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.

This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references).

Conversion of biomass to selected chemical products

In this article, several applications of nanomaterials in food packaging and food safety are reviewed, including: polymer/clay nanocomposites as high barrier packaging materials, silver nanoparticles as potent antimicrobial agents, and nanosensors and nanomaterial-based assays for the detection of food-relevant analytes (gasses, small organic molecules and food-borne pathogens). In addition to covering the technical aspects of these topics, the current commercial status and understanding of health implications of these technologies are also discussed. These applications were chosen because they do not involve direct addition of nanoparticles to consumed foods, and thus are more likely to be marketed to the public in the short term.

Applications of nanotechnology in food packaging and food safety: Barrier materials, antimicrobials and sensors

Thermal stability and flame retardancy of polyurethanes

Today cross-cutting approaches, where molecular engineering and clever processing are synergistically coupled, allow the chemist to tailor complex hybrid systems of various shapes with perfect mastery at different size scales, composition, functionality, and morphology. Hybrid materials with organic–inorganic or bio–inorganic character represent not only a new field of basic research but also, via their remarkable new properties and multifunctional nature, hybrids offer prospects for many new applications in extremely diverse fields. The description and discussion of the major applications of hybrid inorganic–organic (or biologic) materials are the major topic of this critical review. Indeed, today the very large set of accessible hybrid materials span a wide spectrum of properties which yield the emergence of innovative industrial applications in various domains such as optics, micro-electronics, transportation, health, energy, housing, and the environment among others (526 references).

Applications of advanced hybrid organic–inorganic nanomaterials: from laboratory to market

Soybean-oil-based waterborne polyurethane dispersions: effects of polyol functionality and hard segment content on properties.

Morphology and properties of soy protein isolate thermoplastics reinforced with chitin whiskers.

Morphological, thermal and mechanical properties of ramie crystallites—reinforced plasticized starch biocomposites

Veggie-based products: Vegetable-oil-based polymeric materials, prepared by free radical, cationic, and olefin metathesis polymerizations, range from soft rubbers to ductile or rigid plastics, and to high-performance biocomposites and nanocomposites. They display a wide range of thermophysical and mechanical properties and may find promising applications as alternatives to petroleum-based polymers.

Vegetable oils are considered to be among the most promising renewable raw materials for polymers, because of their ready availability, inherent biodegradability, and their many versatile applications. Research on and development of vegetable oil based polymeric materials, including thermosetting resins, biocomposites, and nanocomposites, have attracted increasing attention in recent years. This Minireview focuses on the latest developments in the preparation, properties, and applications of vegetable oil based polymeric materials obtained by free radical, cationic, and olefin metathesis polymerizations. The novel vegetable oil based polymeric materials obtained range from soft rubbery materials to ductile or rigid plastics and to high-performance biocomposites and nanocomposites. These vegetable oil based polymeric materials display a wide range of thermophysical and mechanical properties and should find useful applications as alternatives to their petroleum-based counterparts.

Novel polymeric materials from vegetable oils and vinyl monomers: preparation, properties, and applications.

Environmentally friendly starch biocomposites were successfully developed using a colloidal suspension of cottonseed linter cellulose crystallite as a filler to reinforce glycerol plasticized starch (PS). The cellulose crystallites, having lengths of 350 +/- 70 nm and diameters of 40 +/- 8 nm on average, were prepared from cottonseed linters by acid hydrolysis. The dependence of morphology and properties of the PS-based biocomposites on cellulose crystallites content in the range from 0 to 30 wt.-% was investigated by scanning electron microscopy, differential scanning thermal analysis, dynamic mechanical thermal analysis, and measurements of mechanical properties and water absorption. The results indicate that the strong interactions between fillers and between the filler and PS matrix play a key role in reinforcing the resulting composites. The PS/cellulose crystallite composites, conditioned at 50% relative humidity, undergo an increase in both tensile strength and Young's modulus from 2.5 MPa for PS film to 7.8 MPa and from 36 MPa for PS film to 301 MPa. Further, incorporating cottonseed linter cellulose crystallites into PS matrix leads to an improvement in water resistance for the resulting biocomposites. The mechanical behaviors of the starch-based biocomposites as a function of cellulose crystallites content.

Yongshang Lu

Papers

Soybean-oil-based waterborne polyurethane dispersions: effects of polyol functionality and hard segment content on properties.

Morphology and properties of soy protein isolate thermoplastics reinforced with chitin whiskers.

Morphological, thermal and mechanical properties of ramie crystallites—reinforced plasticized starch biocomposites

Novel polymeric materials from vegetable oils and vinyl monomers: preparation, properties, and applications.

Biocomposites of plasticized starch reinforced with cellulose crystallites from cottonseed linter.