The Pennsylvania State University

The Graduate School

College of Earth and Mineral Sciences

IMPACT OF ATOMIZATION AND PROCESSING GAS ON THE HEAT TREATMENT

RESPONSE OF ADDITIVELY MANUFACTURED 17-4 PH STAINLESS STEEL

A Thesis in

Materials Science and Engineering

by

Scott D. Meredith

© 2018 Scott D. Meredith

Submitted in Partial Fulfillment

of the Requirements

for the Degree of

Master of Science

December 2018
The thesis of Scott D. Meredith was reviewed and approved* by the following:

Todd A. Palmer
Professor of Materials Science and Engineering
Professor of Engineering Science and Mechanics
Thesis Advisor

Allison M. Beese
Assistant Professor of Materials Science and Engineering

Reginald F. Hamilton
Associate Professor of Engineering Science and Mechanics

Jayme S. Keist
Research Associate of the Applied Research Laboratory at Penn State University
Special Signatory

Suzanne E. Mohney
Professor of Materials Science and Engineering and Electrical Engineering
Chair, Intercollege Graduate Degree Program in Materials Science and Engineering

* Signatures are on file in the Graduate School.

ii
 ABSTRACT

Precipitation hardened (PH) grade martensitic stainless steels are commonly used in additive
manufacturing (AM) processes. In order to obtain properties similar to their wrought
counterparts, post-processing solutionizing and aging heat treatments are required. Depending
on the powder feedstock composition, which can be varied by the choice of atomization gas and,
to a lesser extent, the processing gas during component fabrication, the post-process heat
treatment response can be significantly altered. When the standard heat treatment cycles
developed for wrought alloys are applied to as-deposited 17-4 PH grade stainless steel structures
fabricated from argon or nitrogen atomized powder feedstocks on different powder bed fusion
(PBF) systems, the AM components exhibited a difference response. Argon atomized feedstocks
contain approximately 0.01 wt.% nitrogen, possess low levels of retained austenite, and respond
as expected to standard solutionizing and aging heat treatment cycles. In contrast, 17-4 PH grade
stainless steel structures fabricated using nitrogen atomized feedstocks with higher nitrogen
levels (0.06 – 0.14 wt.%) and retained austenite levels (up to 81%) do not respond to standard
solutionizing and aging techniques. Peak aging at these high nitrogen levels occurs at a
temperature of approximately 680°C, which is significantly higher than the standard peak aging
heat treatment at 482°C.

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 TABLE OF CONTENTS

LIST OF FIGURES ....................................................................................................................... vi

LIST OF TABLES ....................................................................................................................... viii

ACKNOWLEDGEMENTS ........................................................................................................... ix

Chapter 1 INTRODUCTION.......................................................................................................... 1

1.1 Background ........................................................................................................................... 1

1.2 Motivation ............................................................................................................................. 4

1.3 Objectives .............................................................................................................................. 4

1.4 Overview ............................................................................................................................... 4

Chapter 2 LITERATURE REVIEW............................................................................................... 6

2.1 Impact of Alloying Elements ................................................................................................ 6

2.2 Impact of Austenite Retention on Precipitation Hardening .................................................. 7

2.3 Powder Bed Fusion of 17-4 PH Stainless Steel .................................................................... 7

Chapter 3 ANALYSIS OF POWDER FEEDSTOCKS ................................................................ 10

3.1 Powder Feedstock Characterization Methods ..................................................................... 10

3.2 Particle Morphology............................................................................................................ 12

3.3 Powder Flow Characteristics ............................................................................................... 15

3.4 Chemical Composition of the Powder Feedstocks .............................................................. 18

3.5 XRD Analysis of the Powder Feedstocks ........................................................................... 18

3.6 Summary and Conclusions .................................................................................................. 23

Chapter 4 ANALYSIS OF AS-BUILT MATERIAL ................................................................... 26

4.1 Additive Manufacturing via Powder Bed Fusion ................................................................ 26

4.2 Chemical Composition of Fabricated Structures ................................................................ 26

4.3 XRD Analysis of Fabricated Structures .............................................................................. 28

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 4.4 Computational Modeling of Phase Equilibria ..................................................................... 28

4.5 Estimation of Martensite Start Temperature ....................................................................... 29

4.6 Metallographic Analysis of Fabricated Structures .............................................................. 33

4.7 Summary and Conclusions .................................................................................................. 36

Chapter 5 ANALYSIS OF HEAT TREATED MATERIAL ....................................................... 38

5.1 Overview of Post-Fabrication Heat Treatments .................................................................. 38

5.2 Direct-Aging Heat Treatment.............................................................................................. 38

5.3 Two-stage Heat Treatment: Solutionizing Followed By Aging.......................................... 41

5.4 Determination of Peak-Aging for Highly Austenitic Material............................................ 45

5.5 Three-stage Heat Treatment: Homogenization + Solutionizing + Aging ........................... 47

5.6 Summary and Conclusions .................................................................................................. 50

Chapter 6 SUMMARY ................................................................................................................. 52

6.1 Primary Conclusions ........................................................................................................... 52

6.2 Potential Next Steps ............................................................................................................ 53

REFERENCES ............................................................................................................................. 54

v
 LIST OF FIGURES
Figure 1.1: Effect of cooling rate on ferrite/austenite boundaries of Schaeffler diagram [10]
(adapted from David et al. [15]), with martensitic regions maintained for reference; dashed box
indicates Creq and Nieq limits calculated per specified composition of 17-4 PH stainless steel [3] 3
Figure 3.1: Micrographs of the four feedstock powders, including (a) argon atomized for the 3D
Systems ProX 200, (b) nitrogen atomized for 3D Systems ProX 200, (c) argon atomized for
EOS M280, and (d) nitrogen atomized for EOS M280 ................................................................ 10
Figure 3.2: Qualitative depiction of convexity and circularity parameters relative to the ideal
value of unity ................................................................................................................................ 11
Figure 3.3: Volume-based Particle Size Distribution of the powder feedstocks, as measured by
light-scattering (dashed line) and image analysis (solid line), for (a) ProX 200 and (b) EOS M280
....................................................................................................................................................... 14
Figure 3.4: Image analysis results for the four powder feedstocks showing distributions of (a)
convexity ratio and (b) circularity ratio ........................................................................................ 15
Figure 3.5: Accumulated charge versus time as measured by the REVOLUTION powder
analyzer when powder is in contact with (a) glass or (b) polycarbonate ...................................... 17
Figure 3.6: Comparison of XRD diffraction patterns of 3D Systems nitrogen atomized powder
when scanned with or without a monochromator, both before and after software corrections .... 21
Figure 3.7: XRD patterns for AM 17-4 PH (a) feedstock and (b) in the as-built condition ......... 24
Figure 4.1: Balmforth diagram [50] showing the standard chemical composition [3] for 17-4 PH
stainless steel (delineated by a dashed box), as well as the position of the six AM builds,
overlayed on a subset of the Schaeffler diagram [10]................................................................... 27
Figure 4.2: Equilibrium phase composition calculated as a function of temperature from the 3D
Systems ProX 200 powder chemistries for (a) argon atomized and (b) nitrogen atomized
feedstocks ...................................................................................................................................... 30
Figure 4.3: Equilibrium phase composition calculated as a function of temperature from the EOS
M280 powder chemistries for (a) argon atomized and (b) nitrogen atomized feedstocks ............ 31
Figure 4.4: Simulated martensite start temperature as a function of nitrogen weight percent for
each build composition ................................................................................................................. 33
Figure 4.5: As-Built microstructures from (a) argon atomized feedstock for the 3D Systems ProX
200 processed under Ar atmosphere or (b) N2 atmosphere; (c) argon atomized feedstock for EOS

vi
M280 (N2 atmosphere); (d) nitrogen atomized feedstock for the ProX 200 processed under Ar
atmosphere or (e) N2 atmosphere; (f) nitrogen atomized feedstock for EOS M280 (N 2
atmosphere) ................................................................................................................................... 35
Figure 4.6: EDS maps showing no observable elemental segregation for builds fabricated on the
EOS M280 system from (a) argon atomized powder or (b) nitrogen atomized powder .............. 36
Figure 5.1: Schematic of various heat treatment cycles, including (a) solutionizing for different
durations, (b) aging directly from the as-built condition, (c) a two-stage heat treatment, and
three-stage processes for which post-solution specimens were either (d) air-cooled or (e) water-
quenched ....................................................................................................................................... 39
Figure 5.2: Vickers hardness measurements compared to specification range for standard
wrought materials when aged for 4 hours directly from the as-built condition for (a) 3D Systems
ProX 200 and (b) EOS M280 system ........................................................................................... 40
Figure 5.3: Vickers hardness measurements following solutionizing at 1040°C for different
durations, as compared to specified maximum for standard wrought materials, for (a) 3D
Systems ProX 200 and (b) EOS M280 system ............................................................................. 43
Figure 5.4: Vickers hardness measurements compared to specification range for standard
wrought materials following two-stage heat treatment consisting of 30-min solutionization
followed by 4-hour aging for (a) 3D Systems ProX 200 and (b) EOS M280 system .................. 44
Figure 5.5: Elemental segregation of chromium and nickel observed in argon atomized material
processed on the EOS M280, after solutionizing followed by aging at 620°C ............................ 45
Figure 5.6: Vickers hardness measurements of highly austenitic feedstock fabricated under
nitrogen, then solutionized for either 30 or 60 min followed by 4-hour aging, with specified
hardness range for H900 peak age condition [3] indicated by brackets ....................................... 46
Figure 5.7: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on 3D Systems ProX 200 ... 48
Figure 5.8: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on EOS M280 .................... 49
Figure 5.9: Comparison of austenite volume fraction and Vickers microhardness of highly
austenitic feedstock fabricated on EOS M280, subjected to three-stage heat treatments ............. 49

vii
 LIST OF TABLES
Table 2.1: Limited chronology of previous work involving 17-4 PH stainless steel fabricated by
powder bed fusion ........................................................................................................................... 8
Table 3.1: Powder characterization data, including morphological and flow properties ............. 13
Table 3.2: REVOLUTION powder analyzer dynamic flowability results ................................... 16
Table 3.3: Chemical compositions of powder feedstocks and fabricated builds, with
corresponding austenite volume fractions .................................................................................... 19
Table 3.4: Ni equivalent and Cr equivalent weight fractions per Balmforth constitution diagram
as calculated from chemical compositions for each feedstock and AM build, as well as volume
fraction of retained austenite as measured by XRD...................................................................... 20
Table 3.5: Summary of parameters used to analyze x-ray diffraction data for determination of
retained austenite volume fractions .............................................................................................. 22
Table 4.1: Summary of phase equilibrium temperatures and Scheil solidification calculations
computed from the chemical compositions of the four powder feedstocks.................................. 32
Table 5.1: Comparison of austenite volume fraction and Vickers microhardness after 4-hour
aging directly from the as-built condition..................................................................................... 40
Table 5.2: Comparison of austenite volume fraction and Vickers microhardness after
solutionizing at 1040°C for different durations ............................................................................ 43
Table 5.3: Comparison of austenite volume fraction and Vickers microhardness after 30-min
solutionizing heat treatment at 1040°C followed by 4-hour aging; fabricated on 3D Systems
ProX 200 ....................................................................................................................................... 44
Table 5.4: Comparison of austenite volume fraction and Vickers microhardness for various 4-
hour aging heat treatments following a 30-min or 60-min solutionizing step for nitrogen
atomized material processed on the EOS M280 system ............................................................... 46
Table 5.5: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on 3D Systems ProX 200 ... 48
Table 5.6: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on EOS M280 .................... 50

viii
 ACKNOWLEDGEMENTS

I wish to extend my sincerest gratitude to my advisor, Dr. Todd A. Palmer, for allowing
me this opportunity to resume my education in a new field. The patience, guidance, and wisdom
provided by both Dr. Palmer and Dr. Jay Keist were invaluable in developing my fundamental
understanding of metallurgy and materials science. As a member of TeamTAP, it was my great
privilege to collaborate with and learn from my fellow group members: Zakariya Khayat,
Marissa Brennan, and Andrew Iams. Their diligence, positivity, and thoughtfulness represented
a constant source of inspiration as well as a target for aspiration.

I also wish to acknowledge some of the many individuals who assisted me these past few
years. I am immensely grateful for the contribution of James Zuback, whose thermodynamic
modeling greatly enhanced the results of this study. Thank you to my thesis committee
members, Dr. Allison Beese and Dr. Reginald Hamilton, who have been gracious in sharing not
only their knowledge, but also access to their groups’ resources! Thank you to the incredible
personnel affiliated with Penn State’s Center for Innovative Materials Processing through Direct
Digital Deposition (CIMP-3D), including Barbra Belko, Ed Good, Jay Tressler, Griffin Jones,
Corey Dickman, Dr. Ken Meinert, and Jared Blecher of 3D Systems, Inc. Thanks to Julie
Anderson, Nichole Wonderling, and Gino Tambourine for their tremendous patience as they
initiated new users like myself to the equipment at the Materials Characterization Lab.
Additional thanks go to Nicholas Carrier for providing SEM of the powders and Evan McHale
for contributing some of the XRD scans.

I will forever be indebted to my family and friends for their unwavering support and
encouragement. In addition, I’d like to express appreciation to my former colleagues Andrew
Albanese, Roland Roberge, Greg Smith, Joe Pellock, Gene Mancini, Charles Hinchman, Edward
Bommarito, and Gary Johnson for their mentorship and contributions toward my personal and
professional development.

Finally, financial support from the Cross Platform System Development (CPSD) program
and Naval Sea Systems Command (NAVSEA) contract #N00024-12-D-6404 is gratefully
recognized.

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 Chapter 1
INTRODUCTION
1.1 Background
Precipitation-hardened (PH) martensitic grade stainless steels are widely used in
aerospace, marine, chemical, food processing, power generation, and paper industries. [1,2] In
addition to the hard martensitic matrix, strengthening is derived through the formation of sub-
micron copper-rich precipitates during post-process aging heat treatments. The temperature and
duration of these heat treatments, which follow a solutionizing heat treatment, can be adjusted to
produce a range of strength levels. [3] In the peak-aged or H900 condition (1 hr, 482°C) [3], the
elliptical Cu-rich precipitates are approximately 25 nm in length. [4] As the material is aged at
higher temperatures or longer times, a minimization of surface energy leads to Ostwald ripening
and an increase in the size of the precipitates. [5] The diminishing number of precipitates, loss
of coherency with the matrix, and tempering of the martensitic matrix during these overaging
cycles causes a decline in mechanical strength but an improvement in other properties such as
ductility and impact toughness. [2]

The weldability of the 17-4 PH alloy system makes it an excellent candidate for additive
manufacturing (AM) processes. [6] Unlike alloys that initially solidify as austenite (A or AF),
the primary ferritic solidification mode (F) of 17-4 PH stainless steel [7,8] increases its resistance
to welding issues such as solidification cracking. [9] Various diagrams have been developed to
predict the solidification mode as a function of composition. For example, the Schaeffler
diagram [10] determines chromium and nickel equivalents using the following relationships (all
concentrations in weight percent):

Creq (wt.%) = [Cr] + [Mo] + 1.5×[Si] + 0.5×[Nb] (1)

Nieq (wt.%) = [Ni] + 30×[C] + 0.5×[Mn] (2)

Vulnerability to solidification cracking has been shown to increase sharply as the

Creq/Nieq ratio falls below a critically low level [9,11] approximated in the range of 1.49 to 1.84
[11–13]. Applying the Schaeffler equations to the specified chemical composition of UNS
S17400 grade stainless steel [3] yields a Cr/Ni equivalency ratio in the range of 2.0 to 6.4,
sufficiently above this threshold. Although higher Creq/Nieq values can also increase

1
susceptibility to solidification cracking [9,11], the F solidification mode still remains superior to
a primarily austenitic solidification mode. [9]

In addition to chemistry, microstructural development can also be influenced by cooling

rate. [14–17] For example, rapid solidification techniques such as splat quenching [14], laser
welding [14,15], and electron beam melting [16] have all produced results that are inconsistent
with the Schaeffler diagram. Though Ni-rich alloys (Ni eq >19) maintained a fully austenitic (A)
solidification mode, different ferrite levels as a function of cooling rate were observed for alloys
with Creq/Nieq ≥1.4 by altering the scanning speed [14–16] or power level [15] of the energy
beam. While alloys within the austenite-ferrite region may exhibit a duplex solidification mode
(AF or FA) at slow to moderate cooling rates, compositions near the single-phase boundaries
were more likely to exhibit single phase solidification modes (A or F) at rapid cooling rates. [14–
16] The proposed mobility of the austenite-ferrite boundaries within the Schaeffler diagram as
function of cooling rates estimated by calculation is depicted in Figure 1.1. [15]

The rapid scanning rates of high energy sources like those associated with additive
manufacturing generally lead to a refined grain structure. [18] Powder bed fusion (PBF) systems
in particular employ rapid scanning rates along narrow melt pools corresponding to high cooling
rates. [17] Fine austenite grains (< 20 µm in size) have been shown to inhibit martensitic
transformation [19,20], contributing to higher austenite retention.

The cooling rate for austenitic stainless steel in a laser powder bed fusion (PBF) process
has been reported to be on the order of 105 to 106 K/s. [21] Cooling rates of this magnitude are
also comparable to production of 17-4 PH powder feedstocks via gas atomization, with rates
increasing to 107 K/s for particle diameters smaller than 10 microns. [22] During gas
atomization, a high velocity gas is directed into a superheated molten stream of the alloy to
disintegrate it into fine droplets, which then minimize surface energy by reforming into spheres
prior to solidification. [23]

While nitrogen is a less expensive atomization gas than argon, its impact on alloy
chemistry must also be considered. Due to the strong austenite stabilizing effect of nitrogen
[24], moderate changes can have a profound impact on the microstructural constituents of 17-4
PH stainless steel. The combination of residual nitrogen from gas atomized feedstocks with the
refined grain structure yielded by the PBF process promotes higher levels of retained austenite.

2
Figure 1.1: Effect of cooling rate on ferrite/austenite boundaries of Schaeffler diagram [10]
(adapted from David et al. [15]), with martensitic regions maintained for reference; dashed box
indicates Creq and Nieq limits calculated per specified composition of 17-4 PH stainless steel [3]

3
As will be discussed in subsequent chapters, these variations in austenite retention affect the heat
treatment response of AM 17-4 PH stainless steel.

1.2 Motivation
Variations in feedstock chemical composition, in conjunction with the rapid cooling
associated with PBF processes, produce microstructures that differ from conventional wrought
material. Although nitrogen concentration can be influenced by the choice of atomizing gas,
ASTM standards for the 17-4 PH stainless steel grade currently do not include a specification for
nitrogen content. The purpose of this work is to show how solidification pathways are
influenced by composition, highlight the strong austenite-stabilizing effect of nitrogen, and
understand how these variations impact the overaged heat treatment response of the alloy.

1.3 Objectives
Four powder feedstocks representing a range of chemical compositions were additively
manufactured under either a nitrogen or argon atmosphere, and then subjected to a series of post-
process heat treatments to achieve the following goals:

 To illustrate how chemical composition, particularly nitrogen, impacts the amount

of retained austenite within additively manufactured 17-4 PH stainless steels
 To investigate how variations in austenite levels influence the hardening response
of the alloy through a series of overaging heat treatments
 To demonstrate the effect of homogenization and solutionizing heat treatments on
the overage response
 To identify a potential heat treatment path that achieves the peak-aged condition
in highly austenitic AM components of 17-4 PH stainless steel

1.4 Overview
The body of this work is divided into six chapters.

The purpose of Chapter 1 is to provide an introductory background on the topic and

convey the scope of the work.

Chapter 2 provides a review of previous studies involving the powder bed fusion of 17-4
PH stainless steel and subsequent post-processing heat treatments.

4
 In Chapter 3, the four powder feedstocks acquired for this study are compared on the
basis of particle morphology, flowability, chemistry, as well as the proportions of primary phases
present.

Chapter 4 focuses on the as-built condition of the additively manufactured components,

relating theoretical modeling of solidification and phase transformations to the respective
chemical compositions and measured phases.

Chapter 5 presents the impact of various post-processed heat treatment paths, including
single stage (aging directly from the fabricated condition), two-stage (solutionization followed
by aging), and three-stage heat treatments (addition of an initial homogenization step).

Finally, Chapter 6 summarizes the work by highlighting the primary conclusions and
discussing potential future work.

5
 Chapter 2
LITERATURE REVIEW
2.1 Impact of Alloying Elements
The selection of atomization gas can affect the nitrogen content of the powder feedstock.
However, the solubility of nitrogen in ferrous alloys depends upon the temperature of the melt as
well as its composition. [25] Certain elements (Ni, C, P, Si, S) reduce nitrogen solubility
whereas a combination of chromium and manganese increases it. [25–28]

While elements like carbon and nitrogen strongly favor austenite retention [28], the
interaction between chromium and manganese is more complicated. At very low concentrations,
such as that found in 17-4 PH stainless steel, manganese is also a slight austenitizer. [29]
However, the austenite stabilizing ability of manganese diminishes as the concentration increases
to the 5-8 % range [29], and actually becomes a ferrite stabilizer above 12 % [27], while also
increasing the ferrite-stabilizing effect of chromium. [30] Conversely, as chromium content
increases to 18-23%, manganese can become a ferrite stabilizer at concentrations as low as
0.5wt.%. [29,31] Therefore, the impact of manganese is partially determined by the chromium
content. Another important effect of chromium is that it promotes martensitic transformation by
lowering the stacking fault energy. [32]

While the Schaeffler constitution diagram [10] serves as a guide to predict solidification,
a well-known deficiency is that it does not account for the strong austenite-stabilizing effect of
nitrogen. Many alternative equivalency equations have been proposed over time, such as those
developed in 2000 for the ferritic-martensitic region (applicable to Ni eq values up to 8) using a
conventional arc welding process, with the weight factors shown in equations (3) and (4):

Creq (wt.%) = [Cr] + 2×[Mo] + 10×[Al] + 10×[Ti] (3)

Nieq (wt.%) = [Ni] + 35×[C] + 20×[N] (4)

Equation (4) demonstrates the strong impact of nitrogen on nickel equivalency, yet no
range for nitrogen is listed among the specified chemical composition for 17-4 PH stainless steel.
[3,33] Therefore, any manufactured lot that otherwise satisfies the alloy’s chemical requirements
could possess higher than expected nickel equivalency values.

6
2.2 Impact of Austenite Retention on Precipitation Hardening
In addition to being softer than martensite [34], higher levels of retained austenite impact
the precipitation kinetics in 17-4 PH grade stainless steel. [35] The primary precipitating
species, copper, has a much higher solubility and lower diffusivity in austenite compared to
ferrite, so increased levels of austenite disrupts the normal heat treat response. [35–37] Peak
aging can still be achieved in the presence of significant amounts of retained austenite, but higher
temperatures are required for sufficient diffusion to occur.

2.3 Powder Bed Fusion of 17-4 PH Stainless Steel

Table 2.1 presents a limited summary of previous studies involving 17-4 PH stainless
steel fabricated via powder bed fusion. Some of the earliest observations of high levels of
retained austenite associated with additively manufactured 17-4 PH stainless steel were
published in 2010. [38,39] While Facchini et al. [38] attributed the 72% austenite to the rapid
cooling rates, Averyanova et al. [39] noted the impact of chemical composition by comparing
powders with different nickel and chromium contents. However, neither commented on the role
of nitrogen.

The impact of nitrogen would be revealed in contemporaneous studies around 2012,

which varied the gas used in the atomization of the feedstock and the PBF atmosphere between
argon or nitrogen. [34,40] While the majority of the builds of the test matrix resulted in the
conventional martensitic structure, in both cases the combination of a nitrogen atomized powder
processed under a nitrogen atmosphere (henceforth abbreviated as N 2/N2) was found to be more
austenitic. Both studies also noted phase disparities in the feedstock itself, with the argon
atomized powder being martensitic while the nitrogen atomized powder consisted of primarily
austenite, with Starr et al. [40] reporting that the latter contained five times the nitrogen content,
but the concentrations of other alloying elements were not revealed. Following an H900 peak-
aging heat treatment (482°C for 1 hr) [3] directly from the as-built condition, Murr et al. [34]
observed an increase in hardness for the martensitic builds, but the N 2/N2 condition exhibited
little change in hardness upon aging.

In 2014, Rafi et al [7] similarly observed a higher proportion of retained austenite in the
as-built product when nitrogen atomized material was processed under nitrogen versus
argon. Although an initial heat treatment (788°C, 2 h) raised the yield strength and ultimate

7
 Table 2.1: Limited chronology of previous work involving 17-4 PH stainless steel fabricated by powder bed fusion

Feedstock AM Reported
Heat Treatment(s)
Atomization Shield Gas Chemistry

2010, Facchini et al. [38] Ar Ar N not reported • stress-relief (SR) only

2010, Averyanova et al.[39] (gas) Ar N, Mo not reported [none]

2012, Murr et al. [34] Ar vs N2 Ar vs N2 ranges reported • peak-aging (1h, 482°C)

2012, Starr et al. [40] Ar vs N2 Ar vs N2 only N, O reported • SR (650°C) vs SR (788°C)

2014, Rafi et al. [36] N2 N2 only N reported • SR (650°C) vs SR (788°C)

• SR (788°C) + peak-aging (1h, 482°C)

2015, Cheruvathur et al. [41] N2 N2 N not reported1 • SR (650°C) vs solutionizing (1h, 1050°C) vs
(2017, Stoudt et al. [42]) homogenization (2h, 1150°C)
• homogenization + solutionizing (0.5h, 1050°C)

2015, LeBrun et al. [37] Water N2 N, Mo not reported • aging (1h, 482°C; 4h, 550°C; 4h, 620°C)
• solutionizing (0.5h, 1040°C) + aging
(1h, 482°C; 4h, 550°C; 4h, 620°C)

2017, Mahmoudi et al. [6] (gas) N2 ranges reported • solutionizing (0.5h, 1040°C) + peak-aging

2017, Clausen et al.[43] N2 N2 (complete) • SR (1h, 650°C) under vacuum (~10-6 Torr)

1
Chemistry, including nitrogen, for AM material fabricated from the same feedstock later reported in 2017 by Stoudt et al. [42]

8
tensile strength compared to the as-built condition, once again no hardening effect was observed
following a subsequent peak-aging heat treatment. Although no aging treatments were
considered for a study by Cheruvathur et al. [41] involving as-built N 2/N2 material containing
50% austenite, their work likewise showed an increased hardness when subjected to the standard
“Condition A” [3] solution heat treatment (1050°C, 1 h), and to a lesser extent following a two-
stage heat treatment of homogenization (1150°C, 2 h) [44] plus solutionizing (1050°C, 0.5 h).

In addition to H900 peak-aging, LeBrun et al. [37] included H1025 and H1150 [8]
overaged conditions in their work. Samples fabricated from water-atomized powder feedstock
under a nitrogen atmosphere were aged directly from the as-built condition and were then
compared to the same set of aging treatments following an initial solutionizing step (1050°C, 0.5
h). The results showed varying degrees of retained and reverted austenite, as well as how aging
directly from the as-built condition can result in mechanical properties that deviate from the
typical downward progression associated with overaging.

These previous studies have demonstrated that the standard heat treatments developed for
martensitic wrought materials do not elicit the same response when applied to AM 17-4 PH
stainless steel, due to increased levels of retained austenite within the AM components inhibiting
precipitation kinetics. Although the presence of austenite was partially attributed to nitrogen
(introduced either by the atomization gas of the feedstock or by the AM shielding gas), as noted
in Table 2.1, complete chemistries were seldom reported. This study provides elemental analysis
for both the feedstock and AM builds, to quantify the impact that atomization and processing
conditions have on the chemical composition, and to further investigate the role that composition
has on austenite retention in AM components. Also, while much of the previous work has
focused on the peak-aged condition [6,34,36,37] (often omitting the standard solution heat
treatment) [34,36], this study explores the heat treat response among different overage
conditions, both directly from the as-built condition and as part of multi-stage heat treatments
consisting of homogenization and solutionizing. Additional non-standard heat treatments were
conducted to identify the peak-aged condition for highly austenitic AM 17-4 PH, which required
4 hours at 680°C.

9
 Chapter 3
ANALYSIS OF POWDER FEEDSTOCKS
3.1 Powder Feedstock Characterization Methods
Four powder feedstocks that satisfied the chemical requirements for 17-4 PH stainless
steel [3] were obtained from different vendors 2,3,4,5, including two argon-atomized powders and
two nitrogen-atomized powders to ensure a range of nitrogen compositions. The original
equipment manufacturer feedstocks for both the 3D Systems ProX 200 and EOS M280 PBF
systems were nitrogen atomized. Powder chemistries were measured by a certified lab 6 using
LECO combustion analysis per ASTM E1019-11 [45] for the elements C, S, O, and N, and
inductively coupled plasma atomic emission spectroscopy (ICP-AES) in accordance with ASTM
E1479-16 [46] for the remainder of the elements. Figure 3.1 shows secondary electron (SE)

(a) (b)

(c) (d)
Figure 3.1: Micrographs of the four feedstock powders, including (a) argon atomized for the 3D
Systems ProX 200, (b) nitrogen atomized for 3D Systems ProX 200, (c) argon atomized for
EOS M280, and (d) nitrogen atomized for EOS M280

2
Phenix Systems, a subsidiary of 3D Systems, Inc; Rock Hill, SC
3
Praxair Surface Technologies; Indianapolis, IN
4
EOS (Electro Optical Systems) of North America, Inc; Novi, MI
5
LPW Technology, Inc; Imperial, PA
6
Westmoreland Testing & Research, Inc; Youngstown, PA

10
images of the powders, captured by a Philips XL-30 Environmental Scanning Electron
Microscope.

The powders were characterized using conventional methods typically applied in powder
metallurgy, as well as more modern instrumentation. Flowability was measured using a standard
Hall funnel [47], and was then combined with a 25 cm 3 brass cup [48] to determine apparent
density. At least three measurements for each powder were performed to calculate average
values. Since all of the powders exhibited a “no flow” condition, flow was assisted by
continuous agitation of the powder to generate results for relative comparisons. The average tap
density [49] was also calculated from three measurements, after the powder had been settled by
at least 3000 cycles on a QuantaChrome Dual Autotap model DA-1.

Particle size distributions of the powders were assessed by a Malvern Masersizer 2000
light scattering technique. Image analysis was also performed using a Malvern Morphologi®
G3, which is capable of providing additional information on particle shape. For example,
convexity ratios offer an indication of surface roughness by comparing convex hull perimeters of
two-dimensional profiles of the particles to their actual perimeters. The convex hull perimeter is
determined by encasing the particle profile within a convex polygon, in which straight lines
connect the farthest-protruding peaks extending from the particle surface. A circularity
parameter simultaneously describes both surface roughness and shape by converting the area of
the two-dimensional profile to a circular equivalent (CE) diameter, and then calculating the ratio
of the CE diameter to the actual perimeter. As depicted in Figure 3.2, for an ideal spherical

Figure 3.2: Qualitative depiction of convexity and circularity parameters

relative to the ideal value of unity

11
particle with a perfectly smooth and circular profile, both the convex hull (shown as red broadly
spaced dashed lines) and circular equivalent diameter (shown as blue finely spaced dashed lines)
match the actual particle perimeter. If, however, the shape is distorted while still maintaining a
smooth surface, the convexity remains close to the ideal value of unity but the circularity ratio
decreases. As both surface roughness and shape continue to deviate from the ideal profile, the
convexity and circularity values both decline.

The flowability of the powders was further assessed using the REVOLUTION powder
analyzer7. A translucent sample drum is charged with 100 cubic centimeters of powder and
loaded into the instrument between a backlight and a camera. The pixel heights corresponding to
the silhouette produced by material blocking out the backlight are converted into potential
energy; as the drum rotates, the changing profile of the powder can then be monitored and
evaluated as changes in energy. For example, break energy is defined as the average maximum
potential energy of the powder, before gravity overcomes the interparticle friction and results in
an avalanche. Higher break energy indicates a greater resistance to flow. Avalanche energy
represents the decline in potential energy following the change in profile. With the addition of
the ION Charge Module, the tribocharging properties of the powders were also assessed. The
drum was rotated at a rate of 10 rpm for a duration of 60 seconds, and then any decay in charge
was also monitored for up to 30 seconds after rotation was terminated.

3.2 Particle Morphology

As observed in the micrographs shown in Figure 3.1, the particle sizes of the feedstocks
for the 3D Systems ProX 200 are slightly smaller than those for the EOS M280 system. This is
verified by the D10, D50, and D90 values listed in Table 3.1, as well as full plots of the normalized
particle size distributions shown in

(b)

Figure 3.3. The Malvern Morphologi G3 classified the particles into 1000 size bands,
spaced logarithmically, while an order of magnitude fewer bands applied to the Mastersizer
scans resulted in smoother curves with lower resolution.

7
Mercury Scientific Inc.; Newtown, CT

12
 The consistent spherical morphology produced by the gas atomization process is evident
in Figure 3.4, which displays percentage distributions of convexity and circularity ratios for each
of the four powders. The surface roughness of the two feedstocks acquired for the EOS M280
system, as measured by the convexity ratio, were similar, but a greater proportion of the nitrogen
atomized powder exhibited more ideal circularity. The superior results for the 3D Systems
nitrogen atomized powder—particularly the low surface roughness—are likely inflated due to
the fine particle size limiting the ability to resolve deviations within the profiles. This
exacerbated the perceived difference from the corresponding argon atomized powder, for which
more than 95% of the analyzed particles still had a convexity ratio of at least 0.8.

Table 3.1: Powder characterization data, including morphological and flow properties

3D Systems ProX 200 EOS M280

Ar atomized N2 atomized Ar atomized N2 atomized
D10 (µm) 15 4 17 26
(Vol. basis)
PSD

D50 (µm) 27 13 28 29

D90 (µm) 47 30 44 58

# Particles Analyzed 94,115 95,072 228,574 81,235

Analysis
Image

Mean Convexity 0.936 0.992 0.983 0.950

Mean Circularity 0.909 0.969 0.944 0.982

Apparent Density (g/cm3) 3.95 2.72 3.45 3.83

Tap Density (g/cm3) 5.0 4.7 4.5 5.1
Hausner ratio (ρT/ρA) 1.27 1.73 1.30 1.33
Hall Flow Rate* (sec/50 g) 24.8 290.2 12.3 24.5
Angle of Repose (±0.5°) 25.5° 51.5° 27.5° 35.0°

(*Note: 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)

13
 (a)

(b)

Figure 3.3: Volume-based Particle Size Distribution of the powder feedstocks, as

measured by light-scattering (dashed line) and image analysis (solid line), for (a) 3D Systems
ProX 200 and (b) EOS M280

14
 (a)

(b)

Figure 3.4: Image analysis results for the four powder feedstocks showing distributions of
(a) convexity ratio and (b) circularity ratio

3.3 Powder Flow Characteristics

Particle size and morphology can influence the flowability of powders, as demonstrated
by the rheological properties presented in Table 3.1. The 3D Systems nitrogen atomized powder
showed the greatest resistance to flow, as evidenced the high angle of repose, Hausner ratio, and
its relative Hall flow time. As the feedstock with the largest proportion of finer particles, the
high surface area associated with these fine particles promotes cohesion through high surface
energy and Van der Waals forces. [50] These fine particles allow more air to be entrapped

15
during packing, resulting in the considerably lower apparent density for the 3D Systems nitrogen
atomized powder.

Select results from the tests performed on the REVOLUTION powder analyzer are
shown in Table 3.2. Consistent with the results of the conventional test methods, the 3D
Systems nitrogen atomized powder exhibited the greatest resistance to flow among the four
powder feedstocks. In general, the slightly coarser powders for the EOS system demonstrated
greater flowability than the finer powders acquired for the ProX 200, as noted by the lower break
energies, avalanche energies, and packed avalanche angles. During the dynamic flow test, the
avalanche angle measured for the argon atomized feedstock for the ProX 200 was lower than
EOS argon atomized powder, but it maintained higher values in other categories. The coarser

Table 3.2: REVOLUTION powder analyzer dynamic flowability results

3D Sys. ProX 200 EOS M280

Ar Atom. N2 Atom. Ar Atom. N2 Atom.

Flow Density (g/cm3) 3.507 3.151 3.322 3.791

Dynamic Flow Test

Avalanche Angle (deg.) 48.8° 54.9° 52.5° 46.2°

Break Energy (kJ/kg) 75.5 74.9 58.2 68.7

Avalanche Energy (kJ/kg) 39.1 45.3 33.2 31.2

Surface Fractal 4.23 3.24 4.17 5.00

Packed Density (g/cm3) 3.706 3.102 3.357 4.192

Packed Test

Volume Change -4.1% -2.2% -3.6% -3.0%

Packed Avalanche Angle (deg.) 64.3° 54.8° 52.2° 48.7°

Max Charge, Glass(V) 80 412 58 66

Charge
Test

Max Charge, Polycarbonate (V) 429 910 333 -236

16
particles for the EOS System were also less likely to accumulate charge, whether in contact with
a glass surface or polycarbonate surface as shown in Figure 3.5 (a) and (b), respectively.

(a)

(b)

Figure 3.5: Accumulated charge versus time as measured by the REVOLUTION powder
analyzer when powder is in contact with (a) glass or (b) polycarbonate

17
3.4 Chemical Composition of the Powder Feedstocks
The chemical compositions of the powder feedstocks are listed in Table 3.3. The obvious
distinction is the higher nitrogen content within the nitrogen atomized feedstocks: 0.06 wt.% and
0.12 wt.% in the 3D Systems and EOS powders, respectively, compared to just 0.01 wt.% within
either argon atomized powder. However, it is notable that that nitrogen atomized feedstocks also
contained less Cr, slightly more Cu, and at least three times the C and Mn. These differences are
important because, in addition to Ni, the elements Cu, Mn, C, and N are all known austenite
stabilizers whereas Cr is a ferritic stabilizer [39].

The nickel and chromium equivalencies for the feedstocks (and subsequent builds), as
calculated from equations (3) and (4) per the Balmforth constitution diagram [51], are also listed
in Table 3.4. While the calculated Creq values for all four feedstocks fall within the range of 16.6
to 17.7, the Nieq values of the nitrogen atomized feedstocks are significantly higher than the
argon atomized material. The sharp contrast in Ni eq consequently suppresses the calculated
Creq/Nieq ratios for the nitrogen atomized powders to a range of 1.9 to 2.8, versus 3.3 to 3.5 for
the argon atomized powders. While higher Cr eq/Nieq ratios are associated with the ferritic region
of the Schaeffler diagram, lower Creq/Nieq ratios predict that the solidification mode shifts closer
to the austenitic region.

It should be noted that the Creq values calculated for the powder feedstocks likely contain
some error due to difficulties in accurately measuring Mo, which has a weight factor of 2 in the
chromium equivalency calculation listed as equation (3). When measuring the very low
concentrations of Mo in plants, the DCP-AES method was shown to produce results an order of
magnitude higher than either ICP-AES or a more sensitive chemical method involving the
catalysis of a KI-H2O2. [52] However, the opposite trend was observed in this study. The Mo
concentration of the powder feedstocks assessed by ICP-AES was an order of magnitude higher
than that observed in the fabricate components analyzed by DCP-AES. While qualitative
comparisons remain of interest, the reported Mo values should be considered with caution.

3.5 XRD Analysis of the Powder Feedstocks

The volume fraction of austenite within the powders (as well as subsequent as-built and
heat treated specimens) was determined by X-Ray Diffraction (XRD) using a PANalytical
X’Pert Pro MPD with an Empyrean Cu anode operated at 45 kV and 40 mA, paired with a

18
 Table 3.3: Chemical compositions of powder feedstocks and fabricated builds, with corresponding austenite volume fractions

3D Systems ProX 200 EOS M280

Ar Atomized Feedstock N2 Atomized Feedstock Ar Atomized Feedstock N2 Atomized Feedstock

Praxair As- As- Phenix As- As- LPW EOS

Specified Ranges As-Built As-Built
lot Built Built lot Built Built lot lot
(wt.%) (N2) (N2)
FE-276-3 (Ar) (N2) 14D1147 (Ar) (N2) UK5032 F471301

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

%Austenite < 1% 0% 0% 21% 9% 14% 3% < 1% 97% 81%

19
 Table 3.4: Ni equivalent and Cr equivalent weight fractions per Balmforth constitution diagram
as calculated from chemical compositions for each feedstock and AM build, as well as volume
fraction of retained austenite as measured by XRD

Creq / Nieq
Creq Nieq % Aust.
ratio

Ar. Atom. Feedstock 17.0 4.9 3.5 < 1%

As-Built (Ar/Ar) 15.8 4.9 3.3 0%

3D Systems ProX 200

As-Built (Ar/N2) 15.6 4.6 3.4 0%

N2 Atom. Feedstock 17.7 6.4 2.8 21%

As-Built (N2/Ar) 16.0 7.1 2.2 9%

As-Built (N2/N2) 16.0 7.3 2.2 14%

Ar Atom. Feedstock 16.6 5.0 3.3 3%

As-Built (Ar/N2) 16.6 5.5 3.0 < 1%

EOS M280

N2 Atom. Feedstock 17.0 8.8 1.9 97%

As-Built (N2/N2) 15.4 9.4 1.6 81%

PIXcel 1D detector. The setup was comprised of a 0.020 mm Ni large β filter, 0.04 mm Soller
slit, 10 mm beam mask, and a 2° antiscatter slit. The default scan covered a 2θ range of 40°-
100° using an automatic spot size of 10 mm, but if necessary, was reduced to 5 mm to
accommodate smaller specimens. The software program MDI Jade 2010 (version 3.6.5) was
used to identify and integrate peaks, from which the amount of retained austenite was calculated
by the direct comparison method. [53,54]

Because a copper radiation source has sufficient energy to eject inner shell elections of iron
atoms, the use of a monochromator is recommended to minimize the resulting fluorescence.
[53,55] Figure 3.6 displays the large background that occurs when a monochromator is not used,
20
followed by the steps taken within the software to correct the diffraction pattern. First, the
pattern observed using an automatic slit is transformed into the corresponding pattern for the
conventional fixed slit. Then the background level is determined and established as the new

Figure 3.6: Comparison of XRD diffraction patterns of 3D Systems nitrogen atomized

powder when scanned with or without a monochromator, both before and after software
corrections

21
baseline. After these corrections, the resulting diffraction patterns with or without a
monochromator were virtually indistinguishable on a normalized basis. Since the purpose of this
study was limited to the direct comparison of the two primary phases and did not need to
distinguish low intensity peaks, a monochromator was not used.

The most prominent peaks for each phase generally appeared at two-theta values of 43.6°
and 44.5°, corresponding to FCC (111) and BCC (110), respectively. The precise position of
these primary peaks was used in conjunction with Bragg’s Law to determine the lattice spacing,
followed by calculation of the lattice constant and unit cell volume. Table 3.5 lists the tabulated
values [56] for multiplicity factor, atomic scattering factor, temperature factor, and the structure
parameter Rihkl [53] for each hkl peak using the Cu Kα source.

Table 3.5: Summary of parameters used to analyze x-ray diffraction data for determination of
retained austenite volume fractions

Atomic Lorentz calculated

Scattering Structure Multiplicity Polarization Temperature proportional
h k l Factor, fFe Factor, F Factor, p Factor, LP Factor, e-2M parameter, Ri

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

BCC Phase

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

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

FCC Phase

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

22
 The austenite volume fraction could then be calculated by equation (5) [53]:

𝑉 = ∑ / ∑ + ∑ (5)

where the average ratio of integrated intensity to the proportional parameter, I/R, is calculated for
the number of peaks being considered for the respective phases over the scanned two-theta
range. The 40° to 100° range used in this study consists of four peaks for the BCC α/α’ phase (P
= 4) and five peaks for the FCC γ phase (q = 5). The low carbon content of ≤ 700 ppm specified
for this alloy ensures that the lattice parameters of BCT martensite would remain quite similar to
those of BCC ferrite [57], and therefore the two phases are considered to be identical in XRD
analysis. The XRD patterns for the powders and as-built specimens are shown in Figure 3.7(a)
and Figure 3.7(b), respectively.

The results of the XRD analysis listed in Table 3.3 demonstrate that the atomization
condition had a significant impact on the austenite volume fractions. The argon atomized
feedstocks with Nieq ≤ 5 retained only trace amounts of austenite. However, with higher
concentrations of austenite stabilizing elements such as nitrogen, the nitrogen atomized
feedstocks retained much larger austenite fractions. For example, 21% austenite was detected in
the 3D Systems nitrogen atomized feedstock with a nitrogen concentration of 0.06 wt.% and a
Nieq value of 6.4. The EOS nitrogen atomized material had the highest nitrogen concentration
(0.12 wt.%) and Nieq value (8.8), and consequently was almost fully austenitic at 97%.

3.6 Summary and Conclusions

Morphology and flowability did not reveal any conclusive distinctions attributable to the
choice of atomization gas. Rheological properties were most significantly impacted by particle
size, with the finer feedstocks acquired for the 3D Systems ProX 200 generally exhibiting greater
resistance to flow than the slightly coarser feedstocks for the EOS M280. Since each of the four
powder feedstocks were acquired from different vendors, some of the dissimilarities could be
attributed to variations in raw materials, processing equipment, or operating conditions.
However, one clear distinction dictated by the atomization condition was the chemistry.
Compared to just 0.01 wt.% nitrogen detected in either argon atomized feedstock, the nitrogen
atomized powders acquired for the 3D Systems ProX 200 and EOS M280 contained nitrogen
levels of 0.06% and 0.12%, respectively. These higher nitrogen concentrations, in

23
 (a)

(b)
Figure 3.7: XRD patterns for AM 17-4 PH (a) feedstock and (b) in the as-built condition

addition to the contribution of other austenite-stabilizing elements like C and Mn, increased the
nickel equivalency of the nitrogen atomized feedstocks. Since the variation in chromium
equivalency was much narrower, the higher nickel equivalency values in the nitrogen atomized
feedstocks suppressed the Creq/Nieq ratios and drove the solidification mode closer to the
austenitic region of the Schaeffler diagram. XRD analysis of the powders confirmed that while
the argon atomized feedstocks were predominantly ferrite/martensite, the volume fraction of

24
austenite within the nitrogen atomized powders were measured as 21% and 97% for the 3D
Systems ProX 200 and EOS M280 systems, respectively.

25
 Chapter 4
ANALYSIS OF AS-BUILT MATERIAL
4.1 Additive Manufacturing via Powder Bed Fusion
The argon and nitrogen atomized powder feedstocks procured for the EOS M280 and 3D
Systems ProX 200 laser PBF systems were additively manufactured using the recommended
operating parameters specific to each system. Separate builds were completed on the 3D
Systems ProX 200 under either an argon or nitrogen atmosphere, while the two powder
feedstocks for the EOS M280 were exclusively processed under nitrogen. Most of the builds
consisted of 30 simple rectangular solids with a nominal cross-section of 63.5 mm × 6.35 mm,
and build heights that ranged from 8.46 to 9.58 mm. However, due to limited feedstock,
production from the argon atomized powder for the 3D Systems ProX 200 was limited to 10 bars
under each atmosphere, with build heights of 7.70 mm when processed under nitrogen and 4.37
mm when processed under argon. Following fabrication, parts were removed from the base plate
by electrical discharge machining. A cutting saw was then used to subdivide bars into 5-6
individual segments. Segments from each of the fabricated builds were sent to a certified testing
laboratory8 to determine the chemical composition through a combination of combustion infrared
detection (C, S) and inert gas fusion (N, O) per ASTM E1019-11 [45], while the remaining
elements were measured by direct current plasma atomic atomic emission spectroscopy (DCP-
AES) per ASTM E1097-12 [58].

4.2 Chemical Composition of Fabricated Structures

The summarized chemistries presented in Table 3.3 show how the composition of the
powder feedstocks correlate to the AM builds. Although some variability was introduced by
altering the shielding gas, the processing atmosphere had only a minor impact on the
composition. When the same feedstock was processed under either argon or nitrogen on the 3D
Systems ProX 200, the as-built weight fraction of nitrogen differed by less than 0.01%.
However, the greater disparities in nitrogen levels that were noted in the feedstocks were evident
in the builds as well. While the components fabricated from argon atomized feedstocks
contained 0.01 to 0.03wt.% nitrogen, the nitrogen atomized material yielded concentrations of
around 0.09% for the 3D Systems material and exceeded 0.14% in the EOS powder. As

8
Luvak Laboratories, Inc; Boylstown, MA

26
observed with the powders, the wide range of nitrogen concentrations leads to significant
differences in the nickel equivalency, as revealed in Table 3.4.

Applying equations (3) and (4) to the specified composition ranges for 17-4 PH stainless
steel [3] and plotting these ranges onto the Balmforth diagram [51], as shown in Figure 4.1,
indicates that virtually all specified compositions of the alloy fall within the martensite+ferrite
region. According to the diagram, only under the limited condition that Ni eq>7.08 and
Creq>16.86 would any fraction of austenite be retained. However, since common standards do
not specify a range for nitrogen [3,33], the calculated nickel equivalency for material that
explicitly satisfies the compositional requirements could be much higher than the expected limit.
For example, while the positions of the argon atomized materials processed on either system
plotted in Figure 4.1 appear in the martensite+ferrite region of both the Balmforth[51] and
Schaeffler[10] diagrams, the higher nickel equivalency of the 3D Systems nitrogen atomized
material crosses into the austenite+martensite+ferrite region of the Schaeffler diagram.
Although the nitrogen atomized material processed on the EOS system does not fall within the

Figure 4.1: Balmforth diagram [51] showing the standard chemical composition [3] for 17-4 PH
stainless steel (delineated by a dashed box), as well as the position of the six AM builds,
overlayed on a subset of the Schaeffler diagram [10]

27
limits of the Balmforth diagram, when the same equivalency equations are applied, it appears in
the austenite+martensite region of the Schaeffler diagram.

4.3 XRD Analysis of Fabricated Structures

Comparing the chemistries in Table 3.3 with the XRD patterns in Figure 3.7(b) shows that
the volume fraction of the austenite phase increased with higher levels of nitrogen. The XRD
results listed at the bottom of Table 3.3 display trends that are consistent with the constitution
diagram shown in Figure 4.1. The argon atomized materials in the martensite+ferrite region
showed little to no retained austenite. The 3D Systems nitrogen atomized material, which
bordered the austenite+martensite+ferrite region, was still primarily martensite+ferrite with only
9% or 14% retained austenite when processed under either argon or nitrogen atmospheres,
respectively. Contrastingly, austenite was the predominant phase detected in the outlying EOS
nitrogen atomized material. In all cases, the level of retained austenite measured in the AM
components was lower than that of their respective powder feedstocks. Unlike the rapid
solidification associated with gas atomization, which approaches an estimated cooling rate of 10 7
K/s for diameters smaller than 10 µm [22], additively manufactured components undergo more
complex thermal histories during which previously deposited layers experience some reheating
that may affect solid state phase transformations [17]. Mechanical transformation to martensite
induced by the metallographic preparation of the as-built surfaces has also been proposed as a
contributing factor. [37]

4.4 Computational Modeling of Phase Equilibria

The chemical composition of the fabricated components is primarily dictated by the
feedstock chemistry, with only minor variations introduced by the selection of processing gas.
The nickel and chromium equivalencies calculated from these chemical differences can influence
the predicted phases that form within the alloy, as shown in Figure 4.1. An alternative method to
predict the phase formation from the four powder feedstocks involved computing equilibrium
mass fractions as a function of temperature according to each respective composition. Point
calculations were used to capture the predicted solidification as well as solid state phase
compositions to temperatures as low as 300°C.

28
 The compositions of the four feedstocks were entered into JMatPro® software 9 to generate
phase stability diagrams as a function of temperature using the CalPhaD thermodynamic
approach. This computational approach was applied over temperatures ranging from about
300°C to above the liquidus temperature. To determine the relative proportions of ferrite and
austenite phase upon solidification, Scheil calculations were used. The Scheil approach assumes
that diffusion is infinitely fast within the liquid but does not occur within a solid once it is
formed, and that equilibrium conditions exist at the solid-liquid interface.

Figure 4.2(a) and Figure 4.2(b) show the calculated phase compositions as a function of
temperature based upon the chemistries of the argon atomized and nitrogen atomized feedstocks,
respectively, processed on the 3D Systems ProX 200 system. Similar diagrams representing the
compositions of both feedstocks for the EOS M280 system are shown in Figure 4.3(a) and Figure
4.3(b). The temperatures delineating phase boundaries are listed in Table 4.1, along with
estimated volume fractions of austenite and ferrite predicted by Scheil solidification calculations.

Most of the feedstocks exhibit the FA solidification mode. After initially solidifying as
ferrite, some austenite also begins to form, but ferrite remains the predominant phase. In
contrast, the EOS nitrogen atomized feedstock represented in Figure 4.3(b) essentially exhibits
fully austenitic (A) solidification.

As the temperature progresses further below the solidus line, additional phases are
predicted to form, including nitrides, various carbides, and a copper phase. The higher levels of
carbon and nitrogen within the nitrogen atomized feedstocks for both systems corresponds to
higher mass fractions of carbides and nitrides, though the net contribution from these minor
phases remains relatively low.

4.5 Estimation of Martensite Start Temperature

In addition to influencing the amount of austenite that forms during solidification, the
chemical composition can also affect the extent of martensitic transformation. For example,
higher concentrations of carbon [59,60] or manganese [61] within ferrous alloys have been
shown to suppress the temperature at which martensitic transformation initiates. Lower

9
Sente Software Ltd; Surrey, UK

29
 (a)

(b)

Figure 4.2: Equilibrium phase composition calculated as a function of temperature from the 3D
Systems ProX 200 powder chemistries for (a) argon atomized and (b) nitrogen atomized
feedstocks

30
 (a)

(b)
Figure 4.3: Equilibrium phase composition calculated as a function of temperature from the EOS
M280 powder chemistries for (a) argon atomized and (b) nitrogen atomized feedstocks

31
 Table 4.1: Summary of phase equilibrium temperatures and Scheil solidification calculations
computed from the chemical compositions of the four powder feedstocks

3D Systems ProX 200 EOS M280

Ar atomized N2 atomized Ar atomized N2 atomized
Equilibrium calculations
Liquidus Temp. (°C) 1453 1441 1444 1429
Solidus Temp. (°C) 1384 1362 1367 1367

1399 – 501, 1409 – 519,

Austenite region(s) (°C) Below 1398 Below 1429
Below 431 Below 405

1453 – 1104, 1441 – 1184, 1444 – 1202,

Ferrite region(s) (°C) Below 695
Below 800 Below 765 Below 781

Cu phase formation Temp. (°C) 944 986 994 1027

Scheil Solidification calculations

Solidification range (°C) 1453 to 1225 1441 to 1225 1444 to 1230 1429 to 1245
Volume fractions
0.80/0.19 0.67/0.32 0.64/0.35 0.004/0.99
(Ferrite/Austenite)

martensite start (Ms) temperatures reduce the likelihood of the transformation nearing completion
at room temperature, corresponding to higher levels of retained austenite.

The Ms temperature was estimated as a function of nitrogen composition for each of the
fabricated conditions. A thermodynamic approach was used to identify the temperature at which
the difference in Gibbs free energy of the austenite and ferrite phases was sufficiently large

enough to initiate nucleation of martensite. [62] Calculations were based exclusively on the
composition of the austenite within each build, after accounting for some consumption of solute
into secondary phases. Grain size of the austenite, however, was not taken into account.

Figure 4.4 reveals how the chemical compositions within the builds affect the M s
temperature, and specifically highlights the significant role of nitrogen. Among the six builds,

32
the highest projected Ms temperature (223°C) corresponded to the argon atomized feedstock for
the 3D Systems ProX 200, which possessed the lowest levels of austenite-stabilizing elements C,
N, Mn, and Cu. Conversely, the austenitic material with the highest nickel equivalency was
projected to be 99° lower at 124.65°C, of which approximately 56°C can be attributed to the
difference in nitrogen alone.

Figure 4.4: Simulated martensite start temperature as a function of nitrogen weight percent for
each build composition

4.6 Metallographic Analysis of Fabricated Structures

In preparation for further characterization, specimens representing each of the different
conditions were individually mounted in an epoxy thermosetting powder using a Struers
ProntoPress-2 operated at approximately 30 kN and 185°C. After grinding the surface of the
specimens through a series of silicon carbide sheets to a rating of 1200 (FEPA P4000) microgrit
on a Struers Pedemax-2, the samples were polished with a 3 µm diamond suspension and 1 µm
diamond suspension for 2 minutes each. A final polishing step with a 0.06 µm colloidal silica
suspension was performed for 8 minutes. To assess the hardening response throughout the heat

33
treatments, a minimum of 30 Vickers microhardness measurements per specimen were recorded
with a Leco M-400-G1 Hardness Tester set to a load of 300 g F. Specified hardness ranges for
wrought 17-4 PH stainless steel are presented on the Rockwell C scale, so to allow for
comparisons, a standard conversion table for non-austenitic steels [63] was used to determine the
corresponding Vickers hardness numbers.

Select specimens were immersed for 6-11 seconds in a solution of Marble’s etchant (50
ml HCl + 50 ml H2O + 10 g CuSO4) [64] diluted 50/50 with glycerol. Optical micrographs were
then captured using a Nikon Epithot microscope connected to a Digital Sight DS-Fi2 camera and
Digital Sight DS-U3 camera controller. Following 12 hours of vibratory polishing, an FEI
Helios NanoLab 660 scanning electron microscope equipped with an X-Max N detector (Model
51-XMX1005) was used in conjunction with Oxford Instruments Aztec 3.1 SP1 software to
acquire energy-dispersive x-ray spectroscopy (EDS) maps.

Though intermediate iso-ferrite lines were not displayed in Figure 4.1, the positions of all
three builds fabricated from the argon atomized powders fell within a range of 40% to 50%
ferrite volume fraction [51]. Correspondingly, as shown in Figure 4.5(a) through (c), the three
argon atomized builds also shared similar microstructures, consisting of long columnar laths that
extended parallel to the build direction across several build layers. The predominantly austenitic
structure shown in Figure 4.5(f) showed far less contrast, while the 3D Systems nitrogen
atomized builds shown in Figure 4.5(d) and (e), which fall within the A+M+F region of the
Schaeffler diagram in Figure 4.1, exhibited a complex microstructure that obscured the visibility
of the semi-elliptical melt pools. EDS maps generated from each of the builds fabricated on the
EOS M280 system did not reveal any distinct elemental segregation, as shown in Figure 4.6(a)
and (b).

Hardness measurements of the as-built material will be presented in greater detail in

Chapter 5, where they serve as a baseline to assess the impact of post-processing heat treatments.
The three argon atomized builds, which had a consistent microstructure containing little to no
retained austenite, all had a hardness of approximately 300 HVN. In contrast, the nitrogen
atomized material produced on the EOS M280 that was primarily comprised of the softer
austenitic phase had lower hardness (260 HVN). Although the 3D Systems nitrogen atomized
builds also retained some austenite (9% and 14%), their placement on the constitution diagram

34
 (a) (b) (c)

(d) (e) (f)

Figure 4.5: As-Built microstructures from (a) argon atomized feedstock for the 3D Systems ProX 200 processed under Ar atmosphere
or (b) N2 atmosphere; (c) argon atomized feedstock for EOS M280 (N2 atmosphere); (d) nitrogen atomized feedstock for the ProX 200
processed under Ar atmosphere or (e) N2 atmosphere; (f) nitrogen atomized feedstock for EOS M280 (N2 atmosphere)

35
 (a) (b)
Figure 4.6: EDS maps showing no observable elemental segregation for builds fabricated on the
EOS M280 system from (a) argon atomized powder or (b) nitrogen atomized powder

shown in Figure 4.1 predicts a lower ferrite content than any of the argon atomized products,
thus allowing for more of the harder martensitic phase. Furthermore, the hardness of the
martensite phase itself increases with higher concentrations of the solute. [65] Even though the
nitrogen atomized feedstocks for both systems possessed greater levels of carbon and nitrogen
compared to either argon atomized material, only the 3D Systems builds had a mostly
martensitic structure, and consequently, had the highest hardness in the as-built condition (~340
HVN). For both feedstocks processed on the 3D Systems ProX 200, the minor increase in
nitrogen content associated with changing the processing atmosphere from argon to nitrogen also
resulted in a slight increase in hardness.

4.7 Summary and Conclusions

The chemical composition of the AM components is primarily dictated by the powder
feedstocks, with only minor variations introduced by the choice of shielding gas. For chemistries
that coincide with the nickel and chromium equivalencies calculated for specified elemental
ranges of the 17-4 PH alloy, thermodynamic calculations predict an initial solidification into
ferrite, and maintaining a predominantly BCC structure. However, differences in nitrogen—a
non-specified element—can sufficiently alter the Creq/Nieq ratios into an austenitic solidification
mode. Higher concentrations of austenite stabilizing elements also suppress the martensite start
(Ms) temperature of the alloy, potentially leading to higher levels of retained austenite. Hardness

36
values ranging from 260 to nearly 350 HVN could be attributed to the different proportions of
the phases present, and ultimately, the chemistry.

37
 Chapter 5
ANALYSIS OF HEAT TREATED MATERIAL
5.1 Overview of Post-Fabrication Heat Treatments
To assess the heat treatment response of the six AM builds, selected segments were
subjected to various heat treatment conditions. A Rapid Temp Furnace 10 was preheated to the
target temperature under a constant flow of argon, and then samples were placed inside. At the
end of the designated duration, samples were removed and permitted to air-cool to room
temperature. Although various standards specify a temperature range for the solutionizing heat
treatment, including 1040±15°C [33], 1052±27°C [3], or 1038±14°C [44], only the latter
specifies a duration (≥30 minutes). Therefore, soak durations of 15, 30, 60, or 90 minutes were
all tested at the solutionizing temperature of 1040°C. Four hour overaging heat treatments were
conducted at temperatures of 495°C, 580°C, and 1150°C, in accordance with the standard H925,
H1075, and H1150 heat treatments [3,33], respectively.

As depicted in Figure 5.1, aging heat treatments followed four possible heat treatment
paths, including aging directly from the as-built condition, as part of a two-stage heat treatment
following an initial 30 minute solutionizing step, and finally within three-stage processes that
incorporated an initial homogenization step of 90 minutes at 1149±14°C [44]. While one version
of the three-stage process maintained the practice of allowing specimens to air-cool following
solutionization, alternate specimens were water-quenched at this step. In the case where the
standard overaged response was not observed, additional multi-stage heat treatments were
conducted at aging temperatures of 550°C, 650°C, 680°C, 720°C, and 760°C, after solutionizing
for either 30 or 60 minutes.

5.2 Direct-Aging Heat Treatment

The differences in the as-built condition discussed in Chapter 4 can be expected to
produce variations in the heat treatment response. The first series of heat treatments conducted
for this study involved aging all of the materials for four hours directly from the as-built
condition at temperatures of 495°C, 580°C, or 620°C. The resulting hardness values and
retained austenite fractions are listed in Table 5.1. The progression of the hardness values is then

10
CM Furnaces, Inc; Bloomfield, NJ

38
 (a)

(b) (c)

(d) (e)

Figure 5.1: Schematic of various heat treatment cycles, including (a) solutionizing for different
durations, (b) aging directly from the as-built condition, (c) a two-stage heat treatment, and
three-stage processes for which post-solution specimens were either (d) air-cooled or (e) water-
quenched

visually depicted in Figure 5.2(a) and (b) for the 3D Systems ProX 200 and EOS M280,
respectively, with specified limits for each condition [3] indicated by brackets. A dashed line is
used to represent the maximum hardness specified for the solutionized state of wrought 17-4 PH

39
 Table 5.1: Comparison of austenite volume fraction and Vickers microhardness after 4-hour
aging directly from the as-built condition

Ar/Ar Ar/N2 N2/Ar N2/N2

%γ HVN %γ HVN %γ HVN %γ HVN
Feedstock <1% — <1% — 21% — 21% —
3D Sys. ProX 200

As-Built 0% 299±12 0% 312±8 9% 339±10 14% 348±8

495°C 0% 382±9 0% 402±12 22% 404±18 15% 422±10
Aging HT

580°C 1% 275±9 <1% 291±7 19% 329±9 20% 338±7

620°C <1% 257±6 <1% 270±4 18% 353±17 18% 349±10

Feedstock 3% — 97% —
As-Built <1% 298±7 81% 260±7
EOS M280

495°C <1% 384±9 87% 256±7

Aging HT

580°C 1% 290±6 48% 279±10

620°C 2% 279±5 40% 367±22

(a) (b)
Figure 5.2: Vickers hardness measurements compared to specification range for standard
wrought materials when aged for 4 hours directly from the as-built condition for (a) 3D Systems
ProX 200 and (b) EOS M280 system

40
grade [3], known as “Condition A.” Because the additively manufactured components generally
satisfy this hardness requirement, the as-built condition has previously been considered
equivalent to the solutionized state [36,66].

Although material fabricated from either of the argon atomized feedstocks met the
specification for the heat treatment closest to the peak age condition, the hardness of materials
overaged at higher temperatures often fell below the minimum. Among the 3D Systems builds,
the higher hardness observed in the as-built condition of nitrogen atomized materials was evident
in the aged conditions as well, allowing both nitrogen atomized builds on the ProX 200 to
generally satisfy hardness requirements. However, contradictory to the expected decline
associated with overaging, hardness values for the 3D Systems nitrogen atomized materials
actually increased following aging at 620°C compared to 580°C. The deviation from the
expected overage response was even more pronounced in the highly austenitic material
processed on the EOS M280 system. Consistent with a previous study[34] that applied the
standard H900 peak-aging heat treatment (1 h at 482°C [3]) to AM 17-4 PH grade with a mostly
austenitic structure, aging at 495°C showed little change from the as-built condition. Hardness
values then proceeded to increase with increasing aging temperature.

The increasing hardness of the EOS nitrogen atomized material coincides with a
reduction in the retained austenite fraction, as it transitions from a primarily austenitic structure
at the low overaging temperature to a mostly martensitic one at higher temperatures. Each of the
other builds, however, showed a slight increase in the austenite volume fraction upon aging,
indicating that reverted austenite was generated. This is attributed to the diffusion of austenite-
stabilizing elements such as Cu and Ni into localized regions, thereby lowering the martensite
start temperature. [2,37,67]

5.3 Two-stage Heat Treatment: Solutionizing Followed By Aging

The prior section showed that when samples were aged directly from the as-built
condition, austenite levels within the AM components heavily influenced the heat treatment
response. Subjecting AM components to a solutionizing heat treatment prior to aging, however,
should lessen variations in the as-built microstructure. [41] However, since the soak duration at
the solutionizing temperature is generally not specified [3,33], different soak times ranging from
15 to 90 minutes were tested.

41
 The results in Table 5.2 and the corresponding hardness plots in Figure 5.3 show that the
majority of the builds exhibited little sensitivity to solutionizing duration, with the exception of
the highly austenitic material. Therefore, the recommended minimum duration of 30 minutes
[44] was selected as the default solutionizing time for subsequent heat treatments.

For the builds fabricated on the 3D Systems ProX 200, Figure 5.3(a) reveals that the
nitrogen atomized material exhibited a greater increase in hardness from the as-built condition
than the argon atomized material, corresponding to a reduction in the volume fraction of the
softer austenite phase. Although the nitrogen atomized material for the EOS M280 also showed
a significant reduction in retained austenite, the γ-phase volume fraction remained above 20%.
Among the builds dominated by the α/α’ phase following solutionizing (≤ 4% γ), hardness values
in the solutionized condition were higher for increasing levels of nitrogen (Table 3.3).

After subjecting each of the specimens to a 30 minute solutionization at 1040°C, the

overaging heat treatments discussed in Section 5.2 were once again applied. Hardness
measurements and austenite fractions following the two-stage heat treatments are presented in
Table 5.3. When compared to the specified hardness ranges for each condition [3], Figure 5.4
shows that the inclusion of the solutionization step improved the aging response. Though the
argon atomized material processed on either system failed to consistently achieve sufficient
hardness levels when aged directly from the as-built condition, the results following a two-stage
heat treatment generally satisfied the wrought specifications. Furthermore, the nitrogen
atomized material fabricated on the 3D Systems ProX 200 now exhibited the expected overage
response of declining hardness values for increased aging temperatures. While the austenite
fraction of the EOS nitrogen atomized material did not substantively change upon aging, the
material with intermediate nitrogen levels ranging from 0.088 to 0.091 wt.% (per Table 3.3)
exhibited increasing levels of reverted austenite with higher nitrogen content. Although less
reverted austenite was observed in the argon atomized material, an example of the elemental
segregation of nickel and chromium following overaging at the higher temperature is visible in
Figure 5.5. Similar to the direct-aging results in Figure 5.2(b), Figure 5.4(b) shows that the
material fabricated from the highly austenitic nitrogen atomized feedstock continued to increase
in hardness at higher aging temperatures, indicative of an underaged condition.

42
 Table 5.2: Comparison of austenite volume fraction and Vickers microhardness after
solutionizing at 1040°C for different durations

Ar/Ar Ar/N2 N2/Ar N2/N2

%γ HVN %γ HVN %γ HVN %γ HVN
Feedstock <1% — <1% — 21% — 21% —
3D Systems ProX 200

As-Built 0% 299±12 0% 312±8 9% 339±10 14% 348±8

15 min <1% 303±11 <1% 315±6 5% 368±15 4% 374±9
Solution HT

30 min 0% 302±15 0% 315±11 4% 351±12 4% 368±13

60 min 0% 301±9 0% 309±10 3% 355±13 1% 371±27
90 min 0% 298±10 0% 306±6 2% 351±22 1% 366±16

Feedstock 3% — 97% —
As-Built <1% 298±7 81% 260±7
EOS M280

15 min 0% 325±4 28% 273±25

Solution HT

30 min 0% 321±5 24% 262±22

60 min 0% 321±5 22% 356±10
90 min <1% 319±5 25% 321±24

(a) (b)
Figure 5.3: Vickers hardness measurements following solutionizing at 1040°C for different
durations, as compared to specified maximum for standard wrought materials, for (a) 3D
Systems ProX 200 and (b) EOS M280 system

43
Table 5.3: Comparison of austenite volume fraction and Vickers microhardness after 30-min
solutionizing heat treatment at 1040°C followed by 4-hour aging; fabricated on 3D Systems
ProX 200

Ar/Ar Ar/N2 N2/Ar N2/N2

%γ HVN %γ HVN %γ HVN %γ HVN
Post-Soln 0% 302±15 0% 315±11 4% 351±12 4% 368±13
3D Sys. ProX

495°C <1% 372±6 5% 373±5 4% 393±9 7% 379±6

Soln+Age

580°C 0% 315±6 6% 319±7 16% 355±5 22% 346±7

620°C 0% 290±7 <1% 299±4 30% 309±6 22% 340±15

Post-Soln 0% 321±5 24% 262±22

EOS M280

495°C <1% 396±4 22% 273±23

Soln+Age

580°C 9% 328±6 24% 391±10

620°C 5% 300±4 20% 414±11

(a) (b)
Figure 5.4: Vickers hardness measurements compared to specification range for standard
wrought materials following two-stage heat treatment consisting of 30-min solutionization
followed by 4-hour aging for (a) 3D Systems ProX 200 and (b) EOS M280 system

44
Figure 5.5: Elemental segregation of chromium and nickel observed in argon atomized material
processed on the EOS M280, after solutionizing followed by aging at 620°C

5.4 Determination of Peak-Aging for Highly Austenitic Material

Because the material fabricated from the highly austenitic feedstock had not yet
demonstrated an overage response, additional two-stage heat treatments were conducted at aging
temperatures up to 760°C. Also, since this material showed a sensitivity to solutionizing
duration (Figure 5.3), the series of four-hour aging heat treatments was repeated for material
solutionized at 1040°C for 60 minutes. As revealed in Table 5.4 and graphically depicted in
Figure 5.6, hardness values proceeded to level off at aging temperatures above 620°C before
finally demonstrating an overage response at temperatures in excess of 700°C. The maximum
observed hardness, following four-hour aging at 680°C, satisfies the hardness range for the
standard peak-aged condition for 17-4 PH stainless steel (1 h at 482°C) [3]. Although the
material solutionized for 60 min possessed a higher initial hardness in the H925 condition
(495°C), the solution duration had little impact at higher aging temperatures.

45
Table 5.4: Comparison of austenite volume fraction and Vickers microhardness for various 4-
hour aging heat treatments following a 30-min or 60-min solutionizing step for nitrogen
atomized material processed on the EOS M280 system

30 min Soln HT 60 min Soln HT

%γ HVN %γ HVN
Post-Soln 24% 262±22 22% 356±10
495°C 22% 273±23 21% 335±25
550°C 21% 374±6 25% 377±10
Solutionized +Aged

580°C 24% 391±10 21% 402±10

620°C 20% 414±11 19% 419±13
650°C 19% 415±19 16% 417±12
680°C 17% 429±14 14% 419±14
720°C 19% 411±13 15% 418±14
760°C 16% 382±17 13% 388±13

Figure 5.6: Vickers hardness measurements of highly austenitic feedstock fabricated under
nitrogen, then solutionized for either 30 or 60 min followed by 4-hour aging, with specified
hardness range for H900 peak age condition [3] indicated by brackets

46
5.5 Three-stage Heat Treatment: Homogenization + Solutionizing + Aging
Similar to solutionizing, the purpose of a homogenization step is to minimize elemental
segregation within the microstructure. [68] A homogenization heat treatment often leads to
reduced ferrite content and increases the likelihood of austenite transforming to martensite upon
cooling. [9] Three-stage heat treatments were carried out along one of two paths: after an initial
homogenization at 1150°C for 90 min, the intermediate 30 min solutionizing step was terminated
either by the same air-cooling method used in the rest of this study or was rapidly cooled using a
water quench. The air-cooled or water-quenched samples were then subjected to the same
overaging heat treatments discussed in previous sections.

The results of the three-stage heat treatments—including measurements of the

intermediate stages—for material fabricated on the 3D Systems ProX 200 are presented in Table
5.5. Unfortunately, the argon atomized components fabricated on this system lacked sufficient
material to perform aging heat treatments within this category, so only intermediate conditions
are provided. However, the low levels of retained austenite within these samples and the
similarity to the solutionized state in Table 5.2 suggests the heat treatment response would be
comparable to the two-stage heat treatment. Overall, the addition of a homogenization step did
not significantly alter the aging conditions of the nitrogen atomized material. However,
compared to the results in Section 5.3, Figure 5.7 indicates that the differences introduced by the
processing gas were minimized. Also, following homogenization, variability in the hardness
measurements of either solutionized state was lower than that observed in the two-stage heat
treatment.

Initial three-stage heat treatment results for material fabricated on the EOS M280 are
shown in Figure 5.8, with extended hardness properties representing the additional aging
temperatures performed on the nitrogen atomized material displayed in Figure 5.9. The
measured hardness values and retained austenite fractions are listed in Table 5.6. As observed
with the 3D Systems builds, the addition of a homogenization step had little impact on the aging
conditions of the primarily α/α’ material. While the underaging and overaging trends still
indicated a peak-aged condition around 680°C, maximum hardness was not observed at this
condition. The additional complexity of applying a three-stage heat treatment introduced greater
variability in the nitrogen atomized material on the EOS M280.

47
 Table 5.5: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on 3D Systems ProX 200

Ar/Ar Ar/N2 N2/Ar N2/N2

%γ HVN %γ HVN %γ HVN %γ HVN
Post-Homog. 3% 303±7 2% 309±8 7% 363±7 13% 366±10
Post-Soln (air) <1% 301±6 <1% 308±10 1% 349±7 1% 361±6
495°C 4% 398±5 14% 392±5
Hom+Sol
+Aged

580°C [insufficient material] 20% 343±5 19% 342±5

620°C 19% 327±9 22% 321±10

Post-Soln (H2O) 0% 304±11 <1% 297±8 <1% 358±6 4% 362±8

495°C 9% 397±7 22% 397±5
Hom+Sol
+Aged

580°C [insufficient material] 21% 354±6 13% 358±5

620°C 21% 314±5 21% 319±6

Figure 5.7: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on 3D Systems ProX 200
48
 Figure 5.8: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on EOS M280

Figure 5.9: Comparison of austenite volume fraction and Vickers microhardness of highly
austenitic feedstock fabricated on EOS M280, subjected to three-stage heat treatments

49
 Table 5.6: Comparison of austenite volume fraction and Vickers microhardness following a
three-stage heat treatment consisting of homogenization, a solutionizing step that terminated in
either air-cooling or a water-quench, then 4-hour aging; fabricated on EOS M280

EOS Ar/N2 EOS N2/N2

air-cool water-quench air-cool water-quench
post solution post solution post solution post solution
%γ HVN %γ HVN %γ HVN %γ HVN
Post-Homog <1% 334±6 <1% 334±6 31% 345±8 31% 345±8
Post-Soln 0% 324±4 <1% 302±6 25% 333±14 25% 298±17
495°C <1% 407±9 <1% 394±8 34% 351±7 42% 253±21
Homog. + Solution + Aged

550°C 20% 365±13 17% 366±8

580°C 7% 324±5 11% 327±5 12% 394±16 37% 361±33
620°C 5% 301±7 5% 305±4 18% 398±14 37% 379±19
650°C 15% 429±11 16% 417±14
680°C 12% 427±24 31% 405±17
720°C 10% 413±16 28% 426±10
760°C 10% 418±8 8% 397±7

5.6 Summary and Conclusions

The heat treatment response of additively manufactured 17-4 PH stainless steel,
representing a range of retained austenite levels as dictated by the chemical composition, was
investigated. The study focused on three overaging conditions specified for wrought [3] product:
H925 (4h at 495°C), H1075 (4h at 580°C), and H1150 (4h at 620°C). Aging heat treatments
were conducted as part of at least three independent paths: directly from the as-built condition, as
part of a two-stage heat treatment following an initial solutionization, and finally, as part of a
three-stage heat treatments that consisted of homogenization, solutionization, then aging. For the
three-stage heat treatments, the intermediate solutionizing step was terminated either by water
quench or permitted to air-cool.

When aged directly from the as-built condition, the heat treatment response is highly
dependent on the amount of retained austenite in the material. A solutionizing heat treatment

50
significantly reduced austenite levels, and among materials with ≤ 4% austenite, generally
satisfied hardness requirements upon aging. However, the highly austenitic material sustained an
aberrant behavior, and did not exhibit peak-aging until approximately 4 hours at 680°C. The
addition of a homogenization step had little impact on the aging response.

51
 Chapter 6
SUMMARY
6.1 Primary Conclusions
The role of feedstock atomization and shielding gas on the heat treat response of AM 17-
4 PH stainless steel was investigated. Four feedstock powders representing a range of nitrogen
levels were used to fabricate components under either a nitrogen or argon atmosphere. The
resulting chemical compositions were used to explain differences in phase proportions by
simulating solidification and martensite start temperatures. As more nitrogen led to greater
levels of retained austenite, the heat treatment response deviated from the expected trend, as
noted in the following observations:

• The atomization condition (and to a lesser extent, the choice of shielding gas) affect the
concentration of nitrogen in AM 17-4 PH stainless steel. Argon atomized feedstocks contained
only 0.01 wt.% N, while the concentration increased to levels of 0.06 to 0.12 wt.% in nitrogen
atomized powders. Nitrogen content within AM builds was 0 to 0.03 wt.% higher than in the
feedstock. Higher nitrogen levels corresponded to increased levels of retained austenite.

• For all conditions, higher austenite levels were observed in the feedstocks than in the fabricated
components. Material fabricated from argon atomized feedstock was fully ferritic/martensitic
regardless of processing gas, while the nitrogen atomized feedstock maintained moderate levels
of retained austenite.

• When aged directly from the as-built condition, the heat treatment response is influenced by the
amount of retained austenite. Primarily ferritic/martensitic materials followed the expected
overaged trend of declining hardness values with increasing temperatures. While partially
austenitic materials also followed this trend at low overaging temperatures, hardness increased at
higher temperatures. Once austenite levels were further reduced following a solutionizing heat
treatment, materials with ≤ 4% austenite generally satisfied hardness requirements upon aging.

• For primarily austenitic material, the lowest hardness values were observed following an
overaging heat treatment closest to the conventional peak age condition for 17-4 PH grade
stainless steel, and contrary to the expected overaging trend, continued to increase at higher
aging temperatures. Although solutionizing reduced the austenite level to < 30%, a peak aged
condition was not observed until 4 hr at 680°C.

52
• While preceding aging heat treatments with a solutionizing step generally improved the heat
treatment response, preceding it with a homogenization step (90 min at 1150°C) had little impact

6.2 Potential Next Steps

While part of this study focused on thermally induced martensitic transformation,
mechanical testing would reveal how higher retained austenite levels impact strain induced
martensitic transformation as well. In addition, the projected martensite start (M s) temperatures
calculated for the different compositions could be compared to empirical data through quenching
dilatometry experiments.

53
 REFERENCES
[1] AK Steel product data bulletin, 17-4 PH Stainless Steel, (n.d.).
http://www.aksteel.com/pdf/markets_products/stainless/precipitation/17-
4_PH_Stainless_Steel_PDB_201512.pdf (accessed August 1, 2017).

[2] R. Bhambroo, S. Roychowdhury, V. Kain, V.S. Raja, Effect of reverted austenite on

mechanical properties of precipitation hardenable 17-4 stainless steel, Mater Sci Eng A.
568 (2013) 127–133. doi:10.1016/j.msea.2013.01.011.

[3] ASTM Standard A693, Standard Specification for Precipitation-Hardening Stainless and
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