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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
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 Contents

List of Contributors xvii 2.5. Pore Structure 91

Preface xxi 2.6. Nanoparticle Design for Drug Delivery System 100
Preface to the Second Edition xxiii 2.7. Nanotubes (Carbon Nanotube) 105
Preface to the First Edition xxv 3. Characteristics and Behavior of
Nanoparticles and Its Dispersion Systems
HIDEHIRO KAMIYA, KUNIAKI GOTOH, MANABU
FUNDAMENTALS SHIMADA, TETSUO UCHIKOSHI, YOSHIO OTANI,
MASAYOSHI FUJI, SHUJI MATSUSAKA, TATSUSHI
MATSUYAMA, JUNICHI TATAMI, KO HIGASHITANI,
1. Basic Properties and Measuring Methods KAZUE KURIHARA, NAOYUKI ISHIDA, MICHITAKA
of Nanoparticles SUZUKI, HIROYA ABE, YASUFUMI OTSUBO, AND
TOYOKAZU YOKOYAMA, HIROAKI MASUDA, MINORU MIYAHARA
MICHITAKA SUZUKI, KENSEI EHARA, KIYOSHI NOGI,
MASAYOSHI FUJI, TAKEHISA FUKUI, HISAO SUZUKI, 3.1. Introduction of Nanoparticle Dispersion and
JUNICHI TATAMI, KAZUYUKI HAYASHI, AND Aggregation Behavior 109
KENJI TODA 3.2. Single Nanoparticle Motion in Fluid 114
3.3. Brownian Diffusion 120
1.1. Size Effect and Properties of Nanoparticles 3 3.4. Adsorption Properties and Wettability of
1.2. Particle Size 9 Nanoparticle Surface 121
1.3. Particle Shape 10 3.5. Interactions Between Particles 123
1.4. Particle Density 13 3.6. Aggregation and Dispersion, Characterization,
1.5. Melting Point, Surface Tension, and and Control 149
Wettability 17 3.7. Rheology of Slurry 158
1.6. Specific Surface Area and Pore 19 3.8. Simulation of Colloidal Dispersion System 162
1.7. Composite Structure 22
1.8. Crystal Structure 27 4. Control of Nanostructure of Materials
1.9. Surface Characteristics 31 HIROYA ABE, YOSHINARI MIYAMOTO, MITSUO
1.10. Mechanical Property 34 UMETSU, TETSUO UCHIKOSHI, TATSUYA OKUBO,
1.11. Electrical Properties 37 MAKIO NAITO, YUJI HOTTA, TOMOKO KASUGA,
1.12. Magnetic Properties 40 AKIHIKO SUDA, HIDETOSHI MORI, REIJI MEZAKI,
1.13. Optical Property of Nanoparticle 44 TSUTOMU MORIMOTO, AKIRA AZUSHIMA,
KATSUYOSHI KONDOU, KEIZO UEMATSU, TAKAHIRO
2. Structural Control of Nanoparticles TAKADA, KIYOSHI NOGI, HIDETOSHI FUJII, JUN AKEDO,
YOSHINOBU FUKUMORI, TOSHIYUKI NOMURA, YOSHIAKI KINEMUCHI, YOSHIO SAKKA, YUKIO
TADAFUMI ADSCHIRI, SATOSHI OHARA, FUMIO SAITO, YAMAGUCHI, YOSHITAKE MASUDA, AND SHINJI
MAKIO NAITO, KIKUO OKUYAMA, MASAYOSHI INAGAKI
KAWAHARA, HISAO SUZUKI, TAKAFUMI SASAKI,
MASAYOSHI FUJI, SHINJI INAGAKI, HIROFUMI
4.1. Assembly of Nanoparticles and
TAKEUCHI, AND YOSHINORI ANDO Functionalization 169
4.2. Nanoparticles-Arranged Structures 170
2.1. Structure Construction and Function 4.3. Nanopore Structure 181
Adaptation of Nanoparticles 49 4.4. Nanocomposite Structure 193
2.2. Particle Size 55 4.5. Structure Control of Nanoparticle
2.3. Particle Shape 69 Collectives by Sintering and Bonding 212
2.4. Composite Structure 76 4.6. Self-Assembly 239

v
vi CONTENTS

5. Characterization Methods for 7.3. Safety of Nanoparticles 379

Nanostructure of Materials 7.4. Removal of Nanoparticles 388
SATOSHI OHARA, TADAFUMI ADSCHIRI,
TAKASHI IDA, MASATOMO YASHIMA, TAKESHI
MIKAYAMA, HIROYA ABE, YUICHI SETSUHARA,
APPLICATIONS
KIYOSHI NOGI, MINORU MIYAHARA, KENJI KANEKO,
AND AKIRA OHTOMO Category A - Medical, Cosmetic, Biological
5.1. Nanostructure and Function 1. Development of New Cosmetics Based on
(Characterization of Local Nanoparticles
Nanostructure) 255
HIROSHI FUKUI
5.2. Crystal Structure 256
5.3. Surface Structure 265 1. Use of Nanoparticles 399
5.4. Nanopore Characterization 282 2. Use as Compound Particles 401
5.5. Grain Boundaries and 3. Future Development 404
Interfaces 288 References 404
5.6. Evaluation Methods for Oxide
Heterostructures 297 2. Design of Nanoparticles for Oral Delivery
of Peptide Drugs
6. Evaluation Methods for Properties of HIDEKI ICHIKAWA
Nanostructured Body
TAKEHISA FUKUI, JUNICHI TATAMI, SHUJI SAKAGUCHI, 1. Particulate Design and Functions 407
FUMIHIRO WAKAI, TETSUYA SENDA, TAKASHI AKATSU, 2. Case Studies 409
TETSUYA BABA, YUJI NOGUCHI, MASARU MIYAYAMA, References 413
ATSUSHI YAMAMOTO, SUSUMU YONEZAWA,
TOMOICHIRO OKAMOTO, MOTOHIDE MATSUDA, 3. Development of Photocatalyst Inserted
MASANOBU AWANO, TSUTOMU KATAMOTO, KENJI
Into Surface of Porous Aluminosilicate
TODA, SOSHU KIRIHARA, AKIHIKO SUDA, AND
KIYOSHI NOGI TOSHIO KAKUI

6.1. Functionality of Nanostructures 1. Structure of TiO2eAluminosilicate Complex 415

and Their Characteristic 2. Photocatalysis of TiO2eAluminosilicate Complex 416
Evaluation 301 3. Photoenduarance of Paper With TiO2e
6.2. Mechanical Properties 306 Aluminosilicate Complex 417
6.3. Thermophysical Properties 318 References 418
6.4. Electric Properties 325
6.5. Electrochemical Properties 338 4. Nanoparticle Formation of DNA
6.6. Magnetic Properties 349 (Globule Transformation)
6.7. Optical Properties 352 SHINJI KATSURA
6.8. Catalytic Property 357
6.9. Properties of Gas Permeation 1. Tolerance of DNA Nanoparticles Against
and Separation Membranes 360 Mechanical Stress 419
2. Micromanipulation of DNA Nanoparticles 420
7. Environmental and Safety Issues With References 422
Nanoparticles
5. Addressing of Nanoparticles by Using
HISAO MAKINO, HITOSHI EMI, AKIMASA YAMAGUCHI,
EIJI IRITANI, NORIKAZU NAMIKI, TOSHIHIKO MYOJO,
DNA Molecules
AND KENJI YAMAMOTO SHINJI KATSURA

7.1. Introduction 365 1. Stretching of DNA Molecules 423

7.2. Nanoparticles and Environment 365 2. Addressing of Nanoparticles 424
References 426
 CONTENTS vii
6. Development of the 3. Functional Cosmetics Using PLGA
Thermoresponsive Magnetic Nanospheres 448
Nanoparticle and Its Deployment References 450
in the Biotechnology Field
10. PLGA Nanoparticle Design and
AKIHIKO KONDO
Preparation for DDS and Medical
1. Magnetic Nanoparticle Material 427 Device
2. What Is a Thermoresponsive HIROYUKI TSUJIMOTO AND YOSHIAKI
Polymer? 427 KAWASHIMA
3. Thermoresponsive Magnetic
Nanoparticles 428 1. Introduction 451
4. Application Examples of the 2. PLGA Nanoparticle DDSs 451
Thermoresponsive Magnetic Nanoparticles 3. Applied Technology With PLGA
to the Biotechnology Field 429 Nanoparticles as Base Carrier 452
5. Future Perspective 434 4. PLGA Nanoparticle System Platforms
References 434 and Implementation in Nanomedical
Systems 454
7. Pinpoint Drug and Gene Delivery 5. Conclusion 459
References 460
SHUN’ICHI KURODA

1. Bio-Nanocapsules 435 11. PLGA Nanosphere Technology for

2. Potential Applications of Bio-Nanocapsule 437 Novel Nanomedicine and Functional
3. Assignment 438 Cosmetics
4. Conclusion 438 YUSUKE TSUKADA, AIKO SASAI, HIROYUKI
References 438 TSUJIMOTO, HIROMITSU YAMAMOTO, AND YOSHIAKI
KAWASHIMA
8. A Cancer Treatment
Strategy That Combines the Use of 1. Introduction 461
2. Preparation Method and Application for
Inorganic/Biocomplex Nanoparticles
Practical Use of PLGA NS 461
With Conventional Radiation 3. Drug Delivery System Formulation and
Therapy Pharmacological Performance of PLGA NS 462
KENTA MORITA, YUYA NISHIMURA, 4. Application of PLGA NS for Cosmetics 464
TAKAHIRO SUZUKI, CHIAKI OGINO, 5. Conclusions 466
AND AKIHIKO KONDO
References 467
1. Introduction 439
2. Screening for Inorganic Nanoparticles
12. Delivery to the Brain
Applicable to Radiosensitizing 440 HIROMITSU YAMAMOTO
3. Cancer Therapy Using a Combination
1. Surface Modification to Improve the Nanoparticle
of Inorganic Nanoparticles and X-Ray
Distribution in the Brain 469
Irradiation 440
2. Effect of Administration Route on the Brain
4. Bio-Nanocapsule 441
Distribution 471
5. Conclusions 442
3. Perspective of Brain Targeting With
References 443
Nanoparticles 472
References 472
9. Development of Functional Skin Care
Cosmetics Using Biodegradable PLGA 13. Bioimaging With
Nanospheres Quantum Dots
HIROYUKI TSUJIMOTO AND KAORI HARA
KENJI YAMAMOTO

1. Nanocosmetics That Whiten Skin 1. Developments of Quantum Dots 473

and Eliminate Wrinkles 445 2. Development of Bioimaging 474
2. Evaluation of the Cutaneous Permeability of 3. Bioimaging and Quantum Dots 474
PLGA Nanospheres and Their Functional 4. Quantum Dots Label for the Antibody 476
Effect 446
viii CONTENTS

5. In Vivo Imaging of the Quantum DotseStained 19. Mechanical Synthesis of Composite

Cell: The Localization in Organs 476 Oxide and Its Application for SOFC
6. Observation of the Localization From Cathode
Outside of the Body 477
KOUHEI HOSOKAWA, TOYOKAZU YOKOYAMA,
Reference 477 AKIRA KONDO, AND MAKIO NAITO

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

TAKEHISA FUKUI 1. Withstand Voltage Characteristics 525

2. Tracking-Resistance and Erosion-Resistance
1. Development Task of Fuel Cells 500
Characteristics 527
2. Development of High-Performance Solid Oxide
3. Thermal Characteristics 527
Fuel Cells Using Nanoparticle Technology 500
References 528
References 503
 CONTENTS ix
23. Collection Technology 3. Smart Recycling of Composite Materials 549
for Nanoparticles in Flue Gas References 550
HISAO MAKINO AND NAOKI NODA
28. Improvement of Lithium-Ion Battery
1. Introduction 529 Performances by Controlling
2. Outline of Dust Collection Technologies 529 Nanocomposite Structure
3. Collection Characteristics of Electrostatic TAKAHIRO KOZAWA AND MAKIO NAITO
Precipitators 530
4. Collection Characteristics of Bag Filters 530 1. Composite Granule Structure Consisting of
Further Reading 531 Nanoparticles 551
2. Composite Granule With a Porous Structure 552
24. Powder Technology 3. High-Voltage Cathode Particle With a Gradient
and Nanotechnology Contributed Composition 553
for Clean Utilization of Coal 4. Nanocomposite Electrode Particles for
HISAO MAKINO AND NAOKI NODA
All-Solid-State Li Batteries 556
References 557
1. Powder Technology and Nanotechnology in
Pulverized Coal Combustion Power Plant 533 29. Dendrimers and Their Application to
2. Powder Technology and Nanotechnology of Organic Electronics Devices
High-Efficiency Coal Utilization System 534 NORIFUSA SATOH AND KIMIHISA YAMAMOTO
3. Investigation of CO2 Capture and
Storage Method 535 1. Synthesis and Structure of Dendrimer 559
4. Upgrading of Low-Rank Coal and Biomass 536 2. Metal-Assembling Property of Dendrimer 559
References 537 3. Application to Electronic Devices 561
References 562
25. Zeolite Membrane
MOTOHIDE MATSUDA
30. Ceramic Filter for Trapping Diesel
Particles
1. Characteristics 539 HARUHIDE SHIKANO
2. Synthesis 539
3. Separation Properties of Zeolite Membranes 541 1. Production of Particulate Matter 563
References 542 2. Trapping of Particulate Matter 563
3. Pressure Loss 565
26. Development of Nanoparticle 4. Features of Porous Silicon Carbide 565
Composite Technique for Low Pt-Loading 5. Functions and Characteristics of Diesel
PEFCs Particulate Filter 566
HIROKAZU MUNAKATA
6. Future of Filters for Trapping Diesel Particles 566
References 567
1. Particle Design for PEFC Catalysts 543
2. Preparation of Pt/CeWC Composite Particle 31. Development of Exhaust Catalyst
for PEFC Anode 543 AKIHIKO SUDA
3. Preparation of Pt/CeSnO2 Composite Particle
for PEFC Cathode 545 1. Supported Metal Catalyst 569
References 546 2. Oxygen-Storage Capacity of Catalyst 570
3. Improvement of OSC of Catalyst 570
27. Novel Recycling of FibereReinforced 4. Improvement of Thermal Resistance of Catalyst 571
Plastics by Using Nanoparticle Bonding References 572
MAKIO NAITO, HIROYA ABE, AKIRA KONDO, AND
NORIFUMI ISU
32. Electrical Conductive
CNT-Dispersed Si3N4 Ceramics
1. Introduction 547 JUNICHI TATAMI
2. The Development of Novel Recycling Process
for GFRP 547 References 577
x CONTENTS

33. Preparation of Solid Electrolyte Particles 3. Tunable Structural Color by Swelling

and Solid-Solid Interfaces for All-Solid- With Liquid 603
State Batteries 4. Tunable Structural Color by Applying
Mechanical Stress 604
MASAHIRO TATSUMISAGO AND AKITOSHI HAYASHI
5. Summary and Outlook 604
1. Introduction 579 References 605
2. Preparation of Lithium-Ion Conducting
Glass Particles via Mechanochemistry 579 38. Practical Issue of Nanosized
3. Formation of Favorable Solid-Solid Colorant Particles
Interfaces in Solid-State Batteries 581 KAZUYUKI HAYASHI
4. Conclusions 584
References 584 1. Introduction 607
2. Preparation of Nanosized Colorant
34. Development and Multi-Functionalization Particles and Improvement of
of High-Functional Separation Membranes Functional Properties 607
3. Conclusion 612
AKIMASA YAMAGUCHI
References 612
1. Gas Separation 585
2. Liquid Separation 587 39. Expression of Optical Function by
References 588 Nanostructure Using Femtosecond Laser
Processing
35. Development of a High-Performance KAZUYUKI HIRAO
Secondary Battery by Controlling the
Surface Structure 1. Space-Selective Valence State Manipulation of
Rare-Earth Ions Inside Glasses 613
SUSUMU YONEZAWA
2. Precipitation Control of Gold Nanoparticles
1. Anode of a NickeleHydrogen Battery 591 Inside Transparent Materials by a
2. Cathode of the NickeleHydrogen Battery 591 Femtosecond Laser 614
3. Cathode of Lithium-Ion Battery 593 3. Nanograting Fabrication 616
4. Anode of the Lithium-Ion Battery 594 References 617
References 594
40. Ceramic Fillers for High Frequency
Category C - Electronic and Magnetic Dielectric Composites
Materials, Memories, Light Emitting YUSUKE IMAI
Materials, Displays
1. Introduction 619
36. Development of Bright Phosphors Using 2. Particle-Filled Polymer Composites
Glasses Incorporating Semiconductor as Dielectric Materials 620
Nanoparticles 3. Design of Dielectric Constants of
Composites 621
MASANORI ANDO, CHUNLIANG LI, AND NORIO MURASE
4. Particle Size Effect on Dielectric Loss 622
1. Syntheses of Highly Photoluminescent 5. Control of Temperature-Dependent
Semiconductor Nanoparticles by an Aqueous Properties of the Composites 622
Solution Method 597 References 623
2. Preparation of Glass Phosphors Incorporating
Semiconductor Nanoparticles by a SoleGel 41. Material Design of Electronic Liquid
Method 598 Powder Used in Novel-Type Bistable
References 600 Reflective Display (QR-LPD)
NORIHIKO KAGA, HIROYUKI ANZAI, AND
37. Closely Packed Colloidal Crystal MASASHI OTSUKI
Assembled With Nanoparticles and Its
Application for Smart Materials With 1. Introduction 625
2. Overview of QR-LPD 625
Tunable Structural Color
3. About Electronic Liquid
HIROSHI FUDOUZI
Powder 626
1. Closely Packed Colloidal Crystal Films 601 4. Measurement of Electrostatic
2. Structural Color of Colloidal Crystal Properties 627
and Its Tuning Mechanism 601 5. Measurement of Adhesive Force 628
 CONTENTS xi
6. Material Design 628 3. Direct Formation of the Electronic Circuit
7. Conclusion 630 Pattern by Inkjet Printing 649
References 630 4. Application as the Joining Materials 650
References 650
42. Sensing Based on Localized Surface
Plasmon Resonance in Metallic 47. Development of Novel Ferroelectric
Nanoparticles Materials
KOTARO KAJIKAWA YUJI NOGUCHI AND MASARU MIYAYAMA

1. Localized Surface Plasmon 631 1. Crystal Structure of Bismuth LayereStructured

2. Two Sensing Methods Using Plasmon 632 Ferroelectrics 651
References 633 2. Crystal Growth and Experimental Procedure 652
3. Layered Structure, Dielectric, and
43. Development of Photonic Crystal Leakage Current Properties of BiTeBBTi
Resonators for Terahertz Wave Sensing by Crystals 652
Using Nanoparticle Stereolithography 4. Giant Polarization in BiTeBBTi
SOSHU KIRIHARA Crystals 653
References 654
References 636
48. Development of Magnetorheological
44. AC Overhead Transmission Line Fluid by Using Iron Nanoparticles and the
Audible-Noise Reduction Measures Using Application to Haptics Devices
Surface Improvement JUNICHI NOMA
KIYOTOMI MIYAJIMA
1. Introduction 655
1. Audible Noise of AC Overhead 2. Preparation of the Nanomagnetorheological
Transmission Lines 637 Fluid 656
2. Wetting Property of Power Lines 637 3. Particle Cluster Behaviors of
3. Preparation of Test Power Lines 638 Magnetorheological Fluids in Shear
4. Features of Titanium Oxide Thermal-Sprayed Flow Mode 657
Films 639 4. Applications of Nanomagnetorheological
5. Audible-Noise Measurement 639 Fluid 658
References 641 References 659

45. Development of Photonic Crystals 49. High Performance Wiring Based on

Based on Nanoparticle Assembly Nanowelding Technology for Printed
HIDEKI T. MIYAZAKI Electronics
JINTING JIU, MINORU UESHIMA AND KATSUAKI
1. Nanoparticle Assembly Technique 643 SUGANUMA
2. Fabrication of Photonic Crystals by
Nanoparticle Assembly Technique 644 1. Introduction 661
References 646 2. The Development of Nanowelding Technology 661
3. The Application of Nanowelding Technology 663
46. Microelectronics Packaging by Metal References 666
Nanoparticle Pastes
MASAMI NAKAMOTO 50. Development of New Phosphors
KENJI TODA
1. Conductive Paste Technique and Metal
Nanoparticle Paste 647 1. History of Development of Nanophosphor 667
2. Low-Temperature Firing and Fine Electronic 2. Properties of Rare-Earth Nanophosphor 667
Circuit Pattern Formation by Screen 3. Development Trend of New Nanophosphor 668
Printing 647 References 669
xii CONTENTS

51. Development of Optical Memory Using 55. Dispersion of Fine Silica Particles Using
Semiconductor Nanoparticles Alkoxysilane and Industrialization
YUKIO YAMAGUCHI HIDEKI GODA

1. Fluorescence Characteristics of Semiconductor 1. SoleGel Hybrid 695

Nanoparticles 671 2. Molecular Design 695
2. Optical Memory Effect of Semiconductor 3. Unmeltable Plastics: Epoxy Resin Hybrid 696
Nanoparticle Thin Films 671 4. Tough Resin: Hybrid of the Phenol Resin
3. Methods of Preparing and Evaluating CdSe System 698
Thin Films 672 5. Soft Silica Hybrid: Hybrid of the Urethane
4. Dependency of Intensity of Fluorescence on the System 698
Excitation Light Intensity 673 6. Cheap Engineering Plastics in Place for Imide:
5. Future Topics 673 Hybrid of the Amideimide System 698
References 674 7. Imide Useful for Electroless Plating: Hybrid of
the Imide System 699
Category D - Synthesis, Dispersion, References 700
Processing
56. Barium Titanate Nanoparticles
52. Nanoparticle Synthesis, Dispersion, and Synthesized Under Sub- and Supercritical
Functionalization for Industrial Application Water Conditions
MUHAMMAD M. MUNIR, TAKASHI OGI, AND KIKUO YUKIYA HAKUTA
OKUYAMA
1. Experiment for Producing Tetragonal BaTiO3
1. Introduction 675 Nanoparticles by Supercritical Hydrothermal
2. Current Status of Nanoparticle Synthesis Synthesis 701
Technologies 675 2. Selective Production of Tetragonal BaTiO3 702
3. New Strategies on the Development of References 704
Nanoparticle Materials 676
4. Conclusion 681 57. Surface Modification of Nanoparticles
References 681 by Silane Alkoxides and Their Application
in Silicone-Based Polymer Nanocomposites
53. Supercritical Hydrothermal Synthesis
MOTOYUKI IIJIMA
of Nanoparticles
AKIRA YOKO, TSUTOMU AIDA, NOBUAKI AOKI, 1. Surface Modification of Functional
DAISUKE HOJO, MASANORI KOSHIMIZU, SATOSHI Nanoparticles Using Silane Alkoxides 705
OHARA, GIMYEONG SEONG, SEIICHI TAKAMI, 2. Silicone-Based Polymer Nanocomposites
TAKANARI TOGASHI, TAKAAKI TOMAI, TAKAO
Using SiO2 Nanoparticles 707
TSUKADA, AND TADAFUMI ADSCHIRI
3. Conclusions 709
1. Introduction 683 References 709
2. Synthesis and Control 684
3. Applications and Evaluation 685 58. Formation of Thick Electronic Ceramic
4. Mechanism and Measurements 687 Films With Bonding Technique of
References 689 Crystalline Fine Particles and Their
Applications
54. Nozzle-Free Inkjet Technology MITSUTERU INOUE
TAKEHISA FUKUI
1. Aerosol Deposition Method 711
1. Principle of Nozzle-Free Inkjet Technology 2. Formation of Thick Electronic Ceramic Films
and Outline of Developed System 691 With Aerosol Deposition Method 712
2. Formation of Slurry Using Nozzle-Free Inkjet 3. Applications of Aerosol Deposition Ceramic
Technology 693 Films 713
References 694 Reference 714
 CONTENTS xiii
59. Development of New Materials by the 63. Fabrication Technique of Organic
Mild Dispersion of Nanoparticles in Slurries Nanocrystals and Their Optical Properties
by Bead Milling and Materialization
TOSHIHIRO ISHII HITOSHI KASAI, HACHIRO NAKANISHI, AND
HIDETOSHI OIKAWA
1. Introduction 715
2. Bead Mill 715 1. The Organic Compounds Used for
3. Overdispersion and Mild Nanocrystallization 739
Dispersion 717 2. Fabrication Techniques of Organic Nanocrystals 739
4. Bead Milling for the Mass Production of 3. Size-Dependence of Optical Properties for
Nanoparticles 719 Organic Nanocrystals 742
5. Conclusions 719 4. Orientation Control of Dispersed Organic
References 719 Nanocrystals by External Field 743
References 743
60. Three-Dimensional Structural Analysis
of Nanocomposite Materials Containing 64. Instantaneous Nanofoaming Method for
Nanoparticulates Fabrication of Closed-Porosity Silica Particle
HIROSHI JINNAI KEN-ICHI KURUMADA

1. Introduction 721 References 749

2. TEMT on Nanocomposite Containing
Particular Fillers 722 65. Creation of Boron Nitride Nanotubes
3. Recent Development in TEMT 722 and Possibility for a Series of Advanced
References 725 Nanocomposite Materials
HIROAKI KUWAHARA
61. Dispersion Control of Al2O3
Nanoparticles in Ethanol 1. Introduction 751
TOSHIO KAKUI 2. Synthesis Methods of Boron Nitride Nanotubes 752
3. Reinforcement of Resins by the Addition
1. Effect of Molecular Weight of of Boron Nitride Nanotubes 753
PEI on Nanoparticle Suspension 4. Use of Boron Nitride Nanotubes Fillers as an
Viscosity 727 Insulating Heat Conductor 756
2. Relationship Between Molecular 5. Characterization of Boron Nitride
Size of PEI and Suspension NanotubesePolymer Interfacial Interactions 757
Viscosity 728 6. Conclusion 758
3. Surface Interaction Between Al2O3 References 758
Nanoparticles Using Nanocolloidal
Probe AFM 728 66. Fabrication of Functional Ceramic
4. Action Mechanism of Polymer Dispersant on Devices Produced by Three-Dimensional
Al2O3 Nanoparticle Suspension 729 Molding Using Microstereolithography
References 730 SHOJI MARUO

62. LiquideCrystalline Inorganic References 763

Nano- and Fine Particles
KIYOSHI KANIE AND ATSUSHI MURAMATSU 67. Morphology Control of Particles and
Their Patterning
1. Organic Liquid Crystals and Lyotropic Liquide YOSHITAKE MASUDA
Crystalline Inorganic Fine Particles 731
2. Development of OrganiceInorganic Hybrid 1. Morphology Control of ZnO Particles and
Liquid Crystals 732 Their Patterning 765
3. Summary and Prospect 736 2. Patterning of Pt Nanoparticles and In2O3 769
References 737 References 774
xiv CONTENTS

68. Development of Ceramic-Bonded 72. Self-Assembly of Oxide Nanosheets:

Carbon Precise Structural Control and Its
YOSHINARI MIYAMOTO, MASAHARU NAKAMURA, Applications
TETSURO TOJO, AND WEIWU CHEN MINORU OSADA AND TAKAYOSHI SASAKI

1. Fabrication of Ceramic-Bonded Carbons 777 1. Introduction 797

2. Microstructure and Properties of Ceramic-Bonded 2. Synthesis of Functional Nanosheets 797
Carbons 778 3. Layer-by-Layer Assembly of Oxide
3. Joining of Ceramic-Bonded Carbons With Nanosheets 798
Ceramics 779 4. Applications to Nanoelectronics 798
4. Potential Applications 780 References 798
References 780
73. Fabrication of Ceramics With Highly
69. Nano/Microcomposite Particles: Controlled Microstructures by Advanced
Preparation Processes and Applications Powder Processing
XING WEI, ATSUSHI YOKOI, AND HIROYUKI MUTO YOSHIO SAKKA

1. Introduction 781 1. Introduction 801

2. Mechanism of Electrostatic Adsorption Method 2. Fabrication of Fine-Grained Ceramics by
and Nano/Microcomposite Particles 781 Colloidal Processing 801
3. Applications on Nano/Microcomposite Materials 783 3. Highly Conductive Carbon-Nanotube-Dispersed
4. Conclusions 785 Ceramics by Heterocoagulation 802
Acknowledgments 785 4. Control of Crystal Orientation by Colloidal
References 785 Processing in Strong Magnetic Field 804
5. Nacre-Like Ceramics 805
70. Generation of Metal Nanoparticles 6. Laminated Composites 806
Using Reactive Plasma Arc Evaporation References 807
NORIYUKI NAKAJIMA
74. Surface Modification of Inorganic
1. Summary of the Reactive Plasma Arc Evaporation Nanoparticles by Organic Functional
Method 787
Groups
2. Nanoparticles by the Reactive Plasma Arc
SEIICHI TAKAMI
Evaporation Method 788
3. The Nanoparticles-Generation Rate, 1. Surface-Modified Noble Metal Nanoparticles 809
Characteristic, and Shape 788 2. Organic Modification of Metal Oxide
4. Application of the Nanoparticle 789 Nanoparticles 810
References 790 3. Hybridization of Inorganic Nanoparticles With
Biomolecules 811
71. Synthesis of Nanoparticles by Radio References 812
Frequency Induction Thermal Plasma
KEITARO NAKAMURA 75. Evaluation and Applications of
Dispersing Carbon Nanotube in the
1. Advantages of the Method of Synthesis of
Nanoparticles by Radio Frequency Induction
Polymers
Thermal Plasma 791 HIROFUMI TAKASE
2. Experimental Configuration and Equipment
1. Carbon Nanotube 813
for the Synthesis of Nanoparticles 791
2. Fracture Model of Agglomerates of Carbon
3. Generation of Nanoparticles by Radio
Nanotube 813
Frequency Induction Thermal Plasma 792
3. Dispersion of CNT by an Extruder 813
4. Conclusions 796
4. Dispersion of Composites and Its Evaluation 813
References 796
 CONTENTS xv
5. Relationship Between the Agglomerate Fraction 3. Dispersion and Composing of Nanoparticles by
Ar and Composite Properties 814 Dry Mechanical Method 825
6. Percolation 816 4. Dispersion of Nanoparticles by Wet Method and
7. Development of CNT Composite Resin Its Application to Advanced Firefighter Uniform 826
Materials 816 References 828
References 817
78. Preparation of Metal Nanoparticles
76. Development of PolymereClay and Their Application for Materials
Nanocomposites by Dispersion of Particles TETSU YONEZAWA
Into Polymer Materials
ARIMITSU USUKI 1. Introduction 829
2. Nanoparticle Preparation by Chemical Reduction 829
1. Nylon 6eClay Hybrid 819 3. Sputtering Processes to Obtain Metal
2. Synthesis and Properties of PolypropyleneeClay Nanoparticles 831
Hybrid 820 4. Applications of Metal Nanoparticles 833
3. Synthesis and Properties of Ethylenee 5. Application of Copper Nanoparticles and Fine
PropyleneeDieneeMethylene (Linkage)eClay Particles for Low-Temperature Sintering 834
Hybrid 820 6. In Situ Heating Experiments 834
4. Morphology Control by Polymers With Clay 821 7. Conclusions 837
References 821 References 837

77. Development of Dispersion and 79. Nanotechnology Challenge in

Composing Processes of Nanoparticles and Mechanochemistry
Their Application to Advanced Firefighter QIWU ZHANG, JUNYA KANO, AND FUMIO SAITO
Uniform
1. Introduction 839
TOYOKAZU YOKOYAMA, SHUJI SASABE, AND
2. Materials Processing 839
KENJI TAKEBAYASHI
3. Conclusion 843
1. Introduction 823 References 843
2. Preparation of Nanocomposite Particles by
Gas-Phase Reaction Method 823 Index 845
This page intentionally left blank
 List of Contributors
Hiroya Abe Joining and Welding Research Institute, Osaka
University
Tadafumi Adschiri Institute of Multidisciplinary Research
for Advanced Materials, Tohoku University, Sendai, Japan
Tsutomu Aida Tohoku University, Sendai, Japan
Takashi Akatsu Materials and Structures Laboratory, Tokyo
Institute of Technology
Jun Akedo National Institute of Advanced Industrial
Science and Technology (AIST)
Masanori Ando National Institute of Advanced Industrial
Science and Technology (AIST)
Yoshinori Ando Department of Materials Science and
Engineering, Meijo University
Hiroyuki Anzai Central Research, Bridgestone Corporation
Nobuaki Aoki Tohoku University, Sendai, Japan
Masanobu Awano National Institute of Advanced
Industrial Science and Technology (AIST)
Akira Azushima Graduate School of Engineering,
Yokohama National University
Tetsuya Baba National Institute of Advanced Industrial
Science and Technology (AIST)
Weiwu Chen Joining and Welding Research Institute, Osaka
University
Kensei Ehara National Institute of Advanced Industrial
Science and Technology (AIST)
Hitoshi Emi Association of Powder Process Industry and
Engineering (APPIE)
Hiroshi Fudouzi Optronic Materials Center, National
Institute for Materials Science
Masayoshi Fuji Ceramics Research Laboratory, Nagoya
Institute of Technology
Hidetoshi Fujii Joining and Welding Research Institute,
Osaka University
Hiroshi Fukui Frontier Science Business Division, Shiseido
Co., Ltd.
Takehisa Fukui Hosokawa Powder Technology Research
Institute
Yoshinobu Fukumori Faculty of Pharmaceutical Sciences,
Kobe Gakuin University
Hideki Goda R&D Department, Photo-electronic Materials
Division, Arakawa Chemical Industries, Ltd.
Kuniaki Gotoh The Graduate School of Natural Science and
Technology, Okayama University
Yukiya Hakuta National Institute of Advanced Industrial
Science and Technology (AIST)
Kaori Hara Hosokawa Powder Technology Research
Institute
Akitoshi Hayashi Osaka Prefecture University, Osaka, Japan
Kazuyuki Hayashi R&D Division, Toda Kogyo Corporation
Ko Higashitani Department of Chemical Engineering,
Kyoto University
Kazuyuki Hirao Department of Material Chemistry, Kyoto
Univerisity
Daisuke Hojo Tohoku University, Sendai, Japan
Kouhei Hosokawa Hosokawa Micron Corporation,
Osaka, Japan
Masuo Hosokawa Hosokawa Micron Corporation
Yuji Hotta National Institute of Advanced Industrial Science
and Technology (AIST), Nagoya, Japan
Hideki Ichikawa Faculty of Pharmaceutical Sciences Kobe
Gakuin University
Takashi Ida Ceramics Research Laboratory, Nagoya Institute
of Technology
Manabu Ihara Research Center for Carbon Recycling
Energy, Tokyo Institute of Technology
Motoyuki Iijima Yokohama National University, Yokohama,
Japan
Yusuke Imai National Institute of Advanced Industrial
Science and Technology, Nagoya, Japan
Shinji Inagaki Toyota Central R&D Labs., Inc.
Mitsuteru Inoue Toyohashi University of Technology
Eiji Iritani Department of Chemical Engineering, Nagoya
University
Yasutoshi Iriyama Nagoya University, Nagoya, Japan
Naoyuki Ishida National Institute of Advanced Industrial
Science and Technology (AIST)
Toshihiro Ishii Ashizawa Finetech Ltd., Narashino-shi,
Japan
Norifumi Isu LIXIL Corporation
Mikimasa Iwata Central Research Institute of Electric Power
Industry
Hiroshi Jinnai Institute for Materials Chemistry and
Engineering (IMCE), Kyushu University
Jinting Jiu Senju Metal Industry Co., Ltd., Tokyo, Japan;
Osaka University, Osaka, Japan
xviii LIST OF CONTRIBUTORS
Norihiko Kaga Central Research, Bridgestone Corporation
Kotaro Kajikawa Tokyo Institute of Technology
Toshio Kakui Chemicals Division, Lion Corporation
Hidehiro Kamiya Institute of Symbiotic Science and
Technology, Tokyo University of Agriculture & Technology
Kenji Kaneko Department of Material Science and
Engineering, Kyushu University
Kiyoshi Kanie Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University
Junya Kano Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University
Hitoshi Kasai Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University
Tomoko Kasuga Electrotechnology Applications R&D
Center, Chubu Electric Power Co., Inc.
Tsutomu Katamoto Creative R&D Center, Toda Kogyo
Corporation
Shinji Katsura Faculty of Engineering, Gunma University
Masayoshi Kawahara Hosokawa Powder Technology
Research Institute
Yoshiaki Kawashima Department of Pharmaceutical
Engineering School of Pharmacy, Aichi Gakuin University,
Nagoya, Japan; Gifu Pharmaceutical University,
Gifu, Japan
Yoshiaki Kinemuchi National Institute of Advanced
Industrial Science and Technology (AIST)
Soshu Kirihara Joining and Welding Research Institute,
Osaka University
Masanori Koshimizu Tohoku University, Sendai, Japan
Akihiko Kondo Kobe University, Kobe, Japan; Department
of Chemical Science and Engineering, Kobe University
Akira Kondo Joining and Welding Research Institute, Osaka
University, Osaka, Japan
Katsuyoshi Kondou Joining and Welding Research Institute,
Osaka University
Takahiro Kozawa Osaka University, Osaka, Japan
Kazue Kurihara Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University
Shun’ichi Kuroda The Institute of Scientific and Industrial
Research, Osaka University
Ken-ichi Kurumada Graduate School of Environment &
Information Sciences, Yokohama National University
Hiroaki Kuwahara Corporate Strategy Division, Teijin Ltd.
Chunliang Li National Institute of Advanced Industrial
Science and Technology (AIST)
Hisao Makino Energy Engineering Research Laboratory,
Central Research Institute of Electric Power Industry,
Yokosuka-shi, Japan
Shoji Maruo Yokoyama National University, Yokohama,
Japan
Hiroaki Masuda Department of Chemical Engineering,
Kyoto University
Yoshitake Masuda National Institute of Advanced
Industrial Science and Technology (AIST), Nagoya, Japan
Motohide Matsuda Graduate School of Environmental
Science, Okayama University
Shuji Matsusaka Department of Chemical Engineering,
Kyoto University
Tatsushi Matsuyama Faculty of Engineering,
Soka University
Reiji Mezaki Nanomateria Center, Institute of Innovation,
The University of Tokyo
Takeshi Mikayama Kohno Patent Office
Minoru Miyahara Department of Chemical Engineering,
Kyoto University
Kiyotomi Miyajima Central Research Institute of Electric
Power Industry
Yoshinari Miyamoto Joining and Welding Research
Institute, Osaka University
Masaru Miyayama Research Center for Advanced Science
and Technology, The University of Tokyo
Hideki T. Miyazaki National Institute for Materials Science
Hidetoshi Mori School of Engineering, Aichi University of
Technology
Tsutomu Morimoto Japan Chemical Innovation Institute
Kenta Morita Kobe University, Kobe, Japan
Hirokazu Munakata Tokyo Metropolitan University
Hiroyuki Muto Toyohashi University of Technology,
Toyohashi, Japan
Muhammad M. Munir Department of Chemical
Engineering, Hiroshima University
Atsushi Muramatsu Institute of Multidisciplinary Research
for Advanced Materials, Tohoku University
Norio Murase National Institute of Advanced Industrial
Science and Technology (AIST)
Toshihiko Myojo Institute of Industrial Ecological Sciences,
University of Occupational and Environmental Health
Makio Naito Joining and Welding Research Institute, Osaka
University, Osaka, Japan
Noriyuki Nakajima Institute of Nanotechnology,
Kurimoto, Ltd.
Masami Nakamoto Osaka Municipal Technical Research
Institute
Masaharu Nakamura Toyo Tanso Co., Ltd.
Keitaro Nakamura Nisshin Seifun Group Inc.
Hachiro Nakanishi Institute of Multidisciplinary Research
for Advanced Materials, Tohoku University
Norikazu Namiki Kyoritsu Gokin Co., Ltd.
Yuya Nishimura Kobe University, Kobe, Japan
Naoki Noda Central Research Institute of Electric Power
Industry, Yokosuka-shi, Japan
Kiyoshi Nogi Joining and Welding Research Institute, Osaka
University
 LIST OF CONTRIBUTORS
Yuji Noguchi The University of Tokyo
Junichi Noma Sumiyoshi Factory, Kurimoto Ltd.,
Osaka, Japan
Toshiyuki Nomura Department of Chemical Engineering,
Osaka Prefecture University
Takashi Ogi Department of Chemical Engineering,
Hiroshima University
Chiaki Ogino Kobe University, Kobe, Japan
Satoshi Ohara Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University; Osaka University,
Osaka, Japan
Akira Ohtomo Institute for Materials Research, Tohoku
University
Hidetoshi Oikawa Institute of Multidisciplinary Research
for Advanced Materials, Tohoku University
Tomoichiro Okamoto Nagaoka University of Technology
Tatsuya Okubo The University of Tokyo
Kikuo Okuyama Graduate School of Engineering,
Hiroshima University
Minoru Osada National Institute for Materials Science
Yoshio Otani Graduate School of Natural Science and
Techonology, Kanazawa University
Yasufumi Otsubo Graduate School of Engineering, Chiba
University
Masashi Otsuki Central Research, Bridgestone Corporation
Fumio Saito Institute of Multidisciplinary Research for
Advanced Materials (IMRAM), Tohoku University
Shuji Sakaguchi National Institute of Advanced Industrial
Science and Technology (AIST)
Yoshio Sakka Nano Ceramics Center, National Institute for
Materials Science, Tsukuba, Japan
Shuji Sasabe Powder Technology Research Institute,
Hosokawa Micron Corporation
Aiko Sasai Hosokawa Micron Corporation, Osaka, Japan
Takayoshi Sasaki International Center for Materials
Nanoarchitectonics, National Institute for Materials
Science
Takafumi Sasaki Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University
Norifusa Satoh Department of Chemistry,
Keio University
Tetsuya Senda National Maritime Research Institute
Gimyeong Seong Tohoku University, Sendai, Japan
Yuichi Setsuhara Joining and Welding Research Institute,
Osaka University
Haruhide Shikano Ibiden Co., Ltd.
Manabu Shimada Graduate School of Engineering,
Hiroshima University
Akihiko Suda Toyota Central R&D Labs., Inc.
Katsuaki Suganuma Senju Metal Industry Co., Ltd., Tokyo,
Japan; Osaka University, Osaka, Japan
xix
Hisao Suzuki Graduate School of Science and Technology,
Shizuoka University
Michitaka Suzuki Department of Mechanical and System
Engineering, University of Hyogo
Takahiro Suzuki Kobe University, Kobe, Japan
Takahiro Takada Murata Manufacturing Co., Ltd.
Chisato Takahashi Aichi Gakuin University, Nagoya, Japan
Chika Takai Ceramics Research Laboratory, Nagoya
Institute of Technology
Seiichi Takami Nagoya University, Nagoya, Japan
Hirofumi Takase R&D Division, Takiron Co., Ltd.
Kenji Takebayashi Powder Technology Research Institute,
Hosokawa Micron Corporation
Hirofumi Takeuchi Laboratory of Phamaceutical
Engineering, Gifu Pharmaceutical University
Junichi Tatami Graduate School of Environment &
Information Sciences, Yokohama National University
Masahiro Tatsumisago Osaka Prefecture University,
Osaka, Japan
Kenji Toda Graduate School of Science and Technology,
Niigata University
Takanari Togashi Yamagata University, Yamagata, Japan
Tetsuro Tojo Toyo Tanso Co., Ltd.
Takaaki Tomai Tohoku University, Sendai, Japan
Hiroyuki Tsujimoto Hosokawa Micron Corporation; Aichi
Gakuin University, Nagoya, Japan
Takao Tsukada Tohoku University, Sendai, Japan
Yusuke Tsukada Hosokawa Micron Corporation,
Osaka, Japan
Tetsuo Uchikoshi Nano Ceramics Center, National Institute
for Materials Science
Keizo Uematsu Nagaoka University of Technology
Minoru Ueshima Senju Metal Industry Co., Ltd.,
Tokyo, Japan
Mitsuo Umetsu Graduate School of Engineering,
Tohoku University
Arimitsu Usuki Toyota Central R&D Labs., Inc.
Fumihiro Wakai Materials & Structures Laboratory, Tokyo
Institute of Technology
Xing Wei Chang’an University, ShaanXi, China
Akimasa Yamaguchi Energy Engineering Research
Laboratory, Central Research Institute of Electric
Power Industry
Yukio Yamaguchi Department of Chemical System
Engineering, The University of Tokyo
Hiromitsu Yamamoto University School of Pharmacy, Aichi
Gakuin University, Nagoya, Japan
Kenji Yamamoto International Clinical Research Center,
International Medical Center of Japan
Kimihisa Yamamoto Department of Chemistry,
Keio University
xx LIST OF CONTRIBUTORS

Atsushi Yamamoto National Institute of Advanced
Industrial Science and Technology (AIST)
Masatomo Yashima Department of Materials Science and
Engineering, Tokyo Institute of Technology
Akira Yoko Tohoku University, Sendai, Japan
Atsushi Yokoi Toyohashi University of Technology,
Toyohashi, Japan
Toyokazu Yokoyama Hosokawa Micron Corporation,
Osaka, Japan
Susumu Yonezawa Faculty of Engineering,
University of Fukui
Tetsu Yonezawa Hokkaido University, Sapporo, Japan
Qiwu Zhang Institute of Multidisciplinary Research for
Advanced Materials, Tohoku University
 Preface
A “powder,” which is an assemblage of small solid
particles, exhibits very unique behavior. For example,
depending on the circumstances, a powder can behave
like a gas, a liquid, or a solid. Furthermore, because of the
larger specific surface area relative to a bulk material,
powders can have very unique properties. This is espe-
cially true for “nanoparticles.” The unique behavior and
properties of particle and powder give them a wide range
of industrial applications that makes them ubiquitous
in our daily lives and makes them promising materials
for creating scientific and technical innovations in the
future.
Although powders have long been important mate-
rials in our daily lives, the academic study of particle and
powder technology has a relatively short history. The
Society of Powder Technology, Japan (SPTJ) was estab-
lished in 1956 with the mission to foster interactions
between society members to enable and facilitate ad-
vances in powder technology as well as in the powder
and powder technology industries. I am serving as the
12th President (2015e18) of the society. SPTJ celebrated
its 60th anniversary in 2016. Now, in collaboration with
academia and industry, we are taking the first steps for
the next 60 years.
Mr. Masuo Hosokawa, the chief editor of the first
edition of this Handbook, was a pioneer in this industry.
When he was the President of Hosokawa Micron Corp.,
he founded Hosokawa Powder Technology Foundation
in 1991 to contribute to advancement of powder tech-
nology on a worldwide scale and published the first
issue of “KONA Powder and Particle Journal” on pow-
der technology in 1983. Since then, KONA has been
published annually and distributed worldwide.
Mr. Hosokawa proposed the concept of “nanoparticle
technology” long before past US President Bill Clinton’s
National Nanotechnology Initiative in 2000. One of the
activities of the Foundation was to publish the Nano-
particle Technology Handbook in Japanese in 2006,
xxi
which was translated into English and published as the
first edition of this Handbook in 2007. Nanoparticle
technology advanced considerably after 2007, prompting
Mr. Hosokawa to start preparing an updated second
edition of the Handbook. He unfortunately passed away
on March 31, 2010, before the second edition was pub-
lished in 2012.
Because nanoparticle technology has rapidly
advanced since 2012, it has been applied more broadly
and in new areas. Mr. Yoshio Hosokawa, the second
President of Hosokawa Powder Technology Foundation
and President of Hosokawa Micron Corporation,
decided to publish a third edition of the Handbook. In
this third edition, the applications section of the Hand-
book has been updated to include the most recent
advances in nanoparticle technology. Nineteen chapters
have been added. The 79 chapters in the applications
section are organized into 4 categories: Category A:
medical, cosmetics, and biologicals; Category B: energy,
batteries, and environmental; Category C: electronic and
magnetic materials, memory, light-emitting materials,
and displays; and Category D: synthesis, dispersion, and
processing. I hope the updated applications section will
give readers state-of-the-art information and knowledge
to develop their own innovative technology and new
products, further enhancing our understanding of the
fundamentals of nanoparticle technology.
Finally, I am grateful to the Hosokawa Powder Tech-
nology Foundation for its support and to all editors and
authors for their great contributions to the third edition.
I especially express my appreciation to the first chief
editor, Mr. Masuo Hosokawa, for his outstanding
contributions to the development and advancement of
nanoparticle technology.
Dr. Makio Naito
Professor, Osaka University
President, The Society of Powder Technology, Japan
This page intentionally left blank
 Preface to the Second Edition
The Nanoparticle Technology Handbook was the first
handbook to be published in the field of nanoparticle
technology around 5 years ago. Since then, nanoparticle
technology has further advanced and been applied in
many new applications. In response to the demand, it
was decided to publish a second edition of the Hand-
book. The editors are very pleased to see the advance-
ment of this technology and to be engaged in the
publication of the second edition.
However, we regret to inform our readers of the sad
news that the chief editor of the Handbook’s first edition,
Mr. Masuo Hosokawa, passed away on March 31, 2010
after a short stay in the hospital, at the age of 85. In fact, he
initiated the idea of publishing a handbook for nano-
particle technology. He had been greatly interested in
particles and fine powders for many years and had
developed various advanced machines such as a unique
fine grinding mill and an air classifier in the 1950s, which
led to many awards for him, including two decorations
from the Japanese government.
His enthusiasm and desire to seek extremely small
particles and their innovative properties resulted in the
invention of the concepts of MechanoFusion and Mech-
anoChemical Bonding technologies, which are in prin-
ciple based on the mechanical activation of fine particles
for particle bonding and surface modification to create
new functional materials. Since the 1980s, he also intro-
duced some useful technologies to generate nano-
particles by the bottom-up method and proposed
nanoparticle technology long before the former President
Bill Clinton’s National Nanotechnology Initiative in 2000.
Starting with the evaporation method to make metal
nanoparticles and then moving to use chemical vapor
deposition methods to create composite nanoparticles, he
succeeded in bringing new systems for nanoparticle
generation to the commercial market. In addition, in 1991
he founded the Hosokawa Powder Technology Founda-
tion and in 1983 published the first issue of the English
technical journal, “KONA Powder and Particle Journal.”
xxiii
In the meantime, publication of the first edition of the
Handbook, Nanoparticle Technology had advanced and
been employed in various applications. In the second
edition, 16 new articles have been added in the applica-
tion section for subjects related to polymer/filler com-
posites; electronic devices such as displays, sensors, and
memories; batteries/fuel cells; cosmetics; drug delivery
system and biomaterials for medical devices; color ma-
terials; environmental protections; etc. During this period
of time, there were some epoch-making incidents in the
commercialization of some technologies. Fuel cells have
been introduced for power generation and heat supply in
residential and commercial uses, and lithium ion batte-
ries have begun to be adopted by electric and hybrid
vehicles for transportation use. Additionally, the nuclear
power plant accident caused by the big earthquake and
tsunami in the Tohoku area of Japan in March 2011 had an
enormous impact on power supply and environmental
protection issues related to the lifestyle and way of
thinking of the country’s population. From these view-
points, nanoparticles have great potential to contribute to
the establishment of a sustainable living environment for
human beings by making use of their high functionality
and excellent performance.
The editors are grateful to the Hosokawa Powder
Technology Foundation for its support and to all the
contributors for their cooperation and wish that the sec-
ond edition of the Handbook would be helpful to readers
in understanding the basics of nanoparticles and to pro-
vide hints to their application.
Dr. Kiyoshi Nogi
Emeritus Professor, Osaka University
Dr. Makio Naito
Professor, Osaka University
Dr. Toyokazu Yokoyama
Fellow, Hosokawa Micron Corporation
This page intentionally left blank
 Preface to the First Edition
During the last few years, the term “Nanotechnology”
is increasingly employed to describe the process tech-
nologies and analytical techniques for material in the
ultrafine range of the order of a millionth of a millimeter.
Because they are sure to take an important part in
shaping the 21st century, great attention is being paid to
these technologies, with many countries actively
involved in R&D. As the link between these new tech-
nologies and the established particle and powder tech-
nology, “Nanoparticle technology” includes the concepts
and know-how to create, process, and apply the ultrafine
particles in the nanometer range and is one of the key
technologies for new material developments.
The technologies that are used to treat powders
arrived with mankind, and countless inventions and
improvements have been made during history. These
particles and powders have very different properties
from the bulk materials from which they are derived.
There are applications to be seen in all industrial areas.
The history of the academic study of particle and
powder technology is not so old. The first related society,
Chubu Association of Powder Technology, was founded
in Japan in 1956. It later became the Society of Powder
Technology, Japan, and celebrated its 50th anniversary in
2006. Correspondingly, the Hosokawa Micromeritics
Laboratory was established in 1956 and published its
50th anniversary issue of the annual technical journal
Funsai (The Micromeritics) also in 2006.
Throughout this period a key issue has been to reduce
the size of particles, to maximize their functional prop-
erties, and thus to find new applications and create new
products with superior performance. Great interest has
been shown in submicron and even finer particles.
Research and development has advanced at a rapid rate
due to the cooperation of academia and industry in many
areas, starting with particle creation and particle size
analysis, expanding to encompass particle design, and
processing in the micron- and nanometer-size ranges.
Japan has been at the forefront in the conception and
development of these technologies.
xxv
Due to this interest, the second World Congress in
Particle Technology (WCPT) was held in Kyoto in 1990.
Eight years later at the third WCPT in Brighton, the
author highlighted the importance of these ultrafine
particles to an audience of about 700 researchers and
engineers during the opening speech. Hosokawa Micron
Corp., which celebrated its 90th anniversary in 2006, has
been engaged in R&D on particle creation by the build-up
(bottom-up) method in both gaseous and liquid phases for
more than 20 years. The result of this research, as com-
bined with that on conventional grinding (top-down)
processes, has led to the establishment of a mass pro-
duction system for nanoparticles and to the foundation
of a business based on application of these nanoparticles
to functional materials.
Founded 15 years ago, the Hosokawa Powder Tech-
nology Foundation holds an annual symposium on
powder technology for the exchange of information on
particle engineering and powder technology. Since 2001,
the main topics of the symposium have, in response to
the requirements of industry, been related to nano-
particles and nanostructure control. The number of grant
proposals received by our Foundation for research into
nanoparticles continues to increase, and currently 40% of
some 120 proposals relate to nanoparticles.
As a result of this trend, we published 3 years ago, the
book Nanoparticle Technology to promote nanoparticle-
related engineering by documenting the technologies
constituting in this field. That book was very well
received, and to continue contributing to the common
welfare through the promotion of powder technology,
we decided to systematically update Nanoparticle Tech-
nology, adding further developments and many exam-
ples of applications. The results of that effort were
published in the form of a handbook, first in Japanese in
the memorable year 2006, and with the present volume,
in English this year. Although R&D in nanoparticle
technology advances rapidly, and the contents of the
future editions are sure to change, we hope the present
collation of state-of-the-art knowledge and information
xxvi PREFACE TO THE FIRST EDITION

will be of assistance to the researchers, engineers, and Masuo Hosokawa

others interested in this vitally important field.
In closing, I express my sincere sense of gratitude
to the authors, the editing committee, and the pub-
lishing staff for their great efforts in spite of their busy
schedules.
President, Hosokawa Micron Corporation
Chairman, Hosokawa Powder Technology
Research Institute
President, Hosokawa Powder Technology Foundation
FUNDAMENTALS
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 C H A P T E R
1
Basic Properties and Measuring Methods of
Nanoparticles
1.1 SIZE EFFECT AND PROPERTIES OF
NANOPARTICLES
Toyokazu Yokoyama
1.1.1 Definition of Nanoparticles
The nanoparticles are ultrafine particles in the size of
nanometer order. “Nano” is a prefix denoting the minus
ninth power of ten, namely one billionth. Here it means
nanometer (nm) applied for the length. One nm is
extremely small length corresponding to one billionth
of 1 m, one millionth of 1 mm, or one thousandth
of 1 mm.
The definition of nanoparticles differs depending on
the materials, fields, and applications concerned. In the
narrower sense, they are regarded as the particles
smaller than 10e20 nm, where the physical properties
of solid materials themselves would drastically change.
On the other hand, the particles in the three digit range
of nanometer from 1 nm to 1 mm could be called as nano-
particles. In many cases, the particles from 1 to 100 nm
are generally called as nanoparticles, but here they will
be regarded as the particles smaller than those called
conventionally “submicron particles,” and concretely
less than the wavelength of visible light (its lower limit
is about 400 nm) as a measure, which need to be treated
differently from the submicron particles. Figs. 1.1.1 and
1.1.2 show examples of nanoparticles and the related
phenomena and an example of electron microscope pic-
ture of gold colloid nanoparticles made by liquid-phase
chemical method [1], respectively.
Nanoparticle Technology Handbook, Third Edition
https://doi.org/10.1016/B978-0-444-64110-6.00001-9
1.1.2 Features of Nanoparticles
1.1.2.1 Activation of Particle Surface
All the solid particles consist of the atoms or the mol-
ecules. As they are micronized, they tend to be affected
by the behavior of atoms or the molecules themselves
and to show different properties from those of the
bulk solid of the same material. It is attributable to the
change of the bonding state of the atoms or the mole-
cules constructing the particles. For example, as shown
in Fig. 1.1.3, if a cube with a side length of 1 cm is
divided into a cube of 1 mm, the particle number in-
creases to 1012 and being divided into the one of
10 nm, then it amounts to 1018, where the fraction of
the atoms or the molecules located at the surface on
the particles plays a great role because they are more
active than those inside the solid particles because of
the free hand, which leads to easy bonding with the con-
tacting materials and causes various changes in particle
properties.
The diameter of the smallest hydrogen atom is
0.074 nm, and that of the relatively large lead atom
(atomic number is 82) is 0.35 nm. From these sizes, it
is estimated that the particle with a size of 2 nm con-
sists of only several tens to thousands atoms. When
the particle is constructed by larger molecules, the
number decreases furthermore. Table 1.1.1 shows the
relationship between the particle size and the fraction
of number of atoms located at the particle surface
with an assumption of atomic distance of 0.2 nm [2].
It is indicated that the fraction of surface atoms of a
3 © 2018, 2012, 2007 Elsevier B.V. All rights reserved.
4 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES

0.01nm 0.1nm (1A) 1 nm 10nm 100nm 1 m 10 m

Wave length X-ray Ultraviolet Visible light Infrared

Pore Micropore Mesopore Macropore

Atomic radius Hydrogen Lead

Gold, silver colloid Ferrite Atomized iron powder

Metal
Magnetic bacteria Blue powder

Inorganic Colloidal silica

TiO2 (catalyst) TiO2 (pigment)

FCM nanocomposite oxide particles

Colloidal CaCO3 Fine ground CaCO3

Fullerene Nanodiamond Carbon black Graphite

Carbon nanotube (diameter)

Organic PMMA nanoparticles

PLGA nanospheres Toner

Liposome Starch

Bio, pharmaceutical DNA dia Red blood cell

Virus Mitochondria Biologic cell

Dry Powder Inhalation

Aerosol Cigarette smoke

FCM : Flash Creation Method

PLGA : Poly-lactic-glycolic acid (Spherical crystallization method)
PMMA : Polymethylmethacrylate

FIGURE 1.1.1 Examples of nanoparticles and related phenomena.

20 mm cubic particle is only 0.006%, but it increases to

0.6% for a 200 nm particle and then it is estimated
almost half of the atoms are situated at the surface of
a 2 nm particle.

1.1.2.2 Increase of Surface Area

On the other hand, as the micronization of solid par-
ticles, the specific surface area increases generally in
reversal proportion to the particle size. In the above-
mentioned case, when the particle of 1 cm is micronized
to 1 mm and 10 nm, the specific surface area becomes ten
thousand times and million times, respectively. As the
increase in the specific surface area directly influences
FIGURE 1.1.2 Transmission electron microscope picture of gold such properties such as the solution and reaction rates
nanoparticles. of the particles, it is one of major reasons for the unique
 1.1 SIZE EFFECT AND PROPERTIES OF NANOPARTICLES
1 cm
(1 piece)
Sw = 6 cm2/g
1 m
(1012 pieces)
Sw = 6 m2/g
10nm
(1018 pieces)
Sw = 600 m2/g
FIGURE 1.1.3 Change of specific surface area by miniaturization
of a solid cube assuming the solid density of 1 g/cm3.
properties of the nanoparticles different from the bulk
material together with the change in the surface proper-
ties of the particles itself.
1.1.3 Evaluation of Size of Nanoparticles
To elucidate the change in properties and characteris-
tics of nanoparticles with the particle size, it is essential
first of all to measure the size of the nanoparticles accu-
rately. The most basic method to measure the size of
nanoparticles is the size analysis from the picture image
using the transmission electron microscope (TEM),
which could also give the particle size distribution. For
this analysis, preparation of the well-dispersed particles
on the sample mount is the key issue. The grain size of
the particles can be obtained from peak width at half
5
height in the X-ray diffraction (XRD) analysis and it is
regarded as an average primary particle size of particles.
Meanwhile, the laser diffraction and scattering
method, which is popular for the size analysis of
micron-sized particles, would hardly measure the parti-
cle size of individual nanoparticles but that of the
agglomerated particles. The photon correlation method
often used for the particle analysis in the nanosized range
might not give accurate results in many cases, when the
particle size distribution is wide. Then the (Brunauere
EmmetteTeller) BET-specific surface measurement based
on the gas adsorption is often applied as a simple method
to evaluate the size of nanosized primary particles.
By this method, it is possible to estimate the particle
size from the specific surface area under the assumption
of spherical particle shape. This equivalent particle size
based on the specific surface area is useful for the eval-
uation of nanoparticle size, though it may differ from
the particle size observed by the electron microscope
depending on the surface state and the inner structure
of the particles.
1.1.4 Properties of Nanoparticle and Size Effect
As mentioned above, with the decreasing particle
size, the solid particles generally tend to show different
properties from the bulk material and even the physical
properties such as melting point and dielectric constant
themselves that have been considered as specific proper-
ties may change, when the particles become in several
nanometer size. These changes in the fundamental prop-
erties with the particle size are called “size effect” in a
narrower sense.
On the contrary, in a broader sense, it could also
include the change in the various characteristics and be-
haviors of particles and powders with the particle size.
The nanoparticles have various unique features in the
morphological/structural properties, thermal proper-
ties, electromagnetic properties, optical properties, and
mechanical properties as described briefly in the
following:
1.1.4.1 Morphological/Structural Properties
The ultrafine size of the nanoparticles itself is one of
useful functions. For example, the finer particles are
apt to be absorbed more easily through the biological
membrane. It is known as the enhanced permeation
and retention effect [3] that the particles having a parti-
cle size from about 50 to 100 nm, which would not be
transferred to the normal cells through the vascular
wall, could be delivered selectively to a certain affected
cells because of the enlarged cell gap of this part.
As mentioned above, the large specific surface area of
the nanoparticles is an important property to the
6 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES

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)

1 m ¼ 1  106 mm ¼ 1  109 nm.

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) (-)

performance of ceramic materials [6].

1.008
1.1.4.3 Electromagnetic Properties
1.006 The nanoparticles are used as the raw material for a
number of electronic devices. The electric properties
1.004 and particle size of these nanoparticles play a great
role for the improvement of the product performance
1.002 [7]. As an example, there is a strong demand for the ma-
terials with a high dielectric constant to develop small
1.000 and thin electronic devices. For this purpose, it has
0.0 0.2 0.4 0.6 0.8 1.0 1.2 been confirmed by the XRD analysis, for instance, that
Particle size ( m) the dielectric constant of PbTiO3 tends to increase
FIGURE 1.1.4 Relationship between particle size and tetragonal considerably as the particles become smaller than about
degree (c/a axis ratio) of BaTiO3 powder. 20 nm. Meanwhile, it is also known that when the
 1.1 SIZE EFFECT AND PROPERTIES OF NANOPARTICLES
dielectric constant is measured with a pellet prepared
by pressing these nanoparticles, it shows a peak with
the raw material around 100 nm and decreases with
the decreasing particle size, which is attributable
to the influence of the grain boundary and void in the
pellet [8].
On the other hand, the minimum particle size to keep
the ferroelectric property (critical size) differs depending
on the kind and composition of the materials. According
to the literature [9] summarizing the data of various kinds
of materials, it varies from 7 nm for PbTiO3 to 317 nm for
BaePbeTi compounds. The Curie point defined as the
point changing from the ferroelectric material to the para-
electric phase of PbTiO3 reduces drastically with the
decreasing particle size below 20e30 nm as shown in
Fig. 1.1.5. As for the Curie point, some equations have
been proposed for its estimation [10].
As for the magnetic property, ferromagnetic fine par-
ticles have a single magnetic domain structure as they
become very small as in the order less than about 1 mm
and show superparamagnetic property, when they get
further finer. In this case, although the individual parti-
cles are ferromagnetic with the single magnetic domain
structure, the particles collectively behave as a paramag-
netic. It is magnetized as a whole in the same direction of
the external magnetic field but the magnetization disap-
pears by the thermal fluctuation, when the external mag-
netic field is taken away. The time for disappearing of
magnetization depends on the particle size, namely the
magnetization of the material responds promptly with
500
Curie point (°C)
450
400
0 50
Particle size (nm)
FIGURE 1.1.5 Change of Curie point PbTiO3 with its particle size.
7
the external magnetic field as a paramagnetic when
the particles are small enough, but it decreases gradually
as the particle size becomes larger. As a result of such
change in the electromagnetic properties of nanopar-
ticles, it is known, for instance, that the gold which is a
stable substance as a bulk shows unique catalytic char-
acteristics as nanoparticles [11].
1.1.4.4 Optical Properties
As the size of particles becomes in the several nano-
meters range, they absorb the light with a specific wave-
length as the plasmon absorption [12] caused by the
plasma oscillation of the electrons and the transmitted
light with different color depending on the kind of metal
and particle size that is obtained [13].
Fig. 1.1.6 shows the plasmon absorption of silver
nanoparticles, where the spectral absorption intensity
differs depending on the particle size, which is deter-
mined by the concentration of the surfactant used for
their preparation [14]. In case of gold nanoparticles, it
is reported that the maximum light absorption wave-
length is 525 nm for the particles of 15 nm but it is
enlarged by about 50 nm for 45 nm particles. In this
way, these gold and silver nanoparticles show the color
phenomena with splendid tinting strength, color satura-
tion, and transparency compared with the conventional
pigments for the paint in the submicron size and the
tinting strength per unit volume of silver nanoparticles
becomes about 100 times higher than that of organic pig-
ments. Furthermore, because the nanoparticles are
smaller than the wavelength of visible light and the light
scattering by the particles becomes negligible, higher
transparency can be obtained with the nanoparticles
than the conventional pigment.
On the other hand, concerning the light emitting per-
formance, the indirect transition type substances such as
silicon and germanium, which do not emit the light as
bulk material, give high light emitting efficiency as the
direct transition type substances as a result of quantum
effect, when the particle size is reduced down to several
nanometers.
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
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
100
is seen that it is extended several to several thousand
times from the original size at the elevated temperature
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
1.2 PARTICLE SIZE
Hiroaki Masuda
Particle size is the most important information in
practical applications of powder particles. Usually, pow-
der is constituted by particles of various sizes and, there-
fore, it is necessary to obtain not only the mean particle
size but also the size distribution for the characteriza-
tion. Recently, the methods for particle size analysis
have been greatly developed. Especially, the analyzers
with prominent characteristics such as rapid response,
high repeatability, and covering wide range of particle
size are developed as in the case of laser scattering
and diffraction method.
1.2.1 Definition of Particle Size
A particle is usually three dimensional and it may
take various shapes. “Particle size” is a term to represent
the three-dimensional particle in one-dimensional scalar
value. The size of any spherical particle can be repre-
sented by its diameter with no ambiguity. For a particle
with irregular shape, the size is represented by a
geometrically obtained one-dimensional scalar value,
geometric size, or an equivalent size in relation to prac-
tical methods of particle size measurements.
The geometric size is obtained through three-
dimensional measurements of a particle to get its width,
thickness, and length and then calculating one-
dimensional value such as arithmetic mean. In practice,
however, one-dimensional value obtained based on the
two-dimensional-projected silhouette is utilized such
as a diameter of a circle having the same area as the
projected area. Statistical diameter based on one-
dimensional measurement is also well applied in prac-
tice such as a Feret diameter, which is determined as
the distance between pairs of parallel tangents to the
particle silhouette in some fixed direction.
As for the equivalent size in relation to practical
methods of particle size measurements, there are many
different definitions such as sieve diameter based on
sieving, equivalent light-scattering diameter, Stokes
diameter based on particle motion in fluid, and the
equivalent diameter based on the Brownian motion.
These equivalent diameters give, usually, different
values depending on the measurement principles unless
the particles are spherical. Specific surface area of pow-
der or equivalent-specific surface diameter is well
applied to the evaluation of nanopowders. However,
in this case, the particles should not be porous. Besides,
the method cannot be applied to get particle size distri-
bution [1,2].
9
1.2.2 Measuring Methods
As discussed in the preceding section, geometric size
is obtained in the microscopic measurements, and equiv-
alent size is applied in the measurements by practically
available instruments such as those based on laser
diffraction and scattering, dynamic light scattering, dif-
ferential mobility analysis, and so on. The equivalent
size obtained by these instruments is practical but does
not give a value directly connected to the unit of length.
The items discussed in the ISO relating to the particle
size measurements are as follows:
1. ISO 13317: Determination of particle size
distribution by gravitational liquid sedimentation
methods (this ISO corresponds to JIS Z 8820).
2. ISO 13318: Determination of particle size
distribution by centrifugal liquid sedimentation
methods (JIS Z 8823).
3. ISO 13319: Determination of particle size
distributiondElectrical-sensing zone method.
4. ISO 13320: Particle size analysisdLaser diffraction
methods (JIS Z 8825).
5. ISO 13321: Particle size analysisdPhoton correlation
spectroscopy (JIS Z 8826).
6. ISO 13322: Particle size analysisdImage analysis
methods.
7. ISO 13323: Determination of particle size
distributiondSingle-particle light interaction
methods.
8. Particle size analysisdDynamic light scattering
(DLS).
9. Determination of particle size
distributiondDifferential electrical mobility
analysis for aerosol particles (DMA).
10. Particle characterization by acoustic
methodsdUltrasonic attenuation spectroscopy.
11. Focused beam techniques.
Some of these methods can be applied to the measure-
ments of nanoparticles. Japanese industrial standard
will also cover the methods in keeping pace with ISO.
1.2.3 Key Points in the
MeasurementsdReference Particles for
Calibration
Important point is that these particle sizes take
different values depending on the principles of the mea-
surements. The particles measured based on these
different principles should, at least, show the same
diameter as far as they are spherical particles. Therefore,
we are now preparing spherical reference particles [3,4].
10 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES
Various monodisperse spherical particles are available
from The Association of Powder Process Industry and
Engineering (APPIE, Japan) [5,6]. However, they are
not suitable for the calibration of such equipment for
the measurement of particle size distribution for the
following reasons [7]:
1. Even if the principle is the same, different equipment
has different feeding system, different transportation
system, and different dispersion system. Therefore,
particle fraction detected in a certain size interval may
differ depending on the equipment through size-
dependent deposition, imperfect dispersion, and
size-dependent segregation.
2. There may be various calculation software for the
transformation of the measured data into particle size
distribution.
3. Number of particles sampled, sample size, in the
measurement may differ for each measuring system.
If the sample size is not large enough, both the mean
diameter and the size distribution cannot be correctly
obtained [8,9].
In the ISO 13320 (1999), laser diffraction, it is recom-
mended that equipment should be tested using
polydisperse reference particles whose particle size is
distributed over 1 decade. Reference particles for
covering nano range is not yet available. However,
MBP 1e10 for 1e10 mm and MBP 10e100 for 10e100
mm, spherical transparent particles, are available from
APPIE. Particle size analyzers should at least be cali-
brated by the use of these spherical reference particles.
Through the calibration using the reference particles,
equivalent size obtained by each instrument is, for the
first time, connected to the unit of length. In other
words, measured value obtained by the measurement
other than microscopy can get traceability only through
the calibration with reference particles. It is very tedious
1.3 PARTICLE SHAPE
Michitaka Suzuki
The fundamental particle properties such as particle
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-
surement equipment based on various principles
can be marketed, and it is easy to measure particle
diameter distribution. But a particle shape analyzer
to measure a great number of particles by electron mi-
croscopy. Therefore, in practice, sedimentation method,
standard sieves, and electrical sensing zone method
are admitted as definitive methods to the certification
of reference particles [5]. However, this is only for the
sake of convenience.
The purpose for using the reference particles is listed
as follows [10]:
1. Calibration of equipment for the particle size
measurement,
2. Verification of measurement procedure,
3. Establishing traceability of measurement,
4. Determination of the uncertainty of the obtained
results.
For representing the particle size distribution in
mathematical equation, lognormal distribution and
RosineRammler distribution can be well applied and
special graph papers are available for them.
References
[1] K. Okuyama, H. Masuda, S. Morooka, Biryuushi Kougaku e Fine
Particle Technology, Ohmsha, Tokyo, 1992, p. 3.
[2] Society of Powder Technology, Japan (Ed.), Terminology Dictio-
nary of Powder Technology, second ed., Nikkan Kogyo Co.,
2000, p. 223.
[3] Standard Powders Committee, APPIE, Powder Sci. Eng. 35 (6)
(2003) 75e79.
[4] H. Yoshida, H. Masuda, K. Fukui, Y. Tokunaga, Adv. Powder
Technol. 12 (2001) 79e94.
[5] H. Masuda, Powder Sci. Eng. 34 (5) (2002) 65e72.
[6] A. Itoh, Powder Sci. Eng. 37 (7) (2005) 72e77.
[7] Y. Mori, H. Yoshida, H. Masuda, Particulate Systems Analysis
2005, Stratford-upon-Avon, UK, 2005.
[8] H. Masuda, K. Iinoya, J. Chem. Eng. Jpn. 4 (1971) 60e66.
[9] H. Masuda, K. Gotoh, Adv. Powder Technol. 10 (1999) 159e173.
[10] ISO Guide35, Certification of Reference Materials e General and
Statistical Principles, 1989, p. 25.
for nanoparticle cannot be easily found, and the
shape index of nanoparticles can be calculated from
particle images observed using various types of
microscopes.
1.3.1 Two-Dimensional Particle Projection
Image
To measure the particle shape, the outline of particle
shape of two-dimensional projection images captured
 1.3 PARTICLE SHAPE
from microscopic photograph is analyzed. Because the
diameter of a nanoparticle is smaller than the wavelength
of visible light, a nanosize particle cannot be observed by
an optical microscope. Usually, the two-dimensional pro-
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
by image analysis software. For the shape analysis of fine
particle over micrometer order, automatic particle shape
analyzers using two-dimensional image of particles in a
sheath flow are available. This analyzer captures particle
images automatically by an optical microscope with
charge-coupled device camera under stroboscope flush
lighting.
1.3.2 Three-Dimensional Particle Image
In the particle shape measurement of flaky particle or
porous particle including hole or space inside the parti-
cle, the shape analysis of a two-dimensional particle pro-
jection picture is inadequate, and three-dimensional
shape analysis is necessary [1].
Although it is difficult to measure the thickness of a
particle by the ordinary electron microscope, the
thickness or surface roughness can be measured by
three-dimensional scanning electron microscope
(3D-SEM). 3D-SEM takes two microscopic pictures
from slightly different angles and obtains the three-
dimensional information including thickness and sur-
face roughness geometrically. However, if one of the
pictures has the hidden area in the shadow of a parti-
cle, the three-dimensional information of the area is
hidden. When well-dispersed nanoparticles adhere
on a flat substrate, the height difference between the
particle surface and the flat substrate can be measured
accurately, and the thickness of nanoparticle is
obtained.
Using the TEM, 120 transmission images are taken
when a sample is rotated 1 degree interval from þ60
to 60 degrees. This three-dimensional imaging tech-
nique called TEM-CT [2], which is similar to the
computer-aided tomography [1], is expected to be
applied for detailed three-dimensional shape measure-
ment of nanoparticles.
Using the scanning probe microscope (SPM)
including atomic force microscope (AFM), the surface
roughness can be measured by tiny probe with the
high resolution under nanometer order. SPMs are very
effective for thickness measurement of nanoparticles.
The vertical direction length such as particle thickness
can be measured accurately by SPM, but the measured
horizontal length becomes bigger about the diameter
of the probe. It means that the particle diameter in hor-
izontal direction measured by SPM is bigger than real
11
particle size. Moreover, for a soft particle or an adhesive
particle, a particle position changes by contact of probe
or a particle adheres to probe, and an accurate image
is not obtained.
1.3.3 Particle Shape Index Using Particle
Diameter Ratio
Once the microscopic particle image is captured,
quantification of particle shape can be performed by
the same method as a coarse particle even if it is a nano-
particle. Quantification of particle shape is classified
roughly into the shape index, which is the ratio of
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
the ratio of two different definition particle diameter,
there are many similar kinds of shape indices such as
degree of elongation (aspect ratio) ¼ major axis/minor
axis, degree of flatness ¼ minor axis/thickness, degree
of circular ¼ equivalent area diameter (Heywood
diameter)/equivalent perimeter diameter, and degree
of sphericity ¼ equivalent volume diameter/equiva-
lent surface area diameter [3]. In addition, unidirec-
tional maximum particle (Feret diameter)/equivalent
perimeter diameter are also used as a particle shape in-
dex, and the value of the shape index of a particle
perimeter without concave shows near unity. Each of
these is a ratio of diameters of a particle, so these shape
indices are nondimensional values and should not be
influenced by the particle size. However, the perimeter
and the projection area of a fine particle have the ten-
dency to decrease with the decrease in particle size
because the resolution of a particle image is getting
worse. Therefore, strictly speaking, the shape indices
are influenced by the resolution of microscopic particle
images.
In these indices, the degree of elongation or aspect ra-
tio is an index with which a particle expresses long and
slender, and the index shows a large value for a slim fi-
ber particle. The high degree of flatness value means
flakey shape. The degree of circularity and the degree
of sphericity are set to 1 of maximum when a particle
has a spherical shape, and the index shows a small value
for a nonspherical particle.
The shape indices, expressed with ratios of two parti-
cle diameters, are divided into two categories. The degree
of elongation, the degree of flatness, etc., in the one cate-
gory show the overall shape of a particle, and the degree
of circularity and the degree of sphericity in the other
category show the surface roughness of a particle. Using
the relation between two shape indices in different cate-
gories, difference in particle shape can be expressed
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
a relation, the unidirectional maximum particle diameter
(Feret diameter)/diameter of equivalent particle perim-
eter is plotted on the horizontal axis and the degree of cir-
cular is plotted on the vertical axis [4].
1.3.4 Particle Shape Expression by Fractal
Dimension
The fractal dimension is a dimension, taking a real nu-
merical value, proposed by Mandelbrot [5] and is also
used for particle shape expression. The divider method
is used to measure the fractal dimension of particle pro-
jection image perimeters. In this method, the number of
the polygonal lines N(r) necessary to go around a particle
perimeter is measured r as shown in Fig. 1.3.1. The line of
length r is changed and the same operation is repeated. If
the relation between r and N(r) shows a straight line on
logelog paper as shown Fig. 1.3.1, the value correspond-
ing to the inclination of this straight line is defined as the
fractal dimension D [6].
D
NðrÞfr
A high value of fractal dimension D means a rough
rugged surface of a particle, and a value of fractal
dimension close to 1 means a smooth surface such as
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
this method, a powder with larger surface area has
103
Number of lines N(r) (−)
higher measurement accuracy, and the average value
showing the three-dimensional shape of many parti-
cles can be obtained. Thus, this method is effective in
shape analysis of a nanoparticle.
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-
ing a projection image or an outline of a particle N(r) and
size r is also used for the particle shape analysis. More-
over, the turning-radius method is well used to obtain
the fractal dimension of an agglomerate particle. In
this method, the circle of a radius R is drawn from the
center of an agglomerate particle, and the number of
the primary particles contained in the circle N(R) is
counted. In this method, the fractal dimension D is ob-
tained from the logelog plot of R and N(R) [7]. From
the logelog plot of the perimeter P and the projection
area A of each particle, the average fractal dimension
of many particle perimeters is obtained from inclination
of the straight line using the following equation [8]:
PfAD=2 (1.3.2)
(1.3.1) The three-dimensional particle shape expressed by
the fractal dimension is also possible from the logelog
plot of the surface area and volume of each particle,
instead of the perimeter and the projection area.
1.3.5 Particle Shape Analysis by Fourier
Analysis
In the Fourier analysis method, the particle shape is
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

The Fourier coefficients an and bn represent the parti-

cle shape.
D = 1.134
102 a0 is the average radius of a particle image and T is the
3
r
cycle of trigonometric functions. In the series of Fourier
2 coefficients an and bn, the low-order coefficients with
1 small n value express the large-scale surface roughness
and the high-order coefficients with large n value ex-
press the small-scale surface roughness. This Fourier-
Profile of precipitated calcium carbonate particle analysis method has the merit to synthesize the original
10 particle perimeter from the Fourier coefficients. Synthe-
−2 −1
10 10 1 sizing the particle shape is impossible by the other
Opening of divider r (−) method. To rebuild the original outline completely, the
FIGURE 1.3.1 Fractal dimension measurement using divider infinite number of Fourier coefficients would be
method. required.
 1.4 PARTICLE DENSITY 13

(A) (B) (C)

Fourier coefficients an,bn

Radius f ( )
f( )

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
A particle shape analyzer is not available for nanopar-
ticle, and so a method based on the microscopic particle
image is used usually. To obtain the average result about
many particles, the ratio of two particle diameters ob-
tained by different kinds of method such as a particle
size by dynamic light scattering method and the specific
surface diameter by the gas adsorption is used. These
particle sizes include the influence of particle shape
and, so the ratio of these diameters can be used for a sim-
ple particle shape expression.
[2] H. Furukawa, M. Shimizu, Y. Suzuki, H. Nishioka, JOEL News 36E
(2001) 50.
[3] J. Tsubaki, M. Suzuki, Y. Kanda, Nyumon Ryushi-Funtaikougaku 8,
Nikkan Kougyo Shinbunsha, 2002.
[4] J. Tsubaki, G. Jimbo, Powder Technol. 22 (1979) 161e169.
[5] B.B. Mandelbrot, Fractal Kikagaku, Nikkei Sci. (1984).
[6] M. Suzuki, Y. Muguruma, M. Hirota, T. Oshima, J. Soc. Powder
Technol. 25 (1988) 287e291.
[7] M. Matsushita, K. Itoh, M. Ohnishi, T. Ogawa, M. Kohno,
M. Tanemura, H. Honda, K. Miyamoto, K. Miyazaki,
N. Yoshimoto, Katachi no kagaku, Asakura shoten, 1987.
[8] M. Suzuki, S. Yamada, H. Kada, M. Hirota, T. Oshima, J. Soc. Pow-
der Technol. 34 (1997) 4e9.
[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.

1.4 PARTICLE DENSITY 1.4.1.1.1 Material Density

Kensei Ehara Material density of a powder is defined as the mass of
the powder divided by the volume occupied by solid
1.4.1 Density Measurement of Powders matter of the powder. It can be regarded as the density
Composed of Nanoparticles of a homogeneous material composed of the same mate-
rial as the constituent particles. It is also referred to as
1.4.1.1 Definitions of Powder Density true density. Material density might be measured after
Powder is an inhomogeneous material in that there removing internal voids by breaking the particles.
are gaps between constituent particles, and there may
be voids within particles themselves. Consequently,
the density of a powder can be defined in several 1.4.1.1.2 Particle Density
ways. Important definitions that are practical and useful Particle density is defined as the mass of the powder
are as follows. divided by the volume occupied by particles including
14 1. BASIC PROPERTIES AND MEASURING METHODS OF NANOPARTICLES
internal closed voids. This volume is equivalent to the
sum of volumes enclosed by the external surfaces of par-
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
small openings at the surfaces of particles might behave
as closed voids. Therefore, the particle density value ob-
tained can depend on the details of the measurement
procedure.
1.4.1.1.3 Bulk Density
Bulk density is defined as the mass of the powder
divided by the volume of the space below the upper sur-
face of the powder when it is placed in a container. The
bulk density refers to the volume including both the
gaps between constituent particles and the voids within
particles. Two types of bulk densities are often used:
initial bulk density is the bulk density when well-
dispersed particles are put gently into a container,
whereas tap density is that obtained after a tapping pro-
cedure in which the powder container is repeatedly
lifted and dropped onto a solid surface. The ratio of
the tap density to the initial bulk density is called the
Hausner ratio and is used as a measure of powder flow-
ability or compressibility.
1.4.1.2 Measurement Methods of Powder Density
In conventional methods of measuring the density of
a powder, the mass of the powder is measured with a
balance and its volume is measured either by the liquid
immersion method or the gas replacement method.
These methods are, of course, applicable also to pow-
ders composed of nanoparticles. For details of the
methods see references [1,2].
It has been reported that bulk density of a powder
tends to remain unchanged by the tapping procedure
when the powder is composed of nanoparticles, which
suggests that the Hausner ratio might not be a good
measure of the flowability or compressibility of nano-
particles [2]. Further study will be required to establish
a method for characterizing nanoparticles in terms of
bulk density.
When the density of individual particles is relatively
homogeneous, the density reference liquid method [3]
may be applicable; particles are put into density refer-
ence liquids that have been prepared to have several
known densities, and the particle density is determined
by judging whether the particles float to the liquid
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.
surface, settle at the bottom, or remain suspended in
the liquid, after a certain holding time.
1.4.2 Density Measurement of Individual
Particles
1.4.2.1 Effective Density of Individual Particles
When particles are not in a powder state, but are
dispersed in a gas or a liquid, the density of individual
particles is often of concern. For particles dispersed in
a gas, there are three major methods of measuring the
density of individual particles: (1) the combined mea-
surement of mobility and mass, (2) the combined
measurement of mass and volume, and (3) the com-
bined measurement of mobility and aerodynamic
diameter.
Let m and db denote the mass and the mobility equiv-
alent diameter (diameter of a sphere with the same me-
chanical mobility as the particle of concern) of a particle,
respectively. The density obtained by methods (1) and
(3) is the effective density defined by
m
re ¼ . (1.4.1)
pdb 3 6 =
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
depends on the particle shape.2 Although the effective
density in such cases is not an intrinsic material prop-
erty, it is still useful for particle characterization. The
density obtained by method (2), on the other hand, is
the particle density and leads to the material density, if
there are no closed voids within the particles.
These methods are also applicable to particles sus-
pended in a liquid, if the liquid suspension can be con-
verted into an aerosol by atomizing the suspension and
drying the droplets thus generated.
1.4.2.2 Mass Classification of Aerosol Particles
The method of classifying aerosol particles according
to their mass, which is employed in methods (1) and (2),
is briefly described here. Fig. 1.4.1 shows the principle of
the aerosol particle mass analyzer (APM) used for this
purpose [4]. Aerosol particles are first passed through
a bipolar charger in which bipolar ions generated by
an ion source such as 241Am, 85Kr, or 210Po bring the par-
ticles to an equilibrium charge state and then introduced
into a thin annular gap between coaxial cylindrical elec-
trodes that rotate at the same angular velocity. In the
 1.4 PARTICLE DENSITY 15
Inner electrode

Aerosols Bipolar charger V

Brush
Centrifugal Electrostatic
force force

Outer electrode

Inner electrode
li g h t p a
s
par ticle

r ticles
heavy
Outer
electrode

Particles having a specific

mass-to-charge ratio

FIGURE 1.4.1 Principle of the aerosol particle mass analyzer.

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)

2003 RPM, 0.6 L/min, 208 nm PSL

0.06 5000
+
0.05
Particle escape rate (-)

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
2 ranging from 50 to 220 nm in mobility equivalent diam-
1.8
1.6
Effective density (g/cm3)
1.4
10% load
1.2
1 1.4.2.5 Combined Measurement of Mobility and
0.8
0.6
70% load
0.4 Lower density particles
0.2 in atmospheric aerosols
(McMurry et al., 2002)
0 DMA. Traditionally, impactors have often been used to
10 100
Mobility equivalent diameter (nm)
FIGURE 1.4.4 Size dependence of the effective density of diesel
exhaust particles. Reconstructed from K. Park, F. Cao, D.B. Kittelson, P.H.
McMurry, Environ. Sci. Technol. 37 (2003) 577e583.
particles with a mobility equivalent diameter of 50 nm,
obtained by using a DMAeAPMeCNC system. The par-
ticles were generated by atomizing and drying an NaCl
solution. The peak observed in the mass distribution is
located at approximately 0.113 fg, indicating that the
effective density of the particles is about 1.7 g/cm3. This
value is smaller than the density of NaCl bulk crystal
(2.2 g/cm3). The exact reason for this difference in density
is not yet known, but it might be due to the dynamic
shape factor of nonspherical NaCl particles.
By varying the mobility of particles classified by the
DMA, db-dependence of re can also be determined.
Fig. 1.4.4 shows the effective density of diesel exhaust
particles (DEPs) with mobility equivalent diameter
ranging from 50 to 300 nm, measured with this method
[5]. The influence of the engine load on the effective den-
sity of DEPs is observed in Fig. 1.4.4. The same method
has also been applied to atmospheric aerosols [6] and
carbon nanotubes (CNTs) [7].
1.4.2.4 Combined Measurement of Mass and
Volume
If the volume of a particle selected by an APM is
measured directly with TEM, the density of the particle
can be determined. The material density of DEPs
eter was measured with this method [8]. It is reported
that, after removing volatile components by heating
particles to 300
C, the density was 1.77  0.07 g/cm3
irrespective of their mobility equivalent diameter.
Aerodynamic Diameter
The effective density of an individual particle can also
be determined if both the mobility and the aerodynamic
diameter are known. This can be achieved by measuring
the aerodynamic diameter of particles selected with a
1000
measure the aerodynamic diameter with this method
[9,10]. Recently, a time-of-flight type device has some-
times been employed instead of an impactor [11,12].
The accuracy of the effective density obtained with
this method is generally much higher than the accuracy
obtained with the combined DMA and impactor
method.
References
[1] R. Utsumi, in: Funtai Kougaku Binran (Powder Engineering
Handbook), second ed., Nikkan Kougyo Shinbun, 1998,
pp. 42e47 (in Japanese).
[2] H. Yanagida, in: Supervised: Engineering System for Fine Parti-
cles, 1, Fujitec Co., 2001 (in Japanese).
[3] JIS Z 8901, Test Powders and Test Particles, Japanese Standards
Association, 2006.
[4] K. Ehara, K.J. Coakley, R.C. Hagwood, J. Aerosol Sci. 27 (1996)
217e234.
[5] K. Park, F. Cao, D.B. Kittelson, P.H. McMurry, Environ. Sci. Tech-
nol. 37 (2003) 577e583.
[6] P.H. McMurry, X. Wang, K. Park, K. Ehara, Aerosol Sci. Technol. 36
(2002) 227e238.
[7] A.D. Maynard, B.K. Ku, M. Emery, M. Stolzenburg, P.H. McMurry,
J. Nanopart. Res. 9 (2007) 85e92.
[8] K. Park, D.B. Kittelson, M.R. Zachariah, P.H. McMurry,
J. Nanopart. Res. 6 (2004) 267e272.
[9] W.P. Kelly, P.H. McMurry, Aerosol Sci. Technol. 17 (1992) 199e212.
[10] S.V. Hering, M.R. Stolzenburg, Aerosol Sci. Technol. 23 (1995)
155e173.
[11] P. DeCarlo, J.G. Slowik, D.R. Worsnop, P. Davidovits, J.L. Jimenez,
J. Aerosol Sci. 38 (2004) 1185e1205.
[12] A. Zelenyuk, Y. Cai, L. Chieffo, D. Imre, Aerosol Sci. Technol. 39
(2005) 972e986.
 1.5 MELTING POINT, SURFACE TENSION, AND WETTABILITY 17
1.5 MELTING POINT, SURFACE 1.0
TENSION, AND WETTABILITY
Kiyoshi Nogi .95
It is well known that melting point and surface ten-
sion, which are the physical properties of materials,

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

1.5.1 Melting Point .80

0 0.05 0.10 0.15 0.20 0.25
A proportion of number of surface atoms to that of
Inverse of particle size (nm-1)
bulk atoms increases with decrease in particle size.
Accordingly, the melting point of nanoparticle falls as FIGURE 1.5.2 Relationship between inverse of particle size of
much as corresponding surface energy. various metal and Tm/To [19]. Tm, measured melting point; To, melting
point of bulk material.
Many researchers have reported melting points of
nanoparticles [1e21] and some examples are shown in where r is the radius of liquid drop, s is the surface ten-
Figs. 1.5.1 and 1.5.2. A melting point of Au declines sud- sion, t is the time, and A and B are constants.
denly when a particle size is less than 15 nm and a As can be seen from Eq. (1.5.1), when the surface ten-
decrease of almost 200 K can be observed at about sion value of liquid drop remains constant, Ln (dr/dt)
6 nm. As shown in Fig. 1.5.2, it has been reported that should be proportional to (1/r). Fig. 1.5.3 shows changes
there is a linear relationship between a ratio of a melting of particle sizes of Au and Pb with time by evaporation.
point of nanoparticle (Tm) to that of bulk material (To)
and a reciprocal number of a particle diameter. 3.0

1.5.2 Surface Tension

Morokhov [22] calculated a change in liquid drop
Au (1348K)
diameter with an evaporation of a liquid drop at a con-
stant temperature based on a molecular dynamics and
Logarithm of time change of particle size

obtained an Eq. (1.5.1). 2.0

lnðdr=dtÞ ¼ ln A þ Bðs=rÞ (1.5.1)

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

Surface tension (mN/m) 150

Sn
800 145

Contact angle (°)

140
Au 1348K
Bi
135 Au
400
0 2 4 6 8 10
1.0 130

125
σ m/σ b

0.8 120

Pb 734K
0.6
0 2 4 6 8 10
Particle size (nm)
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
metal.
It can be found that Ln (dr/dt) and (1/r) does not show
linear relationship when particle sizes of Au and Pb
drops are less than 2 and 5 nm, respectively.
Gladkikh et al. [21] performed theoretical and exper-
imental approach on surface energies of nanoparticles of
metals and reported the results of Au and Pb particles.
As can be found from Fig. 1.5.4, obtained result of Pb
is fairly in good agreement with that by Morokhov [22].
1.5.3 Wettability
As shown in Fig. 1.5.5, a contact angle value is used as
a criterion for wettability of solid by liquid. In general,
when a contact angle is larger than 90 degree (cf.
Fig. 1.5.5A), it is defined as “nonwetting system” and
when a contact angle is smaller than 90 degree (cf.
Fig. 1.5.5B), it is defined as “wetting system.”
115
0 10 20 30 40 50
Radius of particle (nm)
FIGURE 1.5.6 Relationship between contact angles of liquid
metals on graphite and particle sizes.
Over 200 years ago, Eq. (1.5.2) was proposed by treat-
ing the contact angle of a liquid drop as the result of the
equilibrium of mechanical energy between the drop and
a solid surface under the action of three interfacial free
energies.
sL cos q ¼ sS  sSL (1.5.2)
Where q is the contact angle, sL is the surface free en-
ergy of liquid, sS is the surface free energy of solid, and
sSL is the interface free energy between solid and liquid.
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
drop size. Fig. 1.5.6 shows particle size dependence of
contact angles of various liquid metals on carbon sub-
strate [23,24]. It can be found that the contact angles of
all liquid metals decrease at less than 40 nm and a
remarkable decrease of the contact angles is observed
when particle radius is less than 10 nm.

(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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‘The mutton mill? I never heard of such a thing. I will go with you and
witness the process.’ They arrived at the mill; the sheep was thrown
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head handsomely dressed, and two elegantly-carved powder horns.’
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of barrelled pork piled up three tiers high, in open lots, and not less
than six acres more not packed, which would make eighteen acres
of barrels if laid side by side, exclusive of lard in barrels, and pork
bulked down in the curing houses, sheds, &c. Besides the above
slaughtered hogs, there were five or six acres more of live hogs in
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In the Western States pork is the great idea, and the largest owner of
pigs is the hero of the prairie. What coal has been to England, wheat
to the Nile or the Danube, coffee to Ceylon, gold to California and
Victoria, and sheep to the Cape and Australia, pork has been to the
West in America.
The phrase, ‘Going the whole hog,’ must have originated in Ohio, for
there they use up the entire carcases of about three-quarters of a
million of pigs, and the inhabitants are the most ‘hoggish’ community
of the entire Union. What crocodiles were in Egypt, what cows are in
Bengal, or storks in Holland, pigs are in Cincinnati, with this trifling
difference, their sacredness of character lasts but as long as their
mortal coil; and this is abbreviated without ceremony, and from the
most worldly motives. In life, the pig is free, is honored; he ranges
the streets, he reposes in thoroughfares, he walks beneath your
horse’s legs, or your own; he is everywhere respected; but let the
thread of his existence be severed, and—shade of Mahomet!—what
a change! They think in Cincinnati of nothing but making the most of
him.
Historically, socially, gastronomically, the pig demands our careful
attention. The connection with commerce, with the cuisine, and even
with the great interest of fire insurance, have all made him an object
of particular regard. In the early days of the Celestial Empire—as we
learn from the veracious writings of the witty and voracious essayist,
Charles Lamb—a wealthy Chinaman was so unfortunate as to have
his dwelling destroyed by fire. Prowling around the smoking ruins,
and seeking to save some of his valuables which the conflagration
might have spared, his hand came in contact with the smoking
remains of a poor pig which had perished in the flames; instantly,
smarting with the pain, he carried his hand to his mouth, when a
peculiar flavour greeted his palate, such as the gods (Chinese ones I
mean, of course,) might in vain have sighed for. Regardless of pain
he applied himself once more, and drew forth from the smoking
cinders the remains of the pig. Carefully brushing off the ashes, he
regaled himself with the feast before him, but closely preserved the
secret he had learned. In a few short months, however, the taste for
roast pig came back so strong, that John Chinaman’s house was
burned down again, and again was a pig found in the ashes. This
was repeated so often that the neighbours grew suspicious, and
watched until they ascertained that the reason for the conflagration
was the feast that invariably followed. Once out, the secret spread
like wildfire; every hill-top shone with the flames of a burning
habitation—every valley was blackened with the ashes of a
homestead; but roast pig was dearer to a Chinaman than home or
honour, and still the work of destruction went on. Alarmed at a
course which bid fair to ruin every insurance office in the empire, the
directors petitioned in a body to the General Court of China, for the
passing of an Act that should arrest the evil and avert their
threatened ruin; and a careful examination of the revised statutes of
China would probably show stringent resolutions against the crime of
burning houses for the sake of roasting pigs.
Since the invention of the modern cooking stove, however, although
incendiarism has decreased only in a slight degree, still it has
ceased to be attributed to this cause, and a juicy crackling is no
longer suggestive of fallen rafters, or a houseless family.
‘There is an old adage, ‘Give a dog a bad name, and his ruin is
accomplished.’ Such may be true of the canine race; but the noble
family of animals of which I am treating, furnishes a striking
illustration that the proverb applies not to their numbers. A goose, it
is said, saved lordly Rome by its cackling; and had not their list of
Divinities just then been full, a grateful people would have found for
him a sedgy pool and quiet nest in Olympus. How did the ancestors
of that same people repay the pig for a service scarcely less
important?
‘The veriest smatterer in the classics knows, that, when from flaming
Troy ‘Æneas the great Anchises bore,’ seeking in strange lands a
new home for his conquered people, a white sow, attended by thirty
white little pigs, pure as herself, pointed out to him the scene of his
future empire. But what did he and his people do for the pig in
return? Did they load him with honours? Did they cherish him with
corn? Did they treat him with respect? No! with black ingratitude,
which still merits the indignation of every admirer of the pig, they
affixed to the animal the appellation of Porcus; and ‘poor cuss’ the
pig would have been to the present day, had not the Latin tongue
long since ceased to be the language of the world. But, ‘poor cuss’
he is no longer, when in Worcester county he spurns his classic
name, and, adopting the vernacular, he ‘grows the whole hog,’ that
he may ‘pork us,’ in return for the care which we bestow upon him.
‘For the sake of our farmers, who are anxious to make a profit from
pig-raising, it is greatly to be regretted that the thirty-at-a-litter breed
has disappeared from the face of the earth. Breeding swine with
such a rate of increase must be almost as profitable as ‘shaving’
notes at two per cent. per month; but still the impression is irresistibly
forced upon us, that, in a family so numerous, those who came last
to dinner, at least in their infant days, would not have gained flesh
very rapidly. Indeed, in such a family it would seem almost
impossible to dispense with the services of a wet nurse, in order to
bring up profitably the rising generation.
‘The course of the pig, like that of the Star of Empire, has ever
tended westward. From China we trace him to Italy, the gloomy
mountains of the Hartz, the broad plains of Westphalia, the fertile
valleys of France, and to the waving forests of ‘Merrie England;’ all
have known him since the days when their bold barons and hungry
retainers sat down to feast on the juicy chine of the wild boar, and
the savoury haunch of venison. In green Erin, piggy has been an
important member of society; true, he has shared his master’s meal,
and basked in the comfortable warmth of his cabin; but, like a
‘gintleman’ as he is, he has ever paid the ‘rint;’ and St. Patrick, in the
plenitude of his power and influence, never saw the day he could
have banished him from that ‘gem of the ocean.’
‘When the pig first crossed to this western world remains in doubt.
Whether he came with the Pilgrims, pressing with the foot of a
pioneer the Blarney-stone of New England, and scanning with
fearless eye the cheerless prospect before him, or whether,
regardless of liberty of conscience, and careful only of his own
comfort, he waited till the first trials and toils of a new settlement had
been met and overcome, we have no record; enough for us that he
is here; how or where he came concerns us not. He is among us and
of us. From souse to sausage we have loved him; from ham to
harslet we have honoured him; from chine to chops we have
cherished him. The care we have shown him has been repaid a
hundred-fold. He has loaded our tables, and lighted our fire-sides,
and smiling plenty has followed in his steps, where hungry famine
would have stalked in his absence.
‘But still further towards the setting sun has been the arena of the
pig’s greatest triumphs; there have been the fields of his widest
influence. Beneath the vast forests of Ohio, raining to the ground
their yearly harvests of mast—through her broad corn-fields,
stretching as far as the eye can see, he has roamed, and fed, and
fattened. From him, and the commercial interests he has mainly
contributed to establish, has grown a mighty State, scarcely second
to any in this confederacy; from his ashes has arisen a new order in
society—the ‘Bristleocracy of the great West.’
‘A broad levee bustling with business, lofty and spacious stores and
slaughter-houses, crowded pens, and a river bearing on its bosom
steamboats in fleets—all attest the interest which the pig has exerted
on the agricultural and commercial interests of the great State of
Ohio. He has filled the coffers of her bankers, and has bought the
silks which cover her belles. He has built the beautiful palaces which
adorn the ‘Queen City of the West,’ and feeds the princely luxury of
those who inhabit them. There he is almost an object of worship, and
his position is considered as about equivalent to a patent of nobility.
Fancy dimly paints the picture, when a few years hence, the wealthy
pork merchant, who justly boasts his numerous quarterings, shall, in
the true spirit of heraldry, paint on the pannel of his carriage, and on
the escutcheon over his door-way, a lustrous shield, bearing in
brilliant colours a single pig, his bristles all rampant, his tail closely
curlant, and his mouth widely opant, till the lions, the griffins, and the
unicorns of the Old World shall fade into insignificance before the
heraldic devices of the New.’[7]
‘Your Spanish pig, who, by the way, is a no less important character
in his country than is his cousin in Ireland, is not raised for the vulgar
purpose of being fried to lard, or salted down to pork. He has, in fact,
no more fat than he has hair on him. He is a long-legged, long-
snouted, and long-tailed fellow, and would have been described by
Plato as an animal without hairs. But though the pickings on his ribs
be small, they are sweet. The Spaniard rolls the morsels under his
tongue as he does his easily-besetting sins. It is nut-fed flesh; and
has the flavour of acorns. This taste is as much prized in the roasted
joint as that of the skin in the sherry. Pig is game in Spain. The
porker does not live there in the chimney corner, and sit in the best
arm-chair, as in Paddy’s cabin; but he roams the fields, and goes a-
nutting with the boys and girls. He eats grass, as there are no cows
to eat it; and would milk the goats, doubtless, if they would let him.
He evidently knows more than the same animal in other countries;
and is, in consequence, more willing to be driven. He will squeal
when he feels the knife, but for no other reason. Nor is his squeal the
same as that heard at the North. There are more vowel sounds in it.
It is also less through the nose than in New England; and has some
gutturals even farther down the throat than those of a Dutchman.
Your wild boar is a monster compared with him. The flesh of the
latter is to that of the former as the crisp brown of roast pig is to the
tanned hide in your riding saddle. Accordingly, to refuse pork at a
Spanish table is to pronounce yourself ‘of the circumcision;’ and
should you decline a cut of a particularly nice ham, you would be set
down as no better than a heathen. However, you never would do it—
particularly after having read this essay. I assure you that when you
may have eaten up all the chickens which were stowed away in your
saddle bags, you cannot do better than to attack your landlord’s
roast pig—provided you can get it. Only it may cost you dear in the
reckoning, as it is thought a dish to set before the king. You may like
pork, or you may not; but one thing is certain, it is the only meat in
the Peninsula which has juices in it. Mutton may have a very little;
and should you travel far in the country, you would see the day when
you would be glad of a leg of it. But the beef is dry as ‘whittlings.’ An
entire joint of roast beef would kill a man as effectually as a joist of
timber. Whoever should undertake to live on Spanish beef a
twelvemonth, would become at the end of that time what he was, in
fact, at the beginning—wooden-headed. Make up your mind,
therefore, to eat the meat of the uncircumcised, if you have any
thought of going to Spain. You will often have to take your choice
between that and nothing; and my word for it, ’tis much preferable.
For the land is leaner far than pork; and happy is that traveller, who,
when he is reduced to pickings, can find a spare-rib to work upon.
Forewarned—forearmed.[8]’
Pork is the great food of the Brazilian people. It is prepared and
eaten, according to Dr. Walshe, in a peculiar manner. When the pig
is killed, the butcher dexterously scoops out the bones and muscular
flesh, leaving behind only the covering of fat. In this state it is salted,
folded up, and sent in great quantities to Rio, where it is called
toucinho. All the stores and vendas are full of it, and it is used
commonly for culinary purposes, and forms an ingredient in every
Brazilian article of cookery.
The flesh of the peccary (after cutting away the fetid orifice on its
back) and of the wild or musk hog, both known under the Indian
appellation of quanco in Trinidad, is much preferable to that of the
domestic swine.
The flesh of the rhinoceros is eaten in Abyssinia, and by some of the
Dutch settlers in the Cape Colony, and is in high esteem. The flesh
of the hippopotamus used also to be eaten on the east coast of
Africa, roasted or boiled, and fetched a high price as a delicacy. The
fat was used in making puddings, instead of butter. The Portuguese
settlers were permitted by the priests to eat the flesh of this animal in
Lent, passing it off as fish from its amphibious habits, and hence
their consciences were at ease.
The flesh of the tapir, when roasted, closely resembles beef,
especially if it be young; and that of the water hare is also
considered excellent food, being white and delicate, and much of the
same flavour as that of the tapir.

HORSE-FLESH.
At Paris, where all eccentricities are found, and even encouraged,
one of the latest gastronomic innovations is the use of horse-flesh.
The French are always adding to their dietetic regimen by
introducing new articles of food. This social phenomenon of making
the horse contribute to the nourishment of the human race, is not
altogether new. The ancient Germans and Scandinavians had a
marked liking for horse-flesh. The nomade tribes of Northern Asia
make horse-flesh their favorite food. It has long been authorized and
publicly sold in Copenhagen.
With the high ruling prices of butcher’s meat, what think you,
gentlemen and housekeepers, of horse-flesh as a substitute for beef
and mutton? Are you innocently ignorant of the French treatise of
that eminent naturalist and professor of zoology, M. St. Hilaire, upon
horse for food? Banquets of horse-flesh are at present the rage in
Paris, Toulouse, and Berlin. The veterinary schools there pronounce
horse-bone soup preferable beyond measure to the old-fashioned
beef-bone liquid, and much more economical.
Horse-flesh steak without sauce, and cold, is cited as a morsel
superior to the finest game that flies! and cut, too, from a horse
nearly a quarter of a century old; one of the labouring cavalry kind
who pranced at the sound of the trumpet, and snuffed the battle from
afar off, little dreaming he was doomed to steaks, soup, and
washing-day hashes. Horse-flesh pie, too, eaten cold, is a dainty
now at Berlin and Toulouse, and boiled horse, rechauffé, has
usurped the place of ragouts and secondary dishes! What a theme,
hippophology, to write upon. We shall soon hear in our city dining
rooms, ‘A piece o’ horse, my kingdom for a piece of horse!’ ‘Waiter! a
cut from the fore-shoulder, well done.’ ‘A horse sandwich and ale,
and the morning paper.’ Our witty friend Punch had its horse-laugh
recently upon the subject of the sensation this movement has
created in equestrian circles.
A Frenchman, observes a recent writer, was one day remonstrating
against the contempt expressed by Englishmen for French beef, the
inferiority of which he would not admit. ‘I have been two times in
England,’ said he, ‘but I nevere find the beef so supérieur to ours. I
find it vary convenient that they bring it you on leetle pieces of stick
for one penny, but I do not find the beef supérieur.’ ‘Good gracious!’
exclaimed the Englishman, ‘you have been eating cats’ meat for
beef.’ What this Frenchman did in the innocence of his heart, his
countrymen now do, it seems, with malice prepense.
And a Frenchman of considerable reputation, in a letter on
alimentary substances, and especially upon the flesh of the horse,
calls upon the whole world to put aside, what he considers, an
ancient and absurd prejudice, and to realize at home that famous
sentence in the geography we used to read at school, which, under
the head of Norway, informed us ‘horse-flesh is publicly sold in the
markets.’
‘M. Isidore St. Hilaire is very serious. He does not merely advocate
the fillet of horse-flesh—the mare soup and fricasseed colt—in
sarcastic allusion to the practice of Parisian restaurants. He comes
gravely forward, with chapters of scientific evidence and argument,
to contend that, while animal food is absolutely necessary to the
proper nourishment of the human race, millions of Frenchmen eat no
animal food, and every year millions of pounds of excellent meat are
wasted. He knows how the cause he advocates lends itself to
ridicule—he knows how difficult it has always been to get rid of a
prejudice—he knows the fate of innovators; but, though a
Frenchman, he braves ridicule, brings a heavy battery of facts to
destroy what he deems a prejudice, and is already experiencing
some of the triumph which follows a hard-won victory. For seven
years he has been advocating the desirableness of eating horse-
flesh—for seven or eight years he has been collecting evidence and
gaining converts—and now he feels strong enough to appeal to the
European public in a small volume.[9]
‘Since then, Germany has had its ‘Banquets of Horse-flesh’ for the
wits to ridicule—public feastings at which ‘cats’ meat’ was served in
various forms, as soup, as bouilli, as fillet, as cutlet; and all the
feasters left the table converted hippophagists. In 1841, horse-flesh
was adopted at Ochsenhausen and Wurtemburg, where it is now
publicly sold under the surveillance of the police. Every week five or
six horses are brought to market. At the Lake of Constance, a large
quantity of this meat is also sold. In 1842, a banquet of 150 persons
inaugurated its public use at Königsbaden, near Stuttgard. In 1846,
the police of Baden authorized its public sale, and Schaffhausen
followed in the same year. In 1847, at Detmold and at Weimar, public
horse-flesh banquets were held with great éclat—in Karlsbad
(Bohemia) and its environs, the new beef came into general use—
and at Zittau, 200 horses are eaten annually. At Ling, after one of
these banquets, the police permitted the sale of horse-flesh, which is
now general in Austria, Bohemia, Saxony, Hanover, Switzerland, and
Belgium. The innovation made rapid converts. In 1853, Berlin had no
less than five abattoirs, where 150 horses were killed and sold. At
Vienna, in 1853, there was a riot to prevent one of these banquets;
but in 1854, such progress had been made, that 32,000 pounds
weight were sold in fifteen days, and at least 10,000 of the
inhabitants habitually ate horse-flesh.’ And now Parisian banquets of
horse-flesh are common.
These facts are at all events curious. Think of the prejudices to be
overcome, and think how unreasoning is the stomach!
Young horses are too valuable to be brought to the shambles, unless
killed by accident. But our worn-out hacks, of which 250 or 300 die or
are killed weekly in the metropolis,—old horses used up, are
capable, we are assured, of furnishing good meat. An old horse,
which had done duty for twenty-five years, was the substance of a
learned gastronomic feast at Paris.
M. St. Hilaire, the champion of this new addition to our food
resources, reasons in this fashion:—‘Horse-flesh has long been
regarded as of a sweetish disagreeable taste, very tough, and not to
be eaten without difficulty. So many different facts are opposed to
this prejudice, that it is impossible not to recognize its slight
foundation. The free or wild horse is hunted as game in all parts of
the world where it exists—Asia, Africa, and America—and formerly,
and perhaps even now, in Europe. The domestic horse itself is made
use of as alimentary as well as auxiliary—in some cases altogether
alimentary—in Africa, America, Asia, and in some parts of Europe.
‘Its flesh is relished by people the most different in their manner of
life, and of races the most diverse, negro, Mongol, Malay, American,
Caucasian. It was much esteemed up to the eighth century among
the ancestors of some of the greatest nations of Western Europe,
who had it in general use, and gave it up with regret. Soldiers to
whom it has been served out, and people in towns who have bought
it in markets, have frequently taken it for beef. Still more often, and
indeed habitually, it has been sold in restaurants, even in the best,
as venison, and without the customers ever suspecting the fraud or
complaining of it.
‘And further, if horse-flesh has been often accepted as good under a
false name, it has also been pronounced good by those who, to
judge of its qualities, have submitted it to careful experiment, and by
all who have tasted it in a proper condition, that is, when taken from
a sound and rested horse, and kept sufficiently long. It is then
excellent roasted; and if it be not so acceptable as bouilli, it is
precisely because it furnishes one of the best soups—perhaps the
best that is known.
‘It is good also, as experiments prove made by myself as well as
others, when taken from old horses not fattened, whose age was 16,
19, 20, and even 23 years, animals thought worth no more than a
few francs beyond the value of their skin.
‘This is a capital fact, since it shows the possibility of utilizing a
second time, for their flesh, horses which have already been utilized
up to old age for their strength; and, consequently, of obtaining a
further and almost gratuitous profit at the end of their life, after they
had well nigh paid the cost of their rearing and keep by their labour.’
Let us see what additional evidence M. St. Hilaire has to adduce.
First, he appeals to his long experience at the Jardin des Plantes,
where the greater part of the carnivora are habitually fed on horse-
flesh, which keeps them healthy in spite of many unfavourable
conditions. But this will not carry much weight with it. Our digestion is
not quite so good as that of a lion. The condor has been known to
eat, with satisfaction, food which Mrs. Brown would find little to her
taste. No dietetic rule for men can be deduced from the digestions of
tigers. We prefer the experience of human stomachs. Fortunately
this is not wanting, and M. St. Hilaire collects an imposing mass of
evidence. Huzard, the celebrated veterinary surgeon, records, that
during the revolution, the population of Paris was for six months
dieted with horse-flesh, without any ill effects. Some complaints,
indeed, were made when it was found that the beef came from
horses; but, in spite of prejudice and the terrors such a discovery
may have raised, no single case of illness was attributed to the food.
Larrey, the great army surgeon, declares that on very many
occasions during the campaigns, he administered horse-flesh to the
soldiers, and to the soldiers sick in the hospital; and instead of
finding it injurious, it powerfully contributed to the convalescence of
the sick, and drove away a scorbutic epidemic which attacked the
men. The testimony of Parent Duchâtelet is also quoted to the same
effect. M. St. Hilaire feels himself abundantly authorized to declare
that horse-flesh, far from being unwholesome, is one of the most
nutritious and wholesome of alimentary substances: and, to support
this declaration, he adduces the testimony of historians and
travellers, showing how whole tribes and nations have habitually
eaten and highly esteemed it.
Having thus, as he considers, satisfactorily settled the question of
wholesomeness, M. St. Hilaire proceeds to deal with the question of
agreeableness. Is wholesome horse-flesh agreeable enough to
tempt men, not starving, to eat it? It is, of course, of little use that
historians and travellers tell of hippophagists—it is nothing to the
purpose that soldiers in a campaign, or citizens during a siege, have
eaten horses with considerable relish. Under such circumstances,
one’s old shoe is not to be despised as a pièce de résistance; and
one’s grandmother may be a toothsome morsel. The real point to be
settled in the European mind is this—apart from all conditions which
must bias the judgment, is horse-flesh pleasant to the taste? M. St.
Hilaire cites the evidence of eminent men who, having eaten it
knowing what it was, pronounced it excellent—all declaring that it
was better than cow-beef, and some that there was little difference
between it and ox-beef.
But perhaps the reader, having eaten German beef, has a not ill-
grounded suspicion that horse-flesh might bear honourable
comparison with such meat, and yet be at best of mediocre savour.
Let us, therefore, says a writer in the Saturday Review, cite the
example of Parisian banquets, where the convives were men
accustomed to the Trois Frères, Philippe’s, and the Café de Paris. M.
Renault, the director of the great Veterinary College at Alfort, had a
horse brought to him with an incurable paralysis of the hinder
extremities. It was killed, and three days afterwards, on the 1st
December, 1855, eleven guests were invited—physicians,
journalists, veterinary surgeons, and employés of the government.
Side by side were dishes prepared by the same cook, in precisely
the same manner, and with the same pieces taken respectively from
this horse and from an ox of good quality. The bouillon of beef was
flanked by a bouillon of horse, the bouilli of beef by a bouilli of horse,
the fillet of roast beef by a fillet of roast horse; and a comparison was
to be made of their qualities. Dr. Amédée Latour thus writes:—
‘Bouillon de cheval.—Surprise générale! C’est parfait, c’est excellent,
c’est nourri, c’est corse, c’est aromatique, c’est riche de goût.
‘Le bouillon de bœuf est bon, mais comparativement inférieur, moins
accentué de goût, moins parfumé, moins résistant de sapidité.’
The jury unanimously pronounced the horse bouillon superior to that
of the ox. The bouilli, on the contrary, they thought inferior to that of
good beef, although superior to ordinary beef, and certainly superior
to all cow-beef. The roast fillet, again, they found superior to that of
the ox; and M. Latour thus sums up the experiment:—
Un bouillon supérieur;
Un bouilli bon et très-mangeable;
Un rôti exquis.
Similar experiments have been subsequently tried, several times in
Paris and in the provinces. They have been tried under three
different conditions. First, the guests have known what they were
going to eat; secondly, they have been totally ignorant; and thirdly,
they have been warned that they were going to eat something quite
novel. Yet in every case, we are told, the result has been the same.
It is right to add, that the author anticipates the objection that the
animals selected were young horses in splendid condition, and that
such horses are too valuable to be sent to the butcher. The majority
of these experiments have, we are assured, been made at veterinary
colleges, upon horses incapacitated by age or accident from further
work. The horse which M. Renault served up to his friends had
already vingt-trois ans de bons et loyaux services. He was in good
‘condition’—that is to say, well-fleshed, although paralysed. In fact,
all the horses, it is asserted, were such as are sold for fifteen or
twenty francs—not such as are the pride of our stables. The younger
the horse, the better his flesh; and as young horses die daily from
accidents, these, we presume, would form the ‘prime cuts.’ But old
horses, used up, unfit even for cabs, if allowed a little rest, are
capable, we are assured, of furnishing beef better than cow-beef.
But this serving up of horse-flesh is equalled by that of the maître de
cuisine to the Maréchal Strezzi, who, at the siege of Leith, according
to Monsieur Beaujeu, ‘made out of the hind quarter of one salted
horse forty-five couverts, that the English and Scottish officers and
nobility who had the honour to dine with the Monseigneur, upon the
rendition, could not tell what the devil any one of them were made
upon at all.’ M. St. Hilaire discusses at great length many other
objections, with which we need not here trouble ourselves. But the
taste is spreading and the advocates increasing. The public use of
horse-flesh as human food is spoken of approvingly in Blackwood.
The New York Tribune thus endorses the fanatical idea of the French
savans, (more properly ravens,) as to the propriety of eating horse-
flesh:—
‘In the horse we have an animal which is much cleaner in its habits
than the hog, herbivorous like the ox or sheep, whose flesh is rich in
nitrogen, and as pleasant to the taste as that of either of the above-
named animals. What prevents horse-flesh from being found on our
tables? Nothing but a popular prejudice, which recent investigations
in Paris show is entirely without any foundation whatever.
‘8,000 horses die, it is said, in New York annually, or about 22 per
day’ (a great exaggeration no doubt); ‘but instead of fetching 17 or
18 dollars to press the carcase for grease, and to feed the hogs on
to make pork for export, the prices will be greatly enhanced for meat
for home consumption.’
Thus writes the Paris correspondent of the Indépendance Belge:
—‘You know what interest is attached to-day—and very naturally so
—to all questions relating to the public food. In connexion therewith, I
have to mention a fact which is both curious and odd; it is, that there
is being formed in Paris a society of economists, naturalists, and
hardy gourmands, having for aim the introduction of horse-flesh into
the category of butchers’ meat. It may perhaps be said, that this
social phenomenon is not altogether new. Ten years ago,
hippophagy made some noise in Germany, and, if I remember right,
a society of eaters of the horse was formed, and attempted a public
festival, at which all the meat should be of that quadruped, but were
interrupted by the public, who, feeling their prejudices wounded,
broke the tables to pieces. At Paris, where all eccentricities are
found, and even encouraged, there is nothing of that kind to fear.
Accordingly, hippophagy progresses. Do not consider this an
exaggeration. The last number of the Revue des Cours Publics will
prove to you, by means of a summary, that M. Geoffroy de St. Hilaire
has made the subject the theme of one of his recent lectures, and
that the learned professor was greatly applauded. I should add that
his auditors included economists, agriculturists, and heads of
benevolent institutions. When the orator concluded by saying that
the day was come when the horse ought to contribute to the
nourishment of the human race, as well as the ox, the sheep, and
the pig, a hundred voices cried in chorus, ‘Oui! oui! très bien!’ This
question, strange at first sight, has been raised, and it will not sleep
again. I predict that it will have not only numerous adherents, but
eloquent fanatics. As a commencement, many of the auditors wished
to eat horse soup, horse steaks, and the same flesh under other
forms.’ At the time at which I write, dissertations are made,
brochures written, the regulations of a hippophagic society drawn up,
and the establishment of horse shambles demanded. In 1832, M.
Alphonse Karr, mocking the extreme zeal of the society for
protection, exclaimed—‘Philanthropists! the horse has carried man
long enough; it is now for man to carry the horse!’
There is very little doubt that horse-flesh, besides its application for
‘cats’ meat,’ enters, even now, largely into surreptitious use in certain
quarters in this country as food for bipeds. Thus, a Blackburn paper
tells us that ‘on Monday last Mr. Laverty seized and confiscated the
carcase of a horse. The animal had been stuck and bled, and was
taken very near to the premises of a noted brawn and black-pudding
maker. We understand that horse-flesh is used in this town by a
certain vender and manufacturer of brawn.’
Hoffman and Burns, makers and venders of horse-meat sausages,
at Philadelphia, were recently tried, convicted, and sentenced to
eighteen months’ imprisonment. Apropos of sausages, judging from
the following anecdote, home-made ones are the more attractive.
‘A minister in one of our orthodox churches, while on his way to
preach a funeral sermon in the country, called to see one of his
members, an old widow lady, who lived near the road he was
travelling. The old lady had just been making sausages, and she felt
proud of them—they were so plump, round, and sweet. Of course
she insisted on her minister taking some of the links home to his
family. He objected on account of not having his portmanteau along
with him. This objection was soon over-ruled, and the old lady, after
wrapping them in a rag, carefully placed a bundle in either pocket of
the preacher’s capacious great coat. Thus equipped, he started for
the funeral.
‘While attending to the solemn ceremonies of the grave, some
hungry dogs scented the sausages, and were not long in tracking
them to the pockets of the good man’s over-coat. Of course this was
a great annoyance, and he was several times under the necessity of
kicking these whelps away. The obsequies at the grave completed,
the minister and congregation re-passed to the church, where the
funeral discourse was to be preached.
‘After the sermon was finished, the minister halted to make some
remarks to his congregation, when a brother who wished to have an
appointment given out, ascended the steps of the pulpit, and gave
the minister’s coat a hitch to get his attention. The divine, thinking it a
dog having designs upon his pocket, raised his foot, gave a sudden
kick, and sent the good brother sprawling down the steps!
‘You will excuse me, brethren and sisters,’ said the minister,
confusedly, and without looking at the work he had just done, ‘for I
could not avoid it—I have sausages in my pocket, and that dog has
been trying to grab them ever since I came upon the premises!’[10]
The reader may judge of the effect such an announcement would
have at a funeral. Tears of sorrow were suddenly exchanged for
smiles of merriment.
Mr. Richardson, officer of the Local Board of Health of Newton
Heath, near Manchester, gave the following evidence before Mr.
Scholefield’s Committee on Adulteration, before whom I was also
examined as a witness.
‘We have in Newton five knackers’ yards, and there is only one in
Manchester. The reason is, that they have so much toleration in
Newton; and it has been a great source of profit to them, because
they have the means of selling the best portions of the horse-flesh to
mix with the potted meats.
‘I can say for a fact, that the tongues of horses particularly, and the
best portions, such as the hind quarters of horses, are generally sold
to mix with collared brawn, or pigs’ heads, as they are called with us,
and for sausages and polonies. I understand, also, from those who
have been in the habit of making them, that horse-flesh materially
assists the making of sausages; It is a hard fibrin, and it mixes better,
and keeps them hard, and they last longer in the shop window
before they are sold, because otherwise the sausages run to water,
and become soft and pulpy. I believe horse-flesh also materially
assists German sausages; it keeps them hard.’
The instinct of the dog, the cat, and the rat, are so well known that
one anecdote will suffice to illustrate the three. A terrier and a tom
cat were pursuing a large rat down a street. The rat was almost
caught, when it dodged suddenly and ran into a sausage shop. The
cat and dog stopped convulsively at the door; and, looking at the
sausages, hung their heads, and slunk away terror-stricken.
But in other quarters than England, unwholesome and infected meat
is vended, for a year or two ago the editor of the Madras Athenæum
thus wrote:—
‘We question whether since the days of Pelops a more filthy dish
was ever offered to human beings, than those which are daily served
up to the European inhabitants of Madras. With respect to the state
of our market, we have never seen a more disgusting receptacle of
all kinds of abominations than that market presents.

‘A lazar house it seemed, wherein were laid

Numbers of all diseased.’

‘Unfortunate beings in the worst stages of leprosy, naked, and

covered all over with the livid spots of that hideous disease, standing
at the stalls, handling the meat, and talking with the butchers, is a
sight as common as it is horrible. As for the small-pox, that is almost
too abundant to allow of any cases being particularly noticed. It is
very conspicuous on the native, on account of the pustules being
white. The only disease bearing any resemblance to it is the itch. We
have ourselves observed a dirty fellow, with his hands covered all
over with one of these nauseous eruptions, coolly walking down the
whole length of a set of stalls, and clapping those abominable hands,
in a lazy manner, upon every piece of meat within his reach. Faugh!
The very thought smells. When we were last there, the place
swarmed with pariah dogs, the effect of which was to render the
stench and filth accumulated round the stalls perfectly unbearable.
We are aware the subject is a nasty one, but at the risk of spoiling
the breakfast of Brown, Jones, or Robinson, as they take up our
damp sheet this morning, we make the evil conspicuous, and bring it
plainly into notice, that measures may be taken to sink it into oblivion
ever after. If one could jest upon such a subject, one might say, that
the market of Madras is as much the morning lounge of the filthiest
wretches in the place, as the stables of Taylor and Co. are the
morning rendezvous of the rank and fashion, who there do
congregate, to look at the Australians and Arabs ushered to their
notice under the winning smile of the worthy head partner. Is not the
thought horrible, too, that the fairer part of the creation, who should
be fed on

‘Sugar and spice

‘And all that’s nice,

are offered such filthy and infected stuff?

‘We should also recommend attention being called to the practice,
which we are afraid prevails, of ‘blowing the meat,’ to give it a good
appearance. This is a cognizable offence, and butchers have, on
occasion, most deservedly received a dozen or two for it; but the
inducement to make their meat look tempting by filling it with breath,
not quite so ‘fragrant as the flower of Amrou,’ is too profitable, we
fear, to be disregarded upon the vague and distant contingency of a
flogging or a fine. If the functionaries who are employed to
superintend the market are insufficient in number, it would surely be
poor economy not to increase them. If they are inattentive and
remiss, discharge them. It would be pennywise, indeed, for a few
paltry rupees a month, to allow a Secretary to Government, or a
Member of Council, whose wisdom and experience have been
purchased at an immense cost to the country, to be poisoned, which
at present they are liable to be, by infected meat.
‘If by calling attention to the subject, some improvement is made, our
object will be attained. We will gladly run the chance of spoiling a few
dinners. Jones of the club, as he takes the cover off one of Maltby’s
best entrées, may for once think of the leprous hand that has
handled it; Brown may fancy for once he will catch small-pox from
his beef-steak; Robinson may think of the dog licking the leg of
mutton from which his whack is taken, and all may heartily
anathematise the Athenæum for telling them the truth, but we will
cheerfully put up with their wry faces and abuse, if the necessary
reform we advocate be attained.’
Sam Slick, in his truthful, but satirical vein, alludes to the disguises of
fashionable cookery.—‘Veal’ (he says) ‘to be good, must look like
anything else but veal. You mustn’t know it when you see it, or it’s
vulgar; mutton must be incog, too; beef must have a mask on; any
thin’ that looks solid, take a spoon to; any thin’ that looks light, cut
with a knife; if a thing looks like fish, you take your oath it is flesh;
and if it seems real flesh, it’s only disguised, for it’s sure to be fish;
nothin’ must be nateral—natur is out of fashion here. This is a
manufacturin’ country; everything is done by machinery, and that that
aint, must be made to look like it; and I must say, the dinner
machinery is perfect.’
If horses are eaten, why not donkeys? The animal is more rare, and
hence it would be the greater delicacy. The Greeks ate donkeys, and
we must suppose they had their reasons for it. Has any modern
stomach in Europe been courageous enough, knowingly, to try it?
The flesh of the common ass, though never eaten by us, is
esteemed a delicacy in some countries, particularly in Tartary. The
northern climate, pasturage, and freedom may have some effect on
the flesh.
Travellers affirm that dogs’ flesh, which with us is intolerable, is one
of the most savoury meats, when the animal has been kept for some
time in the warm, tropical regions. This cannot, however, apply to the
brutish pariah dogs that infest the streets of Madras, Constantinople,
and other eastern towns.
The Roman peasants found the flesh of the ass palatable, and the
celebrated Mæcenas having tasted it, introduced it to the tables of
the great and rich, but the fashion of eating it lasted no longer than
his life. Galen compares the flesh of the ass to that of the stag. It is
said to be eaten plentifully in the low eating-houses of Paris, under
the denomination of veal. The flesh of the wild ass is eaten by the
Tartars, and is said to be very delicate and good, but when killed in a
tame state, it is hard and unfit for food.
The wild ass, called Koulan by the Persians, is still common in many
parts of Central Asia, from the 48° of North latitude to the confines of
India. The Persians and Tartars hold its flesh in high esteem, and
hunt it in preference to all other descriptions of game. Olearius
assures us, that he saw no fewer than 32 wild asses slain in one
day, by the Shah of Persia and his court, the bodies of which were
sent to the royal kitchens at Ispahan; and we know from Martial, that
the epicures of Rome held the flesh of the Onager, or wild ass, in the
same estimation as we do venison.

Cum tener est Onager, solaque lalisio matre

Pascitur; hoc infans, sed breve nomen habet.
[Martial, xiii. 97.]

From a passage in Pliny (lib. viii., c. 44), it would appear, that the
Onager inhabited Africa; and that the most delicate and best
flavoured lalisiones, or fat foals, were brought from that continent to
the Roman markets. Leo Africanus repeats the same story of wild
asses being found in Africa, but no traveller has since met with them;
and, as far as we at present know, the species is confined to Asia.
The quaggas (Asinus Quagga) are often hunted in Africa by the
Dutch for their skins, of which they make large bags to hold their
grain, and by the Hottentots and other natives, who are very fond of
their flesh.
Lieutenant Moodie (Ten Years in South Africa) says, ‘Being one
morning at the house of a neighbouring farmer who had just shot
one of these animals, I requested that he would have a piece of the
flesh cooked for my breakfast. His ‘frow’ expressed some disgust at
my proposal, but ordered a small bit to be grilled, with butter and
pepper. I did not find it at all unpalatable, and certainly it was better
than horse-flesh, to which I had been treated in the hospital at