JP5578056B2 - Steel sheet having excellent corrosion resistance and method for producing the same - Google Patents

Description

  The present invention can be applied to inner and outer panels of automobiles and home appliances, and is excellent even when exposed to a high-humidity environment with a high salt content for a long time before processing or surface treatment such as plating or painting. The present invention relates to a steel plate having high corrosion resistance and a method for producing the same.

  Improving the corrosion resistance of steel is an important issue in almost all fields where steel materials are used. Therefore, various technologies including rust preventive oil coating and plating technologies have been researched and developed. In particular, suppressing the corrosion that occurs on the steel sheet surface when storing cold-rolled steel sheets or hot-rolled steel sheets before processing or surface treatment such as plating or painting is effective for deterioration of the surface appearance of the product, Or it is important to prevent plating peeling during surface treatment.

  In recent years, as coiled cold-rolled steel sheets and hot-rolled steel sheets have been exported to Southeast Asia, etc., and processing and surface treatment at customers have increased, they have been transported for long periods in high humidity environments with high salinity. Corrosion problems that occur during storage are highlighted. As countermeasures against corrosion that occurs due to long-term exposure to such a high-humidity environment with high salinity, strengthening of oil coating, strengthening of packaging, or management of local steel sheet storage environment as described in Non-Patent Document 1 can be mentioned. It is done. However, the strengthening of oiling gives oil that is harder to remove, and oil components that could not be removed by washing before using the steel sheet may cause defects on the surface of the steel sheet. In addition, the enhancement of oil coating increases the environmental load such as waste liquid, and corrosion may not be sufficiently suppressed in a highly humid environment with a high salt content. On the other hand, strengthening packaging and managing the local steel sheet storage environment are costly, and managing the steel sheet storage environment at the customer is often difficult.

  As the corrosion resistance improvement technology without using oil coating and packaging, the stainless steel plate described in Non-Patent Document 2 using corrosion products and chromium (Cr), copper (Cu) described in Non-Patent Document 3, Steel sheets having excellent corrosion resistance even in a high-humidity environment with a high salt content, such as weather-resistant steel sheets to which phosphorus (P) or the like is added, are known. However, the former is expensive because a large amount of expensive alloy elements are added, and the latter is not applicable to a cold-rolled steel sheet with a small thickness because the thickness of the corrosion product layer needs to be about 100 μm or more. There is a problem.

"Rust and corrosion prevention technology manual", Japan Standards Association, 1984, p.92-93 By Zoffy (translated by Masayoshi Hasegawa), “Introduction to Stainless Steel”, Special Steel Club, 1970, p.27 Matsushima Satoshi, "Low Alloy Corrosion Resistant Steel", Jinshoshokan (Tokyo), 1995

  The present invention can be applied to inner and outer panels of automobiles and home appliances, and is excellent even when exposed to a high-humidity environment with a high salt content for a long time before processing or surface treatment such as plating or painting. An object of the present invention is to provide an inexpensive steel plate having corrosion resistance and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors formed an iron (Fe) oxide layer containing hexavalent tungsten (W) on the steel plate surface, and the W concentration near the surface of the Fe oxide layer was determined. It has been found that if the W concentration near the interface with the steel plate is higher, even a thin Fe oxide layer of 1 μm or less has excellent corrosion resistance in a high-humidity environment with high salinity.

The present invention has been made based on such knowledge, and has a Fe oxide layer containing hexavalent W on the steel plate surface, and a region I from the interface of the Fe oxide layer with the steel plate surface to 2 nm. C _W / when the (C _W + C _Fe) of the a, C _W / region S from the surface of the Fe oxide layer to 2nm a _{(C W + C Fe) B} , to satisfy the a <B of A steel sheet having excellent corrosion resistance is provided. Here, C _W and C _Fe represent the atomic concentrations of W and Fe in the region I or the region S of the Fe oxide layer, respectively.

  In the steel sheet having excellent corrosion resistance according to the present invention, it is preferable that B ≧ 0.010 and B−0.001 ≧ A are satisfied, and more preferably B ≧ 0.050.

  The steel sheet having excellent corrosion resistance according to the present invention is a method in which an Fe oxide layer is formed on the steel sheet surface, and then contacted with an aqueous solution containing tungstic acid, followed by washing and drying. More specifically, Fe oxidizes the steel sheet. After heating for 1 to 300 seconds in a temperature range of 300 to 800 ° C in an atmosphere, or after contact with a 3 to 10% by weight sodium chloride (NaCl) aqueous solution for 1 second or more and leaving it in an atmosphere where Fe is oxidized for 1 second or more Then, it can be produced by a method in which it is brought into contact with an aqueous solution containing 0.01 to 1 mol / L (liter) of tungstic acid for 1 second or longer, followed by washing and drying.

  According to the present invention, a steel sheet that can be applied to inner and outer panels of automobiles and home appliances and has excellent corrosion resistance even when exposed to a high humidity environment with a high salt content for a long period of time can be manufactured at low cost.

It is a figure which shows the two-layer structure of a Fe oxide layer typically. It is a figure which shows an example of the anodic polarization measurement of the steel plate which is an example of this invention.

  A feature of the present invention is that a Fe oxide layer such as iron oxide, iron hydroxide or iron oxyhydroxide containing hexavalent W and having a Fe content of 90% by mass or more is formed on the steel plate surface, and Fe oxidation In addition to stabilizing the layer, the W concentration in the vicinity of the surface of the Fe oxide layer is made higher than the W concentration in the vicinity of the interface with the steel plate surface, thereby greatly improving the corrosion resistance in a highly humid environment with high salinity.

The reason is considered as follows. That is, in a highly humid environment with high salinity, in the corrosion anode part where Fe dissolves, Fe dissolves from the steel sheet side and becomes Fe ²⁺ , and chlorine ions (Cl ⁻ ) enter from the outside, and corrosion progresses. However, when a Fe-based Fe oxide layer containing hexavalent W is provided on the steel plate surface and the W concentration near the surface of the Fe oxide layer is higher than the W concentration near the interface with the steel plate surface, W is tungstate ion ( WO ₄ ^2- ) is present near the surface of the Fe oxide layer, has a negative charge near the surface, is relatively positive near the interface with the steel plate surface, has a negative polarization structure in which the upper layer is negative and the lower layer is positive. Have. Then, the polarization structure Cl from outside ^- as well as inhibit the penetration of the corrosion resistance is improved in order to suppress the dissolution of Fe.

In order to make the W concentration near the surface of the Fe oxide layer higher than the W concentration near the interface with the steel plate surface, a multilayer structure may be provided by providing two or more Fe oxide layers having different W concentrations as shown in FIG. Moreover, it is good also as a single layer structure of the Fe oxide layer which provided the inclination of W concentration in the thickness direction. In any case, C _W / (C _W + C _Fe ) (= B) in the vicinity of the surface of the Fe oxide layer, particularly from the surface to 2 nm, near the interface with the steel sheet surface, particularly from the interface to 2 nm. If it is higher than C _W / (C _W + C _Fe ) (= A) in region I, the effect of the present invention will be exhibited. Therefore, in the case of a multilayer structure, the thickness of the uppermost layer and the lowermost layer needs to be 2 nm or more, and in the case of a single layer structure, the thickness of the layer needs to be 4 nm or more. Further, the effect of the present invention is exhibited even when the thickness of the entire Fe oxide layer is 1 μm or less. Therefore, the present invention can be applied to a cold-rolled steel sheet having a thin plate thickness, can reduce the amount of W used and the formation time of the Fe oxide layer, and does not increase the manufacturing cost.

For further improvement of corrosion resistance, it is desirable to satisfy B ≧ 0.010 and B−0.001 ≧ A. In particular, it is more desirable that B ≧ 0.050. The upper limit of B is not particularly set, but if it exceeds 0.9, an iron oxide layer with an iron tungstate (FeWO ₄ ) structure with good crystallinity is formed, and there are many defects as crystal grain boundaries that facilitate the permeation of ions. since that way, the protective effect of the surface, i.e. Cl ^- for suppression of penetration is likely to be insufficient, B is preferably 0.9 or less.

For the thickness of the Fe oxide layer and C _W / (C _W + C _Fe ), a thin-section sample of the cross section of the steel sheet was prepared by the focused ion beam method, etc., and the Fe oxide layer was measured by a transmission electron microscope equipped with an X-ray spectrometer. It can be measured by Auger electron spectroscopy or X-ray photoelectron spectroscopy while sputtering argon (Ar) ions in the thickness direction.

The steel sheet with excellent corrosion resistance according to the present invention can be subjected to various surface treatments and coatings without problems. The steel sheet with excellent corrosion resistance according to the present invention has a Fe oxide layer on the steel sheet surface by heating or solution treatment. After the formation, it can be produced by a method in which it is brought into contact with an aqueous solution of a soluble tungstate, for example, sodium tungstate (Na ₂ WO ₄ ), that is, the aqueous solution is applied or immersed in an aqueous solution, followed by washing and drying. At this time, the thickness of the Fe oxide layer is adjusted by adjusting the time of heating and solution treatment, and the W in the Fe oxide layer thickness direction is adjusted by adjusting the concentration of tungstate, the temperature of the aqueous solution, or the contact time with the aqueous solution. The concentration can be changed.

  Specifically, the steel sheet is heated in a temperature range of 300 to 800 ° C. for 1 to 300 seconds in an atmosphere where Fe is oxidized, such as air, or is brought into contact with a 3 to 10% by mass NaCl aqueous solution for 1 second or more. After being left in an atmosphere in which Fe is oxidized for 1 second or longer, it is then brought into contact with an aqueous solution containing 0.01 to 1 mol / L tungstate for 1 second or longer, followed by washing with water and drying. At this time, if the heating temperature in the atmosphere in which Fe is oxidized is less than 300 ° C. or if the heating time is less than 1 second, it becomes difficult to form a stable oxide layer, and the heating temperature in the atmosphere in which Fe is oxidized is 800 If it exceeds ℃ or heating time exceeds 300 seconds, the oxide layer grows too thick. Also, if the concentration of the NaCl aqueous solution is less than 3% by mass, the formation of the oxide layer is not sufficient, and if it exceeds 10% by mass, the formation of the oxide layer is fast and difficult to control. If the contact time with the NaCl aqueous solution is less than 1 second, or the standing time in the atmosphere where Fe after contact is oxidized is less than 1 second, stable control becomes difficult. Furthermore, if the concentration of the tungstate aqueous solution is less than 0.01 mol / L or the contact time is less than 1 second, a desirable amount of W cannot be imparted to the steel sheet surface. If the concentration of the tungstate aqueous solution exceeds 1 mol / L, the W concentration becomes too high.

A cold-rolled steel sheet with a thickness of 2 mm (C: 0.15% by mass, Si: 0.28% by mass, Mn: 1.18% by mass contained) was immersed in a 3% by mass NaCl aqueous solution for 20 seconds or more, and left in the atmosphere for 20 seconds. Sample No.1-having an iron oxide layer with an average thickness of 5-6 nm of an upper and lower two-layer structure containing W on the steel sheet surface, immersed in an aqueous Na ₂ WO ₄ solution having a concentration shown in Table 1 for 600 seconds, washed with water and dried 6 was produced. Then, in each sample, the average thickness of the upper and lower Fe oxide layers and A and B in the Fe oxide layers in regions I and S were measured by the method described above. In addition, anodic polarization measurement was performed in a 5% by mass NaCl aqueous solution simulating a high-humidity environment with high salinity, and the presence or absence of a decrease in immersion potential or anode current was determined. In addition, the presence or absence of a decrease in anode current means that a potential region where the current density is smaller than 1/2 of the current density of sample No. 6 (comparative example only of Fe oxide layer not containing W) at a potential of −400 mV or more. The corrosion resistance was evaluated with the case where it was present and the case where it was not present. It can be said that it shows higher corrosion resistance than the case where it is present.

  The results are shown in FIG.

  As shown in FIG. 2, in the sample No. 2 which is an example of the present invention, the immersion potential is changed preciously compared to the sample No. 6 which is a comparative example, and excellent corrosion resistance is obtained. I understand. As shown in Table 1, in Samples Nos. 3 and 4 with B of 0.05 or more, in addition to the change in immersion potential, the anode current at a potential of -400 mV decreased by an order of magnitude or more compared to Sample No. 6. It was found to have high corrosion resistance.

  In addition, when the valence of W of sample No. 1-5 was investigated by XPS, all were 6 valences.

A soft cold-rolled steel sheet with a thickness of 0.7 mm (C: 0.018% by mass, Si: 0.010% by mass, Mn: 0.140% by mass) heated in the atmosphere at 300 ° C, 500 ° C and 800 ° C for 2 minutes, then 0.3 mol A sample having an Fe oxide layer on the steel sheet surface was prepared by immersing in an aqueous solution of Na ₂ WO ₄ / L for 15 minutes, washing with water and drying. At this time, in sample 1 heated at 300 ° C., the thickness of the Fe oxide layer was 8 nm, B was 0.10, A was 0.06, and in sample 2 heated at 500 ° C., the thickness of the Fe oxide layer was 38 nm, B was 0.12, and A was 0.06. In sample 3 heated at 800 ° C., the thickness of the Fe oxide layer was 1 μm, B was 0.13, and A was 0.03. In addition, after immersing in 5% hydrochloric acid for 1 second and squeezing the liquid with a roll, it was dried at room temperature with the liquid attached, washed with water and dried to oxidize the surface, then 0.3 mol / L Na ₂ Sample 4 immersed in an aqueous solution of WO ₄ for 15 minutes, washed with water and dried was prepared. The thickness of the Fe oxide layer of this sample was 0.8 μm, B was 0.15, and A was 0.04. All of the valences of W were hexavalent. Anodic polarization measurement was performed on these four types of samples 1 to 4 and untreated sample 5 in an aqueous 3.5% by mass NaCl solution.

  The results are shown in Table 2. Samples 1 to 4 of the present invention have a higher immersion potential than the sample 5 of the comparative example that has not been treated. In addition, since the current density of both the potential -460 mV and the potential -300 mV of the samples 1 to 4 of the present invention or one of them is smaller than that of the sample 5, excellent corrosion resistance compared to the sample 5 that has not been treated. It became clear to show. In particular, in the sample 3 oxidized at 800 ° C. and the sample 4 oxidized by acid immersion, the −460 mV and −300 mV anode currents are as low as about 1/2 to 1/100 of the value of the sample 5 of the original plate, It became clear that it showed high corrosion resistance.

Claims (6)

The steel plate surface has a Fe oxide layer containing hexavalent tungsten (W), and C _W / (C _W + C _Fe ) in the region I from the interface with the steel plate surface of the Fe oxide layer to 2 nm is A, when the surface of the Fe oxide layer _C W _/ area S to 2nm a _(C W ₊ C _Fe) and B, a <B is satisfied steel sheet having excellent corrosion resistance, characterized in the; wherein, _{C W} , C _Fe represent the atomic concentrations of W and Fe in the region I or region S of the Fe oxide layer, respectively.   The steel sheet having excellent corrosion resistance according to claim 1, wherein B ≧ 0.010 and B−0.001 ≧ A are satisfied.   The steel sheet having excellent corrosion resistance according to claim 2, wherein B ≧ 0.050. After forming the Fe oxide layer on the steel plate surface, it is brought into contact with an aqueous solution containing tungstic acid, washed with water and dried, and has a Fe oxide layer containing hexavalent tungsten (W) on the steel plate surface, C _W / (C _W + C _Fe ) in region I from the interface with the steel plate surface of the Fe oxide layer to 2 nm is A, and C _W / (C _W + C _{Fe in} region S from the surface of the Fe oxide layer to 2 nm. ) Is B, a method for producing a steel sheet having excellent corrosion resistance satisfying A <B .
Here, C _W and C _Fe represent the atomic concentrations of W and Fe in the region I or the region S of the Fe oxide layer, respectively. After heating the steel sheet for 1 to 300 seconds in a temperature range of 300 to 800 ° C. in an atmosphere where Fe is oxidized, the steel sheet is then contacted with an aqueous solution containing 0.01 to 1 mol / L (liter) of tungstic acid for 1 second or more. Washing and drying are performed , the steel plate surface has a Fe oxide layer containing hexavalent tungsten (W), and the C _{W in} region I is 2 nm from the interface with the steel plate surface of the Fe oxide layer. / when a _(C W ₊ C _Fe) was a, _C W _/ a _(C W ₊ C _Fe) B region S from the surface of the Fe oxide layer to 2 nm, the steel plate having excellent corrosion resistance that satisfies a <B Manufacturing method.
Here, C _W and C _Fe represent the atomic concentrations of W and Fe in the region I or the region S of the Fe oxide layer, respectively. The steel sheet was brought into contact with a 3 to 10 mass% sodium chloride (NaCl) aqueous solution for 1 second or longer, left in an atmosphere in which Fe was oxidized for 1 second or longer, and then 0.01 to 1 mol / L (liter) of tungstic acid. Contacted with an aqueous solution containing at least 1 second, washed with water and dried , having a Fe oxide layer containing hexavalent tungsten (W) on the steel plate surface, and the steel plate surface of the Fe oxide layer _{when C} W _/ region I from the interface to 2nm a _{(C W + C Fe) a} , was _C W _/ a _(C W ₊ C _Fe) B region S from the surface of the Fe oxide layer to 2nm, a < A method for producing a steel sheet having excellent corrosion resistance satisfying B.
Here, C _W and C _Fe represent the atomic concentrations of W and Fe in the region I or the region S of the Fe oxide layer, respectively.

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