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NANOPARTICLE TECHNOLOGY HANDBOOK
THIRD EDITION
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NANOPARTICLE
TECHNOLOGY
HANDBOOK
THIRD EDITION
Edited by
MAKIO NAITO
TOYOKAZU YOKOYAMA
KOUHEI HOSOKAWA
KIYOSHI NOGI
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
ISBN: 978-0-444-64110-6
v
vi CONTENTS
14. Application of Quantum Dots for 1. Mechanical Processing for Material Synthesis
Biomedical Engineering and Particle Bonding 505
KENJI YAMAMOTO 2. Mechanical Synthesis of LaMnO3 Using
Nanosized Raw Materials 506
1. Application for Laboratory Test 479 3. The Mechanical Conditions of the
2. Diagnosis by Imaging Analysis 480 Attrition-Type Mill Required for the
Synthesis 506
15. Application of Polymeric Nanoparticles 4. One-Step Mechanical Processing to
and Polymeric Micelles for Treatment of Prepare LSM/ScSZ Composite Particles
Biofilm Infection Disease for the SOFC Cathode 507
HIROMITSU YAMAMOTO AND CHISATO TAKAHASHI 5. Evaluation of SOFC Performance 509
6. Conclusions 510
1. Introduction 481 References 510
2. Antibacterial Effect of PLGA Nanoparticle
Formulations 482 20. A Dye-Sensitized Solar Cell Utilizing
3. Antibacterial Effect of Polymeric Micelle Metal Nanoparticle
Formulations 484 MANABU IHARA
4. Conclusions 486
References 486 1. What Is a Dye-Sensitized Solar Cell? 511
2. Enhancement of the Absorption
Category B - Energy, Batteries, Coefficient of the Ruthenium Dye, With
Environmental the Silver Nanoparticle Produced via
Vacuum Evaporation on the Quartz
16. Development of High-Performance Substrate 512
Electrochemical Reactors 3. Enhancement of the Absorption Coefficient of
MASANOBU AWANO Silver NanoparticleeRuthenium Dye Within
Porous TiO2 514
1. Environmental Purification by References 515
Electrochemical Reactors 487
2. NOx Decomposition in the Exhaust Gas 21. Room Temperature Fabrication of
With Electrochemical Reactors 487 Electrode-Solid Electrolyte Composite for
3. Development of the Electrochemical Reactors
All-Solid-State Rechargeable Lithium
for Simultaneous Purification of NOx/PM 490
References 492
Batteries
YASUTOSHI IRIYAMA
17. Superior Thermal Insulation Film With
1. Introduction 517
Transparency Achieved by Hollow Silica 2. Aerosol Deposition 517
Nanoparticles 3. Densification of Electrode and Solid
MASAYOSHI FUJI AND CHIKA TAKAI Electrolyte Powders 518
4. Conclusions 522
1. Introduction of Thermal Insulation Techniques 493
References 523
2. How to Prepare Nanospaced Polymer Film 494
3. Thermal Insulation Performance on Field Test 495 22. Enhancement of the Performance of
References 497
Insulating Materials
18. Development of Fuel Cells MIKIMASA IWATA
51. Development of Optical Memory Using 55. Dispersion of Fine Silica Particles Using
Semiconductor Nanoparticles Alkoxysilane and Industrialization
YUKIO YAMAGUCHI HIDEKI GODA
Hiroya Abe Joining and Welding Research Institute, Osaka Yukiya Hakuta National Institute of Advanced Industrial
University Science and Technology (AIST)
Tadafumi Adschiri Institute of Multidisciplinary Research Kaori Hara Hosokawa Powder Technology Research
for Advanced Materials, Tohoku University, Sendai, Japan Institute
Tsutomu Aida Tohoku University, Sendai, Japan Akitoshi Hayashi Osaka Prefecture University, Osaka, Japan
Takashi Akatsu Materials and Structures Laboratory, Tokyo Kazuyuki Hayashi R&D Division, Toda Kogyo Corporation
Institute of Technology Ko Higashitani Department of Chemical Engineering,
Jun Akedo National Institute of Advanced Industrial Kyoto University
Science and Technology (AIST) Kazuyuki Hirao Department of Material Chemistry, Kyoto
Masanori Ando National Institute of Advanced Industrial Univerisity
Science and Technology (AIST) Daisuke Hojo Tohoku University, Sendai, Japan
Yoshinori Ando Department of Materials Science and Kouhei Hosokawa Hosokawa Micron Corporation,
Engineering, Meijo University Osaka, Japan
Hiroyuki Anzai Central Research, Bridgestone Corporation Masuo Hosokawa Hosokawa Micron Corporation
Nobuaki Aoki Tohoku University, Sendai, Japan Yuji Hotta National Institute of Advanced Industrial Science
Masanobu Awano National Institute of Advanced and Technology (AIST), Nagoya, Japan
Industrial Science and Technology (AIST) Hideki Ichikawa Faculty of Pharmaceutical Sciences Kobe
Akira Azushima Graduate School of Engineering, Gakuin University
Yokohama National University Takashi Ida Ceramics Research Laboratory, Nagoya Institute
Tetsuya Baba National Institute of Advanced Industrial of Technology
Science and Technology (AIST) Manabu Ihara Research Center for Carbon Recycling
Weiwu Chen Joining and Welding Research Institute, Osaka Energy, Tokyo Institute of Technology
University Motoyuki Iijima Yokohama National University, Yokohama,
Kensei Ehara National Institute of Advanced Industrial Japan
Science and Technology (AIST) Yusuke Imai National Institute of Advanced Industrial
Hitoshi Emi Association of Powder Process Industry and Science and Technology, Nagoya, Japan
Engineering (APPIE) Shinji Inagaki Toyota Central R&D Labs., Inc.
Hiroshi Fudouzi Optronic Materials Center, National Mitsuteru Inoue Toyohashi University of Technology
Institute for Materials Science
Eiji Iritani Department of Chemical Engineering, Nagoya
Masayoshi Fuji Ceramics Research Laboratory, Nagoya University
Institute of Technology
Yasutoshi Iriyama Nagoya University, Nagoya, Japan
Hidetoshi Fujii Joining and Welding Research Institute,
Naoyuki Ishida National Institute of Advanced Industrial
Osaka University
Science and Technology (AIST)
Hiroshi Fukui Frontier Science Business Division, Shiseido
Toshihiro Ishii Ashizawa Finetech Ltd., Narashino-shi,
Co., Ltd.
Japan
Takehisa Fukui Hosokawa Powder Technology Research
Norifumi Isu LIXIL Corporation
Institute
Mikimasa Iwata Central Research Institute of Electric Power
Yoshinobu Fukumori Faculty of Pharmaceutical Sciences,
Industry
Kobe Gakuin University
Hiroshi Jinnai Institute for Materials Chemistry and
Hideki Goda R&D Department, Photo-electronic Materials
Engineering (IMCE), Kyushu University
Division, Arakawa Chemical Industries, Ltd.
Jinting Jiu Senju Metal Industry Co., Ltd., Tokyo, Japan;
Kuniaki Gotoh The Graduate School of Natural Science and
Osaka University, Osaka, Japan
Technology, Okayama University
xviii LIST OF CONTRIBUTORS
Norihiko Kaga Central Research, Bridgestone Corporation Yoshitake Masuda National Institute of Advanced
Kotaro Kajikawa Tokyo Institute of Technology Industrial Science and Technology (AIST), Nagoya, Japan
Toshio Kakui Chemicals Division, Lion Corporation Motohide Matsuda Graduate School of Environmental
Science, Okayama University
Hidehiro Kamiya Institute of Symbiotic Science and
Technology, Tokyo University of Agriculture & Technology Shuji Matsusaka Department of Chemical Engineering,
Kyoto University
Kenji Kaneko Department of Material Science and
Engineering, Kyushu University Tatsushi Matsuyama Faculty of Engineering,
Soka University
Kiyoshi Kanie Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University Reiji Mezaki Nanomateria Center, Institute of Innovation,
The University of Tokyo
Junya Kano Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University Takeshi Mikayama Kohno Patent Office
Hitoshi Kasai Institute of Multidisciplinary Research for Minoru Miyahara Department of Chemical Engineering,
Advanced Materials, Tohoku University Kyoto University
Tomoko Kasuga Electrotechnology Applications R&D Kiyotomi Miyajima Central Research Institute of Electric
Center, Chubu Electric Power Co., Inc. Power Industry
Tsutomu Katamoto Creative R&D Center, Toda Kogyo Yoshinari Miyamoto Joining and Welding Research
Corporation Institute, Osaka University
Shinji Katsura Faculty of Engineering, Gunma University Masaru Miyayama Research Center for Advanced Science
and Technology, The University of Tokyo
Masayoshi Kawahara Hosokawa Powder Technology
Research Institute Hideki T. Miyazaki National Institute for Materials Science
Yoshiaki Kawashima Department of Pharmaceutical Hidetoshi Mori School of Engineering, Aichi University of
Engineering School of Pharmacy, Aichi Gakuin University, Technology
Nagoya, Japan; Gifu Pharmaceutical University, Tsutomu Morimoto Japan Chemical Innovation Institute
Gifu, Japan Kenta Morita Kobe University, Kobe, Japan
Yoshiaki Kinemuchi National Institute of Advanced Hirokazu Munakata Tokyo Metropolitan University
Industrial Science and Technology (AIST)
Hiroyuki Muto Toyohashi University of Technology,
Soshu Kirihara Joining and Welding Research Institute, Toyohashi, Japan
Osaka University
Muhammad M. Munir Department of Chemical
Masanori Koshimizu Tohoku University, Sendai, Japan Engineering, Hiroshima University
Akihiko Kondo Kobe University, Kobe, Japan; Department Atsushi Muramatsu Institute of Multidisciplinary Research
of Chemical Science and Engineering, Kobe University for Advanced Materials, Tohoku University
Akira Kondo Joining and Welding Research Institute, Osaka Norio Murase National Institute of Advanced Industrial
University, Osaka, Japan Science and Technology (AIST)
Katsuyoshi Kondou Joining and Welding Research Institute, Toshihiko Myojo Institute of Industrial Ecological Sciences,
Osaka University University of Occupational and Environmental Health
Takahiro Kozawa Osaka University, Osaka, Japan Makio Naito Joining and Welding Research Institute, Osaka
Kazue Kurihara Institute of Multidisciplinary Research for University, Osaka, Japan
Advanced Materials, Tohoku University Noriyuki Nakajima Institute of Nanotechnology,
Shun’ichi Kuroda The Institute of Scientific and Industrial Kurimoto, Ltd.
Research, Osaka University Masami Nakamoto Osaka Municipal Technical Research
Ken-ichi Kurumada Graduate School of Environment & Institute
Information Sciences, Yokohama National University Masaharu Nakamura Toyo Tanso Co., Ltd.
Hiroaki Kuwahara Corporate Strategy Division, Teijin Ltd. Keitaro Nakamura Nisshin Seifun Group Inc.
Chunliang Li National Institute of Advanced Industrial Hachiro Nakanishi Institute of Multidisciplinary Research
Science and Technology (AIST) for Advanced Materials, Tohoku University
Hisao Makino Energy Engineering Research Laboratory, Norikazu Namiki Kyoritsu Gokin Co., Ltd.
Central Research Institute of Electric Power Industry,
Yuya Nishimura Kobe University, Kobe, Japan
Yokosuka-shi, Japan
Naoki Noda Central Research Institute of Electric Power
Shoji Maruo Yokoyama National University, Yokohama,
Industry, Yokosuka-shi, Japan
Japan
Kiyoshi Nogi Joining and Welding Research Institute, Osaka
Hiroaki Masuda Department of Chemical Engineering,
University
Kyoto University
LIST OF CONTRIBUTORS xix
Yuji Noguchi The University of Tokyo Hisao Suzuki Graduate School of Science and Technology,
Junichi Noma Sumiyoshi Factory, Kurimoto Ltd., Shizuoka University
Osaka, Japan Michitaka Suzuki Department of Mechanical and System
Toshiyuki Nomura Department of Chemical Engineering, Engineering, University of Hyogo
Osaka Prefecture University Takahiro Suzuki Kobe University, Kobe, Japan
Takashi Ogi Department of Chemical Engineering, Takahiro Takada Murata Manufacturing Co., Ltd.
Hiroshima University Chisato Takahashi Aichi Gakuin University, Nagoya, Japan
Chiaki Ogino Kobe University, Kobe, Japan Chika Takai Ceramics Research Laboratory, Nagoya
Satoshi Ohara Institute of Multidisciplinary Research for Institute of Technology
Advanced Materials, Tohoku University; Osaka University, Seiichi Takami Nagoya University, Nagoya, Japan
Osaka, Japan
Hirofumi Takase R&D Division, Takiron Co., Ltd.
Akira Ohtomo Institute for Materials Research, Tohoku
Kenji Takebayashi Powder Technology Research Institute,
University
Hosokawa Micron Corporation
Hidetoshi Oikawa Institute of Multidisciplinary Research
Hirofumi Takeuchi Laboratory of Phamaceutical
for Advanced Materials, Tohoku University
Engineering, Gifu Pharmaceutical University
Tomoichiro Okamoto Nagaoka University of Technology
Junichi Tatami Graduate School of Environment &
Tatsuya Okubo The University of Tokyo Information Sciences, Yokohama National University
Kikuo Okuyama Graduate School of Engineering, Masahiro Tatsumisago Osaka Prefecture University,
Hiroshima University Osaka, Japan
Minoru Osada National Institute for Materials Science Kenji Toda Graduate School of Science and Technology,
Yoshio Otani Graduate School of Natural Science and Niigata University
Techonology, Kanazawa University Takanari Togashi Yamagata University, Yamagata, Japan
Yasufumi Otsubo Graduate School of Engineering, Chiba Tetsuro Tojo Toyo Tanso Co., Ltd.
University
Takaaki Tomai Tohoku University, Sendai, Japan
Masashi Otsuki Central Research, Bridgestone Corporation
Hiroyuki Tsujimoto Hosokawa Micron Corporation; Aichi
Fumio Saito Institute of Multidisciplinary Research for Gakuin University, Nagoya, Japan
Advanced Materials (IMRAM), Tohoku University
Takao Tsukada Tohoku University, Sendai, Japan
Shuji Sakaguchi National Institute of Advanced Industrial
Yusuke Tsukada Hosokawa Micron Corporation,
Science and Technology (AIST)
Osaka, Japan
Yoshio Sakka Nano Ceramics Center, National Institute for
Tetsuo Uchikoshi Nano Ceramics Center, National Institute
Materials Science, Tsukuba, Japan
for Materials Science
Shuji Sasabe Powder Technology Research Institute,
Keizo Uematsu Nagaoka University of Technology
Hosokawa Micron Corporation
Minoru Ueshima Senju Metal Industry Co., Ltd.,
Aiko Sasai Hosokawa Micron Corporation, Osaka, Japan
Tokyo, Japan
Takayoshi Sasaki International Center for Materials
Mitsuo Umetsu Graduate School of Engineering,
Nanoarchitectonics, National Institute for Materials
Tohoku University
Science
Arimitsu Usuki Toyota Central R&D Labs., Inc.
Takafumi Sasaki Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University Fumihiro Wakai Materials & Structures Laboratory, Tokyo
Institute of Technology
Norifusa Satoh Department of Chemistry,
Keio University Xing Wei Chang’an University, ShaanXi, China
Tetsuya Senda National Maritime Research Institute Akimasa Yamaguchi Energy Engineering Research
Laboratory, Central Research Institute of Electric
Gimyeong Seong Tohoku University, Sendai, Japan
Power Industry
Yuichi Setsuhara Joining and Welding Research Institute,
Yukio Yamaguchi Department of Chemical System
Osaka University
Engineering, The University of Tokyo
Haruhide Shikano Ibiden Co., Ltd.
Hiromitsu Yamamoto University School of Pharmacy, Aichi
Manabu Shimada Graduate School of Engineering, Gakuin University, Nagoya, Japan
Hiroshima University
Kenji Yamamoto International Clinical Research Center,
Akihiko Suda Toyota Central R&D Labs., Inc. International Medical Center of Japan
Katsuaki Suganuma Senju Metal Industry Co., Ltd., Tokyo, Kimihisa Yamamoto Department of Chemistry,
Japan; Osaka University, Osaka, Japan Keio University
xx LIST OF CONTRIBUTORS
Atsushi Yamamoto National Institute of Advanced Toyokazu Yokoyama Hosokawa Micron Corporation,
Industrial Science and Technology (AIST) Osaka, Japan
Masatomo Yashima Department of Materials Science and Susumu Yonezawa Faculty of Engineering,
Engineering, Tokyo Institute of Technology University of Fukui
Akira Yoko Tohoku University, Sendai, Japan Tetsu Yonezawa Hokkaido University, Sapporo, Japan
Atsushi Yokoi Toyohashi University of Technology, Qiwu Zhang Institute of Multidisciplinary Research for
Toyohashi, Japan Advanced Materials, Tohoku University
Preface
A “powder,” which is an assemblage of small solid which was translated into English and published as the
particles, exhibits very unique behavior. For example, first edition of this Handbook in 2007. Nanoparticle
depending on the circumstances, a powder can behave technology advanced considerably after 2007, prompting
like a gas, a liquid, or a solid. Furthermore, because of the Mr. Hosokawa to start preparing an updated second
larger specific surface area relative to a bulk material, edition of the Handbook. He unfortunately passed away
powders can have very unique properties. This is espe- on March 31, 2010, before the second edition was pub-
cially true for “nanoparticles.” The unique behavior and lished in 2012.
properties of particle and powder give them a wide range Because nanoparticle technology has rapidly
of industrial applications that makes them ubiquitous advanced since 2012, it has been applied more broadly
in our daily lives and makes them promising materials and in new areas. Mr. Yoshio Hosokawa, the second
for creating scientific and technical innovations in the President of Hosokawa Powder Technology Foundation
future. and President of Hosokawa Micron Corporation,
Although powders have long been important mate- decided to publish a third edition of the Handbook. In
rials in our daily lives, the academic study of particle and this third edition, the applications section of the Hand-
powder technology has a relatively short history. The book has been updated to include the most recent
Society of Powder Technology, Japan (SPTJ) was estab- advances in nanoparticle technology. Nineteen chapters
lished in 1956 with the mission to foster interactions have been added. The 79 chapters in the applications
between society members to enable and facilitate ad- section are organized into 4 categories: Category A:
vances in powder technology as well as in the powder medical, cosmetics, and biologicals; Category B: energy,
and powder technology industries. I am serving as the batteries, and environmental; Category C: electronic and
12th President (2015e18) of the society. SPTJ celebrated magnetic materials, memory, light-emitting materials,
its 60th anniversary in 2016. Now, in collaboration with and displays; and Category D: synthesis, dispersion, and
academia and industry, we are taking the first steps for processing. I hope the updated applications section will
the next 60 years. give readers state-of-the-art information and knowledge
Mr. Masuo Hosokawa, the chief editor of the first to develop their own innovative technology and new
edition of this Handbook, was a pioneer in this industry. products, further enhancing our understanding of the
When he was the President of Hosokawa Micron Corp., fundamentals of nanoparticle technology.
he founded Hosokawa Powder Technology Foundation Finally, I am grateful to the Hosokawa Powder Tech-
in 1991 to contribute to advancement of powder tech- nology Foundation for its support and to all editors and
nology on a worldwide scale and published the first authors for their great contributions to the third edition.
issue of “KONA Powder and Particle Journal” on pow- I especially express my appreciation to the first chief
der technology in 1983. Since then, KONA has been editor, Mr. Masuo Hosokawa, for his outstanding
published annually and distributed worldwide. contributions to the development and advancement of
Mr. Hosokawa proposed the concept of “nanoparticle nanoparticle technology.
technology” long before past US President Bill Clinton’s
Dr. Makio Naito
National Nanotechnology Initiative in 2000. One of the
Professor, Osaka University
activities of the Foundation was to publish the Nano-
President, The Society of Powder Technology, Japan
particle Technology Handbook in Japanese in 2006,
xxi
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Preface to the Second Edition
The Nanoparticle Technology Handbook was the first In the meantime, publication of the first edition of the
handbook to be published in the field of nanoparticle Handbook, Nanoparticle Technology had advanced and
technology around 5 years ago. Since then, nanoparticle been employed in various applications. In the second
technology has further advanced and been applied in edition, 16 new articles have been added in the applica-
many new applications. In response to the demand, it tion section for subjects related to polymer/filler com-
was decided to publish a second edition of the Hand- posites; electronic devices such as displays, sensors, and
book. The editors are very pleased to see the advance- memories; batteries/fuel cells; cosmetics; drug delivery
ment of this technology and to be engaged in the system and biomaterials for medical devices; color ma-
publication of the second edition. terials; environmental protections; etc. During this period
However, we regret to inform our readers of the sad of time, there were some epoch-making incidents in the
news that the chief editor of the Handbook’s first edition, commercialization of some technologies. Fuel cells have
Mr. Masuo Hosokawa, passed away on March 31, 2010 been introduced for power generation and heat supply in
after a short stay in the hospital, at the age of 85. In fact, he residential and commercial uses, and lithium ion batte-
initiated the idea of publishing a handbook for nano- ries have begun to be adopted by electric and hybrid
particle technology. He had been greatly interested in vehicles for transportation use. Additionally, the nuclear
particles and fine powders for many years and had power plant accident caused by the big earthquake and
developed various advanced machines such as a unique tsunami in the Tohoku area of Japan in March 2011 had an
fine grinding mill and an air classifier in the 1950s, which enormous impact on power supply and environmental
led to many awards for him, including two decorations protection issues related to the lifestyle and way of
from the Japanese government. thinking of the country’s population. From these view-
His enthusiasm and desire to seek extremely small points, nanoparticles have great potential to contribute to
particles and their innovative properties resulted in the the establishment of a sustainable living environment for
invention of the concepts of MechanoFusion and Mech- human beings by making use of their high functionality
anoChemical Bonding technologies, which are in prin- and excellent performance.
ciple based on the mechanical activation of fine particles The editors are grateful to the Hosokawa Powder
for particle bonding and surface modification to create Technology Foundation for its support and to all the
new functional materials. Since the 1980s, he also intro- contributors for their cooperation and wish that the sec-
duced some useful technologies to generate nano- ond edition of the Handbook would be helpful to readers
particles by the bottom-up method and proposed in understanding the basics of nanoparticles and to pro-
nanoparticle technology long before the former President vide hints to their application.
Bill Clinton’s National Nanotechnology Initiative in 2000.
Dr. Kiyoshi Nogi
Starting with the evaporation method to make metal
Emeritus Professor, Osaka University
nanoparticles and then moving to use chemical vapor
deposition methods to create composite nanoparticles, he Dr. Makio Naito
succeeded in bringing new systems for nanoparticle Professor, Osaka University
generation to the commercial market. In addition, in 1991
Dr. Toyokazu Yokoyama
he founded the Hosokawa Powder Technology Founda-
Fellow, Hosokawa Micron Corporation
tion and in 1983 published the first issue of the English
technical journal, “KONA Powder and Particle Journal.”
xxiii
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Preface to the First Edition
During the last few years, the term “Nanotechnology” Due to this interest, the second World Congress in
is increasingly employed to describe the process tech- Particle Technology (WCPT) was held in Kyoto in 1990.
nologies and analytical techniques for material in the Eight years later at the third WCPT in Brighton, the
ultrafine range of the order of a millionth of a millimeter. author highlighted the importance of these ultrafine
Because they are sure to take an important part in particles to an audience of about 700 researchers and
shaping the 21st century, great attention is being paid to engineers during the opening speech. Hosokawa Micron
these technologies, with many countries actively Corp., which celebrated its 90th anniversary in 2006, has
involved in R&D. As the link between these new tech- been engaged in R&D on particle creation by the build-up
nologies and the established particle and powder tech- (bottom-up) method in both gaseous and liquid phases for
nology, “Nanoparticle technology” includes the concepts more than 20 years. The result of this research, as com-
and know-how to create, process, and apply the ultrafine bined with that on conventional grinding (top-down)
particles in the nanometer range and is one of the key processes, has led to the establishment of a mass pro-
technologies for new material developments. duction system for nanoparticles and to the foundation
The technologies that are used to treat powders of a business based on application of these nanoparticles
arrived with mankind, and countless inventions and to functional materials.
improvements have been made during history. These Founded 15 years ago, the Hosokawa Powder Tech-
particles and powders have very different properties nology Foundation holds an annual symposium on
from the bulk materials from which they are derived. powder technology for the exchange of information on
There are applications to be seen in all industrial areas. particle engineering and powder technology. Since 2001,
The history of the academic study of particle and the main topics of the symposium have, in response to
powder technology is not so old. The first related society, the requirements of industry, been related to nano-
Chubu Association of Powder Technology, was founded particles and nanostructure control. The number of grant
in Japan in 1956. It later became the Society of Powder proposals received by our Foundation for research into
Technology, Japan, and celebrated its 50th anniversary in nanoparticles continues to increase, and currently 40% of
2006. Correspondingly, the Hosokawa Micromeritics some 120 proposals relate to nanoparticles.
Laboratory was established in 1956 and published its As a result of this trend, we published 3 years ago, the
50th anniversary issue of the annual technical journal book Nanoparticle Technology to promote nanoparticle-
Funsai (The Micromeritics) also in 2006. related engineering by documenting the technologies
Throughout this period a key issue has been to reduce constituting in this field. That book was very well
the size of particles, to maximize their functional prop- received, and to continue contributing to the common
erties, and thus to find new applications and create new welfare through the promotion of powder technology,
products with superior performance. Great interest has we decided to systematically update Nanoparticle Tech-
been shown in submicron and even finer particles. nology, adding further developments and many exam-
Research and development has advanced at a rapid rate ples of applications. The results of that effort were
due to the cooperation of academia and industry in many published in the form of a handbook, first in Japanese in
areas, starting with particle creation and particle size the memorable year 2006, and with the present volume,
analysis, expanding to encompass particle design, and in English this year. Although R&D in nanoparticle
processing in the micron- and nanometer-size ranges. technology advances rapidly, and the contents of the
Japan has been at the forefront in the conception and future editions are sure to change, we hope the present
development of these technologies. collation of state-of-the-art knowledge and information
xxv
xxvi PREFACE TO THE FIRST EDITION
1
Basic Properties and Measuring Methods of
Nanoparticles
Liposome Starch
TABLE 1.1.1 Solid Particle Size and the Fraction of Atoms Located at the Particle Surface
Number ratio of
Number of atoms Number of atoms Total number of surface of atoms Examples of particle
in a side at the surface atoms to the total (%) size and powder
2 8 8 100
3 26 27 97
4 56 64 87.5
5 98 125 78.5
10 488 1000 48.8 2 nm
6
100 58,800 1 10 5.9 20 nm (colloidal silica)
6 9
1000 6 10 1 10 0.6 200 nm (titanium
dioxide)
10,000 6 108 1 1012 0.06 2 mm (light calcium
carbonate)
100,000 6 1010 1 1015 0.006 20 mm (green tea
powder, chalk)
reactivity, solubility, sintering performance, etc., related the cubical crystal increased in the particles from the
with the mass and heat transfer between the particles particle size of about 18 nm [5]. In this way, the critical
and their surroundings from the morphological view- particle size for the crystal structure and the size effect
point apart from the control of the surface and inner differ with the materials concerned.
structures of the nanoparticles. Furthermore, the crystal
structure of the particles may change with the particle 1.1.4.2 Thermal Properties
size in the nanosized range in some cases. As the atoms and molecules located at the particle
Uchino et al. [4] reported that from the XRD analysis surface become influential in the nanometer order, the
of the lattice constant of BaTiO3 powder prepared by hy- melting point of the material decreases from that of the
drothermal synthesis method, the c/a axis length ratio bulk material because they tend to be able to move easier
showing the tetragonal characteristics decreased to indi- at the lower temperature.
cate the increasing symmetric property with the For example, the melting point of gold is 1336 K as a
decreasing particle size from about 200 nm as shown bulk but starts to decrease remarkably below the particle
in Fig. 1.1.4. This is considered to be attributable to the size of about 20 nm and drastically below 10 nm and then
compressive force exerted on the particles as a result becomes more than 500 lower than that of the gold bulk
of the surface tension of the particle itself. For PbTiO3, around 2 nm. The reduction of the melting point of ultra-
it is reported that the tetragonal crystals decreased and fine particles is regarded as one of the unique features of
the nanoparticles related with aggregation and grain
growth of the nanoparticles or improvement of sintering
1.010
Tetragonal degree (c/a axis ratio) (-)
nanometers.
450
1.1.4.5 Mechanical Properties
It is known that the hardness of the crystalline mate-
rials generally increases with the decreasing crystalline
size, and that the mechanical strength of the materials
considerably increases by micronizing the structure of
400 the metal and ceramic material or composing them in
the nano range [15,16]. Furthermore, with the ceramic
material having crystalline size less than several hun-
dred nanometers, the unique superplastic phenomenon
0 50 100
is seen that it is extended several to several thousand
Particle size (nm)
times from the original size at the elevated temperature
FIGURE 1.1.5 Change of Curie point PbTiO3 with its particle size. over 50% of the melting point [17], which may provide
8 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES
2
a : Cs = 0.05 mol/kg
b : Cs = 0.1 mol/kg
c : Cs = 0.2 mol/kg
d : Cs = 0.4 mol/kg
c
Absorbance A (–)
1
b
d
a
0
200 300 400 500 600 700 800 900
Wave length (nm)
FIGURE 1.1.6 Effect of concentration of nonionic surfactants Cs on the plasmon absorption of silver nanoparticles. Cs ¼ (a) 0.05, (b) 0.1, (c) 0.2,
and (d) 0.4 mol/kg.
the possibility of forming and processing of ceramics nanoparticles, which have different properties from
such as metallic materials. the bulk material by the size effects as mentioned above
and in the following sections.
1.1.5 Existing Conditions of Particles and
Their Properties
References
The nanoparticles usually exhibit collective functions.
[1] M. Arakawa, J. Soc. Powder Technol. Jpn. 42 (2005) 582e585.
Therefore, the dispersing state and the surrounding con-
[2] M. Arakawa, Funsai (Micrometr.) (27) (1983) 54e64.
ditions in addition to the physical properties of the par- [3] H. Maeda, J. Control. Release 19 (1992) 315e324.
ticles themselves are important. In many cases, the [4] K. Uchino, E. Sadanaga, T. Hirose, J. Am. Ceram. Soc. 72 (8) (1989)
nanoparticles exist as aggregates of the primary particles 1555e1558.
by the adhesion and bonding during the production [5] H. Suzuki, T. Ohno, J. Soc. Powder Technol. Jpn. 39 (2002)
process because of their high adhesiveness. 877e884.
[6] N. Wada, Chem. Eng. 9 (1984) 17e21.
The existing state of the nanoparticles is greatly influ- [7] I. Matsui, J. Chem. Eng. Jpn. 38 (8) (2005) 535e546.
enced by the surrounding conditions if they are in gas, [8] M. Takashige, T. Nakamura, Jpn. J. Appl. Phys. 20 (1981) 43e46.
liquid, solid, or in a vacuum and what sort of interaction [9] K. Ishikawa, J. Soc. Powder Technol. Jpn. 38 (2001) 731e740.
they have with the surrounding materials. The nanopar- [10] K. Ishikawa, K. Yoshikawa, N. Okada, Phys. Rev. B 37 (1988)
5852e5855.
ticles are rarely used by themselves but dispersed in
[11] M. Haruta, Catalysts 36 (6) (1994) 310e318.
other materials or combined with them. The dispersing [12] Y. Kurokawa, Y. Hosoya, Surface 34 (2) (1996) 100e106.
process of the nanoparticles is a key for the nanoparticle [13] K. Kobayashi, J. Soc. Powder Technol. Jpn. 41 (2004) 473e478.
technology and their preparation methods because the [14] S. Sato, N. Asai, M. Yonese, Colloid Polym. Sci. 274 (1996)
performance of the final products is affected by their 889e893.
dispersing conditions [18]. [15] K. Niihara, J. Ceram. Soc. Jpn. 99 (10) (1991) 974e982.
[16] T. Sekino, Mater. Integr. 13 (11) (2000) 50e54.
In this way, it is expected with great possibility to [17] F. Wakai, Y. Kodama, S. Sakaguchi, N. Murayama, K. Izaki,
develop various new materials and applications by the K. Niihara, Nature 344 (6265) (March 29, 1990) 421e423.
nanoparticle technology producing and processing the [18] T. Yokoyama, Sokeizai 3 (2005) 6e11.
1.2 PARTICLE SIZE 9
Various monodisperse spherical particles are available to measure a great number of particles by electron mi-
from The Association of Powder Process Industry and croscopy. Therefore, in practice, sedimentation method,
Engineering (APPIE, Japan) [5,6]. However, they are standard sieves, and electrical sensing zone method
not suitable for the calibration of such equipment for are admitted as definitive methods to the certification
the measurement of particle size distribution for the of reference particles [5]. However, this is only for the
following reasons [7]: sake of convenience.
The purpose for using the reference particles is listed
1. Even if the principle is the same, different equipment
as follows [10]:
has different feeding system, different transportation
system, and different dispersion system. Therefore, 1. Calibration of equipment for the particle size
particle fraction detected in a certain size interval may measurement,
differ depending on the equipment through size- 2. Verification of measurement procedure,
dependent deposition, imperfect dispersion, and 3. Establishing traceability of measurement,
size-dependent segregation. 4. Determination of the uncertainty of the obtained
2. There may be various calculation software for the results.
transformation of the measured data into particle size
For representing the particle size distribution in
distribution.
mathematical equation, lognormal distribution and
3. Number of particles sampled, sample size, in the
RosineRammler distribution can be well applied and
measurement may differ for each measuring system.
special graph papers are available for them.
If the sample size is not large enough, both the mean
diameter and the size distribution cannot be correctly
obtained [8,9].
References
In the ISO 13320 (1999), laser diffraction, it is recom-
[1] K. Okuyama, H. Masuda, S. Morooka, Biryuushi Kougaku e Fine
mended that equipment should be tested using
Particle Technology, Ohmsha, Tokyo, 1992, p. 3.
polydisperse reference particles whose particle size is [2] Society of Powder Technology, Japan (Ed.), Terminology Dictio-
distributed over 1 decade. Reference particles for nary of Powder Technology, second ed., Nikkan Kogyo Co.,
covering nano range is not yet available. However, 2000, p. 223.
MBP 1e10 for 1e10 mm and MBP 10e100 for 10e100 [3] Standard Powders Committee, APPIE, Powder Sci. Eng. 35 (6)
mm, spherical transparent particles, are available from (2003) 75e79.
[4] H. Yoshida, H. Masuda, K. Fukui, Y. Tokunaga, Adv. Powder
APPIE. Particle size analyzers should at least be cali- Technol. 12 (2001) 79e94.
brated by the use of these spherical reference particles. [5] H. Masuda, Powder Sci. Eng. 34 (5) (2002) 65e72.
Through the calibration using the reference particles, [6] A. Itoh, Powder Sci. Eng. 37 (7) (2005) 72e77.
equivalent size obtained by each instrument is, for the [7] Y. Mori, H. Yoshida, H. Masuda, Particulate Systems Analysis
first time, connected to the unit of length. In other 2005, Stratford-upon-Avon, UK, 2005.
[8] H. Masuda, K. Iinoya, J. Chem. Eng. Jpn. 4 (1971) 60e66.
words, measured value obtained by the measurement [9] H. Masuda, K. Gotoh, Adv. Powder Technol. 10 (1999) 159e173.
other than microscopy can get traceability only through [10] ISO Guide35, Certification of Reference Materials e General and
the calibration with reference particles. It is very tedious Statistical Principles, 1989, p. 25.
1.3 PARTICLE SHAPE for nanoparticle cannot be easily found, and the
shape index of nanoparticles can be calculated from
Michitaka Suzuki
particle images observed using various types of
The fundamental particle properties such as particle microscopes.
diameter, particle shape of nanosize, or fine particles in-
fluence the character of the particle-packed bed. In
these particle properties, the particle diameter mea- 1.3.1 Two-Dimensional Particle Projection
surement equipment based on various principles Image
can be marketed, and it is easy to measure particle To measure the particle shape, the outline of particle
diameter distribution. But a particle shape analyzer shape of two-dimensional projection images captured
1.3 PARTICLE SHAPE 11
from microscopic photograph is analyzed. Because the particle size. Moreover, for a soft particle or an adhesive
diameter of a nanoparticle is smaller than the wavelength particle, a particle position changes by contact of probe
of visible light, a nanosize particle cannot be observed by or a particle adheres to probe, and an accurate image
an optical microscope. Usually, the two-dimensional pro- is not obtained.
jection image of nanoparticles is captured by scanning
electron microscope (SEM) or TEM, and the particle
shape indices can be calculated from the captured images 1.3.3 Particle Shape Index Using Particle
by image analysis software. For the shape analysis of fine Diameter Ratio
particle over micrometer order, automatic particle shape Once the microscopic particle image is captured,
analyzers using two-dimensional image of particles in a quantification of particle shape can be performed by
sheath flow are available. This analyzer captures particle the same method as a coarse particle even if it is a nano-
images automatically by an optical microscope with particle. Quantification of particle shape is classified
charge-coupled device camera under stroboscope flush roughly into the shape index, which is the ratio of
lighting. two kinds of different definition particle diameter
and the other expression such as fractal dimension or
Fourier analysis of particle perimeter. In the case of
1.3.2 Three-Dimensional Particle Image
the ratio of two different definition particle diameter,
In the particle shape measurement of flaky particle or there are many similar kinds of shape indices such as
porous particle including hole or space inside the parti- degree of elongation (aspect ratio) ¼ major axis/minor
cle, the shape analysis of a two-dimensional particle pro- axis, degree of flatness ¼ minor axis/thickness, degree
jection picture is inadequate, and three-dimensional of circular ¼ equivalent area diameter (Heywood
shape analysis is necessary [1]. diameter)/equivalent perimeter diameter, and degree
Although it is difficult to measure the thickness of a of sphericity ¼ equivalent volume diameter/equiva-
particle by the ordinary electron microscope, the lent surface area diameter [3]. In addition, unidirec-
thickness or surface roughness can be measured by tional maximum particle (Feret diameter)/equivalent
three-dimensional scanning electron microscope perimeter diameter are also used as a particle shape in-
(3D-SEM). 3D-SEM takes two microscopic pictures dex, and the value of the shape index of a particle
from slightly different angles and obtains the three- perimeter without concave shows near unity. Each of
dimensional information including thickness and sur- these is a ratio of diameters of a particle, so these shape
face roughness geometrically. However, if one of the indices are nondimensional values and should not be
pictures has the hidden area in the shadow of a parti- influenced by the particle size. However, the perimeter
cle, the three-dimensional information of the area is and the projection area of a fine particle have the ten-
hidden. When well-dispersed nanoparticles adhere dency to decrease with the decrease in particle size
on a flat substrate, the height difference between the because the resolution of a particle image is getting
particle surface and the flat substrate can be measured worse. Therefore, strictly speaking, the shape indices
accurately, and the thickness of nanoparticle is are influenced by the resolution of microscopic particle
obtained. images.
Using the TEM, 120 transmission images are taken In these indices, the degree of elongation or aspect ra-
when a sample is rotated 1 degree interval from þ60 tio is an index with which a particle expresses long and
to 60 degrees. This three-dimensional imaging tech- slender, and the index shows a large value for a slim fi-
nique called TEM-CT [2], which is similar to the ber particle. The high degree of flatness value means
computer-aided tomography [1], is expected to be flakey shape. The degree of circularity and the degree
applied for detailed three-dimensional shape measure- of sphericity are set to 1 of maximum when a particle
ment of nanoparticles. has a spherical shape, and the index shows a small value
Using the scanning probe microscope (SPM) for a nonspherical particle.
including atomic force microscope (AFM), the surface The shape indices, expressed with ratios of two parti-
roughness can be measured by tiny probe with the cle diameters, are divided into two categories. The degree
high resolution under nanometer order. SPMs are very of elongation, the degree of flatness, etc., in the one cate-
effective for thickness measurement of nanoparticles. gory show the overall shape of a particle, and the degree
The vertical direction length such as particle thickness of circularity and the degree of sphericity in the other
can be measured accurately by SPM, but the measured category show the surface roughness of a particle. Using
horizontal length becomes bigger about the diameter the relation between two shape indices in different cate-
of the probe. It means that the particle diameter in hor- gories, difference in particle shape can be expressed
izontal direction measured by SPM is bigger than real more clearly in the two-dimensional figure than the
12 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES
case using only one diameter ratio. As an example of such higher measurement accuracy, and the average value
a relation, the unidirectional maximum particle diameter showing the three-dimensional shape of many parti-
(Feret diameter)/diameter of equivalent particle perim- cles can be obtained. Thus, this method is effective in
eter is plotted on the horizontal axis and the degree of cir- shape analysis of a nanoparticle.
cular is plotted on the vertical axis [4]. In the covering method, a particle projection image is
covered with the square of r instead of a line segment,
and the relation between the number of squares contain-
1.3.4 Particle Shape Expression by Fractal ing a projection image or an outline of a particle N(r) and
Dimension size r is also used for the particle shape analysis. More-
The fractal dimension is a dimension, taking a real nu- over, the turning-radius method is well used to obtain
merical value, proposed by Mandelbrot [5] and is also the fractal dimension of an agglomerate particle. In
used for particle shape expression. The divider method this method, the circle of a radius R is drawn from the
is used to measure the fractal dimension of particle pro- center of an agglomerate particle, and the number of
jection image perimeters. In this method, the number of the primary particles contained in the circle N(R) is
the polygonal lines N(r) necessary to go around a particle counted. In this method, the fractal dimension D is ob-
perimeter is measured r as shown in Fig. 1.3.1. The line of tained from the logelog plot of R and N(R) [7]. From
length r is changed and the same operation is repeated. If the logelog plot of the perimeter P and the projection
the relation between r and N(r) shows a straight line on area A of each particle, the average fractal dimension
logelog paper as shown Fig. 1.3.1, the value correspond- of many particle perimeters is obtained from inclination
ing to the inclination of this straight line is defined as the of the straight line using the following equation [8]:
fractal dimension D [6]. PfAD=2 (1.3.2)
D
NðrÞfr (1.3.1) The three-dimensional particle shape expressed by
A high value of fractal dimension D means a rough the fractal dimension is also possible from the logelog
rugged surface of a particle, and a value of fractal plot of the surface area and volume of each particle,
dimension close to 1 means a smooth surface such as instead of the perimeter and the projection area.
spherical beads. The fractal dimension is also obtained
from the number of adsorbed gas molecules with
different adsorption area instead of a line segment. In 1.3.5 Particle Shape Analysis by Fourier
this method, a powder with larger surface area has Analysis
In the Fourier analysis method, the particle shape is
103 given as a function of the radius f(q) from the center of
mass to perimeter as shown in Fig. 1.3.2A. The Fourier
analysis is carried out by the following equation [9]:
XN
2np 2np
f ðqÞ ¼ a0 þ an cos qþ bn sin q (1.3.3)
n¼1
T T
Number of lines N(r) (−)
Center of mass
0 2 Low High
Angle Frequency
FIGURE 1.3.2 Fourier analysis of particle projective perimeter. (a) Radius of perimeter; (b) relation between rotation angle and radius; (c)
Fourier coefficient distibution.
1.3.6 Particle Shape Analysis of Nanoparticle [2] H. Furukawa, M. Shimizu, Y. Suzuki, H. Nishioka, JOEL News 36E
(2001) 50.
A particle shape analyzer is not available for nanopar- [3] J. Tsubaki, M. Suzuki, Y. Kanda, Nyumon Ryushi-Funtaikougaku 8,
ticle, and so a method based on the microscopic particle Nikkan Kougyo Shinbunsha, 2002.
[4] J. Tsubaki, G. Jimbo, Powder Technol. 22 (1979) 161e169.
image is used usually. To obtain the average result about
[5] B.B. Mandelbrot, Fractal Kikagaku, Nikkei Sci. (1984).
many particles, the ratio of two particle diameters ob- [6] M. Suzuki, Y. Muguruma, M. Hirota, T. Oshima, J. Soc. Powder
tained by different kinds of method such as a particle Technol. 25 (1988) 287e291.
size by dynamic light scattering method and the specific [7] M. Matsushita, K. Itoh, M. Ohnishi, T. Ogawa, M. Kohno,
surface diameter by the gas adsorption is used. These M. Tanemura, H. Honda, K. Miyamoto, K. Miyazaki,
N. Yoshimoto, Katachi no kagaku, Asakura shoten, 1987.
particle sizes include the influence of particle shape
[8] M. Suzuki, S. Yamada, H. Kada, M. Hirota, T. Oshima, J. Soc. Pow-
and, so the ratio of these diameters can be used for a sim- der Technol. 34 (1997) 4e9.
ple particle shape expression. [9] K. Otani, H. Minoshima, T. Uchiyama, K. Shinohara,
K. Takayashiki, T. Ura, J. Soc. Powder Technol. 32 (1995) 151e157.
References
[1] M. Suzuki, K. Kawabata, K. Iimura, M. Hitota, J. Soc. Powder Tech-
nol. 41 (2004) 156e161.
internal closed voids. This volume is equivalent to the surface, settle at the bottom, or remain suspended in
sum of volumes enclosed by the external surfaces of par- the liquid, after a certain holding time.
ticles. When there are no closed voids within particles,
the particle density is the same as the material density.
In actual measurements, open voids that have only 1.4.2 Density Measurement of Individual
small openings at the surfaces of particles might behave Particles
as closed voids. Therefore, the particle density value ob- 1.4.2.1 Effective Density of Individual Particles
tained can depend on the details of the measurement
When particles are not in a powder state, but are
procedure.
dispersed in a gas or a liquid, the density of individual
particles is often of concern. For particles dispersed in
1.4.1.1.3 Bulk Density a gas, there are three major methods of measuring the
Bulk density is defined as the mass of the powder density of individual particles: (1) the combined mea-
divided by the volume of the space below the upper sur- surement of mobility and mass, (2) the combined
face of the powder when it is placed in a container. The measurement of mass and volume, and (3) the com-
bulk density refers to the volume including both the bined measurement of mobility and aerodynamic
gaps between constituent particles and the voids within diameter.
particles. Two types of bulk densities are often used: Let m and db denote the mass and the mobility equiv-
initial bulk density is the bulk density when well- alent diameter (diameter of a sphere with the same me-
dispersed particles are put gently into a container, chanical mobility as the particle of concern) of a particle,
whereas tap density is that obtained after a tapping pro- respectively. The density obtained by methods (1) and
cedure in which the powder container is repeatedly (3) is the effective density defined by
lifted and dropped onto a solid surface. The ratio of m
the tap density to the initial bulk density is called the re ¼ . (1.4.1)
pdb 3 6 =
Hausner ratio and is used as a measure of powder flow-
ability or compressibility. For a spherical particle, db coincides with its geomet-
rical diameter, and hence re is equivalent to the particle
density defined in 1.4.1.1 For a nonspherical particle, db
1.4.1.2 Measurement Methods of Powder Density depends on the particle shape.2 Although the effective
In conventional methods of measuring the density of density in such cases is not an intrinsic material prop-
a powder, the mass of the powder is measured with a erty, it is still useful for particle characterization. The
balance and its volume is measured either by the liquid density obtained by method (2), on the other hand, is
immersion method or the gas replacement method. the particle density and leads to the material density, if
These methods are, of course, applicable also to pow- there are no closed voids within the particles.
ders composed of nanoparticles. For details of the These methods are also applicable to particles sus-
methods see references [1,2]. pended in a liquid, if the liquid suspension can be con-
It has been reported that bulk density of a powder verted into an aerosol by atomizing the suspension and
tends to remain unchanged by the tapping procedure drying the droplets thus generated.
when the powder is composed of nanoparticles, which
suggests that the Hausner ratio might not be a good 1.4.2.2 Mass Classification of Aerosol Particles
measure of the flowability or compressibility of nano- The method of classifying aerosol particles according
particles [2]. Further study will be required to establish to their mass, which is employed in methods (1) and (2),
a method for characterizing nanoparticles in terms of is briefly described here. Fig. 1.4.1 shows the principle of
bulk density. the aerosol particle mass analyzer (APM) used for this
When the density of individual particles is relatively purpose [4]. Aerosol particles are first passed through
homogeneous, the density reference liquid method [3] a bipolar charger in which bipolar ions generated by
may be applicable; particles are put into density refer- an ion source such as 241Am, 85Kr, or 210Po bring the par-
ence liquids that have been prepared to have several ticles to an equilibrium charge state and then introduced
known densities, and the particle density is determined into a thin annular gap between coaxial cylindrical elec-
by judging whether the particles float to the liquid trodes that rotate at the same angular velocity. In the
1
Note, however, that the particle density in 1.4.1 is an average property of particles contained in a powder, whereas the density here is a
property of an individual particle.
2
If we denote the volume equivalent diameter of a particle by dv, the shape dependence of db can be expressed by db/C(db) ¼ k dv/C(dv), where
k is the dynamic shape factor and C(d) the Cunningham slip correction.
1.4 PARTICLE DENSITY 15
Inner electrode
Brush
Centrifugal Electrostatic
force force
Outer electrode
Inner electrode
li g h t p a
s
par ticle
r ticles
heavy
Outer
electrode
gap, particles migrate in the radial direction under the predicted structure, and some other structures corre-
influence of centrifugal and electrostatic forces, and sponding to doubly and triply charged singlet particles
only those particles for which the two forces balance and singly charged doublet particles are also observed
can exit the electrodes. The particle mass that can be at theoretically predicted locations.
classified by this principle ranges roughly from 0.01 to
500 fg (1 fg ¼ 1015 g). This range corresponds approxi- 1.4.2.3 Combined Measurement of Mobility
mately to particle diameter of 30 nm to 1 mm for spher- and Mass
ical particles of 1 g/cm3 in density.
Fig. 1.4.2 shows a mass distribution spectrum ob- The effective density of aerosol particles can be deter-
tained by classifying monodisperse polystyrene latex mined by classifying them according to their mobility
particles with a known mass (208 nm diameter, and mass using a differential mobility analyzer (DMA)
and an APM connected in series, and then detecting the
1.054 g/cm3 density, and 4.97 fg mass) with an APM
exiting particles using a particle counter such as a conden-
and then by counting the number of exiting particles
with a laser particle counter (LPC). The main peak struc- sation nuclei counter (CNC) or an LPC. Fig. 1.4.3 shows a
ture coincides almost exactly with the theoretically mass distribution spectrum of sodium chloride (NaCl)
4000
Particle count (-)
calculated
0.04
3000 Doubly charged particles
++
0.03
2000
0.02 +++
+
1000
0.01
0.00 0
0 2 4 6 8 10 12 0.0 0.1 0.2 0.3 0.4
Particle mass (fg) Particle mass (fg)
FIGURE 1.4.2 Mass distribution spectrum for polystyrene latex FIGURE 1.4.3 Mass distribution spectrum for NaCl particles
particles (PSLs) of 4.97 fg in mass. having mobility equivalent diameter of 50 nm.
16 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES
Tm/To
In
and wettability (contact angle), which is the intrinsic .90
value between liquid and solid, depend on particle Pb
size when the size is nanometer order.
.85 Bi
Sn
1350
Melting point
1336K
1300
1.0
Melting point (K)
Pb (734K)
1250
1200
0 10 20 30 40 0 0.05 0.10
Particle size (nm) Inverse of particle size (A-1)
FIGURE 1.5.1 Relationship between melting point of gold and its FIGURE 1.5.3 Relationship between particle size change of evap-
particle size [8]. orating metal drop and particle size.
18 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES
1200 155
125
σ m/σ b
0.8 120
115
Pb 734K 0 10 20 30 40 50
Radius of particle (nm)
0.6
0 2 4 6 8 10 FIGURE 1.5.6 Relationship between contact angles of liquid
Particle size (nm) metals on graphite and particle sizes.
FIGURE 1.5.4 Effect of particle size of surface tension of Au and
Pb. sm, surface tension of nanoparticle; sb, surface tension of bulk Over 200 years ago, Eq. (1.5.2) was proposed by treat-
metal.
ing the contact angle of a liquid drop as the result of the
equilibrium of mechanical energy between the drop and
It can be found that Ln (dr/dt) and (1/r) does not show a solid surface under the action of three interfacial free
linear relationship when particle sizes of Au and Pb energies.
drops are less than 2 and 5 nm, respectively.
sL cos q ¼ sS sSL (1.5.2)
Gladkikh et al. [21] performed theoretical and exper-
imental approach on surface energies of nanoparticles of Where q is the contact angle, sL is the surface free en-
metals and reported the results of Au and Pb particles. ergy of liquid, sS is the surface free energy of solid, and
As can be found from Fig. 1.5.4, obtained result of Pb sSL is the interface free energy between solid and liquid.
is fairly in good agreement with that by Morokhov [22]. Because the surface free energy (surface tension) of
liquid depends on a liquid drop size as mentioned
above, the contact angle also depends on the liquid
1.5.3 Wettability drop size. Fig. 1.5.6 shows particle size dependence of
contact angles of various liquid metals on carbon sub-
As shown in Fig. 1.5.5, a contact angle value is used as
strate [23,24]. It can be found that the contact angles of
a criterion for wettability of solid by liquid. In general,
all liquid metals decrease at less than 40 nm and a
when a contact angle is larger than 90 degree (cf.
remarkable decrease of the contact angles is observed
Fig. 1.5.5A), it is defined as “nonwetting system” and
when particle radius is less than 10 nm.
when a contact angle is smaller than 90 degree (cf.
Fig. 1.5.5B), it is defined as “wetting system.”
(A) References
[1] M. Takagi, J. Phys. Soc. Jpn. 9 (1954) 359e363.
[2] F.O. Jones, K.O. Wood, Br. J. Appl. Phys. 15 (1964) 185e187.
[3] N.T. Gladkich, R. Niedermayer, K. Spiegel, Phys. Status Solidi 15
(1966) 181e192.
[4] C.R.M. Wronski, Br. J. Appl. Phys. 18 (1957) 1731e1737.
[5] B.T. Boiko, A.T. Pugachev, V.M. Bratsykhin, Sov. Phys. Solid State
(B) 10 (1969) 2832e2834.
[6] J.F. Pocza, A. Barna, P.B. Barna, J. Vac. Sci. Technol. 6 (1969)
472e475.
[7] M. Blackman, J.R. Sambles, Nature 226 (1970) 938.
[8] M.J. Stowell, T.J. Law, J. Smart, Proc. R. Soc. Lond. A 318 (1970)
231e241.
[9] J.R. Sambles, Proc. R. Soc. Lond. A 324 (1970) 339e351.
FIGURE 1.5.5 Liquid drop shape on solid. [10] C.J. Coombes, J. Phys. F. Metal. Phys. 2 (1972) 441e449.
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