CN103604852B - A kind of method preparing the Ag/Agcl working electrode being applicable to monitoring chlorine ion concentration - Google Patents
A kind of method preparing the Ag/Agcl working electrode being applicable to monitoring chlorine ion concentration Download PDFInfo
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- CN103604852B CN103604852B CN201310624990.1A CN201310624990A CN103604852B CN 103604852 B CN103604852 B CN 103604852B CN 201310624990 A CN201310624990 A CN 201310624990A CN 103604852 B CN103604852 B CN 103604852B
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- agcl
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- working electrode
- ion concentration
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- 238000000034 method Methods 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 16
- 238000012544 monitoring process Methods 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 9
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 238000003466 welding Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000010437 gem Substances 0.000 abstract description 2
- 229910001751 gemstone Inorganic materials 0.000 abstract description 2
- 239000010944 silver (metal) Substances 0.000 description 40
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 210000000158 ommatidium Anatomy 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
The present invention relates to the corrosion on-line monitoring of marine port engineering, a kind of method being specifically related to Ag/Agcl working electrode prepared for monitoring chloride ions concentration of concrete.By Ag powder that mass ratio is 9 10:1 and Agcl powder mix homogeneously, mix homogeneously is placed in mortar and is fully ground, adding cetomacrogol 1000 during grinding, the powder after being fully ground, with being rinsed through normal heptane and distilled water successively, is then dried compacting and is Ag/Agcl electrode.The present invention has carried out uniform treatment to powder before tabletting, guaranteeing electrode stability, and by filamentary silver line embedment powder in tableting processes, directly bears against inside electrode, very easy to use, it is to avoid loosening of welding lead or wasting time and energy of jewel hole.The working electrode that the present invention makes both can guarantee that the stability of Ag/Agcl electrode, and utilization rate is close to 100%.
Description
Technical field
The present invention relates to the corrosion on-line monitoring of marine port engineering, be specifically related to one and prepare use
Method in the Ag/Agcl working electrode of monitoring chloride ions concentration of concrete.
Background technology
Ag/Agcl electrode is extensively applied because of advantages such as its current potential is stable, repeatability is good, easy preparations
In every field.Ag/Agcl is applied to surveying laboratory reinforcing steel by Atkins CP etc.
And concrete extrudes chlorine ion concentration in hole solution, result shows measured chlorine ion concentration and basis
The value that activity coefficient Theoretical Calculation goes out is coincide good.The Ag/Agcl of the preparation such as M.A Climent-Llorca
Mortar specimen prepared by the sodium chloride solution of the different chlorine ion concentration of electrode embedment tests its performance, sends out
Existing electrode shows good linear response in certain chlorine ion concentration.Montemo.M.F etc. will
Ag/Agcl electrode embedment mortar and the different depth of concrete sample, monitoring chlorine under chloride solution invades bubble
Ion diffusion process in mortar and concrete, result shows that Ag/Agcl electrode is in whole experimental period
Between there is good stability.Visible Ag/Agcl electrode type chloride ion based on electrochemical principle senses
Device application in concrete works has huge potentiality, and as working sensor electrode
The stability of Ag/Agcl electrode will directly affect Monitoring Data and the accuracy of durability judgement, therefore
The stability of Ag/Agcl electrode has very important effect to the accuracy of sensor.
At present the processing technology of Ag/Agcl electrode probably has three kinds: electrolysis, screen printing technique and
Pressed disc method.Electrolysis: with purity be 99.99% fine silver silk as anode, be the platinum filament of 99.95% with purity
For negative electrode, under these conditions anode electrolysis chlorination, i.e. it is prepared for Ag/Agcl electrode.The party's legal system
Standby Ag/Agcl electrode is to be electrolysed last layer Agcl layer on Ag surface, and mechanical strength is the highest.In group
In dress or experimentation if imprudence grazing, Agcl layer may will be rubbed off, and affects electrode
Stability, and electrolysis prepare Ag/Agcl electrode technique can by Anodic polarization current and electrolysis time
Between impact, the compactness causing Ag/Agcl electrolyte layers is different, thus has influence on stability.Silk screen
Printing technology: this technology is to use a semi-automatic printer, prints the most on a polyimide substrate
One layer of Ag ink, then prints one layer of Agcl layer, on Ag ink by Ag and Agcl layer at 120 DEG C
Dry 20min.Finally at electrolysis last layer overcoat ink, at 120 DEG C, dry 30min equally.The most just
It is prepared for Ag/Agcl electrode.This Technical comparing is new, sees, Technical comparing on the magazine of Japan
Complexity, the domestic exploitation not meeting this type of technology, it is not easy to prepare this electrode by the method, application
Aspect is not the most popularized.Pressed disc method: the method is that Ag and Agcl is blended in one according to a certain percentage
Rise, put into blender high speed stirring 120s, then weigh in the balance and take the powder of certain mass and put into mould
In tool, use tablet machine compressing, prepare Ag/Agcl electrode.The method is relatively easy, one day
More than 40 electrode can be pressed, but poor in terms of stability, and also tabletting only has 1/3-1/2 electricity every time
The most available, utilization rate is relatively low.The electrode that suppresses is follow-up also needs to welding lead or drilling and tapping even
Connect wire, waste time and energy.The limitation existed for said method and deficiency, it is desirable to provide utilization rate is high
Stabilized electrodes.
Summary of the invention
It is an object of the invention to provide a kind of Ag/Agcl work prepared and be applicable to monitor chlorine ion concentration
The method making electrode.
For achieving the above object, the technical solution used in the present invention is:
A kind of method preparing the Ag/Agcl working electrode being applicable to monitoring chlorine ion concentration,
By Ag powder that mass ratio is 9-10:1 and Agcl powder mix homogeneously, mix homogeneously is placed in mortar and fills
Point grind, during grinding, add cetomacrogol 1000, powder after being fully ground with successively through normal heptane and
Distilled water is rinsed, and then dries compacting and is Ag/Agcl electrode.
Described when suppressing Ag/Agcl electrode, directly silver wire is pressed in inside electrode.Specifically by powder
After end is put in mould, first filamentary silver line is penetrated (ommatidium diameter 0.5mm) in the ommatidium bottom depression bar,
Filamentary silver line ommatidium to be grown about about 2mm, then put into depression bar in mould to suppress and i.e. obtain with filamentary silver
The Ag/Agcl electrode of line.
After described mixing, powder is placed in agate mortar grinding 10-15min, then adds Polyethylene Glycol
1000 make Ag powder in mixed-powder and Agcl powder be uniformly dispersed.
After described grinding, powder is with being rinsed through normal heptane and distilled water successively, then 27 DEG C-45 DEG C low
Temperature lower drying compacting is Ag/Agcl electrode.
Preferably, by powder after grinding with being rinsed through normal heptane and distilled water successively, then 27-32 DEG C
Dry under low temperature, grind in mortar again after drying, after grinding under dark, stand-by.
Described normal heptane concentration is 0.1mol/L.
Advantage for present invention: the present invention has carried out uniform treatment to powder before tabletting, with
Guarantee electrode stability, and by filamentary silver line embedment powder in tableting processes, directly bear against electrode
The inside, very easy to use, it is to avoid loosening of welding lead or wasting time and energy of jewel hole.This
The working electrode of bright making both can guarantee that the stability of Ag/Agcl electrode, and utilization rate is close to 100%.
Accompanying drawing explanation
Ag/Agcl electrode OCP (OCP) figure that Fig. 1 provides for the embodiment of the present invention.
The Ag/Agcl electrode 30d potential value variation diagram that Fig. 2 provides for the embodiment of the present invention.
Detailed description of the invention
Embodiment 1
The preparation of electrode:
It is that 9:1 is uniform in stirrer for mixing in mass ratio by Ag powder and Agcl powder, puts into after mixing
Grinding 15min in agate mortar to be fully ground, grinding limit, limit adds cetomacrogol 1000, mixing
Ag powder and Agcl powder in powder are uniformly dispersed, to be ground complete after, powder is poured in beaker,
Normal heptane and distilled water with concentration is 0.1mol/L are rinsed successively, then dry, are put in dark place
Standby.
Taking in the pan paper that a small amount of above-mentioned powder is put on balance with spoon, weighing quality is 2g, by weighing well
Powder slowly pour in the duct of mould, filamentary silver line is penetrated in the ommatidium in depression bar (diameter is about
0.5mm) expose about 2mm length.Depression bar is put into mold tunnel, firmly extrudes depression bar with hands,
And rotate prevent powder be compacted in depression bar and space, duct after the demoulding difficult.Again mould is put into tabletting
On machine platform, manual turn screw rod, (mould is placed on platform to make mould and tablet machine press together
Central authorities, prevent eccentric force from being damaged by pressure by mould).Tighten fuel outlet valve, manually press depression bar pressurization, work as pressurization
Stop during to 10Mpa in 1min, be then pressurized to 20Mpa continuing, unclamp fuel outlet valve, mold removal,
Mould is taken apart, takes out electrode.If depression bar be cannot take out, it is placed on tablet machine, slowly adds
Pressure carries out the demoulding, and (all experiments are all to operate in darkroom, and spoon, beaker etc. are all through anhydrous second
Alcohol and distilled water flushing were also dried).Prepare 12 groups of electrodes the most again.
Application examples
The 13 groups of Ag/Agcl electrodes prepared by above-described embodiment carry out OCP (OCP) detection,
Specifically, using three-electrode system, working electrode is Ag/Agcl electrode, and reference electrode is saturated sweet
Mercury electrode, auxiliary electrode is platinized platinum (seeing Fig. 1).
It addition, above-mentioned 13 groups of electrodes are carried out electrode 30d potential value change detection, result sees Fig. 2.
13 groups of Ag/Agcl electrodes OCP in 10min as seen from Figure 1, all electrodes are at front 300s
Interior left and right is always held at after arithmetic point 6, has persistently observed 10min, and OCP is always at decimal
After Dian 5, have good stability.
During seen from 2, above-mentioned Ag/Agcl electrode is immersed in 0.1mol/L Nacl solution, test constantly
One month potential value variation diagram.Ag/Agcl electrode shows long-term stability, changes when 23d
Nacl solution, potential value fluctuation is relatively big, but in the lasting observation of 10d subsequently potential value one
Directly it is in steady statue, illustrates that electrode has good repeatability and stability.This electrode is at identical bar
Potential value in solution under part floats and within several days, is 2mv to the maximum in beginning, much smaller than limit in specification
10mv, after soaking 10d, two electrode potential values of 6d are always held at-43mv continuously, change molten
Liquid after-potential value is always held between-51mv, shows good repeatability, and same electrode maximum is floated
Moving as 0.5mv, Different electrodes maximum potential value in same one-shot measurement is floated as 0.1mv.
By experimental studies have found that, the present invention makes simple and convenient, and electrode stability and repeatability are good,
Utilization ratio is high.
Claims (4)
1. prepare the method being applicable to monitor the Ag/AgCl working electrode of chlorine ion concentration for one kind, it is characterized in that: by Ag powder that mass ratio is 9-10:1 and AgCl powder mix homogeneously, mix homogeneously is placed in mortar and is fully ground, cetomacrogol 1000 is added during grinding, powder after being fully ground is rinsed through normal heptane and distilled water successively, then dries compacting and is Ag/AgCl electrode；
When suppressing Ag/AgCl electrode, directly silver wire is pressed in inside electrode；
Powder after mixing is placed in agate mortar grinding 10-15min, adds cetomacrogol 1000 during grinding and make the Ag powder in mixed-powder and AgCl powder be uniformly dispersed.
2. the method that the preparation as described in claim 1 is applicable to monitor the Ag/AgCl working electrode of chlorine ion concentration, it is characterized in that: powder after grinding is rinsed through normal heptane and distilled water successively, then dry compacting under 27 DEG C of-45 DEG C of low temperature and be Ag/AgCl electrode.
3. the method that the preparation as described in claim 2 is applicable to monitor the Ag/AgCl working electrode of chlorine ion concentration, it is characterized in that: powder after grinding is rinsed through normal heptane and distilled water successively, then dry under 27-32 DEG C of low temperature, grind in mortar again after drying, after grinding under dark, stand-by.
4. the method that the preparation as described in claim 1 or 2 is applicable to monitor the Ag/AgCl working electrode of chlorine ion concentration, it is characterised in that: described normal heptane concentration is 0.1mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310624990.1A CN103604852B (en) | 2013-11-29 | 2013-11-29 | A kind of method preparing the Ag/Agcl working electrode being applicable to monitoring chlorine ion concentration |
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| CN201310624990.1A CN103604852B (en) | 2013-11-29 | 2013-11-29 | A kind of method preparing the Ag/Agcl working electrode being applicable to monitoring chlorine ion concentration |
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| CN103604852B true CN103604852B (en) | 2016-09-28 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103969306B (en) * | 2014-04-18 | 2016-08-24 | 中国科学院海洋研究所 | A kind of silver/silver chloride electrode being applicable to deep-sea and preparation method thereof |
| CN107271799A (en) * | 2017-06-02 | 2017-10-20 | 中国地质大学（武汉） | A kind of preparation method of the small solid electrode of extreme difference drift |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6690182B2 (en) * | 2000-07-19 | 2004-02-10 | Virginia Technologies, Inc | Embeddable corrosion monitoring-instrument for steel reinforced structures |
| CN1227524C (en) * | 2003-07-24 | 2005-11-16 | 中国科学院海洋研究所 | Full solid state reference electrode |
| CN101337687B (en) * | 2008-08-07 | 2010-09-08 | 中国人民解放军海军工程大学 | Process for preparing nano-grade AgCl powder by semisolid method |
| CN101726525B (en) * | 2009-12-10 | 2012-09-05 | 哈尔滨工业大学 | Embedded-type sensor for detecting concrete chloride ion content and preparation method thereof |
| CN102368059A (en) * | 2011-10-26 | 2012-03-07 | 天津大学 | Method for preparing reference electrode with Ag/AgCl solid powder |
| CN103192070B (en) * | 2013-04-17 | 2015-07-08 | 苏州格林泰克科技有限公司 | Silver/silver chloride electrode material, method for manufacturing same and electrode |
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