CN111500941B - HIC (hydrogen induced cracking) resistant pipeline steel based on structure regulation and preparation method thereof - Google Patents
HIC (hydrogen induced cracking) resistant pipeline steel based on structure regulation and preparation method thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 88
- 239000010959 steel Substances 0.000 title claims abstract description 88
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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
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- 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
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- 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
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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- 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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Abstract
The HIC-resistant pipeline steel based on the structure regulation has stronger HIC resistance, HIC sensitivity indexes are all 0, and trace elements such as B, N, V, Zr and the like are added to design (V, B) N and (Nb, B)xThe high-temperature second phase with high stability of N can effectively refine crystal grains in the controlled rolling and controlled cooling process, the size of the crystal grains is reduced to about 1 mu m, and the comprehensive performance of high HIC resistance and high strength is realized by regulating and controlling the uniform distribution of Mo element.
Description
Technical Field
The invention belongs to the field of steel preparation, and particularly relates to HIC (hydrogen induced cracking) resistant pipeline steel based on structure regulation and a preparation method thereof.
Background
Pipeline network construction is a strategic requirement. The natural gas pipeline transportation has the characteristics of high efficiency, economy, safety and the like, and is a main form for transporting gas in a long distance. With the gradual change of the international energy structure, the proportion of natural gas in energy will increase sharply in the coming decades. The development of natural gas transportation pipelines tends to be large-caliber, high-pressure and thick-walled. The service conditions of pipelines are more and more strict, such as increased conveying pressure and complex conveying media, and a plurality of pipelines need to pass through dense areas or deserts, swamps, severe cold zones and the like, thereby providing higher technical requirements for pipeline steel.
Corrosion is a key factor affecting the reliability and service life of a pipeline delivery system. It not only can cause perforation, cause the leakage of transported substance such as oil, gas, water, etc., but also can bring the loss caused by the waste of materials and manpower produced by maintenance, shutdown and production stoppage, even cause fire, especially the explosion caused by the corrosion of the natural gas pipeline, threaten the personal safety, pollute the environment, and have serious consequences.
Hydrogen Induced Cracking (HIC for short) refers to a stepped crack generated when Hydrogen atoms generated by electrochemical corrosion enter the interior of a metal material in an acidic environment. Acidic environment generally refers to the environment of wet hydrogen sulfide. The hydrogen bubbles are a corrosion form of HIC, and are formed by the fact that after the electrochemical corrosion of metal and sulfur-containing natural gas, cavitation bubbles with the diameter of several to dozens of millimeters are generated in the metal, and the metal on the surface of the bubbles cracks or delaminates. The HIC can cause the steel for the pipeline to crack suddenly without obvious warning, and has great destructiveness and harmfulness.
For microalloyed pipeline steel, non-metallic inclusions and hard phase interfaces are the major hydrogen traps in the steel. The chemical composition is a key factor for determining the HIC resistance of the steel plate. Wherein, the segregation of C, Mn and P elements easily forms a microstructure sensitive to HIC in the center of the steel plate, for example, bainite and even martensite hard phases appear in ferrite plus pearlite steel, and the hard microstructure can become a HIC crack initiation source. High content of carbides forming high pressure CH4Gas, promoting hydrogen induced cracking. In addition, the rhombohedral MnS elongated by rolling is included in the steel sheet and causes voids around the steel sheet after cooling, and the inclusions become hydrogen-concentrated sites and are likely to be sources of HIC initiation. By reducing the content of elements such as C, S, the HIC sensitivity can be significantly reduced. CN102839326B provides a low-carbon alloy, a fine ferrite structure is obtained through a controlled rolling air cooling process, the HIC resistance is improved, but the alloy strength is low, the resistance strength is 437MPa, and the comprehensive properties such as high strength, good toughness, hydrogen induced cracking resistance and the like are difficult to meet. The increasing size and high pressure of the hydrogen pipeline leads the wall thickness of the steel pipeline to be increased continuously, and the manufacturing difficulty of the hydrogen pipeline is further increased.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides HIC-resistant pipeline steel based on structure regulation and a preparation method thereof.
According to the embodiment of the first aspect of the invention, the HIC-resistant pipeline steel based on structure regulation comprises the following preparation raw materials in percentage by mass:
C：0.01～0.1％，
Mn：0.50～1.00％，
Nb：0.01～0.10％，
Cr：1.0～1.5％，
Mo：0.5～1.5％，
V：0.05～0.20％，
B：0.05～0.10％，
N：0.01～0.02％，
Zr：0.01～0.2％，
the balance being Fe.
C is an element for improving the strength of the steel, and the hydrogen induced cracking sensitivity of the alloy can be increased by improving the carbon content. The invention adopts the alloy design with low carbon content, and can obviously reduce the hydrogen induced cracking sensitivity of the alloy. The reduction of the C content generally results in a reduction of the strength of the alloy steel. In the steel-making process, Mn is a good deoxidizer and desulfurizer, and the Mn content is increased, so that the corrosion resistance of steel can be weakened, and the welding performance can be reduced.
Nb can refine grains, reduce the overheating sensitivity and the temper brittleness of steel and improve the strength, but the plasticity and the toughness are reduced. The addition of Nb to ordinary low-alloy steel can improve the resistance to atmospheric corrosion and hydrogen, nitrogen and ammonia corrosion at high temperature. Nb can improve the weldability. Niobium is added into austenitic stainless steel to prevent intergranular corrosion.
The addition of Cr into steel can significantly improve the oxidation resistance of steel and increase the corrosion resistance of steel. Cr can remarkably increase the hardenability of steel and also can increase the temper brittleness tendency of the steel. The steel with high Cr content can also generate secondary hardening phenomenon when being tempered at 400-500 ℃ after being quenched. In the quenched and tempered structural steel, Cr mainly has the function of improving the hardenability of the steel, so that the steel has better comprehensive mechanical properties after quenching and tempering treatment, namely better plasticity and toughness under the condition of a certain strength level. In the bearing steel, because the special carbide of Cr is relatively wear-resistant, and the Cr-containing steel is quenched and then is ground, a better surface finish can be easily obtained. Therefore, Cr-containing steel is often used as the bearing steel. In tool steels and high speed steels, Cr improves the wear resistance of the steel, so Cr has generally been included in alloy tool steels in the past.
Mo can refine the crystal grains of steel, improve hardenability and heat strength, and maintain sufficient strength and creep resistance at high temperature. Mo is added into the structural steel, so that the mechanical property can be improved, and the brittleness of the alloy steel can be inhibited.
V is an excellent deoxidizer for steel. The addition of 0.5% of V in the steel can refine the structure grains and improve the strength and toughness. The carbide formed by V and C can improve the hydrogen corrosion resistance under high temperature and high pressure.
The addition of trace amount of B can improve the compactness and hot rolling performance of steel and raise strength.
N can improve the strength, low-temperature toughness and weldability of steel and increase aging sensitivity.
Zr is a rare metal with high melting point, is a carbide forming element, is the most powerful deoxidizing and denitrifying element in the steel-making process, and has the functions of dehydrogenation and desulfurization. Zr can refine austenite grains of steel, and zirconium dissolved in austenite can improve hardenability of steel, but if it exists in a form of ZrC in a large amount, hardenability is rather reduced.
According to some embodiments of the present invention, the HIC resistant steel for pipes comprises the following raw materials:
C：0.08％，
Mn：0.8％，
Nb：0.10％，
Cr：1.2％，
Mo：1.5％，
V：0.06％，
B：0.10％，
N：0.02％，
Zr：0.01％，
the balance being Fe.
According to some embodiments of the present invention, the steel for HIC-resistant pipes based on texture control has an S content of less than 0.01%.
During hot rolling, S generates MnS extending in the rolling direction, and reduces low-temperature toughness. Therefore, in the steel for HIC-resistant pipes according to the examples of the present invention, the S content needs to be reduced, and the upper limit is limited to 0.01% or less, and the smaller the S content, the better.
According to some embodiments of the present invention, the content of P in the steel for HIC resistant pipes according to texture modulation is less than 0.01%.
P is an impurity element, and when the content exceeds 0.01%, HIC resistance is impaired, and toughness of the HAZ is lowered. Therefore, the upper limit of the content of P is limited to 0.01% or less.
The HIC-resistant pipeline steel based on structure regulation and control provided by the embodiment of the invention at least has the following technical effects:
the HIC-resistant pipeline steel provided by the embodiment of the invention has strong HIC resistance, and the HIC sensitivity indexes are all 0.
The HIC-resistant pipeline steel provided by the embodiment of the invention is added with trace elements such as B, N, V, Zr and designs (V, B) N and (Nb, B)xThe high-temperature second phase with high stability of N can effectively refine crystal grains in the controlled rolling and controlled cooling process, the size of the crystal grains is reduced to about 1 mu m, and the comprehensive performance of high HIC resistance and high strength is realized by regulating and controlling the uniform distribution of Mo element.
The method for preparing the HIC-resistant pipe steel according to the embodiment of the second aspect of the invention comprises the following steps:
s1: weighing the C, Mn, Nb, Cr, Mo, V, B, N, Zr and Fe according to the proportion, melting and continuously casting to obtain a billet;
s2: and (5) performing controlled rolling and controlled cooling treatment on the steel billet obtained in the step (S1) to obtain the HIC-resistant pipeline steel based on structure control.
According to some embodiments of the invention, the controlled rolling and controlled cooling comprises a sequence of rough rolling, finish rolling and water cooling.
According to some embodiments of the invention, the rough rolling has a start rolling temperature of 1070 ℃ and a single reduction of more than 15%.
According to some embodiments of the invention, the finish-rolled intermediate slab has a final thickness of 60 mm.
According to some embodiments of the invention, the finishing rolling has a start rolling temperature of 900 ℃.
According to some embodiments of the invention, the water cooling process has an inlet temperature of 780 ℃, a cooling rate of 13 ℃/s and a final cooling temperature of 620 ℃.
Drawings
FIG. 1 shows (V, B) N and (Nb, B) in the steel sample of example 3xA schematic diagram of a high-temperature second phase morphology with high N stability.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment provides HIC (hydrogen induced cracking) resistant pipeline steel based on structure regulation, which comprises the following components in percentage by mass:
c: 0.01 to 0.1%, Mn: 0.50 to 1.00%, Nb: 0.01-0.10%, Cr: 1.0-1.5%, Mo: 0.5-1.5%, V: 0.05-0.20%, B: 0.05-0.10%, N: 0.01-0.02%, Zr: 0.01-0.2%, and the balance of Fe.
Wherein, the S content is less than 0.01 percent, and the P content is less than 0.01 percent.
Example 2
The embodiment provides a preparation method of HIC (hydrogen induced cracking) resistant pipeline steel based on structure regulation, which comprises the following steps of:
s1: weighing the C, Mn, Nb, Cr, Mo, V, B, N, Zr and Fe according to the proportion, melting and continuously casting to obtain a billet;
s2: and (5) performing controlled rolling and controlled cooling treatment on the steel billet obtained in the step (S1) to obtain the HIC-resistant pipeline steel based on structure control.
Wherein, the controlled rolling and controlled cooling comprises the working procedures of rough rolling, finish rolling and water cooling which are carried out in sequence. The initial rolling temperature of rough rolling is 1070 ℃, and the single-pass reduction rate is more than 15%. The thickness of the finish-rolled intermediate billet to be heated is 60 mm. The initial rolling temperature of finish rolling is 900 ℃. The water inlet temperature of the water cooling process is 780 ℃, the cooling speed is 13 ℃/s, and the final cooling temperature is 620 ℃.
Example 3
In the embodiment, the preparation method of the embodiment 2 is adopted, and the formula of the embodiment 1 is referred to, so that the HIC-resistant pipeline steel based on the structure regulation is prepared, and the HIC-resistant pipeline steel specifically comprises the following components in percentage by mass:
c: 0.1%, Mn: 0.80%, Nb: 0.05%, Cr: 1.5%, Mo: 0.6%, V: 0.06%, B: 0.05%, N: 0.015%, Zr: 0.15 percent, and the balance of Fe and impurity elements.
Example 4
In the embodiment, the preparation method of the embodiment 2 is adopted, and the formula of the embodiment 1 is referred to, so that the HIC-resistant pipeline steel based on the structure regulation is prepared, and the HIC-resistant pipeline steel specifically comprises the following components in percentage by mass:
c: 0.05%, Mn: 0.70%, Nb: 0.08%, Cr: 1.0%, Mo: 0.9%, V: 0.1%, B: 0.08%, N: 0.015%, Zr: 0.15 percent, and the balance of Fe and impurity elements.
The S content is less than 0.01 percent. The P content is less than 0.01 percent.
Example 5
In the embodiment, the preparation method of the embodiment 2 is adopted, and the formula of the embodiment 1 is referred to, so that the HIC-resistant pipeline steel based on the structure regulation is prepared, and the HIC-resistant pipeline steel specifically comprises the following components in percentage by mass:
c: 0.08%, Mn: 0.80%, Nb: 0.1%, Cr: 1.2%, Mo: 1.5%, V: 0.06%, B: 0.1%, N: 0.02%, Zr: 0.10 percent, and the balance of Fe and impurity elements.
The S content is less than 0.01 percent. The P content is less than 0.01 percent.
Comparative example 1
By adopting the same preparation method as that of example 5, the steel for HIC-resistant pipelines based on structure regulation is prepared in the example, and the steel is different from the example 5 in that the steel does not contain B element and specifically comprises the following components in percentage by mass:
c: 0.08%, Mn: 0.80%, Nb: 0.1%, Cr: 1.2%, Mo: 1.5%, V: 0.06%, N: 0.02, Zr: 0.10 percent, and the balance of Fe and impurity elements.
The S content is less than 0.01 percent. The P content is less than 0.01 percent.
Comparative example 2
By adopting the same preparation method as that of example 5, the steel for HIC-resistant pipelines based on structure regulation is prepared in the example, and the steel is different from the example 5 in that the steel does not contain N element and specifically comprises the following components in percentage by mass:
c: 0.08%, Mn: 0.80%, Nb: 0.1%, Cr: 1.2%, Mo: 1.5%, V: 0.06%, B: 0.1%, Zr: 0.10 percent, and the balance of Fe and impurity elements.
The S content is less than 0.01 percent. The P content is less than 0.01 percent.
Test example HIC test
This example performed HIC testing on samples.
The test principle is as follows: in the steel for pipelines, in a corrosive environment containing an aqueous hydrogen sulfide solution, HIC cracks formed by hydrogen absorption include step-type cracks formed inside a sample and hydrogen blisters formed on the surface of the sample. The step-shaped crack is a crack having a special shape crossing the thickness direction and resembling a step, which is generated in the steel for a pipe in an aqueous solution containing hydrogen sulfide, propagates in the rolling direction, and is formed when adjacent cracks are connected to each other. The level of cracking susceptibility of the HIC for a pipe material is determined by the number, length and shape of cracks generated in the steel material in a predetermined environment. In the test, the HIC crack sensitivity of a sample is evaluated according to the number, length and width of cracks generated in the sample by exposing the unstressed sample to a specified test solution, taking out the sample after a specified test time.
Sample size: the length is 100 plus or minus 1mm, and the width is 20 plus or minus 1 mm.
The test solution was a saturated aqueous solution of H2S of 5% NaCl + 0.5% acetic acid.
The test temperature is 25 ℃, and the test time is 96 h.
And (3) evaluating the test sample:
in order to distinguish cracks from small impurities, delamination, scratches and other discontinuities, each section should be polished. The cracks were measured as in figure 1. When measuring the length and thickness of a crack, two or more cracks having a distance of less than 0.5mm should be regarded as one crack. All cracks that can be identified at 100 times magnification are accounted for, except for those where the entire crack is completely within 1mm of the surface of the specimen.
The crack rate sensitivity (CSR), Crack Length Rate (CLR) and crack width rate (CTR) of each specimen were calculated according to the formulas (1) to (3). The method specifically comprises the following steps:
CSR＝∑(a×b)/((W×T)×100％(1)，
CLR＝∑a/W×100％(2)，
CTR＝∑b/T×100％(3)，
wherein a refers to the crack length, mm; b refers to the crack width, mm; w is the width of the sample, mm; t denotes the specimen thickness, mm.
Three steel samples of corresponding numbers prepared in example 5 and comparative examples 1 and 2 were tested as described above, and the specific results are shown in table 1.
TABLE 1 Strength and HIC Performance test results
Further, the microstructure of the steel sample of example 3, which contained (V, B) N and (Nb, B) as shown in FIG. 1, was observedxThe appearance of the high-temperature second phase with high stability of N shows that the HIC-resistant pipeline steel of the embodiment of the invention is added with trace elements such as B, N, V, Zr and the like to form (V, B) N and (Nb, B)xThe high-temperature second phase with high stability of N can effectively refine crystal grains in the controlled rolling and controlled cooling process, the size of the crystal grains is reduced to about 1 mu m, and the comprehensive performance of high HIC resistance and high strength is realized by regulating and controlling the uniform distribution of Mo element.
Claims (9)
1. The HIC-resistant pipeline steel based on structure regulation is characterized by comprising the following preparation raw materials in percentage by mass:
C：0.08％，
Mn：0.8％，
Nb：0.1％，
Cr：1.2％，
Mo：1.5％，
V：0.06％，
B：0.1％，
N：0.02％，
Zr：0.1％，
the balance being Fe.
2. The steel for HIC-resistant pipes according to claim 1, wherein the steel for HIC-resistant pipes has an S content of less than 0.01%.
3. The steel for HIC-resistant pipes according to claim 1, wherein the content of P in the steel for HIC-resistant pipes is less than 0.01%.
4. The method for preparing the HIC-resistant pipeline steel based on the structure regulation as claimed in any one of claims 1 to 3, is characterized by comprising the following steps:
s1: weighing the C, Mn, Nb, Cr, Mo, V, B, N, Zr and Fe according to the proportion, melting and continuously casting to obtain a billet;
s2: and (5) performing controlled rolling and controlled cooling treatment on the steel billet obtained in the step (S1) to obtain the HIC-resistant pipeline steel based on structure control.
5. The method for preparing the HIC-resistant pipeline steel based on the structure control as claimed in claim 4, wherein the controlled rolling and the controlled cooling comprise the processes of rough rolling, finish rolling and water cooling which are sequentially performed.
6. The method for preparing the steel for HIC-resistant pipelines based on texture modulation as claimed in claim 5, wherein the initial rolling temperature of the rough rolling is 1070 ℃ and the single-pass reduction rate is more than 15%.
7. The method for manufacturing steel for HIC-resistant pipelines according to claim 5, wherein the finish-rolled intermediate slab has a final thickness of 60 mm.
8. The method for manufacturing the steel for HIC-resistant pipelines according to claim 5, wherein the finish rolling has a start rolling temperature of 900 ℃.
9. The method for preparing the steel for HIC-resistant pipelines based on texture manipulation as claimed in claim 5, wherein the water cooling process has an entry temperature of 780 ℃, a cooling rate of 13 ℃/s and a final cooling temperature of 620 ℃.
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