WO2021169937A1 - 一种搪玻璃用钢及其制造方法 - Google Patents
一种搪玻璃用钢及其制造方法 Download PDFInfo
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- WO2021169937A1 WO2021169937A1 PCT/CN2021/077405 CN2021077405W WO2021169937A1 WO 2021169937 A1 WO2021169937 A1 WO 2021169937A1 CN 2021077405 W CN2021077405 W CN 2021077405W WO 2021169937 A1 WO2021169937 A1 WO 2021169937A1
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Definitions
- the invention relates to a metal material and a manufacturing method thereof, in particular to a steel material and a manufacturing method thereof.
- the glass lining process is a process in which glassy enamel containing high quartz components is coated on the surface of a metal substrate, and then sintered at a high temperature to make the enamel firmly adhere to the surface of the substrate to form a composite material.
- glass-lined equipment such as glass-lined reactors, glass-lined storage tanks, etc., made of steel plates as the metal base, has good durability due to the stability of glass and the high strength of metal. Abrasiveness, high corrosion resistance to various acids and organic solvents, and good corrosion resistance to alkaline solutions, so it has a wide range of applications.
- the steel plate undergoes repeated enameling and high-temperature firing after forming, welding, and other processing.
- the firing temperature is between 930°C and 870°C.
- coating defects such as scale explosion, poor adhesion and pinholes are often produced. These defects are also the main problems to be solved by the existing special glass-lined steel plates.
- it is also necessary to improve the workability of the steel sheet. Easy to punch, easy to bend and easy to punch, etc., to improve the low temperature toughness of the steel plate to meet the service requirements of glass-lined equipment under -20°C or even -40°C.
- the commonly used steel grades are still Q245R and other ordinary pressure vessel steels.
- this type of steel is not only prone to enamel defects such as scale explosion, but also the manufactured glass-lined steel
- the equipment cannot meet the service requirements of -20°C and below.
- the existing special glass-lined steel has a relatively high yield strength (such as above 0.90), and the yield strength is mostly 350MPa or even 400MPa or more. Due to the high yield strength, the strength fluctuations between the same plate and different steel plates are also large. Molding processing such as reeling and punching brings difficulties, and sometimes requires repeated molding for many times, and the workability is poor, which is not conducive to the production of glass-lined equipment.
- the low-temperature toughness of glass-lined equipment made of the existing dedicated glass-lined steel is also poor, and cannot meet the service requirements under -20°C and lower temperature conditions.
- One of the objectives of the present invention is to provide a glass-lined steel, which aims to solve the problems of difficult processing and poor low-temperature toughness of the existing glass-lined steel.
- the glass-lined steel of the present invention has excellent workability and low-temperature toughness, as well as excellent enameling properties, and can be effectively used for making glass-lined equipment.
- the present invention provides a glass-lined steel whose chemical element mass percentage is:
- the balance is Fe and other inevitable impurities
- the microstructure of the glass-lined steel is ferrite; or ferrite + cementite, preferably the volume percentage content of ferrite is more than 90%.
- the ferrite crystal grains are uniform equiaxed crystal grains, and the average crystal grain diameter is not more than 40 ⁇ m.
- C In the glass-lined steel of the present invention, carbon is an important strengthening element. As the carbon content in the steel increases, the strength increases but the plasticity and toughness decrease.
- the microstructure in the steel is mainly composed of pearlite + ferrite, and the higher the pearlite component, the higher the strength of the steel.
- the carbon content is reduced as much as possible, so that the structure in the steel is composed of ferrite or ferrite + cementite, so as to improve the plasticity and low temperature toughness of the steel, and improve the workability of the steel. Therefore, the mass percentage of C in the glass-lined steel of the present invention is controlled to be between 0.015 and 0.060%.
- the mass percentage of C can be controlled between 0.02 and 0.05%.
- Si is a strengthening matrix element and also a deoxidizing element, and can improve the strength of the steel sheet and the resistance to softening during high-temperature firing.
- Si content is too high, it will also damage the plasticity and toughness of the steel plate while increasing the strength, and it is also not conducive to welding.
- the mass percentage of Si in the glass-lined steel of the present invention is controlled to be between 0.01 and 0.50%.
- the mass percentage of Si can be controlled between 0.10 and 0.40%.
- Mn In the glass-lined steel of the present invention, Mn, like Si, is both a strengthening matrix element and a deoxidizing element. It can also improve the strength of the steel sheet and its resistance to softening during high-temperature firing. In order to avoid excessively high strength or excessive strength fluctuation range that is not conducive to the workability of the steel sheet, and to improve the plasticity and low temperature toughness of the steel sheet, the mass percentage of Mn in the glass-lined steel of the present invention is controlled to be between 0.20 and 1.5%.
- the mass percentage of Mn can be controlled between 0.50 and 1.2%.
- P In the glass-lined steel of the present invention, P is also a useful strengthening element, which can improve the strength of the steel sheet and the resistance to softening during high-temperature firing.
- the mass percentage of P in the glass-lined steel of the present invention is controlled to be 0.005 to 0.10 %between.
- the mass percentage of P is controlled between 0.005 and 0.08%. In some other embodiments, the mass percentage of P is 0.008-0.03%.
- Al is a strong deoxidizing element, which can be used to reduce the oxygen content in the steel, thereby reducing oxide inclusions in the steel, and improving the plasticity and toughness of the steel.
- the mass percentage of Al is controlled between 0.010% and 0.070%.
- Ti is a strong carbon and nitride forming element. Adding enough Ti to the steel can fix carbon and nitrogen, and combine with titanium and sulfur to form a compound.
- the types of second phase particles that can finally be formed include TiC, TiCN, TiN, TiS and Ti 4 C 2 S 2, etc. They can exist in the form of inclusions and precipitated phases.
- these carbonitride precipitates of Ti can also play a role in preventing grain growth in the heat-affected zone during welding, thereby improving welding performance. But when the titanium content is too high, titanium preferentially forms coarse titanium nitride inclusions with nitrogen. Therefore, the mass percentage of Ti in the glass-lined steel of the present invention is controlled to be between 0.10% and 0.30%.
- the glass-lined steel of the present invention also contains at least one of the following elements:
- an appropriate amount of copper, chromium, nickel, and molybdenum can effectively improve the bubbles generated during the enameling process of the steel plate and improve the adhesion of the enamel.
- excessively high content of copper, chromium, nickel and molybdenum will not only increase the cost of the alloy, but also easily affect the adhesion and surface quality of the enamel during the coating process.
- the glass-lined steel of the present invention further contains at least two of Cu, Cr, Ni and Mo; preferably, Cu ⁇ 0.20%, more preferably ⁇ 0.10%; Cr ⁇ 0.20% , More preferably ⁇ 0.10%; Ni ⁇ 0.20%, more preferably ⁇ 0.05%; Mo ⁇ 0.10%, more preferably ⁇ 0.05%.
- Cu 0.01-0.10%; Cr: 0.01-0.10%; Ni: 0.005-0.05%; Mo: 0.005-0.03%.
- the glass-lined steel of the present invention satisfies Ti/C ⁇ 3.0, and Ti and C in the formula respectively represent the mass percentages of the corresponding elements.
- the glass-lined steel of the present invention satisfies Ti/C ⁇ 4.0, and Ti and C in the formula respectively represent the mass percentages of the corresponding elements.
- the amount of titanium added is related to carbon.
- the element body + cementite structure can effectively improve the plasticity and toughness of the steel, reduce the yield strength, and improve the workability and low temperature toughness of the steel.
- the inevitable impurity elements include S and N, wherein: S ⁇ 0.03%; and/or N ⁇ 0.008%.
- sulfur can combine with manganese in the steel to form plastic inclusions manganese sulfide, which is particularly unfavorable to the transverse plasticity and toughness of the steel, so the content of sulfur should be as low as possible.
- plastic manganese sulfide inclusions can be avoided to a certain extent, and composite manganese-titanium sulfide inclusions are formed, which are spherical or round, which reduces the damage of manganese sulfide inclusions to plasticity and toughness.
- These inclusions are beneficial hydrogen traps and can effectively improve the anti-scale explosion performance of the steel plate.
- the sulfur content is controlled at S ⁇ 0.03%. In some embodiments, the content of S is 0.001-0.03%.
- titanium-containing steel nitrogen is very easy to form titanium nitride inclusions. From the solid solubility product of nitrogen and titanium, titanium nitride may precipitate to form coarse inclusions at high temperatures or even in molten steel. This kind of square or prismatic inclusions will greatly damage the plasticity and toughness of steel. Therefore, it is necessary to reduce the nitrogen content in steel as much as possible, that is, control N ⁇ 0.008%. In some embodiments, the content of N is 0.001-0.008%.
- the inventors creatively discovered through multiple experiments that when Ti eff /C ⁇ 4.0, the yield ratio of steel can be significantly reduced, and the tensile strength of steel can be reduced not too much. At the same time of strength, the steel achieves a better yield strength range.
- the glass-lined steel of the present invention further contains at least one of Nb: 0.005 to 0.10%, V: 0.005 to 0.05%, and B: 0.0005 to 0.005%.
- Nb and V are also strong carbon and nitride forming elements like titanium. Adding a suitable amount of niobium and/or vanadium can replace part of the titanium, because the higher the titanium content, the easier The formation of coarse TiN inclusions will damage the plasticity and toughness of the steel plate.
- Nb and V play a role of precipitation strengthening and solid solution strengthening, and the precipitated phases of carbon and nitride are also beneficial irreversible hydrogen storage traps to improve the anti-scaling performance of steel.
- B is very beneficial to improve the anti-scale explosion performance of steel.
- the mass percentage of Nb is controlled between 0.005 and 0.10%
- the mass percentage of V is controlled between 0.005 and 0.05%
- the mass percentage of B is controlled between 0.0005 and 0.005%. between.
- each chemical element satisfies: Ti+(48/93)Nb+(48/51)V ⁇ 4C, where Ti, Nb, V and C each represent the mass percentage of each element.
- the glass-lined steel of the present invention further contains at least one of Ca: 0.001 to 0.005% and Mg: 0.0005 to 0.005%.
- Ca and Mg mainly play a role in changing the characteristics of inclusions. Due to the requirement of improving the hydrogen storage performance of steel plate, steel contains more inclusions and precipitated phases, and the refined and spherical inclusions not only help to improve the hydrogen storage effect, but also help to reduce the damage to the plasticity and toughness of steel. , A small amount of Ca or/and Mg can play a role in changing the characteristics of inclusions. Therefore, in the glass-lined steel of the present invention, the mass percentage of Ca can be controlled between 0.001 and 0.005%, and the mass percentage of Mg can be between 0.0005 and 0.005%.
- each chemical element further satisfies at least one of the following items:
- the content of C element is 0.035-0.045%.
- the glass-lined steel of the present invention its performance satisfies at least one of the following items: the yield strength is 205 ⁇ 345MPa, the elongation A50 ⁇ 30%, and the Charpy impact energy at -40°C is Akv ⁇ 34J, yield ratio ⁇ 0.8. Further, the performance of the glass-lined steel of the present invention also includes at least one of the following items: the tensile strength is 400-440MPa, the Charpy impact energy at 0°C Akv ⁇ 120J, the Charpy impact energy at -20°C Akv ⁇ 100J.
- the yield strength is 205 ⁇ 345MPa, the elongation A50 ⁇ 30%, the Charpy impact energy at -40°C, Akv ⁇ 34J, the yield strength
- the ratio is less than or equal to 0.8; and it is preferably further satisfied: the tensile strength is 400-440 MPa, the Charpy impact energy at 0°C, Akv ⁇ 120J, and the Charpy impact energy at -20°C, Akv ⁇ 100J.
- the preferred yield strength is 245-300MPa; the preferred tensile strength is 405-435MPa; the preferred A50 ⁇ 35%, such as 35%-45%; the preferred yield ratio ⁇ 0.73; the preferred Charpy impact energy at -40°C Akv ⁇ 85J.
- the thickness of the glass-lined steel of the present invention is 10-25 mm.
- another object of the present invention is to provide a method for manufacturing glass-lined steel.
- the glass-lined steel obtained by the manufacturing method has excellent workability and low-temperature toughness, as well as excellent enameling properties. .
- the present invention proposes the above-mentioned manufacturing method of glass-lined steel, which includes the following steps:
- Hot rolling controlling the end temperature of hot rolling to be 800-920°C.
- the method for manufacturing glass-lined steel according to the present invention further includes step (5): heat treatment in addition to the above steps.
- the purpose of converter smelting and refining is to remove harmful elements and impurity elements in the steel, and add necessary alloying elements to achieve the design The target composition requirements.
- Continuous casting is used to cast slabs. Compared with die casting, continuous casting has the characteristics of uniform composition and better surface quality. Therefore, the performance of steel plates manufactured by continuous casting process is more uniform and more suitable for the manufacture of glass-lined steel.
- the heating temperature is controlled within the range of 1100 to 1250°C, so that after the slab is fully heated, the microstructure in the steel is completely austenitized and homogenized, so as to obtain a uniform display after rolling. Micro-organization.
- controlling the temperature at the end of the hot rolling to be 800-920°C can ensure the full transformation of the ferrite structure and the grain growth after rolling, and also prevent the abnormal growth of the grains.
- the alloying elements such as titanium, niobium and vanadium in the solid solution state will re-precipitate as fine and dispersed particles distributed on the ferrite matrix as the hot rolling deformation progresses and the temperature drops. On the one hand, it fixes the carbon in the steel, Elements such as nitrogen, on the other hand, are also conducive to the refinement of ferrite grains.
- step (4) air cooling or water cooling is adopted.
- either a single steel plate or multiple steel plates can be piled up for air cooling, and finally cooled to room temperature.
- the final cooling temperature of the water cooling is controlled to be 650-750°C, and the cooling rate is not more than 50°C/s. Then air-cooled to room temperature.
- the final cooling temperature of water cooling is 650-750°C, and the water cooling is to accelerate the cooling, thereby effectively preventing the further growth of ferrite grains and precipitated phases, which is beneficial to improve the plasticity and plasticity of the steel plate.
- Toughness, to prevent abnormal growth of ferrite grains, and relatively small precipitation is beneficial to improve the hydrogen storage performance of the steel sheet. Accelerated cooling can also speed up the production rhythm, but an excessively high cooling rate will cause bad plate shape and even cause insufficient recrystallization of ferrite and grain growth. Therefore, when water cooling is used for cooling, the cooling rate should be controlled not to be greater than 50°C/s.
- the heat treatment temperature is 880-980°C.
- the heat preservation time is 30 minutes to 3 hours.
- the original structure of the steel plate namely the ferrite structure or the ferrite + cementite structure
- the original structure of the steel plate is austenitized and then transformed into ferrite during the cooling process. It can appropriately reduce the yield strength of the steel, improve the toughness of the steel, and then better improve the workability and low-temperature toughness of the steel plate.
- the glass-lined steel and the manufacturing method thereof of the present invention have the following advantages and beneficial effects:
- the present invention can stably control the yield strength of the steel plate within an appropriate range through the control of the steel composition and processing technology, and reduce the adverse effects of excessively high yield strength or excessive fluctuations on workability.
- the elongation A50 of the glass-lined steel of the present invention is greater than or equal to 30%, which can meet the manufacturing requirements of complex molded parts.
- the manufactured glass-lined container meets the requirements of impact toughness at -40°C or even lower temperature.
- the yield strength of the glass-lined steel of the present invention satisfies 205-345MPa, the elongation A50 ⁇ 30%, the Charpy impact energy at -40°C, Akv ⁇ 34J, and the yield ratio ⁇ 0.8.
- it has excellent workability and low-temperature toughness, as well as excellent enameling properties, and can be effectively used to make glass-lined equipment.
- Fig. 1 shows the microstructure morphology of the glass-lined steel according to the present invention in the hot-rolled state in Example 2.
- Fig. 2 shows the microstructure morphology of the hot-rolled sheet of the glass-lined steel of the present invention after being fired at a simulated high temperature for 5 times in Example 2.
- the glass-lined steel of the present invention is prepared by the following steps:
- Heating The heating temperature is 1050 to 1250°C.
- Hot rolling control the final temperature of hot rolling to be 800-920°C.
- Air cooling or water cooling is adopted.
- air cooling cool to room temperature
- water cooling the final cooling temperature of water cooling is controlled to be 650-750°C, and the cooling rate is not more than 50°C/s, and then air-cooled to room temperature.
- the heat treatment temperature is 880-980°C, and the holding time is 30 minutes to 3 hours.
- Table 1 lists the mass percentages of the chemical elements in the glass-lined steel of Examples 1-6.
- Table 2 lists the specific process parameters of each step of the manufacturing method of Examples 1-6.
- Table 3 lists the relevant performance parameters of the glass-lined steel of Examples 1-6.
- the above-mentioned steel plate is sawed and cut into a block sample with a size of 150mm ⁇ 150mm, and then both sides are polished before shot blasting, and the surface is cleaned with alcohol and then painted.
- the coating is made of glass glaze (the quartz component in the glaze is about 71%), single-sided or double-sided wet spraying method, divided into one base glaze and two top glazes, the firing temperature of the base glaze At 890-920°C, the firing temperature of the two surface glazes is 870-900°C. After enameling, place it at room temperature for a week to observe whether there are any scaly spots on the surface.
- Fig. 1 shows the microstructure morphology of the glass-lined steel according to the present invention in the hot-rolled state in Example 2. It can be seen from Figure 1 that when the glass-lined steel in this embodiment is in the hot rolled state, the microstructure under the optical microscope is mainly composed of ferrite, the crystal grains are uniformly equiaxed, and the average crystal grain diameter Not more than 40 ⁇ m.
- the delivered steel plate has such a microstructure, which is conducive to maintaining a fine and uniform microstructure state, that is, the heritability of the microstructure after being processed and formed and fired at multiple high temperatures, thereby improving the service state of the glass-lined equipment Performance under.
- Fig. 2 shows the microstructure morphology of the hot-rolled sheet of the glass-lined steel of the present invention after being fired at a simulated high temperature for 5 times in Example 2.
- the specific heat treatment process is: 900°C ⁇ 10min+air cooling (1 time) ⁇ 940°C ⁇ 10min+air cooling (1 time) ⁇ 870°C ⁇ 10min+air cooling (3 times).
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Abstract
Description
Claims (15)
- 一种搪玻璃用钢,其特征在于,其化学元素质量百分比为:C:0.015~0.060%;Si:0.01~0.50%;Mn:0.20~1.5%;P:0.005~0.10%;Al:0.010~0.070%;Ti:0.10~0.30%;余量为Fe和其他不可避免的杂质;其中所述搪玻璃用钢的微观组织为铁素体;或者铁素体+渗碳体;优选地,所述铁素体晶粒为均匀的等轴晶粒,平均晶粒直径不大于40μm。
- 如权利要求1所述的搪玻璃用钢,其特征在于,其还含有下述各元素的至少其中之一:Cu≤0.50%;Cr≤0.50%;Ni≤0.50%;Mo≤0.50%;并且满足:Cu+Cr+Ni+Mo≤1.0%。
- 如权利要求1所述的搪玻璃用钢,其特征在于,其满足Ti/C≥3.0;优选地,Ti/C≥4.0。
- 如权利要求1所述的搪玻璃用钢,其特征在于,其中不可避免的杂质元素包括S和N,其中:S≤0.03%;并且/或者N≤0.008%。
- 如权利要求4所述的搪玻璃用钢,其特征在于,其各化学元素还满足:Ti eff/C≥4.0,其中Ti eff=Ti-1.5×S-3.43×N。
- 如权利要求1所述的搪玻璃用钢,其特征在于,还含有Nb:0.005~0.10%、V:0.005~0.05%、B:0.0005~0.005%中的至少其中之一。
- 如权利要求6所述的搪玻璃用钢,其特征在于,当含有Nb和V元素时,各化学元素满足:Ti+(48/93)Nb+(48/51)V≥4C。
- 如权利要求1所述的搪玻璃用钢,其特征在于,还含有Ca:0.001~0.005%、 Mg:0.0005~0.005%中的至少其中之一。
- 如权利要求1所述的搪玻璃用钢,其特征在于,其各化学元素含量进一步满足下述各项的至少其中之一:C:0.02~0.05%;Si:0.10~0.40%;Mn:0.50~1.2%;P:0.005~0.08%。
- 如权利要求9所述的搪玻璃用钢,其特征在于,C元素含量为0.035~0.045%。
- 如权利要求1-10中任意一项所述的搪玻璃用钢,其特征在于,其性能满足下述各项的至少之一:屈服强度为205~345MPa,延伸率A50≥30%,-40℃夏比冲击功Akv≥34J,屈强比≤0.8;优选地,所述搪玻璃用钢的性能还满足下述各项的至少之一:抗拉强度为400~440MPa,0℃夏比冲击功Akv≥120J,-20℃夏比冲击功Akv≥100J。
- 如权利要求1-11中任意一项所述的搪玻璃用钢的制造方法,其特征在于,其包括步骤:(1)冶炼,精炼,连铸,以得到板坯;(2)加热:加热温度1050~1250℃;(3)热轧:控制热轧终了温度为800~920℃;(4)冷却;和任选的(5)热处理。
- 如权利要求12所述的制造方法,其特征在于,在步骤(4)中,采用空冷或水冷进行冷却。
- 如权利要求13所述的制造方法,其特征在于,在步骤(4)中,采用空冷进行冷却,采取单张钢板冷或多张钢板堆冷的方式进行空冷,最终冷至室温;或采用水冷进行冷却,水冷的终冷温度为650~750℃,冷却速率不大于50℃/s,然后空冷至室温。
- 如权利要求12-14中任意一项所述的制造方法,其特征在于,在步骤(5)中,热处理温度为880~980℃,热处理保温时间为30分钟到3小时。
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- 2021-02-23 EP EP21761106.0A patent/EP4112761A4/en active Pending
- 2021-02-23 AU AU2021226442A patent/AU2021226442A1/en active Pending
- 2021-02-23 WO PCT/CN2021/077405 patent/WO2021169937A1/zh unknown
- 2021-02-23 JP JP2022551019A patent/JP2023515558A/ja active Pending
- 2021-02-23 KR KR1020227032678A patent/KR20220144394A/ko unknown
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CN114293092A (zh) * | 2021-09-08 | 2022-04-08 | 武汉钢铁有限公司 | 一种适用于-70℃环境下的低合金高强钢 |
WO2023093798A1 (zh) * | 2021-11-25 | 2023-06-01 | 宝山钢铁股份有限公司 | 一种双面搪瓷内胆用高强度冷轧钢板及其制造方法 |
CN114427066A (zh) * | 2022-01-26 | 2022-05-03 | 北京首钢股份有限公司 | 一种搪瓷钢及其钢基板和制备方法 |
CN114427066B (zh) * | 2022-01-26 | 2023-02-24 | 北京首钢股份有限公司 | 一种搪瓷钢及其钢基板和制备方法 |
CN115491599A (zh) * | 2022-09-19 | 2022-12-20 | 马鞍山钢铁股份有限公司 | 一种400MPa级双面搪瓷用冷轧钢板及其生产方法 |
CN115491599B (zh) * | 2022-09-19 | 2023-07-25 | 马鞍山钢铁股份有限公司 | 一种400MPa级双面搪瓷用冷轧钢板及其生产方法 |
CN115369329A (zh) * | 2022-09-30 | 2022-11-22 | 武汉钢铁有限公司 | 一种宽幅薄规格高表面质量热轧深冲搪瓷钢及生产方法 |
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EP4112761A4 (en) | 2023-08-16 |
CN113373385A (zh) | 2021-09-10 |
KR20220144394A (ko) | 2022-10-26 |
AU2021226442A1 (en) | 2022-10-13 |
EP4112761A1 (en) | 2023-01-04 |
US20230114417A1 (en) | 2023-04-13 |
JP2023515558A (ja) | 2023-04-13 |
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