Acta Materialia 153 (2018) 35e44

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Acta Materialia
journal homepage: www.elsevier.com/locate/actamat

Full length article

Microstructure and mechanical properties of Al-Mg-Zr alloys

processed by selective laser melting
Joseph R. Croteau a, *, Seth Griffiths b, Marta D. Rossell c, Christian Leinenbach b,
Christoph Kenel d, Vincent Jansen a, David N. Seidman a, d, David C. Dunand a, d,
Nhon Q. Vo a
a
NanoAl LLC, 8025 Lamon Ave, Skokie, IL 60077, USA
b
Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Advanced Materials Processing, Überlandstrasse 129, CH-8600
Dübendorf, Switzerland
c
Empa, Swiss Federal Laboratories for Materials Science and Technology, Electron Microscopy Center, Überlandstrasse 129, CH-8600 Dübendorf,
Switzerland
d
Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208, USA

a r t i c l e i n f o a b s t r a c t

Article history: Gas-atomized powders of two ternary alloys, Al-3.60Mg-1.18Zr and Al-3.66Mg-1.57Zr (wt.%), were
Received 4 December 2017 densified via laser powder bed fusion. At energy densities ranging from 123 to 247 J/mm3, as-fabricated
Received in revised form components are near-fully densified (relative density 99.2e99.9%) as verified by X-ray tomography.
7 April 2018
While Mg acts a solid-solution strengthener, Zr creates two types of metastable L12 Al3Zr precipitates,
Accepted 21 April 2018
each playing dual roles: (a) sub-micrometer Al3Zr particles form in the melt upon solidification and act as
Available online 25 April 2018
grain refining agents, nucleating fine aluminum grains, which (i) prevent hot-tearing during the rapid
solidification inherent to laser melting and (ii) enhance tensile strength (Hall-Petch strengthening) and
Keywords:
Aluminum alloys
ductility (influence a heterogenous grain structure) after fabrication; (b) Al3Zr nano-precipitates form in
Additive manufacturing the solid alloy during subsequent aging, which (i) precipitation-strengthen the alloy leading to an in-
Selective laser melting crease of >40% in strength over the as-fabricated value, and (ii) promote thermal stability of the fine
Heterogeneous grain structure grain size (and the associated Hall-Petch strengthening) after exposure to high temperature due to the
slow kinetics of Al3Zr coarsening (from the sluggish diffusivity of Zr in solid Al-Mg). While the Zr-richer
alloy shows higher yield and ultimate tensile strength in the as-fabricated state, both alloys have
identical mechanical properties after peak aging. Interconnected bands of fine (~0.8 mm), equiaxed,
isotropic grains and coarser (~1
10 mm), columnar, textured grains e both containing oxide particles
and Al3Zr precipitates - provide a combination of high yield strength and high ductility (e.g., ~354 MPa,
and ~20%, respectively) with isotropic values in both as-fabricated and peak-aged samples, unlike Al-Si
alloys processed via laser fusion of commercial Al-Si-based powders. The pre-alloyed, gas-atomized Al-
Mg-Zr powders do not contain expensive alloying elements such as Sc, nor do they require blending with
a second powder to nucleate fine grains, making them excellent candidates for economical, large-scale
additive manufacturing applications.
© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction of rapid prototyping to rapid manufacturing [1]. Laser powder bed

fusion techniques, which boast short cycle times, low tooling costs,
The additive manufacture (AM) of metal components from and virtually unlimited design freedom, are part of an AM land-
powder feedstock e i.e. the net-shape, three-dimensional fabrica- scape which is projected to grow into a tens-of-billions dollar in-
tion of a component, layer by layer, from a computer file e has dustry between the years 2031 and 2044 [2]. Aluminum alloys,
gained popularity in the last three decades, evolving from a method despite their prevalence in conventional manufacturing and their
attractive properties (low density, high specific strength, high
thermal and electrical conductivity, excellent oxidation and
corrosion resistance), have experienced a slower adoption in the
* Corresponding author. NanoAl LLC, 8025 Lamon Ave, Skokie, IL 60077, USA

https://doi.org/10.1016/j.actamat.2018.04.053
1359-6454/© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
36 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44

AM field [1,3e5]. This is because of the lack of a strong economic with the additive manufacture of existing aluminum powders, but
driving force to switch from conventional manufacturing methods takes full advantage of the new design space allowed by AM. Most
by which intricate aluminum components are readily created (e.g., notably, the processing conditions in laser melting are far from
via casting, stamping and machining), unlike components made of equilibrium, and this method can thus manufacture bulk quantities
titanium or nickel alloys which are typically associated with low of material with metastable compositions and structures. Towards
formability and high machining costs. There are also specific diffi- this end, we investigate two ternary Al-Mg-Zr alloys fabricated by
culties associated with melting aluminum powders using a laser, the laser powder bed fusion of pre-alloyed powders. By taking
including high laser reflectivity, a tenacious surface oxide, the poor advantage of the unique, localized thermal history and its interac-
spreadability of low-density aluminum powder, the high thermal tion with the alloy chemistry, we seek to design a precipitation-
conductivity of aluminum, and the relatively large freezing ranges strengthened alloy specifically tailored for additive
of many aluminum alloys [1,5]. Finally, the high-strength aluminum manufacturing, which can be produced with near theoretical
alloys of structural relevance, such as those of the Al-Cu-based density and free of cracks, with a combination of high strength at
2000 series, the Al-Mg-Si-based 6000 series, and the Al-Zn-Mg- both room and elevated temperatures, good ductility, as well as
based 7000 series, have very poor weldability [6], making them favorable aging- and creep resistance. These new Al-Mg-Zr alloys
even more ill-suited for laser-melting additive manufacturing are anticipated to have excellent corrosion resistance due to an
where layers of material are fused one on top of another. For these optimal solid-solution concentration of Mg, and to be anodizable to
reasons, commercially-available aluminum powders for AM are to produce a protective and decorative surface.
date limited to near-eutectic Al-Si alloys, such as Al-10Si-1Mg
(nominal wt.%) and Al-12Si (nominal wt.%), which have narrow 2. Materials and experimental methods
freezing windows and are readily welded. Although AM compo-
nents with good aesthetic properties can be fabricated from these Two batches of pre-alloyed Al-Mg-Zr powders, developed by
alloys, they have generally poor strength and ductility compared to NanoAl LLC (Skokie, IL, USA) with tradename Addalloy™, were
wrought aluminum products. Thus, there is a need to develop produced by inert gas atomization (Nanoval GmbH, Berlin, Ger-
higher performing aluminum alloys specifically tailored for addi- many) with compositions of Al-3.60Mg-1.18Zr and Al-3.66Mg-
tive manufacturing. 1.57Zr (both in wt.%). These compositions in at.% are Al-4.0Mg-
The high-strength aluminum alloys of the 2000, 6000, and 7000 0.35Zr and Al-4.0Mg-0.47Zr, respectively. Chemical composition
series are important to the aerospace industry, an early adopter of of the powders was determined by inductively coupled plasma
AM technology, and are thus appealing candidates for alloy optical emission spectroscopy (ICP-OES) at ATI Wah Chang (Albany,
development. However, high concentrations of alloying elements OR, USA). The sieved particle sizes ranged from 10 to 45 mm, with a
and wide freezing ranges make these precipitation-strengthened mean particle diameter d50 ¼ 13.7 mm. Ten, 10
10
10 mm spec-
alloys susceptible to liquation cracking and hot tearing when pro- imens were produced in an argon environment with less than 0.5%
cessed by laser powder bed fusion AM [1], as expected from their oxygen content by selective laser melting using a Concept Laser M2
poor weldability. Karg et al. investigated the processability of instrument equipped with a 200 W fiber laser operating in
aluminum alloys 2022 and 2024 by laser beam melting and found continuous mode at a wavelength of 1071 nm with a beam quality
the latter alloy to be less susceptible to porosity and cracking [7]. M2 ¼ 1.02 and a spot size of 90 mm. The instrument was operated
The authors attributed this observation to the higher concentration with the maximum laser power of P ¼ 200 W, a powder layer
of silicon in the alloy, and thus a decrease in melt pool viscosity. thickness t ¼ 30 mm, a hatch spacing h ¼ 135 or 150 mm, and laser
Similarly, Sistiaga et al. improved the laser powder bed fusion scanning speeds v ranging from 200 to 800 mm/s, so that volu-
processability of aluminum alloy 7075 by blending the alloy pow- metric energy densities E, according to the relationship E ¼ P/vht,
der with elemental silicon powder (from 1 to 4 wt %), with the ranged from 56 to 247 J/mm3. A chess board scanning strategy was
higher additions resulting in dense, crack-free material [8]. The utilized for all samples. The purpose of this limited parametric
authors again attributed the better processability to lower melt study was not to fully investigate the process parameter space, but
pool viscosity resulting from the addition of silicon and noted a rather to focus on parameters providing high-density alloys. A more
strong grain refining effect. detailed investigation of the influence of process parameters,
An alternative to the high-strength 2000, 6000, and 7000 series including the effect of rescanning, is presented elsewhere [16].
alloys are the moderate-strength Al-Mg-based 5000 series alloys. The density of the fabricated cubes was determined both by the
Conventionally denoted as non-heat treatable, these alloys benefit Archimedes method and by image analysis of optical micrographs.
from solid-solution strengthening and strain hardening and have Cross-sections were prepared for scanning electron microscopy
excellent corrosion resistance and good weldability. In recent de- (SEM) and electron backscattered diffraction (EBSD) analysis
cades, there has been intensive research on scandium- and through standard metallographic procedures consisting of grinding
zirconium-modified Al-Mg-based cast and wrought alloys, showing with water-lubricated silicon-carbide discs, polishing with water-
significant effects of grain refining, precipitation-strengthening based diamond suspensions and a colloidal silica suspension, and
from coherent Al3(Sc,Zr) nano-precipitates, and improved coars- etching with Keller's reagent.
ening- and creep-resistance at temperatures as high as 400  C The Vickers microhardness of the alloys was measured in the as-
[9e11]. In recent publications, Scalmalloy® (Al-4.6Mg-0.66Sc- fabricated and artifically aged condition on a metallographically
0.42Zr-0.49Mn, wt.%) was identified as a high-performance polished surface. Furthermore, a block measuring 10
20
40 mm
aluminum alloy well suited for laser melting AM [12e15]. was fabricated from each batch of powder, with the particle size
Although this alloy, when processed by laser powder bed fusion, ranging from 8 to 25 mm, using the highest energy density
has mechanical properties matching or exceeding those of con- (E ¼ 247 J/mm3), with laser power of 200 W, scan speed of 200 mm/
ventional wrought aluminum alloys via formation of Al3(Sc,Zr) s, hatch spacing of 135 mm, and a layer thickness of 30 mm. Sixteen
nanoprecipitates, the high levels of scandium make it very dogbone tensile samples were machined from each block, eight
expensive. each with their tensile axis parallel and orthogonal to the build axis.
The aim of the current study is to design, specifically for additive The tensile sample gauge measured 2.5 mm in diameter and
manufacturing, an economical, Sc-free, age-hardenable aluminum 8.0 mm in length. The tensile mechanical properties were deter-
alloy, which not only overcomes the generic challenges associated mined on a mechanical test frame with a fixed strain rate of
 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44 37

0.5 mm/s, measuring strain via cross-head displacement, after this alloy benefits from solid-solution strengthening from Mg,
correction for machine compliance. Although these samples are grain-boundary strengthening from fine grains nucleated by sub-
smaller than typical tensile bars for metals, the gage diameter en- micrometer Al3Zr precipitates (Fig. 1a), and precipitation-
compasses more than 16 passes of the laser and about 2500 grains, strengthening from nanometric Al3Zr precipitates. Additionally,
so that the measured properties are indicative of full scale tests. both nano- and micro-size Al3Zr precipitates have high thermal
The sample chosen for transmission electron microscopy (TEM) stability due to the very slow diffusivity of Zr in solid Al, insuring
analysis was produced with the same parameters listed above excellent coarsening resistance at high temperatures [18,19]. An
except with a coarser powder (d50 ¼ 37 mm) and a 40 mm layer additional microstructural feature observed in this alloy is nano-
thickness. An electron-transparent sample was extracted from the metric oxide particles homogenously dispersed through the solid-
fine-grain region (transverse microstructure showing) with an FEI ified alloy (Fig. 1b). It is unclear whether these oxide particles
Helios NanoLab 600i focused ion beam (FIB). Since Ga ions were originate from fragmentation of the oxide shell present on the
used during sample preparation, Ga was detected on the edges of atomized powder or from melt oxidation during laser melting.
the analyzed precipitates. The selected area diffraction pattern was Although, these particles may add to the strength of the material
obtained at 200 kV with a JEOL 2200FS microscope. TEM, scanning and are likely too fine and too few to have a negative effect on
transmission electron microscopy (STEM), and energy dispersive x- ductility. A drawback to this alloy composition, however, is the
ray (EDX) spectrosocpy were performed at 300 kV using an FEI magnesium presence, which evaporates at very high temperatures
Titan Themis microscope equipped with a SuperEDX system during both gas atomization and laser melting. This issue is well
(ChemiSTEM technology). known, even in conventional production and processing of Al-Mg
based alloys [20]. In fact, chemical analysis of the laser-melted al-
loys showed a decrease in magnesium concentration from 3.6 to
3. Experimental results
2.7 wt% in the bulk samples processed with the highest laser energy
density.
3.1. Alloy design and processability by selective laser melting

The goal of this study is to develop a age-hardenable, Sc-free, 3.2. Laser melting process and microstructure of printed samples
aluminum alloy specifically tailored for laser powder bed fusion
AM. To accomplish this, an Al-Mg-based alloy family was chosen, The combination of the dynamic solidification conditions of the
which has good weldability and provides solid-solution strength- melt pool and this alloy chemistry, creates a characteristic bi-
ening and corrosion resistance. The relative density of the as- continuous, fan-shell grain boundary pattern in the solidified ma-
fabricated cubes, as measured by the Archimedes method and terial (Fig. 1c). Thus, the metallographic cross-sections exhibit
image analysis, was higher than 99.2% for all laser energy densities bands of (i) interconnected fine grains at the melt pool boundary
in the range of 123e247 J/mm3, reliably producing crack-free and (ii) coarse, columnar grains which solidify along the thermal
samples. The pore microstructure and volume fraction were also gradient towards the top-center of the melt pool. Electron back-
assessed via synchrotron X-ray tomography, as described in the scatter diffraction (EBSD) analysis shows random orientation in the
Supplemental Information. Zirconium additions well beyond the fine grain regions, and a strong [100] texture - the preferred so-
maximum equilibrium solubility of 0.27 wt% (0.083 at.%) take lidification direction of aluminum - in the coarse grain regions
advantage of the extended solid solubility afforded by rapid solid- (Fig. 2). This microstructure is consistent with the findings of other
ification [17]. The main intended role of zirconium is to create two researchers who have processed Al-Mg based alloys modified with
types of precipitates: (i) cubic, sub-micrometer sized Al3Zr pre- additions of both scandium and zirconium by selective laser
cipitates formed upon solidification which are effective grain re- melting [13,14,21,22]. The microstructure in the studied alloy is
finers [6], and (ii) L12-structured Al3Zr nano-precipitates formed at achieved through the grain-nucleation effect of Al3Zr primary
high number density upon subsequent aging of the super-saturated precipitates, which are visible at the center of almost each grain in
Al-Mg-Zr matrix [18,19]. Thus, when processed by laser melting, the fine-grain region and noticeably absent in the coarse-grain

Fig. 1. Backscatter SEM micrograph showing the cross section of as-fabricated Al-
3.60Mg-1.18Zr wt.% alloy fabricated with the highest laser energy density of 247 J/
mm3. Build direction is from bottom to top. (a) Coarse, elongated grains are evident in Fig. 1: (B). Backscatter SEM micrograph showing a cuboidal, sub-micrometer Al3Zr
the top half of the image and fine, equiaxed grains in the bottom half. Cuboidal Al3Zr precipitate (white) in the center of a micrometer-size grain which also contain sub-
precipitates (white) are located in the center of most fine grains, but none are present 200 nm oxide particles (black rounded particles, labeled “o”). Grain boundaries are
in the elongated coarser grains. Oxide particles (dark) are present throughout. darker, using Z-contrast, consistent with Mg and/or nano-size oxide enrichment.
38 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44

boundaries. A low magnification BF-TEM image of a precipitate

located within a grain and a selected area diffraction pattern of the
same precipitate are shown in Fig. 4. The diffraction pattern was
recorded along the [001] zone axis and shows the 100- and 010-
type superlattice reflections from the L12 phase. STEM-EDX
chemical mapping of a typical precipitate is shown in Fig. 5. The
cuboidal precipitate is enriched in Zr. Given the L12 structure of the
precipitates and the enriched Zr content it can be concluded that
these precipitates are L12 Al3Zr, which are known to be coherent
with the matrix. The dark areas in the center of the precipitate
which appear to be slightly enriched in Al and depleted in Zr are
assumed to be porosity. Further TEM analysis can be found in a
recent publication by Griffiths et al. [16].

3.3. Post process heat treating and hardness evolution

The rapid solidification inherent to selective laser melting pro-

duces an alloy highly super-saturated with zirconium, which upon
Fig. 1: (C). Backscatter SEM micrograph showing the cross section of Al-3.60Mg-1.18Zr a subsequent heat-treatment exhibits strong precipitation
wt.% alloy fabricated with a laser energy density of 165 J/mm3. Build direction is from strengthening effects. The average Vickers microhardness of the as-
bottom to top. The alloy shows a fanshell solidification structure consisting of a fabricated Al-3.60Mg-1.18Zr and Al-3.66Mg-1.57Zr alloys are
mixture of coarse, elongated grains and fine, equiaxed grains. Porosity (black) is visible, 875 ± 27 and 961 ± 33 MPa, respectively, independent of the laser
typically at melt pool boundaries, and is likely exaggerated by the chemical etch.
energy density used to fabricate the bulk sample. The higher as-
fabricated hardness observed in the high-Zr alloy may be attrib-
regions (Fig. 1a). uted to an increased level of solid-solution strengthening coming
A low magnification bright field (BF) STEM image of the fine- from more Zr dissolved in the Al matrix, and/or to L12 Al3Zr nano-
grain region of the as-processed sample is shown in Fig. 3. Pre- precipitates formed during manufacturing, i.e., during in situ
cipitates are observed both within the grains and at the grain annealing from the laser reheating layers of previously-deposited

Fig. 2. EBSD map showing the cross section of peak-aged Al-3.60Mg-1.18Zr wt.% alloy fabricated with the highest laser energy density of 247 J/mm3. Build direction is from bottom
to top. Average grain size in fine-grain regions is 770 ± 340 nm. Texturing is present in coarse grains indicated by the overlaid pole figure generated from those regions.
 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44 39

using two-step annealing (360  C/4 h and 420  C/4 h) and when
using one-step annealing at 360  C for a longer time (32 h) [23]. In
this case, a low precipitation strengthening effect was associated
with discontinuous precipitation, and maximum strengthening
was associated with continuous precipitation due to the formation
of nanoscale L12 Al3Zr dispersoids with a mean size of 7 nm. The
two hardness peaks visible in Fig. 7 may be related to this trans-
formation; this hypothesis is tested via extensive TEM in-
vestigations which are currently underway. The microhardness
after aging for 60 h at 400  C falls to ~90% of peak hardness. We
expect the drop in strength to be initially associated with the
coarsening of equiaxed, metastable L12-structured Al3Zr pre-
cipitates and their eventual transformation to the D023 structures
(Fig. 8a), as reported in Refs. [18,19,24]; this would then be followed
by grain coarsening, consistent with Fig. 8b. After aging for 144 h at
400  C, the average grain size in the fine grain regions has grown
from 770 to 1280 nm as determined by EBSD.

3.4. Mechanical properties

Table 1 shows average values of yield strength, ultimate tensile

strength, and elongation to failure determined on tensile samples
machined from solid blocks of laser-melted alloys in both the as-
fabricated and peak-aged conditions. An example tensile bar is
shown in Fig. 9. The as-fabricated properties, i.e., without any post-
Fig. 3. Low magnification BF-STEM image taken from the fine-grain region showing
primary Al3Zr precipitates (dark colored cubes) both within the grains and at the grain process thermal treatment, show a strong dependence on zirco-
boundaries. nium content, with the yield and tensile strength being much
higher, and ductility slightly lower, for the alloy with higher zir-
conium content. However, both alloys have statistically equivalent
solid material. Although both alloys have different as-fabricated strengths and ductility after a post process heat treatment and
microhardness, after aging for 8 h at 400  C the microhardness of show no dependence on build orientation. A two-tailed, difference-
both alloys achieve the same value of 1310 ± 42 MPa (Fig. 6). This between-two-means t-test with a 95% confidence interval was used
would suggest that both alloys, despite having different bulk con- to determine that the yield strength, tensile strength, and elonga-
centrations of Zr, have the same amount of dissolved Zr available for tion of the heat treated materials have no dependence on Zr con-
post-deposition precipitation and supports the latter hypothesis of tent (1.18 vs 1.57 wt%) or build direction.
in situ annealing triggering precipitation in the Zr-richer alloy.
Bulk samples were isothermally aged for times ranging from 0.5 4. Discussion
to 144 h at 400  C to determine the peak aging time for dense
material processed with laser energy ranging from 62 to 247 J/mm3 4.1. Processability by selective laser melting
(Fig. 7). It is evident that a first peak hardness is reached at ~2 h, and
a second peak hardness is reached at ~6e8 h. It has been shown in During the laser powder bed fusion process, a layer of powder is
cast Al-3Mg-0.25Zr wt.% alloys that the metastable L12 Al3Zr pre- spread atop previously deposited material, and a rastering laser
cipitation mechanism changes from discontinuous (elongated fully melts that layer of powder as well as one or more previously
precipitates in fans) to continuous (equiaxed precipitates) when deposited layers [1]. Since it is a laser beam-based process, the

Fig. 4. (A) A low magnification BF-TEM image taken from the fine-grain region showing an Al3Zr precipitate (highlighted by a white circle) within a grain. (b) Selected area
diffraction pattern along [001] taken from the precipitate circled in Fig. 4a showing the 100- and 010-type superlattice reflections of the L12 structure.
40 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44

Fig. 5. STEM-EDX chemical maps of a precipitate in the fine-grain region. The precipitate is enriched in Zr. Dark areas are assumed to be pores. Chemical analysis was performed
using the Zr-K, Al-K, Mg-K lines.

Fig. 6. As-fabricated and aged hardness of Al-3.60Mg-1.18Zr wt.% (black circles) and
Al-3.66Mg-1.57Zr wt.% (blue diamonds, offset slightly to the left for clarity) as a
function of the energy density used to fabricate the bulk component. Ten hardness
measurements were taken on each sample. Both a linear regression and a t-test fail to
show a significant dependence of hardness on energy density in either the as-
fabricated or artificially-aged condition. The alloy with higher Zr content shows a Fig. 7. Hardness evolution upon isothermal aging at 400  C of Al-3.60Mg-1.18Zr wt.%
higher as-fabricated hardness, however after aging at 400  C for 8 h, there is no sta- (black circles) and Al-3.66Mg-1.57Zr wt.% (blue diamonds). Each data point is the
tistical difference between the two alloys. The dashed line represents the mean of all average of multiple samples fabricated with various laser energy densities ranging
measurements and the shaded band represents one standard deviation. (For inter- between 62 and 247 J/mm3. Error bars represent one standard deviation of ten mea-
pretation of the references to color in this figure legend, the reader is referred to the surements of each sample. (For interpretation of the references to color in this figure
Web version of this article.) legend, the reader is referred to the Web version of this article.)
 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44 41

Fig. 8. A) Backscatter SEM micrograph showing the cross section of Al-3.60Mg-1.18Zr wt.% alloy fabricated with the highest laser energy density of 247 J/mm3 and overaged at
400  C for 144 h. Nano-scale Al3Zr precipitates transformed to plates (white phase), likely the stable D023 structure. Black pores are also visible. b) EBSD map showing the same
sample at lower magnification, with build direction from bottom to top. Fine grains have grown to 1280 ± 660 nm.

Table 1
Average tensile properties for two Al-Mg-Zr alloys processed by laser powder bed fusion AM in the as-fabricated and peak-aged conditions. Samples in which the tensile axis is
parallel to the build direction are labelled “Z” whereas those orthogonal to the build direction are labelled “XY”.

As-Fabricated

Alloy Composition (wt.%) Yield Strength (MPa) Ultimate Tensile Strength (MPa) Elongation (%)

Al-3.60Mg-1.18Zr Z 221 ± 1 287 ± 1 25.6 ± 0.8

XY 220 ± 3 292 ± 2 29.0 ± 1.6
Al-3.66Mg-1.57Zr Z 282 ± 8 332 ± 2 24.0 ± 1.0
XY 290 ± 6 329 ± 3 25.2 ± 1.8

Post Heat Treatment

Al-3.60Mg-1.18Zr Z 350 ± 7 382 ± 5 17.1 ± 2.0

XY 353 ± 5 386 ± 3 18.6 ± 0.9
Al-3.66Mg-1.57Zr Z 349 ± 15 383 ± 5 19.5 ± 4.4
XY 365 ± 11 389 ± 4 23.9 ± 4.4

to combat hot-tearing in cast components [6]. The absence of pri-

mary Al3Zr precipitates and fine grains further from the bottom of
the melt pool is attributed to the increasing solidification front
velocity, leading to solute trapping which suppresses the formation
of primary Al3Zr. Without the presence of nuclei, columnar grain
growth along the [100] direction dominates.
Although Sistiaga et al. [8] concluded that the addition of
elemental Si powder to pre-alloyed AA7075 powders improves the
processability of that alloy via a eutectic reaction which decreases
melt pool viscosity, these authors present micrographs of a cross-
Fig. 9. A miniature tensile bar before and after tensile testing orthogonal to the build section of fabricated samples where silicon particles are still
direction, highlighting necking and elongation. The yield strength, ultimate tensile evident in the dense material. This suggests that Si powders were
strength, and elongation for this sample is 376 MPa, 393 MPa, and 27.8% respectively. not fully dissolved in the molten aluminum during the process, and
Sample was fabricated from Al-3.66Mg-1.57Zr wt.% powders with the highest laser
thus acted to nucleate fcc-Al grains upon solidification. Addition-
energy density of 247 J/mm3 and peak-aged prior to testing.
ally, the corresponding X-ray diffraction patterns of these dense
materials show evidence of a Si peak, which increases in intensity
solidification conditions in the melt pool vary depending on loca- with higher levels of added silicon powder. Furthermore, the au-
tion in the melt pool [25]. The solidification interface velocity is thors reported a direct correlation between the fraction of fine
slow at the bottom of the melt pool and rapidly increases as the grains in the deposited material with the amount of added silicon
surface of the melt pool is approached. When these solidification and found that a crack-free component could only be achieved with
conditions are paired with an alloy with a peritectic reaction, such silicon additions of 3 and 4 wt%. In a similar study, Roberts et al.
as Al-Zr, a microstructure as shown in the prior sections forms. The blended commercially pure, gas-atomized aluminum powders and
steps of the microstructure formation are described by Griffiths silicon powders, and produced a fully dense, crack-free component
et al. [16] and is summarized here. When a hyperperitectic Al-Zr through laser melting [26]. In this case, the authors concluded that
alloy solidifies, such as the alloy presented here, Al3Zr pre- there was insufficient time for silicon particles to fully dissolve, and
cipitates will first form in the melt. These precipitates then serve as they remained dispersed in the solidified aluminum matrix. This
a nucleation site for fcc-Al grains, producing a strong grain refining suggests that the main benefit of added silicon is not to improve
effect. The formation of fine grains upon solidification is expected melt pool viscosity, but rather to refine grains which evenly dis-
to contribute to the absence of cracks in the as-fabricated state of tributes internal thermal stresses responsible for hot tearing during
both alloys. This is supported by the aluminum casting industry solidification.
practice to add grain-refining agents, such as Ti, TiB2, Zr, Mn, or Cr Further evidence of this mechanism is disclosed by Martin et al.
42 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44

who describes the semi-passive control of the solidification of laser a high concentration of Zr solute supersaturated within the fcc-Al
melted powders [27,28]. In this approach, the surfaces of aluminum matrix. It is well documented that such supersaturated Al-Zr al-
alloy powders are coated with ceramic nanoparticles or other loys form strengthening L12-structured Al3Zr nano-precipitates
known grain refiners to blunt grain growth during laser melting during a subsequent aging treatment [18,19,23,24]. Investigating
AM. This results in dense, crack-free components fabricated from the structure of the nano-precipitates is outside of the scope of the
otherwise difficult to manufacture alloys. These mechanisms present work, however further TEM investigations are underway.
contrast with the grain refining approach in the present study, in Because some Zr is consumed to form Al3Zr primary precipitates
which the alloy itself undergoes an in situ reaction to form grain during melt/freeze cycling, we expect that this dual effect of Zr can
refiners precipitated from the super-saturated Al-Mg-Zr pre- only be achieved at concentrations exceeding the peritectic value.
alloyed powders. This chemical synthesis reaction is a direct This is possible via far-from-equilibrium processing and highlights
result of the specific interaction of alloy chemistry and the laser the benefits of designing an alloy specifically tailored for additive
melting process, which capitalizes on the off-equilibrium condi- manufacturing. In fact, 0.2 wt% Zr was shown to be insufficient to
tions of AM processing. produce this type of bimodal grain structure in a laser melted Al-
Mg based alloy; however, the addition of 1.0 wt% Sc was enough
4.2. Multiple roles of zirconium in additive manufactured Al-Mg-Zr- to produce a refined grain structure in the fabricated alloy and
based alloys render it age-hardenable after deposition [33].
Finally, Al3Zr precipitates have very high thermal stability due to
In traditional cast and wrought aluminum alloys, Zr is the sluggish diffusivity of Zr in solid Al [34]. For this reason, as
commonly used for grain refinement [29]. Zirconium concentration reported in numerous previous aging studies [18,35e37], for the
in such alloys is limited to <0.3 wt% (<0.09 at.%) because liquid alloys which contain such precipitates, the characteristic grain and
solubility of Zr at a typical casting temperature of ~750  C is precipitate structures, and the mechanical properties which result
~0.09 at.% and maximum solid solubility of Zr in solid aluminum is from them, are retained during the aging treatment at 400  C, e.g.,
0.083 at.% at 660  C [30]. However, in laser powder bed fusion, the grain growth and recrystallization are strongly inhibited. At 300  C,
molten zone is heated for a fraction of a second to temperatures as the diffusion coefficient of Zr is about four orders of magnitude
high as ~2000  C (where Zr solubility is much higher), before it smaller than that of Sc, consistent with Al-Sc alloys being coars-
rapidly cools and solidifies [1]. Like the well-studied rapid solidi- ening resistant up to ~300  C, and Al-Zr alloys up to 400  C.
fication processes, extended Zr solubility can be achieved in the Therefore, the mechanical properties of the studied alloys should
solid material and Zr can thus be utilized to form primary Al3Zr be heat resistant and should survive in the extreme condition of
particles upon solidification and secondary L12-Al3Zr precipitates continuous service at elevated temperatures, for example, 300  C
in the solid upon subsequent aging [18]. The primary Al3Zr in this for ~13 years as estimated from the equivalent diffusion distance
case is the metastable L12-structure [16] rather than the equilib- (~100 nm) at 400  C for 60 h, associated with a drop of 10% from
rium D023 structure typically exhibited by primary Al3Zr particles peak-hardness (Fig. 7).
in cast or wrought aluminum alloys where the cooling rate is much We anticipate that increasing the Zr concentration in the pre-
slower [31]. alloyed Al-Mg-Zr powder will increase the mechanical strength
In the presently studied Al-Mg-Zr alloys, high Zr concentrations obtained after peak-aging. However, maximum Zr concentration in
fulfill several key purposes. First, Zr behaves as a grain refining these alloys will be limited both by the amount of Zr which remains
agent by forming primary Al3Zr particles in the melt. Upon rapid dissolved in solid aluminum during the thermal/phase cycling of
solidification, these precipitates serve as nuclei for a-Al grains and the laser melting process, and by how much Zr can be dissolved in
achieve a strong grain refining effect, effectively managing thermal the liquid aluminum melt from which powders are formed by at-
stresses, and thus improving the processability of this material. omization. The aging response shown in Figs. 6 and 7 can be
Second, this mechanism of grain nucleation via primary Al3Zr compared to literature values on arc-melted and aged Al-0.68Zr
precipitates is responsible in forming the observed bimodal grain wt.% (Al-0.2Zr at.%) alloys [18,19], where a hardness increase of
size distribution. Fine grains with random orientation, nucleated by ~490 MPa is achieved after peak-aging, which is comparable to the
Al3Zr primary precipitates, are evident at the edge of the melt pool, hardness increase shown in Figs. 6 and 7 of the presently studied
where the alloy experiences solidification-front velocities slow Al-Mg-Zr alloys. Thus, Zr solid supersaturation in both our alloys,
enough to allow for primary Al3Zr precipitation. As the remaining independent of Zr content, is believed to be ~0.2 at.%, the same as
melt solidifies, now somewhat depleted of Zr and without forma- reported in the above articles for rapidly quenched, arc-melted
tion of Al3Zr particles, coarse grains are nucleated by the underlying alloys [18,19].
fine grains, and solidify directionally along the thermal gradient
(i.e. towards the top-center of the melt pool). During this stage, 4.3. Ductility enhancement from bimodal grain size distribution
grains oriented with a favorable solidification direction grow faster
than grains with unfavorable orientations, producing a [100] A bimodal grain size distribution was observed in the laser
texture in the coarse-grained region. It was shown in Ref. [16] that melted samples, combining fine equiaxed grains (with a size of
this coarse-grain region is free of primary Al3Zr precipitates 770 ± 340 nm) and coarser columnar grains (with an average width
because the solidification-front velocity increases as it approaches of 1 mm and length of ~5e10 mm). An estimate of yield stress in-
the top of the melt pool and more effectively traps solutes [32]. crease due to grain boundary strengthening can be determined
Close inspection of the cross section of our laser melted alloys at the from the Hall-Petch relation [38],
top of the specimens reveals an average melt pool depth of ~100 mm
with a single band of fine grains at its edge, and coarse grains which Dsg ¼ kD1=2 (1)
span a depth of ~90 mm just below the top surface. This observation
is consistent with the findings of Spierings et al. [14]. This bimodal, where k is an experimental constant determined to be
bi-continuous microstructure enhances mechanical ductility, 0.17 MN m3/2 in a dilute Al-Mg-Li alloy [38]. For a grain size
which is subsequently discussed. D ¼ 770 nm and D z 3e5 mm, Eq. (1) predicts an increase in yield
It is postulated that the laser-processed components exhibit, strength of Ds ¼ 200 MPa and Ds z 90 MPa, respectively. Yield
because of the high speed of solidification and subsequent cooling, strength of a typical cast Al-3.6 Mg wt.% alloy is ~95 MPa [39],
 J.R. Croteau et al. / Acta Materialia 153 (2018) 35e44 43

whereas it is ~220 MPa for the present as-fabricated Al-3.60Mg- (a) Sub-micrometer Al3Zr particles form in the melt during
1.18Zr wt.% (Table 1). Assuming Zr does not significantly contribute solidification and act as a grain refining agent, nucleating
to strength of the as-fabricated sample (as it forms either coarse fine aluminum grains, which
primary precipitates or it remains in solid solution within the (i) prevent hot-tearing during the laser melting processing
matrix), grain boundary strengthening is estimated to be and
Dsg ¼ 220e95 ¼ 125 MPa, which is consistent with the average (ii) enhance tensile strength via Hall-Petch strengthening,
strengthening observed from the bimodal grain size (200 þ 90)/ which influence the formation of a heterogenous grain
2 ¼ 145 MPa. This simple estimation does not consider the volume structure which preserves ductility;
fraction of the coarse and fine-grain region, nor their connectivity (b) Al3Zr nano-precipitates form in the solid alloy during sub-
and interactions. sequent aging, which
The most beneficial property of the bimodal grain size distri- (i) precipitation-strengthen the alloy leading to an increase
bution, though, is the high tensile ductility achieved in both as- of more than ~40% in strength over the as-fabricated
fabricated and aged conditions. We expect that the bimodal grain value, and
size distribution induces strain hardening mechanisms that stabi- (ii) promote thermal stability of the grains (and the asso-
lize the tensile deformation, resulting in a high ductility [40]. In ciated Hall-Petch strengthening) after exposure to high
fact, this mechanism is extensively studied and discussed in the temperature due to the sluggish Al3Zr coarsening (from
nanocrystalline materials literature [41,42]. For example, Witkin the low diffusivity of Zr in solid Al-Mg).
et al. [41] reported a quadrupling in ductility from 1.4 to 5.4% in
high strength Al-7.5 Mg (wt.%) extrusions by blending nanograin,
cryomilled powders with 30% unmilled powders with macro-size Declaration of interests
grains to produce a bimodal grain size distribution. Cheng et al.
[42] reported 65% elongation to failure and 30% uniform elongation NQV, DNS and DCD have financial interests relative to NanoAl,
in nanocrystalline copper, fabricated by a thermomechanical pro- LLC, which could potentially benefit from the outcomes of this
cess that promotes bimodal grain size distribution. Wang et al. research.
described in detail this mechanism in Ref. [43], which is one of the
three strategies to achieve uniform tensile deformation in nano- Acknowledgments
structured metal. Thus, the ability for the present Al-Mg-Zr-based
alloys fabricated by laser powder bed fusion to exhibit a ther- This research was partially sponsored by the Army Research
mally stable, bimodal grain size distribution is highly desirable to Laboratory and was accomplished under Cooperative Agreement
achieve an outstanding combination of strength and ductility in Number W911NF-15-2-0026 (V.K. Champagne, monitor) through
additively manufactured components [44]. Northeastern University, Subaward Agreement Number 504062-
78050 (D. Luzzi, monitor). The views and conclusions contained in
this document are those of the authors and should not be inter-
preted as representing the official policies, either expressed or
5. Conclusions implied, of the Army Research Laboratory or the U.S. Government.
The U.S. Government is authorized to reproduce and distribute
Microstructure and mechanical properties of two ternary alloys reprints for Government purposes notwithstanding any copyright
- Al-3.6%Mg with ~1.2 and 1.6 Zr (wt.%) - fabricated by laser powder notation herein.
bed fusion additive manufacturing were investigated. The
following conclusions are drawn: Appendix A. Supplementary data

- Nearly 100% relative density can be obtained in both as- Supplementary data related to this article can be found at
fabricated alloys when they are processed with a set of laser https://doi.org/10.1016/j.actamat.2018.04.053.
parameters providing energy densities of 123e247 J/mm3 (the
latter corresponding to a laser power of 200 W, powder layer References
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