®
American Chemical Society
MEMBER-
Get-A-
MEMBER
2017 blanket
has all 4 new
super-heavy
COATINGS
elements!
Confronting the looming
Recruit a new
ACS member hexavalent chromium ban
to get yours. Critical corrosion-limiting element is proving
hard to replace in aerospace applications
WWW.ACS.ORG/MGM MARC S. REISCH, C&EN NEW YORK CITY
O
n Aug. 5, 1981, a Boeing 737 took
off from Taiwan’s Taipei Song-
shan Airport with 110 people on
board. Fourteen minutes after
leaving the ground, the aircraft suffered an
explosive decompression and disintegrat-
ed. No one survived.
Investigators attributed the event in
large part to extensive corrosion damage in
the lower fuselage. More recently, the 2014
crash of a 28-year-old F-15 fighter jet in Vir-
ginia was blamed in part on corrosion.
Such failures, thankfully rare, under-
score the danger of corrosion in aircraft and
the importance of corrosion-protecting
surface treatments.
However, bans on the aerospace indus-
try’s main weapon against corrosion, com-
pounds based on hexavalent chromium, is
looming in Europe. Treatment formulators
and paint makers are scrambling to find
effective substitutes, but executives say the
effort is a challenge.
Plating chemical makers such as Coven-
tya, Luster-On, and SurTec and paint mak-
ers such as PPG Industries and AkzoNobel
have known for some time that the bans
were coming. In 2013, the European Union
placed a number of hexavalent chromium
compounds on a list of substances of very
high concern, classifying them as carcino-
genic and mutagenic.
As a result, under Europe’s Registration,
28 C&EN | CEN.ACS.ORG | FEBRUARY 27, 2017
The F-15E military jet’s light weight
depends on aluminum, which must
be treated with corrosion-protecting
compounds to make it durable.
Evaluation, Authorisation & Restriction
of Chemicals (REACH) regulations,
chrome-plating chemicals such as sodium
dichromate may no longer be used after
Sept. 21 of this year. Corrosion-resisting
paint additives, such as strontium chro-
mate, have a sunset date in January 2019.
In addition, the U.S. Occupational Safety
& Health Administration recognizes Cr(VI)
as carcinogenic. The severe restrictions
the agency places on worker exposure to
vapors from chrome-plating baths and dust
from chromium spray paints are also forc-
ing a shift to alternatives in the U.S.
“Hexavalent chromium compounds
have been around for more than 90 years,”
says Brad Durkin, director of product man-
agement at Coventya. Replacing well-char-
acterized older technology with less-well-
known alternatives, especially in critical
applications, isn’t easy, he says.
So industry groups have applied to the
European Chemicals Agency for extensions
to use hexavalent compounds for critical
applications beyond their sunset dates. The
agency has approved Cr(VI) plating treat-
ments for aerospace use through 2024 and
some Cr(VI) additives for aerospace paints
through 2026.
CREDIT: ISTOCK
But the agency’s decision must be ap-
proved by the European Commission,
Durkin points out, and that hasn’t hap-
pened yet. In addition, the seven-year
extensions could be abrogated if acceptable licensee of the Navy’s Cr(III) surface treat-
Cr(VI)-free alternatives are developed, he
says.
Coventya has been working on plating
alternatives, mostly based on the less haz-
ardous trivalent form of chromium. Cr(III)- supplying trivalent-based chemicals. For us
based substitutes, many for decorative and
other less critical uses, have been on the
radar since 2012, when it became clear that
European authorities planned to ban Cr(VI) such as for plane exteriors, the effort to
compounds, Durkin says. But it has been
particularly difficult to get equivalent per-
formance using Cr(III), he notes, especially
for chrome-plating used in heavy-wear ap-
plications such as on landing gear.
One electroplating method based on
trivalent chromium uses varying electrical
pulses instead of a steady
current. Jennings Taylor,
founder of Faraday Tech-
“Hexavalent
nologies, developed the
technique in 2004 and won
chromium
a Presidential Green Chem-
istry Award for it in 2013.
outperforms
He says the process is still
not commercial.
the trivalent
Taylor is working with
Coventya on a Cr(III)
species in
formulation that would
match the wear profile and
cost and
microstructure of a Cr(VI)
finish. Once that is done, he
performance.”
expects a long qualification Joe Ciejka, vice president ings, and some customers
process before it is adapted of development and are now using them, the
for aerospace use. technology, Luster-On firm says. For structural
Luster-On, a supplier
of plating chemicals, has also developed
Cr(III) alternatives that in most cases re-
place the more hazardous standard materi-
als. But trivalent chromium is not a perfect
replacement.
“Hexavalent chromium outperforms the nonchromium corrosion inhibitor, Aero-
trivalent species in cost and performance,”
says Joe Ciejka, vice president of develop-
ment and technology for Luster-On. “The
performance issue is an important consid-
eration for aerospace components, which
have to last between 20 and 40 years.”
Some of Luster-On’s surface treatment
technology is based on patents licensed
from the U.S. Navy. The Navy developed its
own Cr(III) recipes because it needed to
protect maintenance personnel and wasn’t
satisfied with existing trivalent technology.
“Our formulas give excellent adhesion
and corrosion protection on aluminum and
aluminum alloys,” says Craig Matzdorf, a
senior materials engineer in the Naval Air
Systems Command and primary inventor
on the Navy’s seven U.S. patents. Other
formulations, such as those based on rare
earths and magnesium, did not perform to
the Navy’s standards, he says.
The plating specialist SurTec is another
ment patents. “Most of our customers have
made the shift to trivalent-based formula-
tions,” says Dieter Aichert, the firm’s global
sales director. “We ourselves shifted to
Get to Know
and for our customers it’s a way of assuring
the health and safety of workers.”
However, for Cr(VI)-based coatings,
Metrohm
shift technology is much less advanced.
The Navy has developed Cr(III)-treated
aluminum particles to replace hexavalent
chromium in epoxy primers. The Navy’s
“active aluminum-rich primer” system “is
equivalent to Cr(VI) systems in some cas- Titration
es, in some it is not, and in other cases it’s
better,” Matzdorf says.
The aluminum-rich
technology isn’t commer-
cial yet, though Matzdorf
says the Navy is working
Ion Chromatography
with six licensees. Mean-
while, paint makers have
been developing their own
alternative corrosion-in-
hibiting primers and paints.
AkzoNobel, for instance,
Electrochemistry
has patented lithium-based
corrosion inhibition tech-
nology for exterior aero-
space primers and coat-
Spectroscopy
applications, Akzo says
customers still rely on Cr(VI), though the
firm is developing alternatives.
PPG is taking a different approach with
its Aerocron electrodeposited epoxy-based
primer system. Dependent on a proprietary
cron is being used by the U.S. Coast Guard
for parts maintenance, says Mehran Arbab, Laboratory Process
PPG’s global R&D director for aerospace
coatings.
In the Aerocron system, components are
dipped in a treatment tank and then cured
in an oven, providing uniform coverage, Find out more at
even to complex parts. That’s an advantage www.metrohm.com
over Cr(VI)-based spray primers that are
hand applied, Arbab notes. The Aerocron
system also does not pose any of the health
hazards associated with hexavalent chro-
mium, he says.
PPG and other players in the aerospace
coatings sector know they have their work
cut out for them. “There are a lot of barriers
to replacing hexavalent chromium, and www.metrohm.com
the longer something has been around, the
harder it is to change,” the Navy’s Matzdorf
says. But because of the hazards hexavalent
chromium use poses, he says change “is
part of our job.” ◾
FEBRUARY 27, 2017 | CEN.ACS.ORG | C&EN 29