Study on the high-temperature oxidation behavior of high strength steels for photovoltaic applications
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摘要: 采用高温同步热分析仪（TGA）对光伏用高强钢S350GD和S420GD在干燥和潮湿气氛下的高温氧化行为进行了系统研究，并采用X射线衍射（XRD）和场发射电子探针（EPMA）分析氧化铁皮的物相组成、截面形貌及元素分布。结果表明，S350GD和S420GD氧化增重曲线均符合抛物线规律，S420GD的氧化铁皮对比S350GD，厚度更小且高价铁氧化物占比更高；S420GD在氧化铁皮和基体界面处存在Si元素富集层，其中SiO2和Fe2SiO4协同降低Fe2+扩散系数；对比干燥和潮湿气氛，S350GD和S420GD的氧化铁皮生长规律相同，潮湿气氛下氧化铁皮厚度更大且低价铁氧化物占比更高；潮湿气氛下氧化铁皮中产生大量孔洞和微裂纹等缺陷，这些缺陷成为粒子的扩散通道，从而加快了氧化反应。Abstract: The high temperature oxidation behavior of high-strength steels S350GD and S420GD for photovoltaic applications was systematically studied by a high-temperature thermal gravimetric analyzer (TGA) under dry and humid atmospheres. X-ray diffraction (XRD) and electron probe microanalysis (EPMA) were used to characterize the phase composition, cross-sectional morphologies and element distribution of the oxide scales. The results show that the oxidation weight gain curves of both S350GD and S420GD follow a parabolic law. Compared to S350GD, the oxide scale formed on S420GD is thinner and exhibits a higher fraction of high-valence iron oxides. A silicon-enriched interfacial layer was detected at the oxide/metal substrate interface in S420GD, where SiO2 and Fe2SiO4 phases synergistically reduce the diffusion coefficient of Fe2+ ions. When comparing oxidation under dry and humid atmospheres, both steels show similar oxides growth mechanisms; however, the oxide scales are thicker and the content of low-valence iron oxides is increased in humid environments. Moreover, the oxide scales formed under humid conditions contain a significant density of pores and microcracks, which act as fast diffusion pathways for ionic species, thereby accelerating the oxidation process.
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图 2 S350GD和S420GD的氧化增重曲线和高温氧化Arrhenius曲线
(a) 氧化增重曲线; (b) 高温氧化Arrhenius曲线
Figure 2. Oxidation weight curves and high-temperature oxidation Arrhenius plots of S350GD and S420GD
图 3
1000 ℃下S350GD和S420GD在干燥气氛下氧化60 min后XRD衍射峰Figure 3. XRD diffraction peaks of S350GD and S420GD after oxidation at
1000 ℃ for 60 min in dry atmosphere
图 4 S350GD和S420GD氧化60 min后氧化铁皮断面形貌
(a)(e)(i) 干燥下S350GD; (b)(f)(j) 干燥下S420GD; (c)(g)(k) 潮湿下S350GD; (d)(h)(l) 潮湿下S420GD
Figure 4. Cross-sectional morphology of oxide scales on S350GD and S420GD after 60 min of oxidation
图 5 S350GD和S420GD氧化60 min后氧化铁皮厚度及相组成
Figure 5. Thickness and phase compositions of oxide scales on S350GD and S420GD after 60 min of oxidation
图 6 S350GD和S420GD干燥气氛下氧化元素分析
Figure 6. Oxidation elemental analysis of S350GD and S420GD in dry atmosphere
(a) 800 ℃, S350GD; (b) 800 ℃, S420GD; (c) 1000 ℃, S350GD; (d) 1 000 ℃, S420GD
图 7 S420GD的Si元素富集层组成
(a) 1 000 ℃时Fe-Si-O三元相图等温截面; (b) Si富集层元素分析; (c) FeO、SiO2和Fe2SiO4的晶体结构
Figure 7. Composition of the Si-enriched layer in S420GD
图 8
1000 ℃条件下氧化铁皮断面形貌和元素分析S350GD:(a) 干燥气氛, (a1)潮湿气氛, (a2) 潮湿气氛下的元素分析, (a3)(a4)点1、点2的EDS图;S420GD:(b) 干燥气氛, (b1)潮湿气氛, (b2) 潮湿气氛下的元素分析, (b3)(b4)点3、点4的EDS图
Figure 8. Cross-sectional morphology and elemental analysis of oxide scales at
1000 ℃
图 9 不同气氛下的氧化机理
(a) 干燥气氛下; (b) 潮湿气氛下
Figure 9. Schematic diagram of oxidation mechanisms under different atmospheres
表 1 S350GD和S420GD的化学成分
Table 1. Chemical compositions of S350GD and S420GD
% C Mn Si P S Ti N Fe S350GD 0.20 0.4 0.06 0.02 0.045 0.040 0.050 Bal. S420GD 0.20 1.2 0.20 0.02 0.045 0.040 0.050 Bal. 
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表 2 不同温度下S350GD、S420GD的氧化速率常数KP
Table 2. Parabolic rate constant KP of S350GD and S420GD at different temperatures
Temperature/℃ Atmosphere KP/(mg2·cm−4·min−1) S350GD S420GD 800 Dry 13.56 9.47 900 Dry 25.66 15.46 1000 Dry 30.51 27.59 800 Humid 64.59 43.91 900 Humid 82.55 52.67 1000 Humid 109.66 89.77
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表 3 不同温度下Fe2+在不同氧化产物中的扩散系数
Table 3. Diffusion coefficients of Fe2+ in different oxidation products at various temperatures
Oxides Diffusion coefficient/(cm2·s−1) Temperature/℃ DFe DO Wustite(FeO) 9×10−8 1000 Magnetite(Fe3O4) 2×10−9 1000 Hematite(Fe2O3) 2×10−15 8×10−14 1000 4.1×10−15 1200 Silica(SiO2) 1.0×10−20 1.3×10−18 1000 Fayalite(Fe2SiO4) 8×10−16 1000
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[1] WANG K, WANG J. A brief analysis on the current status and development trend of steel for photovoltaic brackets in China[J]. China Steel, 2022(2): 23-25, 34. (王可, 王晶. 我国光伏支架用钢现状及发展趋势浅析[J]. 中国钢铁业, 2022(2): 23-25, 34. doi: 10.3969/j.issn.1672-5115.2022.02.008WANG K, WANG J. A brief analysis on the current status and development trend of steel for photovoltaic brackets in China[J]. China Steel, 2022（2）: 23-25, 34. doi: 10.3969/j.issn.1672-5115.2022.02.008 [2] ZHANG S L. Application of thermal-based zinc-aluminum-magnesium coating materials in photovoltaic scaffolds[J]. Metal World, 2021(6): 32-34. (张树亮. 热基锌铝镁镀层材料在光伏支架领域的应用[J]. 金属世界, 2021(6): 32-34.ZHANG S L. Application of thermal-based zinc-aluminum-magnesium coating materials in photovoltaic scaffolds[J]. Metal World, 2021（6）: 32-34. [3] FAN C L, LIU W D. Development of hot-dip galvanized S390GD(S450GD)+Z products for photovoltaic brackets of Handan Steel[J]. Steel Rolling, 2021, 38(3): 93-97, 103. (范春磊, 刘文栋. 邯钢光伏支架用热镀锌S390GD(S450GD)+Z产品的开发[J]. 轧钢, 2021, 38(3): 93-97, 103.FAN C L, LIU W D. Development of hot-dip galvanized S390GD(S450GD)+Z products for photovoltaic brackets of Handan Steel[J]. Steel Rolling, 2021, 38(3): 93-97, 103. [4] ZHANG M Y, SHAO G J. Effect of microstructure of oxide scales on pickling of hot rolled strips[J]. Shanghai Metals, 2007(3): 41-44. (张孟仪, 邵光杰. 热轧板的氧化皮结构对酸洗效果的影响[J]. 上海金属, 2007(3): 41-44. doi: 10.3969/j.issn.1001-7208.2007.03.010ZHANG M Y, SHAO G J. Effect of microstructure of oxide scales on pickling of hot rolled strips[J]. Shanghai Metals, 2007（3）: 41-44. doi: 10.3969/j.issn.1001-7208.2007.03.010 [5] CAO G M, SHI F C, SUN B, et al. Oxide scales control and spallation behavior of hot-rolled automotive frame steels[J]. Transactions of Materials and Heat Treatment, 2014, 35(11): 161-167. (曹光明, 石发才, 孙彬, 等. 汽车大梁钢的氧化铁皮结构控制与剥落行为[J] 材料热处理学报, 2014, 35(11): 161-167.CAO G M, SHI F C, SUN B, et al. Oxide scales control and spallation behavior of hot-rolled automotive frame steels[J]. Transactions of Materials and Heat Treatment, 2014, 35(11): 161-167. [6] HUANG B, MA X J, ZHENG Y K, et al. Adhesion factors of hot-dip galvanized zinc layer in industrial production[J]. Metallic Functional Materials, 2022, 29(6): 67-73. (黄宾, 马幸江, 郑艳坤, 等. 工业化生产中热镀锌锌层附着力的影响因素[J]. 金属功能材料, 2022, 29(6): 67-73.HUANG B, MA X J, ZHENG Y K, et al. Adhesion factors of hot-dip galvanized zinc layer in industrial production[J]. Metallic Functional Materials, 2022, 29（6）: 67-73. [7] ZHANG H J, CHEN L S. Analysis of surface sliver defect on cold rolled and cold rolled galvanizing sheet[J]. Iron Steel Vanadium Titanium, 2011, 32(3): 76-81. (张贺佳, 陈连生. 冷轧镀锌板表面线状缺陷分析[J]. 钢铁钒钛, 2011, 32(3): 76-81.ZHANG H J, CHEN L S. Analysis of surface sliver defect on cold rolled and cold rolled galvanizing sheet[J]. Iron Steel Vanadium Titanium, 2011, 32（3）: 76-81. [8] CHEN X, JIANG Z, MONAGHAN B J, et al. Breakaway oxidation behaviour of ferritic stainless steels at 1150 C in humid air[J]. Corrosion Science, 2016, 108: 11-22. doi: 10.1016/j.corsci.2016.02.042 [9] MARTINELLI L, DESGRANGES C, ROUILLARD F, et al. Comparative oxidation behaviour of Fe-9Cr steel in CO2 and H2O at 550 ℃: Detailed analysis of the inner oxide layer[J]. Corrosion Science, 2015, 100: 253-266. doi: 10.1016/j.corsci.2015.07.032 [10] YUAN J, WANG W, ZHU S, et al. Comparison between the oxidation of iron in oxygen and in steam at 650-750 ℃[J]. Corrosion Science, 2013, 75: 309-317. doi: 10.1016/j.corsci.2013.06.014 [11] ABULUWEFA H, GUTHRIE R I L, AJERSCH F. The effect of oxygen concentration on the oxidation of low-carbon steel in the temperature range 1000 to 1250 ℃[J]. Oxidation of Metals, 1996, 46(5): 423-440. doi: 10.1007/bf01048639 [12] LEE V H J, GLEESON B, YOUNG D J. Scaling of carbon steel in simulated reheat furnace atmospheres[J]. Oxidation of metals, 2005, 63(1): 15-31. doi: 10.1007/s11085-005-1949-0 [13] XIE F H, YANG H P, CAO X E, et al. Study on high temperature oxidation behavior of typical steel during 2250 mm hot continuous rolling[J]. Iron Steel Vanadium Titanium, 2019, 40(4): 164-168. (谢凤虎, 杨会平, 曹晓恩, 等.2250 mm热连轧典型钢种高温氧化行为研究[J]. 钢铁钒钛, 2019, 40(4): 164-168. doi: 10.7513/j.issn.1004-7638.2019.04.030XIE F H, YANG H P, CAO X E, et al. Study on high temperature oxidation behavior of typical steel during2250 mm hot continuous rolling[J]. Iron Steel Vanadium Titanium, 2019, 40（4）: 164-168. doi: 10.7513/j.issn.1004-7638.2019.04.030[14] MEI P, BAO S Q, GONG L, et al. Effect of oxidizing atmosphere on scale formation of weathering steel containing Si[J]. Iron Steel Vanadium Titanium, 2021, 42(5): 180-185. (梅鹏, 鲍思前, 龚黎, 等. 氧化气氛对含硅耐候钢氧化铁皮形成的影响[J]. 钢铁钒钛, 2021, 42(5): 180-185. doi: 10.7513/j.issn.1004-7638.2021.05.028MEI P, BAO S Q, GONG L, et al. Effect of oxidizing atmosphere on scale formation of weathering steel containing Si[J]. Iron Steel Vanadium Titanium, 2021, 42（5）: 180-185. doi: 10.7513/j.issn.1004-7638.2021.05.028 [15] YUAN X, YAO Y, CHEN L. High-temperature oxidation behavior of a high manganese austenitic steel Fe-25Mn-3Cr-3Al-0.3C-0.01N[J]. Acta Metallurgica Sinica (English Letters), 2014, 27(3): 401-406. [16] KUSABIRAKI K, WATANABE R, IKEHATA T, et al. High-temperature oxidation behavior and scale morphology of Si-containing steels[J]. ISIJ international, 2007, 47(9): 1329-1334. doi: 10.2355/isijinternational.47.1329 [17] WANG W, ZHAO W, MU W, et al. Effect of hot-rolling process on the microstructure, mechanical and corrosion behaviors of dual-phase Co-based entropic alloys[J]. Materials Science and Engineering: A, 2024, 918: 147433. doi: 10.1016/j.msea.2024.147433 [18] ZHANG R, LI Z, ZHANG Y, et al. Numerical simulation of multi-array spray cooling for hot rolled seamless steel pipes[J]. International Journal of Heat and Mass Transfer, 2024, 221: 125017. doi: 10.1016/j.ijheatmasstransfer.2023.125017 [19] ISSAARD W, NILSONTHI T. Adhesion of thermal oxide scales on hot-rolled steels with 0.026 and 0.193 wt.% Si in Ar-20% H2O at 900 ℃[J]. Materials Today: Proceedings, 2023, 77: 1149-1153. doi: 10.1016/j.matpr.2022.12.276 [20] HAO L, JIANG Z, CHEN Z, et al. High temperature oxidation of indefinite chill roll material under dry and humid atmospheres[J]. steel research international, 2016, 87(3): 349-358. doi: 10.1002/srin.201500063 [21] RAHMEL A, TOBOLSKI J. Einfluss von wasserdampf und kohlendioxyd auf die oxydation von eisen in sauerstoff bei hohen temperaturen[J]. Corrosion science, 1965, 5(5): 333-346. doi: 10.1016/S0010-938X(65)90500-7 [22] GONG L, BAO S Q, ZHAO G, et al. Study on high temperature oxidation behavior of weathering steel Q235NH[J]. Iron Steel Vanadium Titanium, 2021, 42(4): 169-174. (龚黎, 鲍思前, 赵刚, 等. 耐候钢Q235NH的高温氧化行为研究[J]. 钢铁钒钛, 2021, 42(4): 169-174.GONG L, BAO S Q, ZHAO G, et al. Study on high temperature oxidation behavior of weathering steel Q235NH[J]. Iron Steel Vanadium Titanium, 2021, 42（4）: 169-174. [23] HAYASHI S, SEKIMOTO T, HONDA K, et al. The effect of S and Mn on the high-temperature oxidation and scale spallation behavior of low-carbon steels[J]. ISIJ international, 2009, 49(12): 1938-1944. doi: 10.2355/isijinternational.49.1938 [24] AGHAEIAN S, SLOOF W G, MOL J M C, et al. Initial high-temperature oxidation behavior of Fe-Mn binaries in air: the kinetics and mechanism of oxidation[J]. Oxidation of Metals, 2022, 98(1): 217-237. doi: 10.1007/s11085-022-10115-5 [25] CAO G M, SHAN W C, LIU X J, et al. High temperature oxidation behavior of Fe-2.2%Si steel in different atmosphere[J]. Iron and Steel, 2022, 57(8): 132-142. (曹光明, 单文超, 刘小江, 等. Fe-2.2%Si钢在不同气氛下的高温氧化行为[J]. 钢铁, 2022, 57(8): 132-142.CAO G M, SHAN W C, LIU X J, et al. High temperature oxidation behavior of Fe-2.2%Si steel in different atmosphere[J]. Iron and Steel, 2022, 57（8）: 132-142. [26] SONG W, RAN C, LI Q, et al. Influence of humid air on the formation of pores and cracks in the scale on high-strength steel: Experimental and first-principle study[J]. Journal of Materials Research and Technology, 2025, 36: 974-983. doi: 10.1016/j.jmrt.2025.03.172 -
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