EP0633326B1 - Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same - Google Patents

Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same Download PDF

Info

Publication number
EP0633326B1
EP0633326B1 EP94305057A EP94305057A EP0633326B1 EP 0633326 B1 EP0633326 B1 EP 0633326B1 EP 94305057 A EP94305057 A EP 94305057A EP 94305057 A EP94305057 A EP 94305057A EP 0633326 B1 EP0633326 B1 EP 0633326B1
Authority
EP
European Patent Office
Prior art keywords
steel
corrosion
hot
sea water
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94305057A
Other languages
German (de)
French (fr)
Other versions
EP0633326A1 (en
Inventor
Kazuhiko C/O Technical Research Div. Shiotani
Tsukasa C/O Technical Research Div. Imazu
Mitsuo C/O Technical Research Div. Kimura
Yoshiyuki C/O Technical Research Div. Saito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
Original Assignee
Kawasaki Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP6105077A external-priority patent/JPH07316722A/en
Application filed by Kawasaki Steel Corp filed Critical Kawasaki Steel Corp
Publication of EP0633326A1 publication Critical patent/EP0633326A1/en
Application granted granted Critical
Publication of EP0633326B1 publication Critical patent/EP0633326B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to steel that is adaptable and resistant to hot and wet environments, for example, severe environments to which ballast tanks or sea-water pipes are exposed, and to a method of manufacturing the same.
  • Tankers that will be manufactured in the future should have a double hull structure of the type shown in Figs. 4A and 4B to meet the regulations of the International Maritime Organization (IMO).
  • a double hull section of a tanker 20 is used as a ballast tank 21 constructed to protect oil tanks 22.
  • the double hull structure has the purpose of preventing oil spills.
  • ballast tank 21 Since the surface area of the ballast tank 21 that is exposed to sea water is considerably enlarged (two to three times) as compared with a conventional single hull structure, various problems arise in the painting process and in corrosion protection generally.
  • the ballast tank 21 must be coated once or twice with coal-tar epoxy resin paint.
  • this is difficult and dangerous for painters because the painting operation is performed in a narrow and confined space.
  • the considerable area to be painted causes the coating work to take a long time and to involve high cost. What is even worse, even higher cost and more labor are required for repairing the double hull structure after extended use, as compared with new ship construction.
  • the corrosion protection employs both paint such as coal-tar epoxy resin paint and cathodic protection measures. Since sea water flows into and out of the ballast tank 21, the ballast tank 21 is exposed to a severely corrosive environment. If sea water is present in the ballast tank 21, corrosion can substantially be prevented, thanks to modern cathodic protection measures. However, the uppermost portion of the ballast tank 21 and the underside of the deck 23 that are not normally immersed in sea water are subjected to a severely corrosive environment, the temperature of which may be very high and which is repeatedly splashed with sea water. If no water is present in the ballast tank 21, the environment becomes hot and wet and therefore the effect of cathodic protection measures cannot be obtained, and the coal-tar epoxy resin paint acts solely to prevent corrosion. The life of the coal-tar epoxy resin paint applied to the ballast tank can be expected to be about ten years, which is about half the life of the ship. In the residual ten years corrosion must be prevented by further painting, with major problems and difficulties.
  • ballast tank Since the ballast tank is in a severely corrosive environment and the coating work under adverse conditions encounters problems, hazards and difficulties, there has been a desire for an improved steel product that is especially effective for use in a ship and which has excellent resistance against sea water corrosion under hot and wet environments.
  • sea-water corrosion resistant steel has been disclosed in Japanese Patent Laid-Open No. 64-79346. It contains 7 to 20% aluminum. It is effective when used as a reinforcing steel when substantially no welding needs to be performed. However, it is not suitable for use where a multiplicity of welding processes are required, for example, in a ballast tank for a ship.
  • the present invention provides a novel steel having excellent corrosion resistance for use in ballast tanks and sea water pipes that are subjected to severe corrosive environments.
  • the corrosive environment to which the ballast tank is subjected is a hot and wet environment in which sea water flows in and out.
  • the oil tanks 22 shown in Fig. 4A contain no oil during the first trip from Japan to the Near or Middle East. Without oil the ballast tank 21 is substantially filled with sea water in order to balance the ship for safe navigation. The portion of tank 21 immersed in sea water and the upper portion of the tank 21 are substantially exposed to splashing sea water. When the ship sails from the Near or Middle East to Japan, it is filled with crude oil. Sea water in the ballast tank 21 is discharged and the ballast tank 21 is empty.
  • ballast tank The space in the ballast tank at that time is exposed to a hot and wet condition by sea water left in the bottom of the ship and by heat transmitted from and through the deck.
  • One cycle, in which the ballast tank is subjected to the foregoing cycle of corrosive environment, may be about forty days.
  • Important objects of the present invention are to provide a special steel capable of overcoming the foregoing problems and exhibiting excellent corrosion resistance against sea water in a hot and wet environment, and to provide a method of manufacturing the same.
  • Another object of the present invention is to provide a new weldable steel having excellent welded portions even when welded with a large heat input. Still another object is to provide a method of manufacturing such a new steel.
  • a sea-water corrosion resistant steel suitable for use in a hot and wet environment comprising: an amount of C of 0.1 wt% or less; an amount of Si of 0.5 wt% or less; an amount of Mn of 1.50 wt% or less; an amount of Al of 0.005 to 0.050 wt%; an amount of Cr of 0.5 to 3.50 wt%; an amount of Ti of 0.005 to 0.05 wt%; and an amount of Nb of 0.005 to 0.05 wt%; such that the total quantity of Ti and Nb is up to 0.05 wt%; the steel optionally further comprising: an amount of REM of 0.0015 to 0.020 wt%; an amount of N of 0.0020 to 0.0120 wt%; an amount of Ni of 1.5 wt% or less; and an amount of Mo of 0.8 wt% or less; wherein the total quantity of Ni and/or Mo is 1.5 wt% or less; and where
  • a sea water resistant steel having a composition as that claimed but comprising 0.2-0.4% copper and no titanium or niobium is disclosed in JP-A-59 64 750. Toughness of such a steel, especially in a zone affected by welding heat, is improved by additions of titanium and niobium as claimed, cf. Tables 6 and 17. The improvement of toughness also applies with respect to a high strength structural steel as disclosed in US-A-3 834 897, which steel has a good weldability and the same composition as that according to the invention but does not comprise titanium.
  • a method of manufacturing a steel having the composition defined above comprising the steps of: casting and hot-rolling the steel; and accelerated cooling the steel at a cooling rate of from 3 to 20°C/sec to a temperature of from 400°C to 600°C immediately after the steel has been cast and hot rolled.
  • An important object of the present invention is to provide a novel sea-water corrosion resistant steel composition which is resistant to hot and wet environments and is capable of reducing corrosion weight loss, and is free from local corrosion while maintaining smooth corrosive surfaces, even in an environment in which sea water and the atmosphere, the humidity of which may be as high as 100%, are repeatedly applied to the steel.
  • Decrease in corrosion weight loss means that generation of rust on the coated surface of a ballast tank, arranged to be protected from corrosion by coating and cathodic protection measures, can be prevented or severely curtailed.
  • the smooth corrosive surface achieved according to this invention helps to prevent occurrence of conditions that cause concentration of distortion or metal fatigue.
  • the advantages of this invention can be achieved by adding effective amounts of Cr, Ni and Mo, more preferably Nb and Ti. Furthermore, restriction of precipitation of carbides after hot rolling further enhances the beneficial effects of Cr and Mo.
  • Another object of the present invention is to improve the toughness of portions of sea-water corrosion resistant steel exposed to a hot and wet environment and joined by welding with large heat input. Addition of effective amounts of REM, Ti and N does not reduce the toughness of the portion that has been welded with large heat input; on the contrary it improves toughness.
  • the upper limit of the content of C is about 0.1 wt% because C is an element that helps to determine strength.
  • Si about 0.50 wt% or less
  • the upper limit of Si is about 0.50 wt%.
  • Mn about 1.50 wt% or less
  • Mn is an important element that influences strength, toughness and weldability, toughness and the weldability are adversely affected if the content of Mn exceeds about 1.50 wt%. Therefore, the upper limit of the content of Mn is about 1.50 wt%.
  • Al about 0.005 to 0.050 wt%
  • Al is added to serve as a deoxidizer, and the content of Al is determined to be about 0.005 to 0.050 wt% so far as weldability is not affected adversely.
  • the most effective element to improve corrosion resistance in the present invention is Cr. Since the contemplated corrosive environment is very severe, addition of not more than about 0.50 wt% Cr cannot significantly reduce corrosion and/or achieving a smooth corrosive surface. Since the foregoing effects can be obtained if Cr is added in an amount of about 0.50 wt% or more, the lower Cr limit is about 0.50 wt%. If the addition of Cr is increased, the effect of reducing corrosion weight loss can be attained. However, if the Cr content exceeds about 3.50 wt%, the steel surface is susceptible to a pitting corrosive state. If the quantity of Cr addition is increased to about 9 wt%, only pitting corrosion is realized, similarly to that observed on stainless steel.
  • the percentage Cr at which corrosion weight loss can be reduced and a smooth corrosive surface can be formed is about 3.50 wt% or less, the upper limit is determined to be about 3.50 wt%. However, it is preferable that the quantity of Cr is about 1.2 to 3.0 wt%.
  • Ni about 1.5 wt% or less
  • Ni be added together with Cr, which improves corrosion resistance.
  • the addition of Ni improves corrosion resistance and makes the corroded surface uniform. If the quantity of Ni exceeds about 1.5%, a tendency toward strengthening and hardening the steel is attained, and problems take place regarding toughness and weldability. Therefore, the quantity of Ni is about 1.5 wt% or less.
  • addition of Mo enables a similar effect to that of Ni, excessive Mo addition is considered to raise critical problems in toughness and weldability. Therefore, the addition of Mo is determined to be about 0.8 wt% or less.
  • Ni + Mo about 1.5 wt% or less
  • Ni and Mo enable substantially the same effect to be obtained. Since both Ni and Mo otherwise have problems of toughness and weldability, the upper limit of Ni + Mo is determined to be about 1.5 wt%.
  • Cr, Ni and Mo are elements that are effective to improve corrosion resistance
  • Cr and Mo readily form carbides which reduce the portion of Cr and Mo which is present in solution that effectively exhibit corrosion resistance. Since Ti is an element that forms carbides and has an affinity that is greater than those of Cr and Mo, Ti carbides are formed with priority. Therefore, forming of Cr carbides and Mo carbides is restricted and reduction of quantity of the solid solutions of Cr and Mo can be prevented. If the quantity of Ti is about 0.005 wt% or less, the foregoing effect cannot be obtained.
  • Ti significantly contributes to toughness of the welded portion of the steel where it has been joined with large heat input, because Ti forms nitrides when it coexists with REM.
  • the effect of Ti cannot substantially be obtained if the quantity is about 0.005 wt% or less. If the same is about 0.005 wt% or more, the increase of Ti causes saturation to take place gradually. If the quantity of Ti exceeds about 0.05 wt% the toughness of the base metal deteriorates. Therefore, the range is limited to about 0.005 to 0.05 wt%.
  • Ti coexists with REM, Ti is a required element. If REM is not present Ti may be present in the range of Nb + Ti discussed in a subsequent paragraph.
  • Nb about 0.005 to 0.05 wt%
  • Nb is an element provided for forming carbides.
  • the addition of Nb restricts forming of Cr and Mo carbides, and accordingly corrosion resistance obtainable from Cr and Mo in solution can be improved effectively. If the Nb content is about 0.005 wt% or less, the foregoing effect cannot be obtained. Since the toughness of the steel deteriorates if the content is about 0.05 wt% or more, the upper limit of Nb is determined to be about 0.05 wt%.
  • Nb + Ti about 0.005 to 0.05 wt%
  • Nb and Ti have similar effects of restricting precipitation of Cr carbide and Mo carbide and effectively improving corrosion resistance by enlarging the quantities of Cr and Mo in solution.
  • the foregoing effects can be obtained only when the quantity of Nb + Ti is about 0.005 wt% or more.
  • the upper Nb + Ti limit is determined to be about 0.05 wt%.
  • REM significantly improves the toughness of the portion welded with a large heat input of about 100 KJ/cm or more since it enhances the effect of Ti. If the percentage of REM is less than about 0.0015 wt%, its effect cannot be obtained. If the quantity exceeds about 0.020 wt%, the toughness of the base metal deteriorates. Therefore, the optimum REM content is determined to be about 0.0015 to 0.020 wt%. As the REM, employment of La or Ce will enable a significant effect to be obtained.
  • N is an element required to form TiN that is important to improve the toughness of the structure of portions welded with large heat input.
  • the N content In order to improve toughness, the N content must be about 0.0020 wt% or more. If the N content exceeds about 0.0120 wt%, the foregoing effect cannot be obtained and toughness sometimes deteriorates. Therefore, the N content is limited to about 0.0020 to 0.0120 wt%.
  • the upper limit of the temperature at which cooling is stopped is determined to be about 600°C. If the temperature at which cooling is stopped is lower than about 400°C, transformation products increase and toughness deteriorates. Therefore, the lower limit of the temperature at which cooling is stopped is determined to be about 400°C.
  • Test samples were subjected to a test simulating a ballast tank of a ship. This was done by using a testing apparatus as shown in Fig. 1.
  • Testing tank 1 was half-filled with artificial sea water 2 conforming to ASTM D1141.
  • Each test sample 4 was immersed in the artificial sea water 2 at position 9 for one week, and then the test sample 4 was raised to position 10 in the atmosphere 3, the humidity of which was 100%, and it was allowed to stand for one week. Then the test sample 4 was immersed in the artificial sea water 2 for one week. The cycle was repeated.
  • a drum 5, to which the test sample 4 was attached, was controlled by the rotation shaft 6 to rotate at 0.5 m/sec in either the artificial sea water or the atmosphere.
  • the temperature in the testing tank was controlled by a heater 7. Since the cover portion of the testing tank 1 was substantially closed tightly, the difference between the temperature of the artificial sea water and that of the atmosphere was 1°C or less and the humidity of the atmosphere was about 100%.
  • a corrosion resistance test was performed. Five cycles were performed each of which consisted of immersion in 40°C artificial sea water for one week and allowing to stand in the atmosphere the humidity of which was 100% and the temperature of which was 40°C.
  • the test sample 4 was manufactured by heating the material to 1150°C for one hour and then it was hot-rolled, followed by air cooling (at a cooling speed of 0.5°C/sec).
  • the corrosion depth was measured such that depths of 10 places were measured in a descending order by using a depth gauge. The maximum corrosion depth and the average corrosion depth were shown.
  • rust was removed and the condition of the corrosive surface was evaluated from the viewpoint of smoothness of the surface.
  • the surfaces each having a uniform corrosive condition with slightly uneven surface were evaluated as satisfactory as indicated by the symbol "o ⁇ ".
  • the surfaces each having a uniform corrosive condition with a rather largely uneven surface condition and those having a largely uneven surface with a small number of shallow pits were indicated by the symbol " ⁇ " and " ⁇ ", respectively.
  • the surfaces having a largely uneven surface with a large number of deep pits were evaluated as unsatisfactory as indicated by the symbol "x".
  • KA36 for ships conforming to the NK (Nihon Kaiji Associates) standard was simultaneously tested. The results of the tests were as follows.
  • the quantity of corrosion (mg/cm 3 ) ) were obtained using the difference between the quantity of initial weight of the test piece and the weight of the test piece from which the rust was removed by the above-mentioned corrosion test and the difference was computed in terms of a unit surface area of a test piece. Mean reduction quantity of plate thickness at one side (mm) was computed using quantity of corrosion.
  • the depth of corrosion is decreased as compared with the comparative material KA36 when the quantity of Cr addition was about 3 to 4 wt%.
  • the quantity of Cr addition was enlarged, both maximum depth of corrosion and the average depth of corrosion were enlarged.
  • Cr content was 3.5 wt% or less, the surface was brought to a uniform corrosive state.
  • a locally corrosive state was realized. Comparative steel examples 2 to 4 were brought to a locally corrosive state. The locally corrosive state raised a problem in use, such that stress concentration took place.
  • compositions of test samples are shown in Table 5.
  • Results of measurement of corrosion weight loss of the test samples, evaluation of the state of the corrosive surface and measurement of the depth of corrosion are shown in Table 6.
  • composition of another test sample is shown in Table 7.
  • Results of measurement of corrosion weight loss of the test samples, evaluation of the state of the corrosive surface and measurement of the depth of corrosion are shown in Table 8.
  • test sample The method of manufacturing the test sample, the test method, the evaluation method and testing conditions for the corrosion resistance test were the same as those described above.
  • Example steel 1 and comparative steel sample 1 each contained about 0.7 wt% Cr.
  • Comparative steel 2 contained about 1 wt% Cr.
  • Example steel 4 and 5 and comparative example steel 3 and 4 each contained Cr 2 wt%.
  • Example steel 6 and comparative example steel 5 each contained Cr 3.4 wt%. As the quantity of Nb + Ti increased, corrosion weight loss and corrosion depth were decreased.
  • Table 8 shows the results of comparisons between example steel and comparative example steel that contained Cr in the same quantity. As described above, the additions of Ni, Mo, Nb and Ti decreased corrosion weight loss and corrosion depth.
  • compositions of the test samples are shown in Table 15.
  • Test samples obtained from the test materials manufactured under the conditions shown in Table 18 were subjected to the corrosion resistance test by using testing apparatus the same as that used in Example 1.
  • the results of the measurements of corrosion weight loss, those of the evaluations of the corrosive surfaces, the results of the measurements of the depths of corrosion, and the results of the Charpy impact test, to which the base metal was subjected, are shown Table 21 and Table 22.
  • Example steel 6 shown Table 21 had the same composition as those shown in Table 5.
  • Example steel 6 shown in Table 22 had the same composition as those shown in Table 7.
  • the method, the evaluation method and the testing conditions for the corrosion resistance test were the same as those according to Example 1.
  • test materials are shown in Table 23.
  • the test materials were heated to 1150°C, hot-rolled and then cooled at 900°C under the conditions shown in table 18 so that the test samples were manufactured.
  • the test samples obtained from the test materials were subjected to a corrosion resistance test by using the testing apparatus the same as that used in Example 1.
  • the method, the evaluation method and the testing conditions for the corrosion resistance test were the same as those according to Example 1.
  • Table 25 shows the results of a Charpy impact test, to which heat affected zone was subjected after a simulated heat cycle corresponding to the heat hysteresis of a submerged arc welding of 100 KJ/cm in a manner of the single layer for one side, the results being shown together with the results of Charpy impact tests to which the base metal was subjected.
  • the employment of the conditions for manufacturing the steel within the scope of the present invention enables corrosion weight loss to be decreased. Also the depth of corrosion can be decreased by employing the manufacturing conditions included within the scope of the present invention. Even if the manufacturing conditions within the scope of the present invention were employed, the toughness of the base metal and that of the simulated heat affected zone did not deteriorate.
  • the sea-water corrosion resistant steel suitable to a hot and wet environment according to the present invention has excellent corrosion resistance when it is adapted to a ballast tank or a sea water pipe for a ship that is subjected to a severe corrosive environment. As a result, a contribution to making a ship maintenance-free of the ship and safety of the ship can be provided and maintained.
  • the welding with a large heat input can be employed and therefore a tanker can be built in an efficient welding manner, and the toughness of the portions joined by welding can be improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Description

The present invention relates to steel that is adaptable and resistant to hot and wet environments, for example, severe environments to which ballast tanks or sea-water pipes are exposed, and to a method of manufacturing the same.
Tankers that will be manufactured in the future should have a double hull structure of the type shown in Figs. 4A and 4B to meet the regulations of the International Maritime Organization (IMO). A double hull section of a tanker 20 is used as a ballast tank 21 constructed to protect oil tanks 22. The double hull structure has the purpose of preventing oil spills.
Since the surface area of the ballast tank 21 that is exposed to sea water is considerably enlarged (two to three times) as compared with a conventional single hull structure, various problems arise in the painting process and in corrosion protection generally.
As for problems arising in the painting process, the ballast tank 21 must be coated once or twice with coal-tar epoxy resin paint. However, this is difficult and dangerous for painters because the painting operation is performed in a narrow and confined space. In addition, the considerable area to be painted causes the coating work to take a long time and to involve high cost. What is even worse, even higher cost and more labor are required for repairing the double hull structure after extended use, as compared with new ship construction.
The corrosion protection employs both paint such as coal-tar epoxy resin paint and cathodic protection measures. Since sea water flows into and out of the ballast tank 21, the ballast tank 21 is exposed to a severely corrosive environment. If sea water is present in the ballast tank 21, corrosion can substantially be prevented, thanks to modern cathodic protection measures. However, the uppermost portion of the ballast tank 21 and the underside of the deck 23 that are not normally immersed in sea water are subjected to a severely corrosive environment, the temperature of which may be very high and which is repeatedly splashed with sea water. If no water is present in the ballast tank 21, the environment becomes hot and wet and therefore the effect of cathodic protection measures cannot be obtained, and the coal-tar epoxy resin paint acts solely to prevent corrosion. The life of the coal-tar epoxy resin paint applied to the ballast tank can be expected to be about ten years, which is about half the life of the ship. In the residual ten years corrosion must be prevented by further painting, with major problems and difficulties.
Since the ballast tank is in a severely corrosive environment and the coating work under adverse conditions encounters problems, hazards and difficulties, there has been a desire for an improved steel product that is especially effective for use in a ship and which has excellent resistance against sea water corrosion under hot and wet environments.
Conventional sea-water corrosion resistant steel, an example of which has been disclosed in Japanese Patent Laid-Open No. 51-25420, is designed for use in marine structures and harbor facilities, which is sharply different from the environment faced by the steel according to the present invention; it is very different from the hot and wet environment in the ballast tank 21 where sea water flows in and out. Therefore, steel typified by the type disclosed in Japanese Patent Laid-Open No. 51-25420 contains copper as a required element. However, the steel according to the present invention should contain no copper, because copper does not resist corrosion of the ballast tank where sea water flows in and out, and even adversely affects corrosion resistance.
Steel having sea water corrosion resistance and containing no copper has been disclosed in Japanese Patent Laid-Open No. 5-302148. It contains silicon and aluminum in relatively large quantities of 0.5 to 2% and 0.5 to 3% respectively, in order to obtain ferromagnetic ferrite.
Another example of sea-water corrosion resistant steel has been disclosed in Japanese Patent Laid-Open No. 64-79346. It contains 7 to 20% aluminum. It is effective when used as a reinforcing steel when substantially no welding needs to be performed. However, it is not suitable for use where a multiplicity of welding processes are required, for example, in a ballast tank for a ship.
Although steel used to construct ships has been manufactured on the basis of component and process designs based upon strength, toughness and weldability, no means to improve corrosion resistance has been employed. In sharp contrast, the present invention provides a novel steel having excellent corrosion resistance for use in ballast tanks and sea water pipes that are subjected to severe corrosive environments.
The corrosive environment to which the ballast tank is subjected is a hot and wet environment in which sea water flows in and out. As a typical example where crude oil is transported from the Near or Middle East to Japan, the oil tanks 22 shown in Fig. 4A contain no oil during the first trip from Japan to the Near or Middle East. Without oil the ballast tank 21 is substantially filled with sea water in order to balance the ship for safe navigation. The portion of tank 21 immersed in sea water and the upper portion of the tank 21 are substantially exposed to splashing sea water. When the ship sails from the Near or Middle East to Japan, it is filled with crude oil. Sea water in the ballast tank 21 is discharged and the ballast tank 21 is empty. The space in the ballast tank at that time is exposed to a hot and wet condition by sea water left in the bottom of the ship and by heat transmitted from and through the deck. One cycle, in which the ballast tank is subjected to the foregoing cycle of corrosive environment, may be about forty days.
In conventional shipbuilding procedures the steel is welded with a large heat input by means of a so-called "single layer for one side" technique. This improves efficiency of the welding process as the tanker is built. When steel containing alloy elements is welded with a large heat input, the toughness of the welded portion deteriorates substantially as compared with usual shipbuilding welding methods.
Important objects of the present invention are to provide a special steel capable of overcoming the foregoing problems and exhibiting excellent corrosion resistance against sea water in a hot and wet environment, and to provide a method of manufacturing the same.
Another object of the present invention is to provide a new weldable steel having excellent welded portions even when welded with a large heat input. Still another object is to provide a method of manufacturing such a new steel.
We have investigated in detail the influence of alloy elements in steels. This was done by using an apparatus arranged as shown in Fig. 1 to simulate a corrosive environment. As a result, it was found that steel having a special chemical composition exhibits excellent corrosion resistance under these conditions. Furthermore, we have found that additions of REM and Ti in particular quantities enables the user to prevent deterioration of toughness in weld heat affected zones (HAZ). ("REM" means rare earth metals, in particular La or Ce, for example.) In addition, another fact was found that employment of a special and novel manufacturing method further improves corrosion resistance.
According to one aspect of the present invention there is provided a sea-water corrosion resistant steel suitable for use in a hot and wet environment comprising: an amount of C of 0.1 wt% or less; an amount of Si of 0.5 wt% or less; an amount of Mn of 1.50 wt% or less; an amount of Al of 0.005 to 0.050 wt%; an amount of Cr of 0.5 to 3.50 wt%; an amount of Ti of 0.005 to 0.05 wt%; and an amount of Nb of 0.005 to 0.05 wt%; such that the total quantity of Ti and Nb is up to 0.05 wt%; the steel optionally further comprising: an amount of REM of 0.0015 to 0.020 wt%; an amount of N of 0.0020 to 0.0120 wt%; an amount of Ni of 1.5 wt% or less; and an amount of Mo of 0.8 wt% or less; wherein the total quantity of Ni and/or Mo is 1.5 wt% or less; and wherein the balance is Fe and incidental impurities.
A sea water resistant steel having a composition as that claimed but comprising 0.2-0.4% copper and no titanium or niobium is disclosed in JP-A-59 64 750. Toughness of such a steel, especially in a zone affected by welding heat, is improved by additions of titanium and niobium as claimed, cf. Tables 6 and 17. The improvement of toughness also applies with respect to a high strength structural steel as disclosed in US-A-3 834 897, which steel has a good weldability and the same composition as that according to the invention but does not comprise titanium.
In another aspect of the present invention, there is provided a method of manufacturing a steel having the composition defined above, the method comprising the steps of: casting and hot-rolling the steel; and accelerated cooling the steel at a cooling rate of from 3 to 20°C/sec to a temperature of from 400°C to 600°C immediately after the steel has been cast and hot rolled.
Other and further objects, features and advantages of the invention will be appear more fully from the following description, and from the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
  • Fig. 1 is an explanatory view showing the schematic structure of a simulation testing apparatus of a ballast tank;
  • Fig. 2 is a graph showing effect of Cr content on corrosion weight loss of test samples;
  • Fig. 3 is a graph showing effect of Cr content on the maximum depth of corrosion and the average depth of corrosion of the test samples;
  • Fig. 4A is a plan view of a tanker having a double hull structure; and
  • Fig. 4B is a cross-sectional view taken along the line X-X of Fig. 4A.
  • An important object of the present invention is to provide a novel sea-water corrosion resistant steel composition which is resistant to hot and wet environments and is capable of reducing corrosion weight loss, and is free from local corrosion while maintaining smooth corrosive surfaces, even in an environment in which sea water and the atmosphere, the humidity of which may be as high as 100%, are repeatedly applied to the steel.
    Decrease in corrosion weight loss means that generation of rust on the coated surface of a ballast tank, arranged to be protected from corrosion by coating and cathodic protection measures, can be prevented or severely curtailed. The smooth corrosive surface achieved according to this invention helps to prevent occurrence of conditions that cause concentration of distortion or metal fatigue.
    The advantages of this invention can be achieved by adding effective amounts of Cr, Ni and Mo, more preferably Nb and Ti. Furthermore, restriction of precipitation of carbides after hot rolling further enhances the beneficial effects of Cr and Mo.
    Another object of the present invention is to improve the toughness of portions of sea-water corrosion resistant steel exposed to a hot and wet environment and joined by welding with large heat input. Addition of effective amounts of REM, Ti and N does not reduce the toughness of the portion that has been welded with large heat input; on the contrary it improves toughness.
    Effective component ranges will be described in the following paragraphs, along with reasons for determining the component ranges and reasons for using the described novel method of manufacturing the sea-water corrosion resistant steel.
    C: about 0.1 wt% or less
    Although reduction of the addition of C will realize advantages in corrosion resistance and weldability, the upper limit of the content of C is about 0.1 wt% because C is an element that helps to determine strength.
    Si: about 0.50 wt% or less
    Since the reduction of addition of Si prevents adverse influences on toughness, the upper limit of Si is about 0.50 wt%.
    Mn: about 1.50 wt% or less
    Although Mn is an important element that influences strength, toughness and weldability, toughness and the weldability are adversely affected if the content of Mn exceeds about 1.50 wt%. Therefore, the upper limit of the content of Mn is about 1.50 wt%.
    Al: about 0.005 to 0.050 wt%
    Al is added to serve as a deoxidizer, and the content of Al is determined to be about 0.005 to 0.050 wt% so far as weldability is not affected adversely.
    Cr: about 0.50 to 3.50 wt%
    The most effective element to improve corrosion resistance in the present invention is Cr. Since the contemplated corrosive environment is very severe, addition of not more than about 0.50 wt% Cr cannot significantly reduce corrosion and/or achieving a smooth corrosive surface. Since the foregoing effects can be obtained if Cr is added in an amount of about 0.50 wt% or more, the lower Cr limit is about 0.50 wt%. If the addition of Cr is increased, the effect of reducing corrosion weight loss can be attained. However, if the Cr content exceeds about 3.50 wt%, the steel surface is susceptible to a pitting corrosive state. If the quantity of Cr addition is increased to about 9 wt%, only pitting corrosion is realized, similarly to that observed on stainless steel. Since the percentage Cr at which corrosion weight loss can be reduced and a smooth corrosive surface can be formed is about 3.50 wt% or less, the upper limit is determined to be about 3.50 wt%. However, it is preferable that the quantity of Cr is about 1.2 to 3.0 wt%.
    Ni: about 1.5 wt% or less
    It is preferable that Ni be added together with Cr, which improves corrosion resistance. The addition of Ni improves corrosion resistance and makes the corroded surface uniform. If the quantity of Ni exceeds about 1.5%, a tendency toward strengthening and hardening the steel is attained, and problems take place regarding toughness and weldability. Therefore, the quantity of Ni is about 1.5 wt% or less.
    Mo: about 0.8 wt% or less
    Although addition of Mo enables a similar effect to that of Ni, excessive Mo addition is considered to raise critical problems in toughness and weldability. Therefore, the addition of Mo is determined to be about 0.8 wt% or less.
    Ni + Mo: about 1.5 wt% or less
    Ni and Mo enable substantially the same effect to be obtained. Since both Ni and Mo otherwise have problems of toughness and weldability, the upper limit of Ni + Mo is determined to be about 1.5 wt%.
    Ti: about 0.005 to 0.05 wt%
    Although Cr, Ni and Mo are elements that are effective to improve corrosion resistance, Cr and Mo readily form carbides which reduce the portion of Cr and Mo which is present in solution that effectively exhibit corrosion resistance. Since Ti is an element that forms carbides and has an affinity that is greater than those of Cr and Mo, Ti carbides are formed with priority. Therefore, forming of Cr carbides and Mo carbides is restricted and reduction of quantity of the solid solutions of Cr and Mo can be prevented. If the quantity of Ti is about 0.005 wt% or less, the foregoing effect cannot be obtained.
    Furthermore, Ti significantly contributes to toughness of the welded portion of the steel where it has been joined with large heat input, because Ti forms nitrides when it coexists with REM. However, the effect of Ti cannot substantially be obtained if the quantity is about 0.005 wt% or less. If the same is about 0.005 wt% or more, the increase of Ti causes saturation to take place gradually. If the quantity of Ti exceeds about 0.05 wt% the toughness of the base metal deteriorates. Therefore, the range is limited to about 0.005 to 0.05 wt%. When Ti coexists with REM, Ti is a required element. If REM is not present Ti may be present in the range of Nb + Ti discussed in a subsequent paragraph.
    Nb: about 0.005 to 0.05 wt%
    Similarly to Ti, Nb is an element provided for forming carbides. The addition of Nb restricts forming of Cr and Mo carbides, and accordingly corrosion resistance obtainable from Cr and Mo in solution can be improved effectively. If the Nb content is about 0.005 wt% or less, the foregoing effect cannot be obtained. Since the toughness of the steel deteriorates if the content is about 0.05 wt% or more, the upper limit of Nb is determined to be about 0.05 wt%.
    Nb + Ti: about 0.005 to 0.05 wt%
    Nb and Ti have similar effects of restricting precipitation of Cr carbide and Mo carbide and effectively improving corrosion resistance by enlarging the quantities of Cr and Mo in solution. However, the foregoing effects can be obtained only when the quantity of Nb + Ti is about 0.005 wt% or more. In order to improve toughness, the upper Nb + Ti limit is determined to be about 0.05 wt%.
    REM: about 0.0015 to 0.020 wt%
    If REM coexists with Ti, REM significantly improves the toughness of the portion welded with a large heat input of about 100 KJ/cm or more since it enhances the effect of Ti. If the percentage of REM is less than about 0.0015 wt%, its effect cannot be obtained. If the quantity exceeds about 0.020 wt%, the toughness of the base metal deteriorates. Therefore, the optimum REM content is determined to be about 0.0015 to 0.020 wt%. As the REM, employment of La or Ce will enable a significant effect to be obtained.
    N: about 0.0020 to 0.0120 wt%
    N is an element required to form TiN that is important to improve the toughness of the structure of portions welded with large heat input. In order to improve toughness, the N content must be about 0.0020 wt% or more. If the N content exceeds about 0.0120 wt%, the foregoing effect cannot be obtained and toughness sometimes deteriorates. Therefore, the N content is limited to about 0.0020 to 0.0120 wt%.
    Beneficial manufacturing steps, which serve to improve the corrosion resistance of the sea-water corrosion resistant steel when exposed to a hot and wet environment, will now be described.
    It is usual that steel is subjected to the usual casting and hot rolling processes. According to this invention, after hot rolling has been completed, cooling of the steel is commenced at the moment the temperature of the steel is about 900°C. Cr carbides and Mo carbides are, in this case, precipitated during the cooling process when the cooling speed is lower than about 3°C/sec. This has the effect of deteriorating the corrosion resistance obtainable from Cr and Mo in solution. Therefore, the lower limit of the cooling speed is determined to be about 3°C/sec. If the cooling speed exceeds about 20°C/sec, transformation products increase and toughness deteriorates. Therefore, the upper limit of the cooling speed is determined to be about 20°C/sec. If the temperature at which cooling is stopped after accelerated cooling has been performed, is higher than about 600°C, Cr carbides and Mo carbides are precipitated after accelerated cooling process has been completed. Therefore, improvement of corrosion resistance against sea water, obtainable from Cr and Mo in solution, deteriorates. Therefore, the upper limit of the temperature at which cooling is stopped is determined to be about 600°C. If the temperature at which cooling is stopped is lower than about 400°C, transformation products increase and toughness deteriorates. Therefore, the lower limit of the temperature at which cooling is stopped is determined to be about 400°C.
    Examples Example 1
    Test samples were subjected to a test simulating a ballast tank of a ship. This was done by using a testing apparatus as shown in Fig. 1. Testing tank 1 was half-filled with artificial sea water 2 conforming to ASTM D1141. Each test sample 4 was immersed in the artificial sea water 2 at position 9 for one week, and then the test sample 4 was raised to position 10 in the atmosphere 3, the humidity of which was 100%, and it was allowed to stand for one week. Then the test sample 4 was immersed in the artificial sea water 2 for one week. The cycle was repeated. A drum 5, to which the test sample 4 was attached, was controlled by the rotation shaft 6 to rotate at 0.5 m/sec in either the artificial sea water or the atmosphere. Air was injected through an air-bubbling pipe 8 to cause bubbling in the lower portion of the testing tank 1 to stir the sea water and introduce oxygen into the sea water. The temperature in the testing tank was controlled by a heater 7. Since the cover portion of the testing tank 1 was substantially closed tightly, the difference between the temperature of the artificial sea water and that of the atmosphere was 1°C or less and the humidity of the atmosphere was about 100%. A corrosion resistance test was performed. Five cycles were performed each of which consisted of immersion in 40°C artificial sea water for one week and allowing to stand in the atmosphere the humidity of which was 100% and the temperature of which was 40°C. The test sample 4 was manufactured by heating the material to 1150°C for one hour and then it was hot-rolled, followed by air cooling (at a cooling speed of 0.5°C/sec).
    The corrosion depth was measured such that depths of 10 places were measured in a descending order by using a depth gauge. The maximum corrosion depth and the average corrosion depth were shown. After the test, rust was removed and the condition of the corrosive surface was evaluated from the viewpoint of smoothness of the surface. The surfaces each having a uniform corrosive condition with slightly uneven surface were evaluated as satisfactory as indicated by the symbol "o ○". The surfaces each having a uniform corrosive condition with a rather largely uneven surface condition and those having a largely uneven surface with a small number of shallow pits were indicated by the symbol "○" and "Δ", respectively. The surfaces having a largely uneven surface with a large number of deep pits were evaluated as unsatisfactory as indicated by the symbol "x". Fig. 2 shows the quantity of corrosion with respect to Cr content, and Fig. 3 shows the depth of corrosion with respect to Cr content. As comparative examples, conventional steel KA36 for ships conforming to the NK (Nihon Kaiji Associates) standard was simultaneously tested. The results of the tests were as follows.
    (1) Corrosion Weight Loss
    When the quantity of Cr added was increased corrosion weight loss was decreased. When the quantity was 5 to 6 wt%, corrosion weight loss is increased. When the quantity of Cr added was further increased, corrosion weight loss decreased.
    The quantity of corrosion (mg/cm3) ) were obtained using the difference between the quantity of initial weight of the test piece and the weight of the test piece from which the rust was removed by the above-mentioned corrosion test and the difference was computed in terms of a unit surface area of a test piece. Mean reduction quantity of plate thickness at one side (mm) was computed using quantity of corrosion.
    (2) Corrosion Depth and Condition of Corrosion
    The depth of corrosion is decreased as compared with the comparative material KA36 when the quantity of Cr addition was about 3 to 4 wt%. When the quantity of Cr addition was enlarged, both maximum depth of corrosion and the average depth of corrosion were enlarged. When Cr content was 3.5 wt% or less, the surface was brought to a uniform corrosive state. When the quantity of Cr was enlarged from the foregoing state, a locally corrosive state was realized. Comparative steel examples 2 to 4 were brought to a locally corrosive state. The locally corrosive state raised a problem in use, such that stress concentration took place. The range of the quantity of addition of Cr in which corrosion weight loss could be prevented satisfactorily, and a smooth corrosive surface could be formed, was 3.5 wt% or less. When Cr content was less than about 0.5 wt%, a satisfactory effect was not obtained.
    The compositions of test samples are shown in Table 5. Results of measurement of corrosion weight loss of the test samples, evaluation of the state of the corrosive surface and measurement of the depth of corrosion are shown in Table 6.
    The composition of another test sample is shown in Table 7. Results of measurement of corrosion weight loss of the test samples, evaluation of the state of the corrosive surface and measurement of the depth of corrosion are shown in Table 8.
    The method of manufacturing the test sample, the test method, the evaluation method and testing conditions for the corrosion resistance test were the same as those described above.
    The range of the quantity of addition of Cr in which corrosion weight loss of the steel was prevented satisfactorily, and a smooth corrosive surface was formed, was about 0.5 to 3.5 wt% or less.
    Table 6 shows the results of comparisons between example steel and comparative example steel. Example steel 1 and comparative steel sample 1 each contained about 0.7 wt% Cr. Comparative steel 2 contained about 1 wt% Cr. Example steel 4 and 5 and comparative example steel 3 and 4 each contained Cr 2 wt%. Example steel 6 and comparative example steel 5 each contained Cr 3.4 wt%. As the quantity of Nb + Ti increased, corrosion weight loss and corrosion depth were decreased.
    As can be understood from comparison between example steel 4 and 5 and comparative example steel 6, 7 and 8, the toughness of the base metal deteriorated when the additions of Nb and Ti were large.
    Table 8 shows the results of comparisons between example steel and comparative example steel that contained Cr in the same quantity. As described above, the additions of Ni, Mo, Nb and Ti decreased corrosion weight loss and corrosion depth.
    Example 2
    When welding with a large heat input is performed, the toughness of the heat affected zone of the joint portion of welding is an important factor. Therefore measurements were performed to evaluate the toughness of simulated heat affected zone of a variety of sea-water corrosion resistant steel. In this case, heat cycle corresponds to the same which the joint portion of welding by a large heat input was subjected. In addition, the steel was subjected to a corrosive test using a sea-water corrosion resistance testing tank that was capable of simulating the hot and wet environment. The method of the corrosion resistance test, the evaluation method and the testing conditions were the same as those according to Example 1.
    Example 3
    The compositions of the test samples are shown in Table 15.
    The results of Charpy impact tests, to which a heat affected zone was subjected after a simulated heat cycle corresponding to the heat hysteresis of submerged arc welding of 100 KJ/cm in the manner of the single layer for one side are shown in Table 17 together with the results of a Charpy impact test to which the base metal was subjected. The results of the corrosion resistance test against sea water are shown in Table 16. The method of the corrosion resistance test, the evaluation method and the testing conditions were the same as those according to Example 1. According to the results shown in Table 17, the limitations of REM, Ti and N to the ranges according to the present invention significantly improved the toughness of the joint portion welded with a large heat input as compared with the comparative example steel such that toughness exhibiting absorbed energy (vEo) exceeding the value of KA36 was obtained.
    As shown in the results of the corrosion resistance test shown in Table 16, corrosion resistance equivalent to or somewhat superior to that of the comparative example steel can be improved if the quantities of Cr, Mo and Ni are in the limited ranges. Thus, the additions do not adversely affect the corrosion resistance obtainable from the additions of Nb and Ti.
    Example 4
    Test samples obtained from the test materials manufactured under the conditions shown in Table 18 were subjected to the corrosion resistance test by using testing apparatus the same as that used in Example 1. The results of the measurements of corrosion weight loss, those of the evaluations of the corrosive surfaces, the results of the measurements of the depths of corrosion, and the results of the Charpy impact test, to which the base metal was subjected, are shown Table 21 and Table 22.
    Example steel 6 shown Table 21 had the same composition as those shown in Table 5. Example steel 6 shown in Table 22 had the same composition as those shown in Table 7. The method, the evaluation method and the testing conditions for the corrosion resistance test were the same as those according to Example 1.
    The employment of the conditions for manufacturing the steel within the scope of the present invention enabled corrosion weight loss to be decreased. Also the depth of corrosion was decreased by employing manufacturing conditions included within the scope of the present invention. Even if the manufacturing conditions within the scope of the present invention were employed, the toughness did not deteriorate. When the cooling speed exceeded the upper limit or if the temperature at which cooling was stopped was lower than the lower limit, the absorbed energy (vEo) was decreased and the toughness deteriorated.
    Example 5
    The compositions of the test materials are shown in Table 23. The test materials were heated to 1150°C, hot-rolled and then cooled at 900°C under the conditions shown in table 18 so that the test samples were manufactured. The test samples obtained from the test materials were subjected to a corrosion resistance test by using the testing apparatus the same as that used in Example 1. The method, the evaluation method and the testing conditions for the corrosion resistance test were the same as those according to Example 1.
    The results of measurements of corrosion weight loss, those of evaluation of the corrosive surfaces and the results of measurements of the depths of corrosion are shown in Table 24.
    Table 25 shows the results of a Charpy impact test, to which heat affected zone was subjected after a simulated heat cycle corresponding to the heat hysteresis of a submerged arc welding of 100 KJ/cm in a manner of the single layer for one side, the results being shown together with the results of Charpy impact tests to which the base metal was subjected.
    The employment of the conditions for manufacturing the steel within the scope of the present invention enables corrosion weight loss to be decreased. Also the depth of corrosion can be decreased by employing the manufacturing conditions included within the scope of the present invention. Even if the manufacturing conditions within the scope of the present invention were employed, the toughness of the base metal and that of the simulated heat affected zone did not deteriorate.
    As described above, the sea-water corrosion resistant steel suitable to a hot and wet environment according to the present invention has excellent corrosion resistance when it is adapted to a ballast tank or a sea water pipe for a ship that is subjected to a severe corrosive environment. As a result, a contribution to making a ship maintenance-free of the ship and safety of the ship can be provided and maintained.
    Furthermore, the welding with a large heat input can be employed and therefore a tanker can be built in an efficient welding manner, and the toughness of the portions joined by welding can be improved.
    Figure 00210001
    Figure 00220001
    Figure 00230001
    Figure 00240001
    Figure 00250001
    Figure 00260001
    Figure 00270001
    Figure 00280001
    Figure 00290001
    Figure 00300001
    Figure 00310001
    Figure 00320001
    Figure 00330001

    Claims (3)

    1. A sea-water corrosion resistant steel suitable for use in a hot and wet environment comprising:
      an amount of C of 0.1 wt% or less;
      an amount of Si of 0.5 wt% or less;
      an amount of Mn of 1.50 wt% or less;
      an amount of Al of 0.005 to 0.050 wt%;
      an amount of Cr of 0.5 to 3.50 wt%;
      an amount of Ti of 0.005 to 0.05 wt%; and
      an amount of Nb of 0.005 to 0.05 wt%;
      such that the total quantity of Ti and Nb is up to 0.05 wt%;
         the steel optionally further comprising:
      an amount of REM of 0.0015 to 0.020 wt%;
      an amount of N of 0.0020 to 0.0120 wt%;
      an amount of Ni of 1.5 wt% or less; and
      an amount of Mo of 0.8 wt% or less;
      wherein the total quantity of Ni and/or Mo is 1.5 wt% or less; and
      wherein the balance is Fe and incidental impurities.
    2. A steel as claimed in claim 1, wherein the REM is La or Ce.
    3. A method of manufacturing a steel having the composition of claim 1 or 2, the method comprising the steps of:
      casting and hot-rolling the steel; and
      accelerated cooling the steel at a cooling rate of from 3 to 20°C/sec to a temperature of from 400°C to 600°C immediately after the steel has been cast and hot rolled.
    EP94305057A 1993-07-09 1994-07-08 Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same Expired - Lifetime EP0633326B1 (en)

    Applications Claiming Priority (10)

    Application Number Priority Date Filing Date Title
    JP16990793 1993-07-09
    JP169907/93 1993-07-09
    JP24793493 1993-10-04
    JP247934/93 1993-10-04
    JP290157/93 1993-11-19
    JP29015793 1993-11-19
    JP5391694 1994-03-24
    JP53916/94 1994-03-24
    JP6105077A JPH07316722A (en) 1994-05-19 1994-05-19 Seawater corrosion resisting steel for high temperature and high humidity environment, capable of large heat input welding
    JP105077/94 1994-05-19

    Publications (2)

    Publication Number Publication Date
    EP0633326A1 EP0633326A1 (en) 1995-01-11
    EP0633326B1 true EP0633326B1 (en) 1998-06-24

    Family

    ID=27523119

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP94305057A Expired - Lifetime EP0633326B1 (en) 1993-07-09 1994-07-08 Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same

    Country Status (3)

    Country Link
    EP (1) EP0633326B1 (en)
    KR (1) KR100264362B1 (en)
    SG (1) SG48369A1 (en)

    Families Citing this family (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    KR20020036270A (en) * 2000-11-09 2002-05-16 이구택 Hot strips having high seawater corrosion resistance
    FR2866352B3 (en) * 2004-02-12 2005-12-16 Trefileurope WIRE OF TEMPERED-INCOME STEEL SHAPE FOR CONDUITS AT SEA
    CN103469094B (en) * 2013-08-21 2015-11-04 日照钢铁控股集团有限公司 Steel for pipe of a kind of anti-chlorine ion corrosion and preparation method thereof
    CN103952634B (en) * 2014-04-02 2016-04-13 攀钢集团成都钢钒有限公司 Anti-CO 2corrosion seamless steel pipe and manufacture method

    Family Cites Families (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3348981A (en) * 1964-02-21 1967-10-24 Yawata Iron & Steel Co High tension low temperature tough steel
    US3834897A (en) * 1971-03-30 1974-09-10 Ovako Oy Low-carbon,high-strength structural steel with good weldability
    US4261768A (en) * 1979-06-27 1981-04-14 Voest-Alpine Aktiengesellschaft Low alloyed steel having improved corrosion behavior, in particular relative to sea water
    JPS5964750A (en) * 1982-09-30 1984-04-12 Nakayama Seikosho:Kk Seawater resistant low alloy steel
    JPH01230713A (en) * 1988-03-08 1989-09-14 Nippon Steel Corp Production of high-strength and high-toughness steel having excellent stress corrosion cracking resistance

    Also Published As

    Publication number Publication date
    KR960014380A (en) 1996-05-22
    SG48369A1 (en) 1998-04-17
    EP0633326A1 (en) 1995-01-11
    KR100264362B1 (en) 2000-08-16

    Similar Documents

    Publication Publication Date Title
    JP4898543B2 (en) Steel sheet with excellent pit resistance and method for producing the same
    KR100663219B1 (en) Steel for crude oil tank and method for manufacture thereof, crude oil tank and method for protecting corrosion thereof
    JP5119595B2 (en) Corrosion resistant steel for shipbuilding
    KR100548116B1 (en) Crude oil tank having welding coupling excellent in corrosion resistance
    JP4525687B2 (en) Corrosion resistant steel for ships
    JP5796409B2 (en) Corrosion resistant steel for ship ballast tank
    JP2007270196A (en) Steel material for cargo oil tank
    JP4506244B2 (en) Steel for bottom plate of crude oil tank
    JP6260755B1 (en) Steel for ship ballast tank and ship
    JP2012177168A (en) Steel material for vessel, which is excellent in resistance to corrosion caused due to coating
    JP6601258B2 (en) Corrosion-resistant steel for ballast tanks
    JP4243863B2 (en) Welded joint for crude oil tank and crude oil tank
    EP0633326B1 (en) Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same
    JP4483107B2 (en) Marine steel with excellent coating life
    EP0546549A1 (en) Line pipe having good corrosion-resistance and weldability
    KR850001766B1 (en) Phosphirous containing seawater-resistance steel of improved weldability
    JP5413392B2 (en) Corrosion resistant steel for shipbuilding
    JPH07310141A (en) Seawater resistant steel for high temperature moisty environment and its production
    JPS6058779B2 (en) High Ni alloy with excellent weldability and corrosion resistance
    US3895940A (en) Corrosion resistant high chromium ferritic stainless steel
    JP4081991B2 (en) Corrosion resistant steel for freight oil tank and method for producing the same
    JPH07316722A (en) Seawater corrosion resisting steel for high temperature and high humidity environment, capable of large heat input welding
    JPH06256905A (en) Clad steel plate excellent in corrosion resistance and toughness at low temperature
    JP4476926B2 (en) Marine steel with excellent HAZ toughness and corrosion resistance during high heat input welding
    Ross New technology stainless steels and nickel alloys for marine applications in the year 2000 and beyond

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): DK GB

    17P Request for examination filed

    Effective date: 19950704

    17Q First examination report despatched

    Effective date: 19970212

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): DK GB

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 19980924

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed
    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DK

    Payment date: 19990714

    Year of fee payment: 6

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20080709

    Year of fee payment: 15

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20090708

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090708