New Corrosion Resistant Materials

for Next Generation Energy Processes

T
Dean Gambale he promise for renewable clean energy performance limits. The materials challenges
Tantaline is not new. In fact, many of the technolo- faced from corrosion, mechanical durability,
Waltham, Mass. gies considered today for the energy of and economics limit the commercialization of
tomorrow such as hydrogen production, fuel these technologies.
Material cells, solar panels, bio-fuels and others have ex- This paper will explore some of the chal-
performance isted for decades. But these exciting technolo- lenges faced specifically with hydrogen produc-
limitations gies have not been readily adopted. For tion via sulfur-iodine (S-I) thermochemical
example, fuel cells were invented by German water splitting, and also will focus on the mate-
have been an scientist Christian Friedrich Schöbein in 1838, rial problems that exist and some of the solu-
obstacle to the and were first used commercially in 1959 by tions that are being applied.
adoption of NASA. In 1838, the first solar cell was built by The sulfur-iodine thermochemical process,
many new Charles Fritts. During World War II, a variety developed by General Atomics, San Diego,
of biofuels were used by the German and Calif., allows producing hydrogen gas without
renewable British forces to supplement fuel shortages. To the use of fossil fuels. The process has extreme
power source a large extent, the limitations of materials operating environments, and, therefore, creates
technologies. needed to make these technologies technically, a variety of significant material challenges. As
Tantalum economically, and commercially feasible and conventional materials are pushed to their lim-
surface alloys competitive with existing fossil-fuel infrastruc- its to achieve the next generation of chemical
ture prevent the adoption of renewable clean processes, new materials are required to meet
open up new energy technologies. those challenges.
opportunities. To be efficient, the next generation of en- This paper discusses the conditions and the
ergy production technologies requires more ag- challenges faced in the sulfur-iodine thermo-
gressive process conditions, potent chemistries, chemical process and how tantalum surface al-
and pure/clean operating conditions that are loys were used to meet these corrosive,
free from contamination. As a result, tradi- mechanical, and economic challenges where
tional materials have been pushed beyond their virtually all other traditional corrosion-resist-
Heat
ant materials like nickel, titanium zirconium
and tantalum metal alloys have failed.
830°C
H2SO4 ½ O2 + SO2 + H2O Taking on an aggressive
process environment
Combustion of fossil fuels currently provides
about 86% of the world’s energy[1, 2]. To reduce
H2SO4, (H2O) SO2, O2, H2O
our dependence on fossil fuels and lessen the en-
vironmental impact, hydrogen fuel (from non-
hydrocarbon feedstock) presents an attractive
120°C alternative. The sulfur-iodine thermochemical
½ O2 H2SO4 + 2HI I2 + SO2 + 2H2O H2O
process requires heat and water as the only in-
Heat puts, and oxygen and hydrogen are the only out-
puts. All of the reagents are self-contained
2HI, (I2, H2O) I2, (H2O) within the process and recycled, creating no
Heat waste. When combining this technology with
solar and nuclear power as a heat source, it be-
320°C comes a very attractive process for hydrogen
2HI I2 + H2
production and a viable alternative to fossil fuels.
The sulfur-iodine water-splitting cycle rep-
resents a leading candidate for thermochemi-
H2
cal hydrogen production, consisting of three
chemical reactions that result in the dissocia-
Fig. 1 — Sulfur-iodine thermochemical process: sulfuric acid concentration
and decomposition (top); recycle and acid generation (middle); and tion of water as shown in Fig. 1[3].
hydrogen iodide concentration and decomposition (bottom). The sulfur-iodine thermochemical process

ADVANCED MATERIALS & PROCESSES • JANUARY 2011 19

 is aggressive both mechanically and
250
5 mpy (0.13 mm/y) chemically. It is a hot process where the
hydrogen production efficiency is a func-
tion of the process temperature. Efficien-
200
cies as high as 55% are possible at a
process temperature of 900°C (1650°F).
Temperature, °C

However, the materials of construction

150
for the process components, including
valves, fittings, vessels, and instrumenta-
tion, are pushed beyond their limits in an
100 environment consisting of high tempera-
tures and pressures, as well as concen-
trated acids. This leads to corrosion
50
failures, creating an unstable, unsafe
process environment, which can often
lead to higher operating costs making the
0 process economically unfeasible. There-
0 5 10 15 20 25 30 35 40
HCl concentration, % fore, new materials are needed to meet
the challenges of the sulfur-iodine ther-
Fig. 2 — HCl corrosion resistance by metal[4] mochemical process and to make it effi-
cient, economical, reliable, and safe.
300 Material choices are limited due to the
5 mpy (0.13 mm/y)
aggressive process environment.
Corrosion is a problem because the
250
process contains mixtures of sulfuric
acid (H2SO4) and hydroiodic acid (HI) at
Temperature, °C

200 temperatures greater than 300°C (570°F)

and pressures between 20 and 30 atmos-
pheres. It is important to note that while
150
hydroiodic acid is not a common acid, it
is one of the strongest acids in the halide
100 group compared with HCl and HBr
(Figs. 2 and 3). This makes containing
the hydroiodic solution (HIx – hy-
50
droiodic acid + water) very difficult.
A solution of sulfuric acid, hy-
0 droiodic acid, and water at temperatures
0 10 20 30 40 50 60 70 80 90 100 to 280°C (535°F) and a pressure of 150 psi
H2SO4 concentration, wt% present the most corrosive conditions
Fig. 3 — H2SO4 corrosion resistance by metal[4] that the materials face. This environ-

100
Ta 1. run
Tantalum concentration, wt%

80 Ta 2. run
Tantalum layer
60
0.5 μm
Alloy zone
40
Stainless steel
Interface

20
Substrate Tantalum surface

0
-800 -600 -400 -200 0 200 400 600 800 10 μm
Distance from interface, nm
Fig. 5 — Cross section of tantalum surface
Fig. 4 — Concentration profile of tantalum alloy in 316 stainless steel. alloy.

20 ADVANCED MATERIALS & PROCESSES • JANUARY 2011

ment is so corrosive that even specialty materials like Hastel-
loy Alloy C276 (Haynes International), a Ni-Cr-Mo-W alloy,
can only survive up to 50 hours[5]. Because of the high temper-
atures and pressures, polymeric materials are not a considera-
tion. Although glass would fare well corrosively, because of the
high process pressures and glass’s brittleness, it also is not fea-
sible option in a production environment, leaving metals as the
only practical option.
A variety of specialty metals were considered including
nickel-base alloys like Monel (Ni-Cu) alloys, Hastelloy Alloy B
(Ni-Mo) and C (Ni-Cr-Mo-W) grades, zirconium, titanium,
tantalum, and gold. Of these materials, only tantalum demon-
strated the corrosion resistance needed to survive in this cor-
rosive environment, and was selected as the material of choice
to deal with the hydroiodic acid solutions.
While tantalum metal is known as the most corrosion-re-
sistant material commercially available, there are many prob-
lems associated with its practical use. First and foremost is the
price, which is about 50 times more than stainless steel. An-
other problem is its unavailability in the form of usable prod-
ucts. It is possible to obtain tantalum in the form of ingots,
rods, tubes, and sheets, but it is difficult, if not impossible, to
obtain tantalum in the form of common process equipment
like valves, fittings, pumps, and instrumentation due to the
price of the metal and poor machinability and weldability. Fur-
thermore, custom fabrication of solid tantalum is not easily
performed, and, therefore, it is typically carried out by special-
ized, highly skilled fabricators.
Although tantalum metal from a purely corrosion point of
view is ideal, designing a process out of solid tantalum metal
has some serious practical limitations, engineering difficulties,
and economical flaws. Because tantalum is the ideal material for
the process environment, the feasibility of designing the sulfur-
iodine thermochemcial system was dependent on finding an al-
ternative to solid tantalum metal without sacrificing the
performance.

Overcoming materials performance challenges

The main driver for deciding on a particular material solu-
tion was based on having the ability to use commercially avail-
able products having a corrosion resistance similar to that of www.asminternational.org/access
solid tantalum at an affordable price. This led the end users to
select Tantaline’s tantalum surface alloy as the material best
suited to meet the challenges of the S-I process.
Tantalum surface alloys are created by chemically reacting
and vaporizing tantalum at high temperatures. The tantalum
metal in the gaseous tantalum atmosphere diffuses into and
continues to grow on the surface of the substrate (Figs. 4 and
5). Because the process occurs at an atomic level and at high
temperatures, an alloy zone is created in the substrate mate-
rial, which is typically stainless steel. Because this is a chemi-
cal/metallurgical bond as opposed to a mechanical bond, the
tantalum surface is extremely rugged and durable and not sus-
ceptible to chipping, spalling, and delamination associated
with coatings.
Once the alloy zone is formed, the process continues to pro-
duce a pure tantalum metal surface having all of the chemical
properties of commercially pure tantalum metal as specified by

ADVANCED MATERIALS & PROCESSES • JANUARY 2011 21

Fig. 6 — Deformation and photomicrograph of tantalum surface alloy after deformation.
ASTM-B364. The tantalum surface is typically 50 μm
(0.002 in.) thick, which has been shown to be the optimal
thickness for most applications, although surface alloy lay-
ers as thick as 200 μm (0.008 in.) have been successfully
produced.
The ruggedness and durability of tantalum surface al-
loys was demonstrated in a study by Dr. Hira Ahluwalia[6]
in an attempt to deform tantalum surface alloys locally and
uniformly over the surface. This was achieved by trying to
puncture the surface using a Rockwell C cone-shaped
hardness indenter and bending the samples 180 degrees
over a 0.5 in. diameter mandrel. The integrity of the surface
was verified by boiling the parts for 24 hours in concen-
trated HCl at 80°C (175°F).
In addition to tantalum surface alloy’s corrosion resist-
ance, availability also was a key factor in its selection. Using
the material for the sulfur-iodine thermochemical process
was feasible because the technology could be used on stan-
dard commercially available stainless steel parts like valves,
fittings, pumps, and heat exchangers. Also, the economics
of tantalum surface alloys make it possible to get the per-
formance of tantalum metal at a price that is competitive
with other specialty metals and alloys such as C276, tita-
nium, and zirconium.
For the sulfur-iodine thermochemical application,
components including valves, Swagelok fittings, reactors,
thermowells, pumps, and heat exchangers were treated to
produce a 50 μm thick tantalum surface alloy.
Performance results
In the extreme corrosive conditions created in the sul-
fur-iodine thermochemical process, parts made of gold, ti-
tanium, Monel, and Hastelloy C276 did not survive longer
than 50 hours. Therefore, tantalum surface alloys were
adopted for all surface areas of the system that were ex-
posed to the corrosive conditions, which amounted to
more than 90% of the surface area of the process valves, fit-
tings, instrumentation, and custom parts.
Since August 2009, more than 1,000 parts have been
installed at General Atomics and the Korean Institute of
Energy Research, or KIER (Daejeon)[7]. With several years
of history and thousands of hours of operation, tempera-
ture cycling, mechanical abuse, and process spikes, the tan-
talum surface alloys have proven to be orders of magnitude
better in corrosion resistance, mechanically rugged, and
economically attractive compared with specialty alloys,
22 ADVANCED MATERIALS & PROCESSES • JANUARY 2011
with no failures to date.
In addition, it was learned in this process that tantalum
surface alloys are resistant to hydrogen embrittlement. Be-
cause the sulfur-iodine thermochemical process generates
hydrogen, there are relatively high concentrations of free
hydrogen in the environment, which has led to hydrogen
embrittlement and premature failure of solid tantalum
components. In the same environment, tantalum surface
alloyed parts resist the effects of hydrogen embrittlement,
surviving much longer than solid tantalum.
Conclusions
Tantalum surface alloys allow providing the required
performance properties of solid tantalum on stainless
steels at a price similar to that of nickel alloys. This not only
makes the process feasible both technically and economi-
cally, but also provides a level of safety that could not be
realized with other materials.
Since the adoption of tantalum surface alloys in the
General Atomics application, KIER built a similar sulfur-
iodine thermochemical process and selected tantalum sur-
face alloys as the material of choice for its corrosion
resistant needs.
References
1. International Energy Outlook 2000: DOE/EIA-0484(2000).
2. Annual Energy Outlook 2000 with projections to 2020:
DOE/EIA-0383 (2000).
3. P.M. Mathias and L.C. Brown, Thermodynamics of the Sul-
fur-Iodine Cycle for Thermochemical Hydrogen Production,
68 Annual Mtg. for Soc. Chem. Engrs., p 1-3, March 2003.
4. Corrosion Engineering Handbook, 1996.
5. B. Russ, program manager, Energy Process Group, General
Atomics.
6. H. Ahluwalia, Materials Selection Resources.
7. Korean Institute of Energy Research.
Monel is a registered trademark of Special Metals Corp.,
Huntington, W.Va.; Hastelloy is a registered trademark of
Haynes International, Kokomo, Ind.; and Swagelok is a regis-
tered trademark of Swagelok Corp., Solon, Ohio.
For more information: Dean Gambale, president, Tantaline,
1050 Winter St. Suite 1000, Waltham MA 02451; tel: 781/209-
0208; fax: 888/292-9243; email; dgambale@tantaline.com;
Web site: www.tantaline.com.