TEMPO-oxidized cellulose nanofibers
TL;DR: The new cellulose-based nanofibers formed by size reduction process of native cellulose fibers by TEMPO-mediated oxidation have potential application as environmentally friendly and new bio- based nanomaterials in high-tech fields.
Abstract: Native wood celluloses can be converted to individual nanofibers 3–4 nm wide that are at least several microns in length, i.e. with aspect ratios >100, by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation and successive mild disintegration in water. Preparation methods and fundamental characteristics of TEMPO-oxidized cellulose nanofibers (TOCN) are reviewed in this paper. Significant amounts of C6 carboxylate groups are selectively formed on each cellulose microfibril surface by TEMPO-mediated oxidation without any changes to the original crystallinity (∼74%) or crystal width of wood celluloses. Electrostatic repulsion and/or osmotic effects working between anionically-charged cellulose microfibrils, the ζ-potentials of which are approximately −75 mV in water, cause the formation of completely individualized TOCN dispersed in water by gentle mechanical disintegration treatment of TEMPO-oxidized wood cellulose fibers. Self-standing TOCN films are transparent and flexible, with high tensile strengths of 200–300 MPa and elastic moduli of 6–7 GPa. Moreover, TOCN-coated poly(lactic acid) films have extremely low oxygen permeability. The new cellulose-based nanofibers formed by size reduction process of native cellulose fibers by TEMPO-mediated oxidation have potential application as environmentally friendly and new bio-based nanomaterials in high-tech fields.
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TL;DR: It is proposed to focus on the barrier properties of MFC used in films, in nanocomposites, or in paper coating to reduce the high energy consumption and produce new types of M FC materials on an industrial scale.
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TL;DR: In this paper, the hierarchical structure of cellulose is exploited to extract nanoparticles from this naturally occurring polymer, which can be used for the processing of polymer nanocomposites.
1,211 citations
TL;DR: This review collocates current knowledge in the research and development of nanocelluloses and emphasizes more particularly on the chemical modification routes developed so far for their functionalization.
Abstract: Nanocelluloses, including nanocrystalline cellulose, nanofibrillated cellulose and bacterial cellulose nanofibers, have become fascinating building blocks for the design of new biomaterials. Derived from the must abundant and renewable biopolymer, they are drawing a tremendous level of attention, which certainly will continue to grow in the future driven by the sustainability trend. This growing interest is related to their unsurpassed quintessential physical and chemical properties. Yet, owing to their hydrophilic nature, their utilization is restricted to applications involving hydrophilic or polar media, which limits their exploitation. With the presence of a large number of chemical functionalities within their structure, these building blocks provide a unique platform for significant surface modification through various chemistries. These chemical modifications are prerequisite, sometimes unavoidable, to adapt the interfacial properties of nanocellulose substrates or adjust their hydrophilic–hydrophobic balance. Therefore, various chemistries have been developed aiming to surface-modify these nano-sized substrates in order to confer to them specific properties, extending therefore their use to highly sophisticated applications. This review collocates current knowledge in the research and development of nanocelluloses and emphasizes more particularly on the chemical modification routes developed so far for their functionalization.
1,179 citations
TL;DR: A review of cellulose nanofibrillated cellulose (CNF) is presented in this article, covering raw materials selection, structural and chemical aspects, conventional and novel mechanical disintegration techniques, as well as biological and chemical pretreatments aimed at facilitating Nanofibril isolation.
1,071 citations
TL;DR: The goal of this study is to review the fundamental structures and chemistries of wood and wood-derived materials, which are essential for a wide range of existing and new enabling technologies.
Abstract: With the arising of global climate change and resource shortage, in recent years, increased attention has been paid to environmentally friendly materials. Trees are sustainable and renewable materials, which give us shelter and oxygen and remove carbon dioxide from the atmosphere. Trees are a primary resource that human society depends upon every day, for example, homes, heating, furniture, and aircraft. Wood from trees gives us paper, cardboard, and medical supplies, thus impacting our homes, school, work, and play. All of the above-mentioned applications have been well developed over the past thousands of years. However, trees and wood have much more to offer us as advanced materials, impacting emerging high-tech fields, such as bioengineering, flexible electronics, and clean energy. Wood naturally has a hierarchical structure, composed of well-oriented microfibers and tracheids for water, ion, and oxygen transportation during metabolism. At higher magnification, the walls of fiber cells have an interes...
1,031 citations
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TL;DR: Dr. Youssef Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research.
Abstract: Cellulose constitutes the most abundant renewable polymer resource available today. As a chemical raw material, it is generally well-known that it has been used in the form of fibers or derivatives for nearly 150 years for a wide spectrum of products and materials in daily life. What has not been known until relatively recently is that when cellulose fibers are subjected to acid hydrolysis, the fibers yield defect-free, rod-like crystalline residues. Cellulose nanocrystals (CNs) have garnered in the materials community a tremendous level of attention that does not appear to be relenting. These biopolymeric assemblies warrant such attention not only because of their unsurpassed quintessential physical and chemical properties (as will become evident in the review) but also because of their inherent renewability and sustainability in addition to their abundance. They have been the subject of a wide array of research efforts as reinforcing agents in nanocomposites due to their low cost, availability, renewability, light weight, nanoscale dimension, and unique morphology. Indeed, CNs are the fundamental constitutive polymeric motifs of macroscopic cellulosic-based fibers whose sheer volume dwarfs any known natural or synthetic biomaterial. Biopolymers such as cellulose and lignin and † North Carolina State University. ‡ Helsinki University of Technology. Dr. Youssef Habibi is a research assistant professor at the Department of Forest Biomaterials at North Carolina State University. He received his Ph.D. in 2004 in organic chemistry from Joseph Fourier University (Grenoble, France) jointly with CERMAV (Centre de Recherche sur les Macromolecules Vegetales) and Cadi Ayyad University (Marrakesh, Morocco). During his Ph.D., he worked on the structural characterization of cell wall polysaccharides and also performed surface chemical modification, mainly TEMPO-mediated oxidation, of crystalline polysaccharides, as well as their nanocrystals. Prior to joining NCSU, he worked as assistant professor at the French Engineering School of Paper, Printing and Biomaterials (PAGORA, Grenoble Institute of Technology, France) on the development of biodegradable nanocomposites based on nanocrystalline polysaccharides. He also spent two years as postdoctoral fellow at the French Institute for Agricultural Research, INRA, where he developed new nanostructured thin films based on cellulose nanowiskers. Dr. Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research. Chem. Rev. 2010, 110, 3479–3500 3479
4,664 citations
TL;DR: In this paper, the technology involved with exfoliated clay-based nanocomposites and also include other important areas including barrier properties, flammability resistance, biomedical applications, electrical/electronic/optoelectronic applications and fuel cell interests.
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TL;DR: The aim of this paper is to review the production techniques for PLAs, summarize the main properties of PLA and to delineate the main advantages and disadvantages of PLA as a polymeric packaging material.
Abstract: Polylactide polymers have gained enormous attention as a replacement for conventional synthetic packaging materials in the last decade. By being truly biodegradable, derived from renewable resources and by providing consumers with extra end-use benefits such as avoiding paying the "green tax" in Germany or meeting environmental regulations in Japan, polylactides (PLAs) are a growing alternative as a packaging material for demanding markets. The aim of this paper is to review the production techniques for PLAs, summarize the main properties of PLA and to delineate the main advantages and disadvantages of PLA as a polymeric packaging material. PLA films have better ultraviolet light barrier properties than low density polyethylene (LDPE), but they are slightly worse than those of cellophane, polystyrene (PS) and poly(ethylene terephthalate) (PET). PLA films have mechanical properties comparable to those of PET and better than those of PS. PLA also has lower melting and glass transition temperatures than PET and PS. The glass transition temperature of PLA changes with time. Humidity between 10 and 95% and storage temperatures of 5 to 40 degrees C do not have an effect on the transition temperature of PLA, which can be explained by its low water sorption values (i.e. <100 ppm at Aw = 1). PLA seals well at temperatures below the melting temperature but an appreciable shrinking of the films has been noted when the material is sealed near its melting temperature. Solubility parameter predictions indicate that PLA will interact with nitrogen compounds, anhydrides and some alcohols and that it will not interact with aromatic hydrocarbons, ketones, esters, sulfur compounds or water. The CO2, O2 and water permeability coefficients of PLA are lower than those of PS and higher than those of PET. Its barrier to ethyl acetate and D-limonene is comparable to PET. The amount of lactic acid and its derivatives that migrate to food simulant solutions from PLA is much lower than any of the current average dietary lactic acid intake values allowed by several governmental agencies. Thus, PLA is safe for use in fabricating articles for contact with food.
2,803 citations
Grenoble Institute of Technology1, National University of Mar del Plata2, Case Western Reserve University3, University of Fribourg4, University of Nottingham5, Virginia Tech6, University of Natural Resources and Life Sciences, Vienna7, University of Leoben8, Kyoto University9, Oregon State University10, Portland State University11, Imperial College London12, Queen Mary University of London13
TL;DR: An overview of recent progress in the area of cellulose nanofibre-based nanocomposites is given in this article, with particular emphasis on applications, such as reinforced adhesives, to make optically transparent paper for electronic displays, to create DNA-hybrid materials, to generate hierarchical composites and for use in foams, aerogels and starch nanocom composites.
Abstract: This paper provides an overview of recent progress made in the area of cellulose nanofibre-based nanocomposites. An introduction into the methods used to isolate cellulose nanofibres (nanowhiskers, nanofibrils) is given, with details of their structure. Following this, the article is split into sections dealing with processing and characterisation of cellulose nanocomposites and new developments in the area, with particular emphasis on applications. The types of cellulose nanofibres covered are those extracted from plants by acid hydrolysis (nanowhiskers), mechanical treatment and those that occur naturally (tunicate nanowhiskers) or under culturing conditions (bacterial cellulose nanofibrils). Research highlighted in the article are the use of cellulose nanowhiskers for shape memory nanocomposites, analysis of the interfacial properties of cellulose nanowhisker and nanofibril-based composites using Raman spectroscopy, switchable interfaces that mimic sea cucumbers, polymerisation from the surface of cellulose nanowhiskers by atom transfer radical polymerisation and ring opening polymerisation, and methods to analyse the dispersion of nanowhiskers. The applications and new advances covered in this review are the use of cellulose nanofibres to reinforce adhesives, to make optically transparent paper for electronic displays, to create DNA-hybrid materials, to generate hierarchical composites and for use in foams, aerogels and starch nanocomposites and the use of all-cellulose nanocomposites for enhanced coupling between matrix and fibre. A comprehensive coverage of the literature is given and some suggestions on where the field is likely to advance in the future are discussed.
2,214 citations
TL;DR: Never-Dried and once-dried hardwood celluloses were oxidized by a 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated system, and highly crystalline and individualized cellulose nanofibers, dispersed in water, were prepared by mechanical treatment of the oxidized celluloses/water slurries.
2,017 citations