WO2011087116A1

WO2011087116A1 - Steel sheet with small welding deformation and excellent corrosion resistance

Info

Publication number: WO2011087116A1
Application number: PCT/JP2011/050628
Authority: WO
Inventors: 上村　隆之; 鹿島　和幸; 幸　英昭; 川畑　友弥; 中村　浩史; 有持　和茂
Original assignee: 住友金属工業株式会社
Priority date: 2010-01-18
Filing date: 2011-01-17
Publication date: 2011-07-21
Also published as: JP4924775B2; JPWO2011087116A1; CN102652181B; KR20110105400A; CN102652181A

Abstract

Disclosed is a steel sheet with small welding deformation and excellent corrosion resistance, which is characterized by having a chemical composition containing, in mass%, 0.02-0.25% of C, 0.01-0.7% of Si, 0.3-2% of Mn, 0.05% or less of P, 0.008% or less of S, less than 0.2% of Cu, 1-2.5% of Cr, 0.05% or less of Mo, 0.005-0.1% of Nb, 0.003-0.1% of Al, 0.01% or less of N and 0.03-0.50% of Sn, with the balance made up of Fe and impurities and a Cu/Sn ratio of 1 or less. The steel sheet is also characterized in that the metallic structure thereof is composed of 10-60% of a ferrite structure and 40-90% of a bainite structure and/or a martensite structure, the ferrite structure has an average particle diameter of 30 μm or less, and the ratio of the hardness of the bainite structure and/or the martensite structure to the hardness of the ferrite structure is 1.5 or more. The steel sheet may additionally contain one or more substances selected from among Ti, Ni, V, B, Zr, Ca, Mg and REM.

Description

Steel sheet with small welding deformation and excellent corrosion resistance

The present invention relates to a steel plate that is small in welding deformation and excellent in corrosion resistance, used in fields such as shipbuilding, offshore structures, building structures, bridges, and civil engineering. In particular, the present invention relates to a thick steel plate that is small in welding deformation that occurs during fillet welding and has excellent corrosion resistance.

Generally, when manufacturing various welded steel structures, deformation occurs due to solidification shrinkage of the weld metal and subsequent shrinkage and expansion due to cooling and phase transformation. As a typical welding deformation, there is an angular deformation of a T-type fillet weld. If the structure is manufactured with the angular deformation left, the buckling strength is greatly reduced due to the deformation of the member, or the fracture characteristics are deteriorated. Therefore, there is a possibility that the structure is not aimed by the designer. In order to prevent such a situation, various measures have been taken to prevent it.

溶接 The welding deformation prevention measures currently applied are roughly divided into the following three (i) to (iii).

(i) Design ingenuity (method to increase the rigidity of the deformed member)
The reason why the welding deformation remains is that the vicinity of the weld toe of the weld metal or the base metal is subjected to plastic deformation. The part that has undergone plastic deformation tends to elastically deform its outer part, but if the rigidity is high, that is, the cross-sectional area is large, the amount of deformation is small. Therefore, changing the design to increase the cross-sectional area can be one preventive measure. However, the design change to increase the cross-sectional area has a lot of loss in terms of cost increase, weight increase and construction period extension of the steel material used.

(ii) Device for welding Welding deformation can be prevented by making some device for welding. There are several methods, but the first is to bend in the opposite direction before welding. Although angular deformation occurs after welding, there is a possibility that it will be finished in a desired shape by bending it in the opposite direction in advance. There is also a method in which the end is constrained during welding and deformation is not allowed. Further, there is a case where a backward torch is installed and bent back by reheating an appropriate position after welding. However, all of them are accompanied by a significant increase in man-hours, which causes a cost increase.

(iii) Straightening after welding There are mechanical straightening and linear heating straightening as methods for straightening after welding. However, these methods also require a significant increase in man-hours and require highly skilled skills.

The above measures (i) to (iii) are all ingenuity in production. For example, Patent Document 1 proposes reducing welding deformation by devising welding materials. However, there are many problems that the cost increase of the welding material hinders the economic efficiency and the effect is insufficient, and the application is not practically progressing.

On the other hand, there is an example of trying to suppress welding deformation by devising a steel material as a base material, and some have been proposed as follows.

Patent Document 2 discloses a method of increasing yield stress by promoting precipitation in welding heat history by adding Nb and Mo in combination. However, since addition of Mo brings about a significant cost increase, it is poor in versatility.

In Patent Documents 3 and 4, by controlling the fraction of bainite and / or martensite of the steel material as the base material to 20% or more and further defining the dispersion state of carbonitride, the yield stress is increased, and There is a description of suppressing welding deformation. However, it has not yet reached a practically sufficient weld deformation reduction effect.

Patent Document 5 describes that welding deformation is suppressed by setting the bainite ratio of a steel material as a base material to 70% or more and further ensuring the solid solution Nb amount to 0.040% or more. However, when the bainite ratio is 70% or more, not only does the strength of the base material deviate from the general-purpose range, but there is a concern that inhibition of weld cracking by Nb may become a problem.

On the other hand, welded steel structures are often used in environments where there is a large amount of incoming salt, such as beach areas and areas where snow melting salt is spread, and in the shipbuilding field, they are often used in seawater spray environments.

Generally, when a weather-resistant steel material is exposed to an atmospheric corrosive environment, a protective rust layer is formed on the surface, and subsequent steel material corrosion is suppressed. For this reason, weathering steel is used for structures such as bridges as a minimum maintenance steel that can be used as it is without being painted.

However, a protective rust layer is formed on the surface of weathering steel not only in the beach area but also in inland areas where there is a large amount of incoming salt, such as areas where snowmelt salt and antifreeze are sprayed. Since it is hard to be done, the effect which suppresses corrosion is hard to be exhibited. Therefore, in these regions, it is not possible to use bare weatherproof steel, and ordinary steel is used by painting on ordinary steel. However, in the case of using such ordinary steel for coating, it is necessary to repaint every 10 years because of coating deterioration due to corrosion, and therefore the cost required for maintenance becomes enormous.

In recent years, weathering steel standardized by Japanese Industrial Standards (JIS) (JIS G 3114: weathering hot rolled steel for welded structures) has an incoming salt content of 0.05 mg / dm ² / day (0. 05mdd) and higher areas, for example, beach areas, where the loss of corrosion is large due to the occurrence of scale-like rust, layered rust, etc., so it cannot be used without painting (Ministry of Construction, Public Works Research Institute, Steel Club) Japan Bridge Construction Association: Joint Research Report on the Application of Weatherproof Steel to Bridges (XX)-Design and Construction Guidelines for Unpainted Weatherproof Bridges (Ref. Rev. 1993.3)).

In this way, in a salty environment such as a beach area, ordinary steel materials are usually coated. However, the current situation is that bridges constructed in the coastal area near the river mouth and roads such as mountainous areas where snow melt is salted are extremely corroded and must be repainted. Since these repainting takes a lot of man-hours, there is a strong demand for steel materials that can be used without painting.

Recently, a Ni-based high weathering steel to which about 1 to 3% of Ni is added has been developed. However, it has been found that in regions where the amount of incoming salt exceeds 0.3 to 0.4 mdd, it is difficult to apply to steel materials that can be used without coating with such Ni addition alone.

Since corrosion of steel materials becomes more severe as the amount of flying salt increases, weathering steel corresponding to the amount of flying salt is required from the viewpoint of corrosion resistance and economy. Moreover, even if it is called a bridge, the corrosive environment of steel materials is not the same by the place and site | part used. For example, outside the girders, they are exposed to rainfall, condensed water and sunlight. On the other hand, inside the girder, it is exposed to condensed water, but there is no rain. In general, in an environment where the amount of incoming salt is large, it is said that the inside of the girders is more corrosive than the outside of the girders.

Also, in an environment where snow melting salt or anti-freezing agent is sprayed on the road, the salt is wound up on the running car and adheres to the bridge that supports the road, resulting in a severe corrosive environment. Furthermore, the eaves under the eaves a little away from the coast are also exposed to severe salt damage environments, and in such areas, the amount of incoming salt becomes a severe corrosive environment with 1 mdd or more.

In order to deal with such problems, the development of steel materials that prevent corrosion in an environment with a large amount of incoming salt has been underway.

For example, Patent Document 6 proposes a weather-resistant steel material having an increased chromium (Cr) content, and Patent Document 7 proposes a weather-resistant steel material having an increased nickel (Ni) content. .

However, although the weathering steel material with the increased chromium (Cr) content proposed in Patent Document 6 can improve the weathering resistance in a region where the amount of incoming salt is below a certain level, it is severer than that. In a salt environment, the weather resistance is deteriorated.

Further, in the case of the weathering steel material with the increased nickel (Ni) content proposed in Patent Document 7, the weather resistance is improved to some extent, but the cost of the steel material itself is increased, and it is used for applications such as bridges. As an expensive material, it becomes expensive. In order to avoid this, if the Ni content is reduced, the weather resistance will not be improved so much, and if the amount of incoming salt is high, layered peeling rust will form on the surface of the steel material, corrosion will be remarkable, and it will be used for a long time. The problem of being unbearable arises.

Japanese Unexamined Patent Publication No. 7-9191 Japanese Laid-Open Patent Publication No.7-138715 JP 2003-268484 A JP 2006-2211 A Japanese Unexamined Patent Publication No. 2006-2198 Japanese Patent Laid-Open No. 9-1779090 Japanese Patent Laid-Open No. 5-118011

Thus, the conventional methods have difficulty from the viewpoints of economic efficiency and reproducibility, and there is much room for improvement in practical use.

In particular, in a welded structure manufactured using a thick steel plate having a thickness of 15 mm or more, even if the amount of deformation at each weld location is small, large deformation can occur as a whole welded structure. It is necessary to do. The upper limit of the thickness is not particularly limited, but it is preferable that a thickness up to 50 mm can be handled.

Furthermore, paint peel resistance is a major problem in welded steel structures used in environments with a large amount of incoming salt. That is, as shown above, in a coastal environment where a large amount of chloride comes in or an environment where a snow melting agent or an antifreezing agent is sprayed, the coating peels off early and corrosion progresses. Therefore, it is necessary to repaint the paint every few to a few dozen years. In addition, when repainting is performed, it is necessary to assemble a scaffold on a once-corroded bridge and perform a reblasting process as a previous process, which is very expensive. And even if it re-blasts, it is difficult to remove rust completely, but even if it paints again on the steel material which has not removed rust completely, the coating life will become remarkably short. The paint peel resistance is largely due to the characteristics including the corrosion resistance of the steel material as the base.

Therefore, it was strongly desired to extend the service life of the coating and greatly extend the repair coating interval. That is, in the marine field and the bridge field where painting is required, there is a high demand for minimizing the life cycle cost, and extending the paint life is very important in considering the life cycle management of the bridge.

In view of the above circumstances, an object of the present invention is to establish a technique for reliably suppressing welding deformation at low cost, and to provide a steel plate having small welding deformation. In particular, in fillet welding, an object is to provide a steel plate with small welding deformation. Note that the target value of the amount of welding deformation is ½ that of conventional steel.

Furthermore, the present invention provides corrosion resistance in a high chloride environment (including that the coating does not peel off and that corrosion at the coating defect is suppressed and corrosion resistance is maintained (including coating peeling resistance) and weather resistance when no coating is applied). It aims to provide an excellent steel material.

In order to solve this problem, the present inventors have specified the chemical composition of the steel sheet and the metal structure as a result of various studies. FIG. 1 shows the independent influence of the physical property values of each material obtained by the thermal coupled FEM analysis conducted in conjunction with the experiment. Moreover, the calculation conditions of FEM analysis are shown in FIG.

In FIG. 1, the horizontal axis represents thermal conductivity (white circle plot), transformation point Ac ₁ (black circle plot), strength TS (square plot), and the vertical axis represents the amount of angular deformation. From FIG. 1, it can be seen that the amount of angular deformation does not change even when the thermal conductivity of the steel sheet is increased, the amount of angular deformation increases as the transformation point increases, and the amount of angular deformation decreases as the strength increases. Therefore, the welding deformation particularly depends largely on the strength and transformation point, and the target value of the welding deformation amount (angular deformation amount) is ½ that of conventional steel (angular deformation amount is about 0.8 mm), that is, 0.4 mm. The strength becomes extremely high and deviates from the general-purpose strength class. Deviations from the general strength class are not desirable because they are not only subject to general commercial transactions, but may also cause structural design problems and weldability problems.

Therefore, the present inventors aimed to develop a steel type in which the high-temperature strength was increased while maintaining the normal temperature strength suitable for the general-purpose strength class.

It should be noted that Mo, which has been said to be effective for increasing the high-temperature strength, is unrealistic because it causes a rise in alloy costs and increases costs. Accordingly, the inventors focused on Cr, which is relatively inexpensive and has a small adverse effect on weldability, and conducted various tests. As a result, the following findings (a) to (d) were obtained.

(A) Cr can increase high temperature strength. When Cr is contained in an amount of 1.0% or more, high-temperature strength can be secured without coexisting Mo, and welding deformation can be sufficiently suppressed. However, if the Cr content is less than 1.0%, the high temperature strength cannot be ensured sufficiently if Mo is not allowed to coexist.

(B) It is essential to contain Nb. By containing Nb, securing of high temperature strength is sufficient. Note that the amount of Nb added may be small, and may be 0.005% or more.

(C) It is essential to include a ferrite structure in order to meet the general-purpose strength level. From the viewpoint of toughness, the crystal grain size of the ferrite structure needs to be 30 μm or less. In addition, in order to minimize welding deformation, the hardness of the hard phase composed of bainite or martensite is better, and the hardness ratio of the hard phase to the soft phase needs to be 1.5 or more.

(D) The manufacturing method of the steel sheet may be under general conditions, but since it tends to have higher hardenability than normal steel, it is preferable to devise in order to adapt it to a general-purpose strength level.

On the other hand, the present inventors examined corrosion in an environment with a large amount of incoming salt. As a result, in such an environment, repeated drying and wetting of the FeCl ₃ solution became an essential condition of corrosion, and due to hydrolysis of Fe ³⁺ It has been found that corrosion is accelerated by lowering the pH and by Fe ³⁺ acting as an oxidizing agent.

The corrosion reaction at this time is as shown below.

As the cathode reaction, the following reaction mainly occurs.
Fe ³⁺ + e ⁻ → Fe ²⁺ (reduction reaction of Fe ³⁺ )

In addition to this reaction, the following cathode reaction also occurs.
2H ₂ O + O ₂ + 2e ⁻ → 4OH ⁻ ,
2H ⁺ + 2e ⁻ → H ₂

On the other hand, the following anodic reaction occurs with respect to the above Fe ³⁺ reduction reaction.
Anode reaction: Fe → Fe ²⁺ + 2e ⁻ (Fe dissolution reaction)

Therefore, the overall reaction of corrosion is as shown in the following equation (1).
2Fe ³⁺ + Fe → 3Fe ²⁺ (1)

Fe ²⁺ generated by the reaction of the above formula (1) is oxidized to Fe ³⁺ by air oxidation, and the generated Fe ³⁺ acts again as an oxidant to accelerate corrosion. At this time, the reaction rate of air oxidation of Fe ²⁺ is generally slow in a low pH environment, but is accelerated in a concentrated chloride solution, and Fe ³⁺ is easily generated. It has been found that due to such a cyclic reaction, in an environment where the amount of incoming salt is very large, Fe ³⁺ is always supplied, corrosion of steel is accelerated, and corrosion resistance is significantly deteriorated.

The present inventors examined the influence of various alloy elements on the weather resistance based on the mechanism of corrosion in such a salt environment, and as a result, obtained the findings shown in the following (e) to (g).

(e) Sn is dissolved as Sn ²⁺ , and the concentration of Fe ³⁺ is reduced by a reaction of 2Fe ³⁺ + Sn ²⁺ → 2Fe ²⁺ + Sn ⁴⁺ to suppress the reaction of formula (1). Sn also has an effect of suppressing anodic dissolution.

(F) Cu is an element that has traditionally been the basis of an effect of improving corrosion resistance in an environment with a large amount of incoming salt, and an effect of improving corrosion resistance is seen in an environment with a relatively long wetting time. However, in an environment where the chloride concentration is further increased and the pH is locally lowered, for example, a relatively dry environment in which salt is deposited and wet and dry are repeated due to changes in humidity and β-FeOOH is generated. Then, it was found that Cu rather promotes corrosion.

(G) Thus, the steel material which contains Sn actively and suppresses the Cu content can be expected to have high corrosion resistance. Furthermore, since corrosion resistance is high, even if it coats on steel materials, there are few peeling of the coating resulting from corrosion of steel materials, and corrosion of a coating defective part is controlled. On the other hand, since the anticorrosion effect by a coating film can also be anticipated, when it coats, the further effect of corrosion resistance can be anticipated. Therefore, in addition to the corrosion resistance, the service life of the coating can be extended and the repair coating interval can be greatly extended. In particular, it is effective in improving paint peeling resistance in the marine and bridge fields.

The present invention has been completed on the basis of the above knowledge, and the gist thereof lies in the steel sheet having the small weld deformation and excellent corrosion resistance shown in the following (1) to (4).

(1) By weight percent, C: 0.02 to 0.25%, Si: 0.01 to 0.7%, Mn: 0.3 to 2%, P: 0.05% or less, S: 0.00. 008% or less, Cu: less than 0.2%, Cr: 1 to 2.5%, Mo: 0.05% or less, Nb: 0.005 to 0.1%, Al: 0.003 to 0.1% , N: 0.01% or less and Sn: 0.03-0.50%, the balance consisting of Fe and impurities, and having a chemical composition with a Cu / Sn ratio of 1 or less, and the metal structure is ferrite The structure is composed of 10 to 60% and bainite structure and / or martensite structure 40 to 90%, and the average grain size of the ferrite structure is 30 μm or less, and the hardness and ferrite structure of the bainite structure and / or martensite structure The welding deformation is characterized by the ratio of the hardness to 1.5 or more. Steel plate with small shape and excellent corrosion resistance.

(2) The steel sheet having a small weld deformation and excellent corrosion resistance according to the above (1), characterized by containing 2% by mass and further containing Ti: 0.1% or less.

(3) At 1% by mass, Ni: 3.5% or less, V: 0.1% or less, B: 0.004% or less and Zr: 0.02% or less A steel sheet having a small weld deformation and excellent corrosion resistance as described in (1) or (2) above.

(4) The above-mentioned, characterized by containing, by mass%, Ca: 0.004% or less, Mg: 0.002% or less, and REM: 0.002% or less (1)-(3) A steel plate with small weld deformation and excellent corrosion resistance.

Considering the present invention from the viewpoint of a welding method with small weld deformation in a steel plate, the weld deformation in the steel plate is substantially a weld deformation in the weld heat affected zone, and therefore satisfies a predetermined requirement in the weld heat affected zone. In addition, if welding is performed, the ability to suppress welding deformation is considered to be improved.

Therefore, from the viewpoint of the welding method, the present invention
“In mass%, C: 0.02 to 0.25%, Si: 0.01 to 0.7%, Mn: 0.3 to 2%, P: 0.05% or less, S: 0.008% Cu: Less than 0.2%, Cr: 1 to 2.5%, Mo: 0.05% or less, Nb: 0.005 to 0.1%, Al: 0.003 to 0.1%, N A steel sheet welding method comprising: 0.01% or less and Sn: 0.03 to 0.50%, comprising a balance Fe and impurities, and having a chemical composition with a Cu / Sn ratio of 1 or less, The metal structure of the part to be the heat affected zone in the steel plate before welding is composed of 10 to 60% ferrite structure and 40 to 90% bainite structure and / or martensite structure, and the average grain size of the ferrite structure is 30 μm or less. And the hardness of the bainite structure and / or martensite structure Welding method the ratio of the hardness of the ferrite structure is characterized in that not less than 1.5. "
It can also be grasped.

Of course, this steel sheet is in% by mass, further Ti: 0.1% or less, Ni: 3.5% or less, V: 0.1% or less, B: 0.004% or less, Zr: 0.02% Hereinafter, one or more of Ca: 0.004% or less, Mg: 0.002% or less, and REM: 0.002% or less may be contained.

As will be described later, the entire steel plate as a base material may be welded after being manufactured so as to satisfy the above requirements, or the part to be welded (welding heat affected zone) of the steel plate as a base material. May be welded after satisfying the above requirements for the part.

And this welding method can also be applied to fillet welding with large welding deformation. Fillet welding is performed on lap joints, T joints, cruciform joints, etc., but this welding method involves fillet welding on T joints and cruciform joints, which cause particularly large welding deformations due to the relative positional relationship of the joint base material. Is particularly effective.

According to the present invention, it is possible to provide a steel sheet that can reliably suppress welding deformation at low cost and is excellent in corrosion resistance.

It is a FEM calculation result which shows the influence of each material physical property value on the amount of welding angle deformation. It is a schematic diagram which shows the calculation conditions of FEM analysis. It is a figure which shows the test piece used in evaluating the welding angle deformation. It is a figure which shows the definition of the welding angle deformation amount.

In the present invention, the reason for limiting the chemical composition and metal structure of the steel sheet with small welding deformation is as follows.

(A) Chemical composition of steel sheet The effects of each component of the steel sheet and the preferred contents of each component are as follows. In addition, "%" regarding content means "mass%".

C: 0.02 to 0.25%
C is the most effective element for improving the strength and is an inexpensive element. However, if it is less than 0.02%, it is necessary to guarantee strength by using other elements in combination, resulting in an increase in cost. Moreover, when it contains exceeding 0.25%, weldability will be inhibited remarkably. Therefore, the C content is 0.02 to 0.25%.

Si: 0.01 to 0.7%
Si is an element contributing to strength improvement. However, if it is less than 0.01%, the required strength cannot be ensured. Moreover, if added over 0.7%, the base metal toughness and the weld heat affected zone (HAZ) toughness will be significantly degraded. Therefore, the Si content is set to 0.01 to 0.7%.

Mn: 0.3-2%
Mn is an element necessary for ensuring strength. However, if it is less than 0.3%, the required strength cannot be ensured. On the other hand, if it exceeds 2%, weldability deteriorates. Therefore, the Mn content is 0.3-2%.

P: 0.05% or less P is an element present in steel as an impurity. If the P content exceeds 0.05%, it not only segregates at the grain boundaries and lowers the toughness, but also causes hot cracking during welding, so the P content is 0.05% or less.

S: 0.008% or less S is an element present in steel as an impurity. If the S content exceeds 0.008%, center segregation is promoted or a large amount of stretched MnS is generated, so that the mechanical properties of the base material and the HAZ deteriorate. Therefore, the upper limit of the S content is 0.008%.

Cu: Less than 0.2% Cu is generally regarded as a basic element for improving weather resistance, and is added to all beach weather resistant steels and corrosion resistant steels, but in a relatively dry environment under high flying salt content. Rather, it reduces the corrosion resistance. Further, if it coexists with Sn, cracking occurs during rolling. Therefore, it is necessary to suppress the Cu content. Even if contained as an impurity, the Cu content needs to be less than 0.2%. Preferably it is less than 0.1%.

Cr: 1 to 2.5%
Cr is an effective element for increasing the strength by improving the hardenability. In order to obtain this effect, addition of 1% or more is necessary. However, if it exceeds 2.5%, the toughness deteriorates. Therefore, the Cr content is 1 to 2.5%. A preferable content of Cr is 1 to 1.8%. As will be described later, Cr is an element that degrades the corrosion resistance in a salt environment, but when it coexists with Sn, its adverse effect is remarkably suppressed.

Mo: 0.05% or less Mo is not added because it causes a significant increase in cost. In some cases, impurities may be mixed in, but even in that case, the Mo content is 0.05% or less.

Nb: 0.005 to 0.1%
Nb has the effect of delaying recrystallization of the metal structure of the steel sheet. However, if the content is less than 0.005%, the effect cannot be obtained. On the other hand, if it exceeds 0.1%, the above effect is saturated while the toughness of the HAZ is significantly impaired. Therefore, the Nb content is set to 0.005 to 0.1%. In addition, the minimum with the preferable range of Nb content is 0.008%, and a preferable upper limit is 0.020%.

Al: 0.003 to 0.1%
Al is an essential element for deoxidation. In order to reliably perform deoxidation, a content of 0.003% or more is necessary. However, if it exceeds 0.1%, the toughness tends to deteriorate particularly in HAZ. This is presumably because coarse cluster-like alumina inclusion particles are easily formed. Therefore, the Al content is set to 0.003 to 0.1%.

N: 0.01% or less N is an element present in steel as an impurity. If the N content exceeds 0.01%, the base material toughness and the HAZ toughness are deteriorated. Therefore, the upper limit of the N content is 0.01%.

Sn: 0.03 to 0.50%
Sn dissolves as Sn ²⁺ and has an action of inhibiting corrosion by an inhibitor action in an acidic chloride solution. Further, rapidly to reduce the Fe ^3+, by having an effect of reducing Fe ³⁺ concentration as oxidizing agent, since inhibit corrosion promoting effect of Fe ^3+, thereby improving the weather resistance in high airborne salt environments. Moreover, Sn has the effect | action which suppresses the anodic dissolution reaction of steel and improves corrosion resistance. Furthermore, by containing Sn, the effect of improving the weather resistance of Cr is exhibited even in an environment with a large amount of incoming salt. These effects are obtained by containing 0.03% or more of Sn, and saturate when it exceeds 0.50%. Therefore, the Sn content is set to 0.03 to 0.50%. The preferable lower limit of the Sn content range is 0.03%, and the preferable upper limit is 0.20%.

Cu / Sn ratio: 1 or less In the case of steel containing Sn, when it coexists with Cu, the corrosion resistance is remarkably lowered. Moreover, when manufacturing steel materials, it becomes a cause of the rolling crack by inclusion of Cu. For this reason, it is necessary to make Cu / Sn ratio, ie, ratio of Cu content with respect to Sn content 1 or less.

The steel sheet according to the present invention has the chemical composition described above, with the balance being Fe and impurities. Here, the impurity is a component that is mixed due to various factors in the manufacturing process including raw materials such as ore and scrap when industrially manufacturing a steel sheet, and does not adversely affect the present invention. It means what is allowed.

The steel sheet according to the present invention may contain one or more components selected from at least one group from the following first group to the third group, if necessary, in addition to the above elements as follows. it can. Hereinafter, components belonging to these groups will be described.

Group 1 ingredients: Ti
Ti: 0.1% or less Since Ti mainly acts as a deoxidizing element, it can be contained if necessary. However, since deoxidation can be performed with Al, it is not always necessary to contain it. However, since Ti oxide or Ti—Al oxide is formed when the Ti content is high, the ability to refine the structure particularly in the heat-affected zone of the small heat input weld is lost. For this reason, Ti content in the case of making it contain shall be 0.1% or less. In addition, in order to acquire the deoxidation effect by containing Ti stably, it is preferable that the content shall be 0.01% or more.

Second group of components: Ni, V, B, Zr
Ni: 3.5% or less Ni is an element that improves the toughness of the base material and contributes to the improvement of the strength by improving the hardenability, and can be contained as necessary. However, since Ni is an expensive element, if Ni is excessively contained, it causes a large cost increase. Moreover, when it coexists with Sn, it will deteriorate the corrosion resistance in the presence of chloride. For this reason, the upper limit of content of Ni in the case of making it contain shall be 3.5% or less. Preferably it is 1.0% or less, More preferably, it is 0.5% or less. In addition, in order to acquire the said effect by containing Ni stably, it is preferable that the content shall be 0.02% or more.

V: 0.1% or less V is an element effective for improving the strength, and can be contained as necessary. However, if the V content exceeds 0.1%, the toughness is greatly deteriorated. Therefore, the V content in the case where V is included is 0.1% or less. In addition, in order to obtain the strength improvement effect by containing V stably, it is preferable to make the content 0.005% or more.

B: 0.004% or less B has an effect of improving hardenability and increasing strength, and can be contained as required. However, when the content of B exceeds 0.004%, the effect of increasing the strength is saturated, and the tendency of toughness deterioration becomes remarkable in both the base material and HAZ. Therefore, when B is included, the B content is 0.004% or less. In order to stably obtain the effect of enhancing the hardenability and strength by containing B, the B content is preferably 0.0003% or more.

Zr: 0.02% or less Zr has the effect of finely dispersing and precipitating nitrides in steel and improving the strength, and can be contained as required. However, if added over 0.02%, coarse precipitates are formed and the toughness is deteriorated, so the content of Zr in the case of inclusion is 0.02% or less. In order to stably obtain the strength improvement effect by containing Zr, the Zr content is preferably 0.0003% or more.

Group 3 components: Ca, Mg, REM
Ca: 0.004% or less Ca reacts with S in steel to form oxysulfide (oxysulfide) in molten steel. Unlike the elongated shaped inclusions such as MnS, this oxysulfide does not extend in the rolling direction during rolling and is spherical after rolling. Therefore, welding with the tip of the elongated shaped inclusions as the starting point of cracking Since there exists an effect | action which suppresses a crack and a hydrogen induction crack, it can be made to contain as needed. However, if its content exceeds 0.004%, toughness may be deteriorated. Therefore, when Ca is contained, the content of Ca is set to 0.004% or less. In addition, in order to acquire the effect which suppresses a weld crack and a hydrogen induction crack stably, it is preferable that content of Ca shall be 0.0003% or more.

Mg: 0.002% or less Mg forms an Mg-containing oxide, serves as a generation nucleus of TiN, and has an effect of finely dispersing TiN. Therefore, Mg can be contained as necessary. However, when the content exceeds 0.002%, the amount of oxide becomes excessive and ductility is reduced. Therefore, the upper limit of the Mg content in the case of inclusion is set to 0.002%. In order to stably obtain the effect of finely dispersing TiN, the Mg content is preferably 0.0003% or more.

REM: 0.002% or less REM contributes to the refinement of the structure of the weld heat affected zone and the fixation of S, and can be contained as necessary. However, if the content exceeds 0.002%, REM becomes an inclusion that adversely affects the toughness of the base material, so the content of REM in the case of inclusion is 0.002% or less. In addition, in order to obtain the refinement | miniaturization of a structure | tissue and the fixing effect of S stably, it is preferable that content of REM shall be 0.0003% or more. Note that REM is a generic name for 17 elements in which Y and Sc are combined with 15 elements of lanthanide, and one or more of these elements can be contained. Further, the content of REM means the total content of these elements.

(B) Metal structure The ferrite fraction of the metal structure is 10 to 60%. From the viewpoint of preventing welding deformation, it is better that the amount of ferrite, which is a structure that tends to yield, is better. However, in order to adapt to the strength range of general-purpose strength steel, the upper and lower limits of the ferrite fraction are 60% and 10%, respectively. The average grain size of the ferrite structure is preferably small from the viewpoint of fracture toughness. And since the sufficient fracture toughness cannot be obtained when the average particle diameter of a ferrite structure exceeds 30 micrometers, the upper limit was made into 30 micrometers.

The structure other than the ferrite structure is a bainite structure and / or a martensite structure. Accordingly, the fraction of bainite structure and / or martensite structure is 40 to 90%. In addition, a bainite structure and / or a martensite structure are a bainite structure, a martensite structure, or a (bainite + martensite) structure.

Here, the ferrite structure is called the soft phase, and the bainite structure and / or the martensite structure is called the hard phase. Since it is necessary to prevent the material from yielding at various temperatures as much as possible, it is desirable that the hardness of the hard phase is high. On the other hand, the presence of the soft phase makes it possible to adjust the yield strength and tensile strength of structural steel to a range that conforms to standards and the like. However, as described above, since the welding deformation is suppressed by keeping the hard phase hard, here, the index of the hardness ratio between the hard phase and the soft phase is used to define the ability to suppress welding deformation. . According to the study by the inventors, when the hardness of the hard phase is 1.5 times or more of the hardness of the soft phase, the improvement in the ability to suppress welding deformation becomes remarkable, so the hardness ratio is 1.5 times or more.

Next, conditions for rolling and heat treatment for obtaining the steel sheet according to the present invention will be described.

Prior to hot rolling, the steel ingot is first heated, but if the heating temperature at this time is set to Ac ₃ or higher, it can be completely austenitic phase and homogenized without any untransformed part. It is preferable that the temperature be Ac ₃ point or higher. Specifically, heating to 900 to 1200 ° C. is preferable. When the rolling finish temperature at the thin end is set to 900 ° C. or lower during hot rolling, the crystal grains become an appropriate size and the fracture toughness of the material becomes sufficient. The lower limit of the rolling finishing temperature is not particularly defined, and any conditions may be used as long as the strength can be adapted to the general-purpose strength range. However, when the rolling finishing temperature is set to 700 ° C. or higher, anisotropy due to two-phase region processing is not noticeable, which is desirable. Subsequent to rolling, accelerated cooling may be performed. In the case of performing accelerated cooling, it is preferable to control the cooling rate of the central portion to 0.5 to 20 ° C./s immediately after rolling or after some standing time. The cooling stop temperature is preferably controlled using 150 to 500 ° C. as a guide. Moreover, you may implement heat processing suitably after rolling. When the heat treatment is performed, it is preferable to perform a normalizing process or a tempering process, and it is preferable to select temperature ranges of 800 to 1100 ° C. and 300 to 700 ° C. respectively.

An example of a steel sheet according to the present invention is shown. Steel ingots having the composition components shown in Table 1 were produced under the heating temperature, finishing temperature, accelerated cooling, and heat treatment conditions shown in Table 2. The plate thickness of the steel plate was 16 mm.

Table 3 shows the yield point YP, tensile strength TS, transition temperature vTrs, ferrite fraction, average ferrite particle size, hardness ratio of the hard phase and soft phase, welding angle deformation, The thickness reduction amount and the peeled area ratio are shown.

In order to measure the tensile properties of the obtained steel sheet, specimens were collected according to the test method described in JIS-Z-2201. The sampling position was in the vicinity of (1/4) t thickness in the plate thickness (t) direction and in the L direction (parallel to the rolling direction). The yield point was determined as a test speed of 10 N / mm · s, and the yield point was 0.2% proof stress when no clear yield point appeared. The target value of the tensile properties, the yield point YP is 350 N / mm ² or more, and the tensile strength TS is set to 490 ~ 720N / mm ^2.

Further, in order to measure the impact characteristics of the obtained steel plate, a specimen was collected according to the test method described in JIS-Z2202. Sampling position is 2mmV notch Charpy specimen in the vicinity of (1/4) t thickness in the plate thickness (t) direction and L direction (parallel to the rolling direction), measured the brittle fracture surface ratio at various temperatures, and transition The temperature was determined. The target value of the Charpy characteristic is that the transition temperature is 0 ° C. or lower. Tissue observation was performed with an optical microscope. The image obtained by observation was subjected to image analysis. For example, when calculating the particle diameter, the short diameter and the long diameter were measured, and the particle diameter was obtained from 1/2 of the sum. The arithmetic average of the particle diameters of the individual particles obtained by observing 100 visual fields in this manner was defined as “average particle diameter”. In addition, the ferrite fraction of the metal structure was obtained by calculating the area ratio of ferrite with respect to the area for 100 field observations obtained by the same observation method as described above. The same applies to the bainite fraction and martensite fraction, but Table 3 shows only the ferrite fraction.

Furthermore, the welding angle deformation by fillet welding was evaluated in the following manner.

As shown in FIG. 3, T-shaped welding test pieces (unit: mm) were prepared for the steel plates, one side was restrained with a triangular steel plate having high rigidity, and the other side was subjected to 1-pass fillet welding. The welding material used was a general 50 kilo steel flux cored wire, and welding conditions were 10.4 kJ / cm (200 A-26 V-30 cm / min). When a sufficient time has elapsed after welding, place the test piece on the surface plate, and measure the angular deformation θ defined in Fig. 4 with three clearance gauges at the welding start position, center position and end position. The average value thereof was taken as the welding angle deformation. In addition, the welding angle deformation amount of ordinary general-purpose 50 kg steel measured by this method is about 1 °, and the target welding angle deformation level of the present invention is 0.5 °.

And about corrosion resistance, the test piece obtained from the obtained steel materials was evaluated by SAE (Society of Automotive Engineers) J2334 test. SAE J2334 test is wet: 50 ° C., 100% RH, 6 hours, salt adhesion: 0.5% NaCl, 0.1% CaCl ₂ , 0.075% NaHCO ₃ aqueous solution, 0.25 hour, dry: 60 It is an accelerated test with 1 cycle (total 24 hours) at ℃, 50% RH, 17.75 hours, and the corrosion form is said to be similar to the atmospheric exposure test (Hiroo Nagano, Masato Yamashita, Hitoshi Uchida) : Environmental Materials Science, Kyoritsu Shuppan (2004), p.74). This test is a test that simulates a severe corrosive environment in which the amount of incoming salt exceeds 1 mdd.

After completion of 120 cycles of SAE２３J2334 test, the rust layer on the surface of each test piece was removed, and the thickness reduction amount was measured. Here, the “plate thickness reduction amount” is an average plate thickness reduction amount of the test piece, and is calculated using the weight reduction before and after the test and the surface area of the test piece.

In addition, in order to investigate the anti-peeling resistance, a test piece with a size of 150 x 70 mm was coated with a modified epoxy paint (Banno 200: made in China) by air spray to a dry film thickness of 150 μm, and the steel substrate After making a crosscut at a depth reaching, the SAE J2334 test was also evaluated.

As a result, in the steel plate of Mark 1-e (comparative example), the finishing temperature was as high as 910 ° C and the cooling conditions were air cooling, so the amount of ferrite produced was large, and the produced ferrite grew and the average grain size Became larger. For this reason, the tensile strength was reduced. Moreover, although the hardness ratio between the hard phase and the soft phase is within the range of the present invention, the welding angle deformation amount is also increased. This is thought to be because the balance between the amount of ferrite as the soft phase and the amount of the hard phase is lost. As described above, the steel plate of Mark 1-e has a low tensile strength and a large amount of welding angle deformation, and is therefore an inappropriate steel material as a structural steel plate.

Next, in the steel plate of Mark 1-f (comparative example), the cooling rate after heating was set to 25 ° C./sec. The toughness was also greatly reduced. Although the welding angle deformation is small, it is an inappropriate steel material for structural steel plates.

Moreover, in the Mark12-b steel sheet (comparative example), the water cooling stop temperature was set to 120 ° C., and the steel was quenched to a relatively low temperature, so the hardness ratio between the hard phase and the soft phase was reduced and the welding angle deformation was increased. .

Furthermore, the steel plates of Mark 40 to 46 (comparative examples) did not satisfy the steel composition defined in the present invention, and the toughness of the steel plate itself was lowered. It is an inappropriate steel material as a structural steel plate. For the steel plate of Mark 47 (comparative example), the test was stopped because cracks occurred during rolling. Further, in the steel plate of Mark 48 (comparative example), the Sn content in the steel composition defined in the present invention was not satisfied and the corrosion resistance was lowered.

On the other hand, in the steel plates according to the examples of the present invention indicated by other marks, the tensile properties are all such that the yield point YP is 350 N / mm ² or more and the tensile strength TS is 490 to 720 N / mm ² grade. General purpose steel with transition temperature vTrs, ferrite fraction, ferrite average particle size, hardness ratio of hard phase to soft phase, and proper welding angle deformation within 0.5 ° of target. Therefore, it turns out that it is suitable as a structural steel plate. Moreover, although it has high corrosion resistance and corrosion was seen in the crosscut part at the time of painting, it turns out that any steel plate has few peeling, Therefore The repair interval of coating can be extended.

As described above, according to the present invention, it is possible to reliably suppress weld deformation in fillet welding at a low cost, and to provide a steel plate having excellent corrosion resistance.

Claims

In mass%, C: 0.02 to 0.25%, Si: 0.01 to 0.7%, Mn: 0.3 to 2%, P: 0.05% or less, S: 0.008% or less Cu: Less than 0.2%, Cr: 1 to 2.5%, Mo: 0.05% or less, Nb: 0.005 to 0.1%, Al: 0.003 to 0.1%, N: 0.01% or less and Sn: 0.03 to 0.50%, the balance is composed of Fe and impurities, and has a chemical composition with a Cu / Sn ratio of 1 or less. 60% and a bainite structure and / or martensite structure 40 to 90%, and the ferrite structure has an average particle size of 30 μm or less, and the hardness of the bainite structure and / or martensite structure and the hardness of the ferrite structure Welding deformation characterized by a ratio of 1.5 or more Excellent steel plate to reduce corrosion resistance.
The steel sheet having small corrosion deformation and excellent corrosion resistance according to claim 1, wherein the steel sheet further contains Ti: 0.1% or less.
Further, by mass%, Ni: 3.5% or less, V: 0.1% or less, B: 0.004% or less, and Zr: 0.02% or less, or one or more of them The steel sheet having small corrosion deformation and excellent corrosion resistance according to claim 1 or 2.
2. From mass%, further comprising one or more of Ca: 0.004% or less, Mg: 0.002% or less, and REM: 0.002% or less. 3. A steel sheet having small corrosion deformation and excellent corrosion resistance according to any one of items 3 to 3.