Table of Contents May 2020

3 When Corrosion’s A
Threat, Coatings Protect
PPG Industries, Inc.

5 The Industrial
Coatings Market
Kerry Pianoforte, Editor

8 The Marine
Coatings Market
Anthony Locicero, Associate Editor

11 Polymer Modification
with Reactive Silicones
Bob Ruckle, Tom-Seung Cheung

20 3D Printing Is
On The Rise
David Savastano, Editor

When Corrosion’s A Threat,
COATINGS PROTECT
PPG Industries, Inc.
W
ork trucks are subjected to harsh conditions: high-
way debris, chemicals and salts on icy roadways,
water, dirt and dust, not to mention the dings and
dents of everyday encounters. The resulting chips, scratches and
accumulated dirt and water damage can lead to corrosion and
overall deterioration that compromise truck components and
ultimately cut lifespan. Whether they’re the huge semis criss-
crossing the country or the pickups on the job at construction
sites, trucks are built to withstand the conditions they face—up
to a point. There are effective ways to address the impacts of the
working world, and savvy truck owners know that protective
commercial coatings can help safeguard their investment and
prolong a truck’s working years.
Corrosion
Frequently referred to as galvanic corrosion, rust costs American
businesses an estimated $276 billion annually to repair the dam-
age it causes. Of that, $50 billion is spent by the transportation
industry on vehicle repair/replacement and infrastructure.
“It’s all about economics,” said Scott Colvin, PPG brand
manager, commercial transport. “A working truck generates
revenue and profits. A truck sidelined for rust repairs pro-
duces nothing.
Once rust starts, it can’t be completely eliminated without
May 2020 ­www.coatingsworld.com Coatings World | 3
Feature Name FEATURE
replacing the parts it’s affected. The trick is to prevent it in
the first place.”
Rust occurs when dissimilar metals are in contact with
each other and exposed to an electrolyte. Here’s how rust
comes about:
1. Using dissimilar metals. . .
Every metal has corrosion potential, or anodic index rat-
ing. The further apart the two different metals are indexed,
the faster the rate of rust.
2. That are in contact . . .
The two metals must be touching for corrosion to occur.
With trucks, its hinges, steps, doorframes, mounting brack-
ets and fasteners often have different metals in contact.
3. And exposed to an electrolyte.
The electrolyte (water or road salt) serves as an electrically
conductive material that transfers corrosion from the more
resistant metal to the weaker one. The most destructive elec-
trolytes are road deicers because they’re excellent conductors
and readily attack truck undercarriages and bodies.
Modern manufacturing all but dictates the use of differ-
ent metals; however, conditions that promote corrosion can
still be reduced. A liquid or solid barrier, e.g., polyethylene
tape, synthetic fasteners, nylon washers and other inserts,
can eliminate or insulate metal-to-metal contact. The barrier
FEATURE When Corrosion’s A Threat, Coatings Protect
also prevents electrolytes from reaching metals and slows
corrosion.
The corrosion process develops slowly, sometimes unseen
and unnoticed until it’s too late. According to Colvin, pre-
vention is critical. Corrosion damage can’t be reversed; you
need to stop it before it starts.
Truck Protection
Rust protection begins with the selection of primers and top-
coats used in truck assembly.
“Truck protection should begin with the build,” Colvin
explained. “Top quality paints provide the fundamentals of
corrosion resistance. Advanced coatings can also help pre-
pare a truck for the working world. Most quality-focused
truck body builders apply a heavy-duty protective coat
during the assembly process. That primary layer provides
a cost-effective barrier between substrate metals and elec-
trolytes and against road debris, abrasives, chemicals and
other types of abuse.”
When ordering a truck body, a variety of primer options
is available; the chemistry of each affects its anticorrosion
strength. Zinc-rich epoxies offer premium protection as
part of a three-coat system that includes epoxy or urethane
primers and topcoats. Epoxy primers present adhesion and
corrosion properties that frequently make them the leading
option for the mid-coat application in a three-coat system.
Polyurethane primers are used in some applications for fast
cure speed and smooth appearance. Climate, humidity, rain,
snow and expected service life can influence primer choice.
Coatings manufacturers, including PPG, recommend select-
ing primers on the basis of performance expectations (ver-
sus cost), since performance is critical to longevity.
While topcoats are generally linked to color, gloss and
vibrancy, they play an essential role in corrosion protection
by guarding primers from deterioration. They serve as the
first line of corrosion defense by slowing down the impact
of water and road salts.
“Technologies are always advancing,” added Colvin.
“At PPG, we have new DTM (direct to metal) topcoats that
provide protection with just one layer and robust universal
primers that are appropriate for multiple substrates — steel,
aluminum, stainless steel.”
Colvin noted that some of today’s post-assembly premium
coatings are based on advanced aliphatic polyurea technology
that provides an increased level of protection over previous
formulas. Coatings of this type offer ideal protection for a
truck’s exterior high-use work areas such as running boards,
steps, truck beds and storage cabinets. “Aliphatic polyurea
is the best in polyurea coatings,” he explained. “The coating
is sprayed on and gives a truck body and chassis exception-
al resistance to corrosive elements. There are several prod-
ucts on the market using this technology. The PPG product,
DURABULL® Extreme Duty Protective Coating, is a particu-
larly robust application. The coating is also extremely color
stable and displays excellent UV weathering characteristics.”
4 | Coatings World ­www.coatingsworld.com May 2020
An aliphatic polyurea layer dries in minutes after ap-
plication, provides superhard impact and crack resistance
and can last up to 10 years. It can also be tinted to match
a company’s color scheme. Mainly applied at the assembly
stage, aliphatic polyurea coatings can also be sprayed onto
vehicles already in use.
ECK® compound, a corrosion resistant coating from
Van Nay LLC is another effective option. This compound
is intended for use in a broad range of body-building and
manufacturing applications in which dissimilar metals may
come in contact with each other. ECK is based on electroly-
sis corrosion control, serving as a barrier against galvanic
corrosion. It resists all types of corrosion, including those
resulting from magnesium-chloride and calcium-chloride
salt residue on roadways. These compounds are generally
safe for painted and unpainted surfaces, can withstand tem-
peratures to 1,000 degrees Fahrenheit and suitable for use
on rubber and plastic. The coating replaces anti-seize, di-
electric-grease and Mylar tape products. Petroleum-based,
it contains no silicone and won’t dry or wash off. When
protected from rust, bolts and fasteners function properly.
Protection doesn’t stop with the body. Shielding the
undercarriage is a lso critical. For that, a heavy-duty, wa-
ter-based layer, such as PPG’s CORASHIELD® anti-chip
coating or other similar product, can be highly effective.
The product can be sprayed, rolled or brushed under wheel
wells and on adjacent areas during assembly or after a truck
has been in service. A heavy coating guards against the con-
stant threat of damage that road debris poses, weakened
parts and deterioration.
Stay Alert
Blistering paint, rough spots, cracking or lifting and peeling of
a truck’s finish may indicate corrosion. Colvin recommends a
comprehensive approach that covers almost the entire vehicle
with a variety of coatings. “PPG’s commercial coatings, for ex-
ample, fight corrosion on all surfaces,” he said. “Since individual
trucks and fleets have different requirements, the best way to
determine what you need is to ask your coating representative
for a corrosion audit. The audit will help you find your most
cost-effective solution.”
Colvin offered one other important piece of advice: Wash
your truck—frequently. The best protective measures can be
compromised if a truck isn’t washed regularly. Washing of-
ten, including spraying the undercarriage, helps remove salt
and dirt, and reduces the chances of corrosion.
“We understand that truck owners want greater durabil-
ity and productivity from their trucks.” summarized Colvin.
“The cost of protective coatings depends on the products,
but that cost is always going to be less expensive than a re-
placement truck or major repairs. Don’t think of protective
coatings as an expense; they’re an important investment in
your business.” CW
 Feature Name FEATURE

The Industrial Coatings

MARKET
Growth in the industrial coatings market has been steady. China leads the way,
but North American and Western Europe also present opportunities.

Kerry Pianoforte, Editor

A
ccording to a recent report from Markets and
Markets, the global industrial coatings market is
expected to grow from $98.30 billion in 2017 to
$130.97 billion by 2022, at a CAGR of 5.91 percent from
2017 to 2022. For the purposes of this report industrial coat-
ings are defined as thin films applied on materials to add or
enhance their specific properties such as corrosion resistance,
wear resistance and conductivity.
Industrial coatings are used in a wide variety of applications
and encompass many end-use industries such as industrial
wood, protective, general industrial, rail, coil coatings OEM
and consumer goods & appliances.
According to research from Markets and Markets, the in-
dustrial coatings market in APAC (Asia Pacific) is expected to
grow at the highest CAGR during the forecast period. APAC
is rapidly expanding the market, owing to the growing econo-
my and increasing middle-class population. The study authors
noted that the increasing number of industrial activities due to
growing urbanization, mainly in China and India, are expected
to drive the market during the forecast period. There is an in-
creased demand from the automotive industry in APAC, which
is mainly backed by the expansion of the region’s industrial

May 2020 ­www.coatingsworld.com Coatings World | 5

FEATURE The Industrial Coatings Market
activities. This increased demand, in turn, drives the industrial
coatings market in APAC.
APAC is the fastest-growing market with most of the
large manufacturers establishing their facilities in this region.
Presence of some of the fastest-growing economies, such as
China, India and South Korea, and rising demand from the au-
tomotive industry play a crucial role in driving the industrial
coatings market in the APAC region.
The industrial coating market recorded growth for 2018,
despite a challenging year.
“Despite the rising costs of raw materials and the impact of
increasingly volatile geopolitical influences on key commod-
ity markets, most sectors where Hempel Industrial focuses on
have shown revenue growth in the last year,” said Michael
Bredfeldt, head of Industrial Group Product Management,
Product and Portfolio, Hempel. “Hempel Industrial is involved
in the heavy-duty equipment, heavy-duty truck, consumer
products and general finishes areas and these are driven by a
number of factors including overall Gross Domestic Product
(GDP), residential and commercial construction, infrastructure
projects, and energy costs. Hempel Industrial will continue to
focus on these sectors as we continue to see growth and market
share gain.”
“The market for industrial coatings has been steady and
growing in line with industrial production at a 3-3.5 percent
rate over the past 12 months,” said Dave Heflin, VP, Global
Industrial Liquid Coatings, Axalta Coating Systems. “A strong
economy and consumer confidence have driven growth, but
other factors like infrastructure spending, a strong agricultural
season, and growth in capital spending have been important
contributors to healthy growth as well.”
“We really see growth across all of our Industrial businesses,
led by the continued mid-single-digit growth in new commer-
cial architecture as well as maintenance of existing facilities,
then followed closely by agricultural, construction and earth-
moving equipment with similar growth rates,” Heflin added.
“We have also seen strong growth in pipeline spending at high
single-digit rates, as oil and gas exploration and transmission
spending has come back online.”
Growth Regions
In line with the paint and coatings industry as a whole, Asia
Pacific region represents the most opportunity for growth, but
even the mature markets in North America and Western Europe
have some bright spots.
Hempel has been focusing its industrial coatings activity in
the North American and Western European markets.
“We have the added benefit that we are supported by
our Centres of Excellence in Dallas, Texas and Kampen,
Netherlands,” said Bredfeldt. “Both sites offer holistic techni-
cal services, from product development to field technical exper-
tise. Furthermore, these Central Distribution and R&D Centres
(Centres of Excellence) allow us to offer further efficiencies to
our customers as orders can be fulfilled and shipped in record
time and at a reduced cost. We anticipate continuing to see
6 | Coatings World ­www.coatingsworld.com May 2020
gains in these regions.”
For Axalta Coating Systems, China is, by far, the fast-
est growing region in the world for industrial coatings.
“But we have also seen very healthy growth rates in our
mature markets in Europe and the U.S.,” noted Heflin. “In
the past year, Axalta launched more than 80 new products
across our Industrial businesses, and, while the thirst for
new products is universal, the demand from China has been
especially strong.”
Meeting Customer Demands
Users of industrial coatings are interested in coatings manufac-
turers increasing the lifecycle of the products that they develop
to extend the service life of their assets.
“Coatings can have a positive impact by improving perfor-
mance in areas such as corrosion resistance and UV durabil-
ity,” said Bredfeldt. “In addition, they are continually seeking
out solutions that will improve their processes by minimizing
waste, conserving energy and water while boosting production
efficiencies and also reducing the impact to the environment and
exposure of workers to hazardous chemicals.”
According to Heflin, the biggest thing customers are look-
ing for is a partner to their business, not just a paint suppli-
er. “In times of growth, coupled with new opportunities for
most of our customers, they are faced with new challenges
like increased production rates, faster turnaround times, more
customization in color and appearance provided by their cus-
tomers – all great challenges to have, but in many cases, the
paint shop can be the lifeblood of growth (or the limiting
factor). Customers who are winning have migrated to those
paint suppliers who have strong technical service to help them
successfully absorb significant growth and position their busi-
nesses to gain share.”
Environmental Compliance
Sustainability is a key driver for the industrial coatings market
in terms of meeting stricter and constantly evolving environ-
mental regulations, as well as increasing public awareness.
“There are a notable trend towards higher solids/lower
volatile organic compounds (VOC) solvent-based coatings and
an increase in demand for water-based (waterborne) coatings
in certain sectors,” said Bredfeldt. “This trend will continue
across all sectors as the demand increases and the coatings
continue to be more robust for application. The focus on de-
veloping ever-more sustainable industrial coatings solutions
also contributes to Hempel’s overarching sustainability agen-
da. This seeks to protect and prolong the lifecycle of assets and
thereby leads to less heavy-duty equipment being produced.
This minimizes waste which helps owners minimize their envi-
ronmental footprint.”
Axalta’s Helfin also sees the drive for more environmentally-
friendly coatings, particularly in China and Europe.
“This shift isn’t just waterborne coatings, but also higher
solids solvent-borne products. As an example, we launched a
zero VOC primer in Europe this past fall, and we can’t keep

up with demand from heavy-duty equip-
ment suppliers as well as metal compo-
nent manufacturers.”
Hempel Industrial will continue to
develop sustainable and scalable solu-
tions that have the potential to expand
our geographic footprint and support
our global customers. Investments
at our two Centers of Excellence in
Dallas, TX and Kampen, Netherlands
support our drive to improve our
customers’ experience.
In overall Hempel terms, 2019 will
be a year of progress. The global coat-
ings market is expected to pick up,
and Hempel anticipates delivering un-
derlying organic growth in line with
or slightly better than the market. As
a leading company within the global
coatings industry, Hempel expects to
bring more new companies into the
Hempel family, as it continues its jour-
ney towards becoming a €3 billion rev-
enue company.
New Products
Hempel is launching a new epoxy primer
for heavy-duty equipment and trucks –
Hempaprime Shield 700 HS.
This new coating is specifically de-
signed to improve productivity and qual-
ity for original equipment manufacturers
(OEMs) by reducing production times and
maximizing service life.
Following its launch in North
America, Hempaprime Shield 700 HS is
now available in Europe.
Hempaprime Shield 700 HS is specifi-
cally designed to optimize production. A
two-component high solids epoxy primer
with exceptional adhesion to ferrous met-
als and substrates that delivers long term
corrosion resistance in the harshest envi-
ronments. It is fast drying and has short
minimum overcoat intervals without com-
promising the high-volume solids content.
This robust coating provides im-
proved crack and wrinkle resistance even
at a high dry film thickness (DFT) and
dries to a smooth finish without the need
for sanding.
“When designing coatings for cus-
tomers it is important to understand
their drivers and these generally in-
clude superior long-lasting protection,
May 2020 ­www.coatingsworld.com Coatings World | 7
The Industrial Coatings Market FEATURE
optimized production, environmentally
friendly, the potential to enhance op-
erational efficiencies, and a finish that
looks good,” Hempel’s Head of Industrial
Group Product Management, Product
and Portfolio, Michael Bredfeldt said.
“Hempaprime Shield 700 HS delivers all
of this and more. It is easy to apply, fast
drying and offers consistent high-quality
performance. There is no need for thin-
ning, and the coating has been optimized
for airless and air spray.
“Importantly, the low VOC content is
better for the environment, safer for the
applicators and meets all legislative re-
quirements. Hempaprime Shield 700 HS
is the ideal primer for OEMs, including
heavy duty equipment such as forklifts,
excavators, harvesters, earth moving
equipment, as well as trucks, trailers and
commercial vehicles.”
Axalta’s Nap-Gard powder coatings
are formulated for use on external and
internal oil, gas and water pipelines with
single, dual and multi-layer application
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options. Nap-Gard also provides cor-
rosion protection solutions for valves,
fittings and rebar. Axalta’s functional
coatings offer innovative solutions for
today’s epoxy-based coating applications
and are designed to provide superior cor-
rosion protection for substrates in harsh,
demanding environments.
Major Market
Developments
• PPG Industries introduced Durastar
Ultra-Cool coatings that enhance the
beauty and extend the service life of
metal roofing, siding, panels, and other
building components.
• Axalta Coating Systems expanded to
optimize manufacturing capabilities for
its Alesta brand at its powder coatings
production facilities in Germany to cater
the growing market demand.
• AkzoNobel N.V. acquired the indus-
trial coatings business of BASF SE. This
strategy would help strengthen its posi-
tion in the coil coatings market. CW
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FEATURE
The Marine Coatings
MARKET
Growth expected despite increasing regulations and raw material supply issues.
Anthony Locicero, Associate Editor
T
he marine coatings market size is forecasted to surpass
$15 billion by 2024 at approximately seven percent
CAGR from 2016 to 2024, according to research by
Global Market Insights.
A growing need for low fuel consumption will enhance the
demand for regular coating by anti-fouling agents, GMI said.
“Predictably, the coatings market remained very competitive
in 2018,” said Christian Ottosen, group VP, head of Marine,
Hempel A/S. “The price for raw materials increased more than
anticipated, which affected the entire coatings industry. There
were sustained tough market conditions in the marine industry
globally. The marine newbuild markets in Asia and Europe con-
tinued to decline but there was a rise within marine maintenance.
“We see 2019 as a year of progress and overall the global
coatings market is expected to pick up.”
8 | Coatings World ­www.coatingsworld.com May 2020
“The commercial marine coatings industry in North America
has seen steady growth since the beginning of 2018, and we
see it continuing at a similar pace through 2019 and into next
year,” added Al Kaminsky, U.S./Canada marine director for PPG
Protective and Marine Coatings.
The Maritime Organization’s Sulphur cap is slated to go into
effect on Jan. 1, 2020. It will rise from 0.5 percent to 3.5 percent.
“Many shipowners have put their vessels in drydock to retrofit
their vessels, install a scrubber, and simultaneously apply marine
coatings,” Ottosen said. “As the industry continues to search for
the most efficient way of operating, suppliers strive to deliver so-
lutions that impact the bottom line for their customers, either by
a low upfront investment or reducing their fuel consumption.”
“Any uptick in the oil and gas industry leads to an uptick
in the North American commercial marine coatings market,”

Kaminsky added. “Barges and tugs up and down the Mississippi
River and throughout the Great Lakes region, either directly
related to the oil and gas industry or to the general economy,
enhance the growth in the marine coatings market.”
Areas of growth
According to GMI, Asia Pacific, led by China, South Korea and
Japan, has made “tremendous” advancements in the shipbuild-
ing industry.
China emerged as the global leader, the research states, with
new orders accounting for more than 33 percent of the global
shipbuilding industry.
Asia Pacific will have a significant share of the overall indus-
try owing to large-scale shipbuilding activities in China, Japan,
South Korea, Philippines and Taiwan, per GMI’s research.
“The areas with the greatest demand for marine coatings di-
rectly correlates with the countries with the highest tonnage,”
Ottosen said. “In Europe, for example, major shipping countries
such as Greece, Germany, Norway (the maritime hubs) continue
to have the highest demand for marine coatings. Asia (specifi-
cally Japan, China, Singapore) also has a high demand.”
Regulations
The Biocidal Products Regulation (BPR, Regulation (EU)
528/2012), as definted by the European Chemicals Agency, con-
cerns the placing on the market and use of biocidal products,
which are used to protect humans, animals, materials or articles
against harmful organisms like pests or bacteria, by the action
of the active substances contained in the biocidal product.
“Now all biocidal products require an authorization by
European Chemicals Agency before they can be placed on the
EU market,” Ottosen said. “What’s more, the active substances
contained in that biocidal product must also be previously ap-
proved. All coatings suppliers, Hempel included, have developed
products that are compliant with these new regulations and use
approved biocidal and active substances.”
Hempel is prepared if China and Korea adopt similar legis-
lature, Ottosen noted.
“There has been a global shift these past 10 years and pro-
tecting the environment is at the top of the agenda,” he said.
“With increasing, and evolving, environmental regulations we
strive to be as up to date as possible to help our customers be
aware of and comply with new regulations and to help them
minimize their environmental footprint.”
Kaminsky said PPG has observed an increase in some states
requiring the use of anti-fouling coatings.
While it’s not mandatory, “we’re addressing those as they
come up,” he added.
Raw materials
In addition to increasing regulations, the industry has faced
challenges with raw materials prices and supply issues.
“Supply issues are always a problem, but the rise of raw ma-
terial prices over the past couple of years has been a challenge to
address,” Kaminsky said. “And trying to keep prices steady – in
May 2020 ­www.coatingsworld.com Coatings World | 9
The Marine Coatings Market FEATURE
light of this – is always a struggle.”
“Raw materials constitute a major part of the cost of manu-
facturing coatings for the protective, marine and decorative in-
dustries,” Ottosen added. “In February 2017, we gave notice
that we were going to increase the prices of certain products and
explained the reasons behind this decision.”
Additionally, Ottosen said Hempel is “very committed to
providing sustainable solutions to our customers that minimize
their impact on the environment and do not jeopardize the
health and safety of their employees.”
Hempel’s Group Health, Safety and Environmental
Policy sets out the company’s commitment to seek out saf-
er materials when developing new products and solutions,
Ottosen explained.
“We also work to phase out materials that are potentially
harmful to the environment and people’s health,” he said.
“We prioritize raw materials based upon their potential haz-
ard and are committed to reducing or phasing out the more
hazardous substances – known as red raw materials,” Ottosen
continued. “Our priority list centers on carcinogenic, mutagenic
and reprotoxic (CMR) substances. In 2018, we also included
substances that the EU has decided to phase out in the future.
“By the end of 2018, we had completely stopped the manu-
facture and sale of all coal tar products,” he added. “We had
also made good progress on other red raw materials by chang-
ing our solvent blends and phasing out raw materials that con-
tain alkyl phenol ethoxylates.”
Hempel phased out 35 red raw materials last year,
Ottosen said.
Trends
The anti-corrosion coatings segment is expected to lead the
marine coatings market through 2022, in terms of value,
per ReportBuyer.
“Energy efficiency continues to be key to successful opera-
tions and has three main drivers – economics (improving profit
margins), compliance (industry regulations) and customer
needs (sustainability and environmental factors),” Ottosen said.
“When looking specifically at marine coatings, ship owners and
operators look for solutions that minimize speed loss thus reduc-
ing fuel consumption and improve operational efficiency. Slow
steaming, though not a new concept, is being adopted more and
more by ship owners across the world as it means vessels burn
less fuel by moving at a slow speed. We have developed trusted
solutions to suit such operating patterns.
“As market pressures continue to drive ship owners to imple-
ment energy efficient solutions that are both environmentally
sustainable and boost their competitiveness, we will continue to
push technological boundaries to meet these needs.”
“The current trend in the North American marine coatings
market is single application tank lining products,” Kaminsky
added. “Minimizing the length of time that an asset is out of the
water for maintenance and repair is critical, so single applica-
tion coating technologies are an important development – to
save time and money.”
FEATURE The Marine Coatings Market
Product releases
This year, Hempel released Globic 7000 and Atlantic+ to
the market.
Globic 7000 is a new antifouling coating with enhanced op-
erational flexibility for all vessel types and a speed loss of 4.5
percent, on average (according to ISO 19030).
Specifically designed to deliver effective protection for up to
60 months, Globic 7000 incorporates an optimum biocide mix
to guard against both hard and soft fouling. With an improved
performance against slime and algae, Globic 7000 is suitable for
wide operational conditions including slow steaming and long
idle periods.
Atlantic+ is designed to protect the hull from fouling
throughout service intervals of up to 60 months.
Ensuring complete operational flexibility, the new antifoul-
ing is suitable for all vessel types and all water temperatures.
Atlantic+ incorporates a powerful biocide package and prov-
en binder system.
This ensures progressive and controlled self-polish-
ing from the moment the hull hits the water and for up to
60 months thereafter.
PPG is offering NOVAGUARD 810 ER and PSX ONE.
NOVAGUARD 810 ER is a single coat solution for ballast
tanks and various cargo vessel applications that provides du-
rable, long-term protection of the asset.
PSX ONE is a single pack acrylic polysiloxane solution that
provides outstanding color and gloss retention in a durable
coating product.
Chugoku Marine Paints introduced a new antifouling coat-
ing containing the barnacle-repellent active agent Selektope,
SEA PREMIER 3000 PLUS, which is the eighth product devel-
oped by CMP that contains Selektope.
SEA PREMIER 3000 PLUS is a self-polishing coating based
on silyl polymer technology. It delivers excellent slime and algal
resistance with the combined power of Selektope and cuprous
oxide for superior hard fouling prevention. Developed initially
for use in the Japanese domestic market by coastal vessels, SEA
PREMIER 3000 PLUS is particularly suitable for vessels operat-
ing with a low activity rate or at low speed. The coating is also
suitable for use in niche areas, such as sea chests and interior-
grating-bow thruster tunnels.
Nippon Paint Marine released Ever Cool, a specially formu-
lated coating designed to reduce the effect of the Sun’s infrared
rays on ship operations.
For example, the temperature difference between a deck
coated with conventional paint system and one with Ever Cool
can be up to about 28°C (82.4°F), with the specially formulated
coating reflecting up to 80 percent of the Sun’s heat from col-
ored coatings.
Requiring no special application tools or processes, Nippon
Paint Marine uses advanced formulated reflective pigments to
prevent surface temperature increases and lower heat transfer
10 | Coatings World ­www.coatingsworld.com May 2020
through steel plate and other structures.
“By reducing the surface temperatures of exposed decks,
shipbuilders can reduce the insulation requirement, while ship
operators can reduce the air conditioning/chiller load, saving
fuel and improving the onboard conditions for passengers and
crew, especially in tropical climates,” said Olaf Töbke, director,
Nippon Paint Marine (Europe).
In addition to decks, the heat resistant coating can also be
applied to the topside of ballast water and cargo tanks, to en-
sure their contents remain at a safe and steady temperature. The
technology is also applicable to LNG insulated tanks to lower
boil-off gases.
Jotun unveiled the next generation of its SeaForce bio-
cidal antifouling range, with three new products featuring
Hydractive technology.
The new solution provides predictable, long-term perfor-
mance for diverse vessel needs.
Jotun originally launched its SeaForce range in 2004.
Since that point, there has been some 27,000 vessel
applications worldwide.
However, according to Dr. Erik Risberg, global marketing
director, Jotun Marine Coatings, evolving customer needs have
spurred Jotun to develop an innovative new solution to satisfy
industry demands today, and far into the future.
“SeaForce is a cornerstone portfolio in our marine coating
range,” he said, “but we felt the time was right to push its per-
formance further, providing next-level protection for our cus-
tomers while consolidating its position within the marketplace.
Shipping has changed over the past decade and a half, creating
a different customer need, and we want to evolve with that de-
mand to keep delivering optimal solutions. That, in essence, led
to the idea for Hydractive technology.”
Hydractive technology effectively slows down the water up-
take of the antifouling, meaning that biocides are released in a
more predictable pattern over the lifetime of the coating. This
results in stable, high-quality performance for the long-term,
with SeaForce keeping customers’ vessel hulls cleaner, for longer.
The range features three core products: SeaForce Shield,
offering effective protection; SeaForce Active, actively work-
ing to safeguard hulls even when vessels are not in use; and
SeaForce Active Plus, delivering premium protection at an
affordable price.
SeaForce Active and SeaForce Active Plus also feature a triple
biocide package, one of which is the same biocide combination
used in the top of the range SeaQuantum product portfolio.
“There is no ‘standard’ ship owner, so there is no one size
fits all coating solution,” Risberg said. “With our proprie-
tary Hydractive technology we can deliver a ‘best in class’
solution for long-term clean hulls and protection. We’re ex-
cited to see industry reaction to what we regard as a sig-
nificant step forward in anti-fouling performance within this
market segment.” CW
 Polymer Modification with
REACTIVE SILICONES
Bob Ruckle, 2Tom-Seung Cheung
1
Siltech Corporation, Toronto, ON Canada
1
Robert@siltech.com, 2Tom2@siltech.com
Overview
Resins used in coatings, composites and other specialty thermoset
systems can generically be thought of as a base polymer and reactive
groups. Although we commonly name the resin by the type of reac-
tive group, for example an epoxy resin, many of the final properties
come from the base polymer itself. Sticking with the epoxy resin
example; aliphatic epoxy, aromatic epoxy, urethane epoxy, and
acrylic epoxy resins are all commonly available. While the epoxy
reactive group gives much of the strength, adhesion and toughness;
the backbone is responsible for UV degradation and gloss in the
aromatic epoxies, oil solubility and UV stability in the aliphatic ep-
oxies, flexibility in the urethane epoxies, and water solubility in the
acrylic epoxies.
The same point can be made of other reactive group named res-
ins such as amine, isocyanate, hydroxyl, acrylate ester, carboxylate,
etc. Some properties result from the connectivity and some from the
base polymer or backbone.
At Siltech, our forte is silicone so the resins which we develop
use silicone as the base polymer. The reactive groups are append-
ed on the ends of the silicone polymer, giving an extender; on the
middle segments of the polymer, giving a cross linker; or both. We
have attached each of the commonly used reactive groups onto the
silicone and have conducted laboratory work to show how the sili-
cone backbone affects the final properties of a cured system. There
is a great deal of commonality to the properties when reactive sili-
cones are used.
As homopolymers, silicones are generally soft, flexible, tough,
water resistant, non-conductive to both heat and electrical poten-
tials and offer extraordinary elongation values. Elongation is rou-
tinely up to 300% for cross-linked, all silicone systems. Hybrid
systems with co-reacted silicone and organic backbone resins are
usually 50-100% elongation.
Hybrid systems, where organic backbones and silicone back-
bones with the same or complementary reactive groups cure,
usually show a compromise of the properties brought by the two
based polymers. In this manner, aliphatic epoxy resins which
can be brittle and non-flexible, can be made to withstand low
temperature impacts and other shear forces by co-polymerizing
May 2020 ­www.coatingsworld.com Coatings World | 11
with a reactive silicone.
These hybrid systems are the primary topic of this white paper.
Reactive Groups
Reactive moieties available for epoxy reactions are glycidyl and
cycloaliphatic epoxy groups. Also, in the case of epoxy resins,
hydroxyls will readily react into this system and amino functional
siloxanes can even be substituted for the amine functional epoxy
hardeners. Siltech has Silmer® NH materials which are primary
amine functional and which work well for this use. More com-
monly available are aminoethylaminopropyl substituted silicones
which have both a secondary and primary amine on the side
chain. It is difficult to cleanly react one in the presence of the
other so the Silmer NH approach gives a much cleaner reaction.
Having said that, the aminoethylaminopropyl silicones do give
interesting results in many cases.
For polyurethane systems, the viable reactive species available
are Silmer OH primary hydroxyl, Silsurf® hydroxyl functional poly-
ether silicones, and Silmer NCO isocyanate functional silicones.
The NCO polymer is important because isocyanate functional pre-
polymers which are available on the market are often made with
an excess of the hydroxyl component to leave the more stable OH
groups on the ends of the prepolymer. If one wants to further react
this, an isocyanate group is needed.
For polyesters, hydroxyl functional and carboxylic acid modi-
fied silicones are used. Polyimides can be modified with the afore-
mentioned Silmer NH products.
For acrylate ester (often called vinyl ester) reactive groups,
a large variety of acrylate functional silicones are available. The
commercial use of these in UV cured overprint varnishes and pa-
per release products has fostered the development of many varia-
tions. Siltech offers Silmer ACR products and Silmer OH ACR
products. Both have the acrylate ester group for UV initiated free-
radical polymerization, but the latter type also offers an hydroxyl
group for secondary cure. Both of these product types can eas-
ily be co-reacted with organic backbone based acrylate resins for
modified properties.
This UV cured acrylate system is the exception to the ultra-high
FEATURE Polymer Modification with Reactive Silicones
elongation expected with silicone polymers.
In these systems, typical elongations are
under 25%. We believe this is because the
main polymer is built incorporating the sili-
cone chains as side-chains instead of in the
main polymer chain. See Scheme 1.
We have recently demonstrated the use
of Silmer SH thiol functional silicones with
multiple reactive sites in a UV initiated thi-
ol-ene reaction which provides elongation
up to 200%. The thiol-ene reaction adds
across the double bond instead of initiating
a polymerization cross-linking is provided
by the highly functionalized silicone base
polymer. We have also used very highly
functionalized Silmer SH Q type silicon res-
ins in this reaction.
Free-radical formed polymers like
acrylic and polyolefin resins are formed
and laid down on a surface by coalescence,
and so do not react with the silicone at
the end use. The properties of these non-
reactive systems can be altered during the
resin manufacture with acrylate or vinyl
functional silicones. Alternatively, our
Silmer TMS trialkoxysilane modified sili-
cone can react with the reactive sites on
the base polymer during coalescence al-
tering some properties of the final matrix.
This group of silicone polymers with
trialkoxy silane groups appended to the
silicones behave like silane cross linkers. As
monomers, alkoxy silanes are well known
and often used to provide improved macro-
adhesion, cross-link density and adhesion
to molecular surfaces. We see all of those
properties with this trialkoxy silane func-
tional silicones in addition to improved
12 | Coatings World ­www.coatingsworld.com May 2020
flexibility and hydrophobicity.
Besides the Silmer TMS chemistry, we
have some other atypical resin cross link-
ers. Another group has multiple hydroxyl
groups on the same side chains. These
Silmer OHT resins are surprisingly effective
at imparting stain resistance, macro-surface
adhesion properties to hybrid systems often
out performing our fluorosilicone products.
With all-silicone systems, a unique
reaction can be used. Silicon-hydride
functional silicones are reacted with vinyl
silicones using a trace of Platinum catalyst
to cause addition of the silicon groups
across the double bond. This hydrosila-
tion is the basis for many LSR or silicone
adhesives. While the reaction of the SiH
functional silicones with organic double
bonds does work, there has not been much
work with curing hybrid resin systems in
that manner.
Solubility Modifiers are
Very Desirable
Early in the work we’ve done we experi-
mented with simple reactive silicones. Due
to the lack of miscibility of the silicone
backbone with organic backbones, it can
be difficult to react these materials. Either
very high shear conditions must be used or
silicone/ organic emulsifiers can be used to
compatibilize the two disparate polymers.
Another approach is to modify the sili-
cone backbone with reactive groups AND
organic groups to provide reactivity as well
as solubility in the resin. The cartoon in
scheme 2 shows this concept in the exam-
ple of epoxy silicones. The organic chains
(blue) provide miscibility with the organic
backbone resins while the epoxy groups
(maroon) are available for the polymeriza-
tion reaction.
The problem and solution are indi-
cated by the following examples in which
we reacted silicones modified with acrylate
moieties. See Figure 1. Some of the Silmer
ACR products are also reacted with poly-
ether chains for solubility and others are
not. This UV cured system and the Silmer
ACR structural variations tested are shown
as well. The silicone is either linear di-func-
tional or pendant multifunctional. There is
an organic modifier on two and not on the
others.
The four materials without organic
Scheme 2: compatibilized reactive silicone
modification all show oily uncured silicone,
defects, tackiness and high tan(delta) values
which indicate incomplete cure. The acry-
late groups on the immiscible silicone are
not available to react with the groups on the
organic resins. This phenomenon is also ex-
pressed in very low COF values and excel-
lent release properties of the samples when
this uncured silicone blooms to the surface.
The Silmer ACR D208 and Silmer ACR
E608, with organic groups, show complete
reaction and incorporation into the matrix.
Typical Properties
Expected
In this example of a hybrid organic/silicone
epoxy resins system, we reacted an organic
cycloaliphatic epoxy with a cycloaliphatic
epoxy modified silicone. The silicone used
is Silmer EPC F418-F, which is also modified
with a EO/PO polyether chains for miscibil-
ity. A silicone concentration ladder study
of this reaction is conducted from 0-50% in
 Polymer Modification with Reactive Silicones FEATURE

FIGURE 1: non-compatible results.

Ingredient Wt % Silmer Silicone Organic Modification

Various Silmer ACR Reactive Silicones 22 ACR Di-10 Linear, small None

Epoxy Acrylate Resin CN104C75 40 ACR Di-50 Linear, medium None

Synergist CN386 15 ACR Di-100 Linear, large None

Photoinitiator Escacure TZT 5 ACR D208 Pendant, small EO small

Photoinitiator Darocur 1173 1.5 ACR E608 Pendant, medium EO Small

Silmer ACR D2 (Defoamer) 0.5 ACR D2 Pendant, small None

Reactive diluent SR 355 DTPTA 10 Above: Silmer ACR Structures

Reactive diluent SR 306 TRPGDA 6

The results are shown below.

Control Di-10 Di-50 Di-100 D208 E608 ACR D2

G' (MPa) 20.1 8.3 18.5 11.91 9.71 11.64 20.06

G" (MPa/10) 1.56 0.71 3.19 1.88 0.82 0.91 1.42
tan(delta)(/100) 7.93 8.71 17.3 15.82 8.58 7.86 7.25
Cure & Appearance Cured Oily Oily, Defects Oily Cured Cured Tacky

units of 10%. The materials are cured at 110°C for 4 hours and, in at 110°C for 4 hours using the formula and showing the results
the last column, another set of similar formulations is UV cured at in Figure 3.
365 nm. See Figure 2. The mechanical properties are reported in the graphs below. As
Mechanical properties show a reduction in Shore D hardness more of the silicone is used in the formulation, hardness is reduced.
which exhibits a dose response that slopes slowly at lower con- The slope of the curve of the reduction in hardness is nearly flat until
centrations. Elongation increases directly with higher concentra- about 20% incorporation, where about 10% of the hardness is lost,
tions of silicone. Interestingly, tensile strength and total energy to and then drops off quickly with more silicone.
break show a maximum peak. This peak is very strong in tensile Similarly, viscosity of the formulation is reduced in a nearly lin-
strength. We believe this is the result of two opposing trends, flex- ear relationship. Tensile strength is reduced but elongation increases
ibility and softness. At lower concentrations the material is still to about 100% at 40% incorporation of the silicone resin. We do
hard but more flexible resulting in strength and toughness. At not see the peak in tensile strength which we have seen in so many
higher concentrations the material becomes too soft. The same systems, this is perhaps because we did not do concentrations be-
two materials were also reacted, with different promoters, under tween 0 and 20% silicone.
UV excitation. A similar trend was seen in properties. Shown on A different aryl epoxy resin, D.E.R. 331, which is harder and
the right in the figure. faster curing than the first example is also reacted with the same
In the next experiment, a different standard aryl epoxy was re- epoxy silicone, Silmer EP D208. See Figure 4.
acted with Silmer EP D208, a different epoxy functional silicone, Interestingly, due to the complex mechanism of epoxy/ anhydride
cured systems, we are able to react a silicone with only hydroxyls
instead of epoxy reactive groups. The Silsurf D208 is similar to the
Ingredient Name Wt% (heat) Wt% (UV) Silmer EP D208 but without epoxy groups. Again, this was cured
at 100°C for 4 hours. See Figure 5.
UVACURE
Organic Cycloali- We have been able to substitute silicone amines in place of
1500 Epoxy 42-16 99-49
phatic Epoxy Resin amine hardeners in epoxy systems with success. In this cus-
Resin
tomer proprietary formulation, we replace 20% of his amine
Anhydride Curative MHHPA 58-24 na hardener in a tough epoxy garage floor coating with these flex-
Cycloaliphatic Epoxy Silmer EPC ible hardeners. In separate experiments, we also replaced some
0-60 0-50
Polyether Silicone F418-F of the resin with OH functional silicones. The amine approach
Catalyst AMI-1 0.06-0.1 na was as effective, if not more effective at improving low tempera-
Photoinitiator UV9380C na 1 ture impact resistance.

May 2020 ­www.coatingsworld.com Coatings World | 13

FEATURE Polymer Modification with Reactive Silicones

Figure 2: epoxy/silicone hybrids by thermal and UV cure.

Ingredient Name Wt%

Organic Epoxy Resin D.E.R. 671-X75 53%-32%

Anhydride Curative MHHPA 23%-17%

Glycidyl Epoxy Polyether Silicone Silmer EP D208 25%-50%

Cycloaliphatic Epoxy Silicone

Silmer EPC D2 0.15%-0.2%
(defoamer)

Catalyst AMI-1 0.06%-0.1%

Figure 3: Silmer D208 with D.E.R. 671-X75

14 | Coatings World ­www.coatingsworld.com May 2020

 Polymer Modification with Reactive Silicones FEATURE

Measured after 1 week of ambient cure, a steel ball bear-
ing was dropped from a set height on pre-cooled molded resin.
Most fractured on 1 drop but some needed a second drop to
fracture. The severity of the fracture pattern was rated 0-10
where 10 is no fracture. Figures 6-9.
catalyzed with 0.9 moles of MHHPA and 0.1% AMI-1 and cured
at 110°C for 8-16 hours.
In Figure 10 we see the mechanical properties as a function of
Silmer EPC Di-10 (chain extender) content. Tensile strength, and
hardness are increased with more of the extender molecule while
elongation and storage modulus are diminished.

Homopolymers of Silicones Beyond Epoxy Resins

One can of course, cure the silicone resins without organic hybrids. Epoxy resins are ubiquitous so much of our work over the years
The resultant resins are typically soft and often tacky with large has been done with them. But we have done similar work on
elongation values. In a cycloaliphatic epoxy system, we cured the other resin systems. For example, another system we have done
linear di-functional epoxy silicone Silmer EPC-Di-10 with mul- a lot of experimentation with is UV cured acrylated silicones.
tifunctional Silmer EPC G36 in varying ratios. The system was An aliphatic epoxy based acrylate functional resin is cured at
365 nm with an acrylate functional polyether silicone, Silmer
ACR D208. See Figure 11.
The mechanical properties show a similar trend to what we
Ingredient Name Wt%
have seen. In this case, where we have put in very high levels
Organic Epoxy Resin D.E.R. 331 37%-25%
of silicone (up to 80%) we see a spike for elongation and total
energy to break but no spike in tensile strength. We believe the
Anhydride Curative MHHPA 37%-25% material is so soft that is dominating the test results.
Glycidyl Epoxy Polyether The hybrid UV cured acylate formulation was also an early
Silmer EP D208 25%-50% development effort for us for 3D printing. Various Silmer ACR
Silicone
Cycloaliphatic Epoxy structures are evaluated in a ladder study of 5%, 10%, 20%,
Silmer EPC D2 0.15%-0.2% and 30% in a formulation of three organic based acrylate resins.
Silicone (defoamer)
These were cured at 365 nM in an SLA printer. See Figure 12.
Catalyst AMI-1 0.06%-0.1%

Figure 4: Tensile Properties of D.E.R. 331 epoxy anhydride system with varying Silmer EP D208 levels.

25% D208
Ingredient Name Wt% 30% D208
35% D208
40% D208
Organic Epoxy Resin D.E.R. 331 37%-25%
45% D208
Anhydride Curative MHHPA 37.5%-25% 50% D208

-OH Polyether Silicone Silsurf D208 25%-50%

Catalyst AMI-1 0.06%-0.1%

Catalyst AMI-1 0.06%-0.1%

Figure 5: hydroxyl only functional silicone with epoxy resin

May 2020 ­www.coatingsworld.com Coatings World | 15

FEATURE Polymer Modification with Reactive Silicones

Figure 6. comparison of amine and hydroxyl silicones in epoxy system

Additive Wt % Shore A Tear (N/mm) Tensile (kPa) Elongation (%) - 15° C - 30° C

Control 0 37 3.2 500 171 5 6*

Silamine D2 EDA 5% 45 3.6 636 114 8 7*
Silamine D2 EDA 10% 49 4.0 943 68 9.5 9*
Silamine D208 EDA 5% 27 2.1 299 191 5 5.5
Silamine D208 EDA 10% 25 1.8 261 164 4.5 2.5
Silmer NH Di-8 5% 31 2.7 354 176 4.5 3
Silmer NH Di-8 10% 43 3.7 543 98 9.5 8*
Silmer OH C50 10% 35 2.6 353 176 6 5
Silmer OH Di 50 10% 30 2.6 430 202 3 4
Silmer OH D2 10% 32 2.2 291 162 4 8.5*
*Indicates two drops were needed to fracture

Figure 7: Impact resistance data Figure 10: homopolymer of epoxy silicone.

Ingredient Name Wt%

Acrylated organic resin CN 104C75 0% to 80%

Organic miscible Silmer ACR
80% to 0%
acrylated silicone D208
Catalyst Esacure TZT 5%
Sartomer CN
Coinitiator 13%
386
Catalyst Irgacure 184 1.5%

Acrylated silicone Silmer ACR D2 0.5%

Figure 8: -15°C fracture pattern examples

Figure 9: -30°C fracture pattern examples

Figure 11: UV cured acrylate hybrid resin

16 | Coatings World ­www.coatingsworld.com May 2020

 Polymer Modification with Reactive Silicones FEATURE

Ingredient 5% 10% 20% 30% Silmer ACR Type Eq. Wt.

Sartomer CN 991 8.4% 8% 7.1% 6.6% Di-1010 Di-functional 650

Laromer UA-9072 47.1% 44.6% 39.6% 34.6% Di-1018-F Di-functional 1000

Laromer LR-8887 34.4% 32.6% 28.9% 25.3% Di-4515-O Di-functional 2500

Sartomer SR833S 3.9% 3.7% 3.3% 2.9% E608 Multi-Functional 600

Silicone ACR xxx 5.0% 10.0% 20.1% 30.1%

TPO 1.0% 1.0% 0.9% 0.8%

Silmer ACR Di-10* 0.17% 0.17% 0.15% 0.13%

*reactive defoamer

Figure 13: simple hybrid urethane waterproofing results.

energy to break and maximum stress measurements show an

increase at 5% and then a drop off.

Urethanes
Silicone modification of urethane resins can be accomplished
with either OH functional reactive silicones such as Silmer OH
or the multifunctional Silmer OHT product families or with iso-
cyanate functional Silmer NCO species.
In a basic example linear di-hydroxyl silicones are react-
ed with a Desmodur W, dicyclo-hexylmethane diisocyanate,
to form a urethane with alternating silicone and cyclohexyl
blocks. The series of urethanes made with Silmer OH Di-50 to
Silmer OH Di-400 represent increasing silicone chain length.
White cotton and red bolt fabrics are treated with a 1% solu-
tion and evaluated with several criteria for water resistance.
The criteria are used to assign a rating from 0-10 (best). These
are compared to the untreated control and an all silicone ure-
thane made from Silmer OH C50 and Silmer NCO Di-50. The
organic hybrid materials are much better than the control and
Figure 12
nearly as effective as the all silicone urethane. See figure 13.

Low use levels

Some properties of the hybrid resins are shown. Flexibility In a more fully formulated urethane system, a series of hy-
and extension are increased and show a dose response, al- droxyl functional silicones were reacted with a 2 part WB/
though at 30% incorporation of silicone that starts to drop off. PU system and evaluated for stain resistance. As we were
Toughness follows a similar pattern as indicated by strain. Total looking to change the surface properties rather than the

May 2020 ­www.coatingsworld.com Coatings World | 17

FEATURE Polymer Modification with Reactive Silicones

mechanical properties, a small use

level of 2% silicone was evaluated.
We did not run tests to confirm that
reaction occurred, but assume that is
has. The results across a wide vari-
ety of different staining materials was
used to generate a rating 1-10 (best).
These ratings are shown in Figure 14
compared to no additive, a commer-
cial competitive additive and our own
fluorosilicone polymers.
In general, the more highly func-
tionalized Silmer OHT products show
better stain resistance and many of
the hydryoxyl silicone materials out-
performed the fluorine containing
Fluorosil products.

Silane and Isocyanate

Silicones
We have done work in a UV cured system
in which we demonstrated a secondary
Figure 14: surface effects with low incorporation in a urethane system condensation cure after the UV initiated
free radical reaction. For this we use
Silmer TMS Di-10 or Silmer TMS Di-
50 trialkoxy silane modified silicones or
Ingredient Amount (when x=50) Purpose
Silmer NCO Di-10 or Silmer NCO Di-50
isocyanate functional silicones. The for-
Silmer OH ACR Di-50 47.50% Energy Cure mulations were UV cured and then left
on a benchtop at ambient for 7 days to
TMS or NCO type 47.50% Secondary Cure ensure complete condensation cure. The
DBTDL 0.25% Condensation Catalyst improvement in pencil hardness and stor-
age moduli show increased cross-linking
Darocur 1173 4.75% Photoinitiator has occurred. See Figure 15.

Property Silmer TMS Di-10 Silmer TMS Di-50 Silmer NCO Di-10 Silmer NCO Di-50

G' (Pa) first cure 6.51*105 9.08*104 6.33*105 2.58*105

G' (Pa) seven days 1.34*106 2.42*107 2.79*106 1.08*107

G' change (%) 106% 26,561% 341% 4086%

G'' (Pa) first cure 2.73*103 3.19*102 9.19*103 3.62*103

G'' (Pa) seven days 8.32*103 1.52*106 5.43*105 4.23*105

G'' change (%) 205% 476,389% 5,809% 11,585%

Tan delta first cure 0.0048 0.004 0.015 0.014

Tan delta seven day 0.0063 0.063 0.195 0.0392

Tan delta change (%) 31% 1,660% 1,238% 180%

Pencil Hardness first cure 2B <6B 2B <6B

Pencil Hardness seven day 7H HB >9H <6B

Figure 15: secondary condensation cure with unique silicones

18 | Coatings World ­www.coatingsworld.com May 2020

 Polymer Modification with Reactive Silicones FEATURE

Component Silmer SH Q20 Silmer SH Q20 Silmer SH J0

Proprietary MQT(SH) or SH Silicone 21.5% 15.6% 15.1%

Silmer VIN 65K 42.3% 51.7% 45.8%

Silmer VQT83-30 35.6% 0 38.6%

Silmer VQ92 0 32.0% 0

TPO-L 0.6% 0.7% 0.6%

SH/vinyl 3.63 4.88 3.63

Properties

Tensile Strength (kPa) 3,495.98 4027.13 2,303.68

Elongation (%) 99.07 202.96 55.87

Total Energy (J/m) 262.95 762.75 104.34

Tear Strength (N/mm) 6.81 8.19 5.33

Shore A Hardness 55.00 46 53.00

G' (Pa) 6.41E+05 4.73E+05 1.20E+06

G" (Pa) 1.14E+05 5.26E+04 5.23E+04

tan delta 0.18 0.1112 0.04

Cure rate (Pa/s) 8.65E+04 7.62E+04 2.87E+05

Figure 16: Silmer SH cured properties and an example being 3D printed.

Sulfur Functional Silicon Resins

In our latest Silmer family, we have developed a series of
thiol silicones and MQT silicon resins. They react with vi-
nyl functional silicones and vinyl functional silicon Q resins.
The cure mechanism is the well known thiol-ene reaction.
The cured materials are strong, tough and flexible and
opaque white. The elongation is up to 200%, something
that cannot be done with acrylate functional UV curing.

Conclusion
Incorporation of reactive silicone into organic based poly-
mers, is readily accomplished. The resultant hybrid poly-
mers or polymerized matrix are usually somewhat softer,
with dramatically improved flexibility, impact resistance and
elongation. In these properties more silicone provides more
of the effect up to a point where the system becomes too soft.
Other mechanical properties such as tensile strength
and total energy to break are often improved likely from
the increased flexibility. In these properties there is an op-
timum degree of incorporation, generally around 20% sili-
cone, which needs to be discovered in each system with a
ladder study.
All of the source papers with more detail are available on
www.siltech.com CW

May 2020 ­www.coatingsworld.com Coatings World | 19

FEATURE
3D Printing
IS ON THE RISE
Advantages in prototyping, costs of customization, less waste are helping drive the
growth of additive manufacturing.
David Savastano, Editor
3
D printing, or additive manufacturing, is growing in inter-
est. The ability to prototyping a part quickly and efficiently
is one benefit. 3D printing also dramatically speeds time to
market for customized work, and the additive process uses only
what it needs, rather than the more traditional subtractive ap-
proach, which results in more waste.
With this growth in 3D printing, there is increasing interest in
equipment, materials and more. It remains a fragmented market
in each of those categories.
In its report, “3D Printing Market Size, Share & Trends
Analysis Report By Material, By Component (Hardware,
Services), By Printer Type (Desktop, Industrial), By Technology,
By Software, By Application, By Vertical, And Segment Forecasts,
2020 – 2027,” Grand View Research (GVR) placed the global 3D
printing market size at $11.58 billion in 2019, adding that 1.42
million units of 3D printers were shipped in 2018. GVR estimates
this number is expected to reach 8.04 million units by 2027.
20 | Coatings World ­www.coatingsworld.com May 2020
GVR places the industrial 3D printing segment at 77% in 2019,
with desktop 3D printers making up the rest. Stereolithography is
considered the most prevalent technology. In terms of materials,
GVR places polymers as more common, followed by metal and
ceramic materials. GVR believes that the metal segment is expected
to expand at the highest CAGR at more than 19% through 2027.
MarketsandMarkets offers similar numbers in its report,
“3D Printing Market by Offering (Printer, Material, Software,
Service), Process (Binder Jetting, Direct Energy Deposition,
Material Extrusion, Material Jetting, Powder Bed Fusion),
Application, Vertical, Technology, and Geography-Global
Forecast to 2024.” MarketsandMarkets estimated the 3D
printing market at $9.9 billion in 2018, up to $34.8 bil-
lion by 2024. MarketsandMarkets said that the healthcare,
aerospace and automotive segments were early adopters of
3D printing.
For example, HP Inc. is working with SmileDirectClub,
 3D Printing Is On The Rise FEATURE

which focuses on the field of teleden-
tistry. According to HP, SmileDirectClub
is utilizing HP’s Jet Fusion 3D printing
solutions to provide customized clear
aligner solutions.
SmileDirectClub creates an average of
more than 50,000 personalized mouth
molds each day, which works out to more
than 18 million a year, and uses 49 HP Jet
Fusion 4210 3D printers.
“SmileDirectClub is digitally trans-
forming the traditional orthodontics
industry, making it more personal, afford-
able and convenient for millions of con-
sumers to achieve a smile they’ll love,” said
Alex Fenkell, co-founder, SmileDirectClub.
“HP’s breakthrough 3D printing and data
intelligence platform makes this level of
disruption possible for us, pushing pro-
ductivity, quality, and manufacturing pre-
dictability to unprecedented levels, all with
economics that allow us to pass on savings
to the consumers seeking treatment using
our teledentistry platform.”
additive manufacturing as a proven tech-
nology for industrial mass production.”
Henkel is partnering with Origin to
develop new materials through optimizing
print processes, developing a 3D printable
photopolymer material with fire, smoke
and toxicity resistance properties for
Origin One printers.
“For a long time, materials have been
a big limiting factor in additive manu-
facturing,” said Ken Kisner, innovation
lead and founder of Molecule Corp.,
part of Henkel since May 2019. “We’re
committed to solving that piece of
the puzzle.”
In May 2019, Evonik Corporation and
Evolve Additive Solutions, Inc. announced
a joint development agreement to for-
mulate Evonik’s thermoplastic materials.
These materials will be used in Evolve’s
selective thermoplastic electrophoto-
graphic process (STEP). The companies
noted that initial development efforts will
focus on polyamide 12, PEBA, transparent
polyamide, and a polymer of the polyamide
6 series.
To meet the growing needs for 3D
printing materials, Arkema opened its new
global center of excellence for 3D print-
ing in Normandy, France in November.
The center will focus on high-performance
polymers. Within the Arkema group,
Sartomer is developing its N3xtDimension
UV-curable resin technology. The compa-
ny recently partnered with EnvisonTEC
on a new E-Aquasol resin for its printers.
“Collaboration is at the heart of our
3D Printing Solutions by Arkema plat-
form vision, aiming to identify new op-
portunities to support the successful
adoption of additive manufacturing,”
said Sumeet Jain, global director for 3D
Printing Business, Sartomer.
In September 2019, Massivit 3D
Printing Technologies, a major 3D printer
company, launched a fire-retardant photo
polymeric 3D printing gel for its Massivit
1800 Pro printer. CW

Materials and
Equipment
With a market that is growing rapidly, it
is not surprising that many major inter-
national companies are vying for a piece
of the material business. BASF, Henkel,
Arkema and Evonik are just a few of the
heavyweights in this field. These compa-
nies are combining in-house work with
some strategic additions.
Through its Forward AM brand,
BASF 3D Printing Solutions’ range of
materials includes powder bed fusion,
advanced plastic and metal filaments
and photopolymers.
In addition to its material offerings,
BASF acquired Sculpteo, an online 3D
printing service provider, in November
2019. The company reported that this will
allow BASF 3D Printing Solutions GmbH,
a wholly-owned subsidiary of BASF New
Business GmbH, to market and establish
new industrial 3D printing materials faster.
“Through the acquisition of Sculpteo,
we can provide customers and partners
with even faster access to our innovative
3D printing solutions,” said Dr. Dietmar
Bender, managing director BASF 3D
Printing Solutions. “Together with Sculpteo,
we are pursuing our goal of establishing

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