▪ Abstract Solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤5%, are presented. Preparation of monodisperse samples enables systematic characterization of the structural, electronic, and optical properties of materials as they evolve from molecular to bulk in the nanometer size range. Sample uniformity makes it possible to manipulate nanocrystals into close-packed, glassy, and ordered nanocrystal assemblies (superlattices, colloidal crystals, supercrystals). Rigorous structural characterization is critical to understanding the electronic and optical properties of both nanocrystals and their assemblies. At inter-particle separations 5–100 A, dipole-dipole interactions lead to energy transfer between neighboring nanocrystals, and electronic tunneling between proximal nanocrystals gives rise to dark and photoconductivity. At separations <5 A, exchange interactions cause otherwise insulating ass...

Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies

Temperature-sensitive aqueous microgels.

The ability to pattern materials in three dimensions is critical for several technological applications, including composites, microfluidics, photonics, and tissue engineering. Direct-write assembly allows one to design and rapidly fabricate materials in complex 3D shapes without the need for expensive tooling, dies, or lithographic masks. Here, recent advances in direct ink writing are reviewed with an emphasis on the push towards finer feature sizes. Opportunities and challenges associated with direct ink writing are also highlighted.

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Direct ink writing of 3D functional materials

Colloidal processing of ceramics is reviewed with an emphasis on interparticle forces, suspension rheology, consolidation techniques, and drying behavior. Particular attention is given to the scientific concepts that underpin the fabrication of particulate-derived ceramic components. The complex interplay between suspension stability and its structural evolution during colloidal processing is highlighted.

/pdf/colloidal-processing-of-ceramics-1f3f618kn7.pdf

Colloidal Processing of Ceramics

Design and Production of Nanoparticles Formulated From Nano-Emulsion Templates-A Review

The properties of aqueous solutions of model HEUR associative thickeners under dynamic and steady shear have been studied as a function of concentration, molecular weight, temperature, and hydrophobic end‐cap length. It is shown that solutions of AT behave as near perfect Maxwell fluids inasmuch that Cole–Cole plots of the dynamic moduli are almost exactly semi‐circular. An Arrhenius law temperature dependence of the static viscosity and relaxation time is also observed, providing confirmation of a single relaxation process. In certain other respects, AT solutions show more complex behavior, e.g., the Cox–Merz rule is not obeyed, with the steady shear viscosity showing a weaker dependence on shear rate than does the complex viscosity upon frequency. Furthermore, weak shear thickening is seen to precede shear thinning in steady shear. The above results are consistent with the predictions of a transient network theory presented recently by Tanaka and Edwards and Jenkins (generalized Green–Tobolsky theory). ...

https://sor.scitation.org/doi/pdf/10.1122/1.550391

The rheology of solutions of associating polymers: Comparison of experimental behavior with transient network theory

The concentration or consolidation of suspensions of fine particles under the influence of a gravitational field has been analysed. The rate and extent of consolidation depends upon a balance of three forces, the gravitational driving force, the viscous drag force associated with flow of liquid in the sediment and a particle or network stress developed as a result of direct particle–particle interactions. In the case of colloidally stable suspensions, this particle stress is the osmotic pressure of the particles; in the case of flocculated or coagulated suspensions, it is the elastic stress developed in the network of particles. A constitutive equation is suggested for irreversibly flocculated suspensions undergoing consolidation which embodies the concept of a concentration-dependent yield stress Py(ϕ). This is then used to analyse the sedimentation behaviour of flocculated sediments and to derive expressions for the initial sedimentation rate. The initial rate of change of sediment height with time in a uniform gravitational or centrifugal field is given approximately by: [graphic ommitted] where B=Δρgϕ0H0/Py(ϕ0), u0 is the sedimentation rate of an isolated particle, ϕ0 is the initial (uniform) volume fraction of solids, r(ϕ0) is a dimensionless hydrodynamic interaction parameter, Δρ is the difference in density between solid and liquid, g is the gravitational or centrifugal acceleration and H0 is the initial sediment height. The theory accounts correctly for the equilibrium consolidation behaviour of strongly flocculated suspensions, and preliminary experimental data suggest that it is not inconsistent with their dynamic behaviour. The estimation of the yield stress Py(ϕ) from a batch centrifuge experiment is also described.

The consolidation of concentrated suspensions. Part 1.—The theory of sedimentation

The instantaneous shear modulus G and compactive strength Py of aggregate networks formed from silica particles with a mean diameter of 26 nm have been determined as a function of particle concentration. The data are compared with similar data obtained earlier for a range of polystyrene spheres with diameters between 60 and 960 nm and with compactive strength data obtained for polystyrene spheres at higher volume fractions by Sutherland. It is shown that clusters of submicron spheres formed by rapid aggregation become spacefilling and form a network at a critical volume fraction Φg of ca. 0.05. Above this concentration the data for Py and G suggest that aggregate networks show universal behaviour which is consistent with the scalings G∼ϕµ, dPy(ϕ)//d ln ϕ∼G(ϕ), with µ= 4 ± 0.5. This latter value for the exponent agrees well with that predicted by Ball and Brown by assuming the clusters comprising the network are fractal. For diffusion-limited cluster–cluster aggregation (DCA) they obtained a value of µ= 3.6. The data for Py imply a particle size dependence of the type Py∼am with m between –2 and –3, where a is the particle radius. More data are required to establish the precise dependence; the observed trend is, however, not inconsistent with what might be expected from a consideration of interparticle forces which implies a scaling of a–2.3. The scaling behaviour of the yield stress in shear flow and the dependence of the shear modulus on strain for non-negligible strains is also discussed.

Scaling behaviour of the rheology of aggregate networks formed from colloidal particles

The rheology of strongly-flocculated dispersions of colloidal particles has been investigated at particle concentrations where a continuous network is formed rather than a collection of discrete flocs. Such networks are shown to possess a true yield stress in both shear and in uniaxial compression (as realised in a centrifuge). Properties measured as a function of particle concentration and particle size include the yield stresses in shear (σ y ) and compression ( P y ); the limiting and strain-dependent, instantaneous shear moduli G O and G (γ); the elastic recovery at finite strains, and the rate of centrifugally-driven compaction. The yield stresses and moduli appear to show a power-law dependence on particle concentration with G O and P y , having the same power-law index and σ y a somewhat lower one. The data are in part consistent with predictions based on the idea that the networks have a heterogeneous structure comprising a collection of interconnected fractal aggregates. The behaviour as a function of particle size and concentration is however not completely scaleable as might be expected on this basis. Thus, whereas the shear yield stress could be scaled to remove its dependence on particle radius a and volume fraction φ (over the measured range 0.25 μm ⩽ a ⩽ 3.4 μm; 0.05 ⩽ φ ⩽ 0.25) as could the strain dependent modulus (0.25 ⩽ a ⩽ 1.3 μm; 0.08 ⩽ 0.25), the particle-size and concentration dependence of P y and G O could only be scaled for particles with radii between 0.16 and 0.5 μm, smaller and larger particles having different and much higher power-law index in respect of their concentration dependencies. In the case of the smaller particles the failure of the scaling is thought to be due to an anomaly since these particles distort significantly under the influence of the strong van der Waals forces and this causes the aggregates to be more compact then they otherwise would be. The reasons for the failure at larger sizes is not clear.

The rheology of strongly-flocculated suspensions

It is demonstrated that weakly flocculated, concentrated colloidal dispersions show slip flow when sheared between smooth concentric cylinders. The precise pattern of behavior seen depends upon the stress and upon how long the flow is left to establish prior to measurement. With delay times of order hours, slip is not seen until a critical stress is exceeded (typically about 1 Pa) and, thus, the true low‐shear viscosity can be determined provided care is taken to ensure the stress does not exceed the critical level. With short delay times of order minutes, slip is seen irrespective of how small the stress is and the low‐shear viscosity can be underestimated by several orders of magnitude. Comparisons of flow curves obtained using smooth and roughened cylinders show that slip only occurs at the inner cylinder, and also that bulk flow is re‐established at higher stresses where the dispersions start to shear thin. The apparent low‐shear, relative viscosity measured in the presence of slip appears, to a first...

Richard Buscall

Papers

The rheology of solutions of associating polymers: Comparison of experimental behavior with transient network theory

The consolidation of concentrated suspensions. Part 1.—The theory of sedimentation

Scaling behaviour of the rheology of aggregate networks formed from colloidal particles

The rheology of strongly-flocculated suspensions

The rheology of concentrated dispersions of weakly attracting colloidal particles with and without wall slip