WO2022171112A1 - 一种低成本高温搪瓷用热轧钢板及其制造方法 - Google Patents

一种低成本高温搪瓷用热轧钢板及其制造方法 Download PDF

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WO2022171112A1
WO2022171112A1 PCT/CN2022/075614 CN2022075614W WO2022171112A1 WO 2022171112 A1 WO2022171112 A1 WO 2022171112A1 CN 2022075614 W CN2022075614 W CN 2022075614W WO 2022171112 A1 WO2022171112 A1 WO 2022171112A1
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temperature
hot
low
rolled steel
enamel
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PCT/CN2022/075614
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English (en)
French (fr)
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王双成
孙全社
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宝山钢铁股份有限公司
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Priority to MX2023009048A priority Critical patent/MX2023009048A/es
Priority to KR1020237026162A priority patent/KR20230128092A/ko
Priority to EP22752272.9A priority patent/EP4273290A1/en
Priority to AU2022219117A priority patent/AU2022219117A1/en
Priority to JP2023547462A priority patent/JP2024506596A/ja
Publication of WO2022171112A1 publication Critical patent/WO2022171112A1/zh

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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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/009—Pearlite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a steel material and a manufacturing method thereof, in particular to a low-cost hot-rolled steel sheet for high-temperature enamel and a manufacturing method thereof.
  • This kind of large-volume water heater inner tank usually needs to use special high-temperature glaze during production, and the high enamelling temperature process is matched with it, and the enamelling temperature can usually reach 870-950°C. Therefore, its requirements for the steel plates used are also increased accordingly. It is necessary for the steel plates to have high temperature resistance while ensuring the enamel performance. After high temperature firing, the steel plates can still have high enough yield strength properties to ensure the final use of the product. performance.
  • the publication number is CN101812630A
  • the publication date is the Chinese patent document on August 25, 2010, and a kind of hot-rolled high-strength enamel steel plate for deep drawing and a manufacturing method thereof are disclosed, and the chemical element composition adopted by this enamel steel plate is C: 0.02 ⁇ 0.10%, Si ⁇ 0.10%, Mn: 0.05 ⁇ 1.00%, P ⁇ 0.05%, S: 0.005 ⁇ 0.035%, Al: 0.01 ⁇ 0.10%, N ⁇ 0.015%, Ti ⁇ 0.10%, the balance is iron and inevitable impurities.
  • the publication number is CN103540845A
  • the publication date is the Chinese patent document on January 29, 2014
  • a hot-rolled sheet enamel steel is also disclosed.
  • Mn 0.10 ⁇ 0.50%
  • P ⁇ 0.020% 0.10 ⁇ 0.010%
  • Ti 0.04 ⁇ 0.10%
  • Al 0.02 ⁇ 0.08%
  • N ⁇ 0.008% the rest are Fe and inevitable inclusions
  • Ti/C 1.0 to 1.5.
  • the publication number is CN102181805A, and the publication date is the Chinese patent document on September 14, 2011, which discloses a thin slab continuous casting and rolling line to produce a steel plate for water heater enamel lining and a method, wherein the steel plate used for water heater lining enamelling adopts
  • the chemical element composition is: carbon 0.03-0.10%, manganese 0.15-0.40%, silicon ⁇ 0.06%, sulfur 0.004-0.040%, phosphorus ⁇ 0.15%, aluminum 0.03-0.05%, nitrogen 0.002-0.008%, titanium 0.02-0.10 %, the rest is iron and inevitable impurities.
  • Ti element is added to the composition.
  • Ti is one of the most commonly used alloying elements in enamel steel. It can form compounds such as TiC and TiN with C and N, and act as a hydrogen storage trap to resist scale explosion.
  • the TiC precipitation phase also has the effect of precipitation strengthening.
  • this design method of adding Ti element not only has a relatively high production cost, but also the TiC precipitation formed by Ti and C will appear coarsening and growing when annealed at high temperature, and the precipitation strengthening effect will be significantly weakened. After sintering at a high temperature above 870°C, the yield strength will drop significantly, usually below 300MPa, which cannot meet the design requirements of large-volume water heater liner.
  • the present invention expects to obtain a low-cost hot-rolled steel sheet for high-temperature enamel, which has a low production cost and can obtain good coating without adding precious alloying elements such as Ti, Nb, and V. Enamel adaptability.
  • the low-cost hot-rolled steel sheet for high-temperature enamelling still has excellent mechanical properties after high-temperature enamelling treatment, and can meet various demands of the inner tank of a large-container water heater for high-temperature enamel steel, which is of great practical significance.
  • One of the objectives of the present invention is to provide a low-cost hot-rolled steel sheet for high-temperature enamel, which has a low production cost, and can obtain good enameling adaptability without adding precious alloying elements such as Ti, Nb, and V.
  • the low-cost hot-rolled steel sheet for high-temperature enamelling still has excellent mechanical properties after high-temperature enamelling treatment, and can meet various demands of the inner tank of a large-container water heater for high-temperature enamel steel, which is of great practical significance.
  • the present invention proposes a low-cost hot-rolled steel sheet for high-temperature enamel, which in addition to Fe and inevitable impurities, also contains the following chemical elements in the following mass percentages:
  • the hot-rolled steel sheet for low-cost high-temperature enamel does not contain Ti, Nb and V;
  • Each chemical element also satisfies: P ⁇ (N-14 ⁇ B/11) ⁇ 10 3 >0.3; during calculation, P, N and B are respectively substituted into the values before the mass percentage of the corresponding element, for example, when P When the mass percentage of is 0.10%, the value substituted into the formula is 0.10.
  • the mass percentage content of each chemical element is:
  • the present invention compared with the conventional enamel steel for water heaters, creatively adopts a composition system with high P, N, and B, avoids the addition of precious alloying elements such as Ti, Nb, and V, and can effectively reduce the production cost.
  • C element is an important strengthening element in steel. It can be solid-dissolved in ferrite or form pearlite structure under certain conditions, thereby strengthening the matrix structure and improving the yield strength of the steel plate.
  • carbide-forming elements such as Ti, Nb, and V are not added in the present invention, when the carbon content is too high, the proportion of pearlite formed is too high, which will lead to the production of a large amount of CO during the enamel firing process. and other gases, resulting in poor bubble structure in the enamel layer and defects such as pinholes, which seriously affect the quality of enamel coating. Therefore, in the low-cost hot-rolled steel sheet for high-temperature enamel according to the present invention, the mass percentage content of element C is limited to 0.03-0.12%.
  • Si element can play a role in solid solution strengthening in steel.
  • Si can also improve the resistance to high temperature deformation and improve the softening resistance of steel plates during high temperature enamel firing.
  • the content of Si element in the steel should not be too high.
  • the mass percentage content of Si element is limited between 0.1 and 0.5%.
  • Mn element is one of the cheapest alloying elements that can improve the strength of the steel sheet, and it is an important element for obtaining high strength of the steel of the present invention.
  • Mn element can also play a role in expanding the austenite phase area and reducing the temperature of the Ac3 point, which is unfavorable for the enamel performance of the steel plate, because the austenite phase has a stronger ability to dissolve hydrogen than the ferrite phase. , it is more likely to cause scaling defects after cooling, so excessive Mn should not be added to the steel. Based on this, in the low-cost hot-rolled steel sheet for high-temperature enamel of the present invention, the mass percentage content of Mn element is limited between 0.3 and 1.5%.
  • P is an important strengthening element, and its solid solution strengthening effect can still be fully exerted after the steel is annealed at high temperature.
  • excessive P should not be added to the steel.
  • the mass percentage content of P element is limited between 0.03 and 0.10%.
  • Al is a strong deoxidizing element. In order to keep the O content in the steel at a low value, it is often necessary to use Al for deoxidation in medium and low carbon steel. In addition, the dissolved Al element in the steel can also combine with free nitrogen to precipitate AlN, and its precipitation temperature is high, which can play a role in refining austenite grains. In the present invention, the steel plate still needs to have high yield strength under the condition of air cooling after high temperature enamelling, and the high temperature grain refinement effect of AlN makes the steel plate still have a fine grain structure after high temperature enamelling, which can give full play to the fine grain structure. Crystal strengthening mechanism. Therefore, in the low-cost hot-rolled steel sheet for high-temperature enamel according to the present invention, the mass percentage content of Al element is limited between 0.02 and 0.10%.
  • Cr and Cu Adding appropriate amount of Cr and Cu elements to steel is beneficial to surface deposition, which can improve the adhesion between it and the enamel, and improve the anti-scalding performance of steel.
  • a part of Cr in the steel can be replaced with Fe to form alloy cementite (Fe, Cr) 3C to improve its stability; another part of Cr can dissolve into ferrite, resulting in solid solution strengthening, thereby effectively improving ferrite. Body strength and hardness.
  • Fe, Cr alloy cementite
  • N Under normal circumstances, the N element in the steel should be as low as possible, and in the present invention, an appropriate amount of free nitrogen is an important prerequisite for the formation of BN and AlN precipitation phases. Therefore, in the low-cost hot-rolled steel sheet for high-temperature enamel of the present invention, the mass percentage content of N element is controlled between 0.007% and 0.020%.
  • the solubility of B in steel is very low, and it can mainly combine with free nitrogen in steel and precipitate in the form of BN.
  • BN is preferentially precipitated at high temperature, and its precipitation temperature is higher than that of AlN.
  • the BN precipitation phase can be used as the main hydrogen storage trap, and play the role of enamel anti-scale explosion.
  • the precipitation process of BN will consume free nitrogen in the steel, so the precipitation temperature of AlN decreases, and the amount of AlN precipitation decreases, which affects the effect of AlN in refining austenite grains, resulting in larger grain size. . Therefore, the content of element B in the steel should not be too high.
  • the mass percentage of element B is controlled between 0.0006 and 0.003%.
  • the hot-rolled steel sheet for low-cost high-temperature enamel according to the present invention also needs to control the elements P, N and B to satisfy the formula: P ⁇ (N-14 ⁇ B /11) ⁇ 10 3 >0.3.
  • the inventor of the present case found through experimental research that when the content of P, N and B elements in the steel satisfies the above relationship, the yield strength of the steel plate after high-temperature enamelling can be guaranteed to decrease within 10%, and the yield strength of 342 MPa and above can still be achieved. Level.
  • microstructure of the hot-rolled steel sheet for low-cost high-temperature enamel of the present invention is ferrite+pearlite.
  • the average grain size of ferrite is 10-12, and the fine grain ensures the full play of the fine-grain strengthening effect.
  • the thickness of the hot-rolled steel sheet for low-cost high-temperature enamel of the present invention is 1.5-3.5 mm.
  • the hot-rolled yield strength of the hot-rolled steel sheet for low-cost high-temperature enamel of the present invention is 364-410 MPa, and after high-temperature enameling in the temperature range of 870-950° C., the yield strength decreases within 10%, and the value is greater than or equal to 10%. 342MPa.
  • another object of the present invention is to provide a method for manufacturing a hot-rolled steel sheet for low-cost high-temperature enamel, which has a simple production process and can obtain a low-cost high-temperature enamel with good enameling adaptability through the manufacturing method.
  • Use hot rolled steel Use hot rolled steel.
  • the present invention proposes the above-mentioned manufacturing method of the above-mentioned low-cost hot-rolled steel sheet for high-temperature enamel, comprising the steps:
  • Hot rolling control the rough rolling temperature to be greater than 850°C, the finish rolling start rolling temperature to be 900 to 1050°C, and the finish rolling finish temperature to be 840 to 900°C;
  • the casting in the above step (1) can be performed by continuous casting or die casting, which can ensure uniform internal composition and good surface quality of the slab.
  • die casting can also be used, and the die-cast steel ingot needs to be rolled into a billet by a blooming mill.
  • the heated cast slab can be rough rolled into an intermediate slab first, and then the intermediate slab can be finished rolled to form a desired slab.
  • the cooling rate is water-cooled to the coiling temperature of the step (5) at a cooling rate of 10-35°C/s, and then air-cooled to room temperature.
  • the invention adopts such a controlled rolling and controlled cooling process to obtain a fine ferrite grain structure, to ensure the full play of the fine grain strengthening effect, to obtain a higher yield strength, to further improve the performance of the steel plate, and to achieve a suitable for large Production of hot-rolled steel plates for low-cost high-temperature enamelling of volumetric water heater liner.
  • the heating temperature is controlled to be 1150-1260°C.
  • the coiling temperature is controlled to be 550-680°C.
  • the coiling temperature is controlled to be 550-680 °C, because: when coiling in this temperature range, it is not only conducive to refining the ferrite grains, but also conducive to the homogenization of the BN precipitation phase. Low-cost hot-rolled steel sheets for high-temperature enamels with excellent mechanical properties and scale resistance can be obtained.
  • the low-cost hot-rolled steel sheet for high-temperature enamel and its manufacturing method has the following advantages and beneficial effects:
  • the present invention creatively adopts a composition system with high P, N, and B, and avoids the addition of precious alloy elements such as Ti, Nb, and V.
  • the invention also optimizes the controlled rolling and controlled cooling process for rapid cooling after rolling, thereby realizing the production of high-temperature-resistant enamel steel suitable for the inner tank of a large-volume water heater, which can reduce the production cost.
  • a low-cost hot-rolled steel sheet for high-temperature enamel with good enameling adaptability is obtained.
  • the yield strength decreases only within 10%, and it can still reach 342MPa and above, and still has excellent mechanical properties.
  • the demand for high-temperature enamel steel for the inner tank of large-container water heaters is of great practical significance.
  • Figure 1 shows the relationship between the chemical element synergistic relationship M* defined in the present invention and the yield strength of the low-cost hot-rolled steel sheet for high-temperature enamel of the present invention after enamelling;
  • Example 2 is a photograph of the metallographic structure of the hot-rolled steel sheet for low-cost high-temperature enamel of Example 1 of the present invention.
  • Hot rolling control the rough rolling temperature to be greater than 850°C, the finish rolling start rolling temperature to be 900 to 1050°C, and the finishing rolling temperature to be 840 to 900°C.
  • Laminar flow cooling perform laminar flow water cooling, and control the cooling rate to be 10 to 35°C/s.
  • Coiling control the coiling temperature to be 550-680°C.
  • Table 1 lists the mass percentages of each chemical element in the hot-rolled steel sheets for low-cost high-temperature enamel of Examples 1-6 and the comparative steels of Comparative Examples 1-3.
  • M* P ⁇ (N-14 ⁇ B/11) ⁇ 10 3 , in the calculation, P, N and B in the formula are respectively substituted into the values before the mass percentage sign of the corresponding element.
  • Table 2 lists the specific process parameters of the hot-rolled steel sheets for low-cost high-temperature enamel of Examples 1-6 and the comparative steels of Comparative Examples 1-3 in the above manufacturing steps.
  • Tensile test According to GB/T 228.1-2010 "Room temperature tensile test method for metal materials", the SCL233 room temperature tensile testing machine was used to test, the tensile speed was 3mm/min, and the tensile sample was JIS5 tensile sample.
  • Hole reaming test According to GB/T 24524-2009 "Hole Enlarging Test Method for Sheet Metals and Thin Strips", the SCL250 cupping testing machine is used for testing, and the test speed is 6mm/min.
  • Drop weight test According to the drop weight test method described in the European standard BS EN 10209-1996, use the corresponding drop weight test device to test the enamel adhesion performance.
  • Average grain size of ferrite According to GB/T 6394-2017 "Method for Determination of Average Grain Size of Metals", with the help of metallographic microscope, the average grain size is evaluated by comparing it with the standard series rating chart.
  • Table 3 lists the performance test results of the low-cost hot-rolled steel sheets for high-temperature enamel of Examples 1-6 and the comparative steels of Comparative Examples 1-3, as well as their microstructures and the grain size of ferrite therein.
  • one-side wet enamel treatment was carried out on the steel plates of the examples and comparative examples by using Flue EMP6515 high-temperature glaze. Steel sheets of Examples 1-6 and Comparative Examples 1-3.
  • Table 4 lists the performance test results after enameling of the hot-rolled steel sheets for low-cost high-temperature enameling of Examples 1-6 and the comparative steels of Comparative Examples 1-3.
  • the thickness of the hot-rolled steel sheet for low-cost high-temperature enamel in Examples 1-6 ranges from 1.5 to 3.5 mm, and its hot-rolled yield strength is 364 mm. ⁇ 410MPa, tensile strength is 456 ⁇ 512MPa, elongation is 27 ⁇ 31%, and hole expansion rate is 80 ⁇ 92%.
  • the yield strength of the steel plates of Examples 1-6 decreased within 10%, and was still greater than or equal to 342MPa, which means that it had good high-temperature enamelling resistance.
  • the finally obtained enamel steel plates of Examples 1-6 were observed on the enamel surface after 48 hours, and no scale explosion occurred; after the drop weight test, the adhesion between the steel plate and the porcelain layer was excellent, which fully met the user's requirements.
  • Comparative Examples 1-3 are significantly inferior to those of the low-cost hot-rolled steel sheets for high-temperature enamel of Examples 1-6.
  • the content of P, N and B elements in the steel cannot satisfy the relational formula P ⁇ (N-14 ⁇ B/11) ⁇ 10 3 >0.3, and the steel is sintered at a high temperature in the temperature range of 870 ⁇ 950°C
  • the yield strength after treatment decreased by more than 18%, and the value was between 220 and 290MPa.
  • FIG. 2 is a photograph of the metallographic structure of the hot-rolled steel sheet for low-cost high-temperature enamel of Example 1.
  • FIG. 2 is a photograph of the metallographic structure of the hot-rolled steel sheet for low-cost high-temperature enamel of Example 1.
  • the microstructure of the hot-rolled steel sheet for low-cost high-temperature enamel of Example 1 is ferrite+pearlite, wherein the average grain size of ferrite is 10.

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Abstract

本发明公开了一种低成本高温搪瓷用热轧钢板，其除了Fe和不可避免的杂质以外还含有质量百分含量如下的下述各化学元素：C：0.03～0.12％，Si：0.1～0.5％，Mn：0.3～1.5％，P：0.03～0.10％，Al：0.02～0.10％，Cr：0.01～0.20％，Cu：0.01～0.30％，N：0.007～0.020％，B：0.0006～0.003％；所述低成本高温搪瓷用热轧钢板不含有Ti、Nb和V，其中，各化学元素还满足：P×（N-14×B/11）×10 3＞0.3；计算时，P、N和B分别代入相应元素的质量百分比百分号前的数值。另一方面，本发明还公开了一种低成本高温搪瓷用热轧钢板的制造方法，其包括步骤：（1）冶炼和铸造；（2）加热；（3）热轧：控制粗轧温度大于850℃，精轧开轧温度为900～1050℃，精轧终轧温度为840～900℃；（4）层流冷却：控制冷却速度为10～35℃/s；（5）卷取。

Description

一种低成本高温搪瓷用热轧钢板及其制造方法 技术领域
本发明涉及一种钢材及其制造方法，尤其涉及一种低成本高温搪瓷用热轧钢板及其制造方法。
背景技术
近年来，随着搪瓷行业的发展和新能源等技术的飞速进步，大容积搪瓷热水器内胆开始越来越受到市场欢迎，其主要可以应用在商用电热水器、空气能热水器和承压式太阳能热水器等方面。
这种大容积热水器内胆在生产时通常需要采用专用的高温釉料，以及高搪烧温度工艺与之匹配，搪烧温度通常可达870～950℃。因此，它对所用钢板的要求也相应提高，需要钢板在保证涂搪性能的同时，还好具有耐高温性能，经高温烧成后仍能具有足够高的屈服强度性能，以保证产品最终的使用性能。
在现有技术中，已有部分研究人员针对热水器内胆的搪瓷用钢取得了一定的研究成果。
公开号为CN101812630A，公开日为2010年8月25日的中国专利文献，公开了一种深冲用热轧高强度搪瓷钢板及其制造方法，这种搪瓷钢板采用的化学元素组分为C：0.02～0.10％、Si≤0.10％、Mn：0.05～1.00％、P≤0.05％、S：0.005～0.035％、Al：0.01～0.10％、N≤0.015％、Ti＜0.10％、余量为铁和不可避免杂质。
公开号为CN103540845A，公开日为2014年1月29日的中国专利文献，也公开了一种热轧薄板搪瓷钢，它采用的化学元素组分为C：0.02～0.07％，Si≤0.05％，Mn：0.10～0.50％，P≤0.020％，S≤0.010％，Ti：0.04～0.10％，Al：0.02～0.08％，N≤0.008％，其余为Fe及不可避免的夹杂，且Ti/C＝1.0～1.5。
公开号为CN102181805A，公开日为2011年9月14日的中国专利文献，公开了一种薄板坯连铸连轧线生产热水器内胆搪瓷用钢板及方法，其中，热水器内胆搪瓷用钢板采用的化学元素组分为：碳0.03-0.10％，锰0.15-0.40％，硅 ≤0.06％，硫0.004-0.040％，磷≤0.15％，铝0.03-0.05％，氮0.002-0.008％，钛0.02-0.10％，其余为铁和不可避免的杂质。
综上所述可以看出，上述现有技术均存在一个共同特点：成分上都加入了Ti元素。Ti是搪瓷用钢最常采用的一种合金元素，其可以与C、N形成TiC、TiN等化合物，作为贮氢陷阱起到抗鳞爆的作用。同时，TiC析出相还具有析出强化的作用。
但是需要注意的是，添加Ti元素的这种设计方式不仅生产成本相对较高，Ti与C形成的TiC析出相经高温搪烧时会出现粗化长大现象，析出强化作用会显著减弱，钢板经870℃以上高温搪烧后屈服强度会大幅下降，通常在300MPa以下，满足不了大容积热水器内胆的设计要求。
基于此，针对现有技术中的缺陷，本发明期望获得一种低成本高温搪瓷用热轧钢板，其生产成本较低，无需添加Ti、Nb、V等贵重合金元素，即可获得良好的涂搪适应性。该低成本高温搪瓷用热轧钢板经高温搪烧处理后依然具有优良的力学性能表现，可满足大容器热水器内胆对高温搪瓷用钢的各项需求，具有十分重要的现实意义。
发明内容
本发明的目的之一在于提供一种低成本高温搪瓷用热轧钢板，其生产成本较低，无需添加Ti、Nb、V等贵重合金元素，即可获得良好的涂搪适应性。该低成本高温搪瓷用热轧钢板经高温搪烧处理后依然具有优良的力学性能表现，可满足大容器热水器内胆对高温搪瓷用钢的各项需求，具有十分重要的现实意义。
为了实现上述目的，本发明提出了一种低成本高温搪瓷用热轧钢板，其除了Fe和不可避免的杂质以外还含有质量百分含量如下的下述各化学元素：
C：0.03～0.12％，Si：0.1～0.5％，Mn：0.3～1.5％，P：0.03～0.10％，Al：0.02～0.10％，Cr：0.01～0.20％，Cu：0.01～0.30％，N：0.007～0.020％，B：0.0006～0.003％；
所述低成本高温搪瓷用热轧钢板不含有Ti、Nb和V；
其中各化学元素还满足：P×(N-14×B/11)×10 3＞0.3；计算时，P、N和B分别代入相应元素的质量百分比百分号前的数值，例如，当P的质量百分比为 0.10％时，其代入式中的数值为0.10。
进一步地，在本发明所述的低成本高温搪瓷用热轧钢板中，其各化学元素质量百分含量为：
C：0.03～0.12％，Si：0.1～0.5％，Mn：0.3～1.5％，P：0.03～0.10％，Al：0.02～0.10％，Cr：0.01～0.20％，Cu：0.01～0.30％，N：0.007～0.020％，B：0.0006～0.003％，余量为Fe和其他不可避免的杂质；其中各化学元素还满足：P×(N-14×B/11)×10 3＞0.3；计算时，P、N和B分别代入相应元素的质量百分比百分号前的数值，例如，当P的质量百分比为0.10％时，其代入式中的数值为0.10。
在本发明中，本发明相比于以往的热水器用搪瓷钢创造性地采用了高P、N、B的成分体系，避免了Ti、Nb、V等贵重合金元素的加入，可以有效降低生产成本。
在本发明的低成本高温搪瓷用热轧钢板中，各化学元素设计原理如下所述：
C：C元素是钢中重要的强化元素，其能够固溶在铁素体中或在一定条件下形成珠光体组织，从而起到强化基体组织的作用，提高钢板的屈服强度。但需要注意的是，因为本发明中未加入Ti、Nb、V等碳化物形成元素，所以当碳含量过高时，形成的珠光体比例过高，会导致搪瓷烧成过程中产生大量的CO等气体，造成搪瓷层气泡结构不良，以及针孔等缺陷，严重影响涂搪质量。因此，在本发明所述的低成本高温搪瓷用热轧钢板中，将C元素的质量百分含量限定在0.03～0.12％之间。
Si：Si元素可以在钢中能够起到固溶强化的作用，另外Si还可以提高抗高温变形能力，提高钢板在高温搪瓷烧成过程中的抗软化能力。但需要注意的是，钢中Si元素含量不宜过高，当钢中Si元素含量过高时，不仅会使钢的塑性变差，还可能会影响钢板与瓷釉间的密着性能。因此，在本发明所述的低成本高温搪瓷用热轧钢板中，将Si元素的质量百分含量限定在0.1～0.5％之间。
Mn：Mn元素是可以提高钢板强度的最廉价的合金元素之一，其是本发明钢种获得高强度的重要元素。但需要注意的是，Mn元素还可以起到扩大奥氏体相区，降低Ac3点温度的作用，这对于钢板的搪瓷性能不利，因为奥氏体相相对于铁素体相溶氢能力更强，冷却后更易导致鳞爆缺陷发生，所以钢中不宜 添加过量的Mn。基于此，在本发明所述的低成本高温搪瓷用热轧钢板中，将Mn元素的质量百分含量限定在0.3～1.5％之间。
P：P是重要的强化元素，其固溶强化作用在钢材经过高温搪烧后仍然能够充分得以发挥，这是保证本发明钢种经高温搪烧后仍具有高屈强度的重要条件。但需要注意的是，钢中不宜添加过量的P，钢中P元素含量过高时，会降低钢的塑性、韧性以及焊接性能。因此，在本发明所述的低成本高温搪瓷用热轧钢板中，将P元素的质量百分含量限定在0.03～0.10％之间。
Al：Al为强脱氧元素，为了使钢中的O含量保持在较低的值，在中低碳钢中常常需要采用Al进行脱氧。此外，钢中溶解的Al元素还可以与自由氮结合析出AlN，其析出温度较高，可以起到细化奥氏体晶粒的作用。在本发明中，钢板经高温搪烧后空冷的条件下仍需要具有高屈服强度，而AlN的高温细化晶粒作用使得钢板经高温搪烧后仍具有细小的晶粒组织，可以充分发挥细晶强化机制。因此，在本发明所述的低成本高温搪瓷用热轧钢板中，将Al元素的质量百分含量限定在0.02～0.10％之间。
Cr、Cu：在钢中添加适量的Cr和Cu元素均有利于表面沉积，能够提高其与瓷釉间的密着性能，改善钢材的抗鳞爆性能。钢中一部分的Cr可以与Fe进行置换，形成合金渗碳体(Fe、Cr)3C，提高其稳定性；还有一部分的Cr可以溶入铁素体，产生固溶强化，从而有效提高铁素体的强度和硬度。但需要注意的是，钢中不宜添加过量的Cr和Cu元素，过高的Cr和Cu元素含量不仅会增加合金成本，而且还会使钢板耐蚀性能增强，反而不利于钢板在搪瓷过程中涂搪密着性能。因此，在本发明所述的低成本高温搪瓷用热轧钢板中，将Cr元素的质量百分含量限定在0.01～0.20％之间，将Cu元素的质量百分含量限定在0.01～0.30％之间。
N：在通常情况下，钢中的N元素应该尽量低，而在本发明中，适量的自由氮是形成BN和AlN析出相的重要前提。因此，在本发明所述的低成本高温搪瓷用热轧钢板中，将N元素的质量百分含量控制在0.007～0.020％之间。
B：在本发明所述的技术方案中，B在钢中的溶解度很低，其主要可以与钢中的自由氮结合，并以BN形式析出。BN在高温情况下是优先析出的，其析出温度高于AlN。在本发明中，BN析出相可以作为主要的贮氢陷阱，并起到搪瓷抗鳞爆的作用。但需要注意的是，BN的析出过程会消耗钢中的自由氮， 因此AlN的析出温度降低，AlN析出量减少，从而影响AlN的细化奥氏体晶粒的效果，导致晶粒尺寸变大。因此，钢中B元素的含量不宜过高，本发明所述的低成本高温搪瓷用热轧钢板中，将B元素的质量百分含量控制在0.0006～0.003％之间。
需要说明的是，本发明所述的低成本高温搪瓷用热轧钢板在控制单一化学元素质量百分含量的同时，还需要控制P、N和B元素满足公式：P×(N-14×B/11)×10 3＞0.3。本案发明人通过试验研究发现，当钢中的P、N和B元素含量满足上述关系式时，能够保证钢板经高温搪烧后的屈服强度下降幅度在10％以内，仍能达到342MPa及以上的水平。这是因为，当满足此关系式时，在钢基体中形成足够量的BN析出相作为贮氢陷阱后，将继续形成足够量的AlN析出相，进而充分发挥AlN析出相的细化晶粒作用，特别是当钢板经高温搪烧处理后，仍能获得非常细小的晶粒组织，从而发挥细晶强化作用，同时结合P元素的固溶强化作用，可以避免钢板的屈服强度大幅下降，其为本发明成分设计的关键创新之一。
进一步地，本发明低成本高温搪瓷用热轧钢板的微观组织为铁素体+珠光体。
进一步地，在本发明低成本高温搪瓷用热轧钢板中，铁素体的平均晶粒度为10～12级，细小的晶粒保证了细晶强化作用的充分发挥。
进一步地，本发明低成本高温搪瓷用热轧钢板的厚度为1.5～3.5mm。
进一步地，本发明低成本高温搪瓷用热轧钢板的热轧态屈服强度为364～410MPa，经870～950℃温度区间内高温搪烧后，屈服强度下降幅度在10％以内，且数值大于等于342MPa。
相应地，本发明的又一目的在于提供一种低成本高温搪瓷用热轧钢板的制造方法，该制造方法生产工艺简单，通过该制造方法可以获得具有良好的涂搪适应性的低成本高温搪瓷用热轧钢板。
为了实现上述目的，本发明提出了上述的低成本高温搪瓷用热轧钢板的制造方法，包括步骤：
(1)冶炼和铸造；
(2)加热；
(3)热轧：控制粗轧温度大于850℃，精轧开轧温度为900～1050℃，精 轧终轧温度为840～900℃；
(4)层流冷却：控制冷却速度为10～35℃/s；
(5)卷取。
在本发明中，上述步骤(1)中的铸造可以采用连铸或模铸的方式，其可以保证铸坯内部成分均匀和表面质量良好。在一些其他实施方式中，也可以采用模铸的方式，模铸的钢锭还需经初轧机轧制成钢坯。
相应地，在上述步骤(3)的热轧过程中，可以先将经过加热后的铸坯粗轧成中间坯，而后再对中间坯进行精轧，精轧轧成所需板坯。
在本发明的步骤(4)中，通过10～35℃/s的冷却速度水冷至步骤(5)的卷取温度，然后空冷至室温。本发明采用这样的控轧控冷工艺，可以获得细小的铁素体晶粒组织，确保细晶强化作用的充分发挥，有利于获得较高的屈服强度，进一步提高钢板的性能，实现适用于大容积热水器内胆的低成本高温搪瓷用热轧钢板的生产。
进一步地，在上述步骤(2)中，控制加热温度为1150～1260℃。
进一步地，在上述步骤(5)中，控制卷取温度为550～680℃。
在上述技术方案中，控制卷取温度为550～680℃，是因为：在这一温度区间进行卷取时，不仅有利于细化铁素体晶粒，还有利于BN析出相的均匀化，可以获得具有优异力学性能和抗鳞爆性能的低成本高温搪瓷用热轧钢板。
本发明所述的低成本高温搪瓷用热轧钢板及其制造方法相较于现有技术具有如下所述的优点以及有益效果：
相较于现有技术，本发明创造性地采用了高P、N、B的成分体系，避免了Ti、Nb、V等贵重合金元素的加入。此外，本发明在合理设计化学成分的同时，还结合优化了轧后快速冷却的控轧控冷工艺，实现了适用于大容积热水器内胆的耐高温搪瓷用钢的生产，可以在降低生产成本的同时，获得具有良好的涂搪适应性的低成本高温搪瓷用热轧钢板。
该低成本高温搪瓷用热轧钢板经870～950℃温度区间内高温搪烧后，屈服强度下降幅度仅在10％以内，且仍可达342MPa及以上，依然具有优良的力学性能表现，可满足大容器热水器内胆对高温搪瓷用钢的各项需求，具有十分重要的现实意义。
附图说明
图1显示了本发明限定的化学元素协同关系M*与本发明的低成本高温搪瓷用热轧钢板经搪烧后的屈服强度的关系；
图2为本发明实施例1的低成本高温搪瓷用热轧钢板的金相组织照片。
具体实施方式
下面将结合说明书附图和具体的实施例对本发明所述的低成本高温搪瓷用热轧钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
实施例1-6及对比例1-3
实施例1-6的低成本高温搪瓷用热轧钢板以及对比例1-3的对比钢的制造方法采用以下步骤制得：
(1)按照下述表1所示的化学成分进行冶炼和铸造：冶炼完成的钢水经真空脱气处理后进行连铸，得到连铸坯。
(2)加热：将所得连铸坯进行加热，并控制加热温度为1150～1260℃。
(3)热轧：控制粗轧温度大于850℃，精轧开轧温度为900～1050℃，精轧终轧温度为840～900℃。
(4)层流冷却：进行层流水冷，控制冷却速度为10～35℃/s。
(5)卷取：控制卷取温度为550～680℃。
表1列出了实施例1-6的低成本高温搪瓷用热轧钢板以及对比例1-3的对比钢中各化学元素质量百分比。
表1.(余量为Fe和其他不可避免的杂质)
Figure PCTCN2022075614-appb-000001
注：M*＝P×(N-14×B/11)×10 3，计算时，式中P、N和B分别代入相应元素的质量百分比百分号前的数值。
表2列出了实施例1-6的低成本高温搪瓷用热轧钢板以及对比例1-3的对比钢在上述制造步骤中的具体工艺参数。
表2.
Figure PCTCN2022075614-appb-000002
将得到的实施例1-6的低成本高温搪瓷用热轧钢板和对比例1-3的对比钢分别取样，对各实施例和对比例钢板的性能进行测试，所得的测试结果列于表3中，相关性能测试方法及手段如下所述：
拉伸试验：按照GB/T 228.1-2010《金属材料室温拉伸试验方法》，利用SCL233常温拉伸试验机进行测试，拉伸速度为3mm/min，拉伸试样为JIS5拉伸试样。
扩孔试验：按照GB/T 24524-2009《金属材料薄板和薄带扩孔试验方法》，利用SCL250杯突试验机进行测试，试验速度6mm/min。
落锤试验：按照欧标BS EN 10209-1996中描述的落锤试验方法，采用相应的落锤试验装置进行搪瓷密着性能测试。
铁素体平均晶粒度：按照GB/T 6394-2017《金属平均晶粒度测定方法》，借助金相显微镜，采用比较法，与标准系列评级图对比来评定平均晶粒度。
表3列出了实施例1-6的低成本高温搪瓷用热轧钢板和对比例1-3的对比钢的性能测试结果及其微观组织和其中铁素体的晶粒度。
表3.
Figure PCTCN2022075614-appb-000003
为了进一步地证明本发明所述的实施例1-6的低成本高温搪瓷用热轧钢板和对比例1-3的对比钢经过搪瓷后的性能。需要对各实施例和对比例的钢板进行搪瓷处理：
具体地，采用福禄EMP6515型高温釉料对各实施例和对比例钢板进行单面湿法搪瓷处理，控制搪烧温度为870～950℃，保温时间为10分钟，然后空冷获得经过搪瓷后实施例1-6和对比例1-3的钢板。
完成上述操作后，再对已经过搪瓷处理的实施例1-6低成本高温搪瓷用热轧钢板以及对比例1-3的对比钢进行观察和试验：搪瓷后将钢板静置48小时后观察表面没有发生鳞爆现象；采用落锤实验验证钢板与瓷釉间密着性能优；采用拉伸试验确定搪瓷后各实施例和对比例钢板的屈服强度，试验测试的结果列于表4中。
表4列出了搪瓷后实施例1-6的低成本高温搪瓷用热轧钢板以及对比例1-3的对比钢的经过搪瓷后的性能测试结果。
表4.
Figure PCTCN2022075614-appb-000004
Figure PCTCN2022075614-appb-000005
由表4可以看出，并结合表1-3可以看出，实施例1-6的低成本高温搪瓷用热轧钢板的厚度范围在1.5～3.5mm之间，其热轧态屈服强度为364～410MPa，抗拉强度为456～512MPa，延伸率为27～31％，扩孔率为80～92％。经870～950℃温度区间内高温搪烧处理后，实施例1-6钢板的屈服强度下降幅度均在10％以内，且仍大于等于342MPa，也就是说其具有良好的耐高温搪烧性能。最终获得的实施例1-6的搪瓷钢板经48小时以后观察搪瓷表面，均无鳞爆现象发生；经落锤实验测试，钢板与瓷层之间密着性能优良，完全满足用户使用要求。
相应地，对比例1-3的对比钢板性能明显劣于实施例1-6的低成本高温搪瓷用热轧钢板。在对比例1-3中，钢中的P、N和B元素含量无法满足关系式P×(N-14×B/11)×10 3＞0.3，经870～950℃温度区间内高温搪烧处理后的屈服强度的下降幅度达18％以上，数值在220～290MPa之间。
图1显示了本案限定的化学元素协同关系对于本发明所述的低成本高温搪瓷用热轧钢板在搪烧后的屈服强度的影响，其中M*＝P×(N-14×B/11)×10 3。
由图1可以看出，在本发明中，搪烧后钢板的屈服强度与M*值之间有明显的相关性，当M*值大于0.3以后，屈服强度值可以保证在342MPa以上，达到产品的设计目标要求。
图2为实施例1的低成本高温搪瓷用热轧钢板的金相组织照片。
如图2所示，实施例1的低成本高温搪瓷用热轧钢板的微观组织为铁素体+珠光体，其中铁素体的平均晶粒度为10级。
需要说明的是，本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式，本案记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。
还需要注意的是，以上所列举的实施例仅为本发明的具体实施例。显然本发明不局限于以上实施例，随之做出的类似变化或变形是本领域技术人员能从本发明公开的内容直接得出或者很容易便联想到的，均应属于本发明的保护范围。

Claims (9)

  1. 一种低成本高温搪瓷用热轧钢板，其特征在于，其除了Fe和不可避免的杂质以外还含有质量百分含量如下的下述各化学元素：
    C：0.03～0.12％，Si：0.1～0.5％，Mn：0.3～1.5％，P：0.03～0.10％，Al：0.02～0.10％，Cr：0.01～0.20％，Cu：0.01～0.30％，N：0.007～0.020％，B：0.0006～0.003％；
    所述低成本高温搪瓷用热轧钢板不含有Ti、Nb和V；
    其中，各化学元素还满足：P×(N-14×B/11)×10 3＞0.3；计算时，P、N和B分别代入相应元素的质量百分比百分号前的数值。
  2. 如权利要求1所述的低成本高温搪瓷用热轧钢板，其特征在于，其各化学元素质量百分含量为：
    C：0.03～0.12％，Si：0.1～0.5％，Mn：0.3～1.5％，P：0.03～0.10％，Al：0.02～0.10％，Cr：0.01～0.20％，Cu：0.01～0.30％，N：0.007～0.020％，B：0.0006～0.003％，余量为Fe和其他不可避免的杂质；
    其中，各化学元素还满足：P×(N-14×B/11)×10 3＞0.3；计算时，P、N和B分别代入相应元素的质量百分比百分号前的数值。
  3. 如权利要求1或2所述的低成本高温搪瓷用热轧钢板，其特征在于，其微观组织为铁素体+珠光体。
  4. 如权利要求3所述的低成本高温搪瓷用热轧钢板，其特征在于，所述铁素体的平均晶粒度为10～12级。
  5. 如权利要求1或2所述的低成本高温搪瓷用热轧钢板，其特征在于，其厚度为1.5～3.5mm。
  6. 如权利要求1-5中任意一项所述的低成本高温搪瓷用热轧钢板，其特征在于，其热轧态屈服强度为364～410MPa，经870～950℃温度区间内高温搪烧后，屈服强度下降幅度在10％以内，且数值大于等于342MPa。
  7. 如权利要求1-6中任意一项所述的低成本高温搪瓷用热轧钢板的制造方法，其特征在于，包括步骤：
    (1)冶炼和铸造；
    (2)加热；
    (3)热轧：控制粗轧温度大于850℃，精轧开轧温度为900～1050℃，精轧终轧温度为840～900℃；
    (4)层流冷却：控制冷却速度为10～35℃/s；
    (5)卷取。
  8. 如权利要求7所述的制造方法，其特征在于，在所述步骤(2)中，控制加热温度为1150～1260℃。
  9. 如权利要求7所述的制造方法，其特征在于，在所述步骤(5)中，控制卷取温度为550～680℃。
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