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Chromium-free nickel alloys for hot sulfuric and sulfur

environments

Joseph W. Newkirk a,*, JenHsien Hsu a, Richard K. Brow a, Thomas Lillo b

a
Materials Science & Engineering, Missouri University of Science and Technology, 223 McNutt Hall, Rolla, MO 65409-0340, United States
b
Material Sciences, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 3415-2218, United States

article info abstract

Article history: There are few adequate materials available for severe corrosion conditions, like those of
Received 21 December 2009 the SeI thermochemical cycle. High Si, Ni-alloys have excellent corrosion resistance,
Received in revised form especially in mineral acids, but have typically been limited by poor mechanical properties
19 May 2010 or difficult fabrication issues. The ductility of nickel silicide, Ni3Si, can be improved
Accepted 4 June 2010 through a combination of micro- and macro-alloying. Nb and other minor alloying
Available online 23 February 2011 elements yield a cast alloy with excellent corrosion resistance to sulfuric acid and good
mechanical properties. In this paper, efforts to optimize the alloys performance are pre-
Keywords: sented along with progress toward the development of a wrought version of the material. It
NieSieNb was found that an appropriate heat treatment provides the largest improvement in the cast
G-phase (Ni16Si7Nb6) NieSi alloy microstructure. Trials have resulted in more than a 50% reduction by the cold
Corrosion rolling process. This process not only increases homogenization but also results in a more
Cold rolling uniform distribution of G-phase particles, which is beneficial for the improvements in
ductility and corrosion resistance. These alloys have great potential for use in future
hydrogen production as well as fossil energy combustion.
Copyright ª 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction The sulfuric acid decomposition loop, which includes a re-

The SulfureIodine thermochemical cycle has been proposed
as a method for producing large quantities of hydrogen gas
from water using the waste heat of a nuclear reactor. Sulfuric
acid is decomposed at temperatures up to 850
C to form SO2,
which is combined with iodine and water to form HI mole-
cules and reform sulfuric acid. The HI molecules decompose
into iodine and hydrogen. The iodine and the sulfuric acid are
re-used in this closed loop cycle. This cycle has a number of
advantages, including a high thermodynamic efficiency and
the ability to produce hydrogen directly from water. One
potential drawback is the extreme corrosion conditions which
limit the possible materials for construction.
concentration of the sulfuric acid after the reaction to form HI,
is a particularly difficult area to find suitable construction
materials. The high temperatures combined with the highly
corrosive nature of sulfuric acid at these concentrations and
pressures leave almost no materials available for use.
Fig. 1 and Table 1 show corrosion rates of several
commercial corrosion resistance alloys in different concen-
trations of boiling sulfuric acid at atmospheric and high
pressure conditions. Duriron (Fe-14.5 wt% Si) has the satis-
factory corrosion resistance over the entire concentration
range indicated. However, the high Si content and the D03
structure make it extremely brittle. The precious metals, like
Pt, have great corrosion resistance, but the price is too high to

* Corresponding author. Tel.: þ1 573 341 4725; fax: þ1 574 341 6934.
E-mail address: jnewkirk@mst.edu (J.W. Newkirk).
0360-3199/$ e see front matter Copyright ª 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.06.007

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 4 5 8 8 e4 5 9 4
2.5
2
Corrosion rate (mm/yr.)
1.5
1 NiMoFe
0.5
0
40 60
Sulfutic acid concentration (wt%)
Fig. 1 e Corrosion of commercial metals and alloys by
boiling sulfuric acid [1e3]. Fe-Si(Duriron) and Ni3Si
(NiSi20Nb3) alloys have excellent corrosion resistance in
high concentrations of sulfuric acid.
be an engineering material. The Ni(Si,Nb) alloy has excellent
corrosion resistance in different concentrations of sulfuric
acid. It easily meets the target of <0.127 mm/year (w5 mpy,
mil per year) at most concentrations, making Ni(Si,Nb) alloys
the most promising material for the SeI cycle.
Nickelesilicon intermetallic alloys are of interest to
corrosion science and corrosion-related industrial applica-
tions. If the concentration of silicon is high enough then under
sufficiently oxidizing conditions silica is expected to form on
the surface, providing a corrosion resistant layer. Another
major advantage is the high temperature strength. At 900
C,
these alloys retain 50% of their room temperature strength. In
addition, Ni3Si-based alloys can be successfully welded with
filler metal by tungsten inert gas (TIG) welding [3].
Although NieSi alloys can resist corrosion, their limited
ductility at room temperature makes the alloys hard to fabri-
cate. Controlling the solidified microstructure size and high
temperature phases, which affect material properties, are also
the issues for cast alloys. The microstructure of as-cast
NieSieNb alloys include at least four micro-constituents [3], a
(Ni) þ b eutectic, b(Ni3Si), G(Ni16Si7Nb6) [4] and g(Ni5Si3) phase. G
and g-phases are brittle and decrease ductility while the a þ b
eutectic corrodes rapidly in acid [3]. Also, the galvanic cells
formed between different phases increase the corrosion rate.
Solidification rate can significantly change the microstructure,
so cast alloys can be inconsistent in their corrosion perfor-
mance in the most aggressive acid solutions. The optimum
microstructure for the best ductility and corrosion resistance
Table 1 e Corrosion rate (mm/yr.) of commercial alloys in high pressure boiling sulfuric acid [1,2].
1 atm
Zecor, Fe base e e
Saramet #35, Fe base >2.54
NiSi20Nb3B0.5, Ni Base 0.07
a Tested on 37.4 atm.
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would be a single-phase material consisting of b-phase exclu-
sively. In order to produce an optimized single b-phase micro-
structure, three major directions were studied in the present
work: 1. A homogenization treatment could result in the elim-
ination of the high temperature phases. 2. Control the Nb
content to maximize its effect on ductility while reducing the
likelihood of forming G-phase. 3. Cold working the alloy prior to
homogenization should increase the rate and also break up the
Zr G-phase particles, resulting in a finer, more uniform distribu-
Mo
tion. The effects of these three approaches on the microstruc-
NiCrSi
Fe-Si ture and properties of several NieSieNb alloys are described.
NiSi20Nb3
80 100
2. Experimental procedures
The alloys were melted in an induction furnace under an
Argon atmosphere. The melt was initially heated to 1500
C. It
was held for about 15 min to homogenize the melt. The
temperature was then lowered to 1350
C and the melt was
held for about 5 min at this temperature before pouring. The
melt was poured into one of two graphite molds. One mold
was a rectangular mold which held 15 lbs of metal. The other
was a cylindrical bottle mold which held 20 lbs of metal. The Si
plus Nb contents were kept close to a combined 23 atomic
percent to increase the chances of a stable b-phase. Table 2
shows the composition, hardness and ultimate strength of
alloys prepared for this study.
An Electro-Discharge Machine (EDM) was used to cut
15 mm long cylindrical compression specimens with a 10 mm
diameter and rolling specimens with dimensions of
30  10  3 mm from the homogenized (950
C 4 days in argon)
ingots. The compression specimen surfaces were abraded by
SiC paper before the test. The tests were conducted in an
argon atmosphere in the temperature range between room
temperature to 950
C. The strain rate used was 3.3  104 s1.
For the cold work process, the samples were rolled either at
room temperature or at 300
C with intermediate anneal of
950
C for 5 h. The rolling reduction per pass was set to 10%.
The hardness and reduced dimensions were recorded at each
step and the microstructures were evaluated after various
steps.
For corrosion tests, rectangular samples were cut to
10  7  3 mm and ground by #1200 SiC paper. The corrosion
tests were done by immersing the samples in 70 wt% H2SO4 at
the boiling temperature (165
C). After each immersion,
specimens were lightly rinsed with water, air-dried, and then
weighed. The weight loss was monitored with time.
The compression test was done with a Gleeble system.
Rockwell C hardness testing was done with an Instron Wilson/
70 wt% 80 wt% 96 wt%
37.4 atm 1 atm 1 atm 13.8 atm
e 2.03 8.00
e >2.54 0.76 3.00
0.10 w0 e 0.10a
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Table 2 e Mechanical properties of alloys [3].
Alloy Hardness (RC)



As cast 900 C 1 Day
NiSi18Nb5B0.5 e 45.0  1.4
NiSi20Nb2B0.5 46.4  2.7 43.3  1.5
NiSi20Nb3B0.5 e 44.4  1.9
NiSi21Nb1.6B0.5 e e
a Heat treatment: 950
C 4 Day.
b Heat treatment: 900
C 1 Day.
Rockwell hardness tester. Microstructure was observed by
optical microscopy and Hitachi S570 SEM. Differential
Thermal Analyses (DTA) was done using a PerkineElmer
DTA7 under argon at a heating rate of 10
C/min.
3. Results and discussion
The goal of this work is to determine how microstructure and
alloy composition affect the ductility and corrosion properties
of NieSi alloys that could be used for components of the SeI
thermochemical cycle for hydrogen production. The effects of
heat treatments, alloy modifications and cold working in
these properties are discussed.
3.1. Heat treatment
For the NieSieNb alloys studied in this paper, the as-cast
microstructure usually includes a þ b eutectic, b, G and g-
phase, see Fig. 2. G and g-phase are brittle, and the a þ b
eutectic corrodes rapidly in strong acids [3]. Further, the
galvanic cell created between phases accelerates corrosion.
Fig. 3 shows the corrosion attack seems to have been focused
on the interdendritic regions. So, a single b-phase micro-
structure should be ideal. There is no complete NieSieNb
phase diagram. An assumption that small additions of Nb and
B do not significantly change the NieSi diagram was made.
The Si þ Nb content of those alloys listed on Table 2 is between
Fig. 2 e Microstructure of as-cast NiSi20Nb3B0.5. It contains
needle-like g-phase, aDb eutectic (black), b-matrix and
G-phase (bright) [3].
UTS (Mpa) Elogation (%)
950 C 4 Day
39.7  2.4 e 0.7b
42.5  1.5 e e
41.2  1.2 876  17a 3.6  1.6a
39.6  1.3 810  33a 1.9  0.6a
22 and 23 at%, so the stable structure of those alloys should be
single b-phase. So, a homogenization heat treatment could be
used.
Fig. 4 shows the DTA results indicating the phase trans-
formation temperatures in each alloy. After comparing these
results to the NieSi phase diagram, 950
C was chosen as an
appropriate homogenization temperature for these alloys.
The peritectoid transformation, a þ b2 / b1, may happen for
some alloys at temperatures over about 1000
C. This trans-
formation should be avoided because it separates b-phase into
two phases. Fig. 5 shows the microstructure for 1 day at 950
C
and it is evident that the alloy was not completely homoge-
nized; a high Si area produced from the dissolved g-phase is
still obvious. Homogenization for four days at 950
C was
found to be necessary to dissolve the g-phase and most of
a þ b eutectic, see Fig. 6. The changes in microstructure are
related to the improvement in corrosion resistance, see Table
3, and reduction in hardness as shown in Table 2.
3.2. Decreasing Nb content
After the homogenization heat treatments, the G-phase was
still prevalent in the microstructure. G-phase is apparently
a stable phase for these compositions. As G-phase is created
when the Nb content exceeds the solubility of Nb in b-phase,
decreasing the Nb content could eliminate or reduce G-phase
in the microstructure. However, Nb was added to improve
Fig. 3 e Optical Micrograph of NiSi20Nb3B0.5 heat treated at
900
C for 1 day, after 352 hrs of exposure in boiling 96%
sulfuric acid at 37.4 atm. The attack seems to have been
focused on the interdendritic regions.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 4 5 8 8 e4 5 9 4
NiSi18Nb5B0.5
Endothermic <------> Exthermic
NiSi20Nb2B0.5
NiSi20Nb3B0.5
NiSi21Nb1.6 B0.5
850 900 950 1000
Temperature (°C)
Fig. 4 e Phase transformation temperatures of Ni-Si alloys
from DTA [3]. All transformation temperatures in these
Ni-Si alloys are greater than 1000
C, so heat treatment at
950
C was chosen for homogenization.
ductility by increasing Ni3Si(b) matrix grain boundary
strength. In order to produce a single-phase alloy, the total
Si þ Nb appears to be limited to the range 22e24.5 at%. In order
to maximize ductility, adding enough Nb to just meet the
solubility limit seems prudent. Additionally, keeping Si levels
high should maintain the stability of the silica film.
Fig. 7 shows the area fraction of G-phase of Ni3(Si,Nb) alloys
with different Nb contents after homogenization at 950
C for
four days, including alloys not reported on here. There is an
apparent linear relationship between Nb content and G-phase
area fraction. Extrapolating from this data, the Nb solubility in
the Ni3Si(b) matrix might be w1.2 at%.
3.3. Rolling process
The heat treatment alone was not able to remove the G-phase
from alloys which exceeded the Nb solubility limit. Even the
Fig. 5 e Backscattered micrograph of NiSi20Nb2B0.5 heat
treated at 950
C for 1 day. The alloy didn’t completely
homogenize; the high Si area where the needle-like
g-phase dissolved is still obvious.
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4591
1097°C
1015°C
1112°C
1092°C
1012°C
1092°C 1111°C
1022°C 1101°C
1137°C
1050 1100 1150
Fig. 6 e Microstructure of NiSi21Nb1.6B0.5 heat treated at
950
C for 4 days. g-phase and most aDb eutectic have
dissolved, but G-phase remains.
alloy whose Nb content was close to the extrapolated solu-
bility of the matrix still contained G-phase. Local variations in
the chemistry due to segregation could lead to the presence of
G-phase, and b-phase with less than the maximum amount of
Nb. Cold working should produce a more complete homoge-
nization process, more uniform microstructure, and finer b-
grain size. The rolling þ annealing process should break up
the G-phase particles and distribute the resulting smaller
particles more uniformly. Mechanical properties are expected
to improve due to the shorter crack paths associated with the
small brittle particles and smaller grain size. Additionally, the
fabricability of the material can be evaluated.
3.3.1. Rolling reductions
NiSi18Nb5B0.5, NiSi20Nb2B0.5 and NiSi21Nb1.6B0.5 alloys were
deformed more than 50% without cracks, using multiple
passes. The reduction per roll pass is about 8% for these three
alloys when rolled at 300
C, using a 10% reduction setting.
The compression test results, Fig. 8, show behavior consistent
with L12 crystal structure intermetallic compounds. The yield
stress increases with temperature from RT up to a peak
strength, before dropping off at higher temperatures. The
alloy still retains significant strength (>200 MPa) up to 900
C.
Based on these characteristics, rolling effectiveness may be
increased by lowering the temperature to less than 300
C,
which many studies recommended [6e9]. However, using the
same (10%) reduction setting, the reduction achieved per roll
pass is smaller when samples were rolled at room tempera-
ture, shown on Fig. 9. On the other hand, the alloys appear to
be able to endure higher pressure without cracking at room
temperature. In the case of NiSi21Nb1.6B0.5, when reduction
was set at 12%, samples rolled at 300
C cracked but ones
rolled at room temperature survived. The reason might be
Ni3(Si,Nb) alloys have higher ductility at room temperature.
3.3.2. Area fraction and distribution of G-phase
For the highest Nb alloy, NiSi18Nb5B0.5, comparing Fig. 10 and
Fig. 11, it is obvious that the microstructure of the alloy was
extended along the rolling direction. After 10 roll þ anneal
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Table 3 e Corrosion rate and microstructure analysis of alloys.

NiSi18Nb5B0.5 NiSi20Nb2B0.5 NiSi21Nb1.6B0.5

HT Rolled HT Rolled HT Rolled

Corrosion rate (mm/yr.) 1.14 0.64 0.05 0.05 0.18 0.08

Passivation time (min) 370 700 300 300 450 90
G phase Size (um) 8.3  4.4 5.3  3.7 4.3  3.6 4.2  3.4 5.5  3.8 2.3  2
Counts/mm2 2500 6100 4700 5200 1330 4700
Area fraction 16  1.5 14  2 5  0.5 41 1.4  0.5 2  0.5
Eutectic area fraction 27  3 25  2 1 w0 1 w0

passes, the average size of the G-phase particles decreased 1200

and the number increased, see Table 3, indicating that the NiSi20.4Nb3B0.5

G-phase was being fractured by the process. However, the NiSi18Nb5B0.5

1000
relative area of the phase, a þ b eutectic, did not change NiSi22

Yield stress (MPa)

significantly. For the lowest Nb alloy, NiSi21Nb1.6B0.5, seen in
800
Figs. 6 and 12, after 10 roll þ anneal passes, the a þ b eutectic
dissolved into the matrix and the distribution of G-phase was
600
more uniform. The quantitative microstructure analysis of all
alloys is given in Table 3.
400

3.3.3. Hardness
Fig. 13 is an example of how the alloy’s hardness changes 200
during the rolling þ annealing process. Annealing successfully
removed strain hardening and the hardness of alloys was 0
-300 0 300 600 900 1200
recovered. However, hardness did not decrease much after
several rolling and annealing passes. The reason might be G- Temperature (°C)
phase did not dissolve in matrix after several rolling pass, Fig. 8 e Compressive yield stress of the Ni3(Si,Nb) alloys as
although G-phase distribution became more uniform, see a function of test temperature. Tested in Argon
Table 3. atmosphere at strain rate of 3310-4 s-1 [5].

4. Corrosion test
After the cold rolling process, the distribution of G-phase was
more uniform for all alloys, see Table 3. Both the heat treated
and rolled alloys were tested in 70% boiling sulfuric acid to
investigate the effect of rolling on the corrosion behavior. For
Ni3(Si,Nb) alloys, medium concentration sulfuric acid is
20
G phase area fraction(%)
a more severe corrosion environment than a high concen-
tration of sulfuric acid [1].
Fig. 14 shows a comparison of the normalized weight loss
with sulfuric acid exposure for Ni3(Si,Nb) alloys in various
conditions. After a period of time, the weight loss rate
decreased significantly for all samples under different condi-
tions. Two important data, average corrosion rate and
passivation time, were obtained from the figure. In this paper,

16 0.15
RT roll; set 10%
300ºC roll; set 10%
12 0.12
Reduction

8 0.09

4 0.06

0 0.03
0 1 2 3 4 5 6
Nb (at%) 0
0 3 6 9 12
Fig. 7 e Linear relationship between Nb addition and area
Rolling pass
fraction of G-phase in heat treated (950
C 4 d) alloys,
including alloys not reported on here. Extrapolating from Fig. 9 e The reduction achieved on NiSi21Nb1.6B0.5 versus
this data, the Nb solubility in the Ni3Si(b) matrix is about number of rolling passes is higher at 300
C than at room
1.2 at%. temperature.
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 4 5 8 8 e4 5 9 4
Fig. 10 e G-phase, aDb eutectic and b-phase in
microstructure of NiSi18Nb5B0.5 heat treated at 950
C
4 days.
the passivation was defined as the alloys’ corrosion rate
decreased significantly. When the normalized weight loss
with exposure time was demonstrated in the natural loga-
rithmic plot, the change of corrosion rate, which relates to the
slope, can be clearly recognized. And the passivation time was
defined as the exposure time that the alloys begin to passivate.
The corrosion rate, was calculated on the basis of weight
losses (Dm, g), testing time (t, year), density (r, g/cm3), and the
original surface area (S, cm2), after alloys passivated, using
following equation:
Corrosion rate ðmm=year; ð¼ 39:37 mpyÞÞ
¼ Dm=ð10  S  r  tÞ
Table 3 compares the corrosion rate and passivation time with
microstructure analysis of alloys. Several important observa-
tions can be made: (a) after rolling, the corrosion rate
improved and all alloys meet the corrosion resistance target
Fig. 11 e The microstructure of NiSi18Nb5B0.5 sectioned
parallel to rolling direction, after 10 roll(300
C)Danneal
passes, total reduction was 52%.
4593
Fig. 12 e The microstructure of NiSi21Nb1.6B0.5 sectioned
parallel to rolling direction, after 10 roll(room temperature)
Danneal passes, total reduction was 61%.
(<0.127 mm/year (5 mpy)), except the low Si NiSi18Nb5B0.5
alloy. (b) Distribution of G-phase particles might be an
important factor for the corrosion rate of Ni(Si,Nb) alloys.
After rolling, the decrease of G-phase size and increase of G-
phase number can be considered to result in a more uniform
distribution of G-phase. The decrease in the corrosion rate is
obvious for NiSi18Nb5B0.5 and NiSi21Nb1.6B0.5 which had a more
uniform distribution of G-phase particles. For NiSi20Nb2B0.5,
whose G-phase particles distribution did not change much,
the corrosion rate did not change after rolling. In AleSi and
ZreFe alloys, other studies have been shown that a more
uniform distribution of the second phase can produce a more
uniform oxide layer and has better corrosion resistance
[10,11]. (c) The a þ b eutectic has a negative effect on corrosion
resistance. The corrosion rate of NiSi18Nb5B0.5 which has more
a þ b eutectic in the microstructure is much higher than other
alloys, even after rolling. (d) Shorter passivation time means
lower weight loss for the alloys. The relationship between
60
As rolled
55 Annealed
Hardness (RC)
50
45
40
35
0 2 4 6 8 10
Rolling pass
Fig. 13 e Hardness appears unaffected by number of rolling
passes for NiSi21Nb1.6B0.5. Annealing successfully restored
pre-rolling hardness.
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0.03
Acknowledgements
Weight loss / Area(g/cm2)

0.025
HT This work was supported by NERI-DOE project, DE-FC07-
0.02 44% reduction
06ID14753. The authors would like to thank Dr. Lillo, Idaho
61% reduction
0.015 National Lab, for the compression tests and high pressure
corrosion tests.
0.01

0.005
references
0
0 2000 4000 6000 8000 10000

Time (min)
Fig. 14 e The normalized weight loss with boiling 70%
sulfuric acid exposure for NiSi21Nb1.6B0.5 for homogenized
and rolled conditions.
passivation time and the microstructure analyses of alloys is
not clear just from the limited data. It needs more study to
understand the relationship.
5. Conclusions
1. After appropriate heat treatment, 950
C for 4 days, most
unstable and detrimental phases were eliminated in the
microstructure of the Ni3(Si,Nb) cast alloys.
2. The homogenized alloys have lower hardness and can be
deformed more than 50% by multiple cold rolling passes.
3. All homogenized and rolled Ni3(Si,Nb) alloys in this paper,
except the low Si alloy, meet the corrosion resistance target
(<0.127 mm/year (5 mpy)) in boiling 70 wt% sulfuric acid.
4. Cold rolling (roll þ anneal) process improves homogeniza-
tion and G-phase uniformity which are positive to corro-
sion resistance.
5. The eutectic constituent is detrimental to corrosion
resistance.
6. The solubility limit of Nb in Ni3Si at 950
C is approximately
about 1.2 at%.
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