EP0101687A1 - Electrode selective aux ions et son procede de realisation - Google Patents

Electrode selective aux ions et son procede de realisation

Info

Publication number
EP0101687A1
EP0101687A1 EP19830900382 EP83900382A EP0101687A1 EP 0101687 A1 EP0101687 A1 EP 0101687A1 EP 19830900382 EP19830900382 EP 19830900382 EP 83900382 A EP83900382 A EP 83900382A EP 0101687 A1 EP0101687 A1 EP 0101687A1
Authority
EP
European Patent Office
Prior art keywords
pellet
hydrophobic substance
electrode material
ion
electrode
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Withdrawn
Application number
EP19830900382
Other languages
German (de)
English (en)
Inventor
Kenneth Otto Ahrens
James Francis Cullerton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beckman Coulter Inc
Original Assignee
Beckman Instruments Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beckman Instruments Inc filed Critical Beckman Instruments Inc
Publication of EP0101687A1 publication Critical patent/EP0101687A1/fr
Withdrawn legal-status Critical Current

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
    • G01N27/26—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
    • G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component

Definitions

  • the invention relates to the field of elec ⁇ trodes. More particularly, the invention relates to the field of solid-state ion-selective electrodes. In still greater particularity, the invention relates to an ion-selective electrode for use in the assay of electrolyte concentrations of bodily fluids and other aqueous solvents.
  • the invention is an ion-selective electrode in which the electrode material has been treated with a hydrophobic substance in order to prevent degradation by the fluids to be measured.
  • Ion-selective electrodes have been utilized in clinical analysis instruments in order to measure particular characteristics of fluids to allow diagnosis of patient illnesses.
  • the ability to quickly respond to changes in activity of the ion being measured is a highly desirable characteristic of a sensing electrode.
  • the fastest response would be attained by exposing the electrode material directly to the liquid to be meas ⁇ ured.
  • degradation of the electrode material from dissolution or corrosion by direct contact with the test solution greatly reduces the useful life of the electrode.
  • Previous ion-selective electrodes have util ⁇ ized a membrane material to enhance ion selectivity and protect the active surface of the electrode. This membrane is usually a resin impregnated with an "ionophoric" substance which contributes to ion selec- tivity.
  • Ion-selective electrodes utilizing an iono- phoric membrane exhibit selectivity toward a particular ion. This ion selectivity results partially from exposing an ionophoric substance to a solution highly concentrated with respect to the ion. However, reduced sensitivity may result if the membrane is exposed to solutions containing appreciable concentrations of another ion. Reduced sensitivity results because exposure of the ionophoric substance to solutions con ⁇ taining appreciable concentrations of another ion con ⁇ verts the ionophoric material to a new species of " ion-selective membrane. As an example, H. Freiser et al. (Analytical Chemistry, Vol. 44, No.
  • a chloride electrode utilizing an ionophoric substance as a membrane could thus be damaged by con ⁇ tinued exposure to a test reagent containing sodium sulfate. Therefore, such an electrode might only be used with a limited variety of reagent systems.
  • a chloride electrode not utilizing such a membrane could, however, be used with a number of reagent systems containing a relatively large concentration of foreign anions. Such a reagent system could minimize activity versus concentration errors by using a constant ionic strength approach.
  • fast and accurate measurements may be made with an ion-selective electrode by exposing the electrode material directly to the substance to be tested.
  • the electrode material is likely to be degraded by dissolution or corrosion by that test solution.
  • An ionophoric membrane while protecting the electrode material, slows the response time of the electrode and thus negatively affects operation of the instrument.
  • the invention is an ion-selective electrode in which the electrode material is protected with a hydrophobic substance. That is, the active electrode material may be impregnated and coated with a hydro ⁇ phobic substance to protect the electrode material from dissolution or corrosion by a test solution. Because the electrode material is exposed directly to the test solution, fast and accurate response time is preserved.
  • the hydrophobic material eliminates the need for an ionophoric membrane and thus improves the response time and the accuracy of the electrode.
  • the hydrophobic substance employed with the preferred embodiment of the invention is silicone oil and a viscous silicone com- pound.
  • FIG. 1 illustrates a preferred embodiment of an ion-selective electrode
  • Fig. 2 illustrates an alternate embodiment of an ion-selective electrode.
  • an ion-selective elec ⁇ trode includes a housing 11 containing a pellet 12 comprised of active electrode material.
  • Pellet 12 is secured to housing 11 by a curable resin seal 13.
  • a front face 14 of pellet 12 is the area contacted by a test solution.
  • FIG. 2 an alternate embodiment of an ion-selective electrode is shown.
  • housing 11 pellet 12, seal 13, and front face 14 are as described with respect to Fig. 1.
  • the alternate embodiment illustrated in Fig. 2 addi ⁇ tionally contains a drain wire 15 imbedded in pellet 12 and a conductive material 16 surrounding drain wire 15.
  • pellet 12 is formed by pressing precipitated silver and silver chloride powders of controlled particle size in a mold.
  • Pellet 12 is secured within housing 11 by a curable resin 13 which acts as a seal to control fluid leakage past pellet 12.
  • Front face 14 of pellet 12 forms the active ion-selective area of the electrode. Electrical contact with pellet 12 may be accomplished by means of a spring-loaded gold or gold-plated contact contained in a detachable cable assembly (not shown). This contact could occur on the rear face of pellet 12 opposite to front face 14.
  • front face 14 of pellet 12 is finished by machining to remove extraneous electrode material or resin and polishing. Successively finer polishing media is used until front face 14 is smooth and shiny.
  • Pellet 12 is then impregnated with silicone oil under a vacuum. After removal from the vacuum treatment, a coating of viscous silicone compound is applied to front face 14. This treatment renders front face 14 hydrophobic, that is, water repellant, so
  • OMPI that attack by the solution to be measured is greatly minimized, thus extending the lifetime o pellet 12. That is, electrode damage due to corrosion of or deposition onto front face 14, or due to absorption of the solution within the pores of pellet 12, is markedly reduced by filling the pores of pellet 12 and coating front face 14 with the hydrophobic substance while at the same time not affecting the sensitivity to the ion of interest.
  • a silver drain wire 15 may be imbedded within pellet 12 at the time of molding to allow an electrical contact to be made to this wire.
  • Electrical contact may be accomplished by soldering wire 15 to another wire to produce a nondetachable cable assembly or by surrounding wire 15 with an electrically conductive (silver-bearing) epoxy compound 16 which in turn contacts a spring-loaded contact assembly.
  • This spring-loaded contact assembly (not shown) may be contained in the detachable cable assembly referred to previously.
  • Silver drain wire 15 and conductive resin contact 16 may be eliminated. Instead, a graded mixture of powders, starting with the desired silver-silver chloride ratio at front face 14 of pellet 12 and ending with a pure silver layer at the opposite face of pellet 12, may be employed. In this arrangement, electrical contact is made by means of the spring-loaded contact assembly (not shown) as discussed previously.
  • pellet 12 may be formed by pressing the powder mixture directly into housing 11 with housing 11 acting as a mold. Ultrasonic energy and/or heat may be employed as aids to compaction of the powder to form pellet 12..
  • Another method of fabricating pellet 12 is to first produce a sintered skeleton structure by means of heat and/or pressure, leaving
  • pellet 12 W ⁇ PO pores of controlled dimensions in pellet 12, which are then filled with the remaining active materials to form a mixture of components with known percentages of composition.
  • Another method for forming pellet 12 is to mix powdered materials with a curable resin which forms a binder possessing appropriate mechanical properties. This mixture may be extruded to shape or machined after curing to form pellet 12.
  • the hydrophobic substance, such as silicone oil, may be applied to a pellet fabricated by any of the above-described processes.
  • Advantages of the invention include allowing the electrode to be presented more intimately to the solution to be evaluated than is possible with a mem ⁇ brane of appreciable thickness while protecting the electrode material from degradation. More intimate contact with the solution allows maximum speed of re ⁇ sponse-
  • the hydrophobic substance eliminates the need for a physical membrane to be used between the pellet and the solution to be measured. Thus, poisoning effects due to chemical changes in the membrane material caused by foreign ions tend to be eliminated. In addition, deterioration of response speed of the electrode material caused by absorption of water or solution is greatly reduced.
  • the protective hydrophobic substance may be readily renewed as needed to further extend the working life of the electrode.

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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Abstract

Electrode sélective aux ions comprenant une pastille (12) fixée dans un boîtier (11) au moyen d'un résine polymérisable (13). La partie antérieure (14) de la pastille (12) est recouverte ou imprégnée d'une huile au silicone.
EP19830900382 1982-02-22 1982-12-13 Electrode selective aux ions et son procede de realisation Withdrawn EP0101687A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35096782A 1982-02-22 1982-02-22
US350967 1994-12-07

Publications (1)

Publication Number Publication Date
EP0101687A1 true EP0101687A1 (fr) 1984-03-07

Family

ID=23378998

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19830900382 Withdrawn EP0101687A1 (fr) 1982-02-22 1982-12-13 Electrode selective aux ions et son procede de realisation

Country Status (2)

Country Link
EP (1) EP0101687A1 (fr)
WO (1) WO1983003004A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3748745A1 (fr) * 2019-06-03 2020-12-09 Total Se Éco-électrode, dispositif de stockage d'énergie électrique et son procédé de préparation
DE102019116288A1 (de) 2019-06-14 2020-12-17 Endress+Hauser Conducta Gmbh+Co. Kg Ionenselektive Elektrode und elektrochemischer Sensor

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3591482A (en) * 1969-04-23 1971-07-06 Ibm Silver-silver chloride electrode and method of making same
US3926764A (en) * 1971-05-19 1975-12-16 Radiometer As Electrode for potentiometric measurements
US4090978A (en) * 1976-12-28 1978-05-23 Uop Inc. Electrocatalysts and a method for the preparation thereof
HU177471B (en) * 1978-03-31 1981-10-28 Magyar Tudomanyos Akademia Process for producing silver-salt-containing electrode of high precision and high stability
US4402464A (en) * 1981-04-27 1983-09-06 Shire Sr Harry E Scrap granulator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8303004A1 *

Also Published As

Publication number Publication date
WO1983003004A1 (fr) 1983-09-01

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Legal Events

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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AK Designated contracting states

Designated state(s): CH DE FR GB LI SE

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: 19840125

RIN1 Information on inventor provided before grant (corrected)

Inventor name: AHRENS, KENNETH OTTO

Inventor name: CULLERTON, JAMES FRANCIS