The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from ≈15 μm down to ≈2 μm as ϕ increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1° up to 4° as ϕ increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases.
Here we demonstrate how monodisperse iron oxide nanocubes and nanospheres with average sizes between 5 and 27 nm can be synthesized by thermal decomposition. The relative importance of the purity of the reactants, the ratio of oleic acid and sodium oleate, the maximum temperature, and the rate of temperature increase, on robust and reproducible size and shape-selective iron oxide nanoparticle synthesis are identified and discussed. The synthesis conditions that generate highly monodisperse iron oxide nanocubes suitable for producing large ordered arrays, or mesocrystals are described in detail.
Mesocrystals composed of crystallographically aligned nanocrystals are present in biominerals and assembled materials which show strongly directional properties of importance for mechanical protection and functional devices. Mesocrystals are commonly formed by complex biomineralization processes and can also be generated by assembly of anisotropic nanocrystals. Here, we follow the evaporation-induced assembly of maghemite nanocubes into mesocrystals in real time in levitating drops. Analysis of time-resolved small-angle X-ray scattering data and ex situ scanning electron microscopy together with interparticle potential calculations show that the substrate-free, particle-mediated crystallization process proceeds in two stages involving the formation and rapid transformation of a dense, structurally disordered phase into ordered mesocrystals. Controlling and tailoring the particle-mediated formation of mesocrystals could be utilized to assemble designed nanoparticles into new materials with unique functions.
We
have followed the structural evolution during evaporation-induced
self-assembly of sulfonated cellulose nanocrystal (CNC) in the presence
of H+ and Li+ counterions by small-angle X-ray
scattering. Drying of CNC-H dispersions results in ordered films that
could not be readily redispersed, while the CNC-Li films were disordered
and prone to reswelling and redispersion. The scaling of the separation
distance (d) between CNC particles and the particle
concentration (c) shows that the CNC-H dispersions
display a unidimensional contraction of the nematic structure (d ∝ c
–1) during
drying, while the CNC-Li dispersions consolidate isotropically (d ∝ c
–1/3), which
is characteristic for hydrogels with no preferential orientation.
Temporal evolution of the structure factor and complementary dynamic
light-scattering measurements show that CNC-Li is more aggregated
than CNC-H during evaporation-induced assembly. Insights on the structural
evolution during CNC assembly and redispersion can promote development
of novel and optimized processing routes of nanocellulose-based materials.
Assembly of bio-based nano-sized particles into complex architectures and morphologies is an area of fundamental interest and technical importance. We have investigated the assembly of sulfonated cellulose nanocrystals (CNC) dispersed in a shrinking levitating aqueous drop using time-resolved small angle X-ray scattering (SAXS). Analysis of the scaling of the particle separation distance (d) with particle concentration (c) was used to follow the transition of CNC dispersions from an isotropic state at 1-2 vol% to a compressed nematic state at particle concentrations above 30 vol%. Comparison with SAXS measurements on CNC dispersions at near equilibrium conditions shows that evaporation-induced assembly of CNC in large levitating drops is comparable to bulk systems. Colloidal states with d vs. c scalings intermediate between isotropic dispersions and unidirectional compression of the nematic structure could be related to the biphasic region and gelation of CNC. Nanoscale structural information of CNC assembly up to very high particle concentrations can help to fabricate nanocellulose-based materials by evaporative methods.
The growth modes of self-assembled mesocrystals and ordered arrays from dispersions of iron oxide nanocubes with a mean edge length of 9.6 nm during controlled solvent removal have been investigated with a combination of visible light video microscopy, atomic force microscopy and scanning electron microscopy. Mesocrystals with translational and orientational order of sizes up to 10 μm are formed spontaneously during the final, diffusion-controlled, drop-casting stage when the liquid film is very thin and the particle concentration is high. Convection-driven deposition of ordered nanocube arrays at the edge of the drying droplet is a manifestation of the so called coffee-ring effect. Dendritic growth or fingering of rapidly growing arrays of ordered nanocubes could also be observed in a transition regime as the growth front moves from the initial three-phase contact line towards the centre of the original droplet.
Understanding and controlling defect
formation during the assembly of nanoparticles is crucial for fabrication
of self-assembled nanostructured materials with predictable properties.
Here, time-resolved small-angle X-ray scattering was used to probe
the temporal evolution of strain and lattice contraction during evaporation-induced
self-assembly of oleate-capped iron oxide nanocubes in a levitating
drop. We show that the evolution of the strain and structure of the
growing mesocrystals is related to the formation of defects as the
solvent evaporated and the assembly process progressed. Superlattice
contraction during the mesocrystal growth stage is responsible for
the rapidly increasing isotropic strain and the introduction of point
defects. The crystal strain, quantified by the Williamson–Hall
analysis, became more anisotropic due to the formation of stress-relieving
dislocations as the mesocrystal growth was approaching completion.
Understanding the formation of the transformation of defects in mesocrystals
and superlattices could assist in the development of optimized assembly
processes of nanoparticles with multifunctional properties.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.