CN115074624A - Steel for hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube and preparation method thereof - Google Patents
Steel for hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube and preparation method thereof Download PDFInfo
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Abstract
The invention discloses steel for a rare earth-containing heat exchange tube with hydrogen sulfide corrosion resistance and a preparation method thereof, wherein the steel comprises the following chemical components in percentage by mass: c: 0.07% -0.10%, Si: 0.17% -0.30%, Mn: 0.40% -0.50%, Cr: 0.20% -0.50%, Mo: 0.15% -0.25%, Re (Ce and La): 0.0010% -0.0050%, Al: 0.010-0.040%, P is less than or equal to 0.012%, S is less than or equal to 0.003%, Ni is less than or equal to 0.03%, V is less than or equal to 0.02%, Cu is less than or equal to 0.05%, Ti is less than or equal to 0.02%, Nb is less than or equal to 0.04%, H is less than or equal to 0.00015%, O is less than or equal to 0.0012%, N is less than or equal to 0.0050%, Pb is less than or equal to 0.0010%, Sn is less than or equal to 0.015%, As is less than or equal to 0.015%, Sb is less than or equal to 0.010%, the sum is less than or equal to 350ppm, and the balance is Fe. From the components, the invention uses conventional alloying elements such as C, Si, Mn and the like to carry out alloying, adds trace rare earth Ce and La and adds a small amount of Cr and Mo to carry out microalloying, so that the performance of the invention has higher obdurability and corrosion resistance than the national Standard 10 Steel of high quality carbon constructional Steel (GB/T699-2015).
Description
Technical Field
The invention relates to the field of steel production for hot-rolled round tubes, in particular to steel for a rare earth-containing heat exchange tube with hydrogen sulfide corrosion resistance and a preparation method thereof.
Background
At present, the raw materials for producing and processing heat exchangers in China are mainly ordinary carbon steel 10 steel, but the 10 steel has defects in hydrogen sulfide corrosion resistance and is not corrosion-resistant. With the import of high acid and the increase of the refining amount of high sulfur crude oil in China, the equipment corrosion problem of each oil refinery and chemical plant becomes more and more serious. The heat exchanger is widely applied in the petroleum and chemical industry, electrochemical corrosion, particularly pitting corrosion, is more prone to occur in an aqueous medium due to low corrosion resistance of carbon steel materials, the heat exchanger becomes one of the devices with the fastest failure and the most serious loss in petrochemical equipment, and hydrogen sulfide is the root cause of corrosion of the heat exchanger. Therefore, how to realize the normal service life of the heat exchanger under the condition that the raw materials are not changed is the content of important research of steel mills and downstream users.
The existing 10-grade steel has poor corrosion resistance because sulfides are not effectively controlled. It is necessary to develop a new steel for heat exchangers which is resistant to corrosion by hydrogen sulfide. H resistance of materials 2 The S corrosion is mainly related to the grain boundary strength of the material, the original austenite grain size is refined and sulfides are improved by adding elements such As Cr, Mo and rare earth (Ce and La), and the content of harmful elements such As P, S, H, O, N, As, Sn, Pb, Sb and Bi is controlled to be low, so that the stability of the steel in a hydrogen sulfide medium is improved.
Disclosure of Invention
The invention aims to: provides a rare earth-containing steel for hydrogen sulfide corrosion-resistant heat exchange tubes and a preparation method thereof. Through the control of high aluminum content in the smelting process, 7-11 alkalinity high-alkalinity furnace slag is manufactured, impurities are further removed through RH high-vacuum molten steel circulation, and rare earth alloy is added in the later stage of vacuum treatment, so that the effective yield and high cleanliness of rare earth elements in steel are ensured. The purity of the molten steel can be controlled at the following level: T.O <15ppm in the steel; the grade requirement of non-metallic inclusions in steel (grading according to GB/T10561A method): class A is less than or equal to 0.5 grade, class B is less than or equal to 0.5 grade, class D is less than or equal to 1.0 grade, and class Ds is less than or equal to 1.0 grade.
The technical scheme adopted by the invention is as follows:
the steel for the hydrogen sulfide corrosion resistant heat exchange tube comprises the following chemical components in percentage by mass: c: 0.07% -0.10%, Si: 0.17% -0.30%, Mn: 0.40% -0.50%, Cr: 0.20% -0.50%, Mo: 0.15% -0.25%, Re (Ce and La): 0.0010% -0.0050%, Al: 0.010-0.040%, P is less than or equal to 0.012%, S is less than or equal to 0.003%, Ni is less than or equal to 0.03%, V is less than or equal to 0.02%, Cu is less than or equal to 0.05%, Ti is less than or equal to 0.02%, Nb is less than or equal to 0.04%, H is less than or equal to 0.00015%, O is less than or equal to 0.0012%, N is less than or equal to 0.0050%, Pb is less than or equal to 0.0010%, Sn is less than or equal to 0.015%, As is less than or equal to 0.015%, Sb is less than or equal to 0.010%, the sum is less than or equal to 350ppm, and the balance is Fe.
The chemical components of the alloy are added with Cr: 0.20% -0.50%, Mo: 0.15% -0.25% of Re (Ce 67% La 33%): 0.0010% -0.0050%, and reduction of Mn: 0.40-0.50%, P is less than or equal to 0.012%, S is less than or equal to 0.003%, and Al: 0.010% -0.040%.
The reasons for the limitations of the chemical composition of the steel for a sulfur-resistant gas cylinder pipe of the present invention are explained in detail below:
c: the carbon content can improve the stress corrosion cracking sensitivity of the steel in sulfide, and the C content is controlled between 0.07 percent and 0.10 percent.
Si: can be dissolved in ferrite and austenite to improve the strength and hardness of steel, especially the yield strength of steel, but the content of more than 0.30 percent is not favorable for resisting the corrosion of hydrogen sulfide, so the content of Si is controlled between 0.17 percent and 0.30 percent.
Mn: the steel has the effect of solid solution strengthening, can enlarge an austenite region, reduce the transformation temperature from austenite to ferrite, further refine ferrite grains, improve the toughness of the steel and compensate the strength loss caused by low carbon, but Mn is an easily segregated element, and segregation is generated when the content is too high, so that the steel is not beneficial to resisting the corrosion of hydrogen sulfide, and therefore, the content of Mn is controlled to be between 0.40 and 0.50 percent.
Cr: the steel added with chromium element can improve the structure stability after heat treatment, so the Cr element of the steel is controlled between 0.20 percent and 0.50 percent.
Mo: is favorable for promoting and improving the bearing capacity of the steel in a hydrogen sulfide medium and improving the pitting corrosion, so 0.15 to 0.25 percent of Mo is added.
Re: the rare earth elements are added into the steel, so that the content of non-metal inclusions in the steel is reduced, the inclusions can be dispersed and spheroidized, and the stability of the steel in a metal hydrogenation medium can be improved, so that 0.0010-0.0050% of Ce and La are added.
P: the phosphorus contained in the steel can inhibit the recombination of hydrogen atoms, so that the hydrogen increasing effect in the steel is increased, the stability of the steel in a hydrogen sulfide-containing medium is reduced, and therefore, the P content is controlled to be less than 0.012 percent and is as low as possible.
S: sulfur is a promoter for hydrogen absorption of steel, sulfide inclusions are sites for hydrogen accumulation, and the content of S in steel should be controlled to 0.003% or less and as low as possible in order to achieve the effect of hydrogen sulfide corrosion resistance.
Ni: the nickel element in the steel can reduce the resistance of the steel to corrosion cracking in a hydrogen sulfide medium, so that the Ni content in the steel is controlled to be less than 0.03 percent and as low as possible
H: hydrogen reduces the plasticity of the steel, mainly the low temperature impact work. Hydrogen can produce "hairlines" or form stress zones in the steel that reduce the stability of the steel against hydrogen sulfide corrosion. Therefore, the invention and the process control the H to be less than 0.00015%.
The five-harmful elements of As, Sn, Pb, Sb and Bi are positioned in the fourth and fifth main groups of the periodic table of elements, the oxidability is lower than that of iron, and the elements cannot be removed in the smelting link; the alloy has large atomic radius, is easy to enrich in crystal boundary and surface, is extremely uneven in distribution, increases the hot brittleness tendency of steel, causes low-temperature brittleness, reduces the thermoplasticity of the steel, leads to surface cracking of a casting blank, and reduces the corrosion resistance of steel. The steel grade contains Pb less than or equal to 0.0010%, Sn less than or equal to 0.015%, As less than or equal to 0.015%, Sb less than or equal to 0.010%, and Bi less than or equal to 0.010%.
The preparation method comprises the following steps:
1) molten iron with the sulfur content of less than 0.003 percent and scrap steel with the sulfur content of less than 0.010 percent are used as raw materials, a top-bottom combined blown converter is adopted for smelting, and the end point of the molten steel isw([S])<0.012 percent of the steel is deoxidized, alloyed and slagged in the tapping process, and the steel is kept away in the later stage of tappingSlag discharging is avoided;
2) and heating, slagging and alloying in the molten steel refining process. Deoxidizing the slag surface, depositing and deoxidizing molten steel by using aluminium deoxidant, and controlling the processw([Al]) = 0.035% -0.055%, end point of refiningw([S])<0.002%；
3) The molten steel is treated by RH vacuum, kept for 15-25 min under the condition that the vacuum is less than or equal to 100pa, and then alloyed by rare earth elements;
4) soft blowing is carried out after RH is broken, the soft blowing time is 5-20 min, then the molten steel is hoisted to be continuously cast to form a blank, and a low-silicon tundish covering agent is used in the casting process.
The invention further improves the scheme that: in the step 1), the deoxidation is as follows: the steel tapping amount is 10-30 percent, 0.5-1.0 kg/t of aluminum cakes are added for precipitating and deoxidizing molten steel, and the condition that the molten steel is refined to a station is ensuredw([Al])= 0.030%～0.060%。
The invention further improves the scheme that: in the step 1), slagging is as follows: the steel tapping amount of the molten steel is 70-90%, lime and premelted refining slag are used for slagging according to the ratio of 2: 1-3: 2, the lime consumption is 7.0-9.0 kg/t, and the slag at the initial stage of refining is enabled to be slagw(CaO)/ w(SiO 2 )=7.0～9.0、w(Al 2 O 3 )= 28%～35%。
The invention further improves the scheme that: in the step 2), calcium carbide and small aluminum strips are used for diffusion deoxidation of the slag surface, wherein the using amount of the calcium carbide is less than or equal to 0.7kg/t, and the using amount of the aluminum strips is less than or equal to 1.0 kg/t; precipitation deoxidation was carried out by feeding an aluminum wire.
The invention further improves the scheme that: in the step 2), the slag making in the refining process is that lime is supplemented according to the sulfur content of the molten steel, and the final slag of refiningw(CaO)/ w(SiO 2 )=8～11、w(CaO)=50%～60%、w(Al 2 O 3 )= 30%～38%、w(TFe+ MnO) <0.5%。
The invention further improves the scheme that: in the step 3), rare earth element alloying: 3-5 min before RH breaking, adding cerium iron and lanthanum iron alloy in a ratio of 1:1 in a vacuum storage bin.
The invention further improves the scheme that: in the step 4), the low-silicon tundish covering agentThe main components are as follows: SiO 2 2 ≤5.0%、w(CaO)=40%～50%、w(Al 2 O 3 )=28%～38%。
The invention has the beneficial effects that:
firstly, according to the steel for the hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube, trace rare earth Ce and La are added, and a small amount of Cr and Mo are added for micro-alloying, so that the strength and the grain refinement of the steel are improved, and the steel has stable hydrogen sulfide corrosion resistance compared with common 10 steel.
Secondly, according to the preparation method of the steel for the hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube, the smelting adopts the process of high aluminum content control, so that the low oxidation property and high cleanliness of molten steel are realized, and the effective yield of rare earth added into the steel is improved.
Thirdly, according to the preparation method of the steel for the rare earth-containing heat exchange tube, which is resistant to hydrogen sulfide corrosion, rare earth loss caused by reaction of rare earth and slag is avoided by adopting high-alkalinity slag and a high-alkalinity covering agent.
Fourthly, according to the preparation method of the steel for the hydrogen sulfide corrosion resistant rare earth-containing heat exchange tube, molten steel is subjected to vacuum circulation degassing to remove inclusions by using RH, rare earth is added from a vacuum storage bin at the later stage of RH, the high-efficiency yield of the rare earth is ensured, the rare earth with stable content in the steel is ensured, the effects of improving the inclusions and refining steel grains are achieved, and the high hydrogen sulfide corrosion resistance is finally ensured.
Fifth, according to the preparation method of the steel for the rare earth-containing heat exchange tube capable of resisting the corrosion of the hydrogen sulfide, the purity of the molten steel can be controlled to be as follows: T.O <13ppm in the steel; the grade requirement of non-metallic inclusions in steel (grading according to GB/T10561A method): class A is less than or equal to 0.5 grade, class B is less than or equal to 0.5 grade, class D is less than or equal to 1.0 grade, and class Ds is less than or equal to 1.0 grade.
Detailed Description
The invention provides a steel for a rare earth-containing heat exchange tube and a preparation method thereof.
The technical solution of the present invention is explained in detail by the following embodiments.
The embodiment is as follows:
1) use of lowThe sulfur molten iron and the low-sulfur scrap steel are used as raw materials, a top-bottom combined blown converter is adopted for smelting, and the molten steel end pointw([S])<0.012 percent of steel liquid is deoxidized, alloyed and slagged in the tapping process, the tapping amount is 10 to 30 percent, 0.5kg/t to 1.0kg/t of aluminum cake is added for the precipitation and deoxidation of the steel liquid, and the steel liquid is refined to the stationw([Al]) = 0.030% -0.060%. . The steel tapping amount of the molten steel is 70% -90%, slag is formed by lime and premelted refining slag according to the ratio of 2: 1-3: 2, and the lime consumption is 7.0-9.0 kg/t. In the later tapping stage, steel retaining operation is adopted to avoid slag falling;
2) and heating, slagging and alloying in the molten steel refining process. Using calcium carbide and small aluminum strips to carry out slag surface diffusion deoxidation, wherein the dosage of the calcium carbide is less than or equal to 0.7kg/t, the dosage of the aluminum strips is less than or equal to 1.0kg/t, carrying out precipitation deoxidation by feeding aluminum wires, and controlling the processw([Al]) And = 0.035% -0.055%. In the refining process, lime is added according to the sulfur content of the molten steel, and the final slag of refiningw(CaO)/ w(SiO 2 )=8～11、w(CaO)=50%～60%、w(Al 2 O 3 )= 30%～38%、w(TFe+ MnO) <0.5%, end point of refiningw([S])<0.002%；
3) The molten steel is subjected to RH vacuum treatment, the molten steel is kept for 15-25 min under the condition that the vacuum is less than or equal to 100pa, the molten steel is kept for 3-5 min before RH vacuum breaking, and cerium iron and lanthanum iron alloy are added through a vacuum bin;
4) soft blowing is carried out after RH is broken, the soft blowing time is 5-20 min, then the molten steel is hoisted to be continuously cast to form a blank, and a low-silicon tundish covering agent is used in the casting process.
The process conditions not limited in the above preparation method can be referred to the conventional techniques in the art.
Obtaining three batches of steel through the steps 1) to 4):
the grade requirement of non-metallic inclusions in steel (grading according to GB/T10561A method): class A is less than or equal to 0.5 grade, class B is less than or equal to 0.5 grade, class D is less than or equal to 1.0 grade, and class Ds is less than or equal to 1.0 grade.
The chemical compositions of the three batches of steel obtained through the steps 1) to 4) are shown in the table 1, and the corrosion resistance is shown in the table 2
| Elemental composition/%) | C | Si | Mn | P | S | Al | Cr | Mo | Re | Ti | Ni |
| Example 1 | 0.09 | 0.20 | 0.45 | 0.010 | 0.0018 | 0.033 | 0.35 | 0.20 | 0.0025 | 0.003 | 0.010 |
| Example 2 | 0.08 | 0.21 | 0.46 | 0.009 | 0.0020 | 0.029 | 0.36 | 0.20 | 0.0033 | 0.002 | 0.010 |
| Example 3 | 0.08 | 0.22 | 0.45 | 0.008 | 0.0014 | 0.026 | 0.35 | 0.20 | 0.0041 | 0.003 | 0.010 |
| Elemental composition/%) | Cu | Nb | V | As | Sn | Pb | Sb | Bi | [H] | [O] | [N] |
| Example 1 | 0.03 | 0.0004 | 0.002 | 0.006 | 0.001 | 0.002 | 0.001 | 0.001 | 0.00010 | 0.00086 | 0.0040 |
| Example 2 | 0.03 | 0.0004 | 0.002 | 0.005 | 0.001 | 0.002 | 0.001 | 0.002 | 0.00011 | 0.00093 | 0.0035 |
| Example 3 | 0.03 | 0.0004 | 0.002 | 0.006 | 0.001 | 0.002 | 0.001 | 0.002 | 0.00010 | 0.00010 | 0.0037 |
TABLE 1
| Steel grade | Corrosion rate/(mm. a) -1 ) |
| Examples 1 to 3 of this patent | 0.05~0.10 |
| Conventional 10 steel | 0.14~0.22 |
TABLE 2
Claims (8)
1. The steel for the rare earth-containing heat exchange tube is resistant to hydrogen sulfide corrosion and is characterized in that: the chemical components by mass percent are as follows: c: 0.07% -0.13%, Si: 0.17% -0.30%, Mn: 0.40% -0.50%, Cr: 0.20% -0.50%, Mo: 0.15% -0.25%, Ce and La in rare earth are in total: 0.0010% -0.0050%, Al: 0.010-0.040%, P is less than or equal to 0.012%, S is less than or equal to 0.003%, Ni is less than or equal to 0.03%, V is less than or equal to 0.02%, Cu is less than or equal to 0.05%, Ti is less than or equal to 0.02%, Nb is less than or equal to 0.04%, H is less than or equal to 0.00015%, O is less than or equal to 0.0012%, N is less than or equal to 0.0050%, Pb is less than or equal to 0.0010%, Sn is less than or equal to 0.0015%, As is less than or equal to 0.0015%, Sb is less than or equal to 0.0010%, the total is less than or equal to 350ppm, and the balance is Fe.
2. The method for preparing the steel for the rare earth-containing heat exchange tube, which is resistant to hydrogen sulfide corrosion, according to claim 1, is characterized in that: the method comprises the following steps:
1) molten iron with the sulfur content of less than 0.003 percent and scrap steel with the sulfur content of less than 0.010 percent are used as raw materials, a top-bottom combined blown converter is adopted for smelting, and the end point of the molten steel isw([S])<0.012 percent, deoxidizing, alloying and slagging the molten steel in the tapping process, and avoiding slag discharging by adopting steel retention operation in the later tapping stage;
2) heating, slagging and alloying in the molten steel refining process; deoxidizing the slag surface, depositing and deoxidizing molten steel by using aluminium deoxidant, and controlling the processw([Al]) = 0.035% -0.055%, end point of refiningw([S])<0.002%；
3) The molten steel is treated by RH vacuum, kept for 15-25 min under the condition that the vacuum is less than or equal to 100pa, and then alloyed by rare earth elements;
4) soft blowing is carried out after RH is broken, the soft blowing time is 5-20 min, then the molten steel is hoisted to be continuously cast to form a blank, and a low-silicon tundish covering agent is used in the casting process.
3. The steel for a rare earth-containing heat exchange tube resistant to hydrogen sulfide corrosion and the preparation method thereof according to claim 1, wherein the steel comprises the following components: in the step 1), the deoxidation is as follows: the steel tapping amount is 10 to 30 percent, 0.5kg/t to 1.0kg/t aluminum cakes are added for precipitating and deoxidizing molten steel, and the condition that the molten steel is refined to a station is ensuredw([Al])= 0.030%～0.060%。
4. The steel for a rare earth-containing heat exchange tube resistant to hydrogen sulfide corrosion and the preparation method thereof according to claim 1, wherein the steel comprises the following components: in the step 1), slagging is as follows: the steel tapping amount of the molten steel is 70-90%, lime and premelted refining slag are used for slagging according to the proportion of 2: 1-3: 2, the lime consumption is 7.0-9.0 kg/t, and the slag at the initial stage of refining is enabled to be slagw(CaO)/ w(SiO 2 ) = 7.0-9.0, whereinw(Al 2 O 3 )= 28%～35%。
5. The steel for a rare earth-containing heat exchange tube resistant to hydrogen sulfide corrosion and the preparation method thereof according to claim 1, wherein the steel comprises the following components: in the step 2), calcium carbide and aluminum strips are used for diffusion deoxidation of the slag surface, wherein the using amount of the calcium carbide is less than or equal to 0.7kg/t, and the using amount of the aluminum strips is less than or equal to 1.0 kg/t; precipitation deoxidation was carried out by feeding an aluminum wire.
6. The steel for a rare earth-containing heat exchange tube resistant to hydrogen sulfide corrosion and the preparation method thereof according to claim 1, wherein the steel comprises the following components: in the step 2), the slag making in the refining process is that lime is supplemented according to the sulfur content of the molten steel, and the final slag of refiningw(CaO)/ w(SiO 2 )=8～11、w(CaO)=50%～60%、w(Al 2 O 3 )= 30%～38%、w(TFe+ MnO) <0.5%。
7. The steel for a rare earth-containing heat exchange tube resistant to hydrogen sulfide corrosion and the preparation method thereof according to claim 1, wherein the steel comprises the following components: in the step 3), rare earth element alloying: 3-5 min before RH breaking, adding cerium iron and lanthanum iron alloy in a ratio of 1:1 in a vacuum storage bin.
8. The steel for a rare earth-containing heat exchange tube resistant to hydrogen sulfide corrosion and the preparation method thereof according to claim 1, wherein the steel comprises the following components: in the step 4), the low-silicon tundish covering agent mainly comprises the following components: SiO 2 2 ≤5.0%、w(CaO)=40%～50%、w(Al 2 O 3 )=28%～38%。
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| CN116732419A (en) * | 2023-05-31 | 2023-09-12 | 包头钢铁（集团）有限责任公司 | Production method of high weather-resistant coating-free steel for photovoltaic bracket |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367550A (en) * | 2011-10-28 | 2012-03-07 | 内蒙古包钢钢联股份有限公司 | Rare-earth-containing wet H2S corrosion resisting steel pipe used in heat exchanger, and production method thereof |
| RU2460822C1 (en) * | 2011-06-20 | 2012-09-10 | Общество с ограниченной ответственностью "Самарский инженерно-технический центр" | Nitrogen-bearing corrosion resistant steel for manufacture of oil-gas pipes |
| CN104928602A (en) * | 2015-06-25 | 2015-09-23 | 江苏省沙钢钢铁研究院有限公司 | H-resistant cable2S-corrosion pipeline steel wide and thick plate and production method thereof |
| CN111809018A (en) * | 2020-06-17 | 2020-10-23 | 包头钢铁（集团）有限责任公司 | Method for improving hydrogen cracking resistance and hydrogen sulfide corrosion resistance of steel blank for 16MnHIC flange |
-
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- 2022-06-22 CN CN202210712958.8A patent/CN115074624A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2460822C1 (en) * | 2011-06-20 | 2012-09-10 | Общество с ограниченной ответственностью "Самарский инженерно-технический центр" | Nitrogen-bearing corrosion resistant steel for manufacture of oil-gas pipes |
| CN102367550A (en) * | 2011-10-28 | 2012-03-07 | 内蒙古包钢钢联股份有限公司 | Rare-earth-containing wet H2S corrosion resisting steel pipe used in heat exchanger, and production method thereof |
| CN104928602A (en) * | 2015-06-25 | 2015-09-23 | 江苏省沙钢钢铁研究院有限公司 | H-resistant cable2S-corrosion pipeline steel wide and thick plate and production method thereof |
| CN111809018A (en) * | 2020-06-17 | 2020-10-23 | 包头钢铁（集团）有限责任公司 | Method for improving hydrogen cracking resistance and hydrogen sulfide corrosion resistance of steel blank for 16MnHIC flange |
Non-Patent Citations (1)
| Title |
|---|
| 唐纳德•皮克纳等, 机械工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116732419A (en) * | 2023-05-31 | 2023-09-12 | 包头钢铁（集团）有限责任公司 | Production method of high weather-resistant coating-free steel for photovoltaic bracket |
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