Additive Manufacturing 58 (2022) 103047

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Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma

Microstructure control during deposition and post-treatment to optimize

mechanical properties of wire-arc additively manufactured 17-4 PH
stainless steel
Tao Zhou a, *, Tao Zheng b, Ahmet Bahadir Yildiz a, Gabriel Spartacus a, Monika Rolinska a,
Robert Cubitt c, Peter Hedström a
a
Department of Materials Science and Engineering, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden
b
3D Printing Research & Engineering Technology Center, AECC Beijing Institute of Aeronautical Materials, 100095 Beijing, China
c
Institut Laue-Langevin, CS 20156, 38042 Grenoble Cedex 9, France

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

Keywords:
Wire-arc additive manufacturing
Maraging stainless steel
Process-structure-property relationship
Computational thermodynamics
Advanced materials characterization
The solidification and microstructural evolution during deposition, as well as the structural evolution during post
heat treatment, determine the mechanical properties of wire-arc additively manufactured maraging stainless
steels. In the present work, we tune the austenite reversion and nanoscale precipitation during post heat treat­
ment and achieve an excellent combination of strength and ductility (ultimate tensile strength ~1340 MPa and
uniform elongation ~10.5 %). The structural evolution is studied through computational thermodynamics,
electron microscopy, in situ small-angle neutron scattering, and synchrotron X-ray diffraction. The as-built
microstructure is composed of mainly martensite and retained austenite (~30 vol%) together with a minor
fraction of δ-ferrite, M23C6, Nb(C, N), spherical and ellipsoidal Cu precipitates and some inclusions. The presence
of these phases cannot be fully predicted by the Scheil-Gulliver model due to the complicated thermal history and
non-homogenous elemental distribution. The reverted austenite formed during the post heat treatments has high
stability and fine grain size (~1 µm), which contributes to the excellent ductility, while the nanoscale precipi­
tation hardening contributes to the achieved high strength.

1. Introduction
Additive manufacturing (AM), with amongst others the advantages
of reduced material waste, shortened time to market and increased
design freedom in comparison to traditional subtractive manufacturing,
is in a rapid development phase. The current most popular AM heat
sources include electron beam, laser, and electric arc with correspond­
ing materials feedstock being mostly powder for the electron beam and
laser sources and wire for electric arc sources [1]. Wire-arc additive
manufacturing (WAAM) has, in comparison to electron beam melting
(EBM) and selective laser melting (SLM), high deposition rates (as high
as 9.5 kg/h for stainless steel has been reported [2]), high raw material
efficiency, low equipment and material cost, suitability for medium to
large scale (meter scale) components with low to medium complexity
[3]. In addition to the cost savings, the usage of wire feedstock for
WAAM avoids several challenges with a powder feedstock for EBM and
SLM, e.g. controlling the particle size distribution, powder health
hazards, contaminations and recycling [4]. Until now, a wide range of
metallic materials have been manufactured using WAAM, where
methods of gas metal arc welding (GMAW), gas tungsten arc welding
(GTAW) and plasma arc welding (PAW) have been used [5]. In GMAW,
the consumable wire electrode is coaxial with the torch, which gives
more movement flexibility and thus more effective scan strategies as
compared to GTAW and PAW with external wire feeding that require
more complicated scanning strategies [3].
Maraging stainless steels, e.g. 17–4 PH and 15–5 PH, are good can­
didates for AM in general due to their good weldability. Their applica­
tion range is wide due to the excellent combination of strength, ductility
and corrosion resistance, and they are for example used as aircraft fit­
tings, pressure vessels and machine components [6]. The combination of
strength and ductility of these materials can be adjusted for the specific
application requirements through tuning of the recovery of lath
martensite and nanoscale Cu precipitation during ageing treatment
[7–9], as well as the reversion to austenite as reported in this work. The

* Corresponding author.
E-mail address: taozhou@kth.se (T. Zhou).

https://doi.org/10.1016/j.addma.2022.103047
Received 28 March 2022; Received in revised form 13 June 2022; Accepted 17 July 2022
Available online 19 July 2022
2214-8604/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
T. Zhou et al. Additive Manufacturing 58 (2022) 103047

additive manufacturing of these kinds of maraging stainless steels pro­ Table 2

cessed by SLM has already been reported [10–14]. It is well established Process parameters for the WAAM of 17-4 PH.
that a solution treatment followed by a peak ageing treatment is Voltage, Current, Wire-feed Printing Shielding gas Interpass
required for the SLM materials to achieve comparable microstructure V A speed, speed, flow, L•min 1
–
colding
and mechanical properties of the corresponding wrought materials [13, m•min 1 m•min 1 time, s
– –

15–17]. However, there are only a few studies on WAAM for 17–4 PH.
Martina et al. [2] investigated the capability of WAAM to achieve high
deposition rates for 17–4 PH as one of the tested materials. Caballero
et al. [18] studied the effects of shielding gas, scanning strategy and
post-heat treatment on the mechanical properties, but they did not
perform an in-depth investigation of the nano- and microstructure.
The process-structure-property relationship must first be well un­
derstood before industrial applications of WAAM for 17–4 PH. In this
work we will present such understanding by: (i) investigating the nano-/
microstructure in the as-built and heat treated conditions by integrating
advanced characterization and computational thermodynamics; (ii)
exploring the potential of improving mechanical properties through
controlling austenite reversion and nanoscale precipitation during post
heat treatments. As these aspects have rarely been reported before for
WAAM on maraging stainless steels, this work can provide insights and
guide the development of high-performance maraging stainless steels
manufactured through WAAM in general.
17.6 157 6.5 0.6 18–20 20
the equilibrium calculations shown in Fig. 1a, MX, i.e. Nb(C, N) in this
work, starts to form at temperature lower than 1200 ◦ C. Cu and M23C6
precipitates form when the temperature is lower than about 900 ◦ C. The
non-equilibrium solidification was predicted using the Scheil-Gulliver
model [20,21], which assumes perfect elemental mixing in the liquid
phase, no diffusion in the solid phases and local equilibrium at
liquid-solid interface. In Fig. 1b, δ-ferrite, austenite (which transforms
into martensite during cooling) are predicted to be the main phases,
together with M23C6 and a slight amount of Laves phase for the as-built
material. In addition, the Scheil-Gulliver model predicts various degrees
of enrichments of Cr, Mn, Cu, Nb and C in the regions that solidify last
(Fig. 1c).
2.3. Heat treatments

2. Experimental methodology
2.1. WAAM
The materials used for WAAM in this work are 17–4 PH stainless
steel. The compositions of the wire material (diameter 1.2 mm), the as-
built bulk material (after WAAM process), and the wrought reference
material, determined by inductively coupled plasma optical emission
spectroscopy (ICP-OES), are shown in Table 1. The composition mea­
surements show a slight difference after printing due to evaporation
losses, Si, Mn, Cr and Nb are slightly less in as-built material compared
to the wire material, and on the other hand the C content is slightly
higher in the bulk material. The build plate used was a mild steel with a
thickness of 10 mm and a cold metal transfer (CMT) power source was
used. CMT is a modified version of metal inert/active gas (MIG/MAG).
The deposition process was carried out with shielding gas composed of
18 % CO2 and 82 % Ar in a chamber with protective gas of Ar using a six-
axis welding robot (further details can be found in supplementary
Fig. S1a). The material was built using a deposition strategy with
oscillating passes and a hatch spacing of 2.8 mm. Detailed process pa­
rameters are provided in Table 2. The final as-built material had a size of
about 180 × 100 × 35 mm3. The as-built component before and after
machining are shown in supplementary Fig. S1b and c.
2.2. Computational thermodynamics
The computational thermodynamics was performed to predict
quantitative microstructural information for the 17–4 PH alloy during
solidification and heat treatments. The thermodynamic calculations are
not only powerful for quickly obtaining an understanding of the
microstructure under various processing conditions prior to performing
experiments, they also support the interpretation of the experimental
results in the present work. The thermodynamic calculations for 17–4
PH using the bulk composition shown in Table 1 was performed using
the Thermo-Calc software [19] with the TCFE10 database. According to
Direct ageing and solution treatment with subsequent ageing treat­
ments were carried out on the as-built materials. The heat treatments of
samples used for microstructural characterization and hardness mea­
surements were performed in Ar protective gas in a tube furnace, and the
heat treatments of samples used for tensile testing were carried out in air
atmosphere using a muffle furnace. For solution treatment, the samples
were heat treated at temperature and time combinations of 1040 ◦ C for
0.5 h, 1100 ◦ C for 0.5 h, 1200 ◦ C for 2 h, and 1200 ◦ C for 15 h, before
quenching in water. The corresponding ageing treatments were per­
formed at 480 ◦ C for 0.5, 1, 2, and 4 h, before cooling in water. The
wrought 17–4 PH used for tensile testing was solution treated at 1040 ◦ C
for 0.5 h before ageing at 480 ◦ C for 2 h.
2.4. Mechanical testing
Vickers hardness measurements using a load of 2000 g were con­
ducted using a MXT-a1 microhardness tester. Seven tests were per­
formed on each sample. The average hardness and standard deviation
were subsequently calculated. Tensile testing of round-bar dog-bone
shaped specimens with a gauge diameter of 5 mm and gauge length of
25 mm were tested. The tests were performed at ambient temperature
using displacement control and a cross-head speed of 0.45 mm/min for
measuring yield strength and thereafter 5 mm/min for measuring of
ultimate tensile strength, following the Chinese standard GB/T
228.1–2010. The extensometer was removed after the yielding of the
samples. The removal of the extensometer and the change of strain rate
may cause some fluctuations in the stress-strain curves. Two tests per
sample condition were performed, except for the ST1200(15 h)-A sam­
ple for which three tests were carried out.
2.5. Microstructural characterization
Samples used for optical microscopy (OM), scanning electron mi­
croscopy (SEM) imaging and energy dispersive X-ray spectroscopy (EDS)
analysis were prepared by mechanical grinding and polishing, before

Table 1
The chemical compositions of 17-4 PH in wire, as-built bulk and wrought reference materials (wt%).
C Si Mn Cr Ni Cu Nb P S

Wire 0.040 0.20 0.51 16.51 4.96 3.42 0.23 0.019 0.014
Bulk 0.066 0.13 0.36 16.10 4.98 3.42 0.15 0.017 0.019
Wrought 0.018 0.28 0.36 15.28 4.42 3.22 0.22 0.032 0.005

2
T. Zhou et al.
Fig. 1. Equilibrium and non-equilibrium calculations of 17–4 PH: (a) equilibrium phase fraction vs. temperature, (b) non-equilibrium solidification simulation using
the Scheil-Gulliver model, (c) Segregation of elements during solidification.
etching with a modified Kalling’s etchant composed of 12 g CuCl2, 20 ml
HCl and 225 ml ethanol for 10–20 s. The samples for electron back­
scatter diffraction (EBSD) measurements were prepared by mechanical
grinding and polishing, and electropolishing in an electrolyte of 10 %
perchloric acid and 90 % ethanol. The EBSD measurements were con­
ducted at an accelerating voltage of 15 kV using a step size of 200 nm.
The mentioned SEM-based characterization was carried out in a SEM
JEOL-7800 F equipped with a Bruker Quantax EBSD system and a
Bruker X-flash silicon drift detector (SDD). Furthermore, scanning
transmission electron microscopy (STEM) with EDS analysis was per­
formed using a FEI Titan Thermis 200 TEM equipped with a probe Cs
corrector and a SuperX EDS detector. The samples used for TEM mea­
surements were thin-foil samples prepared by the standard twin-jet
electropolishing method [22], using an electrolyte composed of 10 %
perchloric acid and 90 % ethanol at 5–10 ºC.
In-situ small angle neutron scattering (SANS) experiments were car­
ried out at the D33 beamline at the Institut Laue-Langevin (ILL), Gre­
noble, France [23] using a neutron wavelength of 4.6 Å at a collimation
length of 5.3 m with sample-to-detector distances of 1.2 m for the front
4-panel detector and 5.3 m for the rear single panel detector. There was
an aperture of ϕ8 mm just before the sample and the source aperture,
5.3 m away, which was 30 × 30 mm2. This experimental setup spanned
a scattering vector (Q) range of 0.008–0.55 Å− 1. Square specimens with
the dimension 20 × 20 × ~0.6 mm3 were used. In situ measurements
were performed using a high-temperature vacuum furnace and Nb en­
velope as a sample container. The heating rate used was 10 ºC/min up to
the ageing temperature of 480 ºC and the samples were held there for
4 h. SANS patterns were acquired with 10 min intervals [24]. GRASP
[25] script application was used for the reduction of the SANS raw data
and for the scaling to absolute units dΣ/dΩ (Q), i.e. total macroscopic
differential scattering cross-section. The interaction of the neutrons with
the atomic nuclei and the magnetic fields results in nuclear and mag­
netic scattering, respectively. As the separation of different scattering
contributions using an external magnetic field was not possible here
(due to the presence of both magnetic, i.e. ferromagnetic, and
non-magnetic matrix phases), the reported dΣ/dΩ (Q) values in the
current work represent the sum of nuclear and magnetic scattering.
Assuming spherical precipitates with radius r, the size distribution of
precipitates Np (r) can be described by [26]:
dΣ
∫ Gulliver modelling (Fig. 1b). Additionally, some inclusions, such as
(Q) = |ΔSLD|2 |F(Q, r) |2 (V(r) )2 Np (r)dr + background (1)
dΩ
where ΔSLD is the scattering length density difference between the
matrix phase and precipitates, F(Q, r) is the form factor of a sphere,
FS (Q, r) = 3(sin(Qr) − (Qr)cos(Qr))/(Qr)3 , V(r) is the volume of pre­
cipitate with a radius r, and the background term includes the inco­
3
Additive Manufacturing 58 (2022) 103047
herent scattering (flat background) and power-law-type scattering BQP
(B is scaling factor and P is low-Q slope in logarithmic graph represen­
tation). The modelling of the SANS patterns was performed using
maximum entropy method [26] on the Irena tool suite [27].
X-ray diffraction (XRD) experiments were performed at the SOLEIL
synchrotron on the DiffAbs beamline in a reflection mode. The mea­
surements were performed ex situ for different heat treatment sample
conditions. An X-ray energy of 17 keV was used and the incidence angle
of the X-ray beam with the sample surface was 10◦ . The beam size was
approximately 1000 × 250 µm2 and the diffraction patterns were ac­
quired using a CIRPAD 2D hybrid pixel detector, allowing for the
simultaneous acquisition of a 2-theta range of 2◦ –135◦ . The acquisition
time was 10 s per diffraction pattern. After azimuthal integration, the
analysis of the diffraction patterns was performed using the MAUD
software [28] on the 2-theta range of 11◦ –97◦ .
3. Results
3.1. Solidification behavior
As seen in Fig. 2a, the solidification structure has a columnar struc­
ture along the building direction and the columnar width is about
20–50 µm. The columnar structure is further divided into polygonal
structures that have a size similar to the width of the columnar struc­
tures (Fig. 3b). The microstructure is composed of lath martensite,
retained austenite, and a small amount of δ-ferrite retained from high
temperature. The δ-ferrite has a granular morphology (Fig. 2b and d)
and low Kernel average misorientation (Fig. 2c). The retained austenite
within each columnar structure has the same orientation (Fig. 2d),
suggesting that the columnar structure is due to the high temperature
parent austenite grains, part of which has transformed into lath
martensite during cooling. Segregations of alloying elements Cr and Mn
are detected at the inter-columnar and inter-polygonal regions (Fig. 3),
which qualitatively agrees with the Scheil-Gulliver modelling (Fig. 1c).
Nb atoms are found in the form of Nb-rich particles (Fig. 3e and n). The
inter-columnar and inter-polygonal regions consist of two phases
(Fig. 3i–n), one Cr- and C-rich phase which has a brighter contrast and
one Cr- and Mn-rich phase which has a darker contrast (Fig. 3j). These
two phases are predicted to be M23C6 and Laves phases by the Scheil-
rhodonite and MnS, are found in the as-built microstructure (further
details can be found in supplementary Fig. S2).
3.2. Mechanical properties
Ageing treatments give rise to an increase in hardness for the as-built
T. Zhou et al.
Fig. 2. Optical microscopy images of the as-built microstructure parallel to the building direction (a) and perpendicular to the building direction (e); EBSD analysis
of the as-built microstructure parallel to the building direction (b-d) and perpendicular to the building direction (f–h): (b and f) inverse pole figure (IPF) + band
contrast; (c and g) Kernel average misorientation + band contrast; (d and h) IPF of austenite + band contrast.
and solution-treated samples (Fig. 4a), but the solution treated samples
show higher hardness compared to the as-built sample both in as-
quenched and aged conditions. It can also be noted that higher solu­
tion treatment temperature or longer holding time leads to higher
hardness. All the solution-treated samples show a peak hardening at
around 2 h ageing, while the as-built sample has an almost constant
hardness for ageing from 0.5 to 4 h. Thereafter, the stress-strain curves
of 2 h aged condition of as-built and solution-treated samples are
compared (labeled “-A” in the Fig. 4b), together with those of the as-
built sample and the wrought reference sample (Fig. 4b). The as-built
microstructure has lower strength (both ultimate tensile strength and
yield strength) and ductility (both total elongation and uniform elon­
gation) compared to the directly aged microstructure that achieves a
combination of high strength (ultimate tensile strength: ~1150 MPa;
yield strength: ~875 MPa) and excellent ductility (total elongation: ~19
%; uniform elongation: ~14.5 %) as shown in Fig. 4b and Table 3.
Combining solution treatment at 1040 ◦ C or 1100 ◦ C and ageing treat­
ments brings no significant improvements in strength and ductility in
comparison with the directly aged sample. However, after sufficient
homogenization at 1200 ◦ C for longer time, the aged sample achieves an
excellent combination of strength (ultimate tensile strength:
~1340 MPa; yield strength: ~1060 MPa) and ductility (total elonga­
tion: ~12.3 %; uniform elongation: ~10.5 %), which represent a sig­
nificant improvement of the mechanical properties in comparison with
the wrought reference material (Table 3).
3.3. Austenite reversion
The columnar structures formed during the solidification process
remain in the as-built-A sample, but they are eliminated after solution
treatments (see the IPFs in Fig. 5). The volume fraction of austenite
remains roughly constant during the ageing of the as-built sample,
without obvious decomposition of the retained austenite. This suggests
that the austenite formed during the WAAM process is thermally stable.
The thermal stability of the retained austenite after WAAM was also
studied through deep cooling of the WAAM samples using liquid
4
Additive Manufacturing 58 (2022) 103047
nitrogen and subsequent XRD analysis, but no clear decrease in volume
fraction of austenite was observed (further details can be found in
supplementary Fig. S3). In the solution treated samples, austenite with
volume fraction below ~4 % remains after water quenching (Fig. 5).
After subsequent ageing treatment, a significant increase in volume
fraction of austenite, i.e. austenite reversion, was observed. The in­
creases in temperature and time of solution treatment can reduce the
volume fraction of austenite in both the solution treated, and the solu­
tion treated and aged samples. The grain size of austenite is statistically
analyzed based on the EBSD measurements (further details can be found
in supplementary Fig. S4). It shows that the number of austenite grains
in the aged conditions is 2–5 times higher than that in the corresponding
solution treated conditions. The average grain size of austenite is around
1 µm in diameter for all the solution treated and solution treated + aged
samples.
3.4. Precipitation characterization
3.4.1. Synchrotron XRD analysis
XRD patterns acquired at several solution treated and aged condi­
tions are displayed in Fig. 6. As the α-ferrite, δ-ferrite and α’-martensite
could not be separated in those measurements due to their very similar
crystalline structure, the label “α” on the graph stands for all bcc/bct
phases. Several secondary phases had been identified, among which, a
small volume fraction of M23C6 (identified as Cr23C6 structure [29]), and
M7C3 (identified as Cr7C3 structure [30]) seems to be present in most
(likely all) of the samples even though their identification were some­
times challenging due to their very low intensity peaks. For the ST1100
(0.5 h) at 1 h and 2 h ageing, the (4 2 0) peak of M23C6 shows a sig­
nificant increase of intensity, which could be linked to a strong texture of
these carbides as already observed in other studies [31], certainly pre­
sent on every sample. Nb(C, N) precipitates [32] are clearly identified on
the ST1040(0.5 h) and ST1100(0.5 h), irrespective of the ageing con­
ditions, even though the ST1100(0.5 h) as-quenched (designated as
“as-Q” in Fig. 6) condition measurement is missing. For the as-built,
ST1200(2 h) and ST1200(15 h), the volume fraction of Nb(C, N) is too
T. Zhou et al. Additive Manufacturing 58 (2022) 103047

Fig. 3. SEM-EDS mapping of elemental segregations at (a–h) inter-polygonal regions and (i–n) inter-columnar regions.

Fig. 4. (a) Vickers hardness with varying ageing treatment time at 480 ◦ C of as-built and solution-treated samples; (b) stress-strain curves of as-built, directly aged
for 2 h, solution treated + 2 h-aged, and heat-treated wrought samples.

5
T. Zhou et al. Additive Manufacturing 58 (2022) 103047

Table 3 3.4.3. In situ SANS analysis

Summary of tensile testing results. Fig. 11a and d show the SANS total macroscopic differential scat­
Ultimate tensile Yield Total Uniform tering cross-section dΣ/dΩ evolution during 4 h ageing at 480 ºC for the
strength, MPa strength, elongation, % elongation, % as-built and the solution treated (1200 ºC for 15 h) samples, respec­
MPa tively. dΣ/dΩ includes both nuclear and magnetic scattering contribu­
As-built 975 ± 16 678 ± 3 12.3 ± 0.1 11.7 ± 0.1 tions and represent the state after removing the initial SANS pattern, i.e.
As-built-A 1149 ± 16 875 ± 24 18.7 ± 1.3 14.5 ± 0.2 the first pattern acquired upon reaching the ageing temperature, as
ST1040 1192 ± 4 898 ± 13 19.0 ± 0.1 14.2 ± 0.3 background. For both samples, ageing results in a gradual increase in the
(0.5 h)-
A
dΣ/dΩ over a wide Q-range, which is also accompanied by the shift of
ST1100 1203 ± 2 844 ± 8 19.8 ± 0.8 15.2 ± 0.2 Guinier region towards the lower Q-range as shown by arrows in
(0.5 h)- Fig. 11a and d. These results indicate the growth and/or coarsening of
A Cu precipitates during the ageing treatment, which is also clearly sug­
ST1200 1340 ± 28 1057 ± 57 12.3 ± 1.6 10.5 ± 1.3
gested by the change of the peak position of the dΣ/dΩ• Q2 curves to
(15 h)-A
W-ST1040 1314 ± 10 1289 ± 10 10.1 ± 1.6 1.4 ± 0.2 lower Q as shown in Fig. 11b and e. Furthermore, the area under the dΣ/
(0.5 h)- dΩ• Q2 vs Q curves, i.e. scattering invariant, is proportional to the vol­
A ume fraction of precipitates and scattering contrast (nuclear and mag­
netic) between the matrix and the precipitates. The nuclear contrast can
vary with the composition of the precipitates, which is likely to happen
low to be measured. This suggests that only a part of Nb atoms form the
as the Cu content in the precipitates had been found increasing with the
Nb(C, N) during the deposition process (see Fig. 3), and more Nb(C, N)
precipitates size [6]. The magnetic contrast is expected to remain con­
precipitates form during solution treatments at 1040 ◦ C and 1100 ◦ C,
stant, as the precipitates can always be considered as magnetic holes
but the precipitates formed during the deposition process mostly
(SLDprecipitates = 0). In our system, the maximum nuclear contrast is
dissolve during solution treatment at 1200 ◦ C that is around the solution
achieved for pure Cu precipitates (ΔSLDnuc)2 = 3.48 × 10 13 Å 4.
– –
temperature of MX (see Fig. 1a). MnS phase [33] is also found, probably
However, this value is ~50 times lower than the magnetic contrast,
in all the samples, even if its only visible intense (2 0 0) peak at ~16.6◦
taking into account a magnetic scattering length density for the Fe
highly overlaps with the (1 1 1) peak of Nb(C, N), which makes the
matrix of 4.08 × 10 6 Å 2 at 480 ◦ C [34], with (ΔSLDmag)2
– –
identification of its presence uncertain in the ST1040(0.5 h) and ST1100 –11 –4
= 1.66 × 10 Å . Thus, the scattering contrast can be considered as
(0.5 h) specimens. MnS inclusions have also been observed by micro­
nearly constant, and the fluctuations of the area under the dΣ/dΩ• Q2 vs
scopy techniques in the as-built sample (supplementary Fig. S2), and are
Q curves can be attributed to variation of the volume fraction of the
probably unable to dissolve during the solution treatment up to 1200 ◦ C,
precipitates.
which strengthen the hypothesis that MnS exists in all the measured
Fig. 11c and f show the volume-averaged particle size distribution of
samples. MnSiO3 rhodonite structure [34] had also been identified in
Cu precipitates with ageing time for the as-built and the solution treated
every samples. This kind of phase is a typical inclusion in steel, and was
samples. The samples include both ferrite and retained austenite and the
identified by microscopy in the as-built sample as well (supplementary
separation of magnetic and nuclear dΣ/dΩ was not possible; therefore,
Fig. S2). Finally, Cu-rich precipitates could not be identified as their
we report the size distributions in relative units. A clear increase in the
structures and cell parameters are expected to be very close to those of
volume fraction at the beginning stage of ageing (up to around 1 h) is
the matrix, but they are identified by TEM and monitored by SANS
observed for both samples. After that, as also suggested by the dΣ/
measurements presented in the following sections.
dΩ• Q2 vs Q curves, the volume fraction increases in a less pronounced
manner with further ageing up to 4 h. With the progressing of ageing, a
3.4.2. STEM analysis
clear shift of the curves from left to right is observed (Fig. 11c and f),
Fig. 7a shows the microstructure in the as-built sample, including
revealing the growth or/and coarsening of Cu precipitates. It is inter­
lath martensite with high density of dislocations formed from the parent
esting that humps on the curves appear at the late ageing stages of both
austenite during cooling, δ-ferrite with few dislocations, and some pre­
samples, suggesting a bimodal size distribution of Cu precipitates. This is
cipitates formed at the interfaces of austenite and δ-ferrite with size of
interpreted in the discussion part.
around 300 nm. EDS mapping (Fig. 7) shows that these precipitates are
For a comparison of Cu precipitation in the two samples, the dΣ/
Cr-, Mn- and C-rich. Quantitative EDS line analysis (Fig. 8) shows that
dΩ vs. Q curves of the two samples after 4 h ageing are shown in
the Fe and Cr contents in these precipitates are similar to those in M23C6
Fig. 11g, where the as-built sample shows an obvious high intensity at
predicted by the Scheil-Gulliver modelling, suggesting these precipitates
the large Q area in comparison to that of the solution treated sample. The
are M23C6 formed during solidification. In addition, the predicted
corresponding volume-averaged size distributions of Cu precipitates are
chemical composition of martensite and δ-ferrite by the Scheil-Gulliver
shown in Fig. 11h, and a finer precipitate distribution is observed for the
model also have good agreement with those characterized by EDS
as-built sample. In addition, the evolution of the Cu precipitate mean
(Fig. 8). Martensite maintains the same Fe and Cr contents as the
size (diameter) in the two samples during ageing are plotted in Fig. 11i,
austenite formed at high temperature due to martensitic transformation
showing that the Cu-precipitates in the as-built sample display a smaller
during cooling. The composition of the austenite is evolving during so­
size during the whole ageing period.
lidification due to segregations as predicted in Fig. 1c, which results in
martensite with Fe and Cr contents of a compositional range as shown in
4. Discussions
Fig. 8. Except for M23C6 that has been predicted to form during solidi­
fication (Fig. 1b), Cu precipitates are also observed in the as-built
4.1. Process-structure-property relationship
microstructure. Cu precipitates are observed around the M23C6 pre­
cipitates, some of which are fine (below 10 nm) and spherical (Fig. 7e),
After ageing treatment, the as-built sample shows clear increases in
and the others are coarse (about 100 nm in length) and ellipsoidal
hardness and strength (Fig. 4), which mainly results from the precipi­
(Fig. 9e and f). After ageing treatment of the as-built sample, a high
tation hardening with Cu precipitates formed during the ageing treat­
density of nanoscale Cu precipitates form within the tempered
ment. As displayed in the STEM analysis (Figs. 7–10), Cu precipitation
martensite matrix (Fig. 10b), and Ni atoms segregate around the Cu
has occurred around some interfaces during the deposition process but
precipitates (Fig. 10f) as widely reported in the wrought state of similar
has not fully precipitated, thus the ageing treatment gives rise to further
maraging stainless steels [7].
precipitation hardening. Not only on the hardness/strength increase, the

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T. Zhou et al. Additive Manufacturing 58 (2022) 103047

Fig. 5. EBSD analysis of microstructural evolution during post-heat treatments using inverse polar figure (IPF) and phase map (the scale bar and the color legends
stand for all the displayed samples; all ageing treatments mentioned here were performed at 480 ◦ C for 2 h).

directly aged sample also has an excellent ductility compared to the as-
built sample, which is mostly due to the recovery of the as-built
microstructure. The decrease of vacancies, dislocation density [9], and
micro- stress/strain are typical microstructural phenomena that occur in
martensite during tempering treatments. Nano-porosities formed during
the deposition process may also be partly or completely filled by Cu
precipitates [13,35]. In addition, it is possible that the austenite stability
in the directly aged sample differs due to partitioning of alloying ele­
ments during the ageing treatment.
The solution treated samples show higher hardness than the as-built
sample on both as-quenched states and aged states (Fig. 4a). Such a
hardness increase in the as-quenched states is a combined effect of the
increased volume fraction of martensite (Fig. 5) through eliminating the
chemical segregations (Fig. 3) and the δ-ferrite (Figs. 2 and 7) formed
during the deposition process, together with the dissolution of precipi­
tate phases such as M23C6, laves, Cu, and even Nb(C, N) for higher
temperature solution treatments. The hardness increase after ageing of
the solution treated samples compared to the as-built sample may

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T. Zhou et al. Additive Manufacturing 58 (2022) 103047

Fig. 6. X-ray diffraction pattern subset of the analyzed data (between 16◦ and 28◦ ) for as-built and solution treated samples at different ageing conditions. The most
intense peaks of the identified precipitate phases that do not overlaps with the matrix phases are indicated.

Fig. 7. STEM-EDS mapping of the as-built sample showing M23C6 and fine spherical Cu precipitates formed at interfaces of δ-ferrite and prior austenite.

8
T. Zhou et al.
Fig. 8. STEM-EDS quantitative line analysis of the regions in Fig. 7a marked by
the yellow line, and predictions of the chemical compositions of martensite
(prior austenite), M23C6 and δ-ferrite by Scheil-Gulliver model implemented in
the Thermo-Calc software.
originate from two main factors: i) the increasing volume fraction of
tempered martensite, together with the potentially higher volume
fraction of Cu precipitates, available thanks to the lower solubility of Cu
in martensite than in austenite; ii) the dissolution of coarse Cu and other
kinds of precipitates formed during deposition and their finer re-
precipitation during ageing. Compared to the as-built-A sample, the
ST1040(0.5 h)-A and ST1100(0.5 h)-A samples display clear increase in
ultimate tensile strength, but similar yield strength and ductility (see
Fig. 4b and Table 3). This is mainly influenced by the fractions of
tempered martensite and austenite. Austenite, as a softer phase,
Fig. 9. STEM-EDS mapping of the as-built sample showing coarse ellipsoidal Cu precipitates formed at the specific interfaces of M23C6.
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Additive Manufacturing 58 (2022) 103047
contributes mainly to the yield strength, while the tempered martensite,
as a harder phase, contributes mainly to the ultimate tensile strength.
The increase in ultimate tensile strength is due to higher contribution
from Cu precipitation hardening resulted from lower volume fraction of
austenite that dissolves less Cu atoms as mentioned before. The differ­
ences in ductility is influenced not only by the volume fraction of
austenite but also by the stability of austenite. The lower volume frac­
tion of austenite, as in the ST1100(0.5 h)-A, usually results in higher
stability of austenite after the partitioning during ageing treatment. The
stabilized austenite needs more strain to trigger the transformation-
induced plasticity (TRIP) effect, thus better ductility could be ach­
ieved (the ST1100(0.5 h)-A sample shows a slight of better ductility). In
contrast, the volume fraction of austenite in the ST1200(15 h)-A sample
is low (around 5 %) and the contribution of TRIP effect to ductility is
relatively decreased. Thus, this sample shows relatively lower ductility,
but much higher strength.
4.2. Cu precipitation and austenite reversion
Some spherical and ellipsoidal Cu precipitates are found in the as-
built sample (Figs. 7 and 9). According to previous understanding [8],
these spherical precipitates are probably metastable Cu precipitates with
a body-centered cubic (bcc) structure, which may form within the su­
persaturated martensite during the cyclic heating of additive
manufacturing. In contrast, the ellipsoidal ones are probably stable Cu
precipitates with a face-centered cubic (fcc) structure, which forms from
liquid phase during solidification or solid state phase transformation at
high temperatures. Interestingly, the SANS results show a clear hump for
the as-built sample and a slight of hump for the solution treated sample
at the larger size side of the curves at the late ageing stages (Fig. 11c and
T. Zhou et al.
Fig. 10. STEM-EDS mapping of the directly aged (480 ◦ C for 2 h) sample showing high dispersion of Cu precipitates.
f), which suggest a bimodal distribution of the Cu precipitates. The
bimodal distribution is possibly due to the formation of Cu precipitates
in different parent phases, i.e martensite and austenite [36], resulting in
different growth rates. Except that, nano-porosities could act as prefer­
ential nucleation sites for the nucleation of Cu precipitates and stimulate
fast growth [13]. Since the solution treatments decrease the volume
fraction of austenite or eliminate most of the nano-porosities, the
bimodal size distribution in the solution treated condition is not as
significant as that in the as-built condition. This interesting phenomenon
requires further detailed investigations. In addition, the as-built sample
shows a finer dispersion of Cu precipitates during ageing compared to
the solution treated sample (Fig. 11g–i). On one hand, this is closely
linked to the volume fraction of austenite in the matrix, as higher vol­
ume fraction of austenite (that has higher solubility of Cu than tempered
martensite) leads to less Cu atoms to precipitate in the tempered
martensite and lower growth rate of precipitates; on the other hand, this
can result from higher density of defects in the as-built sample than the
solution treated sample, which further gives rise to higher density of
nucleation sites for Cu precipitation.
The high combinations of strength and ductility for the directly aged
samples and the solution treated + aged samples (especially the ST1200
(15 h)-A) are mainly a synergistic effect of precipitation hardening from
Cu nanoscale precipitates (and finer re-precipitation of other kinds of
precipitate phases for the solution treated samples) that forms in
martensite during ageing treatment to enhance strength, and TRIP of
retained and reverted austenite that have experienced chemical parti­
tioning during AM process or/and ageing process to become stabilized.
The high stability of austenite is not only related to chemical parti­
tioning, but also to the fine grain size of austenite [37]. Austenite
reversion was also found in conventional wrought maraging stainless
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Additive Manufacturing 58 (2022) 103047
steels [7], but the volume fraction of reverted austenite formed during
ageing treatment is quite low and rarely leads to significant change in
mechanical properties. However, the high degree of non-homogeneity in
chemistry and microstructure caused by the WAAM process opens up
new opportunities for controlling mechanical properties, for instance,
the austenite reversion during post heat treatment as reported in this
work. Together with tuning nanoscale precipitation and recovery of lath
martensite, austenite reversion adds more freedom for tailoring the
combinations of various properties through controlling the post heat
treatment of WAAM maraging stainless steels.
5. Conclusions
1) The solidified microstructure of WAAM 17–4 PH is mainly composed
of martensite, retained austenite (~30 vol%), a slight amount of
δ-ferrite, M23C6, Nb(C, N) and Cu precipitates (spherical and ellipsoidal), which
cannot be fully predicted by the Scheil-Gulliver model. Segregations of alloying elements
like Cr and Mn happen to the finally solidified inter-columnar and inter-polygonal regions,
which are predicted by the computational thermodynamics.
2) Austenite reversion occurs during ageing after solution treatment;
clear increases in the volume fraction and the amount of austenite
grains of aged states in comparison to solution treated states have
been observed. The austenite formed after ageing has high stability,
resulted from the small size of about 1 µm and chemical partitioning
of stabilizing elements towards austenite during deposition or/and
ageing.
3) Through tuning austenite reversion and nanoscale precipitation in
lath martensite by post heat treatment, WAAM 17–4 PH stainless
steel has achieved excellent combinations of strength and ductility
for both the directly aged condition and the solution treated + aged
T. Zhou et al. Additive Manufacturing 58 (2022) 103047

Fig. 11. Time evolution of the dΣ/dΩ after background subtraction as a function of Q measured at 480 ºC up to 4 h for samples of (a) the as-built (AB) and (d)
solution treated (ST) at 1200 ºC for 15 h; the calculated dΣ/dΩ• Q2 as a function of Q for the (b) AB and (e) ST samples; the calculated volume averaged particle size
distribution for the (c) AB and (f) ST samples; a comparison of (g) the dΣ/dΩ vs. Q and (h) particle size distribution of the AB-4 h and ST-4 h aged condition; (i) the
mean diameter of Cu precipitates as a function of ageing time for the two samples.

condition, which not only display better properties in comparison to
the corresponding wrought material but also opens up more oppor­
tunities to tailor the combination of properties for specific
applications.
CRediT authorship contribution statement
Bahadir Yildiz Ahmet: Writing – review & editing, Validation,
Methodology, Formal analysis. Zheng Tao: Writing – review & editing,
Validation, Resources, Methodology. Zhou Tao: Writing – review &
editing, Writing – original draft, Validation, Methodology, Investigation,
Funding acquisition, Formal analysis, Conceptualization. Hedström
Peter: Writing – review & editing, Validation, Supervision, Resources,
Project administration, Funding acquisition, Conceptualization. Cubitt
Robert: Writing – review & editing, Validation, Resources, Methodol­
ogy. Rolinska Monika: Writing – review & editing, Validation, Meth­
odology. Spartacus Gabriel: Writing – review & editing, Validation,
Resources, Methodology, Formal analysis.
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.
Acknowledgements
This research was funded by the Carl Tryggers Foundation (CTS19:
136), the Royal Swedish Academy of Science (ES2019-0013), and the
Competence Center Hero-m 2 Innovation (financed by VINNOVA,
Swedish Industry, and KTH). T.Z., M.R. and P.H. would like to thank ILL
and KTH Materials Platform for travel support, and the staff and Nina-
Juliane Steinke at D33, ILL for the SANS measurements. A.B.Y. and M.
R. gratefully acknowledges the financial support provided by the
Swedish Foundation for Strategic Research (SSF) (grant number: GSn15-

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T. Zhou et al. Additive Manufacturing 58 (2022) 103047

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