This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them. It summarizes cellulose nanoparticles in terms of particle morphology, crystal structure, and properties. Also described are the self-assembly and rheological properties of cellulose nanoparticle suspensions. The methodology of composite processing and resulting properties are fully covered, with an emphasis on neat and high fraction cellulose composites. Additionally, advances in predictive modeling from molecular dynamic simulations of crystalline cellulose to the continuum modeling of composites made with such particles are reviewed (392 references).

/pdf/cellulose-nanomaterials-review-structure-properties-and-2z8x922p3v.pdf

Cellulose nanomaterials review: structure, properties and nanocomposites

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

Biocomposites reinforced with natural fibers: 2000–2010

There have been a number of review papers on layered silicate and carbon nanotube reinforced polymer nanocomposites, in which the fillers have high aspect ratios. Particulate–polymer nanocomposites containing fillers with small aspect ratios are also an important class of polymer composites. However, they have been apparently overlooked. Thus, in this paper, detailed discussions on the effects of particle size, particle/matrix interface adhesion and particle loading on the stiffness, strength and toughness of such particulate–polymer composites are reviewed. To develop high performance particulate composites, it is necessary to have some basic understanding of the stiffening, strengthening and toughening mechanisms of these composites. A critical evaluation of published experimental results in comparison with theoretical models is given.

/pdf/effects-of-particle-size-particle-matrix-interface-adhesion-yv055zq7xi.pdf

Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites

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 describes a novel technique to produce cellulose microfibrils through mechanical methods. The technique involved a combination of severe shearing in a refiner, followed by high-impact crushing under liquid nitrogen. Fibers treated in this way were subsequently either freeze-dried or suspended in water. The fibers were characterized using SEM, TEM, AFM, and high-resolution optical microscopy. In the freeze-dried batch, 75% of the fibrils had diameters of 1 μm and below, whereas in the water dispersed batch, 89% of the fibrils had diameters in this range. The aspect ratio of the microfibrils ranged between 15 and 55 for the freeze-dried fibrils, and from 20 to 85 for the fibrils dispersed in water. These measurements suggest that the microfibrils have the potential to produce composites with high strength and stiffness for high-performance applications. The microfibrils in water were compounded with polylactic acid polymer to form a biocomposite. Laser confocal microscopy showed that the microfibrils were well dispersed in the polymer matrix.

Cellulose microfibrils: A novel method of preparation using high shear refining and cryocrushing

Microcellular foam processing of polymers requires a nucleated cell density greater than 109 cells/cm3 so that the fully grown cells are smaller than 10 μm. A microcellular foam can be developed by first saturating a polymer sample with a volatile blowing agent, followed by rapidly decreasing its solubility in the polymer. In general, the cellular structure of semicrystalline polymer foams is difficult to control, compared to that of amorphous polymer foams. Since the gas does not dissolve in the crystallites (1), the polymer/gas solution formed during the microcellular processing is nonuniform. Moreover, the bubble nucleation is nonhomogeneous because of the heterogeneous nature of the semicrystalline polymer. In this paper, the effects of the crystallinity and morphology of semicrystalline polymers on the microcellular foam processing and on the cellular structure of products are investigated. First, polymer specimens with various crystallinities and morphologies were prepared by varying the cooling rate of the polymer melt. Then, the solubility and diffusivity of the blowing agent in and through specimens were studied. The specimens with differing crystallinities and morphologies were foamed and their cellular structures were compared. The experimental results agree with theoretical predictions, indicating that the crystallinity and morphology of semicrystalline polymers exert a strong influence on the foam processing and the structure of the product.

Effect of the crystallinity and morphology on the microcellular foam structure of semicrystalline polymers

Natural fibre reinforced thermoplastics (NFRT) are increasingly used in a variety of commercial applications, but there has been little theoretical modeling of structure/property relationships in these materials. In this study, micromechanical models available in the short fibre composites literature were used to predict the stiffness of some commercially important natural fibre composite formulations. Also included are equations that correct the Young’s modulus of natural fibres for changes in moisture content and density that occur as a result of processing. Hemp fibres, hardwood fibres, rice hulls, and E-glass fibres were blended into high-density polyethylene in mass fractions of 10–60-wt%. The Young’s modulus of these composites was compared to theoretical values generated by the rule of mixtures, Halpin–Tsai, Nairn’s generalized shear-lag analysis and Mendels et al. stress transfer (micromechanical) models. Based on a sum of errors squared criterion, the Halpin–Tsai equation was found to predict the experimental data most accurately for the NFRT created for this study.

Predicting the elastic modulus of natural fibre reinforced thermoplastics

In this paper, a study on the batch processing and characterization of microcellular foamed high-density polyethylene (HDPE/iPP) blends is reported. A microcellular plastic is a foamed polymer with a cell density greater than 109 cells/cm3 and fully grown cells smaller than 10 µm. Recent studies have shown that the morphology and crystallinity of semicrystalline polymers have a great influence on the solubility and diffusivity of the blowing agent and on the cellular structure of the resulting foam in microcellular batch processing. In this research, blends of HDPE and iPP were used to produce materials with variety of crystalline and phase morphologies to enhance the subsequent microcellular foaming. It was possible to produce much finer and more uniform foams with the blends than with neat HDPE and iPP. Moreover, the mechanical properties and in particular the impact strength of the blends were significantly improved by foaming.

Mark T. Kortschot

Papers

Cellulose microfibrils: A novel method of preparation using high shear refining and cryocrushing

Effect of the crystallinity and morphology on the microcellular foam structure of semicrystalline polymers

Predicting the elastic modulus of natural fibre reinforced thermoplastics

Processing and characterization of microcellular foamed high-density polythylene/isotactic polypropylene blends

Predicting the tensile strength of natural fibre reinforced thermoplastics