CN113913687A - Low-carbon high-strength seawater corrosion resistant steel and manufacturing method thereof - Google Patents
Low-carbon high-strength seawater corrosion resistant steel and manufacturing method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/28—Normalising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
Abstract
The invention provides a low-carbon high-strength seawater corrosion resistant steel and a manufacturing method thereof, wherein the low-carbon high-strength seawater corrosion resistant steel comprises the following components in percentage by weight: c: 0.02 to 0.05%, Si: 0.10 to 0.30%, Mn: 0.10-0.15%, Al: 0.02-0.04%, Cr: 1.00-1.50%, Ni: 0.20-0.40%, Cu: 0.30-0.50%, Zr + Ti: 0.02-0.03%, Re: 0.05-0.08 percent of Fe, less than or equal to 0.015 percent of P, less than or equal to 0.008 percent of S, and the balance of Fe and inevitable impurities. And adopting a TMCP (thermal mechanical control processing) process and normalizing treatment mode. The tensile strength of the seawater corrosion resistant low-alloy high-strength steel prepared by the method is 400-600 MPa; the elongation after fracture is more than or equal to 30 percent; the toughness at the low temperature of minus 40 ℃ is more than or equal to 300, the mechanical comprehensive performance of the steel plate is excellent, and the seawater corrosion resistance is strong.
Description
Technical Field
The invention relates to the technical field of steel materials, in particular to low-carbon high-strength seawater corrosion resistant steel and a manufacturing method thereof.
Background
The low-alloy high-strength steel is widely applied to ocean engineering construction due to excellent mechanical properties and good welding performance. However, in a severe marine environment with high temperature, high humidity, high salt content and alternation of dryness and wetness, common steel materials are extremely easy to corrode, which brings huge economic loss to the society and even threatens personal safety. In the face of severe marine corrosion situation, the steel for marine engineering mainly comprising low-alloy high-performance steel is produced at the same time; the low alloy steel for ocean engineering is based on carbon steel, and is added with one or more alloy elements, such as Mn, Si, Cr, Ni, Cu, and the like, so as to improve the mechanical property and the corrosion resistance of the steel. However, the series of steel grades still face the problems that the inclusions are hard and coarsened and local corrosion is easy to cause, and the like, so that the improvement of the seawater corrosion resistance of the low-alloy high-strength steel by carrying out new component design has important significance.
Patent CN101787485A discloses a medium-low cost seawater corrosion resistant steel, which comprises the following chemical components in percentage by weight: c: 0.06-0.15, Si: 0.05 to 0.40, Mn: 0.50 to 1.20, P: 0.010-0.030, S is less than or equal to 0.020, Als: 0.004-0.070, O: 0.0040 to 0.0100.
Patent CN1974829A discloses a seawater corrosion resistant low magnetic steel, which comprises the following elements by weight percent: c is less than or equal to 0.04 percent; 0.2-0.5% of N; 21-23% of Cr; 12-14% of Ni; 2.0 to 3.5 percent of Mo; 4-6% of Mn; 0.05-0.25% of Nb; s is less than or equal to 0.03 percent; p is less than or equal to 0.035%; the balance of Fe and trace impurities.
The steel material disclosed in the above patent cannot really achieve the effect of corrosion resistance, and has high preparation cost and poor practicability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the seawater corrosion resistant low-alloy high-strength steel, which can overcome the problem that inclusions in the traditional marine low-alloy high-strength steel are easy to cause local corrosion, and aims to provide the marine engineering steel with stronger seawater corrosion resistance and excellent mechanical property.
The technical scheme of the invention is as follows: the seawater corrosion resistant low-alloy high-strength steel comprises the following components in percentage by weight: c: 0.02 to 0.05%, Si: 0.10 to 0.30%, Mn: 0.10-0.15%, Al: 0.02-0.04%, Cr: 1.00-1.50%, Ni: 0.20-0.40%, Cu: 0.30-0.50%, Zr + Ti: 0.02-0.03%, Re: 0.05-0.08 percent of Fe, less than or equal to 0.015 percent of P, less than or equal to 0.008 percent of S, and the balance of Fe and inevitable impurities.
Preferably, the seawater corrosion resistant low-alloy high-strength steel has a tensile strength of 400-600 MPa; the elongation after fracture is more than or equal to 30 percent; the toughness is more than or equal to 300J at the low temperature of minus 40 ℃, and the mechanical property is excellent.
The invention also provides a preparation method of the seawater corrosion resistant low-alloy high-strength steel, and the method adopts a TMCP (thermal mechanical control processing) process and a normalizing treatment mode.
Preferably, the TMCP process + normalizing treatment method specifically comprises the following steps:
s1), the initial rolling temperature of rough rolling is 1160-1200 ℃, the reduction rate is 55-65%, the deformation speed is not more than 4.5m/S, and the final rolling temperature of rough rolling is (1050 soil 10) DEG C.
S2), adjusting the temperature control thickness of the intermediate billet to be not less than 2.5-3.0 times of the thickness of the finished product, and adjusting the temperature of finish rolling to be (920 Shi 10) DEG C and the temperature of finish rolling to be (860 Tu 10) DEG C.
S3), the laminar cooling start cooling temperature is 830 ℃, the final cooling temperature is (640 soil 10) DEG C, and the cooling speed is 5-10 ℃/S.
S4) and normalizing process parameters, wherein the normalizing temperature is 890-910 ℃, the heat preservation time is 10-15 min, and the cooling mode is air cooling.
The invention has the beneficial effects that:
1. the Si can inhibit the generation of acid in corrosion products and prevent the invasion of chloride ions, meanwhile, the addition of the Si element can play a role in solid solution strengthening and improve the mechanical property of steel, if the Si element and the Al element are simultaneously added into the steel, the deoxidizing capacity of the Al can be strengthened, and meanwhile, the addition of the Si element into the steel can improve the fluidity of the molten steel;
2. according to the invention, a compact protective film is formed by enriching Cu between the matrix and the rust layer, so that the corrosion of the matrix can be delayed; cu promotes the steel anode to be passivated, and prevents the steel matrix from further corrosion;
3. according to the invention, the addition of P can promote the matrix to generate a compact and uniformly corroded inner rust layer;
4. according to the invention, the solid solution strengthening effect can be achieved by adding Mn, meanwhile, Mn can promote the formation of pearlite, and the pearlite structure can be refined by cooling after rolling;
5. the Cr added in the invention can effectively refine alpha-FeOOH, promote the conversion of gamma-FeOOH and alpha-FeOOH to amorphous state and form a stable rust layer. When the Cr content in the alpha-FeOOH exceeds 5 percent, corrosive anions such as chloride ions can be effectively prevented from entering the matrix; cr, Cu, P and the like have good composite action and can effectively delay corrosion;
6. the Zr and the Ti are good deoxidizers, and the Zr-Ti composite deoxidation technology can modify the inclusions, has the effects of refining grains and homogenizing tissues on the steel and can improve the welding performance of the steel;
7. the Rare Earth (RE) elements have the characteristic of strong metallicity, and can be combined with S, O and other elements to form rare earth oxysulfide to be precipitated from molten steel, so that the effect of purifying the molten steel is achieved; meanwhile, the addition of the rare earth element can further change the forms of oxygen and sulfur inclusions in steel, so that the quantity of harmful inclusions is reduced, and in addition, the addition of the rare earth element can inhibit the recrystallization and growth of deformed austenite grains, so that the grains are refined.
Drawings
FIG. 1 is an analysis chart showing the inclusion composition of corrosion-resistant low-alloy high-strength steel according to example 1 of the present invention;
FIG. 2 is a graph showing the size distribution of inclusions in the corrosion-resistant low-alloy high-strength steel according to example 1 of the present invention;
FIG. 3 is a structural comparison of a corrosion-resistant low-alloy high-strength steel of example 1 of the present invention with three other similar compositions;
FIG. 4 is a comparison of the seawater corrosion resistance of the corrosion-resistant low-alloy high-strength steel of example 1 of the present invention with the other three similar compositions.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
The embodiment provides seawater corrosion resistant low-alloy high-strength steel which comprises the following components in percentage by weight:
C：0.02～0.04％；
Si：0.10～0.20％；
Mn：0.12～0.15％；
Al：0.02～0.03％；
Cr：1.20～1.50％；
Ni：0.20～0.30％；
Cu：0.30～0.40％；
Zr+Ti：0.02～0.03％；
Re：0.05～0.06％；
p is less than or equal to 0.015 percent, S is less than or equal to 0.008 percent, and the balance is Fe and inevitable impurities.
The production method of the corrosion-resistant low-carbon high-strength steel comprises the following steps: TMCP + normalizing.
The seawater corrosion resistant low alloy high strength steel prepared in example 1 is denoted as Zr-Ti-Re.
Example 2
The embodiment provides seawater corrosion resistant low-alloy high-strength steel which comprises the following components in percentage by weight:
C：0.024％；
Si：0.10％；
Mn：0.12％；
Al：0.02％；
Cr：1.20％；
Ni：0.20％；
Cu：0.30％；
Zr+Ti：0.02％；
Re：0.05％；
p is less than or equal to 0.015 percent, S is less than or equal to 0.008 percent, and the balance is Fe and inevitable impurities.
The production method of the corrosion-resistant low-carbon high-strength steel comprises the following steps: TMCP + normalizing.
Example 3
The embodiment provides seawater corrosion resistant low-alloy high-strength steel which comprises the following components in percentage by weight:
C：0.03％；
Si：0.15％；
Mn：0.13％；
Al：0.024％；
Cr：1.30％；
Ni：0.25％；
Cu：0.34％；
Zr+Ti：0.025％；
Re：0.055％；
p is less than or equal to 0.015 percent, S is less than or equal to 0.008 percent, and the balance is Fe and inevitable impurities;
the production method of the corrosion-resistant low-carbon high-strength steel comprises the following steps: TMCP + normalizing.
Example 4
The embodiment provides seawater corrosion resistant low-alloy high-strength steel which comprises the following components in percentage by weight:
C：0.035％；
Si：0.17％；
Mn：0.14％；
Al：0.028％；
Cr：1.35％；
Ni：0.26％；
Cu：0.36％；
Zr+Ti：0.03％；
Re：0.05％；
p is less than or equal to 0.015 percent, S is less than or equal to 0.008 percent, and the balance is Fe and inevitable impurities.
The production method of the corrosion-resistant low-carbon high-strength steel comprises the following steps: TMCP + normalizing.
Example 5
The embodiment provides seawater corrosion resistant low-alloy high-strength steel which comprises the following components in percentage by weight:
C：0.04％；
Si：0.16％；
Mn：0.12％；
Al：0.02％；
Cr：1.50％；
Ni：0.30％；
Cu：0.40％；
Zr+Ti：0.03％；
Re：0.055％；
p is less than or equal to 0.015 percent, S is less than or equal to 0.008 percent, and the balance is Fe and inevitable impurities.
The production method of the corrosion-resistant low-carbon high-strength steel comprises the following steps: TMCP + normalizing.
Example 6
Performance testing
In the embodiment, the corrosion-resistant low-alloy high-strength steel manufactured in the embodiment 1 is tested, wherein the tensile strength is 400-500 MPa, the elongation after fracture is more than or equal to 30%, the low-temperature toughness at minus 40 ℃ is more than or equal to 300J, and the corrosion-resistant low-alloy high-strength steel has excellent mechanical properties. The addition of RE can spheroidize, refine and modify the inclusions in the steel, and the inclusion with two complex components of RExZryOz-RE2O2S and RExZryOz-RE2O2S-TiN is formed in the steel by adding the RE into the corrosion-resistant low-alloy high-strength steel disclosed by the invention as shown in figure 1. The seawater corrosion resistance of the seawater corrosion resistant low-alloy high-strength steel related to the invention is more excellent through a seawater corrosion resistance test with other steel grades with similar components, as shown in figure 2.
Al formed by conventional Al deoxidized steel2O3The inclusions have high hardness and large size, which easily form a gap with the iron matrix to accelerate the local corrosion rate of the steel. The invention is characterized in that Ti + Zr composite deoxidation and rare earth treatment are adopted to modify inclusions in steel, thereby reducing the local corrosion tendency of the material and improving the seawater corrosion resistance of the steel. Such asAs shown in table 1, the seawater corrosion resistant low-alloy high-strength steel of the present invention has a lower corrosion rate and is more excellent in seawater corrosion resistance.
TABLE 1 comparison of Corrosion rates of inventive example 1 and conventional Steel Material
As can be seen from Table 1, the corrosion-resistant low-alloy high-strength steel (Zr-Ti-Re rare earth steel) of the present invention has the lowest corrosion current density (5.102X 10-6A/cm2) and the best corrosion resistance.
The foregoing embodiments and description have been presented only to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed.
Claims (3)
1. The seawater corrosion resistant low-alloy high-strength steel is characterized by comprising the following components in percentage by weight:
C：0.02～0.05％；
Si：0.10～0.30％；
Mn：0.10～0.15％；
Al：0.02～0.04％；
Cr：1.00～1.50％；
Ni：0.20～0.40％；
Cu：0.30～0.50％；
Zr+Ti：0.02～0.03％；
Re：0.05～0.08％；
p is less than or equal to 0.015 percent, S is less than or equal to 0.008 percent, and the balance is Fe and inevitable impurities;
the tensile strength of the seawater corrosion resistant low-alloy high-strength steel is 400-600 MPa; the elongation after fracture is more than or equal to 30 percent; the low-temperature toughness at minus 40 ℃ is more than or equal to 300J.
2. A method for producing the seawater corrosion resistant low alloy high strength steel of claim 1, characterized in that: the method adopts a TMCP process and normalizing treatment mode.
3. The method for preparing the seawater corrosion resistant low-alloy high-strength steel as claimed in claim 2, wherein the method comprises the following steps:
s1), the initial rolling temperature of rough rolling is 1160-1200 ℃, the reduction rate is 55-65%, the deformation speed is not more than 4.5m/S, and the final rolling temperature of rough rolling is 1050 soil 10 ℃;
s2), adjusting the temperature control thickness of the intermediate billet to be not less than 2.5-3.0 times of the thickness of the finished product, and adjusting the temperature of finish rolling to be (920 ℃ of 10) DEG C and the temperature of finish rolling to be 860 ℃ of 10 ℃;
s3), the laminar cooling start cooling temperature is 830 ℃, the final cooling temperature is (640 soil 10) DEG C, and the cooling speed is 5-10 ℃/S;
s4) and normalizing process parameters, wherein the normalizing temperature is 890-910 ℃, the heat preservation time is 10-15 min, and the cooling mode is air cooling.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118919A (en) * | 1995-10-26 | 1997-05-06 | Sumitomo Metal Ind Ltd | Manufacture of steel product excellent in seawater corrosion resistance |
| JP2005220394A (en) * | 2004-02-04 | 2005-08-18 | Sumitomo Metal Ind Ltd | Seawater corrosion resisting steel |
| JP2006124796A (en) * | 2004-10-29 | 2006-05-18 | Kobe Steel Ltd | Corrosion resistant coated steel |
| JP2011021248A (en) * | 2009-07-16 | 2011-02-03 | Jfe Steel Corp | Steel for ship having excellent coating corrosion resistance |
| CN102011050A (en) * | 2010-07-15 | 2011-04-13 | 秦皇岛首秦金属材料有限公司 | Steel for 36kg-grade ocean platform and production method thereof |
| JP2012177168A (en) * | 2011-02-28 | 2012-09-13 | Jfe Steel Corp | Steel material for vessel, which is excellent in resistance to corrosion caused due to coating |
| CN102747285A (en) * | 2012-07-11 | 2012-10-24 | 秦皇岛首秦金属材料有限公司 | Ultrathick steel plate for ships and ocean platforms and production method thereof |
-
2021
- 2021-09-07 CN CN202111043571.XA patent/CN113913687A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118919A (en) * | 1995-10-26 | 1997-05-06 | Sumitomo Metal Ind Ltd | Manufacture of steel product excellent in seawater corrosion resistance |
| JP2005220394A (en) * | 2004-02-04 | 2005-08-18 | Sumitomo Metal Ind Ltd | Seawater corrosion resisting steel |
| JP2006124796A (en) * | 2004-10-29 | 2006-05-18 | Kobe Steel Ltd | Corrosion resistant coated steel |
| JP2011021248A (en) * | 2009-07-16 | 2011-02-03 | Jfe Steel Corp | Steel for ship having excellent coating corrosion resistance |
| CN102011050A (en) * | 2010-07-15 | 2011-04-13 | 秦皇岛首秦金属材料有限公司 | Steel for 36kg-grade ocean platform and production method thereof |
| JP2012177168A (en) * | 2011-02-28 | 2012-09-13 | Jfe Steel Corp | Steel material for vessel, which is excellent in resistance to corrosion caused due to coating |
| CN102747285A (en) * | 2012-07-11 | 2012-10-24 | 秦皇岛首秦金属材料有限公司 | Ultrathick steel plate for ships and ocean platforms and production method thereof |
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