SK278632B6

SK278632B6 - The dry plate reference electrode and preparation method

Info

Publication number: SK278632B6
Application number: SK1194A
Authority: SK
Inventors: Ivan Stepanek
Original assignee: Ivan Stepanek
Priority date: 1994-01-05
Filing date: 1994-01-05
Publication date: 1997-12-10
Also published as: SK1194A3

Abstract

The dry plate reference electrode consists of the carrying layer (1) having the active part (10), opposite of which the circumferential the part (1000) is placed and between them the junction part (100) is located, while the carrying layer (1) is coated with the conductive layer (2) in the active part (10) and in the circumferential part (1000), however they are connected to each other in the junction part (100) with the use of the first bridge (101), while the conductive layer is coated the conductive silver layer Ag (3) in the active part (10), and through the second bridge (102) in the junction part (100) it is forcing into the circumferential the part (1000), on the silver layer (3) in the active part (10), the conductive AgCl layer (4) coated, on which the fixed network (5) is placed, while in the junction part (100), there is the isolated membrane (6), forcing to the active part (10) partially at least and to the circumferential the part (1000). The conductive layer (2), sliver Ag layer (3), AgCl layer or the layer (34) created based on Ag-AgCl is coated with use of the serigraphy, while the mesh size is 5 up to 30 microns to the appropriate shape and after that they are being hardened at the temperature of 10 up to 400 Celsius degrees, for 3 up to 20 minutes.

Description

Doterajší stav technikyBACKGROUND OF THE INVENTION

Elektróda na ten istý účel pozostáva zo striebornej rotačnej časti, na ktorú je nanesená AgCl vrstva. Iné riešenie pozostáva z plochej striebornej časti, na ktorú je aspoň z jednej strany nanesená AgCl vrstva. Nanesenie AgCl vrstvy sa uskutočňuje elektrolytickou cestou, kde elektrolýza prebieha v roztoku NHC1 prúdom pod 1 mA počas 5 až 6 dní, pričom pri väčších prúdoch, napríklad pri 2 mA nanesenie trvá 30 hodín, pri prúde 8 mA trvá 8 hodín. Známa je tiež príprava AgCl vrstvy na strieborný základ termickou cestou, a to zmiešaním 7 dielov AgO a jedného dielu AgClO, v malom množstve vody za vzniku homogénnej hustej konzistencie, ktorá sa nanesie na Ag elektródu a žíha sa pri teplote 300 - 400 °C výhodne v elektrickej peci. Takto vytvorená elektróda je veľmi pracná a cenovo nákladná.The electrode for the same purpose consists of a silver rotating part on which an AgCl layer is applied. Another solution consists of a flat silver part on which an AgCl layer is applied on at least one side. The deposition of the AgCl layer is carried out by electrolysis, in which the electrolysis takes place in a solution of NHCl with a current below 1 mA for 5 to 6 days, with a deposition time of 30 hours for larger currents such as 2 mA. It is also known to prepare an AgCl layer on a silver base by thermally mixing 7 parts of AgO and one part of AgClO in a small amount of water to form a homogeneous thick consistency, which is applied to the Ag electrode and annealed at 300-400 ° C preferably in an electric furnace. The electrode thus formed is very laborious and costly.

Podstata vynálezuSUMMARY OF THE INVENTION

Uvedené nedostatky odstraňuje suchá plochá referenčná elektróda a spôsob jej prípravy, ktorá pozostáva z nosnej vrstvy, ktorá má aktívnu časť, oproti ktorej je odvodná časť, pričom priestor medzi nimi tvorí prepojovacia časť. Na nosnú vrstvu je nanesená vodivá vrstva v aktívnej a odvodnej časti, pričom v prepojovacej časti sú navzájom prepojené mostíkom. Na vodivú vrstvu je vodivo napojená strieborná Ag vrstva v aktívnej časti a druhým mostíkom v prepojovacej časti zasahuje do odvodnej časti. Na striebornú Ag vrstvu je vodivo napojená AgCl vrstva v aktívnej časti, na ktorú je napojená sieť, pričom na prepojovacej časti je izolovaná membrána, ktorej aspoň časť zasahuje do aktívnej a odvodnej časti. V alternatívnom uskutočnení na vodivú vrstvu je nanesená Ag-AgCl vrstva a to v aktívnej časti a druhým mostíkom v prepojovacej časti zasahuje do odvodnej časti. Vodivá vrstva pozostáva z prachového uhlíka s veľkosťou častíc 0,5 až 30 mikrometrov v spojive, kde sa nachádza od 30 do 90 %. Strieborná Ag vrstva pozostáva z prachového striebra s veľkosťou častíc 0,5 až 30 mikrometrov v spojive, kde sa nachádza od 20 do 90 %. AgCl vrstva pozostáva z prachového chloridu strieborného AgCl s veľkosťou častíc 0,5 až 30 mikrometrov v spojive, kde sa nachádza od 20 do 90 %.Spôsob výroby suchej plochej referenčnej elektródy spočíva vo vytvorení tenkých vodivých vrstiev sieťotlačou na nosnú vrstvu, kde jednotlivé vrstvy vytvárajú vodivé plošné zapojenia. Na nosnú vrstvu sa nanesie vodivá vrstva v nevytvrdenom stave spojiva vytvárajúca obraz vodivého zapojenia daného tvarom krytu sieťky, v danom prípade s bočnými krytmi po okrajoch v prepojovacej časti, na čo sa vodivá vrstva tepelne vytvrdzuje. Po tomto vytvrdení sa sieťotlačou nanesie strieborná Ag vrstva v nevytvrdenom stave spojiva s krytom na odvodnej časti a po bokoch v prepojovacej časti, po čom sa strieborná Ag vrstva tepelne vytvrdzuje. Na striebornú vrstvu Ag sa nanesie AgCl vrstva sieťotlačou v nevytvrdenom stave spojiva na aktívnu časť s krytom na prepojovacej časti a odvodnej časti, po čom sa tepelne vytvrdzuje. Na AgCl vrstvu v aktívnej časti sa nanesie sieť sieťotlačou, prípadne v alternatívnom 5 uskutočnení sa na aktívnu časť upevní pevná sieť bez vytvrdzovania. Na prepojovaciu časť sa ako posledná nanesie izolačná membrána. Vrstvy sa nanášajú sieťotlačou s veľkosťami ôk od 5 do 200 mikrometrov, po čom sa tepelne vytvrdzujú v rozmedzí teplôt od 10 do 400 °C 10 v časovom rozmedzí 3 až 200 minút. Výhodou riešenia je jednoduchosť konštrukcie a nenáročná výroba.These drawbacks are overcome by a dry flat reference electrode and a method for its preparation, which consists of a carrier layer having an active part against which the drain part is, the space between them forming the interconnecting part. A conductive layer is applied to the carrier layer in the active and exhaust portions, and in the interconnecting portion they are interconnected by a bridge. A silver Ag layer in the active part is conductively connected to the conductive layer, and the second bridge in the connecting part extends into the drainage part. The AgCl layer is conductively bonded to the silver Ag layer in the active part, to which the network is connected, the membrane part being insulated, at least a part of which extends into the active and exhaust part. In an alternative embodiment, an Ag-AgCl layer is applied to the conductive layer in the active portion and the second bridge in the interface portion extends into the drainage portion. The conductive layer consists of powdered carbon with a particle size of 0.5 to 30 microns in the binder, where it is from 30 to 90%. The silver Ag layer consists of silver powder with a particle size of 0.5 to 30 microns in the binder, where it is from 20 to 90%. The AgCl layer consists of AgCl silver powder with a particle size of 0.5 to 30 microns in the binder, where it is from 20 to 90%. The method of manufacturing a dry flat reference electrode consists in forming thin conductive layers by screen printing onto the carrier layer where the individual layers form conductive wiring. A conductive layer is applied to the carrier layer in the uncured state of the binder, forming an image of the conductive engagement given by the shape of the mesh cover, in this case with side edges at the interface, for which the conductive layer is thermally cured. After this curing, the silver Ag layer is applied by screen printing in the uncured state of the binder with the cover on the drain and sideways in the interconnecting portion, after which the silver Ag layer is thermally cured. An AgCl layer is applied to the silver Ag layer by screen printing in the uncured state of the binder on the active part with the cover on the interconnecting part and the drain part, after which it is thermally cured. A screen is applied to the AgCl layer in the active part by screen printing, or in an alternative embodiment a fixed network is fixed to the active part without curing. An insulating membrane is applied last to the connecting part. The layers are applied by screen printing with mesh sizes of 5 to 200 microns, after which they are thermally cured in a temperature range of 10 to 400 ° C 10 for a time period of 3 to 200 minutes. The advantage of the solution is simplicity of construction and undemanding production.

Prehľad obrázkov na výkreseOverview of the figures in the drawing

Na priložených výkresoch obr. 1 zobrazuje pohľad na plochú elektródu s vyobrazením jednotlivých vrstiev. Obr. 2 znázorňuje rez plochej elektródy v jej aktívnej časti, kde v alternatívnom uskutočnení má AgCl vrstvu 20 opatrenú sieťou. Obr. 3 znázorňuje jedno uskutočnenie plochej elektródy tvaru obdĺžnika s vyznačením skladby jednotlivých vrstiev.In the accompanying drawings, FIG. 1 is a view of a flat electrode showing individual layers. Fig. 2 shows a cross-sectional view of a flat electrode in its active portion, wherein in an alternative embodiment the AgCl layer 20 has a mesh. Fig. 3 illustrates one embodiment of a rectangular flat electrode indicating the composition of the individual layers.

Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION

Plochá elektróda pozostáva z nosnej vrstvy 1, ktorá je v konkrétnom uskutočnení z nevodivého materiálu, ako napr. keramická alebo silikátová plocha, výhodne 30 obdĺžnikového tvaru. Nie je vylúčená ani fólia z umelých hmôt, ktorá spĺňa uvedené fyzikálne vlastnosti. Hrúbka tejto nosnej vrstvy 1 je 10 až 1000 mikrometrov, ale nevylučuje sa aj väčšia. Na nosnú vrstvu 1 je pevne napojená vodivá vrstva 2, ktorá má zhodné zmrštenie a35 ko nosná vrstva 1. Uvedené je možné dosiahnuť výberom vhodného spojiva - polyméru, ako napr. fenolového, acrylátového, epoxidového, prípadne iného, ale aj ich zmesi, do ktorého je výhodne pridaný prachový uhlík, ale aj iný vodivý materiál, napr. zlato, platina, meď, 40 hliník, s veľkosťou častíc uhlíka od 0,5 do 50 mikrometrov, ktorého sa v zmesi nachádza 30 až 90 %. Na vytvrdenú, prípadne čiastočne vytvrdenú, vodivú vrstvu 2 je pevne sčasti pridaná strieborná Ag vrstva 3, ktorá pozostáva z prachového striebra s veľkosťou častíc 0,5 až 45 50 mikrometrov v spojive, kde sa nachádza od 20 do 90The flat electrode comprises a carrier layer 1, which in a particular embodiment is of a non-conductive material, such as e.g. ceramic or silicate surface, preferably 30 of rectangular shape. Plastic foil that meets the above physical properties is also not excluded. The thickness of this carrier layer 1 is 10 to 1000 microns, but not greater. The conductive layer 2, which has the same shrinkage and 35 as the support layer 1, is firmly bonded to the support layer 1. phenolic, acrylate, epoxy, or other, but also mixtures thereof, to which is preferably added powdered carbon, but also other conductive material, e.g. gold, platinum, copper, 40 aluminum, with a carbon particle size of from 0.5 to 50 microns, which is 30-90% in the mixture. For the cured or partially cured conductive layer 2, a silver Ag layer 3, which consists of silver powder with a particle size of 0.5 to 45 microns in the binder, is present in a fixed part, where it is present from 20 to 90

%. Na striebornú Ag vrstvu 3 sa podobne pevne sčasti napojí AgCl vrstva 4, ktorá pozostáva z prachového AgCl s veľkosťou častíc 0,5 až 30 mikrometrov v spojive, kde sa nachádza od 20 do 90 %. Vodivá vrstva 2, 5θ strieborná Ag vrstva 3 a AgCl vrstva 4 na nosnú vrstvu 1 sa nanášajú v požadovanom poradí a tvare v nevytvrdenom spojive v konzistencii pasty formou sieťotlače s veľkosťou ôk siete od 5 do 200 mikrometrov. Po tomto nastáva vytvrdzovanie v rozmedzí teplôt od 10 do 400 55 °C v časovom rozmedzí 3 až 200 minút. Je výhodné, ak uvedené vrstvy 2, 3 a 4 majú hrúbku od 0,5 do 100 mikrometrov. V alternatívnom uskutočnení je vhodné, ak na AgCl vrstvu 4 je daná sieť 5 s veľkosťou ôk od 5 do 100 mikrometrov. Materiál siete je nevodivý, výhodne polyamid, silon, nylon, sklené vlákna. Účelom siete 5 je zabrániť vniknutiu korpuskulárnym časticiam väčším, ako sú oká siete 5 vo vstupe do aktívnej časti 10 plochej clektródy. V alternatívnom uskutočnení je výhodne možné plochú elektródu vytvoriť v tvare obdĺžnika (podľa 65 obr. 1). V tomto prípade na jej jednom konci pri kratšej strane je aktívna časť 10, na protiľahlom konci pri druhej kratšej strane obvodná časť 1000, medzi ktorými je prepojovacia časť 100. Nosná vrstva 1 má tvar obdĺžnika, na nej je vodivá vrstva 2, ktorá má v prepojovacej časti 100 zúženie do prvého mostíka 101, ktorý vodivo spája plochu v aktívnej časti 10 s plochou v odvodnej časti 1000. Nad vodivou vrstvou 2 je strieborná Ag vrstva 3, ktorá sa nachádza na aktívnej časti 10 a prechádza, zužuje sa do druhého mostíka 102 v prepojovacej časti 100. Vodivú vrstvu 2 a striebornú Ag vrstvu 3 v prepojovacej časti 100 plochej elektródy prekrýva izolačná membrána 6, ktorá pozostáva zo silikónových, epoxidových, imidových, uretanových a iných polymérov. Je vhodné, ak izolačná membrána 6 prekrýva zo strany vrstiev celú plochú elektródu, okrem aktívnej časti 10 a odvodnej časti 1000, lebo jej účelom je zabrániť koróznym účinkom.%. Similarly, an AgCl layer 4 consisting of powder AgCl with a particle size of 0.5 to 30 microns in the binder, where it is from 20 to 90%, is similarly firmly partially bonded to the silver Ag layer 3. The conductive layer 2, 5θ silver Ag layer 3 and AgCl layer 4 on the carrier layer 1 are applied in the desired order and shape in the uncured binder in a paste consistency in the form of a screen printing with a mesh size of 5 to 200 microns. Thereafter, curing occurs in a temperature range of 10 to 400 55 ° C over a time period of 3 to 200 minutes. Preferably, said layers 2, 3 and 4 have a thickness of from 0.5 to 100 microns. In an alternative embodiment, it is preferred that a mesh 5 having a mesh size of from 5 to 100 microns is provided on the AgCl layer 4. The mesh material is non-conductive, preferably polyamide, nylon, nylon, glass fibers. The purpose of the net 5 is to prevent ingress of corpuscular particles larger than the meshes of the net 5 at the entrance to the active part 10 of the flat clatter. In an alternative embodiment, preferably the flat electrode may be rectangular in shape (as shown in FIG. 1). In this case, at one end at the shorter side there is an active portion 10, at the opposite end at the other shorter side, a peripheral portion 1000 between which there is an interconnecting portion 100. The support layer 1 has a rectangular shape, The tapering portion 100 connects to a first bridge 101 that conductively connects the area in the active portion 10 with the area in the discharge portion 1000. Above the conductive layer 2 is a silver Ag layer 3 that is located on the active portion 10 and passes, tapering to the second bridge 102 An insulating membrane 6 consisting of silicone, epoxy, imide, urethane, and other polymers overlaps the conductive layer 2 and the silver Ag layer 3 in the interface portion 100 of the flat electrode. Suitably, the insulating membrane 6 covers the entire flat electrode from the layers side, except for the active portion 10 and the discharge portion 1000, since its purpose is to prevent corrosion effects.

Vytvorenie striebornej Ag vrstvy 3 a AgCl vrstva 4 je taktiež možné aj nanesením zmesnej Ag + AgCl pasty vo vhodnom polyméri, zriedenej vhodným rozpúšťadlom na konkrétny polymér, napr. toluénom, po nanesení sieťotlačou, napr. na vodivú vrstvu 2 tepelným vytvrdením obohacovať sedimentáciou v smere do stredu zeme na Ag /špecifická hmotnosť 10,5.10³ kg/m³/ a v opačnom smere obohacovať na AgCl /špecifická hmotnosť 5,56.10³kg/m³/. Zmesná Ag-AgCl vrstva 34 je variantným uskutočnením obecného riešenia.The formation of a silver Ag layer 3 and AgCl layer 4 is also possible by applying a mixed Ag + AgCl paste in a suitable polymer, diluted with a suitable solvent to a particular polymer, e.g. toluene, after screen printing, e.g. to the conductive layer 2 by thermal curing enrich the sedimentation in the direction of the center of the earth to Ag (specific gravity 10,5.10 ³ kg / m ³ ) and in the opposite direction enrich to AgCl (specific gravity 5,56.10 ³ kg / m ³ ). The mixed Ag-AgCl layer 34 is a variant embodiment of the general solution.

Claims

A dry, flat reference electrode consisting of a carrier layer to which an Ag layer and an AgCl layer is bonded, characterized in that the carrier layer (1) has an active part (10), against which is a drain part (1000) between which a coupling part (100) is provided, wherein a conductive layer (2) is applied to the carrier layer (1) in the active part (10) and the discharge part (1000), in which the first bridge (101) is interconnected in the connecting part (100), on the conductive layer (2) is conductively deposited silver Ag layer (3) in the active part (10) and the second bridge (102) in the connecting part (100) extends into the drain part (1000), on the silver Ag layer (3) in the active part of the part (10) is conductively deposited an AgCl layer (4) on which the net (5) is fixedly applied, on the connecting part (100) is insulated membrane (6), which at least partially extends into the active part (10) and into the drain parts (1000).

Dry flat reference electrode according to claim 1, characterized in that the conductive layer (2) consists of powdered carbon with a particle size of 0.5 to 30 microns in the binder, where it is from 30 to 90%.

Dry flat reference electrode according to claims 1 and 2, characterized in that the silver Ag layer (3) consists of silver powder with a particle size of 0.5 to 50 microns in the binder, where it is from 20 to 90%.

Dry flat reference electrode according to claims 1 to 3, characterized in that the AgCl layer (4) consists of AgCl silver powder having a particle size of 0.5 to 30 microns in the binder, where it is from 20 to 90%.

Dry flat reference electrode according to claims 1 to 3, characterized in that an Ag-AgCl layer (34) is applied to the conductive layer (2) in the active part (10) and a second bridge (102) in the connecting part (100) extends. to the drain (1000).

Method for producing a dry flat reference electrode comprising a backing layer to which thin conductive layers are applied on one side by screen printing, wherein the individual layers form a conductive printed circuit, according to claim 1, characterized in that the backing layer (1) is by screen printing, applies a conductive layer (2) in the uncured state of the binder, forming an image of the conductive engagement given the shape of the mesh cover, in this case with side edges at the interface (100), for which the conductive layer (2) is thermally cured the silver Ag layer (3) is applied by screen printing in the uncured state of the binder, forming an image of the conductive connection given by the shape of the mesh cover, in this case on the drain (1000) and on the sides of the connecting portion (100); cures, by which the AgCl layer (4) is applied by screen printing in the uncured state of the binder to the active part (10) with the cover on the connecting part (1) 00) and of the discharge part (1000), after which it is thermally cured, and on the AgCl layer (4) in the active part (10) a net (5) is applied from the binder in the uncured state, after which it is thermally cured and on the interconnection part (100) In a non-cured state of the binder, an insulating membrane (6) is applied by screen printing, after which it is thermally cured.

Ί. Method according to claim 6, characterized in that the net (5) is fixed to the AgCl layer (4) in the active part (10) by gluing.

Method for manufacturing a flat reference electrode according to claim 6, characterized in that a mixed AgAgCl layer (34) is screen-printed on the conductive layer (2) by a screen printing in the active part (100) and intervenes with a second bridge (102) in the connecting part (100). into the discharged portion after which it is thermally cured.

Method for producing a dry flat reference electrode according to claims 6 to 8, characterized in that the conductive layer (2), the silver Ag layer (3) and the AgCl layer (4) or the mixed Ag-AgCl layer (34) are applied by screen printing. having a mesh size of from 5 to 200 microns, after which they are thermally cured in a temperature range of 10 to 400 ° C over a time period of 3 to 200 minutes.