surface using a laser or LED as a light source, and the reflectance of the reflected light increases. By utilizing this, an oil film is detected. The image monitoring method using a TV camera illuminates the water surface with an illuminating device, takes an image of the water surface with a TV camera, binarizes the obtained image, and uses the fact that the reflectance of the oil film is greater than that of water to form an oil film. It is a method of detecting. The extraction / infrared absorption measurement method is a method of extracting an oil component in an extraction solvent such as carbon tetrachloride and measuring an absorption spectrum with an infrared spectrometer to measure the oil concentration. Emulsification
In the turbidity measurement method and the emulsification / ultraviolet absorption measurement method, the oil component is emulsified with an emulsifier, and the emulsified component is measured with a turbidity meter and U
This is a method of measuring the oil content by performing each measurement with a V meter. Apparatuses utilizing these various measuring methods have been put to practical use.
【０００４】[0004]
【発明が解決しようとする課題】しかし、従来の油分検
知方法や装置には、微量油分の検出が困難であるという
問題点があった。例えば浄水場において河川から取水し
た原水が油により汚染された場合には、飲料に用いられ
る点からも微量でも重大な事故であり、ｐｐｂオーダー
の検出能力が要求される。しかし現状では、油分検知装
置が十分な感度がないことから、人がにおいを嗅いで油
分の有無を判定するという方法が多く用いられている。
また、水中の油分は水面の油膜として存在するだけでは
なく、水中にコロイドとして分散している微量油分もあ
る。従来の光反射式油膜検知法やＴＶカメラによる
画像監視法では、この水中の微量油分を検知することが
できないという欠点がある。一方、抽出・赤外線吸収
測定法、乳化・濁度測定法、乳化・紫外線吸収測定
法は、水中油分の検知は可能であるが、感度としてはｐ
ｐｍまたはサブｐｐｍオーダーであって感度が不足して
いるほか、測定のために試料の前処理を必要とするとい
う欠点がある。However, the conventional oil detecting method and apparatus have a problem that it is difficult to detect a trace amount of oil. For example, when raw water taken from a river at a water purification plant is contaminated with oil, it is a serious accident even in a very small amount from the point of being used for drinking, and a detection capability on the order of ppb is required. However, at present, since the oil content detection device does not have sufficient sensitivity, a method is often used in which a person smells and determines the presence or absence of oil content.
In addition, the oil content in water is not only present as an oil film on the water surface, but also includes a trace amount of oil content dispersed as a colloid in water. The conventional light reflection type oil film detection method and the image monitoring method using a TV camera have a disadvantage that a trace amount of oil in water cannot be detected. On the other hand, the extraction / infrared absorption measurement method, emulsification / turbidity measurement method, and emulsification / ultraviolet absorption measurement method can detect oil-in-water, but the sensitivity is p
In addition to the lack of sensitivity in the order of pm or sub-ppm, there are disadvantages that the sample requires pretreatment for measurement.
【０００５】その他に、検出部の汚れや径時変化による
性能の低下を防ぎ、信頼性を向上させることや、様々な
油分の汚染元を特定するための成分分類を行うことなど
の要望もある。本発明は、上記の課題を解決するために
なされたものであり、その目的は、水などの溶媒に微量
に分散する油分を高感度で、高信頼性をもって検知で
き、また成分の分類もできる装置を提供することにあ
る。[0005] In addition, there are demands for preventing deterioration in performance due to contamination of the detection unit and changes in diameter, improving reliability, and performing component classification for specifying various oil contamination sources. . The present invention has been made to solve the above-described problems, and its object is to detect oil dispersed in a trace amount in a solvent such as water with high sensitivity and high reliability, and to classify components. It is to provide a device.
【０００６】[0006]
【課題を解決するための手段】本発明では「表面プラズ
モン共鳴角度」の測定を利用した３つの手段により、上
記の問題を解決する。本発明の第１の手段は、表面プラ
ズモン光学系を用いて、親油性膜に濃縮された水などの
溶媒中の微量な油分を誘電率（屈折率）の変化として検
出する。ここで「表面プラズモン光学系」とは、光線を
放射する投光部と、この光線の照射により表面プラズモ
ン共鳴を示すことのできる光線反射器と、この光線反射
器の表面を被覆する親油性膜と、この親油性膜表面にサ
ンプル溶媒を接触させる機構と、前記光線反射器から反
射した光の光量または表面プラズモン共鳴角度とを測定
する光検出部の全体を含んだ総称である。According to the present invention, the above-mentioned problem is solved by three means utilizing the measurement of "surface plasmon resonance angle". The first means of the present invention uses a surface plasmon optical system to detect a minute amount of oil in a solvent such as water concentrated in a lipophilic film as a change in dielectric constant (refractive index). Here, the “surface plasmon optical system” is a light emitting unit that emits light, a light reflector that can exhibit surface plasmon resonance by irradiating the light, and a lipophilic film that covers the surface of the light reflector. And a mechanism for bringing a sample solvent into contact with the surface of the lipophilic film, and a light detecting unit for measuring the amount of light reflected from the light reflector or the surface plasmon resonance angle.
【０００７】表面プラズモンとは、金属表面などで電荷
密度が集団的に振動し表面上を進行していくプラズマ波
であり、簡単な発生方法としては、高屈折率プリズムな
どの誘電体の一面に金属薄膜をコーティング（固着）
し、光線を適当な角度（θ）で入射したときに、エバネ
ッセント波の伝播速度と一致することによって、金属薄
膜表面にこのプラズモン波を励起することができる。こ
こで、エバネッセント波とは光線を全反射角で入射した
ときに、プリズムの外側にしみだしてプリズム表面を伝
播する光の表面波のことである。表面プラズモン光学系
で、反射角（θ）を変えながら反射光強度を測定する
と、ある一定の角度で光のエネルギーが表面プラズモン
へ移行するため、その反射角度での反射光出力が著しく
低下する現象が観察される。この反射角度が「表面プラ
ズモン共鳴角度」である。A surface plasmon is a plasma wave in which the charge density oscillates collectively on a metal surface or the like and travels on the surface. As a simple generation method, a surface plasmon is applied to one surface of a dielectric such as a high refractive index prism. Coating (fixing) metal thin film
When a light beam is incident at an appropriate angle (θ), the plasmon wave can be excited on the surface of the metal thin film by matching the propagation speed of the evanescent wave. Here, the evanescent wave is a surface wave of light that penetrates the outside of the prism and propagates on the prism surface when a light ray is incident at a total reflection angle. When the reflected light intensity is measured using a surface plasmon optical system while changing the reflection angle (θ), the light energy is transferred to the surface plasmon at a certain angle, and the reflected light output at that reflection angle is significantly reduced. Is observed. This reflection angle is the “surface plasmon resonance angle”.
【０００８】金属薄膜が十分薄い場合には、表面プラズ
マ波は金属を透過して、サンプル中に電界分布をもつ。
そのために、表面プラズモン共鳴角度は金属表面上にあ
る物質の誘電率（屈折率）によって変化する。この金属
薄膜表面に親油性膜を被覆させると、水などの溶媒中の
微量油分は親油性膜に吸着、濃縮される。これは上記の
「金属表面上にある物質の誘電率（屈折率）の変化」に
相当するため、表面プラズモン共鳴角度の変化をもたら
し、これを測定することにより微量な油分の検出が可能
となる。When the metal thin film is sufficiently thin, the surface plasma wave transmits through the metal and has an electric field distribution in the sample.
Therefore, the surface plasmon resonance angle changes depending on the dielectric constant (refractive index) of a substance on the metal surface. When the surface of the metal thin film is coated with a lipophilic film, a trace amount of oil in a solvent such as water is adsorbed and concentrated on the lipophilic film. Since this corresponds to the above-mentioned "change in the dielectric constant (refractive index) of the substance on the metal surface", it causes a change in the surface plasmon resonance angle, and by measuring this, it becomes possible to detect a minute amount of oil. .
【０００９】この方法が高感度な理由は、表面プラズマ
波のエネルギーは界面で最大、サンプルの深さ方向へ指
数関数的に減衰するため、界面の極近傍にエネルギーが
集中し、界面にある微量物質の誘電率（屈折率）の変化
に対して高い測定感度が得られるためである。本発明の
第２の手段は、親油性膜を備える表面プラズモン光学系
と親油性膜のない表面プラズモン光学系からの信号出力
の差を観測することにより、汚れと経時変化の影響の少
ない微量油分の検知を行う。例えば、河川水の微量油分
を検知しようとするときには、油分以外の汚染物により
検知部の表面が汚染され、表面プラズモン共鳴角度の出
力値が変化してしまう。また、光学系や信号処理部の経
時変化によっても出力は変化する。本方法では、親油性
膜を備える表面プラズモン光学系のほかにリファレンス
として親油性膜のない表面プラズモン光学系を持ってい
る。油分以外の汚染物は親油性膜のある表面と親油性膜
のない表面の両方を汚染するので、親油性膜を備える表
面プラズモン光学系と親油性膜のない表面プラズモン光
学系の出力の差を観測することにより汚れに強い微量油
分の検知を行うことができる。また、光学系や信号処理
部の経時変化については、親油性膜の有無にかかわらず
同様な変化をすると考えられるので、親油性膜有の表面
プラズモン光学系と親油性膜無の表面プラズモン光学系
の出力の差を観測することにより経時変化の影響の少な
い微量油分の検知を行うことができる。The reason for the high sensitivity of this method is that the energy of the surface plasma wave is maximum at the interface and decays exponentially in the depth direction of the sample. This is because high measurement sensitivity can be obtained with respect to a change in the dielectric constant (refractive index) of the substance. A second means of the present invention is to measure a difference in signal output from a surface plasmon optical system having a lipophilic film and a signal output from a surface plasmon optical system without a lipophilic film. Is detected. For example, when trying to detect a trace amount of oil in river water, the surface of the detection unit is contaminated with contaminants other than oil, and the output value of the surface plasmon resonance angle changes. Further, the output also changes due to the temporal change of the optical system and the signal processing unit. In this method, in addition to a surface plasmon optical system having a lipophilic film, a surface plasmon optical system without a lipophilic film is provided as a reference. Since non-oil contaminants contaminate both surfaces with and without lipophilic films, the difference in output between surface plasmon optics with lipophilic films and surface plasmon optics without lipophilic films can be reduced. Observation makes it possible to detect trace amounts of oil resistant to dirt. In addition, the change over time of the optical system and the signal processing unit is considered to be the same regardless of the presence or absence of the lipophilic film, so the surface plasmon optical system with the lipophilic film and the surface plasmon optical system without the lipophilic film By observing the difference between the outputs of the above, it is possible to detect a trace amount of oil that is less affected by the change over time.
【００１０】本発明の第３の手段では、複数の表面プラ
ズモン光学系の各々に種類の異なった親油性膜を被覆す
ることにより、微量油分の検知と同時に油分の分類を行
う。例えば河川水の微量油分としては、灯油、重油、工
業排油類、食用油類など様々な成分のものを含み、それ
ぞれの成分はアルキル基の長さや特徴となる官能基が異
なっている。これらの油分をその性質に従って分類する
には、各々の油成分に特徴的に結合する親油性膜を各々
選択して、各々異なる親油性膜を備える表面プラズモン
光学系からの出力を各々測定することにより可能にな
る。In the third means of the present invention, the classification of the oil component is performed simultaneously with the detection of the trace oil component by covering each of the plurality of surface plasmon optical systems with a different type of lipophilic film. For example, the trace oil content of river water includes various components such as kerosene, heavy oil, industrial waste oils, and edible oils, and each component has a different alkyl group length and a characteristic functional group. In order to classify these oils according to their properties, each of the lipophilic films characteristically binding to each oil component is selected and the output from the surface plasmon optical system having a different lipophilic film is measured. Becomes possible.
【００１１】[0011]
【発明の実施の形態】上記３つの手段を利用した本発明
は、次の構成要素を持った装置によって具体化できる。
まず第１の発明は、光線を放射する投光部と、この光線
の照射により表面プラズモン共鳴を示すことのできる光
線反射器と、この光線反射器の表面を被覆する親油性膜
と、この親油性膜表面にサンプル溶媒を接触させる機構
と、前記光線反射器から反射した光の光量または表面プ
ラズモン共鳴角度を測定する光検出部と、受光光量また
は表面プラズモン共鳴角度の変化をモニタする信号処理
部とを、備えた装置で、水などの溶媒の微量油分を測定
する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention utilizing the above three means can be embodied by an apparatus having the following components.
First, a first aspect of the present invention provides a light projecting unit that emits a light beam, a light reflector capable of exhibiting surface plasmon resonance by irradiating the light beam, a lipophilic film covering the surface of the light reflector, and a lipophilic film. A mechanism for bringing the sample solvent into contact with the surface of the oily film, a light detection unit for measuring the amount of light reflected from the light beam reflector or a surface plasmon resonance angle, and a signal processing unit for monitoring a change in the amount of received light or a change in the surface plasmon resonance angle And measuring a trace amount of oil in a solvent such as water.
【００１２】次に第２の発明は、複数の光線を放射する
投光部と、この複数の光線の照射によって各々の照射位
置に表面プラズモン共鳴を各々示すことのできる光線反
射器と、この光線反射器表面の複数の光線照射位置のう
ちいくつかを被覆する親油性膜と、この親油性膜表面お
よび光線反射器表面の親油性膜で被覆されていない照射
位置の各々にサンプル溶媒を接触させる機構と、前記光
線反射器から反射した各々の光の光量または表面プラズ
モン共鳴角度を各々測定する光検出部と、この親油性膜
で被覆された部位からの反射光と親油性膜で被覆されて
いない部位からの反射光との光量差または表面プラズモ
ン共鳴角度の差をモニタする信号処理部とを、備えた装
置で、試料とリファレンスとの同時測定により汚れと経
時変化の影響の少ない測定環境で、水などの溶媒の微量
油分を測定する。Next, a second aspect of the present invention is a light projecting unit that emits a plurality of light beams, a light beam reflector that can exhibit surface plasmon resonance at each irradiation position by irradiating the plurality of light beams, and a light beam reflector that emits the light. A sample solvent is brought into contact with each of the lipophilic film covering some of the plurality of light irradiation positions on the reflector surface and the irradiation positions not covered with the lipophilic film surface and the light reflector surface on the light reflector surface. A mechanism, a light detection unit for measuring a light amount or a surface plasmon resonance angle of each light reflected from the light beam reflector, and light reflected from a portion covered with the lipophilic film and covered with a lipophilic film. A signal processing unit that monitors the difference in the amount of light from the reflected light from the unexposed part or the difference in the surface plasmon resonance angle. In the stomach measurement environment, to measure the small amount of oil in the solvent, such as water.
【００１３】また第３の発明は、複数の光線を放射する
投光部と、この複数の光線の照射によって各々の照射位
置に表面プラズモン共鳴を各々示すことのできる光線反
射器と、この光線反射器表面上の各々の照射位置に被覆
された各々異なる種類の親油性膜と、各々の親油性膜に
サンプル溶媒を接触させる機構と、前記光線反射器から
反射した各々の光の光量または表面プラズモン共鳴角度
を各々測定する光検出部と、各々の受光光量または共鳴
角度の変化をモニタする信号処理部とを、備えた装置
で、水などの溶媒の微量油分の測定と同時に油分の分類
を行う。According to a third aspect of the present invention, there is provided a light projecting unit for emitting a plurality of light beams, a light beam reflector capable of exhibiting surface plasmon resonance at each irradiation position by irradiating the plurality of light beams, and a light beam reflecting device. A different type of lipophilic film coated on each irradiation position on the vessel surface, a mechanism for bringing the sample solvent into contact with each lipophilic film, and a light amount or surface plasmon of each light reflected from the light reflector. A device equipped with a light detection unit for measuring the resonance angle and a signal processing unit for monitoring the change in the amount of received light or the change in the resonance angle. .
【００１４】[0014]
［実施例１］第１の発明の実施例として水中の微量油分
の検知装置を図１に示す。微量油分を含むサンプル水１
は、取水配管２によりフローセル３に導かれた後、排水
４として排出される。フローセル３の上部には表面プラ
ズモン共鳴発生用の光線反射器５が備え付けられてい
る。光線反射器５はシリンドリカル状のプリズム６の下
面に厚さ約５０ｎｍの銀薄膜７を真空蒸着により固着し
たものである。さらにその下面には後述する方法によっ
て親油性膜８が被覆されている。半導体レーザ光源９か
らの光線はレンズ１０とプリズム６によって絞られ、焦
点が銀薄膜７の表面上に結ばれている。光線は絞られて
いるため光軸から約±１０°の振れ角をもって銀薄膜７
の表面に入射されることになる。このとき表面プラズモ
ン共鳴の発生条件に合うある角度（表面プラズモン共鳴
角度）から銀薄膜７の表面に入射された光の反射光光量
に鋭い減衰が起こる。この表面プラズモン共鳴角度は、
反射光を１０２４素子のリニアイメージセンサ１１で測
定したときに現れる鋭い光の減衰ピーク位置から求めら
れる。[Embodiment 1] FIG. 1 shows an apparatus for detecting a trace amount of oil in water as an embodiment of the first invention. Sample water 1 containing a trace amount of oil
Is guided to the flow cell 3 by the water intake pipe 2 and then discharged as drainage 4. A light reflector 5 for generating surface plasmon resonance is provided above the flow cell 3. The light reflector 5 has a silver thin film 7 having a thickness of about 50 nm fixed to the lower surface of a cylindrical prism 6 by vacuum evaporation. Further, its lower surface is covered with a lipophilic film 8 by a method described later. The light beam from the semiconductor laser light source 9 is converged by the lens 10 and the prism 6, and the focal point is formed on the surface of the silver thin film 7. Since the light beam is narrowed, the silver thin film 7 has a deflection angle of about ± 10 ° from the optical axis.
Will be incident on the surface. At this time, a sharp attenuation occurs in the amount of reflected light of light incident on the surface of the silver thin film 7 from a certain angle (surface plasmon resonance angle) that meets the conditions for generating surface plasmon resonance. This surface plasmon resonance angle is
It is obtained from the sharp light attenuation peak position that appears when the reflected light is measured by the 1024-element linear image sensor 11.
【００１５】サンプルが純水の場合には図４の実線で示
すような吸収波形が観察される。光学系の角度分解能は
約０．０２°である。次にサンプル水中に微量油分１２
が存在するときは、微量油分１２が親油性膜８中に濃縮
され、親油性膜８の誘電率の増加によって、図４の破線
で示すように、表面プラズモン共鳴角は高角度側にシフ
トする。このシフト角はリニアイメージセンサ１１で鋭
い光の減衰位置がシフトして測定される。リニアイメー
ジセンサ１１の測定信号は信号処理部１２に送られ、信
号処理部１２では表面プラズモン共鳴角のシフトを計算
し、あらかじめ設定された値を越えた場合には油分の混
入があったと判定し、必要に応じて外部へ警報の通知を
行う。When the sample is pure water, an absorption waveform as shown by a solid line in FIG. 4 is observed. The angular resolution of the optical system is about 0.02 °. Next, trace oil 12 in the sample water
Is present, the trace oil 12 is concentrated in the lipophilic film 8, and the surface plasmon resonance angle shifts to a higher angle side as shown by the broken line in FIG. . The shift angle is measured by the linear image sensor 11 with the sharp light attenuation position shifted. The measurement signal of the linear image sensor 11 is sent to the signal processing unit 12, and the signal processing unit 12 calculates the shift of the surface plasmon resonance angle. When the shift exceeds a preset value, it is determined that oil has been mixed. Then, an alarm is notified to the outside if necessary.
【００１６】親油性膜の製作方法の例としては、図５に
示すシランカプラーの反応を用いることができる。シラ
ンカプラーは相互に馴染みの悪い無機材料（金属など）
と有機材料（高分子など）の両者と化学結合できる官能
基をもつ有機珪素化合物で、その標準型は、（ＣＨ
3 Ｏ)3Ｓi(ＣＨ2)n Ｘと表される。銀薄膜との結合は加
水分解性の置換基であるアルコキシル基がシロキサン結
合する。Ｘは有機物と反応しやすいビニル基、エポキシ
基、アミノ基などのであり、さらに種々の機能団の導入
に利用される。本発明の請求項４に示した親油性膜は上
述の方法により作製が可能である。疎水性のアルキル鎖
はシランカプラーの（ＣＨ2)n Ｘ部に相当し、金属薄膜
と反応する反応する官能器は（ＣＨ3 Ｏ)3Ｓｉ部に相当
する。As an example of a method for producing a lipophilic film, a reaction of a silane coupler shown in FIG. 5 can be used. Silane couplers are inorganic materials that are not familiar with each other (metals, etc.)
An organosilicon compound having a functional group capable of chemically bonding to both organic and organic materials (such as polymers). The standard type is (CH
3 O) 3 Si (CH 2 ) n X. The bond with the silver thin film is a siloxane bond of an alkoxyl group which is a hydrolyzable substituent. X is a vinyl group, an epoxy group, an amino group, or the like that easily reacts with an organic substance, and is used for introducing various functional groups. The lipophilic film according to claim 4 of the present invention can be manufactured by the above-described method. The hydrophobic alkyl chain corresponds to the (CH 2 ) n X part of the silane coupler, and the functional unit that reacts with the metal thin film corresponds to the (CH 3 O) 3 Si part.
【００１７】［実施例２］第２の発明の実施例として水
中の微量油分の検知装置を図２に示す。この図において
図１に示した符号と同一のものは同一物を示している。
この実施例においては、半導体レーザ光源９からの光線
はハーフミラー１３とミラー１４によって２つの光線に
分けられ、２本の光線が各々銀薄膜７の表面の異なる位
置に入射している。銀薄膜７の表面の異なる位置に入射
した光線は各々表面プラズモン共鳴を励起する。第一の
光線の入射位置には親油性膜８が被覆されているが、第
二の光線の入射位置には親油性膜は被覆されていない。
各々の反射光はリニアイメージセンサ１１と１５で各々
受光され、各々の表面プラズモン共鳴角度が測定され
る。各々の測定値は信号処理部１２に送られ、信号処理
部１２では、２つの表面プラズモン共鳴角度測定値の差
を演算し、差があらかじめ設定された値を越えた場合に
は油分の混入があったと判定し、必要に応じて外部へ警
報の通知を行う。この第２の実施例の装置は、親油性膜
をもたない表面プラズモン光学系の測定値をリファレン
スとして用いているため、親油性膜の有無に関わらず起
こる現象、例えば、汚れ、径時変化の影響をキャンセル
し、信頼性の高い微量油分の検知を行うことができる。[Embodiment 2] FIG. 2 shows an apparatus for detecting a trace amount of oil in water as an embodiment of the second invention. In this figure, the same components as those shown in FIG. 1 indicate the same components.
In this embodiment, the light beam from the semiconductor laser light source 9 is divided into two light beams by a half mirror 13 and a mirror 14, and the two light beams are respectively incident on different positions on the surface of the silver thin film 7. Light rays incident on different positions on the surface of the silver thin film 7 respectively excite surface plasmon resonance. The lipophilic film 8 is coated on the incident position of the first light beam, but the lipophilic film is not coated on the incident position of the second light beam.
Each reflected light is received by each of the linear image sensors 11 and 15, and each surface plasmon resonance angle is measured. Each measurement value is sent to the signal processing unit 12, and the signal processing unit 12 calculates the difference between the two surface plasmon resonance angle measurement values. If the difference exceeds a preset value, the oil component is mixed. It is determined that there is, and an alarm is notified to the outside if necessary. Since the apparatus of the second embodiment uses the measured value of the surface plasmon optical system having no lipophilic film as a reference, phenomena that occur regardless of the presence or absence of the lipophilic film, for example, contamination, time-dependent change in diameter And the effect of high reliability can be detected.
【００１８】［実施例３］第３の発明の実施例として水
中の微量油分の検知装置を図３に示す。この図において
図１及び図２に示した符号と同一のものは同一物を示し
ている。この実施例においては、半導体レーザ光源９か
らの光線はハーフミラー１３、１６とミラー１４によっ
て３つの光線に分けられ、３本の光線が各々銀薄膜７の
表面の異なる位置に入射している。銀薄膜７の表面の異
なる位置に入射した光線は各々表面プラズモン共鳴を励
起する。第１の光線の入射位置には第１の親油性膜８が
被覆されていて、第２の光線の入射位置には性質の異な
る第２の親油性膜１７が被覆されている。また、第３の
光線の入射位置には性質の異なる第３の親油性膜１８が
被覆されている。各々の反射光はリニアイメージセンサ
１１、１５および１９で各々受光され、各々の表面プラ
ズモン共鳴角度が測定される。各々の測定値は信号処理
部１２に送られ、信号処理部１２では、各々の測定値が
あらかじめ設定された値を越えていないか各々判定し、
越えていた場合にはそれそれの親油性膜に対応した油分
の混入があったと判定し、必要に応じて外部へ警報の通
知を行う。３つの異なる親油性膜はいずれも上述のシラ
ンカプラーを用いて作製され、疎水性を示すアルキル鎖
の長さを各々変えてある。アルキル鎖の長い親油性膜は
アルキル鎖の長い油成分と、アルキル鎖の短い親油性膜
はアルキル鎖の短い油成分と結合しやすいので、この第
３の実施例の装置を用いて微量油分の検知と同時に油分
の分類を行うことができる。[Embodiment 3] FIG. 3 shows an apparatus for detecting a trace amount of oil in water as an embodiment of the third invention. In this figure, the same components as those shown in FIGS. 1 and 2 indicate the same components. In this embodiment, the light beam from the semiconductor laser light source 9 is divided into three light beams by the half mirrors 13, 16 and the mirror 14, and the three light beams are respectively incident on different positions on the surface of the silver thin film 7. Light rays incident on different positions on the surface of the silver thin film 7 respectively excite surface plasmon resonance. A first lipophilic film 8 is coated on the incident position of the first light beam, and a second lipophilic film 17 having different properties is coated on the incident position of the second light beam. A third lipophilic film 18 having a different property is coated on the incident position of the third light beam. The respective reflected lights are respectively received by the linear image sensors 11, 15 and 19, and the respective surface plasmon resonance angles are measured. Each measured value is sent to the signal processing unit 12, and the signal processing unit 12 determines whether each measured value does not exceed a preset value,
If it exceeds, it is determined that the oil component corresponding to each lipophilic film has been mixed, and an alarm is notified to the outside if necessary. All three different lipophilic membranes were made using the silane couplers described above, with varying lengths of the hydrophobic alkyl chains. Since the lipophilic membrane having a long alkyl chain easily bonds to the oil component having a long alkyl chain, and the lipophilic membrane having a short alkyl chain easily bonds to the oil component having a short alkyl chain, a small amount of oil is used by using the apparatus of the third embodiment. Oil content can be classified at the same time as detection.
【００１９】実施例１〜３の微量油分検知装置は、親油
性膜表面にサンプル溶媒を接触させる機構として、フロ
ーセルを用いてサンプル水を親油性膜表面へ導いている
が、河川、取水池、排水池、水槽、プールなどの水質測
定には、親油性膜を含む検出表面を直接試料水に浸けて
測定を行ってもよい。また、実施例２および３の微量油
分検知装置は１つの光線反射器に複数の光線を照射して
表面プラズモンを励起しているが、複数の光線反射器に
複数の光線を照射することでも同様の目的が達成でき
る。The trace oil detecting devices of Examples 1 to 3 use a flow cell to guide the sample water to the surface of the lipophilic membrane as a mechanism for bringing the sample solvent into contact with the surface of the lipophilic membrane. For measuring the water quality of a drainage pond, a water tank, a pool, or the like, the measurement may be performed by immersing the detection surface including the lipophilic membrane directly in the sample water. Further, the trace oil detecting devices of Examples 2 and 3 irradiate one light reflector with a plurality of light beams to excite surface plasmons, but the same applies when irradiating a plurality of light reflectors with a plurality of light beams. Can be achieved.
【００２０】[0020]
【発明の効果】本発明の微量油分検知装置は、水などの
溶媒に微量に分散する微量油分を高感度、高信頼に検
知、分類できる。The trace oil detecting device of the present invention can detect and classify a trace amount of a minute amount of oil dispersed in a solvent such as water with high sensitivity and high reliability.
【図１】水中の微量油分検知装置の第１の発明例の模式
図FIG. 1 is a schematic view of a first invention example of a device for detecting a trace amount of oil in water.
【図２】水中の微量油分検知装置の第２の発明例の模式
図FIG. 2 is a schematic view of a second invention example of a device for detecting a trace amount of oil in water.
【図３】水中の微量油分検知装置の第３の発明例の模式
図FIG. 3 is a schematic view of a third invention example of a device for detecting a trace amount of oil in water.
【図４】銀薄膜表面に光を入射した場合の入射角−反射
率特性を示す図FIG. 4 is a diagram showing an incident angle-reflectance characteristic when light is incident on the surface of a silver thin film.
【図５】シランカプラー反応を用いた親油膜製作方法の
例を示す図FIG. 5 is a diagram showing an example of a method for producing a lipophilic film using a silane coupler reaction.
１ サンプル水 ２ 取水配管 ３ フローセル ４ 排水 ５ 光線反射器 ６ プリズム ７ 銀薄膜 ８ 親油性膜 ９ レーザ光源 １０ レンズ １１ リニアイメージセンサ １２ 信号処理部 １３ ハーフミラー １４ ミラー １５ リニアイメージセンサ １６ ハーフミラー １７ 親油性膜 １８ 親油性膜 １９ リニアイメージセンサ REFERENCE SIGNS LIST 1 Sample water 2 Intake pipe 3 Flow cell 4 Drain 5 Light reflector 6 Prism 7 Silver thin film 8 Lipophilic film 9 Laser light source 10 Lens 11 Linear image sensor 12 Signal processor 13 Half mirror 14 Mirror 15 Linear image sensor 16 Half mirror 17 Parent Oily film 18 Lipophilic film 19 Linear image sensor
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野田 直広 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 大戸 時喜雄 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 田中 良春 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 塩川 祥子 静岡県浜松市城北２−25−40 丸二サンハ イツ Ａ303 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naohiro Noda 1-1-1, Tanabe-Nitta, Kawasaki-ku, Kawasaki, Kanagawa Prefecture Inside Fuji Electric Co., Ltd. (72) Inventor Tokio Ohto 1, Tanabe-Nitta, Kawasaki-ku, Kawasaki-ku, Kanagawa Prefecture No. 1 Fuji Electric Co., Ltd. (72) Inventor Yoshiharu Tanaka 1-1, Tanabe Nitta, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Inside Fuji Electric Co., Ltd. (72) Inventor Shoko Shiokawa 2-25-40, Johoku, Hamamatsu City, Shizuoka Prefecture Maruni Sun Heights A303
Claims (4)
により表面プラズモン共鳴を示すことののできる光線反
射器と、この光線反射器の表面を被覆する親油性膜と、
この親油性膜表面にサンプル溶媒を接触させる機構と、
前記光線反射器から反射した光の光量または表面プラズ
モン共鳴が生じる前記光線の入射角度（以下、表面プラ
ズモン共鳴角度と記す）を測定する光検出部と、受光光
量または表面プラズモン共鳴角度の変化をモニタする信
号処理部と、を備える水などの溶媒中の微量油分検知装
置。1. A light projecting unit for emitting a light beam, a light reflector capable of exhibiting surface plasmon resonance by irradiating the light beam, a lipophilic film covering the surface of the light reflector,
A mechanism for bringing the sample solvent into contact with the lipophilic membrane surface,
A light detector that measures the amount of light reflected from the light beam reflector or the incident angle of the light beam at which surface plasmon resonance occurs (hereinafter, referred to as surface plasmon resonance angle), and monitors changes in the amount of received light or surface plasmon resonance angle And a signal processing unit for detecting a trace amount of oil in a solvent such as water.
の光線の照射によって各々の照射位置に表面プラズモン
共鳴を各々示すことのできる光線反射器と、この光線反
射器表面の複数の光線照射位置のうちのいくつかを被覆
する親油性膜と、この親油性膜表面および光線反射器表
面の親油性膜で被覆されていない照射位置の各々にサン
プル溶媒を接触させる機構と、前記光線反射器から反射
した各々の光の光量または表面プラズモン共鳴角度を各
々測定する光検出部と、親油性膜で被覆された部位から
の反射光と親油性膜で被覆されていない部位からの反射
光との光量差または表面プラズモン共鳴角度の差をモニ
タする信号処理部と、を備える水などの溶媒中の微量油
分検知装置。2. A light projecting unit for emitting a plurality of light beams, a light beam reflector capable of exhibiting surface plasmon resonance at each irradiation position by irradiation of the plurality of light beams, and a plurality of light beam reflectors on the light beam reflector surface. A lipophilic film covering some of the light irradiation positions, a mechanism for bringing the sample solvent into contact with each of the irradiation positions not covered with the lipophilic film on the lipophilic film surface and the light reflector surface, and the light beam A light detection unit for measuring the amount of light of each light reflected from the reflector or the surface plasmon resonance angle, and light reflected from a portion covered with a lipophilic film and light reflected from a portion not covered with a lipophilic film. A signal processing unit for monitoring a difference in light amount or a difference in surface plasmon resonance angle with the device, for detecting a trace amount of oil in a solvent such as water.
の光線の照射によって各々の照射位置に表面プラズモン
共鳴を各々示すことのできる光線反射器と、この光線反
射器表面上の各々の照射位置に被覆された各々種類の異
なる親油性膜と、各々の親油性膜にサンプル溶媒を接触
させる機構と、前記光線反射器から反射した各々の光の
光量または表面プラズモン共鳴角度を各々測定する光検
出部と、各々の受光光量または表面プラズモン共鳴角度
の変化をモニタする信号処理部と、を備え、各々の親油
性膜に対応する各々の受光光量または表面プラズモン共
鳴角度の変化から水などの溶媒中の微量油分の検知と油
分の分類を行う微量油分検知装置。3. A light projecting unit for emitting a plurality of light beams, a light beam reflector capable of exhibiting surface plasmon resonance at each irradiation position by irradiation of the plurality of light beams, and a light beam reflector on each of the light beam reflector surfaces. Each of different types of lipophilic films coated on the irradiation position, a mechanism for contacting the sample solvent with each lipophilic film, and measuring the amount of light of each light reflected from the light reflector or the surface plasmon resonance angle, respectively And a signal processing unit that monitors a change in the amount of received light or the surface plasmon resonance angle, and detects a change in the amount of received light or the change in surface plasmon resonance angle corresponding to each lipophilic film. Trace oil detector that detects and classifies trace oil in solvents.
油性膜が疎水性を示すアルキル鎖と金属薄膜と反応する
官能基を有する化合物であることを特徴とする微量油分
検知装置。4. An apparatus according to claim 1, wherein said lipophilic film is a compound having a functional group which reacts with an alkyl chain having hydrophobicity and a metal thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18795396A JP3447478B2 (en) | 1996-07-18 | 1996-07-18 | Trace oil detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18795396A JP3447478B2 (en) | 1996-07-18 | 1996-07-18 | Trace oil detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1038797A true JPH1038797A (en) | 1998-02-13 |
| JP3447478B2 JP3447478B2 (en) | 2003-09-16 |
Family
ID=16215063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18795396A Expired - Fee Related JP3447478B2 (en) | 1996-07-18 | 1996-07-18 | Trace oil detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3447478B2 (en) |
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|---|---|---|---|---|
| WO2001090728A1 (en) * | 2000-05-25 | 2001-11-29 | Katayanagi Institute | Differential spr sensor and measuring method using it |
| EP1306662A1 (en) * | 2000-05-25 | 2003-05-02 | Katayanagi Institute | Differential spr sensor and measuring method using it |
| EP1306662A4 (en) * | 2000-05-25 | 2006-01-18 | Katayanagi Inst | Differential spr sensor and measuring method using it |
| JP2002250690A (en) * | 2001-02-23 | 2002-09-06 | Fuji Photo Film Co Ltd | Measuring method and measuring instrument using attenuation of total reflection |
| JPWO2006022277A1 (en) * | 2004-08-24 | 2008-05-08 | 富士フイルム株式会社 | Calculation method of dissociation constant in surface plasmon resonance analysis |
| WO2006022277A1 (en) * | 2004-08-24 | 2006-03-02 | Fujifilm Corporation | Method for calculating dissociation constant in surface plasmon resonance analysis |
| US7602495B2 (en) | 2004-08-24 | 2009-10-13 | Fujifilm Corporation | Method for measuring dissociation constant by surface plasmon resonance analysis |
| JP4664298B2 (en) * | 2004-08-24 | 2011-04-06 | 富士フイルム株式会社 | Calculation method of dissociation constant in surface plasmon resonance analysis |
| CN100434896C (en) * | 2005-05-08 | 2008-11-19 | 西安交通大学 | Online method for measuring oil density in oil containing sewage and device thereof |
| JP2008057980A (en) * | 2006-08-29 | 2008-03-13 | Sharp Corp | Molecule detector and washing device using it |
| JP4676402B2 (en) * | 2006-08-29 | 2011-04-27 | シャープ株式会社 | Molecular detector and cleaning device using the molecular detector |
| JP2011509414A (en) * | 2008-01-09 | 2011-03-24 | オロノ スペクトラル ソリューションズ インク | Device for measuring the content of an analyte in a fluid |
| CN104713851A (en) * | 2015-03-24 | 2015-06-17 | 吉林大学 | Miniature real-time on-line offshore oil spill detection system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3447478B2 (en) | 2003-09-16 |
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