CN1542431A - Method for accelerating corrosion test in air corrosion course simulation - Google Patents
Method for accelerating corrosion test in air corrosion course simulation Download PDFInfo
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- CN1542431A CN1542431A CNA031115896A CN03111589A CN1542431A CN 1542431 A CN1542431 A CN 1542431A CN A031115896 A CNA031115896 A CN A031115896A CN 03111589 A CN03111589 A CN 03111589A CN 1542431 A CN1542431 A CN 1542431A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 110
- 238000005260 corrosion Methods 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000012360 testing method Methods 0.000 title description 83
- 238000004088 simulation Methods 0.000 title description 18
- 238000010998 test method Methods 0.000 claims abstract description 21
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 abstract description 26
- 229910000831 Steel Inorganic materials 0.000 abstract description 15
- 239000010959 steel Substances 0.000 abstract description 15
- 238000011160 research Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 abstract description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract 1
- 230000004580 weight loss Effects 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003653 coastal water Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
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- 230000003028 elevating effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- -1 goods Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
The present invention relates to atmosphere corrosion simulating technology, and is especially one corrosion speeding test method via simulating atmosphere corrosion. The dipping solution including NaHSO3 of 0.01-0.05 mol/L concentration and NaCl in 0.001-0.005 mol/L concentration is used in the dipping-drying-moistening circulation of 10-30 min each, with the dipping being at 40-50 deg.c for 1-4 min, the drying at 50-60 deg.c for 8-22 min and the moistening at 40-50 deg.c for 1-4 min. The method has fast speed and high repeatability in simulating the atmosphere corrosion in industrial city, and may be used in research of atmosphere corrosion regularity of steel in said environment as well as the research of atmosphere corrosion of steel and corrosion resistance evaluation of various kinds of steel material.
Description
Technical field
The present invention relates to the analogue technique of atmospheric corrosion, be specially a kind of accelerated corrosion test method of simulating the atmospheric corrosion process.
Background technology
Exposure experiment under the physical environment is the most frequently used test method of research atmospheric corrosion, and it can truly reflect the corrosion condition of site, calculates the corrosion rate of material under this environment with this, can be the engineering corrosion-resistant design design considerations reliably rationally is provided.But, because the weather exposure test cycle is very long, pilot region is strong, impel people to carry out simulation accelerated investigation corrosion, in the hope of infer the result of outdoor long term exposure test by the laboratory accelerated corrosion test, and then the atmospheric corrosion life-span of prediction material, goods, protective layer, replace the atmospheric corrosion exposure test with part.The lab simulation accelerated corrosion test must satisfy simulation, acceleration and three pacing itemss of reappearance, and it directly has influence on the result of artificial accelerated test and natural exposure test result's correlativity.
The factor that influences atmospheric corrosion is a lot, mainly contains Atmospheric components, humidity, temperature etc.Wherein the effect of atmosphere pollution is the most outstanding, and under the close situation of meteorological condition, the pollutant difference can cause material corrosion speed to differ tens of times, as villaumite and SO
2Distribution material corrosion is had very big influence.For simulating various natural environment corrosion, the main at present indoor accelerated test of using has:
(1) damp heat test method
Damp heat test method is divided into two kinds of steady-state damp heat test and cyclic damp heat tests.It is to make specimen surface aggegation moisture under high temperature, super-humid conditions, with the reinforcement corrosion environment, thereby quickens the corrosion of sample.Also adopt the condensation corrosion test in order further to quicken atmospheric corrosion, it also is to carry out in the chamber of high temperature, high humidity, different is logical recirculated cooling water in the test piece frame, make its temperature be lower than atmosphere on every side, steam is easier like this condenses in test piece, and the quickening corrosion, the test period is shorter than damp heat test.Above-mentioned two kinds of damp heat test aggegations usually are the globules not of uniform size the test piece surface, and they can not aggegation and trickling, can not form the stabilized uniform moisture film, and simulation is relatively poor.
(2) salt-fog test
The salt-fog test method proposed and was used for corrosion test early than 1914, and purpose is in order to simulate the atmospheric corrosion condition in ocean, coastal waters.ASTM has formally formulated three kinds of salt-fog test standards in 1962: neutral salt spray test, acetic acid salt spray test (AASS) and acetic acid cupric chloride salt-fog test (CASS).Because salt-fog test and weather exposure test do not have comparability, that is to say, its simulation is poor, therefore the application of this method has certain limitation, only can be as a kind of artificial accelerated corrosion test method, metal material is made a service test, can not predict, but still have certain meaning as a kind of accelerated test method of classics to the life-span of material under a certain actual environment for use.
(3) cycle spraying composite corrosion test
Various single salt-fog tests are bad to the simulation of atmospheric exposure, and its main cause is that salt-fog test does not have " wet ← → do " cyclic process.And under the natural atmosphere condition, liquid film owing to formation such as rain, mists on the sample has one by thick attenuation, by the wet periodic cycle process that becomes dry, this is the basic characteristics of atmospheric corrosion, therefore, proposed to have the dry run and the salt fog composite testing method of brine spray periodically afterwards, and compared with simple salt-fog test, atmospheric corrosion can be simulated and quicken to this method better, reproduce physical environment more truly, relatively near the corrosion situation of material in the natural atmosphere environment.
(4) dried wetted perimeter soaks cyclic test
It is the accelerated test method that generally uses at present both at home and abroad that dried wetted perimeter soaks cyclic test.This test is used one and is had the exquisite system of runner or use an elevating mechanism, sample periodically can be immersed in the different maceration extracts to simulate different atmospheric environments, as using distilled water, NaHSO respectively
3Or NaCl solution simulates the atmospheric corrosion situation under rural atmosphere, industrial atmosphere and the marine atmosphere, and sample leaves solution after dipping a period of time, toasts dry sample with hot blast or lamp.Studies show that the experiment in several weeks can be complementary with 1 year or expose testing naturally of longer time.The method has equally been caught the feature of atmospheric corrosion with cycle spraying composite corrosion test---" wet ← → do " cycle alternation, reappeared three kinds of atmospheric corrosion states of metal surface experience: dipping-moistening-drying.
(5) multiple-factor circulation composite corrosion test
Because what material was subjected in physical environment is the combined action of multiple complicated factor, thereby to reproduce the corrosion of material in natural atmosphere really, must as much as possible the environmental factor in the atmosphere be integrated consideration, in recent years, the accelerated test method of simulation atmospheric corrosion developed to the compound accelerated corrosion test direction of multiple-factor.Utilize the CASS testing machine to repack combined testing machine into as Japan, can carry out humidity, spraying, logical SO
2, dry cyclic test; The Q-FOG cyclic corrosion testing machine that the Q-RANEL of the U.S. makes can carry out cyclic tests such as salt dew, drying, well-regulated pause, and the weak point of this method is that the factor that need control is many, operation easier is bigger.
Above-mentioned these test methods all have advantage and deficiency separately, belong to the guiding method of general orientation.Because atmospheric environment is complicated various, various materials there are differences the envirment factor sensitivity of corrosion, therefore, the foundation of any simulated acceleration test method, all will be at concrete environment and material, set many group test parameterss according to environmental characteristic, realize by the test condition that it is all good that a series of experiment sievings go out simulation, acceleration and reappearance.Present many researchers are studying, are designing, explore the test method of demand separately.
Summary of the invention
The object of the present invention is to provide a kind of accelerated corrosion test method with simulation, acceleration and reproducible simulation atmospheric corrosion process.
Technical scheme of the present invention is:
A kind of accelerated corrosion test method of simulating the atmospheric corrosion process is with the NaHSO of 0.01~0.05mol/L
3The NaCl of+0.001~0.005mol/L is a dipping solution, and per 10~30 minutes circulation primary of order are wherein flooded 40~50 ℃, 1~4 minute by " dipping → drying → moistening → "; Dry 50~60 ℃, 8~22 minutes; Moistening 40~50 ℃, 1~4 minute, cycle index can be determined as required.
Advantage of the present invention and beneficial effect are:
(1) adopt test method of the present invention can simulate the corrosion process of steel in atmospheric environment, the atmospheric corrosion resistance of the atmospheric corrosion rule of development test material or quick evaluating material is from the approximate result who infers outdoor long term exposure test of laboratory simulation accelerated corrosion test result.Have significant accelerated corrosion: tens times to hundred times, quickens the multiplying power time to time change.
(2) adopt the main corrosion product of the present invention consistent: all to be Alpha-hydroxy iron oxide and/or γ-FeOOH (alpha-feooh and/or γ-FeOOH) with the main corrosion product of outdoor atmospheric exposure.
(3) adopt the test findings of indoor and outdoor of the present invention all to meet power exponent rule Δ W=Kt preferably
n, and the indoor external enwergy of the corrosion weight of steel order is consistent.
(4) the revision test proof has good repeatability.
(5) applied range of the present invention goes for the atmospheric corrosion research and the corrosion proof quick evaluation thereof of various steel.
Description of drawings
Fig. 1 is the graph of relation of corrosion depth and exposure duration.
Fig. 2 is the graph of relation of embodiment 1 corrosion weight loss and test period.
Fig. 3 is the graph of relation of embodiment 2 corrosion weight losses and test period.
Fig. 4 is the graph of relation of embodiment 3 corrosion weight losses and test period.
Embodiment
The present invention has set up a kind of simulation accelerated corrosion test method, the corrosion process of simulation steel in atmospheric environment.Technical matters to be solved is that the lab simulation accelerated corrosion test must satisfy simulation, acceleration and three pacing itemss of reappearance, and wherein the problem of most critical is to satisfy the simulation condition satisfying on latter two condition basis.
The chemical constitution of table 1 test material (wt%)
Material | ?C | ??Si | ??Mn | ??S | ??P | ??Cu | ????Cr | ??Ni | ??Ti | Re | ???Nb |
??A3 | ?0.3 | ??<0.01 | ??0.43 | ??0.024 | ??0.018 | ??/ | ????/ | ??/ | ??/ | / | ???/ |
??09CuPTiRe | ?0.086 | ??0.47 | ??0.81 | ??0.015 | ??0.086 | ??0.29 | ????/ | ??/ | ??0.035 | <0.005 | ???/ |
??10CrNiCuP | ?0.088 | ??0.358 | ??0.353 | ??0.026 | ??0.088 | ??0.316 | ????0.41 | ??0.364 | ??/ | / | ???/ |
??X60 | ?0.082 | ??0.202 | ??1.086 | ??0.004 | ??0.014 | ??/ | ????/ | ??/ | ??/ | / | ???0.028 |
4 kinds of steel chemical compositions that weather exposure test is used see Table 1.Sample is of a size of 100mm * 50mm * (3~5) mm, through milling machine, grinding machine, be machined to smooth finish 7 or more than, the acetone oil removing, ethanol dehydration is placed in the exsiccator behind the 24h, weighs for the 0.1mg analytical balance with sensibility reciprocal.Rust cleaning liquid adopts 500ml hydrochloric acid+500ml distilled water+20g hexamethylenetetramine, till the Ex-all of will becoming rusty under the room temperature, proofreaies and correct the corrosion of rust cleaning liquid to steel matrix with uncorroded steel sample simultaneously.Carry out weather exposure test with reference to the ISO-4542 standard in areas of Shenyang, test period is 1994.10-2002.10, and wherein 0.5,1,2,4,8 year is the regular sample period, and sample is handled, calculate corrosion weight loss and corrosion depth, carry out corrosion product analysis simultaneously.Adopt the Linear Double logarithmic parabola to carry out regretional analysis to 4 kinds of steel average corrosion depths and time relationship, i.e. log Δ W=A+Blogt or Δ W=kt
n, wherein Δ W is corrosion depth (μ m), and t is exposure duration (year), and A=logk, B=n, A, B are the constant relevant with environment and material.The relation curve of corrosion weight loss and test period is seen Fig. 1, and the regretional analysis of corrosion depth and exposure duration sees Table 2, and the result shows that the corrosion regularity of 4 kinds of steel all meets Δ W=kt preferably
nRule; Main corrosion product is Alpha-hydroxy iron oxide and/or γ-FeOOH (alpha-feooh and/or γ-FeOOH), part Fe
2O
3And/or γ-Fe
3O
4
Table 2
Material | Regression equation | Related coefficient |
????A3 | ??ΔW=23.16t 0.8905 | ????0.965 |
????X60 | ??ΔW=17.98t 0.8915 | ????0.969 |
????09CuPTiRe | ??ΔW=15.43t 0.7986 | ????0.964 |
????10CrNiCuP | ??ΔW=14.64t 0.7481 | ????0.945 |
The environmental parameter of areas of Shenyang during the reference test, and consideration influences the main environment factor of steel corrosion, adopt DW-UD-3 type dipping to do wet combined-circulation experimental provision, design a series of test conditions by orthogonal experiment method, the A3 steel is carried out a series of tests, test findings is carried out variance analysis, according to target filter out suitable test condition, obtain test method of the present invention.
Embodiment 1
Test material is above-mentioned A3,09CuPTiRe, 10CrNiCuP.With 0.01mol/L NaHSO
3+ 0.005mol/L NaCl is a dipping solution, and per 30 minutes circulation primary of order are wherein flooded 40 ℃, 4 minutes by " dipping → drying → moistening → "; Dry 50 ℃, 22 minutes; Moistening 40 ℃, 4 minutes.Simulate industrial city, Shenyang atmospheric corrosion process with this, the relation curve of corrosion weight loss and test period is seen Fig. 2, and corrosion weight loss and the regretional analysis of accelerated test time see Table 3.Corrosion regularity equally all meets Δ W=kt preferably
nRule, wherein Δ W is corrosion weight loss (g/m
2), t be test period (hour), k, n are the constant relevant with test condition and material; Main corrosion product is consistent with the main corrosion product of outdoor atmospheric exposure.
Table 3
Material | Regression equation | Related coefficient |
????A3 | ??ΔW=15.55t 0.5982 | ????0.982 |
????09CuPTiRe | ??ΔW=11.91t 0.5534 | ????0.989 |
????10CrNiCuP | ??ΔW=13.33t 0.4893 | ????0.986 |
Embodiment 2
Test material is A3,20,06CuP, and the chemical constitution of back two kinds of materials sees Table 4.With 0.01mol/LNaHSO
3+ 0.001mol/L NaCl is a dipping solution, and per 20 minutes circulation primary of order are wherein flooded 40 ℃, 4 minutes by " dipping → drying → moistening → "; Dry 50 ℃, 12 minutes; Moistening 40 ℃, 4 minutes.Simulate industrial city, Shenyang atmospheric corrosion process with this, the relation curve of corrosion weight loss and test period is seen Fig. 3, and corrosion weight loss and the regretional analysis of accelerated test time see Table 5.Corrosion regularity equally all meets Δ W=kt preferably
nRule; Main corrosion product is consistent with the main corrosion product of outdoor atmospheric exposure.
Table 4 (wt%)
Material | ?C | ?S | ?P | ?Mn | ?Si | ?Cr | Ni | Cu | ?Al | ?N |
?20 | ?0.23 | ?0.009 | ?0.013 | ?0.47 | ?0.22 | ?0.02 | <0.05 | <0.05 | ?0.03 | ?0.0034 |
?06CuP | ?0.071 | ?0.006 | ?0.061 | ?0.67 | ?0.2 | ?0.02 | <0.05 | 0.27 | ?0.017 | ?0.003 |
Table 5
Material | Regression equation | Related coefficient |
????A3 | ??ΔW=14.23t 0.7944 | ????0.971 |
????20 | ??ΔW=15.17t 0.6872 | ????0.995 |
????06CuP | ??ΔW=8.53t 0.7049 | ????0.993 |
Embodiment 3
Test material is above-mentioned A3 and 10CrNiCuP.With 0.05mol/L NaHSO
3+ 0.005mol/LNaCl is a dipping solution, and per 10 minutes circulation primary of order are wherein flooded 50 ℃, 1 minute by " dipping → drying → moistening → "; Dry 60 ℃, 8 minutes; Moistening 50 ℃, 1 minute.Simulate industrial city, Shenyang atmospheric corrosion process with this, the relation curve of corrosion weight loss and test period is seen Fig. 4, and corrosion weight loss and the regretional analysis of accelerated test time see Table 6.Corrosion regularity equally all meets Δ W=kt preferably
nRule; Main corrosion product is consistent with the main corrosion product of outdoor atmospheric exposure.
Table 6
Material | Regression equation | Related coefficient |
????A3 | ??ΔW=7.07t 0.8944 | ????0.991 |
????10CrNiCuP | ??ΔW=4.71t 0.8704 | ????0.962 |
Embodiment is carried out revision test, and carry out corrosion product analysis, with test findings and above-mentioned weather exposure test result contrast, analysis mode, acceleration and reappearance, the result shows: the result of simulation accelerated atmospheric corrosion test satisfies with respect to the weather exposure test result of areas of Shenyang:
(1) have significant accelerated corrosion: tens times to hundred times, quickens the multiplying power time to time change;
(2) main corrosion product is consistent with the main corrosion product of outdoor atmospheric exposure: all be alpha-feooh and γ-FeOOH;
(3) test findings of indoor and outdoor all meets power exponent rule Δ W=Kt preferably
n, and the indoor external enwergy of the corrosion weight of steel order is consistent;
(4) the revision test proof has good repeatability.
Therefore, adopt this test method can simulate the corrosion of steel in Shenyang atmospheric environment and like environment, from the approximate result who infers outdoor long term exposure test of laboratory accelerated corrosion test result, this has actual application value.
Claims (1)
1. an accelerated corrosion test method of simulating the atmospheric corrosion process is characterized in that: with the NaHSO of 0.01~0.05mol/L
3The NaCl of+0.001~0.005mol/L is a dipping solution, and per 10~30 minutes circulation primary of order are wherein flooded 40~50 ℃, 1~4 minute by " dipping → drying → moistening → "; Dry 50~60 ℃, 8~22 minutes; Moistening 40~50 ℃, 1~4 minute.
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