Small-Angle X-ray Scattering Analysis of Colloidal Crystals and Replica Materials Made from l-Arginine-Stabilized Silica Nanoparticles.

Colloidal crystals made from sub-100 nm silica nanoparticles have provided a versatile platform for the template-assisted synthesis of three-dimensionally interconnected semiconducting, metallic, and magnetic replicas. However, the detailed structure of these materials has not yet been characterized. In this study, we investigated the structures of colloidal crystalline films and germanium replicas by scanning electron microscopy and small angle X-ray scattering. The structures of colloidal crystals made by evaporative assembly depends on the size of l-arginine-capped silica nanoparticles. Particles smaller than ∼31 nm diameter assemble into non-close-packed arrangements (bcc) whereas particles larger than 31 nm assemble into random close-packed structures with disordered hexagonal phase. Polycrystalline films of these materials retain their structures and long-range order upon infiltration at high temperature and pressure, and the structure is preserved in Ge replicas. The shear force during deposition and dispersity of silica nanoparticles contributes to the size-based variation in the structure and to the size of crystal domains in the colloidal crystal films.

Rheo-SAXS study of shear-induced orientation and relaxation of cellulose nanocrystal and montmorillonite nanoplatelet dispersions.

The development of robust production processes is essential for the introduction of advanced materials based on renewable and Earth-abundant resources. Cellulose nanomaterials have been combined with other highly available nanoparticles, in particular clays, to generate multifunctional films and foams. Here, the structure of dispersions of rod-like cellulose nanocrystals (CNC) and montmorillonite nanoplatelets (MNT) was probed using small-angle X-ray scattering within a rheological cell (Rheo-SAXS). Shear induced a high degree of particle orientation in both the CNC-only and CNC:MNT composite dispersions. Relaxation of the shear-induced orientation in the CNC-only dispersion decayed exponentially and reached a steady-state within 20 seconds, while the relaxation of the CNC:MNT composite dispersion was found to be strongly retarded and partially inhibited. Viscoelastic measurements and Guinier analysis of dispersions at the shear rate of 0.1 s-1 showed that the addition of MNT promotes gel formation of the CNC:MNT composite dispersions. A better understanding of shear-dependent assembly and orientation of multi-component nanoparticle dispersions can be used to process materials with improved mechanical and functional properties.

Assembly of cellulose nanocrystals and clay nanoplatelets studied by time-resolved X-ray scattering.

Time-resolved small-angle X-ray scattering (SAXS) was used to probe the assembly of cellulose nanocrystals (CNC) and montmorillonite (MNT) over a wide concentration range in aqueous levitating droplets. Analysis of the SAXS curves of the one-component and mixed dispersions shows that co-assembly of rod-like CNC and MNT nanoplatelets is dominated by the interactions between the dispersed CNC particles and that MNT promotes gelation and assembly of CNC, which occurred at lower total volume fractions in the CNC:MNT than in the CNC-only dispersions. The CNC dispersions displayed a d ∝ φ-1/2 scaling and a low-q power-law exponent of 2.0-2.2 for volume fractions up to 35%, which indicates that liquid crystal assembly co-exists and competes with gelation.

Two-Stage Assembly of Mesocrystal Fibers with Tunable Diameters in Weak Magnetic Fields.

Controlling the morphology and crystallographic coherence of assemblies of magnetic nanoparticles is a promising route to functional materials. Time-resolved small-angle X-ray scattering (SAXS) was combined with microscopy and scaling analysis to probe and analyze evaporation-induced assembly in levitating drops and thin films of superparamagnetic iron oxide nanocubes in weak magnetic fields. We show that assembly of micrometer-sized mesocrystals with a cubic shape preceded the formation of fibers with a high degree of crystallographic coherence and tunable diameters. The second-stage assembly of aligned cuboidal mesocrystals into fibers was driven by the magnetic field, but the first-stage assembly of the oleate-capped nanocubes was unaffected by weak magnetic fields. The transition from 3D growth of the primary mesocrystals to the second stage 1D assembly of the elongated fibers was related to the size and field dependence of isotropic van der Waals and directional dipolar interactions between the interacting mesocrystals.

Temporal Evolution of Superlattice Contraction and Defect-Induced Strain Anisotropy in Mesocrystals during Nanocube Self-Assembly.

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.

Brine rejection and hydrate formation upon freezing of NaCl aqueous solutions.

Studying the freezing of saltwater on a molecular level is of fundamental importance for improving freeze desalination techniques. In this study, we investigate the freezing process of NaCl solutions using a combination of X-ray diffraction and molecular dynamics simulations (MD) for different salt-water concentrations, ranging from seawater conditions to saturation. A linear superposition model reproduces well the brine rejection due to hexagonal ice Ih formation and allows us to quantify the fraction of ice and brine. Furthermore, upon cooling at T = 233 K, we observe the formation of NaCl·2H2O hydrates (hydrohalites), which coexist with ice Ih. MD simulations are utilized to model the formation of NaCl crystal hydrates. From the simulations, we estimate that the salinity of the newly produced ice is 0.5% mass percent (m/m) due to ion inclusions, which is within the salinity limits of fresh water. In addition, we show the effect of ions on the local ice structure using the tetrahedrality parameter and follow the crystallite formation using the ion coordination parameter and cluster analysis.

Mechanical Properties of Tandem-Repeat Proteins Are Governed by Network Defects.

Topological defects in highly repetitive structural proteins strongly affect their mechanical properties. However, there are no universal rules for structure-property prediction in structural proteins due to high diversity in their repetitive modules. Here, we studied the mechanical properties of tandem-repeat proteins inspired by squid ring teeth proteins using rheology and tensile experiments as well as spectroscopic and X-ray techniques. We also developed a network model based on entropic elasticity to predict structure-property relationships for these proteins. We demonstrated that shear modulus, elastic modulus, and toughness scale inversely with the number of repeats in these proteins. Through optimization of structural repeats, we obtained highly efficient protein network topologies with 42 MJ/m3 ultimate toughness that are capable of withstanding deformations up to 350% when hydrated. Investigation of topological network defects in structural proteins will improve the prediction of mechanical properties for designing novel protein-based materials.