Crystallisation is at the heart of various scientific disciplines, but still the understanding of the molecular mechanisms underlying phase separation and the formation of the first solid particles in aqueous solution is rather limited. In this review, classical nucleation theory, as well as established concepts of spinodal decomposition and liquid-liquid demixing, is introduced together with a description of the recently proposed pre-nucleation cluster pathway. The features of pre-nucleation clusters are presented and discussed in relation to recent modifications of the classical and established models for phase separation, together with a review of experimental work and computer simulations on the characteristics of pre-nucleation clusters of calcium phosphate, calcium carbonate, iron(oxy)(hydr)oxide, silica, and also amino acids as an example of small organic molecules. The role of pre-nucleation clusters as solute precursors in the emergence of a new phase is summarized, and the link between the chemical speciation of homogeneous solutions and the process of phase separation via pre-nucleation clusters is highlighted.

High-performance thermally insulating materials from renewable resources are needed to improve the energy efficiency of buildings. Traditional fossil-fuel-derived insulation materials such as expanded polystyrene and polyurethane have thermal conductivities that are too high for retrofitting or for building new, surface-efficient passive houses. Tailored materials such as aerogels and vacuum insulating panels are fragile and susceptible to perforation. Here, we show that freeze-casting suspensions of cellulose nanofibres, graphene oxide and sepiolite nanorods produces super-insulating, fire-retardant and strong anisotropic foams that perform better than traditional polymer-based insulating materials. The foams are ultralight, show excellent combustion resistance and exhibit a thermal conductivity of 15 mW m(-1) K(-1), which is about half that of expanded polystyrene. At 30 °C and 85% relative humidity, the foams retained more than half of their initial strength. Our results show that nanoscale engineering is a promising strategy for producing foams with excellent properties using cellulose and other renewable nanosized fibrous materials.

Cellulose nanocrystals (CNCs), produced by the acid hydrolysis of wood, cotton or other cellulose-rich sources, constitute a renewable nanosized raw material with a broad range of envisaged uses: for example, in composites, cosmetics and medical devices. The intriguing ability of CNCs to self-organize into a chiral nematic (cholesteric) liquid crystal phase with a helical arrangement has attracted significant interest, resulting in much research effort, as this arrangement gives dried CNC films a photonic band gap. The films thus acquire attractive optical properties, creating possibilities for use in applications such as security papers and mirrorless lasing. In this critical review, we discuss the sensitive balance between glass formation and liquid crystal self-assembly that governs the formation of the desired helical structure. We show that several as yet unclarified observations-some constituting severe obstacles for applications of CNCs-may result from competition between the two phenomena. Moreover, by comparison with the corresponding self-assembly processes of other rod-like nanoparticles, for example, carbon nanotubes and fd virus particles, we outline how further liquid crystal ordering phenomena may be expected from CNCs if the suspension parameters can be better controlled. Alternative interpretations of some unexpected phenomena are provided, and topics for future research are identified, as are new potential application strategies. NPG Asia Materials (2014) 6, e80; doi:10.1038/am.2013.69; published online 10 January 2014Keywords: cholesteric; gel; glass; liquid crystal; nanocellulose; photonic crystal; self-assembly INTRODUCTION Nanomaterials based on renewable resources are attracting rapidly growing interest, both from a fundamental scientific point of view and from the perspective of developing novel structural and functional macroscopic materials. 1,2 Using nature-based nanomaterials offers ecological advantages, and the extraordinary mechanical performance and/or photonic crystal character of biological composites such as bone, nacre, wood, beetle scales and butterfly wings is also an important inspiration for the development of new multifunctional materials. [3][4][5] However, full utilization of the intrinsic properties of nanosized starting materials requires the development of robust and versatile synthetic and processing routes to control assembly over several length scales. [6][7][8] Cellulose, one of the most versatile and widely found biopolymers in nature, has been used by humans for millennia as a building material, an energy source, a component of clothing and for storing and sharing knowledge and culture. Today, cellulose materials are used in a wide range of applications, and the paper and pulp industry

No abstract

Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement.

Crystallization of calcium carbonate, typically, progresses sequentially via metastable phases. Amorphous CaCO 3 (ACC) generally forms initially, both in vitro and in vivo, and is the precursor of the predominant anhydrous polymorphs (calcite, aragonite, and vaterite). [1][2][3][4][5][6][7][8][9][10][11][12][13] A new picture of the crystallization of calcium carbonate is emerging, which involves transformations of clusters to ACC and eventually to crystalline polymorphs. [14,15] This stepwise manner has implications for the understanding of biomineralization [16] and of crystallization. ACCs that contain additives display order over atomic length scales that are related to crystalline polymorphs; [1][2][3] ACC synthesized at high supersaturation levels without additives, [17][18][19][20] on the other hand, show no distinct short-range order. [21,22] Herein, we analyze proto-crystalline features of two amorphous intermediates, ACCI and ACCII, [15] and discuss their relevance for crystallization of CaCO 3 . We rationalize the identification of ACCI with pc-ACC (proto-calcite ACC) and ACCII with pv-ACC (proto-vaterite ACC), respectively. These ACCs were precipitated from metastable solutions of calcium carbonate at different pH values by destabilization in excess ethanol.TEM (Figure 1) reveals the ACCs as spherical particles with a diameter of approximately 20 nm. Small-angle X-ray scattering (SAXS) data support this characteristic size

This review summarizes the main processing routes and significant properties of nanocellulose-based foams and aerogels.

Here we demonstrate that the anomalous magnetic properties of iron oxide nanoparticles are correlated with defects in their interior. We studied the evolution of microstructure and magnetic properties of biphasic core|shell Fe(1-x)O|Fe(3-δ)O4 nanoparticles synthesized by thermal decomposition during their topotaxial oxidation to single-phase nanoparticles. Geometric phase analysis of high-resolution electron microscopy images reveals a large interfacial strain at the core|shell interface and the development of antiphase boundaries. Dark-field transmission electron microscopy and powder X-ray diffraction concur that, as the oxidation proceeds, the interfacial strain is released as the Fe(1-x)O core is removed but that the antiphase boundaries remain. The antiphase boundaries result in anomalous magnetic behavior, that is, a reduced saturation magnetization and exchange bias effects in single-phase nanoparticles. Our results indicate that internal defects play an important role in dictating the magnetic properties of iron oxide nanoparticles.