WO2020221350A1 - 一种具有锈层的裸用耐候钢及其制造方法 - Google Patents

一种具有锈层的裸用耐候钢及其制造方法 Download PDF

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WO2020221350A1
WO2020221350A1 PCT/CN2020/088343 CN2020088343W WO2020221350A1 WO 2020221350 A1 WO2020221350 A1 WO 2020221350A1 CN 2020088343 W CN2020088343 W CN 2020088343W WO 2020221350 A1 WO2020221350 A1 WO 2020221350A1
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rust layer
steel
manufacturing
solution
weathering steel
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PCT/CN2020/088343
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French (fr)
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吴玮巍
王宝森
周庆军
祁庆琚
郎丰军
李江文
宋凤明
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宝山钢铁股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a weathering steel and a manufacturing method thereof, in particular to a bare weathering steel with a rust layer and a manufacturing method thereof.
  • weathering steel Compared with carbon steel, weathering steel has good atmospheric corrosion resistance. The main reason is that weathering steel has formed a stable and dense protective rust layer on its surface after long-term atmospheric exposure, which prevents the entry of corrosive media.
  • the rust layer formed on the surface of carbon steel is often loose and has a large number of micro-cracks. , The protection of the substrate is poor.
  • weathering steel At present, in the natural environment, it takes 4 years or more for weathering steel to form a stable protective rust layer. Before weathering steel forms a stabilized rust layer, uneven color of the rust layer, rust liquid sag, The phenomenon of flying rust and slag affects the surrounding environment and perception. However, after 4 years or more, after the surface rust layer is stable, weathering steel can show a strong dark brown or brown appearance with a strong sense of retro art, which is deeply loved by people. Moreover, the color can remain unchanged for many years, which can well hinder the further penetration of corrosive media and prevent the occurrence of corrosion.
  • the prior art mainly focuses on the formulation of rapid rust formation and rust layer stabilization solution.
  • the publication number is CN86103534
  • the publication date is February 11, 1987
  • the title is "The rapid formation method of weather-resistant anti-rust film on steel”.
  • the Chinese patent document discloses a method for rapidly forming a weather-resistant rust-proof film of steel.
  • the technical solution disclosed in the patent document is actually an optimization of the existing method in Japan, using tannin extract to replace the higher-cost tannin.
  • the publication number is CN103173754A
  • the publication date is June 26, 2013,
  • the Chinese patent document titled "weathering steel surface rust layer stabilization treatment agent and its preparation method” discloses a weathering steel surface rust layer stabilization Preparation method of treatment agent.
  • the treatment agent consists of 25-45% alkyd varnish, 4-12% copper pyrophosphate, 2-10% barium chromate, 1-14% Fe3O4, 20 ⁇ It is composed of 50% Fe2O3, 1-10% mineral spirits and 0.5-5% dispersant.
  • the treatment time often takes at least 1 to 2 days. This is because complicated pre-treatments such as degreasing and cleaning are required before treatment, and it is also necessary to spray a special syrup several times and then spray water, which causes the treatment process to be time-consuming Laborious
  • Construction has certain requirements for the site environment, and a special site is needed to stack samples. On-site construction of large buildings is likely to pollute the surrounding environment, and special equipment is required for construction.
  • the publication number is CN207512973U
  • the publication date is June 19, 2018
  • the Chinese patent document titled "A weather-resistant steel plate structure” discloses a weather-resistant steel plate structure, and the products involved in this patent document Although it is a weathering steel product with a rust layer, it must be painted on the basis of the rust plate.
  • the publication number is CN103459670A
  • the publication date is December 18, 2013,
  • the Chinese patent document entitled "Rust-resistant steel material with excellent weatherability in high salinity environments” discloses a method especially in coastal areas. In a severely corrosive environment with a large amount of atmospheric salt spray, it is a rusty steel with excellent corrosion resistance even without coating.
  • the material is not available at the beginning of service Stabilize the rust layer, but the rust layer is naturally formed in the natural environment and gradually stabilized. Therefore, it does not solve the problems of uneven color, instability, yellow rust and rust slag before stabilization.
  • One of the objectives of the present invention is to provide a bare weathering steel with a rust layer.
  • the bare weathering steel has a uniform and stable rust layer, and the rust layer is dense, so that the bare weathering steel has excellent corrosion resistance. It means that it can be used directly without painting, and can be used directly naked in the normal atmosphere for decades.
  • the present invention proposes a bare weathering steel with a rust layer.
  • the surface of the bare weathering steel has a rust layer generated by artificial acceleration. The generation process only takes less than 2 hours, so it can be passed through the production line. Continuous production, so that the product has the rust layer when it leaves the factory.
  • the thickness of the rust layer is 10-200 ⁇ m when leaving the factory, and further, the thickness of the rust layer is 20-150 ⁇ m, which provides adequate protection while having a good
  • the uniformity of the rust layer, and the main composition of the rust layer has a good consistency with the rust layer that weathering steel takes 3 months or more to generate in the natural environment.
  • the rust layer generated artificially will not be destroyed or removed during the later service of the weathering steel, but will only be thickened and darkened continuously. Protection continues to increase.
  • the rust layer generated artificially has strong self-repairing properties, and the rust layer is damaged during the process of product shearing, deformation, scratching, and welding. It will be gradually repaired during service. Usually after 1 to 3 months of repair, the marks caused by shearing, deformation, scratching, and welding have become indistinguishable to the naked eye.
  • the rust layer contains ⁇ -FeO(OH).
  • ⁇ -FeO(OH) the rust layer contains ⁇ -FeO(OH).
  • Shi Zhenjia Wang Lei, Chen Nan, Hao Long, Dong Junhua, and Ke Wei in September 2015 Published in “Corrosion Science and Protection Technology” (Volume 27, Issue 5), “The Status and Development Trend of Rust Layer on Weathering Steel Surface and Its Stabilization Treatment", and Liu Lihong, Qi Huibin, Lu Yanping, and Li Xiaogang published in December 2012 It has been reported in many articles such as “Corrosion and Surface Stabilization Technology of Weathering Steel” in “Corrosion and Protection” (Volume 23, Issue 12) that the rust layer containing this component has good compactness and protection. It is one of the important signs of the stabilization of the rust layer.
  • the color difference value ⁇ E ab ⁇ 10 of the rust layer in the first six months of exposure to the conventional outdoor atmosphere can indicate that the bare weathering steel provided by the present invention
  • the rust layer in it has high color stability.
  • the bare weathering steel with a rust layer of the present invention has a corrosion weight gain value per unit area in the first half year in a conventional low chloride ion (less than 0.05mg*NaCl/dm 2 /day) atmospheric environment
  • the bare weathering steel of the same material without the rust layer has 75% of the corrosion weight per unit area under the same conditions, which is significantly better than the bare weathering steel without the rust layer.
  • the two are bare weathering steel of the same material, and the difference is only that the present invention provides bare weathering steel with a rust layer.
  • another object of the present invention is to provide the above-mentioned manufacturing method of bare weathering steel with a rust layer, which can overcome the shortcomings of the prior art and mass-produce weathering steel with a uniform and stable rust layer.
  • the weathering steel produced has a stable and dense rust layer, has excellent corrosion resistance, and can be directly exposed and used for decades in a conventional atmospheric environment.
  • the weathering steel obtained by this manufacturing method will not have the problems of uneven color, rust dripping, and rust slag falling off before the rust layer is stabilized.
  • This manufacturing method can avoid the rust formation in the prior art on site, labor, environmental protection, etc.
  • the limitation of this aspect greatly facilitates the use of weathering steel and has good application prospects.
  • the present invention proposes the above-mentioned manufacturing method of bare weathering steel with rust layer, which includes the steps:
  • the bare weathering steel can be quickly rusted (within 2 hours) through the various steps of the case, so that the steel surface has a stable and uniform rust layer, and the rust layer is dense. Therefore, it can effectively prevent the corrosive medium from entering the interior to react with the steel substrate, thereby improving the corrosion resistance of the material.
  • the manufacturing method has simple process steps and effectively reducing the manufacturing cost.
  • the bare weathering steel with a rust layer obtained by the manufacturing method of the present invention has a yellow, brown, brown, and dark brown rust layer from light to dark.
  • the thickness of the rust layer is more than 10 microns, and the surface color of the material is uniform, and During outdoor use, the color of the rust layer can gradually become darker as a whole, which has a stronger visual effect than the prior art.
  • step (1) after the hot rolling or pickling of the steel sheet is completed, the surface of the steel sheet is cleaned to remove surface oil stains and enhance adhesion.
  • ferrous ions can be obtained on the surface of the steel by any of the following methods:
  • the pH value of the acid solution is ⁇ 3.
  • the pH value of the acid solution and the reducing acid solution is ⁇ 1.
  • the acid solution is a hydrochloric acid solution.
  • the acid solution is a mixed solution composed of a 36-38% concentrated hydrochloric acid solution and a NaCl solution with a mass concentration of 1-10%.
  • the volume ratio of hydrochloric acid in the mixed solution is less than or equal to 1:2.
  • the surface of the steel sheet is oxidized by coating an oxidizing solution at room temperature to obtain a denser oxide layer.
  • the surface of the steel sheet can also be oxidized by means of high-temperature oxidation to obtain a denser oxide layer and the oxide layer formed during the hot rolling of the steel sheet.
  • the oxidizing solution can be hydrogen peroxide or other oxidizing solutions that those skilled in the art can think of.
  • the oxidizing solution is H 2 O with a mass concentration of 0.1-10% obtained by diluting a NaCl solution with a mass concentration of 1-10%. 2 solutions.
  • the reducing acid solution is a hydrochloric acid solution with a mass concentration of 0.37-15% obtained by diluting a NaCl solution with a mass concentration of 1-10%.
  • the salt solution is an inert metal cation salt solution or a trivalent iron salt solution whose activity is weaker than iron.
  • the ferric salt solution is a FeCl 3 solution with a mass percentage concentration of 1-10%.
  • adding a NaCl solution with a mass concentration of 1-10% for preparation can increase the conductivity and corrosivity of the solution, and increase the rate of rust formation.
  • the temperature of the water and/or the solution sprayed on the surface of the steel plate is 10-90°C. If the temperature is too low, the reaction time is longer, and if the temperature is too high, the solution will evaporate quickly and cannot Sufficient reaction, further, the temperature of the water and/or solution sprayed on the surface of the steel plate is 40-90°C, which can speed up the reaction process and improve the reaction efficiency while ensuring that the solution fully reacts with the surface of the steel plate.
  • the bare weathering steel with rust layer and its manufacturing method according to the present invention have the following advantages and excellent effects:
  • the bare weathering steel produced by the method for manufacturing bare weathering steel with a rust layer of the present invention has a uniform and stable rust layer, which avoids the rust layer of the weathering steel in the prior art during use.
  • the formation is slow and unstable at the initial stage of formation.
  • the unstable rust layer is prone to problems such as uneven color of the rust layer, yellow rust, and rust slag.
  • the bare weathering steel with rust layer produced by the method for manufacturing bare weathering steel with rust layer of the present invention can provide sufficient protection, so that the bare weathering steel with rust layer in this case In the early stage of service, it has excellent performance in corrosion resistance to avoid corrosion damage of bare weathering steel in the early stage of service.
  • the manufacturing method of the present invention can use assembly line equipment to quickly rust the steel, and its process and material costs are far lower than painting.
  • the bare weathering steel with rust layer obtained by the manufacturing method of the present invention can be welded only by grinding the groove when welding, and it can be used normally without any treatment after welding.
  • a protective rust layer will naturally form during the service process, and will be integrated with other parts after the final rust layer is stabilized. If there is a higher requirement for the early appearance, the weld can also be quickly rusted.
  • the manufacturing method of the present invention can greatly shorten the rust-forming time.
  • the rust-forming time can be shortened by 1-2 hours, which is very conducive to mass production, so it can be directly formed with a uniform rust layer. The products are shipped directly.
  • the reagent applied by the manufacturing method of the present invention does not involve the use of precious metal salts, has simpler components, lower cost, and is more suitable for mass production.
  • Fig. 1 schematically shows the structure of the bare weathering steel with a rust layer according to the present invention in some embodiments.
  • Figure 2 is a Raman spectrum of the test plate surface subjected to rapid rusting treatment according to the embodiment of the present invention
  • Figure 3 is a schematic diagram of the exposure model and the collection device.
  • the bare weathering steel with a rust layer of the foregoing Examples 1-11 was prepared by the following steps:
  • the pH value of the acid solution is ⁇ 3.
  • the pH value of the acid solution can be further controlled to be ⁇ 1, and the acid solution can be a hydrochloric acid solution.
  • the acid solution is a mixed solution composed of a 36-38% concentrated hydrochloric acid solution and a NaCl solution with a mass concentration of 1-10%, and the volume ratio of the concentrated hydrochloric acid in the mixed solution is ⁇ 1:2 .
  • the surface of the steel sheet can be oxidized by applying an oxidizing solution at room temperature to obtain a denser oxide layer, or the surface of the steel sheet can be oxidized by high-temperature oxidation to obtain a denser oxide layer.
  • the oxide layer can also be the oxide layer formed during the hot rolling of the steel plate.
  • the oxidizing solution is a H 2 O 2 solution with a mass concentration of 0.1-10%, which is diluted with a NaCl solution with a mass concentration of 1-10%.
  • the pH value of the reducing acid solution can be further controlled to be ⁇ 1.
  • the reducing acid solution is a hydrochloric acid solution with a mass concentration of 0.37-15% diluted with a NaCl solution with a mass concentration of 1-10% .
  • the salt solution is an inert metal cation salt solution or a trivalent iron salt solution with weaker activity than iron, and the trivalent iron salt solution may have a concentration of 1-10% by mass. ⁇ FeCl 3 solution.
  • the temperature of the water and/or solution sprayed on the surface of the steel plate is 10-100°C.
  • Table 1 lists the specific process parameters involved in the manufacturing method of bare weathering steel with rust layer in Examples 1-11, and the solution concentrations are all mass percentages.
  • the measurement of the rust layer thickness of the sample in Table 1 refers to the standard 4.3 gravimetric method of GBT13452.2/ISO2808 "Determination of Paint Film Thickness of Paints and Varnishes".
  • the rust layer was cleaned with reference to the method of code C.3.1 in the attached table A.1 of GBT16545/ISO8407 "Removal of Corrosion Products on Corrosion Corrosion Specimens of Metals and Alloys".
  • the specific calculation method is to obtain the coating quality required by the GBT13452.2/ISO2808 standard according to the quality difference before and after the rust layer is removed, and then according to the rust layer density (5.24g/cm 3 ) to estimate the average thickness of the rust layer (only Accurate to 10 ⁇ m).
  • m 0 192.5907g after the sample returns to room temperature and the quality is stable; according to the following The formula given in 4.3.1 of GBT13452.2 standard calculates the average thickness of the rust layer, and the final result is 60 ⁇ m after being accurate to 10 ⁇ m.
  • the processing time in Table 1 refers to the sum of the processing time of step (2) and step (3), that is, the processing time required after the surface of the template is cleaned until the surface is covered with a uniform rust layer and dehydrated and dried.
  • step (2) the solution is applied to the surface of the steel plate, and once the reaction is completed and dried, it is one time; for step (3), a water film is applied to the surface of the steel plate And dehydration is once.
  • Fig. 1 schematically shows the structure of the bare weathering steel with a rust layer according to the present invention in some embodiments.
  • the bare weathering steel with a rust layer includes a substrate 1 and a rust layer 2 on the surface of the substrate 1.
  • the rust layer 2 is a uniform rust film that is dense and prevents corrosive media from entering the internal corrosive materials. Its thickness is 10-200 ⁇ m. With the prolongation of outdoor exposure time, the color of rust layer 2 changes from light to dark to show yellow, brown, and coffee colors, and finally stabilizes to dark coffee colors after 4 to 8 years.
  • the surface color of the bare weathering steel with a rust layer provided by the present invention is uniform, and the color of the rust layer 2 can gradually become deeper as a whole during outdoor use.
  • the rust layer 2 can prevent corrosion from continuing to occur, and the protective effect varies with As time goes by, the material can be used in the normal low-chloride (atmospheric salt spray content less than 0.05mg*NaCl/dm2/day) atmospheric environment without worrying about corrosion.
  • test plate was a BC550 weathering steel hot-rolled and pickled plate with a side length of 0.1 meters.
  • the control board is a steel plate of this material sealed with metal fluorocarbon paint on the other five sides without any treatment on the front side.
  • the test board is processed in the following steps:
  • the NICOLET DXR laser confocal Raman spectrometer was used to analyze the components of the rust layer at different positions on the surface of the test board processed by the above steps. The results are shown in Figure 2.
  • Figure 2 shows the rapid rust formation test Raman spectroscopy results of the board surface.
  • the Raman spectrum shows obvious characteristic peaks (248.92, 379.51) corresponding to ⁇ -FeO(OH). Therefore, it can be explained that there is a stable ⁇ -FeO(OH) distribution in the rust layer of the test plate subjected to the rapid rust formation treatment. According to the above article, the rust layer containing this component has good compactness and protection, which is one of the important signs of rust layer stabilization.
  • Figure 3 is a schematic diagram of the exposure model and the collection device.
  • the model 3 (test board, control version) is hung above the beaker 4.
  • One diagonal of the model is parallel to the horizontal direction X and the other diagonal is 45 degrees to the vertical direction Y
  • Hanging at an angle the beaker 4 is used to collect corrosion products and other impurities shed from the template.
  • the vertical projection of the template is all within the vertical projection range of the beaker opening to ensure that all substances falling off the template enter the beaker.
  • the control board and test board are placed in a highly consistent manner and the environment. Considering that the color difference and flow performance of the rust layer will be affected by the climate. Choose Shanghai, China (the average salt fog content of the atmosphere is less than 0.05mg*NaCl/dm2/day) for exposure, the shelf time is September of the current year, and the end time is March of the following year. In Shanghai, the weather in September and March is similar. The monthly, quarterly and semi-annual data of the model are measured, as shown in Table 2.
  • the composition of the rust layer is highly consistent with the corrosion products formed during the later exposure process, and the two cannot be removed in a targeted manner.
  • Conventional cleaning and corrosion The method of measuring the weight loss after the product cannot be used to evaluate its corrosion resistance. For this reason, we used the weight gain method to evaluate the corrosion resistance of the sample.
  • the specific method is: hang the template in a diagonal manner as shown in Figure 3. One diagonal of the template is parallel to the horizontal direction X and the other diagonal is inclined at an angle of 45 degrees to the vertical direction Y.
  • the beaker 4 is used In order to collect the corrosion products and other impurities that fall off the template, the vertical projection of the sample is all within the vertical projection range of the beaker mouth to ensure that all the substances falling off the sample enter the beaker. Periodically evaporate the water in the device during the exposure period to ensure that it does not overflow; after the period is over, the sample and the beaker are completely heated and dried and weighed, and the mass changes before and after the period are calculated respectively, and then the result is divided by the sample area (unit square meter) And cycle time (unit month), get the weight gain of the model per unit time (month) per unit area (square meter) and the mass of the material (including corrosion products and other impurities) falling off the model (unit gram) in the cycle.
  • the above mass gain was divided by the sample exposure area to 0.01m 2 , and then divided by the exposure time for 3 months, and finally calculated that the average monthly increase of the sample itself was 2.93g per square meter of the test panel during the 3rd to 6th months of outdoor exposure, 1
  • the average monthly flow of the test board of square meters caused an increase in the mass of the beaker to 4.12g.
  • the weight gain rate of the test plate and its corresponding beaker processed by the manufacturing method of this application was slightly higher in the first month, and then decreased significantly every month thereafter, and tended to be stable.
  • the weight gain rate of the untreated control plate and its corresponding beaker was significantly higher in the first month, and then decreased month by month. Comparing the test board and the control board, it is found that the weight gain rate of the control board and its corresponding beaker is significantly higher than that of the test board in the same period.
  • the weight gain of the treated test board due to corrosion is almost only 75% of the untreated control board in the same period. % Below, see Table 2 for the ratio of the total weight gain of the test board and the control board.
  • the weight gain of the control panel and the corresponding beaker after exposure for more than 3 months to 6 months is basically close to the first month data of the test panel. Since the placement of the test board and the control board is almost the same as the location environment, factors such as environmental dust drop and accidental shedding of corrosion products (such as being blown away by the wind) have basically the same impact on the two. This also means that the total weight gain of the sample plate and the beaker largely represents the strength of the corrosion degree of the sample plate, and the weight gain of the beaker represents the strength of the corrosion product shedding (rusting).
  • the measurement of chromaticity coordinates L, a, b refers to the standard of GBT11186.2 "Method for Measuring the Color of Coating Film Part 2 Color Measurement”.
  • the sample is completely dried every week (drying at 70°C for more than 30 minutes)
  • the MiniScan EZ color difference meter from HunterLab was used to measure the chromaticity coordinates L, a, b near the center point of each plate.
  • the ⁇ E ab value is calculated according to the standard GBT11186.3 "Method for Determination of Coating Film Color Part III Color Difference Calculation" using the following formula, and the ⁇ E ab value is used to evaluate the color change.
  • the test board processed by the manufacturing method of this application has a slight obvious color difference in the first month of exposure, and the color is basically stable after that, and the color difference value in each cycle And the total color difference between the end of each cycle and before exposure The values are all within 10, indicating that the rust layer quickly formed on the surface of weathering steel by the manufacturing method of this application has good color stability in the natural environment.
  • the control panel that is not processed by the manufacturing method of this application has a very significant color change in the first month of exposure, and the ⁇ E ab value exceeds 20, after which the color becomes stable. It started to drop to less than 10, but the color change before the contrast continued to increase, Keep getting bigger, by the 6th month Has exceeded 40.
  • the surface chromaticity coordinates L, a, and b of the control board began to approach the test board before the exposure. After 3 months, the two had a good consistency. After that, it was difficult to see the difference in color between the two.
  • the untreated weathering steel needs to be exposed to the outdoor environment for more than 3 months before the color of the rust layer gradually stabilizes; on the other hand, it also shows that the surface rust layer of weathering steel and weathering steel are obtained by the manufacturing method of this application.
  • the rust layer of more than 3 months has good consistency, which also means that if the rust layer obtained by the manufacturing method of this application is damaged during service, it can basically complete self-repair within 3 months.
  • the rust layer is covered again, and the color of the new rust layer becomes more consistent with the original rust layer, which is difficult to distinguish with the naked eye.
  • the bare weathering steel with rust layer and the manufacturing method thereof according to the present invention have the following advantages and excellent effects:
  • the bare weathering steel produced by the method for manufacturing bare weathering steel with a rust layer of the present invention has a uniform and stable rust layer, which avoids the rust layer of the weathering steel in the prior art during use.
  • the formation is slow and unstable at the initial stage of formation.
  • the unstable rust layer is prone to problems such as uneven color of the rust layer, yellow rust, and rust slag.
  • the bare weathering steel with rust layer produced by the method for manufacturing bare weathering steel with rust layer of the present invention can provide sufficient protection, so that the bare weathering steel with rust layer in this case In the early stage of service, it has excellent performance in corrosion resistance to avoid corrosion damage of bare weathering steel in the early stage of service.
  • the manufacturing method of the present invention can use assembly line equipment to quickly rust the steel, and its process and material costs are far lower than painting.
  • the bare weathering steel with rust layer obtained by the manufacturing method of the present invention can be welded only by grinding the groove when welding, and it can be used normally without any treatment after welding. During service, a protective rust layer will naturally form and become integrated with other parts after the final rust layer is stabilized. If there is a high requirement for early appearance, simple and rapid rusting treatment can also be carried out on the weld.
  • Using the manufacturing method of the present invention can greatly shorten the rust-forming time.
  • the rust-forming time can be shortened by 1-2 hours, which is very conducive to mass production. Products with rust layer are delivered directly.
  • the reagent applied by the manufacturing method of the present invention does not involve the use of precious metal salts, has simpler components, lower cost, and is more suitable for mass production.

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Abstract

本发明公开了一种具有锈层的裸用耐候钢，该裸用耐候钢的表面具有在2小时以内形成的锈层。此外，本发明还公开了上述的具有锈层的裸用耐候钢的制造方法，其包括步骤：(1)将钢板表面进行清洗后去除残余水分；(2)在钢材表面获得亚铁离子；(3)在钢板表面喷涂水以使钢材表面被水膜浸润，待钢板表面水膜干透后，再次至少喷涂一次水膜，以使亚铁离子水解成为铁的氢氧化物沉淀，然后脱水形成锈层。该裸用耐候钢具有均匀的锈层，锈层稳定致密，具有优异的耐腐蚀性，克服了现有技术中常规耐候钢锈层稳定化之前颜色不均等问题，该裸用耐候钢无需在使用现场进行任何表面处理即可直接裸露使用。

Description

一种具有锈层的裸用耐候钢及其制造方法 技术领域
本发明涉及一种耐候钢及其制造方法，尤其涉及一种具有锈层的裸用耐候钢及其制造方法。
背景技术
相对于碳钢，耐候钢具有良好的耐大气腐蚀性能。其主要原因是：耐候钢经过长期大气暴晒其表面上形成了稳定、致密的保护性锈层，阻碍了腐蚀介质的进入，而碳钢表面形成的锈层往往较为疏松，且存在大量的微裂纹，对基体的保护性较差。
目前，在自然环境下，耐候钢形成稳定的保护性锈层需要4年及以上的时间，并且耐候钢在形成稳定化锈层之前，在早期常常出现锈层颜色不均、锈液流挂、锈渣飞扬等现象，影响周围环境及观感。但是，经过4年或更长时间，表面锈层稳定后，耐候钢能显现出具有很强的厚重感的深褐色或咖啡色外观，具有很强的复古艺术气息，深受人们喜爱。而且该颜色能经多年不变，能很好的阻碍腐蚀介质的进一步深入，阻止腐蚀的发生。
现有技术主要集中于快速成锈及锈层稳定化溶液配方方面，例如：公开号为CN86103534，公开日为1987年2月11日，名称为“钢的耐候性防锈膜快速形成法”的中国专利文献公开了一种钢的耐候性防锈膜快速形成法。该专利文献所公开的技术方案实际是对日本已有方法的优化，采用栲胶替代了成本较高的单宁酸。
又例如：公开号为CN103173754A，公开日为2013年6月26日，名称为“耐候钢表面锈层稳定化处理剂及其制备方法”的中国专利文献公开了一种耐候钢表面锈层稳定化处理剂制备方法。在该专利文献所公开的技术方案中，处理剂由25～45％的醇酸清漆、4～12％的焦磷酸铜、2～10％的铬酸钡、1～14％的Fe3O4、20～50％的Fe2O3、1～10％的溶剂油和0.5～5％的分散剂组成。
上述专利文献所公开的技术方案虽然在国内获得一些小规模的应用，但往 往针对加工好的耐候钢材质产品进行现场处理，存在较大局限性，体现在如下所述：
(1)处理的时间往往需要至少1到2天的时间，这是因为处理前需要进行脱脂清洗等复杂的前处理，而且还需要多次喷专门的药水然后再喷水，这导致处理过程费时费力；
2)成锈效果对于施工人员的技术水平有一定的要求，若施工人员的技术水平不够，则会容易出现锈色不均、流淌等问题，影响外观；
3)施工对于场地环境有一定的要求，需要专门的场地堆放样品，对大型建筑物进行现场施工容易污染周边环境，并且需要专门的设备进行施工。
相比而言，针对带锈产品的技术并不多。例如：公开号为CN207512973U，公开日为2018年6月19日，名称为“一种耐气候腐蚀钢板结构”的中国专利文献公开了一种耐气候腐蚀钢板的结构，该专利文献所涉及的产品虽然是带锈层的耐候钢产品，但是其必须在锈板基础上涂装使用。
此外，公开号为CN103459670A，公开日为2013年12月18日，名称为“在高盐度环境下耐候性优异的带锈层的钢材”的中国专利文献公开了一种特别是在海岸地域等大气盐雾含量多的严重腐蚀环境下，在无涂装的状态下耐腐蚀性也优异的带锈层的钢材，然而在该专利文献所公开的技术方案中，材料并不是一开始服役就有稳定锈层，而是在自然环境下自然生成锈层并逐渐稳定，因而，并没有解决稳定化之前颜色不均、不稳定，以及淌黄锈和掉锈渣等问题。
基于此，期望一种新的制造方法，该制造方法可以克服现有技术的不足，批量生产带有均匀稳定锈层的耐候钢，且该耐候钢的锈层稳定致密，具有优异的耐腐蚀性。
发明内容
本发明的目的之一在于提供一种具有锈层的裸用耐候钢，该裸用耐候钢具有均匀稳定的锈层，锈层致密，使得该裸用耐候钢具有优异的耐腐蚀性，裸用是指不涂装，直接使用，可以在常规大气环境中直接裸露使用长达数十年。
为了实现上述目的，本发明提出了一种具有锈层的裸用耐候钢，裸用耐候钢的表面具有通过人工加速方法生成的锈层，该生成过程仅需2个小时以内，因而可通过生产线连续生产，从而使得产品出厂时即带有该锈层。
进一步地，在本发明所述的具有锈层的裸用耐候钢中，出厂时锈层厚度为10-200μm，进一步地，锈层厚度为20-150μm，在提供足够防护的同时，具有很好的均匀性，且锈层主要成分组成与耐候钢在自然环境中需要3个月甚至更长时间才能生成的锈层具有很好的一致性。
进一步地，在本发明所述的具有锈层的裸用耐候钢中，人工加速生成的锈层在耐候钢后期服役过程中不会被破坏或去除，只会被不断增厚、颜色不断加深、防护性不断增强。
进一步地，在本发明所述的具有锈层的裸用耐候钢中，人工加速生成的锈层具有较强的自我修复性，在产品剪切、变形、剐蹭、焊接过程中产生的锈层损害会在服役过程中被逐渐修复，通常在经过1至3个月的修复后，因剪切、变形、剐蹭、焊接导致的痕迹就已经变得肉眼难以分辨了。
进一步地，本发明所述的具有锈层的裸用耐候钢中，锈层中含有α-FeO(OH)，根据石振家、王雷、陈楠、郝龙、董俊华、柯伟在2015年9月发表在《腐蚀科学与防护技术》(第27卷第5期)中的《耐候钢表面锈层及其稳定化处理现状与发展趋势》，以及刘丽宏、齐慧滨、卢燕平、李晓刚在2012年12月发表在《腐蚀与防护》(第23卷第12期)的《耐候钢的腐蚀及表面稳定化处理技术》等多篇文章报道，含该组分的锈层具有很好的致密性和防护性，是锈层稳定化的一个重要标志之一。
进一步地，本发明所述的具有锈层的裸用耐候钢中，锈层暴露在常规户外大气中第一个半年内的色差值ΔE ab≤10，可以说明本发明提供的裸用耐候钢中的锈层具有较高的颜色稳定性。
进一步地，本发明所述的具有锈层的裸用耐候钢，在常规低氯离子(小于0.05mg*NaCl/dm 2/day)大气环境中第一个半年内的单位面积腐蚀增重值≤不具有该锈层的同种材料的裸用耐候钢在同样条件下的单位面积腐蚀增重值的75％，具有明显优于不具有该锈层的裸用耐候钢的耐蚀性。其中，两者为同种材料的裸用耐候钢，区别仅在于本发明提供是的具有锈层的裸用耐候钢。
相应地，本发明的另一目的在于提供上述的具有锈层的裸用耐候钢的制造方法，该制造方法可以克服现有技术的不足，批量生产带有均匀稳定锈层的耐候钢，且所制得的耐候钢的锈层稳定致密，具有优异的耐腐蚀性，能在常规大气环境中直接裸露使用长达数十年。并且通过该制造方法获得的耐候钢不会出 现锈层稳定化之前颜色不均、淌锈、锈渣脱落的问题，该制造方法可以避免现有技术中的成锈处理在场地、人工、环保等方面的限制，大大方便耐候钢的使用，具有较好的应用前景。
为了实现上述目的，本发明提出了上述的具有锈层的裸用耐候钢的制造方法，包括步骤：
(1)将钢板表面进行清洗后去除残余水分；
(2)在钢材表面获得亚铁离子；
(3)在钢板表面喷涂水以使钢材表面被水膜浸润，待钢板表面水膜干透后，再次至少喷涂一次水膜，以使亚铁离子水解成为铁的氢氧化物沉淀，然后脱水并与空气中的氧进一步氧化形成锈层。
在本发明所述的技术方案中，通过本案的各个步骤可以使得所述的裸用耐候钢快速(2小时以内)成锈，使得钢材表面带有稳定均匀的锈层，且该锈层致密，从而能够有效防止腐蚀介质进入内部与钢材的基底发生反应，从而提高材料的耐蚀性，该制造方法工艺步骤简单，有效地降低了制造成本。
由本发明所述的制造方法所获得的具有锈层的裸用耐候钢其表面锈层由浅变深可依次呈现黄色、褐色、咖啡色和深咖啡色，锈层厚度10微米以上，材料表面颜色均匀，且在户外使用过程中锈层颜色可逐渐整体变深，相较于现有技术具有更强的视觉效果。
进一步地，在本发明所述的制造方法中，在步骤(1)中，在钢板热轧或酸洗结束后，对钢板表面进行清洗，以去除表面油污，增强附着性。
进一步地，在本发明所述的制造方法中，在步骤(2)中，可通过以下任意一种方式在钢材表面获得亚铁离子：
(a)在钢板表面涂覆酸溶液，通过氧化单质铁的方式获得亚铁离子；
(b)先将钢板表面氧化得到氧化层，然后再在钢板表面涂覆还原性酸溶液将溶解铁氧化物还原得到亚铁离子；
(c)在钢板表面直接涂覆氧化性的盐溶液，将铁原子氧化成亚铁离子。
进一步地，在本发明所述的制造方法中，当采用方式(a)时，酸溶液的pH值≤3。
进一步地，在本发明所述的制造方法中，酸溶液和还原性酸溶液的pH值≤1。
进一步地，在本发明所述的制造方法中，当采用方式(a)时，酸溶液为盐酸溶液。
进一步地，在本发明所述的制造方法中，当采用方式(a)时，酸溶液为36-38％浓盐酸溶液和质量浓度为1-10％的NaCl溶液组成的混合溶液，所述浓盐酸在所述混合溶液中的体积比≤1：2。
进一步地，在本发明所述的制造方法中，当采用方式(b)时，采用室温下涂覆氧化溶液的方式对钢板表面氧化得到较致密的氧化层。
在一些其他的实施方式中，也可以通过高温氧化的方式对钢板表面氧化得到较致密的氧化层，以及钢板热轧过程中形成的氧化层。
需要说明的是，氧化溶液可以为双氧水或是其他本领域内技术人员可以想到的氧化溶液。
更进一步地，在本发明所述的制造方法中，当采用方式(b)时，氧化溶液为采用质量浓度为1-10％的NaCl溶液稀释得到的质量浓度为0.1-10％的H 2O 2溶液。
进一步地，在本发明所述的制造方法中，当采用方式(b)时，还原性酸溶液为采用质量浓度1-10％的NaCl溶液稀释得到的质量浓度为0.37-15％的盐酸溶液。
进一步地，在本发明所述的制造方法中，当采用方式(c)时，盐溶液是活性弱于铁的惰性金属阳离子盐溶液或三价铁盐溶液。
进一步地，在本发明所述的制造方法中，三价铁盐溶液为质量百分浓度为1-10％的FeCl 3溶液。
上述方案中，添加质量浓度为1-10％的NaCl溶液进行配制，可以增加溶液电导率及侵蚀性，增快成锈速度。
进一步地，在本发明所述的制造方法中，在钢板表面喷涂的水和/或溶液的温度为10-90℃，温度过低，反应时间较长，温度过高，溶液挥发较快，无法充分反应，进一步地，在钢板表面喷涂的水和/或溶液的温度为40-90℃，在保证溶液与钢板表面进行充分反应的同时，加快反应进程，提高反应效率。
本发明所述的具有锈层的裸用耐候钢及其制造方法相较于现有技术，具有如下所述的优点和优异效果：
(1)通过本发明所述的具有锈层的裸用耐候钢的制造方法所制得的裸用 耐候钢具有均匀稳定的锈层，避免了现有技术中的耐候钢在使用过程中锈层形成缓慢，且形成初期时不稳定，不稳定的锈层容易发生锈层颜色不均、淌黄锈、掉锈渣等问题。
(2)通过本发明所述的具有锈层的裸用耐候钢的制造方法所制得的具有锈层的裸用耐候钢可以提供足够的防护性，使得本案的具有锈层的裸用耐候钢在服役初期就在耐蚀性上表现优异，避免裸用耐候钢在服役初期出现腐蚀损伤。
(3)本发明所述的制造方法可以利用流水线设备对钢材进行快速成锈处理，其工艺及物料成本远远低于涂装。
(4)本发明所述的制造方法对耐候钢材进行快速成锈处理时，仅需采用常规盐、弱酸和少量清水进行处理即可，过程中物质均参与反应，无排放，制造过程安全环保。
(5)本发明所述的制造方法所获得的具有锈层的裸用耐候钢在进行焊接时仅需打磨出坡口即可进行焊接，而且焊接后无需进行任何处理即可正常服役，焊缝在服役过程中会自然形成保护性锈层，并在最终锈层稳定后与其他部位浑然一体，如对早期外观有较高要求，也可对焊缝进行简单的快速成锈处理。
(6)采用本发明所述的制造方法可以大大缩短成锈时间，在一些实施方式中，成锈时间可以缩短1-2小时，非常有利于批量生产，因而最终可直接以带有均匀锈层的产品直接出厂。
(7)本发明所述的制造方法所施加的试剂不涉及到贵金属盐的使用，组分更简单，成本更低，更适合批量生产。
附图说明
图1示意性地显示了本发明所述的具有锈层的裸用耐候钢在一些实施方式中的结构。
图2为本发明实施例经快速成锈处理的试验板表面拉曼光谱；
图3为暴晒样板与收集装置的示意图。
具体实施方式
下面将结合附图说明和具体的实施例对本发明所述的具有锈层的裸用耐 候钢及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1-11
上述实施例1-11的具有锈层的裸用耐候钢采用以下步骤制得：
(1)在钢板采用热轧或酸洗工艺生产结束后，采用碱性脱脂剂去除钢板表面油污，然后用清水清洗钢板表面，使得钢板表面形成均匀连续水膜，随后采用压缩空气方式去除钢板表面残余水分。
(2)使钢材表面的单质铁被转变成亚铁离子，其中可以通过以下任意一种方式在钢材表面获得亚铁离子，该过程充分完成后，钢板表面出现绿色或红棕色：
(a)在钢板表面涂覆酸溶液，以将单质铁氧化为亚铁离子；
(b)先将钢板表面氧化得到氧化层，然后再在钢板表面涂覆还原性酸溶液将铁氧化物还原成亚铁离子；
(c)在钢板表面直接涂覆氧化性的盐溶液，如三价铁盐。
(3)在钢板表面喷涂水以使钢材表面被水膜浸润，待钢板表面水膜干透后，再次至少喷涂一次水膜(例如2-8次)，以使亚铁离子水解成为铁的氢氧化物沉淀，然后脱水形成锈层，此时钢板表面形成均匀的锈层，该锈层呈均匀的黄色、橙色或咖啡色，至此，获得了具有锈层的裸用耐候钢。
需要说明的是，在一些实施方式中，当采用方式(a)时，酸溶液的pH值≤3，进一步地，酸溶液的pH值可以进一步控制在≤1，该酸溶液可以为盐酸溶液，并且在一些实施方式中，酸溶液为36-38％浓盐酸溶液和质量浓度为1-10％的NaCl溶液组成的混合溶液，所述浓盐酸在所述混合溶液中的体积比≤1：2。
在一些实施方式中，当采用方式(b)时，可以采用室温下涂覆氧化溶液的方式对钢板表面氧化得到较致密的氧化层，也可以是通过高温氧化的方式对钢板表面氧化得到较致密的氧化层，也可以是钢板热轧过程中形成的氧化层，氧化溶液为采用质量浓度为1-10％的NaCl溶液稀释得到的质量浓度为0.1-10％的H 2O 2溶液，进一步地，还原性酸溶液的pH值可以进一步控制在≤1，在一些实施方式中，还原性酸溶液为采用质量浓度为1-10％的NaCl溶液稀释得到的质量浓度为0.37-15％的盐酸溶液。
在一些实施方式中，当采用方式(c)时，盐溶液是活性弱于铁的惰性金属阳离子盐溶液或三价铁盐溶液，三价铁盐溶液可以为质量百分浓度为1-10％的FeCl 3溶液。
此外，需要说明的是，在钢板表面喷涂的水和/或溶液的温度为10-100℃。
表1列出了实施例1-11的具有锈层的裸用耐候钢的制造方法中涉及的具体工艺参数，且溶液浓度均为质量百分比。
表1
Figure PCTCN2020088343-appb-000001
Figure PCTCN2020088343-appb-000002
表1中样板锈层厚度的测量参考了GBT13452.2/ISO2808《色漆和清漆漆膜厚度的测定》标准4.3重量分析法。其中为了获得锈层质量，参考GBT16545/ISO8407《金属和合金的腐蚀腐蚀试样上腐蚀产物的清除》标准附表A.1中代号C.3.1的方法对锈层进行了清洗。具体计算方法为，根据锈层清除前后的质量差获得了GBT13452.2/ISO2808标准所需要的涂层质量，进而根据锈层密度(5.24g/cm 3)，估计出锈层的平均厚度(仅精确至10μm)。
以实施例9为例，样板为100mm*100mm*3mm的BC550耐候钢板，样板正面按表1中实施例9所示的参数进行了快速成锈处理。处理结束后将样板在70℃环境下烘干30分钟，确保所有水分被去除，待样板恢复至室温且质量 稳定后测量其总质量为m＝195.8396g；之后按GBT16545标准采用添加了六次甲基四胺的稀盐酸将获得的锈层全部去除后，并在70℃环境下烘干30分钟，待样板恢复至室温且质量稳定后测量其总质量为m 0＝192.5907g；根据如下所示GBT13452.2标准4.3.1给出的公式，计算锈层平均厚度，精确至10μm后得到最终结果为60μm。
Figure PCTCN2020088343-appb-000003
公式中，m为带有涂层的样片总质量，本申请中指带锈层的样板总质量；m 0为没有涂层的样片质量，本申请中指去除锈层后样板质量；A为样板面积，单位m 2；ρ为涂料密度，本申请中指锈层密度，为5.24g/cm 3。
表1中处理时间指步骤(2)和步骤(3)处理时间总和，即样板表面清洗之后直至表面覆盖均匀锈层并脱水晾干为止所需要的处理时间。
表1中次数分别指对应该步骤的次数，如对于步骤(2)，在钢板表面涂覆溶液，待反应结束并晾干则为一次；如对于步骤(3)，在钢板表面涂布水膜并脱水则为一次。
最终所获得的具有锈层的裸用耐候钢的结构可以参考图1。图1示意性地显示了本发明所述的具有锈层的裸用耐候钢在一些实施方式中的结构。
如图1所示，具有锈层的裸用耐候钢包括基底1、以及在基底1表面的锈层2，该锈层2为一层结合致密、阻碍腐蚀介质进入内部腐蚀材料的均匀锈膜，其厚度为10-200μm。随着在户外暴露时间的延长，锈层2的颜色由浅变深可呈现黄色、褐色、咖啡色，最终4至8年后稳定为深咖啡色。
本发明提供的具有锈层的裸用耐候钢的表面颜色均匀，且在户外使用过程中锈层2颜色可逐渐整体变深，锈层2能起到防止腐蚀继续发生的作用，且防护效果随时间推移不断增强，因而材料能在常规低氯离子(大气盐雾含量低于0.05mg*NaCl/dm2/day)大气环境中直接裸露使用而不用担心腐蚀问题。
为了验证本案所制得的具有锈层的裸用耐候钢的耐蚀性、色差稳定性以及淌锈性能，进行了对比试验：试验板为边长0.1米的BC550耐候钢热轧酸洗板，对照板为正面没有进行任何处理，其余五面采用金属氟碳漆封闭的该材质钢板，试验板采用如下步骤进行处理：
(1)采用70℃、2％的帕卡SC-364S脱脂剂(碱性)溶液对钢板表面进 行充分的脱脂清洗，去除表面油污。之后用大量清水清洗表面，钢板表面形成均匀连续水膜，采用压缩空气方式去除钢板表面残余水分。
(2)采用金属氟碳漆将样板背面及四周进行封闭，仅露出正面用于测试。
(3)将质量百分比浓度5％的NaCl溶液与质量百分比浓度30％的H 2O 2溶液按体积比4：1混合配置氧化溶液，采用自动喷雾装置将配置好的氧化溶液均匀的喷涂在钢板表面，采用自然晾干方式使氧化溶液的水分完全蒸发，使得氧化溶液与钢板发生充分的化学反应，在钢板表面得到氧化层，然后再在钢板表面涂覆还原性酸溶液溶解氧化层成为铁盐，还原性酸溶液可以通过将质量百分比浓度5％的NaCl溶液与质量百分比浓度36-38％的浓盐酸按体积比5：1混合，采用自动喷雾装置将配置好的还原性酸溶液均匀地喷涂在钢板表面，采用自然晾干方式使还原性酸溶液中的水分完全蒸发，氧化层被溶解，钢板表面呈现绿色。
(4)在钢板表面喷涂水以使钢材表面被水膜浸润，待钢板表面水膜干透后，按照此步骤，再次喷涂三次水膜，以使亚铁离子水解成为铁的氢氧化物沉淀，然后脱水形成锈层。
采用NICOLET DXR激光共聚焦显微拉曼光谱仪对经过上述步骤处理的试验板表面不同位置的锈层组分进行拉曼光谱分析，结果如图2所示，图2为经快速成锈处理的试验板表面拉曼光谱结果。
如图2所示，拉曼光谱显示出明显的α-FeO(OH)所对应的特征峰(248.92、379.51)。因此可以说明，在经快速成锈处理的试验板锈层中具有稳定的α-FeO(OH)分布。根据上述文章报道，含该组分的锈层具有很好的致密性和防护性，是锈层稳定化的一个重要标志之一。
为进一步表征样板颜色稳定性和淌锈性能。我们将对照板与试验板放置户外进行暴晒，对从样板上脱落的杂质及腐蚀产物定期称重，并定期测量样板色度坐标L、a、b。图3为暴晒样板与收集装置的示意图，样板3(试验板、对照版)悬挂于烧杯4的上方，样板一条对角线和水平方向X平行另一条对角线与竖直方向Y成45度角倾斜的方式进行悬挂，烧杯4用于收集从样板脱落的腐蚀产物及其他杂质，样板竖直方向投影全部位于烧杯口竖直方向投影范围内，以确保所有从样板脱落的物质都进入烧杯。对照板和试验板放置方式和所处环境均保持高度一致。考虑到锈层表现出来的色差和流淌性能会受气候的影 响。选择在中国上海(大气平均盐雾含量低于0.05mg*NaCl/dm2/day)进行暴晒，上架时间为当年9月，结束时间为次年3月。在上海地区，9月与3月的气候比较相近。测量了样板每个月、每季度和每半年的数据，具体如表2所示。
表2.户外暴晒对比表
Figure PCTCN2020088343-appb-000004
由于采用本申请制造方法处理的试验板本身就带有锈层，该锈层成分组成与后期暴晒过程中形成的腐蚀产物具有高度的一致性，二者无法有针对性的去除，常规的清洗腐蚀产物后测量失重的方法无法用于评价其耐蚀性。为此，我们采用增重法对样板耐蚀性进行了评估。具体方法是：将样板采用图3所示对角线方式悬挂，样板一条对角线和水平方向X平行另一条对角线与竖直方向Y成45度角倾斜的方式进行悬挂，烧杯4用于收集从样板脱落的腐蚀产物及其他杂质，样板竖直方向投影全部位于烧杯口竖直方向投影范围内，以确保所有从样板脱落的物质都进入烧杯。暴晒周期内定期蒸发装置中的水分以保证不溢出；周期结束后将样板和烧杯分别完全加热烘干后称重，分别计算出周期前后质量变化，然后将该结果除以样板面积(单位平米)和周期时间(单位月)，得到周期内单位时间(月)单位面积(平米)样板的增重及从样板脱落物质(包括腐蚀产物和其他杂质)的质量(单位克)。
以第6个月对应的试验板的数据为例。前一周期结束(第3月)时按前述方法称量试验板质量为196.1006g，下方烧杯质量为98.4342g，当前周期结束(第6月)时按前述方法称量试验板质量为196.1885g，下方烧杯质量为98.5578g。计算周期内样板本身质量增加0.0879g，烧杯质量增加0.1236g。上述质量增重分别除以样品暴露面积为0.01m 2，然后再除以暴晒时间3个月，最终计算得到每平米试验板户外暴晒第3至6个月平均每月样板本身增加 2.93g，1平米的试验板平均每月流淌物造成烧杯质量增加为4.12g。
根据称重结果可以看出：采用本申请制造方法处理的试验板及其对应烧杯的增重率在第一个月略微偏高，之后每个月均明显变少，且趋于稳定。未经处理的对照板及其对应的烧杯增重率在第一个月显著偏高，之后逐月减少。对比试验板和对照板，发现对照板及其对应烧杯的增重率明显高于同时期的试验板，经过处理的试验板因腐蚀发生的质量增重几乎只有同时期未经处理对照板的75％以下，见表格2试验板和对照板增重总和的比值。对照板在经3个月以上直到6个月暴晒后样板和对应烧杯的增重与试验板首月数据基本接近。由于试验板和对照板的放置方式和场所环境几乎完全一致，环境尘降、腐蚀产物意外脱落(如被风刮走)等因素对二者的影响也基本相当。这也意味着，样板及烧杯增重总和很大程度上代表了样板腐蚀程度的强弱，烧杯增重则代表了腐蚀产物脱落(淌锈)情况的强弱。因此，根据前述增重数据，我们可以看出未经处理的耐候钢(对照板)至少需要在户外暴晒3个月以上，其表面锈层耐蚀性和淌锈情况才能接近经本申请制造方法处理样片(试验板)的出厂状态；在此之前，其锈层耐蚀性明显弱于采用本申请制造方法处理的样板，其淌锈情况要明显比采用本申请制造方法处理的样板更为严重。
表2中，色度坐标L、a、b的测量参考GBT11186.2《涂膜颜色的测量方法第二部分颜色测量》标准，每周将样板完全烘干水分(70℃烘干30分钟以上)后采用HunterLab公司的MiniScan EZ色差仪测量各块板中心点附近的色度坐标L、a、b。ΔE ab值根据标准GBT11186.3《涂膜颜色的测定方法第三部分色差计算》采用下述公式计算得到，ΔE ab值用来评价颜色变化情况。
ΔE ab＝[(ΔL) 2+(Δa) 2+(Δb) 2] 1/2
表中
Figure PCTCN2020088343-appb-000005
为样板相对于上一次测量时的ΔE ab值，表征周期内样板表面颜色变化情况；
Figure PCTCN2020088343-appb-000006
为样板相对于开始暴晒前的ΔE ab值，表征测量时样板相对于未暴晒时的表面颜色变化情况。
以对照板为例，在经过第2个月暴晒后，样板对比前一个月表面色差改变情况为：
Figure PCTCN2020088343-appb-000007
对比暴晒前的原始表面色差改变情况则为：
Figure PCTCN2020088343-appb-000008
根据色差结果可以看出：采用本申请制造方法处理的试验板除了在刚开始暴晒第一个月有略微明显的色差外，之后颜色基本比较稳定，每个周期内的色差值
Figure PCTCN2020088343-appb-000009
以及每个周期结束后与暴晒之前的总色差值
Figure PCTCN2020088343-appb-000010
都在10以内，说明采用本申请制造方法在耐候钢表面快速形成的锈层在自然环境中具有较好的颜色稳定性。
未采用本申请制造方法处理的对照板在暴晒第一个月有极为显著的颜色变化，ΔE ab值超过20，之后颜色趋于稳定，
Figure PCTCN2020088343-appb-000011
开始下降至10以内，但对比暴晒前的的颜色变化持续加剧，
Figure PCTCN2020088343-appb-000012
不断变大，到第6个月时
Figure PCTCN2020088343-appb-000013
已经超过40。在暴晒2个月后对照板表面色度坐标L、a、b开始与暴晒前的试验板接近，3个月后二者有较好的一致性，之后基本很难看出二者颜色的差异。这一方面说明未经处理的耐候钢需要在户外环境暴晒3个月以上，其锈层颜色才能逐步趋于稳定；另一方面也说明采用本申请制造方法获得耐候钢表面锈层与耐候钢暴晒3个月以上的锈层具有较好的一致性，这也意味着如果采用本申请制造方法获得的锈层在服役过程中受到损伤后，经过3个月以内的时间即可基本完成自我修复，重新覆盖锈层，且新锈层与原有锈层颜色变得比较一致，肉眼难以分辨。
实施例1-11涉及的化学试剂及满足的产品标准如表3所示：
表3试剂及产品标准
试剂 36.0-38.0％HCl 30％H 2O 2 FeCl 3 六次甲基四胺 NaCl
标准 GB/T622-2006 GB/T6684-2002 HG/T3474-2000 GB/T1400-2014 GB/T1266-2006
综上所述可以看出，本发明所述的具有锈层的裸用耐候钢及其制造方法具有如下所述的优点和优异效果：
(1)通过本发明所述的具有锈层的裸用耐候钢的制造方法所制得的裸用耐候钢具有均匀稳定的锈层，避免了现有技术中的耐候钢在使用过程中锈层形成缓慢，且形成初期时不稳定，不稳定的锈层容易发生锈层颜色不均、淌黄锈、掉锈渣等问题。
(2)通过本发明所述的具有锈层的裸用耐候钢的制造方法所制得的具有 锈层的裸用耐候钢可以提供足够的防护性，使得本案的具有锈层的裸用耐候钢在服役初期就在耐蚀性上表现优异，避免裸用耐候钢在服役初期出现腐蚀损伤。
(3)本发明所述的制造方法可以利用流水线设备对钢材进行快速成锈处理，其工艺及物料成本远远低于涂装。
(4)本发明所述的制造方法对耐候钢材进行快速成锈处理时，仅需采用常规盐、弱酸和少量清水进行处理即可，过程中物质均参与反应，无排放，制造过程安全环保。
(5)本发明所述的制造方法所获得的具有锈层的裸用耐候钢在进行焊接时仅需打磨出坡口即可进行焊接，而且焊接后无需进行任何处理即可正常服役，焊缝在服役过程中会自然形成保护性锈层并在最终锈层稳定后与其他部位浑然一体，如对早期外观有较高要求，也可对焊缝进行简单的快速成锈处理。
(6)采用本发明所述的制造方法可以大大缩短成锈时间，在一些优选的实施方式中，成锈时间可以缩短1-2小时，非常有利于批量生产，因而最终可直接以带有均匀锈层的产品直接出厂。
(7)本发明所述的制造方法所施加的试剂不涉及到贵金属盐的使用，组分更简单，成本更低，更适合批量生产。
需要说明的是，本发明的保护范围中现有技术部分并不局限于本申请文件所给出的实施例，所有不与本发明的方案相矛盾的现有技术，包括但不局限于在先专利文献、在先公开出版物，在先公开使用等等，都可纳入本发明的保护范围。
此外，本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式，本案记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。
还需要注意的是，以上列举的仅为本发明的具体实施例，显然本发明不限于以上实施例，随之有着许多的类似变化。本领域的技术人员如果从本发明公开的内容直接导出或联想到的所有变形，均应属于本发明的保护范围。

Claims (20)

  1. 一种具有锈层的裸用耐候钢，其特征在于，所述裸用耐候钢的表面具有在2小时以内形成的锈层。
  2. 如权利要求1所述的具有锈层的裸用耐候钢，其特征在于，所述锈层厚度为10-200μm。
  3. 如权利要求1所述的具有锈层的裸用耐候钢，其特征在于，所述锈层中含有α-FeO(OH)。
  4. 如权利要求1所述的具有锈层的裸用耐候钢，其特征在于，所述锈层暴露在常规户外大气中第一个半年内的色差值ΔE ab≤10。
  5. 如权利要求1所述的具有锈层的裸用耐候钢，其特征在于，所述裸用耐候钢在常规低氯离子(小于0.05mg*NaCl/dm 2/day)大气环境中第一个半年内的单位面积腐蚀增重值≤不具有锈层的同种材料的裸用耐候钢在同样条件下第一个半年内的单位面积腐蚀增重值的75％。
  6. 一种如权利要求1-5中任一项所述的具有锈层的裸用耐候钢的制造方法，其特征在于，包括步骤：
    (1)将钢板表面进行清洗后去除残余水分；
    (2)在钢材表面获得亚铁离子；
    (3)在钢板表面喷涂水以使钢材表面被水膜浸润，待钢板表面水膜干透后，再次至少喷涂一次水膜，以使亚铁离子水解成为铁的氢氧化物沉淀，然后脱水并与空气中的氧进一步氧化形成锈层。
  7. 如权利要求6所述的制造方法，其特征在于，在钢板表面喷涂的水和/或溶液的温度为10-90℃。
  8. 如权利要求6所述的制造方法，其特征在于，在所述步骤(1)中，在钢板热轧或酸洗结束后，对钢板表面进行清洗。
  9. 如权利要求6所述的制造方法，其特征在于，在所述步骤(2)可通过以下任意一种方式在钢材表面获得亚铁离子：
    (a)在钢板表面涂覆酸溶液；
    (b)先将钢板表面氧化得到氧化层，然后再在钢板表面涂覆还原性酸溶液将铁氧化物还原得到亚铁离子；
    (c)在钢板表面直接涂覆氧化性的盐溶液，将铁原子氧化成亚铁离子。
  10. 如权利要求9所述的制造方法，其特征在于，当采用方式(a)时，所述酸溶液的pH值≤3。
  11. 如权利要求9所述的制造方法，其特征在于，所述酸溶液和所述还原性酸溶液的pH值≤1。
  12. 如权利要求9所述的制造方法，其特征在于，当采用方式(a)时，所述酸溶液为盐酸溶液。
  13. 如权利要求9所述的制造方法，其特征在于，当采用方式(a)时，所述酸溶液为36-38％浓盐酸溶液和质量浓度为1-10％的NaCl溶液组成的混合溶液，所述浓盐酸在所述混合溶液中的体积比≤1：2。
  14. 如权利要求9所述的制造方法，其特征在于，当采用方式(b)时，采用室温下涂覆氧化溶液的方式对钢板表面氧化得到氧化层。
  15. 如权利要求9所述的制造方法，其特征在于，当采用方式(b)时，在钢板热轧过程中形成的氧化层。
  16. 如权利要求9所述的制造方法，其特征在于，当采用方式(b)时，通过高温氧化的方式对钢板表面氧化得到氧化层。
  17. 如权利要求14所述的制造方法，其特征在于，当采用方式(b)时，所述氧化溶液为采用质量浓度为1-10％的NaCl溶液稀释得到的质量浓度为0.1-10％的H 2O 2溶液。
  18. 如权利要求14所述的制造方法，其特征在于，当采用方式(b)时，所述还原性酸溶液为采用质量浓度为1-10％的NaCl溶液稀释得到的质量浓度为0.37-15％的盐酸溶液。
  19. 如权利要求9所述的制造方法，其特征在于，当采用方式(c)时，所述盐溶液是活性弱于铁的惰性金属阳离子盐溶液或三价铁盐溶液。
  20. 如权利要求19所述的制造方法，其特征在于，所述三价铁盐溶液为质量百分浓度为1-10％的FeCl 3溶液。
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