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Alloy Steels MDPI Books Edited by
Robert Tuttle
Printed Edition of the Special Issue Published in Metals

www.mdpi.com/journal/metals
 MDPI Books
Alloy Steels

Special Issue Editor

Robert Tuttle

MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade

 MDPI Books
Special Issue Editor
Robert Tuttle
Saginaw Valley State University
USA

Editorial Office
MDPI AG
St. Alban-Anlage 66
Basel, Switzerland

This edition is a reprint of the Special Issue published online in the open access journal Metals (ISSN
2072-6651) from 2016–2017 (available at: http://www.mdpi.com/journal/metals/special issues/
alloy steels).

For citation purposes, cite each article independently as indicated on the article page online and as
indicated below:

Lastname, F.M.; Lastname, F.M. Article title. Journal Name Year, Article number, page range.

First Editon 2018

Cover photo courtesy of Robert Tuttle.

ISBN 978-3-03842-883-1 (Pbk)

ISBN 978-3-03842-884-8 (PDF)

Articles in this volume are Open Access and distributed under the Creative Commons Attribution
(CC BY) license, which allows users to download, copy and build upon published articles even
for commercial purposes, as long as the author and publisher are properly credited, which ensures
maximum dissemination and a wider impact of our publications. The book taken as a whole is

c 2018 MDPI, Basel, Switzerland, distributed under the terms and conditions of the Creative Commons
license CC BY-NC-ND (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 MDPI Books
Table of Contents

About the Special Issue Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Preface to "Alloy Steels" . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

Robert Tuttle
Alloy Steels
doi: 10.3390/met8020116 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Ghusoon Ridha Mohammed, Mahadzir Ishak, Syarifah N. Aqida and Hassan A. Abdulhadi
Effects of Heat Input on Microstructure, Corrosion and Mechanical Characteristics of Welded
Austenitic and Duplex Stainless Steels: A Review
doi: 10.3390/met7020039 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Min Jung Kim, Muhammad Ali Abro and Dong Bok Lee
Corrosion of Fe-(9˜37) wt. %Cr Alloys at 700–800 ◦ C in (N2 , H2 O, H2 S)-Mixed Gas
doi: 10.3390/met6110291 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Marina V. Karavaeva, Marina M. Abramova, Nariman A. Enikeev, Georgy I. Raab and

Ruslan Z. Valiev
Superior Strength of Austenitic Steel Produced by Combined Processing, including
Equal-Channel Angular Pressing and Rolling
doi: 10.3390/met6120310 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

Yu Liu, Zhao Zhang, Guangqiang Li, Qiang Wang, Li Wang and Baokuan Li
The Structural Evolution and Segregation in a Dual Alloy Ingot Processed by
Electroslag Remelting
doi: 10.3390/met6120325 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Beata Białobrzeska, Łukasz Konat and Robert Jasiński

The Influence of Austenite Grain Size on the Mechanical Properties of Low-Alloy Steel
with Boron
doi: 10.3390/met7010026 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

Yiwa Luo, Hanjie Guo, Xiaolin Sun, Mingtao Mao and Jing Guo
Effects of Austenitizing Conditions on the Microstructure of AISI M42 High-Speed Steel
doi: 10.3390/met7010027 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

Junyu Tian, Guang Xu, Mingxing Zhou, Haijiang Hu and Xiangliang Wan
The Effects of Cr and Al Addition on Transformation and Properties in Low-Carbon
Bainitic Steels
doi: 10.3390/met7020040 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

Chieh Yu, Ren-Kae Shiue, Chun Chen and Leu-Wen Tsay

Effect of Low-Temperature Sensitization on Hydrogen Embrittlement of 301 Stainless Steel
doi: 10.3390/met7020058 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

Angang Ning, Wenwen Mao, Xichun Chen, Hanjie Guo and Jing Guo
Precipitation Behavior of Carbides in H13 Hot Work Die Steel and Its Strengthening
during Tempering
doi: 10.3390/met7030070 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

iii
 MDPI Books
Marek Sroka, Adam Zieliński, Maria Dziuba-Kałuża, Marek Kremzer, Magdalena Macek
and Artur Jasiński
Assessment of the Residual Life of Steam Pipeline Material beyond the Computational
Working Time
doi: 10.3390/met7030082 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

Yi Zhang, Jing Li, Cheng-Bin Shi, Yong-Feng Qi and Qin-Tian Zhu

Effect of Heat Treatment on the Microstructure and Mechanical Properties of Nitrogen-
Alloyed High-Mn Austenitic Hot Work Die Steel
doi: 10.3390/met7030094 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136

Paul C. Okonkwo, Rana Abdul Shakoor, Abdelbaki Benamor, Adel Mohamed Amer Mohamed
and Mohammed Jaber F A Al-Marri
Corrosion Behavior of API X100 Steel Material in a Hydrogen Sulfide Environment
doi: 10.3390/met7040109 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

Jianchun Li, Xinglong Liu, Guoping Li, Peide Han and Wei Liang
Characterization of the Microstructure, Mechanical Properties, and Corrosion Resistance of
a Friction-Stir-Welded Joint of Hyper Duplex Stainless Steel
doi: 10.3390/met7040138 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164

Tomasz Stawicki, Beata Białobrzeska and Piotr Kostencki

Tribological Properties of Plough Shares Made of Pearlitic and Martensitic Steels
doi: 10.3390/met7040139 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179

Yuanchun Huang, Sanxing Wang, Zhengbing Xiao and Hui Liu

Critical Condition of Dynamic Recrystallization in 35CrMo Steel
doi: 10.3390/met7050161 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199

Yu Liu, Zhao Zhang, Guangqiang Li, Qiang Wang, Li Wang and Baokuan Li
Effect of Current on Structure and Macrosegregation in Dual Alloy Ingot Processed by
Electroslag Remelting
doi: 10.3390/met7060185 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

Na Gong, Hui-Bin Wu, Zhi-Chen Yu, Gang Niu and Da Zhang

Studying Mechanical Properties and Micro Deformation of Ultrafine-Grained Structures in
Austenitic Stainless Steel
doi: 10.3390/met7060188 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224

Chengsong Liu, Xiaoqin Liu, Shufeng Yang, Jingshe Li, Hongwei Ni and Fei Ye
The Effect of Niobium on the Changing Behavior of Non-Metallic Inclusions in Solid Alloys
Deoxidized with Mn and Si during Heat Treatment at 1473 K
doi: 10.3390/met7060223 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236

Nephtali Calvillo, Ma. de Jesús Soria, Armando Salinas, Emmanuel J. Gutiérrez,

Iván A. Reyes and Francisco R. Carrillo
Influence of Thickness and Chemical
Composition of Hot-Rolled Bands on the Final Microstructure and Magnetic Properties of
Non-Oriented Electrical Steel Sheets Subjected to Two Different Decarburizing Atmospheres
doi: 10.3390/met7060229 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

Mingxing Zhou, Guang Xu, Junyu Tian, Haijiang Hu and Qing Yuan
Bainitic Transformation and Properties of Low Carbon Carbide-Free Bainitic Steels with
Cr Addition
doi: 10.3390/met7070263 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263

iv
 MDPI Books
Fabien Corpace, Arnaud Monnier, Jacques Grall, Jean-Pierre Manaud, Michel Lahaye and
Angeline Poulon-Quintin
Resistance Upset Welding of ODS Steel Fuel Claddings—Evaluation of a Process Parameter
Range Based on Metallurgical Observations
doi: 10.3390/met7090333 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276

Hanghang Liu, Paixian Fu, Hongwei Liu, Chen Sun, Jinzhu Gao and Dianzhong Li
Carbides Evolution and Tensile Property of 4Cr5MoSiV1 Die Steel with Rare Earth Addition
doi: 10.3390/met7100436 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287

Mumin Tutar, Hakan Aydin and Ali Bayram

Effect of Weld Current on the Microstructure and Mechanical Properties of a Resistance
Spot-Welded TWIP Steel Sheet
doi: 10.3390/met7120519 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300

v
MDPI Books
 MDPI Books
About the Special Issue Editor
Robert Tuttle, Professor of Mechanical Engineering, earned his Ph.D. in Metallurgical Engineering
from the University of Missouri-Rolla in 2004. He has been a faculty member at Saginaw Valley
State University (SVSU) since 2004 where he teaches materials science, manufacturing processes,
metalcasting, and electron microscopy. His teaching has been at the undergraduate and graduate
levels. Dr. Tuttle has been heavily involved in the American Foundry Society where he is currently
serving his third term as the Steel Division Chair. He also advises the Student Chapter of the American
Foundry Society at SVSU. Dr. Tuttle has published over forty papers related to metalcasting and steels.
His current work has focused on understanding the nucleation of steels during solidification.

vii
MDPI Books
 MDPI Books
Preface to "Alloy Steels"
The subject of alloy steels covers a broad range of steels and end use markets. Alloy steels are
used in the automotive, aerospace, industrial machinery, and the energy sectors. When this Special
Issue was started, the goal was to provide readers with a collection of papers from around the
world that reflect the field. Within this book are twenty-three papers that cover the microstructure,
manufacturing, corrosion, and application of alloy steels. These papers cover a broad range of alloys
and research focuses that provide the cutting-edge answers needed for today’s markets. The review by
Dr. Mohammed provides an excellent review about welding austenitic and duplex stainless steels.
As editor, my job is much simpler than those of the authors or reviewers. They are the ones who
have struggled in the lab conducting experiments and analyzing the data. Their considerable effort
in providing high-quality papers should never be underestimated or unappreciated. Reviewers also
deserve appreciation for the time in reading the submitted papers and providing valuable feedback to
improve them. The countless staff at MDPI also contributed to this by helping everyone involved with
the day-to-day functions required in publishing this issue. I want to thank all of these individuals for
helping make this Special Issue the second largest ever published by MDPI.
Robert Tuttle
Special Issue Editor

ix
MDPI Books
 MDPI Books
metals
Editorial
Alloy Steels
Robert Tuttle
Department of Mechanical Engineering, Saginaw Valley State University, 209 Pioneer Hall, 7400 Bay Rd,
University Center, MI 48710, USA; rtuttle@svsu.edu; Tel.: +1-989-964-4676

Received: 15 January 2018; Accepted: 7 February 2018; Published: 8 February 2018

Since their invention in 1865, alloy steels have found broad application in multiple industries; the
automotive, aerospace, heavy equipment, and pipeline industries to name a few. Alloy steels include
a tremendous variation in alloying content. They range from the 1–2 wt. % Cr or Ni in some low
alloy steels to the 15–18 wt. % Cr content of many stainless steels. The topic of alloy steels contains
both the common 4140 and 316 alloys to more exotic alloys such as the Hadfield steels. These steels
can form a wide variety of microstructures such as pearlite, bainite, or martensite, which result in an
equally broad range of properties. It is this range that has made them useful to so many industries.
In some cases, these are the only steel alloys that can provide the required combination of properties.
Their use in the automotive industry has been key to the development of safer vehicles and improved
fuel efficiency. Our modern world would not be possible without the advanced alloy steels employed
to safely transport oil through pipelines. Therefore, continued development is necessary to expand
markets, improve products, and enhance the human condition. It is this importance that has lead us
at Metals to create the special issue on alloy steels that you are reading. What follows are 23 papers
from a wide range of authors and nationalities which represents the current state of the art in alloy
steel research.
This issue, like alloy steels themselves, covers diverse set of articles. There are articles on
manufacturing, microstructure, heat treatment, corrosion, and service conditions. This expansive range
reflects the multifaceted nature of alloy steels. Even the individual areas are extensively represented.
In manufacturing, there are articles on the effects of welding [1–4], electroslag remelting [5,6], and
rolling [7–9]. As is typical in any discussion of steels, many papers focus on microstructure–property
relations [10–14]. These form the basis for improving the alloys and their processing. Another large
section of work focuses on topics of more interest to those who are the final customers of the steel
industry. Many alloy steels are heat treated and understanding the effects of heat treatment and heat
treating parameter selection ensure the correct microstructure and properties are attained. Readers
will find these topics addressed by several authors in our pages [10,15–18]. Those readers interested
in improving the corrosion resistance of alloy steels will find several pieces on this topic [2,19,20].
An aspect often ignored by many journals is performance under actual service conditions in the final
product, there are two articles on wear resistance and pipeline life that remind us of the importance of
understanding the final product [21–23]. Data from the final products created from these steels always
provide a powerful insight which the best labs can never replicate, and their inclusion in this special
issue is a significant contribution to this special issue.
Of particular interest to the readers of Metals should be the excellent review article by
Mohammed et al. that presents a wide review of welded austenitic and duplex stainless steels [3].
Their work covers the effects of heat input on the microstructure, corrosion resistance, and mechanical
properties of this diverse class of steels. Mohammaed et al. also review the current state of stress
corrosion cracking work. They distill the results of over 140 papers in the field of stainless steels
and deliver an accurate view of our current understanding of these alloys. Readers will find this an
invaluable asset in building their understanding of these technical issues. The bibliography alone is
worth reading this article.

Metals 2018, 8, 116 1 www.mdpi.com/journal/metals

 MDPI Books
Metals 2018, 8, 116

As can be seen from the topics in this special issue of Metals, the broad world of alloy steels
remains a current area of research and innovation. My goal as editor at the outset of this issue was to
include papers covering the large variety of research and industrial work being done to address the
challenges facing alloy steels. While it is impossible to cover everything in a single issue, this issue
provides the reader with an excellent understanding of the modern problems needing solutions to
create the alloy steels of the future. Hopefully, the readers will find it as enlightening as everyone here
at Metals believes.
Being my first time as an editor, I would like to thank the staff at MDPI and Metals for their help.
In particular, I appreciate the fine editorial assistants and the managing editor for assisting me in this.
They guided me through the process and helped me understand my options with reviews. I hope I
correctly balanced the request of our reviewers and the needs of our authors in creating as fair a peer
review process as possible. I want to thank all our reviewers for the tireless efforts in examining and
commenting on our papers. This effort is always key to a successful journal. All of the authors also
deserve recognition for their contributions and tireless work to promote alloy steels. Finally, I would
like to thank you the reader since without you there would be no need to write papers or publish
regular issues, let alone special issues.

Conflicts of Interest: The author declares no conflict of interest other than his own passion for alloy steels and
their development.

References
1. Tutar, M.; Aydin, H.; Bayram, A. Effect of Weld Current on the Microstructure and Mechanical Properties of
a Resistance Spot-Welded TWIP Steel Sheet. Metals 2017, 7, 519. [CrossRef]
2. Li, J.; Liu, X.; Li, G.; Han, P.; Liang, W. Characterization of the Microstructure, Mechanical Properties, and
Corrosion Resistance of a Friction-Stir-Welded Joint of Hyper Duplex Stainless Steel. Metals 2017, 7, 138.
[CrossRef]
3. Mohammed, G.; Ishak, M.; Aqida, S.; Abdulhadi, H. Effects of Heat Input on Microstructure, Corrosion and
Mechanical Characteristics of Welded Austenitic and Duplex Stainless Steels: A Review. Metals 2017, 7, 39.
[CrossRef]
4. Corpace, F.; Monnier, A.; Grall, J.; Manaud, J.-P.; Lahaye, M.; Poulon-Quintin, A. Resistance Upset Welding of
ODS Steel Fuel Claddings—Evaluation of a Process Parameter Range Based on Metallurgical Observations.
Metals 2017, 7, 333. [CrossRef]
5. Liu, Y.; Zhang, Z.; Li, G.; Wang, Q.; Wang, L.; Li, B. Effect of Current on Structure and Macrosegregation in
Dual Alloy Ingot Processed by Electroslag Remelting. Metals 2017, 7, 185. [CrossRef]
6. Liu, Y.; Zhang, Z.; Li, G.; Wang, Q.; Wang, L.; Li, B. The Structural Evolution and Segregation in a Dual Alloy
Ingot Processed by Electroslag Remelting. Metals 2016, 6, 325. [CrossRef]
7. Huang, Y.; Wang, S.; Xiao, Z.; Liu, H. Critical Condition of Dynamic Recrystallization in 35CrMo Steel. Metals
2017, 7, 161. [CrossRef]
8. Calvillo, N.; Soria, M.; Salinas, A.; Gutiérrez, E.; Reyes, I.; Carrillo, F. Influence of Thickness and Chemical
Composition of Hot-Rolled Bands on the Final Microstructure and Magnetic Properties of Non-Oriented
Electrical Steel Sheets Subjected to Two Different Decarburizing Atmospheres. Metals 2017, 7, 229. [CrossRef]
9. Karavaeva, M.; Abramova, M.; Enikeev, N.; Raab, G.; Valiev, R. Superior Strength of Austenitic Steel
Produced by Combined Processing, including Equal-Channel Angular Pressing and Rolling. Metals 2016,
6, 310. [CrossRef]
10. Zhou, M.; Xu, G.; Tian, J.; Hu, H.; Yuan, Q. Bainitic Transformation and Properties of Low Carbon
Carbide-Free Bainitic Steels with Cr Addition. Metals 2017, 7, 263. [CrossRef]
11. Liu, H.; Fu, P.; Liu, H.; Sun, C.; Gao, J.; Li, D. Carbides Evolution and Tensile Property of 4Cr5MoSiV1 Die
Steel with Rare Earth Addition. Metals 2017, 7, 436. [CrossRef]
12. Gong, N.; Wu, H.-B.; Yu, Z.-C.; Niu, G.; Zhang, D. Studying Mechanical Properties and Micro Deformation
of Ultrafine-Grained Structures in Austenitic Stainless Steel. Metals 2017, 7, 188. [CrossRef]
13. Tian, J.; Xu, G.; Zhou, M.; Hu, H.; Wan, X. The Effects of Cr and Al Addition on Transformation and
Properties in Low-Carbon Bainitic Steels. Metals 2017, 7, 40. [CrossRef]

2
 MDPI Books
Metals 2018, 8, 116

14. Białobrzeska, B.; Konat, Ł.; Jasiński, R. The Influence of Austenite Grain Size on the Mechanical Properties of
Low-Alloy Steel with Boron. Metals 2017, 7, 26. [CrossRef]
15. Luo, Y.; Guo, H.; Sun, X.; Mao, M.; Guo, J. Effects of Austenitizing Conditions on the Microstructure of AISI
M42 High-Speed Steel. Metals 2017, 7, 27. [CrossRef]
16. Zhang, Y.; Li, J.; Shi, C.-B.; Qi, Y.-F.; Zhu, Q.-T. Effect of Heat Treatment on the Microstructure and Mechanical
Properties of Nitrogen-Alloyed High-Mn Austenitic Hot Work Die Steel. Metals 2017, 7, 94. [CrossRef]
17. Ning, A.; Mao, W.; Chen, X.; Guo, H.; Guo, J. Precipitation Behavior of Carbides in H13 Hot Work Die Steel
and Its Strengthening during Tempering. Metals 2017, 7, 70. [CrossRef]
18. Liu, C.; Liu, X.; Yang, S.; Li, J.; Ni, H.; Ye, F. The Effect of Niobium on the Changing Behavior of Non-Metallic
Inclusions in Solid Alloys Deoxidized with Mn and Si during Heat Treatment at 1473 K. Metals 2017, 7, 223.
[CrossRef]
19. Kim, M.; Abro, M.; Lee, D. Corrosion of Fe-(9~37) wt. %Cr Alloys at 700–800 ◦ C in (N2 , H2 O, H2 S)-Mixed
Gas. Metals 2016, 6, 291. [CrossRef]
20. Okonkwo, P.; Shakoor, R.; Benamor, A.; Amer Mohamed, A.; Al-Marri, M. Corrosion Behavior of API X100
Steel Material in a Hydrogen Sulfide Environment. Metals 2017, 7, 109. [CrossRef]
21. Stawicki, T.; Białobrzeska, B.; Kostencki, P. Tribological Properties of Plough Shares Made of Pearlitic and
Martensitic Steels. Metals 2017, 7, 139. [CrossRef]
22. Sroka, M.; Zieliński, A.; Dziuba-Kałuża, M.; Kremzer, M.; Macek, M.; Jasiński, A. Assessment of the Residual
Life of Steam Pipeline Material beyond the Computational Working Time. Metals 2017, 7, 82. [CrossRef]
23. Yu, C.; Shiue, R.-K.; Chen, C.; Tsay, L.-W. Effect of Low-Temperature Sensitization on Hydrogen
Embrittlement of 301 Stainless Steel. Metals 2017, 7, 58. [CrossRef]

© 2018 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

3
 MDPI Books
metals
Review
Effects of Heat Input on Microstructure,
Corrosion and Mechanical Characteristics of Welded
Austenitic and Duplex Stainless Steels: A Review
Ghusoon Ridha Mohammed 1,2, *, Mahadzir Ishak 1 , Syarifah N. Aqida 1
and Hassan A. Abdulhadi 1,2
1 Faculty of Mechanical Engineering, University Malaysia Pahang, 26600 Pekan, Pahang, Malaysia;
mahadzir@ump.edu.my (M.I.); aqida@ump.edu.my (S.N.A.); h.shamary@gmail.com (H.A.A.)
2 Institute of technology, Middle Technical University, Foundation of Technical Education,
Baghdad-Alzafaranya 10074, Iraq
* Correspondence: Ghusoon_ridha@yahoo.com & PMM_14004@stdmail.ump.edu.my; Tel.: +60-129-457-480

Academic Editor: Robert Tuttle

Received: 19 November 2016; Accepted: 18 January 2017; Published: 30 January 2017

Abstract: The effects of input heat of different welding processes on the microstructure, corrosion,
and mechanical characteristics of welded duplex stainless steel (DSS) are reviewed. Austenitic
stainless steel (ASS) is welded using low-heat inputs. However, owing to differences in the physical
metallurgy between ASS and DSS, low-heat inputs should be avoided for DSS. This review highlights
the differences in solidification mode and transformation characteristics between ASS and DSS
with regard to the heat input in welding processes. Specifically, many studies about the effects of
heat energy input in welding process on the pitting corrosion, intergranular stress, stress-corrosion
cracking, and mechanical properties of weldments of DSS are reviewed.

Keywords: duplex stainless steel; heat input; pitting corrosion; intergranular stress; stress corrosion
cracking; mechanical properties

1. Introduction
Welding is a fabrication process of generating a perpetual joint result from the melting of the
surface of the parts to be joined together, with or without the utilization of pressure and a filler material.
In welding, applying heat source defined as the energy input and studying it is essential to study
the welding process. Energy input is described as the amount of energy entered per unit length of
weld from a moving heat source. The energy input (heat input) is formulated in joules per meter or
millimeter. It can be determined as the ratio of total input power in Watts to welding speed. The heat
input per unit length (H) is calculated according to the following equation [1]:

H = ƒEI/V (1)

where ƒ = Efficiency of heat transfer; E = Volts; I = Amperes; and V = Velocity of heat source (mm/s).
Heat is the controlling factor accountable for thermochemical responses that happen in weld
pools, and led upon cooling to modify the chemistry of weld metal. This is confirmed by Sun and
Wu [2] when they stated that welding heat input is the key factor impacting heat and mass transfer,
liquid flow, and the thermal cycle in the pool.
Stainless steel is recognized as the steel that resists corrosion. This resistance to corrosion is
consequent of chromium oxide film created by chromium on the surface of the metal forming a passive
layer that isolates and preserves the surface. Austenitic stainless steel (ASS) is widely employed
in caustic environments [3–7]. A main downside of ASS is the sensitivity to chloride-induced

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stress-corrosion cracking (SCC) [8,9]. Although ferritic stainless steel is more resistant to such
corrosion, it is inferior to ASS in terms of ductility and weldability. Given an appropriate composition
and thermo-mechanical processing, duplex stainless steel (DSS), which exhibits an austenite–ferrite
dual-phase structure, can be obtained. DSS presents many benefits upon single-phase grades, such as
increased yield strength and resistance against SCC [10–13].
DSS is a popular constitutional material in the oil, gas, and manufacturing sectors. In particular,
DSS is employed in chemical, wastewater, and marine engineering fields, as well as in desalination
industries and marine constructions [14–19]. Given the high corrosion resistance of DSS, this material
is favorable for shipbuilding, petrochemical, paper, and nuclear industries and can gradually substitute
the expensive 300 ASS [20]. DSS is also the preferred material for petroleum and refining industries [21].
The important mechanical properties of DSS help reduce thickness and are especially required in
transportation to address the demand of the industry sector [17,22–27].
For the commonly used ASS, the material should be held in the solution-annealed condition
for optimal corrosion resistance. As such, weld thermal cycles are selected to ensure rapid cooling
of the weld metal and the adjacent Heat-Affected Zone (HAZ), thereby preventing the formation of
deleterious phases, which can adversely affect the corrosion properties [28,29]. Consumables should
be selected to ensure the proportion of 5% to 10% delta ferrite in the welded microstructure, which is
primordial to inhibit solidification cracking. The heat input and temperature are limited to a maximum
of 1.5 KJ/mm and 100 ◦ C, respectively, to avoid extensive precipitation of brittle phases in weld metal
when very slow cooling is applied.
Directions for welding technologies indicate that excessive dilution with the base metal should be
avoided [30]. Basically, instructions to weld DSS are recommended on the expertise with ASS. Thus,
when high heat inputs and slow cooling rates are applied (Figure 1), the properties of DSS weldment
can accurately advance [31].

Figure 1. Heat input influences cooling rate [32].

This review does not aim to specify the welding conditions for DSS, but rather to draw attention
to the difference in transforming behavior between ASS and DSS and consequently determine how this
difference was affected by heat input. Therefore, this review highlights the differences in the physical
metallurgy between ASS and DSS and discusses the existing works about the weldment properties
of DSS.

2. Metallurgy

2.1. Duplex Structure

DSS consists of ferrite and austenite compounds. Table 1 presents the typical compositions of the
common DSS. Many other grades of DSS exist, but most of them would fall in the same compositional

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range (Table 1). Clearly, a wide range of composition exists, extending from 2101 LDX to the super
DSS 2507 [33]. A pseudo-binary phase diagram for Cr and Ni with 70% Fe is illustrated in Figure 2.

Figure 2. Pseudo-binary Fe-Cr-Ni phase at 70% Fe section illustrating areas of detrimental phase
formation [34].

The composition of a representative DSS falls in the (α + γ) phase field. For many stainless
steel compositions, the austenite phase is expanded; hence, the ferrite phase is separated into high
and low-temperature ferrites, which are denoted as delta ferrite and alpha ferrite (formed by the
transformation of austenite), correspondingly. Ferrite exists continuously from solidification to room
temperature for DSS, and such ferrite is denoted as alpha ferrite. Given that α/(α + γ) and (α + γ)/γ
phase boundaries are not vertical, the ferrite-to-austenite ratio in a particular grade would depend on
the exact composition, as well as the thermo-mechanical processing [35–37].

Table 1. Typical compositions (in % atom fractions) of some commonly used duplex stainless steels [38].
LDX (Lean Duplex): DX (Duplex): EN (European standard): No. (Number): UNS (Unified Numbering
System for Metals and Alloys).

Approx. Composition
Grade EN No./UNS Type
C Cr Ni Mo N Mn
2101 LDX 1.4162/S32101 Lean 0.04 21.0–22.0 1.35–1.70 0.3–0.8 0.2–0.25 4–6
DX 2202 1.4062/S32202 Lean 0.03 21.5–24.0 1.0–2.8 0.45 0.18–0.26 2.0
2304 1.4362/S32304 Lean 0.03 21.5–24.5 3–5.5 0.05–0.6 0.05–0.2 2.5
2205 1.4462/S32205 Standard 0.03 22–23 4.5–6.5 3.0–3.5 0.14–0.2 2.0
2507 1.4410/S32750 Super 0.03 24–26 6–8 3–5 0.24–0.32 1.2

Most modern DSS are designed with a similar austenite-to-ferrite ratio. As a result of the duplex
microstructure, partition of alloying components occurs among the phases. Notably, the solidification
method of DSS is definite from that of ASS with remaining delta ferrite. Generally, the microstructure
of (American Iron and Steel Institute) AISI 304 ASS is completely austenitic at room temperature.
In the process of regular welding, the cooling rate is accelerated; thus, the ferrite–austenite alteration
cannot be completed, and some δ-ferrite is kept at room temperature after solidification. High input
heat leads to a low cooling rate, which further contributes to the change from delta-ferrite phase to
austenite phase in weld metal with stainless steel [39–41]. Consequently, the duplex δ + γ structure
will be the definitive composition of the weld metal of ASS [42–45].
In the phase equilibrium, the influence of various alloying elements can be quantified by
employing equivalent amounts of Ni and Cr. For a very long time, many equations have been
used to calculate these two equivalent amounts [46–48]. The Schaeffler diagram [46] and the DeLong

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diagram [47] shown in Figure 3 are possibly the most commonly used approaches to calculate the
ferrite contents in stainless steel weld metals. The equations reported by Datta [49] are listed below:

Creq = 1.5(Mo) + (Cr) + 5.5(Al) + 5(V) + 2(Si) + 1.75(Nb) + 1.5(Ti) + 0.75(W) (2)

Nieq = (Co) + 0.3(Cu) + 0.5(Mn) + (Ni) + 30(C) + 25(N) (3)

Figure 3. Constitution diagrams to predict phase content in stainless-steel weld metal from chemical
composition: (a) Schaeffler diagram [46]; and (b) Delong diagram [47].

These equations have also been previously discussed in detail for stainless steel welding [50,51].
The literature indicated that a Schaeffler alloy with a Creq /Nieq ratio under 1.48 would stabilize
essentially as austenite; moreover, delta ferrite is formed from the chromium- and molybdenum-
enriched residual melts between the austenite cells or dendrites. As expected, this delta ferrite would
be enriched in Cr and Mo.
When the alloy presents a Creq /Nieq ratio between 1.48 and 1.95, primary solidification occurs in the
ferrite–austenite mode. This process also results in the segregation of alloying elements upon solidification,
with the gamma and alpha phases enriched in austenite- and ferrite-forming elements, respectively. For
steels of Creq /Nieq ratio, the remaining ferrite can also undergo solid-state transformation to austenite.
Weldments of DSS with a Creq /Nieq ratio above 1.95 stiffen as a single-phase ferrite.
With the high diffusivity of Cr and Mo in ferrite, the ferrite solidification is not accompanied
by significant segregation. The austenite is formed from the solid-state ferrite via a Widmanstätten
mechanism [51]. Segregation of ferrite stabilizers to alpha, and of austenite stabilizers to gamma,
occurs during the solid-state transformation but not during solidification when the Creq /Nieq ratio
is less than 1.95. Given this solid-state segregation, the phase balance and amount of segregation
will be controlled by factors including the cooling rates for castings and weldments, whereas the
thermo-mechanical processing conditions and annealing treatment are very important for wrought
products. Additionally, the solidification of duplex weldments occurring in the single-phase ferritic
mode largely influences the precipitation of other phases [52–54].

2.2. Precipitation of Other Phases

As the outcome of DSS and super DSS (SDSS) thermal history, one of the significant concerns
to gain the required mechanical performance and resistance to corrosion is to understand their
microstructural evolution. Derivation of the time–temperature history of the occurrence in welding
processes or treatments of technical heat might lead to the deposition of various compounds (e.g., Cr2 N)
and a few other intermetallic phases (e.g., σ phase) as illustrated in Figure 4a,b. Such microstructural
characteristics are often related to harmful effects on the corrosion resistance, as well as the mechanical
behavior of the steel [55]. In fact, σ period deposition can devalue the corrosion features, in which Mo

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and Cr are retained in this phase. Moreover, such deposition can reduce the toughness of DSS and
SDSS [56–60].

Figure 4. Transmission electron micrograph of duplex stainless steel: (a) as received; and (b) image of
σ phase contained with a M23 C6 carbide particle after solution treated at 1080 ◦ C [58].

High toughness can be obtained by implementing suitable solution temperatures and cooling
rates [61–63]. This finding is consistent with a previous report [64] indicating that the optimal solution
temperature and cooling rate result in high toughness. In addition to austenite and ferrite, other phases
may occur depending on the thermal history of the steel, when DSS is exposed to a temperature range
of 300 to 1000 ◦ C [65–68]. Examples of such phases are chromium nitrides, carbides, or carbonitride,
as well as gamma-phase, chi-phase, R-phase, alpha-prime precipitation, [69–72], alpha precipitation,
copper precipitates, and martensite in gamma phase. Generally, the formation of secondary phases
influences the corrosion resistance and mechanical properties [73]. The absence of these phases is
a result of the rapid cooling in the weld zone and prompt growth and nucleation compared with
the fusion process [74]. The temperature–time precipitation curves for various phases observed in
a 2205 type alloy are shown in Figure 5.

Figure 5. Isothermal cooling curve for the ternary Fe-Cr-Ni system showing the effect of alloying
addition on the precipitation of the secondary phases that can form upon cooling [75].

Most of the modern DSS are rich in nitrogen (0.1% to 0.2%). Nitrogen, an austenite stabilizer,
is added as both a solid-solution hardener and resistance promoter against pitting corrosion in
chloride-containing media. As previously reported, chromium nitrides precipitate in the ferritic
phase when a DSS is quenched from a very high annealing temperature [76–78]. Chromium
nitrides precipitated when rapid cooling occurred in weld metal or the HAZ of welded DSS [78–81].
Furthermore, fine Cr2 N precipitates were observed when worked on the rod of UNS S31803 DSS
treated in two stages [82], that is, after treatment at 1050 ◦ C for 1 h and then at 800 ◦ C from 100 to
31,622 min, with water as a quenching medium for the two stages.

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Nevertheless, whether the regulating action is the nucleation rate remains incompletely
understood [28,58,83], although the growth kinetics of this response have been widely investigated [84,85].
The amount of Cr2 N precipitation increases with the rise of annealing temperature. As the annealing
temperature increases, the volume fraction of austenite decreases, and the ferrite must take up more
nitrogen in the solid solution. Although these levels of nitrogen are soluble in ferrite at high temperatures,
Cr2 N precipitates in the ferrite upon rapid cooling because nitrogen is relatively insoluble in ferrite at
low temperatures. For weldments, the same mechanism is operative, and the HAZ regions were heated
to 1300 ◦ C and higher, at which the steel subsisted wholly ferritic with nitrogen in the solid solution.
The degree of sensitivity is associated with the great supplement of Cr and Mo drain region outcome
from intermetallic phases.
Under certain welding conditions, this region can experience a very rapid cooling cycle, and severe
Cr2 N precipitation occurs in an almost completely ferritic HAZ. If the HAZ experiences slower cooling,
austenite is formed and nitrogen is dissolved in the austenite, thus reducing the amount of Cr2 N
precipitation. Additionally, the cooling rate has been proven to decline as the interpass temperature
increases [86].
For ASS, the heat input should be reduced to accelerate the cooling time in the weld metal and
the adjoining HAZ, thereby ensuring that deleterious phases, such as M23 C6 , do not precipitate during
the welding process [87]. By contrast, very low heat inputs can disastrously affect the renitence of DSS
welding against pitting corrosion [88].

3. Properties of Duplex Stainless Steel Weldments

3.1. Pitting Corrosion

El-Batahgy et al. [89] studied the influence of laser welding parameters (simultaneous heat inputs
and shielding gas) on the corrosion resistance of autogenously bead-on plates; their results affirmed
that the corrosion average of plates combined contracts with the rise in welding speed, indicating the
drop in heat input. This effect of heat input can be justified by the cooling time [21,90]. When the
welding process occurs with less heat input, the rapid cooling time leads to a scant measure of austenite
and major chromium nitride precipitation.
The above phenomenon can drive consumption of Cr, N2 all over the residue, which causes
a harmful result on the pitting impedance. The use of N2 as a shielding gas to substitute argon,
below similarly stream situation, has also resulted in an exceptional reduction in corrosion speed of
connecting pieces. This finding is supported by Srinivasan [91] and Lothongkum [92] and advances the
corrosion characteristics of laser joint parts manufactured with nitrogen as a shielding gas relevant to
improve the ferrite–austenite ratio in weld metal WM and HAZ. The corrosion morphology of grains
around precipitates and the precipitate-free zone were left intact and clarified on the substructure of
the chromium exhaustion around the Cr2 N precipitates in ferrite.
Slow cooling rates permit enough time for restoration (Cr redistribution) of the depleted zones
around the Cr2 N precipitates. This phenomenon is considered a beneficial effect from high heat inputs.
Yasuda et al. [93] studied the influence of heat input on the resistance of a 2205 alloy against pitting
corrosion. HAZs were then simulated by heating the samples of 2205 alloy to varying temperatures,
quenching in water and in compressed air, and then by air cooling to yield cooling rates of 300 ◦ C/s,
40 ◦ C/s, or 20 ◦ C/s.
Cr2 N was identified in the ferrite phase after cooling at fast and slow rates. Therefore, the
beneficial effect of slower cooling rates on resistance against pitting corrosion was explained by the
restoration of Cr-depleted areas nearby residues. Higher austenite volume fractions taking more
nitrogen into solid solution with a subsequent decrease in the amount of Cr2 N precipitated in ferrite
may also contribute to the beneficial effect of slow cooling rates. In terms of weld heat input, the heat
inputs greater than 1 kJ/mm can improve the pitting resistance.

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Plasma arc welded 2304 DSS was investigated in terms of pitting corrosion resistance by using
Creq /Nieq ratio; the results revealed that the microstructure is more balanced with austenite phase after
thermal cycles with low Creq /Nieq , and the pitting corrosion resistance decreased with the increase
of Creq /Nieq [94]. Moreover, high heat input and satisfactory time intended for ferrite–austenite
transformation produce superior austenite content, and heat input plays the main role in the corrosion
resistance and microstructure of DSS joints. This finding clearly explains that heat input is directly
related to the strength and metallurgical aspects of DSS [31,95,96].
In addition, Lundquist et al. [97] studied the effects of welding conditions on the resistance of
2205 [85,98] and 2304 DSS against pitting corrosion. The influence of heat input from 0.5 to 3.0 kJ/mm
was examined for Tungsten Inert Gas (TIG) welded bead-on-tube welds with and without the addition
of a filler metal. The pitting resistance was remarkably improved with increasing heat input (Table 2).
The only weld beads made with the highest heat input of 3.0 kJ/mm passed the FeCl3 test for duplicate
specimens. At 25 ◦ C, welds made by heat input of 2.0 kJ/mm by using filler metal and at 2.5 kJ/mm
were autogenously resistant to pitting. When a filler metal is used, lower heat inputs can be tolerated
without affecting the resistance against pitting corrosion. The reason for the detrimental effect of
low heat inputs was also attributed to an appreciable amount of Cr2 N precipitation in ferrite grains.
The amount of precipitation diminished for higher heat inputs was virtually absent at 3.0 kJ/mm.
This finding can be explained by the austenite reformation at the expense of nitride precipitates.
In addition to TIG welding, Lundqvist et al. [97] also performed Shielding Metal Arc (SMA) butt
welding on 20 mm-thick 2205 plate by using heat inputs from 2.0 to 6.0 kJ/mm. Although the entire
top surfaces of the weld metal passed the pitting test in 10% FeCl3 6HP at 30 ◦ C irrespective of heat
input, the weld metal on the root side, which was the first to be deposited, failed. To further investigate
this phenomenon, tests on critical pitting temperature were conducted under 3% NaCl.

Table 2. Pitting tests on TIG-welded bead-on-tube welds of 2205 X/2 = Specimens attacked/specimens
tested solution: 10% FeCl3 ·6H2 O.

Heat Input, kJ/mm

Filler Metal Temperature (◦ C)
0.5 1.0 1.5 2.0 2.5 3.0
Sandvik 25 - 2/2 2/2 0/2 0/2 0/2
22.8.3.L 30 - 2/2 2/2 2/2 1/2 0/2
25 2/2 2/2 2/2 2/2 0/2 0/2
None
30 2/2 2/2 2/2 2/2 1/2 0/2

Critical pitting temperatures of 48, 43 and 40 ◦ C were obtained at heat inputs of 2.0, 4.0 and
6.0 kJ/mm, correspondingly. Microstructural evaluation revealed that extremely fine austenite
precipitated in the first- and second-weld beads. A higher heat input during subsequent weld
passes led to a reformation of more austenite. In addition to nitrides, fine precipitates of austenite,
which were presumed to be reformed at temperatures as low as 800 ◦ C, also negatively affected the
pitting resistance. However, the reformed austenite is less detrimental to pitting resistance than Cr2 N
precipitates. Lundquist et al. also investigated the use of nitrogen as a shielding gas. Although nitrogen
provides adequate protection against oxidation, nitrogen also diffuses into the weld metal and HAZ.
Such diffusion increases the amount of austenite in the root run and effectively suppresses the amount
of chromium nitride precipitated, which can possibly enhance the resistance to pitting corrosion.
It is generally agreed that very low heat inputs should be avoided on DSS and that much higher
heat input can be tolerated for austenitic. This affects the costs of weld fabrication since joints can be
made in fewer passes [99]. It should be noted that heat input alone does not determine the cooling rate,
but that thickness of the parent metal and interpass temperatures also should be considered. The heat
inputs for SAF 2304 and SAF 2205 are specified to be 0.5 to 2.5 kJ/mm, respectively, with the upper

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limit not considered [97,100]. The choice of heat input pertinent with the material thickness, as the
reform of sufficient austenite, needs heat inputs in the upper part of the thick material.
Jang et al. [101] refer to the influence of shielding gas component using N2 on the impedance to
pitting corrosion at the Hyper Duplex Stainless Steel HDSS within quiet massive chloride environment.
After welding, the resistance of the HDSS tube to pitting corrosion was produced using N2 with
Ar shielding gas and was increased due to the decrease of α-phase in the HAZ and weld metal.
Furthermore, the improved corrosion resistance is assigned to the reduction of Pitting Resistance
Equivalent Number (PREN) variation between the α-phase and γ-phase in the weld metal [16,102].
Furthermore, Wang et al. [103] used dissimilar metals to investigate the consequence of welding
conditions in terms of welding process type. Gas Tungsten Arc Welding (GTAW) joint A and Shielded
Metal Arc Welding (SMAW) joint B were applied sequentially, and ER2209 welding wire was used
to join two different materials: 2205 DSS and 16MnR low alloy high-strength steel. To assess the
corrosion resistance of weld metal, the plates were partly tightened with A/B glue and a corrosion
mixture of 3.5% NaCl. Figure 6 and Table 3 present the results of electrochemical corrosion experiments
with 2205 DSS base metal and weld metal, correspondingly. However, their corrosion possibilities
are relatively uneven: joint B < joint A < 2205 DSS. The corrosion possibility is a constant index of
electrochemical corrosion renitency and exhibits the sensitivity to corrosion of the material [77,91,104].

Table 3. Electrochemical parameters of DSS BM and weld metals [103]. DSS: duplex stainless steel.
BM: Base Metal.

Samples Joint A Joint B DSS BM

Corrosion potential/Ecorr (V) −0.394 −0.463 −0.251
Corrosion current/Icorr (A) 0.2932 0.3041 0.2862

Figure 6. Scanning electron microscopy (SEM) micrograph of pitting corrosion.

The weld metal of DSS is more resistant to pitting corrosion than the base metal. Furthermore,
the enhanced response of weld metal to pitting resistance is associated with the addition of Cr and Ni
elements [105]. This finding is supported by Olsson [106], who reported that the stability of passive
films gained from Cr and Ni would reduce the comprehensive decay of Fe and Cr. Overall, the weld
microstructure is influenced by the differences in the heat input between joint A and joint B and leads
to change in the configuration state of the element surface unfavorable layer.
For the common DSS 2205, its composition range was considered as UNS S31803. However,
the N content associated with UNS S31803 may be reduced to 0.08%, and a plane is assured to
be minimized for reliable HAZ and autogenous fusion zone properties in the same status of the
welding process. In addition to the increased requirement of minimum nitrogen for S32205 versus

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S31803, the minimum Mo and Cr contents are enhanced. During welding, nitrogen controls the
ferrite/austenite phase equality [107].
Susceptibility to solidification cracking is one of the problems coupled with fusion welding of
these materials, which is comparatively higher than that of 304L ASS [108]. Nitride precipitation
was noted in HAZ. The presence of δ-ferrite with higher Cr content may deleteriously affect the
corrosion resistance because of the potential difference between the δ-ferrite and austenite phases [109],
but this factor may exert less influence on the corrosion resistance than the others. The corrosion
properties of the welds also include grain boundary effects [110,111]. Experimentally, Shamanian
and Yousefieh [112] studied the differences in heat input result on a DSS, a microstructure of UNS
S32760 in seawater. Remarkably, the heat input at about 0.95 kJ/mm presents the largest component of
corrosion, that is, the lack of harmful phases resulting in sigma and Cr2 N, as well as the attribution of
equal ferrite–austenite.
The GTAW process pulsed current has benefited the representative GTA process, that is, the
ferrite–austenite ratio within the base metal and weld metal relies on the welding energy input.
After welding in DSS pipes of four distinct sizes, metallography tests completed by scanning electron
microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) were conducted to show the
phases of chemical compositions presented in the microstructure, and polarization curves of various
specimens were analyzed. As a result, the formation of sigma and Cr2 N phases decreased the potential
formation of corrosion for a fine and coarse structure in the weld metal. The undercooling level will be
prospected within a welding process, given that in the cap region, the weld metal will chill down more
rapidly because of lower ambient temperatures at the weld surface and adjacent parent material at the
beginning. No evidence shows the existence of secondary austenite (γ’), which is present in all of the
examined weld metal conditions. Furthermore, areas containing the intermetallic phases of any of the
generally prospected carbides were not observed [113].
The detrimental effects of very high heat inputs or multi-pass welding are the formation of
secondary austenite and Cr2 N in the HAZ. Interestingly, the number of thermal cycles is one of the
most related criteria to estimate the deleterious effect of sigma phase development, as previously
reported [99,114,115].

3.2. Intergranular Corrosion

At grain boundaries, the precipitation of the chromium carbides causes susceptibility to
intergranular corrosion, which can be a serious problem in ASS if these materials are held for prolonged
periods in the sensitization region (about 500 to 750 ◦ C) [116–118]. This kind of corrosion occurs from
the Cr deficiency nearby M23 C6 precipitates. As for combating intergranular corrosion in stainless
steels, one way is to reduce carbon content below 0.3% to delay the deposition of M23 C6 , which helps
to avoid any damaging consequence.
One of the exceptional features of DSS is the resistance against sensitization. The ferrite phase
provided the largest amount of Cr in carbides as a result of high diffusivity of Cr and the high Cr
content in the ferrite phase. Accordingly, an extremely broad Cr-consuming region dwells at the ferrite
part of the interface. The austenite phase offered a really scanty Cr volume, leading to a very thin but
penetrating Cr-consuming region on the austenite side of the interface [82]. Intergranular corrosion in
HAZ decreased with the increasing number of weld passes. According to the results, as the number of
passes increased, the corrosion attack of grain boundaries decreased. This behavior is ascribed to the
prolonged retention time above the sensitization temperature range, which promotes the solubilization
of chromium carbides in the grain matrix, thereby avoiding sensitization [119].
The elegant resistance of duplex alloys against sensitization is achieved by recharging the small
region with diffusing Cr from the inside of the austenite grain. Despite this inherent resistance,
many commercial DSS contain less than 0.03% carbon, thus further reducing the risk of sensitization.
In addition to the effect of heat input on the pitting corrosion of DSS weldments as previously detailed,

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Sridhar [78] and Lundquist [97] studied the effect on resistance to intergranular corrosion. In both
cases, excellent resistance was reported, even in the case of high heat inputs.
For the resistance against intergranular corrosion and SCC, no detrimental effect from high heat
inputs was found. The tensile elongation and toughness of welds on DSS are affirmed to increase
when the heat input is raised.

3.3. Stress-Corrosion Cracking

DSS demonstrated desirable impedance to SCC. DSS is not as resistant as ferritic SS but more
resistant than austenitic against SCC [15]. The susceptibility of DSS to SCC depends on many
factors, including alloying elements [120,121], microstructures [122,123], applied stresses [124,125],
and environment [126–129].
Slow-strain rate tests (2.2 × 10−6 s−1 ) at 35% boiling water MgCl2 solution and 125 ◦ C were
performed to determine the sensitivity to SCC [98]. Additional tests in an inoperative environment
(glycerin) were conducted. All specimens with welded joints tested in glycerin at 125 ◦ C showed
sufficient plasticity, and their fracture surfaces were entirely ductile. Detailed examinations revealed
that these samples broke in parent material 316L steel close to HAZ of the weld. Samples tested in
MgCl2 solution broke in a brittle manner. The welded specimens were brittle or mixed, and the
ductile-brittle shape of fracture surfaces. Thus, the consequence of SCC is this succession of
plasticity [130].
The ways of crack diffusion ordinarily continue together with state limits or transverse ferrite grains.
Cracks were frequently prevented on extended, upright austenite grains, or overpass through [131].
The heat input did not influence the susceptibility to SCC.

3.4. Mechanical Properties

The ferrite content of DSS can considerably influence the yield strength, tensile ductility,
and toughness of the alloy [89,97,112,132]. As such, it further assumed that the heat input will
manipulate these properties in a welded part because the austenite-to-ferrite stability is related to
the cooling rate [133]. The toughness was reportedly improved as the heat input was top-up on SAF
2205 [97]. This finding was further correlated to the reduction of ferrite content. They also point out
that sigma phase and 475 ◦ C embrittlement are not troubled when welding modern DSS, owing to
well-balanced chemical compositions and favorable austenite-to-ferrite ratios. From a strength and
toughness viewpoint, the arc powers do not need to be maximized for 2205 [134]. The findings also
proved that even 1% of sigma phase formation in DSS is sufficient to cause embrittlement. Furthermore,
the coarse-grained ferrite structure formed near the fusion line is responsible for the reduction in
impact toughness of the DSS weld [135–137].
For austenite antirust steels, the important relationship between the changes, as well as heat
input in microstructural development, is highly related to the relevant mechanical performance in
the weldments of AISI 304L stainless steel by GTAW [138]. Moreover, little heat input joints show
high ductility and tensile strength, but great heat input joints demonstrate small tensile ductility and
strength. The HAZ photomicrographs of these weldments show that grain coarsening influence is
inducted, which is inclined to recede the joint part and may thus influence the functional performance
of the weld joint in practice. With high heat input, the grain-coarsening degree within this zone is
comparatively higher, but a small heat input helps to inhibit the grain growth by subjecting the zone
to abrupt heat gradients [139]. Hardness is relatively small along the large weld zone of heat input,
which includes long dendrites with larger interdendritic spacing, but hardness is improved along with
the small weld zone of heat input, which contains comparatively few dendrites along with smaller
interdendritic spacing. All HAZs in distinct weldments undergo grain coarsening, of which the extent
is increasingly enhanced with the improvement of welding heat input.
Mourad et al. [140] studied the effects of gas tungsten arc as well as laser beam welding on
2205 properties of DSS. The effects of gas tungsten arc welding and beam welding of carbon dioxide

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laser on the microstructure and size of fusion zone, mechanical as well as corrosion properties of DSS
grade 6.4 mm-thick 2205 plates were comparatively studied. The ferrite–austenite balance of both
HAZ and weld metal are affected by heat input, which is a welding process function.
The impacts of heat input on the mechanical properties of UNS S31803 DSS plates from friction
stir welding were studied recently [31]. The fracture morphology, residence of elements, and their
distribution on joint zone were comprehensively examined through SEM associated with energy
dispersive spectroscopy (EDS). The fracture occurred in the base metal and partially penetrated the
weld zone. The fracture occurred in the weld region, and the strength of friction welded joints was
reduced than the parent material [86]. The fracture did not expand extensively in the base metal
and partly entered the weld zone. The fracture occurred in the weld region, and the strength of the
friction-welded joints decreased more than the parent material. No intermetallic phases were detected
by X-ray diffraction. Outcomes of tensile strength confirmed that the joint strength can be kept when
high heat input was applied. However, at room temperature, toughness declined as the heat input
grew. Microhardness was improved with the rise of heat input owing to the grain perfection.
After a detailed literature review, most of the investigations are found to have focused on the
effects of heat transfer/heat input on DSS by using various welding techniques. The characteristics of
various materials processed after different welding process were also analyzed. Clearly, the irregular
heat input variations of various fusion welding on DSS cause drastic changes in phase balance,
which needs to be balanced. Knowledge about microstructural evolution of such kind of steels, as well
as the result of thermal history, is fundamental to achieve the expected mechanical behavior and
corrosion resistance. The time–temperature history, derived from industrial heat treatments or welding
processes [141–143], may lead to precipitation of various compounds (e.g., chromium carbides and
nitrides) and some other intermetallic phases (e.g., σ phase). The formation of such compounds leads to
losses in both corrosion resistance and fracture toughness [144]. However, extensive research is needed
to deal with the effects of heat input on DSS welds for in-depth understanding of this phenomenon.
Few reports exist on different welding processes of DSS grades. Thus, the full-depth knowledge about
heat input throughout the welding process of DSS is notably essential for controlling and improving
the welding quality. As such, the current research investigated the effects of heat input on mechanical
measures such as tensile strength, Charpy impact toughness, microhardness, metallurgical specifics,
and corrosion of DSS welded joints.

4. Conclusions
The amount of heat input in the welding process affects the properties of both DSS and ASS.
The final properties depend on the variety of solidification modes and the transformation characteristics
of these two alloys, especially the corrosion properties.
The following conclusions can be drawn from this review:

(1) DSS solidifies in the single-phase ferritic mode, whereas ASS solidifies in the austenitic or
austenitic-ferritic mode.
(2) Austenite phase in weldments of DSS is formed by solid-state transformation, which is strongly
affected by the cooling rate.
(3) The resultant ferrite-to-austenite ratio is dependent on the energy input during the welding process.
(4) In duplex weldments, low heat inputs result in high volume fractions of ferrite and severe
precipitation of chromium nitrides, which adversely affect mechanical and corrosion properties.
(5) High heat inputs requisite sufficient time in the DSS welding for austenite reformation at
high temperature.
(6) The number of thermal cycles is significantly associated criteria to evaluate the deleterious impact
of sigma phase extension.
(7) Susceptibility to SCC and the resistance against intergranular corrosion did not affect from high
heat inputs.

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Acknowledgments: The authors are grateful to the Universiti Malaysia Pahang (UMP), Pekan, Malaysia,
and Automotive Engineering Centre (AEC), Pekan, Malaysia, for financial support given under GRS 1503107
(GRS/8/2015/UMP).
Author Contributions: Ghusoon and Ishak conceived and designed the Review; Hassan and Aqida analyzed the
data; Ishak and Ghusoon contributed reagents/materials/analysis tools; Ghusoon wrote the paper
Conflicts of Interest: The authors declare no conflict of interest. And “The founding sponsors had no role in the
design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in
the decision to publish the results”.

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114. Tan, H.; Wang, Z.; Jiang, Y.; Yang, Y.; Deng, B.; Song, H.; Li, J. Influence of welding thermal cycles on
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116. Shimada, M.; Kokawa, H.; Wang, Z.; Sato, Y.; Karibe, I. Optimization of grain boundary character distribution
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118. Vlčková, I.; Jonšta, P.; Jonšta, Z.; Váňová, P.; Kulová, T. Corrosion fatigue of austenitic stainless steels for
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119. Mirshekari, G.R.; Tavakoli, E.; Atapour, M.; Sadeghian, B. Microstructure and corrosion behavior of multipass
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120. Tsai, W.T.; Chen, M.S. Stress corrosion cracking behavior of 2205 duplex stainless steel in concentrated nacl
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122. Nilsson, J.O.; Kangas, P.; Wilson, A.; Karlsson, T. Mechanical properties, microstructural stability and kinetics
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124. Brandolt, C.; Rosa, M.; Ramos, L.; Schroeder, R.; Malfatti, C.; Müller, I. Temperature influence on SCC
behaviour of duplex stainless steel. Mater. Sci. Technol. 2016, 1–7. [CrossRef]
125. Li, H.; Jiao, W.; Feng, H.; Li, X.; Jiang, Z.; Li, G.; Wang, L.; Fan, G.; Han, P. Deformation characteristic
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127. Tseng, C.M.; Tsai, W.T. Environmentally assisted cracking behavior of single and dual phase stainless steels
in hot chloride solutions. Mater. Chem. Phys. 2004, 84, 162–170. [CrossRef]
128. El-Yazgi, A.; Hardie, D. Stress corrosion cracking of duplex and super duplex stainless steels in sour
environments. Corros. Sci. 1998, 40, 909–930. [CrossRef]
129. Örnek, C.; Idris, S.A.; Reccagni, P.; Engelberg, D.L. Atmospheric-induced stress corrosion cracking of grade
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130. Chattoraj, I. Stress Corrosion Cracking of Duplex Stainless Steels. Adv. Mater. Res. 2013, 794, 552–563.
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131. Bhattacharya, A.; Singh, P.M. Effect of heat treatment on corrosion and stress corrosion cracking of S32205
duplex stainless steel in caustic solution. Metall. Mater. Trans. A 2009, 40, 1388–1399. [CrossRef]
132. Muthupandi, V.; Bala Srinivasan, P.; Seshadri, S.K.; Sundaresan, S. Effect of weld metal chemistry and heat
input on the structure and properties of duplex stainless steel welds. Mater. Sci. Eng. A 2003, 358, 9–16.
[CrossRef]
133. Esmailzadeh, M.; Shamanian, M.; Kermanpur, A.; Saeid, T. Microstructure and mechanical properties of
friction stir welded lean duplex stainless steel. Mater. Sci. Eng. A 2013, 561, 486–491. [CrossRef]
134. Reddy, G.M.; Rao, K.S. Microstructure and mechanical properties of similar and dissimilar stainless steel
electron beam and friction welds. Int. J. Adv. Manuf. Technol. 2009, 45, 875–888. [CrossRef]
135. Kordatos, J.; Fourlaris, G.; Papadimitriou, G. The effect of cooling rate on the mechanical and corrosion
properties of SAF 2205 (UNS 31803) duplex stainless steel welds. Scr. Mater. 2001, 44, 401–408. [CrossRef]

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136. Calliari, I.; Straffelini, G.; Ramous, E. Investigation of secondary phase effect on 2205 DSS fracture toughness.
Mater. Sci. Technol. 2010, 26, 81–86. [CrossRef]
137. Ibrahim, O.; Ibrahim, I.; Khalifa, T. Impact behavior of different stainless steel weldments at low temperatures.
Eng. Fail. Anal. 2010, 17, 1069–1076. [CrossRef]
138. Kumar, S.; Shahi, A.S. On the influence of welding stainless steel on microstructural development and
mechanical performance. Mater. Manuf. Process. 2014, 29, 894–902. [CrossRef]
139. Song, T.; Jiang, X.; Shao, Z.; Mo, D.; Zhu, D.; Zhu, M. The interfacial microstructure and mechanical properties
of diffusion-bonded joints of 316L stainless steel and the 4J29 kovar alloy using nickel as an interlayer. Metals
2016, 6, 263. [CrossRef]
140. Mourad, A.H.I.; Khourshid, A.; Sharef, T. Gas tungsten arc and laser beam welding processes effects on
duplex stainless steel 2205 properties. Mater. Sci. Eng. A 2012, 549, 105–113. [CrossRef]
141. Shrikrishna, K.A.; Sathiya, P. Effects of post weld heat treatment on friction welded duplex stainless steel
joints. J. Manuf. Process. 2015, 21, 196–200.
142. Atapour, M.; Sarlak, H.; Esmailzadeh, M. Pitting corrosion susceptibility of friction stir welded lean duplex
stainless steel joints. Int. J. Adv. Manuf. Technol. 2015, 83, 721–728. [CrossRef]
143. Abdulhadi, H.A.; Aqida, S.N.; Ishak, M.; Mohammed, G.R. Thermal fatigue of die-casting dies: An overview.
MATEC Web Conf. 2016, 74, 00032. [CrossRef]
144. Chagas de Souza, G.; da Silva, A.L.; Tavares, S.S.M.; Pardal, J.M.; Ferreira, M.L.R.; Filho, I.C. Mechanical
properties and corrosion resistance evaluation of superduplex stainless steel UNS S32760 repaired by gtaw
process. Weld. Int. 2016, 30, 432–442. [CrossRef]

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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Article
Corrosion of Fe-(9~37) wt. %Cr Alloys at 700–800 ◦ C
in (N2, H2O, H2S)-Mixed Gas
Min Jung Kim, Muhammad Ali Abro and Dong Bok Lee *
School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 16419, Korea;
abc1219@skku.edu (M.J.K.); abromdali@gmail.com (M.A.A.)
* Correspondence: dlee@skku.ac.kr; Tel.: +82-31-290-7371

Academic Editor: Robert Tuttle

Received: 18 October 2016; Accepted: 15 November 2016; Published: 23 November 2016

Abstract: Fe-(9, 19, 28, 37) wt. %Cr alloys were corroded at 700 and 800 ◦ C for 70 h under 1 atm of
N2 , 1 atm of N2 /3.2%H2 O mixed gas, and 1 atm of N2 /3.1%H2 O/2.42%H2 S mixed gas. In this gas
composition order, the corrosion rate of Fe-9Cr alloy rapidly increased. Fe-9Cr alloy was always
non-protective. In contrast, Fe-(19, 28, 37) wt. %Cr alloys were protective in N2 and N2 /3.2%H2 O
mixed gas because of the formation of the Cr2 O3 layer. They, however, became nonprotective in
N2 /3.1%H2 O/2.42%H2 S mixed gas because sulfidation dominated to form the outer FeS layer and
the inner Cr2 S3 layer containing some FeCr2 S4 .

Keywords: Fe-Cr alloy; oxidation; sulfidation; H2 S corrosion

1. Introduction
Fe-Cr alloys are widely used as high-temperature structural materials. They oxidize when exposed
to air or oxygen at high temperatures. When the Cr content in iron was ~5 wt. %, triple oxide layers
such as Fe2 O3 /Fe3 O4 /FeO formed, and the oxidation rate was mainly controlled by the growth
rate of FeO that formed on the alloy side [1]. The non-stoichiometric wustite grows much faster
than the nearly stoichiometric Fe3 O4 and Fe2 O3 . With an increase in the Cr content to ~10 wt. %,
dispersed particles of the FeCr2 O4 spinel formed more inside the FeO layer, and FeCr2 O4 particles
blocked the diffusion of Fe2+ ions to make the FeO layer thinner. With the further increase in the
Cr content to ~15 wt. %, a mixed spinel, Fe(Fe,Cr)2 O4 , formed, which decreased the oxidation rate
significantly. When the Cr content exceeded ~20 wt. %, the oxidation rate dropped sharply, forming
a thin, continuous Cr2 O3 layer containing a small amount of dissolved Fe ions [1–3]. When Fe-Cr
alloys were exposed to S2 gas at 1 atm, an FeS layer formed below 1.86 wt. %Cr, an outer Fe1–x S
layer and an inner (FeS, FeCr2 S4 ) mixed layer formed in the range of 1.86–38.3 wt. %Cr, and a solid
solution of FeS-Cr2 S3 formed above 38.3 wt. %Cr [4]. Although Cr decreased the sulfidation rate, even
Fe-Cr alloys with high Cr contents displayed insufficient corrosion resistance. This is attributed to
the fact that sulfidation rates of common metals are 10–100 times faster than oxidation rates because
the sulfides have much larger defect concentrations and lower melting points than the corresponding
oxides [5]. The sulfidation of Fe-(20, 25, 30) wt. %Cr steels in 94Ar/5H2 /1H2 S mixed gas at 600 ◦ C for
718 h resulted in the formation of the outer FeS layer and the inner FeCr2 S4 layer [6]. On the other
hand, the corrosion of conventional oxidation-resistant alloys by water vapor and H2 S gas has been
a serious problem [3]. Water vapor and H2 S gas release hydrogen atoms, which ingress in the metals
interstitially, form hydrogen clusters, and cause hydrogen embrittlement. Water vapor that is present
in many industrial gases can form metal hydrides, and change not only the reaction at the scale/metal
interface but also the mass transfer in scales, accelerating the corrosion rate [3,7]. In this study, Fe-Cr
alloys were corroded at 700 and 800 ◦ C in (N2 , H2 O, H2 S) mixed gas in order to understand their
corrosion behavior in hostile (H2 O, H2 S)-containing environments for practical applications. The aim

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of this study is to examine the influence of the Cr content and the (N2 , H2 O, H2 S)-containing gas on
the high-temperature corrosion of Fe-Cr alloys, which has not been adequately investigated before.

2. Experimental Procedures
Four kinds of hot-rolled ferritic Fe-Cr alloy sheets, viz., Fe-(8.5, 18.5, 28.3, 36.9) wt. %Cr, were
prepared. They are termed as Fe-(9, 19, 28, 37)Cr, respectively, in this study. They were homogenized
at 900 ◦ C for 1 h under vacuum, cut into a size of 2 mm × 10 mm × 15 mm, ground up to a 1000-grit
finish with SiC papers, ultrasonically cleaned in acetone, and corroded at 700 and 800 ◦ C for 70 h
under 1 atm of total pressure. Each test coupon was suspended by a Pt wire in a quartz reaction tube
within the hot zone of an electrical furnace (Ajeon, Seoul, Korea), as shown in Figure 1. Three kinds
of corrosion atmospheres were employed, viz. 1 atm of N2 , (0.968 atm of N2 plus 0.032 atm of H2 O)
that was achieved by bubbling the N2 gas through the water bath kept at 25 ◦ C, and (0.9448 atm of
N2 plus 0.031 atm of H2 O plus 0.0242 atm of H2 S) that was achieved by bubbling N2 gas through the
water bath kept at 25 ◦ C and simultaneously flowing the N2 -5%H2 S gas into the quartz reaction tube.
The N2 gas was 99.999% pure, and H2 S gas was 99.5% pure. Nitrogen gas was blown into the reaction
tube during heating and cooling stages. After finishing the corrosion test in N2 , N2 /3.2%H2 O, and
N2 /3.1%H2 O/2.42%H2 S gas, the test coupons were furnace-cooled, and characterized by a scanning
electron microscope (SEM, Jeol JSM-6390A, Tokyo, Japan), a high-power X-ray diffractometer (XRD,
Mac Science M18XHF-SRA, Yokohama, Japan) with Cu-Kα radiation operating at 40 kV and 300 mA,
and an electron probe microanalyzer (EPMA, Shimadzu, EPMA 1600, Kyoto, Japan).

Figure 1. Corrosion testing apparatus.

3. Results and Discussion

Table 1 lists the weight gains of Fe-(9, 19, 28, 37)Cr alloys due to corrosion at 700 and 800 ◦ C for
70 h, which were measured using a microbalance before and after corrosion. Fe-9Cr always displayed
the worst corrosion resistance, gaining excessive weight. For example, Fe-9Cr oxidized fast even in
the N2 gas through the reaction with impurities such as 3 ppm H2 O and 2 ppm O2 in the N2 gas
(99.999% pure). Fe-9Cr oxidized faster in the N2 /H2 O gas than in the N2 gas because of water vapor [7].
Water vapor dissociates into oxygen and hydrogen, oxidizes the metal, and forms voids within the
oxide scale according to the equation [1,3],

M + H2 O → MO + (2H or H2 ) (1)

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Table 1. Weight gain of Fe-(9, 19, 28, 37)Cr alloys measured after corrosion at 700 and 800 ◦ C for 70 h
under 1 atm of N2 , N2 /3.2%H2 O, and N2 /3.1%H2 O/2.42%H2 S gas.

Weight Gain (mg/cm2 )

Temp. Gas
9Cr 19Cr 28Cr 37Cr
N2 195 1–2 1–2 1–2
700 ◦ C N2 /H2 O 220 1–2 1–2 1–2
N2 /H2 O/H2 S 2050 470 200 70
N2 235 1–2 1–2 1–2
800 ◦ C N2 /H2 O 400 1–2 1–2 1–2
N2 /H2 O/H2 S massive spalling 1530 690 550

Fe-9Cr corroded the most seriously in N2 /H2 O/H2 S gas, because H2 S was much more harmful
than H2 O. H2 S dissociates into hydrogen and sulfur. Sulfur forms non-protective metal sulfides
according to the following equation:

M + H2 S → MS + (2H or H2 ) (2)

Hydrogen, which is released from H2 S and H2 O, dissolves and ingresses into the alloy and the
scale interstitially, generates lattice point defects, forms hydrogen clusters and voids, causes hydrogen
embrittlement, produces volatile hydrated species, and accelerates cracking, spallation and fracture of
the scale. Hence, no metals are resistant to H2 O/H2 S corrosion. As listed in Table 1, Fe-(19, 29, 37)Cr
displayed much better corrosion resistance in N2 and N2 /3.2%H2 O with weight gains of 1–2 mg/cm2
than Fe-9Cr. Fe-(19, 29, 37)Cr formed 0.3- to 1.3-μm-thick, adherent oxide scales. However, even
Fe-(19, 29, 37)Cr failed in N2 /3.1%H2 O/2.42%H2 S with large weight gains, forming non-adherent,
fragile sulfide scales as thick as 35–750 μm. This scale failure made the weight gains measured in
N2 /H2 O/H2 S gas inaccurate. In N2 /H2 O/H2 S gas, the amount of local cracking, spallation and void
formation in the scale varied for each test run. Although the accurate measurement of weight gains
in N2 /H2 O/H2 S gas was impossible, it was clear that weight gains due to scaling decreased sharply
with the addition of Cr.
Figure 2 shows the XRD patterns of scales formed after corrosion at 800 ◦ C for 70 h. The corrosion
of Fe-9Cr in N2 and N2 /H2 O resulted in the formation of Fe2 O3 and Fe3 O4 , as shown in Figure 2a,b.
Oxide scales formed on Fe-9Cr in N2 and N2 /H2 O were 90 and 100 μm thick, respectively. Since X-rays
could not penetrate such thick oxide scales, FeO and Cr-oxides such as FeCr2 O4 , which might form
next to the alloy [1], were absent in Figure 2a,b. In contrast, Fe-(19, 28, 37)Cr alloys oxidized at much
slower rates in N2 and N2 /H2 O than Fe-9Cr alloy, as listed in Table 1. Fe-(19, 28, 37)Cr alloys formed
the protective Cr2 O3 scale, as typically shown in Figure 2c,d. Here, the Fe-Cr peaks were strong owing
to the thinness of the oxide scales. In Fe-(19, 28, 37)Cr alloys, Cr was dissolved in the α-Fe matrix.
Figure 3 shows the EPMA analytical results on the scales formed on Fe-9Cr after corrosion at
700 ◦ C for 70 h. The oxide scales that formed after corrosion in N2 and N2 /H2 O were about 90 and
140 μm thick, respectively. The scale morphology and elemental distribution in N2 gas were similar to
those in N2 /H2 O gas, as shown in Figure 3, indicating that the same oxidation mechanism operated
in N2 and N2 /H2 O gas. Voids were sporadically scattered in both oxide scales, below which the
oxygen-affected zone (OAZ) existed. Voids formed owing to the volume expansion during scaling,
hydrogen released from the water vapor, and the Kirkendall effect arose due to the outward diffusion
of cations during scaling. In both oxide scales, the outer layer consisted of iron oxides, while the inner
layer consisted of (Fe,Cr) mixed oxides. This indicated that Fe2+ and Fe3+ ions were more mobile than
Cr3+ ions. The oxidation in N2 and N2 /H2 O gas was mainly controlled by the outward diffusion of iron
ions through the inner (Fe,Cr) mixed oxide layer. Iron oxidized preferentially in N2 and N2 /H2 O gas
because iron is the base element and its oxide, FeO, is a non-stoichiometric compound with a relatively
fast growth rate.

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Figure 2. XRD patterns taken after corrosion testing at 800 ◦ C for 70 h. (a) Fe-9Cr in N2 ; (b) Fe-9Cr in
N2 /3.2%H2 O; (c) Fe-37Cr in N2 ; (d) Fe-37Cr in N2 /3.2%H2 O.

Figure 3. EPMA cross-section and line profiles of Fe-9Cr after corrosion at 700 ◦ C for 70 h in (a) N2 ;
and (b) N2 /3.2%H2 O.

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Figure 4 shows the EPMA analytical results on the scales formed on Fe-37Cr after corrosion at
700 ◦ C for 70 h. The oxide scales that formed after corrosion in N2 and N2 /H2 O were about 0.6 and
1.1 μm thick, respectively. In N2 and N2 /H2 O gas, the Cr2 O3 scale formed (Figure 2c,d), in which
Fe was dissolved (Figure 4). The complete dissolution of Fe2 O3 in Cr2 O3 is possible, because Cr2 O3
and Fe2 O3 have the same rhombohedral structure [8]. Like Fe-37Cr, Fe-(19, 28)Cr also formed a
thin Cr2 O3 scale containing some Fe when they corroded in N2 and N2 /H2 O gas. Once the thin
but protective Cr2 O3 scale formed, the outward diffusion of iron ions was suppressed so that good
corrosion resistance was achieved.

Figure 4. EPMA cross-section and line profiles of Fe-37Cr after corrosion at 700 ◦ C for 70 h in (a) N2 ;
and (b) N2 /3.2%H2 O.

In N2 /3.1%H2 O/2.42%H2 S gas, Fe-(9-37)Cr alloys could not form Cr2 O3 , and corroded fast,
as typically shown in Figure 5. The scales formed on Fe-(9, 19, 28, 37)Cr alloys consisted primarily of
the outer FeS layer (Figure 5a), and the inner Cr2 S3 layer containing some FeCr2 S4 (Figure 5b). Since FeS
grows fast owing to its high non-stoichiometry, outer FeS grains were coarser than the inner (Cr2 S3 ,
FeCr2 S4 ) mixed grains. In Figure 5c, cracks propagated inter- and trans-granularly due mainly to the
excessive growth stress generated in the thick outer scale. The scale shown in Figure 5d was about
100 μm thick, and had cracks and voids. A small amount of Cr was dissolved in the outer FeS layer
(Figure 5e). The preferential sulfidation of iron in the outer FeS layer decreased the sulfur potential
underneath, and thereby increased the oxygen potential in the inner Cr2 S3 -rich layer, leading to the
incorporation of oxygen in the inner Cr2 S3 -rich layer. FeS is a p-type metal-deficit compound, which
grows fast by the outward diffusion of Fe2+ ions [5,9,10]. Its defect chemical equation is as follows.

1/2O2 = Oo + 2h· + V"Fe (3)

here, OO , h· and V"Fe mean the O atom on the O site, the electron hole in the valence band with a + 1
charge, and the iron vacancy with a − 2 charge. The defect chemical reaction for the dissolution of
Cr2 S3 in FeS is as follows.
·
Cr2 S3 = 2CrFe + V"Fe + 3Ss (4)

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Hence, the doping of Cr3+ ions would increase the concentration of iron vacancies, leading to the
enhancement of the FeS growth. Oxygen was incorporated in the inner Cr2 S3 -rich layer (Figure 5e).
However, no oxides were detected in Figure 5b, because their amount was small or oxygen was
dissolved in the sulfide scales. Grains in the inner layer were fine owing to the nucleation and growth
of Cr2 S3 , together with some FeCr2 S4 and probably some oxides. In N2 /3.1%H2 O/2.42%H2 S gas,
Fe-(9, 19, 28, 37)Cr alloys sulfidized preferentially owing to the high sulfur potential in the test gas.

Figure 5. Fe-19Cr after corrosion at 700 ◦ C for 40 h in N2 /3.1%H2 O/2.42%H2 S. (a) XRD pattern
after corrosion; (b) XRD pattern taken after grinding off the outer scale; (c) SEM top view; (d) EPMA
cross-section; (e) EPMA line profiles of along A–B denoted in (d).

4. Conclusions
When Fe-9Cr alloy corroded at 700 and 800 ◦ C in N2 and N2 /3.2%H2 O gas, thick, porous oxide
scales formed, which consisted of the outer iron oxide layer and the inner (Fe,Cr) mixed oxide layer.
Under the same corrosion condition, Fe-(19, 28, 37)Cr alloys formed thin, dense, protective Cr2 O3
oxide layers, in which iron was dissolved to a certain extent. In N2 /3.1%H2 O/2.42%H2 S gas, Fe-(9, 19,
28, 37)Cr alloys corroded fast, forming thick, non-adherent, fragile scales, which consisted of the outer
FeS layer and the inner Cr2 S3 layer containing some FeCr2 S4 . The preferential sulfidation of Fe-(9, 19,
28, 37)Cr alloys in the H2 S-containing gas was responsible for the poor corrosion resistance of Fe-(9, 19,
28, 37)Cr alloys.

Acknowledgments: This research was supported by Basic Science Research Program through the National
Research Foundation of Korea (NRF) funded by the Ministry of Education (2016R1A2B1013169), Korea.
Author Contributions: Min Jung Kim conceived and designed the experimental procedure and drafted the paper.
Muhammad Ali Abro prepared the samples, conducted the experiments and analyzed the data. All the results
were discussed with Dong Bok Lee who supervised the experimental work and finalized the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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10. Danielewski, M.; Mrowec, S.; Stolosa, A. Sulfidation of iron at high temperatures and diffusion kinetics in
ferrous sulfide. Oxid. Met. 1982, 17, 77. [CrossRef]

© 2016 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

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metals
Article
Superior Strength of Austenitic Steel Produced by
Combined Processing, including Equal-Channel
Angular Pressing and Rolling
Marina V. Karavaeva *, Marina M. Abramova, Nariman A. Enikeev, Georgy I. Raab
and Ruslan Z. Valiev
Institute of Physics of Advanced Materials, Ufa State Aviation Technical University, 12 K. Marx str.,
Ufa 450008, Russia; abramovamm@yandex.ru (M.M.A.); nariman.enikeev@ugatu.su (N.A.E.);
giraab@mail.ru (G.I.R.); rzvaliev@yahoo.com (R.Z.V.)
* Correspondence: karma11@mail.ru; Tel.: +7-917-781-7784

Academic Editor: Hugo F. Lopez

Received: 27 October 2016; Accepted: 29 November 2016; Published: 8 December 2016

Abstract: Enhancement in the strength of austenitic steels with a small content of carbon can be
achieved by a limited number of methods, among which is ultrafine-grained (UFG) structure
formation. This method is especially efficient with the use of severe plastic deformation (SPD)
processing, which significantly increases the contribution of grain-boundary strengthening, and
also involves a combination of the other strengthening factors (work hardening, twins, etc.). In this
paper, we demonstrate that the use of SPD processing combined with conventional methods of
deformation treatment of metals, such as rolling, may lead to additional strengthening of UFG steel.
In the presented paper we analyze the microstructure and mechanical properties of the Cr–Ni stainless
austenitic steel after a combined deformation. We report on substantial increases in the strength
properties of this steel, resulting from a consecutive application of SPD processing via equal-channel
angular pressing and rolling at a temperature of 400 ◦ C. This combined loading yields a strength
more than 1.5 times higher than those produced by either of these two techniques used separately.

Keywords: stainless steel; severe plastic deformation; strength; ultrafine-grained materials

1. Introduction
Severe plastic deformation (SPD) processing significantly improves the mechanical properties of a
broad range of metallic materials due to the formation of an ultrafine-grained (UFG) structure, ensuring
the concurrent action of several mechanisms of strengthening thanks to the hardening contributions
of solid solution, precipitations and particles, defect structures and, primarily, grain refinement [1–7].
A high-strength state is provided by controlling the microstructural parameters that are sensitive
to SPD processing regimes. SPD parameters that have the greatest effect on the microstructure are
strain, temperature and loading route. The latter has an effect on both the kinetics of microstructural
evolution and the homogeneity of the produced microstructure. For example, when studying the
microstructure transformation of Ti alloys with a change of the deformation path, it was shown that the
substitution of a monotonic loading with an essentially non-monotonic one enabled activation of new
slip systems and thus intensified the process of microstructural refinement [8,9]. With respect to SPD
processing, it was demonstrated that the so-called route of equal-channel angular pressing (ECAP) has
a great effect on structural evolution [10,11]. The best results, in terms of microstructure refinement
and enhancement of mechanical properties, were obtained when using routes B and Bc, in which
the billet is rotated by 90◦ around its axis between ECAP passes. Such a turn changes the schemes
of the principal stresses and strains in a material, and as a result, the deformation process becomes

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non-monotonic. A similar result was obtained for the cyclic HPT when sufficient grain refinement in Ni
and Fe was reported to be achieved at a smaller deformation level than for the one-direction HPT [12].
A vivid example of non-monotonic loading is the SPD technique of multiple forging, in which the
change of the scheme of principal stresses is achieved as a result of a consecutive rotation of the billet
around three axes [13,14].
It is possible to realize the non-monotonic loading process through a consecutive processing of
billets by different methods. This procedure has already been tested successfully for Ti-based [15],
Cu-based [16] and Al-based alloys [17,18]. At the first stage of processing, SPD by ECAP-Conform
was conducted, and at the second stage, rolling or drawing was performed. It is noted in all studies
that a change in the type of loading had a beneficial effect on the properties of the produced materials.
At the second stage of processing, an additional increase was observed in the microhardness and
strength of UFG materials which had been produced by SPD at the first stage of processing. It is more
difficult to unambiguously determine the effect of a change in the deformation type of producing UFG
materials on the features of their microstructure. At the present time, the experimental data reported
in the literature are not sufficient to summarize the results, especially for steels. Besides, of great
importance is the microstructure formed immediately during SPD processing, as well as the nature of
the material itself. After the rolling of even an equiaxed UFG structure, a structure was observed that
was elongated in the direction of plastic straining. For copper, an increase in the structural homogeneity
was revealed [16], and conversely, for an Al alloy, a separation of microstructure into two fractions was
observed, one of which contained shear bands, and the other one contained equiaxed grains [17].
In this paper, we investigate the possibility of increasing the strength of an austenitic stainless
steel through the use of combined strain processing. For this type of steel it is practically impossible to
increase strength by thermal treatment, and thus microstructure refinement by deformation processing
is an efficient means of strengthening.

2. Materials and Methods

Austenitic stainless steel was selected as an object of investigation. The chemical composition
of the steel is given in Table 1. In order to produce a single-phase austenitic structure prior to SPD
processing, the steel was water-quenched from a temperature of 1050 ◦ C (exposure time 1 h). The SPD
processing of rods with a diameter of 10 mm and a length of 100 mm was conducted by ECAP through
8 passes via route Bc at a temperature of 400 ◦ C. The intersection angle of channels in the die-set was
120◦ (Figure 1).

Table 1. Chemical composition (wt. %) of the austenitic steel under investigation.

C Cr Ni Ti Si S P Fe
0.08 16.19 9.13 0.3 0.58 0.03 0.08 bas.

The thermal conditions of ECAP processing were selected in accordance with earlier studies [6,19]
that demonstrated the efficiency of SPD processing for microstructure refinement and enhancement
of the mechanical properties of the austenitic stainless steel at the given temperature, as well as for
the formation of grain-boundary segregations and nanotwins resulting in additional strengthening.
The number of passes was selected in such a way as to be sufficiently large to impose such a strain
under which the hardness and strength of a UFG billet reach saturation. The produced UFG state is
further referred to as “ECAP”.
Rolling was conducted in smooth rolls at the same temperature of billet heating, 400 ◦ C, through
15 passes to a final strip thickness of 2.3 mm. The total reduction was 77% (Figure 1). The produced
UFG state is further referred to as “ECAP + Rol”. This regime was selected on the basis of the
above-mentioned considerations, as well as to preserve the integrity of the billet.

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Figure 1. The principle of the combined processing of the steel (a) Stage I—ECAP, (b) Stage II—Rolling.

To study the effect of the combined processing on the microstructure and properties, we also
investigated the billets subjected to rolling under the same conditions, but without a preliminary
deformation processing by ECAP. This state is further referred to as “Rol”.
The microstructure was studied in the longitudinal section of a rod and a strip. To investigate
the microstructure, electrolytic etching was performed in a chemically pure nitric acid (the mass
fraction of the acid was at least 65%). The etching time was from 5 to 10 s under a voltage of 13–20 V.
Structural studies were performed using an Olympus GX51 optical microscope (Olympus Corp,
Tokyo, Japan), a JEOL JSM-6490VL scanning electron microscope (Jeol Ltd, Tokyo, Japan) and a
JEOL JEM-2100 transmission electron microscope (Jeol Ltd, Tokyo, Japan). The grain sizes were
determined from the dark-field images of the microstructure. At least 300 grains were measured
for each condition. The dislocation density xrd was determined from the results of X-ray studies
according to the expression [20]:
√  1/2
2 3 ε2
XRD =
b · dXRD
where (ε2 )1/2 is the level of elastic microdistortions of the crystal lattice; b is the Burgers vector of
dislocations; dxrd is the size of coherent scattering domains.
Microhardness was measured on a Micromet-5101 device in the longitudinal direction. At least
30 measurements were made for each condition. Uniaxial tensile testing was performed on an
INSTRON 8801 tensile testing machine (Instron Eng. Corp., High Wycomib, UK) at room temperature.
For the tensile tests, flat samples with a gauge length of 4 mm were used, the strain rate was 10−3 s−1 .

3. Results
The microstructure of the steel in the as-received state was represented by equiaxed austenite
grains with a mean size of (9 ± 2) μm (Figure 2a). In some grains, twins were observed. The volume
fraction of grains containing twins was about 10%.
After quenching, the size of austenite grains increased up to an average value of (40 ± 11) μm.
Practically all grains contained wide twins. At the boundaries of austenite grains and at twin
boundary/grain boundary intersections, serrations were observed.

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Figure 2. Microstructure of the austenitic steel: as-received condition (a); after quenching (b).

3.1. Microstructure of the Austenitic Steel after SPD Processing and Rolling
After SPD processing by ECAP, within the austenite grains we observed the formation of
differently-directed shear bands (Figure 3a—the sample axis is vertical). As a result of the intersection
of these bands, new boundaries form and grain refinement takes place. The microstructure is
heterogeneous. At 10,000 times magnification (Figure 3b), relatively coarse grains with sizes of
several μm and fine grains with sizes much smaller than 1 μm are visible. The coarse grains are
elongated in the direction of the sample axis (Figure 3a). The volume fraction of the regions with
relatively coarse grains amounts to about 10%.
When the structure was examined in detail by TEM, structural heterogeneity was also revealed
(Figure 3c). A large volume of the structure (about 60%) is represented by shear bands with thin
boundaries, within which a developed dislocation structure in the form of wide dislocation boundaries
is observed. These boundaries divide the bands into non-equiaxed cells. The cell size amounts
to, on average, about 180 nm in the transverse direction and 370 nm in the longitudinal direction
(Figure 3c). Alongside shear bands, practically equiaxed grains with a reduced dislocation density
and thin equilibrium boundaries are present in the structure. The grain size is about 350 nm. Separate
deformation twins are observed in the grains (about 10 nm in thickness) (Figure 3d). The fraction of
grains with twins does not exceed 5%. The average spacing between the twin boundaries is about
75 nm. The selected area electron diffraction pattern shown in the insert in Figure 3c reveals separate
reflections located circumferentially, which indicates high-angle misorientations of grain boundaries.

Figure 3. Cont.

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Figure 3. Microstructure of the steel after SPD processing (via ECAP) in the longitudinal section
(“ECAP” condition): (a,b) SEM; (c,d) TEM, the aperture size for diffraction patterns ~1 μm2 .

Thus, after SPD processing via ECAP, a heterogeneous austenitic UFG structure is formed.
This structure consisted of grains/subgrains elongated in the direction of straining, with a small
number of twins.
After rolling of the ECAP-processed steel, further grain refinement is observed (Figure 4).
Individual grains are practically not identified by an optical microscope. The boundaries of the
original austenite grains are not visible either (Figure 4a).

Figure 4. Structure of the austenitic steel after ECAP and subsequent rolling to a total reduction in area
of 77% (“ECAP + Rol” condition): (a) optical microscopy; (b–d) TEM, the aperture size for diffraction
patterns ~1 μm2 .

When the microstructure is examined by TEM, it can be seen that the microstructure has become
more homogeneous (Figure 4b) as compared to the one observed in the “ECAP” state (Figure 3c).

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The structure has a grain/cellular character. Shear bands are preserved in separate regions, but the
fraction of banded structure is only about 10%. The dislocation density increases, while the size
of structural elements decreases to 110 nm. Thin twins are observed in the grains (Figure 4d).
The fraction of grains containing twins increases to 14%. The average twin spacing decreases to 30 nm.
The electron diffraction pattern shown in the insert of Figure 4c has a ring-shaped form, which indicates
high-angle misorientation between grains. Thus, combined loading leads to further microstructure
refinement—the mean grain size decreases to 110 nm, and the fraction of nanotwins grows.
In the steel samples after rolling (“Rol” condition) the boundaries of original austenite grains
(Figure 5a), elongated in the rolling direction are still observed. Formation of shear bands is distinctly
observed within the grains there. At the boundaries of the original austenite grains and at the shear
band/grain boundary intersections, ledges are seen. A banded structure (Figure 5b,c) is also observed
in some areas. Inside the bands there are wide boundaries dividing grains into cells (Figure 4b–d).
The average cell size amounts to 560 nm. The structure is characterized by an increased dislocation
density. Twins are almost absent. Thus, in the “Rol” condition, the steel is characterized by a banded
cellular structure with a cell size of 560 nm, which does not contain twins.

Figure 5. Microstructure of the austenitic steel after rolling to a total reduction in area of 77%
(“Rol” condition): (a) optical microscopy; (b–d) TEM.

3.2. Mechanical Properties of the Austenitic Steel

The average microhardness value of the austenitic steel in the as-received state consists
(1970 ± 60) MPa (Figure 6). After quenching microhardness declines slightly to a value of
(1820 ± 30) MPa, which is related to the growth of austenite grains, as well as to a more complete
dissolution of excess phases during heating prior to quenching.

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Figure 6. Microhardness of the austenitic steel after different types of processing.

As a result of microstructure refinement, in the “ECAP” state the average microhardness value
of the steel grows two-fold, reaching (3920 ± 50) MPa. After rolling to 77% without a preliminary
ECAP processing (“Rol”), there is also observed an increase in hardness, very similar to ECAP
processing—to 3800 ± 50 MPa. A combination of ECAP and rolling results in an even greater increase
in microhardness, namely 33%, reaching (5040 ± 40) MPa (Figure 6).
In a similar manner, straining has an effect on the steel's strength as well. Figure 7 shows
the engineering stress-strain curves obtained during tensile tests of the steel samples in different
state. It is obvious that the deformation behavior of the material changes depending of the type of
processing of the steel. The quantitative data on the mechanical properties of the steel in different
state are summarized in Table 2. Peculiar to the quenched condition there is a significant capability
for strengthening: the yield stress is σ0.2 = 200 MPa, the ultimate tensile strength (UTS) is 2.5 times
higher—σult = 720 MPa. The elongation is δ = 65%.

Figure 7. Engineering stress-strain curves of the steel after different types of processing.

35
 Table 2. Mechanical properties of the steel after different types of processing.

Upper Yield Stress Lower Yield Stress Uniform

Offset Yield Stress Ultimate Tensile Elongation Microhardness
Condition (Corresponds to Yield (Corresponds to Yield Elongation δuniform
σ0.2 (MPa) Strength σult (MPa) to Failure δ (%) (MPa)
Drop) σB u (MPa) Plateau) σl (MPa) (%)
Metals 2016, 6, 310

quenching 200 - - 720 62 65 1820

ECAP 950 - - 1020 1 14 3920
Rol - 830 800 855 33 47 3800
ECAP +
- 1925 1700 1720 11 18 5040
Rol

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The steel in the “ECAP” state is characterized by a high value of yield stress σ0.2 = 950 MPa
with a very short period of insignificant strengthening: the uniform elongation is only 1%, the UTS is
σult = 1020 MPa. After that, a rapid strain localization and necking take place, corresponding to the
region with a stress decline in the diagram. The total elongation is δ = 14%. In spite of similar values of
microhardness and yield stress in the “ECAP” and “Rol” states, the deformation behavior of those
differs significantly. In the curve of the rolled sample, there appears a weakly expressed yield drop,
corresponding to the upper yield stress σu = 830 MPa. After that there is observed a yield plateau,
corresponding to the lower (physical) yield stress σl = 800 MPa and the region of weak strengthening.
The UTS is σult = 855 MPa, the elongation to failure is δ = 47%. The highest strength is exhibited by
the samples after the “ECAP + Rol” combined loading. This state is displayed by the curve with a
distinct yield drop. The upper yield stress is σu = 1925 MPa, and the lower yield stress, corresponding
to the yield plateau, is σl = 1700 MPa. The curve does not demonstrate notable strengthening, strain
localization starts as the elongation reaches the value δ = 11%, and the total elongation is δ = 18%.
Thus, the type of deformation processing determines not only the level of properties, but also the
tensile mechanical behavior of the steel.

4. Discussion
Numerous studies on the SPD processing of bulk metallic billets via ECAP have demonstrated that
the increase in hardness and strength is observed after the initial one or two passes, after which further
strengthening becomes much slower [21–23]. Meanwhile, the possibilities for strength enhancement
in a material have not yet been exhausted. This is confirmed by the fact that under processing by
high-pressure torsion, as a rule, the observed hardness values are significantly larger than the ones
that can be attained by ECAP processing [10].
Microstructural features of metallic materials provide activation of the related deformation
mechanisms, which, in their turn, contribute to the strengthening of the given material. Varying SPD
parameters one can purposefully form the targeted features in the produced UFG materials and
put into action the corresponding strengthening mechanisms. In UFG materials produced by SPD,
strengthening can be achieved due to several mechanisms [1–7,23]:

1. Grain-boundary and dislocation strengthening. During the grain refinement the volume fraction
of grain boundaries, which are an efficient impediment for dislocation movement, significantly
increases. For the formation of new strain-induced boundaries, dislocation generation in various
slip systems is necessary.
When analyzing the types of loading realized in the course of SPD, it is necessary to mention two
distinctive features typical of SPD processing:

a. a high hydrostatic constituent, which is especially significant in high-pressure torsion,

but present in all deformation techniques;
b. an essential non-monotony of strain, typical for most SPD techniques, such as ECAP or
multiple forging.

Both of these features enable activating additional slip systems, thus leading to an increase in
dislocation density, formation of new interfaces and microstructure refinement.
2. Solid-solution strengthening and precipitation hardening. These mechanisms are competing ones,
since as a result the alloying of a solid solution, the corresponding strengthening grows, but the
amount of dispersed particles (providing precipitation hardening) decreases. The contribution
of these constituents to strengthening is determined primarily by the deformation temperature.
It has been shown [24,25] that at room temperature the dissolution of second-phase particles
prevails, but as the deformation temperature is increased, precipitation is observed.

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3. Formation of segregations at grain boundaries. This process is also connected with the solid
solution decomposition during SPD and a transfer of solute atoms to the boundaries. The action
of this mechanism is also thermally dependent: at room temperature no segregations were
observed, and at elevated temperatures the formation of the grain boundary segregations was
shown [5,26].
4. Formation of twins. For a number of materials, including austenitic steels, it is typical that
nanotwins form during SPD processing. The high-angle boundaries of nanotwins are also
impediments for dislocation movement and, consequently, they provide additional strengthening.
Twinning may be activated when possibilities for slip are limited. When the scheme of the
stress-strain state is changed (in this particular case, by changing the type of loading), the
direction of action of the maximum tangential stresses changes with respect to the sample's axis.
As a result of such a change, new slip systems should be activated, and the activation of twinning
is also possible.

Thus, a change in the loading scheme may activate at least several of the above-mentioned factors
of strengthening: an increase in dislocation density, grain refinement and an increase in the fraction of
twins. These conclusions are confirmed by studies conducted on various materials. For instance, in [17],
in the Al alloy 5083 after ECAP processing and additional compression, imitating rolling conditions,
an increase in dislocation density was observed. An enhancement of strength after ECAP-Conform
processing and compression of Ti [15], after ECAP processing and rolling of Cu [16], was accounted
for by the formation of additional low-angle boundaries within grains and a transformation of the
low-angle boundaries into high-angle ones. This conclusion is also consistent with the studies on the
microstructure of austenitic steel in different states reported in the present study (see Table 3).

Table 3. Features of the structure of steel after straining.

Dislocation Grain/Cell Size Fraction of Fraction of Grains Twin Spacing

Condition Density (m−2 ) (nm) Shear Bands with Twins (%) (nm)
ECAP 1.28 × 1014 350 60 5 75
ECAP + Rol 7.19 × 1014 110 10 14 30
Rol 4.27 × 1014 560 80 - -

Comparison of the microstructural parameters of steel in different states demonstrates that the
size of structural elements considerably decreases as compared with the “ECAP” and the “Rol” states
as a result of combined loading. This leads to a considerable increase in the density of grain boundaries.
Let us consider a generalized dependence of yield stress on grain size in terms of the Hall-Petch
relation, presented on the basis of literature data in Figure 8.
The results obtained in the present study are also presented in the graph. It can be seen that
the points corresponding to the “ECAP” or “Rol” states have a certain deviation from the line
summarizing literature data towards larger values of yield stress. Moreover, the point corresponding
to the “ECAP + Rol” condition is located much higher than expected in accordance with the
Hall-Petch relation.
As considered above, strengthening of nanostructured steels is provided not only by grain size.
For austenitic steels, additional strengthening is introduced by the dislocation mechanism, as well as
by twin boundaries, as was demonstrated in [6]. In the general case, the contributions of different
mechanisms follow linear additivity [2,3,5–7,23]:

Δσy = ΔσFS + ΔσSS + Δσ + ΔσGB

where σFS is the friction stress of γ-iron’s lattice; ΔσSS is solid-solution strengthening; Δσ is dislocation
strengthening; ΔσGB is grain-boundary strengthening.

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Let us estimate the contribution of these mechanisms into the yield stress of the investigated steel
in each state.

Figure 8. Hall-Petch relation for chromium-nickel austenitic steels, built on the basis of literature
data [6,27–34] (back marks) and the results of the present study (red marks).

The lattice friction stress and solid solution hardening can be defined from the Hall-Petch relation,
displayed in Figure 8, as the stress corresponding to the infinitely large grain size. In the given case,
it is Δσ0 = 195 MPa.
Dislocation strengthening can be estimated according to:

Δσ = αMbG1/2

√ α = 0.3 is a constant; M = 3.05 is the Taylor factor; G = 77 GPa is the shear modulus and
where
b = 2a/2 is the Burgers vector for the investigated steel.
Let us define additional grain-boundary strengthening, taking into account the presence of twins,
as [6]:
ΔσGB = (1 − f ) ky d−1/2 + f ky λ−1/2

where f is the fraction of grains with twins; ky = 0.3 MPa·m1/2 is a constant derived from the
dependence in Figure 8; d is the average grain/cell size; λ is the average twin spacing.
The results of the analysis are given in Table 4.

Table 4. Calculated results for the contribution of different mechanisms to the strengthening of the steel.

ΔσGB Calculated Experimental

Condition Δσ
Δσd Δσtw Δσd + Δσtw Value Value
ECAP 202 481 55 536 933 950
ECAP + Rol 480 778 242 1020 1688 1700
Rol 370 401 - 401 771 800

The calculated yield stress values are very close to the experimental ones. Microstructural studies
and the presented estimations show that strength enhancement of the steel under a combined loading
is provided predominantly by the grain-boundary hardening contribution in accordance with the
Hall-Petch equation. Besides, unlike in ECAP processing, no twins were observed in the structure of
the steel after rolling at a temperature of 400 ◦ C. After the combined loading, the fraction of twins

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