JOM, Vol. 68, No.

11, 2016
DOI: 10.1007/s11837-016-2075-y
Ó 2016 The Author(s). This article is published with open access at Springerlink.com

Fracture Behavior and Delamination Toughening

of Molybdenum in Charpy Impact Tests

K. BABINSKY,1,5 S. PRIMIG,1,2,6 W. KNABL,3,7 A. LORICH,3,8

R. STICKLER,4,9 and H. CLEMENS1,10

1.—Department of Physical Metallurgy and Materials Testing, Montanuniversität Leoben, Franz-

Josef Straße 18, 8700 Leoben, Austria. 2.—School of Materials Science and Engineering, UNSW
Australia, Sydney, NSW 2052, Australia. 3.—Plansee SE, Metallwerk-Plansee-Straße 71, 6600
Reutte, Austria. 4.—University of Vienna, Vienna, Austria. 5.—e-mail: katharina.babin-
sky@unileoben.ac.at. 6.—e-mail: s.primig@unsw.edu.au. 7.—e-mail: wolfram.knabl@plansee.com.
8.—e-mail: alexander.lorich@plansee.com. 9.—e-mail: roland.stickler@univie.ac.at. 10.—e-mail:
helmut.clemens@unileoben.ac.at

This study combines advanced characterization techniques with conventional

Charpy impact tests to relate the mechanical properties to the microstructure
of technically pure molybdenum, especially regarding its toughness. V-not-
ched samples with different orientations were prepared from a rolled molyb-
denum plate in stress-relieved and recrystallized condition. The ductile-to-
brittle transition-temperature was analyzed in terms of the delamination
behavior influenced by the microstructure. A pronounced increase of tough-
ness was found for specific oriented samples, which can be explained by
macroscopic delamination. Elongated grains led to enhanced delamination in
Charpy impact tests with variations for different orientations. In general,
delamination occurs as a result of brittle fracture; however, an increase in
toughness in the Charpy impact test can be provoked. This mechanism is
called thin sheet toughening or delamination toughening. Electron backscat-
ter diffraction measurements were performed to get a deeper knowledge about
crack propagation and delamination behavior in the rolled plate. Recrystal-
lization shifts the transition region to significantly higher temperatures,
which is explained by the globular grain shape as well as grain boundary
segregation. The occurrence of delamination is discussed, taking texture,
grain shape and segregation effects into account.

grain size, grain shape, grain boundary character,

INTRODUCTION
alloying content, and stress state seem to be key
Molybdenum belongs to the group of refractory approaches to influencing the DBTT of molybde-
metals and has a high melting point, high temper- num.4–9 Nevertheless, recrystallization annealing of
ature strength and good electrical and thermal the as-deformed and stress-relieved condition of
conductivity. Due to these outstanding properties, molybdenum leads to a significant increase of the
it is used for several high-performance applications DBTT and even more to intergranular embrittle-
in electronics, coatings, high-temperature engineer- ment, which is believed to be caused by the larger
ing, and lighting technology. Nevertheless, its fab- grain size and segregation enrichments at the grain
rication and processing as well as its applicability as boundaries.4–6,10–13 Recent atom probe investiga-
a high-performance material are limited because of tions revealed phosphor, nitrogen and oxygen impu-
a ductile-to-brittle transition-temperature (DBTT) rities at the grain boundaries of technically pure
around room temperature.1–3 With its body-cen- molybdenum14,15 of which especially segregated
tered cubic (bcc) structure, thermal activation is oxygen is assumed to promote intergranular fail-
necessary to overcome the Peierls potential for ure.6,11,12 By adding small amounts of carbon and
plastic deformation, causing a pronounced transi- boron, the ductility of molybdenum can be
tion from ductile to brittle. However, controlling improved.4,11,16

2854 (Published online September 6, 2016)

Fracture Behavior and Delamination Toughening of Molybdenum in Charpy Impact Tests 2855

However, molybdenum suffers from severe delam- in the DBTTs for different orientations and states
ination, a typical splitting of grains boundaries, in are discussed in terms of delamination related to
the transition and upper shelf regions due to the the apparent texture and grain shape.
anisotropic grain geometry which makes its pro-
cessing challenging. In the past, different investi-
gation methods have been applied to solve the MATERIALS AND METHODS
problem of delamination.17,18 Quasi-static pull tests
led to the assumption that linear arrangements of An industrially processed 14.5-mm-thick plate of
former micropores, which become flattened during technically pure molybdenum in the stress-relieved
hot-deformation, cause the delamination suscepti- and recrystallized state was used for this investiga-
bility of molybdenum.19 Cockeram4,20–23 tested the tion. The concentration of the main impurities in
fracture toughness and mechanisms of wrought this plate are shown in Table I.
molybdenum and molybdenum alloys. He observed The molybdenum plate was produced by a typical
a pronounced dependency of the DBTT on the grain powder-metallurgical production route by cold-iso-
size and grain shape. An elongated, pancake-shaped static pressing followed by a conventional sintering
grain structure leads to an anisotropy in fracture process. Subsequent hot-rolling was performed to
toughness. In the transition and upper shelf reach a final thickness of 14.5 mm.
regions, splitting of grains boundaries occurs and Tensile tests at room temperature were carried
generates a ductile laminate failure mode. This out on round 5 9 25 mm tensile test specimens,
cracking of grain boundaries leaves ligaments based on the DIN 50125, taken longitudinal (L) and
which stretch and fail under a plane stress condition transverse (T) to the rolling direction of the pro-
in a ductile manner. This thin sheet toughening, cessed molybdenum plate in the stress-relieved and
which is also known as delamination toughening, recrystallized state. After passing the yield point
occurs to a differing extent depending on the (Rp0.2 or Re) with 30 MPa s 1, a constant crosshead
specimen orientation in respect to the grain speed of 5 mm min 1 with a gauge length of 25 mm
shape.4,20–27 was used according to DIN EN ISO 6892-1-method
In previous studies, tensile tests were used to B.
characterize the DBTT of molybdenum. Fracture The samples used for the Charpy impact tough-
toughness tests provided more accurate measure- ness tests were 2-mm-deep V-notched specimens
ments of the DBTT for potential applications due to with the dimensions 10 mm 9 10 mm 9 55 mm,
the predominant triaxial stress state during the derived on the DIN EN ISO 148-1 standard. Fig-
experiments ahead of the crack tip.21–23 However, ure 1 shows the extraction directions (L–S, L–T, T–
as structural materials are exposed to impact S, T–L) of the specimens relative to the plate
loadings, the Charpy impact test seems to be an processing geometry according to ASTM E399. The
adequate technique to gain a better understanding two-letter code was used to specify the samples,
of fracture at high deformation speeds and low test with the first letter indicating the normal direction
temperatures at multi-axial stress states.24,25,27 to the crack plane and the second letter describing
This testing method is, besides hardness and tensile the direction of the global crack propagation.
tests, a common method for technical investigations After manufacturing the Charpy specimens, a
in industry due to its simplicity. Charpy impact stress-relief annealing treatment was performed.
tests are a straightforward method to reveal brit- The recrystallization treatment was performed on
tleness caused by an increase of deformation speed the final V-notched samples. Ultrasonic tests were
or a decrease of test temperature, as it preferen- performed to exclude pre-damaged samples. The
tially occurs in bcc metals. In recent studies, the impact tests were conducted between room temper-
mechanical properties of pipeline steels and ultra- ature and 500°C in a Zwick–Roell testing machine
fine-grained bcc steels have been, among other (BRA 342038204) with a RKP300 Joule and RKP450
methods, characterized by Charpy impact tests.27,28 Joule Charpy impact hammer. The specimens were
In this work, Charpy impact tests are combined heated in an HKE furnace and the temperature was
with advanced characterization techniques to relate measured by a thermocouple on the surface of the
mechanical properties to the microstructure of sample. When the set-point temperature was
technically pure molybdenum. Tensile tests and
Charpy impact tests were conducted on samples of a
technically processed molybdenum plate to investi-
gate the role of delamination and crystallography on Table I. Concentration of the main impurities in
the investigated molybdenum plate
the DBTT in order to give an overview of the DBTTs
in differently oriented specimens of a technically Element Concentration (lg/g)
pure molybdenum plate in its stress-relieved and
recrystallized state. Scanning electron microscopy C 19
(SEM) and electron backscatter diffraction (EBSD) O 11
have been used to examine fracture surfaces and Fe 6
delamination cracks in more detail. The deviations W 126
2856 Babinsky, Primig, Knabl, Lorich, Stickler, and Clemens

RESULTS
Microstructure and Tensile Test
In Fig. 2, the microstructures of molybdenum in
the stress-relieved (a) and recrystallized (b) state
are shown. A distinct recovered sub-grain structure
with a weak rotated cube texture is present in the
warm-deformed and stress-relieved state. Recrys-
tallization leads to an almost globular grain shape
with a mean grain size of 92 lm and a random
texture with a small maximum at the weak c-fiber
showing a <111> direction parallel to the normal
direction (ND).
Tensile tests indicate differences in strength and
Fig. 1. The extraction direction of the specimens relative to the plate
processing geometry (RD rolling direction, ND normal direction, TD elongation depending on the specimen orientation
transverse direction) is specified by the two-letter code according to in the plate and the applied heat treatment. Stress-
ASTM E399. L is the direction of principal deformation (maximum relieved molybdenum shows a higher yield
grain flow), T represents the direction of least deformation, and S the (617 MPa and 688 MPa) and tensile strength
third orthogonal direction. The two-letter code was used to specify
the samples with the first letter indicating the normal direction to the
(665 MPa and 685 MPa) as well as a larger fracture
crack plane and the second letter describing the direction of the strain (32.5% and 22.2%) and uniform elongation
global crack propagation. (7.7% and 6%) compared to recrystallized molybde-
num. For all longitudinal samples, a slight increase
in the uniform elongation was measured. Specimens
tested in the transversal direction exhibit a less
ductile behavior and an increase of strength. The
reached, the specimen was moved to the testing
results of all tensile tests are shown in the electronic
machine and analyzed after at least 2 s. According
supplementary Table I.
to DIN EN ISO 148-1, a Charpy impact test is valid
when the absorbed impact energy is lower than 80%
Charpy Impact Tests of Stress-Relieved
of the potential starting energy and the crack
Molybdenum
propagated in the designated crack growth direction
indicated by the V-notch. In Fig. 3a, data of the impact tests on differently
The stress-relieved specimens were measured in oriented stress-relieved molybdenum samples are
the L–S, L–T, T–S, and T–L orientations. The L–S presented. For L–T and T–L oriented samples, a low
and T–S samples were tested with the 450 J ham- upper shelf energy of around 53 J was found,
mer and the L–T and T–L samples with the 300 J whereas the upper shelf energy of L–S and T–S is
hammer. Additionally, recrystallized specimens in significantly higher with energy values of around
the L–S and L–T directions were investigated. The 300 J for the L–S and 150 J for the T–S orientation.
DBTT was determined at the half-value of the upper The transition from brittle to ductile behavior
shelf energy in the obtained Charpy curves. In all occurs for L–S and L–T samples in a similar
curves, the standard deviation is only shown if the temperature range of around 100–250°C and for
value scatters more than 5 J. T–L and T–S of around 200–350°C. The T–L and L–
The samples for EBSD investigations were pre- T oriented specimens exhibit a typical DBTT-curve
pared by mechanically grinding and polishing fol- with no significant scattering. The upper shelf
lowed by an electrolytic polishing with a 12.5 vol.% energy is around 53 J but a slight shift to higher
H2SO4 solution. The EBSD scans were taken with energy values and a lower DBTT (shown in Fig. 3b)
30 kV, 2.5 spot size, 8 9 8 binning and 10 mm is visible for the L–T orientation. The energy values
working distance or with 6 9 6 binning and 15 mm of L–S and T–S show more scattering in comparison
working distance in a FEI Versa 3D DualBeam to the L–T and T–L orientations.
focused ion beam/scanning electron microscope
(FIB/SEM) workstation equipped with an EDAX T–L and L–T Orientation
Hikari XP EBSD system. Inverse pole figure (IPF)
The fracture surfaces close to the notch root of the
maps were used to characterize the microstructural
L–T and T–L specimens at 23°C (lower shelf), 150°C
evolution and texture. The fracture surfaces close to
(transition), and 300°C (upper shelf) are shown in
the V-notch were analyzed in a stereomicroscope
the electronic supplementary Fig. 1. At room tem-
(Zeiss Discovery V20) and the SEM. The macro- and
perature, i.e. in the lower shelf region, both orien-
microscopic delamination was investigated by
tations exhibit transgranular cleavage (electronic
EBSD analyses. The Charpy specimens for EBSD
supplementary Fig. 1a and d). At 150°C, the L–T
analyses were prepared before the impact tests to
oriented sample indicates the transition to a ductile
prevent artifacts due to the grinding and polishing
fracture behavior with dimples visible on the frac-
process.
ture surface. At the same temperature, the T–L
Fracture Behavior and Delamination Toughening of Molybdenum in Charpy Impact Tests 2857

Fig. 2. IPF maps of molybdenum in the (a) stress-relieved and (b) recrystallized state determined by EBSD. The insets in the middle show the
IPF coloring, which indicates the crystal direction perpendicular to the specimen surface, and the orientation of the cube in respect to the rolling
process. In (a) the orientation of the tested samples are marked.

oriented sample still breaks almost in the brittle be observed in Fig. 6 b–d. The L–S oriented samples
fracture mode. The same trend is visible in the did not break into two pieces above 150°C and the T–S
DBTT-curves in Fig. 3 with a higher energy value oriented samples not above 250°C.
for the L–T direction than for the T–L at 150°C. At In the transition region, the T–S oriented speci-
300°C, both sample orientations show a ductile mens also exhibits delamination cracks and large
fracture behavior, prominent for the upper shelf. In deviations from the global crack path. The variation
the transition region, microscopic delamination in the position and the size of delamination cracks
cracks normal to the global crack propagation results in a strong scattering of the energy values in
direction start to appear. In Fig. 4a and b. stereo- the DBTT-curve, as visible in Fig. 3a. In the elec-
graphic images of the fracture surfaces of samples tronic supplementary Fig. 2a, a T–S sample tested at
in the L–T and T–L orientations tested in the 50°C is presented. The arrows mark large delamina-
transition region (225°C) are presented. At this tion cracks.
temperature, ductile laminate features (white To study these cracks in more detail, EBSD
arrows in Fig. 4a and b) start to occur. In L–T investigations were performed. In the electronic
oriented samples, more delamination cracks can be supplementary Fig. 2b–d delamination cracks are
seen than in T–L oriented samples. This is even shown in SEM images and IPF maps. Typically,
more evident by analyzing the SEM images of both delamination takes place between different grain
orientations tested at 400°C in the upper shelf, orientations, as visible in the electronic supplemen-
which are shown in Fig. 4c and d. The L–T orien- tary Fig. 2b. This behavior is shown in more detail
tation exhibits finer ductile sheet-like laminate in high-magnification EBSD analyses in the elec-
features than the T–L orientation. tronic supplementary Fig. 2c and d. These cracks
The microscopic delamination cracks in L–T and propagate between grains of high misorientation;
T–L orientation occur normal to the global crack however, cracks also occur perpendicular to the
growth direction. An EBSD investigation of a longer delamination in regions with small grain misorien-
delamination crack shown in Fig. 5a indicates that tation (white arrow).
cracks propagate between grains with high misori-
entation (see IPF maps in Fig. 5b and c). It seems Charpy Impact Tests of Recrystallized
obvious that delamination occur along high-angle Molybdenum
grain boundaries (HAGB).
After recrystallization, the molybdenum samples
exhibit an almost globular grain structure as shown
T–S and L–S Orientation
in Fig. 2b. In the DBTT-curves of recrystallized molyb-
Figure 6a represents a L–S specimen tested in the denum in the L–T and L–S orientations, shown in
lower shelf region (50°C) with macroscopic delami- Fig. 7a, a clear increase of the DBTT is apparent in
nation cracks. These delamination cracks do not comparison to stress-relieved molybdenum. The L–T
propagate in the designated crack growth direction, oriented samples of the recrystallized state show higher
but branch parallel to the longitudinal direction of upper shelf energy than in the stress-relieved state. For
the impact test bars. With a closer investigation of the the L–S orientation, an upper shelf energy of around
surface of the delamination (marked by the arrow in 300 J for both stress-relieved and recrystallized molyb-
Fig. 6a), a typical intergranular fracture surface can denum can be observed. Both orientations in the
2858 Babinsky, Primig, Knabl, Lorich, Stickler, and Clemens

Fig. 3. (a) Charpy impact test curves for molybdenum in the stress-relieved state in all four orientations. The vertical dashed lines indicated the
temperatures above which the samples did not break anymore during the impact test (red for L-S orientation, black for T-S orientation). (b) Data
of the upper shelf region of T-L and L-T, marked by the inset in (a), between 320 and 420°C. Note: In (a) the standard deviation is only shown if
values scatter more than 5J. Only in (b) the scattering for values lower than 5J, is presented.

Fig. 4. Analyses of the fracture surfaces in the transition region (225°C) and upper shelf region (400°C). (a) Stereomicroscope image of the L-T
orientation tested at 225°C. (b) Stereomicroscope image of the T-L orientation tested at 225°C. (c) SEM image close to the former V-notch of the
L-T orientation tested at 400°C. (d) SEM image close to the former V-notch of the T-L orientation tested at 400°C.

recrystallized condition indicate a similar DBTT lying elevated temperatures, the samples did not break. No
between 400 and 450°C. The image visible in Fig. 7b large delamination cracks can be observed in both
represents a characteristic specimen tested at 450°C in tested orientations. The DBTT of the L–T orientation is
the upper shelf region. Due to the ductile behavior at slightly shifted to lower values.
Fracture Behavior and Delamination Toughening of Molybdenum in Charpy Impact Tests 2859

Fig. 5. (a) Stereomicroscope image of the half impact bar (side view) tested in L-T orientation in the transition region (150°C). (b) IPF map of
delamination cracks marked in Fig. 6a. Two cracks are visible. (c) 90 degree rotated IPF map. The inset in the lower right corner shows the IPF
coloring which indicates the crystal direction perpendicular to the (b) ND and (c) TD direction.

Fig. 6. (a) Stereomicroscope image of a L-S specimen tested in the lower shelf region (50°C) with macroscopic delamination cracks. (b)
Stereomicroscope image of the delamination marked by the arrow in (a). (c) SEM image of the delamination shown in (b). (d) Higher magni-
fication SEM image of the delamination visible in (c).

In the electronic supplementary Fig. 3a–c, the observed in both orientations in the lower shelf
fracture surfaces of the L–T and L–S oriented region. However, in the transition and upper shelf
samples in the recrystallized state in the lower regions, the L–T specimens exhibit a small tendency
shelf are shown (sample tested at 23°C and 375°C towards delamination. In the electronic supplemen-
for the L–T orientation and 250°C for the L–S tary Fig. 3d, the SEM image of the fracture surface
orientation). Intergranular fracture behavior with of a L–T oriented sample tested in the transition
small transgranular cleavage regions can be region (375°C) is presented, where small
2860 Babinsky, Primig, Knabl, Lorich, Stickler, and Clemens

Fig. 7. (a) Charpy impact test curves of recrystallized molybdenum in the L-T and L-S orientation. (b) Photograph of a tested L-T sample at
450°C.

delamination cracks can be observed (marked with pipeline steel,27 which was explained by a closer
an arrow). The L–S oriented samples show no spacing of grain boundaries in the transversal
delamination in the transition- and upper shelf orientation.
region.
Stress-Relieved Molybdenum in the Charpy
Impact Test
Ductile-to-Brittle Transition Temperatures
In general, the stress-relieved samples can be
To compare the obtained results, all DBTTs are
classified in two groups. Firstly, there are the L–T
summarized in Table II. In the stress-relieved state,
and T–L oriented samples, where the global crack
the lowest DBTT with 169°C was determined for the
propagates in the designated crack growth direc-
L–T orientation. The L–S oriented specimens show
tion. Secondly, in the L–S and T–S oriented sam-
a slightly higher DBTT (181°C), followed by the T–L
ples, the crack deviates from the designated
oriented samples with 229°C. T–S oriented samples
direction due to macroscopic delamination. Due to
indicate the highest DBTT with 280°C. After recrys-
the additional delamination cracks, the local driving
tallization, the DBTT increased significantly. Both
force for the crack propagation is reduced for L–S
orientations, L–T and L–S, exhibit equal transition
and T–S and a larger surface area is created,
values of around 429–442°C. Only a small difference
leading to higher upper shelf energies. However, it
can be observed.
seems that the DBTT values are more influenced by
the orientation of the crack plane than by the crack
DISCUSSION
propagation direction for L–T and L–S. The T–L and
In the following, the results from tensile tests at T–S show similar transition regions. In the follow-
room temperatures and Charpy impact experiments ing, the characteristics of the two groups will be
between 23°C and 500°C are discussed, with special discussed in more detail.
focus on the orientation dependency and micro-and
macroscopic delamination in technically pure T–L and L–T Orientation
molybdenum.
L–T and T–L samples show quite similar DBTT
curves, with a slightly higher upper shelf energy
Tensile Tests
and a lower DBTT for L–T. Both orientations have
The tensile tests exhibit the typical decrease in in common that cracks propagate without large
yield and tensile strength due to recrystallization of deviations in the designated crack growth direction.
molybdenum. The embrittlement is deduced by the The DBTTs are in good accordance with the
uniform elongation, which is reduced from 6%–8% fracture surface observations indicating the transi-
to 2%–3%. By a closer examination of the stress- tion from a transgranular cleavage to a ductile
relieved condition of the transversal sample (T), a laminate failure mode with dimples. In these orien-
slight increase of yield and tensile strength as well tations, the designated crack growth direction is
as a drop of fracture strain and uniform elongation parallel to the long axis of the elongated grains.
can be observed. The same tendencies were found Thus, the crack can easily propagate along the
for stress-relieved molybdenum4 and for an API-X80 HAGBs. However, microscopic delamination was
Fracture Behavior and Delamination Toughening of Molybdenum in Charpy Impact Tests 2861

Table II. Summary of all DBTTs

DBTT (°C)

L–T T–L L–S T–S

Mo stress-relieved 169 229 181 280
Mo recrystallized 429 442

found on both fracture surfaces perpendicular to the T–S and L–S Orientation
crack growth direction in the transition and upper
Both orientations exhibit a higher upper shelf
shelf region. It is well known that the occurrence of
energy than the T–L and L–T orientations which is
these delamination cracks, which look like thin
related to large deviations in the crack path, caused
sheet ligaments, generate a toughening mechanism,
by macroscopic delamination. The cracks branch
also known as delamination toughening.4,20,24,27,28
perpendicular to the designated propagation direc-
These thin ligaments deform plastically under a
tion, whereby the local crack driving force is
plane stress state introducing a larger plastic zone.
reduced and, even more, a much larger new surface
The fracture toughness is increased due to the
is created. As a consequence, the upper shelf energy
relaxation of the triaxial stress state at the crack
is significantly higher than in the T–L and L–T
tip. By the formation of microscopic delamination
orientations and depends on the degree of macro-
cracks, the thickness of the original sample is
scopic delamination.26 Each sample showed delam-
reduced to a bunch of many small thin sheet
ination of a different extent, which explains the
ligaments. The triaxial stress component decreases
intense scattering of the energy values especially in
causing a plane stress state. The sample acts like a
L–S oriented samples. The vertical dashed lines in
stack of many thin samples instead of one thick
the DBTT-curves in Fig. 3 indicate the temperature
sample. Thinner delamination segments will have a
at which the specimens did not break into two pieces
larger tendency for plane stress with the result of a
due to pronounced delamination. In the L–S sam-
higher toughness.27 Delamination toughening can
ples, the designated crack plane is perpendicular to
be observed, for example, in the L–T oriented
the longer axis of the elongated grains, causing the
samples in Fig. 4. Comparing the fracture surfaces
strongest delamination effect (visible in Fig. 6). In
of the T–L and L–T orientations, the L–T samples
the T–S oriented specimens, the grain elongation is
exhibit thinner ligaments which lead to an
less pronounced (visible in Fig. 2a), leading to less
improved toughness in the upper shelf energy
pronounced delamination (electronic supplemen-
apparent in the DBTT-curves, shown in Fig. 3b.
tary Fig. 2a). The occurrence of delamination in
Hence, an increase of around 2 J of the upper shelf
the Charpy impact test is related to weak interfaces
energy for the L–T orientation can be observed. The
or planes normal to the V-notch and the designated
same toughening effects were studied by Joo
crack growth direction of the samples.26 EBSD
et al.24,28,29 in an API-X80 steel, by Song et al.27,30
investigations of the T–S oriented samples (visible
and by Kimura et al.26 in an ultrafine grained steel,
in the electronic supplementary Fig. 2b–d) reveal a
by Hohenwarter31 in an ultrafine-grained fully
splitting of grain boundaries between grains with
perlitic steel, and by Cockeram20,22 in wrought
high misorientation. High-magnification SEM
molybdenum and its alloys. EBSD investigations
images indicate that the crack tips grow along
of such delamination cracks (Fig. 5) indicate crack-
HAGB, especially between the strong partial a-fiber
ing along HAGB which correlates well with the
with<110>//RD and the weak c-fiber with<111>//
result of Cockeram,20,22 who describes delamination
ND.33,34 Kimura et al.26 identified the anisotropic
as the splitting of grain boundaries. In recent atom
grain shape as the main reason for the occurrence of
probe studies, oxygen, phosphorus and nitrogen
delamination. Strength, toughness and ductility are
segregations at HAGB were found, which can
significantly increased at low temperatures due to
decrease the grain boundary strength causing these
ultrafine elongated grains along the rolling direc-
grain boundary cracks.15 Additionally, it is believed
tion and nanometer particles which promote split-
that the HAGBs of molybdenum are intrinsically
ting between the grain boundaries. In this study,
weak.7,8,32
the molybdenum plate shows a weak texture, but
The DBTT of the L–T oriented sample is lower,
the crack follows the interfaces between the slight c-
which can be correlated with the premature
and a-fibers along HAGBs. Between these bound-
occurrence of delamination cracks causing an
aries, a transgranular fracture is also observed,
increase in toughness. This phenomenon seems
where the crack connects elongated grain bound-
to be mainly influenced by the orientation of the
aries, as visible in the electronic supplementary
crack plane independent of the crack propagation
Fig. 2b (marked by an arrow). By a closer
direction.
2862 Babinsky, Primig, Knabl, Lorich, Stickler, and Clemens

investigation of the fracture surface of the delam- enhanced delamination in Charpy impact test
ination (visible in Fig. 6b–d), a typical intergranular depending on the specimen orientation. Microscopic
fracture mode is apparent. It is interesting that delamination in the L–T and T–L samples in the
delamination, which is a result of brittle fracture, stress-relieved state were found to be beneficial due
causes an increase in Charpy impact toughness. to the effect of delamination toughening. A pro-
Therefore, the L–S oriented samples in the stress- nounced increase of toughness is apparent in the L–S
relieved state seem to be the toughest orientation and T–S samples, which is related to macroscopic
due to enhanced macroscopic delamination. delamination. These delamination cracks follow
grain boundaries between grains of high misorienta-
Recrystallized Molybdenum in the Charpy tion, which are weakened by impurities at the
Impact Test interfaces. Although delamination is a result of
brittle fracture, an increase in toughness in the
In order to study the effect of texture and grain
Charpy impact test is provoked. Therefore, the L–S
elongation on the DBTT and the delamination
oriented samples reveal the highest toughness, fol-
behavior, the recrystallized condition of the molyb-
lowed by the T–S and L–T samples. The T–L oriented
denum plate in the L–T (microscopic delamination
samples showed the lowest resistance against crack
in the stress-relieved state) and L–S orientations
propagation. Recrystallization leads to a significant
(macroscopic delamination in the stress-relieved
increase of the DBTT, caused by the globular grain
state) has been studied.
structure and impurities present at the grain bound-
After recrystallization, an almost globular grain
aries. In conclusion, the elongated grain structure
structure with a weak c-fiber can be observed.
plays a significant role for the toughness of bcc-
However, the grains are still slightly elongated
structured metals, especially in correlation with the
along the rolling direction, as visible in Fig. 2b.
weak bonding of random high-angle grain bound-
The DBTT-curves of the recrystallized molybde-
aries in molybdenum, which are related to either an
num reveal a clear increase in the DBTT compared
extrinsic (grain boundary segregation) or an intrinsic
to the stress-relieved condition. In the lower shelf,
(microstructure) property.
intergranular facture is apparent for both orienta-
tions (visible in the electronic supplementary ACKNOWLEDGEMENT
Fig. 3a–c). On the one hand, this embrittlement is
Open access funding provided by Montanuniver-
a result of impurities, which segregate to the grain
sität Leoben. Thanks to Walter Kopper, the
boundaries. Especially, oxygen segregation weakens
responsible technician of the Charpy impact test
the grain boundaries.6,11,12 On the other hand, it is
machine at our Department, who conducted all im-
believed that the embrittlement is an intrinsic
pact tests for this study. Furthermore, the authors
property of molybdenum.7,8,32 Intergranular frac-
are grateful to Dipl.-Ing. Thomas Leitner from the
tures occur more often in microstructures with
Chair of Materials Physics of the Montanuniversität
many random high-angle grain boundaries. Low-
Leoben for his scientific and technical input in
angle and special boundaries, such as sigma grain
terms of fracture mechanics.
boundaries, seem to cause transgranular fractures.8
In addition, the shape of the grains influences the OPEN ACCESS
DBTT. The slight elongation of the grains causes no
This article is distributed under the terms of the
branching of the crack and, therefore, no delamina-
Creative Commons Attribution 4.0 International Li-
tion occurs which leads to an increase in the DBTT.25
cense (http://creativecommons.org/licenses/by/4.0/),
In the transition region of the L–T samples, small
which permits unrestricted use, distribution, and
ductile laminate features can be observed which are
reproduction in any medium, provided you give ap-
similar to the ligaments in the L–T samples in the
propriate credit to the original author(s) and the
stress-relieved state. A small decrease in the DBTT
source, provide a link to the Creative Commons li-
for the L–T sample is apparent compared to L–S (L–
cense, and indicate if changes were made.
T at 429°C, L–S at 442°C), which can be related to
this delamination toughing effect.

CONCLUSION ELECTRONIC SUPPLEMENTARY

MATERIAL
In this study, advanced characterization tech-
niques were successfully combined with simple
Charpy impact tests to relate the mechanical prop- The online version of this article (doi:10.1007/
erties to the microstructure of technically pure s11837-016-2075-y) contains supplementary mate-
molybdenum, especially regarding its toughness rial, which is available to authorized users.
and delamination behavior. An anisotropy of fracture
toughness in stress-relieved molybdenum was REFERENCES
observed due to a pancake-shaped, elongated grain 1. W. Martienssen and H. Warlimont: Springer Handb. Con-
structure. Hence, the grain geometry controls the dens. Matter Mater. Data (Berlin, Heidelberg, New York:
crack propagations. Elongated grains led to Springer, 2005), pp. 304–318.
Fracture Behavior and Delamination Toughening of Molybdenum in Charpy Impact Tests 2863

2. T. Watanabe and S. Tsurekawa, J. Mater. Sci. Eng. A 387– 17. C. Stickler: Plansee Report 97DEL2a 6 (1997).
389, 447 (2004). 18. R. Stickler and H. Hödl: Plansee Report 96DEL2a 12
3. L. Northcott, Metallurgy of the Rarer Metals – 5 (Molyb- (1996).
denum (London: Butterworths Scientific Publications, 19. R. Stickler and H. Hödl: Plansee Report 96DEL3a 4 (1996).
1956), p. 222. 20. B.V. Cockeram, J. Mater. Sci. Eng. A 528, 288 (2010).
4. B.V. Cockeram, E.K. Ohriner, T.S. Byun, M.K. Miller, and 21. B.V. Cockeram, Metall. Mater. Trans. A 36, 1777 (2005).
L.L. Snead, J. Nucl. Mater. 382, 229 (2008). 22. B.V. Cockeram, J. Mater. Sci. Eng. A 418, 120 (2006).
5. H. Kimura, Trans. Jpn. Inst. Met. 29, 521 (1988). 23. B.V. Cockeram, Metall. Mater. Trans. A 33, 3685 (2002).
6. A. Kumar and B.L. Eyre, Proc. R. Soc. A 370, 431 (1980). 24. M.S. Joo, D.-W. Suh, J.H. Bae, and H.K.D.H. Bhadeshia, J.
7. J.B. Brosse, R. Fillet, and M. Biscondi, Scr. Metall. 15, 619 Mater. Sci. Eng. A 546, 314 (2012).
(1981). 25. Y. Hiraoka, H. Kurishita, M. Narui, and H. Kayano, Mater.
8. S. Tsurekawa, T. Tanaka, and H. Yoshinaga, J. Mater. Sci. Trans., JIM 36, 504 (1995).
Eng. A 176, 341 (1994). 26. Y. Kimura, T. Inoue, F. Yin, and K. Tsuzaki, Science 320,
9. A. Tahir, R. Janisch, and A. Hartmaier, Modell. Simul. 1057 (2008).
Mater. Sci. Eng. 21, 075005 (2013). 27. R. Song, D. Ponge, and D. Raabe, Acta Mater. 53, 4881
10. E. Pink and R. Eck, in Mater. Sci. Technol., ed. R. W. Cahn, (2005).
P. Haasen, E. J. Kramer, and K. H. Matucha (Weinheim, 28. M.S. Joo, D.W. Suh, J.H. Bae, N.S. Mouriño, R. Petrov,
New York, Basel, Cambridge, Tokyo: VCH, 2006), pp. 591– L.A.I. Kestens, and H.K.D.H. Bhadeshia, J. Mater. Sci.
638. Eng. A 556, 601 (2012).
11. M.K. Miller and A.J. Bryhan, J. Mater. Sci. Eng. A 327, 80 29. M.S. Joo, D. Suh, J. Bae, and H.K.D.H. Bhadeshia, Mater.
(2002). Sci. Technol. 30, 439 (2014).
12. A.S. Drachinskiy, A.V. Kraynikov, and V.N. Slyunyayev, 30. R. Song, D. Ponge, D. Raabe, J.G. Speer, and D.K. Matlock,
Phys. Met. Metallogr. 66, 111 (1988). J. Mater. Sci. Eng. A 441, 1 (2006).
13. A. Krajnikov, A. Drachinskiy, and V. Slyunyaev, Int. J. 31. A. Hohenwarter, A. Taylor, R. Stock, and R. Pippan, Me-
Refract. Met. Hard Mater. 11, 175 (1992). tall. Mater. Trans. A 42A, 1609 (2011).
14. K. Babinsky, J. Weidow, W. Knabl, A. Lorich, H. Leitner, 32. T. Watanabe and S. Tsurekawa, Acta Mater. 47, 4171
and S. Primig, Mater. Charact. 87, 95 (2014). (1999).
15. K. Babinsky, W. Knabl, A. Lorich, R. De Kloe, H. Clemens, 33. S. Primig, H. Leitner, and W. Knabl, Metall. Mater. Trans.
and S. Primig, Ultramicroscopy 159, 445 (2015). A 43, 4794 (2012).
16. T. Kadokura, Y. Hiraoka, Y. Yamamoto, and K. Okamoto, 34. S. Primig, H. Leitner, W. Knabl, A. Lorich, H. Clemens,
Mater. Trans. 51, 1296 (2010). and R. Stickler, J. Mater. Sci. Eng. A 535, 316 (2012).