metals

Article
Characterization of an Extruded Mg-Dy-Nd Alloy
during Stress Corrosion with C-Ring Tests
Petra Maier 1, * , Benjamin Clausius 1 , Jens Wicke 1 and Norbert Hort 2
1 School of Mechanical Engineering, University of Applied Sciences Stralsund, 18435 Stralsund, Germany;
benjamin.clausius@hochschule-stralsund.de (B.C.); jens.wicke@fh-stralsund.de (J.W.)
2 Helmholtz-Zentrum Geesthacht, Magnesium Innovation Center, 21502 Geesthacht, Germany;
norbert.hort@hzg.de
* Correspondence: petra.maier@hochschule-stralsund.de; Tel.: +49-3831-456419




Received: 11 April 2020; Accepted: 28 April 2020; Published: 29 April 2020


Abstract: This study focuses on the characterization of the failure behavior of an extruded Mg10Dy1Nd
alloy during stress corrosion. The microstructure, hardness, strength and corrosion behavior of binary
alloys Mg10Dy and Mg1Nd are compared to those of the ternary alloy system. The ternary alloy
Mg-Dy-Nd that is not fully recrystallized has the highest hardness but lacks ductility. The investigated
alloys twin during plastic deformation. Static C-ring tests in Ringer solution were used to evaluate
the stress corrosion properties, and stress corrosion could not be found. None of the alloys failed
by fracturing, but corrosion pits formed to various extents. These corrosion pits were elliptical
in shape and located below the surface. Some of the pits reduced the remaining wall thickness
significantly, but the stress increased by the notch effect did not lead to crack initiation. Furthermore,
the C-ring specimen was subjected to compressive loading until fracture. Whereas the Mg1Nd
alloy showed ductile behavior, the alloys containing Dy fractured on the tensile side. The crack
initiation and growth were mainly influenced by the twin boundaries. The Mg10Dy1Nd alloy had an
inhomogeneous microstructure and low ductility, which resulted in a lower fracture toughness than
that of the Mg10Dy alloy. There were features that indicate hydrogen-assisted fracture. Although
adding Nd decreased the fracture toughness, it reduced the grain size and had a positive influence on
the corrosion rate during immersion testing.

Keywords: magnesium; Mg-Dy-Nd; C-ring test; stress corrosion; corrosion morphology

1. Introduction
Temporary implants made of biodegradable magnesium have been widely accepted; the challenges
are known, and first applications are already in use [1–6]. Regarding the regeneration of musculoskeletal
tissue, Mg alloys seem to be promising for customized engineering of degradable implants [7].
Biomechanical approaches have shown that a degraded Mg pin is well connected with bone [8], and
the understanding of the degradation layer is increasing [9]. WE43, a rare earth-containing alloy
(primarily Nd), is a high-strength alloy with an acceptable biologic response when the grain size is
controlled to be very small [10–12]. According to the available data, WE43 does not show significant
toxicity to living cells [12]. Although WE43 was originally developed as a creep-resistant alloy for
aerospace applications, the alloys in this study are binary and ternary base alloys for Resoloy®, which
was developed by MEKO Laser Materials Processing, Sarstedt, Germany and the Helmholtz Center
Geesthacht, Geesthacht, Germany, specifically for absorbable implants [13–16]. Resoloy®is an alloy
based on Mg-Dy-Nd with additional alloying elements Zn and Zr that showed excellent strength,
ductility and corrosion behavior with an optimized microstructure, as demonstrated in previous

Metals 2020, 10, 584; doi:10.3390/met10050584 www.mdpi.com/journal/metals

Metals 2020, 10, 584 2 of 16

literature reports [17]. To eliminate Zn and Zr from Resoloy®, the alloy system Mg-Dy-Nd and its
combinations are the focus of this study and used for comparison.
Research by Yang et al. [18] showed that the binary cast Mg-Dy alloy exhibits the best combination
of mechanical and corrosion properties with 10 wt% Dy when alloying Dy between 5 and 20 wt%.
Dy has a very high solubility in Mg (25.3 wt%) and alloying with Dy can adjust both the mechanical
and corrosion properties by heat treatment; Dy alloys and its Dy-enriched corrosion layer also
show good cytocompatibility, according to an in vitro study of the cytotoxicity and inflammatory
response [19,20]. In situ solidification experiments on Mg20Dy found Mg24 Dy5 as a secondary
phase [21]. The equilibrium β phase has also been studied by Li et al. [22] and Smola et al. [23], and an
aging response with an increase in hardness has been found. Nd has a low solid solubility in Mg and
forms stable intermetallic phases at grain boundaries; therefore, it is added to provide precipitation
strengthening. It also improves the corrosion resistance of Mg alloys by reducing the effect of galvanic
corrosion between the secondary phases and the matrix and by providing an improved protective
surface film. Furthermore, a Nd-implanted WE43 alloy exhibited a remarkably enhanced cell adhesion
and biocompatibility [24–27]. A study on Mg2Nd demonstrated good in vivo biocompatibility and
histological analysis showed moderate mucosal hyperplasia with a mild, nonspecific inflammatory
response [27,28]. In addition to alloying Nd, Zn and Zr in Mg-Dy alloys, as is done in Resoloy® [17],
combinations of Al, Zn, Zr [29] and Gd and Zr [30] have also been explored, mostly to tailor the
mechanical and corrosion properties by heat treatment.
A uniform corrosion morphology, a moderate corrosion rate and low hydrogen evolution are
required in biodegradable implant materials. The corrosion morphology is often described by the
appearance of local corrosion: the amount, size and shape of corrosion pits. According to guidance
by the ASTM, pitting can be examined by visual inspection using cross-sectional micrographs [31].
Harmful pits are deep and narrow, causing a strong reduction in the cross-sectional area and an
increased stress intensity during mechanical loading; these pits act as notches and therefore as crack
initiators. Harmless pits are wide and shallow; if they overlap during corrosion, a uniform corrosion
morphology develops. Furthermore, the pitting factor resulting from the deepest corrosion pits in
relation to the average corrosion rate is used to describe the corrosion morphology [32]. The relationship
between the maximum local corrosion of the most intense pit and the average corrosion all over is
determined by cross-sectional micrographs providing the deepest corrosion pit and the corrosion rate
from the immersion test. Pitting factor equivalent of 1 showed uniform corrosion.
Some magnesium alloys are susceptible to stress corrosion cracking due to their inherent reactivity
in aqueous environments, resulting in the production of hydrogen, but certain alloying elements
increase the stress corrosion cracking (SCC) resistance [33,34]. According to Choudhary et al. [10],
ZX50 suffers greater SCC than WZ21 and WE43. This was attributed to its higher susceptibility
towards localized corrosion in m-SBF. The SCC mechanism for these alloys was the combination of
hydrogen-assisted cracking (major contribution of SCC in WE43) and anodic dissolution (predominant
mechanism for WZ21 alloy). Another study by Kannan et al. [35] showed an increased resistance
to SCC in both distilled water and 0.5 wt% NaCl solution for EV31A compared to ZE41 and QE22.
Intergranular SCC in a 0.5 wt% NaCl solution was associated with the second-phase particles along
grain boundaries. Rare earth elements, like Nd, can improve the SCC resistance of magnesium alloys,
as seen in EV31A. A slow strain rate test indicated that EV31A was less susceptible to SCC than
AZ91E [36]. Under the low intense loading of a constant load, EV31A was even found to be resistant.
Fractography of EV31A showed little evidence of hydrogen embrittlement. There are no data found in
the literature on stress corrosion or hydrogen embrittlement of Mg-Dy-Nd.
C-ring specimens are preferred for determining the susceptibility of alloys to SCC in forms like
tubes, rods and bars in the short transverse direction [37–39]. A C-ring can be regarded as a metal
O-ring with an open side or split rings. The specimens are typically bolt loaded to a constant strain or
constant load, per ASTM G 338 [40]. The C-ring configuration results in a complex strain field with
very high local strains: there is a gradient through the thickness, varying from a maximum tension on
Metals 2020, 10, 584 3 of 16

one surface to a maximum compression on the opposite surface. This provides the ability to investigate
microstructural differences between tensile and compressive deformation processes. According to
ASTM G 338 [40], a bending load is applied to cause a tensile strain on the outer surface; however,
a compression load (or tension load) is often used to describe the loading condition [41–43]. U-bend or
C-ring tests are rarely applied to magnesium alloys. C-ring tests have been established as a useful
quality control for brittle materials, like ceramic composites [44]. On the other hand, exceeding a
deformation of 40% defines the ductile behavior of the tested material [43]. Higher plastic strains
were observed near grain boundaries after stressing because the boundaries acted as a barrier to
dislocation motion by slip [45]. Stress corrosion cracks are usually investigated by optical micrographs,
but they can be investigated by advanced methods, like polychromatic X-ray microdiffraction [46] or
3D electron backscatter diffraction [42]. Ringer solution is often used when the corrosion behavior of
biodegradable metals is of interest; it is found to be more aggressive than HBSS or DMEM [32,47,48].
This study aims to reveal the stress corrosion susceptibility of a Mg-Dy-Nd alloy, and the influence
of the Nd alloying element is of particular interest. Furthermore, the influence of microstructural
features, like twins and grain boundaries, on the fracture toughness, here evaluated as fracture energy,
is studied and evaluated by the crack initiation and propagation.

2. Materials and Methods

2.1. Processing and Mechanical Testing

The Mg-Dy-Nd (Mg10Dy, Mg10Dy1Nd and Mg1Nd) alloys were cast at the Helmholtz Centre in
Geesthacht, Germany. High purity Mg (99.94%) (MEL, UK) was melted in a mild steel crucible under
a protective gas atmosphere (Ar + 2% SF6 ). An amount of 10 wt% of pure Dy (99.5%) and 1 wt% of
Nd (99.5%) (Grirem, Beijing, China) were added at a melt temperature of 720 ◦ C. The melt was then
mechanically stirred with a stirrer rotating at 200 rpm for 30 min. After a short annealing at 500 ◦ C
for 15 min, tubes were indirectly hot-extruded at the Extrusion Research and Development Center
TU Berlin at an overall temperature of 400 ◦ C, a ram speed of 1.5 mm/s and an extrusion ratio of 19:1.
The outer diameter of the as-extruded tubes was 35 mm, and the wall thickness was 5 mm.
The chemical composition Dy was analyzed by using X-Ray micro fluorescence M4 Tornado
(Bruker, Billerica, MA, USA), Nd by using a spark optical emission spectroscopy Spectrolab M12 Hybrid
(Ametek-Spectro, Kleve, Germany) and the impurities Fe, Cu, Ni were analyzed by using atomic
absorption spectrometry 240FS AA(Agilent, Santa Clara, CA, USA). The grain size was determined
by the line intercept method with a cross-sectional micrograph obtained on a Leica DMi8 A (Leica
Microsystems GmbH, Wetzlar, Germany), which was also used for micrographic investigations of the
corrosion morphology and crack initiation and propagation.
The Vickers hardness (HV1 and HV0.2) was determined on the tube material with approximately
30 indents using a ZHU2.5 (ZwickRoell, Ulm, Germany), and the average value is reported. To evaluate
the amount of strain hardening on the tensile and compressive sides as well as the neutral region
of the C-rings (up to a displacement of 7 mm), the hardness was measured at a 60-degree angle
opposite the C-ring opening, where the highest strain was expected and compared to that of the tube
material. To analyze the fracture appearance in the crack openings on the surface of the C-rings,
scanning electron microscopy (SEM) was performed with a Carl Zeiss EVO40 (Carl Zeiss Microscopy
GmbH, Jena, Germany). The tensile properties were measured at room temperature with a TIRA test
28100 mechanical testing machine (Tira GmbH, Schalkau, Germany) at an initial speed of 0.45 mm/min
that changed to 2.4 mm/min after elastic deformation. The samples had a gauge length of 20 mm and
were 2 mm thick and 6 mm wide. The compression tests were performed on cylindrical samples with a
height of 6 mm and a diameter of 4 mm.
Metals 2020, 10, 584 4 of 16

2.2. Immersion and C-Ring Tests, Fracture Energy and Corrosion Morphology
Metals 2020, 8, x FOR PEER REVIEW 4 of 16
Immersion tests were performed on tube segments with a width of 10 mm, outer diameter of
corrosion
34 mm and rate (mm/a)
wall was measured
thickness of 2 mm by in using
500 mLtheRinger
following equation,
solution where Δof
(2 samples m each
is thealloy)
weightatchange
37 ◦ C.
in g, weight
The A is theloss
surface
wasarea of the sample
measured in cm²,the
by removing t is corrosion
the immersion time with
products in h (in our study,
chromic acid.7 The
days) and
mean
ρ is the density in g/cm³:
corrosion rate (mm/a) was measured by using the following equation, where ∆ m is the weight change
in g, A is the surface area of the sample in cm8.76 2 , t is the immersion time in h (in our study, 7 days) and ρ
× 10 × ∆
is the density in g/cm3 : = (1)
×
8.76 × 10 × ∆m4 ×
CRm = (1)
C-ring samples with a width of 10 mm wereAmachined × t × ρ from the extruded tubes with an outer
diameterC-ringof samples
34 mm. The withwall thickness
a width of 10was mmchosen to be 2 mm.
were machined fromFigure 1a shows tubes
the extruded their position
with an in the
outer
initial extruded tubes according to [39] and the sketch in Figure
diameter of 34 mm. The wall thickness was chosen to be 2 mm. Figure 1a shows their position in the 1b the related dimensions. A
transition from tubes
initial extruded tensileaccording
to compressive
to [39] and stresses from in
the sketch theFigure
outer 1bto the
the related
inner surface
dimensions.developed in the
A transition
C-rings upon loading. To evaluate the stiffness, the elastic-plastic transition,
from tensile to compressive stresses from the outer to the inner surface developed in the C-rings upon the amount of elastic
energy
loading.(spring back) and
To evaluate ductility,the
the stiffness, a compressive
elastic-plastic load (also sometimes
transition, the amount described
of elasticas aenergy
bending load
(spring
[39])
back) was applied atocompressive
and ductility, the C-ringsload (3 samples each) without
(also sometimes describedcorrosion
as a bending media loadfor upwas
[39]) to applied
17 mm
(geometrical restriction). The applied deformation speed was 2 mm/min.
to the C-rings (3 samples each) without corrosion media for up to 17 mm (geometrical restriction). The force needed for the
displacement was monitored. The deformation was calculated
The applied deformation speed was 2 mm/min. The force needed for the displacement was monitored.in% according to the deformation of
the diameter
The deformation [42]wasby setting
calculatedthe in%displacement
according (the to the initial height ofof34
deformation themm minus[42]
diameter the by
height
settingof the
the
deformed C-ring) in relation to the initial height, which provided
displacement (the initial height of 34 mm minus the height of the deformed C-ring) in relation to the information on the ductility. A
maximum
initial height, deformation of 50% was
which provided possible.on
information Whenthe a deformation
ductility. of 40% is deformation
A maximum exceeded, theofmaterial50% was is
supposed to have ductile behavior. The following values were used
possible. When a deformation of 40% is exceeded, the material is supposed to have ductile behavior. to describe the fracture behavior:
the force
The at which
following valuesthe werefracture
used tostarted
describe(evaluated
the fractureby the reduction
behavior: the force inatthe
whichforce thewith increasing
fracture started
displacement), its displacement value and its resulting fracture energy
(evaluated by the reduction in the force with increasing displacement), its displacement value and (the area underneath the force-
its
displacement curve during crack propagation up to its turning point
resulting fracture energy (the area underneath the force-displacement curve during crack propagation towards the end of the curve).
From
up to the force-displacement
its turning point towards curve,the itend
wasofdetermined
the curve). that Froma displacement of 7 mm was
the force-displacement within
curve, the
it was
plastic
determinedregion, so athis
that value was used
displacement of 7 mmto investigate
was within thetheinfluence
plastic of the plastic
region, so thisdeformation
value was used (tensile to
and compressive strain hardening) on the extent of the corrosion
investigate the influence of the plastic deformation (tensile and compressive strain hardening) on and its morphology. For these
the
associated
extent of the investigations,
corrosion and theitsC-ring samplesFor
morphology. were compressed
these associated 7 mm in a testingthe
investigations, machine,
C-ringremoved
samples
to relieve the spring back and then corroded over 7 days
were compressed 7 mm in a testing machine, removed to relieve the spring back and then in 330 mL Ringer solution (3 samples
corrodedeach)
at 37 °C. Before corrosion, the samples were cleaned in an ultrasonic
◦
over 7 days in 330 mL Ringer solution (3 samples each) at 37 C. Before corrosion, the samples were bath in ethanol. For the stress
corrosion
cleaned in tests with a sustained
an ultrasonic stress, the
bath in ethanol. For C-ring
the stress samples
corrosion were elastically
tests and plastically
with a sustained deformed
stress, the C-ring
in the POM (Polyoxymethylene) apparatus for up to a 7 mm
samples were elastically and plastically deformed in the POM (Polyoxymethylene) apparatus fordisplacement and kept for 20 days up into
500 mL Ringer solution (3 samples each) at 37 °C (see sample in Figure
a 7 mm displacement and kept for 20 days in 500 mL Ringer solution (3 samples each) at 37 C (see 1c) by being clamped between
◦
2sample
plates.inThe POM
Figure 1c) apparatus
by being clampedconsisted of polymer
between 2 plates. plates
TheandPOM screws,
apparatus which were designed
consisted of polymer to
eliminate creep. The distance of 27 mm between the POM plates
plates and screws, which were designed to eliminate creep. The distance of 27 mm between the POM did not change during the test
duration.
plates didDistilled
not change water was used
during the testto cover the samples
duration. Distilledinwaterthe POM was apparatus
used to cover andthe wassamples
refilled in every
the
5POM
days.apparatus and was refilled every 5 days.

Figure 1.
Figure C-ring samples,
1. C-ring samples, position
position in
in the
the initial
initial extruded
extruded tubes
tubes (a),
(a), sketch
sketch with
with dimensions (b) and
dimensions (b) and
during stress corrosion in the polyoxymethylene (POM) apparatus
during stress corrosion in the polyoxymethylene (POM) apparatus (c). (c).

After the immersion tests, evaluation of the influence of the plastic deformation on the corrosion
and stress corrosion, the C-rings were compressed under quasi-static loading in Ringer solution with
a deformation speed of 2 mm/min, either up to fracturing or up to the geometrical restriction of 17
mm. These experiments enabled the influence of the corrosion media and possible hydrogen
Metals 2020, 10, 584 5 of 16

After the immersion tests, evaluation of the influence of the plastic deformation on the corrosion
and stress corrosion, the C-rings were compressed under quasi-static loading in Ringer solution with a
Metals 2020, 8, x FOR PEER REVIEW 5 of 16
deformation speed of 2 mm/min, either up to fracturing or up to the geometrical restriction of 17 mm.
These experiments
embrittlement at a enabled the influence
higher strain of thetocorrosion
deformation be testedmedia
underand possible hydrogen
quasi-static loading. Toembrittlement
evaluate the
at a higher strain deformation to be tested under quasi-static loading. To
corrosion morphology, the corroded tubes from the immersion tests, the plastically deformed evaluate the corrosion
C-rings
morphology,
and the C-rings theexposed
corrodedto tubes
stressfrom the immersion
corrosion, tests, the
all with a width plastically
of 10 mm, were deformed C-rings
“sectioned” and the
transversely
C-rings exposed
by grinding them to down
stress to
corrosion,
7.5 mm,all5 with
mm aand width of 10
finally to mm, wereFor
2.5 mm. “sectioned”
each step,transversely
the corrosion by
grinding
morphology themwas down to 7.5 mm,
determined 5 mm
from theand finally to 2.5
micrographs andmm. For each
described step, the to
according corrosion morphology
ASTM G46–76 [30],
was determined from the micrographs and described according to ASTM
which is a standard visual chart for the rating of pitting corrosion. The depth and width G46–76 [30], whichof isthe
a
standard visual chart for the rating of pitting corrosion.
corrosion pits were used to describe the amount of corrosion behavior. The depth and width of the corrosion pits
were used to describe the amount of corrosion behavior.
3. Results and Discussion
3. Results and Discussion
3.1. Microstructure
3.1. Microstructure andand Mechanical
Mechanical Properties
Properties
The detailed
The detailed chemical
chemical composition
composition and and impurity
impurity levels
levels of
of the
the three
three hot-extruded
hot-extruded alloys
alloys are
are listed
listed
in Table 1. The alloys differ in terms of their grain size and homogeneity. The transverse
in Table 1. The alloys differ in terms of their grain size and homogeneity. The transverse grain size grain size of
Mg10Dy1Nd
of Mg10Dy1Nd (Figure
(Figure2a)2a)
waswas33.633.6
± 9.67 µm.µm.
± 9.67 ThisThis
ternary alloyalloy
ternary has not
has been fullyfully
not been recrystallized, and
recrystallized,
the extrusion direction can be seen by the alignment of the second phases and
and the extrusion direction can be seen by the alignment of the second phases and their small their small surrounding
grains (see longitudinal
surrounding microstructure
grains (see longitudinal in Figure 2d).
microstructure in Very
Figurefew
2d).grains
Very show deformation
few grains twins. The
show deformation
Mg10Dy alloy has a homogeneously recrystallized microstructure (Figure
twins. The Mg10Dy alloy has a homogeneously recrystallized microstructure (Figure 2b,e) 2b,e) with a transverse
with a
grain size of 36.2 ± 10.2 µm. There was no significant difference between the transverse
transverse grain size of 36.2 ± 10.2 µm. There was no significant difference between the transverse cross-section
and the longitudinal
cross-section microstructure
and the longitudinal (the extrusion
microstructure (thedirection
extrusion is direction
indicatedisby the vertical
indicated by theline). The
vertical
microstructure was free of twin boundaries. The Mg1Nd alloy contains small
line). The microstructure was free of twin boundaries. The Mg1Nd alloy contains small grains withgrains with an average
grain
an size ofgrain
average 20.1 size
± 4.74 µm that
of 20.1 ± 4.74were
µmheavily
that weretwinned
heavily (Figure
twinned 2c,f). There2c,f).
(Figure was There
also nowassignificant
also no
difference between
significant differencethe transverse
between cross-section
the transverse and the longitudinal
cross-section microstructure.
and the longitudinal microstructure.

Table 1.
Table 1. Chemical
Chemical composition
composition and
and impurity
impurity level
level of
of the
the extruded
extruded alloys
alloys in
in wt%.
wt%.

Alloy Dy Nd Fe Cu Ni Mg
Alloy Dy Nd Fe Cu Ni Mg
Mg1Nd - 0.96 0.003 0.0006 0.0001 balance
Mg1Nd - 0.96 0.003 0.0006 0.0001 balance
Mg10Dy
Mg10Dy
12.43
12.43
- - 0.004
0.004
0.0010
0.0010
0.0004
0.0004
balance
balance
Mg10Dy1Nd
Mg10Dy1Nd 13.07
13.07 0.90
0.90 0.006
0.006 0.0011
0.0011 0.0002
0.0002 balance
balance

Figure 2. Optical micrographs of the Mg10Dy1Nd (a,d), Mg10Dy (b,e) and Mg1Nd (c,f) alloys.
Figure 2. Optical
Transverse micrographs
(a–c) and longitudinalofcross
the sections,
Mg10Dy1Ndwhere(a,d), Mg10Dydirection
the extrusion (b,e) andwas
Mg1Nd
vertical(c,f) alloys.
(d–f).
Transverse (a–c) and longitudinal cross sections, where the extrusion direction was vertical (d–f).

Although adding Nd reduces the average grain size, there was no significant positive effect on
the tensile and compression properties (Figure 3a,b). The difference in the mechanical properties was
very small, the values were within the range of the standard deviations. The average value of the
Metals 2020, 10, 584 6 of 16

Although adding Nd reduces the average grain size, there was no significant positive effect on the
tensile and8,compression
Metals 2020, properties (Figure 3a,b). The difference in the mechanical properties was6very
x FOR PEER REVIEW of 16
small, the values were within the range of the standard deviations. The average value of the tensile
tensilestrength
yield yield strength
(TYS) at(TYS)
0.2% atfor0.2% for the Mg10Dy
the Mg10Dy alloy wasalloy was slightly
slightly higher thanhigher
thethan the average
average value for value
the
for the Mg10Dy1Nd.
Mg10Dy1Nd. However, However,
the averagethe average values
values for TYS for TYS at
at 0.1%, 0.1%, ultimate
ultimate tensile strength
tensile strength (UTS) and (UTS)
the
and the
stress stressup
values values up to necking
to necking were slightly
were slightly higher forhigher for the Mg10Dy1Nd
the Mg10Dy1Nd alloy;
alloy; the lowertheductility
lower ductility
caused
caused
the the material
material to fail
to fail (see also(see also
Table Table
2.). The 2.).
areaThe area containing
containing the aligned
the aligned second within
second phases phasesthe within
not
the not fully recrystallized material that was shown in the longitudinal micrographs
fully recrystallized material that was shown in the longitudinal micrographs was assumed to be the was assumed to
be the area with an elevated brittleness and the area where the material started
area with an elevated brittleness and the area where the material started to fail. The Mg1Nd alloy was to fail. The Mg1Nd
alloy was
heavily heavilyand
twinned twinned
showed and
anshowed
overall an overall tensile
decreased decreased tensile
strength but strength
elevatedbut elevated elongation
elongation to fracture.
to fracture. The average values of compression strength followed the
The average values of compression strength followed the same general trend. However, the same general trend. However,
average
the average compression yield strength (CYS) at 0.1 and 0.2% for the
compression yield strength (CYS) at 0.1 and 0.2% for the Mg10Dy1Nd alloy was lower than that Mg10Dy1Nd alloy was lower
for
thanMg10Dy
the that for alloy
the Mg10Dy
(which hadalloythe
(which hadstandard
highest the highest standard
deviation deviation
herein), herein),
and the andcompression
ultimate the ultimate
compression
strength (UCS) strength
was also(UCS) wasdecreased
slightly also slightly(thedecreased
stress up(the stress up
to necking wasto above
necking was
that forabove that for
the Mg10Dy
the Mg10Dy
alloy). alloy). elongation
The average The average toelongation
compressive to fracture
compressive fracture (thestrain
(the compressive compressive
(CS)) was strain (CS)) was
the lowest for
the lowest for the Mg10Dy1Nd alloy. Only the Mg1Nd alloy had a higher
the Mg10Dy1Nd alloy. Only the Mg1Nd alloy had a higher TYS at 0.2% than CYS at 0.2%, and the TYS at 0.2% than CYS at
0.2%, and the yield ratio (yield strength asymmetry = CYS/TYS) for the
yield ratio (yield strength asymmetry = CYS/TYS) for the Mg10Dy and Mg10Dy1Nd alloys was above Mg10Dy and Mg10Dy1Nd
alloys
one, was above
which one, which
was slightly wasfor
elevated slightly elevated
the ternary for the ternary alloy.
alloy.

Figure
Figure 3. Stress–strain curves
3. Stress–strain curves for
for the
the Mg10Dy1Nd,
Mg10Dy1Nd, Mg10Dy
Mg10Dy and
and Mg1Nd
Mg1Nd alloys
alloys under
under tension
tension (a)
(a) and
and
compression (b).
compression (b).
Table 2. Tensile and compressive properties and yield strength asymmetry of the extruded alloys.
Table 2. Tensile and compressive properties and yield strength asymmetry of the extruded alloys.
TYS TYS CYS CYS CYS/
UTS El. UCS CS
Alloy TYS
(0.1%) TYS
(0.2%) CYS
(0.1%) CYS
(0.2%) CYS/
TYS
(MPa)
UTS (%)
El. (MPa)
UCS (%)
CS
Alloy (MPa)
(0.1%) (MPa)
(0.2%) (MPa)
(0.1%) (MPa)
(0.2%) (0.2%)
TYS
60.5 71.3 (MPa)
178.7 (%)
29.7 62.9 66.4 (MPa)
301.8 (%)
24.3
Mg1Nd (MPa) (MPa) (MPa) (MPa) (0.2%)
0.93
± 6.2 ± 4.9 ± 3.3 ± 2.5 ± 2.7 ± 1.4 ± 9.9 ± 1.3
60.5 71.3 178.7 29.7 62.9 66.4 301.8 24.3
Mg1Nd 83.5 109.5 215.0 16.5 119.1 131.8 351.9 24.1 0.93
Mg10Dy 1.20
±±6.2
2.7 ±± 4.9
2.6 ±± 3.3
2.9 ± 2.0
± 2.5 ±±16.6
2.7 ±±9.4
1.4 ± ±24.0
9.9 ±±2.1
1.3
86.4
83.5 105.9
109.5 216.9
215.0 14.5
16.5 114.6
119.1 129.9
131.8 347.8
351.9 20.1
24.1
Mg10Dy1Nd 1.23
Mg10Dy ± 4.1 ± 3.7 ± 3.9 ± 2.2 ± 11.4 ± 6.0 ± 11.9 ± 0.4 1.20
± 2.7 ± 2.6 ± 2.9 ± 2.0 ± 16.6 ± 9.4 ± 24.0 ± 2.1
86.4 105.9 216.9 14.5 114.6 129.9 347.8 20.1
Figure 4a shows the force-displacement curves from the compression testing of the C-rings1.23
Mg10Dy1Nd up to
a displacement of 17± 4.1 ± 3.7results
mm. These ± 3.9
provide± information
2.2 ± 11.4about
± 6.0 ± 11.9(and±resulting
the stiffness 0.4 spring
back) and evaluate the elastic-plastic region, the strain-hardening amount (slope in the plastic region)
Figure 4a shows the force-displacement curves from the compression testing of the C-rings up
and the ductility. The Mg10Dy1Nd and Mg10Dy (all 3 curves run close to each other and are almost
to a displacement of 17 mm. These results provide information about the stiffness (and resulting
seen as one) alloys showed similar stiffness values, and the Mg10Dy alloy yielded at a decreased force,
spring back) and evaluate the elastic-plastic region, the strain-hardening amount (slope in the plastic
but both alloys showed a similar strain-hardening behavior. The Mg1Nd (all 3 curves also run close to
region) and the ductility. The Mg10Dy1Nd and Mg10Dy (all 3 curves run close to each other and are
each other and are almost seen as one) alloy showed a decreased stiffness and yielded at a decreased
almost seen as one) alloys showed similar stiffness values, and the Mg10Dy alloy yielded at a
force. Even though there was a small grain size, which would increase the strength according to the
decreased force, but both alloys showed a similar strain-hardening behavior. The Mg1Nd (all 3 curves
also run close to each other and are almost seen as one) alloy showed a decreased stiffness and yielded
at a decreased force. Even though there was a small grain size, which would increase the strength
according to the Hall-Petch relationship, the twinned microstructure, lack of solid solution
strengthening of the Dy alloying element, and low Nd composition of only 1 wt% caused an elastic-
bars in Figure 4b) obtained herein for the Mg10Dy1Nd alloy may be explained by the high amount
of Dy that caused solid solution strengthening and by the formation of stable intermetallic phases
with Nd. The formation of the Mg41Nd5 equilibrium phase at the grain boundaries also decreases the
grain size; the Mg10Dy1Nd alloy has a smaller average grain size than the Mg10Dy alloy. Up to a
Metals 2020, 10, 584
displacement of 7 mm, an average value of 145 N was needed for the Mg10Dy1Nd alloy and 130 7 of N
16

for the Mg10Dy alloy. Based on the mechanical properties evaluated from the C-ring compression at
a 7 mm displacement
Hall-Petch relationship, andthehigher
twinned deformations, it can
microstructure, be of
lack seen that
solid the Mg10Dy1Nd
solution strengtheninghadofa the
higher
Dy
strength. The Mg10Dy alloy strength may have exceeded that for the
alloying element, and low Nd composition of only 1 wt% caused an elastic-plastic transition atMg10Dy1Nd alloy hadlow a
deformation
forces. Because higher than
of the low17 stiffness
mm beenofpossible (it wasalloy,
the Mg1Nd geometrically
the amount restricted here)
of spring backand thethe
was force may
lowest
have increased. The low ductility in the C-ring compression test-in agreement
herein. Because of the low stiffness, during the static load test to a displacement of 7 mm, the ratio with tensile andof
compression tests-caused crack initiation in Mg10Dy1Nd before 17 mm. The force
plastic to elastic deformation was higher than in the Dy-containing alloys. All three alloys showed a values at a 7 mm
displacement
very allowedunder
ductile behavior a comparison to Resoloy® and
C-ring compression, in the as-extruded
only condition,
the Mg10Dy1Nd which
alloy showedwas very
studied
small in
[17], and reveals a force of 180 N at a 7 mm displacement. The higher force needed
cracks (the longest crack was ~150 µm) on the surface of the tensile side. These cracks started just for Resoloy® was
mainly17
before duemm; to see
the the
grain refinement
reduction and in
in force formation
Figure 4aof(black
lamellar long-period
curves). stacking-ordered
The Mg10Dy and Mg1Nd(LPSO) alloys
structures within the
were free of surface cracks.matrix when Zn and Zr were added.

Figure
Figure 4. Force-displacement curves
4. Force-displacement curves of
of C-ring
C-ring tests
tests of
of the
the Mg10Dy1Nd,
Mg10Dy1Nd, Mg10Dy
Mg10Dy and
and Mg1Nd
Mg1Nd alloys
alloys
(a) and hardness before and after C-ring tests up to a displacement of 7 mm (b).
(a) and hardness before and after C-ring tests up to a displacement of 7 mm (b).

The highest strength and hardness (see the hardness values of the tube materials in the open bars
Figure 4b shows the hardness values for the Mg10Dy1Nd, Mg10Dy and Mg1Nd alloys (for the
in Figure 4b) obtained herein for the Mg10Dy1Nd alloy may be explained by the high amount of Dy
extruded tubes and C-rings after plastic deformation at the tensile and compression side as well as
that caused solid solution strengthening and by the formation of stable intermetallic phases with Nd.
neutral region and the amount of strain hardening during deformation of the C-rings in comparison
The formation of the Mg41 Nd5 equilibrium phase at the grain boundaries also decreases the grain size;
to the extruded tubes by the increase in hardness. Pretesting showed that the transverse and
the Mg10Dy1Nd alloy has a smaller average grain size than the Mg10Dy alloy. Up to a displacement of
longitudinal hardness of the tube material did not differ. All C-ring samples showed an increase in
7 mm, an average value of 145 N was needed for the Mg10Dy1Nd alloy and 130 N for the Mg10Dy alloy.
the hardness due to strain hardening during the C-ring tests. The increase on the tensile side was
Based on the mechanical properties evaluated from the C-ring compression at a 7 mm displacement
found to be the highest for the Mg10Dy alloy by 19.4% and the lowest for the Mg1Nd alloy by 9.7%.
and higher deformations, it can be seen that the Mg10Dy1Nd had a higher strength. The Mg10Dy alloy
The average Mg10Dy1Nd strain hardening was slightly more increased on the compression side
strength may have exceeded that for the Mg10Dy1Nd alloy had a deformation higher than 17 mm been
(12.8%) compared to that on the tensile side (11.2%). There was no pronounced strain hardening
possible (it was geometrically restricted here) and the force may have increased. The low ductility in
under compression in the Mg1Nd alloy according to the Vickers hardness: 0.4%. However, the stress–
the C-ring compression test-in agreement with tensile and compression tests-caused crack initiation
strain curve of the compression test showed significant hardening (Figure 3b). The twinned
in Mg10Dy1Nd before 17 mm. The force values at a 7 mm displacement allowed a comparison to
microstructure even before deformation influences the fact that the hardness did not show an
Resoloy®in the as-extruded condition, which was studied in [17], and reveals a force of 180 N at a
increase. The Dy-containing alloys were almost twin-free after extrusion and twin during plastic
7 mm displacement. The higher force needed for Resoloy®was mainly due to the grain refinement
deformation during testing; the twinning in the Mg10Dy alloy was slightly elevated, especially on
and formation of lamellar long-period stacking-ordered (LPSO) structures within the matrix when Zn
the compression side. The initial number of twins in the Mg1Nd alloy significantly increased during
and Zr were added.
Figure 4b shows the hardness values for the Mg10Dy1Nd, Mg10Dy and Mg1Nd alloys (for the
extruded tubes and C-rings after plastic deformation at the tensile and compression side as well as
neutral region and the amount of strain hardening during deformation of the C-rings in comparison to
the extruded tubes by the increase in hardness. Pretesting showed that the transverse and longitudinal
hardness of the tube material did not differ. All C-ring samples showed an increase in the hardness
due to strain hardening during the C-ring tests. The increase on the tensile side was found to be the
highest for the Mg10Dy alloy by 19.4% and the lowest for the Mg1Nd alloy by 9.7%. The average
Mg10Dy1Nd strain hardening was slightly more increased on the compression side (12.8%) compared
to that on the tensile side (11.2%). There was no pronounced strain hardening under compression in
the Mg1Nd alloy according to the Vickers hardness: 0.4%. However, the stress–strain curve of the
compression test showed significant hardening (Figure 3b). The twinned microstructure even before
deformation influences the fact that the hardness did not show an increase. The Dy-containing alloys
Metals 2020, 10, 584 8 of 16

Metals almost
were 2020, 8, xtwin-free
FOR PEERafter
REVIEW
extrusion and twin during plastic deformation during testing; the twinning8 of 16
in the Mg10Dy alloy was slightly elevated, especially on the compression side. The initial number of
deformation
twins on the alloy
in the Mg1Nd tensile side, but only
significantly by a small
increased duringband of approximately
deformation 100 µm.
on the tensile side,The hardness
but only by a
small band of approximately 100 µm. The hardness values of the tube material—and in general ofand
values of the tube material—and in general of the C-rings—agree with the data from the tension the
compression tests
C-rings—agree withwithin thefrom
the data uniform deformation
the tension region in tests
and compression addition to the
within theuniform
data fordeformation
the C-ring
deformation
region strength.
in addition to the data for the C-ring deformation strength.

3.2. Corrosion
3.2. Corrosion Rate
Rate and
and Morphology of the
Morphology of the Stress
Stress Corrosion
Corrosion
The following
The following corrosion
corrosion rates
rates were
were evaluated
evaluated from from immersion
immersion tests tests over
over 77 days:
days: Mg10Dy1Nd
Mg10Dy1Nd
corrodes at 1.53 mm/a, Mg10Dy at 2.46 mm/a and Mg1Nd at 0.79 mm/a.
corrodes at 1.53 mm/a, Mg10Dy at 2.46 mm/a and Mg1Nd at 0.79 mm/a. The twinned microstructure of The twinned microstructure
of Mg1Nd
Mg1Nd hadhad
no no negative
negative effect
effect on the
on the corrosion
corrosion rate.rate. Adding
Adding Nd toNdMg10Dy
to Mg10Dy lowerslowers the corrosion
the corrosion rate.
The electrochemical potential of Dy is −2.35 V, which is similar to that of Mg that has a value of −2.37of
rate. The electrochemical potential of Dy is −2.35 V, which is similar to that of Mg that has a value V.
−2.37
Dy in V. Dysolution
solid in solidissolution
not causing is not causing microgalvanic
microgalvanic corrosion. The corrosion.
material The material
in this studyinconsisted
this study of
consisted
Mg-Dy andofMg-Dy-Nd
Mg-Dy andsecond Mg-Dy-Ndphases,second
like Mg phases, like Mg24Dy5 and Mg5(Nd,Dy), which accelerate
24 Dy5 and Mg5 (Nd,Dy), which accelerate microgalvanic
microgalvanic corrosion, compared to Mg1Nd
corrosion, compared to Mg1Nd and cause pitting corrosion. and cause pitting corrosion.
According to [18],According
the corrosionto [18],
filmtheis
corrosion film
nonuniform andis nonuniform
has a porousand has a porous
structure. structure.
A corrosion layerA corrosion layer mainly
mainly consisting of MgOconsisting
and Mg(OH)of MgO2
and be
can Mg(OH) can be easily
easily 2penetrated penetrated
by Cl-ions and by wasCl-ions and was
not effective [49];not
theeffective
film was[49]; the film
slightly was slightly
improved when
improved when
alloyed with Nd. alloyed with Nd.
The cross-sectional
The cross-sectional micrographs
micrographs in in Figure
Figure 55 show
show thethe amount
amount and and size
size ofof the
the corrosion
corrosion pitspits and
and
that the Mg10Dy alloy (Figure 5b,e) corroded more severely under
that the Mg10Dy alloy (Figure 5b,e) corroded more severely under the influence of plastic deformation the influence of plastic
deformation
than than the (Figure
the Mg10Dy1Nd Mg10Dy1Nd 5a,d) and (Figure
Mg1Nd 5a,d) and (Figure
alloys Mg1Nd5c,f). alloys
The(Figure
largest 5c,f). The pits
corrosion largeston
corrosion
each alloy pits on eachThe
are shown. alloy are shown.
Mg1Nd The Mg1Nd
alloy exhibited alloy exhibited
evidence of corrosion evidence
but only of has
corrosion but only
a few corrosion
has aEven
pits. few the
corrosion
materialpits.
was Even the material
heavily twinned, was heavily
an almost twinned,
uniform an almost
passive uniform passive
layer prevented from stronglayer
preventedand
corrosion from strongThe
pitting. corrosion
pit seenand pitting.
in Figure The an
5f had pitelliptical
seen in shape;
Figure its5f pitting
had anfactorelliptical
was shape;
4. Due its to
pitting factor was 4. Due to the number of twins, a stronger corrosion attack
the number of twins, a stronger corrosion attack was expected. The area opposite the C-ring opening was expected. The area
opposite
on the side,
the tensile C-ring opening
where on thestrain
the highest tensilewas side, whereand
expected thethehighest
corrosionstrain was expected
product and the
could delaminate,
corrosion
was foundproduct could delaminate,
to be corroded preferentially. wasThe found
Mg10Dy to bealloy
corroded
showed preferentially.
more and much Thelarger
Mg10Dy alloy
corrosion
showed more and much larger corrosion pits than the Mg10Dy1Nd alloy.
pits than the Mg10Dy1Nd alloy. The pit on the Mg10Dy1Nd alloy in Figure 5a had a semicircle shape The pit on the Mg10Dy1Nd
alloystarts
and in Figure 5a had athe
to undercut semicircle
surface. shape and factor
Its pitting starts towasundercut
20. The thepitssurface.
in Mg10Dy Its pitting
were allfactor was 20.
subsurface,
Theongoing
the pits in corrosion
Mg10Dy were all subsurface,
overlapped, the ongoing
and the deepest corrosion
accumulation of overlapped,
pits had a pitting and thefactordeepest
of 23.
accumulation of pits had a pitting factor of 23. Narrow and deep pits caused
Narrow and deep pits caused high stresses, and the pits in the Mg-Dy-(Nd) alloy were more wide than high stresses, and the
pits incausing
deep, the Mg-Dy-(Nd)
a moderate alloy were
stress more wide than deep, causing a moderate stress intensity.
intensity.

Figure 5. Optical micrographs of corroded C-rings after plastic deformation over 7 days for Mg10Dy1Nd
FigureMg10Dy
(a,d), 5. Optical
(b,e) micrographs of corroded
and Mg1Nd alloys (c,f). C-rings after plastic deformation over 7 days for
Mg10Dy1Nd (a,d), Mg10Dy (b,e) and Mg1Nd alloys (c,f).

Already by visual appearance of the Mg10Dy1Nd and Mg10Dy samples (not shown in this
study) after the immersion tests, corrosion products were not formed uniformly, large accumulations
Metals 2020, 8, x FOR PEER REVIEW 9 of 16

of white
Metals 2020,corrosion
10, 584 products were seen. The area underneath the strong local formation of corrosion 9 of 16
products was the one, where the pits have developed, see also [18,31]. Mg1Nd showed hardly any
local corrosion products on the outer surface of the C-ring after 7 days. However, all samples had lost
Already by visual appearance of the Mg10Dy1Nd and Mg10Dy samples (not shown in this study)
their metallic gloss.
after the immersion tests, corrosion products were not formed uniformly, large accumulations of
Figure 6 shows representative micrographs of the C-rings after stress corrosion for over 20 days.
white corrosion products were seen. The area underneath the strong local formation of corrosion
It can be seen very clearly that the Mg10Dy alloy (Figure 6b,e) corroded the most and very severely
products was the one, where the pits have developed, see also [18,31]. Mg1Nd showed hardly any
on the tension and compression sides on both sides of the ring. Whereas the Mg10Dy1Nd alloy
local corrosion products on the outer surface of the C-ring after 7 days. However, all samples had lost
(Figure 6a,d) forms elliptical and semicircular pits (slightly subsurface) that started overlapping and
their metallic gloss.
the Mg10Dy alloy (Figure 6b,e) forms subsurface-undercutting pits. The corrosion of the Mg1Nd
Figure 6 shows representative micrographs of the C-rings after stress corrosion for over 20 days.
alloy after 20 days also increased; however, the number of pits was far less than that in the Dy-
It can be seen very clearly that the Mg10Dy alloy (Figure 6b,e) corroded the most and very severely
containing alloys, and the subsurface pits were not very deep and were rather wide. In agreement to
on the tension and compression sides on both sides of the ring. Whereas the Mg10Dy1Nd alloy
the discussion above, the pits were formed, where the accumulation of corrosion product were found.
(Figure 6a,d) forms elliptical and semicircular pits (slightly subsurface) that started overlapping and
The formation of these wide and shallow corrosion pits did not cause a significant stress increase
the Mg10Dy alloy (Figure 6b,e) forms subsurface-undercutting pits. The corrosion of the Mg1Nd alloy
when mechanical loading was applied. Because of the severe corrosion on the Mg10Dy alloy and the
after 20 dayson
overlapped also increased;
both however,
sides after the number
20 days, it was notof pits was far
possible to less than that
determine in pitting
the the Dy-containing
factor. The
alloys,
Mg10Dy1Nd alloy had a pitting factor of 37 and Mg1Nd has a factor of 15. These were verydiscussion
and the subsurface pits were not very deep and were rather wide. In agreement to the high and
above, the pitsvalues.
unacceptable were formed, where the
The corrosion accumulation
morphology, of corrosion
as shown product
in Figure 5c,d,were
wasfound. The formation
acceptable if the pits
of these
were notwide andand
narrow shallow
deepcorrosion pits did
but overlapped tonot
formcause a significant
a wide and shallow stress increaselayer.
corrosion when mechanical
loading wascorrosion
Stress applied.didBecause of thethe
not change severe corrosion
corrosion on the Mg10Dy
morphology alloycompared
significantly and the overlapped on
to that for the
both sides after 20 days, it was not possible to determine the pitting factor. The
corrosion on samples that were only plastically deformed, but due to the increase in the corrosionMg10Dy1Nd alloy had
atime,
pitting
the factor of 37amount
corrosion and Mg1Nd has aAll
increased. factor
alloysof 15. These were
investigated didvery high and
not show unacceptable
a hint values.
of stress corrosion
The corrosion
cracking, and morphology,
none of the alloysas shown in Figure
showed 5c,d,initiation
any crack was acceptable
near the if the
areapits werethe
where notpits
narrow and
had their
deep but overlapped to form
deepest depth into the material. a wide and shallow corrosion layer.

Figure 6. Optical micrographs

6. Optical micrographs of
of corroded
corroded C-rings
C-rings after
after stress corrosion for over 20 days for the
Mg10Dy1Nd (a,d),
(a,d), Mg10Dy
Mg10Dy (b,e)
(b,e) and
and Mg1Nd
Mg1Nd alloys
alloys (c,f).
(c,f).

Stress corrosion
3.3. Fracture Energy anddidCrack
not change the corrosion morphology significantly compared to that for the
Propagation
corrosion on samples that were only plastically deformed, but due to the increase in the corrosion
time,Figure 7a shows
the corrosion the force–displacement
amount curves
increased. All alloys of the C-rings
investigated did not under
show acompressive
hint of stressloading in
corrosion
Ringer solution up to fracture for the Mg10Dy1Nd and Mg10Dy alloys and up to the geometrical
cracking, and none of the alloys showed any crack initiation near the area where the pits had their
restriction
deepest of 17
depth mm
into thefor the Mg1Nd alloy. The Mg10Dy1Nd alloy yielded at an elevated force and
material.
fractures at lower displacements between 10 and 12 mm. With that, the average deformation to
fracture
3.3. wasEnergy
Fracture found and
to be approximately
Crack Propagation32%. The binary alloy Mg10Dy started fracturing at 12 mm,
but 2 C-rings reached values above 14 mm. The average deformation value was approximately 41%.
Figure 7a shows the force–displacement curves of the C-rings under compressive loading in Ringer
According to [42], fracturing above 40% was defined as ductile failure. Alloy Mg1Nd showed a very
solution up to fracture for the Mg10Dy1Nd and Mg10Dy alloys and up to the geometrical restriction of
ductile behavior, and the force-displacement curve did not give the appearance of a fracture or even
17 mm for the Mg1Nd alloy. The Mg10Dy1Nd alloy yielded at an elevated force and fractures at lower
 of alloying prevent the Mg1Nd from fracturing. This alloy seemed to be resistant to hydrogen
embrittlement, in contrast to the Mg10Dy and Mg10Dy1Nd alloys.
The following values have been used to describe the fracture behavior: the force at which the
fracture started (evaluated by the reduction in the force with increasing displacement), its
displacement
Metals 2020, 10, 584 value and the fracture energy (the area underneath the force–displacement curve 10 of 16
during crack propagation). Figure 7b shows that the fracture energy and the displacement needed to
initiate a crack were noticeably higher in the Mg10Dy alloy than in the Mg10Dy1Nd alloy, whereas
displacements
the force needed between 10 and
to initiate 12 mm.
a crack didWith that, much.
not differ the average deformation
However, to fracture wascurve
the force–displacement foundof to
be the
approximately 32%. The binary alloy Mg10Dy started fracturing at 12 mm, but
Mg10Dy1Nd alloy was elevated; see Figure 7a for data within the strain hardening region up to 2 C-rings reached
values
10 mm;above 14 mm.
however, The
since average
alloy deformation
Mg10Dy1Nd value
has a low was approximately
ductility, 41%.
this alloy fractures According
at low to [42],
displacement
fracturing
values. Theabove
high40% was defined
ductility of Mg10Dy as ductile failure.
allows the forceAlloy Mg1Nd
to increase (seeshowed a very from
also properties ductile
thebehavior,
tensile
andandthecompressive tests in Table
force-displacement curve 2).did
Therefore,
not givethethehigh fracture toughness
appearance in Mg10Dy
of a fracture was based
or even crack on
initiation.
its high ductility. The elevated force values within the strain hardening region
Even though the microstructure was heavily twinned, the fine grains and low content of alloying in the C-rings tests for
the Mg10Dy
prevent the Mg1Ndalloy and
fromitsfracturing.
earlier fracture
This(Figure 7a) agreetowith
alloy seemed values from
be resistant tensile andembrittlement,
to hydrogen compressive
tests (see Figure 3a,b).
in contrast to the Mg10Dy and Mg10Dy1Nd alloys.

Figure 7. Force–displacement curves of C-rings tests under compressive loading in Ringer solution up
Figure 7. Force–displacement curves of C-rings tests under compressive loading in Ringer solution
to fracture for the Mg10Dy1Nd, Mg10Dy and Mg1Nd alloys (a) and their properties (b).
up to fracture for the Mg10Dy1Nd, Mg10Dy and Mg1Nd alloys (a) and their properties (b).

The following values have been used to describe the fracture behavior: the force at which the
Figure 8 shows micrographs of the crack path in the C-ring samples after compressive loading
fracture started (evaluated by the reduction in the force with increasing displacement), its displacement
in Ringer solution up to fracture. Figure 8a–c,g and h show the full wall thickness of the C-ring and
value and8d–f,i–m
Figure the fracture
showenergy (the area
micrographs of underneath the force–displacement
higher magnification revealing detailed curve during crack
interaction of
propagation). Figure 7b shows that the fracture energy and the displacement
microstructure and crack growth. In the Mg10Dy1Nd (Figure 8a,d,g,k) and Mg10Dy alloys (Figure needed to initiate a crack
were noticeably
8b,e,h,l), higher
the crack in the Mg10Dy
propagates almostalloythroughthanthe
in full
the Mg10Dy1Nd
wall thicknessalloy,
of thewhereas the forceand
C-ring sample, needed
in
to initiate a crack
alloy Mg1Nd did not
(Figure differ much.
8c,f,i,m), only very However, the tips
small crack force–displacement
were seen (Figurecurve 8i,m).ofAccording
the Mg10Dy1Nd to the
alloy was elevated; see
force-displacement Figure
curves in 7a for data
Figure within
7a, these the cracks
small strain hardening region
initiate without up to 10 mm;
a noticeable drophowever,
in the
since alloy
force Mg10Dy1Nd
values. has a lowofductility,
One characteristic the crack this alloy
paths infractures at low displacement
the Mg10Dy1Nd and Mg10Dyvalues. The high
alloys (Figure
ductility of was
8a,b,g,h) Mg10Dy allowsinthe
the change force to increase
appearance when they (see also properties
reached and crossedfromthethe tensile
neutral and compressive
region: additional
secondary
tests in Tablecracks were developed,
2). Therefore, the higheven at a distance
fracture toughness from inthe main crack
Mg10Dy was (and
based not
onconnected in the
its high ductility.
The elevated force values within the strain hardening region in the C-rings tests for the Mg10DyThe
chosen layer), and follow microstructural features, like twin boundaries (intragranular fracture). alloy
andcracks emanating
its earlier fracturefrom the main
(Figure crackwith
7a) agree in parallel
values (see
fromcircled
tensilemarkers in Figure 8a,k)
and compressive wereFigure
tests (see assigned3a,b).
to Figure
the presence
8 shows ofmicrographs
hydrogen inof[50]. the The
crackcracks
path inwerethe then
C-ringcarried overafter
samples the compressive
grain boundaries loadingby in
cleavage cracks, which were mostly twin-initiated, and the grain boundaries
Ringer solution up to fracture. Figure 8a–c,g and h show the full wall thickness of the C-ring were not really part of
the crack path. Twins will act as a potent stress concentrator in the
and Figure 8d–f,i–m show micrographs of higher magnification revealing detailed interaction nucleation of cracks, like seen in
twinning-induced plasticity steels [51]. Most of the secondary microcracks
of microstructure and crack growth. In the Mg10Dy1Nd (Figure 8a,d,g,k) and Mg10Dy alloys grow within the grain by
thickening before they propagate into the neighboring grain. That correlates to the shape of the twins,
(Figure 8b,e,h,l), the crack propagates almost through the full wall thickness of the C-ring sample, and
which become lenticular and indicate that the materials have a certain toughness. There was also
in alloy Mg1Nd (Figure 8c,f,i,m), only very small crack tips were seen (Figure 8i,m). According to the
favorable twin transmission across the grain boundaries [52], where the twins grow from a common
force-displacement curves in Figure 7a, these small cracks initiate without a noticeable drop in the force
grain boundary (adjoining twin pairs). Some of these twins develop into cracks. Only a few twins
values. One characteristic of the crack paths in the Mg10Dy1Nd and Mg10Dy alloys (Figure 8a,b,g,h)
and cracks were transmitted across the grain boundary without growing. The compressive side of
wasthe
theC-ring
change in appearance
sample showed awhen very they
twinnedreached and crossedThis
microstructure. the neutral region:
region has additionalhardness,
an increased secondary
cracks were developed, even at a distance from the main crack (and not connected in the chosen
layer), and follow microstructural features, like twin boundaries (intragranular fracture). The cracks
emanating from the main crack in parallel (see circled markers in Figure 8a,k) were assigned to the
presence of hydrogen in [50]. The cracks were then carried over the grain boundaries by cleavage cracks,
which were mostly twin-initiated, and the grain boundaries were not really part of the crack path.
Twins will act as a potent stress concentrator in the nucleation of cracks, like seen in twinning-induced
plasticity steels [51]. Most of the secondary microcracks grow within the grain by thickening before
they propagate into the neighboring grain. That correlates to the shape of the twins, which become
lenticular and indicate that the materials have a certain toughness. There was also favorable twin
Metals 2020, 10, 584 11 of 16

transmission across the grain boundaries [52], where the twins grow from a common grain boundary
(adjoining twin pairs). Some of these twins develop into cracks. Only a few twins and cracks were
Metals 2020, 8, x FOR PEER REVIEW
transmitted across the grain boundary without growing. The compressive side of the C-ring11sample
of 16

showed a very twinned microstructure. This region has an increased hardness, especially in alloy
especially in alloy Mg10Dy1Nd (see Figure 4b). It was difficult to evaluate how the propagation of
Mg10Dy1Nd (see Figure 4b). It was difficult to evaluate how the propagation of the crack tip through
the crack tip through the twinned microstructure increases the fracture toughness because of unstable
the twinned microstructure increases the fracture toughness because of unstable crack growth.
crack growth.

Figure
Figure8. Cross-sectional optical
8. Cross-sectional micrographs
optical of theofcrack
micrographs the path in path
crack the C-ring
in thesamples
C-ringafter compressive
samples after
loading
compressive loading in Ringer solution: Mg10Dy1Nd (a,d,g,k), Mg10Dy (b,e,h,l) and Mg1Nd (c,f,i,m).
in Ringer solution: Mg10Dy1Nd (a,d,g,k), Mg10Dy (b,e,h,l) and Mg1Nd alloys alloys
Micrographs showing fullshowing
(c,f,i,m). Micrographs wall thickness of thickness
full wall C-ring (a–c,g,h) and(a–c,g,h)
of C-ring micrographs of higher magnification
and micrographs of higher
revealing detailedrevealing
magnification interaction of microstructure
detailed interaction of and crack growthand
microstructure (d–f,i–m), circled (d–f,i–m),
crack growth markers highlights
circled
parallel
markerssubcracks emanating
highlights from the main
parallel subcracks crackfrom
emanating (a,k).the main crack (a,k).

Figure
Figure8d,e,k,l show
8d,e,k,l showthethesecondary
secondarycracks
cracks at
at aa high
high magnification, indicatingthat
magnification, indicating thatthe
theinitiation
initiation
waswas
strongly
stronglyinfluenced
influenced bybythe
thetwin
twinboundaries.
boundaries. Microstructural features,like
Microstructural features, likegrain
grainand
andother
other twin
twin
boundaries
boundaries as as well
well as as secondary
secondary phases,
phases, hinder
hinder straight
straight crack
crack propagation,redirect
propagation, redirectthe
thecrack
crackup uptotothe
theinterface
next next interface and increase
and increase the fracture
the fracture toughness.
toughness. Twinboundaries
Twin boundariesseem
seem to to depress
depresscrack
crackdriving
driving
force,
force, resulting
resulting in crack
in crack energy
energy dissipation,
dissipation, retarding
retarding crack
crack propagation.The
propagation. Theinfluence
influenceofoftwins
twinsononthe
thepropagation
crack crack propagation
has alsohasbeen
alsoobserved
been observed in Mg10Gd-based
in Mg10Gd-based alloysalloys [53].
[53]. In Instudy,
this this study,
wherewhere the
the as-cast
as-cast Mg10Gd alloys with and without Nd have large grains up to 1000 µm
Mg10Gd alloys with and without Nd have large grains up to 1000 µm in size, the alloys were tested in size, the alloys were
by tested by three-point
three-point bending.bending.
During During
this test,this test, substantial
substantial crack reorientation
crack reorientation (zigzag)(zigzag)
by thebytwins
the twins
occurs
occurs as a result of plastic deformation (the twin boundaries seem to "carry" the crack
as a result of plastic deformation (the twin boundaries seem to "carry" the crack from grain to grain). from grain to
grain). Hydrogen-assisted failure in twinned areas, which cannot be excluded, has been mainly
Hydrogen-assisted failure in twinned areas, which cannot be excluded, has been mainly studied in
studied in twinning-induced plasticity steels, such as in Fe-Mn-C steels [54] but also in Mg alloys [55].
twinning-induced plasticity steels, such as in Fe-Mn-C steels [54] but also in Mg alloys [55]. According
According to [54], hydrogen-assisted cracking starts at a deformation twin boundary or a
noncoherent grain boundary, where the propagation path aligns to a deformation twin boundary. In
[55], the localized corrosion area in wrought Mg-Zn-Y-Zr was studied, where low surface energy
Metals 2020, 10, 584 12 of 16

to [54], hydrogen-assisted cracking starts at a deformation twin boundary or a noncoherent grain

boundary, where the propagation path aligns to a deformation twin boundary. In [55], the localized
Metals 2020, 8, x FOR PEER REVIEW 12 of 16
corrosion area in wrought Mg-Zn-Y-Zr was studied, where low surface energy planes accumulated
hydrogen atoms and initiated
planes accumulated hydrogen cracks.
atoms Hydrogen is known
and initiated cracks. toHydrogen
diffuse to lattice
is known defects, like dislocations
to diffuse to lattice
anddefects,
twin boundaries.
like dislocations and twin boundaries. According to Figure 7b, the fractureMg10Dy,
According to Figure 7b, the fracture energy was elevated in alloy energy was which
was mostlyin
elevated because of its elevated
alloy Mg10Dy, which ductility.
was mostly Upon
becausestudying the micrographs
of its elevated ductility. of crack
Upon propagation
studying the
(Figure 8), it can be concluded that alloy Mg10Dy has an increasing number
micrographs of crack propagation (Figure 8), it can be concluded that alloy Mg10Dy has an increasing of large subcracks, which
leads to theofincrease
number of fracture
large subcracks, energy,
which leadsand alloy
to the Mg10Dy1Nd
increase hasenergy,
of fracture a large andnumber
alloyof small crackshas
Mg10Dy1Nd that
originate at the main
a large number crack.
of small Thisthat
cracks explains
originatetheatdecreased
the main crack.resistivity to SCC in
This explains thethe Mg10Dy1Nd
decreased resistivityalloy;
it was
to SCCmostlyin thebased on low ductility,
Mg10Dy1Nd alloy; itwhich makes based
was mostly it moreonsusceptible
low ductility,to hydrogen
which makes embrittlement.
it more
susceptible
A high ductility to hydrogen
enlarges the embrittlement.
deformation A high
zone ductility
and energy enlarges the deformation
in front of the crack zone and energy
tip, which allows
in front of such
deformation, the crack tip, whichmovement,
as dislocation allows deformation,
twinning such as dislocation movement,
and microcracking, before finaltwinning
fracture;and these
microcracking,
factors increase the before final fracture;
fracture toughness. theseAfter
factorsall,increase
the cracksthe fracture
initiated toughness. After all, the cracks
in alloy Mg10Dy1Nd during
initiated
C-ring in alloy Mg10Dy1Nd
compression in air (Figureduring3a) C-ring
also show compression in air (Figure
twin boundary 3a) also
cracking butshow
at a twin boundary
decreased level.
The parallel subcracks off the main crack according to [50] were not found. Testing in air alsowere
cracking but at a decreased level. The parallel subcracks off the main crack according to [50] showed not a
veryfound. Testing
twinned in air also showed
microstructure on thea tensile
very twinned microstructure
side, where hydrogenon the tensile side,
embrittlement where
was hydrogen
eliminated, and
embrittlement was
additional cold work occurs. eliminated, and additional cold work occurs.
Figure 9 shows SEM images of cracks on the surface of the C-ring samples after compressive
Figure 9 shows SEM images of cracks on the surface of the C-ring samples after compressive
loading in Ringer solution. SEM images offer the view into the crack opening on the fracture surface
loading in Ringer solution. SEM images offer the view into the crack opening on the fracture surface and
and its area nearby to discuss the amount of corrosion products. Figure 9a to c show representative
its area nearby to discuss the amount of corrosion products. Figure 9a to c show representative crack
crack openings and their surrounding surface in the Mg10Dy1Nd, Mg10Dy and Mg1Nd alloys in an
openings and their surrounding surface in the Mg10Dy1Nd, Mg10Dy and Mg1Nd alloys in an overview
overview image. The extent of the small surface cracks in alloy Mg1Nd and the corroded surface
image. The extent of the small surface cracks in alloy Mg1Nd and the corroded surface nearby can be
nearby can be seen in the SEM images in Figure 9c,f. Other than seen in the immersion tests, the
seenexposureSEM
in the of theimages in Figure
C-ring during 9c,f. Other than seen
compression test in in the immersion
Ringer solution tests,
for the
overexposure
8.5 minof (17 the C-ring
mm
during compression test in Ringer solution for over 8.5 min (17 mm
displacement with 2 mm/min) caused significant corrosion at the crack opening in alloy Mg1Nd. The displacement with 2 mm/min)
caused significant corrosion
corrosion-product-free at the
surface crack
area opening in
surrounding the alloy Mg1Nd.
corrosion The corrosion-product-free
indicates that the local stress increase surface
areaat the crack tip accelerates the corrosion process and formation of corrosion products at the outerthe
surrounding the corrosion indicates that the local stress increase at the crack tip accelerates
corrosion
surface process and formation
of the C-ring of corrosion
and the fracture products
surface. at the outerpassive
The air-formed surfacelayer
of theonC-ring and the
the C-ring fracture
protects
surface.
Mg1NdThe air-formed
during immersion, passive
even layer on the C-ring
the microstructure wasprotects
heavilyMg1Nd
twinnedduring immersion,
(see smallest corrosion even ratethe
microstructure
and uniform was heavily
corrosion twinned
in Figure 5c (see smallest corrosion
for immersion over 7 days).rateOnce
and uniform
the passive corrosion
layer was in Figure
channeled 5c for
and broken,
immersion overthe twins Once
7 days). in Mg1Nd seem to
the passive accelerate
layer the corrosion
was channeled (see here
and broken, thethe strongly
twins corroded
in Mg1Nd seem
fracture surface
to accelerate in Figure(see
the corrosion 9f). here the strongly corroded fracture surface in Figure 9f).

Figure 9. SEM images of the cracked surface of the C-rings after compressive loading in Ringer solution:
Figure 9. SEM images of the cracked surface of the C-rings after compressive loading in Ringer
Mg10Dy1Nd (a,d), Mg10Dy (b,e) and Mg1Nd alloys (c,f).
solution: Mg10Dy1Nd (a,d), Mg10Dy (b,e) and Mg1Nd alloys (c,f).
Metals 2020, 10, 584 13 of 16

Figure 9a shows one main crack in alloy Mg10Dy1Nd and a few very small surrounding cracks,
whereas the crack opening in alloy Mg10Dy in Figure 9b looks fairly severe with more than one main
crack, which indicates an increased fracture toughness. It takes an average of 6.9 min to initiate a crack
in alloy Mg10Dy and severe surface corrosion, C-ring outer surface and fracture surface, did not occur.
The surface of alloy Mg10DyNd must be exposed to the solution for 5.4 min on average before crack
initiation was also free of strong corrosion. This indicates that a rather sudden crack initiation occurs
due to hydrogen embrittlement, whereas in alloy Mg1Nd, the local stress increase builds up over some
time, accelerating the corrosion nearby (Figure 9c,f). Even the Dy-containing alloys have a higher
corrosion rate due to a less protective and porous passive/corrosion layer, the fracture surface was free
of corrosion. The smaller number of twins will be benefiting the situation.
Figure 9d,e show the fracture surface of Mg10Dy1Nd and Mg10Dy in a higher magnification and
cleavage facets were present, which ascertain the transgranular crack propagation mode. Some cleavage
planes show cleavage steps. Referring to the cross-sectional micrographs in Figure 8, this fracture
mechanism was assisted by the deformation twin boundaries, underlining the crystallographic
relationship on crack growth. Microcracks following twin boundaries and cleavage rivers being
terminated by twin boundaries are also discussed by Smida and Bosansky in [56].
Future work will show whether the fracture toughness upon the addition of Zn and Zr alloying
elements will be improved as it was for Resoloys®mechanical properties, like the hardness and force
needed in C-ring tests. The reduced grain size and improved corrosion behavior due to the LPSO
phase [17] is cause for optimism. Small grains and high-volume fraction of second phases are known
to suppress twinning [53].

4. Conclusions
The mechanical and stress corrosion properties of ternary alloy Mg10Dy1Nd were obtained and
compared to those for binary alloys Mg10Dy and Mg1Nd in this study. The microstructure, hardness,
strength and corrosion behavior differ among the alloys. The following main conclusions can be made:
Mg10Dy1Nd has not been fully recrystallized, has the highest hardness herein but lacks ductility.
Mg1Nd was heavily twinned after extrusion and has the smallest grain size herein. The alloys twin
under plastic deformation and the twinning was pronounced under compression. Mg10Dy corrodes
at 2.46 mm/a, Mg10Dy1Nd at 1.53 mm/a and Mg1Nd at 0.79 mm/a. During static stress corrosion at
a deformation of 20%, none of the alloys fail by fracturing, but large corrosion pits develop in alloy
Mg10Dy1Nd and even more develop in alloy Mg10Dy. The pits were elliptical in shape and started to
overlap. Wide and shallow pitting corrosion was identified for Mg1Nd. The C-ring specimen subjected
to compressive loading until fracture in Ringer solution reveals a higher fracture toughness, evaluated
as fracture energy, for Mg10Dy than that for the other alloys because of its ductility. Mg10Dy1Nd has a
higher susceptibility to hydrogen embrittlement than the other alloys and Mg1Nd did not experience
hydrogen-assisted fracture. The C-ring compression tests in Ringer solution show a deformation before
fracture of 41% for alloy Mg10Dy and 32% for alloy Mg10Dy1Nd and crack initiation and growth were
mainly influenced by twins.

Author Contributions: Conceptualization, P.M. and N.H.; Methodology, P.M. and B.C. Validation, P.M. and B.C.
and J.W.; Formal analysis, Investigation, B.C. and J.W.; Writing—original draft preparation, P.M.; Writing—review
and editing, P.M. and N.H. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors acknowledge Sören Müller (Extrusion Research and Development Center TU
Berlin) for extruding the tubes and the support of Hartmut Habeck (University of Applied Sciences Stralsund) for
the corrosion measurements. Furthermore, David Barkowsky, Fabian Landt and Jan-Malte Kapust (University
of Applied Sciences Stralsund) are thanked for supporting the mechanical testing, metallographic work and
corrosion experiments.
Conflicts of Interest: The authors declare no conflict of interest.
Metals 2020, 10, 584 14 of 16

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