CN112695247A - Stress corrosion resistant low-alloy high-strength steel for ocean engineering and preparation method thereof - Google Patents
Stress corrosion resistant low-alloy high-strength steel for ocean engineering and preparation method thereof Download PDFInfo
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Abstract
The invention provides stress corrosion resistant low-alloy high-strength steel for ocean engineering, which is characterized in that the low-alloy high-strength steel comprises the following chemical elements in percentage by mass: 0.04 to 0.08 percent of C, 0.2 to 0.3 percent of Si, 1.45 to 1.65 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.4 to 0.5 percent of Cr, 0.25 to 0.35 percent of Cu, 0.75 to 0.85 percent of Ni, 0.005 to 0.015 percent of Ti, 0.03 to 0.06 percent of Nb, 0.05 to 0.1 percent of Sb and the balance of Fe. The low-alloy high-strength steel plate with the yield strength of more than 690MPa is finally manufactured, so that the stress corrosion resistance of the low-alloy high-strength steel is improved by more than 50% compared with that of the low-alloy high-strength steel without the addition of the control steel.
Description
Technical Field
The invention belongs to the technical field of low-alloy high-strength steel, and particularly relates to stress corrosion resistant low-alloy high-strength steel for ocean engineering and a preparation method thereof.
Background
At present, with the overall implementation of strategies such as ocean development and the like in China, the demand and performance requirements of low-alloy high-strength steel for ocean engineering are continuously rising. The low-alloy high-strength steel for ocean engineering generally has the characteristics of poor working environment, high temperature, high humidity, high salt spray, harsh stress load and the like. Under the comprehensive action of environmental and mechanical factors, the low-alloy high-strength steel for ocean engineering is easy to generate stress corrosion cracking, and the problem of stress corrosion of ocean engineering materials is increasingly prominent along with the large scale of ocean equipment and the gradual improvement of material strength, thereby seriously threatening the safety and reliability of ocean engineering.
Stress corrosion crack tip in marine environment is Cl-The autocatalytic acidic microenvironment, leading to its stress corrosion mechanism, is a hybrid control mechanism of anodic dissolution and hydrogen embrittlement. Anodic dissolution process and local acidity and Cl content-The electrochemical activity in the environment is related, the hydrogen embrittlement process is related to hydrogen evolution reaction caused by local acidity, hydrogen atom concentration in steel and hydrogen diffusion and distribution, both can cause the initiation and the expansion of microcracks, and have synergistic action to aggravate stress corrosion cracking.
The microalloying element design is a main means for improving the performance of the low-alloy high-strength steel for ocean engineering, but the prior corrosion resistant element design is difficult to realize the improvement of the stress corrosion resistance, and the reverse microalloying design based on the stress corrosion mechanism is an effective means for improving the stress corrosion resistance of the low-alloy high-strength steel.
However, as the research progresses at home and abroad, more researches are focused on improving the hydrogen resistance of steel at present, and researches on the design of corrosion-resistant materials aiming at anode dissolution and hydrogen embrittlement coupling mechanisms are rarely reported. The Nb microalloying treatment can optimize the microstructure, improve the hydrogen distribution in the steel by forming a nano precipitated phase, and improve the hydrogen induced cracking resistance of the microstructure; sb particle size distributionThe gold treatment can reduce the Cl content of the high-strength steel in the acid-Electrochemical activity in the environment, corrosion product film property improvement and local anodic dissolution process under the rust layer alleviation. Therefore, the Nb and Sb elements are added in a compounding manner, anode dissolution and hydrogen embrittlement mechanisms can be inhibited at the same time, and the stress corrosion resistance of the high-strength steel in the marine environment is improved. However, no patent report exists on the stress corrosion resistance of Nb and Sb double-mechanism microalloyed high-strength steel in the marine environment at present, and whether the influence mechanism of the synergistic control of the two elements on the stress corrosion resistance of the high-strength steel in the marine environment meets the requirement of solving the anode dissolution and hydrogen embrittlement coupling mechanism is not found.
Disclosure of Invention
The invention aims to provide stress corrosion resistant low-alloy high-strength steel containing Nb and Sb microalloy elements for ocean engineering and a preparation method thereof, and the low-alloy high-strength steel for ocean engineering with yield strength of more than 690MPa and excellent stress corrosion resistance can be produced.
The invention provides stress corrosion resistant low-alloy high-strength steel for ocean engineering, which utilizes Sb and Nb alloying to realize the inhibition of the anodic dissolution process and the hydrogen embrittlement process of the low-alloy high-strength steel in a synergic manner, thereby preparing the stress corrosion resistant low-alloy high-strength steel for ocean engineering with the obdurability reaching E690 steel.
Preferably, the Sb alloy element is Cl in a rust layer under the marine environment-Enrichment and its induced acidification phenomena while reducing the Cl content of the matrix in acidic conditions-One or more electrochemically active alloying elements in the environment; the Nb alloy element is one or more alloy elements which can inhibit the cathodic hydrogen evolution process in the marine environment, form an irreversible hydrogen trap and improve the microstructure.
Preferably, the inhibition of the cathodic hydrogen evolution process in the marine environment is realized by reducing the hydrogen evolution current density, the formation of the irreversible hydrogen traps is realized by increasing the hydrogen trap density in the steel, and the improvement of the microstructure is realized by improving the hydrogen resistance at a special interface.
Preferably, the stress corrosion resistant low-alloy high-strength steel for ocean engineering comprises the following chemical elements in percentage by mass: 0.04 to 0.08 percent of C, 0.2 to 0.3 percent of Si, 1.45 to 1.65 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.4 to 0.5 percent of Cr, 0.25 to 0.35 percent of Cu, 0.75 to 0.85 percent of Ni, 0.005 to 0.015 percent of Ti, 0.03 to 0.06 percent of Nb, 0.05 to 0.1 percent of Sb and the balance of Fe.
Preferably, the preparation method of the stress corrosion resistant low-alloy high-strength steel for ocean engineering is as follows:
smelting according to chemical components, casting the materials into blanks, heating the steel blanks to an austenitizing temperature of 1180-1220 ℃, preserving heat for 1.5-2.5 hours to homogenize the steel blanks, and preparing for hot rolling; the initial rolling temperature is controlled to be 980-1020 ℃, the steel is rolled into a target plate thickness through multiple passes, and the final rolling temperature is controlled to be 860-900 ℃; and (3) after rolling, cooling in a water laminar flow area, controlling the cooling rate at 25-30 ℃/s, ensuring the outlet water temperature of the billet to be 420-440 ℃, and finally air-cooling to room temperature to obtain the stress corrosion resistant marine low-alloy high-strength steel finished product.
Preferably, the finished stress corrosion resistant marine low alloy high strength steel is subjected to a slow strain rate tensile test using 3.5 wt.% NaCl +0.05M NaHSO at 100% humidity3Simulating polluted marine atmospheric environment under the condition of moisture, wherein the experimental temperature is room temperature, and the slow strain stretching rate is 0.5 multiplied by 10-6～1.5×10-6s-1Moisture is maintained throughout the stretching process.
Preferably, the stress corrosion sensitivity of the finished product of the stress corrosion resistant marine low-alloy high-strength steel in a simulated polluted marine atmosphere environment is evaluated by calculating the elongation loss and the reduction of area loss of the low-alloy high-strength steel.
Preferably, the elongation loss of the low-alloy high-strength steel is 11.05-15.21%, the reduction of area loss is 12.1-14.33%, and the maximum reduction of the stress sensitivity is close to 60% compared with the traditional low-alloy high-strength steel.
The functions of the elements in the low-alloy high-strength steel are as follows:
c: the low alloy steel designed by the method adopts ultra-low carbon, which is beneficial to the formation of bainite to obtain a lath bainite structure on one hand, and needs enough C content to ensure the precipitation of a carbide hydrogen trap on the other hand. Therefore, the content is defined to be 0.04% to 0.08%.
Si: is a basic element in steel, can be deoxidized in the smelting process, and can reduce the low-temperature toughness and the welding performance of the steel due to the over-high content of Si. Therefore, the content of the compound is 0.2 to 0.3 percent.
Mn: is a main solid solution strengthening element in steel, can make up for the insufficient strength caused by low carbon in the steel, but the excessively high Mn content is easy to form strip MnS inclusions, and simultaneously reduces the welding performance. Therefore, the content of the compound is 1.45 to 1.65 percent.
P and S: p and S are generally considered to be harmful elements in steel, and the content thereof should be minimized. Therefore, the invention provides that P is less than or equal to 0.015 percent and S is less than or equal to 0.005 percent.
Cr: can raise bainite transformation temperature and is one of the most common corrosion resisting elements in weather resisting steel. Cr can promote the stabilization of a rust layer, refine grains of the rust layer, effectively prevent the permeation of chloride ions and sulfate ions and improve the protection effect of the rust layer. Therefore, the content of the compound is 0.4 to 0.5 percent.
Cu: the Cu is one of effective elements for improving the atmospheric corrosion resistance of steel, and can obviously reduce the corrosion rate of the low-alloy steel in an acid environment. When the Cu content exceeds 0.25%, the low alloy steel exhibits better corrosion resistance, and when the Cu content exceeds 0.45%, the corrosion resistance is not further improved, and grain boundary embrittlement may also be caused. Therefore, the content of the compound is regulated to be 0.25 to 0.45 percent
Ni: is a thermodynamically stable element and can improve the self-corrosion potential of steel. The addition of the Ni element can refine the crystal grains of the inner rust layer, increase the compactness of the inner rust layer, improve the corrosion resistance of the steel, and simultaneously, the addition of a small amount of Ni can prevent the defects caused by Cu in rolling and improve the low-temperature toughness of the steel. Therefore, the content of the compound is 0.75 to 0.85 percent.
Ti: is a microalloying element, a small amount of Ti can improve the strength, cold workability and welding performance of the steel, and defects are easily formed by adding excessive Ti. Therefore, the content is defined to be 0.005% to 0.015%.
Sb: is a micro-alloying element and can inhibit the anode dissolution effect in the stress corrosion process through an Sb-Cu synergistic mechanism. When the content of Sb is 0.05%, the effect of suppressing the metal oxide is not remarkable, and when the content of Sb is 0.1%, the effect of suppressing the metal oxide is good. Therefore, the Sb content is regulated to be 0.05-0.1 percent.
Nb: is a microalloying element, can form a nanometer precipitated phase NbC, refine grains, capture hydrogen atoms, reduce the cathodic hydrogen evolution reaction and improve the hydrogen resistance of the organization structure. The multiple-effect hydrogen inhibition effect of Nb can inhibit hydrogen embrittlement in the process of stress corrosion. When the content of Nb is 0.03%, the inhibition effect is not obvious, when the content of Nb is 0.06%, the inhibition effect is better, and when the content of Nb is continuously increased, the inhibition effect is not obviously enhanced. Therefore, the Nb content is regulated to be 0.03-0.06%.
The technical scheme of the invention has the following beneficial effects:
the invention provides stress corrosion resistant low-alloy high-strength steel for ocean engineering and a preparation method thereof, the obdurability of the low-alloy high-strength steel obtained by the method can meet the requirement of E690 steel, and the low-alloy high-strength steel has excellent stress corrosion cracking resistance under the ocean environment.
Drawings
The technical solution in the embodiments of this patent will be further described below with reference to the drawings in the embodiments of this patent.
FIG. 1 is a microstructure diagram of an example 1 of the stress corrosion resistant low alloy high strength steel for ocean engineering of the present invention;
fig. 2 is a microstructure diagram of example 2 of the stress corrosion resistant low alloy high strength steel for ocean engineering of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is made with reference to the accompanying drawings and specific embodiments.
The invention aims to solve the technical problem of how to improve the stress corrosion resistance of low-alloy high-strength steel in the marine atmospheric environment.
In order to solve the technical problems, the invention provides the stress corrosion resistant low-alloy high-strength steel for the ocean engineering, and Sb and Nb alloying treatment is utilized to realize the inhibition of the anodic dissolution process and the hydrogen embrittlement process of the low-alloy high-strength steel in a synergic manner, so that the stress corrosion resistant low-alloy high-strength steel for the ocean engineering with the strength and toughness reaching E690 steel is prepared.
Particularly, the Sb alloy element is Cl in a rust layer under the marine environment-Enrichment and its induced acidification phenomena while reducing the Cl content of the matrix in acidic conditions-One or more electrochemically active alloying elements in the environment; the Nb alloy element is one or more alloy elements which can inhibit the cathodic hydrogen evolution process in the marine environment, form an irreversible hydrogen trap and improve the microstructure.
Particularly, the inhibition of the cathodic hydrogen evolution process in the marine environment is realized by reducing the hydrogen evolution current density, the formation of irreversible hydrogen traps is realized by increasing the hydrogen trap density in steel, and the improvement of the microstructure is realized by improving the hydrogen resistance at a special interface.
Particularly, the stress corrosion resistant low-alloy high-strength steel for ocean engineering comprises the following chemical elements in percentage by mass: 0.04 to 0.08 percent of C, 0.2 to 0.3 percent of Si, 1.45 to 1.65 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.4 to 0.5 percent of Cr, 0.25 to 0.35 percent of Cu, 0.75 to 0.85 percent of Ni, 0.005 to 0.015 percent of Ti, 0.03 to 0.06 percent of Nb, 0.05 to 0.1 percent of Sb and the balance of Fe.
In particular, the preparation method of the stress corrosion resistant low-alloy high-strength steel for ocean engineering is as follows:
smelting according to chemical components, casting the materials into blanks, heating the steel blanks to an austenitizing temperature of 1180-1220 ℃, preserving heat for 1.5-2.5 hours to homogenize the steel blanks, and preparing for hot rolling; the initial rolling temperature is controlled to be 980-1020 ℃, the steel is rolled into a target plate thickness through multiple passes, and the final rolling temperature is controlled to be 860-900 ℃; and (3) after rolling, cooling in a water laminar flow area, controlling the cooling rate at 25-30 ℃/s, ensuring the outlet water temperature of the billet to be 420-440 ℃, and finally air-cooling to room temperature to obtain the stress corrosion resistant marine low-alloy high-strength steel finished product.
In particular, the finished stress corrosion resistant marine low alloy high strength steel was subjected to a slow strain rate tensile test using 3.5 wt.% NaCl +0.05M NaHSO at 100% humidity3Simulating polluted marine atmospheric environment under the condition of moisture, wherein the experimental temperature is room temperature, and the slow strain stretching rate is 0.5 multiplied by 10-6～1.5×10-6s-1Moisture is maintained throughout the stretching process.
Particularly, the stress corrosion sensitivity of the finished product of the stress corrosion resistant marine low-alloy high-strength steel in a simulated polluted marine atmosphere environment is evaluated by calculating the elongation loss and the reduction of area loss of the low-alloy high-strength steel.
Particularly, the elongation loss of the low-alloy high-strength steel is 11.05-15.21%, the reduction loss of area is 12.1-14.33%, and the maximum reduction amplitude of the stress resistance sensitivity is close to 60% compared with that of the traditional low-alloy high-strength steel.
The specific stress corrosion resistant low-alloy high-strength steel for ocean engineering and the preparation method thereof are described by combining the following embodiments and the attached drawings:
1. the chemical composition weight percentages of examples 1 to 7 prepared using the present invention are shown in table 1;
2. the chemical compositions of comparative examples 1 to 4 prepared by the present invention are shown in table 2 in weight percentage, and include three types of cases of no Nb and no Sb element, only Nb element, and only Sb element, respectively;
3. smelting by a vacuum induction furnace according to the components to obtain a billet;
4. the plate-shaped steel is prepared by adopting the following controlled rolling process: firstly, heating a blank to 1180-1220 ℃, and preserving heat for 2 hours to achieve complete austenitization; then furnace cooling is carried out to the initial rolling temperature of 980-1020 ℃, a 12mm steel plate is obtained after rolling is carried out for 15-20 times, and the final rolling temperature is 860-900 ℃; and (3) after rolling, cooling the steel billet in a water laminar flow area at a cooling rate of 25-30 ℃/s, ensuring the water outlet temperature of the steel billet to be 420-440 ℃, and finally cooling the steel billet to room temperature in air.
4. Stress corrosion slow strain rate tensile tests were conducted on 7 examples and 4 comparative examples under 3.5 wt.% NaCl +0.05M NaHSO at 100% humidity3Used for simulating the polluted marine atmosphere environment, the experimental temperature is room temperature, and the slow strain stretching rate is 1 multiplied by 10-6s-1Moisture is maintained throughout the stretching process.
5. The elongation loss and the reduction of area loss were used to evaluate the stress corrosion susceptibility of the examples and comparative examples in a contaminated marine atmosphere environment.
Table 3 shows the comparison of the stress corrosion sensitivities of examples 1 to 7 and comparative examples 1 to 4 in the polluted marine atmosphere environment, and it can be seen from the table that the stress corrosion sensitivity of the low alloy high strength steel in the polluted marine atmosphere environment is significantly reduced due to the simultaneous addition of Nb and Sb elements. When the contents of Nb and Sb in the steel are 0.06% and 0.1%, respectively, the stress corrosion resistance of the low alloy high strength steel is increased by nearly 60% compared with that of comparative example 1.
TABLE 1 chemical composition (% by mass) of alloying elements in examples of the present invention
TABLE 2 chemical composition (% by mass) of alloying elements of comparative examples in the present invention
TABLE 3 comparison of the stress corrosion resistance of the examples of the present invention and the comparative examples
In conclusion, the invention provides the alloy components of the stress corrosion resistant marine steel and the preparation process thereof, the obdurability of the low-alloy high-strength steel obtained by the method can meet the requirement of E690 steel, and the low-alloy high-strength steel has excellent stress corrosion cracking resistance in marine environment.
The foregoing is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should be considered as the protection scope of the present invention.
Claims (8)
1. The stress corrosion resistant low-alloy high-strength steel for the ocean engineering is characterized in that Sb and Nb alloying treatment is utilized to realize the inhibition of the anode dissolution process and the hydrogen embrittlement process of the low-alloy high-strength steel in a synergistic manner, so that the stress corrosion resistant low-alloy high-strength steel for the ocean engineering with the strength and toughness reaching E690 steel is prepared.
2. The stress-corrosion-resistant low-alloy high-strength steel for ocean engineering according to claim 1, wherein the Sb alloy element is Cl in a rust layer in a marine environment-Enrichment and its induced acidification phenomena while reducing the Cl content of the matrix in acidic conditions-One or more electrochemically active alloying elements in the environment; the Nb alloy element is one or more alloy elements which inhibit a cathodic hydrogen evolution process in a marine environment, form an irreversible hydrogen trap and improve a microstructure.
3. The stress-corrosion-resistant low-alloy high-strength steel for ocean engineering according to claim 2, wherein the inhibition of cathodic hydrogen evolution in the ocean environment is achieved by reducing the hydrogen evolution current density, the formation of irreversible hydrogen traps is achieved by increasing the hydrogen trap density in the steel, and the improvement of microstructure is achieved by increasing the hydrogen resistance at a specific interface.
4. The stress-corrosion-resistant low-alloy high-strength steel for ocean engineering according to claim 1, wherein the stress-corrosion-resistant low-alloy high-strength steel for ocean engineering comprises the following chemical elements in percentage by mass: 0.04 to 0.08 percent of C, 0.2 to 0.3 percent of Si, 1.45 to 1.65 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.4 to 0.5 percent of Cr, 0.25 to 0.35 percent of Cu, 0.75 to 0.85 percent of Ni, 0.005 to 0.015 percent of Ti, 0.03 to 0.06 percent of Nb, 0.05 to 0.1 percent of Sb and the balance of Fe.
5. The method for preparing the stress-corrosion-resistant low-alloy high-strength steel for ocean engineering according to claim 1, wherein the method for preparing the stress-corrosion-resistant low-alloy high-strength steel for ocean engineering is as follows:
smelting according to chemical components, casting the materials into blanks, heating the steel blanks to an austenitizing temperature of 1180-1220 ℃, preserving heat for 1.5-2.5 hours to homogenize the steel blanks, and preparing for hot rolling; the initial rolling temperature is controlled to be 980-1020 ℃, the steel is rolled into a target plate thickness through multiple passes, and the final rolling temperature is controlled to be 860-900 ℃; and (3) after rolling, cooling in a water laminar flow area, controlling the cooling rate at 25-30 ℃/s, ensuring the outlet water temperature of the billet to be 420-440 ℃, and finally air-cooling to room temperature to obtain the finished product of the stress corrosion resistant marine low-alloy high-strength steel.
6. The method for preparing the stress corrosion resistant low-alloy high-strength steel for ocean engineering according to claim 5, wherein the finished product of the stress corrosion resistant low-alloy high-strength steel for ocean is subjected to a slow strain rate tensile test by using 3.5 wt.% NaCl +0.05M NaHSO at 100% humidity3Simulating the polluted marine atmospheric environment under the condition of moisture, wherein the experimental temperature is room temperature, and the slow strain stretching rate is 0.5 multiplied by 10-6～1.5×10-6s-1Moisture is maintained throughout the stretching process.
7. The method for preparing the stress corrosion resistant low-alloy high-strength steel for ocean engineering according to claim 5, wherein the stress corrosion sensitivity of the finished product of the stress corrosion resistant low-alloy high-strength steel in the simulated polluted ocean atmosphere environment is evaluated by calculating the elongation loss and the reduction of area loss of the low-alloy high-strength steel.
8. The method for preparing the stress corrosion resistant low-alloy high-strength steel for ocean engineering according to claim 7, wherein the elongation loss of the low-alloy high-strength steel is 11.05-15.21%, the reduction of area loss is 12.1-14.33%, and the reduction of the stress sensitivity is maximally close to 60% compared with that of the traditional low-alloy high-strength steel.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807784A (en) * | 2022-05-11 | 2022-07-29 | 重庆大学 | Corrosion-fracture-resistant high-strength steel in marine environment and preparation method thereof |
| CN114855092A (en) * | 2022-07-05 | 2022-08-05 | 北京科技大学 | Additive manufacturing high-strength and high-toughness stainless steel and preparation process thereof |
| CN114990433A (en) * | 2022-05-17 | 2022-09-02 | 钢铁研究总院有限公司 | Corrosion-resistant steel suitable for high-humidity and high-heat marine environment and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807784A (en) * | 2022-05-11 | 2022-07-29 | 重庆大学 | Corrosion-fracture-resistant high-strength steel in marine environment and preparation method thereof |
| CN114807784B (en) * | 2022-05-11 | 2023-01-24 | 重庆大学 | Corrosion-fracture-resistant high-strength steel in marine environment and preparation method thereof |
| CN114990433A (en) * | 2022-05-17 | 2022-09-02 | 钢铁研究总院有限公司 | Corrosion-resistant steel suitable for high-humidity and high-heat marine environment and preparation method thereof |
| CN114855092A (en) * | 2022-07-05 | 2022-08-05 | 北京科技大学 | Additive manufacturing high-strength and high-toughness stainless steel and preparation process thereof |
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