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MARINE CORROSION AND BIOFOULING
Dr. R. Venkatesan
Scientist G & Programme Director
ESSO‐ National Institute of Ocean Technology Chennai
13 September 2014
• Economic power is driven by technology,
industry and trade.
• An important aspect of industry & trade ‐
energy security
• Main source of energy is transported by sea
• Over 70% of world’s oil reserves are in
Persian gulf
• We imports 70% of its oil by sea.
• About NIOT
• Materials for marine applications
• Marine Corrosion
• Marine biofouling
• Deep Sea Corrosion
• Case studies
• Biomimitics
National Institute of Ocean Technology
Focus areas
Gas Hydrates
Vessel Management
Marine Bio Technology
Low Temperature Thermal Desalination (LTTD)
plants at Lakshdweep Islands
Surface Buoy
Water level
Sub Surface
Floats
Surface
Acoustic
Modem
Acoustic Link
Mooring
BPR Sensor
Sea Bed
Unmanned Systems
WET & DRY CORROSION
• Wet / aqueous corrosion is the major form of
corrosion which occurs at or near room
temperature and in the presence of water
MARINE ENVIRONMENT
• Sea water is a complex, delicately balanced
solution of many salts containing living matter,
suspended silt, dissolved gases and decaying
organic material.
• Because of interrelation between many of
variables in seawater – an alteration in one
may affect the relative magnitude of others
MATERIALS FOR MARINE APPLICATIONS
• MORE AND MORE EFFORTS
ARE BEING MADE TO
EXPLORE MARINE
RESOURCES
• NEW TECHNOLOGIES ARE
TO BE EVOLVED
• REQUIRES KNOWLEDGE ON
BEHAVIOUR OF MATERIALS
AND DEVELOPMENT OF
NEW MATERIALS.
Seawater
• Most critical – tank lining application
• Material must be resistant to corrosion and be free of pinholes
Four areas of contact for tank lining
• Vapour phase ‐ area above liquid level
• Interphase ‐ area where vapour phase meets liquid phase
• Immersed ‐ Area always immersed
• Bottom of tanks – where moisture and other contaminants of greater
density may settle
Which is most severe?
• Each of the above – one time or other may be severe
• Depending on type of material contained impurities present, amount of oxygen
and water present
Coating selection
• Primary function – to protect substrate
Conditions – two categories
• Chemical to which coating will be exposed
• Conditions of operation
As a result necessary to verify chemical resistance‐ physical properties of coating
• What is being handled primary chemical
• Secondary chemical
• Trace Impurities
• Solids present – particle size and concentration
• Any agitation
• Fluid purity requirements
• What will be present in vapour phase
• What will be physical or mechanical properties
• What is normal operation temperature and temperature range
• Peak temp can be reached during shutdown start‐up process upset etc.,
• Will any mixing areas exist where exothermic heat of mixing temp may develop
• What is normal operating pressure
• What is vacuum conditions and range are possible
Surface preparation techniques
• Blast cleaning Ideal
• Hydro jetting
• Mechanical wire brushing
• Manual brushing Poor
• Note:
Hydro jetting is increasingly popular.
But it poses some specific problems
Parameters that affect coating
• Design of vessel
• Vessel preparation prior to coating
• Application technique
• Curing
• Inspection
• Operating instruction
• Temperature limitations
Drying times and pot life ‐ Additional comments
• The coatings are often stored in a heated warehouse to prevent
addition of solvent to adjust the viscosity to spray viscosity.
• The epoxy – amine reaction is exothermic
Increase of the pot temperature after mixing of the 2
components
• Coatings drying time dominated by the temperature of the
substrate and by the degree of ventilation.
Faster reaction kinetics in the pot than in applied paint film,
especially in winter time.
• Generally lower viscosity epoxies have a lower EEW (a higher
oxirane content)
Higher levels of hardener needed or hardeners with higher
NH content needed.
High solids / solvent free coatings have a higher
concentration of reactive groups in the mixed paint, which
goes against pot-life.
Examples of commercial
coating systems
• Zinc silicate 70 µ Steel protection,
•
•
•
Epoxy tie coat
High built epoxy coat
Weatherable PUR
50 µ
200 µ
50 µ
} e.g. off shore,
above splash zone
• Epoxy primer 30 µ
• Epoxy mineral flakes coat 300 µ } Interior tank
lining
Estimated Service Lives of High‐Performance Anticorrosion Coatings (years)
Source: GH Brevoort et al
DENTISTRY
Piling
APPLICATIONS FOULING
SHIPPING DESALINATION PLANTS
POWER PLANTS
Ship
Fouling control practices
Physical methods
1) Construction of barriers.
2) Provision of increased flow velocities.
3) Heat treatment.
4) Mechanical cleaning.
Offer only temporary relief.
Blocked condenser tubes of a
Nuclear Power Plant
Silt deposits
Treatments
Chemical Treatments
BIOCIDES
1) Oxidizing ‐ Chlorine ‐ Gaseous
Sodium Hypochlorite
Bromine ‐ Bromine chloride
Chlorine dioxide
Ozone
Hydrogen peroxide / paraacetic acid (Recirculatory)
2) Non‐oxidizing
Quanternamonium compounds (Recirculatory / Fresh water)
Clam Trol ‐ Alkyl dimethyl benzyl ammonium chloride
Calgon ‐ didecyl dimethyl ammomium chloride
Bulab ‐ Poly [oxyethylene (dimethylimino) ethylene
(dimethyliminio) ethylene dichloride]
Treatments
Mechanical Cleaning
• Removes Biofilm
• Increases Effectiveness of chemical treatments
Typical methods
‐ PIGS
‐ BRUSHES
‐ SPONGE BALLS
‐ FLUID MOVEVMENT
‐ AIR BUMPING
‐ SANDJETTING
‐ HYDROLAZING
Treatments
Antifouling Paints
1. Coatings based on copper or copper alloy system.
2. Coatings containing active biocides.
Contact leaching type
Contact diffusion type
Soluble matrix type
Co‐polymer ablative type
3. Coatings with low energy surfaces.
Industry
• Tanir Bavi Power plant, Mangalore
• Surya Chakra Power Plant, Port blair
• Talchar Power Plant, Orissa – NTPC
• Ratnagiri Gas and Power Plant ‐ NTPC
• Indira Gandhi Centre for Atomic Research
• Desalination Plant‐ LTTD ‐ Lakshadweep
Fouling of PHE’s in Tuticorin Harbour waters
Within 3 days of operation
Chlorinated
Untreated
Plate Heat Exchangers
Advantages of PHE
Compactness,
large surface area,
high degree of turbulence,
keeps particle in suspension,
easy to clean,
high heat transfer coefficient.
Surface area ½ to 1/3rd of shell and tube
exchanger for the same heat duty -
Occupies less space - suitable for offshore
Specification
Thickness of plate – 0.7 mm
Material - Titanium
Gap between the heat exchanger
plates is 3.7 mm
Biofouling on plate heat exchangers
IGCAR project – PFBR fast breeder reactor
project
Experimental set up
flow through system erected
inside Madras Atomic Power
Station (MAPS)
Velocity of seawater ‐ 1 & 2m/sec
First of such data being collected
Coastal Waters
Stainless Steel - cumulative observation
Material: AISI Type 316L Stainless steel 0.3m Surface
CONTROL 1st Month 2nD Month 3rd Month 4th Month 5th Month 6th Month
Not a unique form of corrosion
Ubiquitous
Microbes are essentially everywhere
Survive wide range of conditions
Highly adaptable
Sense and move to nutrients
Establish consortia
Materials are susceptible
MIC- Initiation Mechanism
SEM images of natural crevice assembly observed on the basal side of the barnacle shell
Gallionella sp.
Iron oxidizing bacterial
Corroded coupon attack on 316 L Stainless
3m steel
SS 304
NUT Location : CB 02
Lat : 10.873 o N
Long : 72.21 o E
Carbon fibre reinforced composite (CFRP)
OCEANOGRAPHIC DATA - GEOSECS experiment
0 0
1000 1000
Depth metres
Depth metres
2000 2000
3000
3000
4000
4000
5000
5000
0 200 400
Dissolved Oxygen um/kg 0 20 40
Seawater temperature deg C
1a 1c
0 0
1000 1000
Depth metres
Depth metres
2000 2000
3000 3000
4000
4000
5000
5000
34.50 35.00 35.50
Salinity ppt 0 1000 2000 3000 4000 5000
Pressure dB
1b 1d
Mild steel
500m
1000
Depth metres
2000
3000
4000
5000
0 200 400
Dissolved Oxygen um/kg
5100m
• No change in tensile strength, compression
strength, Flexural strength, Interlammellar
shear strength
• No change in weight loss measurement
SEM
No deterioration of fiber, fiber-matrix
interface, fiber pull-out or any other
defect.
5100m ; 174 days 3500m ; 174 days
ANTI FOULING PAINT
Weed fouling upto 10%
increase in drag
•NATURE
Rights ofKNOWS
fishermen and other fish workers need to be protected
BEST
• Environmentally and economically sound management of fish
stock should be propagated
WITH MILLIONS OF YEARS TO PERFECT HER TECHNOLOGIES,
• Public awareness campaign on importance of fisheries/oceans to
be launched
•NATURE IS AN EXCELLENT
Consonance SOURCE
in implementation of FOR INNOVATION
human activities to minimise
the adverse impacts on the ecosystem, water quality, etc.
• Coordinated and integrated management of all activities
BY JOSEPHto
WILSON
sustain the resources and protection and conservation of critical
habitats
The for long-termiseconomic
word biomimetics relativelygrowth of the country
new; however, our
ancestors looked to nature for inspiration and development of
various materials and devices many centuries ago (Ball
2002; Bar-Cohen 2006;
Non-stick fouling release
Desired Properties
A flexible, linear backbone
which introduces no undesirable
interactions.
Molecules which combine all the above factors & are stable in
marine environment.
LOW SURFACE ENERGY
Surface Modification Approach to control POLY-SILOXANE COATINGS
Biofouling (Indo-Bulgarian Project):
• Settlement of micro and macro fouling
organisms on different foul release
properties of formulations of
Polydimethylsiloxanes (PDMS) were studied
and their performance were ranked.
71
Objectives of the work
72
Scientific approach & Methodology
Immersion of coated & On-site experiments, NIOT,
uncoated coupons in Immersion of coupons
&
marine waters
removal, every month from the
ocean
Over the radial channels the complex Primary duct is ~0.4 µm wide whereas the sub-ducts
cement ducts connecting the concentric are 0.17 µm wide.
rings are visible. The primary cement channel subdivides itself to a
During each molting (growth) cycle a complex network to ensure that the cement is available
concentric ring is produced. throughout the base-plate for firm adhesion.
R. Sangeetha et.al., Materials Science and Engineering C 30 (2010) 112–119 74
Morphological differences in cement structure
Titanium SE SS316L SE
75
Thickness of cement
Base-plate Titanium Base-plate SS316L
Cement Cement
BSE BSE
Cement
Second level: Macro hollow channels in the parietal & basal shell
Third level: The concentric rings of the base-plate that corresponds to growth
Fourth level: Complex cement carrying microducts that fasten each ring to
the substrate
Sixth level: Radial plates that interconnect the six parietal plates
Seventh level: Barnacle cement which anchors the barnacle to the substrate
Eighth level: Mesh-like structure of cement that gives a cushioning effect when
the ocean currents hits the creature
77
Study of unknown deep sea corrosion
of Tsunami equipment BPR
Unusual corrosion and deposit of unknown material on deep sea instrument at
3298m depth from 29‐08‐2011 to 02‐04‐2013
Lat 12° 32.93’ N, Long 85° 31.38’E
1.45
1.44
1.43 Sulphur
1.42
1.41
1.40
1.39
1.38
Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct
2011 2012
Microbial Corrosion????
New Bacteria Found on Titanic; Eats Metal
First it was an iceberg, now it's bacteria: Rust‐eating species 'will destroy
wreck of Titanic within 20 years
India has established Ocean Observatory in
ARCTIC
Different materials will be exposed ion land and
underwater
CII – Corrosion Management Committee (CMC)
CII‐Faraday Council of Corrosion (FCC) &
National Institute of Ocean Technology (NIOT)
National Competition on “Corrosion
Awareness Video”
Create a video in any style you like that tells about corrosion of materials/
components
Video Criteria
Videos will be judged on their topic selected, audio narration of the corrosion problem, ability to convey the message through animation, creativity,
technical production, and accuracy. A panel of national experts will act as the judges for the selection of Winners.
You are welcome to choose your own topic or use one of the following ideas for inspiration:
• Corrosion seen in Public : Day to day visual observation of corrosion leading to loss in any sector, neglect of corrosion
• Becoming a Corrosion Engineer – The exciting transformation from human to engineer, specialising in the profession of corrosion
• Suggest Design change to mitigate corrosion – What is your opinion on existing design and design change suggested by you to avoid corrosion
• Awareness to the public – How every individual can contribute to know the evils of corrosion
• Shaping the World – How Information Technology and Multimedia Design enhance our lives to provide information on the menace of corrosion, its
manifestation and management
CHALLENGES
EARTH SYSTEM STILL NOT UNDERSTOOD
TECHNOLGICAL
SITE SPECITIFIC
To conclude
The marine and ocean technology sector facilitates the study and utilization of
ocean and coastal resources by developing, producing or adding value to
products and/or services based primarily on technological innovation
Understanding protection of materials and Development of newer materials
play major role
BPR
Thank you for your kind attention
dr.r.venkatesan@gmail.com