WO2021169941A1 - 一种矿用链条钢及其制造方法 - Google Patents

一种矿用链条钢及其制造方法 Download PDF

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WO2021169941A1
WO2021169941A1 PCT/CN2021/077430 CN2021077430W WO2021169941A1 WO 2021169941 A1 WO2021169941 A1 WO 2021169941A1 CN 2021077430 W CN2021077430 W CN 2021077430W WO 2021169941 A1 WO2021169941 A1 WO 2021169941A1
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steel
mining
strength
chain steel
rolling
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PCT/CN2021/077430
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English (en)
French (fr)
Chinese (zh)
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高加强
赵四新
王维
章军
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宝山钢铁股份有限公司
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Priority to EP21760437.0A priority Critical patent/EP4089197A4/en
Priority to BR112022016824A priority patent/BR112022016824A2/pt
Priority to KR1020227028750A priority patent/KR20220129609A/ko
Priority to US17/800,800 priority patent/US20230235435A1/en
Priority to MX2022010591A priority patent/MX2022010591A/es
Priority to JP2022550659A priority patent/JP7497447B2/ja
Publication of WO2021169941A1 publication Critical patent/WO2021169941A1/zh

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    • C21D9/0087—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for chains, for chain links
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21L—MAKING METAL CHAINS
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Definitions

  • the invention relates to high-strength steel, in particular to a high-strength and tough mining chain steel and a manufacturing method thereof.
  • High-strength and tough steel bars are usually used in high-safety machinery and structural parts.
  • mining circular chains are the key vulnerable parts of coal mining machinery. They should have high strength, high toughness, wear resistance, corrosion resistance and high fatigue. Performance, etc.
  • Mn-Cr-Ni-Mo series alloy steel is widely used in construction machinery, automobiles, bridges, marine equipment and other fields because of its good strength and toughness. Its safe use strength level is generally 900 ⁇ 1000MPa, while the higher strength level steel Application can not only make the equipment lighter, but also save resources, so the high strength of alloy steel is the inevitable trend of future development. However, as the strength of steel increases, the difficulty of processing and manufacturing increases, and its susceptibility to hydrogen embrittlement is bound to increase. Microstructure refinement, microalloying, grain boundary strengthening and the addition of alloying elements can greatly reduce the hydrogen-induced delayed fracture sensitivity of high-strength steels.
  • the highest strength level of steel for circular chain for mining is 1180MPa
  • the mechanical performance indicators are: yield strength R eL ⁇ 1060MPa, tensile strength R m ⁇ 1180MPa, elongation A ⁇ 10%, reduction of area Z ⁇ 50%, Charpy Impact energy A kv ⁇ 60J.
  • the highest-strength grade mining chain steel in use by China's coal mining machinery is quenched and tempered (880°C quenched + 400°C tempered).
  • the mechanical performance indicators are: yield strength R eL ⁇ 980MPa, tensile strength R m ⁇ 1180MPa, elongation A ⁇ 10%, reduction of area Z ⁇ 50%, Charpy impact energy A kU ⁇ 40J.
  • Mn-Cr-Ni-Mo series alloy steel chains are subject to heavy loads and dynamic impacts, and are prone to stress corrosion, severely brittle fractures can occur, causing huge economic losses and even safety accidents.
  • the purpose of the present invention is to provide a high-strength and toughness mine chain steel and its manufacturing method.
  • the high-strength steel has good impact toughness, elongation and area shrinkage, is resistant to stress corrosion cracking and has good weather resistance and wear resistance. It can be used in applications requiring high-strength and tough steel such as engineering machinery and marine engineering.
  • a kind of high-strength and toughness chain steel for mining its composition mass percentages are: C: 0.20 ⁇ 0.28%, Si: 0.01 ⁇ 0.40%, Mn: 0.50 ⁇ 1.50%, P ⁇ 0.015%, S ⁇ 0.005%, Cr: 0.30 ⁇ 2.00%, Ni: 0.50 ⁇ 2.00%, Mo: 0.10 ⁇ 0.80%, Cu: 0.01 ⁇ 0.30%, Al: 0.01 ⁇ 0.05%, Nb: 0.001 ⁇ 0.10%, V: 0.001 ⁇ 0.10%, H ⁇ 0.00018%, N ⁇ 0.0150%, O ⁇ 0.0020%, the balance is Fe and unavoidable impurities; and,
  • microalloying element coefficient r M/N is: 1.0 ⁇ 9.9;
  • J H ([P]+[Sn]+[As]+[Pb]+[Sb]+[Bi])*([Si]+[Mn])*10000.
  • [Al], [Nb], [V], [N], etc. in the formulas of the present invention represent the mass percentages of the corresponding elements in the steel.
  • [Al], [Nb], [V ], [N], etc. are the values before the percent sign. For example, if the Al content in Example 1 is 0.020%, the value should be 0.020 instead of 0.00020. The substitution of other elements can be deduced by analogy. ,No longer.
  • B Preferably, among the unavoidable impurities, B ⁇ 0.0010%, Ti ⁇ 0.003%, and Ca ⁇ 0.005%.
  • the microstructure of the high-strength and toughness mining chain steel of the present invention is tempered martensite, a small amount of bainite and retained austenite, wherein the volume content of bainite is less than or equal to 10%.
  • the high-strength and toughness mining chain steel of the present invention has a yield strength R p0.2 ⁇ 1000MPa, a tensile strength R m ⁇ 1200MPa, an elongation rate A ⁇ 12%, a section reduction rate Z ⁇ 50%, and a Charpy impact energy A kv ⁇ 60J, hydrogen embrittlement coefficient ⁇ (Z) ⁇ 15%.
  • C can improve the hardenability of steel and make the steel form a phase transformation structure with higher hardness during the quenching and cooling process.
  • Increasing the C content will increase the hard phase ratio and increase the hardness of the steel material, but will result in a decrease in toughness. Too low C content will result in low content of phase transformation structures such as martensite and bainite, and high tensile strength cannot be obtained.
  • the C content is set to 0.20 to 0.28%.
  • Si is beneficial to strength improvement in steel.
  • a proper amount of Si can avoid the formation of coarse carbides during tempering, but a higher Si content will reduce the impact toughness of the steel.
  • the present invention adopts a low Si component system, and the Si content is set to be 0.01 to 0.40%.
  • Mn mainly exists in the form of solid solution in steel. It can improve the hardenability of steel, form a high-strength low-temperature phase transformation structure during quenching, and the obtained steel has good wear resistance. Too high Mn content will lead to the formation of more retained austenite, reduce the yield strength of the steel, and easily lead to center segregation.
  • the Mn content is set to 0.50 to 1.50%.
  • the P content is set as: ⁇ 0.015%.
  • S will segregate in steel and form more sulfide inclusions, reducing impact resistance.
  • the S content is set as: ⁇ 0.005%.
  • Cr can improve the hardenability of steel, form a hardened martensite structure, and increase the strength of steel. If the Cr content is too high, coarse carbides will be formed and the impact performance will be reduced. In the present invention, the Cr content is set to 0.30 to 2.00%.
  • Ni exists in the steel as a solid solution, which can improve the low-temperature impact performance of the steel.
  • an excessively high Ni content will cause the retained austenite content in the steel to be too high, thereby reducing the strength of the steel.
  • the Ni content is set to 0.50% to 2.00%.
  • Mo can dissolve in the steel and help to improve the hardenability of the steel and increase the strength of the steel. Tempering at a higher temperature will form fine carbides to further increase the strength of the steel. Considering the cost of the precious alloy Mo element, in the present invention, the Mo content is set to 0.10 to 0.80%.
  • the Cu can increase the strength of steel and is beneficial to improve the corrosion resistance of steel. If the Cu content is too high, it will be concentrated in the grain boundary during heating, causing the grain boundary to weaken and cause cracking. In the present invention, the Cu content is set to 0.01 to 0.30%.
  • Al forms fine AlN precipitates in steel, which can inhibit the growth of austenite grains. Too high Al content will lead to the formation of larger Al oxides, and coarse AlN hard inclusions will reduce the impact toughness and fatigue properties of the steel.
  • the Al content is set to be 0.01 to 0.05%.
  • Nb is added to steel to form fine precipitated phases, which can inhibit the recrystallization of steel and can refine grains. If the Nb content is too high, coarse NbC particles will be formed during the smelting process, which will reduce the impact toughness. Grain refinement plays an important role in improving the mechanical properties of steel, especially the strength and toughness. At the same time, grain refinement also helps reduce the hydrogen embrittlement sensitivity of steel.
  • the Nb content is set to 0.001 to 0.10%.
  • V can form precipitates with C or N in steel to increase the strength of steel. If the content of C and V is too high, coarse VC particles will be formed. In the present invention, the V content is set to be 0.001 to 0.10%.
  • the Ti content is set as: ⁇ 0.003%.
  • the content of B is controlled to be less than or equal to 0.0010%.
  • Ca element to steel can improve the size and morphology of sulfide inclusions and avoid deterioration of impact toughness.
  • Ca element is easy to form inclusions and affect the fatigue performance of the final product. Control the Ca content to: ⁇ 0.005%.
  • N is an interstitial atom and also an MX-type precipitate-forming element.
  • the N content in the composition design of the present invention as: ⁇ 0.015%. Control the ratio of the content of microalloying elements Al, Nb, V to the N content, and define the coefficient of microalloying elements r M/N : 1.0 ⁇ 9.9,
  • the microalloying coefficient is related to the nano-scale precipitates.
  • a higher microalloying coefficient will result in the presence of coarse precipitates in the steel, which cannot play a precipitation strengthening effect. Instead, it will cause the adverse effects of similar inclusions and reduce the fatigue strength.
  • a lower microalloy coefficient will result in a smaller number of precipitates, which cannot achieve the effect of dispersion strengthening.
  • the microalloying element coefficient r M/N is 1.0 to 6.0.
  • Sn, Sb, As, Bi, Pb and other trace elements segregate to the grain boundary at the tempering temperature, which weakens the intergranular bonding force. Mn and Si can promote the segregation of harmful elements and increase embrittlement. And Sn, Sb, As, Bi, Pb and other elements are harmful to the environment. In the present invention, As: ⁇ 0.05%, Pb: ⁇ 0.05%, Sn: ⁇ 0.02%, Sb: ⁇ 0.01%, Bi: ⁇ 0.01 %. And considering the influence of P, define the harmful element coefficient J H ⁇ 500;
  • J H ([P]+[Sn]+[As]+[Pb]+[Sb]+[Bi])*([Si]+[Mn])*10000.
  • H will accumulate at defects in steel, and hydrogen-induced delayed fracture will occur in steel with a tensile strength level of more than 1000MPa.
  • the tensile strength exceeds 1200 MPa, and the H content is controlled to be less than or equal to 0.00018%.
  • N forms nitrides or carbonitrides in the steel to refine the austenite grains, but too high N content will form coarse grains, which will not play the role of grain refinement. It acts as interstitial atoms in Enrichment at grain boundaries and defects will reduce impact toughness.
  • the N content is controlled within: ⁇ 0.0150%.
  • O and Al in the steel form oxides and composite oxides. In order to ensure the uniformity of the steel structure, low-temperature impact energy and fatigue performance, in the present invention, the content of O is controlled as follows: ⁇ 0.0020%.
  • Ceq carbon equivalent
  • the atmospheric corrosion resistance index I value is: ⁇ 7.0.
  • the microstructure of the high-strength and toughness mining chain steel of the present invention is tempered martensite, a small amount of bainite and retained austenite.
  • the previous chain steel is a low-temperature tempered martensite structure, and the chemical composition designed by the present invention makes full use of the influence of various alloying elements and microalloying elements on the phase transformation and microstructure. After quenching + tempering heat treatment, it forms The multiphase microstructure of tempered martensite, a small amount of bainite and retained austenite.
  • the method for manufacturing high-strength and toughness mining chain steel of the present invention includes smelting, casting, heating, forging or rolling, quenching heat treatment and tempering heat treatment steps; in the heating process, the heating temperature is 1050-1250°C, The holding time is 3 ⁇ 24h; in the forging or rolling process, the final rolling temperature or final forging temperature is ⁇ 800°C; the heating temperature of quenching heat treatment is 850 ⁇ 1000°C, and the holding time is 60 ⁇ 240min. After austenitizing, water is used Quenching treatment; the tempering temperature of tempering heat treatment is 350 ⁇ 550°C, the holding time is 60 ⁇ 240min, air cooling or water cooling after tempering.
  • the smelting may adopt electric furnace smelting or converter smelting, and undergo refining and vacuum treatment.
  • the casting adopts die casting or continuous casting.
  • the heating temperature of the intermediate billet is 1050 ⁇ 1250°C, and the holding time is 3 ⁇ 24h.
  • the billet is discharged from the heating furnace and then rolled after being descaled by high-pressure water, and air cooling or slow cooling is adopted after the rolling.
  • the high-strength and toughness mining chain steel of the present invention has a yield strength R p0.2 ⁇ 1000MPa, a tensile strength R m ⁇ 1200MPa, an elongation rate A ⁇ 12%, a section reduction rate Z ⁇ 50%, and a Charpy impact energy A kv ⁇ 60J, hydrogen embrittlement coefficient ⁇ (Z) ⁇ 15%.
  • Such high-strength and tough steels have good strength, plasticity and toughness, as well as good weather resistance and stress corrosion resistance.
  • the high-strength and toughness mining chain steel of the present invention can be used in applications requiring high-strength bars such as mining, and the size range of the bars is ⁇ 50-170mm.
  • the high-strength and toughness mining chain steel of the present invention is fully austenitized by heating at 1050°C to 1250°C.
  • Al, Nb, V carbides and nitrides and carbonitrides, Cr and Mo carbides are partially or completely dissolved in austenite.
  • Al, Nb and V form fine precipitates.
  • Mn, Cr and Mo dissolved in austenite can improve the hardenability of steel and increase the hardness and strength of martensite.
  • Under the condition of final rolling or final forging temperature ⁇ 800°C a complex matrix structure with refined martensite, a small amount of bainite and retained austenite is formed, and there are fine dispersed precipitates.
  • the steel After the steel is rolled or forged, it is heated to 850 ⁇ 1000°C for heat preservation and then quenched. Fully austenitizing is achieved during this heat preservation process. During the heating process, the precipitates of the carbide forming elements Al, Nb, V, Cr and Mo partially dissolve, and the undissolved precipitates pin the grain boundaries and inhibit the coarse austenite grains (austenite grain size ⁇ 6 ). During the quenching and cooling process, the alloying elements in solid solution in austenite make the steel have high strength and good toughness. The quenched steel is subjected to tempering heat treatment at 350-550°C. Al, Nb, V, Cr and Mo will form fine precipitates with C and N, which improves the strength and ductility of the steel. Within the quenching + tempering temperature range of the present invention, the steel can be guaranteed to have good strong plasticity and toughness, which is beneficial to the processing and use of bars, such as the production of high-performance mining chains by forging or welding.
  • the "Alloy steel composition and chain products fabricated in such alloy steel" disclosed in US patent US006146583 has the following composition: C: 0.15 to 0.28%, Cr: 0.2 to 1.0%, Mo: 0.1 to 1.0%, Ni: 0.3 to 1.5% , V: 0.05-0.2%, the balance is Fe and unavoidable impurities, the strength can reach 800MPa, and it has stress corrosion resistance. After forging, welding and heat treatment, a high-strength chain is formed.
  • the present invention has different Cu content in the composition, and the present invention optimizes the content of C, N and alloying elements such as Mn, Cr, Ni, Mo and microalloying elements Al, V, Nb and other elements.
  • the invention utilizes the design of C, Ni and Cu elements, combined with the optimization of Mn, Cr, Mo and other elements, to form a complex microstructure of tempered martensite and a small amount of bainite and retained austenite. And the mechanical properties are obviously better than the patent.
  • Chinese Patent Publication No. CN103276303A discloses "a high-strength mining chain steel and its preparation method", its composition is: C: 0.21 ⁇ 0.25%, Mn: 0.20 ⁇ 0.25%, Si: 0.15 ⁇ 0.35%, Cr: 0.40 ⁇ 0.65%, Ni: 0.60 ⁇ 0.70%, Cu: 0.07 ⁇ 0.15%, Alt: 0.02 ⁇ 0.05%, N ⁇ 0.012%, S ⁇ 0.015%, P ⁇ 0.015%, the balance is Fe.
  • the preparation method includes: electric furnace or converter smelting process, out-of-furnace refining process, billet continuous casting process and heating rolling process to obtain straight bars with a specification of ⁇ 20-50mm, and then obtain high-strength mining chain steel after annealing.
  • the present invention has completely different contents of Cr, Mn, Ni, and Mo in the composition, and the present invention optimizes the composition range of C, Cu, Al, Nb, V, etc., and limits the contents of N and Ca.
  • the alloy element range of the present invention a microstructure of tempered martensite and retained austenite is formed, which has high strength and toughness mechanical properties.
  • H in the environment will be adsorbed to cause delayed cracking, and large-size high-strength steel bars are more sensitive to hydrogen. Therefore, the H element in the steel is limited in the present invention.
  • the tensile strength of the present invention is R m ⁇ 1200MPa
  • the yield strength R p0.2 is ⁇ 1000MPa
  • the impact energy A kv ⁇ 60J is the impact energy A kv ⁇ 60J.
  • the strength grade of the present invention is better than that of the patent, and it has excellent impact toughness and stress corrosion cracking resistance.
  • the present invention develops high-strength and tough steel by rationally designing the chemical composition and combining the optimization process.
  • the rolled or forged bar After quenching, the rolled or forged bar adopts a tempering heat treatment process to form tempered martensite and a small amount of bainite and residues.
  • composition and process design of the steel are reasonable, and the process window is loose, and mass commercial production can be realized on the bar or high-speed wire production line.
  • the steel produced by the present invention has a yield strength R p0.2 ⁇ 1000MPa, a tensile strength R m ⁇ 1200MPa, an elongation A ⁇ 12%, a reduction of area Z ⁇ 50%, and a Charpy impact energy A kv ⁇ 60J.
  • the engineering field usually adopts the change of elongation under environmental conditions to reflect the stress corrosion tendency.
  • the present invention refers to the requirements of Det Norske Veritas for hydrogen embrittlement sensitivity in accordance with GB/T2975-2018 "Steel and Steel Product Mechanical Performance Test Sampling Position and Sample Preparation ⁇ Prepare a circular cross-section sample with a diameter of 10mm.
  • the tensile test is carried out according to the national standard GB/T 228.1, the strain rate is ⁇ 0.0003/s, the reduction of area Z is obtained, and the hydrogen embrittlement coefficient ⁇ (Z) is defined to evaluate the stress corrosion resistance of the steel:
  • the hydrogen embrittlement coefficient ⁇ (Z) of the steel produced by the invention is less than or equal to 15%, and has good stress corrosion resistance.
  • Figure 1 is a metallographic photo of the microstructure of round steel in Example 2 of the present invention (magnification 500 times);
  • Figure 2 is a metallographic photograph of the microstructure of the chain prepared in Example 2 of the present invention (magnification 500 times).
  • composition of the round steel examples and comparative examples of the present invention are shown in Table 1.
  • the high-strength and tough steels of Examples 1 to 7 of the present invention and Comparative Examples 1 to 3, and the composition coefficients are shown in Table 2. It can be seen that the ratio coefficient r M/N of the microalloying elements Al, Nb, V content and the N content of the examples is in the range of 1.0 ⁇ 9.9; carbon equivalent Ceq ⁇ 0.80; harmful element coefficient J H ⁇ 500.
  • the implementation is the same as in Example 1, wherein the heating temperature is 1080°C, the holding time is 3h, the final rolling temperature is 880°C, and the intermediate billet size is 220 ⁇ 220 mm.
  • the intermediate billet is heated to 1120°C, the holding time is 3h, the final rolling temperature is 850°C, and the finished bar specification is ⁇ 75mm.
  • Air cooling after rolling Quenching heating temperature is 870°C, heating time is 100min, tempering temperature is 550°C, tempering time is 60min, water cooling after tempering.
  • the implementation is the same as in Example 1, wherein the heating temperature is 1120°C, the holding time is 8h, the final rolling temperature is 940°C, and the intermediate billet size is 260 ⁇ 260 mm.
  • the intermediate billet is heated to 1200°C, the holding time is 5h, the final rolling temperature is 880°C, and the finished bar specification is ⁇ 100mm.
  • Air cooling after rolling Quenching heating temperature is 890°C, heating time is 150min, tempering temperature is 430°C, tempering time is 100min, air cooling after tempering.
  • the implementation is the same as in Example 1, wherein the heating temperature is 1250°C, the holding time is 14h, hot continuous rolling is formed, the final rolling temperature is 900°C, and the finished bar specification is ⁇ 150mm. Air cooling after rolling. Quenching heating temperature is 990°C, heating time is 210min, tempering temperature is 350°C, tempering time is 180min, water cooling after tempering.
  • the chemical composition shown in Table 1 it is smelted in a converter, refined and vacuum treated, and then cast into a steel ingot.
  • the heating temperature is 1180°C
  • the holding time is 3.5h
  • the final rolling temperature is 980°C
  • the intermediate billet size is 280 ⁇ 280mm.
  • the intermediate billet is heated to 1250°C
  • the holding time is 12h
  • the final rolling temperature is 950°C
  • the finished bar specification is ⁇ 160mm.
  • the quenching heating temperature is 900°C
  • the heating time is 210min
  • the tempering temperature is 450°C
  • the tempering time is 190min. After tempering, it is water-cooled.
  • the implementation mode is the same as that in Example 5, in which the heating temperature is 1220°C, the holding time is 24h, the forging is formed, the final forging temperature is 920°C, and the finished bar specification is ⁇ 170mm. Air-cooled after forging.
  • the quenching heating temperature is 920°C
  • the heating time is 240min
  • the tempering temperature is 420°C
  • the tempering time is 240min. After tempering, it is air-cooled.
  • the implementation mode is the same as in Example 2, wherein the heating temperature is 1080°C, the holding time is 3h, the final rolling temperature is 880°C, and the intermediate billet size is 220 ⁇ 220mm.
  • the intermediate billet is heated to 1100°C, the holding time is 3h, the final rolling temperature is 850°C, and the finished bar specification is ⁇ 65mm.
  • Air cooling after rolling The quenching heating temperature is 880°C, the heating time is 150min, the tempering temperature is 400°C, and the tempering time is 100min. After tempering, it is water-cooled.
  • the comparative example 1 contains high Nb, the microalloy coefficient is 10.1, the precipitation strengthening effect is poor, the strength is low, the impact toughness is low, and the fatigue life is short;
  • the comparative example 2 contains high P content and harmful elements The coefficient is 678, the atmospheric corrosion resistance coefficient is 5.3, the impact toughness and stress corrosion cracking resistance are poor, and the hydrogen embrittlement coefficient is high; the high content of S in Comparative Example 3 results in poor impact toughness.
  • the yield strength of the high-strength and tough steel materials in Examples 1-7 of the present invention are all R p0.2 ⁇ 1000MPa, tensile strength R m ⁇ 1200MPa, elongation A ⁇ 12%, reduction of area Z ⁇ 50%, Charpy impact Work A kv ⁇ 60J, hydrogen embrittlement coefficient ⁇ (Z) ⁇ 15%.
  • Example 6 due to the one-time heating and rolling process and the large bar size, the structure compactness is slightly worse. Compared with other examples, the strength and impact performance are reduced; in Example 7, due to atmospheric corrosion resistance The coefficient is relatively low, resulting in a slightly inferior effect on impact toughness, hydrogen embrittlement coefficient, and anti-corrosion cracking performance compared with other embodiments.
  • the microstructure of the round steel prepared in Example 2 and the mining chain prepared in Example 2 as raw materials were studied.
  • the optical microscope photos are shown in Figure 1 and Figure 2. It can be seen from the figure that the microstructure of the round steel is tempered martensite and a small amount of bainite and retained austenite, while the microstructure of the chain obtained by further preparing the round steel prepared in Example 2 is refined Tempered martensite and a small amount of bainite.

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US17/800,800 US20230235435A1 (en) 2020-02-28 2021-02-23 Steel for mining chain and manufacturing method thereof
MX2022010591A MX2022010591A (es) 2020-02-28 2021-02-23 Acero para cadena de mineria y metodo de fabricacion del mismo.
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