Technical

Bulletin
Issue No. 103 Oct – Dec 2014

CONTENTS

• Waterproofing Invention ticks all the boxes for Sustainability

• Water-based Temporary Coating for Corrosion Protection

• Blue Resins turn Clear on exposure to UV

• Short Term Scratch Fix New from Spies Hecker

• DTM Acrylic Polyol for 2k Polyurethane Coatings

• The Next Step in Wood Coatings

• A Coating that Protects against Heat and Oxidation

• Novel Inexpensive Hydrolysable Polymer

• New Material makes Water and Oil Roll Off

• Efficient Method to produce Nanoporous Metals

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WATERPROOFING INVENTION TICKS ALL THE BOXES FOR SUSTAINABILITY

Researchers from Australia's Queensland University of Technology have developed waterproof coating
for boxes that is both recyclable and renewable.Albert Tietz and Adjunct Associate Professor Les
Edye's lignin-based coating is currently being trialled on fruit boxes in North Queensland's banana
belt. If successful, they anticipate the product will be on the market in mid-2015.

Professor Edye said lignin is a naturally occurring by-product from pulped wood and grasses. "We
discovered the potential of lignin as a waterproof coating while researching ways to add value to
bagasse in the sugar industry," Professor Edye said. "After some investigation and research, we're now
using lignin extracted from a commercially-grown and processed grass. "What's most exciting is that
our lignin barrier coating is sustainable - traditional wax coatings are made from petrochemicals and,
once it's on the paper or cardboard, that paper or cardboard can no longer be recycled. "We've proven
that our lignin coating is cost-comparable, is 100% recyclable, provides a high level of waterproofing
and strengthens the boxes to a higher degree than wax - not bad for a product made from a
renewable resource." Professor Edye said around four hundred thousand tonnes of wax-coated
cardboard is added to landfill in Australia every year because it cannot be recycled. QUT's innovation
arm, qutbluebox, has been working closely with the researchers for two years, providing more than
$250,000 in proof-of-concept funding to develop and scale the coating for industry.

Asia Pacific Coatings Journal, December 2014, Pg. 6

WATER-BASED TEMPORARY COATING FOR CORROSION PROTECTION

Cortec has launched VpCI-389, an environmentally friendly water-based, temporary coating that
delivers exceptional multimetal protection for outside applications and salt-spray resistance. This
contemporary coating is an advanced, safe replacement for hazardous oil-based products. An
excellent choice for long-term indoor protection, that lasts up to five years and short to medium-term
(6-24 months) unsheltered outdoor protection.

This safe and easy to use coating cures to a soft film and eventually hardens. It is efficient in SO2 and
H2S environments. The product leaves a translucent, waxy coating that is easily removable, it is low
in VOCs and dilutable with water. VpCI-389 can be easily removed with alkaline cleaners, such as
Cortec VpCI-414.

Asia Pacific Coatings Journal, December 2014, Pg. 8

BLUE RESINS TURN CLEAR ON EXPOSURE TO UV

UV-cured field-applied floor coatings give high performance and are quick to apply and cure; but their
high clarity makes it challenging to differentiate between the cured and uncured portions of the
floor. Two new resins from Allnex solve this by appearing blue when first applied, then becoming
clear on exposure to UV. This makes it easy to ensure that both the coating and the UV are applied
evenly. “Ucecoat 7892” is a water-based UV polyurethane dispersion with a good balance of flexibility
and hardness, making it suitable for wood coating applications. “Ebecryl 894” is a low-viscosity 100%
solid polyester acrylate resin for concrete and vinyl composite floor coatings, giving good weathering
resistance, high gloss and fast cure rates.

European Coatings Journal, November 2014, Pg. 40

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SHORT TERM SCRATCH FIX NEW FROM SPIES HECKER

Spies Hecker has introduced a quick remedy for small scratches that bodyshops can use. Called
Stick'n'Go! this paint 'plaster' offers bodyshop customers short-term protection for small paint defects.

Stick'n'Go! works when a special adhesive film is sprayed at the same time as the repaired part, and
with the same high-quality, original Spies Hecker basecoat colour and clear coat. When returning the
refinished vehicle to its owner, the bodyshop then gives the customer the paint plaster. When the
next small scratch or defect occurs, vehicle owners simply have to cut the film to the right size and
shape. Stick’n’Go! comes in a special mirror hanger, with full instructions on how to use it, that is
hooked onto the vehicle’s rear view mirror. After covering the defect with the paint plaster, vehicle
owners should wait no longer than three months to bring the vehicle into the bodyshop to have it
repaired professionally. “Stick ’n’ Go! offers vehicle owners the option to carry out short-term small
cosmetic repairs to their vehicles, giving them the time to take their vehicle to the bodyshop of their
choice,” Hinz explains.

Surface Coatings International, December 2014, Pg. 283

DTM ACRYLIC POLYOL FOR 2K POLYURETHANE COATINGS

Acrylic polyols are typically used in the 2K polyurethane vehicle refinish primers because of their fast
cure and hardness development. They usually cure well so that it can be sanded in about two hours.
However depending on the substrate the adhesion of the 2K acrylic polyurethane system to metal can
be a problem. To overcome this issue an etch-primer is typically applied on the metal before the
application of the acrylic primer. Coatings applicators are under constant pressure to reduce cost and
improve their throughput; therefore any elimination of an application step is beneficial.

To overcome this issue, a novel acrylic polyol that provides excellent adhesion to various metal
substrates was developed. Clear and pigmented 2K polyurethane coatings were prepared using a novel
acrylic polyol and evaluated as direct-to-metal (DTM) vehicle refinish coatings over various
substrates. The effect of solvents and their blends, the role of additives and pigments in the
formulation and the adhesion characteristics of the coating with different substrates was studied.
Typically for vehicle refinish (VR) primer applications, the Tg of the resins lies between 25 and 70° C.
A high Tg helps the sanding characteristics. APO-5 and APO-6 are traditional acrylic polyols used in
refinish primer applications. The acrylic polymer backbone was modified to develop the novel DTM
acrylic polyol (APO-9). Acid values, which play a major role in adhesion to metal, were comparable in
the set of resins tested. Also, the hydroxyl equivalent weight which is also important for the crosslink
density, and thereby affects permeability, was kept constant. For screening purposes and to focus on
the adhesive properties of the resin alone, the adhesion was tested using an unpigmented formula. No
surface tension or flow modifiers were used, in order to avoid their possible influence on adhesive
properties of the resins. The dry and wet adhesion to various metal substrates of unpigmented clear
coat formulations based on the new polyol was found to be superior to that of two conventional
acrylic resins.

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A formulated DTM primer was tested against two commercial refinish urethane based primers. All
were evaluated over cold rolled steel with and without etch primer and tested for adhesion, corrosion
and humidity resistance. The DTM primer using the novel acrylic polyol gave excellent performance in
corrosion and humidity tests without etch (wash) primer. It shows that by using the novel DTM acrylic
polyol one can eliminate a layer of paint. This helps the paint formulator to reduce VOCs and
generate cost savings by eliminating the etch primer layer without sacrificing performance.

European Coatings Journal, November 2014, Pg. 28

THE NEXT STEP IN WOOD COATINGS

Evonik has developed a new and versatile product family of crosslinkers/binders for high performance
wood coatings. The innovative approach combines the benefits of silane chemistry with the
performance of polyurethanes enabling excellent scratch resistance, while maintaining urethane
properties in coatings. 3-Isocyanatopropyltrimethoxysilane (IPMS) is the core building block of the
novel technology platform and responsible for a high freedom of design creating tailor-made binders
and crosslinkers.

The resin concept also enables non-isocyanate (NISO) technology exhibiting and exceeding
polyurethane performance. This technology can be realised generally in one and two component
coating formulations. Modern aliphatic 2K-polyurethane wood coatings are considered as today’s
benchmark to environmental etch, durability and are, in general, well-known for their excellent
balance of flexibility and hardness. Furthermore, superb overall properties and good adhesion to
wooden substrates are advantages, which helped the technology to set the benchmark in the wood
coating industry in the last decades. Here, especially the multilayer coatings, which are easy to use
with their universal use in sanding or filling primer and top coat.

Fig.1 - IPMS-based silane/urethane-hybrid crosslinker, containing urethane groups,

terminated by tri-functional alkoxy-silane structures

An appropriate way to gain reliable enhancements, in matters of increasing scratch resistance of clear
coats and to satisfy the market needs and trends concerning a further integration of functions, is
ensured by the use of silane/urethanehybrid crosslinkers. As shown in Fig. 1, IPMS can be reacted
with any kind of (isocyanate) reactive groups (R-group) preferably with hydroxyl groups of diols,
polyols or oligomeric diols to build an alkoxy-silane functional urethane linked nonisocyanate (NISO)
crosslinker/binder. The choice of R-group will primarily determine the properties of the crosslinker or
binder and, hence, will also influence significantly the attributes of the coating. For example the
longer the backbone of the crosslinker or binder the more it acts as a flexibiliser in the coating. In
contrast a branched and short R-group will result in a higher hardness.

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The Vestanat EP-M range is a family of silane/urethanehybrid crosslinkers to generate multifunctional,
scratch resistant coatings applicable on a variety of substrates. Due to specific modifications curing
even at ambient temperature is possible. These crosslinkers and binders can be used in several
application fields, ie also beyond wood coatings. This technology enables high performance NISO-
coatings even exceeding PUR performance. But also ‘traditional’ 2K-PUR coatings can be improved
significantly in scratch resistance by substitution of the isocyanate hardener.

Polymer Paint Colour Journal, October 2014, Pg. 24

A COATING THAT PROTECTS AGAINST HEAT AND OXIDATION

Researchers have developed a coating technique that they plan to use to protect turbine engine and
waste incinerator components against heat and oxidation. A topcoat from micro-scaled hollow
aluminium oxide spheres provides heat insulation, in the lab, already proved more economical than
conventional techniques.

Fig. Hollow spheres of aluminum oxide are filled with gas.

Gases don't conduct heat as well as solids do. Cellular or aerated concretes take advantage of this
effect, which experts call "gas-phase insulation." The heat barrier is achieved by air encased in the
cavities of the concrete. But gas-phase insulation has far greater potential than keeping our homes
warm. It can also be used to protect turbine engine and waste incinerator components when
subjected to intense heat. All you need to do is transfer this effect to a coating that is just a few
hundred micrometers thick.

Scientists at the Fraunhofer Institute for Chemical Technology ICT in Pfinztal have not only done just
that, they've also done it in a particularly economical way. They've designed a coating that consists of
an outer topcoat from conjoined aluminium oxide spheres. "These spheres are hollow and filled with
gas," explains coatings expert Dr. Vladislav Kolarik from the ICT's Energetic Systems department.
When the outer side of a part is exposed to temperatures of 1000 degrees Celsius, these gas-filled
spheres reduce temperatures on the part's inner side to under 600 degrees Celsius -- as the ICT
scientists have demonstrated in their laboratories. Since gas and steam turbines used for energy
generation, combustion chambers, waste incinerator generators and temperature sensors, and
reactors in the chemical and petrochemical industries are all subjected to temperatures of up to 1000
degrees Celsius, there is considerable demand of thermal protection.

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What's most remarkable is that the heat insulating layer from hollow aluminium oxide spheres is
obtained on the basis of a conventional, economic process. Operators only have to do some simple
math to see the benefits: conventional thermal barrier techniques -- most of which are based on
ceramic materials -- are expensive. The process the scientists adapted was originally designed to
protect metallic components from oxidation. "We've optimized the technique so that the coat not only
retains its oxidation protection, but furthermore protects against heat," says Dr. Kolarik.

The basic coating layer forms by interaction of aluminum particles and the metallic component. This
is done by depositing aluminum powder on the surface of the metal and heating it all up to a suitable
temperature over several hours. The result is an aluminum-rich coating on the component's surface
that protects against oxidation at high temperature. With the new procedure the topcoat from the
hollow aluminum oxide spheres is additionally formed. "Up to now, it never occurred to anyone to use
these spheres to produce another coating layer -- they were just a waste product," says Dr. Kolarik.
Now the scientists have refined the process so they can produce both coating layers in the required
thickness. The way it works is to take aluminum particles and mix them with a viscous liquid bonding
agent. This produces a substance similar to a paint or slurry, which the scientists then manually paint,
spray or brush onto the metallic component. "All that's left is to add a fair bit of heat," says Dr.
Kolarik. But it's all easier said than done: Dr. Kolarik and his team have had to precisely fine tune the
size and size distribution of the aluminum particles, the temperature and duration of the heating
stage and the viscosity of bonding agents. "Just like a master chef, the first job was to come up with a
winning recipe."

"We're currently in the process of putting the findings from the EU-funded PARTICOAT project into
practice. This involves coating bigger and bigger components without exceeding the temperature
limits for each application area. At the same time we're trying out techniques to automate the whole
coating process. Our plan is to follow in the footsteps of the aerated concrete that helps insulate our
homes -- that's been in series production for a long time now," says Dr. Kolarik.

http://www.sciencedaily.com/releases/2014/11/141121082905.htm

NOVEL INEXPENSIVE HYDROLYSABLE POLYMER

Researchers at the University of Illinois at Urbana-Champaign have figured out how to reverse the
characteristics of a key bonding material -- polyurea -- providing an inexpensive alternative for a
broad number of applications, such as drug delivery, tissue engineering, and packaging.

"Polymers with transient stability in aqueous solution, also known as hydrolyzable polymers, have
been applied in many biomedical applications, such as in the design of drug delivery systems,
scaffolds for tissue regeneration, surgical sutures, and transient medical devices and implants,"
explained Jianjun Cheng, an associate professor of materials science and engineering at Illinois.
"Polyurea materials are widely used in our daily life as coating, painting, and adhesive materials. The
highly inert urea bond makes the inexpensive polymer extremely stable, a property that is suitable for
some long-lasting applications."

Fig. Hindered urea bond-containing polymeric materials (PHUs)

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Through some inventive chemistry, Cheng and his colleagues have developed a class of "hindered urea
bond-containing polymeric materials" or "poly(hindered urea)s" (PHUs) -- cheap polymers that can be
designed to degrade over a specified time period, making them potentially useful in biomedical and
agricultural applications.

"While conventional polyurea are very stable against hydrolysis, PHUs can be completely hydrolyzed
within a few days," Cheng added. "Since 'hindrance' is the cause of the bond destabilization, the
hydrolysis kinetics of PHUs can be easily tuned as needed for a specific application. They can
potentially be environmentally friendly green and sustainable materials as well."

"Polyurea usually contain ester and other hydrolyzable bonds, such as anhydride, acetal, ketal, or
imine, in their backbone structures," said Hanze Ying, a graduate student in Cheng's research group
and first author of the paper published in the Journal of American Chemical Society. "In this study, we
demonstrated the potential of PHUs for the design of water degradable polymeric materials that can
be easily synthesized by mixing multifunctional bulky amines and isocyanates, expanding the family of
hydrolyzable polymers."

"Hydrolyzable polymers have also been applied in the design of controlled release systems in
agriculture and food industries and used as degradable, environmentally friendly plastics and
packaging materials," Cheng said. "These applications usually require short functioning time, complete
degradation and clearance of materials after their use."
According to the researchers, the new PHUs potentially have great advantages over many other
hydrolyzable polymers. PHUs can be made with inexpensive chemical precursors in ambient conditions
via simple and clean chemistry with no catalyst or by-products, making it possible for end-users to
control the copolymer recipe for specific use without the need of complicated synthesis apparatus.

http://www.sciencedaily.com/releases/2014/12/141202123850.htm

NEW MATERIAL MAKES WATER AND OIL ROLL OFF

Car finish, to which no dirt particles adhere, house fronts, from which graffiti paints roll off, and
shoes that remain clean on muddy paths - the material "fluoropore" might make all this possible. Both
water and oil droplets roll off this new class of highly fluorinated super-repellent polymers. The
Federal Ministry of Education and Research (BMBF) has now decided to fund its further development
at the KIT with EUR 2.85 million. Fundamental research in this area is aimed among others at making
use of this new type of material for universal protective coatings.

The phenomenon is known from lotus plants as well as from cabbage leaves: Water droplets simply
roll off. For some time, this classical lotus effect has been used technically for producing rough
surfaces with special chemical properties. "However, this trick does not work for oils - the lotus plant
repels water, but no oil," Dr.-Ing. Bastian Rapp of the KIT Institute of Microstructure Technology (IMT)
says. "Oil-repellent surfaces need to have another chemical structure, fluoropolymers are required for
this purpose," the scientist explains. Fluoropolymers are high-performance plastics with a high heat
resistance and chemical stability. Teflon, the known anti-stick coating material for frying pans,
belongs to this category of substances.

"When combining the chemical properties of fluoropolymers with the roughness of the lotus plant,
surfaces are obtained, from which both water and oil droplets will roll off," Rapp says. He has already
succeeded in producing such super-repellent surfaces with the lotus 2.0 effect in the laboratory. In
practical use, however, they turned out to have an insufficient stability. A big problem is sensitivity
to abrasion. Rapp therefore works on developing a new class of fluorinated polymers, from which
water and oil roll off and which are far more robust in practical application. These polymers, called
"fluoropore," are to possess the lotus 2.0 effect on nearly any surfaces.

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The research project of the young KIT scientist was recently successful in the NanoMatFutur
competition for young scientists launched by the Federal Ministry of Education and Research (BMBF).
Rapp's project "Fluoropore - chemically inert, micro- to nanoporous 'teflon' with an adjustable wetting
behavior" is granted EUR 2.85 million for the establishment of a young investigator group in the next
four years. By the NanoMatFutur competition, the BMBF supports highly qualified young scientists in
the areas of materials research and nanotechnology. Funds are granted to application-oriented
fundamental research projects with a high industrial implementation potential.

With "fluoropore," universal protective coatings against any type of staining can be produced. An
example is a coating of car window panes to prevent water from condensing and freezing in winter.
Other examples are fine-pore screens, whose chemistry and structure allow for the separation of
oil/water mixtures used as cooling lubricants in processing industry.

In the young investigator group headed by mechanical engineer Rapp, chemical process engineers and
experts of organic chemistry, materials chemistry, and process technology work on the development
of the new material. "At the KIT Institute of Microstructure Technology and its Karlsruhe Nano Micro
Facility, we can use a large variety of analysis and structurization methods for our work, for example,
scanning force and scanning electron microscopes," Rapp emphasizes.
http://www.sciencedaily.com/releases/2014/11/141128080652.htm

EFFICIENT METHOD TO PRODUCE NANOPOROUS METALS

Nanoporous metals -- foam-like materials that have some degree of air vacuum in their structure --
have a wide range of applications because of their superior qualities.

They possess a high surface area for better electron transfer, which can lead to the improved
performance of an electrode in an electric double capacitor or battery. Nanoporous metals offer an
increased number of available sites for the adsorption of analytes, a highly desirable feature for
sensors. Lawrence Livermore National Laboratory (LLNL) and the Swiss Federal Institute of Technology
(ETH) researchers have developed a cost-effective and more efficient way to manufacture nanoporous
metals over many scales, from nanoscale to macroscale, which is visible to the naked eye.

The process begins with a four-inch silicon wafer. A coating of metal is added and sputtered across
the wafer. Gold, silver and aluminum were used for this research project. However, the
manufacturing process is not limited to these metals. Next, a mixture of two polymers is added to the
metal substrate to create patterns, a process known as diblock copolymer lithography (BCP). The
pattern is transformed in a single polymer mask with nanometer-size features. Last, a technique
known as anisotropic ion beam milling (IBM) is used to etch through the mask to make an array of
holes, creating the nanoporous metal. During the fabrication process, the roughness of the metal is
continuously examined to ensure that the finished product has good porosity, which is key to creating
the unique properties that make nanoporous materials work. The rougher the metal is, the less evenly
porous it becomes.

"During fabrication, our team achieved 92 percent pore coverage with 99 percent uniformity over a 4-
in silicon wafer, which means the metal was smooth and evenly porous," said Tiziana Bond, an LLNL
engineer who is a member of the joint research team.

The team has defined a metric -- based on a parametrized correlation between BCP pore coverage
and metal surface roughness -- by which the fabrication of nanoporous metals should be stopped when
uneven porosity is the known outcome, saving processing time and costs.

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"The real breakthrough is that we created a new technique to manufacture nanoporous metals that is
cheap and can be done over many scales avoiding the lift-off technique to remove metals, with real-
time quality control," Bond said. "These metals open the application space to areas such as energy
harvesting, sensing and electrochemical studies."

The lift-off technique is a method of patterning target materials on the surface of a substrate by using
a sacrificial material. One of the biggest problems with this technique is that the metal layer cannot
be peeled off uniformly (or at all) at the nanoscale. The research team's findings were reported in an
article titled "Manufacturing over many scales: High fidelity macroscale coverage of nanoporous metal
arrays via lift-off-free nanofrabication." It was the cover story in a recent issue of Advanced Materials
Interfaces. Other applications of nanoporous metals include supporting the development of new
metamaterials (engineered materials) for radiation-enhanced filtering and manipulation, including
deep ultraviolet light. These applications are possible because nanoporous materials facilitate
anomalous enhancement of transmitted (or reflected) light through the tunneling of surface
plasmons, a feature widely usable by light-emitting devices, plasmonic lithography, refractive-index-
based sensing and all-optical switching.

http://www.sciencedaily.com/releases/2014/11/141125154731.htm

A Quarterly Information Service – Compiled by Library, R&T Centre, Turbhe