CN103469094B - Steel for pipe of a kind of anti-chlorine ion corrosion and preparation method thereof - Google Patents
Steel for pipe of a kind of anti-chlorine ion corrosion and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to steel for pipe of a kind of anti-chlorine ion corrosion and preparation method thereof, contained chemical element composition is: C:0.008-0.02wt%, Si:0.05-0.15wt%, Mn:0.50-0.85wt%, below P:0.01wt%, below S:0.01wt%, Mo:0.8-2.0wt%, Al:0.001-0.02wt%, Ni:0.50-1.2wt%, W:0.02-0.08wt%, surplus is that Cr and Fe and inevitable impurity are formed, and wherein the content of Cr meets the condition of following described inequality: 2.4-0.49 [Mo]+11.8 [C]+12.2 [W]≤[Cr]≤3.2-0.57 [Mo]+9.8 [C]+7.2 [W].The tensile strength of steel of the present invention higher than 800MPa, and in the soil of high chloride ion content, has excellent anti-chlorine ion causticize stress cracking performance, is applicable to the areas such as coasting port containing buried pipeline steel under high chloride ion environment.<pb pnum="1" />
Description
Technical field
The present invention relates to and be suitable for comprising the steel used in the corrosive environment of the harshness of the corrosive atmospheres such as chlorion.Specifically, the present invention relates to coastland, steel of steel pipe, Welded Steel Pipe etc. and preparation method thereof are stitched containing buried pipeline weldless steel tube, electricity under high chloride ion environment in the such as area such as coasting port.
Background technology
All the time, as buried pipeline, such as, for transmitting the steel of the buried pipeline of oil and Sweet natural gas etc., general use carbon steel or low alloy steel, but in coastland, because chloride ion content in soil is higher, its erosion resistance is not good.
For adapting to the needs of ferrous materials corrosion resistance nature in ocean environment, in prior art, also develop the steel of some chlorine-resistant corrosion.Such as No. 334286th, Japanese Patent Patent discloses a kind of high-strength steel and the manufacture method with good welds and sea water resistance performance, this steel weight percent consists of: C:0.03 ~ 0.10%, Si:0.10 ~ 0.60%, Mn:0.40 ~ 1.50%, Cu:0.20 ~ 0.60%, Al:0.3 ~ 2.0%, Ni:0.05 ~ 0.50%, Cr:0.50 ~ 1.50%, Ti:0.005 ~ 0.10%, Nb:0.005 ~ 0.10%, V:0.005 ~ 0.30%, remaining is Fe and inevitable impurity; But it is under the edatope of high chloride ion content, the tendency of corrosion stress cracking clearly.
CN1103672A discloses and is a kind ofly suitable for Seawate-corrosive-resisting steel under many wet environments and manufacture method thereof, this steel weight percent consists of: C < 0.10%, Si < 0.50%, Mn < 1.50%, Cr:0.50 ~ 3.50%, Al:0.005 ~ 0.050%, Ni < 1.50%, Mo < 0.80%, Ti:0.005 ~ 0.05%, Nb:0.005 ~ 0.05%, N:0.0020 ~ 0.0120%, RE:0.0015 ~ 0.020%, remaining is Fe and inevitable impurity.With the speed accelerating cooling of 3 ~ 20 DEG C/s after the casting and hot rolling of routine, 400 ~ 600 DEG C time, stop this this accelerating cooling, then air cooling.But its its solidity to corrosion under edatope also haves much room for improvement.
But applicant find the above-mentioned corrosion-resistant steel being applied to briny environment to be applied to containing in high Cl-concentration edatope time, have that overall corrosion resisting property is poor, toughness is not enough, and the phenomenon of the stress corrosion crack caused by chlorion and cause and local spot corrosion, above-mentioned steel of the prior art are used for the area such as coasting port containing under high chloride ion environment during buried pipeline, the military service phase in life-span will be caused short, and cause Frequent Accidents.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the object of the present invention is to provide one to have enough tensile strength and toughness, and there is excellent corrosive steel for pipe and preparation method thereof under high chloride ion edatope.
A first aspect of the present invention, relate to a kind of steel for pipe of anti-chlorine ion corrosion, described steel for pipe, chemical element composition contained by it is: C:0.008-0.02wt%, Si:0.05-0.15wt%, Mn:0.50-0.85wt%, below P:0.01wt%, below S:0.01wt%, Mo:0.8-2.0wt%, Al:0.001-0.02wt%, Ni:0.50-1.2wt%, W:0.02-0.08wt%, surplus is that Cr and Fe and inevitable impurity are formed, and Cr wherein meets the inequality described in formula (1): 2.4-0.49 [Mo]+11.8 [C]+12.2 [W]≤Cr≤3.2-0.57 [Mo]+9.8 [C]+7.2 [W] ... (1).
Applicant is found by research, and the proportioning of alloying elements cr, Mo, W, C alloy element is under the toughness of material and edatope, and the performance of anti-chlorine ion corrosion has material impact.In the edatope of chloride ion-containing, add appropriate Cr and be conducive to improving its corrosion resisting property, and can stress corrosion be suppressed by adding appropriate Mo, and add the acid etching that appropriate W can suppress to be caused by Cr; And Cr, Mo, W, C wherein only have the stoichiometry relation meeting formula (1) as point combination, and the anti-chlorine ion corrosion ability that steel for pipe has significantly improves, especially anti-local corrosion and suppression stress corrosion crack tendency are obviously.
A second aspect of the present invention, also relates to the preparation method of the steel for pipe of above-mentioned anti-chlorine ion corrosion.
Described preparation method comprises the following steps:
1) smelt: by mentioned component at converter or electrosmelting, then through vacuum oven secondary refining, be cast into strand or ingot casting;
2) heat: strand reheats to 1150 ~ 1200 DEG C, is incubated 1 ~ 2 hour;
3) high-pressure water descaling;
4) finish rolling after roughing, start rolling temperature 1120 ~ 1180 DEG C, more than 1000 DEG C accumulative deflections are greater than 60%, finishing temperature 850 ~ 900 DEG C;
5) cool: after being cooled to 400 ~ 600 DEG C with 5 ~ 20 DEG C/s speed laminar flow after hot rolling, air cooling is as room temperature.
As preferably, the steel plate laminar flow cooling termination temperature after hot rolling is 480 DEG C.
Anti-chlorine ion corrosion steel for pipe of the present invention, the employing section cooling after hot rolling, if speed of cooling be less than 5 DEG C/s, Cr, Mo carbide be easy to separate out, and can affect the corrosion-resistant fruit of use to a certain extent.And speed of cooling more than 20 DEG C time, steel toughness deterioration, so being defined as within the scope of 5 ~ 20 DEG C/s of speed of cooling is good for adding.When cooling stops temperature more than 600 DEG C, after accelerating cooling, the element carbide such as Cr, Mo is separated out, and erosion resistance effect reduces.Therefore cooling stop temperature on be defined as 600 DEG C.Because when the cooling after accelerating cooling stops temperature being less than 400 DEG C, the toughness of steel is obviously deteriorated, so cooling stops tailor-made 400 DEG C of the lower limit of temperature, preferable temperature is 480 DEG C.
Embodiment
Chemical element composition of the present invention is: C:0.008-0.02wt%, Si:0.05-0.15wt%, Mn:0.50-0.85wt%, below P:0.005wt%, below S:0.01wt%, Mo:0.8-2.0wt%, Ni:0.50-1.2wt%, Al:0.001-0.02wt%, W:0.02-0.08wt%, surplus is Cr and Fe and inevitable impurity, and Cr wherein meets following inequality: 2.4-0.49 [Mo]+11.8 [C]+12.2 [W]≤Cr≤3.2-0.57 [Mo]+9.8 [C]+7.2 [W].
Its reason is described as follows:
C：0.008-0.02wt%
Although C is solution strengthening element in the intensity improving steel, in order to improve anti-chlorine ion corrosion performance and welding property, C content is more few more favourable.But when its content is less than 0.008wt%, because intensity does not reach more than 800MPa, therefore the lower limit of its content is set to 0.008wt%.On the other hand, when its content is more than 0.02wt%, the hardness after tempering uprises, and welding property will significantly reduce.
Si：0.05-0.15wt%
Si is as the required element of reductor, in order to obtain larger deoxidation effect, its content is set to more than 0.05%; But when its content is more than 0.15wt%, toughness reduces, and hot workability can be made to reduce.
Mn：0.50-0.85wt%
Mn is solid-solution in ferrite and causes solution strengthening effect obvious, and also helps the resistivity improved chlorion when its content controls in 0.50-0.85wt%.
Below P:0.005wt%
Although P is acknowledged as improve the useful in the seawater and element of cheapness of steel, its negative effect worsening welding is also remarkable especially.And contriver also finds, in the soil containing high Cl-concentration, P content maintains the level of 0.01-0.02wt%, to resisting the ability of anti-chlorine ion corrosion without any meaning.Therefore, minimum content should be controlled to when permitting under production conditions as far as possible, its content is limited to below 0.005wt%.
Below S:0.01%
S is impurity contained in steel, and its content is as far as possible more few better.Especially, when its content is more than 0.01%, erosion resistance and toughness significantly reduce.Therefore, the content of S is set to less than 0.01%.
Cr and W:
In the edatope of chloride ion-containing, add appropriate Cr and be conducive to improving its corrosion resisting property, and can stress corrosion be suppressed by adding appropriate Mo, and add the acid etching that appropriate W can suppress to be caused by Cr; When applicant finds by meeting 2.4-0.49 [Mo]+11.8 [C]+12.2 [W]≤Cr≤3.2-0.57 [Mo]+9.8 [C]+7.2 [W] when Cr content, described steel are embedded in containing in high chloride ion edatope, do not find local corrosion and stress corrosion crack by visual; And when Cr content does not meet the relational expression of above-mentioned inequality, all local corrosion and stress corrosion crack can be caused.
Mo：0.8-2.0wt%
Mo is conducive to improving the stress corrosion crack that caused by chlorion of material, in order to obtain this effect, is necessary its content to be limited to more than 0.8wt%, and Mo add the intensity also helping and improve steel.But when Mo content is higher than 2.0wt% time, may have a negative impact to welding property.
Ni：0.50-1.2wt%
Being added with of Ni is beneficial to adds fine and close oxide compound and is conducive to improving its corrosion resisting property, and it also helps and improves low-temperature flexibility; But when its content is lower than 0.50wt% time, the effect improving low-temperature flexibility is not obvious; And when its content is higher than 1.2wt% time, the effect improving low-temperature flexibility has significantly reduced, therefore consider, within the content of Ni is limited to 1.2wt% from economy point.
Al：0.001-0.02wt%
Al uses as reductor in fusion process, and can crystal grain thinning.In order to obtain this effect, be necessary its content to be set to more than 0.001wt%.But when its content is more than 0.02wt%, inclusion becomes many, and erosion resistance suffers damage.
The preparation method of above-mentioned steel comprises the following steps:
1) smelt: by mentioned component at converter or electrosmelting, then through vacuum oven secondary refining, be cast into strand or ingot casting;
2) heat: strand reheats to 1150 ~ 1200 DEG C, is incubated 1 ~ 2 hour;
3) high-pressure water descaling;
4) finish rolling after roughing, start rolling temperature 1120 ~ 1180 DEG C, more than 1000 DEG C accumulative deflections are greater than 60%, finishing temperature 850 ~ 900 DEG C;
5) cool: after being cooled to 400 ~ 600 DEG C with 5 ~ 20 DEG C/s speed laminar flow after hot rolling, air cooling is as room temperature.
Steel of the present invention must have described chemical constitution, when meeting described, not only described steel can be had the required intensity higher than 800MPa, and has the stress corrosion crack problem that excellent resisting chloride ion penetration causes.
The test steel chemical composition of embodiment 1-14 and comparative example 1-4 is as shown in table 1.In order to contrast experiment, making thickness is 20mm, and width is 120mm, and length is the steel plate of 1000mm, uses as experiment.And strength trial is undertaken by pole sample (diameter 6.35mm, parallel portion length 25.4mm), stretching experiment shows: tensile strength is all greater than 800MPa.Then the sample making 100mm × 50mm × 8mm carries out corrosion experiment, and the saline soak of preparation 3.5wt% is crossed and dry soil, is imbedded in by described sample in the dark soil of 1.0m, and the temperature controlled around soil is 5-35 DEG C, and the time is 1 year.Then, measure corrosion weight loss, utilize visual confirmation experiment slice surface whether to create local corrosion and etching crack in addition.
Table 1
Table 2
Do not produce being labeled as " O " of corrosion local corrosion, what produce local corrosion is labeled as "×".Do not produce being labeled as " O " of etching crack, what produce etching crack is labeled as "×".
Those of ordinary skill in the art, is to be understood that and can without departing from the scope of the present disclosure, equivalent replacement or equivalent transformation form can be adopted to implement above-described embodiment.Protection scope of the present invention is not limited to the specific embodiment of embodiment part, as long as no the embodiment departing from invention essence, within the protection domain being all interpreted as having dropped on application claims.
Claims (8)
1. the steel for pipe of an anti-chlorine ion corrosion, it is characterized in that contained chemical element composition is: C:0.008-0.02wt%, Si:0.05-0.15wt%, Mn:0.50-0.85wt%, P:0.01 below wt%, below S:0.01 wt%, Mo:0.8-2.0 wt%, Al:0.001-0.02 wt%, Ni:0.50-1.2 wt%, W:0.02-0.08wt%, surplus is that Cr and Fe and inevitable impurity are formed, and wherein the content of Cr meets the condition of following described inequality:
2.4-0.49[Mo]+11.8[C]+ 12.2[W]≤[Cr]≤3.2-0.57[Mo]+9.8[C]+7.2[W]，
Wherein: [Mo], [C], [W] and [Cr] represent the mass percent of Mo, C, W and Cr in steel respectively; And its preparation method comprises the following steps:
1) smelt: by mentioned component at converter or electrosmelting, then through vacuum oven secondary refining, be cast into strand or ingot casting;
2) heat: strand reheats to 1150 ~ 1200 DEG C, is incubated 1 ~ 2 hour;
3) high-pressure water descaling;
4) finish rolling after roughing, start rolling temperature 1120 ~ 1180 DEG C, more than 1000 DEG C accumulative deflections are 60 ~ 90%, finishing temperature 850 ~ 900 DEG C;
5) cool: after being cooled to 400 ~ 600 DEG C with 5 ~ 20 DEG C/s speed laminar flow after hot rolling, air cooling is as room temperature.
2. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.008wt%, Si:0.10wt%, Mn:0.75wt%, P:0.0020 wt%, S:0.0010 wt%, Cr:2.32wt%, Mo:1.52wt%, Al:0.005 wt%, Ni:0.82 wt%, W:0.025wt%, and Fe and inevitably impurity form.
3. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.010wt%, Si:0.12wt%, Mn:0.68wt%, P:0.0012 wt%, S:0.0020 wt%, Cr:2.30wt%, Mo:1.65wt%, Al:0.002 wt%, Ni:0.78 wt%, W:0.032wt%, and Fe and inevitably impurity form.
4. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.012wt%, Si:0.08wt%, Mn:0.58wt%, P:0.0015 wt%, S:0.0016 wt%, Cr:2.50wt%, Mo:1.72wt%, Al:0.003 wt%, Ni:0.68 wt%, W:0.052wt%, and Fe and inevitably impurity form.
5. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.013wt%, Si:0.07wt%, Mn:0.81wt%, P:0.0022 wt%, S:0.0012wt%, Cr:2.91wt%, Mo:1.16wt%, Al:0.004wt%, Ni:1.12 wt%, W:0.061wt%, and Fe and inevitably impurity form.
6. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.012wt%, Si:0.09wt%, Mn:0.85wt%, P:0.0026 wt%, S:0.0012wt%, Cr:2.32wt%, Mo:1.92wt%, Al:0.015wt%, Ni:0.57 wt%, W:0.048wt%, and Fe and inevitably impurity form.
7. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.010wt%, Si:0.08wt%, Mn:0.77wt%, P:0.0051 wt%, S:0.0008wt%, Cr:2.71wt%, Mo:1.08wt%, Al:0.010wt%, Ni:0.51 wt%, W:0.039wt%, and Fe and inevitably impurity form.
8. the steel for pipe of anti-chlorine ion corrosion according to claim 1, it is characterized in that contained chemical element composition is: C:0.008wt%, Si:0.14wt%, Mn:0.79wt%, P:0.0020 wt%, S:0.0012wt%, Cr:2.66wt%, Mo:1.81wt%, Al:0.012wt%, Ni:0.72 wt%, W:0.075wt%, and Fe and inevitably impurity form.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0633326A1 (en) * | 1993-07-09 | 1995-01-11 | Kawasaki Steel Corporation | Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same |
| CN1292429A (en) * | 2000-10-30 | 2001-04-25 | 宝山钢铁股份有限公司 | Low-alloy steel for oil casing pipe capable of resisting corrosion of CO2 and sea water |
| CN101994063A (en) * | 2009-08-18 | 2011-03-30 | 宝山钢铁股份有限公司 | Weathering steel with yield strength of more than 700MPa and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3456743B2 (en) * | 1994-01-17 | 2003-10-14 | 新日本製鐵株式会社 | Coastal weathering steel |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0633326A1 (en) * | 1993-07-09 | 1995-01-11 | Kawasaki Steel Corporation | Sea water corrosion resistant steel suitable for hot and wet environments and method of manufacturing the same |
| CN1292429A (en) * | 2000-10-30 | 2001-04-25 | 宝山钢铁股份有限公司 | Low-alloy steel for oil casing pipe capable of resisting corrosion of CO2 and sea water |
| CN101994063A (en) * | 2009-08-18 | 2011-03-30 | 宝山钢铁股份有限公司 | Weathering steel with yield strength of more than 700MPa and manufacturing method thereof |
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Inventor after: Li Mingxian Inventor after: Liu Hongzhi Inventor after: Wang Xuelun Inventor after: Zhu Guojun Inventor after: Jiao Anjie Inventor after: Zhang Baoju Inventor after: Zhu Jingtao Inventor before: Ren Mingxin Inventor before: Li Mingxian Inventor before: Wang Xuelun Inventor before: Zhu Guojun Inventor before: Jiao Anjie Inventor before: Zhang Baoju |
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Denomination of invention: The invention relates to a pipeline steel resistant to chloride ion corrosion and a preparation method thereof Effective date of registration: 20211222 Granted publication date: 20151104 Pledgee: Rizhao Bank Co., Ltd Pledgor: RIZHAO STEEL HOLDING GROUP Co.,Ltd. Registration number: Y2021980015819 |