The Corrosion Chronicle

Spring 2017

Derakane™ 470HT resin pushes the IN THIS ISSUE

envelope for high temperature, FRP trimphs over RLCS

corrosion-resistant laminates Ultra large FRP vessels

becoming commonplace
Derakane epoxy vinyl ester resins long ago established themselves as
Derakane Momentum 640
the “go to” technology when outstanding corrosion resistance in harsh
chemical environments was required. From chlor alkali to bleach to ASME new piping standards
hydrochloric acid and beyond, Derakane resins set the standard for
corrosion resistance in liquid storage and transport equipment. More
recently, however, asset owners have been asking for exemplary WHERE YOU CAN
corrosion performance in high temperature gaseous environments. SEE THE ASHLAND
To accomplish this, Ashland’s Derakane scientists embarked upon a CORROSION TEAM 2017
new path, resulting in technology that surpassed the high temperature
performance of the workhorse resins of yesterday. Pultrusion Conference
Atlanta, GA April 3-5
High temperature fiber reinforced plastics (FRP) are commonly used
in chimney liners, gas scrubbers and industrial coatings systems where AIA
temperatures can reach 430 degrees F (230 C) and beyond. Often these Orlando, FL April 27-29
environments not only require outstanding heat resistance, but also COM
resistance to strong acids as well. This is especially true in gas scrubbers Vancouver, Canada Aug 27-30
where acidic by-products and other pollutants are removed from the flue
gas. These hot gases often contain highly corrosive mineral acids such SPE ACCE
as sulfuric, hydrochloric and hydrofluoric acid. As the gases are being Novi, MI Sept 6-8
sprayed with water, the containment walls will be exposed to a hot, wet China Composites
corrosive atmosphere as well as thermal shocks caused by the cooling Shanghai, China Sept 6-8
effect of the water and the heating effect to the flue gases. Derakane CAMX
resins have been used for many years in such composite applications Orlando, FL Sept 11-14
where resistance to corrosive environments, good mechanical and
excellent thermal performance are the major property requirements.

Materials Options
Various construction materials have been evaluated by design engineers
for these severe conditions. Rubber linings can often resist the corrosion
and thermal shock but the temperatures encountered are too high –
leading to degradation of the rubber. Stainless steel and high nickel
alloys have also been employed. They are capable of resisting the heat
and thermal shock but not the long term hot, wet mineral acid attack –
thus resulting in short life expectancies. In fact, it is not unusual to see a

continued on page 2
high nickel alloy showing severe corrosion after only Heat aging studies conducted with Derakane 470HT
a single year’s time. Brick linings are the traditional show very little impact on mechanical properties up to
material of choice as bricks resist acid attack, heat 355 F (180C) other than a change in color - even after
and thermal shock rather well. With brick, however, the 12 months. If the temperature is raised to 390 F (200 C),
difficulty lies in the choice of the mortar system used to however we start to observe slight reductions in Barcol
adhere the bricks to the vessel wall. The mortar systems hardness and flexural properties after 9-12 months. At
are quite susceptible to chemical attack, resulting in 430 F (220 C), we see a significant loss of weight, Barcol
bricks falling off the wall and long shut downs as the hardness and flexural properties after only 6 months.
brick lining is repaired. It should be noted that these observations pertain
Derakane vinyl ester resins can be produced from a only to the corrosion barrier portion of the laminate
variety of epoxy resin precursors depending on the construction. Due to the insulating nature of FRP, the
material science properties that the design engineer load bearing portion of the laminate (structural layers)
desires. For instance, a novolac-based epoxy will give is protected by the corrosion barrier from both thermal
high thermal resistance and tetrabromo-bisphenol A stresses and corrosion attack.
epoxy will greatly improve cured vinyl ester resin fire
retardance. Rubber modified epoxy resins, can be
used to impart high impact resistance to the laminate.
Bisphenol A based epoxies have the best all-around
performance, balancing excellent corrosion resistance
with outstanding mechanical properties and good
thermal resistance.
FRP systems utilizing standard Derakane novolac
epoxy vinyl ester resins perform admirably when faced
with most high temperature corrosive environments
and thermal shocks; however even these high
performing resins can be challenged by temperatures
approaching 430 F (230 C) and beyond. Through
modification of the polymer backbone and an
adjustment of the resin co-monomer ratio, Ashland
scientists have opened a new application window for
FRP in high heat applications. Depending upon the
post-cure schedule, Derakane 470HT novolac epoxy
vinyl ester resin offers an increased Tg into the range of
375 – 430F (190 – 220 C). The polymer structure upgrade
also improves the resin’s acid resistance which makes Cross Section of Derakane 470HT coupon exposed to 390 F
(200 C) for one year
it very suitable for use in the corrosive environments
commonly found in scrubber gas inlet sections. It is also crucial to balance resin thermal properties
Moreover, with a 3% tensile elongation value, Derakane with mechanical properties. Often when a resin is
470HT maintains the traditional toughness advantage designed to deliver very high thermal resistance (HDT
of vinyl ester resins, considerably outperforming and Tg), mechanical properties such as toughness
competitive high cross-link resin systems. This feature and elongation to break are sacrificed. Previous
allows laminates fabricated with the product to more developments, aiming to reach superior thermal
easily withstand the thermal shocks commonly found in properties at the expense of mechanical properties
scrubber quench applications. have generated resins that were incompatible with
industrial manufacturing processes. These brittle resins
Glass transition temperature (Tg) is not the only
often resulted in heavy delamination during production
determinant of high temperature application suitability,
and/or after short service intervals.
however. Many resins have been introduced to the
market over the years with impressively high Tg values.
Further study, unfortunately has found that these resins,
although high in Tg were not thermally stable and began
to decompose when put into service. Design engineers
are wise to look beyond a resin manufacturer’s Tg and
HDT (heat distortion temperature) data before selecting
a high heat resin for this kind of service.

2 | Corrosion Chronicle
 Case Histories instrumentation nozzles was first placed into service
in 1995. Due to the positioning of the spray nozzles,
The following are some examples of FRP designs
an abnormal degree of thermal shock was induced
actually in use at high temperatures.
during service and by mid-1995 some delamination
1. Turow, Poland / Power Plant Chimney liner and was encountered. Protective thermal shields were
Ducting system designed using a carbon/graphite in the FRP and an
The FGD (Flue gas desulfurization) unit operates at a insulating air gap. The new design resulted in very
temperature of 160 F (70C) under normal conditions. good performance.
However, during the construction period, two of the
4. Terragona, Spain / Industrial Waste Incinerator
four units were not operative and ran in the bypass
This chimney was designed for 300 – 390F (150 –
mode. During the by-pass operation one of the units
200 C) normal operating temperatures and an
ran for two years at temperatures up to 320F (160
upset temperature of 430 F (220C) which occurs
C). The previous chimney liners were made out of
in combination with a rapid temperature change
borosilicate blocks which needed to be replaced
during the heat up and cool down cycle. The liner
due to the wet circumstances and the huge swings in
is 5 feet (1.6 m) in diameter and greater than 200
temperature 70 – 320 F (20 – 160 C). Each of the four
feet (60 m) in height. Originally the chimney liner
units consisted of a chimney liner 17 feet (5.3 m) in
was fabricated with a competitive high temperature
dia and 395 feet (120 m) tall. In addition, there was a
resin which blistered badly on post cure and had
total of 1100 feet (330 m) of ductwork with the same
to be removed. A new chimney liner made with
diameter. FRP fabricated with Derakane 470HT was
Derakane 470HT was put in place and tested with a
selected for this project due to its chemical resistance
series of severe thermal cycles to represent normal
to the wet flue gas and its ability to manage the huge
upset conditions. The new chimney liner performed
swings in temperature up to and beyond 320F (160 C).
admirably and has remained in service since 1998.
2. Heidelberg, Germany / Municipal Waste Incinerator It was inspected recently (after 16 years of service)
The original quench section of this scrubber was and found to still be in good condition.
made in Hastelloy™ C (>70% Nickel). After only 6000
hours service, holes began to appear in the walls In Conclusion
of the vessel. When the piece was taken out of Derakane 470HT is a novolac epoxy vinyl ester type
service, the wall thickness was found to have been resin with corrosion resistance similar to the proven
reduced from 5 mm to 2 mm – far under the required performance of Derakane 470 but with increased
structural strength and stiffness for a safe design with acid resistance. It also demonstrates very good
the actual mechanical loading. An FRP solution thermal stability both in the lab and in the field. It is
based on Derakane 470HT replaced the damaged quite capable of withstanding the temperatures and
Hastelloy construction. After 30 months of service corrosive environments found in scrubber gas inlets
at an operating temperature of 430F (220 C), it was and chimney liners. Experience has shown that the use
inspected and found to still be structurally sound of FRP in advanced applications up to 430 F (230 C),
without any holes. Another year later it was inspected should not be undertaken lightly. Careful consideration
again and reported to be in excellent condition. should be given to laminate design, including use of
3. Alkamar, The Netherlands / Municipal Waste heat-conducting additives in the inner liner section,
Incinerator inclusion of an air insulating gap and the standard resin
The quench section in this incinerator has a design structural component all need to be considered for
temperature of 445 F (230 C) and normally operates top performance in these aggressive conditions. The
between 390 – 430F (200 – 220 C). An FRP part fabricator, design engineer and asset owner should all
based on Derakane 470HT with many spray and be involved as early as possible in the project.

Ashland Corrosion Science Center

Trusted support for FRP applications in
corrosive environments.
Contact Kevin Lambrych / [email protected]

Spring 2017 | 3
FRP triumphs over rubber lined carbon steel (RLCS)
Rubber lined carbon steel (RLCS) is often chosen Case Histories
as a means to manage corrosion and abrasion in
1. Soutern United States / FGD Plant
challenging environments. It can commonly be found
In 1996 an electric utility in the southern US added
in chemical service and slurry piping. Durability is
pollution control equipment to an existing 2000
affected by the degree of severity of the chemical
MW coal fired boiler to remove sulfur dioxide
environment. In slurry systems, performance is also
from the boiler flue gases. Wet limestone flue
tempered by variables such as particle size and
gas desulfurization (FGD) scrubbers were added
morphology, slurry concentration and flow rate.
downstream of the boilers. Flue gases enter the tower
Properly designed and installed, RLCS can deliver up to
and as they rise to the top, limestone slurry is sprayed
a decade of uninterrupted service to the asset owner.
counter current to the gases. The SO2 in the flue
Unfortunately, RLCS is not without its issues and is far
gases is absorbed by the limestone slurry scrubbing
from a panacea for corrosion control.
liquor. The slurry is then recycled from a sump in the
The problem with rubber lined piping systems is that bottom of the tower and pumped through external
the rubber can be permeated by a wide variety of recycle slurry pipes back to the top of the absorber.
corrosive media. Once permeated, the corrosive
The FGD plant for this 2000 MW station included 10
media is able to freely attack the substrate behind
absorber towers with 6 spray levels in each absorber.
the rubber lining (typically steel) and corrode it
The limestone slurry reagent is both abrasive and
significantly. Ultimately, the rubber liner loses adhesion
corrosive. The original recycle slurry piping as
to the steel substrate and breaks away to plug filters,
supplied with the FGD plant was rubber lined carbon
nozzles and pumps which lie downstream from the
steel. The plant was experiencing significant problems
lined equipment. Expensive, unplanned outages are
with the RLCS pipe within only a few years of start-up.
the result.
Permeation of the slurry reagent through the rubber
lining was causing corrosion of the steel pipe and
leaks through the pipe wall. Moreover, the rubber
lining was blistering and in some locations peeling
completely away from the pipe wall. This rubber
would then become lodged in spray nozzles inside
the absorber tower.
After several years of significant maintenance cost
associated with repairing and relining the RLCS pipe,
the plant operators and engineers evaluated their
options for replacement of the RLCS pipe. Alloy pipe,
RLCS steel pipe and FRP with an erosion resistant liner
were all considered. Based on decades of proven
performance in erosion resistant pipe systems, RPS
Composites Inc’s abrasion resistant FRP pipe was
chosen as the preferred replacement material. RPS
pipe was constructed using Ashland Hetron™ FR
Chemical attack behind a rubber lined carbon steel pipe 992 fire retardant vinyl ester resin and a proprietary
FRP systems conversely, are much more resilient reinforced erosion resistant liner. This liner has a
to chemical attack than RLCS. Moreover, with the proven track record in over 150 FGD plant installations
addition of a hard filler (e.g. silicon carbide), FRP dating back to 1970. The fittings were fabricated with
systems can also be very resistant to erosion corrosion Derakane™ 510C epoxy vinyl ester resin.
from slurry environments. In the end result, properly Ultimately all 10 FGD units were retrofitted with
designed and installed FRP equipment (e.g. piping RPS piping. The first two have now been in service
and scrubbers) can deliver 20 or more years of for more than fourteen years. Based on installed
uninterrupted service. Incorporation of smooth flow experience it is expected this recycle pipe will
fittings and long radius elbows can extend service in provide more than twenty years of maintenance free
piping systems even further. service providing the plant owners with an excellent
return on their investment.

4 | Corrosion Chronicle
 FRP chosen to replace RLCS in FGD
Operation
2. Belgium / Leach Tanks
In 2012, Plasticon Composites
engaged Nystar Belgium to
replace several rubber-lined steel
and stainless steel tanks from
their hot leaching process. The
vessels were 21 feet (6.5 m) in
diameter and 20 feet (6 m) tall. In
this leaching process a range of
metals (zinc, lead and copper)
are leached from an ore slurry at
185 – 200 F (85 – 95 C). The original
tanks had a life expectancy
of 12 years but with significant
ongoing maintenance costs.
The new vessels were fabricated
with Derakane 441 epoxy vinyl
ester resin. Plasticon has thus
far replaced five of the original
12 rubber lined steel vessels for
Nystar. An inspection conducted
in 2016 showed them all to be in
very good condition. The client
plans to replace the remaining 7
vessels later this year.

Spring 2017 | 5
Ultra large FRP vessels becoming commonplace
At one time it was thought that FRP vessels could not be of ultra large hydrochloric acid tanks for the Vale Nickel
fabricated larger than 12 feet (3.5 m) in diameter. Many project in Newfoundland. Three vessels measuring 44
asset owners and design engineers were certain that feet in diameter (13 m) and heights up to 51 feet (16 m)
FRP technology could not be made structurally sound were called for. Initially, Vale was unconvinced that
beyond those diameters. Moreover, it would be far too such large vessels could be made from FRP. In the end,
difficult to transport tanks beyond these dimensions however, Ershigs was able to persuade Vale that it was
on public roadways. Today we know different. Tanks indeed feasible to fabricate and transport vessels of this
fabricated to 50 feet (15 m) in diameter are commonly size. Part of that persuasive argument was to visit flue
seen. Some vessels are over 100 feet (30 m) in diameter. gas desulfurization (FGD) projects in the power industry
Similarly, these fabricated structures can be over 50 where Ershigs and Augusta Fiberglass had each built
feet (15 m) tall. In fact, if we include chimney liners in this even larger FRP structures. In fact, the current record for
discussion, FRP structures have been constructed which large diameter FRP structures is the six 119-foot diameter
are more than 900 feet (274 m) tall. Jet Bubbling Reactors (JBR) located in major Power
Ultra large FRP vessels are being specified for projects Generation Plants in the Southeast US. Once Vale toured
around the world. There seems to be no limit to the size to one of these air pollution control facilities and inspected
which these structures can be designed. With the advent the enormous JBR scrubber, feasibility was no longer in
of modern field winding technology, transportation to doubt.
the construction site is no longer a limitation. World class The FGD market is home to another ultra large structure.
fabricators can now build these vessels right in place. That being the absorber hoods used in Southern
And if on site field winding is not an option, fabricators Company’s Plant Scherer air pollution control unit. Each
can construct the tanks elsewhere, oblate them prior to FRP hood was approximately 128 feet (39 m) in length,
shipment and bring them to the job site for final erection. 34 feet (10 m) wide and 32 feet (10 m) high, weighing
There are numerous examples of ultra large FRP vessels about 270,000 pounds (122 MT). In all, a total of four FRP
and ducting. One such example are the hydrochloric hoods were installed on Scherer units, saving a total of
acid tanks fabricated by Plasticos Industriales de Tampico about $16.9 million vs construction in Hastelloy C. In Brazil,
(PITSA) for the Goro Nickel project in New Caledonia. The Techniplas has fabricated a 3 million cubic meter fire
tanks ranged in diameter from 30-45 feet (10 - 14 m) in water storage tank for Vale Fertilizer. That’s nearly 800
diameter and 25 – 60 feet (8 – 18 m) tall. “We had to use million gallons! The vessel was 50 feet (15 m) in diameter.
the best materials available,” said Engineer Francisco These a but a few of the ultra large FRP vessels that reside
Sainz Inguanzo, general manager – PITSA, “including at industrial sites around the world. Contact a member
Derakane™ epoxy vinyl ester resins from Ashland.” A few of the Ashland Derakane team to learn where you might
years later, Ershigs won a project to fabricate a number see one such engineering marvel near you.

6 | Corrosion Chronicle
 Derakane Momentum™ 640 – a resin for rough edges
Derakane Momentum 640-900 meets the requirements 2. Ma’aden, Saudi Arabia / Cooling Towers
of demanding pultrusion applications where premium The Ras Al Zour fertilizer complex in Ma’aden, Saudi
mechanical properties are required along with rapid Arabia includes a total of 16 large, draft-cell type
line-speeds and outstanding corrosion resistance. Such cooling towers developed by Hamon Thermal
demands typically exclude the use of UPR resins as well Europe. Structural profiles and wall panels for
as anhydride-cured epoxies. DM 640-900 can produce the towers were fabricated with pultruded glass-
demanding profile geometries with sharp edges, reinforced plastic (GRP) and DM 640 Resin. Derakane
undercuts etc. and superior surface quality. In addition, resin was critical to achieve superior corrosion
its low styrene content lowers workplace emissions, thus resistance to the aggressive chemical environment.
making a positive contribution to the environment. A long lifetime without maintenance is projected and
High strength and thermal resistance with impressive so fulfills the requirements of the owner.
toughness round out the performance properties
CSSI’s 118 foot
of DM 640, making it a preferred resin for structural communications
applications. Profiles fabricated with this resin also tower built
deliver very good fatigue and creep resistance. with Derakane
Momentum 640-900
Case Histories
1. Transport Trailer
A light-weight all composite transport trailer
was developed to minimize trailer weight and
consequently increase its net payload. Pultruded
structural beams made with DM 640 resin provide
high strength and stiffness into the trailer chassis.
It also incorporates unique sandwich panels
made with three-dimensional stitched composite
technology for the floor and side walls. DM 640 Resin 3. Massachusetts USA / Communications Tower
met the project’s demanding mechanical property Dr. Clement Hiel, founder of Composite Support &
requirements and need for excellent corrosion Solutions (CSSI), recently won a prestigious Tibbett’s
resistance. The resin also delivered the fatigue and award from the Small Business Administration for a
creep resistance these large trailers require when 118-foot (36 m) communications tower installed by
used rough environments. Comprehensive road the Air Force at Hanscom AFB in Massachusetts. The
tests showed that the ‘all composite trailer’ had a tower was fabricated using Ashland Derakane™ 640
far better ‘road grip’ compared to standard trailers. resin designed for pultrusion.
The full composite chassis and superstructure design
on this innovative trailer is clearly is a door opener The pultruded composite tower was erected using
for further light weighting applications in automotive fastener-less joining technology where individual
and industrial markets. components, such as the lattice cross members,
“snap” together without the need for metallic bolts.
CSSI selected Derakane because of its mechanical
properties and its outstanding corrosion resistance.
“CSSI’s snap-join approach is an enabling
technology for the fabrication of modular
composites. There is great interest these days in
lightweight, easy-to-assemble, easy-to-disassemble
materials. This award-winning technology should
spur widespread interest in the automotive,
aerospace, and construction industries.” said Joe
Fox of Ashland. The CSSI tower is the first of a new
generation of composite towers with the distinct
advantage of significantly reducing long-term
maintenance costs and dramatically shortened
Pultruded profiles and panels for cooling tower in corrosive
environment construction times.

Spring 2017 | 7
ASME primed to release new non-metallic piping standards
Nonmetallic piping design standards, including FRP
and thermoplastics, have long challenged plant
owners and engineers alike. The industry today
contains a myriad of guides and reference standards,
many of which are not very comprehensive or
consistent in their direction. Generally, most piping
codes and standards are recognized as being
deficient in both detail and direction when it comes
to nonmetallic piping. There are a number of ASTM
product standards that provide guidance on product
design and testing. AWWA also has a guide which
provides design guidance for aboveground and buried
piping. And there are still many other national and
international standards to wade through. Depending
on the source, guidance and critical factors may vary.
Plant owners and design engineers needing to specify
/ design nonmetallic piping must have a thorough
knowledge and understanding of a great many
standards in order not to be confused or conflicted by a multitude of Subject Matter Experts and practitioners
the guidance therein. from the piping and materials community, all under the
guidance of ASME.
In 2011, ASME commissioned its Nonmetallic Pressure
Piping Standards (NPPS) Committee to develop These will be world-class standards and are expected
comprehensive standards for nonmetallic piping, to be recognized and adopted internationally. Jeff
covering Fiberglass Reinforced Plastic (FRP/GRP), Eisenman put it best when he said, “Plant Owners and
thermoplastics, lined steel and multi-layer composite Engineers have asked for better FRP standards for many
piping. Representatives of Maverick Applied Science, years.  We believe these standards will be impactful
Inc. including its Director of Engineering and and will provide the needed guidance that will create
Technology – Jeff Eisenman - have been involved with an increased confidence in FRP piping systems.” After
the development of FRP piping standards since the a tremendous effort by many, it is quite exciting to see
early days of this effort. ASME is now in the final stages this work come to fruition with the publication of these
of review and publication of these groundbreaking comprehensive nonmetallic piping standards.
standards. They should become available to the public Keep an eye out for these new ASME standards from
in July of this year. These standards will represent the ASME later this Summer.
culmination of literally thousands of volunteer hours by

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Do you have a technical question about using an Ashland resin? Want to know what resin is
suitable for a given application? Send your inquiries to [email protected]. We’re also
looking for interesting news stories and welcome your ideas. Simply send in your question or
idea — we’ll be in touch soon!

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8 | Corrosion Chronicle