EP0493576A1 - Process for producing the ion-sensitive probe electrode of a heavy-metal-ion sensor - Google Patents
Process for producing the ion-sensitive probe electrode of a heavy-metal-ion sensorInfo
- Publication number
- EP0493576A1 EP0493576A1 EP19910913708 EP91913708A EP0493576A1 EP 0493576 A1 EP0493576 A1 EP 0493576A1 EP 19910913708 EP19910913708 EP 19910913708 EP 91913708 A EP91913708 A EP 91913708A EP 0493576 A1 EP0493576 A1 EP 0493576A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- heavy metal
- ion
- heavy
- mixture
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 title 1
- 239000000523 sample Substances 0.000 title 1
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052946 acanthite Inorganic materials 0.000 abstract 1
- 229910052976 metal sulfide Inorganic materials 0.000 abstract 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
Definitions
- the invention relates to a method for producing an ion-sensitive working electrode of a heavy metal honing sensor, which contains a mixture of Ag 2 S and Mes, where Me is the heavy metal to be determined.
- the above-mentioned working electrode forms a heavy metal ion sensor.
- a reference electrode preferably an Ag / AgCl reference electrode
- the principle of these sensors is described, for example, in the book by Cammann "Working with ion-sensitive electrodes", Springer-Verlag, Berlin, Heidelberg, New York, 1977, there in particular pages 59 to 66.
- Such conventional working electrodes are relatively large. They are also fragile because a glass tube is used as a covering. In particular, the disadvantage is that they are relatively expensive to manufacture (approx. DM 200 to DM 800 purchase price per piece). It is also possible to detect only a single heavy metal with the known sensor.
- DE-OS 36 39 312 describes a solid-state electrode for determining sodium concentrations in solutions, which is produced using thick-film technology.
- the various layers, which together form the solid-state electrode, are applied to a substrate one above the other or next to one another. If necessary, the layers are provided with a cover which also allows access to the solid electrolyte membrane provided there.
- no heavy metal ions can be detected with this known solid-state electrode. Only a single material can be detected, namely the concentration of sodium ions in solutions.
- DE-OS 36 19 802 describes a sensor manufactured in thick-film technology for monitoring oxygen concentrations in gases.
- GB 2 102 963-A describes in several embodiments an ion-electric electrode in film form, which has a conductive layer and an ion-selective layer laminated thereon, which covers at least one edge of the conductive layer.
- the invention has for its object to design it so that different heavy metals can be detected with the sensor in an inexpensive manufacture of the working electrode.
- the sensor should also be able to be easily miniatu rised and easy to handle, in particular it should not be fragile.
- the invention is characterized in that a plurality of conductor layers are applied next to one another on a substrate in thick-film technology and a plurality of layers from the mixture of Ag 2 S and MeS are applied thereon, which differ from one another by different heavy metals Me, and then again a cover layer which protects the conductor layer from a measurement solution containing the heavy metal ions to be determined and which allows the measurement solution to access the mixture layer Ag 2 S / MeS.
- These measures produce a heavy metal sensor with a homogeneous solid membrane electrode based on Ag 2 S using thick film technology, with which the concentration or activity of heavy metal ions in solutions can be determined potentiometrically.
- the ion-selective layer In contrast to GB 2 102 963-A, the ion-selective layer, the Ag 2 S / MeS mixture, is applied as a mixture, ie it is no longer modified chemically or electrochemically.
- glass cladding is no longer required because unbreakable materials, preferably plastic, can be used for the cover layer.
- the thick-film technology allows inexpensive production of the working electrodes or correspondingly completed sensors, whereby when applying the batch layer it is only necessary to ensure that it contains, next to and separately from one another, different metals to be detected. All of this can be produced in a very labor-saving manner very well in the thick-film technology used.
- DE 3 734 636 A1 shows a side-by-side arrangement of sensitive and selective areas in suspended gate field-effect transistors, but they are manufactured completely differently, namely by fully automatic potentiostatic or galvanostatic deposition.
- these procedural measures cannot be applied to the above-mentioned other types of arrangements to be produced in thick-film technology, on the other hand they would lead to Ag / Ag 2 S / MeS arrangements which would not meet the required properties of good layer adhesion and tightness of the cover layers.
- An Ag layer is preferred for the conductor layer.
- the thick-film technique is to be understood as the screen printing technique or the film casting technique or combinations of both techniques.
- Figure 1 shows schematically a section through a working electrode according to the invention.
- FIG. 2 shows a top view of the working electrode according to FIG. 1.
- a layer 3 which consists of a mixture of Ag 2 S and MeS, is applied to this in turn using thick-film technology, where Me means the heavy metal to be determined.
- a cover layer 4 covers the conductor layer 2 at least in the area in which the sensor is immersed in a measurement solution. This protects the Ag layer 2 from the measurement solution.
- the covering layer 4 made of glass and plastic leaves a window open in area 5 through which the measuring solution has access to layer 3.
- Fig. 1 also shows a connecting conductor 6, via which the potential can be removed.
- FIG. 2 makes it clear that if the structure shown in FIG. 1 is maintained, several of the batch layers 3 are applied next to each other separately on the Ag layer 2, namely batch layers 3a, 3b and 3c. These differ from each other by different metals in the batches. If the sensor - completed by a reference electrode - is immersed in a measuring solution, then those heavy metal ions are detected or the concentration of the relevant heavy metal ions is determined, the metals of which are contained in the batch histories 3a, 3b and 3c.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Il est décrit un procédé pour la fabrication d'une électrode de travail ionosensible d'un capteur d'ions de métal lourd, laquelle contient un mélange de Ag2S et de MeS, Me désignant le métal lourd à déterminer. Selon l'invention, les éléments de l'électrode de travail sont imprimés sur un substrat par la technique des couches épaisses, les différentes couches de mélange juxtaposées contenant plusieurs des métaux lourds à déterminer. Le capteur fabriqué selon le procédé pour l'invention peut être fabriqué à un prix avantageux et réagit à différents ions de métal lourd.A method is described for the manufacture of an ionosensitive working electrode of a heavy metal ion sensor, which contains a mixture of Ag2S and MeS, Me designating the heavy metal to be determined. According to the invention, the elements of the working electrode are printed on a substrate using the thick layer technique, the different juxtaposed mixture layers containing several of the heavy metals to be determined. The sensor manufactured according to the method for the invention can be manufactured inexpensively and reacts to different heavy metal ions.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4023130A DE4023130A1 (en) | 1990-07-20 | 1990-07-20 | METHOD FOR PRODUCING AN ION-SENSITIVE WORKING ELECTRODE OF A HEAVY METAL ION SENSOR |
DE4023130 | 1990-07-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0493576A1 true EP0493576A1 (en) | 1992-07-08 |
Family
ID=6410702
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19910913708 Withdrawn EP0493576A1 (en) | 1990-07-20 | 1991-07-18 | Process for producing the ion-sensitive probe electrode of a heavy-metal-ion sensor |
Country Status (5)
Country | Link |
---|---|
US (1) | US5262205A (en) |
EP (1) | EP0493576A1 (en) |
JP (1) | JPH05504630A (en) |
DE (1) | DE4023130A1 (en) |
WO (1) | WO1992001929A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10311031B4 (en) * | 2003-03-13 | 2005-04-21 | Siemens Ag | Electrochemical sensor and method for its production |
CN102507698A (en) * | 2011-09-23 | 2012-06-20 | 广东省微生物研究所 | Novel sensor for synchronously detecting copper ions and lead ions |
CN102590310B (en) * | 2012-02-03 | 2014-01-29 | 广州科城环保科技有限公司 | Cuprous ion selective electrode and cuprous ion measuring method thereof |
CN102944591B (en) * | 2012-11-20 | 2014-10-29 | 广东省微生物研究所 | Novel microbial sensor for detecting chromium ions |
CN102937608B (en) * | 2012-11-20 | 2014-10-29 | 广东省微生物研究所 | Novel microbial sensor for detecting cadmium ions |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1002271A (en) * | 1972-11-10 | 1976-12-28 | Masumi Hattori | Method of making an ion-selective electrode |
US4400243A (en) * | 1979-10-25 | 1983-08-23 | Ebdon Leslie C | Monitoring of heavy metal ions, electrode therefor and method of making a membrane sensitive to heavy metal ions |
JPS5810645A (en) * | 1981-07-13 | 1983-01-21 | Fuji Photo Film Co Ltd | Film-shaped ion selection electrode and ion concentration measuring device using the same |
EP0126452B1 (en) * | 1983-05-19 | 1991-05-08 | Hnu Systems Inc. | Electrochemical cell |
DE3639312A1 (en) * | 1986-11-17 | 1988-05-26 | Battelle Institut E V | SOLID ELEMENT FOR DETERMINING SODIUM CONCENTRATIONS IN SOLUTIONS |
DE3639802A1 (en) * | 1986-11-21 | 1988-05-26 | Battelle Institut E V | SENSOR FOR MONITORING HYDROGEN CONCENTRATIONS IN GASES |
JPH0743338B2 (en) * | 1987-07-03 | 1995-05-15 | テルモ株式会社 | Multi-sensor |
DE3734634A1 (en) * | 1987-10-13 | 1989-05-03 | Josowicz Mira | Integrated process for the electrochemical modification of a chemical sensor and an array of chemical sensors |
-
1990
- 1990-07-20 DE DE4023130A patent/DE4023130A1/en not_active Withdrawn
-
1991
- 1991-07-18 JP JP3512985A patent/JPH05504630A/en active Pending
- 1991-07-18 WO PCT/EP1991/001346 patent/WO1992001929A1/en not_active Application Discontinuation
- 1991-07-18 EP EP19910913708 patent/EP0493576A1/en not_active Withdrawn
-
1992
- 1992-05-20 US US07/886,229 patent/US5262205A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9201929A1 * |
Also Published As
Publication number | Publication date |
---|---|
JPH05504630A (en) | 1993-07-15 |
US5262205A (en) | 1993-11-16 |
DE4023130A1 (en) | 1992-01-23 |
WO1992001929A1 (en) | 1992-02-06 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19920316 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: LEONHARD, VOLKER Inventor name: ERDMANN, HARTMUT Inventor name: CHU, WING, FONG |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19950201 |