Materials Science & Engineering A 738 (2018) 44–56

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Materials Science & Engineering A

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

Impact of composition on the heat treatment response of additively T

manufactured 17–4 PH grade stainless steel
S.D. Mereditha,b, J.S. Zubackb, J.S. Keista, T.A. Palmerb,c,
⁎

a
Applied Research Laboratory, The Pennsylvania State University, University Park, PA 16802, USA
b
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802, USA
c
Department of Engineering Science and Mechanics, The Pennsylvania State University, University Park, PA 16802, USA

ARTICLE INFO ABSTRACT

Keywords: Precipitation hardened (PH) martensitic grade stainless steels are commonly used in additive manufacturing
Stainless steel (AM) processes, but the heat treatment response can vary depending upon the powder feedstock composition.
Precipitation hardening (PH) As-built AM 17–4 PH grade stainless steel fabricated using argon and nitrogen atomized feedstocks in separate
Additive manufacturing (AM) powder bed fusion systems responded differently to standard heat treatment cycles. Materials fabricated from
Nitrogen
argon atomized feedstocks, containing low levels of nitrogen (0.01 wt%) and retained austenite (< 1%), re-
Gas atomization
Aging
sponded as expected to standard solutionizing and aging heat treatment cycles. In contrast, materials fabricated
from nitrogen atomized feedstocks, containing between 0.06 and 0.12 wt% nitrogen and up to 81% retained
austenite, did not display peak aging with standard heat treatments and deviated from the expected overaging
response with increasing aging temperatures. At the highest nitrogen and retained austenite levels, peak aging is
found to occur at temperatures in excess of 680 °C, even though the material still contains retained austenite
levels in the 20% range. These unexpected changes in the heat treat response are closely linked to differences in
the nitrogen composition of the powder feedstock. Changes in the Ni and Cr equivalent values determined by
other primary alloying elements also impact the heat treat response, even though the alloy compositions still fall
within standard alloy element composition ranges.

1. Introduction
Precipitation-hardened (PH) martensitic grade stainless steels are
widely used in the aerospace, marine, and power generation industries
[1–4]. Strengthening in these alloys is derived from a combination of
the martensitic microstructure and the formation of sub-micron copper-
rich precipitates. These precipitates form during post-process heat
treatments, which can be tailored to change the precipitate size and
shape and the hardness and strength of the post-processed component
[2–6]. In the peak-aged (H900) condition [7], elliptical Cu-rich pre-
cipitates approximately 25 nm in length are formed [5]. As the material
is over-aged, Ostwald ripening mechanisms become dominant, leading
to a coarsening of the precipitates, a decrease in their number, a loss of
coherency with the matrix, and tempering of the martensitic matrix
[4–6,8,9]. The combination of these changes in the precipitate and
matrix morphologies results in a decrease in mechanical strength but an
improvement in ductility and impact toughness [1,7].
The weldability of 17–4 PH grade (UNS S17400) stainless steel
makes it an attractive alloy system for additive manufacturing (AM)
processing, and it is seeing widespread use in powder bed fusion (PBF)
processes [10–19]. In the wrought condition, the nitrogen level is not
specified, but AM processed 17–4 PH grade stainless steel can display
wide variations in nitrogen concentration originating primarily from
the atomization conditions for the powder feedstock or to a lesser ex-
tent through the selection of processing gases. For example, previous
studies [2,20] have shown that Ar-atomized feedstock was consistently
martensitic, whereas nitrogen atomized feedstock, containing five times
the nitrogen content [20], was primarily austenite. Increases in the
nitrogen concentration can influence mechanical properties by sup-
pressing the martensite start temperature (Ms) and thereby promote
greater retention of austenite at room temperature [2,21–24], which
could explain the large variations of measured properties [25]. In ad-
dition to being softer than martensite [2], higher levels of austenite
slow the formation of precipitates within the 17–4 PH grade due to the
higher solubility and lower diffusivity of copper within the austenite
phase [3,20,26].
Previous investigations of AM 17–4 PH grade stainless steels have
been primarily directed at evaluating the heat treatment response of as-

⁎
Corresponding author.
E-mail addresses: ScottM@psu.edu (S.D. Meredith), jsz125@psu.edu (J.S. Zuback), jsk25@arl.psu.edu (J.S. Keist), tap103@psu.edu (T.A. Palmer).

https://doi.org/10.1016/j.msea.2018.09.066
Received 19 July 2018; Received in revised form 17 September 2018; Accepted 18 September 2018
Available online 19 September 2018
0921-5093/ © 2018 Elsevier B.V. All rights reserved.
S.D. Meredith et al.
built material through hardness measurements in the solutionized
[6,24,27], solutionized and aged [6,12,13], and aged only conditions
[2,3,6,11]. For example, Murr et al. [2] applied conventional peak-
aging heat treatments directly to as-deposited laser PBF AM 17–4 PH
grade stainless steel and found that as-built materials which exhibited a
predominantly martensitic structure showed an increase in hardness.
On the other hand, other as-built materials, which were primarily
austenitic, did not respond to the aging heat treatment. Similarly, Rafi
et al. [3] observed a higher proportion of retained austenite in the as-
built material when nitrogen atomized powder was processed under a
nitrogen atmosphere (resulting in 0.15 wt% N) rather than an argon
atmosphere. An initial heat treatment (788 °C, 2 h), which falls below
the standard solutionizing temperature (1038 ± 14 °C) [28], raised the
yield and ultimate tensile strengths, but no additional hardening was
observed following a subsequent standard peak-aging heat treatment.
Additional work directed at exploring the heat treatment response of
water atomized powder feedstocks, which are not as susceptible to wide
changes in nitrogen concentrations, also has shown varying degrees of
retained and reverted austenite. Aging of these AM materials directly
from the as-built condition resulted in mechanical properties that de-
viated from those obtained in wrought materials subjected to peak-
aging and overaging heat treatments [6].
Although standard wrought heat treatments are insufficient for
consistently achieving peak aging in AM 17–4 PH grade stainless steel
[6,12], the role of composition on the retained austenite levels and the
resulting heat treat response has not been systematically addressed. In
order to identify the role of chemistry on the resulting heat treatment
response, as-built and post-process heat treated AM 17–4 PH grade
stainless steels produced using several nitrogen and argon atomized
powder feedstocks were characterized and compared to the expected
heat treat response for wrought components. The heat treat response of
AM material fabricated from argon atomized powder feedstocks with
low nitrogen concentrations, on the order of 0.01 wt% N, is closest to
that expected in wrought materials. On the other hand, nitrogen ato-
mized feedstocks, which can contain nitrogen concentrations in excess
of 0.12 wt% N, display extremely large retained austenite levels on the
order of 81%, which shift peak aging temperatures to levels in excess of
680 °C. While nitrogen concentrations play a prominent role in de-
termining the heat treatment response, other alloying elements such as
Cr, Ni, C, Mo, and Mn can also impact the amount of retained austenite
[29] and heat treatment response of this alloy system. The role of these
alloying elements, even though they fall within the specified composi-
tion ranges, are also shown to impact the resulting heat treat response.
2. Experimental
The specified alloying element compositions for wrought 17–4 PH
grade stainless steel are listed in Table 1 [7]. Like other commercial
alloy systems, individual alloying element compositions can vary over
rather wide ranges and still meet chemistry requirements. Since the
standard specification for this alloy does not include nitrogen, its
composition can vary rather widely and impact the properties of AM
fabricated material in unknown ways. In order to investigate the impact
of nitrogen composition on the heat treat response, four powder feed-
stocks satisfying the 17–4 PH martensitic grade stainless steel chemical
requirements [7] were sourced from selected powder vendors to meet
the particle size distribution suitable for use on a 3D Systems ProX 200
and an EOS M280 PBF system. Nitrogen atomized and argon atomized
powder feedstocks were obtained for each AM PBF system, and a
summary of the powder feedstock chemistries, measured at a certified
testing laboratory,1 is provided in Table 1. It is clear that the choice of
atomization gas impacts the nitrogen concentration, with the nitrogen
atomized powder feedstock displaying much higher nitrogen
1
Westmoreland Testing & Research, Inc., Youngstown, PA.
45
Materials Science & Engineering A 738 (2018) 44–56
concentrations than the argon atomized powder feedstocks.
Due to differences in the recoating and process parameters for the
two systems, there are different powder size requirements for each AM
PBF system used. While the powder suppliers specified the particle size
distributions, other powder characteristics required additional analysis.
Each as-received powder feedstock was characterized using a range of
conventional powder metallurgy methods for evaluating the flowability
[30], apparent and tap density [31,32], as well as the particle size
distribution [33]. A standard Hall funnel [30] was used to measure
flowability by the Hall flow test and combined with a 25 cm3 brass cup
[31] to measure apparent density. Average values were calculated from
at least three measurements for each powder. Since no powder flowed
freely, flow was assisted by continuous agitation of the powder. An
average tap density was also determined from at least three measure-
ments, after settling the powder with a QuantaChrome Dual Autotap
model DA-1. The particle size distributions of the powders were as-
sessed by both a light scattering technique (Malvern Masersizer 2000)
as well as image analysis (Malvern Morphologi® G3), with the latter
providing additional information on particle shape, including mea-
surements of the convexity and circularity of the particles. Convexity
represents the ratio of the convex hull perimeter of two-dimensional
profiles of the particles to the actual perimeters, and therefore ap-
proaches unity as surface roughness decreases. Circularity accounts for
deviations in either surface roughness or shape by comparing the actual
particle perimeters to the circumference of a circle with an equivalent
area to the two-dimensional profile.
The measurement of retained austenite fractions in the powders and
AM fabricated materials was performed using X-Ray Diffraction (XRD)
techniques on a PANalytical X′Pert Pro MPD with an Empyrean Cu
anode (λ = 1.54059 Å) operated at 45 kV and 40 mA. XRD data were
obtained using a PIXcel 1D detector with a 0.020 mm Ni β filter,
0.04 mm Soller slit, 10 mm beam mask, and a 2° antiscatter slit. A 2θ
range of 40°–100° was used with an automatic spot size of 5 or 10 mm,
depending upon the size of the specimen. Individual peaks, which are
schematically shown in Fig. 1, were indexed and the integrated in-
tensities for each peak measured using MDI Jade 2010 (version 3.6.5).
The amount of retained austenite was then calculated using the direct
comparison method [34,35].
The most prominent peaks for each phase were generally FCC (111)
and BCC (110) at approximate two-theta values of 43.6° and 44.5°,
respectively. These two peaks were used to determine the lattice spa-
cing by Bragg's Law, from which the lattice constant and unit cell vo-
lume could be calculated. The proportional parameter Rihkl [34] was
then determined for each hkl peak using tabulated values [36] for the
multiplicity factor, atomic scattering factor, temperature factor, and the
structure factor appropriate for each phase, as listed in Table 2. The
austenite volume fraction, Vγ, was then calculated using the following
relationship [34]:
q P q
1 I j 1 Ii 1 I j
V = / +
q R P R i q R
j=1 j i=1 j=1 j
(1)
where the ratio of integrated intensity, I, to the corresponding pro-
portional parameter, R, is averaged over the number of peaks con-
sidered for each phase over the selected two-theta range (40–100°). For
this study, the value of P corresponds to four peaks for the α phase and
q corresponds to five peaks attributed to γ phase. Due to the low carbon
content of this ferrous alloy system (≤ 700 ppm), the lattice parameters
of BCT martensite would not significantly differ from BCC ferrite [37],
so the two phases were considered comparable in XRD analysis.
The appropriate powder feedstocks were then used on 3D Systems
ProX 200 and EOS M280 laser PBF systems using the recommended
operating parameters to fabricate a series of simple build geometries.
Each build consisted of a series of bars, each having an approximate
cross-section of 400 mm2, with build heights between 4.31 and
9.52 mm. During processing, either an argon or nitrogen atmosphere
S.D. Meredith et al. Materials Science & Engineering A 738 (2018) 44–56

Table 1
Summary of chemical compositions for wrought [7], nitrogen and argon atomized powder feedstocks, and as-built materials for 17–4 PH grade stainless steels.
Additional calculations of the Nickel and Chromium Equivalents as calculated per the DeLong constitution diagram [42] as well as austenite volume fraction as
measured by XRD.
3D Systems ProX 200 EOS M280

Ar atomized feedstock N2 atomized feedstock Ar atomized feedstock N2 atomized feedstock

Specified ranges (wt%) Praxair lot As-built As-built Phenix lot As-built As-built LPW lot As-built EOS lot As-built
FE-276–3 (Ar) (N2) 14D1147 (Ar) (N2) UK5032 (N2) F471301 (N2)

15.0–17.5 Cr 16.6 15.6 15.7 15.8 15.7 15.7 16.4 16.5 15.2 15.2
3.0–5.0 Ni 4.3 4.2 4.2 4.1 4.2 4.2 4.1 4.3 4.3 4.6
3.0–5.0 Cu 3.2 3.3 3.3 3.7 3.9 4.0 4.0 4.2 4.3 4.3
≤ 1.00 Si 0.81 0.70 0.68 0.80 0.66 0.66 0.43 0.38 0.72 0.67
≤ 1.00 Mn 0.19 0.14 0.17 0.61 0.54 0.51 0.19 0.15 0.68 0.57
0.15–0.45 Nb(+Ta) 0.20 0.22 0.23 0.24 0.24 0.23 0.29 0.25 0.26 0.25
≤ 0.07 C 0.01 0.005 0.010 0.03 0.04 0.03 0.02 0.017 0.06 0.058
≤ 0.040 P 0.013 0.010 0.010 0.017 0.019 0.019 0.016 0.019 0.008 0.018
≤ 0.030 S 0.006 0.004 0.004 0.004 0.002 0.003 0.002 0.002 0.004 0.005
— Mo 0.13 0.012 0.020 0.92 0.098 0.100 0.06 0.009 0.89 0.098
— N 0.01 0.010 0.017 0.06 0.088 0.091 0.01 0.027 0.12 0.142
— O 0.06 0.052 0.085 0.09 0.084 0.098 0.04 0.036 0.02 0.031
Delong equivalent Nieq (wt%) 5.0 4.8 5.1 7.1 8.3 8.1 5.1 5.7 10.0 10.8
Creq (wt%) 18.0 16.8 16.8 18.0 17.0 16.9 17.3 17.2 17.3 16.4
Creq/Nieq ratio 3.6 3.5 3.3 2.5 2.1 2.1 3.4 3.0 1.7 1.5
%Austenite < 1% 0% 0% 20% 9% 14% 3% < 1% 97% 81%

alloying element compositions in the as-built condition is shown in

Table 1.
Selected samples were then subjected to a series of heat treatments
to measure the heat treatment response in the as-built AM material.
Samples were placed in a preheated, argon-purged CM, Inc Rapid Temp
Furnace for a selected time and then allowed to air cool to room tem-
perature. Three sets of standard wrought heat treatment cycles were
performed on the as-built AM material, including direct aging heat
treatments, solution only heat treatments, and a two-stage solution and
aging heat treatment. For the standard solution heat treatment, a re-
commended temperature of 1040 °C [28] was used, but since a specific
duration is not specified, times of 15, 30, 60, and 90 min were in-
vestigated. An initial solutionizing step of 30 min was used for the
combined heat treatment, and aging treatments of four hours in dura-
Fig. 1. Representative XRD pattern showing observed peaks in the 40–100°
two-theta range for AM 17–4 PH material.
tion were carried out at temperatures of 495 °C, 580 °C, and 620 °C to

Table 2
Summary of coefficients for analyzing X-ray diffraction data for measurement of retained austenite levels.
h k l Atomic scattering Structure factor, Multiplicity factor, p Lorentz polarization Temperature factor, Calculated proportional
factor, fFe F factor, LP e−2M parameter, Ri

BCC phase 1 1 0 17.5 2f 12 11.4 0.95 283.2

2 0 0 14.8 2f 6 4.9 0.92 41.6
2 1 1 13.0 2f 24 3.1 0.88 80.1
2 2 0 11.8 2f 12 2.7 0.84 27.3
FCC phase 1 1 1 17.6 4f 8 11.9 0.96 211.2
2 0 0 16.5 4f 6 8.4 0.94 97.7
2 2 0 13.7 4f 12 3.7 0.89 55.2
3 1 1 12.3 4f 24 2.8 0.86 65.9
2 2 2 11.9 4f 8 2.7 0.85 19.8

was used on the 3D Systems ProX 200 system, while only a nitrogen
atmosphere was used on the EOS M280 system. Fabricated specimens
were removed from the base plate by electrical discharge machining.
The chemistry of the as-built material from each build was then ana-
lyzed at a certified testing laboratory2 using a combination of com-
bustion infrared detection (C, S), inert gas fusion (N, O), and direct
current plasma emission spectroscopy. A summary of the measured
2 2 min each on a Struers Pedemax-2. A final polishing step using a
Luvak Laboratories, Inc; Boylstown, MA.
replicate the H925, H1075, and H1150 standard heat treatments, re-
spectively [7]. Additional aging temperatures of 550 °C, 650 °C, 680 °C,
720 °C, and 760 °C, after solutionizing for either 30 or 60 min, were also
performed on selected specimens.
Prior to XRD characterization and microhardness measurements,
specimens were mounted in an epoxy thermosetting powder, and then
ground through a series of silicon carbide abrasive grinding media to a
FEPA P4000 rating microgrit. Specimens were then polished with a
3 µm diamond suspension followed by a 1 µm diamond suspension for

46
S.D. Meredith et al.
0.06 µm colloidal silica suspension was performed for 8 min to produce
a mirror finish. A Nikon Epithot microscope equipped with a Digital
Sight DS-Fi2 camera was used to capture optical micrographs of the
fabricated material following 6–11 s immersion in a solution of Marble's
etchant (50 ml HCl + 50 ml H2O + 10 g CuSO4) [38] diluted with an
equal weight of glycerol. To assess the hardening response throughout
the heat treatments, a minimum of 30 Vickers microhardness mea-
surements were recorded on each specimen at a load of 300 gF with a
Leco M-400-G1 Hardness Tester. Since hardness specifications for
wrought 17–4 PH grade are provided on the Rockwell C scale [7], a
hardness conversion table for non-austenitic steels was used to identify
the corresponding Vickers hardness numbers [39]. A Philips XL-30
Environmental Scanning Electron Microscope was used to capture
secondary electron (SE) images of the powders. Energy-dispersive X-ray
spectroscopy (EDS) maps were acquired using Oxford Instruments
Aztec 3.1 SP1 software in conjunction with an X-MaxN detector (Model
51-XMX1005) affixed to an FEI Helios NanoLab 660 scanning electron
microscope.
Since 17–4PH stainless steel is a multicomponent alloy with over 10
alloying elements comprising roughly one fourth of the alloy mass, a
computational thermodynamic approach was used to investigate phase
equilibria and transformation temperatures. All calculations were per-
formed using JMatPro® (Sente Software Ltd., United Kingdom), which
uses the CALPHAD approach to determine phase equilibria as a function
of temperature and alloy composition. To compare phases of builds
fabricated with different feedstocks, equilibrium calculations were
performed spanning temperature ranges to include the solid and liquid
regions. Additionally, Scheil simulations were used to compare the re-
lative amounts of ferrite and austenite formed upon solidification. The
Scheil calculations take elemental segregation into account and use the
assumptions that there is no diffusion in the solid phases, diffusion in
the liquid is infinitely fast, and local equilibrium exists at the solid-
liquid interface. To highlight the effect of nitrogen content on mar-
tensite formation, the chemical compositions for each fabricated com-
ponent were used to estimate the martensite start (Ms) temperature as a
function of nitrogen composition while assuming the other elements
remained as measured. The calculations were performed exclusively for
the austenite composition to account for some solute being consumed
by secondary phases coexisting in equilibrium with austenite.
3. Results and discussion
3.1. Role of atomization condition on powder feedstock
Differences in the two AM PBF systems employed here require
powder feedstocks with different particle size distributions. These dif-
ferent particle size requirements are based, in part, on the recoating
systems and powder spreading used for each machine. For example, the
3D Systems ProX 200 uses a blade and roller system to place the in-
dividual powder layers, whereas the EOS M280 system uses a stiff metal
recoating blade. Images of the as-received powder feedstocks are shown
in Fig. 2(a) and (b) for those used in the 3D Systems ProX 200 and
Fig. 2(c) and (d) for those used in the EOS M280 system. In all cases, the
gas atomization process produces relatively spherical particles, with the
powders used for the EOS M280 appearing to be coarser than those
used for the 3D Systems ProX 200 system.
Results of additional characterization of the powder size, mor-
phology, and associated flowability and density measurements are
summarized in Table 3. Differences in the particle size distribution for
the powder feedstocks used in each system are apparent, even though
the powders generally have a D50 value around 28 µm. The nitrogen
atomized powder feedstock for the 3D Systems ProX 200 machine,
which is the size recommended by the machine manufacturer, dis-
played the lowest particle sizes, which fall between 4 and 30 µm. Since
finer particles entrap more air during packing, the apparent density was
considerably lower than that displayed by the other powders. In
47
Materials Science & Engineering A 738 (2018) 44–56
addition, the higher surface area associated with fine particle sizes also
promotes cohesion through Van der Waals forces and high surface en-
ergy [40]. These factors inhibit flowability and resulted in the higher
flow times and angle of repose for the finer powder feedstock. The other
powder feedstocks display similar particle size distributions and fewer
differences in other measurements that might impact the resulting
fabrication of test specimens. Image analysis results of the powders
shown in Table 3 revealed that flowability generally worsened as cir-
cularity and convexity, which is a measure of surface roughness, de-
viated from the ideal value of unity.
In addition to these traditional particle characterization measure-
ments, the chemical compositions of the argon and nitrogen atomized
powder feedstocks were measured and summarized in Table 1. Even
though the alloying elements in each powder feedstock fall within the
specified composition limits, there are notable differences in composi-
tions for the Cr, Cu, and Mn alloying elements. The switch from argon
to nitrogen atomization also produces rather significant differences in
the nitrogen composition. In the nitrogen atomized feedstocks, the ni-
trogen concentrations fell in a range between 0.06 wt% and 0.12 wt%,
while the argon atomized feedstocks displayed nitrogen concentrations
at the 0.01 wt% level. These differences are important because nitrogen
is a well-known austenite stabilizer and has an impact on the micro-
structure formed during AM processing [2,3,24].
Differences in the other alloying element compositions, such as Cr,
Ni, and Cu, among others, have additional impacts on both solidifica-
tion and solid state phase transformations during cooling and post
process heat treatments. The impact of changes in these alloying ele-
ments can be captured through the calculation of Cr and Ni equivalent
values (Creq and Nieq) and the use of the Schaeffler diagram [41]. The
Creq and Nieq values are calculated based upon the following relation-
ships [42] and summarized in Table 1:
Ni eq (wt%) = [Ni] + 30 × [C] + 30 × [N] + 0.5 × [Mn] (2)
Creq (wt%) = [Cr] + [Mo] + 1.5 × [Si] + 0.5 × [Nb] (3)
where all elements are given in wt%. While the Creq values do not
display significant differences with changes in the atomization gas,
there is a large increase in the Nieq values for the nitrogen atomized
feedstocks. These changes in Nieq values have a significant impact on
the Creq/Nieq ratio, with the nitrogen atomized powder feedstocks
displaying much lower values (1.7–2.5) than the argon atomized
powder feedstocks (3.4–3.6). In general, the higher Nieq values and
lower Creq/Nieq ratios indicate that the austenite phase becomes more
stable.
These Creq/Nieq ratios can also help predict the solidification mode
for a given stainless steel composition when plotted on the Schaeffler
diagram [41], as shown in Fig. 3. Values corresponding to the powder
feedstock compositions in this work are compared to the highlighted
region representing the elemental ranges specified for wrought 17–4 PH
grade material [7], as well as reported chemistries in the as-built con-
dition from other AM studies. The argon atomized powder feedstocks
for both systems and the nitrogen atomized feedstock for the 3D Sys-
tems ProX 200 system fall in the specified 17–4 PH grade range on the
plot. For these Creq/Nieq ratios, which fall in a range between 2.5 and
3.6, the solidified material is expected to contain a combination of
ferrite and martensite, with some austenite also present in the nitrogen
atomized feedstock for the 3D Systems ProX 200 system. However, the
nitrogen atomized feedstock for the EOS M280 system has a Creq/Nieq
ratio of 1.7 and falls in a region of the Schaeffler diagram that is
dominated by austenite during solidification. Clausen et al. [23] simi-
larly observed a fully austenitic product in this region while Stoudt
et al. [24,27] reported a retained austenite level of 50%. Retained
austenite fractions of 36% [6], 72% [43], 62% and 94% [44] have also
been observed at lower Nieq values, but the nitrogen compositions were
not reported and not taken into account when calculating these values.
Measurements of the retained austenite using XRD techniques
S.D. Meredith et al. Materials Science & Engineering A 738 (2018) 44–56

Fig. 2. Micrographs of feedstock powders for (a) argon atomized for ProX 200, (b) nitrogen atomized for ProX 200, (c) argon atomized for EOS M280, and (d)
nitrogen atomized for EOS M280.

confirm the presence or absence of austenite with the changes in

composition of the powder feedstocks. The argon atomized powder
feedstocks, which displayed nitrogen concentrations in the range of
0.01 wt% and Creq/Nieq ratios between 3.4 and 3.6, exhibited low levels
of retained austenite, ranging from < 1–3% volume fractions. In con-
trast, the nitrogen atomized powders exhibited much higher levels of
retained austenite, which can be correlated with the much higher ni-
trogen concentrations. For example, the nitrogen atomized powder
feedstock for the 3D Systems ProX 200 displayed a retained austenite
level of 21% with a nitrogen concentration of 0.06 wt% and a Creq/Nieq
ratio of 2.5. However, the highest retained austenite level of 97% was
observed in the nitrogen atomized powder feedstock for the EOS M280,
which had a nitrogen concentration of 0.12 wt% and a Creq/Nieq ratio of
only 1.7, largely driven by its high Nieq value of 10.
Fig. 3. Modified Schaeffler diagram [41] showing the range of Nieq and Creq
3.2. Impact of powder feedstock composition on as-built material values expected for the wrought specification as well as the four powder
feedstocks and as-built compositions from literature as calculated from the
In order to evaluate the impact of the different powder feedstock DeLong diagram equations [42].
compositions on the resulting as-built microstructures, builds were
fabricated from each of the powder feedstocks sourced for the re- After processing, the compositions of the primary alloying elements
spective PBF machines. However, the selection of the shielding gas used and retained austenite levels were measured and compared with those
to establish the processing atmosphere can also impact the as-built in the respective powder feedstocks and are summarized in Table 1.
chemistry. Separate builds processed with either argon or nitrogen Overall, there was little change in the compositions of the primary al-
shielding gases was performed on the 3D Systems ProX 200 machine, loying elements, such as Cr, Ni, and Cu, for all the builds except the
while only nitrogen shielding gas was used on the EOS M280. argon atomized feedstocks used in the 3D Systems ProX 200. In this
Representative microstructures orientated perpendicular to the layer case, a decrease in Cr content for both the argon and nitrogen proces-
planes are shown in Fig. 4. EDS maps did not exhibit observable ele- sing conditions is observed, but the change in Cr content still falls
mental segregation for components fabricated on the EOS M280 from within the specified composition range. This loss in Cr content, though,
either the argon atomized or nitrogen atomized feedstock.

Table 3
Summary of powder characterization results for the 17–4 PH grade stainless steel powder feedstocks.
Feedstock PSD (volume basis) Image analysis App. density (g/cm3) Tap density (g/cm3) Hall flow ratea (s/50 g) Angle of repose ( ± 0.5°)

D10 D50 D90 Convexity Circularity

(µm) (µm) (µm)

ProX Ar atom. 15 27 47 0.936 0.909 3.95 5.0 24.8 25.5°

N2 atom. 4 13 30 0.992 0.969 2.72 4.7 290.2 51.5°
EOS Ar atom. 17 28 44 0.983 0.944 3.45 4.5 12.3 27.5°
N2 atom. 26 29 58 0.950 0.982 3.83 5.1 24.5 35.0°

a
Standard Hall flow method resulted in “no flow” condition for all powders; the listed flow times correspond to continuous agitation of the powder and should be
considered for relative comparisons only.

48
S.D. Meredith et al.
Fig. 4. Micrographs of as-built condition for (a) argon atomized and (b) nitrogen atomized for EOS M280 under N2 atmosphere.
had a minimal impact on the Creq/Nieq ratios for the as-built material,
indicating that this change in chemistry will have minimal impact on
the resulting solidification and microstructural development during AM
processing.
Even though changes in processing gases had no discernible impact
on the compositions of the other major alloying elements, the nitrogen
and oxygen concentrations are more likely to be impacted by changes in
the processing conditions. When an argon shielding gas was used in the
3D Systems ProX 200 system, there was little change in the nitrogen
levels in the builds when compared with the as-received powder com-
position shown in Table 1. With the use of a nitrogen shielding gas,
slight increases were observed in the nitrogen concentration of the as-
built material, but the overall magnitude of this increase was rather
minimal. The oxygen content varied within 0.03 wt% of the levels ob-
served in the feedstock, indicating that the process did not suffer from
significant atmospheric contamination.
A further examination of the as-built microstructures shows a
change in the amount of retained austenite for the different powder
feedstocks. Based on the retained austenite measurements summarized
in Table 1, there is a decrease in the measured retained austenite when
moving from the powder feedstock to the as-built microstructure for all
conditions. The retained austenite levels for both argon atomized
powder feedstocks approach zero when processed on either system,
regardless of shielding gas. In the case of the nitrogen atomized powder
feedstocks, the retained austenite levels also decreased in the as-built
conditions from that observed in the powder feedstock. For example,
the nitrogen atomized powder feedstock used in the 3D Systems ProX
200 system decreased from a level of 21% to between 9% and 14%
when processed in argon and nitrogen shielding gases, respectively. The
nitrogen atomized powder with the highest Nieq value (10) also showed
a decrease in retained austenite, albeit only from 97% to 81%.
These differences in the amount of retained austenite in the builds
fabricated from the different powder feedstocks correspond to differ-
ences in the hardness measurements. As shown in Table 4, the as-built
material fabricated using the nitrogen atomized feedstock in the EOS
M280 system displayed the highest level of retained austenite (ap-
proximately 81%) and the lowest hardness levels (260 ± 7 HVN). For
the builds fabricated from the argon atomized feedstock in both AM
systems, little or no retained austenite is present, and the hardness le-
vels increase to approximately 300 HVN. However, the builds fabri-
cated from the nitrogen atomized powder feedstock on the 3D Systems
ProX 200 system, which display austenite levels of approximately 14%
when processed in nitrogen and 9% when processed in argon, display
much higher hardness values, on the order of 350 HVN. Even though
the as-built material fabricated under a nitrogen shielding gas displays
a higher retained austenite level, there is not a substantial increase in
hardness between the nitrogen and argon shielding gases. This increase
in hardness, though, appears to be related to the rather high nitrogen
concentration, which is in the range of 0.09 wt%. While this level of
49
Materials Science & Engineering A 738 (2018) 44–56
nitrogen does not seem to substantially increase the austenite fraction
in the build, it has been shown in previous work to impact the micro-
structure and hardness of the martensite phase [45–47].
3.3. Heat treatment response of as-built material
Given the differences in the as-built hardness and retained austenite
levels for the four powder feedstocks, changes in the heat treat response
of these materials are expected. Since several post-processing heat
treatment routes have been previously explored
[2,3,6,12,13,20,24,27], the impact of similar heat treatments on these
different as-built microstructures is investigated. The standard heat
treatments for wrought material includes an optional homogenizing
step at 1149 °C for at least 90 min [48] followed by a solutionizing step
at 1040 °C (“Condition A”) and a subsequent precipitation heat treat-
ment, such as 1 h at 482 °C for the peak-aged condition [1,7,28]. The
first heat treatment routes to be investigated here involve overaging
directly from the as-built condition. Measurements of the retained
austenite levels after aging for four hours at temperatures of 495 °C,
580 °C, and 620 °C are summarized in Table 4. The hardness results are
graphically compared to the expected heat treatment responses for
standard solutionizing and aging heat treatments for wrought materials
[7] in Fig. 5(a) and (b) for the 3D Systems ProX 200 and EOS M280
processing systems, respectively.
In the as-built condition, the hardness values for the different
components consistently fall below the maximum hardness require-
ments for the solutionizing heat treatment. At these hardness levels, PH
grades in the as-built condition have previously been considered
equivalent to the solutionized condition specified for wrought materials
[3,49], and were subjected to follow on aging treatments without so-
lutionizing [2,3,6,49]. When going from the as-built condition directly
into an aging heat treatment, the hardness values change depending
upon the amount of retained austenite, which is dictated primarily by
the original atomization condition for the powders. For example, the
argon atomized materials maintained low levels of retained austenite
regardless of system or shielding gas, and exhibit near-peak aging fol-
lowing treatment at 495 °C. While slightly higher hardness levels were
observed when the 3D Systems feedstock was processed under nitrogen,
all of the argon atomized feedstocks satisfy the standard wrought
hardness requirements [7] for this condition. When the same feedstock
was processed under the different atmospheres, slightly higher hardness
levels were observed for the builds processed under nitrogen.
As expected with overaging, the measured hardness levels in the
argon atomized powder feedstock builds decrease when aged at higher
temperatures. At both the 580 °C and 620 °C aging heat treatment
temperatures, the argon atomized materials consistently fell below the
minimum hardness values for wrought materials [7]. Although the
austenite fraction in the as-built materials was lower than the feedstock,
the austenite levels increased after aging, as shown in Table 4,
S.D. Meredith et al. Materials Science & Engineering A 738 (2018) 44–56

Table 4
Measured percentages of retained austenite for the powder feedstock, as-built material, and after various
post-processing steps.

indicating that reverted austenite formed.
The nitrogen atomized feedstock processed in the 3D Systems ProX
200, also shown in Fig. 5(a), generally met the hardness requirements
for the three aging temperatures [7]. Following the near-peak aging
heat treatment at 495 °C, similar hardness levels to those obtained with
the argon atomized feedstocks are observed, and the use of a nitrogen
shielding gas also results in slightly higher hardness values. For the
overaging treatments at temperatures of 580 °C and 620 °C, the builds
fabricated using the nitrogen atomized feedstocks also easily met the
minimum hardness values defined by the wrought standard [7]. An
increase in the hardness values is observed in the builds aged at 620 °C,
representing an unexpected deviation from the typical over-aging re-
sponse but generally still satisfied the acceptable range of hardness
values.
Deviations from the expected heat treat response of the as-built
material are most pronounced in the nitrogen atomized feedstock builds
fabricated on the EOS M280. While the argon atomized feedstock
processed in this system displays a similar aging response as the cor-
responding builds processed in the 3D Systems machine, the highly
austenitic material builds display the opposite behavior. As shown in
Fig. 5(b), the nitrogen atomized powder feedstock builds showed no
change in the as-built hardness value following the 495 °C aging
treatment. However, the hardness values began to increase as the aging
temperatures increased, with the highest hardness values observed after
aging at a temperature of 620 °C. This behavior can be connected, in
part, to the high levels of retained austenite in these builds, which
decrease as the aging temperature is increased. In the as-built condi-
tion, the retained austenite level is measured to be 81%, which in-
creases to 87% after aging at 495 °C and decreases to 40% after aging at
620 °C.
Since these builds were subjected to aging heat treatments without a
prior solutionizing heat treatment, the as-built microstructure, which
was dominated by the rapid solidification conditions prominent in the
PBF process, governed the aging response. The solutionizing heat

Fig. 5. Comparison of Vickers microhardness measurements made on materials aged directly from the as-built condition processed in the (a) 3D Systems ProX 200
and (b) EOS M280 system. The minimum and maximum specified hardness values for wrought materials shown as bars at each aging temperature [7].

50
S.D. Meredith et al.
Fig. 6. Summary of Vickers microhardness measurements for variations in solutionizing times on materials fabricated on the (a) 3D Systems ProX 200 and (b) EOS
M280 processing systems. The maximum specified hardness for solutionized wrought material is shown by the bar [7].
treatment, however, is designed to minimize this variation in the
starting microstructure prior to the aging heat treatment. While 30 min
at 1040 °C is the minimum recommendation [48], it is not clear whe-
ther this time frame is sufficient to adequately solutionize the as-built
microstructure prior to aging. In order to evaluate the impact of the
duration of the solutionizing heat treatment, times between 15 and
90 min at a temperature of 1040 °C were then investigated to determine
if the difference between a thermo-mechanically processed micro-
structure and an AM as-built microstructure is significant.
The impact of changing solutionizing times on the hardness of these
AM specimens is shown in Fig. 6(a) and (b) for builds fabricated in the
3D Systems ProX 200 and EOS M280 systems, respectively. Measure-
ments of the retained austenite fractions were also performed and are
summarized in Table 4. Similar to the as-built condition, the hardness
values generally fall below the specified limit for solutionized wrought
materials [7]. In the case of the argon atomized feedstocks, little to no
retained austenite was measured in the solutionized material, and the
retained austenite levels in the as-built nitrogen atomized material also
decreased. Among the fully martensitic components (< 5% FCC), in-
creased nitrogen and carbon content corresponded to higher hardness
values. For these materials, duration of the solutionizing heat treatment
had no meaningful impact on the hardness measurements, and there-
fore a 30 min solutionizing time was maintained. However, the nitrogen
atomized feedstock processed on the EOS M280 system, which had the
highest nitrogen concentration and Nieq value, still retained more than
20% austenite and exhibited a shift at longer solutionizing times.
The impact of a solutionizing heat treatment on the aging response
of builds fabricated from these four powder feedstocks was then in-
vestigated. Microstructures obtained after this combined solutionizing
and aging heat treatments for the four powder feedstocks fabricated
under nitrogen are shown in Fig. 7. The corresponding hardness values
compared to the wrought specifications for these different heat treat-
ments are illustrated in Fig. 8(a) and (b) for the respective processing
systems. Overall, the materials fabricated on the 3D Systems ProX 200
from the argon and nitrogen atomized feedstocks, meet the wrought
specifications for each heat treatment [7], as shown in Fig. 8(a). While
the argon and nitrogen atomized feedstocks have minimal amounts of
retained austenite when processed under argon, the same material
shows increasing levels of retained austenite when processed with a
nitrogen shielding gas. These higher nitrogen levels also consistently
produce higher hardness levels across all of the heat treatment tem-
peratures.
On the other hand, the materials fabricated from the argon and
nitrogen atomized feedstocks in the EOS M280 system displayed op-
posite behaviors, as observed when aged directly from the as-built
condition. As shown in Fig. 8(b), the material fabricated from the argon
atomized feedstock met the wrought specifications for hardness across
the range of aging heat treatments [7]. The material fabricated from the
51
Materials Science & Engineering A 738 (2018) 44–56
nitrogen atomized feedstock, however, displayed an inverse trend, with
the hardness values increasing as the aging temperature increased.
After the significant decline in retained austenite following the solution
heat treatment, the retained austenite fractions measured after the
different aging heat treatments remained relatively unchanged.
Since the hardness values were continuing to increase for the ni-
trogen atomized feedstock, it could be deduced that the material is still
in an underaged condition. In order to identify the peak aging condi-
tions, a range of higher temperatures were investigated for the mate-
rials fabricated from the nitrogen atomized feedstocks on the EOS M280
system. Non-standard aging heat treatments up to 760 °C were used to
monitor the continued aging response by the hardness and retained
austenite levels. Solutionizing times of both 30 min and 60 min were
tested to determine whether the longer duration would impact the
aging response. As shown in Fig. 9, increasing aging temperatures up to
approximately 680 °C produces an increase in hardness levels, with the
hardness at 680 °C producing a peak aged condition which meets the
general wrought specification for the standard H900 heat treatment
(1 h at 482 °C)[7]. Aside from an initial increase in hardness at the
lower temperatures, the longer solutionizing time had minimal impact
on the resulting aging behavior. Even with this shift to higher tem-
peratures, the retained austenite levels nevertheless remained around
20% and did not significantly change.
3.4. Role of composition on phase equilibrium
Differences in the heat treat responses for the different materials can
be correlated with the composition of the powder feedstocks. Each of
the alloying elements influence the evolution of the microstructure;
however, some elements, particularly nitrogen, have a much larger
effect on phase equilibrium. The selection of argon and nitrogen ato-
mization gases has the greatest impact on the nitrogen concentration in
the powder feedstock, with nitrogen levels an order of magnitude
higher in the nitrogen atomized feedstock than in the argon atomized
feedstock. Since the nitrogen concentration is not specified in the
wrought condition, it can vary widely, as demonstrated in the measured
nitrogen compositions of these four powder feedstocks summarized in
Table 1.
These changes in chemistry can then lead to variations in the phase
regions and solidification behavior for each of the powder feedstocks.
As shown in the Schaeffler diagram in Fig. 3, the Nieq and Creq values
for the highly austenitic nitrogen atomized feedstock used in the EOS
M280 system place it outside the delineated region representing the
wrought specification [7,41,42]. However, the powder feedstocks that
fall within this range display heat treatment responses much closer to
that expected for the wrought material. While the impact of these
compositions on the solidification can be captured here, the role that
changes in composition play on the phase equilibrium and resulting
S.D. Meredith et al.
heat treat response can be further explored.
Point calculations were used to determine the mass fraction of each
phase and then plotted as a function of temperature for the chemistries
for each system and atomization condition. Liquid, austenite, ferrite,
carbides/nitrides, and Cu phases were all considered in the calcula-
tions. For both systems, the amount of carbon and nitrogen in the
powder feedstock is higher for the nitrogen atomized conditions. As a
result, the mass fractions of carbides and nitrides in the nitrogen ato-
mized feedstock is higher than in the argon atomized feedstock, and
their phase regions also extend to higher temperatures. However, the
combined mass fraction of all carbides and nitrides is very small, in-
dicating that these phases have little to no effects on austenite and
ferrite equilibrium. Additionally, the changes in powder chemistries for
all conditions have little effect on the Cu-phase equilibrium as the mass
fractions and temperature ranges show negligible changes.
Fig. 8. Summary of Vickers microhardness measurements for as-built materials subjected to a two-stage solutionizing and aging heat treatment fabricated on the (a)
3D Systems ProX 200 and (b) EOS M280 processing systems. The minimum and maximum specified hardness values for wrought materials shown as bars at each
aging temperature [7].
52
Materials Science & Engineering A 738 (2018) 44–56
Fig. 7. Microstructures following a two-stage
heat treatment of builds fabricated from each
of the feedstocks under a nitrogen atmosphere,
consisting of a 30 min solutionization plus
aged 4 h at the specified temperature, (a) argon
atomized for ProX 200, aged @495 °C; (b) ni-
trogen atomized for ProX 200, aged @495 °C;
(c) argon atomized for EOS M280, aged @
495 °C; and (d) nitrogen atomized for EOS
M280, aged @680 °C.
Fig. 10(a) and (b) show the equilibrium phases for the argon and
nitrogen atomized feedstock chemistries fabricated on the EOS M280
system. Table 5 provides a summary of the temperature boundaries for
the phase regions calculated for each of the powder feedstock compo-
sitions. Overall, the impact of the differences in chemistry between the
nitrogen and argon atomized powder feedstocks is significant. While
the argon atomized feedstock solidifies first as ferrite and continues to
austenite, the first phase to solidify in the nitrogen atomized feedstock
is austenite, with no ferrite appearing until a temperature of approxi-
mately 700 °C. When elemental segregation is taken into account during
solidification, the nitrogen atomized feedstock is fully austenitic com-
pared to just 35% austenite in the argon atomized material as the last
liquid solidifies under Scheil conditions. The change in chemistry be-
tween the nitrogen and argon atomized powder feedstocks also im-
pacted the temperature ranges for the liquidus and solidus regions as
S.D. Meredith et al.
Fig. 9. Summary of Vickers microhardness measurements on as-built materials
subjected to a combined solutionizing and aging heat treatment for nitrogen
atomized feedstocks processed in the EOS M280 system. The minimum and
maximum specified hardness values for the peak aged H900 heat treatment for
wrought materials shown as dashed bars [7].
Fig. 10. Plots showing the phase stability over the solid and liquid regions for
the (a) argon atomized feedstock and (b) nitrogen atomized feedstock materials
fabricated in the EOS M280 system.
well as the solid state austenite and ferrite phase fields.
Changes in the phase regions for the argon and nitrogen atomized
powder feedstocks fabricated on the 3D Systems ProX 200 system,
however, are much less pronounced. As shown in Fig. 11(a) and (b), the
change in atomization conditions and nitrogen concentrations do not
significantly impact the primary phase regions for the austenite and
ferrite phases. Upon Scheil solidification, the solid fraction of austenite
for both atomization conditions is much more comparable than for the
53
Materials Science & Engineering A 738 (2018) 44–56
EOS M280 feedstock chemistries. In addition, the changes in the tem-
peratures, as summarized in Table 5, are much lower than those ob-
served for the powder feedstocks used in the EOS M280 system.
In addition to the impact of these composition changes on the phase
regions for the primary phases, there is also a rather significant impact
on the martensite start (Ms) temperatures. In general, lower values of Ms
that approach room temperature signify that the martensite transfor-
mation is less likely to complete, resulting in higher fractions of re-
tained austenite. The Ms temperature for the different powder feed-
stocks is often experimentally determined using a linear combination of
alloying elements in the following form:
Ms = k 0 + ki (wt %i) (4)
i
where k0 is a positive constant and ki are coefficients that highlight the
effect of each alloying element on martensite formation. The de-
termined ki coefficients for interstitial elements like C and N are often
an order of magnitude larger than those for common substitutional
elements such as Cr, Ni, Mo, and Mn [50]. The accuracy of these em-
pirical approaches often suffers when extending the relations to wider
ranges of chemical compositions, and some important elements are
often not investigated. Thermodynamic approaches are more favorable
since they allow for more versatility over larger ranges of chemical
composition and do not treat each element exclusively as an austenite
or ferrite stabilizer [51]. In these calculations, the Ms temperature is
defined as the temperature at which the difference between the Gibbs
free energy of the austenite and ferrite phases reaches a critical value
for martensite nucleation [52]. The calculations are performed for the
austenite composition, removing the possibility of secondary phases
impacting the martensite transformation from the austenite parent
phase. Although previous work has shown larger prior austenite grain
size to favor higher Ms temperatures [50], the calculations do not take
this effect into account.
Fig. 12 illustrates how the Ms temperature changes with both the
composition of the as-built material and the nitrogen concentration.
Each curve on the plot represents the composition measured for each of
the six builds, with the actual nitrogen concentration marked, and
clearly reveals the role of chemistry on the Ms temperature. Even dis-
regarding differences in nitrogen concentration, the variation in com-
positions within the different components results in a change of nearly
60 °C in the Ms temperature. When changes in nitrogen concentration
are taken into account, the disparities between the predicted Ms tem-
perature become amplified. The highest projected Ms temperatures
corresponds to the builds with the lowest nitrogen concentrations and
retained austenite measurements, while the Ms temperature for the
components with the highest nitrogen concentrations and retained
austenite levels is estimated to be nearly 100 °C lower.
4. Summary and conclusions
The heat treatment response of AM PBF 17–4 PH grade stainless
steels has been shown to deviate from standard wrought heat treatment
practices. These variations in the heat treat response have been corre-
lated with changes in the composition of the powder feedstock, which
can be further connected with the gas atomization conditions. As-built
material fabricated using argon and nitrogen atomized feedstocks in
different PBF systems has been subjected to a series of post process heat
treatment cycles, including aging directly from the as-built condition
and following an initial solutionizing heat treatment. AM material
fabricated from argon atomized feedstocks, which contained 0.01 wt%
nitrogen and retained austenite levels < 1%, displayed heat treatment
responses most closely resembling those expected in wrought materials.
In contrast, nitrogen atomized feedstocks, containing 0.12 wt% ni-
trogen and up to 81% retained austenite significantly deviate from
standard wrought heat treatment responses. For these highly austenitic
components, the observed peak aging temperature increases from
S.D. Meredith et al. Materials Science & Engineering A 738 (2018) 44–56

Table 5
Summary of calculated equilibrium phase regions and volume fractions during Scheil solidification for the four powder feedstock chemistries.
3D Systems ProX 200 EOS M280

Ar atomized N2 atomized Ar atomized N2 atomized

Equilibrium calculations
Liquidus temperature (°C) 1453 1441 1444 1429
Solidus temperature (°C) 1384 1362 1367 1367
Austenite region(s) (°C) 1399–501, Below 431 Below 1398 1409–519, Below 405 Below 1429
Ferrite region(s) (°C) 1453–1104, Below 800 1441–1184, Below 765 1444–1202, Below 781 Below 695
Cu phase formation temperature (°C) 944 986 994 1027
Scheil solidification calculations
Solidification range (°C) 1453–1225 1441–1225 1444–1230 1429–1245
Volume fractions (Ferrite/Austenite) 0.80/0.19 0.67/0.32 0.64/0.35 0.004/0.99

Fig. 12. Calculated martensite start temperature as a function of weight percent

nitrogen for each build composition.

equivalence, increasing from 5 wt% for the argon atomized feed-

stocks to levels above 10 wt%, thus promoting higher levels of re-
tained austenite in the powder feedstocks.
• A decrease in the measured retained austenite when moving from
the powder feedstock to the as-built microstructure was observed for
all conditions. The retained austenite levels for both argon atomized
powder feedstocks approached zero, regardless of production
system or shielding gas. However, higher austenite levels, reaching
levels of 81% for the nitrogen atomized feedstocks, were observed in
materials with higher concentrations of austenite-stabilizing ele-
ments, which was primarily dictated by the feedstock composition
and only marginally influenced by the choice of shielding gas.

Fig. 11. Plots showing the phase stability over the solid and liquid regions for
• Increased levels of retained austenite impede the normal overaged
heat treat response. The AM components fabricated from low aus-
the (a) argon atomized feedstock and (b) nitrogen atomized feedstock materials tenite feedstocks followed the expected trend of declining hardness
fabricated in the 3D Systems ProX 200 system.
values as the material was overaged at increasing temperatures.
Although partially austenitic AM specimens responded normally at
482 °C to temperatures nearing 680 °C. An analysis of the role of com- low overaging temperatures, hardness deviated from the trend and
position has shown that increasing levels of nitrogen leads to higher increased at higher temperatures.
levels of retained austenite, causing the phase regions in the alloys to be
shifted and a decrease in the Ms temperature. The combination of these
• Highly austenitic material with retained austenite levels ap-
proaching 22% actually exhibited its lowest hardness values for heat
effects causes the heat treatment response in these AM components to treatments closest to the conventional peak age condition for 17–4
deviate from the expected wrought conditions. The primary conclusions PH grade stainless steel. For the material fabricated from the ni-
in this work are provided below: trogen atomized powder processed under nitrogen, the peak aged
condition was not achieved until 4 h at 680 °C.
• The atomization condition plays a prominent role in altering the
nitrogen concentration in 17–4 PH grade stainless steel powder
feedstocks. Argon atomized feedstocks contained approximately
• Changes in composition, particularly of nitrogen originating from
the atomization gas, influence the phase equilibrium, even though
0.01 wt% N, while the nitrogen concentration in the nitrogen ato- the compositions remain within specified ranges. As more nitrogen
mized powders increased to levels between 0.06 and 0.12 wt%. is introduced, the temperature boundaries of the austenite phase
These higher nitrogen concentrations have a strong impact on nickel region significantly widens. A shift of nearly 100 °C in the

54
S.D. Meredith et al.
martensite start temperature is predicted between the builds with
the highest and lowest nickel equivalency values, which is heavily
influenced by nitrogen concentration.
Acknowledgements
The authors wish to thank the Office of Naval Research
Manufacturing Technology program and the Applied Research
Laboratory’s Institute for Manufacturing and Sustainment Technologies
which is funded under the Naval Sea Systems Command (NAVSEA),
United States, contract #N00024-12-D-6404 for funding this work, as
well as the resources of Penn State's Center for Innovative Materials
Processing through Direct Digital Deposition (CIMP-3D), where sample
fabrication was performed by Mr. J.J. Blecher of 3D Systems and Mr.
C.J. Dickman and Dr. K.C. Meinert. The authors also extend their gra-
titude to several individuals who provided significant contributions,
such as E.A. Good in metallographic specimen preparation, E.T. McHale
for contributing XRD scans, and N.J. Carrier for providing SEM of the
powders.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.msea.2018.09.066.
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