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

Cellulose nanocrystals: chemistry, self-assembly, and applications.

Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.

Nanocelluloses: A New Family of Nature-Based Materials

Carbon nanotubes (CNTs) hold the promise of delivering exceptional mechanical properties and multi-functional characteristics. Ever-increasing interest in applying CNTs in many different fields has led to continued efforts to develop dispersion and functionalization techniques. To employ CNTs as effective reinforcement in polymer nanocomposites, proper dispersion and appropriate interfacial adhesion between the CNTs and polymer matrix have to be guaranteed. This paper reviews the current understanding of CNTs and CNT/polymer nanocomposites with two particular topics: (i) the principles and techniques for CNT dispersion and functionalization and (ii) the effects of CNT dispersion and functionalization on the properties of CNT/polymer nanocomposites. The fabrication techniques and potential applications of CNT/polymer nanocomposites are also highlighted.

Dispersion and functionalization of carbon nanotubes for polymer-based nanocomposites: a review

Due to their abundance, high strength and stiffness, low weight and biodegradability, nano-scale cellulose fiber materials (e.g., microfibrillated cellulose and bacterial cellulose) serve as promising candidates for bio-nanocomposite production. Such new high-value materials are the subject of continuing research and are commercially interesting in terms of new products from the pulp and paper industry and the agricultural sector. Cellulose nanofibers can be extracted from various plant sources and, although the mechanical separation of plant fibers into smaller elementary constituents has typically required high energy input, chemical and/or enzymatic fiber pre-treatments have been developed to overcome this problem. A challenge associated with using nanocellulose in composites is the lack of compatibility with hydrophobic polymers and various chemical modification methods have been explored in order to address this hurdle. This review summarizes progress in nanocellulose preparation with a particular focus on microfibrillated cellulose and also discusses recent developments in bio-nanocomposite fabrication based on nanocellulose.

Microfibrillated cellulose and new nanocomposite materials: a review

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.

/pdf/review-current-international-research-into-cellulose-vduhai1vrx.pdf

Review: current international research into cellulose nanofibres and nanocomposites

Nano- and micron-sized cellulose crystals were prepared and utilized as reinforcements for polyurethane composites. The cellulose crystals obtained from microcrystalline cellulose (MCC) were incorporated into a polar organic solvent, dimethylformamide (DMF), and ultrasonicated to obtain a stable suspension. The suspension was an effective means for incorporating the cellulose crystals into the polyol-isocyanate mixture, utilized to produce polyurethane composite films. The use of DMF presents an interesting alternative for the use of cellulose crystals as reinforcement of a broad new range of polymers. Moreover, the rheology of the uncured liquid suspensions was investigated, and analysis of the results indicated the formation of a filler structure pervading the liquid suspension. Besides, films were prepared by casting and thermal curing of the stable suspensions. Thermomechanical and mechanical testing of the films were carried out to analyze the performance of the composites. The results indicated that a strong filler-matrix interaction was developed during curing as a result of a chemical reaction occurring between the crystals and the isocyanate component.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400082327

Cellulose micro/nanocrystals reinforced polyurethane

Two new single-component, highly cross-linked polymeric materials have been developed that are capable of undergoing repeated cycles of mending. On the basis of the thermally reversible Diels−Alder (r-DA) cycloaddition reaction, these materials are comprised of a dicyclopentadiene core which acts as both diene and dienophile in the r-DA reaction. Polymer specimens have been prepared from two monomeric units, monomers 400 and 401, and the thermal and mechanical properties of these materials have been studied via differential scanning calorimetry, dynamic mechanical analysis, and three-point bending, compression, and fracture tests. After fracture, these hard, colorless, transparent materials are capable of thermal mending at 120 °C, effectively healing cracks formed in the specimen.

Synthesis and Characterization of a Single-Component Thermally Remendable Polymer Network: Staudinger and Stille Revisited

BACKGROUND: Shape memory polymers are capable of fixing a transient shape and of recovering their original dimensions by the application of an external stimulus. Their major drawback is their low stiffness compared to smart materials based on metals and ceramics. To overcome this disadvantage, nanocellulose was utilized as reinforcement.



RESULTS: Composites were prepared by casting stable nanocellulose/segmented polyurethane suspensions. The heat of melting of the polyurethane soft segment phase increased on cellulose addition. Composites showed higher tensile modulus and strength than unfilled films (53% modulus increase at 1 wt% nanocellulose), with higher elongation at break. Creep deformation decreased as cellulose concentration increased (36% decrease in 60-minute creep by addition of 1 wt% nanocellulose). The nanocomposites displayed shape memory properties equivalent to those of the neat polyurethane, with recoveries of the order of 95% (referred to second and further cycles).



CONCLUSIONS: It is possible to markedly improve the rigidity of shape memory polymers by adding small amounts of well-dispersed nanocellulose. However, this improvement did not have substantial effects on the material shape fixity or recovery. Shape memory behavior seems to continue to be controlled by the polymer properties. Copyright © 2007 Society of Chemical Industry

Characterization of nanocellulose‐ reinforced shape memory polyurethanes

Fiber-reinforced epoxy foams were synthesized with chopped glass and aramid fibers The influence of fiber loading and length was investigated in order to optimize the properties of these materials The mechanical performance of the foams was measured under compression and shear loading and compared with competing phenolic and polyurethane foams for calibration, as well as with unreinforced epoxy foam In general, the mechanical behavior of the reinforced samples showed improvements with respect to the unreinforced foam The microstructure of the reinforced samples was examined and revealed a homogeneous distribution of cells The cell distribution was only modified when aramid fibers were used in the manufacture of composites The thermal stability of the samples was analyzed by thermogravimetric analysis (TGA) Samples reinforced with glass fibers exhibited thermal stability superior to those reinforced with aramid fibers

Short-fiber-reinforced epoxy foams

This work has been mainly focused on the development and optimization of the processing methodology to produce epoxy modified phenolic foams. This study analyzes the relation between the composition and the structure as well as the mechanical and flammability performance of epoxy-phenolic (E-P)-based foams. Phenolic foams modified with different types and compositions of epoxy resin were successfully synthesized and characterized, showing uniform pore structure. Two epoxy resins were used for this approach. One is regular diglycidyl ether of bisphenol A (Epon 826) type and the other is a brominated bisphenol A (DER 542), which has halogen groups in the structure to improve the flammability properties of the resulting foams. Cone calorimeter (ASTM E 1354) was used to measure the heat release rate, the time to ignition, and other flammability properties of the E-P foams with different types of epoxy resins, under well-controlled combustion conditions. The mechanical performance of the system was studied and compared with competing foams, such us phenolic, epoxy, and polyurethanes, in aspects of compression, friability, and shear performances. Compared with conventional phenolic foams, E-P foams exhibit significant improvement in mechanical performance, lower friability and similar resistance to flame. These results demonstrate the potential of the E-P foam as a flame resistant and high performance core material for sandwich structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1399–1407, 2007

Maria L. Auad

Papers

Cellulose micro/nanocrystals reinforced polyurethane

Synthesis and Characterization of a Single-Component Thermally Remendable Polymer Network: Staudinger and Stille Revisited

Characterization of nanocellulose‐ reinforced shape memory polyurethanes

Short-fiber-reinforced epoxy foams

Flammability properties and mechanical performance of epoxy modified phenolic foams