Journal of Alloys and Compounds 965 (2023) 171390

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Review

Additive manufacturing of ultra-high strength steels: A review

Kun Li a, b, *, Tianbao Yang a, b, Na Gong c, Jinzhou Wu a, Xin Wu d, **, David Z. Zhang e,
Lawrence E. Murr f
a
College of Mechanical and Vehicle Engineering, Chongqing University, Chongqing 400044, China
b
Chongqing Key Laboratory of Metal Additive Manufacturing (3D Printing), Chongqing University, Chongqing 400044, China
c
Institute of Materials Research and Engineering (IMRE), A*STAR (Agency for Science, Technology and Research), 138634, Singapore
d
School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, Guangdong 519082, China
e
College of Engineering, Mathematics and Physical Sciences, University of Exeter, North Park Road, Exeter EX4 4QF, UK
f
W.M. Keck Center for 3D Innovation, University of Texas at El Paso, El Paso, TX 79968, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Ultra-high strength steels (UHSSs) have excellently comprehensive mechanical properties, which has attracted
Ultra-high strength steels significant interest in their advanced manufacturing. Additively manufactured UHSSs have a unique micro­
Additive manufacturing structure that provides significant potential to achieve good mechanical properties. This paper reviews the latest
Microstructure
research progress in the additive manufacturing (AM) of UHSSs with a special focus on defect optimization,
Defect optimization
microstructure-property regulation and the application of advanced assisted techniques for additively manu­
Process-microstructure-property regulation
factured UHSSs. The property origin of UHSSs is firstly summarized in detail, including the influence of different
alloying elements and phase composition in the microstructure on the mechanical properties of UHSSs. The AM
techniques used to fabricate UHSSs and the characteristics of their forming microstructure are further illustrated,
which involve laser powder bed fusion (L-PBF), laser direct energy deposition (L-DED), and wire arc additive
manufacturing (WAAM). The research progress on the three typical techniques for UHSSs is also reviewed.
Moreover, the property regulation methodology of UHSSs is reviewed, mainly in the optimization of defects and
the adjustment of the whole forming process. Significantly, the shortcomings of the present researches on AMed
UHSSs and future challenges for development are discussed. This work is important for a better scientific un­
derstanding of AMed UHSSs and provides vital meaningful guidelines for the future work in UHSSs
manufacturing.

1. Introduction
Ultra-high strength steels (UHSSs) are a series of steels developed
based on traditional alloying steels by adding a variety of alloying ele­
ments to improve mechanical properties. Based on alloying element
composition, they are classified into low alloy ultra-high strength steels
(LUHSSs), medium alloy ultra-high strength steels (MUHSSs), and high
alloy ultra-high strength steels (HUHSSs). As shown in Table 1, Some
typical UHSSs have ultra-high strength and high ductility with high
specific strength and stiffness to suit the goals of miniaturization,
lightweight, and high functionality [1,2]. Thus, UHSSs are widely used
in the aerospace, defense, mineral exploration, deep-sea submarine, and
ocean-going ferry industries.
With the development of aerospace and maritime technology, higher
demands are being placed on the performance of all aspects of steel.
Therefore, a variety of UHSSs have been developed and the sequence of
development of typical UHSSs is summarized in Fig. 1 in this work. In
the 1940 s, AISI 4340 steel was developed in the USA. During the same
period, US Steel developed 17–4 precipitation-hardening stainless steels
with ultra-high strength, good plasticity and corrosion resistance. In
order to suppress the temper brittleness of LUHSSs, International Nickel
Company developed 300 M ultra-high strength steel in 1952. The US
also developed a series of 18Ni maraging steels and HY180 steels in the
1960 s to meet the requirements of high fracture toughness and corro­
sion resistance. In the 1970 s, in order to obtain materials with high
toughness, the US successfully developed 9Ni-4Co type steel and
developed AF1410 steel on the basis of HY180 steel. In 1992, American
Carpenter Company developed Aermet 100 steel, which has

* Corresponding author at: College of Mechanical and Vehicle Engineering, Chongqing University, Chongqing 400044, China.
** Corresponding author.
E-mail addresses: kun.li@cqu.edu.cn (K. Li), wuxin28@mail.sysu.edu.cn (X. Wu).

https://doi.org/10.1016/j.jallcom.2023.171390
Received 17 March 2023; Received in revised form 12 July 2023; Accepted 14 July 2023
Available online 17 July 2023
0925-8388/© 2023 Elsevier B.V. All rights reserved.
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Table 1 better ductility, and longer durability. The special microstructure com­
Mechanical properties of typical UHSSs. bined with suitable post-treatment methods has a tremendous potential
UHSSs UTS (MPa) YS (MPa) EL (%) RA (%) Ref. to achieve excellently comprehensive mechanical properties.
AM has a special thermal history process while the microstructure
AISI4140 1571 1411 12.8 29.8 [3]
2022 1080 7.9 — [4] and mechanical properties of UHSSs are hardly controlled. The species
AISI4340 1510 1330 14.3 58 [5] and amounts of alloying elements vary considerably among different
300 M 1890 1605 22 35 [6] UHSSs, which leads to mechanical properties discrepancies. More
1217 1058 12.6 96.5 [7] insightful investigations are needed on the element-microstructure-
1932 1661 12.8 52.9 [8]
H11 2148 — 8.8 — [9]
property relationship and printing processes of UHSSs. Several excel­
1459 — 13.3 — [10] lent reviews of additive manufactured (AMed) steels have been reported
H13 1921 1534 11.8 — [11] focused on stainless steel and tool steels [37–42]. In addition, a lot of
1737 1460 8.7 39.3 [12] work has been conducted. Philipp et al. [43] produced Fe19Ni5Ti steel
Aermet 100 1997 1799 61.5 [13]
—
consisting of alternating soft and hard layers based on the principle of in
15–5PH 1496 1317 14.4 — [14]
17–4PH 1323 1132 16.6 — [15] situ precipitation strengthening and local microstructure control. The
18Ni(250) 1938 1837 6.4 — [16] material had a strength of 1300 MPa and an elongation of 10%.
1900 1833 10.3 64.5 [17] Krakhmalev et al. [44] studied the evolution of the microstructure of the
18Ni(300) 1802 1666 5.3 — [18] AISI420 steel by selective laser melting (SLMed). They analyzed the
1820 1775 [19]
thermal activation process occurring in situ using numerical simulations
—
18Ni(350) 2400 2300 4.0 — [20]
and found that the thermal process could be controlled by varying the
UTS—ultimate tensile strength, YS—yield strength, EL—elongation, laser energy input. Mei et al. [45] also studied the microstructure evo­
RA—reduction of area.
lution behavior of 18Ni(300) maraging steel by laser powder bed fusion
(L-PBF) at different scales of aging temperature and evaluated important
significantly increased strength, a slight decrease in toughness and issues such as cell structure changes, precipitation sequence, and
excellent overall performance. However, as the mechanical properties austenite reversion. Huang et al. [46] investigated the process of pre­
are enhanced, traditional manufacturing technologies have encountered paring H13 tool steel by high laser power L-PBF and found that the laser
difficulties in the fabrication of UHSSs. For example, the forging pres­ energy power reaches the maximum relative density (>99.5%) at
sure provided by forging presses is no longer fully sufficient for the 40 J/mm3, which provides a potential way to achieve high-strength
production of UHSS parts with larger size. The microstructure of cast H13 steel with high build rate. At present, most studies related to AM
components has serious microscopic segregation, oversized grains, and of UHSSs are limited to process optimization, microstructural charac­
other critical defects, which cannot meet the application requirements terization, mechanical behavior studies, and heat treatment exploration
[21]. Conventional manufacturing techniques require multiple complex [47–50]. There are still many scientific issues that remained to be
processes to produce flexible geometries and lightweight parts, and addressed in the additive manufacturing of UHSSs, including variability
some complex structures cannot even be produced, which significantly of microstructure and mechanical properties, build direction anisotropy,
limits the application scope of UHSSs and prevents them to demonstrate low printability, high residual stresses, and low ductility and fatigue
their full value of high-performance. In addition, UHSSs produced by resistance[51,52]. Unfortunately, a comprehensive review of AMed
conventional methods require multiple processes, such as casting, UHSSs has not been reported yet. With the continued study on AMed
forging, heat treatment, and machining. These processes are complex UHSSs, a comprehensive review is important.
with long production cycles, which results in higher production costs In this work, we review the recent study on AM of UHSSs, focusing on
[22]. Therefore, the exploration of advanced manufacturing technolo­ property regulation in three process states by laser powder bed fusion (L-
gies to produce UHSSs has become an increasing concern for PBF), laser direct energy deposition (L-DED), and wire arc additive
researchers. manufacturing (WAAM). Firstly, we elucidate the influence of alloying
In recent decades, additive manufacturing (AM), also known as elements, precipitated phases, and microstructure on the mechanical
three-dimensional (3D) printing, has been seen as a revolutionary properties of UHSSs, which are the property origin of UHSSs. Secondly,
manufacturing technology. It enables the manufacturing of geometrical we describe the process features of the 3 AM technologies (L-PBF, L-
complexity and near-net shape components directly from the 3D model DED, WAAM) and the microstructure characteristics of AMed UHSSs.
through layer-by-layer deposition. AM technologies can also minimize Thirdly, we discuss the causes of AMed defects of UHSSs and optimi­
material waste and shorten production cycle time which is economical. zation methods, as well as summarize the approaches of property
As a promising advanced manufacturing technology, AM technology regulation for pre-treatment, forming process, and post-treatment.
produces UHSS parts with tremendous potential applications in indus­ Finally, we illustrate the gaps beyond the existing research on AM of
trial applications. Compared to traditional manufacturing technologies, UHSSs and scientific issues that are still challenging as well as indicate
the production processes of AM have special characteristics, including directions for future work, which will guide the subsequent researches.
the interaction of materials and high-energy beams, layer-by-layer The paper reviews the progress of researches on additive manufacturing
accumulation, high cooling rates, and cyclic heating [23]. These fea­ of UHSSs in the last decade, analyzes the shortcomings and challenges of
tures result in unique microstructure including high-density disloca­ the current work, and proposes future work priorities, which are
tions, fine grains, metal cell structure, and phase composition, which important for the development of the field.
introduce outstanding mechanical propertiesfor UHSSs [24–26]. Recent
reports on the additive manufacturing of ultra-high strength steels are 2. Property origin of UHSSs
shown in Fig. 2a and include LUHSSs [27,28], Medium alloy tool steels
(MTSs) [29,30], secondary hardening steels (SHSs) [31,32], The superior mechanical properties of UHSSs are mainly derived
precipitation-hardening stainless steels (PHSSs) [33,34], and maraging from alloying elements and multiple precipitated strengthening phases.
steels (MSs) [35,36], where studies on H13 steels, 17–4 PH steels and For example, Si can suppress the temper brittleness of martensite [53].
18Ni300 steels dominate the reports. Overall, MTSs steels, PHSSs steels Molybdenum (Mo) and Vanadium (V) elements can precipitate fine
and MSs account for close to 90% of the research reports (Fig. 2b) and diffuse Mo2C and V4C3 particles in martensite to achieve secondary
represent the hotspot for research on additive manufacturing of hardening [54]. Alloying element compositions of some typical UHSSs
ultra-high strength steels. The future trend of AMed UHSSs is towards are listed in Table 2. In this section, the influence of alloying elements
better comprehensive mechanical properties, such as higher strength, and microstructure on the performance of UHSSs is discussed.

2
K. Li et al.
2.1. Alloying contribution to the property
2.1.1. Alloying in LUHSSs
LUHSSs have a high carbon content (0.3–0.5%) and a low alloying
element level (less than 5%), where the carbon (C) element is the main
factor affecting their strength [66,67]. Fig. 3a refers to a hot working
route for a low alloy ultra-high strength steel, consisting of four stages:
homogenization, warm rolling (TF method), reheating and tempering.
The microstructure after TF method contains ultra-fine and elongated
ferrite with a large number of fine carbides precipitated in the grain and
along the grain boundaries, while in the microstructure after TFR the
ferrite evolves into martensite with some undissolved spherical carbides
are distributed in the martensitic matrix. Subsequently, the precipitation
Fig. 1. The developing sequence of typical UHSSs (Color should be used for all figures).
3
Journal of Alloys and Compounds 965 (2023) 171390
of nanoscale Fe3C and Fe5C phases during tempering produce a pre­
cipitation strengthening effect. After a simple heat treatment and sec­
ondary tempering, the low alloyed high carbon steel achieves a tensile
strength of 2.6 GPa and has good ductility, as shown in Fig. 3b. How­
ever, excessive C element damages other performance of the steel, for
example, when the carbon composition is higher than 0.6%, the
toughness and weldability of the steel are significantly reduced [68].
Therefore, the C content of the steel should be minimized at a certain
level to maintain strength.
The main alloying elements added to LUHSSs are Silicon(Si), Man­
ganese(Mn), Nickel(Ni), C, Mo, and appropriate amounts of Titanium
(Ti), Niobium (Nb), and V. These alloying elements directly or indirectly
affect the performance of LUHSSs by engaging in phase transformation
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

strength of the D steel.

2.1.2. Alloying in MUHSSs

Similar to LUHSSs, MUHSSs have a high carbon content (0.25–0.5%
C) and alloying elements of 5–10%. The mechanical properties and
processability of these steels largely depend on the C content, which
helps to achieve ultra-high strength. The major alloying elements of
MUHSSs are Cr, Mo, Wolfram (W), and V [70]. These elements induce
high hardenability to medium alloy steels and tend to form carbides
during tempering, producing a secondary hardening effect that further
increases the strength of the steel.

2.1.3. Alloying in HUHSSs

Fig. 2. Commonly used UHSSs for AM: (a) Number of published papers on AM
of typical UHSSs, (b) Percentage of research work on AM of different UHSSs.
Data were summarized from papers published in Web of Science.
[69]. For example, Si, Ni, and Mo elements can improve the toughness of
LUHSSs, and Mn, Ni, Mo, and V elements can improve the hardenability
of LUHSSs. Ti, Nb, and V elements can refine the grain structure and
significantly enhance the strength and toughness of LUHSSs. Fig. 3c and
d respectively show the microstructure of two TM steels (steel A and D)
with differences in alloying elements. Compared to steel A, steel D has
an additional 1% wt. Cr and 0.05% wt. Nb in its chemical composition.
As a result of the addition of these two alloying elements to the D steel,
the martensitic lath matrix of the TM steel becomes finely homogeneous
and the priori austenite grains are refined. In addition, the Cr and Nb
elements eliminate residual austenite films and inhibit the precipitation
of carburized bodies, resulting in an increase in the tensile and yield
The elemental composition of HUHSSs varies significantly from the
two groups of steels mentioned above. By reducing the C content and
adding different types and amounts of alloying elements, a series of
HUHSSs have been developed, namely precipitation-hardening stainless
steels (PHSSs), maraging steels (MSs), secondary hardening steels
(SHSs).
PHSSs achieve precipitation hardening by adding a multitude of
alloying elements precipitating a variety of intermetallic compounds to
obtain ultra-high strength and hardness. Fig. 4a shows an atomic probe
maps of 17–4 PH steels after solid solution ageing, where it can be
observed that in addition to the Cr elements, Copper Cu, Ni, Mn, Si and
Nb elements all appear in clusters. This phenomenon is consistent with
the precipitation behaviors of the Cu-rich phases (CRPs) and the Ni-, Mn-
, Si- and Nb-rich (NMSN) precipitates in Fig. 4b. The 1D profile con­
centration distribution of the CRPs and NMSN precipitates (ROI-1, ROI-2
and ROI-3) are shown in Fig. 4c-e. The extensive nucleation of CRPs
during ageing is responsible for the significant initial hardening. As the
ageing time increases, the NMSN precipitates and grow with the CRPs,
while Cr atoms were rejected from CRPs into the matrix enabling
nucleation of Cr-rich α′ domains [71]. In general, the process demon­
strates that the precipitation of multiple alloying element precipitation
phases and their interactions provide PHSSs with ultra-high strength and
hardness. The 15–5 PH steels have similar precipitation behaviors and
strengthening mechanisms to 17–4 PH steels [72]. To ensure the
toughness, corrosion resistance and weldability of the steel, the C con­
tent of these PUSSs generally does not exceed 0.03%. In addition, PHSSs
also generally contains the element cobalt (Co), which enhances the heat
treatment of the steel. Aluminum (Al), phosphorus (P), Ti and other
elements can also be added as strengthening elements. Trace amounts of
B, V and N can also enhance the properties of HUSS [73].
MSs have a martensitic matrix with no or very low carbon content.

Table 2
Chemical composition of typical UHSSs (mass%).
UHSSs Element Ref.

C Si Mn Cr Ni Mo Co Other Fe

AISI4140 0.39 0.25 0.78 0.85 — 0.16 — — Bal. [55]

AISI4340 0.40 0.28 0.73 0.78 1.73 0.21 — — [56]
300 M 0.34 2.1 0.73 0.92 2.23 0.41 — V0.07 [57]
Cu0.17
H11 0.40 0.85 0.42 4.96 — 1.18 — V0.45 [58]
H13 0.37 1.10 0.396 4.70 — 1.27 — V0.97 [59]
W0.04
Aermet100 0.24 — 0.01 3.10 11.10 1.20 13.40 — [60]
15–5PH 0.0028 0.60 0.69 15.70 4.92 0.42 — Cu3.29 [61]
Mo0.42
17–4PH 0.01 0.72 0.68 16.90 4.74 0.68 — Cu4.35 [62]
Nb0.33
18Ni (250) 0.008 0.02 0.03 — 17.86 5.20 7.93 Al0.14 [63]
Ti0.58
18Ni(300) 0.01 0.009 0.05 0.13 17.27 4.57 8.53 Al0.09 [64]
Ti0.68
Cu0.02
18Ni(350) 0.01 0.035 0.02 0.04 18.0 4.8 12.0 Ti1.4 [65]
Al0.09

4
K. Li et al.
They are not relying on carbide strengthening, but on intermetallic
compounds precipitated by aging in ultra-low carbon martensite for
strengthening [74]. Because of the ultra-low carbon, the steel has a low
hardenability and is difficult to produce martensitic transformation,
while the addition of Ni elements can prompt the transformation process
to proceed. Precipitation hardening is realized by adding Mo, Co, and Ti
elements for ultra-high strength and high toughness to the steel. In
Fig. 5a, the martensitic composition to the concentration of the three
precipitates is shown from left to right. According to the compositional
composition, the type i, type ii and type iii precipitates are (Fe,Ni,
Co)3(Ti,Mo), (Fe,Ni,Co)3(Mo,Ti) and (Fe,Ni,Co)7Mo6 respectively. The
difference between the type i and type ii precipitates is that the former is
dominated by the Ti element and the latter by the Mo element. After
ageing, these intermetallic compounds precipitated around regions of
the retained austenite are the source of the ultra-high strength and good
toughness of MSs [75].
SHSs precipitate alloy carbides, introducing a secondary hardening
effect to obtain ultra-high strength [76]. The main alloying elements in
SHSs include Ni, Co, Cr, Mo, and V. Among them, Ni and Co are the key
components of steel. Mo and Cr are the major secondary hardening el­
ements, which can precipitate M2C-type and M23C6-type carbides in the
martensitic matrix [77]. Fig. 5b and c show the martensitic plates and
the nano-scale precipitated phases in the martensite after tempering,
respectively. The needle-like precipitates in Fig. 5c are M2C-type pre­
cipitates and the square precipitates are M23C6-type precipitates. These
nano-precipitates allow the SHSs to produce a secondary hardening ef­
fect and obtain ultra-high strength steel and hardness. In addition, Ni
improves the hardenability of steel, and Co reduces the solid solution of
Mo in martensite to enhance the strengthening effect [78,79].
2.2. Microstructure contribution to the property
2.2.1. Microstructure in LUHSSs
During the non-equilibrium solidification of LUHSSs, austenite
grains are divided and refined by lower bainite laths, resulting in a fine-
grained martensitic phase. This fine-grained martensite with high-
density dislocation substructures can cause dislocation strengthening
5
Journal of Alloys and Compounds 965 (2023) 171390
Fig. 3. Effect of alloying elements on mechan­
ical properties: (a) Hot working route for a low
alloy ultra-high strength steel, consisting of four
stages: homogenization, warm rolling (TF
method), reheating and tempering. Significant
differences in microstructure after TF and TFR
treatment. (b) Engineering stress-strain curves
after tempering plus reheating (TFR) [66]. The
phase composition: (c) A steels and (d) D steels,
where γR, αm, θ, and M-A represent retained
austenite, martensite, cementite, and
martensite-austenite constituent (M-A) phase,
respectively [69].
[80]. This microstructure provides the steel with ultra-high strength,
excellent plasticity, and toughness. After heat treatment, there are fine
diffuse precipitation phases precipitated along dislocations in the
structure of LUHSSs, producing a precipitation-strengthening effect. The
residual austenite is distributed in a membrane between the martensite
and lower bainite laths, which can reduce the stress concentration at the
crack tip and inhibit crack propagation, effectively improving the
toughness of the steel [81]. Fig. 6 shows the microstructure of a typical
LUHSS after heat treatment. When the heat treatment temperature ex­
ceeds the martensitic phase transformation temperature, most of the
austenite has transformed into initial martensite (M1) and then
tempered. A small fraction of CFB can be observed in the tempered
microstructure (Fig. 6a), which consists of bainitic ferrite and retained
austenite (RA). Some film-like RA is also found to be located between
martensite and bainite due to the carbon partitioning effect from
martensite lath into neighbored austenite. The film-like RA is able to
remove microstructural tip stresses and improve its toughness. Notably,
it is that considerable amount of plate-like carbide is observed inside
M1, which is easily etched to obtain interior tempered structure
(Fig. 6b). Further observation of the tempered martensite by TEM
revealed abundant dislocation units within the martensite lath (Fig. 6c)
and a large number of ε-carbides with a rod-like morphology (Fig. 6d),
both of which contribute to the strength of LUHSSs.
2.2.2. Microstructure in MUHSSs
The microstructure of MUHSSs contains refined martensite. As
shown in Fig. 7, during the tempering process, the elements Mn, Cr, Mo,
and V precipitated a large number of finely dispersed rod-like carbides
(M2C), and parallelogram-shaped intragranular carbides (M7C3) in the
martensite, which achieved secondary hardening. With increasing
tempering time, rod-like carbide dissolution, plate-like carbide (M6C)
precipitation, and intergranular carbide (M23C6) coarsening became
significant, and this resulted in a decrease in hardness [83]. Compared
with LUHSSs, MUHSSs have higher tempering stability and perform well
at a medium temperature environment of 500 ◦ C, while not better than
LUHSSs at room temperature.
K. Li et al.
Fig. 4. Distribution of alloying elements in the precipitated phase: (a) Atomic probe maps of 17–4 PH steel after solution-aging treatment, (b) Cu-rich precipitates
(yellow)and Ni, Mn, and Si-rich (green) phase. The 1D profile concentration distribution across (c) ROI-1 and (e) ROI-3 center along the direction of the arrow, and
(d) ROI-2 center and perpendicular to the map [71].
2.2.3. Microstructure in HUHSSs
Variations in the major alloying and hardening elements in PHSSs
can lead to large differences in the phases and microstructure of the
steel. Depending on the degree of martensitic transformation, PHSSs are
classified into martensitic, semi-austenitic, and austenitic structures.
Martensitic PHSSs have a slatted martensitic matrix which is strength­
ened by the precipitation of Cu-rich nano-precipitation phases from the
matrix after aging [84]. As shown in Fig. 8a, Cu can solute in the matrix
of martensitic PHSSs under quenching conditions and can precipitate
the Cu-rich nanometer phase (ε-Cu) during tempering. Cu is helpful for
grain refinement and promotes the formation of reversed austenite
during tempering. Cu in PHSS can cause solid solution strengthening,
precipitation strengthening, and grain refinement strengthening, which
greatly improves the mechanical properties [85]. As shown in Fig. 8b
and c, semi-austenitic PHSSs have an austenitic-martensitic structure in
the solid solution and quenched states. The steel can be transformed into
a fully martensitic composition after heat treatment or deformation
treatment, then increase strength by aging precipitation [86]. Austenitic
PHSSs are stable austenitic microstructure in both quenched and aged
6
Journal of Alloys and Compounds 965 (2023) 171390
states, and therefore have relatively stable properties at high tempera­
tures. The main strengthening phase of Austenitic PHSSs is the spherical
γ′-Ni3(Ti, Al) precipitation phase, but these precipitation phases are
easily transformed into flaky η-Ni3(Ti, Al) precipitation phases during
aging treatment [87]. As shown in Fig. 8d-f, austenitic PHSSs precipitate
the η-Ni3(Ti, Al) phase at grain boundaries during aging. However, as
the aging time increases, the stacking faults in the η-phase bind with
dislocations during deformation, leading to a slight increase in strength
and a significant increase in brittle behavior, which has a detrimental
effect on the creep properties of the steel. These PHSSs have different
microstructures due to differences in alloying elements, while they all
have remarkably high strength and ductility, excellent corrosion resis­
tance, outstanding formability, and weldability.
MSs are highly pure with very high Ni levels and ultra-low carbon,
which allows the steel to be martensitic even when quenched at low
cooling rates. After solid solution, quenching, and aging treatment, the
steel can complete the transformation of the whole martensite and
precipitate intermetallic compounds such as Ni3Mo and Ni3Ti [88]. As
Azizi et al. found that the MS1 steel precipitates the Ni-rich (Fe(Mo, Ni,
K. Li et al.
Fig. 5. Effect of alloying elements on the properties of UHSSs: (a) Type (i) precipitates (Fe,Ni,Co)3(Ti,Mo), Type (ii) precipitates (Fe,Ni,Co)3(Mo,Ti), and Type (iii)
precipitates (Fe,Ni,Co)7Mo6 from top to bottom [74], which show the elemental concentrations inside the three kinds of precipitates. AF1410 steel with (b)
martensitic matrix and (c) M2C-type and M23C6-type carbides[77].
Al)3) and Ni3(Ti, Mo) phases during aging that lead to increased strength
[89]. Relying on a carbon-free or slightly carbon-free martensitic matrix
and intermetallic compounds precipitated by aging, MSs have excellent
comprehensive mechanical properties, such as high toughness, excellent
impact toughness, and outstanding weldability [90,91].
The microstructure of SHSs is high Ni-Co low carbon slate-martensite
with a high density of dislocations. A large number of alloying elements
are solidly dissolved within the martensitic matrix, enabling the steel to
obtain high tensile strength and hardness [77]. Veerababu et al. inves­
tigated the behavior of alloying element clusters in SHSs after hardening
and aging treatment [92]. Statistical distributions for the different solute
elements were listed in Fig. 9a-c, which revealed that only carbon ex­
hibits clustering even in the as-quenched condition, whereas Cr and Mo
show clustering in all tempered conditions. Using the maximum sepa­
ration envelope method (MSEM), they observed that clusters can be
broadly classified into carbon-rich and carbon-deficient according to
their carbon content Fig. 9d and e. These clusters most likely can be
precursors for carbides and intermetallic compounds. Therefore, the
heat-treated secondary hardened steel can precipitate many precipitated
phases from the matrix structure, which significantly increases the yield
strength, plasticity, and toughness and maintains high tensile strength.
UHSSs are based on the conventional strengthening-toughening
theory of alloys (solution strengthening, precipitation strengthening)
and various alloying elements (Ni, Co, Cr, Mo). Varying the kind and
proportion of alloying elements can adjust the microstructure and pre­
cipitation phase of UHSSs to improve performance. LUHSSs and
MUHSSs have high C content which makes them economical, but the
higher C content impairs the performance of the steel such as fracture
toughness and weldability. Poor corrosion resistance and inadequate
high-temperature p are also disadvantages of LUHSSs and MUHSSs,
which make them have certain limitations in the application of force
impact, acid, alkali, and high temperature. Compared with the two types
of steel mentioned above, HUHSSs possess ultra-high strength, fine
plasticity, ductility, excellent fatigue strength, and corrosion resistance.
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Journal of Alloys and Compounds 965 (2023) 171390
However, HUHSSs contain a large number of valuable alloying ele­
ments, which increases the cost substantially. In addition, to avoid se­
vere segregation of these alloying elements, complex preparation and
heat treatment processes are used and production costs are further
increased.
3. Characteristics and research progress of AMed UHSSs
Additive manufacturing technology techniques widely used in UHSS
are L-PBF, L-DED and WAAM, each with different process characteris­
tics. L-PBF employs layer-by-layer scanning, using a high-energy laser
beam to rapidly melt metal powder along a specified laser path to pro­
duce high-precision, complex-shaped parts [93]. LDED uses a laser beam
with higher energy, resulting in high deposition efficiency but producing
an unstable melt pool. WAAM uses a high-energy arc as the heat source,
providing high deposition efficiency and the ability to produce large
parts. The application scenarios differ due to the heat source and feed­
stock. However, all three additive manufacturing technologies, with
their layer-by-layer formation, cyclic thermal history and rapid solidi­
fication, offer a promising solution to the challenges encountered in
traditional manufacturing methods [94]. This section details the process
characteristics of different additive manufacturing technologies and the
potential for forming microstructures, and provides an overview of
research progress of AMed UHSSs.
3.1. Characteristics of AM technologies
3.1.1. Laser powder bed fusion
Laser powder bed fusion (L-PBF) equipment generally consists of an
optical path unit, a mechanical unit, a control unit, process software,
and a protective gas sealing unit (Fig. 10a). Based on 3D model slices and
pre-designed scan paths, the L-PBF device controls the laser beam to
selectively scan and melt the metal powder by controlling the scanning
oscillator. As the forming chamber descends and the powder chamber
K. Li et al.
Fig. 6. The SE micrographs of typical heat treatments: (a) carbide free bainite, which consists of bainitic ferrite and retained austenite, (b) plate-like carbide in initial
martensite. Typical TEM micrographs of heat treatments: (c) lath martensite and retained austenite between laths, (d) ε-carbide precipitated in martensite [82].
rises, the powder is uniformly laid flat on the forming platform and
scanned layer by layer. The process is repeated until the solid part is
formed [95]. To avoid oxidation of the metal powder, the entire L-PBF
molding process is conducted in a molding chamber filled with inert
protective gas.
L-PBF has a small laser beam and lower input energy. Accordingly,
the powder particle size is small (15–53 µm) and the melt pool feature
size is also small (100 µm). Thus, L-PBF formed parts have a remarkably
fine microstructure that can be near full density. As shown in Figs. 10c
and 10d, the SLMed 420 stainless steel parts were fully dense with
̃99.8% relative density and were characterized by ultrafine and hetero­
geneous microstructure, containing colonies of cells with the size be­
tween 0.5 and 1 µm and martensitic needles in submicron scale. The
advantage of L-PBF is that the printed parts have uniform microstruc­
ture, fine grain size, and high comprehensive mechanical properties of
the formed parts. However, L-PBF has weaknesses, such as costly
equipment, slow forming speed, and small size of formed parts [96].
L-PBF technology is moving towards faster forming speeds and larger
forming volumes. Due to the characteristics of L-PBF technology, it tends
to lead to higher crack sensitivity when the varieties of alloying elements
in UHSSs are complex. Therefore, LUHSSs and MSs are more suitable for
preparation with L-PBF. MUHSSs are often used as mold steels, which
require high precision and are also suitable to be prepared by L-PBF.
3.1.2. Laser direct energy deposition
Laser direct energy deposition (L-DED) equipment generally consists
of a laser system, an optical path system, a dynamic mechanism, a
powder feeding system, an atmosphere protection system, and a control
system. A schematic diagram of L-DED and an actual production dia­
gram are shown in Fig. 11a and b respectively. In addition, the printing
8
Journal of Alloys and Compounds 965 (2023) 171390
principle of L-DED is the same as the L-PBF. Both are based on a 3D slice
model of the part and the computer numerical control system is stacked
layer by layer along a defined scanning strategy to form a solid part [99].
The distinction between the two processes is that the L-DED process uses
simultaneous powder feeding laser cladding, and it is also possible to use
simultaneous wire feeding to form parts [100].
PHSSs have a high crack sensitivity due to the high content of pre­
cipitation hardening elements such as cu. They also usually contain the
element Al, which has a high laser reflectivity. Using L-PBF has a
negative impact on the manufacture of PHSSs due to the low energy
input, the small melt pool and the rapid cooling rate. Compared to L-
PBF, L-DED has a higher power laser and a larger spot size, allowing for a
higher energy input, thus making it more suitable for the production of
some UHSS parts with high crack sensitivity. D2 tool steel is a high C and
high Cr steel content with a high thermal cracking rate. Yadav et al.
[101] successfully fabricated crack-free D2 bulk structures using L-DED.
Fig. 11c and d show the microstructure of D2 steel, free of cracks and
other defects, with a high relative area density of > 99.9%. L-DED can
therefore be used as a method for producing steels with high crack
sensitivity. Due to the simultaneous powder feeding, L-DED is able to
fabricate parts with structural and functional gradients and can also be
used to repair and remanufacture partially damaged parts [102,103].
Without the support function of the powder bed, L-DED is more difficult
to form complex structures and has a lower accuracy of formed parts
than the L-PBF process [104]. With higher energy input and lower
cooling rate, L-DED enables the manufacture of LUHSSs, PHSSs with
high cracking sensitivity, and refractory second-hardened UHSSs.
3.1.3. Wire arc additive manufacturing
Wire arc additive manufacturing (WAAM) is an advanced
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 7. Main strengthening precipitation phases of MTSs: (a) M2C-type carbides, (b) M7C3-type carbides, (c) M6C-type carbides, and (d) M23C6-type carbides [83].

Fig. 8. Microstructural characteristics of PHSSs: (a) morphology of martensite matrix, austenite, and tiny precipitated phase of martensitic PHSSs [85]. Micro­
structure of semi-austenitic PHSSs: (b) metastable austenite, martensite, and inherited δ-ferrite, (c) The austenite transformed into lath martensite after rod-drawn
deformation [86]. TEM images of η-phase precipitated in samples aged at 750 ◦ C for (d) 4 h, (e) 16 h, and (f) 64 h, where the arrows indicate stacking faults [87].

manufacturing technology developed on the basis of tungsten arc
welding, metal inert gas welding and submerged arc automatic welding.
WAAM uses an electric arc as the heat source and a metal wire as the raw
material. Under the control of CAD/CAM software, the arc melts the
wire to form a molten pool and builds up layer by layer into a 3D solid
part. Three commonly used methods of WAAM are illustrated in
Fig. 12a-c. Of these, GMAW uses a welding wire as the melting electrode,
forming an arc between the wire and the tapping material for additive
manufacturing, while GTAW and PAW use a tungsten electrode for ad­
ditive manufacturing. Compared to GTAW arc, PAW has a narrow high

9
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 9. Atom maps in the as-quenched sample for (a) C, (b) Mo, and (c) Cr, revealing C clustering, while Cr and Mo are in random solid solution. Delineation of
clusters from random solid solution: (d) The random distribution of C, Cr, Mo, and V before the application of MSEM, (e) The distribution of C, Cr, Mo, V, and Fe
atoms clusters after the application of MSEM [92].

Fig. 10. Equipment diagram of L-PBF technology and microstructure of forming specimens: (a) Schematic diagram and (b) equipment diagram of L-PBF [97]. SEM
images of SLMed 420 material: (c) cellular structure and martensite needles, (d) martensitic needles of submicron size inside the cells [98].

temperature zone, however PAW can have up to three times the arc
energy of GTAW, which allows for less welding distortion and higher
welding speeds.
The raw material for WAAM is wire and the heat input is high,
enabling the technique to have high material utilization and deposition
efficiency to meet the fabrication requirements of large monolithic
structural components [105]. In addition, WAAM is more cost-effective
because there is no need to consider powder safety, and the forming
process does not require a vacuum environment and expensive equip­
ment. Due to the high material utilization and high forming rate,
However, WAAM has disadvantages, such as poor forming stability of
parts, limited variety of forming materials, poor comprehensive me­
chanical properties of parts, and the need for more post-finishing pro­
cesses [106]. At present, WAAM has been used for specimen preparation
and mechanical property studies of MS. Fig. 12d shows a specimen block
of P91 steel fabricated by WAAM with good forming morphology. The
microstructure of WAAM P91 steel in different areas during homoge­
nization is shown in Fig. 12e-g. After the homogenization process, some
δ ferrite remains in the middle and top positions. And due to the high
amount of remaining δ ferrite, the hardness at the top position is the

10
K. Li et al.
Fig. 11. Equipment diagram of L-DED technology and microstructure of forming specimens: (a) Schematic diagram and (b) equipment diagram of L-DED [99]. The
deposited D2 tool steel microstructure: (c) interface region of deposited, (d) top region of deposited [101].
lowest. Additionally, the martensitic slats in the top position are much
smaller than those in the middle and bottom positions due to the higher
cooling rate at the top during quenching, which significantly affects the
diffusion-free transformation from austenite to martensite.
3.2. Characteristics of AMed microstructure
The rapid melting and solidification cycle in additive manufacturing
creates a non-equilibrium environment. The solid-liquid interface may
move near or even faster than the diffusion rate of the solute, and a large
amount of solute is "trapped" in the solid phase by the rapidly growing
solid-liquid interface, which induces metastable microstructure. These
metastable microstructures include solute heterogeneity, trans­
formation of columnar crystals to equiaxed crystals, and dislocation cell
structure, which contribute to the strength of additively manufactured
alloys [109]. Many studies on the microstructure of additive
manufacturing have been reported. Conde et al. [110] observed the
microstructure characteristics of AMed UHSSs and the clear melt pool
can be seen in the microstructure (Fig. 13a). They consider that the
typical cellular morphology exhibited by the as-built microstructure is
related to local compositional segregation. The non-uniform micro­
structure is also reflected in the existence of residual austenite. Wang
et al. [111] investigated that with the high-temperature gradient and
growth rate in the molten pool, fine and uniform dendrite arrays were
formed in the columnar grains observed, where the epitaxial columnar
dendrites show the preferred growth orientation along the deposition
direction (Fig. 13b). In addition, the band structure (Fig. 13c) in the
samples is evidence of the remelting process, and the bottom boundary
of the melt pool formed by scanning laser remelting can be identified by
these bands. Similarly, Zhao et al. [112] observed solidification micro­
structure mainly consists of rapid directionally solidified columnar
grains with interior well-aligned cellular dendrite structures, showing
several deposited layers. As shown in Fig. 13d, the deposited layer
microstructure of the AMed UHSSs consists of alternating cytosolic and
columnar crystals. Laminar bands appear between adjacent deposited
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Journal of Alloys and Compounds 965 (2023) 171390
layers (Fig. 13e), which are due to partial remelting of the solidified
deposited layers during the deposition of the next layer. The cellular
structure is shown in Fig. 13f, which is a typical structure for AMed
UHSSs. The first solidified parts constrain the deformation of the latter
parts, leading to increased internal stress and promoting dislocation
density. The dislocations eventually aggregate by sliding, leading to the
formation of cell walls.
3.3. Research progress of AMed UHSSs
3.3.1. Processes of L-PBF UHSSs
At present, L-PBF is the most mature technology in metal additive
manufacturing and the most widely used in AM of UHSSs. This tech­
nology has successfully printed LUHUSSs, MTSs, PHSSs and MSs, with
the focus of AMed LUHSSs being mainly on the forming process and its
effect on microstructure and properties. For instance, Jing et al. [113]
used SLM to print 300 M steel and investigated the effects of low and
high laser power on its microstructure evolution and mechanical
properties.
The thermal conductivity of SLMed H13 tool steel exhibits significant
individual anisotropy, being smaller along the building direction (z).
Fine microstructure significantly increases the boundary area that in­
hibits heat transfer. In the cellular region, heat transfer in the cellular
zone is generally slower, favoring heat transfer in the x-y plane. The
columnar region is aligned with the direction of heat flow during so­
lidification, which generally benefits heat transfer in the z-direction. Sun
et al. [114] investigated the effect of laser body energy density and heat
treatment on the thermal conductivity of H13. As shown in Fig. 14, the
area fraction of the cellular zone in the low VED melt cell is relatively
high. Both the melt cell boundary and the lack of fusion holes enhance
anisotropy, allowing for heat transfer in the x-direction. As VED in­
creases, the area of the cellular zone decreases and the area of the
columnar region increases. At high VED, the columnar crystal region
dominates, hindering heat transfer in the x-direction, while the melt
pool boundary inhibits heat transfer in the z-direction and the
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 12. Equipment diagram of WAAM technology and macrostructure of forming specimens: (a) GMAW, (b) GTAW, and (c) PAW process [107]. Forming specimens
side view (d) and microstructure at top (e), middle (f) and bottom (g) locations of WAAM P91 steels [108].

Fig. 13. Microstructure of AMed UHSSs: (a) SEM image of the melt pool structure, (b) Columnar dendrite structure, (c) Band structure, (d) Deposited layer consisting
of alternating cytosolic and columnar crystals, (e) Laminar bands, and (f) Dislocation cell structure [110–112].

12
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

anisotropy of thermal conductivity tends to decrease. It is worth noting

Fig. 14. Schematics for microstructural features affecting heat transfer
behavior with different VEDs of SLM [114].
that both quench and temper (QT) and direct temper (DT) eliminate
anisotropy by inducing elemental diffusion, which reduces cellular
columnar structure and carbon-rich /RA regions. Both heat treatment
options increase the thermal conductivity. In addition, a review of
SLMed H13 steels has been reported, the paper presents the current
status of H13 tool steels printed by SLM and reviews the current research
progress in this field in terms of microstructure, defects and mechanical
properties [115]. This review shows the promise of SLMed H13 steels for
a wide range of applications and is a catalyst for subsequent research.
PHSSs made by SLM have the potential to achieve ultra-high strength
and hardness by customizing the microstructure. Therefore, many re­
searchers view the use of the SLM process to induce precipitated phases
to improve the properties of the steel. In a forming chamber with an
oxygen content of 500 ppm, Xu et al. [116] used the SLM process to
successfully produce oxide dispersion strengthening of a 17–4 PH
stainless steel. Ozsoy et al. [117] successfully printed TiN-reinforced
17–4 PH stainless steels. The TiN nanoparticles can be used both as a
breeder to obtain an isometric microstructure and as a dislocation

Fig. 15. Optical micrographs of the polished DT300 steel specimens in horizontal section and the corresponding porosities: the green dotted box represents the low
laser energy density (about 40 J/mm3), the blue dotted box represents the medium laser energy density (83–89 J/mm3), and the yellow dotted box represents the
high laser energy density (138.89 J/mm3), the spatter defect, LoF defect, spherical pore and unmelt powder is indicated by the yellow, green, water green and white
arrow respectively [119].

13
K. Li et al.
barrier to improve mechanical properties.
SLM technology has been more maturely used for the production of
MSs. The microstructural evolution and mechanical properties, the ef­
fect of heat treatment and corrosion resistance of SLMed maraging steels
have been studied. For example, Cheng et al. [118] prepared highly
ductile FeCo15Cr14Ni4Mo3 martensitic steels using laser-selective
melting and observed the evolution of the microstructure during the
forming process. Jiang et al. [119] used SLM to print DT300 maraging
steel and successfully prepared fully dense (relative density >99%) parts
and discussed in detail the types of defects and the formation mecha­
nisms under different conditions. As shown in Fig. 15, large equiaxed
and elongated pores (>200 µm) with sharp edges caused by large spatter
particles (spatter defect) staying on the linear laser tracks, small pores
with sharp edges (<50 µm) stemming from lack of fusion (LoF defect)
and small (<20 µm) spherical pores are observed in the six specimens of
low laser energy density parameters, resulting in the porosities of more
than 2%. With the increase of laser energy density, small size LoF defects
and spherical pores become the main defects in the specimens of me­
dium and high laser energy densities. In addition, An review on the
additive manufacturing of MSs has also been reported by Tan et al.
[120], which analyzed the advantages specific to the preparation of MS
by selected-area laser melting (SLM) and provided a systematic pre­
sentation of five aspects of MS parameters and performance optimiza­
tion for SLM forming, forming anisotropy, aging strengthening
mechanisms, gradient materials and mold applications. This is a good
guide for the subsequent research on selected area laser melting of
maraging steels.
3.3.2. Processes of L-DED UHSSs
Due to the process characteristics of L-DED technology, the tech­
nology can be used for the parts repair [121,122] and gradient material
forming [123,124]. Unfortunately, these advantages have not yet been
well applied to AMed UHSSs. Currently, L-DED has been successfully
applied to the manufacture of LUHSSs, MTSs, MSs and PHSSs, where
studies have focused on the microstructural evolution and mechanical
properties. For example, Liu et al. [125] found that the microstructural
composition of 300 M steel before and after heat treatment remained
invariable, with only the composition content changing. The hardness
gradually decreased with increasing heat treatment time, while the
Fig. 16. IPF maps of positions 0%, 25%, 50%, 75% and 100%. The maps are oriented in the building direction (y axis) and from 0% to 100% refers to the height of
the thin wall along the building direction [127].
14
Journal of Alloys and Compounds 965 (2023) 171390
tensile and yield strengths changed less. Wang et al. [126] discovered
that adding the suitable amount of Mo could promote grain refinement
and martensitic transformation of M2 steel with increased hardness and
impact toughness and decreased wear resistance. Appropriate tempering
treatment resulted in grain refinement of the samples, while promoting
the transformation of martensite to ferrite. After heat treatment the
hardness is significantly increased and the impact toughness and wear
resistance are improved.
AM processes for tool steel parts are of high complexity due to the
complex thermal history and martensitic transformation involved. Sil­
veira et al. [127] used high energy synchrotron radiation to explain the
microstructural changes in different parts of the printed thin walls of
L-DED H13 steel. As shown in Fig. 16, at position 100% the martensitic
slats are well defined and many of the grain planes are vertically ori­
ented. At position 75%, the microstructure shows very fine equiaxed
grains with no particular preferred orientation. Positions 50% and 25%
have the same small equiaxed grain characteristics, but larger areas can
be seen to exist, possibly due to tempering effects. At the 0% position, a
clear shift in grain size is observed (grey arrow), which is defined by the
transition between the matrix and the thin wall.
It is well known that the fabrication of UHSSs with all combinations
of high strength and high ductility is a goal that has always been pur­
sued. Yu et al. [128] obtained a periodic layer (PL) structure with spaced
distribution of austenite in 17–4 PH steel by L-DED and ageing. Excellent
strength-ductility combinations were obtained for the PL structure of
17–4 PH stainless steel by the synergistic effect of strain-distribution
hardening and austenitic phase transformation-induced plasticity.
18Ni300 is one of MSs with ultra-high strength and superior toughness.
Chen et al. [129] explored the evolution of microstructure and defects in
18Ni300 MSs printed by L-DED. The results showed that the main in­
fluences on the morphology of 18Ni300 MSs were laser power, powder
feed rate and scanning speed. Along the print height, the grains change
from columnar to equiaxed with an increase in primary spacing, indi­
cating a reduction in temperature gradients during the fabrication pro­
cess. Grain size was also found to be the main factor affecting
microhardness, with the main defects being non-dense defects porosity
and cracks.
K. Li et al.
3.3.3. Processes of WAAM UHSSs
WAAM has been used to produce MTS, PHSS and MS with the ad­
vantages of high deposition efficiency, high material utilization and low
cost. WAAM H13 is subject to stress and deformation in industrial ap­
plications, so controlling its deformation is significant. Li et al. [130]
examined the deformation of H13 steel printed with four deposition
strategies: sequential, symmetric, inside-out and outside-in. The results
showed that the parts deposited in sequential had the greatest defor­
mation, while the deformation was reduced by 68.6% for the outside-in
deposition. In contrast, Hackenhaar et al. [131] compared the effects of
cold metal transfer (CMT), low sputter control (LSC) and pulsed synergy
(PS) deposition modes on the geometry and mechanical properties of the
deposits. Specimens in all three deposition modes exhibited very high
tensile strength both and brittle fracture with low elongation.
Fig. 17a shows the macrostructure of WAAM H13 prepared by Tanvir
et al. [132]. Four different types of microstructure combinations were
found in the WAAM H13 specimens: (1) martensitic slats and residual
austenite (Fig. 17b), (2) thin martensitic slats with fully transformed
austenitic grain boundaries (Fig. 17c), (3) martensitic slats with fully
transformed austenitic grain boundaries (Fig. 17d), and (4) fully
tempered martensite and ferrite (Fig. 17e). The formation of these phase
compositions is closely related to the temperature distribution during
layer-by-layer deposition. The microstructure during deposition and
after heat treatment determines the mechanical properties of WAAM
PHSSs. Zhou et al. [133] found that the microstructure of WAAM 17–4
PH deposited state specimens consisted of martensite, residual austenite,
a small amount of δ ferrite, M23C6, Nb(C,N) and Cu precipitates. And
Fig. 17. Phases evolution of H13 steel by WAAM: (a) macrostructure of the H13 solid block. Microstructural phases at different locations: (b) Martensite and retained
austenite, (c) Martensite and austenitic grain boundary, (d) Tempered Martensite, ferrite and austenitic grain boundary, (e) Tempered martensite and ferrite [132].
15
Journal of Alloys and Compounds 965 (2023) 171390
after heat treatment, the reversed austenite and nanoscale precipitation
in the slatted martensite achieves an excellent combination of strength
and ductility.
The thermal cycling and heat accumulation in WAAM leads to the
complexity of the microstructural evolution of MSs and it is significant
to reveal the microstructural evolution during this process. Xu et al.
[134] investigated the variation of hardness, grain and precipitation
phases of WAAM maraging 250-grade steel with the height of deposi­
tion, and indeed these variations were qualitatively related to the
thermal conditions during fabrication. The microstructure of the
deposited MSs is predominantly martensitic and to a lesser extent
austenitic, lacking a strengthening phase [135]. This can be improved
considerably by the precipitation of multiple precipitation phases by
heat treatment. The microstructural changes in WAAM MSs under
deposition and heat treatment conditions were investigated by Deng
et al. [136]. In the deposited samples, a large number of dislocations and
residual austenite could be found at the boundaries of typical martens­
itic slats (Fig. 18a), while some ε-Cu nanoprecipitates could be observed
inside the martensitic slats (Fig. 18b). The ageing process resulted in the
formation of reversed austenite in Fig. 18d with a tendency for the
martensitic slats to refine and abundant ε-Cu particles dispersed in the
martensitic slats and significantly increasing in size (Fig. 18e and f). As
shown in Fig. 18g, the solution ageing heat treatment further refined the
martensitic laths with ε-Cu particles still dispersed in the martensitic
laths (Fig. 18h), and nanoscale twins were produced in the martensitic
laths (Fig. 18i). In addition, a review on the additive manufacturing of
18% Ni maraging steel has been reported by Guo et al. [137]. They
K. Li et al.
Fig. 18. Microstructure characterization by TEM: Dislocation and retained austenite (a) and ε-Cu particles (b and c) in as-deposited state; reversed austenite (d)and
ε-Cu particles (e and f) in aging state; and reversed austenite (g), ε-Cu particles (h) and nanoscale twins (i) in solid solution aging state [136].
review recent research advances in AMed 18% nickel MSs and outline
the effect of the processing parameters of the AM technique on the de­
fects formed in the fabricated parts. The macrostructure, microstructural
characteristics and mechanical properties of the as-built and
heat-treated MSs are then described in detail. This work provides a
future direction for AM work on 18% nickel maraging steel.
4. Property regulation of AMed UHSSs
Because of the imperfection of additive manufacturing technology,
the structures of AM UHSSs inevitably exist defects that significantly
affect the behavior of UHSSs. Manufacturing processes employing pre­
treatment, process parameter optimization, and post-treatment pro­
cesses can realize composition optimization of microstructure and defect
elimination, which can enhance the mechanical properties of printed
specimens. This section describes the causes of defect formation and the
corresponding optimization approaches and details the methods of
property regulation during the AM of UHSSs, where advanced assisted
technologies can contribute to the whole process of defect optimization
and property modulation.
4.1. Defect optimization
AM process of UHSSs suffers from defects, among which porosity,
residual stresses, and spatter have a significant impact on the mechan­
ical properties of the formed parts. Therefore, the causes of common
defects and the corresponding optimization approaches are presented in
16
Journal of Alloys and Compounds 965 (2023) 171390
detail in a separate subsection below.
4.1.1. Porosity
Pores are prevalent in AMed UHSS components and directly affect
the forming density and mechanical properties of parts. Pores include
gas pores, latchkey pores, and incompletely fused pores, thus under­
standing the formation mechanism of different pores is instructive to
optimize the porosity. In the rapid forming process, the gas in the melt
pool is not released in sufficient time and is solidified in the micro­
structure to form regular spherical pores of small size [138]. When the
irradiation energy of the powder is too high and the melt pool is large
and deep, the strong impact of the heat source will form a key-shaped
hole in the melt pool. The incompletely fused pores are caused by the
low energy density of the heat source so that the powder is not
completely melted.
The appropriate laser power is important to reduce the formation of
pores. For example, Kudzal et al. [139] investigated the effect of laser
power on the forming morphology of ES-1 variant UHSSs. As shown in
Fig. 19a, ES-1 specimens printed at high laser power exhibited many key
pores. By reducing laser power applied to the powder bed, the pore
density of the keyhole can be effectively reduced, resulting in a dense
forming morphology in Fig. 19b with a dense density of over 99.9%. In
contrast, Moghazi et al. [140] found many pores in 17–4 PH steel made
by PTA, and they reduced the porosity of the steel significantly by
increasing the heat input to ensure the complete melting of the powder.
Thus, rational adjustment of laser power according to the cause of
porosity formation can significantly reduce porosity and result in
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 19. Effect of laser power on sample porosity: (a) High laser power, (b) Low laser power [139]. Gaussian prediction model: (c) Observed results of porosity, (d)
Cross-validation of prediction model [141].

Fig. 20. Influence of powder spattering on forming process: (a) D10, D50, and D90 powder size distribution of virgin, under-size (US) spatter, and over-size (OS)
spatter powders, and scanning electron microscope etched powder results from (b) Virgin powder (c) US spatter powder and (d) OS spatter powder [149].

17
K. Li et al.
high-density formed parts. In order to reduce the cost of process
parameter regulation, a prediction model based on the Gaussian algo­
rithm was developed by Tapia et al. [141]. Fig. 19c shows the training
model between the actual observed porosity and the corresponding laser
power and scan speed. Laser power and scan speed, which have a sig­
nificant effect on porosity, were used to train the model, after which the
trained model was used to predict the porosity of the part. The adaptive
sampling method was used to improve the model to reduce the model
uncertainty. New sampling points and observation experiments were
added to the original dataset, which reduced the uncertainty of porosity
prediction. As shown in Fig. 19d, this model was well validated in the
17–4 PH steel fabrication process, and more accurately predicted the
porosity of the parts.
In addition, many reports indicate that they have achieved nearly full
density by reducing porosity [142–145]. For various types of porosity
defects, suitable optimization methods should be selected to reduce the
defects according to their forming mechanisms to improve the density of
the parts. The use of data-driven can significantly reduce the cost of
porosity optimization, however, the prediction accuracy of the model
needs to be further improved.
4.1.2. Spatters
Normally the heat source carries a strong impact, and the impact in
the melt pool tends to cause powder spattering resulting in defects in
Fig. 21. (a) Laser cladded sample of the AISI H13 tool steel (top view) with directions marked by N(z), L(x) and T(y) for normal, longitudinal and transverse. Map of
surface macroscopic residual stresses of the clad in the L direction (b) and T direction (c) [152].
18
Journal of Alloys and Compounds 965 (2023) 171390
parts. Molten metal droplets or incompletely melted particles ejected
from the laser irradiated area fall back onto the powder bed, which will
change the particle morphology and spatial distribution of the powder
bed [146]. In the case of high spattering, lack of fusion may be caused by
insufficient energy received by the particles [147]. Larger particles
partially melt can adhere to the part boundaries, resulting in high sur­
face roughness [148]. Ali et al. [149] studied virgin powder, under-sized
(US) and over-sized (OS) spatters with Fig. 20a showing the particle size
distribution of the three powders. A comparison of the particle size be­
tween the virgin and spatters shows a significant difference in powder
size and morphology. The results show equiaxially large particles in the
pristine powder (Fig. 20b), while the US spatters show a microstructure
similar to some of the smaller particles (Fig. 20c). The OS spatters
consisted mainly of epitaxy and therefore additional microstructural
features were observed in these powders, showing a finer grain structure
(Fig. 20d). The spattered areas typically have high surface roughness
and porosity, which leads to reduced ductility. Controlling spatters is
important to improve the surface quality as well as the mechanical
properties of formed parts. Kaserer et al. found that spattering is greatly
reduced under vacuum conditions. As the pressure decreases, the
laser-plasma interaction is reduced and the penetration depth of the
laser increases, allowing for improved process stability [150].
K. Li et al.
4.1.3. Residual stresses
AMed microstructure commonly has large residual stresses process
features due to process features, which decrease the mechanical prop­
erties of the part, especially fatigue strength. Processing parameters
have a significant influence on the microstructure. The effect of DED
process parameters on the residual stresses in 1.2709 maraging steel was
investigated by Aleksandr et al. [151]. It was found that when the laser
energy was increased from 28.0 J/mm2 to 48.2 J/mm2, the compressive
residual stress increased to three times the original value of about
450–580 MPa. In addition, increasing the powder feeding rate or
decreasing the scanning speed can significantly reduce the residual
stress. A bidirectional strategy achieves less stress compared to a uni­
directional scanning strategy. The use of additive manufacturing tech­
niques to repair H13 steel is a new way to save manufacturing costs, and
residual stresses are an important factor in its repair effectiveness. The
residual stresses generated during the fusion cladding process were fully
described by Trojan et al. [152] through X-ray diffraction, and Fig. 21a
shows a clad specimen of H13 steel. Figs. 21b and 21c show the surface
macroscopic residual stresses in the deposition direction (L) and later­
ally (T) for H13 steel and finds that the residual stresses are predomi­
nantly compressive in the L direction, with areas of tensile stress only at
the edges. In contrast, tensile residual stresses dominate in the T-direc­
tion; only a few values have the opposite characteristic. It is noteworthy
that the compressive residual stresses have a positive effect on the
possible slowing of crack extension, which spreads laterally to the bead.
Tensile stresses in the T-direction reduce the fatigue life and promote
crack extension along the beads. The surface residual stresses and the
outer surface layer of cracks are better removed by grinding and surface
compressive residual stresses are obtained. The behavior of the residual
stresses in different directions leads to differences in crack susceptibility,
which is crucial for the engineering application of the part. Therefore,
suitable residual stress optimization solutions need to be established in
order to improve the quality of the parts. Residual stresses inherent in
the additive manufacturing process may lead to part deformation, which
is very unfriendly for parts requiring high accuracy. Kamat et al. [153]
developed a novel analytical model based on the Euler-Bernoulli beam
bending theory to predict the deformation caused by residual stresses in
horizontally printed internal channels. The model considers compen­
sation at the design stage, so the Root Mean Square deviation of the
predicted values of circular channel deformation is reduced by a factor
of two. This method is expected to be a valuable tool for improving the
shape accuracy of internal channels. Microcracks occur mostly in areas
of stress concentration. Residual stresses tend to induce the emergence
and development of cracks in the part, thus reducing the fatigue strength
of the part. Excessive residual stresses could also cause cracking or
deformation of the molded part which would lead to a scrap of the part.
Therefore, appropriate methods (such as preheating) should be used to
reduce the harm caused to the part by residual stresses.
4.2. Process-microstructure-property regulation
The methods for property regulation of UHSSs can be roughly clas­
sified into three groups: pre-treatment, process parameter regulation,
and post-treatment. Substrate preheating is one of the pre-treatments,
which can reduce thermal stress and crack. Process parameter optimi­
zation and post-treatment are widely used adjustment methods, both of
which can change the microstructure and adjust the mechanical prop­
erties of the part. The printing process of UHSSs is a synergy of multiple
parameters, and parameter optimization can improve the mechanical of
parts. The post-treatment process is used as an auxiliary tool to further
adjust the microstructure and mechanical properties, but the results
depend mainly on the original microstructure.
4.2.1. Pre-processing regulation
Rapid heating and cooling cycles during AM processes can generate
large temperature gradients, leading to severe thermal stresses and
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Journal of Alloys and Compounds 965 (2023) 171390
cracking [154]. Preheating is widely applied before metal AM as one of
the main pretreatment processes[155–159]. It can be a more uniform
temperature distribution for AM and is one of the most effective methods
to mitigate thermal stresses and cracks. Wild et al. compared the defect
formation and cracking behavior of SLMed samples of AISI H10 steel at
200 ◦ C and 250 ◦ C substrate preheating temperatures [160]. They found
that a small amount of defective microstructure was obtained at a pre­
heating temperature of 200 ◦ C and a laser energy density of 107 J/mm3.
In contrast, a preheating temperature of 250 ◦ C and a lower energy
density of 99 J/mm3 significantly improved the crack-related mechan­
ical properties. Thus, proper pre-treatment can effectively enhance the
forming quality of additively manufactured metal parts. Effects of pre­
heating on the fabrication thermal history include temperature distri­
bution, thermal cycling, and temperature gradients. To fully understand
the mechanism of preheating, Xiong et al. [161] established a 3D tran­
sient heat transfer finite element model (Fig. 22a) of a circular
thin-walled part. The simulation results showed that substrate pre­
heating led to a smoother thermal cycle and reduced the cooling rate of
the melt pool. The maximum temperature gradient of the melt pool also
decreased as the substrate preheating temperature increased (Fig. 22b).
Substrate preheating has a relative impact on adjusting thermal
stress and cracking, while it has little or no effect on other defects.
Substrate preheating essentially reduces the cooling rate by decreasing
the temperature gradient, which leads to coarser grains and more severe
microsegregation. This reduces the finesse of AMed microstructure to a
certain extent. Substrate preheating is mostly applied to additive
manufacturing techniques using a laser or electron as the heat source
and is mainly used for titanium alloys [162–164], low strength carbon
steel [165–167], and some maraging steels [168,169]. Pretreatment
processes applicable to other UHSSs need to be further explored.
4.2.2. Forming process regulation
AM process for UHSSs are synergistic consequences of numerous
parameters. Many process parameters are capable of influencing the
thermal history to change the microstructure and mechanical properties
of parts. It is critical to maintaining a positive thermal history by
adjusting process parameters to obtain high-performance AMed UHSS
parts. This part focuses on the heat source parameters, scanning strat­
egy, and build direction during the forming process.
4.2.2.1. Heat source parameters. Taking the laser heat source as an
example, the heat source parameters include laser power, scanning
speed, and spot diameter. Changing heat source parameters induces a
change in heat input, which modifies the heat history of the part being
formed. Consequently, the heat source parameters have a significant
influence on the mechanical properties of the part. Adjusting the heat
source parameters can improve mechanical properties and the forming
quality of materials. When the heat input is high, the heat source im­
pacts the melt pool forcefully and the bottom of the melt pool solidifies
before it is filled, resulting in high porosity. AF9628 ultra-high strength
martensitic steel is sensitive to the high-volume energy density of the
laser. As shown in Fig. 23a, the Eagar-Tsai model was developed and
used to predict the geometry of the melt pool by Seede et al. [142].
Ultimately an optimal process parameter model of laser power-scan
speed-scan spacing was established as in Fig. 23b. The specimens pre­
pared according to the optimized parameters of the model significantly
reduced the porosity and achieved a high tensile strength of 1.4 GPa and
an elongation of 11%. Similarly, Kudzal et al. [139] demonstrated that
low energy input can increase the density of the parts. The ultimate and
yield strengths of the specimens printed with low laser work exceeded
1800 MPa and 1500 MPa, respectively. Bai et al. [170] found that too
high a laser power increased vaporization and spatters in the melt pool,
leading to high porosity, Fig. 24a shows a schematic of the spatters
formation. Spatters can be observed when the laser power exceeds
130 W and becomes more severe with increasing laser power (Fig. 24b),
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 22. Finite element analysis of the influence of substrate preheating temperature on forming thermal history: (a) Temperature distribution of thin-walled parts
deposited with various substrate preheating temperatures, (b) Axial temperature gradients in the molten pool at the middle points from the first layer to tenth
layer [161].

Fig. 23. Optimization framework for laser power and scanning speed: (a) Eagar-tsai model, (b) Prediction of molten pool geometry [142].

Fig. 24. Influence of heat source parameters on spatters: (a) Schematic of spatters formation, (b) Spatters caused by high laser power [170].

which severely affected the quality of the formed part. In addition, the
scanning space also affects the density. When the scan pitch is so small,
the heat in the overlap area increases dramatically, producing similar
negative effects of excessive laser power. When the scan spacing is
excessive, incomplete fusion holes are formed and the relative density of
the part is reduced.
4.2.2.2. Scanning strategy. Scanning strategy can also impact the ther­
mal history of the manufacturing process to adjust the mechanical
properties of the part. Fig. 25 shows EBSD images on the microstructure
of 18% Ni (grade 300) steels printed using the X and XY laser scanning
strategies, respectively. Bhardwaj et al. [171] found higher densities and
surface finish with the X-scan strategy, while the austenite phase

20
K. Li et al.
Fig. 25. Microstructure of different scanning strategies: Side surface (a) and
top side (b) of X unidirectional printing, and Side (c) and top (d) of XY bidi­
rectional printing [171].
formation rate was close to 60% with the XY-scan strategy. Rotation of
heat flux and conversion of strong to weak crystal textures were pro­
duced with XY-scan. Preferential growth of columnar cells occurs in
both X and Y directions, which leads to lower anisotropy, lower residual
stresses, and enhanced mechanical properties of the specimen. The
Fig. 26. Four scanning strategies for adjacent melt channels and interlayer
printing direction [172].
21
Journal of Alloys and Compounds 965 (2023) 171390
research indicates that the crystallographic texture of martensitic aged
steel can be controlled by scanning strategy adjustment to obtain parts
with excellent surface finish, high densities, and favorable mechanical
properties. Ge et al. [172] printed H13 steel specimens according to the
four WAAM deposition strategies as shown in Fig. 26. Comparing the
WAAM H13 steel specimens under the four strategies, it was found that
the variation in interlayer scan direction had a greater effect on the
microstructure size and distribution of the specimen blocks than the
variation in scan direction of the fusion channel. They attributed this
phenomenon to larger differences in thermal history caused by a change
in interlayer scan strategy. Unfortunately, the experimental results only
analyzed the effects of different scanning strategies on microstructure
and mechanical properties without examining intrinsic mechanisms and
optimization schemes.
4.2.2.3. Building direction. Build orientation is also one of the process
parameters that affect the thermal history of parts [173]. Printing
orientation changes result in a different number of melted layers for part
forming, for example, fewer layers are required to create cylindrical
samples in a horizontal direction than in a vertical direction. Different
build orientations result in variable laser beam scanning times as well as
thermal histories [174]. Shamsdini et al. [175] used the LPBF technique
to produce specimens of 18Ni-300 maraging steel along the horizontal
and vertical directions respectively. Fig. 27a and b show the micro­
structure of the deposited specimens, which show an elongated grain
structure in the build direction. This grain structure is not completely
eliminated after heat treatment either, but allows the grain structure to
evolve from < 100 > and < 111 > to < 110 > directions. Their study
showed faster horizontal printing, less material waste, and higher
strength and ductility of heat-treated specimens. The relationship be­
tween forming texture and force direction should be considered during
part design.
AM processes are deposited layer by layer, so vertically constructed
samples possess a slower cooling rate. The tendency to have larger
elongated grains in the vertical direction leads to lower hardness values,
which may give rise to structural anisotropy [176]. Although heat
treatment can weaken anisotropy generated during material processing,
Podgornik et al. discovered that the build orientation still plays an active
role in the wear resistance of the part [177]. As shown in Fig. 28a and b,
the interfacial features and cellular substructure between the melt
channels almost disappeared after ageing treatment, but the weak
texture of the nanoparticles and build orientation remained, which can
provide high strength, resistance to cracking extension and wear resis­
tance. In contrast, the solid solution treatment homogenizes the micro­
structure and eliminates nano-bias (Fig. 28c and d), but may also result
in reduced strength and wear resistance, although it still provides
excellent resistance to crack extension. The horizontal build orientation
proved to provide higher strength, crack resistance and wear resistance,
while the vertical build orientation possessed better resistance to crack
extension.
AM processes can change forming thermal history of UHSS parts by
adjusting printing parameters to change the energy input, which affects
the microstructure and mechanical properties of the part. The amount of
laser power directly determines energy input, while scan speed and scan
spacing also change energy absorbed by powder through irradiation
time and irradiation range. Many other process parameters involved in
AM, such as scanning strategy, build direction and powder layer thick­
ness also have an important influence on the forming thermal history of
UHSS parts. However, based on current reports, AM processes for UHSSs
have not been sufficiently studied. The mechanism of many parameters
in thermal history is still unclear and yet to be studied in more depth.
4.2.3. Post-processing regulation
Although the microstructure of directly printed UHSSs is defective,
they also have fine microstructure, supersaturated elemental solubility,
K. Li et al.
Fig. 27. The influence of building direction on microstructure: STEM micrographs for (a) Horizontal and (b) Vertical of as-built samples, and STEM micrographs for
(c) Horizontal and (d) Vertical of heat-treated samples [175].
Fig. 28. SEM image of microstructure after heat treatment: (a)-(b) Aging
treatment, (c)-(d) Solution treatment [177].
and no macroscopic segregation, which is a great potential for steel
enhancement. Post-treatment adjustment is an essential step to realizing
its potential. For instance, heat treatment can provide UHSSs with more
residual austenite, martensite, and bainite, increasing the ductility and
toughness of the parts. Heat treatment can also eliminate microscopic
segregation and significantly improve the impact toughness of the parts
[178,179]. In addition, machining can effectively improve the surface
finish, dimensional accuracy, and residual stress state of the part surface
[180].
4.2.3.1. Heat treatment. Heat treatment is widely reported as the
dominant post-treatment for additive manufacturing. Tempering heat
treatment can homogenize microstructure and eliminate texture fea­
tures [181]. Ran et al. investigated the grain morphology and phase
composition of LMDed AerMet100 steel and discovered that the
boundary cracking resistance along the grooved structure was poor
[182]. Fatigue crack propagation along the grain boundary (intergran­
ular fracture) led to anisotropy in crack growth rate. After tempering,
fatigue crack growth changed from intergranular fracture to a trans­
granular fracture mode and the resistance to fatigue crack propagation
was significantly improved. It also induced the formation of fine
22
Journal of Alloys and Compounds 965 (2023) 171390
equiaxed austenite grains in AerMet100 steel, which significantly
improved the tensile properties [183]. Tempering is also able to diffuse
precipitated carbides and induce a metastable solid solution, thus
enhancing ductility [184]. The microstructure of AF1410 steel after
tempering was observed by Li et al. [185] to consist mainly of slatted
martensite and thin film-like inverted austenite along the slat bound­
aries (white arrows in Fig. 29a and b). After tempering at 505 ◦ C, the
thickness of the inverse austenite between the martensite is very thin,
while the width and volume fraction of the inverse austenite increases
significantly after tempering at 515 ◦ C. TEM works of carbon replicas of
steels after heat treatment are shown in Fig. 29c and d. The precipitated
phases in the microstructure after tempering can be identified as three
carbides, the spherical MC and M23C6 carbides (Fig. 29e and f) and the
short rod M2C carbide (Fig. 29g). As the tempering temperature in­
creases, the type of carbide in the microstructure does not change, while
its size becomes coarser. This change results in a substantial increase in
ultimate tensile strength and a slight increase in elongation with better
comprehensive mechanical properties. Similarly, Liu et al. observed that
as the tempering temperature increased, carbide and Fe3C gradually
precipitated from martensite and internal stresses were released [186].
Katancik et al. showed that the microhardness values of SLM H13
samples were higher than those of forged samples at different tempering
temperatures. The high microhardness values were attributed to the
high dislocation density, fine grains, and high volume fraction of
nanocarbon [144].
Solution and aging heat treatments are capable of precipitation
strengthening of ultra-high strength steels by precipitating large
amounts of intermetallic compounds [187,188]. Sarkar et al. [189]
obtained high yield strength and hardness by forming fine Cu-rich pre­
cipitates after standard aging treatment of SLMed 15–5 PH stainless
steel. However, the material became brittle, which resulted in low
elongation and a high wear rate. As the aging temperature increases, the
steel sacrifices yield strength and hardness for higher elongation and
lower wear rate. Solution treatment homogenizes microstructure and
reduces its anisotropy. They recommended solution treatment before
aging treatment to achieve homogeneous precipitation throughout the
specimen. Alafaghani et al. [190] also found that extending the solid
solution time improved homogeneity. A new maraging steel was sub­
jected to different forms of heat treatment by Wang et al. [191].
Fig. 30a-c show the microstructure of the as-built sample, where a melt
boundary consisting of fine cellular structures can be clearly seen. The
melt boundary gradually blurs after the ageing heat treatment, the
K. Li et al.
Fig. 29. Microstructure evolution at different fire temperatures: TEM images of AF1410 steels reversed austenite tempered at (a) 505 ◦ C and (b) 515 ◦ C, (c) and (d)
Carbon replicas of AF1410 steels: (e) MC precipitates, (f) M2C precipitates, (g) SAD pattern of M23C6 precipitates [185].
melting point boundary eventually disappears after a long period of
ageing (Fig. 30d-f), while it definitely disappears after a half-hour so­
lution treatment (Fig. 30g-i). After solid solution ageing treatment, the
melt pool boundary disappears completely very quickly and the micro­
structure becomes more homogeneous (Fig. 30j-l). Thus, the solid so­
lution treatment prior to ageing promotes rapid homogenization of the
microstructure prior to ageing. In addition, the volume fraction of
martensite reached 99.9% after solid solution treatment and a high
dislocation density was distributed over the martensitic slats, which was
more favorable for the precipitation of fine precipitates during ageing.
This point was also confirmed in the study of Hadadzadeh et al. in which
the pre-existing dislocation network plays a key role in the strength of
the aged material [192].
The excellent strength and toughness of maraging steels arise from
the combination of martensitic structure and age-hardening features.
Chen et al. found that AMed maraging steel grade 300 after solid solu­
tion aging had a high percentage of martensitic microstructure and a
significant increase in tensile strength and elongation due to precipita­
tion strengthening [193]. Kanan et al. focused on the aging temperature
of Ti-free maraging steel grade 300 made by LPBF. Kanan et al. found
that the printed structures of the Ti-free maraging steel grade 300 were
characterized by solute segregation, non-equilibrium organization, and
lack of precipitated phases, which are more suitable for direct aging
strengthening [194]. After heat treatment, it was noticed that samples
aged below 440 ◦ C or for a shorter period had no strain hardening before
necking because of the lower fraction of reduced austenite. Aged sam­
ples at higher temperatures produced extensive austenite reversion,
recrystallization of martensite, and coarsening of precipitates, which
resulted in softening of the fabricated part. The best strength-ductility
combination was obtained by direct aging at 440 ◦ C for 6 h.
Tempering treatment is mostly used to improve the mechanical
properties of LUHSSs, MTSs, and SHSs. Tempering eliminates significant
grain orientation and reduces residual stresses in the microstructure,
thereby reducing crack susceptibility. Tempered steel precipitates Fe3C,
ε-carbide, and other strengthening phases, which significantly increase
tensile and yield strength. For PHSSs and MSs with high alloying
element levels, solution aging is a better choice. Solid solution treatment
23
Journal of Alloys and Compounds 965 (2023) 171390
obtains a high density of dislocation martensite while aging treatment
precipitates a large number of intermetallic compounds in the
martensitic matrix. Precipitation strengthening is achieved in this way
to substantially increase tensile strength and elongation.
4.2.3.2. Machining treatment. The formed surfaces obtained by AM are
usually inferior to the surface quality of conventional manufacturing
because AMed surface roughness is usually not less than 1 µm [195,
196]. The use of machining as a post-treatment method can dramatically
improve the surface finish of AMed parts. Compared to the milling
behavior of forged H13, Montevecchi et al. [197] found higher cutting
forces and cutting coefficients for additively manufactured parts. Bai
et al. studied the milling behavior of AMed maraging steels under
different heat treatment conditions [198]. They observed that AMed
maraging steels show minimal wear areas in the printed (Fig. 31a) and
solid solution states (Fig. 31c), while the age-treated ones both resulted
in a significant increase in tool wear (Fig. 31b and d). This is due to the
formation of precipitated particles such as Ni3Ti, Ni3Mo, and Ni3Al
during aging treatment which is dispersed in the martensitic matrix and
has a severe scratching effect on the tool. The effect of cutting speed (vc)
and feed per tooth (fz) on the average roughness and residual stress
during milling of L-PBF maraging steel 300 was investigated by Oliveira
et al. [199]. Fig. 31 shows the best (a) and worst surface conditions (b)
obtained in the study. A combination of surface roughness reduction and
residual stress correction can be achieved with appropriate cutting pa­
rameters. Among fz and vc, feed per tooth was more significant to refine
roughness levels. Cutting speed also affected roughness, but the inter­
action between fz and vc did not present statistical significance for
roughness.
4.2.3.3. Other methods. Vibratory finishing and sandblasting are also
available as post-treatment for surface modification of AMed parts.
Elangeswaran et al. [200] analyzed the fatigue properties of L-PBF
18Ni300 maraging steel with untreated, vibratory finishing and sand­
blasting treatments. The untreated samples exhibited the lowest fatigue
property, which may be attributed to surface residual stresses and
roughness. Compared to untreated conditions, fatigue property was
K. Li et al.
Fig. 30. OM and SEM images for the microstructure of SLMed samples after heat treatment: (a)-(c) As-fabricated, (d)-(f) Direct aging treatment), (g)-(i) Solution
treatment, and (j)-(l) Solution and aging treatment [191].
significantly enhanced after vibratory finishing (Fig. 32a and b), which
is explained by the smoothness of the treated surface and the lack of
stress concentration on the vibratory finishing. Sandblasting enhances
fatigue properties but also has high surface roughness. This is due to the
small plastic deformation generated by the impact of high-speed parti­
cles on the surface (Fig. 32c and d). In addition, the mechanical prop­
erties of the unheat-treated specimens were better after vibration
finishing, while after heat treatment, the vibration-finished specimens
had high residual stresses and the sandblasted specimens had better
mechanical properties. Non-heat treatment methods usually change
only the surface condition of parts, such as surface roughness and sur­
face residual stresses. The internal microstructure morphology, phase
size, and distribution can be adjusted by the heat treatment process. A
suitable post-treatment process should be selected according to the
performance requirements of the part.
4.3. Application of advanced assisted technologies
4.3.1. Process monitoring
The process of additive manufacturing is complex and producing
virtually defect-free parts with high reliability and durability remains a
24
Journal of Alloys and Compounds 965 (2023) 171390
challenge. By using a variety of process sensors that record optical,
acoustic and thermal signals, process monitoring is beginning to be
widely adopted in additive manufacturing pick-up, with optical sensors
dominating [201]. Process monitoring provides a more visual view of
the manufacturing process in real time. Feedback from the monitoring
results enables better adjustment of the manufacturing process, thus
reducing process defects and producing parts with good performance.
Altenburg et al. [202] compared and analyzed the results of visible
(VIS), short wavelength infrared (SWIR) and mid wavelength infrared
(MWIR) cameras for temperature monitoring during the LMD process.
Fig. 33a-c show that the most significant difference between MWIR and
VIS thermographic intensity images is the different macroscopic size of
the heated zone, which is due to the limited dynamic temperature range
of the VIS camera. Fig. 33d-g show the thermal images from the MWIR
and SWIR cameras. A distinct cold spot is observed in the center of the
melt pool in Fig. 33e, which is most likely due to reduced emissivity in
the molten state and supercooling in the molten state. There is a clear
extended area of ’halo’ in the zone below the wall structure in the SWIR
image (Fig. 33f). Compared to MWIR, the VIS camera has a very limited
measurable temperature range, while the SWIR camera has a medium
temperature dynamic. MWIR can be used to detect spatial
K. Li et al.
Fig. 31. Tool wear morphologies of different processes. (a) As-built, (b) Aging treatment, (c) Solution treatment, and (d) Solution and aging treatment [198]. Milling
surfaces obtained for (a) the lower roughness (fz = 0.02 mm/tooth and vc = 250 m/min) and (b) the higher roughness (fz = 0.08 mm/tooth and vc
= 150 m/min) [199].
inhomogeneities in heated regions and the SWIR camera combines the
advantages of both mid-wave infrared and visible cameras. In addition,
Yang et al. [203] monitored the printing process of SLM 17–4 PH steel in
situ with a high-speed camera and compared the melt pool behavior
between spiral and raster scanning strategies. The melt pool was
consistently larger for spiral scanning at the same laser power level. It is
hypothesized that the larger melt pool and the reheating of the helical
scanning strategy significantly alter the solidification process.
Due to the limitations of the forming equipment and the forming
environment, process monitoring is currently mostly used for SLM. For
example, Lu et al. [204] report on the design and development of an
optically based image processing in-situ monitoring system imple­
mented on a selective laser melting process. Features captured in optical
images during the printing process are identified and quantified by
image processing techniques. However, process monitoring has less
application in other additive manufacturing technologies and is still in
its infancy for the study of process monitoring in the forming of
ultra-high strength steels for additive manufacturing, which still re­
quires more intensive further research.
25
Journal of Alloys and Compounds 965 (2023) 171390
4.3.2. Numerical simulation
The additive manufacturing process involves complex physical
phenomena, such as heat transfer, thermal, phase change and flow
[205]. Numerical simulation methods at different scales combined with
experimental validation can enable the understanding, control and
optimization of complex physical phenomena in the additive
manufacturing process, providing powerful support for the forming of
high quality, high precision and high-performance metal parts. Nong
et al. [206] implemented finite element simulation for deposited cuboid
(Fig. 34a) and deposited wall (Fig. 34b). The simulation results for the
thermal gradient show that the average value of the transverse section is
about 8 × 105 ◦ C/m higher than the value of about 5 × 105 ◦ C/m for the
transverse section at the same position. Austenite is therefore more
efficiently converted to martensite in the transverse direction during
solidification. In addition, the melt pool is elongated along the laser
trajectory and the horizontal cross-section is exposed to high tempera­
tures for a longer. The heat will escape more efficiently down the hor­
izontal cross-section (direction of deposition), thus reducing the
formation of residual austenite. The process of enhancing part me­
chanical properties via print parameter optimization is costly and
time-consuming, while numerical simulation can effectively simplify the
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 32. Surface of a vibratory-finished sample in low (a) and high (b) magnification. The surface of a sand-blasted sample in low (c) and high (d) magnifica­
tion [200].

Fig. 33. Apparent temperature and intensity images recorded during the build of the third layer of the wall: (a) recorded with the MWIR camera, (b) recorded with
the VIS camera with NIR filter and (c) enlarged view of (b). Intensity image and thermograms recorded during the build of the ninth layer of the wall: (d) raw data
and (e) corrected data recorded with the MWIR camera, (f) raw data and (g) corrected data with the SWIR camera [202].

process. As shown in Fig. 34c, a three-dimensional temperature and motion of the liquid metal in the molten pool is mainly driven by the
velocity field model of a single-track WAAM H13 steel process was surface tension gradient and the free surface deformation of the molten
constructed by Ou et al. [207], where the melt pool extends in the pool is depicted in Fig. 34d. The liquid metal is pushed to the rear of the
opposite direction of the arc source motion due to rapid scanning. The molten pool and forms a crown as it solidifies. The model considered

26
K. Li et al. Journal of Alloys and Compounds 965 (2023) 171390

Fig. 34. Simulation of the complex thermal history of UHSSs forming process: (a) Temperature distribution contour and thermal gradient versus deposited time of
deposited cuboid part; (b) Temperature distribution contour and temperature versus deposited time at different location of deposited wall part [206]. Temperature
and velocity fields: (c) a single track H13 deposition, (d) Magnified views of temperature fields in (a) [207].

molten metal convection and the calculated results were consistent with
the experimental data. Subsequently, they used an adaptive meshing
method to the improved original model, which led to a significant in­
crease in computational speed. The arc pressure and fluid flow were
found to be the main factors determining melt pool shape during the
simulation of multi-layer and multi-track WAAM printing [208]. Nu­
merical simulation is now widely used as an indispensable and advanced
aid in additive manufacturing processes, which greatly simplifies the
experimental process, saves experimental costs and visualizes complex
physical changes at multiple scales.

4.3.3. Machine learning

Fig. 35. A detailed illustration of the VAE algorithm architecture, where the
The performance decline of AMed parts is mainly attributed to de­ green part represents the encoder, the red part indicates the hidden variable Z
fects in the printing process [209]. Machine Learning (ML), with Arti­ and the blue part is the decoder [211].
ficial Intelligence (AI) at its core, is capable of discovering potential
relationships between numerous research problems and is expected to
Gaussian models have good potential for anomaly detection. However,
be an effective tool for LPBF-related research [210]. For example,
this technique is sensitive to noise information and may lose some
applying machine learning (ML) for online defect detection in additive
important information, resulting in inaccurate results. The VAE algo­
manufacturing can effectively improve product quality and process
rithm is able to obtain general features of the signal and use them as
reliability. Mohammadi et al. [211] compared three ML methods for the
input to a machine learning classifier. Fig. 35 shows the architecture of
real-time detection of defects in L-PBF H13. The hierarchical K-Means
the VAE algorithm, which is divided into three parts: the encoder, the
algorithm allows for fast processing of large amounts of data and helps
hidden variable and the decoder. The encoder learns the input signal to
to generate meaningful intuitions about the structure of the data. The
form a specific distribution and samples it to obtain the hidden variable
algorithm is able to reduce the intensity of machine learning, while the
Z. The decoder part takes the hidden variable z as input and outputs a
drawback is the large amount of training required and the large amount
dataset with the same distribution as the real data. In brief, VAE is an
of noise collected with the data. PCA-GMM techniques based on normal
unsupervised machine learning algorithm that learns the hidden

27
K. Li et al.
variables in the input data and outputs new samples. As a result, the VAE
algorithm requires no training and can be extended to use with different
materials. Later, the VAE method was applied to the 316 L defect dataset
for classification, confirming that the method can be successfully
applied to other materials.
Uncertainty in fatigue properties is one of the key challenges in the
use of additive manufacturing technologies for critical structural parts.
Li et al. [212] developed an integrated data-driven analytical framework
for defect criticality (IDADC). It can be used to analyses the geometric
features of critical defects on fracture surfaces to assess the fatigue
performance of L-PBF 17–4 PH steel. The correlation of key features of
different types of defects in additively manufactured parts with L-PBF
process parameters through ML can be used to investigate the effect of
defects on the fatigue behavior of AMed parts. The results can be used to
optimize process parameters to reduce or to avoid such defects and
hence improve the fatigue life of AM parts.
5. Challenges and perspectives
To review previous work by numerous scholars, this work proposes a
framework for additive manufacturing of high performance UHSSs, as
shown in Fig. 36. The framework proposes a scheme: 3D part solids are
obtained by layer-by-layer deposition from discrete to aggregate using
advanced additive manufacturing techniques, including typical additive
manufacturing techniques (L-PBF, L-DED and WAAM). During the
deposition process, the process parameters are optimized (including but
not limited to substrate preheating, heat source parameters and printing
strategy) to obtain formed parts with good shape and defect-free or less
defective microstructure. Post-treatment (heat treatment and
machining) of the formed parts to obtain a good formed surface or to
regulate the microstructure results in high performance additive man­
ufactured parts. The use of advanced assisted techniques (numerical
simulation, machine learning and process monitoring) can be used to
simplify and visualize the results of these processes. Based on the
existing research results, future work in AMed UHSSs will focus on
improving the ability to manufacture complex structural parts while
maintaining the performance of the formed parts.
Fig. 36. A comprehensive framework for achieving high-performance manufacturing and complex structural forming of UHSSs. (Green arrows indicate the
manufacturing process. Yellow arrows indicate participation in the manufacturing process and play a supporting role. The Blue arrow indicates future goals to be achieved.).
28
Journal of Alloys and Compounds 965 (2023) 171390
Currently, these researches are mainly focused on certain UHSSs
(some LUHSSs, H13 tool steel, 17–4 PH steel, 18Ni(300) maraging steel)
and specific processes (L-PBF, L-DED, WAAM), and there is a lack of
studies on other UHSSs and AM technologies. Dedicated UHSSs for AM
also have a large gap, and many existing UHSSs cannot fully meet the
application requirements. Considering the design and development of
new steels dedicated to AM may lead to a breakthrough in this field. In
addition, most of the work that has been reported was conducted under
laboratory conditions. Direct application of laboratory data to actual
engineering remains difficult and producing UHSS parts with complex
geometries remains challenging. Finally, test data on the performance of
AMed UHSS parts are still incomplete and cannot yet be applied to
critical load-bearing components. Therefore, this paper proposes di­
rections for future work.
(1) To investigate deeply the influence of the complex geometry of
UHSS parts on mechanical properties. Complex geometry affects
the thermal history of the part to influence the melt pool state and
microstructure, which can significantly change the mechanical
properties of parts. To ensure the stable forming quality of
complex structured UHSS parts, the mechanisms of the intrinsic
influence between geometry shapes, process parameters, micro­
structure, and mechanical properties require to be studied
deeply.
(2) Enhance the control of forming process of AMed UHSSs. Due to
melt pool characteristics, printed microstructure has many
metallurgical defects such as porosity, cracks, anisotropy, and
residual stresses. The future expectation is to establish a quanti­
tative model among process parameters, microstructure, and
mechanical properties to achieve optimal microstructure and
performance. Ideally, the operators can define the process pa­
rameters and customize the microstructure to match the perfor­
mance requirements of parts, allowing for defect-free printing.
This process no longer requires post-processing, realizing true 3D
printing.
(3) Strengthen the application of advanced assisted equipment in AM
processes. Numerical simulation can simulate various complex
K. Li et al.
thermal and force fields in the printing process, providing a
clearer understanding of the effects of process parameters on
microstructure and mechanical properties, which can also save
significant experimental costs. Machine learning can be used to
learn the morphology of defects in large numbers and correlate
them with process parameters to obtain a training model, which
can be used to predict the causes of defects and thus tune the
parameters to reduce them. Process monitoring allows for a more
visual observation of the melt pool response through infrared
cameras, which helps to provide a deeper understanding of the
printing process.
6. Conclusions
AM technologies are increasingly being used to manufacture UHSSs
parts due to their unique forming process characteristics which offer
great economic benefits and a wide range of application scenarios. This
work reviews the current research on AM technologies for UHSSs with
the most important issues focusing on property modulation of AMed
UHSSs, particularly process-microstructure-property modulation. A
comprehensive review and discussion of the property origin of UHSSs
and the characteristics of AM technologies and their microstructures are
presented, with some of the most important notes given below.
• UHSSs have attracted much attention for their excellent properties.
The alloying elements and the precipitated phases in the micro­
structure are the origin of the excellent mechanical properties of
UHSSs. However, the high carbon content of LUHSSs and MUHSSs
reduces the toughness and weldability of the steel, while the multiple
alloying elements in HUSSs lead to high production costs. There is a
lack of dedicated UHSSs for additive manufacturing, which results in
the advantages of AM not being fully exploited.
• Additive manufacturing of UHSSs offers unique technological ad­
vantages. Rapid melting and solidification cycles lead to sub-stable
structures, which have the potential to increase the strength of
additively manufactured alloys. Nevertheless, the extreme non-
equilibrium solidification process is also prone to defects such as
porosity, spatter and residual stresses, which have not yet been fully
overcome. It results in a high proportion of AMed UHSS parts not
being used in critical areas.
• A large number of articles have been reported on the additive
manufacturing of UHSSs. Although there is a relatively profound
study of the microstructural evolution and mechanical properties of
AMed UHSSs, this is however limited to a few UHSSs. The applica­
tion of additive manufacturing technology to many other ultra-high
strength steels is not ideal, and it is also important to improve the
general applicability of additive manufacturing technology to
UHSSs.
• Property regulation is essential for additive manufacturing of high
performance UHSS parts. Understanding the causes of defects en­
ables the development of targeted optimization strategies to obtain a
defect-free or defect less microstructure. Pre-treatment, forming
process and post-treatment regulation provide favorable methods for
the additive manufacturing of high performance UHSSs, however the
advantages of their combination have not yet been explored. Their
combined solutions and effects need further research.
• Advanced assisted technologies help the whole process of additive
manufacturing of UHSSs. How to better combine numerical simula­
tion, machine learning and process monitoring with additive
manufacturing technologies is an issue that needs to be studied in
depth. The first is how to make good use of existing technologies to
integrate them into the whole experimental process in a more
simplified and intuitive way. The second is whether more advanced
assisted technologies can be developed to fine observation and
control of the additive manufacturing process and achieve a true
"print-to-use" approach.
29
Journal of Alloys and Compounds 965 (2023) 171390
CRediT authorship contribution statement
Kun Li: Investigation, Methodology, Supervision, Writing − original
draft, Writing − review & editing, Funding acquisition. Tianbao Yang:
Investigation, Methodology, Writing − original draft, Writing − review
& editing. Na Gong: Investigation, Methodology, Writing − review &
editing. Jinzhou Wu: Methodology, Writing − review & editing. Xin
Wu: Investigation, Methodology, Supervision, Writing − review &
editing. David Z. Zhang: Investigation, Methodology, Writing − review
& editing; Lawrence E. Murr: Investigation, Methodology, Writing −
review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors gratefully acknowledge all the researchers and labs to
provide the experimental facilities. K.L. acknowledges the support from
National Natural Science Foundation of China (52201105), Natural
Science Foundation of Chongqing (CSTB2022NSCQ-MSX0992), Funda­
mental Research Funds for the Central Universities in China
(2021CDJQY-024), Research Project from Chongqing Key Laboratory of
Metal Additive Manufacturing (3D Printing) in Chongqing University
(02090011044158), Foundation of the State Key Laboratory of Me­
chanical Transmission (SKLMT-ZZKT-2022R03), Guangdong Basic and
Applied Basic Research Foundation (2021A1515111067). The authors
also would like to express their gratitude to EditSprings (https://www.
editsprings.cn) for the expert linguistic services provided.
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