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Transverse Creep of Nickel-Base Superalloy Bicrystals

Article  in  Metallurgical and Materials Transactions A · June 2015

DOI: 10.1007/s11661-015-2869-5

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Transverse Creep of Nickel-Base Superalloy Bicrystals
J.C. STINVILLE, K. GALLUP, and T.M. POLLOCK

A liquid metal cooled (LMC) solidification technique was used to produce nickel-base GTD 444
and René N4 superalloy bicrystals with varying degrees of misorientation. Creep experiments
with loading normal to the bicrystal boundaries were conducted at 1255 K (982 C). Despite the
similar overall compositions of these two alloys, the GTD 444 alloy with higher levels of carbon
and boron displayed significantly higher tolerance to high-angle boundaries. Creep ductilities at
rupture of greater than 5 pct were observed in GTD444 for boundaries misoriented by greater
than 20 deg. Electron backscatter diffraction analysis showed significant lattice rotation adja-
cent to the bicrystal boundary in GTD444. In contrast, the René N4 bicrystal accumulated
damage along the grain boundary early in creep, failing at less than 2 pct strain.

DOI: 10.1007/s11661-015-2869-5
 The Minerals, Metals & Materials Society and ASM International 2015

I. INTRODUCTION necessary to understand their influence on the mechan-

SINGLE-CRYSTAL nickel-based superalloys pre-
vail as the material of choice for high-temperature gas
turbine applications. The Bridgman[1,2] or Liquid Metal
Cooled (LMC)[3,4] single-crystal growth techniques are
commonly used to produce directionally solidified
turbine blades. During solidification of complex turbine
airfoil shapes, it is challenging to maintain uniform
thermal gradients and solidification velocities to yield a
monolithic single crystal through the seed and subse-
quently throughout the entire withdrawal process.[5–7]
While low-angle boundaries may not degrade high-
temperature mechanical properties, high-angle bound-
aries will have a strong detrimental effect, particularly
on creep properties.[8–10] From an engineering point of
view, the presence of low-angle boundaries must be
tolerated to maintain casting as an economically viable
production technique. It is, therefore, important to
determine the level of grain boundary misorientation
that can be tolerated without any significant loss in
mechanical performance. In addition, a more funda-
mental understanding of the mechanisms of damage
development and failure at the low-angle boundaries
would provide directions for development of more
failure-resistant alloy compositions. Minor element
additions have been studied as a means of making
boundaries more damage resistant in a range of com-
mercial alloys.[8–12] Significant improvement of tolerance
to high-angle grain boundaries with minor element
additions of carbon and boron have been observed in
these alloys at temperatures between 1033 K and
1373 K (760 C and 1100 C).[8–12] However, creep
ductility remains limited compared to defect free single
crystals. To optimize these minor alloying additions, it is
J.C. STINVILLE, Post Doc, K. GALLUP, Graduate Student, and
T.M. POLLOCK, Professor, are with the Materials Department,
University of California, Santa Barbara, Santa Barbara, CA 93106-
5050. Contact e-mail: stinville@engineering.ucsb.edu
Manuscript submitted August 8, 2014.
Article published online April 2, 2015
isms inducing the loss of mechanical properties. This
paper investigates the effects of creep deformation at
high temperature on two alloys with very similar
nominal composition but with differences in minor
elements. The first alloy, GTD444,[13] was developed as
a columnar-grained alloy, while the second alloy, René
N4, was designed as a single-crystal alloy.[8,14–17] Both
alloys have been produced using the liquid metal cooling
method[3,4,18] allowing production of bicrystals with
varying misorientation. Creep properties and damage
accumulation for loading transverse to the boundaries
have been studied in detail.
II. EXPERIMENTAL APPROACH
The composition of the two alloys studied is given in
Table I. Bicrystalline slabs of each alloy were solidified
by the LMC method.[3] The liquid metal cooling
container held a 500 kg Sn bath maintained at 523 K
(250 C) and was combined with a dynamic, floating
ceramic baffle. The 1.5-cm-thick baffle consisted of a
mixture of hollow and solid beads, ranging from ~0.5 to
1.5 mm in diameter, each comprising zirconium silicate.
Ingots of the superalloy were induction melted with a
maximum temperature of 1823 K (1550 C) and poured
into a pre-heated investment mold. Bicrystals were
withdrawn at a rate of 8.5 mm/min. Double-seeded
molds were used with seeds rotated in the X-Y plane
(Figure 1) to achieve a single boundary of specific
misorientation and produce a solidification (Z direction)
along the h001i direction (Figure 1). The desired bicrys-
tal boundary misorientation was achieved by rotating
one seed relative to the other around its normal axis.
Conventional tensile creep specimens with a gage
length of 24.7 mm and gage diameter of 3 mm were
machined from solution heat treated and aged slabs
along the transverse direction (Figure 1). The creep
testing condition employed in this investigation was
982 C/207 MPa. The loading axis (X direction) was

2516—VOLUME 46A, JUNE 2015 METALLURGICAL AND MATERIALS TRANSACTIONS A

 Table I. Chemical Composition of the Alloys (Weight Percent)
Alloy Al W Mo Cr Co
René N4 4.2 6 1.5 9.7 7.5
GTD 444 4.2 6 1.5 9.6 7.5
Fig. 1—Sketch of the bicrystal slab casting.
perpendicular to the bicrystal boundary. Interrupted
tests were also carried out after 1, 2, and 5 pct creep
strain with rapid cooling to room temperature under
load following testing.
An FEI XL 30 scanning electron microscope
equipped with an EBSD TSL OIM system was used to
examine fracture surfaces, bulk specimens, and crystal-
lographic orientation. Bicrystal boundary misorienta-
tion angle was determined using EBSD measurements.
EBSD scans were performed using a 0.1-lm hexagonal
grid for high-magnification scans (1000 times) and
0.5 lm for low-magnification scans (500 times), an
acceleration voltage of 25 kV, and a beam current
typically 0.2 nA. No clean-up treatment was used. Large
EBSD scans are achieved using stitching of EBSD scans
and stage displacement.
Bicrystal boundary misorientation angle refers to the
average angle to bring crystalline lattices from one side
of the bicrystal into coincidence with the crystal lattice
of the other side. Bicrystal boundary misorientation
describes the misorientation with the smallest possible
rotation angle out of all symmetrically equivalent
misorientations, which falls within the fundamental
zone (standard stereographic triangle).
A laser scanning Mitutoyo 500S micrometer was used
to measure the cross-sectional shape of creep gage
sections before and after creep tests. The laser mi-
crometer allows extraction of the position of one point
at the specimen surface sample compared to a reference
point. So, by rotating the specimen, it is thus possible to
acquire the entire shape of the specimen and the creep
induced changes in shape.
METALLURGICAL AND MATERIALS TRANSACTIONS A
Ti Hf Nb Ta C B Ni
3.4 0.12 0.5 4.8 0.06 0.004 bal.
3.6 0.12 0.5 4.7 0.09 0.009 bal.
Fig. 2—Inverse pole figure showing the orientation of the single-
crystal and bicrystal specimens along the loading direction. For
bicrystal specimens, only one orientation is reported which is the ori-
entation of one crystal. The other crystal is misoriented along a rota-
tion about the Z direction.
The orientations of the creep specimens on both sides
of the bicrystal boundary determined by EBSD mea-
surements are plotted on the standard stereographic
triangle along the loading direction (X) in Figure 2. For
all samples, both sides of the bicrystal boundary are
close to the h001i to h011i line due to the seeding
approach. Single-crystal creep specimens were also
machined in section of the cast plates away from the
boundary. Their orientations are also plotted in Fig-
ure 2.
III. RESULTS
A. Low- and High-angle Bicrystal Boundary
Morphology
The bicrystal boundaries in both alloys were charac-
terized by optical microscopy and EBSD measurements.
Typical micrographs of low-angle and high-angle
boundary, Figure 3, display the dendrite structure in
the X-Y plane (see Figure 1) of the slab. A dashed line
indicates the location of the bicrystal boundary, with
high-angle boundaries exhibiting a higher amplitude of
waviness in the X-Y plane, compared to low-angle
boundaries (Figures 3(a) and (b)).
Figures 3(c) and (d) display typical EBSD grain ID
maps for a high-angle boundary along the X-Y and X-Z
plane (see Figure 1) of the slab respectively. The EBSD
grain ID map provides a random color for each
crystallographic grain, allowing visualization of
bicrystal boundaries. For all slabs, especially for the
high-angle boundaries, a higher amplitude waviness
VOLUME 46A, JUNE 2015—2517
Fig. 3—Low- (a) and high- (b through d) angle bicrystal boundaries in the X-Y (a through c) and X-Z (d) planes of the GTD 444 slab casting.

Fig. 4—Creep test results for (a) René N4 and (b) GTD444 single crystal, low- and high-angle boundaries of bicrystal creep specimens. Single
crystals are labeled ‘‘SC A’’ and ‘‘SC B’’ for the René N4 alloy and ‘‘SC A’’ for the GTD 444 alloy. For the René N4 (Fig. 4(a)), creep test re-
sults are displayed for bicrystal creep specimens with misorientation angle (mo.) of 10, 20, and 36 deg. For the GTD 444 (Fig. 4(b)), creep test
results are displayed for bicrystal creep specimens with misorientation angle (mo.) of 28 and 37 deg.

boundary was observed in the X-Y plane compared to
the X-Z plane, which is the plane of the primary
dendrite growth (Figure 1).
B. Creep Curves for High- and Low-angle Bicrystal
Boundary Specimens
Creep specimens were extracted from low- and high-
angle boundary slabs and tested transverse to the bound-
aries at 982 C/207 MPa. Single-crystal specimens were
also machined from the slabs to compare the creep
properties of single-crystal and bicrystal specimens.
Crystallographic orientations along the loading direction
of single crystal and bicrystals are reported in Figure 2.
Results of creep tests for René N4 and GTD 444
specimens are given in Figures 4(a) and (b), respectively.
Figure 5 displays rupture life as a function of boundary
misorientation. Bicrystal creep specimens are labeled
according to the alloy and the bicrystal misorientation
angle and single crystals labeled ‘‘SC A’’ and ‘‘SC B’’
which correspond to an orientation close to h001i and
away from h001i are also shown.

2518—VOLUME 46A, JUNE 2015 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 5—Creep rupture life of René N4 and GTD444 bicrystals as a
function of misorientation angle. Arbitrarily, a 0 deg misorientation
angle has been chosen to plot the single-crystal creep rupture life.
Crosses specify specimens that reach the tertiary creep regime. Num-
bers indicate final creep elongation (Pct).
A René N4 low-angle boundary specimen (misorien-
tation angle of 10 deg) labeled ‘‘RN4 10 deg mo.’’ in
Figure 4(a) shows an intermediate creep rate compared
to the René N4 single crystals which correspond to the
single-crystal orientations on either side of the bound-
ary. Rupture occurs during the tertiary regime with
rupture ductilities in excess of 10 pct for the single
crystals and the low-angle boundary bicrystals. Howev-
er, the René N4 high-angle boundary specimens failed
during the secondary regime with low rupture ductility.
For the high-angle GTD 444 specimens, rupture was
observed to occur during the tertiary regime for all
samples (Figure 4(b)). A strain to rupture between 5 and
10 pct was observed even for high-angle boundaries
bicrystals. Lifetimes were similar to GTD 444 single-
crystal specimens.
C. Creep Properties as a Function of Misorientation
Angle
The dependence of creep rupture life on boundary
misorientation is summarized in Figure 5 for both René
N4 and GTD444 bicrystal creep specimens. Creep
rupture life and strain at rupture are also reported for
single-crystal creep tests. It is apparent that the creep
rupture life decreases with the boundary misorientation
angle for the René N4 bicrystal creep specimens, while
the creep rupture life for GTD444 bicrystal creep
specimens is independent of the boundary misorienta-
tion angle. Significantly higher creep rupture life is
observed for high-angle boundaries in GTD444 bicrystal
creep specimens compared to René N4 samples. The
dependence of the creep strain at rupture on the
boundary misorientation angle for the René N4 bicrys-
tal creep specimens is similar to the trend observed
between rupture life and boundary misorientation angle.
It should be noted that the final creep elongation drops
precipitously to below 2 pct for boundary misorienta-
tions greater than 20 deg for the René N4 bicrystal creep
METALLURGICAL AND MATERIALS TRANSACTIONS A
specimens. All the GTD444 high-angle boundary bicrys-
tal creep specimens reached the tertiary creep regime,
with creep strains at rupture between 5 and 8 deg.
D. Fracture Surfaces
Single-crystal and bicrystal creep specimens exhibited
different fracture surface morphologies. Typical fracture
surfaces for single-crystal and bicrystal creep specimens
are given in Figure 6. Examination of the single crystals
of René N4 and GTD444 indicates that the deformation
had occurred non-uniformly; the fracture surfaces of the
failed specimens were visibly elliptical (see Figures 6(a)
and (c)). All tested bicrystal creep specimens failed at
bicrystal boundaries for both alloys. Similar fracture
surfaces are observed for high-angle boundary bicrystal
creep specimens for both alloys. A typical example of
fracture surface for a high-angle boundary bicrystal
creep specimen is shown in Figure 6(b). An arrow
depicts the Z-axis of the slab (see Figure 1). The
roughness of the fracture surface of low- and high-angle
boundary bicrystals correlates with the waviness of the
grain boundary observed in the X-Y plane of the slabs
(Figures 3(b) and (c)). The fact that the waviness is more
pronounced in the X-Y plane explains that the rough-
ness is mainly perpendicular to the Z direction. Unlike
the corresponding single crystals, the fracture surface of
all failed high-angle boundary bicrystal creep specimens
remained quasi-circular for both alloys. Conversely,
fracture surface of low-angle boundary sample was
visibly elliptical (see Figure 6(d)).
Crystallographic orientation gradients in the failed
specimens were investigated using EBSD measurements
on cross sections along the gage length of the creep
specimens, along both the X-Y and X-Z planes. René
N4 high-angle bicrystals possessed a homogenous ori-
entation along the gage length. However, in the
GTD444 bicrystals, strong gradients in orientation close
to the fracture surface were observed along the X-Y
plane. Figure 7(a) shows inverse pole figure maps along
the loading direction for a cross section in the X-Y
plane. The associated image quality map is shown in
Figure 7(b). EBSD analysis was also performed using
grain reference orientation deviation (GROD) tech-
niques (Figure 7(c)).[19] For the GROD-based analyses,
the orientation reference was the average orientation of
the grain. After rupture close to the fracture surface,
GROD map displays strong gradients distributed along
two perpendicular directions inclined to the loading
direction. Gradients appear along bands with a typical
width of 50 lm with several degrees of disorientation.
No such gradients were observed on cross sections along
the X-Z plane.
E. Interrupted Creep Tests
To detail the evolution of the microstructure and
damage during creep, interrupted creep tests were
performed after 1 pct of creep stain for René N4 high-
angle boundary bicrystals and at 1, 2 and 5 pct of creep
strain for GTD444 high-angle boundary bicrystals.
Interrupted creep specimens were subject to a rapid
VOLUME 46A, JUNE 2015—2519
Fig. 6—Fracture surface in (a) GTD444 single crystal, (b) GTD444 high-angle boundary bicrystal, (c) René N4 single crystal, (d) René N4 low-
angle boundary bicrystal and (e) René N4 high-angle boundary bicrystal.
cooling to room temperature under load. For each alloy,
several creep specimens from the same casting slab
(same bicrystal misorientation) were used for the inter-
rupted tests.
1. GTD444 alloy
Figure 8 depicts inverse pole figure maps along a
cross section (X-Y plane) of a GTD444 bicrystal creep
specimen interrupted at 5 pct creep strain. Inverse pole
figure maps are plotted with reference to the Z, Y, and X
directions, along the entire gage length. Figure 9 gives
the plot of the orientation gradient (Figure 9(a)) with
respect to the origin and the lattice rotation induced
after 5 pct creep strain along the profile labeled ‘‘profile
1’’ in Figure 8, using the standard stereographic triangle
along the loading direction (X) (Figure 9(b)) and the Y
direction (Figure 9(c)). A high degree of orientation
rotation around the X- and Y-axis is apparent on the
side labeled ‘‘side 2’’ in Figure 8.
Using the standard stereographic triangle along the
loading direction (X), Figure 10 depicts the orientations
of the same bicrystal creep specimen before creep test
and after 2 pct (Figure 10(a)) and 5 pct (Figure 10(b))
creep strain for the crystals on both sides of the
boundary. The average orientation on all the area
labeled ‘‘side 1’’ is considered; the average orientations
in the area labeled ‘‘zone 1’’ and ‘‘zone 2’’ in Figure 8
2520—VOLUME 46A, JUNE 2015
are considered for the other side of the bicrystal
specimen.
After 5 pct creep strain, significant lattice rotation is
observed during creep on both sides of the bicrystal
boundary. From Figures 9(b) and 10, it can be observed
that lattice rotation occurs such that the orientation
along the loading direction evolves toward the h001i-
h111i line. After 2 pct creep strain, a relatively uniform
orientation change was observed on side 1 of the
bicrystal. No lattice rotation was detected on the other
side of the bicrystal. After 5 pct creep strain, significant
orientation gradients are detected along the gage length
on the side labeled ‘‘side 2’’ in Figure 8.
Figure 11(a) shows the inverse pole figure of the area
at the bicrystal boundary depicted in Figure 8 with a
dashed box in the IPF along the Z direction. An
associated optical micrograph and GROD map are
plotted in Figures 11(b) and (c), respectively. Black and
white lines depict the location of the bicrystal boundary.
In addition to the gradient along the gage length,
crystallographic gradients along bands are observed
after 5 pct creep strain close to the bicrystal boundary.
Significant misorientation gradients (higher than 10 deg)
are observed close to the boundary at the macroscopic
scale. At this scale, these gradients are distributed along
bands with a high angle of tilt relative to the loading
direction. Optical micrographs allowed location of the
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 7—EBSD results on a cross section along the X-Y plane after rupture of a GTD444 high-angle boundary bicrystal: (a) inverse pole figure
map along the loading direction, (b) associated image quality map (c) grain reference orientation deviation map. Fracture surface is along the
bottom of the maps.

Fig. 8—EBSD results on a cross section along the X-Y plane after 5 pct creep for a GTD444 high-angle boundary bicrystal creep specimen:
inverse pole figure map along Z, Y, and X (loading direction).

exact position of these bands. The misorientation
gradients are observed in regions aligned along the
interdendritic regions (see Figures 11(b) and (c)).
Close to the boundary at the microscopic scale, in
addition to the rotation gradients along bands, sig-
nificant lattice rotation gradients are observed around
eutectics (‘‘zone 4’’ in Figures 12(a) and (b)) and
carbides (‘‘zone 3’’ in Figures 12(a) and (b)). Interest-
ingly, GTD444 specimens interrupted at 1 pct creep
stain do not show any rotation gradients on creep
specimen cross sections. At the same scale at the
specimen surface, Figures 12(c) and (d) show EBSD
results on a cross section at the bicrystal boundary at the
specimen surface of an interrupted creep test at 2 pct
creep strain. The specimen surface is indicated with an
arrow in Figure 12(c). High misorientation gradients are
observed close to the surface at the boundary. The
EBSD results (Figures 12(c) and (d)) show that gradi-
ents from each side of the bicrystal boundary assume
‘‘butterfly-like’’ shapes, indicating significant plastic
deformation.
Figure 13 presents the microstructure on both sides of
the high-angle boundary GTD 444 bicrystal specimen
after 5 pct creep strain. Micrographs have been acquired
from the cross section presented in Figure 8. In
Figure 13, ‘‘Side 1’’ and ‘‘Side 2’’ refer to both sides of
the bicrystal creep specimens previously seen in
Figure 8. Rafting occurs during creep on both sides of

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 46A, JUNE 2015—2521

Fig. 9—(a) Misorientation with respect to origin along the profile depicted in Fig. 8. Inverse pole figure along the loading direction (b) and the
Y direction (c): crystallographic rotation induced after 5 pct creep strain along the profile depicted in Fig. 8.

Fig. 10—Inverse pole figure along the loading direction (X): crystallographic rotation induced after (a) 2 pct and (b) 5 pct creep strain. ‘‘Side 1’’
and ‘‘Side 2’’ refer to both sides of the bicrystal creep specimens previously seen in Fig. 8.

Fig. 11—EBSD results on a cross section along the X-Y plane after 5 pct creep for a GTD444 high-angle boundary bicrystal creep specimen: (a)
inverse pole figure map (b) associated optical micrograph (c) grain reference orientation deviation map. ‘‘Side 1’’ and ‘‘Side 2’’ refer to both sides
of the bicrystal creep specimens previously seen in Fig. 8.

the sample with the c channels aligned along a h001i
direction and not perpendicular to the loading direction.
The cross-sectional shapes of the specimens interrupt-
ed at 2, 5 pct creep strain, and after rupture are shown in
Figure 14. Figures 14(a) and (b) depict the shape change
induced far from the bicrystal boundary on both sides of
the boundary for a GTD 444 bicrystal creep specimen
after 5 pct creep strain. Following Reference 20, the
shape change due to creep deformation is presented as a
polar plot of the local radius. The dashed black line
presents the shape of the creep specimen before creep
and the red line after 5 pct creep strain. A metallo-
graphic cross section along the plane normal to the
loading direction of the associated elliptical gage area on
‘‘side 2’’ at 5 pct creep strain is shown in Figure 14(c).
The projection in the plane Y-Z of a h001i direction is

2522—VOLUME 46A, JUNE 2015 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 12—EBSD results on a cross section along the X-Y plane after 2 pct (c through d) and 5 pct (a through b) creep for a GTD444 high-angle
boundary bicrystal creep specimen: (a through c) inverse pole figure map (b through d) grain reference orientation deviation map.
reported in Figures 14(a) and (b). Significant shape
changes due to creep deformation are observed on both
sides of the bicrystal boundary. Elliptical sections were
observed after 5 pct creep strain on both sides of the
bicrystal boundary. Along the gage length, it is possible
to extract the value of the shape ratio, as the ratio
between the major and minor axis of the perfect ellipse.
Figure 14(d) depicts the shape ratio of creep specimens
before testing, after 2 and 5 pct creep strain on
interrupted specimens and after creep failure. Zero on
the X-axis indicates the position of the bicrystal bound-
ary. No significant shape change is observed right at the
bicrystal boundary due to the local constraint. However,
further away from the boundary, the transverse section
is elliptical on both sides after 5 pct creep strain and on
one side after 2 pct creep strain. On ‘‘side 1’’, the shape
after 2 and 5 pct creep strain is similar. On ‘‘side 2’’, no
shape change is observed after 2 pct creep strain.
Interestingly, the major axis of the ellipse is differently
oriented on either side of the boundary. Moreover, the
rotation angle (30.1 deg) between the major axis of
METALLURGICAL AND MATERIALS TRANSACTIONS A
ellipse on both sides of the boundary (see Figures 10(a)
and (b)), i.e., the angle to bring the ellipse on one side of
the boundary in coincidence with the ellipse of the other
side approximates the bicrystal misorientation angle
(28 deg) of the specimen. After 2 pct creep strain, one
side (labeled ‘‘side 1’’) of the specimen takes an elliptical
shape, while the other side remains circular. After 5 pct
creep strain, the other side (labeled ‘‘side 2’’) assumes an
elliptical shape but not along the entire gage length.
After creep failure, both sides possess an elliptical shape.
Close to the bicrystal boundary, the shape remains
nearly circular.
Figure 15 directly correlates the shape deformation
and the lattice rotation for an interrupted test at 5 pct
creep strain for a GTD 444 bicrystal creep specimen.
Shape deformation ratio and misorientation profile
along the gage length are reported for the same
specimens after 5 pct creep strain.
In addition to rafting, orientation evolution, and
shape deformation, GTD444 bicrystal creep specimens
interrupted at 5 pct creep strain show localized damage
VOLUME 46A, JUNE 2015—2523
Fig. 13—Microstructure on both sides of the bicrystal boundary for a high-angle boundary GTD 444 specimen in dendritic region (a and b) and
interdendritic region (c and d). ‘‘Side 1’’ (a and c) and ‘‘Side 2’’ (b and d) refer to both sides of the bicrystal creep specimens previously seen in
Fig. 8.
in the vicinity of the bicrystal boundary. Figures 16(a)
and (b) shows damaged carbides and eutectic regions.
Cracks associated with carbides or eutectic regions do
not propagate in the c matrix. However, macroscopic
cracks with a high degree of opening are observed at the
grain boundary, only at regions adjacent to the speci-
men surface. Figures 16(c) and (d) shows two examples
of crack observed on a cross section of a GTD444
bicrystal creep specimen interrupted at 5 pct creep strain
in grains that are misoriented by 28 deg.
Figure 17 indicates the location and size of the cracks
in surface after 2 and 5 pct creep strain. Blue and red
areas indicate that a crack is observed in surface at the
bicrystal boundary after 2 and 5 pct creep strain,
respectively. Shape deformation on both sides of the
bicrystal boundary is plotted to indicate major axis and
minor axis of the ellipses. Cracks localize at the bicrystal
boundary and more specifically close to the major axis
of the ellipse induced by shape deformation. At 2 pct
creep strain, only the side labeled ‘‘side 1’’ experiences
shape changes and cracks are localized close to the
major axis associated with ‘‘side 1’’.
2524—VOLUME 46A, JUNE 2015
2. Rene´ N4 alloy
Microstructure during creep was also investigated for
René N4, using interrupted creep tests close to rupture
(after 1 pct of creep stain). EBSD measurement after
1 pct creep strain and after creep failure indicated no
significant orientation gradients across the gage length.
Figure 18 presents the microstructure at the bicrystal
boundary of a high-angle boundary René N4 at 1 pct
creep strain. Rafting was observed after 1 pct creep
strain along the gage length (Figure 18). In addition to
rafting, damage in the form of small cracks initiated at
interfaces of large c¢ precipitates all along the bicrystal
boundary was observed (see Figure 18). Figure 19
depicts the shape ratio of high-angle boundary René
N4 creep specimens before testing, after 1 pct creep
strain, and after creep failure. Zero on the X-axis
indicates the position of the bicrystal boundary. The
shape ratio of a single René N4 single crystal and low-
angle boundary bicrystal is given in Figure 19 for
comparison. Shape deformation is observed on single
crystal and low-angle boundary bicrystal indicating that
the deformation had occurred non-uniformly. However,
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 14—Shape deformation induced after 2, 5 pct creep strain and after creep failure: shape measurement on a cross section on side 1 (a) and
side 2 (b) perpendicular to the loading direction after 5 pct creep. (c) Associated metallographic section after 5 pct creep. (d) Shape deformation
ratio (bicrystal boundary at 0 on the X-axis); ‘‘Side 1’’ and ‘‘Side 2’’ refer to both sides of the bicrystal creep specimens previously seen in Fig. 8.

no shape change is observed along the gage length for
high-angle boundary bicrystal.
IV. DISCUSSION
The dependence of creep properties on bicrystal
boundary misorientation is strikingly different for
GTD444 compared to René N4, in spite of very similar
nominal compositions. A steady decrease in creep
rupture life and creep strain at rupture with the
increasing misorientation angle for René N4 bicrystal
creep specimens was observed in the present study. For
the René N4 alloy with lower levels of grain boundary
strengthening elements (carbon and boron), a drop in
creep performance occurred when the bicrystal bound-
ary misorientation angle exceeded 10 deg. Ross and
O’Hara,[8] in their study of the alloy René N4, conclud-
ed that addition of minor elements at low level enhance
the grain boundary tolerance to only 12 deg misorein-
tation. Similar results are reported in the literature for
other superalloys, including PWA1483[9] and
RR2072[10]. A significant improvement in creep perfor-
mance has been shown for the high-angle boundary
GTD 444 bicrystal creep specimens in comparison to the
René N4 creep specimens. Creep strain at rupture
exceeds 5 pct and lifetime is similar to single-crystal
specimens. This is apparently due to the higher level of
grain boundary strengthening elements present in the
GTD 444 (with 50 pct higher carbon and boron at a
level of more than a factor of 2). Improvement in
transverse properties for higher level of minor elements
has been observed for several other alloys.[8–12] Howev-
er, the details of damage development associated with
these chemical changes have not been examined in
detail. Chen et al.[10] mention several possible factors

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 46A, JUNE 2015—2525

that are responsible for the enhanced creep perfor-
mance. Firstly, the higher concentration of carbon
Fig. 15—Black and red curve: shape deformation ratio before and
after 5 pct creep strain along the gage length on ‘‘side 2’’ in Fig. 8.
Blue curve: misorientation profile along the same gage length
(bicrystal boundary at 0 on the X-axis).
Fig. 16—Damage in carbides (a), eutectic (b), and at the specimen surface (c, d) induced after 5 pct creep strain on a high-angle boundary GTD
444 creep specimen. ‘‘Zone 3’’ (a) and ‘‘Zone 4’’ (b) refer to Fig. 12.
2526—VOLUME 46A, JUNE 2015
causes a larger density of particles on the grain
boundaries. The second is the higher boron composition
at the boundary. Segregation of boron has previously
been observed to impart beneficial effects on Ni3Al and
RR2072 grain boundaries.[21–23].
In these previous studies,[8–10] no differences in the
damage accumulation processes due to the minor
element additions were reported. Interestingly, no sig-
nificant drop in lifetime is observed between low- and
high-angle boundary bicrystal creep specimens.[8–10]
Shah et al.[9] report an identical rupture life for high-
and low- angle boundary bicrystals on PWA1483 alloy
with the addition of grain boundary strengthening
elements (addition of hafnium and boron). However, a
drop in creep strain at rupture is observed on these
modified alloys between low- and high-angle boundary
bicrystal creep specimens. Similar results were observed
in the present study for the GTD 444 bicrystal creep
specimens. All high-angle boundary GTD 444 bicrystal
creep specimens reached the tertiary regime with a creep
strain at rupture between 5.3 and 7.3 pct. In this regime,
creep strain increases drastically with time; so the total
lifetime is only reduced by a few percent due to the
presence of the boundary.
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Examination of the single-crystal René N4 and GTD
444 crystal specimens indicated that the deformation
occurred non-uniformly along the bicrystal gage length
(Figures 6 and 19). The cross sections of the gage areas
of the failed specimens were visibly elliptical. Moreover,
significant lattice rotation was observed along the gage
length. At temperatures in excess of 1123 K (850 C), all
Fig. 17—Crack location in the bicrystal boundary section after 2
and 5 pct creep strain. ‘‘side 1’’ and ‘‘side 2’’ refer to Fig. 8.
Fig. 18—Damage at the bicrystal boundary for a high-angle boundary René N4 specimen after 1 pct creep strain.
METALLURGICAL AND MATERIALS TRANSACTIONS A
known superalloy single crystals exhibit a logarithmic
strain-softening behavior consistent with tertiary
creep,[24] in addition lattice rotation and shape defor-
mation are observed.[25,26] For crystals oriented near
h001i, the dominant deformation mode is glide-climb by
dislocations that glide predominantly on the {111}h110i
octahedral slip systems.[27,28] Material loaded uniaxially
along a direction away from h001i, particularly near
h111i, exhibits macroscopic deformation characteristics
consistent with slip on {111}h110i system.[28] Matan
et al.[25] have shown for CMSX-4 the dependence of
creep properties on crystal orientation away from h001i
Fig. 19—Shape deformation ratio induced after 1 pct and after creep
failure for René N4 High- and Low-angle boundary bicrystals and
René N4 Single crystal. (bicrystal boundary at 0 on the X-axis).
VOLUME 46A, JUNE 2015—2527
along the h001i-h101i direction is relatively weak and the
lattice rotation and shape deformation observed here is
in agreement with a dominant deformation mode of the
form {111}h110i. At high temperature (1223 K
(950 C)), Matan et al.[25] indicate that the misorienta-
tion dependence can be rationalized on the basis of
Schmid’s law. Pan et al.[20] report similar results for
dependence of creep on crystal orientation on SRR99
single crystal.
High-angle boundary René N4 bicrystal creep speci-
mens do not reach the tertiary regime and failure occurs
during the secondary regime when the creep strain rate
is constant. During this early stage of deformation
(<2 pct), no lattice rotation or shape deformation is
observed. Conversely, single crystals and low-angle
boundary bicrystals reach the tertiary regime and
undergo a change in shape of the gage section during
deformation (Figure 19).
High-angle boundary GTD 444 bicrystal creep speci-
mens do reach the tertiary regime. The results clearly
suggest that additions of minor elements have increased
the tolerance to damage initiation at high-angle grain
boundaries. This increase is significant and results in an
increase in the creep strain at rupture by several percent,
permitting enough deformation to induce lattice rota-
tion and shape deformation on both sides of the high-
angle boundary GTD 444 creep specimens (Figures 8,
10, and 14).
For the GTD444 specimens in the test interrupted
after 2 pct strain, Figure 10(a), boundary lattice rota-
tion occurred all along the gage length on only one side
of the bicrystal. After 5 pct creep strain, on the other
side, lattice rotation occurred within a few millimeters of
the bicrystal boundary. Due to the different orientations
along the loading direction on both sides of the
bicrystal, the creep response on each side differs. The
side labeled ‘‘side 1’’ in Figure 8 reaches the tertiary
regime earlier than the other side of the bicrystal,
inducing early lattice rotation and shape deformation.
The Schmid factors associated with the orientation on
‘‘side 1’’ and ‘‘side 2’’ before creep are 0.49 and 0.47,
respectively. Such differences between Schmid factors
may not be sufficient to explain an early tertiary regime
in side labeled ‘‘side 1’’.
Lattice rotation occurs in such a way that the orienta-
tion along the loading direction evolves toward the h001i-
h111i line (see Figures 9(c) and 10). Such lattice rotation
in cubic materials is commonly associated with single slip
along a h110i direction.[29,30] Lattice rotation along h112i
direction is also possible, indicating a lattice deformation
on {111}h112i.[25] Such lattice deformation mode is
observed during creep at lower temperatures (under
1123 K (850 C)), but not under the testing conditions
investigated here. The degree of lattice rotation of both
sides of the bicrystal indicates very high local strains (see
Figure 10(b)) on a {111}h110i system as higher than
14 pct[31] on either side of the boundary for an average
uniaxial strain of 5 pct.
In addition to the lattice rotation, shape changes were
reported on both sides of the bicrystal boundary for a
GTD 444 bicrystal creep specimen after 5 pct creep
strain (see Figure 14). Figures 14(a) and (b) depicts the
2528—VOLUME 46A, JUNE 2015
projection in the plane Y-Z of a h001i direction in
relation the shape change. The minor and major axis is
slightly misaligned with h001i. With a dominant defor-
mation mode of the form {111}h110i, the minor and
major axis should be aligned with the projection of h001i
in the Y-Z plane. With a dominant deformation mode of
the form {111}h112i, the minor axis should be at 45 deg
from a h001i direction. The case is complex since the
orientation along the loading direction is slightly tilted
from a h001i i.e., the plane Y-Z is not a {001} plane.
Moreover, the bicrystal boundary constrains the defor-
mation, and can affect the deformation on both sides of
the boundary.
Shape deformation occurs progressively during creep.
For the GTD444 specimens using interrupted tests, after
2 pct creep strain, shape change is observed on one side
of the boundary (see Figure 14(d)). At 5 pct creep
strain, shape deformation occurs on the other side close
to the bicrystal boundary but not exactly at the bicrystal
boundary. After rupture, shape change had occurred all
along the gage length (see Figure 14(d)).
The creep response of GTD444 bicrystal can be
estimated as the contribution from both sides of the
bicrystal as two individual single crystals, inducing creep
deformation (lattice rotation, rafting, shape change).
The different creep response on either side of the
bicrystal induces significant constraint near boundary.
Since the shape deformations are not the same on both
sides of the sample due to different crystallographic
orientations on both sides, significant stresses at the
bicrystal boundary are induced where the bicrystal
boundary intersects the surface. Butterfly-like-shaped
crystallographic gradients appear after initiation of
surface cracks (see Figures 12(c) and (d)). In general,
local crystallographic gradients correlate with the degree
of damage due to plastic strain.[32–35] Finally, high
crystallographic gradients were observed within the
vicinity of the bicrystal boundary and take the shape
of bands along the interdendritic regions in the X-Y
plane. These bands are the traces of shear bands induced
by deformation. Thus, the interdendritic spaces are
more susceptible to accommodation of deformation.
The results here indicate that the incompatibility of
deformation due to differential shape changes on both
sides of the boundary plus the constraint of the
boundary drives the surface damage initiation that
ultimately results in the rupture of high-angle boundary
GTD 444 creep specimens. Crack initiation location and
local lattice rotation in surface near the major axis of
ellipses induced by shape deformation is a direct
indication that rupture is droved by the constraint of
the boundary. Conversely for the René N4 high-angle
bicrystal, local crack initiation occurred more uniformly
along the boundary area clearly indicating that rupture
is a direct consequence of the creep damage accumula-
tion. This early damage accumulation at the boundary
appears before tertiary creep regime and no shape
change and lattice rotation are observed.
The overall results clearly suggest that minor additions
of boron and/or carbon in the GTD 444 alloy have
significantly increased the tolerance to damage initiation
at grain boundaries. The presence of a similar carbide
METALLURGICAL AND MATERIALS TRANSACTIONS A
 morphology and distribution at the boundary in both
alloys indicate that enhanced rupture properties are not
due to differences in the carbides. Segregation of boron
and/or carbon along the entire boundary may explain
increased tolerance to damage for GTD444 bicrystals.
Using first-principles density functional theory calcula-
tions, Sanyal et al.[36] report that boron additions results
in an enhancement of grain boundary cohesion while
carbon weakens the boundary, indicating that boron may
be the key element for boundary strengthening in GTD
444 bicrystals. Moreover, Buchon et al.[37] report using
transmission electron microscopy and atom probe field-
ion microscopy that boron enrichment appears at every
grain boundary while carbon enrichment is not frequently
observed. Furthermore, boron-enriched regions are con-
tinuous along the boundaries,[37] i.e., no isolated pre-
cipitates were reported along the boundaries. Further
systematic studies of segregation with crystals containing
varying levels of boron would clearly be useful.
V. CONCLUSIONS
1. The tolerance of high-angle boundaries to creep de-
formation is higher in the GTD 444 alloy containing
higher levels of carbon and boron, compared to the
René N4 alloy. Creep strain at rupture and creep life-
time is independent of the degree of misorientation
of the high-angle boundaries in GTD 444.
2. Lattice rotation induced by creep is observed in
GTD 444 high-angle boundary creep specimens.
Premature creep rupture of René N4 high-angle
boundary bicrystals does not result in a significant
degree of shape deformation and lattice rotation in
these specimens.
3. Differences in plastic shape change on both sides of
the GTD 444 bicrystal plus creep elongation induce
a large local misorientation at bicrystal boundary,
with enhanced local plasticity in the vicinity of the
boundary.
4. Crack initiation and large local misorientations at
the intersection of the bicrystal boundary with the
sample free surface indicate that the incompatibility
of deformation and constraint of the boundary limit
the rupture life of GTD 444 bicrystals while uniform
creep damage accumulation along the boundary in
René N4 bicrystals is the life-limiting mechanism.
5. Significant lattice rotations and local damage at car-
bides and eutectics are observed at the microscopic
scale near the grain boundary in GTD 444 bicrys-
tals. However, cracks do not extend from these fea-
tures and are not the primary damage mechanism.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the support of GE
Power and Water (S. Balsone, J. Schaeffer, A. Peck) and
NSF Grant DMR 1233704. The authors also acknowl-
edge the assistance of J. Cormier and P. Villechaise.
METALLURGICAL AND MATERIALS TRANSACTIONS A
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