CN104007158A - All-solid-state integrated pH composite electrode device and preparation method of electrode - Google Patents
All-solid-state integrated pH composite electrode device and preparation method of electrode Download PDFInfo
- Publication number
- CN104007158A CN104007158A CN201410215729.0A CN201410215729A CN104007158A CN 104007158 A CN104007158 A CN 104007158A CN 201410215729 A CN201410215729 A CN 201410215729A CN 104007158 A CN104007158 A CN 104007158A
- Authority
- CN
- China
- Prior art keywords
- electrode
- antimony
- hollow needle
- solid state
- stainless steel
- 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.)
- Granted
Links
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to an all-solid-state integrated pH composite electrode device and a preparation method of the electrode. The all-solid-state integrated pH composite electrode device comprises an Ag/AgCl reference electrode, an antimony electrode, a copper wire and an insulated rubber sleeve, wherein the antimony electrode is embedded at the bottom of a stainless steel hollow needle of the reference electrode through the insulated rubber sleeve; the reference electrode is formed by taking the stainless steel hollow needle as a substrate, electroplating a silver layer on the surface, performing ultrasonic cleaning by using deionized water, plating an AgCl layer on the surface, cleaning through deionized water, and finally coating the reference electrode by using perfluorinated sulfonic acid resin solution dissolved with supersaturated KCl; the antimony electrode is formed by oxidizing a common antimony electrode in molten sodium peroxide to form an oxidation layer film, coating the antimony electrode by using the perfluorinated sulfonic acid resin solution with the mass percent of 5-10 percent and forming a hydrogen ion selective semi-permeable membrane. The composite electrode has certain mechanical strength and piercing ability, and pH of solids, semi-solids, paste and solutions can be tested.
Description
Technical field
The present invention relates to the preparation field of electrochemical sensor, relate in particular the preparation method of a kind of all solid state integral type pH combination electrode device and electrode thereof, for realizing solid, semisolid, the pastel to some strength, and the pH of solution test.
Background technology
Traditional pH test macro is made up of contrast electrode and the working electrode of two separation, and it is very inconvenient to use, and cannot realize the pH test of solid to some strength, semisolid, pastel.Therefore there is the all-solid-state reference electrode of certain puncture ability and the pH combination electrode of all solid state integral type becomes one of focus of Recent study.
Contrast electrode, as the reference electrode of measuring electric potential difference, common are hydrogen electrode, and mercurous chloride electrode, and some contrast electrodes based on difficulty soluble salt, as Ag/AgCl contrast electrode.The condition that hydrogen electrode is realized is harsher, seldom uses in test, and mercurous chloride electrode has certain danger owing to using when noxious material mercury uses, Ag/AgCl contrast electrode because cost is low, use safety, easily preparation, become modal contrast electrode.Traditional Ag/AgCl contrast electrode mainly uses in water solution system, and reference solution in needing often to change, and uses very inconvenient.Therefore Ag/AgCl all-solid-state reference electrode is one of contrast electrode Main Trends of The Development.The research of Ag/AgCl all-solid-state reference electrode is mainly concentrated on to three aspects: the one, replace traditional interior reference solution with fuse salt or the resin gel that is dissolved with salt, as the precious medium people that shuts out adopts the mixed gel of Lauxite and KCl powder, the people such as W.Vonau adopt the KCl of melting, but the response performance of electrode is unsatisfactory; The 2nd, with the mixture of powders direct pressing moulding of Ag and AgCl, as number of patent application CN102368059A prepares the method for contrast electrode with Ag/AgCl pressed powder, the flat cylindrical Ag/AgCl solid state reference electrode that a kind of powder compressing machine is pressed into is disclosed, but need to be kept in KCl solution, use inconvenient; The 3rd, the dull and stereotyped contrast electrode research of based thin film printing technology, as number of patent application CN101915794A all-solid-state reference electrode and preparation method thereof, discloses a kind of plate all-solid-state reference electrode based on thick film screen printing technology, but complex process.
At present, the research of pH electrode is had a lot, but the research of all solid state integral type pH combination electrode is also relatively lacked, technology is also immature.As the antimony metal pH electrode preparation method of a number of patent application CN102565164A duplicature modification, disclose a kind of through oxide film and the film modified novel antimony electrode of perfluorinated sulfonic resin, greatly improved antimony electrode interference free performance and permanance, but do not relate to the method for making of the compound pH electrode of all solid state integral type.And for example patent publication No. CN101236170A integrated all-solid-state pH electrochemical sensor based on nanometer tungsten oxide and preparation method thereof, a kind of integrated flat all-solid-state pH electrochemical sensor is disclosed, but measuring accuracy is not high, response time is longer, the pH real-time testing bad adaptability of solid, semisolid, pastel and the solution to some strength.
Summary of the invention
The present invention is directed to current all-solid-state reference electrode complex manufacturing technology, response performance is general, the preparation method of a kind of all solid state integral type pH combination electrode device and electrode thereof is proposed, for the pH real-time testing of the solid to some strength, semisolid, pastel and solution.
The all solid state integral type pH combination electrode of one of the present invention device, comprise copper conductor, all solid state Ag/AgCl contrast electrode, insulating gum cover and antimony electrode, described antimony electrode is embedded in the bottom of described all solid state Ag/AgCl contrast electrode by described insulating gum cover, described copper conductor is drawn from described all solid state Ag/AgCl contrast electrode and described antimony electrode respectively.
In such scheme, described all solid state Ag/AgCl contrast electrode is made up of stainless steel hollow needle, silver layer, silver chloride layer and perfluorinated sulfonic resin film from inside to outside successively.
In such scheme, described antimony electrode is made up of common antimony electrode, oxide layer film and hydrogen ion selective semi-permeable diaphragm from inside to outside successively.
In such scheme, described insulating gum cover is PVC insulating material, and described copper conductor is fixed on the common antimony electrode inside described antimony electrode from described insulating gum cover top tapping.
Described all solid state Ag/AgCl contrast electrode preparation method, feature is: taking stainless steel hollow needle as substrate, silver layer, silver chloride layer on its plated surface successively, then be coated with the perfluor sulfoacid resin solution that is dissolved with supersaturation KCl, form perfluorinated sulfonic resin film, its preparation method's concrete steps are as follows:
(1) choose the stainless steel hollow needle of external diameter 5-8mm, length 80-100mm, carry out polishing grinding with 400 orders and 800 object sand paper successively, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
(2) oil removing activation.By the stainless steel hollow needle through polishing grinding, be placed on oil removal treatment 10-20 minute in degreaser, then carry out ultrasonic cleaning flash baking in vacuum drying oven with deionized water;
(3) nickel preplating.At the bottom 30-50mm surface preplating skim nickel through the hollow needle of activation processing, and use deionized water ultrasonic cleaning by electrochemical plating, in vacuum drying oven, dry;
(4) electrosilvering.Stainless steel hollow needle bottom 30-50mm is carried out to electrodeposition process, at its plated surface last layer argent, and carry out ultrasonic cleaning with deionized water, in vacuum drying oven, dry;
(5) electrolytic chlorination.By silver-plated stainless steel hollow needle part and platinum electrode composition electrolysis system continuous current chlorinolysis 1-2 hour, obtain silver chloride coating, and carry out ultrasonic cleaning with deionized water, put into baking oven lucifuge and dry;
(6) resin-coated film.Oversaturated KCl is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, by this solution be coated in through superchlorination processing stainless steel hollow needle bottom, repeatedly smear several times, then in 70-80 DEG C of vacuum drying oven, dry;
(7) burn-on a copper conductor on the top of stainless steel hollow needle as lead-in wire.
The described antimony electrode preparation method through modifying, feature is: by first oxidation formation oxide layer film in the sodium peroxide of melting of common antimony electrode, then with the perfluor sulfoacid resin solution that massfraction is 5%～10%, antimony electrode is coated, form hydrogen ion selective semi-permeable diaphragm, its preparation method's concrete steps are as follows:
(1) heating high pure metal antimony powder end is to molten condition;
(2) metallic antimony of melting is injected to specific mold, and by one end quick insertion of a copper conductor in mold, be cooled to room temperature, obtain front end and be elliptoid antimony electrode;
(3) by the antimony electrode making, vertically to insert in the sodium peroxide of melting 5 minutes, the surface of antimony electrode forms oxide film, is cooled to room temperature, then dries by washed with de-ionized water and in vacuum drying oven;
(4) surface of the antimony electrode after oxidation processes coating quality mark is 5%-10% perfluor sulfoacid resin solution, forms hydrionic selectivity see through film on its surface, in 70-80 DEG C of vacuum drying oven, dries.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
(1) the present invention adopts the perfluor sulfoacid resin solution that is dissolved with supersaturation KCl to be coated in Ag/AgCl contrast electrode surface, prepare all solid state Ag/AgCl contrast electrode, do not need interior reference solution and barrier film in traditional Ag/AgCl contrast electrode, avoid reference solution in frequent replacing, be convenient to preserve, and technique is simple, easy to use.(2) the present invention adopt through modification antimony electrode as working electrode, antijamming capability improves greatly, permanance and better reliability.(3) the present invention adopts stainless steel hollow needle to prepare the pH combination electrode of all solid state integral type as substrate, preparation technology is simple, easy to use, can not only be used for the pH real-time testing of solution, and because base material and working electrode material are all that metal object has very high physical strength, in use, be not easy to damage, also can show good adaptability for solid, semisolid, the pastel of the some strength with certain water cut.
Brief description of the drawings
Below in conjunction with accompanying drawing, embodiment is described.
Fig. 1 is all solid state integral type pH combination electrode installation composition structural representation.
Wherein, the 1st, copper conductor; The 2nd, all solid state Ag/AgCl contrast electrode; The 3rd, insulating gum cover; The 4th, antimony electrode; The 21st, stainless steel hollow needle; The 22nd, silver layer; The 23rd, silver chloride layer; The 24th, perfluorinated sulfonic resin film (being dissolved with oversaturated KCl); The 41st, common antimony electrode; The 42nd, oxide layer film; The 43rd, hydrogen ion selective semi-permeable diaphragm.
Embodiment
As shown in Figure 1, all solid state integral type pH combination electrode of one of the present invention device, feature is: comprise copper conductor 1, all solid state Ag/AgCl contrast electrode 2, insulating gum cover 3 and form through the antimony electrode 4 of modifying; Copper conductor 1 is drawn from all solid state Ag/AgCl contrast electrode 2 and antimony electrode 4 respectively; Antimony electrode 4 is embedded in stainless steel hollow needle 21 bottoms of all solid state Ag/AgCl contrast electrode 2 by insulating gum cover 3.
Described insulating gum cover 3 is PVC insulating material, for connecting all solid state Ag/AgCl contrast electrode 2 and the antimony electrode 4 through modifying, working electrode 4 is positioned to stainless steel hollow needle 21 bottoms of contrast electrode 2.
The all solid state integral type pH method for preparing composite electrode of one of the present invention, comprises all solid state Ag/AgCl contrast electrode 2 preparation methods and antimony electrode 4 preparation method two aspects through modifying.
Described all solid state Ag/AgCl contrast electrode 2 preparation methods, feature is: taking stainless steel hollow needle 21 as substrate, silver layer 22, silver chloride layer 23 on its plated surface successively, then be coated with the perfluor sulfoacid resin solution that is dissolved with supersaturation KCl, form perfluorinated sulfonic resin film 24, its preparation method's concrete steps are as follows:
(1) choose the stainless steel hollow needle 21 of external diameter 5-8mm, length 80-100mm, carry out polishing grinding with 400 orders and 800 object sand paper successively, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
(2) oil removing activation.Will be through the stainless steel hollow needle 21 of polishing grinding, be placed on oil removal treatment 10-20 minute in the degreaser of 40-70 DEG C, then carry out ultrasonic cleaning flash baking in vacuum drying oven with deionized water.Wherein the formula of degreaser is: NaOH:40-60g/L, Na2CO3:15-25g/L, Na3PO4:20-40g/L, OP surfactant: 1-2g/L.
(3) nickel preplating.In the mixed solution of the NiCl2 of 180-200g/L and the HCl of 50-150g/L, use larger cathode-current density, carry out anode electrolysis 1-2 minute, at the bottom 30-50mm of the hollow needle 21 through activation processing surface preplating skim nickel, then use deionized water ultrasonic cleaning, and dry in vacuum drying oven;
(4) electrosilvering.Stainless steel hollow needle 21 bottom 30-50mm are put into the K2CO3 mixed solution of free KCN, the 15-30g/L of KCN, the 30-40g/L of 60-80g/L, cathode-current density is 0.5-2A/dm2, electro-deposition 3-5 minute, at its plated surface last layer argent 22, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
(5) electrolytic chlorination.By silver-plated stainless steel hollow needle part 22 and platinum electrode composition electrolysis system continuous current chlorinolysis 1-2 hour in 0.1mol/LKCl solution, current density 1-2A/dm2, obtain silver chloride coating 23, then carry out ultrasonic cleaning with deionized water, and put into the oven dry of baking oven lucifuge;
(6) resin-coated film.Oversaturated KCl is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, by this solution be coated in through superchlorination processing stainless steel hollow needle 21 bottoms, repeatedly smear several times, and dry in 70-80 DEG C of vacuum drying oven;
(7) burn-on a copper conductor 1 on the top of stainless steel hollow needle 21 as lead-in wire.
Described antimony electrode 4 preparation methods through modifying, feature is: by first oxidation formation oxide layer film 42 in the sodium peroxide of melting of common antimony electrode 41, then with the perfluor sulfoacid resin solution that massfraction is 5%～10%, antimony electrode is coated, form hydrogen ion selective semi-permeable diaphragm 43, its preparation method's concrete steps are as follows:
(1) heating high pure metal antimony powder end is to molten condition;
(2) metallic antimony of melting is injected to specific mold, and one end of a copper conductor (other end is as signal output) quick insertion, in mold, is cooled to room temperature, obtain front end and be elliptoid common antimony electrode 41;
(3) by the common antimony electrode 41 making, vertically to insert in the sodium peroxide of melting 5 minutes, the surface of antimony electrode forms oxide layer film 42, is cooled to room temperature, then dries by washed with de-ionized water and in vacuum drying oven;
(4) surface of the antimony electrode after oxidation processes coating quality mark is 5%-10% perfluor sulfoacid resin solution, forms hydrogen ion selective semi-permeable diaphragm 43 on its surface, in 70-80 DEG C of vacuum drying oven, dries.
With regard to several zwitterions, Oxidizing and Reducing Agents, described electrode is carried out respectively the impact research of response performance by fixing interfering ion method, the selectivity factor recording
k ij all much smaller than 1, as shown in table 1, show through the film modified all solid state integral type pH combination electrode of perfluorinated sulfonic resin common zwitterion (Na in soil
+, K
+, Ca
2+, Cl
-, Br
-) there is good selectivity, and to oxidation, reduction ion [Fe (CN)
6]
3-, [Fe (CN)
6]
4-and citrate ion (C
6h
5o
7 3-) also there is good selectivity, it is former in electronegative after the ionization of perfluorinated sulfonic resin film, can, by disturbing negative ion every outside film, avoid the electrode contact with pH, and the antijamming capability of electrode, reliability are greatly improved.
Table 1
| Ion | Concentration/(molL -1) | K ij | Ion | Concentration/(molL -1) | K ij |
| Na + | 1.0 | 2.6E-12 | NO 3- | 1.0 | 2.10E-10 |
| K + | 1.0 | 2.8E-12 | SO 4 2- | 1.0 | 2.5 E-11 |
| Ca 2+ | 1.0 | 3.0E-10 | [Fe(CN) 6] 3- | 0.1 | 4.2E-06 |
| Cl - | 1.0 | 1.6E-12 | [Fe(CN) 6] 4- | 0.1 | 5.1E-06 |
| Br - | 1.0 | 1.2E-10 | C 6H 5O 7 3- | 0.1 | 3.5E-06 |
Claims (6)
1. an all solid state integral type pH combination electrode device, it is characterized in that, comprise copper conductor (1), all solid state Ag/AgCl contrast electrode (2), insulating gum cover (3) and antimony electrode (4), described antimony electrode (4) is embedded in the bottom of described all solid state Ag/AgCl contrast electrode (2) by described insulating gum cover (3), described copper conductor (1) is drawn from described all solid state Ag/AgCl contrast electrode (2) and described antimony electrode (4) respectively.
2. all solid state integral type pH combination electrode of one according to claim 1 device, it is characterized in that, described all solid state Ag/AgCl contrast electrode (2) is made up of stainless steel hollow needle (21), silver layer (22), silver chloride layer (23) and perfluorinated sulfonic resin film (24) from inside to outside successively.
3. all solid state integral type pH combination electrode of one according to claim 1 and 2 device, it is characterized in that, described antimony electrode (4) is made up of common antimony electrode (41), oxide layer film (42) and hydrogen ion selective semi-permeable diaphragm (43) from inside to outside successively.
4. all solid state integral type pH combination electrode of one according to claim 3 device, it is characterized in that, described insulating gum cover (3) is PVC insulating material, and described copper conductor (1) is fixed on common antimony electrode (41) inside described antimony electrode (4) from described insulating gum cover (3) top tapping.
5. a preparation method for all solid state Ag/AgCl contrast electrode, comprises following steps:
A chooses the stainless steel hollow needle of external diameter 5-8mm, length 80-100mm, carries out polishing grinding successively with 400 orders and 800 object sand paper, then carries out ultrasonic cleaning with deionized water, and dries in vacuum drying oven;
B oil removing activation: by the stainless steel hollow needle through polishing grinding, be placed on oil removal treatment 10-20 minute in degreaser, then carry out ultrasonic cleaning flash baking in vacuum drying oven with deionized water;
C nickel preplating: use electrochemical plating at the bottom 30-50mm of the hollow needle through activation processing surface preplating skim nickel, and use deionized water ultrasonic cleaning, dry in vacuum drying oven;
D electrosilvering: stainless steel hollow needle bottom 30-50mm is carried out to electrodeposition process, at its plated surface last layer argent, and carry out ultrasonic cleaning with deionized water, dry in vacuum drying oven;
E electrolytic chlorination: by silver-plated stainless steel hollow needle part and platinum electrode composition electrolysis system continuous current chlorinolysis 1-2 hour, obtain silver chloride coating, and carry out ultrasonic cleaning with deionized water, put into baking oven lucifuge and dry;
The resin-coated film of F: oversaturated KCl is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, by this solution be coated in through superchlorination processing stainless steel hollow needle bottom, repeatedly smear several times, then in 70-80 DEG C of vacuum drying oven, dry;
G burn-ons a copper conductor as lead-in wire on the top of stainless steel hollow needle.
6. a preparation method for antimony electrode, comprises following steps:
H heating high pure metal antimony powder end is to molten condition;
The metallic antimony of melting is injected specific mold by I, and by one end quick insertion of a copper conductor in mold, be cooled to room temperature, obtain front end and be elliptoid antimony electrode;
J is the antimony electrode making, and vertically inserts in the sodium peroxide of melting 5 minutes, and the surface of antimony electrode forms oxide film, is cooled to room temperature, then dries by washed with de-ionized water and in vacuum drying oven;
The antimony electrode surface coating quality mark of K after oxidation processes is 5%-10% perfluor sulfoacid resin solution, forms hydrionic selectivity see through film on its surface, in 70-80 DEG C of vacuum drying oven, dries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410215729.0A CN104007158B (en) | 2014-05-21 | 2014-05-21 | The preparation method of complete solid-state integral type pH combined electrode device and electrode thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410215729.0A CN104007158B (en) | 2014-05-21 | 2014-05-21 | The preparation method of complete solid-state integral type pH combined electrode device and electrode thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104007158A true CN104007158A (en) | 2014-08-27 |
| CN104007158B CN104007158B (en) | 2016-06-15 |
Family
ID=51367913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410215729.0A Expired - Fee Related CN104007158B (en) | 2014-05-21 | 2014-05-21 | The preparation method of complete solid-state integral type pH combined electrode device and electrode thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104007158B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105675682A (en) * | 2015-12-28 | 2016-06-15 | 中国人民大学 | Size-controllable nanowire microelectrode, preparation method and application thereof |
| CN106018516A (en) * | 2016-05-09 | 2016-10-12 | 江苏大学 | Method for preparing graphene modified composite slab pH sensor |
| CN106018504A (en) * | 2016-05-09 | 2016-10-12 | 江苏大学 | PH detection double compensating method for soil matrix culture multi-parameter compound sensor |
| CN106596682A (en) * | 2016-12-28 | 2017-04-26 | 上海应用技术大学 | Go-Nafion composite film Ag/AgCl reference electrode for ocean exploration and preparation method thereof |
| CN108169302A (en) * | 2017-11-20 | 2018-06-15 | 深圳大学 | A kind of three-electrode system and its application method |
| CN108562751A (en) * | 2018-05-04 | 2018-09-21 | 深圳市西尔曼科技有限公司 | The detection method of enzyme membrane and preparation method thereof, glycosylated hemoglobin |
| CN108828329A (en) * | 2018-04-27 | 2018-11-16 | 中国科学院地质与地球物理研究所 | A kind of ocean electric field measurement sensor and preparation method thereof |
| CN109342520A (en) * | 2018-09-29 | 2019-02-15 | 中国科学院长春应用化学研究所 | A kind of all-solid-state pH combination electrode device and preparation method thereof |
| CN112189132A (en) * | 2018-05-11 | 2021-01-05 | 斯泰诺有限责任公司 | Apparatus and method for in situ soil analysis |
| CN113406167A (en) * | 2021-06-29 | 2021-09-17 | 江苏大学 | Super-hydrophilic pH thick film sensor based on chemical corrosion method and preparation method |
| US11307169B2 (en) | 2019-07-24 | 2022-04-19 | Jiangsu University | PH sensor with automatic water storage and replenishment |
| PL441669A1 (en) * | 2022-07-07 | 2024-01-08 | Heart Guard Spółka Z Ograniczoną Odpowiedzialnością | Electrode array for measuring the pH of animal tissues, a probe containing such an array, and a kit containing said probe |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4575410A (en) * | 1982-03-11 | 1986-03-11 | Beckman Industrial Corporation | Solid state electrode system for measuring pH |
| CN2219497Y (en) * | 1994-05-12 | 1996-02-07 | 厦门大学 | Long-acting solid composite electrode |
| WO1996007111A1 (en) * | 1994-09-01 | 1996-03-07 | Applied Research Associates, Inc. | SURFACE MOUNTED pH SENSOR FOR CONE PENETRATION TESTING |
| CN101542275A (en) * | 2006-11-21 | 2009-09-23 | 恩德莱斯和豪瑟尔测量及调节技术分析仪表两合公司 | Electrode and single-rod measuring chain for determining electrochemical potentials |
| US8128989B1 (en) * | 2003-05-07 | 2012-03-06 | Millar Instruments | System, method, and probe for monitoring pH levels of a sample medium |
| CN102565164A (en) * | 2012-02-01 | 2012-07-11 | 江苏大学 | Method for producing antimony pH electrode modified by two layers of films |
-
2014
- 2014-05-21 CN CN201410215729.0A patent/CN104007158B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4575410A (en) * | 1982-03-11 | 1986-03-11 | Beckman Industrial Corporation | Solid state electrode system for measuring pH |
| CN2219497Y (en) * | 1994-05-12 | 1996-02-07 | 厦门大学 | Long-acting solid composite electrode |
| WO1996007111A1 (en) * | 1994-09-01 | 1996-03-07 | Applied Research Associates, Inc. | SURFACE MOUNTED pH SENSOR FOR CONE PENETRATION TESTING |
| US8128989B1 (en) * | 2003-05-07 | 2012-03-06 | Millar Instruments | System, method, and probe for monitoring pH levels of a sample medium |
| CN101542275A (en) * | 2006-11-21 | 2009-09-23 | 恩德莱斯和豪瑟尔测量及调节技术分析仪表两合公司 | Electrode and single-rod measuring chain for determining electrochemical potentials |
| CN102565164A (en) * | 2012-02-01 | 2012-07-11 | 江苏大学 | Method for producing antimony pH electrode modified by two layers of films |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105675682A (en) * | 2015-12-28 | 2016-06-15 | 中国人民大学 | Size-controllable nanowire microelectrode, preparation method and application thereof |
| CN105675682B (en) * | 2015-12-28 | 2019-03-26 | 中国人民大学 | A kind of nano wire microelectrode and the preparation method and application thereof that size is controllable |
| WO2017193415A1 (en) * | 2016-05-09 | 2017-11-16 | 江苏大学 | Method for preparing graphene modified composite planar ph sensor |
| CN106018516A (en) * | 2016-05-09 | 2016-10-12 | 江苏大学 | Method for preparing graphene modified composite slab pH sensor |
| US11150211B2 (en) | 2016-05-09 | 2021-10-19 | Jiangsu University | Method for preparing graphene modified composite planar pH sensor |
| CN106018504A (en) * | 2016-05-09 | 2016-10-12 | 江苏大学 | PH detection double compensating method for soil matrix culture multi-parameter compound sensor |
| CN106018516B (en) * | 2016-05-09 | 2018-08-21 | 江苏大学 | A kind of compound slab pH transducer production methods of graphene modified |
| CN106018504B (en) * | 2016-05-09 | 2018-10-09 | 江苏大学 | A kind of pH detection double compensation methods of soil matrix cultivation multi-parameter compound sensor |
| CN106596682B (en) * | 2016-12-28 | 2019-03-19 | 上海应用技术大学 | A kind of hydrospace detection Go-Nafion composite membrane Ag/AgCl reference electrode and preparation method |
| CN106596682A (en) * | 2016-12-28 | 2017-04-26 | 上海应用技术大学 | Go-Nafion composite film Ag/AgCl reference electrode for ocean exploration and preparation method thereof |
| CN108169302A (en) * | 2017-11-20 | 2018-06-15 | 深圳大学 | A kind of three-electrode system and its application method |
| CN108169302B (en) * | 2017-11-20 | 2020-05-12 | 深圳大学 | Three-electrode system and using method thereof |
| CN108828329A (en) * | 2018-04-27 | 2018-11-16 | 中国科学院地质与地球物理研究所 | A kind of ocean electric field measurement sensor and preparation method thereof |
| CN108562751A (en) * | 2018-05-04 | 2018-09-21 | 深圳市西尔曼科技有限公司 | The detection method of enzyme membrane and preparation method thereof, glycosylated hemoglobin |
| CN112189132A (en) * | 2018-05-11 | 2021-01-05 | 斯泰诺有限责任公司 | Apparatus and method for in situ soil analysis |
| CN112189132B (en) * | 2018-05-11 | 2023-10-20 | 斯泰诺有限责任公司 | Apparatus and method for in situ soil analysis |
| CN109342520A (en) * | 2018-09-29 | 2019-02-15 | 中国科学院长春应用化学研究所 | A kind of all-solid-state pH combination electrode device and preparation method thereof |
| US11307169B2 (en) | 2019-07-24 | 2022-04-19 | Jiangsu University | PH sensor with automatic water storage and replenishment |
| WO2023272978A1 (en) * | 2021-06-29 | 2023-01-05 | 江苏大学 | Superhydrophilic thick-film ph sensor based on chemical etching method, and preparation method therefor |
| CN113406167B (en) * | 2021-06-29 | 2023-10-10 | 江苏大学 | Super-hydrophilic pH thick film sensor based on chemical corrosion method and preparation method |
| CN113406167A (en) * | 2021-06-29 | 2021-09-17 | 江苏大学 | Super-hydrophilic pH thick film sensor based on chemical corrosion method and preparation method |
| US12099029B2 (en) | 2021-06-29 | 2024-09-24 | Jiangsu University | Superhydrophilic thick-film pH sensor based on chemical etching, and preparation method thereof |
| PL441669A1 (en) * | 2022-07-07 | 2024-01-08 | Heart Guard Spółka Z Ograniczoną Odpowiedzialnością | Electrode array for measuring the pH of animal tissues, a probe containing such an array, and a kit containing said probe |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104007158B (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104007158A (en) | All-solid-state integrated pH composite electrode device and preparation method of electrode | |
| CN106645245B (en) | Electrolytic extraction and determination method for non-metallic inclusions in steel | |
| KR101745485B1 (en) | Method for manufacturing metal-filled microstructure | |
| CN103290247B (en) | Nano porous metal material that aperture changes in gradient and preparation method thereof | |
| CN111521656B (en) | High-sensitivity high-stability boron-doped diamond microelectrode and preparation method and application thereof | |
| CN103129048A (en) | Manufacturing method of metal and plastic combination body and combination body | |
| CN103521864B (en) | Fine group's line electrode living broadcast and wire electrochemical micro-machining method | |
| CN107614756A (en) | Porous nickel film and its manufacture method | |
| CN104818503A (en) | Preparation method of porous copper full-impregnated film of three-dimensional network structure | |
| CN111074317A (en) | Surface treatment method of copper foil and copper foil material | |
| CN106676619B (en) | A kind of preparation method of glassy metal nano-porous structure | |
| CN109295327B (en) | Micron porous copper and preparation method and application thereof | |
| CN103931034A (en) | Collector plate for fuel cells and method for producing same | |
| CN106549168B (en) | The preparation method of the three-dimensional Pd-Ni nano-wire array catalyst of catalyzing hydrogen peroxide electroreduction | |
| JP7324912B2 (en) | Electrolytic method for extracting tin and/or lead contained in electrically conductive mixtures | |
| CN111591953A (en) | Needle-shaped microelectrode and preparation method thereof | |
| CN107083559B (en) | The method of high-quality nickel is chemically electrolysed out in nickel-plating waste water | |
| CN113466271B (en) | Method for accurately determining type, morphology and elemental composition of intermetallic compounds in steel | |
| CN104466589A (en) | Nickel plating method for kovar alloy glass sealed connector | |
| CN109148895B (en) | Electrochemical roughening treatment method for positive current collector of lithium ion battery | |
| JP2019157160A (en) | Manufacturing method of copper and electrolytic device for manufacturing copper | |
| JP2020055728A (en) | Method of producing sulfuric acid solution | |
| CN105463544A (en) | Electroplating method for iron-made frame | |
| US3772086A (en) | Method of making anodes for hydrazine fuel cells | |
| JP2014192089A (en) | Separator for fuel cell and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160615 Termination date: 20170521 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |