Microstructure, Microhardness, and Corrosion Resistance of Nanocrystalline 304 Stainless Steel Plates

doi:10.11900/0412.1961.2024.00253

Acta Metall Sin

2026, Vol. 62

Issue (9): 1566-1580 DOI: 10.11900/0412.1961.2024.00253

Research paper

Current Issue | Archive | Adv Search

Microstructure, Microhardness, and Corrosion Resistance of Nanocrystalline 304 Stainless Steel Plates

CHEN Yuan¹^,², GONG Chunbo³, WANG Shenggang¹^,²(

), MA Song¹^,², ZHANG Zhidong¹^,²

1 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3 Fuxin Ruiguang Fluorine Chemistry Co. Ltd., Fuxin 123129, China

Cite this article:

CHEN Yuan, GONG Chunbo, WANG Shenggang, MA Song, ZHANG Zhidong. Microstructure, Microhardness, and Corrosion Resistance of Nanocrystalline 304 Stainless Steel Plates. Acta Metall Sin, 2026, 62(9): 1566-1580.

Download:

HTML

PDF(4662KB)
Export: BibTeX | EndNote (RIS)

Abstract

To understand the relations between the corrosion behaviors of nanocrystalline and conventional polycrystalline 304 stainless steels and their microstructures and microhardness, the microhardness of nanocrystalline 304 stainless steel plate (NSSP-304) produced using severe rolling technology and its counterpart of a conventional polycrystalline 304 stainless steel (CPSS-304) were investigated on the three planes perpendicular to each other. The microstructures of NSSP-304 and CPSS-304 were characterized using XRD, TEM, and EBSD. The microhardnesses on the three planes of NSSP-304 were higher than those of CPSS-304, which was unrelated to the martensite phase. The microhardness distributions on the three planes of NSSP-304 were more uniform than those of CPSS-304. The microhardness of NSSP-304 on the rolling plane was approximately 40 HV higher than on the other two planes, attributed to its weak texture ({110}<211>). Despite the weak texture, the corrosion rates of NSSP-304 varied with corrosion time within the narrower ranges than those of CPSS-304 during potentiostatic polarization in 0.5 mol/L HCl solution at room temperature and in 6%FeCl₃ solution (35 ^oC). NSSP-304 exhibited lower corrosion rates compared to CPSS-304, while the pitting corrosion resistance of the former was higher than those of the latter in both kinds of aqueous solutions. These results demonstrated that the texture, the high microhardness, the twins, and high-density dislocations of NSSSP-304 did not degrade its uniform and pitting corrosion resistances despite undergoing severe deformation during production (total deformation > 70%). Compared to CPSS-304, the higher microhardness, improved uniformity, and pitting corrosion resistances of NSSP-304 were attributed to its distinct configurations of valence electrons (i.e., their higher binding energies, higher weight values at higher energy levels, lower weight values at lower levels, and larger work function) derived from its grain refinement, dislocation accumulation, deformation twins, and larger fraction of low angle grain boundaries.

Key words: 304 stainless steel microhardness texture dislocation deformation twin isotropy corrosion

Received: 25 July 2024

ZTFLH:

TG178

Fund: National Natural Science Foundation of China(52031014);National Natural Science Foundation of China(51171199)

Corresponding Authors: WANG Shenggang, professor, Tel: 13909837801, E-mail: sgwang@imr.ac.cn

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	CHEN Yuan
	GONG Chunbo
	WANG Shenggang
	MA Song
	ZHANG Zhidong

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2024.00253 OR https://www.ams.org.cn/EN/Y2026/V62/I9/1566

Fig.1 Location distributions of microhardness measurement on the three planes (perpendicular to each other) of NSSP-304 and CPSS-304 (CPSS-304—conventional polycrystalline 304 stainless steel, NSSP-304—nanocrystalline 304 stainless steel plate, RD—rolling direction, ND—normal direction, TD—transverse direction)
(a) along the ten lines on RD-TD plane
(b, c) along the two lines on RD-ND plane (b) and TD-ND plane (c)

Fig.2 Microhardness curves on the RD-TD planes of NSSP-304 and CPSS-304 samples
(a-c) microhardnesses on the lines 1-3 (a), lines 4-6 (b), and lines 7-10 (c)
(d) average microhardnesses on the ten lines
(e) relative standard deviations of microhardness

Fig.3 Microhardnesses on the two lines on the RD-ND (a, b) and TD-ND (c, d) planes of NSSP-304 and CPSS-304 samples (12 measurement positions on each line)
(a, c) microhardness distributions
(b, d) relative deviation values of microhardness

Fig.4 Uniform and pitting corrosion properties of NSSP-304 and CPSS-304 samples in 0.5 mol/L HCl (at room temperature) (a-c) and 6%FeCl₃ solutions (at 35 ^oC) (d-f) (i and t denote current density and time, respectively; k₁-k₅ are the slopes of curves in Fig.4d within different time ranges)
(a) potentiostatic polarization curves in 0.5 mol/L HCl solution and partially enlarged view (inset)
(b, c) surface SEM images of corroded NSSP-304 (b) and CPSS-304 (c) samples after the potentiostatic polarization
(d) mass loss curves of NSSP-304 and CPSS-304 samples during immersion test in 6%FeCl₃ solution
(e, f) surface SEM images of corroded NSSP-304 (e) and CPSS-304 (f) samples after the immersion test

Fig.5 High-resolution Cl^-2p XPS on corroded NSSP-304 and CPSS-304 samples after the potentiostatic polarization in 0.5 mol/L HCl solution at room temperature (a) and immersion in 6%FeCl₃ solution (35 ^oC) (b)

Fig.6 Average microhardnesses (the same position N on different lines) of NSSP-304 and CPSS-304 samples on the RD-TD plane, TD-ND plane, and RD-ND plane

Fig.7 Indentation images of NSSP-304 (a-c) and CPSS-304 (d-f) samples on the three planes perpendicular to each other
(a, d) RD-TD plane (b, e) TD-ND plane (c, f) RD-ND plane

Fig.8 XRD patterns of NSSP-304 and CPSS-304 samples

Fig.9 TEM images of NSSP-304 sample on different planes
(a, b) dislocation accumulation (a) and deformation twins (b) on the RD-TD plane
(c, d) TEM images on RD-ND (c) and TD-ND (d) planes

Fig.10 OM images of CPSS-304 sample on the three planes perpendicular to each other
(a) RD-TD plane (b) TD-ND plane (c) RD-ND plane

Fig.11 EBSD characterization of NSSP-304 sample (The color bands in pole figures and inverse pole figures denote the variation of pole density, the same in Fig.12)
(a) crystal orientation map
(b) misorientation angle distribution
(c) {100}, {110}, and {111} pole figures
(d) {100}, {110}, and {111} inverse pole figures

Fig.12 EBSD characterization of CPSS-304 sample
(a) crystal orientation map
(b) misorientation angle distribution
(c) {100}, {110}, and {111} pole figures
(d) {100}, {110}, and {111} inverse pole figures

[1]	Zou Z C, He L, Zhou T, et al. Research on microhardness prediction of 304 stainless steel turning based on dislocation density [J]. J. Manuf. Processes, 2022, 83: 522 doi: 10.1016/j.jmapro.2022.08.035
[2]	Ocak-Araz S, Birden A, Bayca S U, et al. Effect of powder-pack boronizing on the microhardness, wear and corrosion behaviors of AISI 304L steel [J]. J. Mater. Eng. Perform., 2024, 33: 166 doi: 10.1007/s11665-023-07966-7
[3]	Picard S, Memet J B, Sabot R, et al. Corrosion behaviour, microhardness and surface characterization of low energy, high current ion implanted austenitic stainless steel [J]. Mater. Sci. Eng., 2001, A303: 163
[4]	Chen K‚ Zhao W L. Study on organization and performance of nitrogen ion implantation layer of 304 austenitic stainless steel [J]. Surf. Technol., 2011, 40(2): 18
	陈康, 赵玮霖. 304奥氏体不锈钢氮离子注入层的组织与性能研究, 表面技术， 2011, 40(2): 18
[5]	Zhang L J, Li P, Pan L, et al. Surface microstructure, hardness and corrosion resistance of austenitic stainless after gas carburizing at low temperature [J]. Mater. Mech. Eng., 2014, 38(3): 44
	张良界, 李朋, 潘邻等. 奥氏体不锈钢低温气体渗碳后的表面组织、硬度与耐蚀性能 [J]. 机械工程材料, 2014, 38(3): 44
[6]	Wei X L, Zhang C, Ling X. Effects of laser shock processing on corrosion resistance of AISI 304 stainless steel in acid chloride solution [J]. J. Alloys Compd., 2017, 723: 237 doi: 10.1016/j.jallcom.2017.06.283
[7]	Chen Y, Li X, Liu J, et al. Effect of laser surface remelting of 304stainless steel [J]. J. Appl. Mech. Tech. Phys., 2023, 64: 491 doi: 10.1134/S002189442303015X
[8]	Li D Q, Wang T, Yang Z F, et al. Optimization of laser polishing parameters of 304 stainless steel and performance analysis of polishing layer [J]. Chin. J. Lasers 2023, 50: 0402021
	(李道齐, 王涛, 杨紫璠等，304不锈钢激光抛光的参数优化及抛光层性能分析[J]. 中国激光, 2023, 50: 0402021
[9]	Tao H M, Ding M M, Shen C, et al. Inconsistent evolvement of micro-structures and corrosion behaviors in cold/warm deformed austenitic stainless steel [J]. Mater. Res. Express, 2022, 9: 096520
[10]	Feng Z Y, Wang J, Zhang F J, et al. Effect of high current pulsed electron beam on surface microstructure and properties of cold-rolled austenitic stainless steel [J]. J. Mater. Res. Technol., 2024, 29: 1183 doi: 10.1016/j.jmrt.2024.01.103
[11]	Singh D, Basha D A, Singh A, et al. Microstructural and passivation response of severely deformed AISI 304 steel surface: The role of surface mechanical attrition treatment [J]. J. Mater. Eng. Perform. 2020, 29:6898 doi: 10.1007/s11665-020-05161-6
[12]	Zheng Z J, Liu J W, Gao Y. Achieving high strength and high ductility in 304 stainless steel through bimodal microstructure prepared by post-ECAP annealing [J]. Mater. Sci. Eng., 2017, A680: 426
[13]	Yang C W, Jiang X L, Zhang W Q, et al. Prediction of surface microstructure, grain size,martensite content, and microhardness of 316L austenitic stainless steel in surface mechanical grinding treatment process [J]. J. Mater. Eng. Perform., 2024, 33: 9112 doi: 10.1007/s11665-023-08556-3
[14]	Garcia D, Wang T H, Escobar J D, et al. In-situ measurement and control of the tool-workpiece interface temperature during friction stir processing of 304/304L stainless steel [J]. Mater. Today Commun., 2024, 38: 107672
[15]	Hajizadeh K, Kurzydlowski K J. On the possibility of fabricating fully austenitic sub-micron grained AISI 304 stainless steel via equal channel angular pressing [J]. Mater. Today Commun., 2023, 35: 105641
[16]	Wang S G, Sun M, Xu Y H, et al. Enhanced localized and uniform corrosion resistances of bulk nanocrystalline 304 stainless steel in high-concentration HCl solutions at room temperature [J]. J. Mater. Sci. Technol., 2018, 34: 2498 doi: 10.1016/j.jmst.2018.06.006
[17]	Li J C, Pei W Y, Zhao M Y, et al. Study of cold rolling on the transformation mechanism, microstructure, and properties of 304 austenitic stainless steel [J]. Steel Res. Int., 2022, 93: 2100341 doi: 10.1002/srin.v93.4
[18]	Shri D N A, Zahari Z S, Yamamoto A. Effect of ECAP die angle on mechanical properties and biocompatibility of SS316L [J]. Metals, 2021, 11: 1513 doi: 10.3390/met11101513
[19]	Xu H Q, Wei K X, Wei W, et al. Microstructure and mechanical properties evolution of Ti-13Nb-13Zr alloy processed by ECAP-conform and rotary swaging [J]. J. Alloys Compd., 2023, 969: 172351 doi: 10.1016/j.jallcom.2023.172351
[20]	Rogachev S O, Nikulin S A, Rozhnov A B, et al. Multilayer “steel/vanadium alloy/steel” hybrid material obtained by high-pressure torsion at different temperatures [J]. Metall. Mater. Trans., 2017, 48A: 6091
[21]	Zhang H Y, Zheng L W, Wang T, et al. Interrelationship between hydrogen and α′-martensite of SUS 304 austenitic stainless steel revealed by tensile tests [J]. Mater. Sci. Eng., 2022, A831: 142169
[22]	Zhang W Q, Wang X L, Hu Y J, et al. Predictive modelling of microstructure changes, micro-hardness and residual stress in machining of 304 austenitic stainless steel [J]. Int. J. Mach. Tools Manuf., 2018, 36-48: 130
[23]	Amininejad A, Jamaati R, Hosseinipour S J. Improvement of strength-ductility balance of SAE 304 stainless steel by asymmetric cross rolling [J]. Mater. Chem. Phys., 2020, 256: 123668 doi: 10.1016/j.matchemphys.2020.123668
[24]	Zhan X H, Zhang J H, Wang J F, et al. Microstructure characteristics and mechanical properties of fiber-diode hybrid laser welded 304 austenitic stainless steel [J]. Mater. Sci. Eng., 2022, A854: 143884
[25]	Burkhardt C, Wendler M, Lehner R, et al. Fine-grained microstructure without texture obtained by electron beam powder bed fusion for AISI 304 L-based stainless steel [J]. Addit. Manuf., 2023, 69: 103539
[26]	Du M, Meng B, Liu Y Z, et al. Flow characteristics and microstructural evolution in pulsed current assisted micro-scaled compression of stainless steel sheet [J]. J. Mater. Res. Technol, 2021, 15: 4397 doi: 10.1016/j.jmrt.2021.10.076
[27]	Thirathipviwat P, Onuki Y, Umemura K, et al. Microstructure, dislocation density and microhardness of 1%C-doped CoCrFeNi complex concentrated alloys during isochronal annealing [J]. J. Alloys Compd., 2023, 930: 167504 doi: 10.1016/j.jallcom.2022.167504
[28]	Tong Z P, Liu H L, Jiao J F, et al. Microstructure, microhardness and residual stress of laser additive manufactured CoCrFeMnNi high-entropy alloy subjected to laser shock peening [J]. J. Mater. Process. Technol., 2020, 285: 116806 doi: 10.1016/j.jmatprotec.2020.116806
[29]	Nataraj M V, Swaroop S. Effect of laser peening without coating on mechanical and microstructural behaviour of SS 304 stainless steel [J]. Mater. Today Commun., 2022, 33: 104200
[30]	Xu L, Wang R Z, Wang J, et al. On multiaxial creep-fatigue considering the non-proportional loading effect: Constitutive modeling, deformation mechanism, and life prediction [J]. Int. J. Plast., 2022, 155: 103337 doi: 10.1016/j.ijplas.2022.103337
[31]	Nataraj M V, Swaroop S. Deformation-induced phase transition and nanotwins in SS 304 steel during cryogenic laser shock peening without coating [J]. J. Mater. Res. Technol., 2022, 19: 2611 doi: 10.1016/j.jmrt.2022.06.005
[32]	Guo D W, Kwok C T, Tam L M, et al. Hardness, microstructure and texture of friction surfaced 17-4PH precipitation hardening stainless steel coatings with and without subsequent aging [J]. Surf. Coat. Technol., 2020, 402: 126302 doi: 10.1016/j.surfcoat.2020.126302
[33]	Liu Q, Hua J Y, Fan D, et al. High-speed perforation of high-entropy alloy CrMnFeCoNi plates: Experiments and modeling [J]. Mater. Today Commun., 2024, 38:108083
[34]	Han Z L, Zhuang W H, Lai P, et al. General corrosion behavior and mechanism of low-temperature plasma nitrided 17-4PH stainless steel in high temperature water [J]. Mater. Charact., 2024, 209: 113702 doi: 10.1016/j.matchar.2024.113702
[35]	Zhu Q C, Sun W T, Yoo Y, et al. Enhance corrosion resistance of 304 stainless steel using nanosecond pulsed laser surface processing [J]. Surf. Interfaces, 2023, 42: 103479
[36]	Kumar V, Pruncu C I, Wang Y P, et al. The response of 316L steel manufactured by selective laser melting route to high-temperature oxidation behaviour: The role of microstructure modification [J]. Mater. Charact., 2024, 207: 113531 doi: 10.1016/j.matchar.2023.113531
[37]	Huang B H, Ye Y X, Wang K, et al. Corrosion damage repair of 7075-T6 aluminum alloy by ultrasonic nanocrystal surface modification [J]. Surf. Coat. Technol., 2023, 474: 130085 doi: 10.1016/j.surfcoat.2023.130085
[38]	Wang S G, Sun M, Liu S Y, et al. Synchronous optimization of strengths, ductility and corrosion resistances of bulk nanocrystalline 304 stainless steel [J]. J. Mater. Sci. Technol., 2020, 37:161 doi: 10.1016/j.jmst.2019.05.073
[39]	Keist J S, Palmer T A. Development of strength-hardness relationships in additively manufactured titanium alloys [J]. Mater. Sci. Eng., 2017, A693: 214
[40]	Wang S G, Sun M, Cheng P C, et al. The electrochemical corrosion of bulk nanocrystalline ingot iron in HCl solutions with different concentrations [J]. Mater. Chem. Phys., 2011, 127: 459 doi: 10.1016/j.matchemphys.2011.02.035
[41]	Wang S G, Sun M, Han H B, et al. The high-temperature oxidation of bulk nanocrystalline 304 stainless steel in air [J]. Corros. Sci., 2013, 72: 64 doi: 10.1016/j.corsci.2013.03.008
[42]	Wang S G, Huang Y J, Han H B, et al. The electrochemical corrosion characterization of bulk nanocrystalline aluminium by X-ray photoelectron spectroscopy and ultra-violet photoelectron spectroscopy [J]. J. Electroanal. Chem., 2014, 724: 95 doi: 10.1016/j.jelechem.2014.04.014
[43]	Wang S G, Huang Y J, Sun M, et al. The electrochemical corrosion of bulk nanocrystalline aluminum in acidic sodium sulfate solutions at room temperature [J]. J. Phys. Chem., 2015, 119C: 8420
[44]	Chen J, Lee H B, Jeong C, et al. Oxidation behavior of the directed energy deposited 316L stainless steel in supercritical carbon dioxide environment: Effect of post-manufacturing heat treatment [J]. Addit. Manuf., 2024, 81: 103998
[45]	Zhang B, Liu L, Li T S, et al. Adsorption and diffusion behavior of Cl^- on sputtering Fe-20Cr nanocrystalline thin film in acid solution (pH = 2) [J]. J. Mater. Sci. Technol., 2015, 31: 1198 doi: 10.1016/j.jmst.2015.10.016
[46]	Liu X G, An Z L, Lan H Q, et al. Enhancement of DC flashover voltage of epoxy insulators and gap breakdown voltage in SF₆ gas by direct fluorination of metal electrodes [J]. IEEE Trans. Dielectr. Electr. Insul., 2024, 31: 22 doi: 10.1109/TDEI.2023.3337212

[1]	LI Shuaiyu, LIU Zedong, YANG Jieren, JIN Wei, PENG Bo, DU Xin, ZHOU Siman. Microstructural Inheritance Behavior and Mechanical Property Control of TA18 Alloy From Ingot to Tube Blank[J]. 金属学报, 2026, 62(9): 1487-1502.
[2]	SHI Xianbo, ZHANG Shuzhan, SU Yuanfei, JIAO Shengxuan, YAN Wei, RONG Lijian. High-Temperature Microstructural Stability of High-Si Austenitic Steels for Lead-Cooled Fast Reactor Fasteners[J]. 金属学报, 2026, 62(8): 1347-1356.
[3]	DENG Siying, DONG Jiaxuan, CHEN Shuaifeng, SONG Hongwu, ZHANG Shihong. Texture Evolution and Deformation Modes for Zr-4 Alloy During Stamping: Experiments and Modeling[J]. 金属学报, 2026, 62(8): 1417-1426.
[4]	LI Ruixue, ZHOU Chenxi, YANG Huimin, YONG Xingyue, LIU Jingjun. Microstructural Evolution and Dynamic Failure Mechanism of B10 Cu-Ni Alloy Under Multiple Stress Coupling in Flowing Seawater[J]. 金属学报, 2026, 62(7): 1273-1287.
[5]	QIN Zhiwei, WANG Bin, ZHAO Qiang, LI Jiachen, SUN Yutao, HONG Xiaolong, LI Peng, DONG Honggang. Effect of Heat Treatment on Interfacial Microstructure of Inertial Friction Welded Joints for GH4065A/IN718 Dissimilar Superalloys[J]. 金属学报, 2026, 62(6): 1032-1042.
[6]	DENG Gaping, ZHAO Jie, GAO Kai, WANG Wei, LIU Huan, CAO Tieshan, CHENG Congqian. Hot Corrosion Behavior of DZ411 Nickel-Based Superalloy NiCoCrAlY Coating at 950 ^oC[J]. 金属学报, 2026, 62(6): 1059-1068.
[7]	WU Fan, LIU Huahui, BIAN Wenshan, CAI Junyu, JIN Shijie, LUO Zhongbing. Microstructural Evolution and Slip Mechanisms in TC4 Titanium Alloy During Cyclic Deformation[J]. 金属学报, 2026, 62(6): 1082-1090.
[8]	LI Wei, FENG Jietao, FANG Canfeng, FENG Xiao, GAO Wu, LIU Min, WANG Yingmin. Sensitization Failure Mechanism and Reversion Regulation of TIG Welded Joints in 5A06 Alloy[J]. 金属学报, 2026, 62(6): 1105-1116.
[9]	WU Xinqiang, TAN Jibo, ZHANG Ziyu, XUE Baoquan, KE Wei. Research Advance on Corrosion Fatigue Behavior of Metallic Materials in High-Temperature Pressurized Water, Liquid Pb-Bi, and Marine Environments[J]. 金属学报, 2026, 62(5): 822-834.
[10]	CHANG Songtao, ZHANG Fang, SHA Yuhui, ZUO Liang. Spatial Distribution and Evolution Mechanism of Texture in Non-Oriented Silicon Steel Influenced by the Grain Boundary Segregation Element Sb[J]. 金属学报, 2026, 62(4): 627-635.
[11]	LIU Yongkang, LU Yuanyuan, YANG Ying, LIU Xingguang, ZHENG Jun, ZHANG Shihong. Deposition Mechanism and Defect Control of CrN/NbN Coatings with Excellent Tribocorrosion Performance[J]. 金属学报, 2026, 62(4): 649-668.
[12]	XIAO Siming, LIU Tianhao, SU Chen, GUO Shengfeng. Effect of Chromium on Thermal Stability and Corrosion Resistance in FeWB Bulk Metallic Glasses[J]. 金属学报, 2026, 62(3): 458-466.
[13]	ZHANG Zhefeng, HOU Jiapeng, LIU Rui, LI Xiaotao, ZHANG Zhenjun, ZHANG Peng. Quantitative Relationships Between the Strength-Plasticity and Strength-Electrical Conductivity of Metallic Materials[J]. 金属学报, 2026, 62(2): 253-262.
[14]	LUO Haiwen, LIN Xiong, LIU Gaoyang, HU Bin. Progress and Perspectives on Metallic Bipolar Plates in Fuel Cells[J]. 金属学报, 2026, 62(2): 263-274.
[15]	ZHAO Zibo, TAN Haibing, ZHANG Bohua, LIU Yujing, LIU Jianrong, GUO Huiming, ZENG Weidong, TIAN Wei, WANG Qingjiang. *Review: Microtextures in Near α and α + β* Dual-Phase Titanium Alloys**[J]. 金属学报, 2026, 62(2): 275-288.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed