Ci Advanced

February 2015
www.ceramicindustry.com
a supplement to Ceramic Industry
INSIDE
Top Advanced Manufacturers
Ceramic Matrix Composites
Smart Auto Glass
Ceramic Coatings
11
22 Contents
Features
8
Rare Earths Worldwide

Rare earths supply and demand patterns will likely undergo several changes in
the next few years.
Industry Focus #glass #automotive #energy
11
2014 CI Top 10: Leading Worldwide Manufacturers

of Advanced Ceramics, Glasses and Refractories
We evaluated survey details combined with information gleaned from
company websites, annual reports, press releases, etc. to develop the rankings.
Industry Focus #automotive #electronics #defense #energy
16
High-Temperature Energy Recovery Using Thermoelectric Ceramics

Research is underway to optimize oxide ceramics that can help thermoelectric
harvesting reach its full energy-saving potential.
Industry Focus #automotive #aerospace #energy
20
Modern Mechanical Carbon Materials for Aircraft Seal Applications

Many commercial and military aircraft seal applications could benefit from
mechanical carbon solutions.
Industry Focus #aerospace #defense #carbon
28
Melt-Infiltrated Refractory Ceramic Matrix Composites

Melt infiltration processing can produce CMCs capable of withstanding ultrahigh temperatures.
February 2015
Volume 1
Issue Number 1
Columns
Inside CI
Departments
Industry News
Market Trends: Advanced and

Nanoscale Ceramic Powders
Materials Innovation: NRL

Researchers Develop Harder
Ceramic for Armor Windows
22
Market Trends: Smart Auto Glass

Continues Growth
24
Whats New
35
Industry Focus #composites #aerospace #defense #coatings
32
All-Inorganic Ceramic Performance Coatings

Ceramic coatings have been developed that can provide the benefits of
polymer coatings without their inherent shortcomings.
Industry Focus #coatings #energy #sustainability
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2 Februar y 2015 www.ceramicindustr y.com/ciadvanced
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Inside CI
By Susan Sutton
Editor-in-Chief, Integrated Media
We All Things
Advanced
ts February, and love is in the air. Here at Ceramic Industry, we particularly

love all things advanced in our industrywhether ceramics, glass or refractories. According to The Freedonia Group, the advanced ceramics market is projected to reach nearly $14 billion by 2017.* And thats just the ceramic part of
the picture; incorporating advanced glasses and refractories makes that figure much,
much larger. So you can see why were smitten.
These versatile advanced technologies can be found throughout industries ranging from automotive and aerospace to defense and biomedical/dental. This year,
were launching special CIAdvanced Digital Editions to highlight all of these exciting
advancements. Welcome to the first edition!
Case in point: cars, airplanes and industrial processes throw away waste heat every
day, and researchers are working to harness that energy in order to produce electricity.
Waste heat from diesel or gasoline engine exhaust can increase fuel efficiency while
reducing weight, carbon deposit and manufacturing costs of both military and commercial vehicles, writes TAM Ceramics Eric Hanson in this issue.
One drawback has traditionally been the high temperatures of these exhaust
streams. Hmmmm, what materials can easily withstand high temperatures? You
guessed it: ceramics! Read Erics article entitled High-Temperature Energy Recovery
Using Thermoelectric Ceramics on pp. 16-19 to learn more.
This special edition also includes our popular annual CI Top 10 listing of the leading worldwide manufacturers of advanced ceramics, glasses and refractories. The
industry is so dynamic that, after reviewing all of the information, we felt we had to
add a +1! Be sure to check it out on pp. 11-15.
What makes your heart go pitty-pat about advanced ceramics, glasses and
refractories? Please share your comments by contacting me at (248) 786-1704 or
suttons@bnpmedia.com.
this month on
ceramicindustry.com
Glass Innovation: Enabling
More Vibrant LED Displays
GE has discovered that the use of
potassium fluorosilicate phosphor in
LED systems results in less color bleed
and a richer picture. Learn more at
www.ceramicindustry.com/extras.
CIAdvanced Microsite
This easy-to-navigate microsite
provides features, columns, news and
new technologies related to all things
advancedceramics, glass, refractories,
composites, and more!
Advance your knowledge at
www.ceramicindustry.com/CIAdvanced.
Lets Get Social!

Join our social media community
on LinkedIn, Twitter, Facebook and
Google+ for the latest industry news,
trends and discussions!
Connect at www.ceramicindustry.com/connect.
*Advanced Ceramics, published November 2013, www.freedoniagroup.com.
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In the News
CoorsTek Finalizes Acquisition
of Covalent Materials Corp.
CoorsTek recently announced that it
has finalized its acquisition of Covalent
Materials, a leading Japanese engineered
ceramics manufacturer. According to
CoorsTek, this strategic acquisition furthers its leadership in engineered ceramics, through a market-leading portfolio
of over 300 materials, including alumina, carbon, silica, silicon, silicon carbide, quartz, yttria and zirconia, reportedly supported by the industrys largest
and most sophisticated research and
development infrastructure, with centers
in North America, Europe, and Asia.
CoorsTek now has over 50 production facilities in 14 countries across four
continents, and 6,000 employees. The
Covalent facilities are now a part of the
CoorsTek Semiconductor and Medical
group led by Jonathan Coors, its CEO.
Toshio Nagahama, president and CEO
of Covalent, will remain in his position,
reporting to Coors. For more information, visit www.coorstek.com.
Ceramic Fuel Cells Announces

Fully Funded BlueGEN Program
Ceramic Fuel Cells Ltd. (CFCL) recently
announced the commencement of the
first fully funded BlueGEN program,
where the BlueGEN is installed at no
cost to the end user. The program, comprising a 100 kW fleet of BlueGENs (a
minimum of 65 units) is targeted primarily at public-sector organizations
that can take advantage of the carbon
and energy savings offered by BlueGEN. The funding structure allows
BlueGENs to be installed in end-user
premises at no upfront cost. End users
pay for the costs of gas and BlueGEN
maintenance and receive the benefits of
the electricity generated and the heat
recovered for hot water. This program
has been developed and will be run by
one of CFCLs UK distributors, iPower
Energy Limited (iPower).
Earlier this year, we announced our
intention to revise our sales strategy in
order to focus primarily on larger-scale
projects, said Bob Kennett, CEO of
CFCL. We are very pleased to see the

first of a number of projects of this type
come to fruition. It clearly demonstrates
the commercial viability of this contractual structure whereby third-party funding is used to support the project and
provide end users with attractive benefits. Additional details are available at
www.cfcl.com.au.
Kyocera and Century Tokyo

Leasing to Develop Floating
Solar Power Plant
Kyocera Corp. and Century Tokyo
Leasing Corp. recently announced
that Kyocera TCL Solar LLC, a
joint venture established by the two

companies, will develop and operate a 13.4-megawatt (MW) floating
solar power plant on the Yamakura
Dam reservoir, managed by the Public Enterprises Agency of Chiba Prefecture in Japan for industrial water
services. The plant will reportedly
become the largest floating solar
installation in the world (in terms of
output, as of December 22, 2014).
When we first started R&D for
solar energy in the mid-1970s, the technology was only viable for small applications such as street lamps, traffic
signs and telecommunication stations
in mountainous areas, said Nobuo
Kitamura, senior executive officer and
general manager of the Corporate Solar
Energy Group at Kyocera. Since then,
we have been working to make solar
energy use more ubiquitous in society, and have expanded our business
to residential, commercial and utilityscale solar applications. We are excited
to work with our partners on this
project, taking another step forward
by utilizing untapped bodies of water
as solar power generation sites. Visit

http://global.kyocera.com for more
information.
GE to Build Manufacturing
Facility in Pennsylvania
GE recently announced that it will
build a new manufacturing facility to
drive innovation and implementation
of advanced manufacturing technologies across GE. The new facility represents a $32 million investment over
three years by the company and will
result in the creation of 50 high-tech
engineering jobs initially, in disciplines
ranging from mechanical and electrical to systems and software engineering. These technologists will join GEs
global network of 50,000 scientists,
engineers, and skilled labor who are
working to solve some of the worlds
toughest challenges.
The new facility reflects GEs belief
that the intersection of technology and
manufacturingmarrying hardware
with softwareis bringing a new era
of manufacturing. Advanced manufacturing is about making things better
and faster for customers. It includes
new digital fabrication technology, lean
manufacturing methods and rapidprototyping, advanced materials sciences, supply chain efficiency and open
innovation. The facility will reportedly
focus on improving capabilities and
usage of additive manufacturing across
GE while advancing materials sciences
and inspection technologies. Construction is expected to begin in March
2015 and be completed by September 2015. Visit www.ge.com for more
information.
PPG to Supply Gulfstream

Windows, Assemblies
PPG Industries Aerospace transparencies group has recently been selected
by Gulfstream to supply G500 and
G600 business jet windshields, side
cockpit windows and passenger cabin
window assemblies that will reportedly provide superior performance for
operators and maximum efficiencies for

Gulfstream. The passenger cabin windows will use OPTICOR advanced
transparency material to maintain
optical clarity and provide a quieter
cabin. The equipment has been proven
through its use on the Gulfstream
G650 program.
According to Mark Hood, PPG Aerospace global platform manager for general aviation transparencies, the windshields and windows will offer clean aerodynamics, reliability, acoustic and safety
benefits, and fuel economies. PPGs
transparencies have a demonstrated history of performance, said Hood. Aircrews will appreciate the enhanced visibility through the wide windshields and
broad side cockpit windows. Passengers
will enjoy better viewing through the passenger cabin windows that are aviations
largest in a bright, quieter cabin.
PPG will produce the cockpit windows and passenger cabin window
assemblies at its Huntsville aircraft
products plant for delivery to Gulfstreams Savannah, Ga., facility. Opticor advanced transparency material is
manufactured at PPGs Sylmar, Calif.,
Aerospace transparencies plant.
PPG earned a 2013 Gulfstream Supplier of the Year award for its transparencies produced in Huntsville and Sylmar, and by its Ampaspace subsidiary
in Casaletto Vaprio, Italy. Visit www.
ppgaerospace.com for more information.
ANH Refractories Becomes

HarbisonWalker International
One of the worlds leading refractories
materials and services providers, ANH
Refractories Co., recently announced
the decision to rebrand itself under the
new name of HarbisonWalker International (HWI), effective immediately.
The decision was made following an
exhaustive market research and branding initiative in which one of the companys legacy brands, Harbison-Walker,
returned the highest awareness and positive customer perception of all of the
companys brands, as well as the brands
of the companys refractory competitors.
Headquartered in Pittsburgh, Pa.,

HarbisonWalker International has a
network of 18 manufacturing facilities and 28 distribution centers to
serve markets across North America, manufacturing facilities in the
UK, Indonesia, and Mexico, as well
as a lab/testing facility located in
China. For more information, visit
www.anhrefractories.com.
Ceramics to Benefit from

Biocompatible Material Demand
U.S. demand for biocompatible materials is forecast to increase 4.9% annually to $5.6 billion in 2018. Synthetic
polymers will remain the top-selling
product group by far, due to quality,
performance, and cost advantages in a
broad range of applications, said Bill
Martineau, analyst.
Ceramic materials will generate the
fastest long-term growth in demand
among all biocompatible materials as
advances in nanotechnology lead to the
introduction of new and improved compounds for orthopedic implants, spinal
fixation devices, and dental repair and restoration products. Spurred by increasing
applications in cosmetic surgery, wound
management, and arthritis therapy, hyaluronic acid will post the fastest revenue
gains among natural biocompatible polymers. Titanium and titanium alloys will
grow the fastest in demand among biocompatible metals as high strength, lightweight, and shape memory advantages
promote their expanding use in cardiac,
orthopedic, and dental implants. These

and other trends are presented in Biocompatible Materials, a recent study
from The Freedonia Group, Inc.
Advances in alumina-zirconia nanocomposites will broaden the use of
biocompatible ceramics in dental and
orthopedic implants. For more information, visit www.freedoniagroup.com.
Murata Joins Singapores

EcoCampus Initiative
Murata and the Nanyang Technological University (NTU Singapore)
recently signed a research collaboration
agreement that marks Muratas entry
into the EcoCampus research program,
led by the Energy Research Institute at
NTU (ERI@N). The NTU Singapores
EcoCampus initiative is a campus-wide
sustainability framework with demonstration sites to achieve 35% reduction
in energy, water and waste intensity by
2020, reportedly thus transforming the
university campus into one of the most
environmentally friendly university
campuses in the world.
This research collaboration enables
Murata to test, demonstrate and further develop the companys Smart
Energy Management System installed
in various areas of the campus buildings. The project is expected to span
over two years. Visit www.murata.com
for more information.
Find more news
at
www.ceramicindustry.com/CIAdvanced!
World First at Ceramics Expo 2015

THE CERAMIC INDUSTRY IS GEARING UP for the launch of Ceramics Expo on April 28-30,
with some of the worlds largest technical ceramic manufacturers confirmed as exhibitors and sponsors,
including Saint-Gobain, Morgan Advanced Materials, Corning and CeramTec. Taking place in Cleveland, Ohio,
the show will be dedicated to providing a marketplace for raw materials, equipment, machinery and technology used within the ceramic manufacturing supply chain.
The event will also showcase a world first, SolidCAMs debut of iMachining for Ceramicsa technology
for precision shaping that reportedly saves 70% in CNC machining time. This CAM software will be taking
center stage with live exhibitions demonstrating the machines high levels of speed, accuracy and efficiency.
With preliminary tests yielding consistent cycle time improvements ranging from 20-40 times faster than
traditional machining methods, this technology reportedly has proven results of increased profitability for its
users. For more information, visit www.ceramicsexpousa.com.
Industry Focus
Market Trends
#oxides #electronics
#nanomaterials
Advanced and Nanoscale

Ceramic Powders on the Rise
The global market for advanced and nanoscale ceramic powders
is expected to grow to $12.1 billion by 2018.
he global market for advanced

and nanoscale ceramic powders is expected to grow to
$12.1 billion by 2018, with
a five-year compound annual growth
rate (CAGR) of 6.2%, according to
Advanced Ceramics and Nanoceramic
Powders, a recent report from BCC
Research, a publisher of technology market research reports based in Wellesley,
Mass. The nanoceramic category is the
fastest moving segment in this market,
growing at a significant CAGR of 13.5%.
Advanced ceramic and nanoceramic
powdersoxides, carbides, nitrides,
and boridesare sold as starting materials for solid commercial articles.

Oxides are by far the highest value
of the advanced ceramic powders and
ceramic nanopowder market, with over
80% of the market value, said William
Davison, Ph.D., analyst. Nanopowders
are expected to command an increasing market share, from over 10% in
2013 to nearly 20% by 2018. Carbides,
nitrides, and borides are expected to
retain a market share totaling less than
5%. These powders enable technology critical to a wide range of applications, including electronic devices and
systems, high-temperature applications,

and applications such as abrasives, cutting tools, and guide fixtures.
The advanced ceramics category, the
largest segment in the overall market, is
expected to grow to nearly $10 billion
by 2018 and register a CAGR of 5%.
However, the nanoceramic segment,
which was valued at just about $958
million in 2012, is expected to jump to
$2.1 billion in 2018.
Advanced ceramics are a significant
category of engineered materials pushing the performance of technology-based
components and systems, said Davi-
2012
2013
CAGR%
20132018
2018
Material
Pounds
Pounds
Pounds
Advanced Ceramic
3,144.9
7,413.8
3,342.7
7,841.7
3,844.7
9,984.4
5.0
2,121.9
13.5
12,106.3
6.2
Nanosized
Ceramic
Total
957.9
3,144.9
8,373.7
1,126.3
3,342.7
8,968.0
3,844.7
Table 1. Global consumption of advanced and nanoscale ceramic powders through 2018 (million lbs/millions).
Note: Only market value figures are reported for nanopowders due to the industry structure of internal consumption of these materials. (Source: BCC Research)
son. The market for these materials is
beginning to expand at pre-2009 recession levels, including certain segments
that had experienced slow growth due
to conservative business planning and
exhaustion of existing inventory stocks.
The Evolution of
Advanced Ceramics
Advanced ceramic and nanoceramic
powders generally refer to inorganic
nonmetallic granular materials that are
fabricated from chemical processes, as
differentiated from what are termed
industrial minerals. The latter group is
mined directly from the earth and purified and reduced in size to particular
specifications.
The origination of advanced ceramic
powders in the post-World War II era
was due to two factors: a need for
higher purity of ceramics for dielectric
applications, and a need for a lowerand smaller-size defect population for
higher-temperature performance parts.
These properties were not obtainable
with processed minerals and therefore
necessitated starting powder production by chemical precipitation and other
methods. The fact that precipitated aluminum oxide (alumina) is an intermediate via the Bayer Process in the HallHeroult plating of aluminum metal contributed an already existing advanced
ceramic powder for use in advanced
ceramic applications.
From the initial uses of alumina
powder for ceramic substrates, where
The combination of
the factors of reduced
production costs
and identification of
appropriate markets
has enabled nanoscale
ceramic powders to
find a commercial
presence.
reproducible electric properties were
required, use of precipitated powders
spread to areas such as the barium
titanate family of high-dielectricconstant capacitor materials, where in
order to produce the proper ceramic
material, pure small-particle-size precursors of barium and titanium oxides
are necessary. Structural ceramics such
as silicon carbide and silicon nitride
had long been identified as favorable materials in high-temperature
strength applications, but due to the
small internal or surface defect size of
these materials (which can cause fracture), more uniform, chemically pure
starting materials became desired than
were commonly available in the mid20th century.
The two critical properties of
advanced ceramic powders that dominate the quality of fabricated ceram-
ics derived from them include particle

size distribution and chemical purity.
The use of chemical precipitation or
other controlled powder synthesis techniques enable the tailoring of particle
size, size distribution and shape, while
purity can be established at the level
of the starting chemicals used in powder manufacturing. These properties
are important in controlling every step
of the ceramic manufacturing process,
including ceramic slurry rheology, particle compaction during pressing, initially
formed article (green body) strength
and drying behavior, microstructure
development during heat treatment (sintering) and any subsequent annealing,
and the properties of the finished part.
The latter include the critical performance properties of the finished part,
for which controlled starting powder is
necessary.
The combination of the factors of
reduced production costs and identification of appropriate markets has enabled
nanoscale ceramic powders to find a
commercial presence. Initially only
obtainable in microgram quantities via
vapor phase condensation techniques,
more economical production methods
have surfaced, including those adapted
from chemical precursor methods developed for ceramic powders.
For additional details, visit www.bccresearch.com.
WANT TO LEARN MORE ABOUT ADVANCED CERAMICS?
Visit www.ceramicindustry.com/CIAdvanced for features,
news and more!
Industry Focus
#glass #automotive
#energy
Rare Earths
Worldwide
Rare earths supply and demand patterns will likely
undergo several changes in the next few years.
By Ted Dickson, Director, TAK Industrial Minerals, and

Nick Dellow, Consultant, Materials Technology Publications
he rare earths industry is in a state of transition. China, which currently

dominates in the production and supply of rare earths, as well as in many
downstream product areas, is being challenged by new producers from other
regions. This global diversification will potentially result in greater stability
in terms of both supply and pricing.
Rare Earths Overview

Rare earths are categorized into two main groups: light and heavy. The heavy rare
earths tend to be rarer and thus generally command higher prices, though there are
exceptions. The proportions of light and heavy rare earths mined from any given
deposit rarely match the market demand for the individual rare earth elements, with
excesses of some of the light rare earth elements (e.g., cerium and lanthanum) but
tight supply of several of the heavy rare earths.
Much of the new production outside

of China involves deposits rich in light
rare earths, a factor that is expected to
exacerbate these excesses unless new
applications can be developed. Even
deposits that are promoted as being rich
in heavy rare earths usually have significant volumes of light rare earths.
Imbalances in supply are likely to
remain, although some of the previous
predictions of shortages of rare earths
have not come to pass. The general
easing of supply since 2011 is a major
reason for this, but shortages have also
diminished as technological developments have reduced the requirement for
rare earths in several applications (e.g.,

dysprosium in magnets).
Current global demand for rare
earths is estimated to be 125,000 metric tons in terms of rare earth oxides,
and this is expected to grow to 160,000
metric tons by 2017 (see Table 1). The
sectors that consume rare earths tend to
be technology led; therefore, developments in technology can result in significant changes in demand patterns.
China accounted for about 95% of
the global supply of rare earths in 2012.
This is set to fall steadily, to around
60% by 2020, as new non-Chinese production of rare earths comes onstream;
Molycorp, Inc. of the U.S. and Lynas
Corp. of Australia have already begun
the first phases of their rare earths production. Currently, several hundred rare
earth exploration projects are being
conducted worldwide, with notable
deposits discovered in every continent except Antarctica. However, only
a relatively small proportion of these
projects are likely to reach the production phase in the next five years, since
forecast demand rates for rare earths
predict that there would be large-scale
surpluses if many of these projects were
to begin commercial operation within
this time period.
Successful new projects will require
integration from mining the rare earth
ores through to production of mixed
rare earth concentrates to the separation of individual rare earths. Mixed
rare earths obtain only a relatively
small percentage of the value of separated products, with light rare earth
mixtures achieving some 15-20% of the
value of the contained rare earth oxides
(although 30% is more common), rising to 40-50% in the case of heavy rare
earths. However, as yet, there is little
independent capacity for separation
outside of China. A possible alternative
is a centralized toll processing operation
that can accommodate a range of ores.
China is not only the largest producer of rare earths but also the largest
consumer, manufacturing significant
quantities of rare earth magnets and
other downstream products. Developing a market share within China could
Table 1. Global rare earth demand by rare earth oxides, 2005-2017 (in metric tons).
prove to be a challenge for the new nonChinese suppliers of rare earths. However, a number of consumers situated
in other countries are already taking an
interest in developing relationships with
rare earth companies based outside of
China, in order to secure long-term supplies that are not dependent on Chinese
exports. Such relationships will help to
foster the further development of production bases for downstream products
outside of China. This process is likely to
take some time in the face of continued
competition from Chinese companies.
Consumption by
Market Sector
The permanent magnets industry is the
largest single consumer of rare earths,
and consumption rates are expected to
grow at an average of 8.5% per year
through 2017. Though this is a strong
growth rate, it is less than predicted
a few years ago due to lower growth
being experienced in the wind turbine
and hybrid/electric automobile sectorstwo major applications for rare
earth magnets. The main rare earth
elements used are neodymium and praseodymium, as well as dysprosium and
terbium. There had been fears that there
would be significant shortages of dysprosium for this application, but consumersparticularly major Japanese
companieshave developed technologies that enable them to substantially
reduce the amounts required while
retaining the advantages gained from
the dysprosium additions.
The second largest consumer is the

catalysts sector, encompassing fluid
catalytic cracking (FCC) catalysts for
petroleum refining, and automobile
exhaust catalysts. Demand for rare
earths from this sector is expected to
grow by almost 10.5% a year, though
the growth will be skewed higher in
2014 and 2015 due to new regulations covering emissions from diesel
engines coming into force in the European Union; growth is then predicted
to moderate and in the longer term
is expected to level out at about 6%
per year.
As with permanent magnets, FCCs
have been subject to technical developments that have resulted in lower
amounts of rare earthsprimarily lanthanumbeing needed. The spike in
rare earth prices in 2010-2011 encouraged such developments. As prices and
supplies have eased, however, the incentive to reduce the amount of lanthanum
used has waned, and consumption levels are expected to increase as a result.
Demand for rare earths in metal
alloys (including rare earths in both
NiMH batteries and steel additives)
is expected to grow at an average of
3.4% per year through 2017, although
growth rates may decline after that
as lithium-based batteries continue
to replace NiMH batteries in many
applications. Rare earths for polishing
powders, primarily for glass, are also
expected to show growth in demand,
averaging 4.5% per year over the next
three years, after a period in which the
] Rare Earths Worldwide

ruption, such as an escalation of the
dispute over the sovereignty of islands
claimed by both China and Japan,
could undermine the current perceived
stability of supply from China. Supplies
from new producers outside of China
would help negate the worst aspects of
any such disruptions, though this is of
course dependant on how far forward
such new non-Chinese rare earths projects move toward commercialization.
Environmental Issues
industry has made efforts to reduce consumption because of escalating prices.
Demand for rare earths used in phosphors is expected to average a modest
3% a year through 2017 and possibly
may slow further or even decline after
2017 due to the replacement of compact fluorescent lighting by LED types,
which require smaller additions of rare
earths and have considerably longer
operational lifecycles. Rare earths for
glass additives are expected to grow at
an average rate of 4.5% a year to 2017,
while the wide range of other applications is predicted to grow on average at
rates of 3% per year.
Prices
Rare earth prices have shown significant
volatility over the past five years, and
much of this has been the direct result of
specific policies implemented by China.
Prices of rare earths escalated severalfold in 2010 and reached a peak in mid2011, mainly in reaction to Chinas lower
export quotas for 2010, which restricted
global supplies, causing near panic and
providing the impetus for exploration
companies to seek new deposits outside
of China. Concerned about shortages of
supply, consumers built up rare earths
stocks following the price spikes of 20102011, but their fears were unfounded and
companies have since been running down
these stocks, resulting in lower demand
and lower prices.
From the dramatically inflated peaks
in 2011, prices for rare earths have
since fallen significantly and are now
closer to levels witnessed before the
global economic downturn that began

in 2008. Prices are currently viewed as
being too low to encourage new suppliers, especially those processing light
rare earthscerium and lanthanum,
in particular. The cost of setting up
mines and plants to process rare earths
through to separation requires substantial investment. However, prices are
expected to strengthen through 2014,
as demand picks up in line with general
global economic improvements and by
2015 should stabilize at levels whereby
a reasonable return could be expected
among the new producers.
Chinas rare earths industry is now
entering a process of rationalization
and consolidation. From a current base
of as many as 200 companies involved
with the mining and processing of
rare earths, this process of rationalization may ultimately result in a reduction to just 10 major companies. This
will address the excess capacity within
Chinas rare earths industry and result
in a more organized industry with a
substantial reduction of illegal production and better environmental practices, all of which is expected to put
upward pressure on rare earths prices.
In addition, the Chinese government
has started purchasing rare earths to
build up a stockpile, and a rare earths
exchange has been startedcurrently
only dealing in the spot marketto give
more clarity on prices and introduce a
level of longer-term stability.
A repeat of the price spikes seen in
2010-2011 is not expected through
2017, although a major political dis-
Chinas poor environmental record

with regard to the mining of rare
earths has come under considerable
criticism. Part of the problem can
be attributed to widespread illegal
mining practices, which the Chinese government is now trying to
eliminate through its rationalization
and consolidation program. Meanwhile, legitimate producers are being
forced to adopt more stringent environmental practices or face severe
penalties.
An environmental issue that needs
to be addressed by many of the new
producers of rare earths involves the
safe handling and long-term storage
of radioactive waste generated by the
processing of rare earth ores. There
can be up to 0.1% of thorium oxide
(ThO 2) in bastnasite ore, and 4-10%
ThO 2 and 0.1-0.5% uranium oxide
(U3O8) in monazite and xenotime ores.
Monazite and xenotime are of particular interest to potential new producers since they contain higher levels of
the more valuable heavy rare earths.
The disposal cost of radioactive waste
streams can be significant, as they
require long-term secure storage, and
this needs to be factored into the overall costs of establishing commercially
viable rare earths operations.
For additional information, email nick.dellow@gmail.com.
Editors note: This article provides summary information from a recent market
report by Ted Dickson and Peter Harben
of Materials Technology Publications
entitled The Rare Earths Industry Worldwide 2014-2017.
CI Top 10 (+1)
Our exclusive ranking details the leading worldwide manufacturers
of advanced ceramics, glasses and refractories.
ere pleased to present the second annual CI Top 10! Following the success of the inaugural ranking last year, and taking into account your suggestions, weve expanded the scope of the CI Top 10
to include not only the leading worldwide manufacturers of advanced ceramics, but also advanced
glasses and refractories.
To develop the rankings, we provided a survey on our website so that company representatives could nominate
their company for inclusion. The survey, which was also sent to key industry players, requested details such as annual
revenues and number of employees, as well as views on the companys past performance and future outlook. Thank
you to those of you who completed the survey!
We evaluated all of the information provided in the survey and combined those details with information gleaned
from company websites, annual reports, press releases, etc. in order to develop the rankings. Once wed evaluated all
of the information, we found that we couldnt limit the ranking to just 10 companiesso we included a +1!
If you would like your company to be considered for the 2015 CI Top 10, or if you have any suggestions for
future rankings, please contact Kelsey Seidler, managing editor, at (252) 509-4120 or seidlerk@bnpmedia.com.
] CI Top 10
1.
Saint-Gobain
Tour Les Miroirs, 18 Avenue dAlsace, 92 096 La Dfense Cedex, France

www.saint-gobain.com
CEO: Pierre-Andr de Chalendar
With nearly 190,000 employees and a presence in 64 countries, Saint-Gobain is a global designer, producer and distributor of a variety of building and high-performance materials, ranging from photovoltaic glass to industrial ceramic
components and more. Saint-Gobains Innovative Materials
group, which represents 21% of total net sales, produces
products such as flat glass, abrasives and ceramics.
According to Pierre-Andr de Chalendar, chairman and
CEO, a 2.7% decline in net sales for 2013 is not a major cause
for concern in the upcoming year. In 2014, trends for our
different markets should improve even though the climate is
likely to remain uncertain, he said.
Saint-Gobain Crystals, a Saint-Gobain company, provided
its 100th set of sapphire-engineered armor to the U.S. Army
and Marine Corps in November 2013. The advanced ceramicbased armor was designed to improve the performance of bulletproof windshields and door windows on the M142 High
Mobility Artillery Rocket Launcher.
Earlier this year, Saint-Gobain announced plans for a new,
state-of-the-art North American corporate headquarters in
Malvern, Pa. The relocation is intended to position SaintGobain and its CertainTeed Corp. subsidiary for greater
growth and expansion in North America.
Last month, Saint-Gobain completed its acquisition of
Z-Tech LLC. The Bow, N.H.-based Z-Tech produces zirconia
powders for applications such as pigments for ceramic tile and
thermal coatings for the aeronautics industry. Z-Tech will be
integrated within Saint-Gobains Ceramic Materials business.
Sources: company website, press releases
2.
AGC Group
1-5-1, Marunouchi, Chiyoda-ku, Tokyo 100-8405, Japan

www.agc.com
CEO: Kazuhiko Ishimura
With more than
50,000 employees
in over 30 countries, the AGC
Group is segmented
in four main areas
of operation: Glass
AGCs glass roofs were featured on all player
(48% of sales),
benches at the 2014 FIFA World Cup Brazil.
which produces
products such as float, low-e and automotive glasses; Electronics (25%), including glass substrates for various electronics
applications, synthetic quartz glass, and glass frit/paste; Ceramics/Other (6%), which produces refractory materials, fine
ceramics and sputtering targets; and Chemicals (21%).
In October of last year, AGC announced it would build its
third automotive glass plant in China; the group also began
production of an architectural glass facility in Brazil. In

November, AGC announced plans to establish a new automotive manufacturing base in Mexico. A groundbreaking
ceremony for a new automotive glass plant in Villa de Reyes,
San Luis Potos, Mexico, was held in June 2014. The plant is
expected to begin production in 2016.
Early this year, AGC unveiled plans to build an ultra-thin
glass facility in Thailand. The new plant is expected to boost
the groups production capacity for ultra-thin glass used in
touchscreens for notebook computers and other electronic
devices by 50%.
In June-July, the world was able to view AGCs glass
roofs on all player benches during the 2014 FIFA World Cup
Brazil. The roofs chemically strengthened glass showed that
the technology, which had been originally developed for small
electronic devices like smartphones and tablets, could be used
in larger fixtures.
Sources: company website, annual report
3.
Corning Inc.
One Riverfront Plaza, Corning, NY 14831

www.corning.com
CEO: Wendell P. Weeks
According to the companys website, Cornings products
enable diverse industries such as consumer electronics, telecommunications, transportation, and life sciences. They
include damage-resistant cover glass for smartphones and tablets; precision glass for advanced displays; optical fiber, wireless technologies, and connectivity solutions for high-speed
communications networks; trusted products that accelerate
drug discovery and manufacturing; and emissions-control
products for cars, trucks, and off-road vehicles.
Corning employs about 30,000 people at nearly 130 locations worldwide, including research centers in North America, Europe and Asia. Segments include Display Technologies
(glass substrates for flat panel displays and LCDs), Environmental Technologies (ceramic substrates and filters for cars
and trucks), and Specialty Materials (formulations for glass,
glass ceramics and fluoride crystals), among others.
Last year marked the 40th anniversary of the companys
automotive ceramic substrate business. Since 1973, Corning
has reportedly produced more than 1.5 billion light-duty substrates to help control mobile emissions. Our substrates have
helped capture billions of tons of air pollutants over the past
40 years, said Hal Nelson, division vice president and business director of Corning Environmental Technologies.
Early this year, Corning completed its acquisition of Koreabased LCD glass manufacturer Samsung Corning Precision
Materials Co. Ltd., which was formerly an unconsolidated
equity venture with Samsung Display Co. Ltd. By gaining
full control of its global fusion glass manufacturing platform,
Corning anticipates greater flexibility in asset use, improved
operational efficiencies, and better positioning for new specialty glass market opportunities.
4.
Murata Manufacturing Co. Ltd.
10-1, Higashikotari 1-chome, Nagaokakyo-shi, Kyoto 617-8555, Japan

www.murata.com
CEO: Tsuneo Murata
applications; Automotive (50%); and Technical Glass (10%),

which manufactures products like LCD glass and glass cord.
The company operates with 28,000 employees in 30 countries
and serves customers in 130 countries.
Beginning in January 2013, NSG reduced its architectural
float glass capacity by placing its Cowley Hill, UK, line on
hold due to the overcapacity in the European glass market.
Earlier this summer, the group lit up its new ultra-thin glass
float line at NSG Vietnam Glass Ltd. The new line, which is
the second float line dedicated to ultra-fine flat glass for NSG,
will begin production in the second half of this fiscal year.
6.
Kyocera Corp.
6 Takeda Tobadono-cho, Fishimu-ku, Kyoto 612-8501, Japan

www.kyocera.com
Chairman: Tetsuo Kuba
Muratas RCE Series MLCC.

Murata specializes in the manufacture of technical ceramic
components for electronics applications. Its 48,000 worldwide
employees produce products such as multilayer ceramic capacitors (MLCCs) and piezoelectric ceramic components.
The companys Capacitors segment saw nearly 21% growth
in the 2014 fiscal year, due partially to increasing demand for
applications in smartphones and automotive. The Piezoelectric
Components segment, which produces products such as surface acoustic wave (SAW) filters, ceramic resonators, piezoelectric sensors, and ceramic filters, also increased sales in fiscal 2014, by over 19%. Rising mobile phone demand led to
growth for SAW filters, while automotive and home electronics helped bump sales for ceramic resonators.
Murata anticipates that its 2015 fiscal year (ending March
31, 2015) sales will increase by nearly 9% due to continually increasing demand for smartphones and tablets, as well
as automotive electronics. Significant capital expenditures will
target increasing production for new and high-growth products, more efficient production processes, and R&D.
Sources: company website, annual report, press releases
5.
The NSG Group
Sumitomo Fudosan Mita Twin Building,

West Wing, 5-27, Mita 3-Chrome, Minato-ku, Tokyo 108-6321, Japan
www.nsg.com
CEO: Keiji Yoshikawa
The NSG Group produces high-performance glass and glazing
solutions in three business areas: Architectural and Building
Products (40% of fiscal 2014 sales), producing products such
as solar control glass, self-cleaning glass, and glass for solar
Kyocera employs nearly 70,000 people via 230 group companies located worldwide. Revenue within the Fine Ceramics
segment increased 6.9% in the 2014 fiscal year, while revenue
in the Semiconductor Parts segment increased 12.3%, according to Elly Yoshikawa, deputy manager of Corporate Communications. Kyoceras financial forecast for the 2015 fiscal year
calls for total consolidated revenue to increase 9.2%. (This
forecast includes all business segments, both ceramic and nonceramic. Separate forecasts for individual business segments
are not available.)
In its Fine Ceramic Parts Group, Kyocera is working to
develop new products in a wide range of markets by leveraging fine ceramic materials technology, processing technology, and design technology accumulated since its founding
in 1959. In the industrial machinery market, the company is
strengthening its development of parts for next-generation
semiconductor fabrication equipment to support the trend
toward larger silicon wafers; parts for the environment and
energy markets, such as fuel cells; and LED-related products,
which are growing in demand with the proliferation of LED
lighting systems.
In the automotive market, Kyoceras R&D efforts include
camera modules for rearview detection and collision avoidance, where demand is forecast to increase due to new safety
regulations in the U.S. At the same time, Kyocera is concentrating development efforts on ceramic parts for diesel engines
to reduce carbon dioxide and other harmful emissions. In the
digital consumer equipment market, including smartphones
and TVs, the company is strengthening development of Smart
Sonic Receiver and Smart Sonic Sound technologies that make
maximum use of the exceptional piezoelectric properties of
ceramics.
In order to respond to these and other market trends and
expand business opportunities, Kyocera is working to develop
new, high-value-added products that leverage its material,
design and layering technologies. Specifically, in the ceramic
packages and substrates business, Kyocera is developing
high-strength, high-rigidity, ultra-small and thin microelecwww.ceramicindustr y.com/ciadvanced Februar y 2015 13
] CI Top 10
tronic device packages made of ceramics that employ microwiring, as well as ceramic packages for optical communications devices capable of higher frequency operation.
Sources: company contact, company website
7.
RHI AG
Wienerbergstrasse 9, Vienna, Austria 1100

www.rhi-ag.com
CEO: Franz Struzl
With roughly 8,000 employees, 33 production facilities
and more than 70 sales offices, RHI serves over 10,000
customers in the steel, cement, nonferrous metals, glass,
energy and chemical industries in nearly all countries of the
world. RHI produces more than 1.7 million tons of refractory products per year and supplies customized product
and system solutions.
According to Randolf Fochler, head of Corporate Communications, sales declined slightly (4.4%) in 2013 compared
to the previous year and are expected to remain fairly flat for
2014. The business climate for refractories remains challenging because many end-user industries tend to cautious investment behavior, he said.
In May 2013, RHI announced that it would reduce production capacity in Europe by closing its Duisburg, Germany
plant, which produced primarily magnesia-carbon brick. This
move was made as a result of decreasing demand from the
steel industry in the European Union.
RHI invested over $70 million in a raw material plant and
mining rights in Turkey last year. It also acquired almost 70%
of the shares of New Delhi-based Indian Orient Refractories
Ltd. last year for about $65 million.
Sources: company contact, company website, press releases
8.
SCHOTT AG
Hattenbergstrasse 10, 55122 Mainz, Germany

www.schott.com
Chairman of the Management Board: Frank Heinricht
SCHOTTs workforce of 15,400 employees provides customers with specialty glass and materials and advanced
technologies for the architecture, pharmaceutical, electronics, transportation and optics industries. According
to the 2013 annual report, SCHOTTs recent withdrawal
from the polycrystalline photovoltaics business caused a
decline in sales, but a strengthened focus on pharmaceutical packaging is expected to see significant growth in the
coming months.
In May 2013, SCHOTT introduced a high-temperature
infrared (IR) grill using heat-tolerant glass-ceramics capable of
evenly dispersing heat to sear meats perfectly without drying
them out. SCHOTTs concept home barbecue combines the
advantages of IR and high-performance glass-ceramic materials to inspire the next generation of grills for the benefit of
home cooks and chefs everywhere, said Karen Elder, market14 Februar y 2015 www.ceramicindustr y.com/ciadvanced
The IR concept grill uses a high-performance glass-ceramic grate system to

ensure no loss of IR heat.
ing manager at SCHOTT North America.
Earlier this year, SCHOTT North America announced the
creation of SCHOTT Defense as a specialized segment. The
final completion of the SCHOTT Defense transition allows
us to further strengthen and secure our long-term partnership
with the U.S. military, as well as optimize market access to the
most sensitive U.S. defense, intelligence, and homeland security programs, said Major General Scott Custer, USAF (Ret.),
president and CEO of SCHOTT Defense. As the defense
community continues to seek sensitive technology solutions
to enhance operational capability and performance, SCHOTT
Defense now has more access and flexibility to deliver innovations to protect the warfighter while reducing redundancy and
minimizing lifecycle costs.
9.
Morgan Advanced Materials
Quadrant, 55-57 High St., Windsor, Berkshire SL4 1LP, England

www.morganadvancedmaterials.com
CEO: Mark Robertshaw
As the company name implies, Morgan Advanced Materials
produces advanced materials, including ceramics, carbonbased materials and composites. Products range from insulating refractories and silicon carbide seals to piezoelectrics and
lightweight armor systems. With customers in over 100 countries, the company has more than 100 manufacturing sites and
employs over 9,000 people.
Earlier this year, Morgan Advanced Materials announced
that it had increased capabilities at its facility in Wilkes-Barre,
Pa. The site produces injection molded ceramic components for
use in the investment casting of turbine engine blades, as well
as vanes for aircraft and power generation, aircraft hardware,
pumps, valves, and sporting goods.
ally high-end components to their international base of customers, said Mark Chenoweth, COO of CoorsTek. We will
significantly expand their offering to include advanced materials and capabilities for an even broader range of products.
CoorsTek recently announced the opening of a new plant in
the Coors Technology Center producing lightweight ceramic
proppants. Leveraging more than a century of ceramics manufacturing experience, ceramic scientists, analytical labs, and a
breadth of ceramic materials, CoorsTek has developed exceptionally strong and lightweight ceramic proppants to optimize
conductivity in formations with high closure stress.
Sources: company contact, company website, press releases
Morgan Advanced Materials survivability solutions are being used in

customized armored composite crew compartments.
The company also announced an agreement to acquire
microporous insulation materials producer Porextherm
Dmmstoffe GmbH. (Completion of the acquisition is subject
to customary closing conditions, including approval from the
German competition authority.) The addition of Porextherm
to the Morgan Group enhances our existing portfolio of highperformance insulating systems, and also gives us the chance
to share knowledge and processes that will lead to future
product development, said Mark Robertshaw, CEO. In line
with our strategic priorities, the acquisition brings with it the
opportunity to explore new markets and expand our range to
benefit both new and existing customers.
Last month, Morgan Advanced Materials announced that
it will partner with The University of Manchester to develop
a new process for manufacturing graphene. With decades
of expertise in developing specialist carbon-based materials, Morgans material scientists will be based full-time at
the university, working closely with academic colleagues to
understand the manufacturing mechanism and properties of
graphene, helping us explore the applications where the technology can be used for optimum benefit, said Mike, Murray,
Ph.D., Morgan Advanced Materials chief technology officer.
10.
CoorsTek, Inc.
16000 Table Mountain Pkwy., Golden, CO 80403

www.coorstek.com
CEO: John K. Coors
CoorsTek has 48 facilities located in 13 countries on four continents. The company produces hundreds of technical ceramic
products for applications in aerospace and defense; semiconductor; oil and gas; automotive; household durables; and heavy
industries such as rail, energy, and mining.
Last year, CoorsTek acquired Dynamic-Materials (Ceramics) Ltd. and its wholly owned subsidiary, Dynamic-Ceramic
Ltd., which specializes in advanced ceramic manufacturing,
trading and consulting. Dynamic-Ceramic offers exception-
+1
Vesuvius plc
165 Fleet St., London EC4A 2AE, England

www.vesuvius.com
CEO: Franois Wanecq
Vesuvius plc was created in late 2012, following the decision
of Cookson Group plc to spin off its Engineered Ceramics
and Precious Metals Processing divisions. According to the
companys website, Vesuvius is a global leader in metal flow
engineering, providing a full range of engineering services and
solutions to its customers worldwide, principally serving the
steel and foundry industries.
The companys 10,800 employees primarily work with
steel flow control, foundry technologies and advanced refractories for a range of end markets. Vesuvius engineered
refractory linings aim to reduce energy consumption and
maintenance downtime via specialized compositions and
installation techniques.
The company has embarked on a restructuring (particularly in South America and the NAFTA region) following its
creation, which has reportedly resulted in increased efficiencies and product performance. New facilities are in development in Ras Al Khaima, United Arab Emirates; Port Kembla,
Australia; and Sao Paolo, Brazil.
Sources: company website, annual report
Editors note: The CI Top 10

ranking is based, in part, on
publically available financial
information, including annual
sales, along with details supplied by company contacts.
Where this information was not
readily available, some companies unfortunately had to
be left out. For details regarding how to have your company
considered for future CI Top 10
rankings, please contact Managing Editor Kelsey Seidler at seidlerk@bnpmedia.com. Dont
miss the CI Top 10 Fast Facts Infographic, available with this
article online at www.ceramicindustry.com!
Industry Focus
#automotive #aerospace
#energy
High-Temperature
Energy Recovery
Using Thermoelectric
Ceramics
Research is underway to optimize oxide ceramics
that can help thermoelectric harvesting reach its full
energy-saving potential.
Figure 1. Structures have been developed for use as a substrate in oxygen transport membrane applications for CO2
sequestration.
By Eric Hanson
Vice President, Sales & Marketing, TAM Ceramics
hermoelectric (TE) heat recovery technologies can frequently reduce the

operating costs for facilities by increasing energy productivity and efficiency.
New systems using advanced ceramic materials are being developed, showing promising results at higher temperatures up to 1,000C. Further, they
are demonstrating that the material is not only functioning, but at potential device
efficiency thr ee tim es hig her than current, state-of-the-art thermoelectric materials.
Waste heat recovery from diesel or gasoline engine exhaust can increase fuel
efficiency while reducing weight, carbon deposit and manufacturing costs of both
military and commercial vehicles. In an extreme case, jet-based aircraft have a
huge available temperature difference between the jet exhaust and the passing air.
The greater the temperature difference between the two sides of the thermoelectric materials, the more electricity can be harvested. The problem with current
thermoelectric materials is they have not been able to operate efficiently above
300C, or the materials are cost-prohibitive for industrial applications. Either the
material or the system begins to break down under this heat. Thus, current technologies have been unable to capture energy where most of it is available, in the
700-1,000C range.
The market demands a low cost

of production, as well as flexibility in
use. The technology solution must be
adaptable to harvesting heat in different
applications, ranging from power production plants to smaller vehicle power
trains. Above 300C, it can no longer
function as a result of the materials or
modules losing stability. Another example is in a coal power plant, where the
furnace heats water to 370C in order
to make steam; however, to increase
energy output, the steam is superheated
above 540C. Many industrial processes
generate waste heat above 800C. In
order to integrate thermoelectric waste
heat recovery in power plants, these systems and materials will have to be resistant to much higher temperatures.
Thermoelectric Markets
Although thermoelectric phenomena have
been extensively used for heating and cooling applications, electricity generation has
only seen limited market niche applications. It is only in recent years that interest
has increased regarding new applications
of energy generation through thermoelectric harvesting. This growth in interest is
expected to continue, characterized by an
overall market for thermoelectric energy
harvesters that will reach $750 million by
2022. The four main markets for hightemperature thermoelectrics include
vehicle waste heat recovery, consumer
applications, military and aerospace
applications, and industrial applications.
Waste Heat Recovery in Vehicles

The Environmental Protection Agency (EPA) reports that only
15% of fuel energy is used to move a vehicle down the road or run
useful accessories, such as air conditioning. According to BMW,
automobiles are an example of high energy usage with low efficiency. Roughly 75% of the energy produced during peak combustion is lost in the exhaust and engine coolant in the form of heat.
A large number of car companies, including Volkswagen,
Volvo, Ford, and BMW, in collaboration with NASA and the
U.S. Department of Energy (DOE), have been developing thermoelectric waste heat recovery systems in-house. Each company has achieved different types of performance, but all are
expected to lead to improvements of 3-5% in fuel economy,
while the power generated out of these devices could potentially reach up to 1,200 W.
Other automotive companies researching thermoelectrics
include General Motors, Toyota/Denso, Bosch, Amerigon/
BSST, Siemens, and Cummins. To date, the Ford Fusion, BMW
X6, and Chevrolet Suburban concept cars have all been produced with thermoelectric generators in the exhaust stream.
One highly visible application might be to increase energy
efficiency in combustion-engine-based transport, thereby
reducing the U.S.s carbon footprint and dependency on foreign oil imports. Converting waste heat produced by motors
into electricity would make cars far more efficient. There is an
untapped opportunity that exists to harvest energy from the
engine and exhaust infrastructure.
Already, BMW states that fuel efficiency has been increased
by 12% with early thermoelectric prototypes. With DOE
funding, BMW and Ford are working on these prototypes
for passenger cars. If successful, alternators would no longer
be needed to recharge a car battery (in both hybrid and nonhybrid models). This would translate to reduced weight and
air pollution, leading to improved fuel efficiency. Elimination of an alternator has another advantage with vehicles that
operate under industrial and field environments.
Consumer Applications
In these applications, the type of solution that thermoelectric generators provide varies and could be related to saving
energy while cooking or heating your home.
Military and Aerospace Applications
These applications have already become a market of several
million dollars, having supported mature thermoelectric harvesting technologies for several decades now (e.g., radioisotope thermoelectric generators in space probes and satellites).
These are purely performance-driven applications in a segment
where cost considerations are not as important as the ability
to efficiently and reliably provide power when needed most
i.e., in hostile, remote environments and applications.
Industrial Applications
In certain industrial applications, such as the melting of steel
and glasses or to power nuclear or coal plants, heat is gener-
Table 1. Potential waste heat by industry.

(Source: 2006 DOE Engineering Scoping Study of Thermoelectrics.)
ated from the production facilities. In other words, waste heat
is generated as part of the industrial manufacturing process
and is then lost to the environment. Aluminum, glass, metal
casting and steel: all have process furnaces discharging hightemperature waste heat combustion gases and melt pool
gases (e.g., aluminum, ~ 775C; and glass, ~ 1,425C).
In some industries, this heat can be used to raise steam, preheat raw materials or combustion air, or be integrated with
other processes at the manufacturing site. Other industries have
limited opportunities to reuse this thermal energy, however. This
is what makes the thermoelectric generator (TEG) so attractive.
The opportunity to recover waste heat should be large in
metals industries, which use numerous heat-treatment furnaces (with relatively clean flue streams of combustion gases
only), as well as in chemical industries, where process heaters are widely used (e.g., direct-fired reboilers, reactors, etc.).
Additional waste heat opportunities exist in lime kilns, cement
kilns, etc. Table 1 shows a breakdown of the potential waste
heat by industry.
Proposed Solutions
With the increasing cost of fossil fuels, improved efficiencies
can result in substantial cost savings. Current commercially
available thermoelectric conversion systems and materials
can only function at waste heat temperatures below 500C.
This limitation leaves out many industrial processes where
waste heat is generated at high temperatures. The limitation
is largely due to three factors: a lack of suitable low-cost,
high-temperature thermoelectric materials; mechanical failure
caused by thermal expansion mismatch between thermoelectric component and conductive or metalized materials; and
design limitation in heat management. This has created an
opportunity to develop new thermoelectric materials for harvesting the wasted energy.
Before discussing the current state of research in this
area, it is worthwhile to define some basic terminology used
in this field. The energy conversion efficiency of a TE material is gauged by a parameter called figure of merit (ZT).
] High-Temperature Energy Recovery
Figure 2. Multi-layer structures of dense and porous layers.

(Image courtesy of ENrG.)
ZT is a dimensionless parameter and is
defined as:
ZT = (Q2 x s x T)/k
where Q (V/K) is the Seebeck coefficient of the material, s (S/cm) is the
electrical conductivity of the material,
T (K) is the absolute temperature and k
(watt/m-K) is the thermal conductivity
of the material.
Early TE materials research in the
1950s and 1960s yielded bismuth telluride (Bi2Te3), lead telluride (PbTe) and
silicon-germanium (SiGe) alloys as the
materials with the best ZTs in three somewhat distinct temperature ranges. Bi2Te3
and its alloys have been used extensively
in TE refrigeration applications and some
niche low-power generation applications,
and have a useful temperature range of
180-450 K. PbTe and SiGe materials have
been used extensively in higher-temperature power generation applications, particularly spacecraft power generation, and
have a useful temperature range of 500900 K and 800-1,300 K, respectively.
The discovery of these materials
as good candidates for TE devices led
to the development of a fledgling TE
industry. Many of its early participants
are still active in the area today; they
are focused on using BiTe for heating
and cooling applications, PbTe for moderate temperature energy harvesting,
and SiGe for high temperatures.
Proposed Technology
Research work will first focus on the
development of high-temperature p-type
Figure 3. Sample configuration for TE measurement.

and n-type ceramic oxide thermoelectric materials. The proposed technical
approach is to increase the electrical conductivity of oxide ceramic thermoelectric
compounds through doping and decrease
the thermal conductivity through the
introduction of structured porosity.
Some success has been achieved in
developing such structures for use as a
substrate in oxygen transport membrane
applications for CO2 sequestration (see
Figure 1, p. 16). The integrated system
developed through this approach will be
far more efficient and can harvest thermal waste energy at temperatures current
materials cannot tolerate. It can also be
produced in a low-cost manner and formfitted to different industrial applications.
Multi-layer structures consisting of
dense and porous layers will be built
as shown in Figure 2. Figure 3 shows a
sample configuration for TE measurement. Real devices based on the previously described concept can be designed
and fabricated. Such a system is advantageous in that:
It pushes the operating temperature
to a 700-1,000C range, at which no
TE materials are currently available
It is based on conventional multilayer ceramics technology currently
practiced in the electronics industry
It leads to lower-cost TE material
The most important technical goal
is to develop n-type and p-type oxide
thermoelectric materials with ZT >
0.5. Particle size of the thermoelectric
powders should be < 600 nm, and their
sintering temperature should be lower
than 1,500C. Other goals include the
development of a process to manufacture porous tape and a process to make

ceramics with a porosity designed to
enhance their thermoelectric properties. With respect to cost, the aim is that
TEG produced using this technology
would meet a metric of < $4 (cost to
own) per watt (output to gain).
Bismuth chalcogenides (Bi2Te3 and
Bi2Se3) comprise some of the best-performing room temperature thermoelectrics, as they have the highest percentage
of Carnot efficiency for thermoelectric
generators. Bismuth tellurium is the best;
however, overall telluride compounds tend
to be limited in use due to toxicity, rarity
and the high cost of tellurium. For highertemperature applications, lead telluride and
selenide have shown good ZT values (at
Oak Ridge National Laboratory) between
1.4 and 1.8, with predictions of p-type ZT
as high as 2 at 1,000 K; however, there are
cost and toxicity issues with Pb.
Silicon-germanium alloys are currently the best-developed thermoelectric
materials for applications up to 1,000C
and are therefore used in advanced aerospace applications such as radioisotope
thermoelectric generators (RTG). However, energy conversion has historically
been low, and ZT values above 1 have
not been commercialized, with ZT starting to degrade above 800C. Oak Ridge
National Laboratory considers the practicality threshold ZT greater than 2.0.
Silicon-germanium material is also very
expensive compared to strontium-, niobium-, and titanium-containing oxides.*
To date, oxide thermoelectrics demonstrate exceptional thermal stability,
*TAMs n-type material
Projected Benefits
This thermoelectric
technology could
reduce the fuel
consumption of U.S.
drivers by over 10%.
especially at high temperatures, but their
figure of merit is relatively low (0.34 at
1,000 K, although research suggests that
some layered oxides can reach ZT values up to 2.7 at 900 K). The approach is
to use low-cost, low-toxicity, and highabundance materials and minerals, then
process these raw materials using historically inexpensive processing techniques,
such as solid-state reaction, ultimately
realizing quick commercialization.
When this thermoelectric technology is

fully developed and broadly adopted, it
is expected that in the automobile industry alone, it could reduce the fuel consumption of U.S. drivers by over 10%,
resulting in savings of as many as 2.1
million barrels of crude per day, according to the CIA World Factbook. Not
only would drivers save at least 10% of
the money they spend on fuel, but they
would benefit due to the reduction in
cost of buying and maintaining a car.
Initial expectations are that the system would cost only 50% of the cost of
an alternator, and would have a much
longer lifetime and fewer maintenance
problems. When applied to other industrial processes such as a coal power
plant, or a jet combustion engine, this
technology could be equally as large
and significant.
Such a new technology brings a
significant opportunity to recapture
wasted energy generated at high temperatures (1,000C). Capturing waste

heat generated from the broad spectrum
of industries that developed during the
worlds industrial revolution has a profound impact. We may experience total
efficiency from the many great inventions of engines for vehicles, power generation, and industrial processes. The
future of new thermoelectric systems
using advanced ceramic materials harvesting these high-temperature waste
heat energies and converting them into
electricity looks promising.
For more information, visit www.tamceramics.com.
Note: Funding for this project has been
provided by the New York State Energy
Research and Development Authority
(NYSERDA) under Agreement Number
30370. NYSERDA has not reviewed the
information contained herein, and the opinions expressed in this report do not necessarily reflect those of NYSERDA or the State of
New York.
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Industry Focus
#aerospace #defense
#carbon
Modern Mechanical
Carbon Materials for
Aircraft Seal Applications
Many commercial and military aircraft seal
applications could benefit from mechanical
carbon solutions.
By Glenn H. Phelps
Technical Director, Metallized Carbon Corp.
odern mechanical carbon materials are being used in a

variety of applications, including aircraft gear boxes,
air turbine motor starters, and main shaft seals for
both aircraft turbine engines and aircraft auxiliary
power units (APUs). These self-lubricating materials are composed of
fine-grained electrographite substances that are impregnated with proprietary inorganic chemicals to improve their lubricating qualities and oxidation resistance.
These modern carbon-based materials are ideal for use in aircraft applications
because of their low coefficient of friction, low wear rate at high sliding speed, high
thermal conductivity, and resistance to oxidation in high-temperature air. These
properties also make the materials of interest to designers of other high-speed, rotating equipment (e.g., high-speed rotary gas compressors and steam turbines).
Mechanical Carbon Materials

Aircraft gearboxes are used to reduce the main engine shafts rotational speed from
as high as 26,000 rpm down to about 3,400 rpm, so the shaft can drive such system components as hydraulic pumps, generators, and air conditioning compressors.
To seal the oil lubricant within the gearbox and protect it from leaking out at the
point where the shaft enters and exits the gearbox, most aircraft gearboxes use face
seals. The face seals usually contain a carbon-graphite stationary ring and a silicon
carbide or tungsten carbide rotating ring. The rings that make the dynamic face seal
are both lapped flat and held together with springs or magnets so that liquids cannot flow between the ring faceseven though they are spinning against each other
at high rpm.
The two rings in relative motion that make the dynamic seal are sealed to the
shaft or the gear box housing with static seal rings such as polymeric o-rings. Seal
designers use spiral grooves, straight grooves, and wedges to channel or pump a thin
film of air or oil between the two sliding sealing faces. This creates aerodynamic or
hydrodynamic lift, which greatly reduces the friction and wear of the seal faces.
Withstanding High Speed

Air turbine motor starters typically use
the same carbon-graphite vs. silicon
carbide or tungsten carbide dynamic
face seal materials that are used in gearbox seals, but the sliding speed is much
higher. These air turbine motor starters
are actually small turbines that use the
exhaust gas from the auxiliary power
unit to create the power necessary to
start the main engines.
The shaft speed on air motor starters can be as high as 180,000 rpm, or a
sliding speed of about 1,000 ft/s, which
is nearly the speed of sound. The seals
are designed by aircraft seal manufactures with wedges and gas flow passages to produce aerodynamic or hydrodynamic lift-off.
Main Shaft Seals

Face seal rings with carbon-graphite
primary rings, and carbon-graphite circumferential seal rings are used in air-
Carbon graphite circumferential and face seals like these are typically used in mechanical seal assemblies for aerospace applications.
craft engine main shaft seals to control
the air flow and combustion gas flow
inside the engine. They also seal the oil
lubricant in the main engine bearings
that allow the compressor shaft and the
combustion gas turbine shaft to rotate
freely. Both circumferential and face
type seal ring are used.
For circumferential main shaft seal
rings, carbon-graphite segments that fit
with close end clearance in slots in the

stationary housing are used. The carbongraphite segments are tensioned against
a ceramic or hard metal coating on the
rotating shaft using a garter spring.
Lifting wedges and machined configurations are used to create lift so
that these seals run on an aerodynamic
or hydrodynamic film. Rotating speeds
can be as high as 26,000 rpm, and tem-
peratures in the seal rings can reach as

high as 800F.
Auxiliary power units (APUs) are
small gas turbine engines that are used
to create electric power, air conditioning or cabin heat when the main engines
are turned off at the gate to save fuel.
APUs contain carbon-graphite seals that
are similar to, but smaller than, main
engine seals.
Unique Characteristics
Oil-free, self-lubricating mechanical
carbon materials have a unique combination of characteristics that makes
them ideal for use in both commercial
and military aircraft seal applications.
The materials are self-lubricating,
self-polishing and dimensionally stable,
which ensures a good sealing mate. The
materials are heat resistant and have a
high thermal conductivity, which helps
conduct frictional heat away from the
sliding surface. In addition, these materials are readily machinable to exacting
aerospace dimensional tolerances, and
they can be supplied lapped and polished to a flatness specification of one
helium light band.
Typical graphite piston rings used for air bleed control valves.
For more information, contact the author at (914) 9413738 or ghphelps@metcar.com, or visit www.metcar.com.
Industry Focus
Materials Innovation
#spinel #nanomaterials
#defense #electronics
NRL Researchers Develop Harder

Ceramic for Armor Windows
he U.S. Department of
Defense (DoD) needs materials for armor windows that
provide essential protection
for both personnel and equipment while
maintaining a high degree of transparency. To meet that need, scientists at
the U.S. Naval Research Laboratory
(NRL) have developed a method to fabricate nanocrystalline spinel that is 50%
harder than the current spinel armor
materials used in military vehicles. With
the highest reported hardness for spinel,
NRLs nanocrystalline spinel demonstrates that the hardness of transparent
ceramics can be increased simply by
reducing the grain size to 28 nm. This
harder spinel offers the potential for
better armor windows in military vehicles, which would give improved protection and other benefits to both personnel and equipment, such as sensors.
A New Approach
Spinel windows can have applications as electro-optical/infrared deckhouse windows in the new class of U.S. Navy
destroyers, like the USS Elmo Zumwalt pictured here, that feature a low radar signature compared with current vessels. (U.S. Navy photo courtesy of General Dynamics.)
To create the harder spinel, the NRL

research team sintered commercial
nanopowders into fully dense nanocrystalline materials. Through its development of the enhanced high-pressure sintering (EHPS) approach, the NRL team
is reportedly the first to succeed in making this harder spinel, explains James
Wollmershauser, Ph.D., NRL researcher
and lead author in the research paper
published in the January 30, 2014, issue
of the journal Acta Materialia. The
EHPS approach, developed largely as a
result of scientist Boris Feigelson, Ph.D.s
ideas and experience in high-pressure
research, uses high pressures to simultaneously retard bulk diffusion rates,
break powder agglomerates, and reposition nanoparticles very close to each
other to help eliminate porosity in the

sintered ceramic. Researchers can then
exploit the increased surface potential of
nanoparticles for surface-energy-driven
densification without coarsening.
Using this EHPS approach to create the nanocrystalline spinel, the
NRL research team did not observe
any decline in density or fracture resistance due to residual porosity. Other
researchers have tried to make nanocrystalline spinel, but they have all had
problems with the final product, such
as a reduced density, reduced fracture
resistance, or reduced transparency.
Reduced density is caused by voids that
cannot be removed during processing,
which can reduce hardness, fracture

resistance and transparency. Wollmershauser notes that some theories suggest fracture resistance should decrease
when you make a ceramic material
nanocrystalline. However, in their
work, the NRL researchers have shown
that the fracture resistance does not
change, suggesting that nanocrystalline
ceramics can have an equivalent toughness to microcrystalline ceramics, which
is important for high window lifetimes.
Material Benefits
The Hall-Petch relationship has been
used to describe the phenomenon where
a materials strength and hardness can be
increased by decreasing the average crystallite grain size. However, prior experimental work has shown a breakdown in
this relationship (where hardness starts
reducing with decreasing grain size) for
certain ceramics at ~130 nm. The NRL
researchers have disproved that a breakdown in the Hall-Perch effect exists at
these nanoscale grain sizes by measuring
an increasing hardness down to at least a
28 nm crystallite grain size. The new highhardness values were measured on samples with these extremely small average
grain sizes.
In current applications, spinel and
sapphire (which is also very hard)
are used to create materials for military armor windows. A drawback
with sapphire is that it is expensive to
make into windows. By increasing the
hardness of spinel even further, NRL
researchers can make a material harder
than sapphire and possibly replace sapphire windows with those made out
of nanocrystalline spinel. In addition,
Harder
nanocrystalline
spinel windows can
be made thinner
and still meet
current military
specifications.
harder nanocrystalline spinel windows
can be made thinner and still meet current military specifications. This thinness translates to weight savings on
the vehicle. Thus, the nanocrystalline
spinel brings improvements in hardness, window thickness and weight,
and cost.
A final benefit is that the NRLdeveloped nanocrystalline spinel is
highly transparent, making it useful in
ultraviolet (UV), visible and infrared

optics. The armor material used by the
military must be transparent so that
both equipment and personnel can see.
Different sensors see varying wavelengths of light: infrared is important
for heat-seeking capabilities, while UV
imaging can be used to detect threats
not seen in the visible spectrum. UV
detectors also have applications in
space-borne astronomy missions. A single window produced using the NRLdeveloped nanocrystalline spinel would
be transparent across many technologically important wavelengths, easing
design and weight requirements.
Beyond the use for a harder spinel in armor windows, there could be
other potential DoD and civilian applications in better/stronger office windows, smartphones and tablets screens,
military/civilian vehicles, space vehicles,
and even extraterrestrial rovers.
For more information, visit www.nrl.navy.mil.
Focusing on advanced products

and applications for ceramics, glass,
composites, refractories, and more!
Find out how these advanced technologies
can help improve your finished products
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Industry Focus
Market Trends
#automotive #electronics
#windows #displays
Smart Auto Glass Continues Growth

Multiple applications will drive the increased use of smart glass in the automotive industry.
mart glass in the automotive industry is expected to

become a $2.1 billion market by 2019, compared with
$1 billion in 2014, according to Smart
Glass Opportunities in the Automotive
Industry2014, a recent report from
NanoMarkets. The report defines smart
auto glass as any kind of glass used
in the automotive sector that is made
intelligent with the addition of layers of smart materials or the embedding
of sensors and other kinds of electronic
and electrical functionality into the glass.
This is not everyones definition of smart
auto glass; some consider self-dimming
glass to be smart glass; sometimes the
definition is even more narrow.
However, in order to understand

the opportunities that smart auto glass
presents, it is important to use a broad
interpretation of smart glass. Opportunities for the several technologies/
products include:
Self-dimming windows using electrochromic, photochromic, thermochromic and suspended particle device
(SPD) technology. SPD is a proprietary
technology that currently seems to be
doing better than most of the others.
Smart privacy glass such as polymerdispersed liquid crystal (PDLC).
PDLC is another type of selfdimming glass, but sold as a privacy product because it is never
quite clear and doesnt make a
great product for general window

applications.
Smart mirrors are the one reasonably
mature part of the smart auto glass
sector. Gentex has been selling smart
mirrors for cars for decades, and the
business continues to grow.
Self-healing glass could mean anything from aftermarket coatings that
reduce scratching to nanomaterial
combinations that actually remove
cracks in glasses and mirrors. The
utility of such products does not
need to be explained, but the more
advanced products in this category
are not yet available.
Self-cleaning glass is similar to selfhealing glass. Various coatings are
currently available; however, talk of
the wiperless windshield seems
premature.
Electronics-embedded glass, incorporating elements such as antennas
and heaters, has been available for
decades. Now, the market for other
kinds embedded glass seems full of
potential.
Key Factors
The use of smart glass in the automotive sector as driven by factors that
are central to the automotive industry.
More specifically, the revenue potential for specific smart glass strategies
in automobiles and trucks should be
appraised against four criteria: safety,
comfort, fuel economy, and design/style
(see Table 1).
There is nothing new about these factors. They have not changed since the
earliest days of the automobile industry,
although what has changed is the degree
that some of these factors are controlled
by legislation. In addition, smart glass is

only one of numerous technologies that
will help achieve the necessary goals
required for each of the factors.
Self-Tinting Glass
Several self-tinting (i.e., self-dimming)
technologies are available (see Table 2,
p. 27). At the present time, the major
part of the self-tinting glass market
seems to be based on SPD technology.
However, this partly reflects the fact
that SPD is being pushed heavily by RFI
licensees in the automotive space.
If electrochromic glass can be
designed so that it can work better on
curved surfaces, the auto firms could
be quite interested in an electrochromic
solution that is less proprietary than
SPD. In addition, it is not certain that
electrochromic technology can make
the necessary technological adaption.
In addition, photochromism and electrochromism are being combined in
some smart auto windowsnotably
by SWITCH Materialsand the active
nature of this technology will help promote its use. The use of thermochromic technology for self-tinting smart
windows seems marginal at best.
The automotive industry has made

use of tinted glass for decades. What
smart glass adds to the conventional
tinted glass and retrofit films is an
aspect of dynamism. However, in terms
of sales, self-tinting auto windows provide small revenue when compared to
retrofit films; it is not yet clear what
will convince major automotive firms
that this type of glass should be widely
used. One potential factor is the ability
of such films to reduce the energy drain
of air conditioning.
Finally, cost is always a factor in this
area and some kind of manufacturing breakthrough could either change
the relative merits of the available selftinting technologies or help to make
self-tinting technologies more widely
available. For example, consider electrochromic windows, which have
tended to be created with sputtering.
Wet coating and printing technologies
have also been investigated, for example, by the National Renewable Energy
Lab (NREL). It is anticipated that more
wet coating and printing will be used
in this space, if the performance of the
final smart glass can be preserved. If
wet coating was available for electro-
chromic glass, the cost of this glass may

go down considerably.
PDLC Privacy Glass

As mentioned previously, PDLC technology is just another kind of selftinting technology, but because it never
gets all that clear, it isnt suitable for
standard windows applications. It
is therefore used mostly as privacy
glass, or a glass that is attractively
translucent for much of the time, but
turns opaque at the flip of a switch.
Most PDLC will be used in buildings and not in the automotive sector,
but there are privacy applications in
cars tooprincipally when one wants
to shut off the driver from the passengers (e.g., in limousines and taxis).
This technology might also be used in
sunroofs.
Smart Mirrors
While smart (or self-tinting) mirrors
are the most mature part of the smart
auto glass segment, it is hard to characterize them as an opportunity. This is
because the sector is dominated by one
company, Gentex. While there are other
suppliers of these types of mirrors, it
Table 1. Factors shaping demand for smart glass in the automotive sector.
Self-cleaning
Self-repairing
Self-tinting
Deviceembedded
glass
Safety
Comfort
Cleaner windshields make for safer

driving. This is a strong incentive for
using self-cleaning coatings, but the
performance of these coatings is not
yet ready for auto applications.
Clear views of what is going on

outside the car or truck enhance the
driving experience for both the driver
and passengers.
Design/Style
Fuel Economy
Self-cleaning, self-repairing and self- Impact on fuel economy not clear.

dimming windows would be a cool
addition to any vehicle and so might
be considered a style feature, even if
they are primarily being introduced
for their functionality.
Self-repairing coatings may make

auto windows more protected from
scratches and cracks. However, this
capability is already provided by
conventional auto glass.
Already well-deployed for auto
mirrors, could add more control to
tinted windows.
Glare and bright sunlight can be

directly controlled, making for more
comfort for drivers and passengers.
Touchscreens and HUDs may be the

safest way to interact with complex
dash displaysor not.
Touchscreens and entertainment

features may make some
contribution to comfort.
Tinted films are already an

important part of keeping the inside
of vehicles cool. Self-dimming glass
can enhance the capability.
Dashboards are often a key focus
Device-embedded glass may
of design in cars, and embedded
have some impact in the area of
sensors and other devices may help environmental control systems.
in this regard. Augmented reality
displays in windshields could also be
regarded as a style feature.
Source: NanoMarkets, LC
Market Trends
given enough time, self-cleaning glass
could become a reality fairly fast. Secondly, the addressable market is huge
compared with self-tinting glass. Only
a relatively small subset of vehicle owners are going to be interested in tintingand this is even more the case with
dynamic tinting. However, the percentage of vehicle owners who want/need
clean windows is much larger.
Self-Healing Glass
Figure 1. Eight-year forecast of smart automotive glass by technology ($ millions).

seems very unlikely that the market
while still growingwill spawn any
more significant companies offering
basic self-dimming mirrors.
The opportunity here seems to be
where self-tinting mirrors are combined with additional embedded functionality of some kind, whether simple
things like lights or multifunctional
information subsystems. The integration of smart glass and embedded
intelligence may open up the market
to new players in this space, although
Gentex is itself enthusiastically following this path. All of Gentexs products
use electrochromic technology, but
there is always the possibility of some
other firm coming into the market with
smart mirrors based on some other
self-tinting technology.
The smart mirror market is expected
to continue to grow through 2019. However, rear-view mirrors face some future
competition from camera- and sensorbased systems. These technologies potentially give a more accurate and comprehensive view to drivers, especially in large
vehicles. Gentex and possibly others are
already combining such technologies
with smart mirrors in optimal ways.
Self-Cleaning Glass
There is a big safety-driven potential
market for self-cleaning glass in the auto
sector. Such glass could be effectively

applied to windshields, where it would
enhance safety. At the present time, however, self-cleaning glass for automobiles
really goes no further than some fairly
simple coatings that allow rain or a good
soaking with a hose to wash dirt off the
windshield more effectively. Thus, some
automotive aftermarket products can be
wiped on windshields and other surfaces
that will help keep them clean, but these
are not really that effective or long lasting. They are mostly sold by small suppliers to car enthusiasts.
Although there are references in the
literature to wiperless windshields,
this is not seen as commercially viable
at the present time. Before self-cleaning
glass makes any real impact in the auto
sector, there will have to be significant
performance improvements in what
it has to offer. As to wiperless windshields, these seem to be a long way
off. Self-cleaning glass technology simply isnt up to it, and regulatory factors
are likely to rule it out for some time
to come.
By the end of 2019, self-cleaning
glass may have improved sufficiently
from a technological standpoint to
begin to generate significant revenues,
for two reasons. Performance improvements in self-cleaning glass do not seem
to be matters of fundamental physics;
Self-healing glass has some points

in common with self-cleaning glass,
in that it is a technology at the early
stage of development that has a large
and obvious utility in the marketplace.
However, there are also big differences. Primarily, a material that really
deserves the name self-healing seems to
be quite some way off in terms of commercialization. Self-healing materials
are much more of a difficult problem
to create than self-cleaning materials
from a technical perspective. In addition, if such materials actually come
to market in the automotive segment,
they will be much more expensive than
self-cleaning windows.
There are good reasons why such a
product might sell, though. Aesthetics is
one reasonvehicle owners dont like
having cracked mirrors and windshields
and may not want to pay for replacing
them if they are minimally damaged.
This is exactly the kind of situation in
which self-healing glass could make a
difference. Self-healing glass might also
be considered a safety feature to the
extent that it could help prevent drivers and passengers being showered with
glass in the event of an accident.
Embedded Intelligence
Automobiles and trucks are increasingly equipped with electronics, not just
for control purposes (as they have for
many years), but also for information
and entertainment. In a few cases, these
may be embedded into glass. To date,
embedding this kind of functionality
into glass has occurred more in mirrors
than in window glass, but embedded
functionality of this kind will spread to
transparent glass and will create a variety of opportunities.

In addition, while all the other
opportunities mentioned previously in
smart auto glass involve smart coatings,
embedded intelligence is an entirely
different kind of thingelectronic
intelligence, not chemical intelligence.
Following are some applications for
embedded intelligence in automotive
applications:
Heads-up displays have been installed
in cars for many years, mainly taking
the form of systems that project an
image onto the windshield. As such,
the glass-related aspect of the headsup display is fairly minimal (e.g.,
simply preparing glass so that one
can project images onto it). However,
more sophisticated heads-up displays
may emerge in which the windshield
becomes a genuine transparent display. This would impact the type of
glass being used and how windshields
are constructed. The market driver
here would be the increasing sophistication and deployment of augmented
reality (AR) applications in the automotive space.
Touch controls are

already present in
cars and trucks, and
this will increase in
the future.
Gentex already has a mirror with a
video display that can be used for
information delivery, alerts and notifications, and owners manual information. This could be a serious model
for the future of car displays in general, with competition among such
displays for location in mirrors, windows and opaque segments of the car.
Map lights or soft cabin lights can be
embedded in glass. Consider a sunroof that became an OLED lighting
panel and provided cabin lighting at
night; the functionality of windows
and lighting could merge.
Solar panels integrated with windows could have more applications in
buildings than in cars; however, solar

panels could theoretically run heating and lighting in cars. Commercial
products that integrate solar into windows are just beginning to appear.
Touch controls are already present in cars and trucks, and this will
increase in the future. Gestural controls will follow, although this may
take some time. These are potentially big opportunities, but the revenue stream from them is likely to be
stretched over a fairly long period of
time. However, these opportunities
are strongly glass related. Touchscreen displays include a large-area
touch sensor embedded in the top
glass. Augmented reality and gestural control featureslikely to
become more and more common in
cars and trucks in the near future
will require special kinds of display
glass, including those with embedded sensors or cameras, or coated
in a way that they can better serve
as transparent projection screens for
heads-up displays.
For more information, visit http://nanomarkets.net.
Table 2. Types of self-tinting auto glass.

Electrochromic
Photochromic
Status
Dominant smart windows

materials platform
Niche
Materials
Polymers and transition

metal oxides
Photochromic film
Thermo-chromic
Niche with limited dimming
capabilities
PDLC
Possibly limited to privacy
glass only
SPD
Niche product mainly used
in autos
Hybrid materials
Catalytic
platforms
Enormous potential range

Vanadium dioxide often
referenced, but seldom used
Opportunities
EC seems to have more

New sales territories
practical materials platforms
that can be commercialized
More hybrid
solutions
New materials platforms

have considerable
opportunities
Better power consumption,

PDLC/EC hybrids, reverse
PDLCs, etc.
Limited by RFI franchise, but

better materials are being
sought out
Good switching times and

low power consumptions
Unclear maybe price
Low price and easy to

integrate into IGUs
Switching times and level

of light blocking Especially
suitable for large panels
Seems to be mainly
competition for conventional
retrofit window film, but with
more functionality
PDLC is just a form of

Could be more widely used
privacy glass has potential to perhaps in a version using
break out from this niche
new materials RFI seems
open to new products
Advantage
Future
Liquid crystals of various

kinds
Better manufacturing options Not likely to present

and lower prices
much of a challenge to
electrochromic windows,
but plenty of opportunity for
innovation
Polyiodide and similar

materials in a polymer film
Source: NanoMarkets, LC
Industry Focus
#composites #aerospace
#defense #coatings
Melt-Infiltrated
Refractory Ceramic
Matrix Composites
Melt infiltration processing can produce CMCs capable
of withstanding ultra-high temperatures.
By Tim Stewart, Senior Program Manager; Brian Williams, Research Director; and
Jerry Brockmeyer, Consultant, Ultramet
efractory ceramic matrix composites (CMCs) are of considerable interest for a range of high-temperature and severe environment applications,
including space and defense, and have potential for commercial and industrial applications that impose extreme thermal and environmental demands
on materials. Among the more mature CMCs are silicon carbide fiber-reinforced silicon carbide matrix (SiCf/SiC) CMCs which, after decades of development, are being
commercially introduced for aircraft engine component applications. These SiCf/SiC
CMCs are limited to use at temperatures considerably less than 1,480C (2,700F),
which constitutes a dramatic gain over conventional superalloy use temperatures.
The success of the current generation of CMCs has led to an Air Force-sponsored
effort to push the use temperature to 1,480C (2,700F) or above. Parallel developments are underway to advance capabilities to ultra-high temperaturessignificantly greater than 1,650C (3,000F).
Improving Capabilities
A range of benefits is driving the motivation for the use of these materials:
Gains in efficiency (e.g., enhanced fuel economy) traceable to the high-temperature
operation of aircraft engines with reduced requirements for cooling air to maintain
acceptable component operating temperatures
Weight reduction of components as a result of the relatively low density of the
composites
Enabling selected applications in which conventional materials temperature constraints preclude their use in the operating environment.1-3
A number of monolithic ceramic materials, while providing high-temperature
capability and potentially acceptable operating environment resistance, lack the requisite toughness to meet design and use requirements.
Continuous fiber-reinforced refractory CMCs address many of these limitations.
Typical fiber reinforcements include a range of non-oxide ceramic fibers (such as
SiC), oxide ceramic fibers (generally alumina or silica-alumina based) and carbon
fibers. For temperatures above those achievable with SiC matrices, ceramic matrix
Figure 1. Scanning electron photomicrograph showing

slip and fiber pullout achieved in a CMC as a result of
the interface coatings applied onto the reinforcement
fibers.
materials include a number of options,
including materials from the family
comprising hafnium-zirconium-siliconcarbide (Hf-Zr-Si-C) and their respective nitrides and borides.1
For ultra-high temperatures, oxide
fibers are limited in applicability
predominately due to low elevatedtemperature strength and poor creep
resistance. SiC ceramic fibers are also
limited to < 1,480C (2,700F) as previously noted, leaving carbon fibers as the
primary commercially available fibers
of interest for ultra-high temperatures.
Manufacturing Effective
Composites
Accordingly, to address extreme temperature demands, work has been focused
on carbon-fiber-reinforced refractory
CMCs including, but not limited to:
C / Z r C , C / H f C , C / Z r- S i - C , a n d
C/Hf-Si-C. Various processes, each with
limitations and benefits, have been used
for producing such composites, includ-
Figure 2. Schematic depiction of the MI process sequence.

ing chemical vapor infiltration (CVI),
pre-ceramic polymer infiltration and
pyrolysis (PIP), and melt infiltration
(MI) of the matrices into the reinforcement fiber preforms.
CVI provides high-purity matrices.
Precursors for CVI densification are
relatively costly and process times are
lengthy, leading to high composite cost.
In addition, even with extended infiltration times, considerable residual porosity remains within the completed CVI
composites.
Individual PIP cycles are faster and
typically less costly than CVI cycles;
however, achieving acceptable density
requires multiple iterations of the PIP
process, which leads to extended process times. PIP precursors, especially
for SiC matrices, are commercially
available but can be costly. Also, the
pyrolysis step must be performed in a
controlled atmosphere to achieve the
desired matrix composition (comprising
a mixture of Si-O-C-N depending on
details of the precursor and the processing conditions).
MI processing is rapid, requiring
only a few hours to achieve nearly full
density, and starting materials require
only the availability of the respective metal or alloy (e.g., Zr metal for
ZrC CMCs), which is generally costeffective. However, the MI process does
expose the fiber preforms to temperatures at or above the melting temperature of the respective alloy. The process
thus calls for high-temperature process
equipment and requires that the rein-
forcement fibers be protected from the

melt during the MI process. In addition,
not all of the metal reacts in situ during
infiltration such that the matrix comprises a mix of the metal carbide and
the unreacted metal.
In CMCs, a fiber interface is essential to achieving the desired mechanical
performance. The interface is needed
to provide limited slip between the
fibers and the matrices, resulting in
pseudo-ductile behavior of the composite and higher toughness than that
afforded by the monolithic ceramic
matrix, as shown in Figure 1. For MI
CMCs, the interface may also need to
protect the fibers from degradation
or consumption by the incoming molten metal. Selected interfaces may also
serve to promote wetting and infiltration of the molten metal into the preform porosity.
Clearly, ultra-high-temperaturecapability refractory MI CMCs
are complex and evolving materials. Research and development has
advanced MI refractory CMC processing and demonstrated such materials in
potential application environments.
MI Refractory
CMC Processing
MI processing of refractory CMCs follows a process sequence as depicted
schematically in Figure 2. In the first
step of the process, a suitable fiber preform is procured or prepared. Depending on the details of the application
and properties requirements, the pre-
form may consist of woven or braided

fabric layers in a two-dimensional (2D)
fiber architecture, a pierced fabric or
other three-dimensional (3D) architecture, or a possible multi-D architecture, etc. Fiber type and architecture
are keys to achieving desired properties, which are relatively predictable
based on composites models such as
discussed by Kainer.2
Suitable fiber interface coatings are
applied onto the fibers in the second
step (or may be coated onto the fibers
prior to laying up the preform). Such
interfaces serve various needs, including promoting wetting and infiltration, preventing damage to the fibers
by the incoming melt and/or providing
slip and improved mechanical behavior. The preform is then partially
densified with reactive carbon using
proprietary processing. The amount,
type and distribution of carbon are
controlled to optimize reaction with
incoming molten metal. 3 The target
is typically to achieve a high degree
of conversion to the carbide such that
the matrix exhibits predominately
ceramic behavior.
The matrix is then melt infiltrated
using the selected metal or alloy to
achieve the desired matrix chemistry.
Preferably, the preform is wetted, and
infiltration is achieved without application of pressure, although pressure infiltration is also feasible. During the infiltration step, reaction with the previously
added reactive carbon occurs, such that
the resultant matrix constitutes the
selected metal carbide, for a carbide
matrix CMC. In one typical example,
reactive carbon is added to a carbon
fiber preform and zirconium metal is
infiltrated to create a Cf/ZrC CMC.
It should be noted that the fiber
preform may be prepared as a simple
geometric structure (e.g., a block or
billet) from which desired parts can be
excised. Alternatively, and often preferably, the preform will be produced
as either a net- or near-net shape to
minimize the need for machining, to
improve on infiltration and to minimize
waste. A near-net-shape fiber preform
for an axisymmetric component, in this
] Melt-Infiltrated Refractory CMCs
Figure 4. Oxide interface coatings (white rings

surrounding circular fibers) as deposited onto SiC
fibers for an MI CMC.
Figure 3. Near-net-shape fiber preform for an axisymmetric component prior to MI processing.

case a CMC rocket engine combustion
chamber, is shown in Figure 3.
For certain MI composites, ultraviolet chemical vapor deposition
(UVCVD) can be and often is used for
the deposition of the fiber interface
coatings prior to infiltration with the
molten metal. The UVCVD process
provides for uniform coating of a number of interface materials onto the individual filaments within the fiber tows,
as shown in Figure 4.
To date, using variants of the abovedescribed process, a number of ultrahigh-temperature-capability CMC formulations have been produced, including ZrC, HfC, Zr-Si-C and Hf-Si-C
ceramic matrices. One example of such
a composite is shown in Figure 5, in
which the nearly fully dense matrix has
surrounded and partially infiltrated the
carbon fiber bundles, or tows.
The selection of the matrix material is based on the application needs.
For example, HfC matrices provide
preferred performance at extreme temperatures in oxidizing environments. In
such applications, the outer surface of
the HfC converts to its respective oxide
(HfO 2) which, under very high temperature conditions, is tenacious and
relatively protective. However, HfC is
relatively dense. For slightly lower tem-
peratures in oxidizing environments,

a matrix such as ZrC is preferred. The
ZrC has a lower density than HfC,
and the outer ZrO 2 that forms during service has a service temperature
approaching that of HfO2. For oxidizing environments that do not require
the ultimate temperature capability of
HfC or ZrC, matrices with some added
Si (which forms SiC) have enhanced
intermediate temperature oxidation
resistance and have lower density than
HfC or ZrC without the added SiC.
An added benefit of the MI process
is that the melt infiltrates readily and
quickly into even, thick cross-sections,
resulting in high-density, thick structures without the need for lengthy
infiltration times. One such example,
a nominally 2.5 cm (1 in.) thick panel,
is shown in Figure 6. Other structures
have been infiltrated to thicknesses of
6.5 cm (2.5 in.) while achieving low
porosity in the matrix.
MI Refractory CMC
Properties and Behavior
Figure 5. Example of a refractory metal matrix

composite (MMC) microstructure produced using MI
processing with a 2D reinforcement fiber architecture.
As previously noted and described by

Kainer and others, the properties and
behavior of the MI CMCs are largely
predictable based on constituent level
models that analyze and predict composite behavior based on the fiber rein-
forcement type and fiber architecture

(fiber orientation and relative fiber
loading) and matrix properties.2 Properties of selected CMC materials of
interest are presented for reference in
Table 1.
sectioned, revealing the formation of a

tenacious surface oxide at the chamber
inner wall and showing that the oxide
only penetrated about one laminate
layer deep into the composite structure.
Conclusions
Table 1. Selected properties of ultra-high-temperature composite matrix materials and structural ultra-hightemperature metals.4-6
Figure 6. Nominally 2.5 cm (1 in.) thick CMC panel produced using MI process.
The Zr, Hf and Si carbides provide
high-temperature capability (as discussed)
but are subject to the limitations of their
respective oxides (also noted in the table)
resulting from high-temperature oxidizing
environment use. Iridium (Ir), which is
known to provide ultra-high-temperature
oxidation protection, and rhenium (Re),
which provides ultra-high-temperature
structural capability, are included particularly to show the lower density achievable with the CMC while maintaining
high-temperature performance capability. Although not shown in the table, the
density of carbon fibers is about 2 g/cm3.
The incorporation of the carbon fiber
reinforcement additionally contributes to
lowering the composite density relative to
that of monolithic materials.
The presence of residual metal in the
MI CMCs, while lowering the peak use
temperature relative to that of the pure

ceramic matrix, imparts some metallic
behavior and added toughness to the
matrix. This has been demonstrated
by high-speed particle impact testing.
Both high-speed water drop and nylon
bead impact testing have been successfully performed, showing the excellent
impact resistance of the MI CMC.
As a result of the ultra-hightemperature capabilities exhibited by
these materials, they have potential for
and have been demonstrated to be effective in a number of extremely demanding applications. MI CMC rocket
engine combustion chambers have been
successfully tested at temperatures in
excess of 2,200C (4,000F) in an environment that is oxidizing with respect
to the ZrC chamber material. Following the testing, the chamber was cross-
Melt infiltration processing provides

a rapid, cost-effective alternative for
the fabrication of ultra-high-temperature-capability CMCs. By control of
the fiber reinforcement type and fiber
architecture and the matrix chemistry, MI refractory CMCs have been
produced with a range of properties suited to a number of demanding
applications, including potential space,
defense, commercial and industrial
applications.
Control of the carbide content in
the matrices is particularly well-suited
to achieve a range of matrix characteristics from predominately or solely
ceramic in nature (i.e., for a fully carbide matrix) to a mix of ceramic and
metallic behavior. The use of refractory ceramic matrices that form selfprotective and tenacious oxide surface
layers during service provides for materials that are durable in ultra-hightemperature oxidizing environment
applications. Work on these and related
materials is continuing in a number of
related programs.
For additional information, visit www.ultramet.com.
References
1. Bull, J., White, M.J., and Kaufman, L., U.S. Patent
5,750,450, Ablation Resistant Zirconium and Hafnium Ceramics, May 12, 1998.
2. Kainer, K.U., Basics of Metal Matrix Composites,
in Metal Matrix Composites: Custom-Made Materials for Automotive and Aerospace Engineering, K.U.
Kainer, ed., Wiley, Weinheim, Germany, 2006.
3. Margiotta J.C., et al, Formation of Dense Silicon
Carbide by Liquid Silicon Infiltration of Carbon with
Engineered Structure, J. Mater. Res. 23, 5, 2008,
pp. 1237-1248.
4. Engineering Property Data on Selected Ceramics,
Volume III: Single Oxides, MCIC-HB-07, Volume III,
Metals and Ceramics Information Center, Battelle
Columbus Laboratories, Columbus, Ohio, July 1981.
5. Engineering Property Data on Selected Ceramics,
Volume II: Carbides, MCIC-HB-07, Volume II, Metals
and Ceramics Information Center, Battelle Columbus
Laboratories, Columbus, Ohio, August 1979.
6. Materials Engineering Materials Selector 1993, Penton Publishing, December 1992.
Industry Focus
#coatings #energy
#sustainability
All-Inorganic
Ceramic Performance
Coatings
Ceramic coatings have been developed that can provide
the benefits of polymer coatings without their inherent
shortcomings.
Therefore, it is time to search for alternative coatings that provide the benefits
of polymer coatings without their inherent shortcomings.
Chemically Bonded
Ceramics Development
By Arun S. Wagh, President, Inorganic Polymer Solutions, Inc.

and Greg Dicosola, Lead Engineer, Unitel Technologies
n the coatings world, all products are polymer based. In fact, it is almost
impossible to think of coatings without polymers. Whether architectural or
performance, all coatings are produced from some kind of polymer emulsion.
Polymer emulsions are easy to pump and spray, and are easy to store without
component separation. When applied, polymer emulsions exhibit a smooth, glasslike appearance that is appealing. These coatings are impermeable to water and resistant to commonly used chemicals.
Unfortunately, polymer coatings are also known to produce volatile organic
compounds (VOCs), are generally flammable, produce hazardous emissions when
they burn, have a high carbon footprint, and are known to damage the ozone layer.
Chemically bonded phosphate ceramic

(CBPC) technology was developed to
address these challenges. CBPCs are
formed by reacting inorganic minerals
and/or oxides with acid-phosphate solutions. Their pastes can be pumped or
sprayed like polymer coatings, provide
excellent corrosion protection to the substrate in a wide range of environments,
protect the substrate from heat with heatreflective and non-flammable surfaces,
and can be produced in different colors.
While products are entering markets
for several applications in normal conditions, efforts are underway to produce
coatings for specialty applications in
harsh environments, such as in hightemperature and acidic conditions created by the presence of hydrogen sulfide
and sulfuric acid, for deep and saline
water applications for steel structures
(e.g., on oil rigs), or to protect against
corrosion in a marine environment due
to the attack of marine organisms and
attachment of barnacles. For example,
pipelines that are thousands of miles
long connect the Arctic to the Gulf and
are exposed to hot and cold conditions,
along with abrasive flying particulates
and objects. CBPC coatings, with their
hard ceramic surface and excellent
freeze-thaw performance, are ideal for
this application. Chemical attack on the
interior surface of tankers carrying highly acidic or alkaline

chemicals leads to the need for specialty ceramic coatings for
long-term performance. With their tolerance to a wide range
of pH values, these coatings may be an answer to such extreme
chemical conditions.
The durability of natural minerals in harsh conditions is
common knowledge. Glass and ceramics, which are made of
these minerals, have the ability to withstand extreme chemical, thermal, and biological attack. The concept of all-ceramic
coatings has evolved over the years at the Argonne National
Laboratory in Lemont, Ill. One researcher and his group
showed that it is possible to produce CBPCs through a roomtemperature chemical reaction, as an alternative to the hightemperature sintering used in conventional ceramics.1
The first CBPCs were developed for the immobilization of
nuclear waste stored within the U.S. Department of Energy
(DOE) complex. CBPCs are now being used by the DOE for
the safe storage of nuclear materials. These coatings have also
made their way in the commercial market as rapid-setting
cements and building components. A natural next step now
is to produce coating products. All-inorganic ceramic coatings
are the result of this evolution.
X-ray diffraction analyses show that CBPCs are composed

of unreacted oxides or oxide minerals bonded by the phosphate reaction products. The phosphate binders are inherently
stable in any conditions. Therefore, the choice of the oxides
will guide the coatings performance in harsh environments.
This selection of oxides and oxide minerals is aided by the
electrochemistry of aqueous solutions. For example, if corrosion is due to acid attack, an oxide should be selected that is
resistant to the acid but can be slightly dissolved and reacted
to form the coating at a different pH. If corrosion is a result
of a saline environment, an oxide or an oxide mineral suitable
to withstand saline water should be selected. Electrochemical
phase diagrams of oxides and knowledge of solubility of minerals at different pH and Eh (redox potential) from the mineralogy literature aid this process.3
Interestingly, these phase diagrams also explain why and
under what conditions a metal corrodes. All-ceramic coatings
are synthesized by using the same chemistry, first to determine
under what conditions the corrosion occurs and then to decide
which materials will work for the best protection. Because of
this, all-ceramic coatings can get to the root cause of the problem and remedy it precisely.
Chemistry
Ceramics are produced by packing inorganic powders and firing the monolith at high temperatures until the particles fuse
with each other and form a hard ceramic. This process, though
highly successful in producing intricate ceramic objects, is
not useful for coatings, which need to be sprayed as paste
and allowed to set like polymer coatings. Since this ambienttemperature-setting was not possible with ceramic powders in
the past, there was no attempt to develop all-ceramic coatings.
CBPCs solved this problem. They are synthesized using two
aqueous solutions and by chemical reaction in ambient conditions, so it is possible to employ this process to produce allceramic coatings. The two pastes can be pumped and mixed in a
static mixer and allowed to react prior to spraying. Subsequently,
the reacting paste can be atomized and sprayed on any substrate
prior to completion of the reaction. The initial sprayable CBPC
was demonstrated in Argonne National Laboratory and then
improvised into a product by small businesses.2
The basic components in these coatings are magnesium
oxide (MgO) and monopotassium phosphate (KH2PO4). The
paste formed by these two powders sets into a ceramic.* The
reaction is given by:
MgO + KH2PO4 + 5 H2O = MgKPO46H2O
The reaction product is the binder for particles that forms
phosphate ceramic, or a ceramic coating. Since a range of
phosphate ceramics can be produced by acid-base reaction, it
should be equally possible to produce a variety of ceramic coatings. Alternatively, it should be possible to produce specialty
ceramic protective coatings tailored to specific harsh conditions
with a correct choice of the oxides or oxide minerals.
*named Ceramicrete by Argonne National Laboratory.
Figure 1. Simulation of the structure of an all-ceramic coating.
Figure 2. Osmotic blistering in polymer and all-ceramic coatings. Note that there is no
peeling off of the top coat in the all-ceramic coating, nor creeping of the corrosion
layer below the top coat.
Corrosion Protection Mechanism

As shown in Figure 1, when the reacting mixture of the acidic and
alkaline pastes is deposited on a substrate (e.g., steel or concrete),
it reacts first with the substrate, forming a passivation layer and
bonding to the substrate. A subsequent acid-base reaction forms
the protective ceramic coat, while the passivation layer is mostly
amorphous (or glassy); the protective layer consists of oxide or
mineral particles bonded by phosphate reaction products. The
two layers bond to each other. The passivation layer provides corrosion protection while the top layer imparts ceramic properties to
the surfaceall in one application of the reacting paste.
] All-Ceramic Coatings
This configuration is distinct from
that of polymer coatings, where the
coating is only skin deep. There is
no passivation layer underneath, and
a primer needs to be applied prior to
applying the polymer layer. All-ceramic
coatings do not need a primer, which
also eliminates the time needed to apply
and dry the primer. This is an economic
advantage of all-ceramic coatings in
field applications.
Additional advantages are evident
in performance. While the topcoat has
properties equal to or better than equivalent polymer coats, all-ceramic coatings
do not exhibit osmotic blistering; if the
coating is breached at a certain spot, the
corrosion front does not creep under the
remaining coating. The breached spot
can be simply repainted and, because
the ceramic coating bonds chemically to
itself, repair is easy. Most polymer coatings, being only a physical cover on the
substrate, do not have this advantage.
In addition, the damaged spot cannot
be simply repainted. A significant area
would need to be peeled off to repaint it.
Fire Protection
Ceramics are inherently non-flammable
and good insulators, and some ceramics are good reflectors of heat. As a
result, they exhibit excellent fire protection properties. In the standard flamespread test (ASTM E84), ceramics show
zero flame spread, implying that, in the
event of a fire, the coating will not burn
and the flame will not propagate. This
is unlike most polymer coatings, which
have a specified duration beyond which
the coating will catch fire.
Many oxides, such as titanium
dioxide (TiO 2 ) or magnesium oxide
(MgO), are excellent reflectors of
infrared (heat) radiation. All-ceramic
coatings can be produced with such
oxides, either in large proportion as
the reacting components or as fillers
in the coating. Tests carried out with
such formulations have shown that it
is possible to maintain a temperature
difference of about 200F between the
coated surface of a 1-in.-thick steel
plate exposed to > 1,000F heat and an
uncoated back surface. Spectrophoto-
Because the coatings are produced

from inorganic materials, VOC
emissions are zero.
metric measurements of the coated surface have shown that as much as 80%
of infrared radiation is reflected back
to the atmosphere.
When exposed to high temperatures, all-ceramic coatings convert
the coatings into refractory ceramic
coatings. These refractory coatings
are good high-temperature insulators.
Their durability, reflectivity to heat
radiation, and insulating properties
make them ideal for use as refractory
liners; heat reflectors on roof shingles
in the tropics; and zero-flame-spread
coatings for dwellings, offices, and
industrial complexes.
Environmental Impact
Assessment
Because climate change is here and
real, any new product introduced in
the market should go through scrutiny
of its impact on the environment. At
the minimum, its environmental impact
should not be worse than the product it
is replacing. To test this, greenhouse gas
emissions and their effect on ozone layer
were estimated and compared to those
of conventional polymer coatings.4
Greenhouse gas emissions arise from
the manufacture of the raw materials
used in the coatings. These raw materials are produced from ore mined
from the Earths crust, which are then
subjected to mechanical grinding, calcining, pulverizing, and in the case of
phosphates, reaction to acids. Each one
of these uses energy, which is produced
from some fuel that gives off greenhouse gases. In addition, the ore itself
consists of carbonates, which decompose and emit carbon dioxide.
Using the EPA-suggested model for
the estimation of carbon footprint for
Portland cement, greenhouse emissions for the raw materials can be
estimated. 5 The estimates will vary
depending on which oxides are used

because oxides are produced by different processes; some can be more energy
intensive and some less. In addition,
the ore itself consists of carbonates,
which decompose and emit carbon
dioxide. However, mining, crushing,
pulverizing, etc. are generally similar in
all mineral industries. Greenhouse gas
emissions amount to approximately
700 lbs per ton of the product used.
This number is roughly the same for
solvent-based alkyd paint, but only
30% of solvent-based varnish.
The real environmental benefit of allceramic coating, however, comes from
the fact that, because the coatings are
all produced from inorganic materials,
VOC emissions are zero. As a result,
there is no ozone depletion due to production or use of all-ceramic coatings.
In addition, the absence of VOCs makes
the coatings safer for manufacturers,
applicators and consumers.
Finally, the disposal of leftover paint
or end-of-use coatings has no effect on
the environment. At the most, they will
only enrich the soil because they are
very slow-releasing phosphate fertilizers. These long-term benefits of allceramic phosphate coatings and their
superior performance and economic
advantages gained from the performance should make them very attractive in the market.
For additional information, visit www.uniteltech.com.
References
1. Wagh, Arun S., Chemically Bonded Phosphate
Ceramics, Elsevier pub., 2004.
2. Wagh, Arun S., and V. Drozd, Inorganic Phosphate Corrosion Resistant Coatings, U.S. Patent
8.557,342, B2, issued October 15, 2013.
3. Pourbaix, M., Atlas of Electrochemical Equilibria in
Aqueous Solutions, NACE, Houston, 1974.
4. Swedish Environmental Research Institute (IVL), Lifecycle Assessment of Paint, Summary of IVL, Report
B 1338.A.
5. U.S. Environmental Protection Agency, Climate Leaders, Direct Emissions from Cement Sector, Climate
Leaders Greenhouse Gas Inventory Protocol Core
Module Guidance, 2003.
Whats New
MORGAN ADVANCED
MATERIALS
Ceramic Core Material
This company recently announced its new
P-59 ceramic core material, a high-silica
core type with a fine particle size distribution. The P-59 material is a development
of P-52 and is intended for directionally
solidified (DS) and single crystal (SX)
applications with thin cross-sections that
P-52 and P-57 core material cannot fill.
Used in the manufacture of jet
engine turbine blades as part of the
investment casting process, P-59
reportedly provides critical benefits
to the final product, such as increased
fuel efficiency. In order to achieve
greater efficiency, engines must run at
extremely high temperatures, which
demands superior air cooling capabilities. One element of that air cooling capability is a small, thin, trailing
edge portion of the core; P-59 material,
with its fine particle size distribution,
is reportedly able to achieve a trailing
edge that is up to 20% thinner than
that produced by other materials. Visit
www.morgantechnicalceramics.com.
SCHOTT
Glass Wafers
packaging (WLCSP) possible. Thanks

to its extremely high reliability, HermeS
wafers reportedly provide advantages
for MEMS devices used in industrial,
medical, and radio frequency (RF)
applications. Visit www.us.schott.com.
CORNING
KYOCERA
Cover Glass
This company recently announced its latest breakthrough innovation in consumer
electronics material design, Corning
Gorilla Glass 4, which is reportedly up
to two times tougher than any competitive
cover glass design now in the market. The
new Gorilla Glass 4 has been formulated
to address consumers number-one issue:
screen breakage from everyday drops.
Hybrid Cermet Materials

This company recently announced that
it has developed a new series of hybrid
cermet materials that reportedly offer
a 50% improvement in abrasion resistance and fracture resistance over conventional materials used as industrial
cutting tool inserts (compared to conventional Kyocera cermet, based on
research by Kyocera). The new TN620
and PV720 cermet grades are reportedly ideal for a variety of metal-cutting applications ranging from high- to
low-speed machining.
TN620 and PV720 reportedly
exceed conventional materials in both
hardness and strength through proprietary material technologies, such as a
special hybrid-structure surface hardening that distributes ultrafine particles
within the cermet in a more optimal
manner; hybrid bonded phase, including special metal phase with high melting points; and hybrid hard phase with
superior compressive stress effects. Visit
http://global.kyocera.com.
Gorilla Glass 4 is manufactured

using Cornings proprietary fusion draw
process. It reportedly maintains the
thinness, durability, and optical clarity
for which Gorilla Glass is known, while
improving drop performance. Over 40
manufacturers have designed Gorilla
Glass into a total of 1,395 product
models, and have branded Gorilla Glass
touch cover glass as a key selling feature. Visit www.corning.com.
INNOVNANO
This company is expanding its HermeS
wafers with hermetically sealed, solid
through-glass vias (TGV) into microelectromechanical systems (MEMS)
applications. HermeS glass substrates
are reportedly fully gastight, and therefore enable long-term, robust enclosures
for MEMS devices. The fine-pitched
vias reliably conduct electrical signals
and guide power into and out of the
MEMS device. Since HermeS glass can
be placed directly under the silicon
MEMS, it makes miniaturized, fully
hermetic, 3-D wafer-level chip-size
emulsion detonation synthesis (EDS)

technology to yield an ultrafine nanostructure, which is reportedly ideal in
the production of sputtering targets
for the deposition of thin films. Visit
www.innovnano-materials.com.
AZO Powders
A range of nanostructured aluminumdoped zinc oxide (AZO) was recently
developed, specifically for the production of high-density sputtering targets.
These AZO sputtering targets reportedly
provide researchers with an optimized,
cost-effective tool for the development
of next-generation transparent conducting oxide (TCO) thin films, applicable
to numerous research areas ranging
from solar cells to conducting glass.
The AZO powders are manufactured using the companys patented
ASAHI GLASS CO. (AGC)

Anti-Reflective Glass
This company recently announced it
will start sales of Clearsight in Japan.
Clearsight is an anti-reflective glass
with improved weather and chemical
resistant coating, reportedly suitable for
both indoor and outdoor use. The companys anti-reflective glass has a special
coating applied on both surfaces, which
reduces light reflectance on the glass
surface and minimizes reflection on the
glass. Visit www.agc.com.
Have Product Announcements to
Share? Send press releases regarding your new
product announcements to Kelsey Seidler
at seidlerk@bnpmedia.com!
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February 2015

a supplement to Ceramic Industry

Rare Earths Worldwide

2014 CI Top 10: Leading Worldwide Manufacturers

High-Temperature Energy Recovery Using Thermoelectric Ceramics

Modern Mechanical Carbon Materials for Aircraft Seal Applications

Melt-Infiltrated Refractory Ceramic Matrix Composites

Market Trends: Advanced and

Materials Innovation: NRL

Market Trends: Smart Auto Glass

Industry Focus #composites #aerospace #defense #coatings

All-Inorganic Ceramic Performance Coatings

2 Februar y 2015 www.ceramicindustr y.com/ciadvanced

Editor-in-Chief, Integrated Media

ts February, and love is in the air. Here at Ceramic Industry, we particularly

Lets Get Social!

*Advanced Ceramics, published November 2013, www.freedoniagroup.com.

Susan Sutton, Editor-in-Chief, Integrated Media

Steve Kulikowski, Midwest, West, Southwest U.S.,

Ann Kalb, Single Copy Sales

Amy Schuler Group Audience Marketing Manager

Kevin Collopy, Postal & Email Contacts,

Michael Costantino, Senior Account Manager

Publishing: John R. Schrei

EDITORIAL ADVISORY BOARD

Jesse Hamilton, Director of Process Excellence,

2401 W. Big Beaver Rd., Suite 700 Troy, MI 48084-3333

BNP Media Helps People Succeed

www.ceramicindustr y.com/ciadvanced Februar y 2015 3

Ceramic Fuel Cells Announces

CFCL. We are very pleased to see the

Kyocera and Century Tokyo

joint venture established by the two

4 Februar y 2015 www.ceramicindustr y.com/ciadvanced

as solar power generation sites. Visit

PPG to Supply Gulfstream

operators and maximum efficiencies for

ANH Refractories Becomes

Headquartered in Pittsburgh, Pa.,

Ceramics to Benefit from

orthopedic, and dental implants. These

Murata Joins Singapores

World First at Ceramics Expo 2015

Advanced and Nanoscale

he global market for advanced

and boridesare sold as starting materials for solid commercial articles.

6 Februar y 2015 www.ceramicindustr y.com/ciadvanced

systems, high-temperature applications,

ics derived from them include particle

www.ceramicindustr y.com/ciadvanced Februar y 2015 7

By Ted Dickson, Director, TAK Industrial Minerals, and

he rare earths industry is in a state of transition. China, which currently

Rare Earths Overview

Much of the new production outside

rare earths in several applications (e.g.,

The second largest consumer is the

www.ceramicindustr y.com/ciadvanced Februar y 2015 9

] Rare Earths Worldwide

global economic downturn that began

10 Februar y 2015 www.ceramicindustr y.com/ciadvanced

Chinas poor environmental record

Tour Les Miroirs, 18 Avenue dAlsace, 92 096 La Dfense Cedex, France

1-5-1, Marunouchi, Chiyoda-ku, Tokyo 100-8405, Japan