CN1542431A - Method for accelerating corrosion test in air corrosion course simulation - Google Patents

Method for accelerating corrosion test in air corrosion course simulation Download PDF

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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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corrosion
test
atmospheric
dipping
accelerated
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CN1235031C (en
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王振尧
于国才
韩薇
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Institute of Metal Research of CAS
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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

A kind of accelerated corrosion test method of simulating the atmospheric corrosion process
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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CN100437084C (en) * 2005-04-30 2008-11-26 华为技术有限公司 Method for quantizing ionic pollution degree on circuit board
CN100533117C (en) * 2007-04-26 2009-08-26 同济大学 Equipment for simulating dry-wet circulation and fresh water to sea water circulation
CN101059418B (en) * 2007-05-28 2010-10-13 重庆交通大学 Stayed-cable bridge cable erosion state evaluation method
CN102207446A (en) * 2010-03-31 2011-10-05 中广核工程有限公司 Test method for simulating corrosion course of low alloy steel under marine industrial atmospheric environment
RU2448338C1 (en) * 2010-11-15 2012-04-20 Федеральное Государственное Унитарное Предприятие "Центральный научно-исследовательский институт черной металлургии им. И.П. Бардина" (ФГУП "ЦНИИчермет им. И.П. Бардина") Testing method of automobile steel sheets for resistance to atmospheric corrosion
CN102607919A (en) * 2012-03-22 2012-07-25 山东电力工程咨询院有限公司 Biomass combustion smoke corrosion analog system, preparation method thereof and application
CN101685061B (en) * 2008-09-23 2012-09-19 宝山钢铁股份有限公司 Simulation accelerated test method and device of corrosion performance of metal in atmosphere
CN103115864A (en) * 2013-01-22 2013-05-22 北京科技大学 Indoor simulation/rapid assessment device for comprehensive atmospheric environment corrosion
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
CN105277479A (en) * 2014-07-15 2016-01-27 中国科学院金属研究所 Corrosion simulation method and corrosion resistance evaluation method of galvanized steel coating in sea atmospheric environment
CN106769828A (en) * 2017-01-23 2017-05-31 广西玉柴机器股份有限公司 The corrosion rate decision method that neutral salt spray test is interrupted
CN110068531A (en) * 2019-05-30 2019-07-30 中国科学院金属研究所 A kind of test method for simulating stainless steel corrosion process in the atmospheric environment of salt lake
CN110763614A (en) * 2019-08-02 2020-02-07 北京福田戴姆勒汽车有限公司 Accelerated test method for simulating atmospheric corrosion
CN112394026A (en) * 2020-12-07 2021-02-23 国网福建省电力有限公司 Rapid evaluation method for performance of weather-resistant steel rust layer for transmission tower in rural atmospheric environment
CN112394025A (en) * 2020-12-07 2021-02-23 国网福建省电力有限公司 Rapid evaluation method for performance of weather-resistant steel rust layer for transmission tower in industrial atmospheric environment
CN113390777A (en) * 2021-05-17 2021-09-14 中国科学院金属研究所 Indoor dry-wet alternative acceleration test method for simulating coastal atmospheric corrosion process
CN114252391A (en) * 2020-09-21 2022-03-29 宝山钢铁股份有限公司 Method for evaluating industrial atmospheric corrosion resistance of steel welding joint

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CN100437084C (en) * 2005-04-30 2008-11-26 华为技术有限公司 Method for quantizing ionic pollution degree on circuit board
CN100533117C (en) * 2007-04-26 2009-08-26 同济大学 Equipment for simulating dry-wet circulation and fresh water to sea water circulation
CN101059418B (en) * 2007-05-28 2010-10-13 重庆交通大学 Stayed-cable bridge cable erosion state evaluation method
CN101685061B (en) * 2008-09-23 2012-09-19 宝山钢铁股份有限公司 Simulation accelerated test method and device of corrosion performance of metal in atmosphere
CN102207446A (en) * 2010-03-31 2011-10-05 中广核工程有限公司 Test method for simulating corrosion course of low alloy steel under marine industrial atmospheric environment
CN102207446B (en) * 2010-03-31 2013-05-15 中广核工程有限公司 Test method for simulating corrosion course of low alloy steel under marine industrial atmospheric environment
RU2448338C1 (en) * 2010-11-15 2012-04-20 Федеральное Государственное Унитарное Предприятие "Центральный научно-исследовательский институт черной металлургии им. И.П. Бардина" (ФГУП "ЦНИИчермет им. И.П. Бардина") Testing method of automobile steel sheets for resistance to atmospheric corrosion
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CN103115864A (en) * 2013-01-22 2013-05-22 北京科技大学 Indoor simulation/rapid assessment device for comprehensive atmospheric environment corrosion
CN103115864B (en) * 2013-01-22 2015-08-26 北京科技大学 A kind of device of indoor comprehensive simulation/Fast Evaluation atmosphere environment corrosion
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
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CN106769828A (en) * 2017-01-23 2017-05-31 广西玉柴机器股份有限公司 The corrosion rate decision method that neutral salt spray test is interrupted
CN106769828B (en) * 2017-01-23 2019-07-30 广西玉柴机器股份有限公司 The corrosion rate determination method that neutral salt spray test interrupts
CN110068531A (en) * 2019-05-30 2019-07-30 中国科学院金属研究所 A kind of test method for simulating stainless steel corrosion process in the atmospheric environment of salt lake
CN110763614A (en) * 2019-08-02 2020-02-07 北京福田戴姆勒汽车有限公司 Accelerated test method for simulating atmospheric corrosion
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