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Progress in Nanotechnology

Applications

A Progress in Ceramic Technology series publication

@WILEY A John Wiley & Sons, Inc., Publication

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Applications

A Progress in Ceramic Technology series publication

@WILEY A John Wiley & Sons, Inc., Publication

Copyright 0 2010 by The American Ceramic Society. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada.

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Progress in nanotechnology. Applications. p. cm. - (A progress in ceramic technology series) Includes index. ISBN 978-0-470-40840-7 (cloth) 1. Ceramic materials. 2. Nanotechnology. 3. Nanostructured materials.. I . American Ceramic Society. TA455.C43P78 201 0 620.1'4-dc22 2009034626

Printed in the United States of America

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Contents

Introduction

MARKET OVERVIEWS

Rolling Nanotech Out of the Lab and Into the Market J. Sawyer Am. Ceram. SOC. Bull., Vol. 86, No. 5, p. 25-30, 2007

Ceramic Revolution May Yet Arrive via Nanotechnology K. Blakely Am. Ceram. SOC. Bull., Vol. 85, No. 9, p. 30-32, 2006

Powder Market Update: Nanoceramic Applications Emerge T. Abraham Am. Ceram. SOC. Bull., Vol. 83, No. 8, p. 23-25, 2004

BIOMEDICAL TECHNOLOGY

Fabrication of Nano-Macro Porous Soda-Lime Phosphosilicate Bioactive Glass by the Melt-Quench Method

H. M. M. Moawad and H. Jain CESe Vol. 28, NO. 9, p. 183-195, 2008

Biological Response Mechanisms to Microparticulate and Nanoparticulate Matter M. Chary, R. Baier, P. Nickerson, and J. Natiella Am. Ceram. SOC. Bull., Vol. 86, No. 7, p 40-42, 2007

AlumindZirconia Micro/Nanocomposites: A New Material for Biomedical Applications With Superior Sliding Wear Resistance

J. Bartolome, A. De h a , A. Martin, J. Pastor, J. Llorca, R. Torrecillas, and G. Bruno J. Am. Ceram. SOC., Vol. 90, No. 10, p. 31 77-31 84, 2007

Creation of Nano-Macro-Interconnected Porosity in a Bioactive Glass-Ceramic by the Melt-Quench-Heat-Etch Method

H. Moawad and H. Jain J. Am. Ceram. Soc., Vol. 90, No. 6, p. 1934-1936, 2007

Processing and Properties of Nano-Hydroxyapatite(n-HAp)/Poly(Ethylene-Co-Ac~lic Acid)(EAA) Composite Using a Phosphonic Acid Coupling Agent for Orthopedic Applications

N. Pramanik, S. Mohapatra, P. Pramanik, and P. Bhargava J. Am. Ceram. SOC., Vol. 90, No. 2, p. 369-375, 2007

Hydroxyapatite-Carbon Nanotube Composites for Biomedical Applications: A Review A. White, S. Best, and I. Kinloch lnt. J. of Appl. Ceram. Techno/., Vol. 4, No. 1, p. 1-1 3, 2007

Contents

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Synthesis and Structural Characterization of Nanoapatite Ceramics Powders for Biomedical Applications 71 K. Ando, M. Ohkubo, S. Hayakawa, K. Tsuru, A. Osaka, E. Fujii, K. Kawabata, C. Bonhomme, and F. Babonneau CJ Vol. 195, p. 125-131,2006

High-Frequency Induction Heat Sintering of Mechanically Alloyed Alumina-Yttria-Stabilized Zirconia Nano-Bioceramics

S. Kim and K. Khalil J. Am. Ceram. SOC., Vol. 89, No. 4, p. 1280-1285, 2006

79

Merging Biological Self-Assembly with Synthetic Chemical Tailoring: The Potential for 3-D Genetically Engineered Micro/Nano-Devices (3-D GEMS)

85

K. Sandhage, S. Allan, M. Dickerson, C. Gaddis, S. Shian, M. Weatherspoon, Y. Cai, G. Ahmad, M. Haluska, R. Snyder, R. Unocic, F. Zalar, Y. Zhang, R. Rapp, M. Hildebrand, and B. Palenik Int. J. ofAppl. Ceram., Vol. 2, No. 4, p. 317-326, 2005

CONSTRUCTION AND MANUFACTURING

Effect of Nanosilica Additions on Belite Cement Pastes Held in Sulfate Solutions J. Dolado, I. Campillo, E. Erkizia, J. Ibaiiez, A. Porro, A. Guerrero, and S. Goiii J. Am. Ceram. SOC., Vol. 90, No. 12, p. 3973-3976, 2007

Effect of Nano-Size Powders on the Microstructure of Ti(C,N)-xWC-Ni Cermets J. Jung and S. Kang J. Am. Ceram. SOC., Vol. 90, No. 7, p. 2178-2183, 2007

In Situ Preparation of Si3N,/SiC Nanocomposites for Cutting Tools Application I? Sajgalik, M. Hnatko, Z. LenEeS, J. Dusza, and M. KaSiarova lnt. J. of Appl. Ceram., Vol. 3, No. 1, p. 41 -46, 2006

How Nanotechnology Can Change the Concrete World, Part One K. Sobolev and M. Gutierrez Am. Ceram. SOC. Bull., Vol. 84, No. 10, p. 14-17, 2005

How Nanotechnology Can Change the Concrete World, Part Two K. Sobolev and M. Gutierrez Am. Ceram. SOC. Bull., Vol. 84, No. 1 1, p. 16-1 9, 2005

ELECTRONIC AND OPTICAL DEVICES

Will Silicon Survive Moore’s Law? L. Sheppard Am. Ceram. SOC. Bull., Vol. 87, No. 4, p. 18-22, 2008

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Nanosize Engineered Ferroelectric/Dielectric Single and Multilayer Films for Microwave Applications 129 R. Wordenweber, E. Hollmann, M. Ali, J. Schubert, and G. Pickartz Advances in Electronic Ceramics, Ed. C. Randall et a/, CESP, Vol. 28, No. 8, p. 9-16, 2008

Effect of Calcination on Crystallinity for Nanostructured Development of Wormhole-Like Mesoporous Tungsten Oxide

137

W. Lai, L. Teoh, Y. Su, J. Shieh, and M. Hon J. Am. Ceram. SOC., Vol. 90, No. 12, p. 4073-4075, 2007

Mg-Cu-Zn Ferrites for Multilayer Inductors J. Murbe and J. Topfer Int. J. ofAppl. Ceram., Vol. 4, No. 5, p. 415-422, 2007

141

Microwave Dielectric Properties of Sintered Alumina Using Nano-Scaled Powders of (Y Alumina and TiO, 149 C-L Huang, J-J Wang, and C-Y Huang J. Am. Ceram. SOC., Vol. 90, No. 5, p. 1487-1493, 2007

PbZr,,,Ti,,,O,-Based Reflectors with Tunable Peak Wavelengths G. J. Hu, X. K. Hong, A. Y. Liu, J. Chen, J. H. Chu, and N. Dai J. Am. Ceram. SOC., Vol. 89, No. 4, p. 1453-1454, 2006

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vi Progress in Nanotechnology: Applications

Morphologies-Controlled Synthesis and Optical Properties of Bismuth Tungstate Nanocrystals by a Low-Temperature Molten Salt Method

L. Xie, J. Ma, J. Zhou, Z. Zhao, H. Tian, Y. Wang, J. Tao, and X. Zhu J. Am. Ceram. SOC., Vol. 89, No. 5, p. 171 7-1 720, 2006

Synthesis of High Density and Transparent Forsterite Ceramics Using Nano-Sized Precursors and Their Dielectric Properties

S. Sano, N. Saito, S. Matsuda, N. Ohashi, H. Haneda, Y. Arita, and M. Takernoto J. Am. Ceram. SOC., Vol. 89, No. 2, p. 568-574, 2006

Design and Nanofabrication of Superconductor Ceramic Strands and Customized Leads A. Rokhvarger and L. Chigirinsky Int. J. ofAppl. Ceram., Vol. 1, No. 2, p.129-139, 2004

Built-in Nanostructures in Transparent Oxides for Novel Photonic and Electronic Functions Materials H. Hosono Int. J. of Appl. Ceram.Technol., Vol. 1, No. 2, p. 106-1 18, 2004

ENERGY AND THE ENVIRONMENT

Preparation and Characterization of Samaria-Doped Ceria Electrolyte Materials for Solid Oxide Fuel Cells Y.-P. Fu, S.-B. Wen, and C.-H. Lu J. Am. Ceram. SOC., Vol. 91, No. 1, p. 127-131, 2008

Design of High-Quality Pt-CeO, Composite Anodes Supported by Carbon Black for Direct Methanol Fuel Cell Application

M. Takahashi, T. Mori, F. Ye, A. Vinu, H. Kobayashi, and J. Drennan J. Am. Ceram. SOC., Vol. 90, No. 4, p. 1291-1294, 2007

Rapid Formation of Active Mesoporous TiO, Photocatalysts via Micelle in a Microwave Hydrothermal Process

H.-W. Wang, C.-H. Kuo, H.-C. Lin, I.-T. Kuo, and C.-F. Cheng J. Am. Ceram. SOC., Vol. 89, No. 11,3388-3392, 2006

Development of Visible-Light Photocatalysts by Nitrogen-Doped Titanium Dioxide Am. Ceram. SOC. Bull., Volume: 85, Issue: 10, p. 23, 2006

Synthesis of Nanophased Metal Oxides in Supercritical Water: Catalysts for Biomass Conversion C. Levy, M. Watanabe, Y. Aizawa, H. Inornata, and K. Sue Int. J. of Appl. Ceram. Techno/., Vol. 3, No. 5, p. 337-344, 2006

Synthesis and Characterization of Nano-Composite Alumina-Titania Ceramic Membrane for Gas Separation

A. L. Ahmad, M. R. Othrnan, and N. F. ldrus J. Am. Ceram. SOC., Volume 89, Issue 10, p. 3187-3193, Oct 2006

Hydrothermal Synthesis of Nan0 Ce-Zr-Y Oxide Solid Solution for Automotive Three-Way Catalyst H. Yucai J. Am. Ceram. SOC., Volume 89, Issue 9, p. 2949-2951, Sept 2006

Comparison Between Micrometer- and Nano-Scale Glass Composites for Sealing Solid Oxide Fuel Cells M. Brochu, B. D. Gauntt, R. Shah, and R. E. Loehman J. Am. Ceram. SOC., Vol. 89, No. 3, p. 810-816, 2006

Preparation of Nanocrystalline CeO, by the Precipitation Method and Its Improved Methane Oxidation Activity

H.-J. Choi, J. Moon, H.-B. Shim, K.-S. Han, E.-G. Lee, and K.-D. Jung J. Am. Ceram. SOC., Vol. 89, No. 1, p. 343-345, 2006

Preparation and Characterization of Nano-Crystalline LiNi,,,Mn, Combustion Reaction Method

Cathode Material by the Soft

Z. Zhao, J. Ma, H. Tian, L. Xie, J. Zhou, P. Wu, Y. Wang, J. Tao, and X. Zhu J. Am. Ceram. SOC., Vol. 88, No. 12, p. 3549-3552, 2005

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Contents vii

Synthesis and Characterization of Nano-Hetero-Structured Dy Doped CeO, Solid Electrolytes Using a Combination of Spark Plasma Sintering and Conventional Sintering

T. Mori, T. Kobayashi, Y. Wang, J. Drennan, T. Nishimura, J-G Li, and H. Kobayashi J. Am. Ceram. SOC., Vol. 88, No. 7, p. 1981-1984, 2005

Fabrication and Performance of Impregnated Ni Anodes of Solid Oxide Fuel Cells S. Jiang, S. Zhang, Y. Zhen, and W. Wang J. Am. Ceram. SOC., Vo. 88, No. 7, p. 1779-1 785, 2005

Advances in Nano-Structured Electrochemical Reactors for NOx Treatment in the Presence of Oxygen M. Awano, Y. Fujishiro, K. Hamamoto, S. Katayama, and S. Bredikhin Int. J. of Appl. Ceram. Techno/., Vol. 1, No. 3, p. 277-286, 2004

SENSORS

Prussian Blue Nanoparticles Encapsulated Within Ormosil Film P. Pandey and B. Singh CESF: Vol. 28, NO. 8, p. 109-1 24, 2008

High-Yield Synthesis of Nanocrystalline Tin Dioxide by Thermal Decomposition for Use in Gas Sensors C. Agashe, R. Aiyer, and A. Garaje Int J. ofAppl. Ceram. Techno/., Vol. 5, No. 2, p. 181-187, 2008

Effect of Firing Temperature on Electrical and Gas-Sensing Properties of Nano-Sn0,-Based Thick-Film Resistors

A. Garje and R. Aiyer Int. J. of Appl. Ceram. Techno/., Vol. 4, No. 5, p. 446-452, 2007

Preparation of Ru-C Nano-Composite Films and Their Electrode Properties for Oxygen Sensors T. Kimura and T. Goto Novel Processing of Ceramics and Composite, Ed. N. Bansal et al., Ceramic Transactions, Vol. 195, p.13-19, 2006

Electrical and Gas-Sensing Properties of a Thick Film Resistor of Nanosized SnO, with Variable Percentage of Permanent Binder

A. D. Garje and R. C. Aiyer Int. J. of Appl. Ceram. Techno/., Vol. 3, No. 6, p. 477-484, 2006

Non-Nernstian Planar Sensors Based on YSZ with Ta (1 0 at.%)-Doped Nanosized Titania as a Sensing Electrode for High-Temperature Applications

L. Chevalier, M. Grilli, E. Di Bartolomeo, and E. Traversa Int. J. of Appl. Ceram. Techno/., Vol. 3, No. 5, p. 393-400, 2006

Improvement of NO, a Sensing Performances by an Additional Second Component to the Nano-Structured NiO Sensing Electrode of a YSZ-Based Mixed-Potential-Type Sensor

V. Plashnitsa, T. Ueda, and N. Miura Int. J. of Appl. Ceram. Techno/., Vol. 3, No. 2, p. 127-133, 2006

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viii Progress in Nanotechnology: Applications

Introduction

Although nanotechnology is still an emerging industry, it represents a huge potential in a variety of markets that include biomedical, electronics, and energy. For example, according to one market analyst, the market for nano-enabled electronics will reach over $82 billion in 201 1. Some of these applications include memory products, nanosensors, and display technology. Biomedical applications is another promising area, with powders and composites being developed for orthopedic implants and other devices. Contrast agents for tomography of bone microstructure are also under development. In the areas of energy and the environment, applications include fuel cell electrodes, photocatalysts, and gas separation membranes.

This edition of Progress in Ceramic Technology series is a select compilation of articles on nanotechnology applications and markets previously published in ACerS publications, including The American Ceramic Society Bulletin, Journal of the Ameri- can Ceramic Socieq, International Journal of Applied Ceramic Technology, Ceramic Engineering and Science Proceedings (CESP) and Ceramic Transactions (CT).

The American Ceramic Society contributes to the progress of nanotechnology by providing forums for information ex- change during its various meetings and by publishing articles in its various journals and proceedings.

For other books on nanotechnology, including Progress in Nanotechnology: Processing, visit the ACerS bookstore at www.ceramics.org or the ACerS-Wiley webpage at www.wiley.com/go/ceramics.

Introduction ix

Market Overviews

Photo courtesy of Mercedes-Benz USA

You might say that Mercedes-Renz started from scratch when it went looking for a inore durable paint f c x its automobiles. What the automak- cr wound up with is a clear lacquer that contains microscopically small ceramic particles. As the paint hardens in the assembly plant’s paintshop oven, the ceramic particles interact on the nanoscale and make the lacquer even harder.

The lacquer top coat is quite effective in protecting the pigment-bear- ing paint under it h m scratches, particularly those that can he inflicted by mechanical car washes. Mercedcs engineers have seen as much as R 40% improvement in paint gloss cotnpared to conventional clear lac- quers in cars subjected to repeated washes.

Mercedcs- Aenz has been using this example of nanottchnology on its production vehicles since late 2001.

This is hut one example of how, almost unheralded, nano-applications arc popping up in the marketplace like flowers after a spring rain. O r

Top: Beginning in late 2003, Mercedes-Benz began using paint with scratch- resistant properties provided via ceramic nanoparticles.

Market Overviews 3

weeds, as some may say, concerned over what manipulating materials at such a miniscule scale may do to human health and the environment.

While it remains to be seen what if any threat efforts to “domesticate atoms” (as the Project on Emerging Nanotech- nologies at the Woodrow Wilson International Center for Scholars has termed it) pose, the perceived and potential benefits are widely anticipated. As noted, some of these benefits have already appeared. Many more are on the way.

First, though, it helps to understand how far-reaching the impact of nanotechnology is expected to be. Nothing seems to be immune from being dealt with on the nanolevel. Even a material as commonplace as concrete is being looked at in the light of nanotechnology.

Virtually as old as construction itself, cement from which concrete is made is the world’s most widely used material. It is produced at the rate of more than 2 billion tons per year. That something so old and so common could hold surprises is in itself surprising. But then nanotechnology is a surprising thing because it works in so many-and so many unex- pected-areas. What a group of engineers at MIT are looking to improve upon is not the hardness of concrete, nor its strength, nor its cost. They are looking to significantly reduce the amount of CO, generated as cement is produced.

Concrete is a significant contributor to global warming, accounting for 5-10% of CO, emissions. Franz-Josef Ulm and Georgios Constantinides are looking at the source of concrete’s strength, the organization of its nanoparticles, as the way to achieve their goal.

“If everything depends on the organi- zational structure of the nanoparticles that make up concrete, rather than on the material itself, we can conceivably replace it with a material that has concrete’s other characteristics-strength, durability, mass availability and low cost -but does not release so much CO, into the atmosphere during manufacture,”

Photo courtesy of Ohio Dept. of Transportatlon

Perhaps the most ubiquitous material in the world thanks to its use in roadways and other types of construction, concrete derives its strength and durability from the nano- structure of the cement from which it is formed.

said Ulm, a professor of civil and environmental engineering.

“The construction industry relies heavily on empirical data, but the physics and structure of cement were not well understood,” said Constantinides, a postdoctoral researcher in materials science and engineering. “Now that the nano-indentation equipment is becoming more widely available-in the late 1990s, there were only four or five machines in the world and now there are five at MIT alone-we can go from studying the mechanics of structures to the mechanics of material at this very small scale.”

The equipment he mentions is in a way the alpha and the omega of the explosion in nanoresearch. Things have always existed on a nanoscale. We just were not aware of it.

According to “Nanotechnology: The Future is Coming Sooner Than You Think”, a study conducted by the Congressional Joint Economic Committee, “nanotechnology has begun to blossom ... due to the development

of new instruments that allow researchers to observe and manipulate matter at the atomic level.” The report cites scanning tunneling microscopy, magnetic force microscopy and electron microscopy as among the developments that have contributed. “As better instru- mentation for observing, manipulating and measuring events a t this scale are developed, further advances in our understanding and ability will occur.”

The Project on Emerging Nanotech- nologies concurs. “Nanotechnology would not exist if there were not tools for working at this otherwise invisible scale,” writes Karen Schmidt in the project’s publication Nanofrontiers: Visions for the Future of Nanotechnology, which highlights the findings of a meeting organized by the project and NSF and the National Institutes of Health. “Nanotools have not been around long. In the late 1960s, researchers at the US. National Bureau of Standards - now NET-developed the Topografiner, an instrument for scanning and visualizing the surfaces of materials on a microscop- ic scale. That helped lead in the 1980s to a groundbreaking nanotool, the scan-

4 Progress in Nanotechnology: Applications

ning tunneling microscope (STM). The STM enabled scientists to better control the position of the scanning tip and, for the first time, see things just one nanometer in length.”

It’s hard to fully appreciate where you are if you don’t know how you’ve gotten there. Now that that has been defined, it’s time to look around and see where nanotechnology is currently.

I t is in no one place, actually. I t is in numerous research facilities around the country (see sidebar, page 28) . And it cuts across many disciplines.

The Joint Economic Committee study specifically identifies half a dozen fields that impact and are impacted by nanotechnology. It should be of no small concern that a congressional study of this magnitude does not recognize materials science or engineering let alone ceramics in this list. The areas that are mentioned are, in alphabetical order:

Biology,

Chemistry,

Computer science,

Electrical engineering,

Mechanical engineering,

September by John Wiley & Sons in partnership with ACerS. )

BASF, Bayer, Buhler and Rice University were among the organiza- tions represented during this section.

The Bayer presentation focused not just on the nanotechnology research the company’s Bayer Materialscience (BMS) group is currently conducting, but also on products that have been successfully commercialized. Others are on the way. Early in April it was announced at the JEC Composites Show in Paris

that BMS’ high-performance Carbon Nanotubes Baytubes will be used. to make surfboards and skis.

BASF’s presentation was entitled “Nanotechnology at BASF: Innovations for a Sustainable Future”. Noting that working with materials that involve “the creation or presence of elements that are at least one spatial dimension smaller than a few hundred nanometers ... is nothing new for BASF”, the presentation expounded on how the company’s focus is the environment and energy

conservation: “Examples range from new materials for the storage, conversion and conservation of energy in different forms, like meso- and nanoporous materials for superior insulation or more efficient hydrogen storage devices for portable fuel cells to engineered plastics like Ultradur High Speed.”

Buhler’s presentation most directly cited ceramics. Titled “Industrial Converting of Ceramic Nanoparticles in Real-World Products: Unfolding the Innovation Potential”, it delved into the need of effective dispersion of ceramic nanoparticles as additives in coatings, plastics, electronics, consumer goods and other products. It called for advanced processing techniques to fully unlock the potential of the nanoparticles.

The Rice presentation, “Industrial Applications of Nanomaterials and Technology Transfer Issues”, investigat- ed what the hurdles are for nanomaterials in the marketplace and where the best applications are. Among the other practical issues it raised were the protec- tion of intellectual property amidst over- lapping claims and whether nanomaterials as a category will move from special- ty to commodity products.

Predicting exactly where this will all lead and when is about as certain as accurately predicting what the weather will be like at the foot of Pike’s Peak on Jan. 1, 2057. Still, some sense of the direction things will take can be divined. Congress’ Joint Economic Committee turned to M.C. Roc0 to provide that sense of direction. Given his credentials-senior advisor for nanotechnology at NSF, and chair of the US. National Science & Technology Council’s subcommittee on nanoscale science, engineering and technology as well as a key architect of the National Nanotechnology Initiative (”1)- Roco is a solid choice.

He sees four generations of nanotechnology development. The congressional paper envisions another stage that might follow, at which point the advance of nanotechnology will have reached a stage of exponential growth where the


rate of growth “becomes almost infi- nite.” Posited to arrive around 2020, the report contends, “Technology is likely to continue, but at this stage some observers forecast a period at which scientific advances aggressively assume their own momentum and accelerate at unprecedented levels, enabling products that today seem like science fiction.”

While all that might come about, it seems more reasonable to focus on the 2000-20 timeframe, during which more predictable events are likely to occur. The following description of this period based on Roco’s assessment is taken ver- batim from the Joint Economic Committee’s report:

Passive Nunostructures (2000-05) During the first period products will

take advantage of the passive properties of nanomaterials, including nanotubes and nanolayers. For example, titanium dioxide often is used in sunscreens because it absorbs and reflects ultravio- let light, eliminating the white cream appearance associated with traditional sunscreens. Carbon nanotubes are much stronger than steel but only a fraction of the weight. Tennis rackets containing them promise to deliver greater stiffness without additional weight. As a third example, yarn that is coated with a nanolayer of material can be woven into stain-resistant clothing. Each of these products takes advantage of the unique property of a material when it is manufactured at a nanoscale. However, in each case the nanomaterial itself remains static once it is encapsulated into the product.

Active Nanostructures (2005-1 0) Active nanostructures change their

state during use, responding in predictable ways to the environment around them. Nanoparticles might seek out cancer cells and then release an attached drug. A nanoelectromechanical device embedded into construction material could sense when the material is under strain and release an epoxy that repairs any rupture. Or a layer of nanomaterial might respond to the presence of sunlight by emitting an electrical charge to power an appliance. Products in this phase require a greater under-

Market Overviews 7

Photo by Tommy Lavergne, Rice University

To promote the development of nanotechnology, in 2005 students at Rice University created what Guiness recognizes as the world‘s largest model of a single-wall nanotube.

standing of how the structure of a nanomaterial determines its properties and a corresponding ability to design unique materials. They also raise more advanced manufacturing and deploy- ment challenges.

Systems of Nanosystems (2010-15) In this stage, assemblies of nanotools

work together to achieve a final goal. A key challenge is to get the main components to work together within a net- work, possibly exchanging information in the process. Proteins or viruses might assemble small batteries. Nanostructures could self-assemble into a lattice on which hone or other tissues could grow. Smart dust strewn over an area could sense the presence of human beings and communicate their location. Small nanoelectromechanical devices could search out cancer cells and turn off their reproductive capacity. A t this stage significant advancements in robotics, biotechnology and new generation information technology will begin to appear in products.

Molecular Nanosystems (201 5-20) This stage involves the intelligent

design of molecular and atomic devices,

leading to “unprecedented understanding and control over the basic building blocks of all natural and man-made things.” Although the line between this stage and the last blurs, what seems to distinguish products introduced here is that matter is crafted at the molecular and even atomic level to take advantage of the specific nanoscale properties of different elements. Research will occur on the interaction between light and matter, the machine-human interface, and atomic manipulation to design molecules. Among the examples that Roco foresees are “multifunctional molecules, catalysts for synthesis and controlling of engineered nanostructures, subcellular interventions, and biomimetics for complex system dynamics and control.” Since the path from initial discovery to product application takes 10-1 2 years, the initial scientific foundations for these technologies are already starting to emerge form laboratories. At this stage a single product will integrate a wide variety of capacities including independent power generation, information processing and communication, and mechanical operation. Its manufacture implies the ability to rearrange the basic build-

ing blocks of matter and life to accom- plish specific purposes. Nanoproducts regularly applied to a field might search out and transform hazardous materials and mix a specified amount of oxygen into the soil. Nanodevices could roam the body, fixing the DNA of damaged cells, monitoring vital conditions and displaying data in a readable form on skin cells in a form similar to a tattoo. Computers might operate by reading the brain waves of the operator.

Optimism Abounds

Whether nanotechnology will ever generate products that operate at this science-fiction-like level remains to he seen. What is certain is that nanotechnology is generating a level of optimism among academics, researchers, investors and entrepreneurs that hasn’t been seen since the dot-com frenzy of the late ’90s.

Besides the numerous research facilities popping up on university campuses and elsewhere around the nation, there are a large number of nanotech seminars and symposia that are popping up on the calendar. One such is Commercializa- tion of NanoMaterials 2007 to he held Nov. 11-13 in Pittsburgh. It is cospon- sored by The American Ceramic Society. And even as this is being written, E-mails are arriving announcing no fewer than five seminars and workshops on nanotechnology that are or will be held in Europe.

A survey released in January conducted by the University of Massachusetts at Lowell found that nanotechnology exec- utives “are bullish on their own firms’ potential sales.” The study garnered responses from 407 nanotechnology business leaders across the nation. Roughly 60% claim to have the resources-including capital and infra- structure-to successfully commercialize their products.

They also expressed some uncertainty about intellectual property issues and the effects of nanotechnology on the environment and human health. Overall, however, they expect good big things to come out of small packages.


Application of ceramics nanotechnology to solid-oxide fuel cells, thermoelectric materials and other systems could lead to the long-awaited ceramics revolution.

Keith A. Blakely

In many ways, the past 30 years have been a revolutionary period for advanced ceramics. During that time, we have seen the advent of high-temperature structural ceramics-such as pressureless-sintered silicon carbide and reaction-bonded silicon nitride, phase- transformed and toughened oxide, ceramics, ceramic-matrix composites, high-temperature superconducting ceramics and transparent ceramics.

From a purely scientific standpoint, there is no question that the advances in material properties and process understanding have been revolutionary. However, for those of us who were in the midst of the “ceramic fever” of the mid-

to-late 1980s, the ceramic revolution never seemed to materialize.

Major initiatives have been made in the United States and elsewhere to insert these emerging materials into broad industrial applications: high-temperature heat exchangers, adiabatic car engines, power transmission and energy storage. However, they never achieved the commercial traction that had been eagerly anticipated.

That is not to say that these new materials and capabilities did not have a significant impact on the global economy. The introduction of the ceramic honeycomb catalytic converter was one of the most important applications of

ceramics of the 20th century. It impacted environment, energy and quality of life worldwide.

Advances in biomedical components made from or coated by tough ceramics-such as zirconia-also have had a tremendous impact.

The global semiconductor industry would not have been able to advance its products, processes and capabilities without the parallel advances in corro- sion-resistant, high-temperature components used in etch chambers, wafer transfer processes, diffusion furnaces and deposition chambers.

It is difficult to estimate how much of Intel’s growth was enabled by these new

Market Overviews 9

materials that have been used by OEMs- such as Applied Materials, Novellus and LAM. The explosion in telecommunica- tions was similarly impacted by high-performance substrates and packages as well as passive and active components. The composition and manufacture of these components was not possible or not affordable 30 years ago because of the lack of adequate materials understanding and commercial availability.

Therefore, on the one hand, it is difficult to put forth the proposition that the ceramics revolution has not arrived. I t has, but in perhaps a much less obvi- ous and subtle manner than we had anticipated during the heyday of ceramics fever.

Webster defines “revolution” as something of a more disruptive and sudden nature than what we have experienced in ceramics during the past 30 years. Therefore, I suggest that another-perhaps a second-ceramics revolution is coming. I believe this revolution will stand on the shoulders of nanotechnology-a disruptive force in its own right.

To many in the ceramics world, nanotechnology is not new. Ceramists have used nanomaterials for decades. Fumed silica has been used as a thickening agent, a constituent of many ceramic formulations and a building block of many ceramic components.

Similarly, carbon black has been used as furnace insulation, constituent in electronic pastes and reactant for car- bothermal synthesis of carbide, boride and nitride powders. Nanosized oxide ceramics have been used in chemical mechanical polishing, battery electrode materials, fuel-cell components and catalyst supports.

The nanomaterials industry has emerged capable of synthesizing a broad range of compositions, formulations, particle sizes and distributions, core- shell materials and acicular morphologies. This has given ceramics an entirely new set of tools to use in the design and development of revolutionary products.

Many of these new products truly

impact of nanomaterial content on SOFC elements.

have the potential to create sudden and disruptive changes-in a positive way- in our world and the quality of life available to this and generations to come.

Perhaps no segment of our economy has the potential to be as disrupted by this convergence of nanotechnology and ceramics as does energy. The possibilities are numerous, and outstanding progress is being made in a broad range of conservation and production approaches to energy use. There are two that I believe will prove particularly significant: fuel cells and bulk thermoelectric materials.

Fuel cells were first described in the late 19th century. However, they have failed to make significant penetration into the energy production market. Similar to other technologies, this is a function of economic efficiency. When either the cost of capital or the cost of operation of a power generation system is too high to be competitive, its use will be limited to applications where other considerations are more important.

For example, if a fuel cell requires hydrogen fuel to generate electricity and the cost of producing, delivering, storing and then converting hydrogen into power is more than competing technolo-

gies-such as batteries, internal combustion engines or nuclear power plants- the market will reject such solutions most of the time.

The development of ceramic-based fuel cells (e.g., molten carbonate and solid oxide) has progressed rapidly during the past 20 years. However, it has failed-with rare exception-to achieve adequate economic efficiency to dis- place alternative energy sources.

During the past five years, we have been able to engineer highly specific electrode and electrolyte architectures within the solid-oxide fuel cell (SOFC). This has resulted from the availability and use of nanosized starting materials and ultrathin coatings prepared from colloids and sol-gel formulations of nanoparticles.

These advances have given us the ability to use tightly controlled nanoparticles in the creation of highly porous, catalytic and electrically active microstructures. Therefore, the amount of power that can be extracted from hydrogen and hydrocarbon fuels using a specific mass and volume of ceramics has increased dramatically. This has paved the way for affordable systems and power production compared with conventional and readily available fuels.


The temperature stability of ceramics in these systems also leads to other benefits. Besides power output, there is high-quality heat and water generated in a SOFC. These can be captured and used in cogeneration systems.

Furthermore, the lightweight nature of ceramics can lead to more-portable power-generating systems. These can be transported to and located in difficult to reach areas or underdeveloped regions, where power and transportation infra- structure is nonexistent.

Bulk thermoelectric materials have been used for decades, primarily in applications where there were limited options, such as spacecraft. Again, the economic efficiency question is involved.

A thermoelectric material generates power through a thermal gradient, which often can be created from a waste heat stream. In the case of the vacuum of space, exposure to unidirectional radiant heating creates an essentially free “fuel.”

However, the cost of the most efficient thermoelectric materials i s high and must be considered in calculating the economic efficiency of the power- generating system. In other words, similar to batteries, thermoelectric materials can produce energy in a steady-state mode. However, if the cost of the thermoelectric component is excessive, the value of the energy produced cannot jus- tify its use.

There have been significant performance advances during the past two

Twenty nanometer (20 nm) core-shell thermoelectric nanoparticles.

decades as materials and understanding of the thermoelectric phenomenon have improved. We are building on this knowledge base and the performance baselines achieved by specific material sets. Researchers have begun to attack- with encouraging results-the challenge of creating bulk thermoelectric materials that offer the combination of affordabili- ty-driven largely by material selection and consolidation costs-and efficiency performance. This paves the way for their potential broad adoption into a significant number of important energy production and conservation applications.

Core-shell versions of previously researched thermoelectric materials- 20-50 nm in diameter-have been con- solidated into useful bulk structures. They demonstrate performance metrics that are three to five times those of conventional-sized particles of the same composition.

Imagine the impact of converting waste heat in an industrial process stream (gas or liquid) to electricity at no additional cost beyond the installation of the thermoelectric system.

Consider the potential energy savings and the impact on consumption of for- eign oil if the conventional automobile radiator-which weighs 40-60 lb-was replaced by 10 lb of thermoelectric material. It could cool the engine or the passenger cabin-using the available electricity from the alternator-without the need for cooling fluids, water pumps or fan belts.

Additionally, the thermoelectric material could take waste engine heat and generate electricity to power ancil- lary systems or recharge the batteries. The weight savings alone would have a dramatic impact on fuel efficiency.

O n a smaller scale, thermoelectric materials could be placed beneath the ICs in laptop computers, which run hot. This could provide enough power to trickle charge and dramatically extend the life of laptop batteries. This is not the perpetual motion machine, but it is getting close!

The performance and economics of

LED lighting have been vastly improved with the availability of highly controlled nanomaterials. The shift from incandes- cent to LED lighting in homes and busi- nesses has the potential to decrease energy needs by billions of Btu’s annually.

New photovoltaics with improved cost and performance are built around a combination of old and the new technologies. Conventional titanium dioxide particles and deposited nanosized clusters can create highly effective Graetzl cells.

The potential impact of affordable solar panels to supplement grid power as well as to energize major parts of the world where electricity is not available is enormous.

Advanced batteries for hybrid vehicles are being developed around nanoceramic electrode and electrolyte materials. The charge and discharge cycles possible using nanosized lithium cobaltite, tin-doped carbon nanotubes and other unique materials are far superior to conventional materials. Therefore, the performance and acceptance of these vehicles by mass markets is much more likely, which could revolutionize the automobile sector.

Imagine future generations using high- performance SOFCs, thermoelectrics, photovoltaics, and high-performance batteries to produce power. Imagine the energy savings possible from nanoen- abled LED lighting, lighter-weight vehicles and waste heat recovery. Imagine the impact on energy use and, therefore, the truly revolutionary worldwide improvement in the quality of life.

About the Author

Keith A. Blakely is CEO of NanoDynamics Inc., Buffalo, N.Y.

Editor’s Note

This article is based on a paper presented at the 1st International Congress on Ceramics, June 25-29, 2006. John Wiley & Sons, along with ACerS, will publish the 1st International Congress on Ceramics Global Roadmap (book and CD-Rom), ISBN 0470104910 in January 2007. Order info at www.~vilcy .comlgo/ccramics.

Market Overviews 11

dvanced ceramic powders are a necessary ingredient for making advanced ceramic components for structural, electronic, chemical processing and environmental-related applications, and thermal spray coatings.

through special compositions and microstructures that require careful control throughout the successive stages of processing: powder synthesis, powder sizing, rheology control, consolidation and forming processes, sintering, final machining, and inspection.

With large-scale use of advanced ceramics for electronic, magnetic, chemical processing, and catalysts and catalyst supports, the ceramic powder market for advanced ceramics applications continues to see healthy growth. These powders include oxides, carbides, nitrides, borides and complex oxides.

Now, a revolutionary new material has emerged-nanosized ceramic powders-with an array of new high-tech applications ranging from catalysts for solid fuel rockets to magnetic ferrofluids to chemical mechanical polishing (CMP).

Advanced ceramics’ outstanding properties are achieved

EXPECT CONTINUED GROWTH According to a recently updated Business Communications Co. (BCC) report, “High Tech Ceramics Review 2003,” advanced

Market Overviews

ceramics is expected to continue its growth in this decade. After reporting negative growth in 2001 because of the

economic downturn and the 9/11 terrorist attacks on the United States, the market improved slightly in 2002 and picked up further by mid-2003. Stepped-up military spending and huge orders for ceramic armor have meant increased activities for the military-related application segments.

In terms of market share, electronic ceramics continues to command the largest piece of the pie. However, structural ceramics will experience the fastest growth rate. The total value of the 2003 U.S. advanced ceramic components market is estimated to be $8.6 billion. This will increase to $12.9 billion by 2008, with an 8.3% annual average growth rate (AAGR).

Electronic ceramics makes up a major segment of the components market and is considered a “mature market.” Some of its segments continue to grow strongly. Structural ceramics got a boost from the wars in Afghanistan and Iraq, with military demand for armor reaching an all-time high.

Demand for ceramic coatings for military and commercial aircraft engines also rebounded from the slump of the early 2000s. Wear-resistant and other industrial applications also picked up, as did ceramic coatings for tool inserts, enabling the overall market to grow. Higher emissions standards for automobiles and trucks, buoys the demand for ceramic catalyst supports.

NANOCERAMICS EMERGE Nanoceramic powders are becoming an important segment of the ceramic powder industry, constituting -90% of the total

13

market among nanostructured materials, if we leave out nanocarbon-black and nanosilica used as fillers. These powders are used in microelectronics, optical, chemical and environmental-related, and magnetic recording applications.

Currently, the most commercially important nanoparticulate materials are simple metal oxides, such as silica (SiO,), titania (TiO,), alumina (A1203), iron oxide (Fe304, Fe,03), zinc oxide (ZnO), ceria (CeO,) and zirconia (Zr0,). Also of increasing importance are the mixed oxides, indium-tin oxide (In,O,-SnO, or ITO) and antimony-tin oxide (ATO), as well as titanates, in particular barium titanate (BaTiO,). Silica and iron oxide nanoparticles have a commercial history spanning half a century or more, while nanocrystalline titania, zinc oxide, ceria and I T 0 entered the marketplace more recently.

Other types of nanoparticles, including various complex oxides, metals, semiconductors and nonoxide ceramics, such as tungsten carbide (WC), are under development and available from some companies in small or pilot-scale quantities. With the exception of semiconducting oxides such as titania and ITO, semiconductor nanocrystals are not yet used in large-scale commercial applications. The technology to produce and utilize nanocrystalline semiconductors, often called quantum dots, is relatively new and rapidly developing.

POWDER MARKETS GROW

The total U.S. market for advanced ceramic powders in 2002, including nanosized powders, is estimated to be 918 million Ib, worth $1,605 million. This is projected to

increase to 1,178 million Ib, worth $2,286 million by 2007. The AAGR is projected at 7.3%.

In 2002, advanced ceramic powders still constituted 97.5% in volume and 90.4% in value. However in the next five years, the volume will drop to 95.9%, while the value will decline to 89.5% as a result of increased usage of nanoceramic powders.

Among the advanced ceramic powders, oxides made up 99.7% of the market in volume and 97.9% in value in 2002. However, by 2007, volume share of the oxides will be maintained at 99.8%, while the value share will dip slightly.

The largest growth rate goes to the structural ceramics area with a 9.6% AAGR, followed by electronics with a 7.5% AAGR. The chemical and environmental sector will see an annual growth rate of 6.9%, followed by thermal spray coatings with 5.3%.

However, by 2007, both electronic and structural applications will increase their shares at the expense of coatings and chemical and environmental-related applications.

NANOCERAMIC POWDER MARKETS

Nanomaterial products manufactured in industrial-scale quantities are sold in the form of powders or dispersants. Nanostructured silica and iron oxide powders have a commercial history spanning nearly half a century, while nanocrystalline alumina, titania, antimony oxide and other materials have more recently-within the past couple of decades- entered the market place.

as well as in experimental, developmental and prototype quantities. There are several companies using these materials while several others are attempting to find new uses for them. Applications include fine abrasives for CMP, burning catalysts for solid-fuel rockets, magnetic recording media, optical fiber coatings, magnetic materials in ferrofluids, fuel cells, oxygen sensors, optoelectronic devices, and developmental and prototype ceramic components.

according to various segments, electronic/magnetic/optical, structural/biologicaI, coatings and chemicaUenvironmenta1- related. Excluding the multibillion-dollar market for nanophase silica, the 2002 U.S. market for nanocrystalline ceramic powders is estimated to be 23.3 million Ib, worth $154.5 million. This is projected to increase to 48.8 million

Nanoceramic powders are available in commercial quantities

The major markets for nanoceramic powders are presented


Ib worth $241 million by 2007 with an AAGR of 9.3%.

value, followed by magnetic recording media. Silica and alumina powders dominate the CMP market while iron oxide contributes to the magnetic recording media segment.

Structural, mechanical and bioceramic segments have smaller markets; however, their potential to grow is large.

Auto catalyst coatings and sunscreens will dominate the chernical/environmental-related applications. Along with these, MRI contrast agents will provide a smaller segment of the market. With more stringent emissions standards worldwide, the automotive catalyst market is seeing changes in catalyst materials and engineering.

Nanoceramic powders for thermal spray coatings is still in its infancy. The U.S. Navy has boosted interest in thermal

CMP constitutes the largest market share in volume and

spray applications for nanoparticulate feedstock. We expect a large growth rate, as much as 35% annually, although it is starting from a smaller base.

In 2002, the combined electronic/magnetic/optical applications constituted 60% of the total market, followed by chemical/energy/environmental-related applications (37.7%) and structural/mechanical/bioceramics applications (1.9%). However, by 2007, structuraUmechanical applications are expected to grow more quickly, capturing a 3.3% market share, while the electronic/magnetic/optical segment grows its share to 62.4%. These increases will come at the expense of the chemical/energy/environmental segment, which will drop from

37.7% in 2002 to 34% in 2007. High-performance coatings using nanoceramic powders will have a large growth rate through 2007 but is starting from a smaller base.

Author’s Note: This article is based on two BCC studies “Advanced and Nan0

Ceramic Powders: Material Types, Processing Technologies, New Developments, Industry Structure, Markets and International Competition,” and “High Tech Ceramics Review 2003.” The table of contents for theses studies can be viewed at www.bccresearch.com.

ABOUT THE AUTHOR Thomas Abraham is vice presi- dent of research for Business Communications Co. Inc., a market and industry analysis company in Norwalk, C0nn.A graduate of Columbia University, he worked for the University of Denver and Brookhaven National Lab before joining BCC.Abraham also is

editor of BCC’s High-Tech Ceramics News.

Market Overviews 15

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