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 PDFInfo
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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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- rolled steel
- enamel
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 134
- 239000010959 steel Substances 0.000 title claims abstract description 134
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000004534 enameling Methods 0.000 title abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000005096 rolling process Methods 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 5
- 238000004364 calculation method Methods 0.000 claims abstract description 5
- 238000005266 casting Methods 0.000 claims abstract description 5
- 238000005098 hot rolling Methods 0.000 claims abstract description 5
- 210000003298 dental enamel Anatomy 0.000 claims description 75
- 229910000859 α-Fe Inorganic materials 0.000 claims description 14
- 229910001562 pearlite Inorganic materials 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000005728 strengthening Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000005275 alloying Methods 0.000 description 5
- 238000009749 continuous casting Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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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
- 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
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- 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
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- 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
- 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
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- 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
Description
Claims (9)
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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℃。
- 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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KR1020237026162A KR20230128092A (ko) | 2021-02-09 | 2022-02-09 | 고온 에나멜링용 저비용 열연 스틸 플레이트 및 그제조방법 |
JP2023547462A JP2024506596A (ja) | 2021-02-09 | 2022-02-09 | 高温ホーロー用低コスト熱延鋼板及びその製造方法 |
US18/262,810 US20240309481A1 (en) | 2021-02-09 | 2022-02-09 | Hot-rolled steel plate for low-cost high temperature enameling, and manufacturing method theefor |
MX2023009048A MX2023009048A (es) | 2021-02-09 | 2022-02-09 | Placa de acero laminada en caliente de bajo costo para esmaltado a alta temperatura y metodo de fabricacion de la misma. |
EP22752272.9A EP4273290A4 (en) | 2021-02-09 | 2022-02-09 | HOT-ROLLED STEEL SHEET FOR HIGH-TEMPERATURE AND LOW-COST ENAMELING, AND METHOD FOR MANUFACTURING SAME |
AU2022219117A AU2022219117B2 (en) | 2021-02-09 | 2022-02-09 | Hot-rolled steel plate for low-cost high temperature enameling, and manufacturing method therefor |
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CN115537653A (zh) * | 2022-09-09 | 2022-12-30 | 首钢集团有限公司 | 一种热轧搪瓷钢板及其制备方法 |
CN116623087A (zh) * | 2023-05-26 | 2023-08-22 | 鞍钢股份有限公司 | 薄坯生产厚规格240MPa高韧性管桩用钢及生产方法 |
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AU2022219117A9 (en) | 2024-10-17 |
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AU2022219117A1 (en) | 2023-08-17 |
EP4273290A4 (en) | 2024-06-12 |
CN114908285B (zh) | 2023-04-11 |
AU2022219117B2 (en) | 2024-10-24 |
JP2024506596A (ja) | 2024-02-14 |
CN114908285A (zh) | 2022-08-16 |
US20240309481A1 (en) | 2024-09-19 |
KR20230128092A (ko) | 2023-09-01 |
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