JP2853302B2 - Double temperature control conductivity detector - Google Patents
Double temperature control conductivity detectorInfo
- Publication number
- JP2853302B2 JP2853302B2 JP2230984A JP23098490A JP2853302B2 JP 2853302 B2 JP2853302 B2 JP 2853302B2 JP 2230984 A JP2230984 A JP 2230984A JP 23098490 A JP23098490 A JP 23098490A JP 2853302 B2 JP2853302 B2 JP 2853302B2
- Authority
- JP
- Japan
- Prior art keywords
- conductivity detector
- joint
- tube
- conductivity
- detector
- 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.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2291/00—Indexing codes associated with group G01N29/00
- G01N2291/04—Wave modes and trajectories
- G01N2291/048—Transmission, i.e. analysed material between transmitter and receiver
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、被測定液中の目的成分をクロマトグラフィ
ックに分離・分析する装置などの検出器として使用され
た流体の導電率を検出する二重温調付導電率検出器に関
する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for detecting the electrical conductivity of a fluid used as a detector such as an apparatus for chromatographically separating and analyzing a target component in a liquid to be measured. The present invention relates to a conductivity detector with heavy temperature control.
＜従来の技術＞ 周知の如く、液体クロマトグラフは移動相に液体を用
い被測定液中の目的成分をクロマトグラフィックに分離
して分析する装置である。このような液体クロマトグラ
フにおいては、被測定液が一定量採取されて移動相たる
溶離液でもって分離カラムに搬送され、該分離カラムで
被測定液中の測定対象物（即ち、陽イオンや陰イオンな
ど）をクロマトグラフィックに分離し、その後、導電率
検出器に導いて導電率を検出し、該検出信号に基いて作
成されるクロマトグラムから前記被測定液中の測定対象
物を測定するようになっていた。<Prior Art> As is well known, a liquid chromatograph is a device that uses a liquid as a mobile phase to separate and analyze a target component in a liquid to be measured by chromatography. In such a liquid chromatograph, a certain amount of a liquid to be measured is collected and conveyed to a separation column with an eluent as a mobile phase, and the object to be measured (that is, a cation or an anion) in the liquid to be measured is separated by the separation column. Ion, etc.), and then conducts it to a conductivity detector to detect the conductivity, and measures the measurement target in the liquid to be measured from a chromatogram created based on the detection signal. Had become.
然しながら、液体クロマトグラフ（イオンクロマトグ
ラフを含む）においては、導電率検出器が極めて温度に
敏感であって、流体の導電率が同一であるにも拘らず、
温度が１℃変化すると導電率検出器の検出信号が約２％
も変化していた。このため、導電率検出器の周囲温度が
微妙に変化したりポンプの脈動によって移動相の温度が
変化したりすると、導電率検出器の検出信号にノイズや
揺らぎを生じ、導電率の高感度検出に大きな支障をきた
すようになっていた。However, in liquid chromatographs (including ion chromatographs), despite the fact that conductivity detectors are extremely temperature sensitive and the fluid conductivity is the same,
When the temperature changes by 1 ° C, the detection signal of the conductivity detector is about 2%
Had also changed. For this reason, if the ambient temperature of the conductivity detector changes minutely or the temperature of the mobile phase changes due to the pulsation of the pump, noise or fluctuations occur in the detection signal of the conductivity detector, and high sensitivity detection of the conductivity is performed. Was causing great problems.
また、高安定化・高感度化を図るため、熱交換式の予
熱管を導電率検出器の前に設置することにより、ピーク
の拡散が最小限で且つ高い安定性を得ることが試みられ
ていた。この方法は検出部に特別な温度調節機構を持た
せることなく簡便に高感度・高安定性を得ることができ
るという大きな特徴を有している。In addition, in order to achieve high stability and high sensitivity, it has been attempted to obtain a high stability with minimum peak diffusion by installing a heat exchange type preheating tube in front of the conductivity detector. Was. This method has a great feature that high sensitivity and high stability can be easily obtained without having a special temperature control mechanism in the detection unit.
しかし、装置の設置環境の急激な温度変化に対しては
必ずしも有効でなく、温度変化の大きい環境ではベース
ラインのドリフトや長期間なうねりが生ずるという欠点
があった。However, it is not always effective against a rapid temperature change in the installation environment of the apparatus, and there is a drawback that a baseline drift or a long-term swell occurs in an environment where the temperature change is large.
＜発明が解決しようとする問題点＞ 本発明は、かかる状況に鑑みてなされたものであり、
その目的は、外部環境の急激な温度変化に対してもベー
スラインの変動を小さくするできるできるような二重温
調付導電率検出器を提供することにある。<Problems to be solved by the invention> The present invention has been made in view of such a situation,
It is an object of the present invention to provide a dual temperature regulation conductivity detector that can reduce the fluctuation of the baseline even with a rapid temperature change in the external environment.
＜問題点を解決するための手段＞ 上述のような問題点を解決する本発明の特徴は、被測
定液中の目的成分をクロマトグラフィックに分離・分析
する装置の検出器として使用される二重温調付導電率検
出器において、二重管構造の熱交換式予熱管と、該予熱
管の入口側に設けられた第１ジョイントと、前記予熱管
の出口側に設けられた第２ジョイントと、流体の導電率
を検出する導電率検出器と、前記熱交換式予熱管，第１
ジョイント，第２ジョイント，及び導電率検出器を収容
するヒーティングボックスと、該ヒーティングボックス
を両側から加熱する第１及び第２のヒータとを設け、前
記第１ジョイントを介して前記熱交換式予熱管の内管に
供給される流体が前記第２ジョイントを通って前記導電
率検出器に供給されると共に、該導電率検出器から排出
された流体が前記第２ジョイントを通って前記交換式予
熱管の外套管内を流れ、その後、前記第１ジョイントを
経由して排出されるように構成したことにある。<Means for Solving the Problems> The feature of the present invention that solves the above-mentioned problems is that a dual component used as a detector of a device that chromatographically separates and analyzes a target component in a liquid to be measured is used. In the temperature-regulated conductivity detector, a heat exchange type preheating pipe having a double pipe structure, a first joint provided on an inlet side of the preheating pipe, and a second joint provided on an outlet side of the preheating pipe, A conductivity detector for detecting the conductivity of a fluid;
A heating box accommodating a joint, a second joint, and a conductivity detector; and first and second heaters for heating the heating box from both sides, and the heat exchange type is provided via the first joint. The fluid supplied to the inner tube of the preheating tube is supplied to the conductivity detector through the second joint, and the fluid discharged from the conductivity detector is passed through the second joint to the exchange type. It is configured to flow in the outer tube of the preheating tube, and then to be discharged via the first joint.
＜実施例＞ 以下、本発明について図を用いて詳細に説明する。第
１図は本発明実施例の構成説明図であり、第２図は本発
明実施例の収納応対を示す構成断面図である。第１図及
び第２図において、１は二重管構造の熱交換式予熱管、
1aは予熱管の内管、1bは予熱管の外套管、２は入口側の
ジョイント、2aはジョイント本体、2b〜2dはチューブを
ジョイント本体2aに接続するための第１〜第３のオシ
ネ、３は出口側のジョイント、3aはジョイント本体、3b
〜3dはチューブをジョイント本体3aに接続するための第
１〜第３のオシネ、４は導電率検出器、4aは電極部、4b
は電極部4aを覆う樹脂製の筒、4c,4c′は筒4bを介して
電極部4aを固定するホルダー、4d,4eはチューブ1a,5aを
導電率検出器４に接続するためのオシネ、6a,6bはヒー
タ、7a,7bはリード線、８はアルミ製のボックス、９は
断熱材、10はアルミ製のカバーである。<Example> Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a configuration explanatory view of an embodiment of the present invention, and FIG. 2 is a cross-sectional view of the configuration showing a storage response of the embodiment of the present invention. 1 and 2, reference numeral 1 denotes a heat exchange type preheating tube having a double tube structure,
1a is the inner tube of the preheating tube, 1b is the outer tube of the preheating tube, 2 is the joint on the inlet side, 2a is the joint body, 2b to 2d are the first to third osine for connecting the tube to the joint body 2a, 3 is an outlet side joint, 3a is a joint body, 3b
3d is a first to third osine for connecting the tube to the joint body 3a, 4 is a conductivity detector, 4a is an electrode section, 4b
Is a resin cylinder covering the electrode section 4a, 4c and 4c 'are holders for fixing the electrode section 4a via the cylinder 4b, 4d and 4e are osine for connecting the tubes 1a and 5a to the conductivity detector 4, 6a and 6b are heaters, 7a and 7b are lead wires, 8 is an aluminum box, 9 is a heat insulating material, and 10 is an aluminum cover.
このような構成からなる本発明の実施例において、第
１図や第２図の太線矢印方向から導入された流体は、内
管1a→導電率検出器４の電極部4a→チューブ5a→出口側
ジョイント３の内部→予熱管１の外套管1b→入口ジョイ
ント２の内部→チューブ5bの流路を流れ、太線矢印方向
へ排出される。このため、二重管構造の熱交換式予熱管
１の内管1a内を流れる液体（即ち、導電率検出器４への
流入液）と外套管1b内を流れる液体（即ち、導電率検出
器４からの流出液）の間で熱交換が行われ、導電率検出
器４への流入液の温度と導電率検出器４からの流出液の
温度が大略同一となる。従って、導電率検出器４への流
入液の温度が大略一定に保たれるようになり、その結
果、導電率検出信号のベースラインが安定するようにな
る。In the embodiment of the present invention having such a configuration, the fluid introduced from the direction of the thick arrow in FIGS. 1 and 2 is the inner tube 1a → the electrode portion 4a of the conductivity detector 4 → the tube 5a → the outlet side. The inside of the joint 3 → the outer tube 1b of the preheating tube 1 → the inside of the inlet joint 2 → flows through the flow path of the tube 5b, and is discharged in the direction of the thick arrow. For this reason, the liquid flowing through the inner tube 1a of the double-tube heat exchange type preheating tube 1 (that is, the liquid flowing into the conductivity detector 4) and the liquid flowing through the outer tube 1b (that is, the conductivity detector) 4), the temperature of the liquid flowing into the conductivity detector 4 and the temperature of the liquid flowing out of the conductivity detector 4 become substantially the same. Therefore, the temperature of the liquid flowing into the conductivity detector 4 is kept substantially constant, and as a result, the baseline of the conductivity detection signal becomes stable.
第３図は上述のような本発明実施例を組込んだイオン
クロマトグラフ（液体クロマトグラフの一種）であっ
て、本発明の使用例構成説明図である。この図におい
て、11aは例えば5mMのHNO3溶液でなる溶離液が貯溜され
てなる槽、12aは移動相である溶離液を一定流量で送液
するポンプ、13は試料を一定量（例えば100μ）採取
して溶離液の流れるラインに注入する試料注入器、14は
例えば陽イオン交換樹脂が充填されてなる分離カラム、
15はサプレッサ、16は本発明に係わる二重管式導電率検
出器である。FIG. 3 is an ion chromatograph (a type of liquid chromatograph) incorporating the above-described embodiment of the present invention, and is an explanatory diagram of a use example configuration of the present invention. In this figure, reference numeral 11a denotes a tank in which an eluent composed of, for example, a 5 mM HNO 3 solution is stored, 12a denotes a pump which sends a mobile phase eluent at a constant flow rate, and 13 denotes a fixed amount of a sample (for example, 100 μ). A sample injector which collects and injects it into a line through which an eluent flows, 14 is a separation column filled with a cation exchange resin,
Reference numeral 15 denotes a suppressor, and 16 denotes a double tube conductivity detector according to the present invention.
尚、本発明に拘わる導電率検出器16はヒーティングボ
ックス17内に収容されて一定温度（例えば45℃）に保た
れている。また、試料注入器13,分離カラム14,サプレッ
サ15,予熱管1,導電率検出器4,及びヒーティングボック
ス17は恒温槽内に収容されて一定温度に保たれることが
多い。The conductivity detector 16 according to the present invention is housed in a heating box 17 and is maintained at a constant temperature (for example, 45 ° C.). In addition, the sample injector 13, the separation column 14, the suppressor 15, the preheating tube 1, the conductivity detector 4, and the heating box 17 are often housed in a thermostat and kept at a constant temperature.
第３図のような構成からなるイオンクロマトグラフに
おいて、送液ポンプ12aが駆動すると、槽11a内の溶離液
が例えば2ml/min.の流量で、送液ポンプ12a→試料注入
器13→分離カラム14→サンプレッサ15の内室を経由し本
発明に係わる二重管式導電率検出器16に達し（即ち、予
熱管１の内管→導電率検出器４→予熱管１の外管を流
れ）、最終的に廃液槽（図示しない）へと流れる。In the ion chromatograph having the configuration as shown in FIG. 3, when the liquid sending pump 12a is driven, the eluent in the tank 11a flows at a flow rate of, for example, 2 ml / min., And the liquid sending pump 12a → the sample injector 13 → the separation column. 14 → the inner tube of the sampler 15 reaches the double tube conductivity detector 16 according to the present invention (that is, flows through the inner tube of the preheating tube 1 → the conductivity detector 4 → the outer tube of the preheating tube 1). And finally flows to a waste liquid tank (not shown).
一方、試料注入器13をオンにすると、被測定液が溶離
液のラインに注入され該溶離液で搬送されて分離カラム
14に達し、ここで、該被測定液中のイオン種がクロマト
グラフィックに分離される。このようにして分離された
イオン種は、再び溶離液に搬送されて、サンプレッサ15
の内室→予熱管１の内管→導電率検出器４→予熱管１の
外管を通り、最終的に廃液槽（図示しない）へと流れ
る。On the other hand, when the sample injector 13 is turned on, the liquid to be measured is injected into the line of the eluent, transported by the eluent, and
At this point, the ionic species in the liquid to be measured are separated chromatographically. The ion species separated in this way is transported again to the eluent,
Through the inner tube of the preheating tube 1 → the conductivity detector 4 → the outer tube of the preheating tube 1 and finally to a waste liquid tank (not shown).
第４図乃至第７図は本発明実施例を用いた場合のベー
スラインの改善度を従来例との比較において示す特性図
であり、各図において横軸は保持時間Ｔ（単位は分）を
示し縦軸は導電率Ｓ（μS/cm）を示している。また、第
４図は本発明実施例を組込んだイオンクロマトグラフで
長期的な（具体的には40分程度）ベースラインの安定性
を見たものであり、第６図は前記従来例を組込んだイオ
ンクロマトグラフで長期的な（具体的には40分程度）ベ
ースラインの安定性を見たものである。更に、第５図は
本発明実施例を組込んだイオンクロマトグラフで短期的
な（具体的には９分程度）ベースラインの安定性を見た
ものであり、第７図は前記従来例を組込んだイオンクロ
マトグラフで短期的な（具体的には９分程度）ベースラ
インの安定性を見たものである。4 to 7 are characteristic diagrams showing the degree of improvement of the baseline in the case of using the embodiment of the present invention in comparison with the conventional example. In each figure, the horizontal axis represents the holding time T (unit is minutes). The vertical axis indicates conductivity S (μS / cm). FIG. 4 shows the long-term (specifically, about 40 minutes) baseline stability of an ion chromatograph incorporating the embodiment of the present invention, and FIG. 6 shows the conventional example. Long-term (specifically, about 40 minutes) baseline stability with an embedded ion chromatograph. Further, FIG. 5 shows a short-term (specifically, about 9 minutes) baseline stability of an ion chromatograph incorporating the embodiment of the present invention, and FIG. 7 shows the conventional example. This is a short-term (specifically, about 9 minutes) baseline stability observation with an incorporated ion chromatograph.
第４図乃至第７図の特性図から明らかなように、本発
明実施例を組込んだ装置の方がベースラインのうねりが
大幅に小さくなることが分かる。因みに、第６図で10nS
/cmであった長期的なうねりが第４図では5nS/cmに半減
しており、うねり自体が滑らかなものとなっている。As is clear from the characteristic diagrams of FIGS. 4 to 7, it is understood that the device incorporating the embodiment of the present invention significantly reduces the waviness of the baseline. Incidentally, 10 nS in FIG.
In FIG. 4, the long-term undulation which was / cm was halved to 5 nS / cm in FIG. 4, and the undulation itself was smooth.
尚、本発明は上述の実施例に限定されることなく種々
の変形が可能であり、例えば温度変化の影響を受けやす
い液体クロマトグラフ用検出器であれば導電率検出器以
外の検出器にも適用できる。In addition, the present invention is not limited to the above-described embodiment, and various modifications are possible.For example, a liquid chromatograph detector that is easily affected by a temperature change may be used for a detector other than the conductivity detector. Applicable.
＜発明の効果＞ 以上詳しく説明したような本発明の実施例によれば、
被測定液中の目的成分をクロマトグラフィックに分離・
分析する装置の検出器として使用され流体の導電率を検
出する二重温調付導電率検出器において、二重管構造の
熱交換式予熱管と、該予熱管の入口側に設けられた第１
ジョイントと、前記予熱管の出口側に設けられた第２ジ
ョイントと、導電率検出器と、前記熱交換式予熱管，第
１ジョイント，第２ジョイント，及び導電率検出器を収
容するヒーティングボックスと、該ヒーティングボック
スを両側から加熱する第１及び第２のヒータとを設け、
前記第１ジョイントを介して前記熱交換式予熱管の内管
に供給される流体が前記第第２ジョインを通って前記導
電率検出器に供給されると共に、該導電率検出器から排
出された流体が前記第２ジョイントを通って前記熱交換
式予熱管の外套管内を流れ、その後、前記第１ジョイン
トを経由して排出されるように構成した。<Effect of the Invention> According to the embodiment of the present invention described in detail above,
Chromatographic separation of target components in the liquid to be measured
In a double temperature-regulated conductivity detector used as a detector of an analyzer for detecting the conductivity of a fluid, a heat exchange type preheating pipe having a double pipe structure and a second pipe provided on an inlet side of the preheating pipe. 1
A joint, a second joint provided on the outlet side of the preheating tube, a conductivity detector, and a heating box containing the heat exchange type preheating tube, the first joint, the second joint, and the conductivity detector. And first and second heaters for heating the heating box from both sides,
Fluid supplied to the inner tube of the heat exchange type preheating tube via the first joint is supplied to the conductivity detector through the second join and discharged from the conductivity detector. The fluid is configured to flow through the jacket of the heat exchange type preheating tube through the second joint, and then discharged through the first joint.
このため、外部の温度変動に起因するベースライン変
動を低減でき長期間安定して高感度測定ができるような
二重温調付導電率検出器が実現する。For this reason, a double temperature regulation conductivity detector that can reduce baseline fluctuations due to external temperature fluctuations and can stably perform high-sensitivity measurement for a long time is realized.
第１図は本発明実施例の構成説明図、第２図は本発明実
施例の収納状態を示す構成断面図、第３図は本発明の使
用例構成説明図、第４図乃至第７図は本発明実施例を用
いた場合のベースラインの改善度を従来例との比較にお
いて示すための特性図である。 １……予熱管、1a……内管、1b……外套管、 2,3……ジョイント、 ４……導電率検出器、4a……電極部、 4b……筒、4c,4c′……ホルダー、 4d,4e……オシネ、6a,6b……ヒータ、 7a,7b……リード線、８……ボックス、 ９……断熱材、10……カバー、 11a,11b……槽、 12a,12b……送液ポンプ 13……試料注入器、14……分離カラム 15……サプレッサ、 16……本発明に係わる二重管式導電率検出器 17……ヒーティングボックスFIG. 1 is an explanatory view of a configuration of an embodiment of the present invention, FIG. 2 is a cross-sectional view of a configuration showing a housed state of the embodiment of the present invention, FIG. 3 is an explanatory view of an example of use of the present invention, and FIGS. FIG. 4 is a characteristic diagram showing the degree of improvement of the baseline when the example of the present invention is used in comparison with the conventional example. 1 ... preheating tube, 1a ... inner tube, 1b ... outer tube, 2,3 ... joint, 4 ... conductivity detector, 4a ... electrode part, 4b ... cylinder, 4c, 4c '... Holder, 4d, 4e… osine, 6a, 6b… heater, 7a, 7b… lead wire, 8… box, 9… thermal insulation, 10… cover, 11a, 11b… tank, 12a, 12b …… Liquid sending pump 13 …………………………………………………………………………………………………………………………………………………………………………………………………….
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−98248（ＪＰ，Ａ) 特開 昭62−201358（ＪＰ，Ａ) 特開 昭56−4042（ＪＰ，Ａ) 実開 昭51−79394（ＪＰ，Ｕ) 実開 昭61−84861（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.6，ＤＢ名) G01N 27/00 - 27/24 G01N 30/00 - 30/96──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-62-98248 (JP, A) JP-A-62-201358 (JP, A) JP-A-56-4042 (JP, A) 79394 (JP, U) Fully open 1986-84861 (JP, U) (58) Fields investigated (Int. Cl. 6 , DB name) G01N 27/00-27/24 G01N 30/00-30/96
Claims (1)
ックに分離・分析する装置の検出器として使用される二
重温調付導電率検出器において、二重管構造の熱交換式
予熱管と、該予熱管の入口側に設けられた第１ジョイン
トと、前記予熱管の出口側に設けられた第２ジョイント
と、流体の導電率を検出する導電率検出器と、前記熱交
換式予熱管，第１ジョイント，第２ジョイント，及び導
電率検出器を収容するヒーティングボックスと、該ヒー
ティングボックスを両側から加熱する第１及び第２のヒ
ータとを具備し、前記第１ジョイントを介して前記熱交
換式予熱管の内管に供給される流体が前記第２ジョイン
トを通って前記導電率検出器に供給されると共に、該導
電率検出器から排出された流体が前記第２ジョイントを
通って前記熱交換式予熱管の外套管内を流れ、その後、
前記第１ジョイントを経由して排出されるように構成さ
れた二重温調付導電率検出器。1. A double temperature-regulated conductivity detector used as a detector of an apparatus for chromatographically separating and analyzing a target component in a liquid to be measured. A first joint provided on an inlet side of the preheating tube, a second joint provided on an outlet side of the preheating tube, a conductivity detector for detecting conductivity of a fluid, and the heat exchange type preheating tube , A first joint, a second joint, and a heating box for accommodating the conductivity detector, and first and second heaters for heating the heating box from both sides. The fluid supplied to the inner tube of the heat exchange type preheating tube is supplied to the conductivity detector through the second joint, and the fluid discharged from the conductivity detector passes through the second joint. Heat exchange It flows through the mantle tube of the preheating pipe, and then,
A dual temperature regulated conductivity detector configured to be discharged via the first joint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2230984A JP2853302B2 (en) | 1990-08-31 | 1990-08-31 | Double temperature control conductivity detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2230984A JP2853302B2 (en) | 1990-08-31 | 1990-08-31 | Double temperature control conductivity detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04110760A JPH04110760A (en) | 1992-04-13 |
| JP2853302B2 true JP2853302B2 (en) | 1999-02-03 |
Family
ID=16916407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2230984A Expired - Fee Related JP2853302B2 (en) | 1990-08-31 | 1990-08-31 | Double temperature control conductivity detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2853302B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19921079C2 (en) | 1999-04-30 | 2002-09-19 | Stiftung A Wegener Inst Polar | Method for determining the salinity of liquids and device for carrying out the method |
| WO2018150562A1 (en) * | 2017-02-20 | 2018-08-23 | 株式会社島津製作所 | Electrical conductivity detector and ion chromatograph |
-
1990
- 1990-08-31 JP JP2230984A patent/JP2853302B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04110760A (en) | 1992-04-13 |
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