CN105699280A - Method for simulating corrosion of weathering resistant steel in high-moist-heat marine atmosphere - Google Patents
Method for simulating corrosion of weathering resistant steel in high-moist-heat marine atmosphere Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/006—Investigating resistance of materials to the weather, to corrosion, or to light of metals
Abstract
The invention relates to a method for simulating corrosion of weathering resistant steel in high-moist-heat marine atmosphere. The method comprises the following test parameters that a weathering resistant steel test specimen is subjected to the circulation processes of steeping, moistening and drying in an alternate immersion corrosion testing machine; the circulation period is 60min+/-5min; the steeping time is 2min+/-1min; the moistening time is 10min+/-2min; a dipping solution is a NaCl solution; the NaCl solution concentration is 2.00 percent+/-0.05 percent; the steeping solution temperature is 35 DEG C+/-2 DEG C; the humidity in the alternate immersion corrosion testing machine is 80 percent RH+/-5 percent RH; the total corrosion time of the weathering resistant steel test specimen in the alternate immersion corrosion testing machine is greater than or equal to 72h; a baking lamp in the alternate immersion corrosion testing machine is kept open. The method has better simulation performance, acceleration performance and reproducibility, and provides bases for studying the corrosion rule and the corrosion resistance of the weathering resistant steel in high-moist-heat marine environment.
Description
Technical field
The present invention relates to the technical field of simulation weathering steel corrosion process in an atmosphere, particularly relate to and a kind of simulate the method that weathering steel corrodes in high damp and hot marine atmosphere。
Background technology
Weathering steel in use can form one layer of corrosion scales fine and close, that continuous print attaches to matrix in surface due to it, can stop extraneous oxygen, water and other Korrosionsmediums that the corrosion further of matrix is had good atmospheric corrosion resistance, have both the serviceability such as high-corrosion resistance and excellent mechanics, welding simultaneously。
Test of being exposed to the sun on the spot by material is the test method that Atmospheric Corrosion is conventional, and the method can truly reflect on-site corrosion condition, provides reliable test data foundation for reasonable material in engineering construction。For this, China, also according to different regions, climate difference, set up several Atmospheric Corrosion Test Sites, have accumulated certain data。But, the uncertainty of long periodicity, the complexity of environment and external interference that atmospheric exposure is tested, the features such as sample loss of being exposed to the sun even occur, people are promoted to seek to carry out laboratory simulation accelerated corrosion experimental study, to obtaining, the test period is short, it is controlled to stablize, test data that is that be referred to, thus the atmospheric corrosion resistance life-span of the selection of material is predicted。Indoor accelerated corrosion test is meeting on simulation, acceleration and reproducible basis, it is possible to consistent with result of the test of being exposed to the sun on the spot well, and conveniently corrosion process can be carried out dynamic monitoring。
High damp and hot naval air environment is the typical climatic environment in China South Sea, compared to other naval air environment areas, such as Qingdao, Zhoushan, Wanning etc., owing to the South Sea is typical high temperature, high humidity, high salt fog, long-day area, thus this area's etching condition in the coastal area of China is the most severe。In recent years, along with the intensification of South Sea situation, the exploitation at the South Sea, utilization and defence are risen to unprecedented height by country, show proposing tightened up requirement in the research of marine engineering equipment material, exploitation and use the most exactly。Existing data shows, the corrosion condition that metal material is exposed to the sun 1 year in the Nanhai area, is equivalent to be exposed to the sun in Hainan 4 years, is exposed to the sun 5 years in Guangzhou, and according to ISO9223 standard, the corrosivity of the Nanhai area has exceeded highest C5 level。
Test method currently for simulated atmosphere corrosion is more, but is confined to respective environmental quality more and uses region restriction, as heavily contaminated industrial atmospheric environment, marine industry environment。And have no report about simulation weathering steel in the test method of high damp and hot naval air environment corrosion process。The present invention attempts according to this high damp and hot naval air environment of specific concrete atmospheric environment, by setting test parameters, carry out series of experiments and filter out the experimental condition of simulation, acceleration and favorable reproducibility, simulate the weathering steel test method in high damp and hot naval air environment corrosion process providing a kind of。
Summary of the invention
In view of above-mentioned analysis, the method that weathering steel corrodes in high damp and hot marine atmosphere is simulated it is desirable to provide a kind of, the method has good simulation, acceleration and repeatability, provides foundation for studying weathering steel corrosion regularity under high damp and hot marine environment and corrosion resistance。
The purpose of the present invention realizes mainly by techniques below scheme:
The present invention is a kind of simulates the method that weathering steel corrodes in high damp and hot marine atmosphere, by regulating and controlling the test parameters in week leaching corrosion testing machine, weathering steel corrosion behavior in high damp and hot marine environment air is simulated at the corrosion behavior that week soaks in corrosion testing machine with weathering steel sample, test parameters in described week leaching corrosion testing machine includes: described weathering steel sample is experience dipping in described week leaching corrosion testing machine, moistening and dry cyclic process, described cycle period is 60min ± 5min, wherein dip time is 2min ± 1min, MEBO ribbon gauze is 10min ± 2min；Dipping solution is NaCl solution, and wherein NaCl solution concentration is 2.00% ± 0.05%；Described dipping solution temperature is 35 DEG C ± 2 DEG C；Described week leaching corrosion testing machine humidity is 80%RH ± 5%RH；Described weathering steel sample in described week leaching corrosion testing machine total etching time be more than or equal to 72h；In described week leaching corrosion testing machine, drying lamp stays open。
Further, every 24h fills into deionized water or distilled water to described dipping solution, to ensure described dipping solution liquid level stabilizing。
Further, described weathering steel sample total etching time in described week leaching corrosion testing machine is 96h。
Further, described weathering steel specimen size is 60mm × 40mm × (3mm～5mm)。
Further, described weathering steel sample carried out surface deburring before putting into week leaching corrosion testing machine internal corrosion, cleans and dry up process, and wherein said cleaning process is first clean with gasoline or petroleum ether, then with washes of absolute alcohol, finally clean with acetone。
Further, described week leaching corrosion testing machine is drum-type week leaching corrosion testing machine。
Further, described drying lamp temperature is 70 DEG C～80 DEG C, dries the surface of sample。
Further, described drying lamp temperature is 75 DEG C
The meteorologic parameter of the damp and hot marine atmosphere of height that the present invention simulates is: year-round average temperature 27.0 DEG C, annual relative humidity 82%, and dry and wet time in year ratio is about 1:5, Cl-Deposition 1.123mg 100cm-2·d-1, SO2Deposition is less than 0.001mg 100cm-2·d-1。
The present invention has the beneficial effect that:
(1) the test method main corrosion product adopting the present invention is consistent with the corrosion product being exposed to the sun on the spot, is all alpha-feooh, γ-FeOOH and Fe3O4。
(2) test method of the present invention is adopted all to have similar rule in the result of the test of indoor and outdoor, i.e. the corrosion resistance sequence consensus of weathering steel sample。
(3) repeated trials proves have good repeatability。
(4) present invention has simulation, acceleration and repeatability, it is possible to suitable in the corrosion process research under high damp and hot naval air environment of the various low-alloy weathering steels and corrosion proof Fast Evaluation, provides foundation for reasonable material。
Other features and advantages of the present invention will be set forth in the following description, and, becoming apparent from description of part, or understand by implementing the present invention。The purpose of the present invention and other advantages can be realized by structure specifically noted in the description write, claims and accompanying drawing and be obtained。
Accompanying drawing explanation
Accompanying drawing is only for illustrating the purpose of specific embodiment, and is not considered as limitation of the present invention, and in whole accompanying drawing, identical reference marks represents identical parts。
Fig. 1 is week leaching corrosion testing machine structural principle schematic diagram；
Fig. 2 is that 1 four kinds of samples of embodiment are at the average corrosion rate curve chart soaked in week in corrosion testing machine under the simulation hot naval air environment of high humidity；
Fig. 3 is the 0# sample XRD figure spectrum in the corrosion rusty scale thing phase soaked in week in corrosion testing machine under the simulation hot naval air environment of high humidity；
Fig. 4 is the 1# sample XRD figure spectrum in the corrosion rusty scale thing phase soaked in week in corrosion testing machine under the simulation hot naval air environment of high humidity；
Fig. 5 is the 2# sample XRD figure spectrum in the corrosion rusty scale thing phase soaked in week in corrosion testing machine under the simulation hot naval air environment of high humidity；
Fig. 6 is the 3# sample XRD figure spectrum in the corrosion rusty scale thing phase soaked in week in corrosion testing machine under the simulation hot naval air environment of high humidity；
Fig. 7 is that 2 four kinds of samples of embodiment are exposed to the sun on the spot average corrosion rate block diagram；
Fig. 8 be 0# sample be exposed to the sun on the spot corrosion rusty scale thing phase XRD figure spectrum；
Fig. 9 be 1# sample be exposed to the sun on the spot corrosion rusty scale thing phase XRD figure spectrum；
Figure 10 be 2# sample be exposed to the sun on the spot corrosion rusty scale thing phase XRD figure spectrum；
Figure 11 be 3# sample be exposed to the sun on the spot corrosion rusty scale thing phase XRD figure spectrum；
Wherein, 1-casing, 2-rotating disk and specimen mounting, 3-tank liquor, 4-cooling tube, 5-heater, 6-compressor, 7-drimeter, 8-air circulation device, 9-drying lamp, 10-motor and accelerator, 11-humidifier。
Detailed description of the invention
Specifically describing the preferred embodiments of the present invention below in conjunction with accompanying drawing, wherein, accompanying drawing constitutes the application part, and is used for together with embodiments of the present invention explaining principles of the invention。
Embodiments provide and a kind of simulate the method that weathering steel corrodes in high damp and hot marine atmosphere, the meteorologic parameter of the damp and hot naval air environment of height simulated in the present invention is as follows: year-round average temperature 27.0 DEG C, annual relative humidity 82%, dry and wet time in year ratio is about 1:5, Cl-Deposition 1.123mg 100cm-2·d-1, SO2Deposition is less than 0.001mg 100cm-2·d-1, it is substantially free of contamination naval air environment。Therefore, this test method will according to above meteorologic parameter, after simulation test carries out the screening of series of parameters, it is provided that one possesses simulation, acceleration and reproducible test method。
In order to verify that analogy method of the present invention has good simulation, acceleration and repeatability, it is necessary to contrast with exposing corrosion sample on the spot in the damp and hot marine environment of described height, then compare from the material phase analysis of corrosion weight loss and corrosion rusty scale。
Drum-type week leaching corrosion testing machine used by the embodiment of the present invention is as shown in Figure 1。
Described test method comprises the steps: to add dipping solution in the casing of week leaching corrosion testing machine, wherein said dipping solution is preferably the NaCl solution at room temperature prepared, tank liquor 3 as shown in Figure 1, then and adopt insulant to be hung on by the weathering steel sample of pre-processed preliminary dimension on the specimen mounting of week leaching corrosion testing machine, rotating disk as shown in Figure 1 and specimen mounting 2；By controlling the casing test parameters of week leaching corrosion testing machine, sample is carried out repeatedly cyclic corrosion experiment by dipping, order moistening, dry, so that sample stands corrosion；Sample after corrosion is carried out processing of rust removing, then carries out corrosion weight loss analysis and rusty scale material phase analysis, thus obtaining sample corrosive nature under the high damp and hot naval air environment of this simulation。
Embodiment of the present invention sample is put into before corroding in week leaching corrosion testing machine and exposed experiment on the spot before carrying out exposing experiment, the surface treatment of sample must be carried out, including deburring, clean and hot blast drying, gasoline or petroleum ether is first used to clean when wherein cleaning, again with washes of absolute alcohol, finally clean with acetone, then measure and record original size (being accurate to 0.1mm) and the quality (being accurate to 1mg) of sample, the specimen size that analogy method of the present invention adopts is 60mm (length) × 40mm (width) × (3mm～5mm) (thickness), the sample being exposed to the sun on the spot is of a size of 150mm (length) × 75mm (width) × (3mm～5mm) (thickness), and it is provided with 3 parallel samples, error is precisely reduced with what really test。
The NaCl solution that embodiments of the invention are at room temperature prepared by following step: at room temperature analytical pure NaCl is dissolved in deionized water or distilled water is formulated, wherein, the mass fraction of NaCl solution is 2.00% ± 0.05%。If NaCl solution concentration is less than about 2.00% (error is less than ± 0.05%), then along with the increase of NaCl solution concentration, the corrosion rate of sample increases, and presents downward trend afterwards。Use the sea water (0.02%Cl of dilution 100 times in coastal area according to Belgium's corrosion centers (CEBELCOR)-) Cl under the damp and hot naval air environment of height that cruelly leaks on the spot of this literature basis and the present invention-Deposition, and in conjunction with the speed-up ratio needs of accelerated corrosion test, in the present invention the concentration of NaCl solution is defined as 2.00% ± 0.05%。
Test parameters of the present invention includes casing humidity, the temperature of solution, cycle period and total etching time, wherein casing humidity controls by soaking humidifier 11 in corrosion testing machine week, and utilize the humidifier 11 humidity to measure in casing, casing humidity is controlled at 80%RH ± 5%RH by the present invention, because when humidity is 80%RH, the corrosion of sample is the most serious, and with amblent air temperature humidity is consistent on the spot；Solution temperature is controlled by heater 5, and the temperature of dipping solution of the present invention controls at 35 DEG C ± 2 DEG C；Cycle period includes dipping, moistening and dry three processes, one cycle period is 60min ± 5min, sample is immersed in dipping solution and is dipping process, leaves the moistening process that is before solution is not dried, and is then passed through being dry run after specimen surface is dried by drying lamp；In stipulated time immersion and dipping solution is left by motor and accelerator 10 Control Assay, and coordinate the temperature of drying lamp to control the time of each process in cycle period, dip time process time 2min ± 1min in cycle period of the present invention, moistening process time is 10min ± 2min, the temperature of drying lamp of the present invention is 75 DEG C, so can guarantee that the surface drying sample completely。
The rusty scale of specimen surface after corrosion is carried out XRD thing detect mutually, detect thing phase constituent；Remove the rusty scale of specimen surface after etching with rust removing solution, then measure and recording quality and size, contrast with the sample before corrosion, calculate corrosion weight loss；Then the simulation experiment data of the present invention are contrasted with the experimental data exposed on the spot, verify the simulation of analogy method of the present invention, acceleration and repeatability。
Embodiment 1
Adopting four kinds of weather-proof steel grades, the method carrying out the high damp and hot sea atmosphere corrosion of simulation of the present invention, wherein 0# is compared steel, is the conventional weathering steel of certain steel mill domestic production, and 1#, 2# and 3# are the weathering steels that laboratory is smelted, and its material composition is as shown in table 1。
The chemical composition of 14 kinds of table experiment weathering steel
| steel | C | S | P | Mn | Si | Cr | Ni | Cu | Nb |
| 0#(Q450NR1) | 0.075 | 0.0068 | 0.012 | 0.80 | 0.39 | 0.50 | 0.19 | 0.24 | 0.035 |
| 1# | 0.070 | 0.0045 | 0.0050 | 0.88 | 0.40 | 0.54 | 0.95 | 0.27 | 0.0046 |
| 2# | 0.069 | 0.0058 | 0.0058 | 0.87 | 0.36 | 0.51 | 1.90 | 0.27 | 0.0033 |
| 3# | 0.081 | 0.0058 | 0.0062 | 0.90 | 0.40 | 0.51 | 2.93 | 0.27 | 0.0038 |
Sample weathering steel is cut into the small sample being of a size of 60mm (length) × 40mm (width) × (3mm～5mm) (thickness), then deburring is carried out, clean and hot blast drying, gasoline or petroleum ether is first used when wherein cleaning, again with dehydrated alcohol, finally with acetone, then measure and record original size (being accurate to 0.1mm) and the quality (being accurate to 1mg) of sample, adopt non-woven insulant to be hung on by 3 parallel samples of the experimental steel of each grade of steel to soak in week as shown in Figure 1 on the test stand 2 of corrosion testing machine, and the suspension height keeping each sample is consistent, and record the position of each sample。Soaking the NaCl testing liquid such as tank liquor 3 injecting new preparation in the liquid bath of corrosion testing machine to week to regulation scale, its total amount is 10.0L ± 0.5L。Reducing door number of times of unpacking during test as far as possible, within every 24 hours, be not to be exceeded at most twice, each time is not to be exceeded 2 minutes, should close air circulation device 8 during enabling。Within every 24 hours, add a bulking liquor, add about 500mL deionized water or the distilled water initial level position to test。Whole interpolation bulking liquor process consuming time short as much as possible。Tank liquor 3 is only used for one-time continuous test, it is impossible to reuse, it is impossible to new sample is inserted on way in test。
The temperature that week soaks the tank liquor in testing machine is set as 35 DEG C ± 2 DEG C, holding tank humidity is 80%RH ± 5%RH, keep all illumination, it is circulated experiment by " dipping → moistening → dry " order, cycle period is 60min ± 5min, wherein, the dipping profit time is 2min, and MEBO ribbon gauze is 10min。Corroding total time respectively 24h, 48h, 72h, 96h, each corrosion carries out surface derusting after terminating, and carries out corrosion rate and rusty scale material phase analysis。
Fig. 2 is the 1 four kinds of samples of embodiment average corrosion rate curve charts under simulating high damp and hot naval air environment；Fig. 3-Fig. 6 is the XRD figure spectrum of 0#-3# sample corrosion rusty scale thing phase under simulating high damp and hot naval air environment；
Embodiment 2
4 kinds of weathering steel test materials are cut into the small sample being of a size of 150mm (length) × 75mm (width) × (3mm～5mm) (thickness), then deburring, cleaning and hot blast drying are carried out, gasoline or petroleum ether is first used when wherein cleaning, again with dehydrated alcohol, finally with acetone, then measure and record original size (being accurate to 0.1mm) and the quality (being accurate to 1mg) of sample, carrying out atmospheric exposure test, test standard of being exposed to the sun carries out in somewhere, the South Sea with reference to ISO-4524。Test period is 2014.4-2015.4。The sample that is exposed to the sun is of a size of 150mm (length) × 75mm (width) × (3mm～5mm) (thickness), and the cycle of being exposed to the sun is 1 year。It is exposed to the sun after off-test, sample is processed, carry out corrosion weight loss and rusty scale material phase analysis。
Fig. 7 is that 2 four kinds of samples of embodiment are exposed to the sun average corrosion rate block diagram on the spot；Fig. 8-Figure 11 be 0#-3# sample on the spot be exposed to the sun corrosion rusty scale thing phase XRD figure spectrum。
By result of the test and above-mentioned comparison of test results of being exposed to the sun on the spot, analysis mode, acceleration and repeatability。Known, adopt the analogy method of the present invention and two kinds of test methods of being exposed to the sun on the spot, test steel according to four kinds and can be seen that the weathering steel corrosion behavior rule when two kinds of experimental enviroments is consistent at indoor etch rate data with the etch rate data being exposed to the sun on the spot, the corrosion resistance sequence consensus of test steel, the composition of rusty scale thing phase is also consistent, under two kinds of experimental conditions, the corrosion resistance order of test steel is 3# > 2# > 1# > 0#；Corrosion rusty scale product composition is alpha-feooh, γ-FeOOH and Fe3O4, illustrate that the application analogy method has good simulation and repeatability。The corrosion rate of the corrosion rate/be exposed to the sun on the spot of corrosion accelerator coefficient=indoor of four kinds of test steel, is each about 80～90 times of explanation the present processes and has good acceleration。
In sum, embodiments provide and a kind of simulate the method that weathering steel corrodes in high damp and hot marine atmosphere, the corrosion in high damp and hot naval air environment and like environment of the low-alloy weathering steel can be simulated, achieve acceleration and repeatability and simulation, can be used for studying various low-alloy weathering steel corrosion behavior under this atmospheric environment and corrosion proof Fast Evaluation thereof。
The above; being only the present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, any those familiar with the art is in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should be encompassed within protection scope of the present invention。
Claims (10)
1. simulate the method that weathering steel corrodes in high damp and hot marine atmosphere for one kind, by regulating and controlling the test parameters in week leaching corrosion testing machine, weathering steel corrosion behavior in high damp and hot marine environment air is simulated at the corrosion behavior that week soaks in corrosion testing machine with weathering steel sample, it is characterized in that, the test parameters in described week leaching corrosion testing machine includes:
Experience dipping, the moistening and dry cyclic process in described week leaching corrosion testing machine of described weathering steel sample, described cycle period is 60min ± 5min；Wherein dip time is 2min ± 1min, and MEBO ribbon gauze is 10min ± 2min；
Dipping solution is NaCl solution, and wherein NaCl solution concentration is 2.00% ± 0.05%；
Described dipping solution temperature is 35 DEG C ± 2 DEG C；
Described week leaching corrosion testing machine humidity is 80%RH ± 5%RH；
Described weathering steel sample in described week leaching corrosion testing machine total etching time be more than or equal to 72h；
In described week leaching corrosion testing machine, drying lamp stays open。
2. the method that simulation weathering steel corrodes in high damp and hot marine atmosphere according to claim 1, it is characterised in that every 24h fills into deionized water or distilled water to described dipping solution, to ensure described dipping solution liquid level stabilizing。
3. the method that simulation weathering steel corrodes in high damp and hot marine atmosphere according to claim 1, it is characterised in that described weathering steel sample total etching time in described week leaching corrosion testing machine is 96h。
4. the method that simulation weathering steel corrodes in high damp and hot marine atmosphere according to claim 2, it is characterised in that described weathering steel sample total etching time in described week leaching corrosion testing machine is 96h。
5. according to any one of claim 1-4, simulate the method that weathering steel corrodes in high damp and hot marine atmosphere, it is characterized in that, described weathering steel sample carried out surface deburring, and cleaned and dries up process before putting into week leaching corrosion testing machine internal corrosion, wherein said cleaning process is first clean with gasoline or petroleum ether, again with washes of absolute alcohol, finally clean with acetone。
6. the simulation method corrode in high damp and hot marine atmosphere of weathering steel according to claim 5, it is characterised in that described weathering steel specimen size: long is 60mm, wide for 40mm, thickness is 3mm～5mm。
7. the method corroded in high damp and hot marine atmosphere according to the arbitrary described simulation weathering steel of claim 1-4 or 6, it is characterised in that described week leaching corrosion testing machine is drum-type week leaching corrosion testing machine。
8. the method that simulation weathering steel corrodes in high damp and hot marine atmosphere according to claim 5, it is characterised in that described week leaching corrosion testing machine is drum-type week leaching corrosion testing machine。
9. the method corroded in high damp and hot marine atmosphere according to the arbitrary described simulation weathering steel of claim 7 or 8, it is characterised in that described drying lamp temperature is 70 DEG C～80 DEG C。
10. the method corroded in high damp and hot marine atmosphere according to the arbitrary described simulation weathering steel of claim 7 or 8, it is characterised in that described drying lamp temperature is 75 DEG C。
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| CN112394024B (en) * | 2020-12-07 | 2022-10-21 | 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 coastal 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 |
| CN113686764A (en) * | 2021-07-27 | 2021-11-23 | 中联先进钢铁材料技术有限责任公司 | Corrosive liquid for simulating corrosion of steel in south sea environment and simulation method |
| CN114486696A (en) * | 2021-11-29 | 2022-05-13 | 中国船舶重工集团公司第七二五研究所 | Method for evaluating intergranular corrosion performance of high manganese steel |
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