Cellulose Based Composites E-Book
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- Herausgeber: Wiley-VCH
- Kategorie: Fachliteratur
- Sprache: Englisch
Aimed at researchers involved in this emerging field in both academia and industry, this book is unique in its focus on cellulose nanofibers, especially nano-composites, nanomoities and other plant based-resins and their composites. Despite its concise presentation, this handbook and ready reference provides a complete overview, containing such important topics as electrospinning, isolation, characterization and deposition of metallic nanoparticles.
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Seitenzahl: 538
Veröffentlichungsjahr: 2014
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Table of Contents
Cover
Related Titles
Title Page
Copyright
List of Contributors
Preface
Section I: Cellulose Nanofiber- and Microfiber Based Composites
Chapter 1: Cellulose-Nanofiber-Based Materials
1.1 Introduction
1.2 The Percolation and Entanglement Phenomena of Cellulose Nanofibers
1.3 Cellulose-Nanofiber-Based Materials
1.4 Extraction of Cellulose Nanofibers
1.5 Cellulose-Nanofiber-Based Materials for Structural and Semistructural Applications
1.6 Optically Transparent Materials Reinforced with Cellulose Nanofibers
1.7 Green Cellulose-Nanofiber-Based Materials
1.8 Future Prospects
Abbreviations
References
Chapter 2: Fabrication and Evaluation of Cellulose-Nanofiber-Reinforced Green Composites
2.1 Introduction
2.2 Cellulose Nanofiber
2.3 Preparation of Cellulose Nanofibers
2.4 Fabrication of Cellulose-Nanofiber-Reinforced Composites
2.5 Properties of Cellulose-Nanofiber-Reinforced Composites
2.6 Summary
Abbreviations
References
Chapter 3: Cellulose Microfibrils Isolated from Musaceae Fibrous Residues
3.1 Introduction
3.2 Vascular Bundles
3.3 Isolation and Purification of Cellulose Microfibrils from Vascular Bundles
3.4 Chemical Characterization of Cellulose Microfibrils
3.5 Structure and Morphology of Cellulose Microfibrils
3.6 Thermal Behavior of Cellulose Microfibrils
3.7 Conclusions
3.8 Materials and Methods
Acknowledgments
Abbreviations
References
Chapter 4: Nanocomposites Based on Matrices Extracted from Vegetable Oils and Bacterial Cellulose
4.1 Introduction
4.2 Vegetable Oils
4.3 Bacterial Cellulose
4.4 Bacterial and Plant-Based Cellulose Nanocomposites with Polymer Matrices
4.5 Applications
References
Chapter 5: Nano- and Microfiber Composites Reinforced with Cellulose Nanocrystals
5.1 Introduction
5.2 Cellulose Nanocrystals
5.3 Electrospinning
5.4 Cellulose Nanocrystals (CNs) for the Production of Composites
5.5 Electrospun Nanofibers Reinforced with CNs
5.6 Applications of CN-Based Composites
5.7 Conclusions
Acknowledgments
References
Chapter 6: Hydrolytic Degradation of Nanocomposite Fibers Electrospun from Poly(Lactic Acid)/Cellulose Nanocrystals
6.1 Introduction
6.2 Experiments
6.3 Results and Discussion
6.4 Conclusions
Acknowledgment
References
Section II: Cellulose-Fiber-Based Composites
Chapter 7: Environment-Friendly “Green” Resins and Advanced Green Composites
7.1 Introduction
7.2 Experimental
7.3 Results and Discussion
7.4 Conclusions
Acknowledgments
Abbreviations
References
Chapter 8: Toughening and Strengthening of Natural Fiber Green Composites
8.1 Introduction
8.2 Preloading Effect
8.3 Effect of Alkali Treatment
8.4 Conclusion
References
Chapter 9: Composites of Nanocellulose and Lignin-like Polymers
9.1 Introduction
9.2 Experimental
9.3 Results and Discussion
9.4 Conclusions
Acknowledgments
References
Chapter 10: Biodegradable Polymer Materials from Proteins Produced by the Animal Coproducts Industry: Bloodmeal
10.1 Introduction
10.2 Materials and Experimental Procedures
10.3 Results and Discussion
10.4 Conclusions
Acknowledgments
References
Section III: Cellulose and Other Nanoparticles
Chapter 11: Biocomposites Made from Bovine Bone and Crystals of Silver and Platinum
11.1 Introduction
11.2 Bovine Bone–Platinum Composites
11.3 Bovine Bone–Silver Composites
11.4 Conclusions
Acknowledgments
References
Chapter 12: Bio-Inspired Synthesis of Metal Nanoparticles Using Cellulosic Substrates as Nature Templates
12.1 Introduction
12.2 Synthesis of Metal Nanoparticles Using Wood as a Template
12.3 Summary
References
Chapter 13: Conformal Coating of Antimicrobial Silver Nanoparticles on Cationic and Anionic Cellulosic Substrates
13.1 Introduction
13.2 Preparation of Anionic and Cationic Cotton Fabrics
13.3 Results and Discussion
13.4 Conclusions
Acknowledgments
References
Chapter 14: Wood/Biopolymer/Nanoclay Composites
14.1 Biopolymers
14.2 PLA/Clay Nanocomposites
14.3 PLA/Wood Flour Composites
14.4 PLA/Clay/Wood Composites
14.5 Conclusions
Acknowledgments
References
Index
End User License Agreement
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Guide
Table of Contents
List of Illustrations
Figure 1.1
Figure 1.2
Figure 1.3
Figure 1.4
Figure 1.5
Figure 1.6
Figure 2.1
Figure 2.2
Figure 2.3
Figure 2.4
Figure 2.5
Figure 2.6
Figure 2.7
Figure 2.8
Figure 3.1
Figure 3.2
Figure 3.3
Figure 3.4
Figure 3.5
Figure 3.6
Figure 3.7
Figure 3.8
Figure 3.9
Figure 3.10
Figure 4.1
Figure 4.2
Figure 4.3
Figure 4.4
Figure 4.5
Figure 4.6
Figure 4.7
Figure 4.8
Figure 4.9
Figure 5.1
Figure 5.2
Figure 5.3
Figure 5.4
Figure 5.5
Figure 5.6
Figure 5.7
Figure 5.8
Figure 5.9
Figure 5.10
Figure 5.11
Figure 5.12
Figure 5.13
Figure 6.1
Figure 6.2
Figure 6.3
Figure 6.4
Figure 6.5
Figure 6.6
Figure 6.7
Figure 6.8
Figure 6.9
Figure 6.10
Figure 6.11
Figure 6.12
Figure 6.13
Figure 6.14
Figure 7.1
Figure 7.2
Figure 7.3
Figure 7.4
Figure 7.5
Figure 8.1
Figure 8.2
Figure 8.3
Figure 8.4
Figure 8.5
Figure 8.6
Figure 8.7
Figure 8.8
Figure 8.9
Figure 8.10
Figure 8.11
Figure 8.12
Figure 8.13
Figure 8.14
Figure 8.15
Figure 8.16
Figure 8.17
Figure 8.18
Figure 8.19
Figure 9.1
Figure 9.2
Figure 9.3
Figure 9.4
Figure 9.5
Figure 9.6
Figure 9.7
Figure 9.8
Figure 10.1
Figure 10.2
Figure 10.3
Figure 10.4
Figure 10.5
Figure 10.6
Figure 10.7
Figure 10.8
Figure 10.9
Figure 11.1
Figure 11.2
Figure 11.3
Figure 11.4
Figure 11.5
Figure 11.6
Figure 11.7
Figure 11.8
Figure 11.9
Figure 11.10
Figure 11.11
Figure 11.12
Figure 11.13
Figure 12.1
Figure 12.2
Figure 12.3
Figure 12.4
Figure 12.5
Figure 12.6
Figure 12.7
Figure 12.8
Figure 12.9
Figure 12.10
Figure 12.11
Figure 12.12
Figure 12.13
Figure 12.14
Figure 12.15
Figure 12.16
Figure 12.17
Figure 12.18
Figure 13.1
Figure 13.2
Figure 13.3
Figure 13.4
Figure 13.5
Figure 13.6
Figure 13.7
Figure 13.8
Figure 14.1
Figure 14.2
Figure 14.3
Figure 14.4
Figure 14.5
Figure 14.6
Figure 14.7
Figure 14.8
Figure 14.9
Figure 14.10
Figure 14.11
Figure 14.12
List of Tables
Table 2.1
Table 2.2
Table 2.3
Table 3.1
Table 5.1
Table 6.1
Table 7.1
Table 7.2
Table 7.3
Table 7.4
Table 7.5
Table 8.1
Table 8.2
Table 8.3
Table 8.4
Table 8.5
Table 8.6
Table 8.7
Table 8.8
Table 8.9
Table 8.10
Table 9.1
Table 12.1
Table 12.2
Table 12.3
Table 14.1
Table 14.2
Table 14.3
Table 14.4
Table 14.5
Table 14.6
Table 14.7
Table 14.8
Table 14.9
Table 14.10
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Cellulose Based Composites
New Green Nanomaterials
Edited by
P. Hinestroza and Anil N. Netravali
Editors
Prof. Juan P. Hinestroza
Cornell University
Department of Fiber Science & Apparel~Design
242 MVR Hall
37 Forest Home Dr.
Ithaca
NY 14853
USA
Prof. Anil N. Netravali
Cornell University
Department of Fiber Science & Apparel~Design
233 Human Ecology Building (HEB)
37 Forest Home Dr.
Ithaca
NY 14853
USA
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978-3-527-32719-5
ePDF ISBN: 978-3-527-64947-1
ePub ISBN: 978-3-527-64946-4
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List of Contributors
Justin R. Barone1
Biological Systems Engineering
Virginia Tech
Ag Quad Lane
Blacksburg
VA 24061
USA
and
Virginia Polytechnic Institute and State University
Department of Biological Systems Engineering
Seitz Hall (0303)
Blacksburg
VA 24061
USA
Ignacio Guadalupe Becerril-Juarez
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM
Carretera Toluca-Atlacomulco Km 14.5
San Cayetano
Toluca
Estado de México
Mexico 50200
Mexico
Cristina Castro Herazo
Pontificia Bolivariana University
New Materials Research Group
School of Engineering
Circular 1 # 70-01
Bloque 11
Medellín
Colombia
Daniel De Kee
Tulane University
Department of Chemical and Biomolecular Engineering
Tulane Institute for Macromolecular Engineering and Science
St. Charles Avenue
New Orleans
LA 70118
USA
Hong Dong
Cornell University
Department of Fiber Science & Apparel Design
MVR Hall
Forest Home Drive
Ithaca
NY 14850
USA
Margaret W. Frey
Cornell University
Department of Fiber Science & Apparel Design
MVR Hall
Ithaca
NY 14853
USA
Sergio Gama-Lara
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM
Carretera Toluca-Atlacomulco Km 14.5
San Cayetano
Toluca
Estado de México
Mexico 50200
Mexico
Piedad Gañán Rojo
Pontificia Bolivariana University
New Materials Research Group
School of Engineering
Circular 1 # 70-01
Bloque 11
Medellín
Colombia
Koichi Goda
Yamaguchi University
Science and Engineering
Deparment of Mechanical Engineering
Tokiwadai, 2-16-1 Ube
Yamaguchi 755-8611
Japan
Youssef Habibi
CRP Henri Tudor
29, avenue J.F. Kennedy
Luxembourg
Luxembourg
Juan P. Hinestroza
Cornell University
Department of Fiber Science & Apparel Design
MVR Hall
Forest Home Drive
Ithaca
NY 14853
USA
James N. Hodges
Clemson University
School of Materials Science and Engineering
Sirrine Hall
Clemson
SC 29634
USA
Xiaosong Huang
Chemical Sciences & Materials Systems Laboratory
General Motors Research & Development Center
Warren
MI 48090
USA
Martin A. Hubbe
North Carolina State University
Department of Forest Biomaterials
Campus Box 8005
Faucette Drive
Raleigh
NC 27695-8005
USA
Igor Luzinov
Clemson University
School of Materials Science and Engineering
Sirrine Hall
Clemson
SC 29634
USA
Qingkai Meng
Tulane University
Department of Chemical and Biomolecular Engineering
Tulane Institute for Macromolecular Engineering and Science
St. Charles Avenue
New Orleans
LA 70118
USA
Iñaki Mondragon
Universidad del País Vasco/Euskal Herriko Unibertsitatea
Chemical & Environmental Engineering Department
Polytechnic School
Pza Europa, 1, 20018
Donostia-San Sebastián
Spain
Raul Alberto Morales-Luckie
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM
Carretera Toluca-Atlacomulco Km 14.5
San Cayetano
Toluca
Estado de México
Mexico 50200
Mexico
Antonio Norio Nakagaito
The University of Tokushima
Institute of Technology and Science
Minamijosanjima-cho 2-1
Tokushima
770-8506
Japan
Rie Nakamura
Nihon University
Department of Mechanical Engineering
Nakakawahara, Tamura
Koriyama 963-8642
Fukushima
Japan
Anil N. Netravali
Cornell University
Department of Fiber Science & Apparel Design
HEB
Ithaca
NY 14853
USA
Maria S. Peresin
North Carolina State University
Department of Forest Biomaterials
Campus Box 8005
Faucette Drive
Raleigh
NC 27695-8005
USA
Jean-Luc Putaux
Université Joseph Fourier
Institut de Chimie Moléculaire de Grenoble
Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS), BP 53
Grenoble Cedex 9
France
Aloña Retegi Miner
Universidad del País Vasco/Euskal Herriko Unibertsitatea
Chemical & Environmental Engineering Department
Polytechnic School
Pza Europa, 1, 20018
Donostia-San Sebastián
Spain
Orlando J. Rojas
North Carolina State University
Department of Forest Biomaterials
Campus Box 8005
Faucette Drive
Raleigh
NC 27695-8005
USA
and
Aalto University
School of Chemical Technology
Department of Forest Products Technology
Vuorimiehentie 1
Espoo Finland
P.O.Box 16300
FI-00076, Aalto
Victor Sanchez-Mendieta
Universidad Autónoma del Estado de México
Facultad de Química
Paseo Colón y Paseo Tollocan
Toluca
Estado de México
Mexico 50120
Mexico
Suraj Sharma
Clemson University
School of Materials Science and Engineering
Sirrine Hall
Clemson
SC 29634
USA
and
University of Georgia
Department of Textiles
Merchandising and Interiors
Dawson Hall
Athens
GA 30602
USA
Hitoshi Takagi
The University of Tokushima
Institute of Technology and Science
Advanced Materials Division
2-1 Minamijosanjima-cho
Tokushima 770-8506
Japan
Maria E. Vallejos
Universidad Nacional de Misiones
Facultad de Ciencias Exactas
Químicas y Naturales
Félix de Azara 1552
Misiones
Posadas 3300
Argentina
Fehime Vatansever
Clemson University
School of Materials Science and Engineering
Sirrine Hall
Clemson
SC 29634
USA
Juan Manuel Vélez
National University of Colombia
Science and Engineering Materials Group
Materials and engineering department
Carrera 80, # 65-223
Medellín
Colombia
Alfredo Rafael Vilchis-Nestor
Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM
Carretera Toluca-Atlacomulco Km 14.5
San Cayetano, Toluca
Estado de México
Mexico 50200
Mexico
Chunhui Xiang
Iowa State University
Department of Apparel
Events and Hospitality Management
1084B LeBaron Hall
Ames
Iowa 50011
USA
Hiroyuki Yano
Kyoto University
Research Institute for Sustainable Humanosphere
Gokasho, Uji
Kyoto 611-0011
Japan
Justin O. Zoppe
North Carolina State University
Department of Forest Biomaterials
Campus Box 8005
Faucette Drive
Raleigh
NC 27695-8005
USA
Robin Zuluaga Gallego
Pontificia Bolivariana University
New Materials Research Group
School of Engineering
Circular 1 # 70-01
Bloque 11, Medellín
Colombia
Preface
In this book, we have aimed at providing a broad review of the recent advances in the use of natural materials in the fabrication of composites. The 14 chapters presented in the book are divided into the following three sections:
Section I: Cellulose nanofiber- and microfiber-based composites
Section II: Cellulose-fiber-based composites
Section III: Cellulose and other nanoparticles.
The topics covered in the book are highly relevant as cellulose-based and natural materials have become the first choice for the fabrication of green composites because of their abundance, renewability, and biodegradable characteristics.
In the first section, Nakagaito and Yano discuss nanofibrillated cellulose (NFC) obtained from plant cell walls as well as some of the processes used to obtain this unique material. The authors also provide some examples of the use of NFC in the fabrication of green nanocomposites. Takagi discusses some unique features of cellulose nanofibers and green composites made of cellulose nanofibers. Characteristics of such nanocomposites are also discussed in detail in Chapter 2. Ganan and colleagues discuss cellulose microfibrils isolated from Musaceae residues from plantain and banana plants. Currently, most of these residues are simply wasted and using them as fillers in composites opens a new avenue in the area of sustainable materials. Retegi et al. discuss nanocomposites formed by bacterial cellulose and vegetable-oil-based resins. Bacterial cellulose is being used increasingly in many applications because of its high mechanical strength derived from high degree of polymerization, molecular orientation, and crystallinity. Rojas and colleagues discuss the possibility of using cellulose nanocrystals as reinforcing material in hydrophilic and hydrophobic microfibers. These microfibers have potential applications in nonwovens, bioactive filters, and smart textiles. Finally, Xiang and Frey discuss fully biodegradable fibers using cellulose nanocrystals and polylactic acid (PLA). They show that electrospun nonwovens with reinforced PLA nanofibers have higher strength even though the adhesion between the two is much lower than desired.
In the second section Huang and Netravali present green composites made using soy protein based resin and linen and liquid crystalline cellulose fibers. The resin used was modified with agar and nanoclay to improve mechanical properties. Composites made using liquid crystalline cellulose fibers result in high strength composites termed as ‘advanced green composites’. Goda and Nakamura discuss the elastic properties of green composites made using natural-fiber-twisted yarns and starch-based resins. Also discussed in Chapter 8 is the effect of alkaline treatment of natural cellulose fiber yarns and its influence on the properties of the resulting composites. In Chapter 9, Barone introduces nanocomposites made using nanocellulose and lignin-based polymers. A new way of enzymatic polymerization is used in an attempt to mimic native lignocellulose. Sharma and colleagues describe the fabrication and properties of polymeric materials made from partially denatured proteins produced by the animal coproduct industry. Specifically, they have used partially denatured feather meal and bloodmeal proteins using a compression molding process. The composites prepared using these materials exhibited properties comparable to those of petroleum-based plastics and are fully biodegradable.
In the last section, Morales-Luckie et al. discuss biocomposites made from bovine bones. The bone is used as a template in the synthesis of silver and platinum nanoparticles with applications in catalysis, medicine, and environmental chemistry. In Chapter 12, Sanchez-Mendieta and collaborators discuss the direct synthesis of nanoparticles in solid matrices such as cellulose of wood. The importance of this class of bioinspired and biomimetic materials to form bionanocomposites highlights its low cost and environment friendliness. In Chapter 13, Dong and Hinestroza describe the controlled deposition of silver nanoparticles on cationic and anionic cellulose fibers. The method provides uniform and conformal coverage of the fibers which should find applications in wound dressings, active filtration of bacteria, as well as flexible low-pressure drop catalytic mantles. In Chapter 14, De Kee and colleagues review wood/biopolymer/nanoclay hybrid composites. Such hybrid composites can be optimized to provide excellent mechanical and thermal properties and, hence, they may be used in many applications.
We expect that this current overview will provide the readers with a unique perspective on the rapidly evolving field of green composites as well as the potential uses of cellulose as a high performance and functional material.
We are grateful to all the contributors of the book for their patience, hard work, and willingness to share their cutting edge research work with the community.
Juan P. HinestrozaAnil N. Netravali
Section I
Cellulose Nanofiber- and Microfiber Based Composites
Chapter 1Cellulose-Nanofiber-Based Materials
Antonio Norio Nakagaito and Hiroyuki Yano
1.1 Introduction
Cellulose is the main constituent of the structural framework of the fibrous cell wall in higher plants, and it is the most abundant polysaccharide in nature. As an organic substance, a considerable fraction of the available carbon in the Earth is sequestered in the cellulose molecules. Among the primary sources of cellulose is wood, with the usual benefits that satisfy the current needs, as being a renewable, sustainable, and carbon-neutral source of biofuels and monomers [1] in addition to cellulose nanofibers. These nanofibers, mostly known as cellulose microfibrils by the wood science community, are found embedded in a matrix of hemicelluloses and lignin in the cell wall. The tubular cell wall structure comprises a helically wound arrangement of cellulose microfibrils, nanofibers (4 nm × 4 nm) [2] consisting of semicrystalline cellulose molecular chains parallel to their axes. In the crystalline domains, the cellulose chains are arranged in a way such that each long molecule is connected by hydrogen bonds to the neighboring chains forming a highly ordered crystalline form. Every molecule of these chains is made of glucose rings joined together without foldings, just as the benzene rings are joined in aramid. Even the density and the modulus of the two materials are very similar [3]. The cellulose microfibril possesses a Young's modulus close to that of a perfect cellulose crystal, 138 GPa [4], and considering that the strength of a single kraft pulp fiber can reach a tensile strength of 1.7 GPa [5], the estimated tensile strength lays well beyond 2 GPa. That is to say that we can easily find in nature a renewable equivalent of a strong synthetic fiber currently used in aerospace and military applications. It can be obtained from any cellulose source, be it trees, agricultural crops, or even agricultural waste, and if combined with a proper bio-based matrix resin, it has the potential to replace petroleum-based plastics.
This chapter does not intend to be a thorough review of the research activities concerning cellulose nanocomposites, but just aims to introduce the reader to an ebullient field that promises to bring alternatives to the oil-based materials that we became so used to in the past century. More comprehensive surveys can be found in recent review articles by Hubbe et al. [6], Siro and Plackett [7], and Moon et al. [8].
1.2 The Percolation and Entanglement Phenomena of Cellulose Nanofibers
The reinforcing effect of cellulose nanofibers was extensively studied during the past decade, and as reviewed by Berglund [9], the research concentrated basically on attempts to understand the cellulose microfibril or cellulose whisker reinforcement mechanisms in film composites analyzed in the rubbery state.
The most probable first report on cellulose nanocomposites is attributed by Berglund [9] to Boldizar et al. [10]. In 1987, the production of thermoplastics reinforced with hydrolyzed pulp fibers was described. The embrittlement brought by the hydrolytic treatment was intended as a means to facilitate the disintegration of the original fiber into fibrillar entities, or nanofibers, suggesting the possibility to exploit their unusually high modulus and strength values to make composites. Prehydrolyzed cellulose was treated mechanically by a beater or a high-pressure homogenizer, compounded with a thermoplastic matrix (PS (polystyrene)-latex, PP (polypropylene)), and injection molded. The modulus of the composites increased up to three times relative to the pure matrix at a 40 wt% cellulose content, but the tensile strength practically did not change, and in some cases even decreased. The achieved reinforcement was not as high as anticipated because of the possible agglomeration of the fibrils resulting in a poor dispersion inside the matrix. Notwithstanding, PVAC (polyvinyl acetate)-latex mixed with microfibrillated cellulose (MFC) films prepared by casting method revealed the inherent stiffening properties of cellulose microfibrils. Young's modulus of PVAC was improved from 63 MPa to 1.6–2.9 GPa at a 40 wt% cellulose content.
Extensive works involving cellulose microfibrils and whiskers have been carried out by researchers at the Centre de Recherches sur les Macromolécules Végétales–Centre National de la Recherche Scientifique (CERMAV-CNRS), France. In 1995, Favier et al. [11, 12] reported the production of polymer films reinforced with cellulose whiskers extracted from sea animals, tunicates. Whiskers are very thin single-crystal fibrils having a nearly perfect crystalline structure. An aqueous suspension of latex obtained by copolymerization of styrene and butyl acrylate was mixed with aqueous suspension of tunicin whiskers and the water was let to evaporate slowly at room temperature. In this method, whiskers were well dispersed throughout the composite. Films up to 6 wt% of cellulose exhibited an increase in shear modulus in the rubbery state of more than two orders of magnitude. Moreover, while the modulus of the matrix decreased with temperature, the modulus of the composites remained constant up to the temperature at which cellulose started to decompose. The unusually large reinforcing effect was explained assuming that a strong interaction between whiskers occurs and is governed by a percolation mechanism, forming a rigid network linked by hydrogen bonds. Helbert et al. [13] used the same latex reinforced with whiskers extracted from wheat straw. Water suspensions of latex and whiskers were mixed and freeze dried and then hot pressed. Above the glass-transition temperature (Tg), a 30 wt% whisker composite had a storage modulus of almost two orders of magnitude higher than the matrix. The higher extent of reinforcement was again attributed to the formation of a whisker network. Chazeau et al. [14–16] produced plasticized polyvinyl chloride (PVC) reinforced with tunicin whiskers. Aqueous suspensions of whiskers and microsuspensions of PVC were mixed and freeze dried. Then the freeze-dried powder plus plasticizer were hot mixed and compression molded into sheets. The shear elastic modulus at 380 K (above Tg) for a sample with whisker volume content of 12.4% increased almost two orders of magnitude relative to the modulus of the matrix. However, the modulus did not stabilize over Tg, having a decreasing slope similar to that of the matrix materials. In this case, the formation of a flexible whisker network connected by an interphase of immobilized matrix was assumed, instead of a rigid network linked by hydrogen bonds, as a consequence of the processing method by hot mixing and compression. Dufresne et al. [17] produced elastomeric Mcl-PHA (medium-chain-length poly(hydroxyalkanoate)) latex reinforced with tunicin whiskers. The storage tensile modulus of a 6 wt% whisker content composite above Tg increased almost an order of magnitude compared to the matrix. Similar to the previous case, the reinforcing effect was attributed to the formation of a whisker network connected by transcrystalline layers grown on cellulose surface instead of a rigid network because of the semicrystalline nature of the matrix.
Other research reporting the production of composites reinforced with tunicin whiskers using different matrix materials, such as PHO (poly(β-hydroxyoctanoate)) [18], resulted in the storage modulus drop above Tg being reduced from 3 GPa for the matrix to 0.5 GPa for a film reinforced by 6 wt% whiskers; and epoxy [19], where storage modulus above Tg for a 2.5 wt% whisker was 38 MPa compared to that of the matrix, 1.9 MPa. In both cases, the formation of a rigid network of hydrogen-bond-linked whiskers reinforcing the composites was observed. Further research was reported with reinforcing whiskers of chitin instead of cellulose, which showed varied results regarding the formation of whisker networks. Chitin is another abundant polysaccharide found in the exoskeleton tissue of marine crustaceans and insects. The chemical structure of chitin is identical to that of cellulose except that a hydroxyl group on each glucose ring is replaced with an acetamido group [20]. Poly(caprolactone) matrix composites [21] exhibited a partial formation of whisker networks, while latex matrix composites [22] showed formation of rigid networks. The reinforcement by chitin whiskers of natural rubber [23, 24] showed that only the casting method leads to the formation of whisker networks while freeze drying and hot pressing does not. Only the slow evaporation process gives enough time for whiskers to move and form a rigid network within the matrix. Chemical modification of the surface of chitin whiskers [25] improved their adhesion to the natural rubber matrix but led to a decrease in mechanical properties of the composites, indicating a partial or complete avoidance of the chitin whisker network formation. Yet, all these studies attribute the reinforcing effect of the whisker-filled composites to the formation of a percolated network.
In a percolated system, all the reinforcing elements are connected in a way such that there are paths linking one element to the next forming an unbroken cluster spanning the whole material from edge to edge. In other words, the reinforcing phase of the composite forms some sort of a stiff skeleton that firmly supports the matrix, rather than a multitude of individual reinforcing elements. These elements could be strongly connected by hydrogen bonds or less strongly by other means depending on the processing of the composite. Evaporation methods from aqueous suspensions seem to preferentially produce hydrogen bondings.
While whisker-filled composites were considered as model systems to enable theoretical predictions, microfibrils were also used as reinforcements. In a communication [26] in 1996, Dinand et al. reported the extraction of MFC from sugar beet pulp and later described a more thorough analysis of these microfibril suspensions [27]. The parenchymal cell cellulose could be disrupted by high-pressure homogenization yielding aqueous suspensions of nonflocculating individual or bundles of cellulose microfibrils. Dufresne et al. [28] produced films by evaporation casting of aqueous suspension of sugar beet pulp microfibrils. They concluded that the individualization of microfibrils by the mechanical treatment leads to the formation of a network of microfibrils inside the material, similar to what happened to cellulose whiskers. In the following research [29, 30], Dufresne reinforced plasticized potato starch with potato parenchymal microfibrils and improved thermal stability (modulus stabilization above Tg) and water sensitivity, which were typical drawbacks of starch. Above Tg, a modulus increase of about two orders of magnitude was reported even at a filler content of just 5 wt%. But when Angles and Dufresne [31, 32] produced composites filling plasticized starch with tunicin whiskers, it was observed that the reinforcing effect was very low compared to the previous whisker-filled composites. For instance, the storage modulus of a 25 wt% whisker at 365 K (above Tg) was just about 20 times higher than that of the matrix. It was postulated that plasticizing agents such as glycerol and water hindered the formation of hydrogen bonded network within the matrix. However, this result disagrees with the high reinforcing effect of plasticized starch filled with cellulose microfibrils [29]. Hence, they concluded that the differences were due to the differences in flexibility, that is, stiff and straight whiskers in contrast to flexible hairy microfibrils. They suggested that in composites with whiskers, the reinforcing effect is based on the formation of hydrogen bonded network, whereas for composites with microfibrils, the reinforcement is accomplished by the rigid network and also by an entangling effect. The entangling effect of microfibrils was confirmed in a more recent study by Samir et al. [33]. An aqueous suspension of latex obtained by copolymerization of styrene and butyl acrylate was mixed with aqueous suspension of sugar beet microfibrils and microfibrils hydrolyzed by 20 and 60 wt% aqueous acid solutions. When composites were subjected to tensile test, the highest reinforcing effect was observed for the unhydrolyzed microfibril composite, from 0.2 MPa modulus and 0.18 MPa strength of the matrix to 114 and 6.3 MPa, respectively, of the unhydrolyzed microfibril composite. As the hydrolysis intensity increased, the tensile modulus and the strength of the composite decreased, showing the diminishing effect of entanglements in the reinforcement. This is probably the most interesting finding concerning the morphological differences of cellulose affecting the mechanical properties of composites. It demonstrated that in order to achieve proper reinforcement in nanocomposites, it is not always necessary to progress the extraction of nanofibers to obtain cellulose crystallites, but maintaining the elements as microfibrils or bundles of microfibrils with lateral dimensions in the nanoscale has the advantage of better reinforcing efficiency and less energy input required to produce the nanofibers.
1.3 Cellulose-Nanofiber-Based Materials
A definite evidence of the MFC reinforcing potential was shown by Yano and Nakahara [34], when they described the production of molded materials based on microfibrillated pulp fibers without any adhesive with a bending strength of 250 MPa. MFC is a commercially available cellulose morphology consisting of cellulose nanofibers in the form of microfibril bundles (details of its extraction are described in Section 1.4). With the addition of only 2 wt% oxidized starch, the yield strain doubled and the bending strength increased to 310 MPa. This unusually high strength was attributed to the interactive forces (hydrogen bonds or van der Waals forces) developed between the nanometer unit web-like network of cellulose fibrils. The initial water content of about 90 wt% of MFC is slowly extracted while applying the molding pressure, and so during drying, the capillary forces of the intervening water being evaporated draw the fibrils together bridging them by hydrogen bonds. Although the process is highly time consuming, it marked the beginnings of completely “green” high-strength cellulose-nanofiber-based materials.
The properties of a composite depend on the properties of their constituents, the matrix and the reinforcing phase, and on the interfacial interaction between them. In other words, basically three factors are of primary importance to composites: the resin properties, the fiber properties, and the fiber/resin interface characteristics [35]. The fiber and matrix are generally made of two chemically distinct materials so that the interface between them often has poor compatibility leading to deficiencies in stress transfer and water uptake. One of the most interesting ways to overcome this issue is perhaps the concept of self-reinforced polymers such as all-PP composites [36]. As both fiber and matrix are made of the same material, the composites are easily recyclable and have excellent interfacial compatibility. The all-cellulose composite, where both fibers and matrix consist of cellulose was first developed by Nishino et al. [37]. Inspired by their pioneering studies, Gindl and Keckes [38] produced the first all-cellulose nanocomposite by selectively dissolving the surface of microcrystalline cellulose (MCC) in a solution of N,N-dimethylacetamide (DMAc) containing 8 wt% LiCl after dehydrating MCC by successive immersions in ethanol, acetone, and DMAc. The films obtained after removal of the solvent were optically transparent and exhibited a tensile modulus of 13.1 GPa, a strength of 242.8 MPa, and a strain at fracture of 8.6%.
Using different approaches, Gindl and Yano tackled the same problem of interfacial compatibility by obtaining composites comprising different phases of the same material. While Gindl chemically dissolved cellulose to serve as the matrix resin, Yano took advantage of the hydrophilic nature of cellulose to adhere the fibers by hydrogen bonds similar to the approach in paper making. Interestingly, the cellulose nanopaper made from wood nanofibers developed by Henriksson et al. [39] with a tensile modulus of 13.2 GPa, a strength of 214 MPa, and remarkable toughness is also based in cellulose interfibril interactions through secondary bonds and the mechanical properties are quite close to those of Gindl's all-cellulose nanocomposites.
In principle, the ultimate mechanical properties of the individual reinforcing elements is realized when cellulose whiskers are obtained, which are essentially nanorods consisting of cellulose monocrystals. However, if we consider these elements collectively as part of the reinforcing phase, the interaction between them becomes the weakest link. It is important to note that the cellulose nanofibers or cellulose microfibrils are made up of crystalline and amorphous domains, but even in these less ordered regions, the molecular chains are aligned in the axial direction, roughly similar to the threads of a string. Therefore, cellulose in the form of nanofibers is almost as strong as their whisker counterparts but is flexible enough to mutually entangle in addition to the hydrogen bond percolation. This seems to be the reason why researchers have preferentially chosen nanofibers instead of whiskers to make composites.
1.4 Extraction of Cellulose Nanofibers
Lignocellulosic materials are vastly distributed in the form of plants, crops, and primarily trees. Just to illustrate the complexity of the structure in which cellulose nanofibers are found, let us look at single fibers from wood (Figure 1.1). These are hollow tubes made up of cellulose microfibrils cemented by a matrix of hemicelluloses and lignin. Most of the cell wall materials are located in the S2 layer, which consists of a helically wound framework of microfibrils [5], as depicted in Figure 1.1. The extraction of cellulose microfibrils or microfibril bundles, here referred to as nanofibers, is of supreme importance because damage to the elements should be minimal in order to secure the nanoscale diameter and keep the long axial length to preserve the high aspect ratio. The mainstream fibrillation processes reported so far rely on mechanical treatments that subject the fibers to shear forces and they can be summarized in the following methods.
Figure 1.1 The cell wall structure of wood fibers. P is the primary wall; S1, S2, and S3 are the outer, middle, and inner layers of the secondary wall, respectively.
In the early 1980s, a new type of cellulose morphology was developed by Turbak et al. [40], called microfibrillated cellulose (MFC). This was a new form of expanded high-volume cellulose, moderately degraded and greatly expanded in surface area, obtained through a homogenization process. Microfibrillation is accomplished in a piece of equipment called high-pressure homogenizer, where a dilute slurry of refiner-treated cellulose pulp fibers is pumped at high pressure and fed through a spring loaded valve which opens and closes in a reciprocating motion. The fibers are subjected to a large pressure drop, with shearing and impact forces with the valve seat. The combination of these forces promotes fibrillation and ultimately a high degree of microfibrillation [41]. This cellulose morphology is commercially available and can be considered as consisting of nanofibers as most of the microfibril bundles have submicrometer widths.
Almost two decades later, in the late 1990s, Taniguchi and Okamura [42] reported a process of microfibrillation called super-grinding method. A small commercial grinder with a specially designed super-grinding disk was used to treat a dilute slurry of natural fibers by several passes through the disk. The longitudinal fibrillation is accomplished with very little transverse cutting of the microfibrils, keeping the inherent tensile strength of the fibrils intact and generating a large surface area per unit mass. Iwamoto et al. [43] used a similar process to extract cellulose nanofibers to produce optically transparent composites. The starting material was the MFC produced by the high-pressure homogenizer previously developed by Turbak et al. [40], further treated by the super grinder to result in more dimensionally uniform nanofibers.
Another method of cellulose microfibrillation was described by Zimmermann et al. [44], a disintegration process using a high-speed stirrer and a microfluidizer. In a microfluidizer, a previously split fluid stream containing cellulose are reunited under high pressure in an interaction chamber, where shearing stress is applied to the fibers axis, separating the fibrils. An improvement of the process based on the same principle, called counter collision in water, was developed by Kondo [45]. A variation of the use of a microfluidizer, along with a clever enzymatic pretreatment of the fibers, was described by Paakko et al. [46]. Instead of a strong acid hydrolysis that produces low aspect ratio elements, a less aggressive enzymatic hydrolysis is used before mechanical fibrillation. After a refiner treatment to increase the accessibility of the enzyme into the cell wall of the fiber, a monocomponent endoglucanase provides selective hydrolysis of the amorphous cellulose regions of the fibers that facilitates a posterior mechanical fibrillation by a high-pressure microfluidizer.
Some creative approaches have been reported of late. Cryocrushing under liquid nitrogen was proposed by Sain's group in Canada [47], where the pulp slurry is pretreated by a fiber disintegrator and a PFI refiner and afterward immersed in liquid nitrogen to freeze the water contained in the interstices of the fibers. The fibers are subjected to a high impact grinding with a cast iron mortar and pestle to break the fibers cell wall and separate into fibrils. Another interesting method based on mechanical waves was described by Zhao et al. [48], which relies on ultrasonication of fibers in aqueous medium. Fibers were fibrillated by applying ultrasound at 20 kHz to various natural fibers composed of silk, chitin, and cellulose. They explained the fibrillation mechanism based on the creation, growth, and collapse of microbubbles in the aqueous solution caused by acoustic cavitation of the high-frequency ultrasound. The shockwaves produced by the collapse of the bubbles causes erosion of the surface of the fibers, splitting them in the axial direction.
Abe et al. [49], in an attempt to simplify the grinding method of Taniguchi and Okamura [42] and Iwamoto et al. [43], succeeded in fibrillating wood fibers into uniform nanofibers with 15 nm in diameter in only one pass through the grinder, so the damage was the least among the described fibrillation processes (Figure 1.2). In a previous study by Iwamoto et al. [50], the severity of mechanical shear applied by the grinder to fibrillate was evaluated based on the mechanical properties of the final nanocomposites. The transparency of composites increased up to five passes through the grinder and beyond that neither transparency nor the morphology of the nanofibers seemed to change. On the other hand, the tensile and thermal expansion properties were significantly degraded, in accordance with the decrease of crystallinity and degree of polymerization of cellulose. Later, they also clarified the role of hemicelluloses on nanofibrillation [51]. According to this study, when the pulp fibers are dried, the presence of hemicelluloses impedes the formation of irreversible hydrogen bonds between microfibrils, known as hornification. And by rewetting, hemicelluloses are plasticized by absorbing water, favoring the ease of posterior nanofibrillation. The essence of Abe's approach was to keep the fiber in a water-swollen state after chemical removal of hemicelluloses and lignin, skipping the drying process in a typical pulp production that causes shrinkage and formation of irreversible hydrogen bonds that mutually adhere the fibrils. This new protocol made possible obtaining perhaps the most undamaged cellulose nanofibers extracted using only mechanical means. This is only rivaled by the nanofibers from never-dried native cellulose obtained by Saito et al. [52], who oxidized the surface of the microfibrils by a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-radical-catalyzed process, so that just a posterior mechanical agitation by a Waring Blender was enough to individualize the original fibers into nanofibers of 3–5 nm in diameter.
Figure 1.2 Cellulose nanofibers obtained by the grinding treatment from never-dried wood fibers.
In recent times, many new fibrillation processes to obtain nanofibers were developed but still the production yield is low and the energy required to mechanically fibrillate is too high to be economically viable for materials aiming toward their use in commodity products. Perhaps the best approach would be to just obtain a degree of fibrillation to fulfill the needs of each application. For instance, submicrometer fibrils with a broad distribution of lateral sizes would be enough for mechanical reinforcement of composites for semistructural applications, whereas uniform nanofibers with diameters of tens of nanometers (nanofibrillated) would be necessary for optically transparent composites where the nanosized elements are essential for enhanced optical properties. Instead of pursuing the holy grail of perfect fibrillation, different ways to fibrillate will be developed to satisfy the demand in terms of both performance and cost.
1.5 Cellulose-Nanofiber-Based Materials for Structural and Semistructural Applications
Although the utilization of MFC morphology to make high-performance composites was realized rather recently, attempts to exploit the mechanical properties of cellulose microfibrils in strong materials started years earlier. In 1997, Yano et al. [53] taking advantage of the high negative correlation between microfibril angle (MFA) and specific Young's modulus in the longitudinal direction of wood, selected raw materials based on sound velocity, hand-picking wood samples containing fibers with the lowest MFAs (Figure 1.1), which gave them the highest modulus and strength. The wood samples were impregnated with a low-molecular-weight phenolic resin and hot pressed at pressures of 30–50 MPa. The resin acted as a plasticizer during compression and after curing, fixed the deformed and densified condition. The Young's modulus and bending strength of the compressed wood achieved values around 40 GPa and 400 MPa, respectively, with some samples exceeding 50 GPa in modulus and 500 MPa in strength for certain species of wood. With a density of only 1.4 g cm−3, such values were comparable to those of soft steel with a density of 7.8 g cm−3 or even Duralumin whose density is 2.7 g cm−3. In a subsequent attempt [54], in order to increase the cellulose microfibril content in the composites, the matrix substances were removed by a cyclical treatment in 1 wt% NaClO2 aqueous solution at 45 °C for 12 h followed by rinsing, which was repeated three times to remove lignin, and by soaking in a 0.1 wt% NaOH solution at 20 °C for 24 h to extract hemicelluloses. This mild treatment resulted in a total weight reduction of about 30%, the treated veneers were impregnated with phenolic resin and hot pressed as before. Young's modulus and the bending strength increased 48 and 43%, respectively, in relation to the untreated compressed wood, showing that the removal of matrix substances by a mild treatment causing minimal damage to the cellulose microfibrils is an effective way to exploit the strength of cellulose nanofibers. Ultimately, the combination of raw material selection, removal of noncellulosic constituents, and low-molecular-weight phenolic resin impregnation and compression led to the feat of a bending modulus of 62 GPa and a strength of 670 MPa [55]. Figure 1.3 shows the linear relationship between Young's modulus and bending strength of these composites. Even though these compressed wood composites could not be called nanocomposites per se, they are, however, in essence capitalizing on the reinforcing potential of cellulose microfibrils which are nanofibers. Instead of disintegrating wood into individualized fibrils, the original structure of unidirectionally oriented fibers and fibrils of wood was maintained to achieve ultimate strength.
Figure 1.3Effect of the combination of NaClO2 and NaOH treatments on the mechanical properties of phenolic-resin-impregnated compressed wood. untreated and treated.
Following the successful attempt by Yano et al. [53] to make compressed wood and to utilize the MFC morphology to make strong materials, and considering the good compatibility between cellulose and phenolic resin, sheets similar to paper obtained by filtration of MFC slurries were impregnated with a thermoset resin phenol formaldehyde (PF), stacked in layers and compression molded under pressures as high as 100 MPa [56, 57]. The mechanical properties obtained were substantial, Young's modulus achieved was 19 GPa, and the bending strength attained was about 370 MPa, figures comparable to those of commercial magnesium alloy (Figure 1.4). When compared to composites based on nonfibrillated pulp fibers fabricated following the same compression molding of PF impregnated sheets, MFC nanocomposites had slightly higher Young's modulus but exhibited about 1.5 times higher bending strength. Having similar modulus, the higher bending strength was a direct consequence of a higher strain at fracture of MFC-based composites. The enhanced elongation resulted not only in higher strength but also in higher toughness. The work of fracture is attributable to the highly extended surface area of networked nanofibers, which generates an increased bond density that slows down crack propagation. As a consequence of the nanoscalar dimensions of the fibrils, fracture sites will be smaller and more widely distributed in the material volume delaying the formation of critical crack necessary for catastrophic failure. The nanostructured material failure is therefore delayed, and the strength is increased.
Figure 1.4 Flexural stress–strain curves comparing cellulose nanocomposites with conventional materials.
In order to determine how the degree of fibrillation of kraft pulp reinforcements affects the final composite's strength, samples were produced using wood pulp with different levels of refining and homogenizing treatments [58]. MFC is obtained by repeated mechanical action of a high-pressure homogenizer on wood pulp previously treated by a disk refiner. The number of passes through the homogenizer as well as the number of passes through the refiner determines the degree of fibrillation, resulting in different cellulose morphologies. The degree of fibrillation was evaluated indirectly by water retention values, as it is a physical characteristic related to the exposed surface area of cellulose [40] and serves as an approximate estimate of fibrillation. PF resin was used again as the binder, and the method to produce the composites followed the procedure described earlier. Figure 1.5 shows the bending strength as a function of the degree of fibrillation of pulp fibers, characterized as water retention values. There was no change in strength for composites prepared using pulp fibers treated by refiner up to 16 passes; however, a stepwise increase occurred when the treatment attained 30 passes through the refiner.
Figure 1.5 Bending strength of composites against water retention of kraft pulp with PF resin contents of 2.4–3.9%. Plots labeled R relate to kraft pulp treated by refiner only, and those labeled H refer to kraft pulp additionally treated by a homogenizer after 30 passes through the refiner. Numerals denote the number of passes through the refiner or homogenizer.
Scanning electron microscopy (SEM) observations, as also shown in Figure 1.5, revealed that fibrillation of the fibers surface solely did not increase fiber interactions. Only the complete breakage and fibrillation of the cell wall of the fibers resulted in an increment of mechanical properties, and additional fibrillation by homogenization treatment led to a linear increase of strength. Microfibrillation not only eliminates defects or weaker parts of the original fibers that would act as the starting point of cracks but also increases interfibrillar bond densities, creating a structure that favors ductility.
In a subsequent study, cellulose nanofibers of animal origin instead of plants were utilized by Nakagaito et al. [59]. Bacterial cellulose (BC) is secreted extracellularly by Acetobacter species cultivated in a culture medium containing carbon and nitrogen sources. It consists of a networked structure of ribbon-shaped pure cellulose fibrils less than 100 nm in width, which in turn are made up of a bundle of finer microfibrils. These fibrils are relatively straight, continuous, dimensionally uniform, and extremely strong, forming a network that macroscopically takes the form of pellicles containing about 99 wt% water. In contrast to MFC, which is obtained in a top-down process by mechanical fibrillation, BC is produced by nature in a bottom-up way, resulting in extremely fine and uniform biosynthesized nanofibers. The composites based on BC were fabricated with sheets obtained from the original BC pellicles by applying pressure to squeeze out the excess water. After drying, the sheets were impregnated with PF resin and compression molded in the same way as with MFC composites. Young's modulus achieved was 28 GPa with bending strength exceeding 400 MPa. Nevertheless, the BC composites were brittle compared to the MFC composites, most likely due to the straight and continuous nanofiber structure contrasting to loose and individualized fibrils of MFC. This was confirmed when BC pellicles were crushed with a grinder, the mechanical properties of composites became very similar to MFC composites, and the fragmented BC morphology observed by SEM revealed to be equally similar to MFC.
All of these materials were fiber-rich composites having high fiber contents up to 70–90 wt%, so an assessment of mechanical properties as a function of fiber content in a wider range was detailed in a later study [60]. Even though the composites based on MFC and PF made by the lamination method have exhibited very good mechanical properties, there was, however, one important deficiency. Because of low resin contents in these fibrous composites and the intrinsic brittleness of PF resin, higher amounts of resin resulted in lower strain at fractures and consequently in lower strengths. Higher resin contents are desirable to make cellulose-based composites less susceptible to degrading agents such as water or moisture. Inspired by studies of Gomes et al. [61] and Goda et al. [62] that improved the toughness of natural fiber-based microcomposites by alkali treatment of the fibers, the MFC was treated with a strong (20 wt%) NaOH aqueous solution to verify its effectiveness on nanocomposites [63]. As a result of the mercerization of the cellulose nanofibers, the composites with a resin content of about 20 wt% had the strain at fracture increased twice to that of untreated MFC composites with the same resin content. Young's modulus decreased slightly, but the bending strength remained practically unaltered because of the increased strain. Ishikura and Nakano [64] observed that woods treated with strong alkali solutions show reduction in Young's modulus accompanied by a contraction along the fibers direction [65] and surmised that the latter was a direct result of the contraction of the cellulose microfibrils. In the case of mercerized MFC sheets, a similar in-plane contraction was observed. As the lignin in wood hinders the conversion from the crystalline structure cellulose I to cellulose II, Nakano et al. [66] proposed that the contraction would be related to an entropy increase in less ordered regions along the microfibril direction. On that basis, one of the possible explanations for the NaOH-treated MFC composites enhanced ductility might be the straightening of contracted cellulose molecules in amorphous regions when under load. Despite the fact that the real reason is uncertain, the study revealed that only a strong alkali solution treatment results in ductile composites.
1.6 Optically Transparent Materials Reinforced with Cellulose Nanofibers
The current display industry (for TVs, computers, etc.) is largely based on glass-based devices, a market dominated by liquid crystal displays (LCDs), but there is a clear trend toward the development of flexible displays. This new technology offers substantial advantages as the possibility to make displays that are thinner, lighter, robust, and conformable and can be easily rolled away, transported, and stored when not in use. One of the material candidates to replace glass is plastics, but in order to do so plastic substrates have to offer the properties of glass, in addition to being just flexible. One of the major challenges for polymeric substrates is the process temperature required to produce the display panels, thus requiring an extremely low coefficient of thermal expansion (CTE) [67]. The functional materials deposited onto the plastic substrates are susceptible to damage because of the mismatch between the CTEs of the different materials.
A transparent nanocomposite reinforced with BC with high fiber content was reported by Yano et al. in 2005 [68]. It was the first example of an optically transparent composite at a fiber content as high as 70 wt%, with a mechanical strength about five times that of engineered plastics, and CTE similar to that of silicon crystal. BC pellicles were compressed to remove the excess water and were afterward dried at 70 °C to completely remove the remaining water. Dried BC sheets were impregnated with acrylic, epoxy, and PF resins. The latter PF resin is a transparent type, different from the previously used PF resin for making high-strength MFC composites. After impregnation, epoxy and acrylic resins were cured by ultraviolet (UV) light and phenolic-resin-impregnated sheets were hot pressed at 150 °C and 2 MPa for 10 min. As the sheets before impregnation had a density of 1.0 g cm−3 and considering that the density of cellulose microfibrils is about 1.6 g cm−3, the interstitial cavities of BC sheets accounted for about one-third of the sheet's volume. These cavities were filled with transparent thermosetting resins, resulting in final composites with fiber contents between 60 and 70 wt%.
When the light transmittance was measured in the wavelength interval between 500 and 800 nm, the BC/epoxy nanocomposite transmitted more than 80% of the light, surface (Fresnel's) reflection included. Besides, when the transmittance of the BC/epoxy nanocomposite was compared with that of the neat epoxy resin, the reduction in light transmission owing to the reinforcing nanofiber network was less than 10 percentage points. Even considering that for composite materials, the transparency depends primarily on matching the refractive indexes of reinforcing elements and matrix, the BC-reinforced nanocomposite seems to be less sensitive. The refractive index of cellulose is 1.618 along the fiber and 1.544 in the transverse direction, whereas that of the impregnated epoxy resin is 1.522 at 587.6 nm and 23 °C. Similarly, the refractive indexes of acrylic resins are 1.596 and 1.488 and PF is 1.483, all at 587.6 nm and 23 °C. The high transparency is due primarily to the nanosize effect, that is, elements with sizes much smaller than the wavelength of light prevents its scattering.
Another very attractive property of BC nanocomposites is the unusually reduced thermal expansion. The CTE of the BC/epoxy combination was 6 × 10−6 K−1, an extremely low value compared to 120 × 10−6 K−1 of the epoxy matrix. The CTE of BC/PF was even lower at 3 × 10−6 K−1, a figure as low as that of silicon crystal. The tensile strength measured reached values up to 325 MPa, with Young's modulus around 20–21 GPa. In addition, BC nanocomposites are light, flexible, and easy to mold, making them promising candidate materials for a broad field of applications from flexible displays to windows of vehicles.
In subsequent studies, Nogi et al
