Battelle's
self-healing smart coating uses a novel variation on microencapsulation. Rather
than using a thermosetting resin, a thermoplastic resin is encapsulated. When
damage occurs, the capsules break and the resin flows out and into the crack.
Unlike a thermosetting resin, the thermoplastic resin does not need to
encounter the catalyst to heal the coating. Catalyst stability and
compatibility with the host coating is no longer an issue.
Corrosion is a wide-spread problem across many industries.
Corrosionrelated costs to the pipeline industry
are estimated anywhere from $5.4 billion to $8.6 billion annually in a report
by NACE and CC Technologies. These costs include failures, capital, and
operations and maintenance.
Improved
methods of detection, as well as improved corrosion prevention coatings, can help reduce
these costs. New technologies such as self-repairing coatings reduce the need
for field repairs or extend the intervals between repairs.
Coatings are
widely used for corrosion
prevention on oil and gas pipelines. Battelle has a number of new developments in the
detection, evaluation and prevention of corrosion. Battelle continually
builds on experience across multiple market sectors to develop new technologies
for corrosion control.
Some of the examples presented here were originally developed for bridges,
aircraft or marine use but the technology can be transferred to pipeline use.
Corrosion Modeling
Battelle has
two modeling efforts related to corrosion.
The first is the Environmental Severity Index (ESI). This model uses data on
temperature, humidity, chlorides concentration and UV radiation intensity to
predictcorrosion rates
for bom ferrous and non-ferrous alloys. Battelle has collected sensor data from
over 2,000 sites worldwide. Predicted corrosion rates are shown in Figure 1. Rates for a number
of locations have been verified experimentally. Battelle 's facility in Daytona
Beach, FL, shown at the top of Figure 1 , is one of the most corrosive marine
environments available. Sensors deployed in various locations also allow real
time assessment of conditions for corrosion prevention or monitoring. These sensors do not
directly measurecorrosion of
a structure, but they do provide information on the corrosive severity of the
local environment, which can serve as a leading indicator for corrosion.
The second
type of modeling incorporates corrosion damage
into mechanical models. Once the rate ofcorrosion and type of corrosion occurring are known, this information
can be included in mechanical models. Damage tolerant corrosion modeling applies
fracture mechanics to corrosion.
Custom algorithms developed by Battelle include the effect of corrosion in Finite Element
Analysis (FEA) by treating corrosion pits
as cracks. The custom algorithm predicts how the cracks will grow, permitting predictions
of service life based on structures and loads and environmental conditions.
Testing shows that corroded structures have shorter lives and lower failure
stresses. The new models incorporate this effect and accurately predict
real-life behavior.
Non-Destructive
Imaging Or Detection
Battelle is
working with a range of technologies for non-destructive evaluation of coatings
and corrosion inpipelines and other
applications. Corrosion underneath
a coating often cannot be detected by visual means until the coating fails.
Early detection allows for timely mitigation or repair of corrosion damage.
Ultrasonic
inspection techniques have been in use for several years. Ultrasonic inspection
will detect cracks and significant changes in wall thickness due to metal loss.
However, depending on the resolution of the system, ultrasonics may miss early
surface corrosion.
Battelle has been working on an alternative non-destructive evaluation approach
using Terahertz (THz) imaging. THz imaging has been found to be effective at
imagingcorrosion through
intact coatings on metal surfaces. This method uses THz electromagnetic waves,
which fall between infrared and microwave radiation on the electromagnetic
spectrum. Many organic coatings are transparent to THz radiation while metal
substrates will reflect an incoming signal. The technique has been demonstrated
for early detection of corrosion on
aircraft. High-resolution laser scanning also has been demonstrated for corrosion detection. This
technique does not penetrate the coating, but picks up subtle defects caused by
the underlying corrosion.
Corrosion Prevention Coatings: Primers And Top Coats
Many
traditional corrosion preventive
compounds used in coatings are based on hexavalent chromium and other toxic
metals and compounds. However, the new restriction of hazardous substances
(ROHS) requirements implemented in 2006 have limited the use of hexavalent
chromium. Battelle evaluated a variety of non-chromium surface pre-treatments
for metals. The Prekote(TM) surface pretreatment is a silane based treatment,
while AC- 131(TM) isa sol-gel treatment. Both of these are used in place of
chromium, cadmium and other toxic pretreatments used on metal surfaces before
painting.
Advanced
primers also are replacing hexavalent chromium. Battelle developed a series of
ferrate compounds for corrosion
prevention and incorporated them into existing MIL-spec primers
without corrosion preventioncompounds.
Samples with these ferrate compounds are currently undergoing exposure at
Battelle's Florida Marine Research Facility (FMRF). After three years of
continuous exposure, the ferrate compounds are performing as well as hexavalent
chromium compounds, and far better than other hexavalent chromium replacements.
Battelle
also has developed an Extended Life Topcoat (ELT) or Advanced Performance
Coating (APC) based on polyurethane and fluoropolymers that is used by the U.S.
Air Force to prevent corrosion of
aircraft. The topcoat is resistant to degradation from aging and exposure to
the elements and will last longer than traditional topcoats. The topcoat has
been qualified to MIL specs and is produced commercially by an existing
coatings supplier. This has the advantage of extending the maintenance
intervals, reducing the frequency for repair or replacement of the coating.
Self-Healing
Smart Coatings
Corrosion prevention coatings inevitably will suffer damage over
their lifetime. When damage is detected the coating can be repaired or
replaced. The traditional approach has been to wait until visible damage has
occurred, such as cracks, blisters, or peeling of the coating, or a raised
surface caused by corrosion of
the substrate. However, a significant amount of damage to the substrate can
occur before this visible evidence appears. One approach is to use the
non-destructive imaging capabilities discussed above. As an alternative,
Battelle has developed a novel type of smart coating that incorporates both
self-healing and damage indicator functionalities.
Numerous
reports of self-healing coatings have appeared in the literature in recent
years. A common technique is to use microencapsulation techniques to
encapsulate a thermosetting resin inside a thin shell. These microcapsules are
dispersed in the coating along with a catalyst for the thermosetting resin inside
the microcapsules. When the coating is damaged capsules rupture at the damage
site, and the catalyst initiates curing of the resin as it flows into the
damage zone. There are a few challenges with this approach. The catalyst must
not react with the original coating resin. It must also be stable over many
years so that it can still react with the healing resin inside the
microcapsules when damage occurs. Enough catalyst must be present to ensure a
good cure of the healing resin, because the resin won't start curing until it
encounters the catalyst.
Battelle's
self-healing smart coating uses a novel variation on microencapsulation. Rather
than using a thermosetting resin, a thermoplastic resin is encapsulated. When
damage occurs, the capsules break and the resin flows out and into the crack.
Unlike a thermosetting resin, the thermoplastic resin does not need to
encounter the catalyst to heal the coating. Catalyst stability and
compatibility with the host coating is no longer an issue. Battelle has tested
both acrylic oligomers and polymers as the thermoplastic healing resin. The
oligomers had lower viscosity and filled the cracks better as a result.
Improved healing was demonstrated by reduced corrosion in test panels exposed to a standard
corrosive environment. Control panels had the mostcorrosion at induced flaws, panels with polymer
healing agents were in the middle for performance, and panels with oligomer
healing agents had the least corrosion.
In addition
to improved healing characteristics, Battelle's smart coating incorporates a
damage indicator compound. Molecules of 8-hydroxyquinoline (8-HQ) are tethered
to the outside of the capsules during the microencapsulation process. When corrosion of
aluminum or steel occurs, the metal ions form a complex with the 8-HQ. This
complex fluoresces under ultraviolet light, making corrosion visible by inspection with a
handheld UV lamp. The complex also has high contrast to
THz imaging, improving corrosion detection
with THz imaging methods discussed earlier.
Chrome
Reduction In Coating Removal And Maintenance
As noted
earlier, new primers and coatings have replaced toxic hexavalent chromium with
alternative corrosion
prevention compounds. However, older structures often have primers
with hexavalent chrome. Performing maintenance on these structures, including
stripping and repainting, can expose workers to toxic dust or release
hexavalent chromium into the environment. Battelle has developed a process for
converting hexavalent chrome into less toxic trivalent chrome. The reducing
material can be mixed with liquids, incorporated into wet sanding, or wiped
onto the coated surface. A color change indicates that the process is working.
Reductions as great as 99.9% have been observed. This improves worker safety
and reduces harm to the environment.
Corrosion Testing And Evaluation
A wide range
of technologies and methods are used for testing and evaluation of corrosion and corrosion prevention coatings.
One popular option is real-time outdoor exposure. As noted earlier, Battelle's
FMRF provides one of the most corrosive natural environments available in the
US. The environment is classified as "Humid Subtropical" by the
National Oceanic and Atmospheric Administration (NOAA), with an average
temperature of 22°C (72°F) and an average relative humidity of 78%. The
oceanfront property has a high site surf intensity resulting in levels of
atmospheric chlorides averaging 200 mg Cl/m2/day, contributing to the
aggressive corrosive environment. Marine exposure for biofouling studies is
also available from docks along the Halifax River estuary.
In cases
where outdoor exposure is not practical, or accelerated testing is desired, a
variety of indoor exposure systems are available. Coated samples can be exposed
to salt fog, acidic salt fog, or continuous aqueous immersion, with periodic
visual evaluations of corrosion according
to ASTM and other standard methods. Prohesion is a modified salt fog test that
alternates salt spray with drying cycles. This creates a more aggressive corrosion environment.
Samples can be scribed to create controlled flaws in the coating, and thecorrosion creep away from
the scribe can be measured. Exposure chambers with an ultraviolet light (UV)
component, such as QUV cabinets and the Atlas Weatherometer, simulate both
daylight and rain cycles in an outdoor environment for realistic accelerated
weathering of coatings.
Another
common laboratory test for the durability and effectiveness of corrosion prevention coatings
is Electrochemical Impedance Spectroscopy (EIS). An RC circuit is created
between an electrode in the conductive liquid on top of the coating and the
metallic substrate under the coating. Equivalent Circuit Analysis (ECA) is used
to model the degradation behavior of the coating and allow measurement of
instantaneous corrosionrates
of the substrate. Tests can be run for short times as a screening tool for
coatings. Longer tests, weeks to months in duration, can be used to predict the
long-term effectiveness of coatings.
New
technologies are reducing the cost and impact of corrosion. Corrosion can be monitored and predicted based on the
local environment, allowing for adjustments to maintenance schedules. Improved
detection methods find corrosion before
it's visible to the naked eye. New coatings and additives resist corrosion and extend the
life of coatings, reducing the need for repainting while being friendlier to
the environment.Corrosion cannot
be eliminated completely, but it can be managed effectively.
Sumber : Thurston, Rachel M. "Battelle Acts on Corrosion Detection and Prevention". 27 Januari 2014. http://search.proquest.com/docview/1326775132?accountid=31562
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