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Advantages of fast-curing polyurethanes for BWTs

The use of ballast water is critical to the safe operation of ships, but also poses challenges due to the need to maintain the structural integrity of ballast water tanks (BWTs) despite highly corrosive conditions. Appropriate protective coatings act as barriers to corrosion and if applied carefully to properly prepared surfaces can significantly extend the life of BWTs. Two-coat epoxy systems are commonly used today, but rapid curing polyurethanes have performance properties that make them attractive as alternative coating solutions, including tunable properties that allow the formulation of flexible yet hard coatings that resist cracking, excellent adherence to steel, high resistance to corrosion, chemicals, and abrasion and fast return to service.

Ballast tanks located at the bottom, around cargo holds, and near the bow and stern of ships provide a mechanism for maintaining balance. Water is filled or released from the tanks to stabilize and trim ships during sailing and to keep them evenly afloat during the loading and unloading of cargo. Ballast water tanks (BWTs) are typically dedicated for this purpose. Ballast tanks are also used to adjust the buoyancy of submarines and stabilize offshore oil platforms and floating wind turbines.

In marine vessels (tankers, bulk carriers, etc.), ballast tanks typically comprise the largest surface area of steel. Corrosion of these tanks can therefore significantly reduce ship safety and operational life. In the past, ships suffering from severely corroded ballast tanks have experienced total failure of their hull shell plates. There is general agreement in the industry that prevention of corrosion in BWTs is the second most important factor after design integrity in determining the operating life of a ship.

Corrosion prevention in BWTs is not a simple matter, however. The water in ballast tanks can have a high salt content, vary in the type and concentration of other ions and have a wide range for pH and may also contain corrosive chemicals. Empty ballast tanks, on the other hand, are exposed to corrosive atmospheres that cycle with the temperature of the tank. Tanks, when partially full, are also subject to continuous movement of the water.

In fact, different parts of ballast tanks corrode via different mechanisms and at different rates, and empty tanks behave differently than tanks that are often filled with water.  For Example, some parts of tanks are exposed to cyclic heating and cooling and/or local heating from warm, adjacent cargo tanks and engine rooms. Additionally, the exterior of the BWT is exposed to the weather above the water line and the differing temperatures of the sea below the water line.  Therefore the same tank can experience uneven thermal cycling due to the extreme differences in its exterior exposure. Because the upper portion of the tank is exposed to extreme thermal cycling and repetitive wet and dry service, anodic oxidation is the main source of corrosion in this part of the tank. On the other hand, the bottom area of a tank is constantly exposed to the sea and therefore is maintained at a lower temperature and is subject to cathodic blistering.  Any microbes in sediment on the bottom can also cause microbial corrosion.

Many other factors such as bacterial biofilm, mechanical vibration and effectiveness of sacrificial or impressed current anodic protection play a moderate role in determining the rate of corrosion in ballast water tanks.

To prevent corrosion in BWTs, high-performance protective coatings are applied during construction of the ship. Typically two thin layers of a suitable coating with a total dry-film thickness of approximately 300-320 microns are sufficient to provide an effective barrier against corrosion. Such coatings must meet many regulatory requirements related to their environmental and performance characteristics.

Current Coating Technologies
Preferred coatings not only provide a long lifetime of protection (15 years or more is required by the International Maritime Organization (IMO) Performance Standard for Protective Coatings (PSPC)¾see below), they must be easy to apply under the varying conditions found at different shipyards around the world and easy to maintain. Coatings that provide greater coverage for less material usage and are more tolerant of poorer surfaces are also in demand. A low volatile organic compound (VOC) content (< 250 g/l) is also necessary.

The majority of BWT coatings applied today are epoxy-based systems. Most are solvent-based, high solids formulations, although some European shipbuilders use solvent-free coatings to meet the requirements of the EU Solvent Emissions Directive (SED). The latter 100% solids epoxy systems have good performance properties, but tend to suffer from poor wetting properties and slower curing rates at low temperatures. Good wettability is necessary to ensure that pitted areas are filled rather than bridged, and thus do not leave a void below the paint film that can act as a starting point for corrosion.

Rapid curing is a very desirable property for BWT coatings because it translates into shorter construction times for new builds and reduced time in dry-dock for recoating and repair. The US Navy has developed a series of 100% solids coatings based on amino polyols prepared from either alkanol amines and polyfunctional epoxy materials or polyamines and monofunctional epoxides that are applied using plural component equipment, which eliminates the poor flow concerns.  They are referred to as “single-coat” systems because the necessary two coats can be applied in one day, rather than in two. The technology for a light-to-medium-duty coating based on a medium-viscosity resin has been licensed and is commercially available. In a study at a commercial shipyard in Asia, the rapid curing coating, which meets the IMO PSPC requirements, was shown to provide a nearly 40% increase in painting productivity and a 20% overall cost savings.

Advantages of Polyurethanes
Certain polyurethane (PU) coatings have also been shown to have significant potential as highly protective barrier coatings for ballast water tanks. Specifically, 100% solids rigid and structural polyurethane coatings are promising because they cure very rapidly, even at cold temperatures, and have superior resistance properties.

One of the major issues with epoxy coatings is their inability to build desired dry film thickness at sharp edges, corners, weld seams and other defect sites. Coating failures generally occur first in these areas, usually do to crack formation. Unfortunately, there are many of these sites present in BTWs. While the PSPC does require that sharp edges be addressed prior to coating, this problem remains a concern in the industry. Advances in epoxy coating technology have helped, but further improvements are still desired.

Polyurethanes have the key advantage of property tunability. Careful selection of the polyisocyanate and polyol segments can provide coatings with very specific properties. For ballast water tank applications, a hard coating is needed that retains some flexibility to allow for high film builds at edges, seams and defect sites. This unique mix of properties, which cannot be achieved with epoxy systems, is possible with polyurethane coatings. Careful preparation of the PU resin and development of the formulated PU coating can provide coatings with desirable edge retention properties.

With the appropriate choice of starting materials, it is also possible to formulate polyurethane systems with curing times that allow for the application of perfectly smooth, high-build coatings. These barrier coatings are applied with no defects in one continuous application and serve as abrasion- and impact-resistant protective barriers to corrosion. Furthermore, because they contain no solvent, 100% solids polyurethane coatings are “green” coatings that meet stringent environmental regulations, and most are odor-free, providing a better shipyard application environment than high-solids epoxies.

Surface adhesion, as for all coating applications, is crucial for BWT coatings and has  a significant impact on coating performance. More forgiving coatings that have strong adhesion to the different types of steel used in shipbuilding and the different types of surface conditions that can be present are therefore highly desired for the protection of ballast water tanks. Polyurethanes meet this requirement and generally surpass the adhesion properties of many epoxy systems.

The inherent barrier properties of polyurethane coatings are also excellent. PUs show high resistance to corrosion and chemicals. In addition, they provide superior abrasion and impact resistance, which is not true for epoxies systems. Finally, the very rapid curing of polyurethanes over a wide temperature range makes them suitable for application to water ballast tanks regardless of where they are built or dry-docked and ensures reduced coating times during newbuilding and fast return to service for repair/maintenance operations.

Performance Requirements: PSPC and Invasive Species Control
The IMO PSPC became effective in 2008 and provides specific requirements for the types of corrosion control coatings that can be used on ballast water tanks, as well as appropriate application, inspection and maintenance procedures. Extensive documentation is also specified in the standard. The intent is to have all BWTs coated with systems that will provide a 215-year service life.

Coating systems must be pre-qualified/certified prior to use in ballast water tanks. Certification can be obtained from an approved, independent testing laboratory, through demonstrated performance in the field for a minimum of five years, or by presenting results from previous, relevant tests. Coating application during the newbuilding process must be extensively monitored, and inspections performed at numerous phases. For example, testing of the surface profile and water-soluble salt content are required before application of the first coat, and a thorough inspection of the first coat is necessary before the second coat can be applied. These requirements can slow down the coating process and increase the cost. Consequently, rapid-cure coatings that allow the application of two coatings in a single day are attracting significant attention.

Recent regulations attempting to prevent the spread of invasive species through ballast water must also be considered when installing BWT coatings. There have been several cases of the transport of invasive species around the world, some of which have had severe ecological and/or economic impacts. However, many of the current chemical technologies available for destroying harmful marine organisms in ballast water are based on oxidizing agents (e.g., chlorine dioxide, ozone) that are damaging to the coatings and can lead to corrosion problems. Mechanical systems based on filtration/separation and those that use ultraviolet radiation tend to be less problematic. Therefore, it is crucial that testing of corrosion control coatings for ballast water tanks be performed under maximum treatment conditions for a given application.

A Word about Surface Preparation, Quality Assurance and Maintenance
As with all coatings, surface preparation is critical to the performance of BWT coatings. In fact, lack of proper surface preparation is one of the main causes for coating failures in ballast water tanks. It is imperative that appropriate surface preparation standards (SSPC/NACE/ASTM) be met. Attention should be paid to both surface profile and soluble salt content.

Application conditions must also be considered, as temperature and relative humidity during application can affect the ultimate performance of many coating systems, particularly epoxies. While most large, modern shipyards have enclosed areas for conducting abrasive sand blasting and painting (with temperature and humidity control), some smaller facilities do not. Work is therefore performed under ambient conditions using power tools, which can result in poor surfaces for coating. Polyurethanes offer advantages in these situations, as they have superior adhesion to poor surfaces and temperature and humidity do not impact their curing or ultimate performance properties.

PUs are Good for Potable Water Tanks
The properties of polyurethanes that make them ideal as corrosion protection coatings for ballast water tanks also make them well-suited for use as protective systems for marine potable water tanks. Many polyurethanes meet the requirements of the ANSI (American National Standards Institute)/NSF (National Sanitation Foundation) Standard 61 – Drinking Water System Components, which establishes stringent requirements for the control of leachables and extractables from materials that come in contact with either potable water or products that support the production of potable water.

Conclusion
Preventing corrosion in ballast water tanks is crucial for ensuring the safety and longevity of on marine vessels. While epoxy systems are currently the most common coatings used in this application today, properly formulated, fast-curing polyurethanes are attractive alternatives with significant potential to reduce lengthy coating processes, increase shipyard productivity and thus reduce costs.

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Tank Cleaning: Seeking Common Ground

 

“Tank cleaning is where companies try to establish a competitive edge,” says Ajay Gour, INTERTANKO’s chemicals and vetting expert and Regional Manager for the Indian Sub-Continent, Middle East and Africa. “This is where they can claim to be better than the competition. But the majority of ship operators are all experienced, and the technology and methodology are pretty much the same across the board. Cleaning chemicals have seen some significant advances, but where we found the biggest change was not in cleaning, but in tank testing.”

Testing technology has improved immensely, Gour relates, but operators have not necessarily been the drivers behind improvements. “There are many different external influences, including scientific community, and testing today can measure levels of cleanliness far beyond the original requirements for the same cargoes.”

Ever more sensitive testing methods beg the question: Should tanks be as clean as possible? Or just sufficiently clean?

Lacking a working standard
INTERTANKO studied cases emanating from Houston, a major chemical tanker hub.
“We looked at over 250 different listings,” Ajay Gour recalls. “We found that there were various cleaning standards and varying results for the same cargo with the same end-use. There was evidence that resources were being wasted in over-cleaning, including manpower, energy, time, chemicals, and the resulting emissions were excessive.”

In response, INTERTANKO has proposed a simplified set of standards in order to bring the high-flying cleanliness requirements back down to sea level. “Product manufacturers realize that they have been pushing unduly stringent standards, and they understand that this is a cost driver. In a number of cases, small deviations will not push the cargo off-spec,” Gour maintains.

A working group of chemical tanker operators, owners, charterers, and manufacturers is in the early stages of reviewing existing standards, not for tank cleaning, but for tank cleanliness. “We are not telling anybody how to clean in order to achieve a certain standard,” Gour clarifies, “just advising on what standard they need to clean to.”

Nor do the proposed standards advise on how to test. “For example wall washing,” Gour relates. “It’s been around for a long time, but it has its weaknesses. It gives only a snapshot, not the status of the entire tank.” All the same, INTERTANKO is not singling out wall wash tests, or any other particular method.

“We are simply trying to refine cleanliness standards,” he says, “to make sure they are appropriate for today’s needs. High sensitivity testing is feeding anxiety in cargo owners and charterers, and our intention is to ensure quality while improving efficiency in the use of resources.”

Regarding the timeline for change, Ajay Gour’s advice to owners and operators: Watch this space. “The process is set in motion, and the first draft of new guidelines should be presented by the end of 2016,” he reports. “For this to happen, though, operators, shippers, and cargo buyers must all be on board. The drafting process will be used to quantify the overall benefits, but the end result should be that the goalposts are fixed for everybody.”

Taking the confusion out of tank cleaning
Understanding the required cleanliness standard for your vessels’ next cargo is one thing, but consistently achieving it can be a challenge. With decades of experience in the field, here are some words of wisdom from service leader Wilhelmsen Ships Service (WSS) on how not to go astray in the critical business of keeping tanks and cargoes up to spec.
Regardless of whether it is the result of poor preparation, lack of knowledge, time constraints or inadequate equipment, an unsatisfactory tank cleaning can become very costly, very quickly. Extra time in port, additional labour and chemicals, added surveyor charges, and in the worst cases demurrage claims, can turn what should be a routine exercise into a laborious and dreaded task.

To make matters worse for owners and operators, the issues affecting the tank cleaning process are amplified by the increasingly vigorous ad-hoc cleanliness standards currently being demanded by charterers and cargo owners. Often over-zealous and in many cases totally unnecessary, when it comes to the actual chemistry of contamination, there is unfortunately no officially-defined, universal set of cleanliness standards at present.
Instead, there are just two, very broad and de-facto criteria covering the various tank cleaning requirements currently demanded by charterers.

An inadequate pair
The first is the Water White Standard, which means the tank is visually clean, dry and odour-free. A suitable standard for CPP/vegetable oils, this standard does not involve a wall wash test.

The second, the High Purity Standard (HPE), is required for sensitive cargoes to be loaded such as products applied in food processing (Food Grade) or in pharmaceutical production (USP), where any contamination is unacceptable. All active solvents, such as chlorinated hydrocarbons, glycol ethers, light alcohols, for example, methanol, ketones such as acetone and many hydrocarbons like hexane also require the HPE.

In addition, many chemical companies require the HPE because the application of the product during processing is very sensitive to contamination.

Though there are guidelines on the procedures and typical level of cleanliness required by the High Purity Standard for each and every product available, many companies have additional, off-spec requirements. Creating unwanted confusion for cleaning crews and posing considerable problems when it comes to demurrage claims, these ad-hoc requirements are why bodies such as Intertanko are eager to establish a new, detailed set of cleaning standards. An ongoing initiative aimed at creating an industry wide set of rules, its acceptance is by no means guaranteed. So, for now we’re stuck with the existing pair of standards and the numerous company-by-company and cargo-by-cargo variations demanded by charterers.

In spite of this, with detailed planning, preparation and access to some basic information on the cargo’s properties and the conditions inside and outside the tanks, tank cleaning should actually become a matter of routine. Systematic, efficient and completed quickly to the required standard, whatever that may be. No rejections, hold-ups, incidents or accidents.

Chemistry 101
Knowing the properties of the products you’re discharging and loading, along with understanding how they interact with each other and with the surface of your tanks is obviously key. However, learning this from scratch can seem a daunting prospect, hence the ongoing success of Supercargo specialists. But in practice, the vast majority of commercially traded cargoes and their associated tank cleaning processes can comfortably be managed in-house with access to a specific cargo-handling database, such as Miracle or Milbros, and just a little basic knowledge on the major product groups, as outlined below.

Water-soluble or water-miscible
Water-Soluble substances and water-miscible substances are easy to clean with water. In addition, the solubility of such substances might increase at higher temperatures. While the use of a cleaning agent is not required, it can help reduce cleaning times.

High melting point
Such products should be washed at a temperature of 15-20C above melting point. During washing there should be no ballast water or cold cargoes adjacent to the tank to be cleaned. Special attention must also be given to liquid and vapor line systems to avoid freezing/solidification at cold line segments. Beginning the tank cleaning process as soon as possible after discharge is strongly recommended.

High viscosity
These products should be washed at higher temperatures. In general the viscosity is closely related to the temperature and will decrease at higher temperatures. During washing there should be no ballast water or cold cargoes adjacent to the tank to be cleaned. As with products with a high melting point, washing should begin as soon as possible after discharge.

High vapor pressure/boiling point
Products with a high vapor pressure (higher than some 50 mbar at 20 C) can actually be removed from the tank by evaporation. As always, during ventilation, special care must be taken to prevent the risk of explosion (flammable products) and emissions (toxic vapors).

Polymerization
The initial wash of products that tend to polymerize should be carried out with cold (ambient) water. Washing with hot water results in polimeric residues being left in tanks and lines, meaning an incredibly difficult clean-up job.

Evaporation of volatile substances
Cargoes consisting of mixtures with different vapor pressures should neither be cleaned by evaporation, nor prewashed hot. The evaporation of the light substances from a mixture could result in non-volatile residues, which are very difficult to remove.

Isocynates
Must never come into contact with water, not even the residues, because the reaction product and insoluble urethane (plus CO2) are very difficult to remove. Such products must be washed with a suitable solvent that does not contain any water.

Reaction with oxygen
Drying and semi-drying vegetable and animal oils react with oxygen to form a varnish-like polymeric film. This is very difficult to remove from bulkheads. Since heat increases the speed of the reaction the initial washing of these products must be done with water at ambient temperature, and as quickly as possible.

Reaction with hard water
Formed by the calcium and magnesium present, seawater, for example, has a very high water hardness. This poses no problem for most products, but fatty acids and vegetable oils with a high free fatty acid content will form white sticky residues if they are cleaned with a water of a high water hardness.

Smell
Minor residues of a smell-producing cargo left in lines, valves and pumps (including pump cofferdams) can contaminate a sensitive cargo. To neutralise the smell of some chemicals (e.g. Acrylate, Nitrobenzene or Pygas) the use of a smell killer may be recommended.

Understanding the conditions. Inside and out
Along with product knowledge, an understanding of just how the conditions in and outside tanks can affect a cleaning job is vital for consistently successful cleaning:

The neighboring areas
Temperature is one of the major parameters in any tank cleaning procedure and it must be monitored and managed carefully. The temperature in the cargo tank can be significantly influenced by the surrounding conditions, including outside temperature, seawater temperature, ballast conditions, and the temperature of adjacent cargoes.

Deviations from the desired operating temperature can affect the entire tank or just parts of the tank, typically around bulkheads, tank bottoms or tank walls. Two common results are freezing due to lower than allowed temperature, and polymerization/drying due to higher than allowed temperature.

The Tank Surface
Having managed the surrounding conditions, focus should turn to the surface of the tanks. Their composition and condition can have significant implications for the cleaning process.

Stainless steel
Corrosion can occur if there is surface contamination. Both pickling and passivation are chemical treatments applied to the surface of stainless steel to remove contaminants and assist the formation of a continuous, passive chromium oxide film. Pickling and passivation are both acid treatments and neither will remove grease or oil. If the steel is dirty, it may be necessary to use a detergent or alkaline cleaning before pickling or passivation.

Zinc silicate coating
An anti-corrosive paint system made from zinc dust, with certain additives and a binder. The high levels of zinc dust produce a zinc-zinc metal contact resulting in cathodic protection, similar to that obtained from galvanizing. However, zinc coatings are inherently porous, presenting a variety of cleaning problems. It is believed that the cargo migrates into the pores and capillaries, similar to fluid adsorption processes. Zinc coatings have a good resistance against solvents, but are not resistant to strong acids and bases.

Epoxy coatings
Pure epoxy, phenolic epoxy and isocyanate epoxy form cross linkages resulting in relatively good resistance to a greater range of cargoes. Epoxy systems are usually resistant to some weak acids and strong alkalis and do not absorb oil-like substances. Epoxy coatings are, however, prone to absorbing some solvent-like cargoes. This absorption is caused by swelling and subsequent softening of the coating. After transporting aggressive cargoes, the coated tank has to be ventilated until the cargo has been desorbed (released) from the coating film, which results in hardening and decreased swelling. This can take up to several days, depending on the type of cargo, type of coating and film thickness. Water may not be used for cleaning until this ventilation process is finalized. Otherwise the water can lead to blistering and subsequent serious damage of the coating. The more solvency power a cargo has, the more cargo residues could still be present in the coating. This could lead to either contamination of the next or subsequent cargoes, or breakdown of the coating film.

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DNV GL and Hempel cooperate on performance analytics

The agreement is based on the use of DNV GL’s ECO Insight portal.

Torsten Büssow, Head of Fleet Performance Management at DNV GL, says that ECO Insight’s state of the art hull degradation analytics will not give Hempel customers transparent and verified data with only a few simple measurement inputs while giving Hempel access to advanced analytics for the further optimization of its coatings.

“We’ve already seen the benefits our customers have gained from having real fleet performance analytics easily available – especially in the area of hull and propeller performance – and we’d like to welcome Hempel customers to the ECO Insight family,” says Mr. Büssow.

The potential for improvements in hull and propeller performance on the energy efficiency of vessels is significant, with estimates of potential savings in the range of ten percent in terms of fuel and greenhouse gas emissions savings.

ECO Insight can offer better performance baselines and demonstrate a more explicit relationship between hull and propeller performance and the actual fuel consumed. This allows customers who have invested in Hempel’s coatings the ability to better quantify the value of their investment.

“At Hempel we place great importance in being close to our customers and providing the best individual service,” says Christian Ottosen, Group Vice President Marine Marketing, Hempel. “With the data analyzed by DNV GL, we will be able to optimize our customers’ fuel performance, improving hull performance matching specifications precisely to individual needs and trade, dry dock intervals and technical service in dock. This will benefit our customers and support their businesses being more efficient in their operations. So far, we have been very pleased to cooperate with DNV GL, and we look forward to working even more closely with their staff from now on.”

With one of the most sophisticated analysis methodologies for hull and propeller performance on the market, ECO Insight uses advanced normalization algorithms to increase the accuracy of its analysis and is able to benchmark a vessel’s performance relative to other similar vessels. Additionally, by tapping into additional ship specific data (beyond what is used to calculate performance) ECO Insight’s analytics can be used to further customize paint specifications up front and to proactively manage performance once the ship enters service.

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Get Green Financing

October 13, 2015 — Liberian Registry, EfficientShip Finance launch Eco-Upgrade Financing Initiative (Extended coverage from Marine Log’s October 2015 issue). To remain competitive with the new generation of Eco-ships, ship owners of

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Hempel launches Hempadur Quattro XO

MARCH 11, 2015 — Coatings manufacturer Hempel today launched  Hempadur Quattro XO – a high performance range of pure epoxy PSPC (IMO Performance Standard for Protective Coatings) compliant coatings for marine newbuildings.

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Carnival Corporation reports big fuel savings

OCTOBER 2, 2014 — Carnival Corporation & plc (NYSE/LSE: CCL; NYSE: CUK) says that, across its nine cruise lines, by the end of 2014 its multi-year Fleet Fuel Conservation Program will have

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Software tracks vessel fouling risk

APRIL 4, 2014 — International Paint Ltd, Felling, U.K., has developed Intertrac. It is claimed to be the shipping industry’s first, patented applied for software system that enables shipowners and operators to

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Jotun launches new antifouling at Cruise Shipping Miami

MARCH 12, 2013 — Jotun AS is now offering SeaLion Resilient, a high performance marine antifouling coating based on epoxy-polysiloxane technology. Epoxy-polysiloxane, a compound of resins and hardeners, provides highly resilient hull

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NSRP to fund 12 new shipbuilding R&D projects

OCTOBER 1, 2012 —The Executive Control Board of the National Shipbuilding Research Project (NSRP) has selected 12 new R&D projects as part of the program’s core mission to reduce the costs associated