CN102967639A - Long-life reference electrode suitable for deep-sea high hydrostatic pressure environment - Google Patents
Long-life reference electrode suitable for deep-sea high hydrostatic pressure environment Download PDFInfo
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- CN102967639A CN102967639A CN2012102391744A CN201210239174A CN102967639A CN 102967639 A CN102967639 A CN 102967639A CN 2012102391744 A CN2012102391744 A CN 2012102391744A CN 201210239174 A CN201210239174 A CN 201210239174A CN 102967639 A CN102967639 A CN 102967639A
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Abstract
The invention provides a long-life reference electrode suitable for a deep-sea high hydrostatic pressure environment. The reference electrode comprises a shell, which is internally provided with an inner electrode core body, a salt bridge and a diaphragm from top to bottom. The electrode is characterized in that: the salt bridge is composed of a saturated potassium chloride sol gel and potassium chloride particles that are uniformly and diffusely distributed in the saturated potassium chloride sol gel. The diaphragm is a super-microporous ceramic column. The upper end of the inner electrode core body is provided with an epoxy seal filler and is connected to an electrode lead wire that passes through the epoxy seal filler and then extends out of the shell. The lower end of the inner electrode core body contacts the upper end of the salt bridge, the lower end of which contacts one side of the super-microporous ceramic column diaphragm, and the other side of the super-microporous ceramic column diaphragm is in connection with the external environment. The invention can satisfy the electrochemical measurement requirements under a deep-sea high hydrostatic pressure environment, and can be widely applied to corrosion signal monitoring and detection, electrochemical protection, automatic control equipment probes, and the like of marine constructions, deep-sea petroleum pipelines, and deep-sea detection equipment.
Description
Technical field
What the present invention relates to is a kind of contrast electrode, the especially a kind of long service life reference electrode that can stablize use in the high hydrostatic pressure force environment of deep-sea.
Background technology
Contrast electrode is used for the cathodic protection of electrode potential, metal and the works thereof of the metal of Measurement accuracy place environment and works thereof, can also provide the control of Electric potentials signal for automatic control equipment, and application is very extensive.At present, the contrast electrode that uses in the known marine environment is generally selected silver/silver chloride contrast electrode, and the basic structure of contrast electrode is made by shell, filamentary silver behind superchlorination that salt bridge filling liquid and barrier film form in interior electrode, the electrode.Marine environment is its huge hydrostatic force of deep-marine-environment, low temperature, LDO content etc. particularly, and its complex environment parameter has with ocean, top layer environmental facies than more abominable Service Environment deep-marine-environment.Therefore, also there is not so far a kind of contrast electrode appearance that in deep-marine-environment, can long-term, non-maintaining, stablely use on the market.
Contrast electrode because silver chloride can form deliquescent silver-colored chlorine complex ion in the Chloride Solution of high concentration, reacts as follows when work:
If its reaction counter movement formed silver chloride sediment when this silver-colored chlorine complex ion ran into the Chloride Solution of low concentration at the liquid junction boundary place of contrast electrode, stop up thereby meet the barrier film place at liquid; Secondly since the solution of external environment since the effect of concentration difference diffusion to the diluting effect of salt bridge solution in the contrast electrode, interior salt bridge is filled solution and also need be regularly replaced; Also have, may enter salt bridge filling liquid in the electrode by barrier film by the pollutant in marine environment, and then pollute interior electrode, thereby make its serviceable life of electrode potential generation bias effect of contrast electrode.In addition, the contrast electrode cavity is interior owing to be the liquid salt bridge, in processing, transportation, store, cause easily the salt bridge filling liquid of contrast electrode inside to ooze out or run off in the process of using, if not being found in use its salt bridge filling liquid oozes out or runs off and directly use, particularly in the high hydrostatic pressure force environment of deep-sea, use, because the obstruction of barrier film and outside huge pressure-acting are easy to cause deformation or the pressure break of contrast electrode shell, cause contrast electrode to lose efficacy, lose the function of Measurement accuracy electrode potential, thereby cause erroneous judgement, even cause huge economic loss.
Summary of the invention
The object of the present invention is to provide a kind of high pressure resistant, non-maintaining, long-life long service life reference electrode that is applicable under the high hydrostatic pressure force environment of deep-sea.
The object of the present invention is achieved like this:
Comprise shell, be arranged in the interior electrode core body in the shell from top to bottom, salt bridge and barrier film, described salt bridge is made of the potassium chloride shot-like particle that saturated potassium chloride collosol and gel and even dispersion are distributed in the saturated potassium chloride collosol and gel, described barrier film is the ultramicropore ceramics pole, the upper end of interior electrode core body arranges the epoxy sealing filling material, the upper end of interior electrode core body is connected with passes the contact conductor of drawing shell behind the epoxy sealing filling material, the upper end in contact of the lower end of interior electrode core body and salt bridge, one side contacts of the lower end of salt bridge and ultramicropore ceramics pole barrier film, the opposite side of ultramicropore ceramics pole barrier film links to each other with external environment.
The present invention can also comprise:
1, described shell by fixing seal cover, sleeve pipe and fixedly pressure cap form, sleeve pipe is the titanium pipe and applies teflon at inside and outside wall, fixing seal cover and fixing pressure cap are connected respectively top and bottom with sleeve pipe by screw thread, and the through hole that ultramicropore ceramics pole barrier film is linked to each other with external environment is fixedly arranged on the pressure cap.
2, inlay the fine silver cylinder in the upper end of the columned interior electrode core body that is formed by silver and silver chloride pressed by powder sintering, an end of contact conductor links together by scolding tin node and fine silver cylinder.
Short serviceable life in order to overcome the contrast electrode that uses in the existing marine environment; need frequent salt bridge solution in the use procedure; in deep-marine-environment, use and be out of shape by the high hydrostatic pressure effect easily even the problem of fracture failure; the present invention proposes a kind of long service life reference electrode that is applicable to deep-sea high hydrostatic pressure force environment; this contrast electrode can not only the common marine environment of Measurement accuracy in the electrode potential of metal and works thereof; the cathodic protection of metal and works thereof; for automatic control equipment provides the control of Electric potentials signal; need not to regularly replace salt bridge; non-maintaining; especially can medium-term and long-term stable use of deep-sea high hydrostatic pressure force environment, realize that contrast electrode is high pressure resistant; non-maintaining; long-life characteristics.
Technical scheme of the present invention has solved three large technical barriers: use the inside and outside wall of titanium pipe to apply teflon at the contrast electrode shell, the intensifier electrode outer cover intensity, the huge pressure differential in contrast electrode outer shell cavity inside and outside causes shell deformation or the pressure break of contrast electrode when avoiding using in the high hydrostatic pressure force environment of deep-sea.Use saturated potassium chloride collosol and gel salt bridge in that contrast electrode is inner, use solid-state salt bridge, slow down silver ion and silver-colored chlorine complex ion spreads to liquid junction boundary, the sedimentation velocity of silver chloride on liquid junction boundary sharply reduces; Secondly, the ultramicropore pottery is as the second liquid junction boundary of contrast electrode, thereby prevents the silver nitride precipitation that silver ion on the electrode core body and silver-colored chlorine complex ion form at the first interface and the drift of the electrode potential that the liquid junction boundary of the obstruction electrode that causes causes; In addition, a large amount of even dispersion distribute and place potassium chloride particle in the saturated potassium chloride collosol and gel of contrast electrode, make silver/chlorination Ag inner electrode be in stable saturated chlorine ion concentration, without frequent always.By adopting above-mentioned three kinds of technical measures greatly to reduce the dissolution velocity of potassium chloride, effectively prevent the drift of electrode potential, obtained stable electrode potential, realized that contrast electrode of the present invention can use high pressure resistant, non-maintaining, the long-life result of use of realization in the high hydrostatic pressure force environment of deep-sea.
Design science of the present invention; rational in infrastructure; dependable performance; resistance to pressure is good; can prevent effectively that similar common contrast electrode is owing to long-time the use causes the ion obstruction that the phenomenon of contrast electrode electrode potential unstability or inefficacy is occured; anti-polarizability is strong; stability is high; the contrast electrode steady quality; because the inner filling material that is solid and gel; so can satisfy especially the electrochemical measurement requirement under the high hydrostatic pressure force environment of deep-sea, be widely used in marine structure; the deep-sea oil pipeline; the corrosion signal prison of deep-sea detecting equipment detects; electrochemical protection; automatic control equipment probe etc.
Description of drawings
Fig. 1 is structural representation of the present invention.
Fig. 2 is that the electrokinetic potential polarization of measuring under the 80atm condition is bent.
Fig. 3 a measures electrochemical impedance spectroscopy Nyquist figure under the 80atm condition.
Fig. 3 b measures electrochemical impedance spectroscopy Bode figure under the 80atm condition.
Embodiment
The invention will be further described for example below in conjunction with accompanying drawing:
In conjunction with Fig. 1.Contact conductor 1 one ends link together by scolding tin node 5 and fine silver cylinder 6 in columned interior electrode core body 7 upper surfaces that are embedded in silver/silver chloride pressed by powder sintering, interior electrode core body 7 is placed on electrode sleeve pipe 10 middle parts, utilize epoxy sealing filling material 4 fixing, electrode core body 7 exposes lower surface in requiring, and remaining surface is used 4 sealings of epoxy sealing filling material; Contact conductor 1 other end passes and passes 10 upper sheds of electrode sleeve pipe behind the epoxy sealing filling material 4 and pass the electrode fixing seal and overlap 3 through holes and extend to outside the contrast electrode main body as the usefulness that connects the signaling interfaces such as prison, checkout equipment and electrochemical workstation; The electrode sleeve pipe is processed with external thread in 10 upper ends, the electrode fixing seal overlaps 3 inwall machining screw, the internal thread of electrode sleeve pipe 10 upper end outer walls processing and electrode fixing seal cover 3 to be being threaded, between add pressure-resistant seal pad 2 and realize the fixing of electrodes upper end and seal; Fill saturated potassium chloride collosol and gel 8 in the whole space of electrode sleeve pipe 10 interior lower end, and in saturated potassium chloride collosol and gel 8 disperse distribution potassium chloride particle thing 9, electrode sleeve pipe 10 lower end outer wall machining screw realize interlock with the internal thread of electrode lower end electrode locking cap 12 inwalls processing; Utilize pressure-resistant seal pad 2 in electrode locking cap 12 and the electrode sleeve pipe 10 interlock spaces and realize fixing and sealing ultramicropore ceramics pole 11; There is through hole electrode locking cap 12 lower ends, realize that ultramicropore ceramics pole 11 lower surfaces link to each other with external environment, and ultramicropore ceramics pole 11 upper surfaces link to each other with saturated potassium chloride collosol and gel.
Claims (3)
1. long service life reference electrode that is applicable under the high hydrostatic pressure force environment of deep-sea, comprise shell, be arranged in the interior electrode core body in the shell from top to bottom, salt bridge and barrier film, it is characterized in that: described salt bridge is made of the potassium chloride shot-like particle that saturated potassium chloride collosol and gel and even dispersion are distributed in the saturated potassium chloride collosol and gel, described barrier film is the ultramicropore ceramics pole, the upper end of interior electrode core body arranges the epoxy sealing filling material, the upper end of interior electrode core body is connected with passes the contact conductor of drawing shell behind the epoxy sealing filling material, the upper end in contact of the lower end of interior electrode core body and salt bridge, one side contacts of the lower end of salt bridge and ultramicropore ceramics pole barrier film, the opposite side of ultramicropore ceramics pole barrier film links to each other with external environment.
2. the long service life reference electrode that is applicable under the high hydrostatic pressure force environment of deep-sea according to claim 1, it is characterized in that: described shell by fixing seal cover, sleeve pipe and fixedly pressure cap form, sleeve pipe is the titanium pipe and applies teflon at inside and outside wall, fixing seal cover and fixing pressure cap are connected respectively top and bottom with sleeve pipe by screw thread, and the through hole that ultramicropore ceramics pole barrier film is linked to each other with external environment is fixedly arranged on the pressure cap.
3. the long service life reference electrode that is applicable under the high hydrostatic pressure force environment of deep-sea according to claim 1 and 2, it is characterized in that: the fine silver cylinder is inlayed in the upper end at the columned interior electrode core body that is formed by silver and silver chloride pressed by powder sintering, and an end of contact conductor links together by scolding tin node and fine silver cylinder.
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| CN2012102391744A CN102967639A (en) | 2012-07-11 | 2012-07-11 | Long-life reference electrode suitable for deep-sea high hydrostatic pressure environment |
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| CN2012102391744A CN102967639A (en) | 2012-07-11 | 2012-07-11 | Long-life reference electrode suitable for deep-sea high hydrostatic pressure environment |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104237317A (en) * | 2014-09-15 | 2014-12-24 | 中国石油天然气股份有限公司 | Pressure-resistant sealing device of saturation test circuit |
| WO2015169097A1 (en) * | 2014-05-04 | 2015-11-12 | 苏州久润能源科技有限公司 | Double-salt-bridge reference electrode for analysing valence state of iron ions in fe-cr flow battery |
| PL423032A1 (en) * | 2017-10-02 | 2019-04-08 | Politechnika Śląska | System with the reference electrode with liquid connection, intended for electroanalytical subsurface and abyssal measurements |
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| CN1010254B (en) * | 1986-12-11 | 1990-10-31 | 株式会社堀场制作所 | Reference electrode |
| JPH0712776A (en) * | 1993-06-21 | 1995-01-17 | Power Reactor & Nuclear Fuel Dev Corp | Reference electrode for measuring oxidation-reduction potential |
| EP1193495A2 (en) * | 2000-09-30 | 2002-04-03 | Cha, Geun Sig | Polymeric reference electrode membrane and reference electrode with the membrane |
| CN1514235A (en) * | 2003-07-24 | 2004-07-21 | 中国科学院海洋研究所 | Full solid state reference electrode |
| CN201429582Y (en) * | 2009-05-04 | 2010-03-24 | 北京科技大学 | Reference electrode |
| CN102944594A (en) * | 2012-06-04 | 2013-02-27 | 哈尔滨工程大学 | Long-life reference electrode suitable for deep-sea high-hydrostatic pressure environment |
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2012
- 2012-07-11 CN CN2012102391744A patent/CN102967639A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1010254B (en) * | 1986-12-11 | 1990-10-31 | 株式会社堀场制作所 | Reference electrode |
| JPH0712776A (en) * | 1993-06-21 | 1995-01-17 | Power Reactor & Nuclear Fuel Dev Corp | Reference electrode for measuring oxidation-reduction potential |
| EP1193495A2 (en) * | 2000-09-30 | 2002-04-03 | Cha, Geun Sig | Polymeric reference electrode membrane and reference electrode with the membrane |
| CN1514235A (en) * | 2003-07-24 | 2004-07-21 | 中国科学院海洋研究所 | Full solid state reference electrode |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015169097A1 (en) * | 2014-05-04 | 2015-11-12 | 苏州久润能源科技有限公司 | Double-salt-bridge reference electrode for analysing valence state of iron ions in fe-cr flow battery |
| CN105092673A (en) * | 2014-05-04 | 2015-11-25 | 苏州久润能源科技有限公司 | Double-salt-bridge reference electrode used for analyzing valence in Fe-Cr redox flow battery |
| CN104237317A (en) * | 2014-09-15 | 2014-12-24 | 中国石油天然气股份有限公司 | Pressure-resistant sealing device of saturation test circuit |
| CN104237317B (en) * | 2014-09-15 | 2016-08-31 | 中国石油天然气股份有限公司 | Pressure-resistant sealing device of saturation test circuit |
| PL423032A1 (en) * | 2017-10-02 | 2019-04-08 | Politechnika Śląska | System with the reference electrode with liquid connection, intended for electroanalytical subsurface and abyssal measurements |
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Application publication date: 20130313 |