CN103792181A - Constant-current dissolution method for evaluating negative electrode protection performance of zinc-rich coating - Google Patents
Constant-current dissolution method for evaluating negative electrode protection performance of zinc-rich coating Download PDFInfo
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Abstract
The invention discloses a constant-current dissolution method for evaluating negative electrode protection performance of a zinc-rich coating. According to the constant-current dissolution method for evaluating negative electrode protection performance of the zinc-rich coating, active dissolution time is measured by recording change of electrode potential of a steel sheet electrode of the zinc-rich coating in a constant-current positive electrode dissolving process; the negative electrode protection performance of the zinc-rich coating is evaluated by using the active dissolution time; the active dissolution time is longer, the negative electrode protection performance of the coating is better. The method is strong in pertinence for evaluating the negative electrode protection performance of the zinc-rich coating without the aid of a coating zinc content requirement; the method can be used for reasonably forecasting the corrosion resistance of the zinc-rich coating; the method is quick in measurement; only less than a few hours are needed, so that the time is shorter than thousands of hours needed in salt spray test frequently and 2400 hours needed in an open circuit potential method frequently. Compared with a special device salt-fog cabinet, requirement on an operation space of an electrochemical workstation of a general device used in the method is greatly reduced; and corrosion and pollution to operation environment are avoided.
Description
Technical field
The present invention relates to a kind of continuous current dissolving method of evaluating zinc-rich coating cathodic protection performance, can be used for the corrosion stability of the various coatings that are rich in metal zinc such as fast prediction zinc rich paint coating, Dacromet/steel (also claiming zinc-chromium coating), chromium-free Dyclo coating (comprising Geomet, Delta and BNC aqueous chromium-free Aluminum Coating etc.).
Background technology
Common zinc-rich coating mainly contains zinc rich paint coating, Dacromet/steel and chromium-free Dyclo coating.In application, the main salt-fog test that adopts accelerated corrosion of corrosion stability check of these coatings.
According to the requirement of CNS HG/T3668-2009 " zinc rich primer ", what the corrosion stability check of zinc rich paint coating was adopted is cut salt-fog test method, by the regulation of CNS GB/T1771-2007 " mensuration of the resistance to neutral salt spray performance of paint and varnish ", the cut that standardized road is parallel to the long limit of test plate (panel) on test plate (panel) carries out salt-fog test.The standard SSPC-paint20 of protective coating association of the U.S., also stipulates in SSPC-paint29 and SSPC-paint30 by the corrosion stability of cut salt fog evaluation zinc rich paint coating.
According to the requirement of CNS GB18684-2002 " zinc-chromium coating technical conditions ", what the corrosion stability check of Dacromet/steel (zinc-chromium coating) adopted is salt-fog test, carries out salt-fog test by the regulation of CNS GB/T10125-1997 " artificial atmosphere corrosion test-salt-fog test ".
The corrosion stability check of chromium-free Dyclo coating there is no national standard, often adopt salt-fog test method the same as Dacromet/steel of its corrosion stability check.
The corrosion stability of check zinc-rich coating, cut salt mist experiment is than non-cut salt-fog test science, because cut salt fog can embody the cathodic protection performance of coating, cut salt fog can not.Be rich in the coating of metal zinc to the anti-corrosion protection of steel substrate; except there being the shielding protection of general coating to also have special cathodic protection;; under corrosive medium exists; coating is as anode; matrix becomes negative electrode and obtains electrochemical protection, and cathodic protection performance is the important performance of zinc-rich coating, while evaluating zinc-rich coating corrosion stability, must pay attention to its cathodic protection performance.Non-cut salt-fog test, do not check the cathodic protection effect of coating---the coating that-Nai Fei cut salt fog time is long, not necessarily cathodic protection effect is strong.Such as, the coating salt spray resistance for a long time of simple shielding, and it does not have cathodic protection effect.For another example, the good Dacromet/steel of salt spray resistance, after the damage of colliding with in actual applications, matrix is easy to corrosion, and its cathodic protection performance is strong not as seen.And cut salt fog can be checked cathodic protection performance, because iron-based body has been exposed at cut place, there is no screen layer, the iron-based body at cut place must lean on coating around to provide electrochemical protection could not go out red rust.
The corrosion stability of zinc rich paint coating is up to standard, not only will meet salt-fog test requirement, also will meet zinc content requirement.In the standard SSPC-paint29 of CNS HG/T3668-2009 and protective coating association of the U.S., all stipulated the zinc content in zinc rich paint coating, this has also reflected from a side that salt-fog test is for checking zinc rich paint corrosion resistance coating reliable not.About zinc content, while having stipulated different film forming matter in the standard SSPC-paint29 of protective coating association of the U.S., require different, in CNS HG/T3668-2009, inorganic and organic binder are not treated with a certain discrimination, and, in Sino-U.S.'s standard, be also different to the required value of zinc content, in document to the requirement of zinc content higher than the requirement in Sino-U.S.'s standard, more than reaching 90wt%.And also there are some researches show: the key factor that affects really zinc rich paint corrosion resistance coating of zinc content, but be not unique key factor; Its corrosion stability of coating that zinc content is high may not be certain than low strong of zinc content; Regulation about zinc content is not suitable for zinc flake.The subsidiary conditions visible, zinc content requires as salt-fog resistant test, not only on numerical value, opinions vary, also scientific and reasonable not.
In addition, no matter whether cut to be, and salt-fog test all exists such shortcoming: need specialized equipment salt fog cabinet and air compressor machine, when salt-fog test easily corrosion peripheral facility, have noise pollution, proving time is longer, generally needs hundreds of to arrive thousands of hours.
In practical study; evaluate the corrosion stability of zinc-rich coating; except adopting salt-fog test; also generally adopt open circuit potential method (open circuit potential is called for short OCP); this method for be the cathodic protection performance of coating, simple to operate, only the steel sample that has applied zinc rich paint need be immersed in salt solution; regularly survey open circuit potential, use instrument also only to need to survey the instrument of electrode potential.But this method is consuming time longer than salt-fog test, often need 2400 hours.
There is following problem in the check extensively adopting at present in sum, and the corrosion proof method of evaluation zinc-rich coating: non-cut salt fog can not be checked the cathodic protection performance of zinc-rich coating; Although cut salt-fog test and open circuit potential method can be checked the cathodic protection performance of zinc-rich coating, consuming time very long; The corrosion stability of zinc rich paint coating is up to standard, except meeting the requirement of cut salt-fog test, also will meet zinc content requirement; And salt-fog test needs specialized equipment salt fog cabinet and air compressor machine, when test, easily corrode peripheral facility and have noise pollution.
Summary of the invention
In order to overcome salt-fog test method and open circuit potential method test evaluation zinc-rich coating corrosion stability long, non-cut salt fog consuming time can not check cathodic protection performance, cut salt-fog test need to be aided with the deficiencies such as zinc-content determination; the invention provides a kind of method of the cathodic protection performance of zinc-rich coating being carried out to Fast Evaluation, for predicting the corrosion stability of zinc rich paint coating, Dacromet/steel and chromium-free Dyclo coating.
The cathodic protection effect of considering zinc-rich coating is similar to sacrificial anode (kirsite, aluminium alloy and the magnesium alloy that are directly connected with protected steel product by wire), has designed the continuous current dissolution method for zinc-rich coating with reference to CNS GB/T17848-1999 " sacrificial anode electrochemical performance test method ".
In order to solve the technical matters of above-mentioned existence, the present invention is achieved by the following technical solutions:
Evaluate a continuous current dissolving method for zinc-rich coating cathodic protection performance, the test unit that the method relates to and the instrument three-electrode system including Electrode, auxiliary electrode and contrast electrode, thermostat water bath, electrolytic cell and electrochemical workstation;
The method content comprises the steps:
Before first step check, prepare
Electrode is the steel disc that has encapsulated and applied zinc-rich coating, and working area is fixed;
Auxiliary electrode adopts inert electrode, and the working area of Electrode is fixed and be greater than to working area;
Contrast electrode adopts saturated calomel electrode, silver silver chloride electrode etc. to be applicable to the electrode of Neutral Chloride ionic system;
Electrolytic cell material is unorganic glass, and size is appropriate to keep electrolytic solution to stabilize in course of dissolution, and electrolytic solution adopts 3.5% NaCl solution;
Second step starts check
The electrolytic solution the parallel electrolytic cell both sides that are placed on that Electrode and auxiliary electrode are placed in to electrolytic cell, working area is relative, and distance is as far as possible far away, and contrast electrode is put near Electrode;
Test condition and parameter setting: controlling electrolyte temperature is 40 ℃, by the galvanostatic method on electrochemical workstation, records the potential change of Electrode in continuous current anodic dissolution processes; Design parameter arranges as follows: anodic current density can be fixed as 1mA/cm
2, 0.5mA/cm
2or 0.1mA/cm
2deng; Electrolysis time can be made as 6000s, 36000s, and 72000s etc., sampling interval can be made as 30s, 60s, 120s, 240s etc., test stops the electrode potential that this value of current potential-0.75VvsSCE(is dissolved for iron matrix); Before test starts, Electrode fully soaks until its open circuit potential drops to minimum in 3.5% NaCl solution;
The 3rd step evaluation test result
Data processing method: electrode potential-time curve is divided into different two sections of slope, early stage, the stage of platform is born and approached to current potential, there is zinc solubilizing reaction, be referred to as the active dissolution stage, later stage electrode potential sharply becomes the positive stage and is referred to as the anode polarization stage, after fast anode polarization, dissolved ferric iron reaction can occur; The reading platform duration from electrode potential-time plot, be designated as active dissolution duration; The cathodic protection performance of evaluating zinc-rich coating with active dissolution duration, active dissolution duration is longer, and the cathodic protection performance of coating is better.
Active dissolution duration is measured in the variation that the present invention has applied steel disc electrode electrode potential in continuous current anodic dissolution processes of zinc-rich coating by record; evaluate the cathodic protection performance of zinc-rich coating with active dissolution duration; active dissolution duration is longer, and the cathodic protection performance of coating is better.
Owing to adopting technique scheme, the present invention compared with prior art its beneficial effect is:
The first, it is with strong points that the inventive method is used for evaluating the cathodic protection performance of zinc-rich coating, without being aided with coating zinc content requirement.Zinc-rich coating belongs to the combination product of coating and sacrificial anode.Existing zinc-rich coating corrosion stability method of testing; no matter being that cut salt-fog test is also non-cut salt-fog test, is all the coating corrosion stability method of testing of using for reference, and the present invention uses for reference the chemical property detection method of sacrificial anode; the cathodic protection performance of emphasizing coating, specific aim is stronger.；
The second, the inventive method can be used for the corrosion stability of reasonable prediction zinc-rich coating.Zinc-rich coating avoids corrosion by cathodic protection effect and shielding action protection steel substrate, and its corrosion protection process is divided into cathodic protection stage and shielding protection stage subsequently.The coating that cathodic protection performance is strong, the shielding protection performance that the hole of the product filling coating that zinc dissolves causes is also strong.So, predict that with cathodic protection Evaluation results total corrosion stability of zinc-rich coating is rational.
The 3rd, the inventive method is measured fast, long several hours, and short a few minutes can test.Often need within thousands of hours, often need to compare for 2400 hours with open circuit potential method with salt-fog test, greatly shortened the test duration, improved the efficiency of coating performance check and exploratory development work;
The 4th, the common apparatus electrochemical workstation that the present invention adopts, compared with specialized equipment salt fog cabinet, reduces greatly to the requirement of operating space, has avoided corrosion and pollution to operating environment.
Embodiment
Below in conjunction with embodiment, the inventive method is described in further detail:
A continuous current dissolving method of evaluating zinc-rich coating cathodic protection performance, test unit comprises LK2005 electrochemical workstation, electrolytic cell, three-electrode system and thermostat water bath.Also can be with direct supply, can tune up resistance, reometer, voltage table and voltameter replaces electrochemical workstation to realize the function of constant current, recording voltage and time.
Electrode is epoxy packages the Q235 steel disc that has sprayed zinc rich paint coating, working area 3cm
2; Auxiliary electrode adopts graphite cake, and working area is 25cm
2; Contrast electrode adopts saturated calomel electrode; Electrolytic cell material is unorganic glass, is of a size of 15cm*30cm*20cm; Electrolytic solution adopts 3.5% NaCl solution.Electrode and auxiliary electrode are placed on electrolytic cell both sides and are immersed in completely in electrolytic solution, and distance is approximately 30cm, and contrast electrode is put near Electrode.
Electrode preparation method: the 1. PVC long tube of diameter 32mm is cut into the long segment in 1cm left and right.Segment saw kerf place is polished to (attenuating successively with three kinds of sand paper) with sand paper, then water washes away dust by pvc pipe segment and is dried up with hair-dryer.2. steel disc be cut into the length of side and be the square of 1.73cm and pound flat with hammer.3. wire be cut into 10cm length and expose the copper cash of 1.5cm left and right at wire two ends.4. with sand paper, the steel disc polishing shearing is removed to surperficial rust, and remove dust by alcohol wipe.One end of wire is soldered in the one side of steel disc with electric soldering iron.5. with adhesive tape, pvc pipe segment one end is shut.6. will stick on adhesive tape with the steel disc of wire, then keep flat on the table.7. preparation gasket coating, according to quality than epoxy resin E-44: this step of ethylenediamine=4: 0.75(should be done because ethylenediamine has pungent smell in fuming cupboard), be stirred to evenly.8. gasket coating is poured in pvc pipe, do not had exposed wire.Leave standstill and within one day, treat above that it solidifies.9. after being cured, the adhesive tape of sealing use is removed, the glue of electrode surface remnants removes by wipes of alcohol, and base electrode has prepared.10. require the pre-treatment of steel disc electrode, application and solidify according to coating application, controlling coating thickness is 60 microns ± 5 microns, and Electrode has prepared.
Test condition and parameter: controlling electrolyte temperature is 40 ℃, with the control current electroanalysis coulometry in galvanostatic technique.Design parameter arranges as follows: anodic current density 1mA/cm
2, electrolysis time 36000s, sampling interval 120s, test stops current potential-0.75v.Before test starts, Electrode fully soaks until its open circuit potential drops to minimum in 3.5% NaCl solution.
Data processing method: electrode potential-time curve is divided into different two sections of slope, early stage, the stage of platform is born and approached to current potential, there is zinc solubilizing reaction, be referred to as the active dissolution stage, later stage electrode potential sharply becomes the positive stage and is referred to as the anode polarization stage, after fast anode polarization, dissolved ferric iron reaction can occur.The reading platform duration from electrode potential-time diagram, be designated as active dissolution duration.The cathodic protection performance of evaluating zinc-rich coating with active dissolution duration, active dissolution duration is longer, and the cathodic protection performance of coating is better.
Claims (1)
1. evaluate a continuous current dissolving method for zinc-rich coating cathodic protection performance, the test unit that the method relates to and the instrument three-electrode system including Electrode, auxiliary electrode and contrast electrode, thermostat water bath, electrolytic cell and electrochemical workstation;
It is characterized in that: the method content comprises the steps:
Before first step check, prepare
Electrode is the steel disc that has encapsulated and applied zinc-rich coating, and working area is fixed;
Auxiliary electrode adopts inert electrode, and the working area of Electrode is fixed and be greater than to working area;
Contrast electrode adopts saturated calomel electrode, silver silver chloride electrode etc. to be applicable to the electrode of Neutral Chloride ionic system;
Electrolytic cell material is unorganic glass, and size is appropriate to keep electrolytic solution to stabilize in course of dissolution, and electrolytic solution adopts 3.5% NaCl solution;
Second step starts check
The electrolytic solution the parallel electrolytic cell both sides that are placed on that Electrode and auxiliary electrode are placed in to electrolytic cell, working area is relative, and distance is as far as possible far away, and contrast electrode is put near Electrode;
Test condition and parameter setting: controlling electrolyte temperature is 40 ℃, by the galvanostatic method on electrochemical workstation, records the potential change of Electrode in continuous current anodic dissolution processes; Design parameter arranges as follows: anodic current density can be fixed as 1mA/cm
2, 0.5mA/cm
2or 0.1mA/cm
2deng; Electrolysis time can be made as 6000s, 36000s, and 72000s etc., sampling interval can be made as 30s, 60s, 120s, 240s etc., test stops the electrode potential that this value of current potential-0.75VvsSCE(is dissolved for iron matrix); Before test starts, Electrode fully soaks until its open circuit potential drops to minimum in 3.5% NaCl solution;
The 3rd step evaluation test result
Data processing method: electrode potential-time curve is divided into different two sections of slope, early stage, the stage of platform is born and approached to current potential, there is zinc solubilizing reaction, be referred to as the active dissolution stage, later stage electrode potential sharply becomes the positive stage and is referred to as the anode polarization stage, after fast anode polarization, dissolved ferric iron reaction can occur; The reading platform duration from electrode potential-time plot, be designated as active dissolution duration; The cathodic protection performance of evaluating zinc-rich coating with active dissolution duration, active dissolution duration is longer, and the cathodic protection performance of coating is better.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502263A (en) * | 2014-12-16 | 2015-04-08 | 哈尔滨工业大学 | Anode material acceleration test device and anode material service life prediction method for corrosion control of steel-concrete structure cathode |
| CN105241806A (en) * | 2014-06-19 | 2016-01-13 | 上海梅山钢铁股份有限公司 | Quick evaluation test method of anti-corrosion performance of tin-plated board |
| CN113514528A (en) * | 2021-03-10 | 2021-10-19 | 首钢集团有限公司 | Method for measuring compactness of hot-dip galvanized sheet inhibition layer |
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| CN113514528B (en) * | 2021-03-10 | 2024-05-10 | 首钢集团有限公司 | Method for measuring compactness of inhibition layer of hot dip galvanized sheet |
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Application publication date: 20140514 |