JP2012001810A - Welded joint having excellent corrosion resistance and crude oil tank - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a welded joint which is capable of significantly reducing overall corrosion or local corrosion that occurs in a crude oil tank, and a crude oil tank which comprises the welded joint.SOLUTION: The crude oil tank comprises a welded joint which is formed by welding steel materials each containing, in mass%, 0.03-0.16% C, 0.05-1.50% Si, 0.1-2.0% Mn, ≤0.025% P, ≤0.010% S, 0.005-0.10% Al, ≤0.008% N, >0.1% and ≤0.5% Cr and 0.03-0.4% Cu and additionally containing one or more elements selected from 0.01-1.0% W, 0.01-0.5% Mo, 0.001-0.2% Sn and 0.001-0.4% Sb. Here, Cu, Mo and W in the welded metal satisfy the following relations: 3<{(Mo+W) in the welded metal}/{(Mo+W) in the matrix}≤8 and 0.2≤(Cu in the welded metal)/{(Mo+W) in the welded metal}≤3.

Description

  The present invention relates to an oil tank of a crude oil tanker formed by welding steel materials or a tank for transporting or storing crude oil (hereinafter collectively referred to as “crude oil tank”). The present invention relates to a welded joint that reduces local corrosion (pitting corrosion) and a crude oil tank having the welded joint. The steel materials used in the crude oil tank of the present invention include thick steel plates, thin steel plates and shaped steels.

It is known that the steel used on the inner surface of a tanker's crude oil tank, particularly on the back of the upper deck and the upper part of the side wall, is totally corroded. As a cause of this total corrosion,
(1) Repeated condensation and drying (wet and dry) on the steel sheet surface due to temperature difference between day and night,
(2) Inert gas sealed in the crude oil tank for explosion protection (O ₂ about 5 vol%, CO ₂ about 13 vol%, SO ₂ about 0.01 vol%, boiler N ₂ or the exhaust gas of the engine, etc.) Dissolution of O ₂ , CO ₂ , SO ₂ in condensed water,
(3) Dissolution of corrosive gas such as H ₂ S volatilized from crude oil into condensed water,
(4) Residual seawater used for cleaning crude oil tanks. These can also be known from the fact that sulfate ions and chloride ions (Cl ⁻ ) were detected in strongly acidic condensed water in surveys of actual ship docks conducted every 2.5 years. .

Furthermore, when H ₂ S is oxidized using iron rust generated by corrosion as a catalyst, solid S is formed in layers in the iron rust, but these corrosion products are easily peeled off and dropped off, resulting in crude oil tanks. Deposit at the bottom of the. For this reason, in the dock inspection, the current situation is that repair of the upper part of the tank and collection of deposits at the bottom of the tank are performed with great expense.

On the other hand, the steel used for the bottom plate of a tanker's crude oil tank, etc. does not corrode due to the corrosion inhibition effect of the crude oil itself or the corrosion inhibition effect of the protective coat (oil coat) derived from the crude oil formed on the inner surface of the crude oil tank. It was considered a thing. However, recent research has revealed that bowl-shaped local corrosion (pitting corrosion) occurs in the steel of the tank bottom plate. As a cause of this local corrosion,
(1) presence of condensed water in which salts represented by sodium chloride are dissolved at a high concentration;
(2) Oil coat detachment due to excessive cleaning,
(3) High concentration of sulfides contained in crude oil,
(4) Increasing the concentration of O ₂ , CO ₂ , SO _2, etc. in the inert gas for explosion protection dissolved in dew condensation water,
Items such as are listed. Actually, when the water stayed in the crude oil tank was analyzed during the dock inspection of the actual ship, high concentrations of chloride ions and sulfate ions were detected.

  By the way, the most effective method of preventing the above-mentioned general corrosion and local corrosion is to apply heavy coating on the surface of the steel material to shield the steel material from the corrosive environment. However, the painting operation of crude oil tanks requires an enormous area to be applied, and the paint film must be repainted once every 10 years due to the deterioration of the coating film. To do. Furthermore, it has been pointed out that corrosion is promoted on the damaged part of the heavy-painted coating film in the corrosive environment of the crude oil tank.

For the corrosion problem as described above, several techniques for improving the corrosion resistance of the steel material itself in the corrosive environment of the crude oil tank have been proposed. For example, in Patent Document 1, in mass%, C: 0.001 to 0.2%, Si: 0.01 to 2.5%, Mn: 0.1 to 2%, P: 0.03% or less, S: 0.02% or less, Cu: 0.01 to 1.5%, Al: 0.001 to 0.3%, N: 0.001 to 0.01%, and Mo: 0.0. When forming a welded joint by welding steel materials containing 01 to 0.5% and W: 0.01 to 1% or two types, the balance being Fe and inevitable impurities, in the weld metal A technique for forming a welded joint so that the contents of Cu, Mo, and W satisfy the following three formulas is disclosed.
3 ≧ Cu content of weld metal (mass%) / Cu content of steel (mass%) ≧ 0.15
3 ≧ (Mo content of weld metal + W content (mass%)) / (Mo content of steel material + W content (mass%)) ≧ 0.15
−0.3 ≦ (Cu content of weld metal (mass%) − Cu content of steel (mass%)) ≦ 0.5

Moreover, in patent document 2, in mass%, C: 0.001-0.2%, Si: 0.01-2.5%, Mn: 0.1-2%, P: 0.03% or less , S: 0.02% or less, Cu: 0.01 to 1.5%, Al: 0.001 to 0.3%, N: 0.001 to 0.01%, and Mo: 0 When forming a crude oil tank by welding steel materials containing 0.01 to 0.5% and W: 0.01 to 1% or two of which are composed of Fe and inevitable impurities. A technique for forming a welded joint so that the content of Cu, Mo, W in the inside satisfies the following two formulas is disclosed.
3 ≧ Cu content of weld metal (mass%) / Cu content of steel (mass%) ≧ 0.15
3 ≧ (Mo content of weld metal + W content (mass%)) / (Mo content of steel material + W content (mass%)) ≧ 0.15

Japanese Patent Laid-Open No. 2005-21981 Japanese Patent Laid-Open No. 2005-23421

  However, with the techniques described in Patent Document 1 and Patent Document 2, it is difficult to suppress local corrosion (pitting corrosion) generated in the tanker bottom plate and the welded joint to 4 mm or less in 2.5 years. This is because, in recent years, corrosion surveys of actual ships have revealed that the pH of the solution inside the pitting corrosion generated on the tanker bottom plate and the welded portion is 1.0 or less (edited by “Crude Oil Tanker”, edited by the 242nd Research Committee). New Corrosion Behavior Research Report 2001, published by Japan Shipbuilding Research Group). In general, steel material corrosion in an acidic solution is rate-determined by a hydrogen reduction reaction, and it is well known that the corrosion rate dramatically increases as the pH decreases. Therefore, the immersion test at pH 2.0 as described in the Examples of Patent Document 1 and Patent Document 2 does not sufficiently reflect the corrosive environment in an actual ship.

  Moreover, although the steel materials of the prior art such as Patent Document 1 and Patent Document 2 described above contain Cu as an essential element for improving corrosion resistance, the addition of Cu causes surface cracks during hot rolling, so that production stability is improved. Have the problem of harming.

  Therefore, the object of the present invention is to form a steel plate excellent in manufacturability that does not cause problems such as cracking during hot rolling. An object of the present invention is to provide a welded joint having excellent corrosivity and a crude oil tank having the welded joint.

  The inventors have intensively studied to solve the above problems. As a result, when forming a crude oil tank by welding steel materials with improved corrosion resistance by controlling the component composition of steel, the content of Cu, Mo and W contained in the weld metal of the welded joint is within the proper range. It has been found that by controlling to the above, it is possible to remarkably reduce the general corrosion and local corrosion generated in the welded joint of the crude oil tank, and the present invention has been completed.

That is, the present invention includes C: 0.03-0.16 mass%, Si: 0.05-1.50 mass%, Mn: 0.1-2.0 mass%, P: 0.025 mass% or less, S: 0 0.010 mass% or less, Al: 0.005 to 0.10 mass%, N: 0.008 mass% or less, Cr: more than 0.1 mass%, 0.5 mass% or less, Cu: 0.03 to 0.4 mass% And W: 0.01-1.0 mass%, Mo: 0.01-0.5 mass%, Sn: 0.001-0.2 mass%, and Sb: 0.001-0.4 mass% 1 type or 2 types or more, and the above component is further represented by the following formula (1):
X value = (1−0.8 × Cu ^0.5 ) × {1- (0.8 × W + 0.4 × Mo) ^0.3 } × {1- (Sn + 0.4 × Sb) ^0.3 } × {1- (0.05 × Cr + 0.03 × Ni + 0.03 × Co) ^0.3 } × {1 + 2 × (S / 0.01 + P / 0.025)} (1)
X value defined by is 0.5 or less, the following formula (2);
Z value = (1 + 10 × Sn) × (Cu−0.7 × Ni) (2)
In a welded joint of a crude oil tank formed by welding steel materials composed of Fe and unavoidable impurities, with the Z value defined by ≦ 0.15 or less, welding in the base material and welded joint Cu, Mo and W in the metal are represented by the following formula (3):
3 <{(Mo + W) in the weld metal} / {(Mo + W) in the base metal} ≦ 8 (3)
And (4) formula;
0.2 ≦ (Cu in weld metal) / {(Mo + W) in weld metal} ≦ 3 (4)
It is a welded joint characterized by containing. Here, the element symbol in each of the above formulas indicates the content (mass%) of the element.

In addition to the above component composition, the steel material used for the welded joint of the present invention further includes at least one component of the following groups A to D.
Group A; Ni: 0.005 to 0.4 mass% and Co: 0.01 to 0.4 mass%, one or two types selected from Group B; Nb: 0.001 to 0.1 mass%, Ti : 0.001 to 0.1 mass%, Zr: 0.001 to 0.1 mass% and V: 0.002 to 0.2 mass%, one or more C groups; Ca: 0.0002 ~ 0.01 mass%, REM: 0.0002 to 0.015 mass% and Y: 0.0001 to 0.1 mass%, one or more selected from group D; B: 0.0002 to 0.003 mass %

  Moreover, this invention is a crude oil tank characterized by having the said weld joint.

  According to the present invention, the overall corrosion and local corrosion generated in a crude oil tank formed by welding, such as an oil tank of a crude oil tanker or a tank for transporting or storing crude oil, can be observed in all parts including not only steel plates but also welded joints. Since it can be suppressed, it has a remarkable industrial effect.

In the Example of this invention, it is a figure explaining the test apparatus used for the general corrosion test. In the Example of this invention, it is a figure explaining the test apparatus used for the pitting corrosion test. It is a figure which shows the influence of the weld metal composition on the corrosion resistance of the welded joint of a tanker bottom plate and a top plate.

First, the component composition of the steel material used for the crude oil tank of the present invention will be described.
C: 0.03-0.16 mass%
C is an element that enhances the strength of steel. In the present invention, 0.03 mass% or more is added in order to secure a desired strength. On the other hand, addition exceeding 0.16 mass% reduces weldability and toughness of the heat affected zone. Therefore, C is set to a range of 0.03 to 0.16 mass%. Preferably it is the range of 0.06-0.16 mass%.

Si: 0.05-1.50 mass%
Si is an element added as a deoxidizer, but is also an effective element for increasing the strength of steel. Therefore, in the present invention, 0.05 mass% or more is added in order to ensure a desired strength. However, addition exceeding 1.50 mass% reduces the toughness of steel. Therefore, Si is set to a range of 0.05 to 1.50 mass%. Preferably it is the range of 0.15-0.50 mass%.

Mn: 0.1 to 2.0 mass%
Mn is an element that increases the strength of steel, and in the present invention, 0.1 mass% or more is added in order to obtain a desired strength. On the other hand, addition exceeding 2.0 mass% reduces the toughness and weldability of steel. Therefore, Mn is in the range of 0.1 to 2.0 mass%. In addition, the range of 0.5-1.6 mass% is preferable and the range of 0.7-1.4 mass% is more preferable from the viewpoint of suppressing the formation of inclusions that maintain high strength and reduce corrosion resistance.

P: 0.025 mass% or less P is a harmful element that segregates at the grain boundaries and lowers the toughness of the steel, and is desirably reduced as much as possible. In particular, if added over 0.025 mass%, the toughness is greatly reduced. Moreover, when P is added exceeding 0.025 mass%, it will also have a bad influence on the corrosion resistance in a tank oil tank. Therefore, P is set to 0.025 mass% or less. Preferably it is 0.015 mass% or less.

S: 0.010 mass% or less S is a harmful element that forms MnS, which is a non-metallic inclusion, and serves as a starting point for local corrosion and reduces local corrosion resistance. It is desirable to reduce it as much as possible. In particular, addition exceeding 0.010 mass% leads to a significant decrease in local corrosion resistance. Therefore, the upper limit of S is 0.010 mass%. Preferably, it is 0.005 mass% or less.

Al: 0.005-0.10 mass%
Al is an element added as a deoxidizer, and 0.005 mass% or more is added in the present invention. However, if added in excess of 0.10 mass%, the toughness of the steel decreases, so the upper limit of Al is 0.10 mass%. Preferably it is 0.01-0.05 mass%, More preferably, it is the range of 0.02-0.04 mass%.

N: 0.008 mass% or less N is a harmful element that lowers toughness, and is desirably reduced as much as possible. In particular, if added over 0.008 mass%, the toughness is greatly lowered, so the upper limit is made 0.008 mass%. Preferably it is 0.006 mass% or less, More preferably, it is 0.004 mass% or less.

Cr: 0.1mass% Ultra 0.5 mass% or less Cr is with the progress of corrosion proceeds to rust layer, Cl ^- of by blocking the entry into rust layer, the interface between the rust layer and base iron Inhibits the concentration of Cl ⁻ . In addition, when a Zn-containing primer is applied, a complex oxide of Cr or Zn centering on Fe can be formed, and Zn can be kept on the surface of the steel sheet for a long period of time, thus dramatically improving the corrosion resistance. Can do. The above-mentioned effect is particularly remarkable in a portion that comes into contact with a liquid containing a high concentration of salt separated from a crude oil component, such as a bottom plate portion of a tanker oil tank, and a Zn-containing primer treatment is applied to the steel material in the above-mentioned portion containing Cr. As a result, the corrosion resistance can be remarkably improved as compared with a steel material not containing Cr. For the effect of Cr, addition of 0.1 mass% or less is not sufficient, while addition exceeding 0.5 mass% deteriorates the toughness of the weld. Therefore, Cr is in the range of more than 0.1 mass% and less than 0.5 mass%. Preferably it is 0.11-0.3 mass%, More preferably, it is the range of 0.12-0.2 mass%.

Cu: 0.03-0.4 mass%
Cu is an element that increases the strength of the steel, and also exists in the rust generated by the corrosion of the steel and has the effect of increasing the corrosion resistance. These effects cannot be sufficiently obtained with addition of less than 0.03 mass%. On the other hand, addition over 0.4 mass% saturates the effect of improving corrosion resistance and causes problems such as surface cracking during hot working. . Therefore, Cu needs to be added in the range of 0.03 to 0.4 mass% from the viewpoint of stably producing the steel material of the present invention. In addition, since the effect of Cu addition is saturated as the amount of addition increases, the range of 0.008 to 0.15 mass% is preferable and the range of 0.01 to 0.14 mass% is preferable from the viewpoint of cost effectiveness. More preferred.

The steel material of this invention needs to contain 1 type, or 2 or more types chosen from W, Mo, Sn, and Sb other than the said component in the following range.
W: 0.01-1.0 mass%
W has the effect of suppressing pitting corrosion at the tanker tank bottom plate and the effect of suppressing overall corrosion of the tanker upper deck. The above effect is manifested by addition of 0.01 mass% or more. However, if it exceeds 1.0 mass%, the effect is saturated. Therefore, W is added in the range of 0.01 to 1.0 mass%. Preferably it is 0.01-0.5 mass%, More preferably, it is the range of 0.02-0.3 mass%.

The reason why W has the above-described effect of improving corrosion resistance is that WO ₄ ²⁻ is generated in the rust generated as the steel sheet corrodes, and the presence of this WO ₄ ²⁻ causes chloride ions to be generated. Intrusion into the steel sheet surface is suppressed, and furthermore, FeWO ₄ is generated at the site where the pH is lowered, such as the anode part on the steel sheet surface, and the presence of this FeWO ₄ also suppresses the entry of chloride ions into the steel sheet surface. Because it is done. Further, even by the inhibitor effect of adsorption to WO ₄ ^2-steel surfaces, believed to corrosion of the steel material is prevented.

Mo: 0.01-0.5 mass%
Mo not only suppresses pitting corrosion on the bottom plate of the tanker tank, but also improves overall corrosion resistance on the back of the tanker's upper deck and corrosion resistance after painting in a corrosive environment where salt water is repeatedly immersed and highly humid like a ballast tank. There is an effect to make. The effect of Mo is manifested by addition of 0.01 mass% or more, but the effect is saturated when it exceeds 0.5 mass%. Therefore, Mo is set to a range of 0.01 to 0.5 mass%. Preferably it is 0.02-0.5 mass%, More preferably, it is the range of 0.03-0.4 mass%.
The reason why Mo has the above-described effect of improving corrosion resistance is that, like W, MoO ₄ ²⁻ is generated in the rust generated along with corrosion of the steel sheet, and the presence of MoO ₄ ²⁻ causes chloride ions. This is thought to be because the penetration of steel into the steel sheet surface is suppressed.

Sn: 0.001-0.2 mass%, Sb: 0.001-0.4 mass%
Sn and Sb have the effect of suppressing pitting corrosion on the tanker tank bottom plate and the effect of suppressing the overall corrosion of the tanker upper deck. The above effects are manifested by the addition of Sn: 0.001 mass% or more and Sb: 0.001 mass% or more. On the other hand, even if Sn: more than 0.2 mass% and Sb: more than 0.4 mass% are added, the effect is saturated. Furthermore, the addition of a large amount of Sn promotes surface cracking during hot working with Cu. Therefore, Sn and Sb are preferably added in the above ranges.

Moreover, it is preferable that the steel material of this invention contains 1 type or 2 types chosen from Ni and Co other than the said essential component in the following range.
Ni: 0.005-0.4 mass%, Co: 0.01-0.4 mass%
Ni and Co have the effect of refining the generated rust particles to improve the corrosion resistance in the bare state and the corrosion resistance in the state where the epoxy primer is applied to the zinc primer. Therefore, these elements are preferably added in an auxiliary manner when it is desired to further improve the corrosion resistance. The above effects are manifested by adding Ni: 0.005 mass% or more and Co: 0.01 mass% or more. On the other hand, even if Ni is added in excess of 0.4 mass% and Co is added in excess of 0.4 mass%, the effect is saturated. Further, Ni has an effect of suppressing surface cracks during hot working that occur in steel containing Cu or Sn. Therefore, Ni and Co are preferably added within the above ranges.

Moreover, in addition to the above essential components and the selectively added components (Ni, Co) being contained in the above appropriate range, the steel material of the present invention further includes the following formula (1):
X value = (1−0.8 × Cu ^0.5 ) × {1- (0.8 × W + 0.4 × Mo) ^0.3 } × {1- (Sn + 0.4 × Sb) ^0.3 } × {1- (0.05 × Cr + 0.03 × Ni + 0.03 × Co) ^0.3 } × {1 + 2 × (S / 0.01 + P / 0.025)} (1)
Here, the element symbol in the above formula indicates the content (mass%) of the element, and the element not contained is calculated as 0 (zero).
It is necessary to contain so that the X value defined by may satisfy 0.5 or less.

  The above equation (1) is an equation for evaluating the influence of each component on the corrosion in the tanker oil tank, and the coefficient of the component that improves the corrosion resistance is expressed as negative, and the coefficient of the component that deteriorates the corrosion resistance is expressed as positive. Yes. Therefore, the steel material having a smaller value of X has better corrosion resistance. As a result of investigating the relationship between the value of X and the corrosion resistance of the steel material in the corrosive environment in the tanker oil tank, the inventors have found that if X is 0.5 or less, the corrosion resistance in the corrosive environment in the tanker oil tank is reduced. Although it is excellent, it discovered that the said corrosion resistance deteriorated when X exceeded 0.5. Therefore, in determining the content of P, S, Cr, Cu, W, Mo, Sn, Sb, Ni and Co, the steel material of the present invention is designed so that the X value is 0.5 or less. There is a need.

Furthermore, the steel material of the present invention contains Cu, Sn, and Ni in the following formula (2) in addition to containing the above components in the appropriate range described above;
Z value = (1 + 10 × Sn) × (Cu−0.7 × Ni) (2)
Here, the element symbol in the above formula indicates the content (mass%) of the element, and the element not contained is calculated as 0 (zero).
It is necessary to contain so that the Z value defined by (1) may be 0.15 or less. The reason is that Cu is an element that causes surface cracking during hot working, and Sn is an element that promotes cracking due to Cu. On the other hand, Ni is an effective element for preventing the harmful effects of the above elements, but in order to exhibit the above effects of Ni, it is necessary to satisfy the above formula (2) and to add Ni. .

In addition to the above components, the steel material of the present invention may further contain one or more selected from Nb, Ti, V and Zr in the following range in addition to the above components. it can.
Nb: 0.001-0.1 mass%, Ti: 0.001-0.1 mass%, Zr: 0.001-0.1 mass% and V: 0.002-0.2 mass%
Nb, Ti, Zr and V are all elements that increase the strength of the steel material, and can be appropriately selected and added according to the required strength. In order to acquire the said effect, it is preferable to add Nb, Ti, and Zr each 0.001 mass% or more, and V to add 0.002 mass% or more. However, if Nb, Ti, Zr exceeds 0.1 mass%, and V exceeds 0.2 mass%, the toughness decreases, so Nb, Ti, Zr, V are added within the above ranges, respectively. Is preferred.

Furthermore, in order to increase the strength or improve the toughness, the steel material of the present invention further includes one or more selected from Ca, REM and Y in the following range in addition to the above components. Can be added.
Ca: 0.0002 to 0.01 mass%, REM: 0.0002 to 0.015 mass%, and Y: 0.0001 to 0.1 mass%
Ca, REM, and Y are all effective in improving the toughness of the weld heat affected zone, and can be added as necessary. The above effect can be obtained by adding Ca: 0.0002 mass% or more, REM: 0.0002 mass% or more, Y: 0.0001 mass% or more, but Ca: 0.01 mass%, REM: 0.015 mass%, Y: If added in excess of 0.1 mass%, the toughness is reduced, so Ca, REM, and Y are preferably added in the above ranges.

Furthermore, the steel material of this invention can contain B in the following range in addition to the said component.
B: 0.0002 to 0.003 mass%
B is an element that increases the strength of the steel material, and can be added as necessary. In order to acquire the said effect, adding 0.0002 mass% or more is preferable. However, when it exceeds 0.003 mass%, toughness will fall. Therefore, it is preferable to add B in the range of 0.0002 to 0.003 mass%.

In addition, it is preferable to manufacture the steel materials used for the crude oil tank of the present invention by the following method.
That is, the steel material of the present invention is prepared by melting a steel adjusted to a component composition suitable for the present invention using a known refining process such as a converter, electric furnace, vacuum degassing, etc. It is preferable that a steel material (slab) is formed by a block rolling method, and then this material is reheated and hot-rolled to obtain a steel material such as a thick steel plate, a thin steel plate and a shaped steel.

  The reheating temperature before the hot rolling is preferably 900 to 1200 ° C. If heating temperature is less than 900 degreeC, a deformation resistance is large and it will become difficult to hot-roll. On the other hand, when the heating temperature exceeds 1200 ° C., the austenite grains become coarse, leading to a decrease in toughness, and a scale loss due to oxidation becomes remarkable, resulting in a decrease in yield. A more preferable heating temperature is 1000 to 1150 ° C.

  Further, when rolling into a steel material having a desired shape and size by hot rolling, the finish rolling finishing temperature is preferably 750 ° C. or higher. If the temperature is lower than 750 ° C., the deformation resistance of the steel increases, the rolling load increases, it becomes difficult to roll, and a waiting time occurs until the rolled material reaches a predetermined rolling temperature, so the rolling efficiency decreases. It is because.

  The steel material after hot rolling may be cooled by either air cooling or accelerated cooling. However, when higher strength is desired, accelerated cooling is preferable. In addition, when performing accelerated cooling, it is preferable to make a cooling rate into the range of 2-80 degree-C / sec and the cooling stop temperature in the range of 650-300 degreeC. When the cooling rate is less than 2 ° C./sec and the cooling stop temperature exceeds 650 ° C., the effect of accelerated cooling is small and sufficient strength cannot be achieved. On the other hand, if the cooling rate exceeds 80 ° C./sec and the cooling stop temperature is less than 300 ° C., the toughness of the obtained steel material may be reduced, or the shape of the steel material may be distorted.

Next, a weld joint of a crude oil tank formed by welding the steel material of the present invention will be described.
In the welded joint of the crude oil tank formed by welding steel plates produced by adjusting to the appropriate components, Mo and W in the weld metal have the following formula (3);
3 <{(Mo + W) in the weld metal} / {(Mo + W) in the base metal} ≦ 8 (3)
It is necessary to satisfy and contain.
Generally, when the corrosion resistance of the weld metal is inferior to the corrosion resistance of the base material (steel material), in the acid immersion test that simulates the inside of the pitting corrosion of the tanker bottom plate, which will be described later, the dissolution of the metal in the welded portion is promoted. Moreover, if Sn or Sb is added to the weld metal in order to improve the corrosion resistance of the weld metal to the same level as the base metal (steel material), the low temperature toughness of the welded joint cannot be ensured. Therefore, it is necessary to improve the corrosion resistance of the weld metal to the same level as the base material (steel material) without containing Sn or Sb in the weld metal. Therefore, the present invention limits the value of {(Mo + W)} / {(Mo + W)} in the base metal to the range defined by the above formula (3) as means for improving the corrosion resistance of the weld metal. There are features.

  When {Mo + W in the weld metal} / {(Mo + W) in the base metal} is 3 or less, the corrosion resistance of the weld metal is inferior to that of the base material (steel material). In the acid immersion test simulating the inside, the dissolution of the metal in the welded portion is promoted. On the other hand, when {(Mo + W)} / {(Mo + W)} in the base metal exceeds 8, the addition of Mo or W more than necessary increases the cost of the welding material (welding wire). In addition, since the corrosion resistance of the weld metal greatly exceeds that of the base metal, selective corrosion of the base metal occurs in an actual corrosion environment. Therefore, Mo and W in the weld metal must satisfy the above formula (3). Note that {(Mo + W)} / {(Mo + W)} in the base metal is preferably in the range of 3-7, more preferably in the range of 3-6.

In the weld joint of the crude oil tank of the present invention, Cu, Mo and W in the weld metal are represented by the following formula (4):
0.2 ≦ (Cu in weld metal) / {(Mo + W) in weld metal} ≦ 3 (4)
It is necessary to satisfy and contain.
The inventors have found that when Cu and Mo or W are added in combination, the corrosion resistance of the welded joint is greatly improved by the synergistic effect of these elements. However, when (Cu in the weld metal) / {(Mo + W) in the weld metal} in the formula (4) is less than 0.2, the Cu is compared with the Mo or W content in the weld metal. Therefore, the corrosion resistance of the welded joint is lowered. On the other hand, when (Cu in weld metal) / {(Mo + W) in weld metal} in the formula (4) exceeds 3, the content of Mo or W compared to the Cu content in the weld metal Is too low, the above-mentioned synergistic effect cannot be expected, so that the corrosion resistance of the welded joint is lowered. Therefore, Cu, Mo, and W in the weld metal must satisfy the above formula (4). In addition, as long as the content of Mo and W in a weld metal is in the range with which the said content satisfy | fills the said Formula, it does not need to contain any one of Mo and W. Note that (Cu in the weld metal) / {(Mo + W) in the weld metal} is preferably in the range of 0.5 to 3, and more preferably in the range of 0.5 to 2.5.

In addition to the above conditions, the inventors of the present invention further have a Cu in the weld metal and a base material (steel material) represented by the following formula (5):
1 ≦ (Cu in weld metal) / (Cu in base material) ≦ 8 (5)
When satisfy | filling, it discovered that the corrosion resistance in all the parts including a base material (steel material) and a welded joint further improved.
As described above, the present invention improves the corrosion resistance of the weld metal to the same level as the base material (steel material) without reducing the low temperature toughness of the welded joint, so that the weld metal does not contain Sn or Sb. The point is to control the value of (Mo + W)} / {(Mo + W)} in the base metal within an appropriate range defined by the equation (3). However, in order to improve the corrosion resistance of the weld metal more stably, in addition to the above formula (3), the value of (Cu in the weld metal) / (Cu in the base metal) should be 1 or more. More preferred. On the other hand, if (Cu in the weld metal) / (Cu in the base metal) exceeds 8, addition of Cu more than necessary increases not only the cost of the welding material (welding wire) but also the corrosion resistance of the weld metal. However, since it greatly exceeds that of the base material, there is a risk of selective corrosion of the base material. Therefore, it is preferable that Cu in the weld metal and the base material (steel material) satisfy the formula (5).

  In order to control the contents of Cu, Mo and W in the weld metal within the above range, a welding material (welding wire) used for welding is appropriately selected according to the component composition of the steel (base material) and welding conditions. It is preferable to select. For example, a welding wire having a composition obtained by dividing the target composition of Cu, Mo, and W in the weld metal by the dilution rate of the base material is produced and welded using this.

The welding method used for welding the crude oil tank according to the present invention is a single-sided one-pass submerged arc welding method such as FAB welding, FCB welding, RF welding, carbon dioxide arc welding (CO ₂ welding), or the like. However, from the viewpoint of controlling the chemical component composition of the weld metal to an appropriate range, it is necessary that the welding method uses a welding wire.
Here, the FAB welding is a registered trademark relating to the welding method of Kobe Steel Co., Ltd. The backing material composed of glass tape, solid flux, etc. is directly applied to the back surface of the steel plate, and the back bead is formed by one pass welding. The method of forming. The FCB welding is a registered trademark related to the welding method at Kobe Steel, Ltd., and a backside flux is sprayed on a copper plate and pressed against the backside of the steel plate to form a back bead by one pass welding. How to do. Moreover, the RF method is a registered trademark relating to the welding method of Kobe Steel, Ltd., and a jig frame in which an underlay flux is piled under a backing flux containing a welding thermosetting resin is applied to the back surface of the steel plate, It refers to a method of forming a backside bead by one-pass welding by pressing the inside flux.

No. shown in Table 1-1 and Table 1-2. Steel having different component compositions of 1 to 36 is melted in a vacuum melting furnace to form a steel ingot, or melted in a converter, continuously cast to form a steel slab, these are reheated to 1150 ° C., and then finish-rolled Hot rolling with an end temperature of 800 ° C. was performed to obtain a thick steel plate having a thickness of 25 mm.
No. obtained in this way. About the thick steel plates 1-36, the presence or absence of the crack in the steel plate surface was investigated in the magnetic particle flaw detection test, and the thing in which the crack was not detected was determined to be (circle), and the thing in which the crack was detected was determined to be x.

Then, the above No. 1 to 36 were welded to each other by the welding methods described in Table 2-1 and Table 2-2 to prepare welded joints. In addition, the heat input of each welding method was 146 kJ / cm for FCB welding, 180 kJ / cm for FAB welding, and 1.5 kJ / cm for CO ₂ welding. All the grooves were V grooves. Here, the composition control of Cu, Mo, and W in the weld metal of each welded joint is performed by setting the target composition of Cu, Mo, and W to the base material dilution ratio (about 11% for CO ₂ welding, about 47% for FAB welding, FCB welding). A welding wire having a composition obtained by rebating by about 67% was produced, and welding was performed using this. For FCB welding, a flux (PF-I55E / manufactured by Kobe Steel) and a back flux (PF-I50R / manufactured by Kobe Steel), and for FAB welding, a flux (PF-I52E / ( Kobe Steel, Ltd.), filler (RR-2 / Kobe Steel) and backing material (FA-B1 / Kobe) were used.
As described above, FCB welding refers to a method in which a backing flux is spread on a copper plate and pressed against the back surface of the steel plate to form a back bead by one-pass welding. FAB welding refers to a method in which a backing material composed of glass tape, solid flux or the like is directly applied to the back surface of a steel plate to form a back bead by one-pass welding.

About the welded joint produced as mentioned above, content of Cu, Mo, and W in a weld metal was measured using the atomic absorption analysis method.
Furthermore, a full corrosion test simulating the upper deck back and a local corrosion resistance test simulating the tanker bottom plate environment were conducted as follows.
(1) Overall corrosion test simulating the tanker upper deck environment In order to evaluate the corrosion resistance against the overall corrosion on the back side of the tanker upper deck, A rectangular piece of width 25 mm × length 60 mm × thickness 5 mm so that the weld metal is positioned in parallel with the width direction of the test piece from the position of the plate thickness ¼ of the thick steel plate welded joints 1 to 36. It was cut out and its surface was polished with 600th emery paper. The back surface and the end surface were sealed with tape so as not to corrode, and a full surface corrosion test was performed using the corrosion test apparatus shown in FIG.
This corrosion test apparatus is composed of a corrosion test tank 2 and a temperature control plate 3. Water 6 having a temperature of 36 ° C. is injected into the corrosion test tank 2, and the water 6 Into the corrosion test tank 2, a mixed gas (introduction gas 4) consisting of 12 vol% CO ₂ , 5 vol% O ₂ , 0.01 vol% SO ₂ , 0.3 vol% H ₂ S and the balance N ₂ is introduced. It is filled with supersaturated water vapor and reproduces the corrosive environment behind the upper deck of a crude oil tank. Then, a temperature change with a cycle of 25 ° C. × 3 hours + 50 ° C. × 21 hours is applied to the corrosion test piece 1 set on the upper and rear surfaces of the test tank via a temperature control plate 3 incorporating a heater and a cooling device. It is repeatedly applied for one day to cause dew condensation water on the surface of the test piece 1 to cause overall corrosion. In FIG. 1, 5 indicates the exhaust gas from the test tank.
After the above test, the rust on the surface of each test piece was removed, and the decrease in mass due to corrosion was determined from the change in mass before and after the test, and this value was converted into a reduction in sheet thickness per year (corrosion rate on one side). As a result, when the corrosion rate is 0.08 mm / y or less and no local corrosion is observed in either the base metal part or the welded part, the overall corrosion resistance is good (O), more than 0.08 mm / y, or When the local corrosion was visually recognized in either the base metal part or the welded part, the overall corrosion resistance was evaluated as poor (x).

(2) Local corrosion (pitting corrosion) test simulating tanker oil tank bottom plate environment In order to evaluate the corrosion resistance against pitting corrosion on the tanker oil tank bottom plate, A rectangular piece of width 25 mm × length 60 mm × thickness 5 mm so that the weld metal is positioned in parallel with the width direction of the test piece from the position of the plate thickness ¼ of the thick steel plate welded joints 1 to 36. It was cut out and the entire surface was polished with 600th emery paper.
Next, a 10 mass% NaCl aqueous solution was prepared using concentrated hydrochloric acid to prepare a test solution having a Cl ion concentration of 10 mass% and a pH of 0.85. The test solution was suspended in a 3 mmφ hole opened in the upper part of the test piece, and suspended per test piece. A corrosion test was conducted by immersing in 2 L of test solution for 168 hours. The test solution was preheated and maintained at 30 ° C. and replaced with a new test solution every 24 hours.
The apparatus used for the corrosion test is shown in FIG. This corrosion test apparatus is a double-type apparatus of a corrosion test tank 8 and a thermostatic tank 9, and the test solution 10 is put in the corrosion test tank 8, and the test piece 7 is suspended and immersed in the tegs 11 therein. ing. The temperature of the test solution 10 is maintained by adjusting the temperature of the water 12 placed in the thermostatic chamber 9.
After removing the rust generated on the surface of the test piece after the corrosion test, the mass difference before and after the test is calculated, the difference is divided by the total surface area, and the reduction in thickness (corrosion rate on both sides) per year is calculated. It was. As a result, when the corrosion rate is 0.8 mm / y or less and local corrosion is not visually recognized in the base metal part and the welded part, the local corrosion resistance is good (◯), and the corrosion rate exceeds 0.8 mm / y. When the corrosion rate is 1.0 mm / y or less and no local corrosion is visually recognized in the base metal part and the welded part, the local corrosion resistance is generally good (Δ), the corrosion rate is over 1.0 mm / y, or The case where local corrosion was visually recognized in either the material part or the welded part was evaluated as poor (×) in the local corrosion resistance.

  The results of the magnetic particle flaw detection test and the corrosion resistance test are shown in Tables 2-1 and 2-2 together with the X and Z values obtained from the component composition of each steel sheet. From these tables, the base metal and the weld metal satisfy the component composition of the present invention and satisfy the conditions of X value and Z value. Thick steel plates of 1-4, 6, 7, and 10-29 are free of cracking during rolling, and have good corrosion resistance in both the corrosion resistance test that simulates the upper deck and the corrosion resistance test that simulates the tanker bottom plate environment. Although shown, No. which does not satisfy the conditions of the present invention. The thick steel plates of 5, 8, 9, and 30 to 36 have not obtained good results in any of the corrosion resistance tests.

  FIG. 3 shows No. 1 described in Table 2-1 and Table 2-2. The effect of the weld metal composition on the corrosion resistance of the welded joint when 1 to 36 thick steel plates are used for the tanker bottom plate and the top plate is expressed as (Cu in weld metal) / {(Mo + W) in weld metal}. And the vertical axis is shown as {(Mo + W)} in the weld metal / {(Mo + W) in the base metal}. From FIG. 3, (Cu in the weld metal) / {(Mo + W) in the weld metal} is 0.2 to 3 and {(Mo + W) in the weld metal} / {(Mo + W) in the base metal} is 3 to 3. In the range of 8, in both the corrosion resistance test simulating the upper deck back and the corrosion resistance test simulating the tanker bottom plate environment, good corrosion resistance (○ mark and △ mark in Table 2-1 and Table 2-2) is shown. On the other hand, those outside the above range are inferior in any of the upper-air corrosion resistance tests (X marks in Table 2-1 and Table 2-2).

DESCRIPTION OF SYMBOLS 1, 7: Test piece 2, 8: Corrosion test tank 3: Temperature control plate 4: Introducing gas 5: Exhaust gas 6, 12: Water 9: Thermostatic bath 10: Test liquid 11: Tegus

Claims (6)

C: 0.03-0.16 mass%,
Si: 0.05-1.50 mass%,
Mn: 0.1 to 2.0 mass%,
P: 0.025 mass% or less,
S: 0.010 mass% or less,
Al: 0.005 to 0.10 mass%,
N: 0.008 mass% or less,
Cr: more than 0.1 mass% and 0.5 mass% or less,
Cu: 0.03-0.4mass% is contained, and
W: 0.01 to 1.0 mass%, Mo: 0.01 to 0.5 mass%, Sn: 0.001 to 0.2 mass%, and Sb: 0.001 to 0.4 mass% Or contains two or more,
Further, the above components are contained so that the X value defined by the following formula (1) is 0.5 or less and the Z value defined by the following formula (2) is 0.15 or less, with the balance being Fe and inevitable In a crude oil tank weld joint formed by welding steel materials made of impurities,
A welded joint characterized in that Cu, Mo, and W in the base metal and the weld metal in the welded joint satisfy the following formulas (3) and (4).
X value = (1-0.8 × Cu ^0.5 ) × {1- (0.8 × W + 0.4 × Mo) ^0.3 } × {1- (Sn + 0.4 × Sb) ^0.3 } × {1- (0.05 × Cr + 0.03 × Ni + 0.03 × Co) ^0.3 } × {1 + 2 × (S / 0.01 + P / 0.025)} (1)
Z value = (1 + 10 × Sn) × (Cu−0.7 × Ni) (2)
3 <{(Mo + W) in the weld metal} / {(Mo + W) in the base metal} ≦ 8 (3)
0.2 ≦ (Cu in weld metal) / {(Mo + W) in weld metal} ≦ 3 (4)
Here, the element symbol in the above formula indicates the content (mass%) of the element. In addition to the above component composition, the steel material further includes one or two selected from Ni: 0.005 to 0.4 mass% and Co: 0.01 to 0.4 mass%. The welded joint according to claim 1. In addition to the above component composition, the steel material further includes Nb: 0.001 to 0.1 mass%, Ti: 0.001 to 0.1 mass%, Zr: 0.001 to 0.1 mass%, and V: 0.002. The welded joint according to claim 1 or 2, comprising one or more selected from -0.2 mass%. In addition to the above component composition, the steel material is further selected from Ca: 0.0002 to 0.01 mass%, REM: 0.0002 to 0.015 mass%, and Y: 0.0001 to 0.1 mass%. The weld joint according to any one of claims 1 to 3, comprising seeds or two or more kinds. The said steel material contains B: 0.0002-0.003mass% further in addition to the said component composition, The welded joint of any one of Claims 1-4 characterized by the above-mentioned. A crude oil tank comprising the welded joint according to claim 1.

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