CN100397710C - Copper/saturated copper sulphate gel reference electrode - Google Patents
Copper/saturated copper sulphate gel reference electrode Download PDFInfo
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- CN100397710C CN100397710C CNB2006100684571A CN200610068457A CN100397710C CN 100397710 C CN100397710 C CN 100397710C CN B2006100684571 A CNB2006100684571 A CN B2006100684571A CN 200610068457 A CN200610068457 A CN 200610068457A CN 100397710 C CN100397710 C CN 100397710C
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Abstract
The invention relates to a novel long-life reference electrode, especially a copper/saturated bluestone gel reference electrode, belonging to chemical corrosion and protection technical field, and its main structure is a liquid-in-column double-layer structure, comprising cable, sealing cover, sealing fillings, ceramic inner shell, ceramic outer shell, spiral copper wire, saturated bluestone, ceramic feet and gel electrolyte, where a space is formed between the ceramic inner and outer shells and filled with the gel electrolyte, the bottom of the ceramic inner shell is made by firing with three equidistant triangular symmetrical ceramic feet, the center of the ceramic inner shell is vertically made with the spiral copper wire and the spiral copper wire runs through the tops of the ceramic inner and outer shells, sealing cover and sealing fillings to connect with the cable, the ceramic inner shell is filled with the saturated bluestone around the spiral copper wire electrode, the sealing fillings is arranged between the top surface of the saturated bluestone and the ceramic inner shell, the top surface of the ceramic outer shell is made with the sealing cover, and the reference electrode has characters of long life, simple structural principle, preparing safety, and less pollution.
Description
Technical field:
A kind of novel long-life reference electrode that The present invention be directed to the soil environment application conditions and develop, particularly a kind of copper/copper/saturated copper sulphate gel reference electrode belongs to chemical corrosion and guard technology field.
Technical background:
Reference electrode is meant when carrying out electrochemical gaging, keeps constant potential and can be used as the electrode that the current potential of indication or work electrode is observed, measured or controls for one.In the electrochemical protection field, measure the electrode potential of metal structures and must use reference electrode.And in soil environment, general usefulness copper/copper/saturated copper sulphate reference electrode when measuring the current potential of embedded metal pipeline, structures etc.At present often copper/copper/saturated copper sulphate the reference electrode that uses has two kinds: promptly comprise portable and bury for a long time type.Portable copper/copper/saturated copper sulphate reference electrode is shorter owing to the life-span, and is not suitable for the embedded metal pipeline and the metal structures of long distance are measured for a long time.Therefore, need the development long-life to bury ground type reference electrode to satisfy the demand of metalloid structures such as buried pipeline being carried out long-term electrochemical protection.
Chinese patent publication number CN2116970; in open day on September 23rd, 1992, the project that name is called long-life buried copper, copper sulphate reference electrode discloses a kind of reference electrode that is applicable to the electrochemical field such as cathodic protection of buried pipeline, cable and metal structures.Copper in this patent/copper/saturated copper sulphate reference electrode is constituted by copper (tubulose or spring) and copper sulfate crystal are housed in the biscuit ware jar, soaks 24 hours in water before using, and forms copper/saturated copper sulphate solution, constitutes Cu/CuSO
4Half-cell.Its weak point is: because the biscuit ware jar plays a part and the environment exchange ion, the life-span that the explosive payload of jar and permeability have determined electrode, and as the reference electrode that uses with burying, directly bury ground with the biscuit ware jar, the porousness of ceramic pot will cause jar interior crystal to run off and the soil media intermediate ion to the pollution of solution in the jar, therefore electrode body exists copper ion to run off too fast and problem such as still can be polluted, thereby influences the useful life of electrode.So,, still to seek the useful life that new approach further improves copper/copper/saturated copper sulphate reference electrode in order to satisfy demand to the long-term electrochemical protection monitoring of some buried metal structures.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that exists in the prior art, electrode body at existing buried copper/copper/saturated copper sulphate reference electrode is polluted easily, copper ion runs off too fast in jar, have a strong impact on problems such as electrode actual life, by at electrode body outer wrap layer of gel electrolyte, alleviate the contamination of outer ion to electrode body, reduce the infiltration bleed rate of tank interior copper ion, thereby effectively prolong the useful life of the copper/copper/saturated copper sulphate reference electrode that uses with burying.
To achieve these goals, the present invention has proposed the reference electrode that a kind of new structure is formed to the existing existing problem of conventional reference electrode, this reference electrode is a double-decker, internal layer is an electrode body, skin is a gel electrolyte, gel electrolyte can alleviate the contamination of outer ion to electrode body effectively, reduces the infiltration bleed rate of internal copper ion.Agent structure of the present invention is a cylinder internal-filling liquid body formula, comprise cable, seal cover, airtight and watertight padding, the pottery inner casing, ceramic package, the helical form copper wire, copper/saturated copper sulphate, pottery leg and gel electrolyte, form the space between pottery inner casing and the ceramic package and be filled with gel electrolyte, the pottery inner shell bottom is by firing the ceramic leg that method is shaped on three equidistant triangular symmetry, pottery inner casing center vertically is shaped on the helical form copper wire and passes ceramic inner casing, ceramic package top and seal cover and airtight and watertight padding electric connection jump lead, be full of copper/saturated copper sulphate around the helical form copper wire in the pottery inner casing, be equipped with airtight and watertight padding between copper/saturated copper sulphate end face and the ceramic inner casing, the ceramic package end face is shaped on sealing shape and reinforces seal cover.
Gel electrolyte used in the present invention consist of nano silicon 65～72g/L, the concentrated sulfuric acid 368～650g/L and polyacrylamide 1.0～2.0g/L, the rest is distilled water; The gel electrolyte thicknesses of layers is 5～10mm; Airtight and watertight padding is an epoxy putty; Charge into copper/saturated copper sulphate solution in the pottery inner casing and have cupric sulphate crystal to exist.
In the laboratory, the traditional electrical polar body that utilizes the reference electrode that the present invention makes and do not use gel to carry out outer parcel has been carried out the test contrast.The result shows: it is 3.0 * 10 that the electrode copper ion that adopts the present invention to make oozes out speed
-6Molh
-1Cm
-2, the copper ion leaching rate 8.5 * 10 of traditional electrode
-6Molh
-1Cm
-2, the existence of gel electrolyte has slowed down the tendency that the external contamination thing spreads to electrode body effectively among the present invention simultaneously.The electrode life that adopts the present invention to make is about 3 times of traditional electrode.
Description of drawings:
Fig. 1 is an agent structure principle schematic of the present invention.
Embodiment:
During the invention process, its electrode integral body has double-decker, and its composition comprises cable 1, seal cover 2, airtight and watertight padding 3, ceramic inner casing 4, ceramic package 5, helical form copper wire 6, copper/saturated copper sulphate 7, ceramic leg 8 and gel electrolyte 9.Pottery inner casing 4 and ceramic package 5 are fired by biscuit ware and to be formed.Rely on three ceramic legs 8 to fixedly connected the position with ceramic package 5 at the bottom of pottery inner casing 4 shells.Three ceramic leg 8 equidistant triangle position symmetries are fixing.Three ceramic legs 8 are all fixed by firing way.The internal layer of this structure is filled copper/saturated copper sulphate solution, and maintains cupric sulphate crystal, and outer gel filled electrolyte, internal layer are the main bodys of electrode.Gel filled electrolyte 9 between pottery inner casing 4 and the ceramic package 5.Gel electrolyte added before not becoming glue fully, and carried out in fixed position and direction, to guarantee that gel electrolyte can not produce bubble between ceramic inner casing 4 and ceramic package 5.Gel electrolyte 9 is made up of materials such as nano silicon, the concentrated sulfuric acid, polyacrylamides.The nano silicon and the concentrated sulfuric acid are the Main Ingredients and Appearances that forms gel, and polyacrylamide is an additive.This additive molecule amount is 500～1,000 ten thousand, has the effect of pinning moisture.It is added in the glue, can expand after entering water, its active group can with the nano silicon molecular action, form polymer gel.The composition of gel electrolyte 9 consists of: nano silicon 65～72g/L, and the concentrated sulfuric acid 368～650g/L, polyacrylamide 1.0～2.0g/L the rest is water.The thicknesses of layers of gel electrolyte 9 is 5mm～10mm.This thicknesses of layers is the distance between ceramic inner casing 4 and the ceramic package 5.
Embodiment 1: the polarization performance research of gel reference electrode
According to ceramic inner casing 4 is Φ 25mm * 100mm, and ceramic inner casing 4 and shell 5 spacings are that the specification of 5mm is carried out firing of electrode assembly, and equidistant triangle position symmetry is fired three ceramic legs in the bottom of ceramic inner casing 4 simultaneously.In ceramic inner casing 4, fill it up with copper sulfate crystal, and select for use conventional epoxy putty it to be sealed, with adding distilled water between ceramic inner casing 4 and the shell 5, placed 24 hours then to seal cover 2 places as airtight and watertight padding 3.
Take by weighing nano silicon 65g, polyacrylamide 1.0g takes by weighing concentrated sulfuric acid 368g, adds water and is prepared into one liter of gel electrolyte.Then the distilled water between ceramic inner casing 4 and the shell 5 is outwelled, the gel electrolyte of being prepared is added wherein, after filling it up with, seal with seal cover.The helical form copper wire is drawn with the cable electric connection.
As work electrode, platinum filament is made auxiliary electrode with prepared gel reference electrode, and saturated calomel electrode is a reference electrode, carries out the polarization performance test.Under the cathode and anode polarization current of 10 μ A, the potential drifting of cathodic polarization, anode polarization is respectively 1.5mV and 2.5mV.After experiment finished, electrode potential returned to initial potential rapidly.This test shows that the anti-polarization performance of prepared electrode is better.
Embodiment 2: the potential stability research of gel reference electrode
According to ceramic inner casing 4 is Φ 25mm * 100mm, and ceramic inner casing 4 and ceramic package 5 spacings are that the specification of 10mm is carried out firing of electrode assembly, and equidistant triangle position symmetry is fired three ceramic legs in the bottom of ceramic inner casing 4 simultaneously.In ceramic inner casing 4, fill it up with copper sulfate crystal, and utilize airtight and watertight padding 3 that it is sealed, with adding distilled water between ceramic inner casing 4 and the shell 5, placed 24 hours then to seal cover 2 places.
Taking by weighing nano silicon respectively is 72g, concentrated sulfuric acid 650g, and polyacrylamide 2.0g adds water and is mixed with one liter of gel electrolyte.Then the distilled water between ceramic inner casing 4 and the shell 5 is outwelled, the gel electrolyte of being prepared is added wherein, after filling it up with, seal with seal cover, the helical form copper wire is drawn with cable.
Utilize digital voltmeter and saturated calomel electrode to measure the current potential of gel reference electrode.Measure once every day, and the time is 50 days.The potential change scope is 7～8mV.The stability of electrode potential better.
Claims (2)
1. copper/copper/saturated copper sulphate gel reference electrode, comprise cable, seal cover, airtight and watertight padding, ceramic inner casing, ceramic package, helical form copper wire, copper/saturated copper sulphate, ceramic leg and gel electrolyte, it is characterized in that electrode body is a cylinder internal-filling liquid body formula double-decker, internal layer is an electrode body, and skin is a gel electrolyte; Form the space between pottery inner casing and the ceramic package and be filled with gel electrolyte, the pottery inner shell bottom is by firing the ceramic leg that method is shaped on three equidistant triangular symmetry, pottery inner casing center vertically is shaped on the helical form copper wire and passes ceramic inner casing, ceramic package top and seal cover and airtight and watertight padding electric connection cable, be full of copper/saturated copper sulphate around the helical form copper wire in the pottery inner casing, be equipped with airtight and watertight padding between copper/saturated copper sulphate end face and the ceramic inner casing, the ceramic package end face is shaped on sealing shape and reinforces seal cover.
2. copper/copper/saturated copper sulphate gel reference electrode according to claim 1, what it is characterized in that gel electrolyte consists of nano silicon 65～72g/L, the concentrated sulfuric acid 368～650g/L and polyacrylamide 1.0～2.0g/L, the rest is distilled water; The gel electrolyte thicknesses of layers is 5～10mm; Airtight and watertight padding is an epoxy putty; Charge into copper/saturated copper sulphate solution in the pottery inner casing and have cupric sulphate crystal to exist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100684571A CN100397710C (en) | 2006-08-25 | 2006-08-25 | Copper/saturated copper sulphate gel reference electrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100684571A CN100397710C (en) | 2006-08-25 | 2006-08-25 | Copper/saturated copper sulphate gel reference electrode |
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|---|---|
| CN1949595A CN1949595A (en) | 2007-04-18 |
| CN100397710C true CN100397710C (en) | 2008-06-25 |
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| CNB2006100684571A Expired - Fee Related CN100397710C (en) | 2006-08-25 | 2006-08-25 | Copper/saturated copper sulphate gel reference electrode |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101226164B (en) * | 2008-01-16 | 2010-11-17 | 中国船舶重工集团公司第七二五研究所 | Embedment type reference electrode for inspecting/detecting steel reinforced concrete erosion |
| RU187916U1 (en) * | 2018-03-07 | 2019-03-22 | Общество с ограниченной ответственностью "Завод газовой аппаратуры "НС" | GEL COPPER-SULPHATE COMPARISON NON-POLARIZING COMPARISON |
| CN115598190A (en) * | 2021-07-07 | 2023-01-13 | 上海罗素科技有限公司（Cn） | Electrochemical potential sensing electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2116970U (en) * | 1991-11-22 | 1992-09-23 | 中国船舶工业总公司第七研究院七二五研究所 | Long life buried copper and cupric sulfate reference electrode |
| CN2465187Y (en) * | 2001-02-21 | 2001-12-12 | 中国科学院海洋研究所 | Copper/cupric sulfate electrode |
| WO2002023179A1 (en) * | 2000-09-15 | 2002-03-21 | Schroeder Knut | Electrode for analytical voltammetry |
| CN1812946A (en) * | 2003-06-25 | 2006-08-02 | 梅特勒-托莱多有限公司 | Method for the production of a reference electrode |
-
2006
- 2006-08-25 CN CNB2006100684571A patent/CN100397710C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2116970U (en) * | 1991-11-22 | 1992-09-23 | 中国船舶工业总公司第七研究院七二五研究所 | Long life buried copper and cupric sulfate reference electrode |
| WO2002023179A1 (en) * | 2000-09-15 | 2002-03-21 | Schroeder Knut | Electrode for analytical voltammetry |
| CN2465187Y (en) * | 2001-02-21 | 2001-12-12 | 中国科学院海洋研究所 | Copper/cupric sulfate electrode |
| CN1812946A (en) * | 2003-06-25 | 2006-08-02 | 梅特勒-托莱多有限公司 | Method for the production of a reference electrode |
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Assignee: Qingdao Sunrui Corrosion and Fouling Control Company Assignor: No.725 Inst. China Shipping Heavy Industry Group Corp. Contract fulfillment period: 2008.8.28 to 2018.8.27 contract change Contract record no.: 2008370000100 Denomination of invention: Copper/saturated copper sulphate gel reference electrode Granted publication date: 20080625 License type: Exclusive license Record date: 2008.11.7 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.8.28 TO 2018.8.27; CHANGE OF CONTRACT Name of requester: QINGDAO SHUANGRUI CORROSION PROTECTION ANTIFOULING Effective date: 20081107 |
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