EBSD paper2
EBSD paper2
0964-1726/12/055024+10$33.00 1 c 2012 IOP Publishing Ltd Printed in the UK & the USA
Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
Table 1. Experimental parameters and sulfur segregation mechanisms on the sample surface.
Alloy Alloy Total Final Annealing Segregation Annealing
ID composite reduction (%) thickness (mm) atmosphere mechanism conditions
A (Fe0.813 Ga0.187 )99 B1 95.5 0.35 Elemental S in Vaporization and 1200 ◦ C for 1–5 h
argon adsorption
B (Fe0.813 Ga0.187 )99.5 B0.5 96.0 0.30 Argon Diffusion from 1200 ◦ C for 0.5–4 h
doped with 50 ppm S interior
C (Fe0.81 Ga0.19 )99 (NbC)1 94.0 0.45 0.5%H2 S in Decomposition 1200 ◦ C for 1–3 h
argon and adsorption
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
Figure 7. ODF plots (ϕ2 = 45◦ ) of (Fe0.813 Ga0.187 )99 B1 alloy sheets: (a) as-rolled, (b) annealed in argon at 1200 ◦ C for 6 h and water
quenched, and (c) annealed at 1200 ◦ C for 2 h in a quartz ampoule filled with argon and 6.4 mg S and then water quenched.
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
Figure 10. Inverse pole figure images along normal direction of the sheet surface for both annealed (Fe0.81 Ga0.19 )99 (NbC)1 samples at
1200 ◦ C for 3 h under 0.5% H2 S in argon, where red, green, and blue colors indicate (001), (011), and (111) grains, respectively.
at concentration levels of below ∼0.5% and an annealing as described section 3.2 of this study. According to these
duration of less than ∼1 h. A maximum magnetostriction results of Fe–Ga–B in sections 3.1 and 3.2, surface energy
of 198 ppm was obtained in the 2 h-annealed sheet which control by sulfur segregation on the sample surface played
had a texture close to a {001} h100i cubic texture, and an important role in the development and growth of {001}
occurred with only a slight increase of sulfur concentration grains, accompanied by an increase of magnetostriction up to
(∼0.5–0.7%). However, an increase in annealing time to ∼200 ppm. Although near {001} h100i a cubic texture was
3 h resulted in a steep increase in the concentration of developed in Fe–Ga–B alloy sheet annealed under a sulfur
surface segregated sulfur, a dramatic texture change to atmosphere, it shows multi-grains with an average size of
{111} h110i and {011} h211i and a steep drop in saturation ∼282 µm and the magnetostrictive value of ∼200 ppm is 58%
magnetostriction, down to 84 ppm. of saturation magnetostriction along the h001i direction in the
In figure 9, estimates can be made of the bounds on single crystal of this composition ((3/2)λ100 = 342 ppm for
annealing time, t{hkl} , and of the concentration of surface 18.7 at.% Ga).
sulfur contamination, C{hkl} , that are associated with the With the goal of reaching the magnetostrictive capability
onset of a {hkl} texture. For development of a {001} texture, of single crystal, the desirable texture needs to be more fully
annealing for t{001} with a surface sulfur contamination developed and sharper along the RD, so as to more closely
concentration of C{001} is required. For development of a resemble the (001) h100i texture found in the single crystal.
{111} texture, an anneal time of t{111} and a surface sulfur According to Kramer’s results, it is not easy to achieve a
contamination level of C{111} is needed. In figure 9, the (001) single-crystal-like texture because the optimum surface
surface concentrations of sulfur, C{001} and C{111} , that seem sulfur contamination condition needed to form a high fraction
to bound selective {001} grain growth are 0.5 and 1.35 at.%, of (001) grains (10–25 ppm) is very sensitive to multiple
respectively. This is also supported by that for the sample parameters [20]. The approach we employed for surface
in figure 6, which was annealed in a sulfur atmosphere for segregation of sulfur involved using H2 S gas in argon during
longer than the time associated with the peak magnetostriction annealing at 1200 ◦ C for 3 h. This annealing schedule was
(indicated in figure 3), the surface concentration of sulfur is used for (011) Goss grain growth in a (Fe0.81 Ga0.19 )99 (NbC)1
greater than 1.5 at.%. sheet annealed under argon. Figure 10 shows that a red (001)
grain was abnormally grown to as much as 74.5% and 88.3%
3.3. Sulfur-annealed Fe–Ga–NbC alloy (C alloy) in the scanned areas from two different samples (the scanned
area is equal to half the surface area of the whole sample,
In our previous work [29] we demonstrated abnormal growth i.e. 6 mm×12 mm). The same time and temperature annealing
of a (011) Goss grain texture in Fe–Ga–NbC alloy sheets protocol was used for both of the samples in figure 10;
annealed at a temperature of 1200 ◦ C for 3 h under an however, the gas flow rate was allowed to vary. Interestingly,
argon atmosphere. The Goss-textured sample exhibited one noticeably different (100) grain growth patterns are evident,
abnormally large (011) grain relative to the size of the suggesting that differences in H2 S flow rate (0–30 sccm) cause
(001) and (111) grains, with grain size ranging from 42 to different patterns of abnormal grain growth (AGG). In order
4200 µm and an average grain size of around 130 µm. to verify this, we are acquiring a capability that will allow for
The observed magnetostriction of 163 ppm is similar to that control of the gas flow rate and content using two mass flow
of the Goss-textured Fe–Ga–B alloy annealed under argon controllers for 0.5% H2 S+Ar and argon gas. The combination
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
Both (011) Goss and (001) cubic textures with h100i orienta-
tion are produced by AGG during secondary recrystallization.
The AGG phenomenon in Goss grain-oriented silicon steels
and Fe–3% Si alloys is known to be dependent on the presence
of a precipitation or dispersion of fine second phase particles
such as MnS and AlN, inhibiting normal grain growth (NGG),
i.e. primary recrystallization with continuous growth and
random orientation [30, 31]. The dispersion of NbC particles
as second phase particles has been shown to play a major
role in producing Goss-textured ternary Fe–Ga alloys [29].
However, the presence of these particles is not sufficient
for fully developed AGG over the entire sample surface,
because dispersed NbC particles will ultimately retard grain
boundary movement by acting as a pinning site that acts as
a barrier to movement during grain growth. Figure 12 shows
the distribution of NbC particles in Fe–Ga matrix grains and
at grain boundaries between (001) and (111) grains. When
Figure 11. (a) Pole figure, and (b) observed magnetostriction along a moving boundary encounters a second phase particle, the
the rolling direction and h100i orientation of the annealed particle exerts a restraining force upon the boundary, which
(Fe0.81 Ga0.19 )99 (NbC)1 sample at 1200 ◦ C for 3 h under 0.5% H2 S causes the boundary to be pulled back at the particle location
in argon, respectively, corresponding to the right image in figure 10.
as indicated by arrows in figure 12. The grain boundary is
finally pinned and stabilized by the particles which lower
their interface energy and grain boundary energy. In addition,
of the two controllers will allow for exact control of the partial
the boundaries intersecting the sample surface tend to form
pressure of H2 S to examine the effect of gas flow rate and
grooves. These grooves also impede grain boundary motion.
content on abnormal grain growth.
Thus, an additional driving force is required for the continuous
The growth of (001) grains relative to small (110) and grain boundary movement needed to form highly textured
(111) grains is dominant in the left image, corresponding to and even single-crystal-like rolled sheets. Surface energy
magnetostriction of 193 ppm and possessing a [100] direction differences associated with the misorientation angle between
off from the RD by as much as 17◦ . In the right image, the grains have also been considered as an explanation of the
matrix (001) cubic grain with an area fraction (f001 ) of 88.3% observed extent of single (001) grain as a driver for AGG [17,
is tilted by as much as 24◦ from the RD, calculated from the 20].
(001) pole figure as shown in figure 11(a). In figure 11(b), A summary of observed cubic texture and magne-
the observed magnetostriction value along the RD is 222 ppm tostriction values in ternary Fe–Ga alloys annealed under
and along the [100] orientation it is 314 ppm. This matches various conditions is shown in table 2. Even though the
quite well with an estimate of 309 ppm calculated along segregation process for surface-active elements such as sulfur
the [100] direction based on an 88.3% area fraction of a and oxygen is different, the predominant development of
single crystal of the same composition of 19% Ga (350 ppm {001} h100i cubic texture was observed in ternary Fe–Ga
((3/2)λ100 ) × 0.883(f001 )). alloys where the presence of Fe2 B precipitates, Nb-dissolved
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
Table 2. Observed texture and magnetostriction for various annealing conditions in ternary Fe–Ga alloys.
Max. contour
Alloy Annealing Annealing Predominant intensity of Magnetostriction
composition condition atm. texture PF|ODF (λk − λ⊥ )
(Fe0.83 Ga0.17 )99 B1 a 1100 ◦ C for 5 h O2 (40 ppm) in argon {001} h100i — 10.00 206 ppm
(Fe0.813 Ga10.187 )99 B1 1200 ◦ C for 2 h Elemental S in argon Near {001} h100i 4.34 12.49 201 ppm
(Fe0.813 Ga0.187 )99.5 B0.5 1200 ◦ C for 2 h Argon Near {001} h100i 4.74 10.20 198 ppm
doped with 50 ppm S
(Fe0.81 Ga0.19 )99 Nb1 b 1200 ◦ C for 5 h Argon {001} h100i — 6.00 134 ppm
(Fe0.85 Ga0.15 )99 (NbC)1 1300 ◦ C for 2 h
c
Argon Near {001} h100i 3.15 — N/A
(Fe0.85 Ga0.15 )99 (NbC)1 c 1300 ◦ C for 24 h Argon {001} h100i 3.97 — N/A
(Fe0.81 Ga0.19 )99 (NbC)1 1200 ◦ C for 3 h 0.5% H2 S in argon (001) h210i matrix 32.18 158.3 222 ppm, k RD
grain 314 ppm, k h100i
Single crystal As-grown — (001) h100i 39.90 203.6 350 ppm
Fe81.2 Ga18.8
a Li et al [9].
b Li et al [10].
c Srisukhumbowornchai and Guruswamy [16].
precipitates and NbC particles which exist in the matrix of and shown to correlate to changes in sample texture under
starting materials acts as a primary grain growth inhibitor. high temperature anneals. A theory is postulated to explain
Cubic-textured Fe–Ga–B alloys, which are independent the observed results in which changes in surface energy due to
of surface-active elements and segregation mechanisms, slight sulfur segregation correlate to the preferential formation
exhibited magnetostriction values of around 200 ppm and the of {001} cubic grain growth. Three separate approaches to
almost same values for maximum intensity of PF and ODF producing surface segregation of sulfur yielded similar results.
images. In the case of Nb-added alloy, the observed properties In one approach, (Fe0.813 Ga0.187 )99 B1 alloy was annealed in a
(e.g. magnetostriction, sharpness of texture) are lower than in sulfur atmosphere using elemental sulfur to be vaporized and
the other cases, although it has cubic texture. Of interest, the adsorbed. In the second approach, (Fe0.813 Ga0.187 )99.5 B0.5
(Fe81 Ga19 )99 (NbC)1 alloy shows a large area fraction of AGG doped with 50 ppm sulfur was annealed in a pure argon
with (001) plane, accompanied by a high magnetostriction of atmosphere and thereby sulfur atoms diffused from the bulk
314 ppm along the [100] orientation. Compared to the results interior to the surface. Hydrogen sulfide (0.5% H2 S) gas
for a single crystal, 90% of magnetostriction was achieved in argon was used for sulfur decomposition and adsorption
and the maximum contour intensities are close to those of during annealing of a (Fe0.81 Ga0.19 )99 (NbC)1 rolled sheet as
a single crystal. From these results and EBSD analysis, the a third approach.
magnetostriction strongly depends on the coverage of (001) These sets of samples were studied by surface chemistry
grains and the deviation angle of preferred orientation from analysis (AES and XPS), texture analysis (EBSD) and
h100i orientation, which are proportional to the observed magnetostriction measurement. The results showed that sulfur
contour intensity [32]. was adsorbed (diffused) from a sulfur atmosphere (the bulk
In conclusion, recrystallized (011) Goss grains in ternary interior) then segregated at the surface. The segregated
Fe–Ga alloys may be replaced by (001) cubic grains, after sulfur was preferentially combined with iron and iron sulfide
which AGG of (001) grains will be facilitated if a difference (FeS) formed at the surface. Although the mechanism of
in surface energy, γ , provides a driving force for the AGG of sulfur segregation is different for these three cases, sulfur
adsorption in two cases and sulfur diffusion in the other,
(001) grains. This will occur when the surface energy of (001)
the surface-energy-induced selective grain growth with a
surface planes is lower than that of (011), i.e. γ011 > γ001 .
preference for a specific plane/texture is very similar.
These results demonstrate that variations in the segregation
Observations indicate that {011} grains were dominant
of active elements on the surface of a sample influences
under very clean surface conditions, corresponding to a low
surface energy. Furthermore, under a very clean surface
sulfur atmosphere (limited adsorption) or short annealing
condition γ001 > γ011 , AGG of (011) grains arises because the
times (limited diffusion). The {001} grains occurred under
closed-packed (011) plane is the plane with the lowest energy
‘slight’ surface contamination with sulfur, at concentration
in body-centered cubic (bcc) structures. The qualitative
levels of between ∼0.5 and ∼1.35 at.%, due to adsorption
surface chemistry analysis of Fe–Ga–B doped sulfur indicates or diffusion of sulfur to the sample surface, then maximum
a range of 0.5–1.35 at.% for surface segregation of sulfur magnetostriction values of approximately 200 ppm were
correlated to selective {001} grain growth. obtained in the both Fe–Ga–B alloys. Moreover, abnormal
growth of a (001) grain that covered up to 88.3% of the sample
4. Conclusions area was developed and promoted in Fe–Ga–NbC alloy which
displayed a magnetostriction of 314 ppm, approaching that of
The effect of sulfur contamination on the surface of single crystal Fe–Ga alloy of similar Ga composition, along
polycrystalline ternary Fe–Ga-based alloys has been studied the [100] direction.
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Smart Mater. Struct. 21 (2012) 055024 S M Na and A B Flatau
Finally, these results offer both a theory for the [14] Restorff J B, Wun-Fogle M, Clark A E and
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Acknowledgments Fe–Al alloys Metall. Mater. Trans. A 35A 2963–70
[17] Köhler D J 1960 Promotion of cubic grain growth in 3%
This work was supported by ONR MURI silicon iron by control of annealing atmosphere
grant N000140610530. The authors acknowledge Miji Seo at composition J. Appl. Phys. 31 408–409S
Sungkyunkwan University in Korea, for XPS operation and [18] Foster K and Kramer J J 1960 Effect of directional orientation
on the magnetic properties of cube-oriented magnetic
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