CN104532266B - Corrosion resistant water electrolysis polar board surface processing method - Google Patents
Corrosion resistant water electrolysis polar board surface processing method Download PDFInfo
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- CN104532266B CN104532266B CN201410813984.5A CN201410813984A CN104532266B CN 104532266 B CN104532266 B CN 104532266B CN 201410813984 A CN201410813984 A CN 201410813984A CN 104532266 B CN104532266 B CN 104532266B
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Abstract
The present invention relates to a kind of corrosion resistant water electrolysis polar board surface processing method, specific steps include：A. the polar board surface of carbon steel material is cleaned；B. pole plate is immersed in the acid etching solution that temperature is 50 DEG C, acid corrosion is carried out to polar board surface；C. pole plate is immersed in the copper ion solution that temperature is 40 DEG C, with copper ion displacement reaction occurs for iron；D. pole plate is immersed in the caustic corrosion solution that temperature is 35 DEG C, caustic corrosion is carried out to polar board surface；The caustic corrosion solution is mixed by the sodium hydroxide solution of 10g/L and the sodium nitrate solution of 30g/L；E. pole plate is put into the strong acid solution that temperature is 40 DEG C and stirred, remove the impurity of polar board surface；F. pole plate is immersed in 25 DEG C for the treatment of fluid, is rinsed and dried with clear water after taking-up；Polar board surface forms corrosion-resisting protective film.
Description
The application is divisional application, the invention and created name of original application：Water electrolysis polar board surface processing method, application number：
201210538399.X the applying date：2012-12-13.
Technical field
Corrosion treatment is carried out the present invention relates to a kind of surface to carbon steel pole plate and forms the process of protective film, is belonged to
Field of metal surface treatment technology.
Background technology
Water electrolysis is that water is made to decomposite hydrogen or oxygen under the action of direct current.Electrolytic cell is in a whole set of water electrolysis equipment
One of its most crucial device.Industrial common water electrolyser presses rule by dozens of to a electrolytic chamber up to a hundred as needed
Laminate composition.Each electrolytic chamber is by anode plate, oxygen catalysis electrode, choke membrane, insulated enclosure gasket, hydrogen catalysis electrode, the moon
The compositions such as pole plate.Anode plate and cathode plate generally use carbon steel steel plate is made.
Since the electrolyte of Strong acidic electrolyte composition has strong corrosivity to metal, so the electrolyte of electrolytic cell
It is general use concentration for 25% to 30% potassium hydroxide or sodium hydroxide solution.Under the action of electric field, potassium ion or sodium ion
It is moved to cathode, hydroxide ion is moved to anode, so as to which hydrogen and oxygen be precipitated.In order to reduce overpotential, reduce electric energy and disappear
Consumption, the operating temperature of electrolytic cell are generally 85 DEG C to 90 DEG C.Such alkali concn and temperature easily cause alkaline etching to carbon steel steel plate,
So preservative treatment must be carried out to anode plate and cathode plate.Since the caustic corrosion resistance performance of pure nickel is very excellent, at present, water electrolysis
Cathode-anode plate of the carbon steel steel plate of industry generally use nickel plating as water electrolyser.
It is shown according to result of study, since the carbon steel pole plate of nickel plating actually and can not possibly be plated nickel layer and be completely coated with,
Inevitably there is micropore on nickel coating.When in the electrolyte that pole plate is in harmful ion formation, these harmful ions can
It into the micropore of nickel coating, and is enriched in micropore, hydrolysis occurs with iron ion, formed the extremely strong acid of corrosivity, hold
It is continuous that pole plate is corroded.Further, since nickel coating is a kind of coating of cathodic, the standard electrode potential of nickel is -0.25V,
The standard electrode potential of iron is -0.44V, and nickel coating can form a pair of of galvanic couple with plain steel, when they are simultaneously exposed to electrolysis
Electrochemical reaction will occur in liquid.Iron in micropore is anode, loses electronics and is dissolved；Nickel outside is cathode, is obtained
Electronics, and water electrolysis is released into hydrogen.It follows that the possibility pole being corroded using nickel plating carbon steel pole plate made of general technology
Greatly.Once serious corrosion, which occurs, in pole plate can cause hydrogen or oxygen gas mutually to be gone here and there, leak alkali and electric short circuit, it is more likely that it sets off an explosion,
Threat personnel and the safety of equipment.
The content of the invention
The technical problem to be solved by the present invention is to propose that a kind of surface to carbon steel pole plate carries out corrosion treatment and forms guarantor
Cuticula can effectively improve the water electrolysis polar board surface processing method of the corrosion resistance after pole plate nickel plating.
The technical solution that its is proposed to solve above-mentioned technical problem of the present invention is：A kind of water electrolysis polar board surface processing method,
Comprise the following steps：
A. the polar board surface of carbon steel material is cleaned；
B. pole plate is immersed in 5min to 15min in acid etching solution, acid corrosion, the acid corrosion is carried out to polar board surface
The ingredient of solution is the nitric acid of 8wt% to 15wt%, and the ethanedioic acid of 2wt% to 8wt%, remaining is water；
C. pole plate is immersed in 3min to 8min in copper ion solution, with copper ion displacement reaction occurs for iron；
D. pole plate is immersed in 5min to 15min in caustic corrosion solution, caustic corrosion, the caustic corrosion is carried out to polar board surface
Solution is mixed by the sodium hydroxide solution of 10g/L to 30g/L and the sodium nitrate solution of 10g/L to 30g/L；
E. pole plate is put into strong acid solution of the concentration more than or equal to 30%, removes the impurity of polar board surface；
F. pole plate is immersed in 10min to 20min in treatment fluid, protective film is formed in polar board surface, the treatment fluid
Ingredient be 5wt% to 12wt% complexon I, the complexing agent of 0.5wt% to 3wt%, the corrosion inhibiter of 0.2wt% to 2wt%,
The surfactant of 0.1wt% to 0.5wt, the pH adjusting agent of 0.02wt% to 2wt%, remaining is water；The pH value of the treatment fluid is
3 to 6.
Above-mentioned complexing agent is the one or more in sodium citrate, sodium lactate, natrium malicum.
Above-mentioned corrosion inhibiter is the one or more in benzotriazole, potassium iodide, methylbenzotrazole.
Above-mentioned surfactant is one kind in lauryl sodium sulfate, neopelex or n-octyl sodium sulphate
It is or a variety of.
Above-mentioned pH adjusting agent is one or both of triethanolamine, triethylamine.
Above-mentioned copper ion solution is the copper-bath or copper chloride solution of 150mg/L to 500mg/L.
Above-mentioned strong acid solution is salpeter solution, hydrochloric acid solution or the sulfuric acid solution that temperature is 25 DEG C to 50 DEG C.
The temperature of above-mentioned acid etching solution is 40 DEG C to 60 DEG C, and the temperature of the copper ion solution is 30 DEG C to 45 DEG C, institute
The temperature for stating caustic corrosion solution is 30 DEG C to 45 DEG C.
The temperature of above-mentioned treatment fluid is 25 DEG C to 45 DEG C, and pole plate is rinsed and dried with clear water after being taken out from treatment fluid, is dried
Dry temperature is 80 DEG C to 150 DEG C.
The present invention has positive effect：The water electrolysis polar board surface processing method of the present invention is that first pole plate is corroded
Processing, then protective film is formed in polar board surface, corrosion treatment causes the tiny micropore of the Surface Creation of pole plate, and surface becomes thick
It is rough, be conducive to protective film and be preferably compounded on pole plate.During corrosion treatment, it is micro- in polar board surface generation first to carry out sour corrosion
Hole, then carry out alkaline corrosion and more tiny micropore is generated in polar board surface and micropore, so that micropore is located at deeper
Position, it is weaker to occur the partial alkaline corrosive effect of displacement reaction, so that the distribution of micropore is more scattered, is conducive to increase
Overstriking rugosity improves the composite effect of protective film.Treatment fluid is using complexon I as main component, with complexing agent, inhibition
Agent, surfactant can form fine and close protective film on the surface of pole plate, be effectively isolated iron and nickel plating as auxiliary element
Layer contact effectively promotes the corrosion resistance of pole plate.Complexon I is made two by respective oxygen and nitrogen by three carboxyls and is matched somebody with somebody
Position to four-coordination can form complex compound with iron ion, and sequestering power is extremely strong；Adding in complexing agent and corrosion inhibiter can further carry
The corrosion resistance of high protective film, the surface tension that addition surfactant can significantly improve protective film cause pole plate protective film more
Add densification.Do not use passivator in the treatment fluid of the present invention, not too much using complexing agent, corrosion inhibiter, but it is a large amount of using into
This cheap complexon I can substantially reduce production cost on the premise of quality of forming film is ensured, widely should have
Use prospect.
Specific embodiment
Embodiment 1
The water electrolysis polar board surface processing method of the present embodiment, is as follows：
A. the polar board surface of carbon steel material is cleaned：Successively by oil removing, washing, pickling process, pole will be attached to
The removings such as greasy dirt, dust, the corrosion of plate surface.
B. acid corrosion processing is carried out to polar board surface.Pole plate is immersed in 10min in the acid etching solution that temperature is 60 DEG C,
So that polar board surface is tentatively corroded, small pit is formed, the diameter of pit is less than 10 μm.The ingredient of the acid etching solution
For the nitric acid of 10wt%, the ethanedioic acid of 5wt%, remaining is water.
C. ion exchange processing is carried out to polar board surface.Pole plate is immersed in the copper ion solution that temperature is 40 DEG C
5min so that with copper ion displacement reaction occurs for the part iron in polar board surface and pit, and copper is precipitated.The copper ion solution is
The copper-bath of 250mg/L.
D. caustic corrosion processing is carried out to polar board surface.Pole plate is immersed in 10min in the caustic corrosion solution that temperature is 30 DEG C,
So that more more tiny pits are formed in polar board surface and pit.The caustic corrosion solution by 20g/L sodium hydroxide solution
It is mixed with the sodium nitrate solution of 20g/L.
E. de-sludging processing is carried out to polar board surface.Pole plate is put into the strong acid solution of room temperature and stirred, remove pole plate
The impurity on surface, is then rinsed with clear water.The strong acid solution is the salpeter solution that concentration is 30%.
F., pole plate is immersed to 15min in 40 DEG C for the treatment of fluid, is rinsed and is dried with clear water after taking-up, drying temperature 90
℃.Polar board surface forms corrosion-resisting protective film.The ingredient of the treatment fluid is：The complexon I of 10wt%, the lemon of 3wt%
Sour sodium, the benzotriazole of 1wt%, the lauryl sodium sulfate of 0.3wt%, remaining is water, and it is 3 to adjust pH value with triethanolamine.
Embodiment 2
The water electrolysis polar board surface processing method of the present embodiment, is as follows：
A. the polar board surface of carbon steel material is cleaned：Successively by oil removing, washing, pickling process, pole will be attached to
The removings such as greasy dirt, dust, the corrosion of plate surface.
B. acid corrosion processing is carried out to polar board surface.Pole plate is immersed in 15min in the acid etching solution that temperature is 50 DEG C.
The ingredient of the pre-etching solution is the nitric acid of 8wt%, and the ethanedioic acid of 8wt%, remaining is water.
C. ion exchange processing is carried out to polar board surface.Pole plate is immersed in the copper ion solution that temperature is 40 DEG C
8min so that with copper ion displacement reaction occurs for the part iron in polar board surface and pit, and copper is precipitated.The copper ion solution is
The copper-bath of 200mg/L.
D. caustic corrosion processing is carried out to polar board surface.Pole plate is immersed in 5min in the caustic corrosion solution that temperature is 35 DEG C,
So that more more tiny pits are formed in polar board surface and pit.The caustic corrosion solution by 10g/L sodium hydroxide solution
It is mixed with the sodium nitrate solution of 30g/L.
E. de-sludging processing is carried out to polar board surface.Pole plate is put into the strong acid solution that temperature is 40 DEG C and is stirred, is gone
Except the impurity of polar board surface, then it is rinsed with clear water.The strong acid solution is the hydrochloric acid solution that concentration is 40%.
F., pole plate is immersed to 20min in 25 DEG C for the treatment of fluid, is rinsed and is dried with clear water after taking-up, drying temperature 80
℃.Polar board surface forms corrosion-resisting protective film.The ingredient of the treatment fluid is：The complexon I of 8wt%, the lactic acid of 1wt%
Sodium, the potassium iodide of 0.5wt%, the neopelex of 0.2wt%, remaining is water, and it is 4.5 to adjust pH value with triethylamine.
Embodiment 3
The water electrolysis polar board surface processing method of the present embodiment, is as follows：
A. the polar board surface of carbon steel material is cleaned：Successively by oil removing, washing, pickling process, pole will be attached to
The removings such as greasy dirt, dust, the corrosion of plate surface.
B. acid corrosion processing is carried out to polar board surface.Pole plate is immersed in 8min in the acid etching solution that temperature is 55 DEG C.
The ingredient of the pre-etching solution is the nitric acid of 15wt%, and the ethanedioic acid of 3wt%, remaining is water.
C. ion exchange processing is carried out to polar board surface.Pole plate is immersed in the copper ion solution that temperature is 40 DEG C
5min so that with copper ion displacement reaction occurs for the part iron in polar board surface and pit, and copper is precipitated.The solion is
The copper chloride solution of 300mg/L.
D. caustic corrosion processing is carried out to polar board surface.Pole plate is immersed in 8min in the caustic corrosion solution that temperature is 40 DEG C,
So that more more tiny pits are formed in polar board surface and pit.The caustic corrosion solution by 30g/L sodium hydroxide solution
It is mixed with the sodium nitrate solution of 15g/L.
E. de-sludging processing is carried out to polar board surface.Pole plate is put into the strong acid solution of room temperature and stirred, remove pole plate
The impurity on surface, is then rinsed with clear water.The strong acid solution is the salpeter solution that concentration is 40%.
F., pole plate is immersed to 12min in 35 DEG C for the treatment of fluid, is rinsed and is dried with clear water after taking-up, drying temperature 120
℃.Polar board surface forms corrosion-resisting protective film.The ingredient of the treatment fluid is：The complexon I of 12wt%, the apple of 2wt%
Sour sodium, the methylbenzotrazole of 0.5wt%, the n-octyl sodium sulphate of 0.2wt%, remaining is water, and adjusting pH value with triethanolamine is
4。
Nickel plating is carried out using common process to the pole plate of the water electrolysis polar board surface processing method Jing Guo embodiment 1 to 3, so
After carry out salt spray test.Sample is put into salt spray test chamber, using 5% NaCl solution, humidity 70%, temperature is 50 DEG C,
Persistently spray 8h daily, and continuous 10 days, polar board surface was without apparent corrosion phenomenon.
Claims (1)
1. a kind of water electrolysis polar board surface processing method, comprises the following steps：
A. the polar board surface of carbon steel material is cleaned；
B. pole plate is immersed in 5min to 15min in acid etching solution, acid corrosion is carried out to polar board surface, the acid corrosion is molten
The ingredient of liquid is the nitric acid of 8wt% to 15wt%, and the ethanedioic acid of 2wt% to 8wt%, remaining is water；
C. pole plate is immersed in 3min to 8min in copper ion solution, with copper ion displacement reaction occurs for iron；
D. pole plate is immersed in 5min to 15min in caustic corrosion solution, caustic corrosion is carried out to polar board surface, the caustic corrosion is molten
Liquid is mixed by the sodium hydroxide solution of 10g/L to 30g/L and the sodium nitrate solution of 10g/L to 30g/L；
E. pole plate is put into strong acid solution of the concentration more than or equal to 30%, removes the impurity of polar board surface；
F. pole plate is immersed in 10min to 20min in treatment fluid, protective film, the ingredient of the treatment fluid is formed in polar board surface
For the complexon I of 5wt% to 12wt%, the complexing agent of 0.5wt% to 3wt%, the corrosion inhibiter of 0.2wt% to 2wt%,
The surfactant of 0.1wt% to 0.5wt, the pH conditioning agents of 0.02wt% to 2wt%, remaining is water；The treatment fluid
PH value is 3 to 6；
The complexing agent is sodium citrate；The corrosion inhibiter is benzotriazole；
The surfactant is lauryl sodium sulfate；The pH conditioning agents are triethanolamines.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410813984.5A CN104532266B (en) | 2012-12-13 | 2012-12-13 | Corrosion resistant water electrolysis polar board surface processing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410813984.5A CN104532266B (en) | 2012-12-13 | 2012-12-13 | Corrosion resistant water electrolysis polar board surface processing method |
| CN201210538399.XA CN103088350B (en) | 2012-12-13 | 2012-12-13 | Water electrolysis pole plate surface treatment method |
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| CN201210538399.XA Division CN103088350B (en) | 2012-12-13 | 2012-12-13 | Water electrolysis pole plate surface treatment method |
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| CN104532266B true CN104532266B (en) | 2018-06-05 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793425A (en) * | 2005-12-30 | 2006-06-28 | 东北大学 | Process for compound surface sheilding of metal magnesium and magnesium alloy |
| CN102021552A (en) * | 2009-09-21 | 2011-04-20 | 邵阳市创捷化工有限公司 | Modifier for black metal surface matrix and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793425A (en) * | 2005-12-30 | 2006-06-28 | 东北大学 | Process for compound surface sheilding of metal magnesium and magnesium alloy |
| CN102021552A (en) * | 2009-09-21 | 2011-04-20 | 邵阳市创捷化工有限公司 | Modifier for black metal surface matrix and production method thereof |
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Effective date of registration: 20180507 Address after: 528400 Guangdong, Zhongshan Delta town Xinhua Road 6 base two phase 5 floor B513, 515 room Applicant after: Zhongshan Mei Lun Chemical Co., Ltd. Address before: 213022 26-, Ding -701, long Jin Road, Xinbei District, Changzhou, Jiangsu. Applicant before: Wu Xiaozai |
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