Nanoparticle Technology Handbook 3rd

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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
This page intentionally left blank
 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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doctrine, and fills up the greater part of the epistle with reproofs of
these errors.

His argument against the doctrines of the servile Judaizers is

made up in his favorite mode of demonstration, by simile and
metaphor, representing the Christian system under the form of the
offspring of Abraham, and afterwards images the freedom of the true
believers in Jesus, in the exalted privilege of the descendants of
Sara, while those enslaved to forms are presented as analogous in
their condition to the children of Hagar. He earnestly exhorts them,
therefore, to stand fast in the freedom to which Christ has exalted
them, and most emphatically condemns all observance of
circumcision. Thus pointing out to them, the purely spiritual nature of
that covenant, of which they were now the favored subjects, he
urges them to a truly spiritual course of life, bidding them aim at the
attainment of a perfect moral character, and makes the conclusion of
the epistle eminently practical in its direction. He speaks of this
epistle as being a testimony of the very particular interest which he
feels in their spiritual prosperity, because, (what appears contrary to
his practice,) he has written it with his own hand. To the very last, he
is very bitter against those who are aiming to bring them back to the
observance of circumcision, and denounces those as actuated only
by a base desire to avoid that persecution which they might expect
from the Jews, if they should reject the Mosaic ritual. Referring to the
cross of Christ as his only glory, he movingly alludes to the marks of
his conformity to that standard, bearing as he does in his own body,
the scars of the wounds received from the scourges of his Philippian
persecutors. He closes without any mention of personal salutations,
and throughout the whole makes none of those specifications of
names, with which most of his other epistles abound. In the opening
salutation, he merely includes with himself those “brethren that are
with him,” which seems to imply that they knew who those brethren
were, in some other way,――perhaps, because he had but lately
been among them with those same persons as his assistants in the
ministry.
 On this very doubtful point, I have taken the views adopted by Witsius, Louis Cappel,
Pearson, Wall, Hug and Hemsen. The notion that it was written at Rome is supported by
Theodoret, Lightfoot, and Paley,――of course making it a late epistle. On the contrary,
Michaelis makes it the earliest of all, and dates it in the year 49, at some place on Paul’s
route from Troas to Thessalonica. Marcion and Tertullian also supposed it to be one of the
earliest epistles. Benson thinks it was written during Paul’s first residence in Corinth.
Lenfant and Beausobre, followed by Lardner, conjecture it to have been written either at
Corinth or at Ephesus, during his first visit, either in A. D. 52, or 53. Fabricius and Mill date it
A. D. 58, at some place on Paul’s route to Jerusalem. Chrysostom and Theophylact, date it
before the epistle to the Romans. Grotius thinks it was written about the same time. From all
which, the reader will see the justice of my conclusion, that nothing at all is known with any
certainty about the matter.

the ephesian mob.

Paul having now been a resident in Ephesus for nearly three

years, and having seen such glorious results of his labors, soon
began to think of revisiting some of his former fields of missionary
exertion, more especially those Grecian cities of Europe which had
been such eventful scenes to him, but a few years previous. He
designed to go over Macedonia and Achaia, and then to visit
Jerusalem; and when communicating these plans to his friends at
Ephesus, he remarked to them in conclusion――“And after that, I
must also visit Rome.” He therefore sent before him into Macedonia,
as the heralds of his approach, his former assistant, Timothy, and
another helper not before mentioned, Erastus, who is afterwards
mentioned as the treasurer of the city of Corinth. But Paul himself
still waited in Asia for a short time, until some other preliminaries
should be arranged for his removal. During this incidental delay
arose the most terrible commotion that had ever yet been excited
against him, and one which very nearly cost him his life.

It should be noticed that the conversion of so large a number of

the heathen, through the preaching of Paul, had struck directly at the
foundation of a very thriving business carried on in Ephesus, and
connected with the continued prevalence and general popularity of
that idolatrous worship, for which the city was so famous. Ephesus,
as is well known, was the chief seat of the peculiar worship of that
great Asian deity, who is now known, throughout all the world, where
the apostolic history is read, by the name of “Diana of the
Ephesians.” It is perfectly certain, however, that this deity had no
real connection, either in character or in name, with that Roman
goddess of the chase and of chastity, to whom the name Diana
properly belongs. The true classic goddess Diana was a virgin,
according to common stories, considered as the sister of Apollo, and
was worshiped as the beautiful and youthful goddess of the chase,
and of that virgin purity of which she was supposed to be an
instance, though some stories present an exception to this part of
her character. Upon her head, in most representations of her, was
pictured a crescent, which was commonly supposed to show, that
she was also the goddess of the moon; but a far more sagacious
and rational supposition refers the first origin of this sign to a deeper
meaning. But when the mythologies of different nations began to be
compared and united, she was identified with the goddess of the
moon, and with that Asian goddess who bore among the Greeks the
name of Artemis, which is in fact the name given by Luke, as the
title of the great goddess of the Ephesians. This Artemis, however,
was a deity as diverse in form, character and attributes, from the
classic Diana, as from any goddess in all the systems of ancient
mythology; and they never need have been confounded, but for the
perverse folly of those who were bent, in spite of all reason, to find in
the divinities of the eastern polytheism, the perfect synonyms to the
objects of western idolatry. The Asian and Ephesian goddess
Artemis, had nothing whatever to do with hunting nor with chastity.
She was not represented as young, nor beautiful, nor nimble, nor as
the sister of Apollo, but as a vast gigantic monster, with a crown of
towers, with lions crouching upon her shoulders, and a great array of
pictured or sculptured eagles and tigers over her whole figure; and
her figure was also strangely marked by a multitude of breasts in
front. Under this monstrous figure, which evidently was no invention
of the tasteful Greeks, but had originated in the debasing and
grotesque idolatry of the orientals, Artemis of the Ephesians was
worshiped as the goddess of the earth, of fertility, of cities, and as
the universal principle of life and wealth. She was known among the
Syrians by the name of Ashtaroth, and was among the early objects
of Hebrew idolatry. When the Romans, in their all-absorbing
tolerance of idolatry, began to introduce into Italy the worship of the
eastern deities, this goddess was also added there, but not under
the name of Diana. The classic scholar is familiar with the allusions
to this deity, worshiped under the name of Cybele, Tellus and other
such, and in all the later poets of Rome, she is a familiar object, as
“the tower-crowned Cybele.” This was the goddess worshiped in
many of the Grecian cities of Asia Minor, which, at their first
colonization, had adopted this aboriginal goddess of those fertile
regions, of whose fertility, civilization, agricultural and commercial
wealth, she seemed the fit and appropriate personification. But in
none of these Asian cities was she worshiped with such peculiar
honors and glories as in Ephesus, the greatest city of Asia Minor.
Here was worshiped a much cherished image of her, which was said
to have fallen from heaven, called from that circumstance the
Diopetos; which here was kept in that most splendid temple, which
is even now proverbial as having been one of the wonders of the
ancient world. Being thus the most famous seat of her worship,
Ephesus also became the center of a great manufacture and trade in
certain curious little images or shrines, representing this goddess,
which were in great request, wherever her worship was regarded,
being considered as the genuine and legitimate representatives, as
well as representations of the Ephesian deity.

This explanation will account for the circumstances related by

Luke, as ensuing in Ephesus, on the success of Paul’s labors among
the heathen, to whose conversion his exertions had been wholly
devoted during the two last years of his stay in Ephesus. In
converting the Ephesians from heathenism, he was guilty of no
ordinary crime. He directly attacked a great source of profit to a large
number of artizans in the city, who derived their whole support from
the manufacture of those little objects of idolatry, which, of course,
became of no value to those who believed Paul’s doctrine,――that
“those were no gods which were made with hands.” This new
doctrine therefore, attracted very invidious notice from those who
thus found their dearest interests very immediately and unfortunately
affected, by the progress made by its preacher in turning away the
hearts of Ephesians from their ancient reverence for the shrines of
Artemis; and they therefore listened with great readiness to
Demetrius, one of their number, when he proposed to remedy the
difficulty. He showed them in a very clear, though brief address, that
“the craft was in danger,”――that warning cry which so often bestirs
the bigoted in defence of the object of their regard; and after hearing
his artful address, they all, full of wrath, with one accord raised a
great outcry, in the usual form of commendation of the established
idolatry of their city,――“Great is Artemis of the Ephesians!” This
noise being heard by others, and of course attracting attention, every
one who distinguished the words, by a sort of patriotic impulse, was
driven to join in the cry, and presently the whole city was in an
uproar;――a most desirable condition of things, of course, for those
who wished to derive advantage from a popular commotion. All
bawling this senseless cry, with about as much idea of the occasion
of the disturbance as could be expected from such a mob, the
huddling multitudes learning the general fact, that the grand object of
the tumult was to do some mischief to the Christians, and looking
about for some proper person to be made the subject of public
opinion, fell upon Gaius and Aristarchus of Macedonia, two traveling
companions of Paul, who happened to be in the way, and dragged
them to the theater, whither the whole mob rushed at once, as to a
desirable scene for any act of confusion and folly which they might
choose to commit. Paul, with a lion-like spirit, caring naught for the
mob, proposed to go in and make a speech to them, but his friends,
with far more prudence and cool sense than he,――knowing that an
assembly of the people, roaring some popular outcry, is no more a
subject of reason than so many raging wild beasts,――prevented
him from going into the theater, where he would no doubt have been
torn to pieces, before he could have opened his mouth. Some of the
great magistrates of Asia, too, who were friendly to him, hearing of
his rash intentions, sent to him a very urgent request, that he would
not venture himself among the mob. Meanwhile the outcry
continued,――the theater being crowded full,――and the whole city
constantly pouring out to see what was the matter, and every soul
joining in the religious and patriotic shout, “Great is Artemis of the
Ephesians!” And so they went on, every one, of course, according to
the universal and everlasting practice on such occasions, making all
the noise he could, but not one, except the rascally silversmiths,
knowing what upon earth they were all bawling there for. Still this
ignorance of the object of the assembly kept nobody still; but all, with
undiminished fervor, kept plying their lungs to swell the general roar.
As it is described in the very graphic and picturesque language of
Luke,――“Some cried one thing, and some, another; for the whole
assembly was confused;――and the more knew not wherefore they
were come together,”――which last circumstance is a very common
difficulty in such assemblies, in all ages. At last, searching for some
other persons as proper subjects to exercise their religious zeal
upon, they looked about upon the Jews, who were always a
suspected class among the heathen, and seized one Alexander, who
seems to have been one of the Christian converts, for the Jews
thrust him forward as a kind of scapegoat for themselves. Alexander
made the usual signs soliciting their attention to his words; but as
soon as the people understood that he was a Jew, they all drowned
his voice with the general cry, “Great is Artemis of the Ephesians!”
and this they kept up steadily for two whole hours, as it were with
one voice. Matters having come to this pass, the recorder of the city
came forward, and having hushed the people,――who had some
reverence for the lawful authorities, that fortunately were not
responsible to them,――and made them a very sensible speech,
reminding them that since no one doubted the reverence of the
Ephesians for the goddess Artemis, and for the Diopetos, there
surely was no occasion for all this disturbance to demonstrate a fact
that every body knew. He told them that the men against whom they
were raising this disturbance had neither robbed their temples nor
blasphemed the goddess; so that if Demetrius and his fellow-craft
had anything justly against these men, as having injured their
business, they had their proper remedy at law. He hinted to them
also that they were all liable to be called to account for this manifest
breach of Roman law, and this defiance of the majesty of the Roman
government;――a hint which brought most of them to their senses;
for all who had anything to lose, dreaded the thought of giving
occasion to the awfully remorseless government of the province, to
fine them, as they certainly would be glad to do on any valid excuse.
They all dispersed, therefore, with no more words.

“‘Silver shrines,’ verse 24. The heathens used to carry the images of their gods in
procession from one city to another. This was done in a chariot which was solemnly
consecrated for that employment, and by the Romans styled Thensa, that is, the chariot of
their gods. But besides this, it was placed in a box or shrine, called Ferculum. Accordingly,
when the Romans conferred divine honors on their great men, alive or dead, they had the
Circen games, and in them the Thensa and Ferculum, the chariot and the shrine, bestowed
on them; as it is related of Julius Caesar. This Ferculum among the Romans did not differ
much from the Graecian Ναὸς, a little chapel, representing the form of a temple, with an
image in it, which, being set upon an altar, or any other solemn place, having the doors
opened, the image was seen by the spectators either in a standing or sitting posture. An old
anonymous scholiast upon Aristotle’s Rhetoric, lib. i. c. 15, has these words: Ναοποιοὶ οἱ
τοὺς ναοὺς ποιοῦσι, ἤτοι εἱκονοστάσια, τινα μικρὰ ξύλινα ἅ πωλοῦσι, observing the ναοι here to
be εικονοστάσια, chaplets, with images in them, of wood, or metal, (as here of silver,) which
they made and sold, as in verse 25, they are supposed to do. Athenaeus speaks of the
καδισκος, ‘which,’ says he ‘is a vessel wherein they place their images of Jupiter.’ The
learned Casaubon states, that ‘these images were put in cases, which were made like
chapels. (Deipnos. lib. ii. p. 500.) So St. Chrysostom likens them to ‘little cases, or shrines.’
Dion says of the Roman ensign, that it was a little temple, and in it a golden eagle, (Ρωμαικ,
lib. 40.) And in another place: ‘There was a little chapel of Juno, set upon a table.’ Ρωμαικ,
lib. 39. This is the meaning of the tabernacle of Moloch, Acts vii. 43, where by the σκηνη,
tabernacle, is meant the chaplet, a shrine of that false god. The same was also the ‫סכות דנות‬
the tabernacle of Benoth, or Venus.” Hammond’s Annotations. [Williams on Pearson, p. 55.]

Robbers of temples.――Think of the miserable absurdity of the common English

translation in this passage, (Acts xix. 37,) where the original ἱεροσυλοι is expressed by
“robbers of churches!” Now who ever thought of applying the English word “church,” to
anything whatever but a “Christian assembly,” or “Christian place of assembly?” Why then is
this phrase put in the mouth of a heathen officer addressing a heathen assembly about
persons charged with violating the sanctity of heathen places of worship? Such a building
as a church, (εκκλησια, ecclesia) devoted to the worship of the true God, was not known till
more than a century after this time; and the Greek word ἱερον, (hieron,) which enters into the
composition of the word in the sacred text, thus mistranslated, was never applied to a
Christian place of worship.

first epistle to the corinthians.

Paul’s residence in Ephesus is distinguished in his literary history,

as the period in which he wrote that most eloquent and animated of
his epistles,――“the first to the Corinthians.” It was written towards
the close of his stay in Asia, about the time of the passover;
according to established calculations, therefore, in the spring of the
year of Christ 57. The more immediate occasion of his writing to the
Corinthian Christians, was a letter which he had received from them,
by the hands of Stephanas, Fortunatus and Achaicus. Paul had
previously written to them an epistle, (now lost,) in which he gave
them some directions about their deportment, which they did not fully
understand, and of which they desired an explanation in their letter.
Many of these questions, which this epistle of the Corinthians
contained, are given by Paul, in connection with his own answers to
them; and from this source it is learned that they concerned several
points of expediency and propriety about matrimony. These are
answered by Paul, very distinctly and fully; but much of his epistle is
taken up with instructions and reproofs on many points not referred
to in their inquiries. The Corinthian church was made up of two very
opposite constituent parts, so unlike in their character, as to render
exceedingly complicated the difficulties of bringing all under one
system of faith and practice; and the apostolic founder was, at one
time, obliged to combat heathen licentiousness, and at another,
Jewish bigotry and formalism. The church also, having been too
soon left without the presence of a fully competent head, had been
very loosely filled up with a great variety of improper
persons,――some hypocrites, and some profligates,――a difficulty
not altogether peculiar to the Corinthian church, nor to those of the
apostolic age. But there were certainly some very extraordinary
irregularities in the conduct of their members, some of whom were in
the habit of getting absolutely drunk at the sacramental table; and
others were guilty of great sins in respect to general purity of life.
Another peculiar difficulty, which had arisen in the church of Corinth,
during Paul’s absence, was the formation of sects and parties, each
claiming some one of the great Christian teachers as its head; some
of them claiming Paul as their only apostolic authority; some again
preferring the doctrines of Apollos, who had been laboring among
them while Paul was in Ephesus; and others again, referred to Peter
as the true apostolic chief, while they wholly denied to Paul any
authority whatever, as an apostle. There had, indeed, arisen a
separate party, strongly opposed to Paul, headed by a prominent
person, who had done a great deal to pervert the truth, and to lessen
the character of Paul in various ways, which are alluded to by Paul in
many passages of his epistle, in a very indignant tone. Other
difficulties are described by him, and various excesses are reproved,
as a scandal to the Christian character; such as an incestuous
marriage among their members,――lawsuits before heathen
magistrates,――dissolute conformity to the licentious worship of the
Corinthian goddess, whose temple was so infamous for its
scandalous rites and thousand priestesses. Some of the Corinthian
Christians had been in the habit of visiting this and other heathen
temples, and of participating in the scenes of feasting, riot and
debauchery, which were carried on there as a part of the regular
forms of idolatrous worship.

The public worship of the Corinthian church had been disturbed

also by various irregularities which Paul reprehends;――the abuse
of the gift of tongues, and the affectation of an unusual dress in
preaching, both by men and women. In the conclusion of his epistle
he expatiates too, at great length, on the doctrine of the resurrection
of the body, vehemently arguing against some Corinthian heretics,
who had denied any but a spiritual existence beyond the grave. This
argument may justly be pronounced the best specimen of Paul’s
very peculiar style, reasoning as he does, with a kind of passion, and
interrupting the regular series of logical demonstrations, by fiery
bursts of enthusiasm, personal appeals, poetical quotations,
illustrative similes, violent denunciations of error, and striking
references to his own circumstances. All these nevertheless, point
very directly and connectedly at the great object of the argument,
and the whole train of reasoning swells and mounts, towards the
conclusion, in a manner most remarkably effective, constituting one
of the most sublime argumentative passages ever written. He then
closes the epistle with some directions about the mode of collecting
the contributions for the brethren in Jerusalem. He promises to visit
them, and make a long stay among them, when he goes on his
journey through Macedonia,――a route which, he assures them, he
had now determined to take, as mentioned by Luke, in his account of
the preliminary mission of Timothy and Erastus, before the time of
the mob at Ephesus; but should not leave Ephesus until after
Pentecost, because a great and effectual door was there opened to
him, and there were many opposers. He speaks of Timothy as being
then on the mission before mentioned, and exhorts them not to
despise this young brother, if he should visit them, as they might
expect. After several other personal references, he signs his ♦ own
name with a general salutation; and from the terms, in which he
expresses this particular mark already alluded to in the second
epistle to the Thessalonians, it is very reasonable to conclude, that
he was not his own penman in any of these epistles, but used an
amanuensis, authenticating the whole by his signature, with his own
hand, only at the end; and this opinion of his method of carrying on
his correspondence, is now commonly, perhaps universally, adopted
by the learned.

♦ “ownn,ame” replaced with “own name”

“Chapter xvi. 10, 11. ‘Now, if Timotheus come, see that he may be with you without fear;
for he worketh the work of the Lord, as I also do: let no man therefore despise him, but
conduct him forth in peace, that he may come unto me, for I look for him with the brethren.’

“From the passage considered in the preceding number, it appears that Timothy was
sent to Corinth, either with the epistle, or before it: ‘for this cause have I sent unto you
Timotheus.’ From the passage now quoted, we infer that Timothy was not sent with the
epistle; for had he been the bearer of the letter, or accompanied it, would St. Paul in that
letter have said, ‘if Timothy come?’ Nor is the sequel consistent with the supposition of his
carrying the letter; for if Timothy was with the apostle when he wrote the letter, could he say,
as he does, ‘I look for him with the brethren?’ I conclude, therefore, that Timothy had left St.
Paul to proceed upon his journey before the letter was written. Further, the passage before
us seems to imply, that Timothy was not expected by St. Paul to arrive at Corinth, till after
they had received the letter. He gives them directions in the letter how to treat him when he
should arrive: ‘if he come,’ act towards him so and so. Lastly, the whole form of expression
is more naturally applicable to the supposition of Timothy’s coming to Corinth, not directly
from St. Paul, but from some other quarter; and that his instructions had been, when he
should reach Corinth, to return. Now, how stands this matter in the history? Turn to the
nineteenth chapter and twenty-first verse of the Acts, and you will find that Timothy did not,
when sent from Ephesus, where he left St. Paul, and where the present epistle was written,
proceed by a straight course to Corinth, but that he went round through Macedonia. This
clears up everything; for, although Timothy was sent forth upon his journey before the letter
was written, yet he might not reach Corinth till after the letter arrived there; and he would
come to Corinth, when he did come, not directly from St. Paul, at Ephesus, but from some
part of Macedonia. Here therefore is a circumstantial and critical agreement, and
unquestionably without design; for neither of the two passages in the epistle mentions
Timothy’s journey into Macedonia at all, though nothing but a circuit of that kind can explain
and reconcile the expressions which the writer uses.” (Paley’s Horae Paulinae, 1
Corinthians No. IV.)

“Chapter v. 7, 8. ‘For even Christ, our passover, is sacrificed for us; therefore let us keep
the feast, not with old leaven, neither with the leaven of malice and wickedness, but with the
unleavened bread of sincerity and truth.’

“Dr. Benson tells us, that from this passage, compared with chapter xvi. 8, it has been
conjectured that this epistle was written about the time of the Jewish passover; and to me
the conjecture appears to be very well founded. The passage to which Dr. Benson refers us,
is this: ‘I will tarry at Ephesus until Pentecost.’ With this passage he ought to have joined
another in the same context: ‘And it may be that I will abide, yea, and winter with you:’ for,
from the two passages laid together, it follows that the epistle was written before Pentecost,
yet after winter; which necessarily determines the date to the part of the year, within which
the passover falls. It was written before Pentecost, because he says, ‘I will tarry at Ephesus
until Pentecost.’ It was written after winter, because he tells them, ‘It may be that I may
abide, yea, and winter with you.’ The winter which the apostle purposed to pass at Corinth,
was undoubtedly the winter next ensuing to the date of the epistle; yet it was a winter
subsequent to the ensuing Pentecost, because he did not intend to set forwards upon his
journey till after the feast. The words, ‘let us keep the feast, not with old leaven, neither with
the leaven of malice and wickedness, but with the unleavened bread of sincerity and truth,’
look very much like words suggested by the season; at least they have, upon that
supposition, a force and significancy which do not belong to them upon any other; and it is
not a little remarkable, that the hints casually dropped in the epistle, concerning particular
parts of the year, should coincide with this supposition.” (Paley’s Horae Paulinae. 1
Corinthians. No. XII.)

second voyage to europe.

After the disturbances connected with the mob raised by

Demetrius had wholly ceased, and public attention was no longer
directed to the motions of the preachers of the Christian doctrine,
Paul determined to execute the plan, which he had for some time
contemplated, of going over his European fields of labor again,
according to his universal and established custom of revisiting and
confirming his work, within a moderately brief period after first
opening the ground for evangelization. Assembling the disciples
about him, he bade them farewell, and turning northward, came to
Troas, whence, six or seven years before, he had set out on his first
voyage to Macedonia. The plan of his journey, as he first arranged it,
had been to sail from the shores of Asia Minor directly for Corinth.
He had resolved however, not to go to that city, until the very
disagreeable difficulties which had there arisen in the church, had
been entirely removed, according to the directions given in the
epistle which he had written to them from Ephesus; because he did
not desire, after an absence of years, to visit them in such
circumstances, when his Corinthian converts were divided among
themselves, and against him,――and when his first duties would
necessarily be those of a rigid censor. He therefore waited at Troas,
with great impatience, for a message from them, announcing the
settlement of all difficulties. This he expected to receive through
Titus, a person now first mentioned in the apostle’s history. Waiting
with great impatience for this beloved brother, he found no rest in his
spirit, and though a door was evidently opened by the Lord for the
preaching of the gospel in Troas, he had no spirit for the good work
there; and desiring to be as near the great object of his anxieties as
possible, he accordingly took leave of the brethren at Troas, and
crossed the Aegean into Macedonia, by his former route. Here he
remained in great distress of mind, until his soul was at last
comforted by the long expected arrival of Titus. Luke only says, that
he went over those parts and gave them much exhortation. But
though his route is not given, his apostolic labors are known to have
extended to the borders of Illyricum. At this time also, he made
another important contribution to the list of the apostolic writings.

the second epistle to the corinthians.

There is no part of the New Testament canon, about the date of

which all authorities are so well agreed, as on the place and time, at
which Paul wrote his second epistle to the Corinthians. All
authorities, ancient and modern, decide that it was written during the
second visit of Paul to Macedonia; although as to the exact year in
which this took place, they are not entirely unanimous. The
passages in the epistle itself, which refer to Macedonia as the region
in which the apostle then was, are so numerous indeed, that there
can be no evasion of their evidence. A great topic of interest with
him, at the time of writing this epistle, was the collecting of the
contributions proposed for the relief of the Christian brethren in
Jerusalem; and upon this he enlarges much, informing the
Corinthians of the great progress he was making in Macedonia in
this benevolent undertaking, and what high hopes he had
entertained and expressed to the Macedonians, of the zeal and
ability of those in Achaia, about the contributions. This matter had
been noticed and arranged by him, in his former epistle to them, as
already noticed, and he now proposed to send forward Titus and
another person, (who is commonly supposed to be Luke,) to take
charge of these funds, thus collected. He speaks of coming also
himself, after a little time, and makes some allusions to the difficulties
which had constituted the subject of the great part of his former
epistle. Of their amendment in the particulars then so severely
censured, he had received a full account through Titus, when that
beloved brother came on from Corinth, to join Paul in Macedonia.
Paul assures the Corinthians of the very great joy caused in him, by
the good news of their moral and spiritual improvement, and renews
his ardent protestations of deep affection for them. The incestuous
person, whom they had excommunicated, in conformity with the
denunciatory directions given in the former epistle, he now forgives;
and as the offender has since appeared to be truly penitent, he now
urges his restoration to the consolations of Christian fellowship, lest
he should be swallowed up with too much sorrow. He defends his
apostolic character for prudence and decision, against those who
considered his change of plans about coming directly from Ephesus
to Corinth, as an exhibition of lightness and unsettled purpose. His
real object in this delay and change of purpose, as he tells them,
was, that they might have time to profit by the reproofs contained in
his former epistle, so that by the removal of the evils of which he so
bitterly complained, he might finally be enabled to come to them, not
in sorrow, nor in heaviness for their sins, but in joy for their
reformation. This fervent hope had been fulfilled by the coming of
Titus to Macedonia, for whom he had waited in vain, with so much
anxiety at Troas, as the expected messenger of these tidings of their
spiritual condition; and he was now therefore prepared to pass on to
them from Macedonia, to which region he tells them he had gone
from Troas, instead of to Corinth, because he had been disappointed
about meeting Titus on the eastern side of the Aegean. With the
exception of these things, the epistle is taken up with a very ample
and eloquent exhibition of his true powers and office as an apostle;
and in the course of this argument, so necessary for the re-
establishment of his authority among those who had lately been
disposed to contemn it, he makes many very interesting allusions to
his own personal history. The date of the epistle is commonly
supposed, and with good reason, to be A. D. 58, the fifth of Nero’s
reign, and one year after the preceding epistle.

MILETUS. Acts xx. 15‒17.

“Chapter ii. 12, 13. ‘When I came to Troas to preach Christ’s gospel, and a door was
opened unto me of the Lord, I had no rest in my spirit, because I found not Titus my brother;
but taking my leave of them, I went from thence into Macedonia.’

“To establish a conformity between this passage and the history, nothing more is
necessary to be presumed, than that St. Paul proceeded from Ephesus to Macedonia, upon
the same course by which he came back from Macedonia to Ephesus, or rather to Miletus
in the neighborhood of Ephesus; in other words, that, in his journey to the peninsula of
Greece, he went and returned the same way. St. Paul is now in Macedonia, where he had
lately arrived from Ephesus. Our quotation imports that in his journey he had stopped at
Troas. Of this, the history says nothing, leaving us only the short account, ‘that Paul
departed from Ephesus, for to go into Macedonia.’ But the history says, that in his return
from Macedonia to Ephesus, ‘Paul sailed from Philippi to Troas; and that, when the disciples
came together on the first day of the week, to break bread, Paul preached unto them all
night; that from Troas he went by land to Assos; from Assos, taking ship and coasting along
the front of Asia Minor, he came by Mitylene to Miletus.’ Which account proves, first, that
Troas lay in the way by which St. Paul passed between Ephesus and Macedonia; secondly,
that he had disciples there. In one journey between these two places, the epistle, and in
another journey between the same places, the history makes him stop at this city. Of the
first journey he is made to say, ‘that a door was in that city opened unto him of the Lord;’ in
the second, we find disciples there collected around him, and the apostle exercising his
ministry, with, what was even in him, more than ordinary zeal and labor. The epistle,
therefore, is in this instance confirmed, if not by the terms, at least by the probability of the
history; a species of confirmation by no means to be despised, because, as far as it
reaches, it is evidently uncontrived.

“Grotius, I know, refers the arrival at Troas, to which the epistle alludes, to a different
period, but I think very improbably; for nothing appears to me more certain, than that the
meeting with Titus, which St. Paul expected at Troas, was the same meeting which took
place in Macedonia, viz. upon Titus’s coming out of Greece. In the quotation before us, he
tells the Corinthians, ‘When I came to Troas, I had no rest in my spirit, because I found not
Titus, my brother; but, taking my leave of them, I went from thence into Macedonia.’ Then in
the seventh chapter he writes, ‘When we were come into Macedonia, our flesh had no rest,
but we were troubled on every side; without were fightings, within were fears; nevertheless,
God, that comforteth them that are cast down, comforted us by the coming of Titus.’ These
two passages plainly relate to the same journey of Titus, in meeting with whom St. Paul had
been disappointed at Troas, and rejoiced in Macedonia. And amongst other reasons which
fix the former passage to the coming of Titus out of Greece, is the consideration, that it was
nothing to the Corinthians that St. Paul did not meet with Titus at Troas, were it not that he
was to bring intelligence from Corinth. The mention of the disappointment in this place,
upon any other supposition, is irrelative.” (Paley’s Horae Paulinae. 2 Corinthians No. VIII.)

second journey to corinth.

Among his companions in Macedonia, was Timothy, his ever

zealous and affectionate assistant in the apostolic ministry, who had
been sent thither before him to prepare the way, and had been
laboring in that region ever since, as plainly appears from the fact,
that he is joined with Paul in the opening address of the second
epistle to the Corinthians,――a circumstance in itself sufficient to
overthrow a very common supposition of the critics,――that Timothy
returned to Asia; that Paul at that time “left him in Ephesus,” and at
this time wrote his first epistle to Timothy from Macedonia. It is also
most probable that Timothy was the personal companion of Paul, not
only during the whole period of his second ministration in
Macedonia, but also accompanied him from that province to Corinth;
because Timothy is distinctly mentioned by Luke, among those who
went with Paul from Macedonia to Asia, after his brief second
residence in that city. No particulars whatever are given by Luke of
the labors of Paul in Corinth. From his epistles, however, it is learned
that he was at this time occupied in part, in receiving the
contributions made throughout Achaia for the church of Jerusalem,
to which city he was now preparing to go. The difficulties, of which so
much mention had been made in his epistles, were now entirely
removed, and his work there doubtless went on without any of that
opposition which had arisen after his first departure. There is
however, one very important fact in his literary history, which took
place in Corinth, during his residence there.

the epistle to the romans.

From the very earliest period of apostolic labor, after the

ascension, there appear to have been in Rome, some Jews who
professed the faith of Jesus. Among the visitors in Jerusalem at the
Pentecost, when the Holy Spirit first descended, were some from
Rome, who sharing in the gifts of that remarkable effusion, and
returning to their home in the imperial city, would there in themselves
constitute the rudiment of a Christian church. It is perfectly certain
that they had never been blessed in their own city with the personal
presence of an apostle and all their associated action as a Christian
church, must therefore have been entirely the result of a voluntary
organization, suggested by the natural desire to keep up and to
spread the doctrines which they had first received in Jerusalem,
under such remarkable circumstances. Yet the members of the
church would not be merely those who were converted at the
Pentecost; for there was a constant influx of Jews from all parts of
the world to Rome, and among these there would naturally be some
who had participated in the light of the gospel, now so widely
diffused throughout the eastern section of the world. There is
moreover distinct information of certain persons of high
qualifications, as Christian teachers, who had at Rome labored in the
cause of the gospel, and had no doubt been among the most
efficient means of that advancement of the Roman church, which
seems to be implied in the communication now first made to them by
Paul. Aquilas and Priscilla, who had been the intimate friends of Paul
at Corinth, and who had been already so active and distinguished as
laborers in the gospel cause, both in that city and in Ephesus, had
returned to Rome on the death of Claudius, when that emperor’s
foolish decree of banishment, against the Jews, expired along with
its author, in the year of Christ, 54. These, on re-establishing their
residence in Rome, made their own house a place of assembly for a
part of the Christians in the capital,――probably for such as resided
in their own immediate neighborhood, while others sought different
places, according as suited their convenience in this particular. Many
other persons are mentioned by Paul at the close of this epistle, as
having been active in the work of the gospel at Rome;――among
whom Andronicus and Junias are particularly noticed with respect,
as having highly distinguished themselves in apostolic labors. From
all these evangelizing efforts, the church of Rome attained great
importance, and was now in great need of the counsels and
presence of an apostle, to confirm it, and impart to its members
spiritual gifts. It had long been an object of attention and interest to
Paul, and he had already expressed a determination to visit the
imperial city, in the remarks which he made to the brethren at
Ephesus, when he was making arrangements to go into Macedonia
and Achaia. The way was afterwards opened for this visit, by a very
peculiar providence, which he does not seem to have then
anticipated; but while residing in Corinth, his attention being very
particularly called to their spiritual condition, he could not wait till he
should have an opportunity to see them personally, to counsel them;
but wrote to them this very copious and elaborate epistle, which
seems to have been the subject of more comment among dogmatic
theologians, than almost any other portion of his writings, on account
of its being supposed to furnish different polemic writers with the
most important arguments for the peculiar dogmas of one or another,
according to the fancy of each. It undoubtedly is the most doctrinal
and didactic of all Paul’s epistles, alluding very little to local
circumstances, which are the theme of so large a part of most of his
writings, but attacking directly certain general errors entertained by
the Jews, on the subject of justification, predestination, election, and
many peculiar privileges which they attributed to themselves as the
descendants of Abraham.
 This epistle, like most of the rest, was written by an amanuensis,
who is herein particularly named, as Tertius,――a word of Roman
origin; but beyond this nothing else is known of him. It was carried to
Rome by Phebe, an active female member of the church at
Cenchreae, the port of Corinth, who happened to be journeying to
Rome for some other purposes, and is earnestly recommended by
Paul to the friendly regard of the church there.

return to asia.

After passing three months in Corinth, he took his departure from

that city, on his pre-determined voyage to the east, the direction of
which was somewhat changed by the information that the Jews of
the place where he then was, were plotting some mischief against
him, which he thought best to avoid by taking a different route from
that before planned, which was a direct voyage to Syria. To escape
the danger prepared for him by them, at his expected place of
embarkation, he first turned northward by land, through Macedonia
to Philippi, and thence sailed by the now familiar track over the
Aegean to Troas. On this journey, he was accompanied by quite a
retinue of apostolic assistants,――not only his faithful disciple and
companion Timothy, but also Sosipater of Beroea, Aristarchus and
Secundus of Thessalonica, Gaius, or Caius of Derbe, and Luke also,
who now carries on the apostolic narrative in the first person, thus
showing that he was himself a sharer in the adventures which he
narrates. Besides these immediate companions, two brethren from
Asia, Tychicus and Trophimus, took the direct route from Corinth to
Troas, at which place they waited for the rest of the apostolic
company, who took the circuitous route through Macedonia. The
date of the departure of Paul is very exactly fixed by his companion
Luke, who states that they left Philippi at the time of the passover,
which was in the middle of March; and other circumstances have
enabled modern critics to fix the occurrence in the year of Christ 59.
After a five days’ voyage, arriving at Troas on Saturday, they made a
stay of seven days in that place; and on the first day of the week, the
Christians of that place having assembled for the communion usual
on the Lord’s day, Paul preached to them: and as it was the last day
of his stay, he grew very earnest in his discourse and protracted it
very late, speaking two whole hours to the company, who were met
in the great upper hall, where, in all Jewish houses, these festal
entertainments and social meetings were always held. It was, of
course, the evening, when the assembly met, for this was the usual
time for a social party, and there were many lights in the room,
which, with the number of people, must have made the air very
warm, and had the not very surprising effect of causing drowsiness,
in at least one of Paul’s hearers, a young man named ♦ Eutychus,
whose interest in what was said, could not keep his attention alive
against the pressure of drowsiness. He fell asleep; and the
occurrence must appear so very natural, (more particularly to any
one, who has ever been so unfortunate as to be sleepy at an
evening meeting, and knows what a painful sensation it is, though
the drowsiness is wholly beyond the control of the reason,) that it
can hardly be thought worth while to take pains, as some venerable
commentators do, to suppose that the devil was very specially
concerned in producing the sleep of Eutychus, and that the
consequences which ensued, were an exhibition of divine wrath
against the sleepy youth, for slumbering under the preaching of Paul.
If the supposition holds equally good in all similar cases, the devil
must be very busy on warm Sunday afternoons; and many a
comfortable nap would be disturbed by unpleasant dreams, if the
dozer could be made to think that his drowsiness was the particular
work of the great adversary of souls, or that he was liable to suffer
any such accident as Eutychus did, who, falling into a deeper sleep,
and losing all muscular control and consciousness, sunk down from
his seat, and slipping over the side of the gallery, in the third loft, fell
into the court below, where he was taken up lifeless. But Paul
hearing of the accident, stopped his discourse, and going down to
the young man, fell on him and embraced him, saying, “Trouble not
yourselves, for the life is in him.” And his words were verified by the
result; for they soon brought him up alive, and were not a little
comforted. Paul, certain of his recovery, did not suffer the accident to
mar the enjoyment of the social farewell meeting; but going up and
breaking bread with them all, talked with them a long time, passing
the whole night in this pleasant way, and did not leave them till day-
break, when he started to go by land over to Assos, about twenty-
four miles south-east of Troas, on the Adramyttian gulf, which sets
up between the north side of the island of Lesbos and the mainland.
His companions, coming around by water, through the mouth of the
gulf, took Paul on board at Assos, according to his plan; and then
instead of turning back, and sailing out into the open sea, around the
outside of Lesbos, ran up the gulf to the eastern end of the north
coast of the island, where there is an other outlet to the gulf between
the eastern shore of Lesbos and the continent. Sailing southward
through this passage, after a course of between thirty and forty
miles, they came to Mitylene, on the southeastern side of the island.
Thence passing out of the strait, they sailed southwestwards, coming
between Chios and the main-land, and arrived the next day at
Trogyllium, at the southwest corner of Samos. Then turning their
course towards the continent, they came in one day to Miletus, near
the mouth of the ♠Meander, about forty miles south of Ephesus.

♦ “Entychus” replaced with “Eutychus”

♠ “Maeander” replaced with “Meander”

Landing here, and desiring much to see some of his Ephesian

brethren before his departure to Jerusalem, he sent to the elders of
the church in that city, and on their arrival poured out his whole soul
to them in a parting address, which for pathetic earnestness and
touching beauty, is certainly, beyond any doubt, the most splendid
passage that all the records of ancient eloquence can furnish. No
force can be added to it by a new version, nor can any recapitulation
of its substance do justice to its beauty. At the close, took place a
most affecting farewell. In the simple and forcible description of
Luke, (who was himself present at the moving scene, seeing and
hearing all he narrates,)――“When Paul had thus spoken, he
kneeled down and prayed with them all.” The subjects of this prayer