Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (similar to 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.

Online study of the formation of PA6 droplets in PP matrix under shear flow

Breakup process of polyamide 6 (PA6) in polypropylene (PP) matrix under shear flow was online studied by using a Linkam CSS 450 stage equipped with optical microscopy. Both tip streaming and fracture breakup modes of PA6 droplets were observed in this study. It was reported that the droplet would break up by tip streaming model when the radio of the droplet phase viscosity to the matrix phase viscosity (n(r) = n(d)/n(m)) is smaller than 0.1 (Taylor, Proc R Soc London A 1934, 146, 501; Grace, Chem Eng Commun 1982, 14, 225; Bartok and Mason, J Colloid Sci 1959, 14, 13; Rumscheidt and Mason, J Colloid Sci 1961, 16, 238; de Bruijn, Chem Eng Sci 1993, 48, 277). However, the tip streaming model was observed even when the viscosity ratio was much greater than 0.1 (n(r) = 1.9). In this study for the tip streaming mode, small droplets were ruptured from the tip of the mother droplet. On the other hand, the mother droplet was broken into two or more daughter droplets with one or several satellite droplets between them for the fracture mode. It was found that PA6 droplet was much elongated at first, and then broke up via tip streaming or fracture to form daughter droplets or small satellite droplets with the shape of fiber or ellipse.

Shape-gradient composite surfaces: Water droplets move uphill

The approach of water droplets self-running horizontally and uphill without any other forces was proposed by patterning the shape-gradient hydrophilic material (i.e., mica) to the hydrophobic matrix (i.e., wax or low-density polyethylene (LDPE)). The shape-gradient composite surface is the best one to drive water droplet self-running both at the high velocity and the maximal distance among four different geometrical mica/wax composite surfaces. The driving force for the water droplets self-running includes: (1) the great difference in wettability of surface materials, (2) the low contact angle hysteresis of surface materials, and (3) the space limitation of the shape-gradient transportation area. Furthermore, the average velocity and the maximal distance of the self-running were mainly determined by the gradient angle (alpha), the droplet volume, and the difference of the contact angle hysteresis. Theoretical analysis is in agreement with the experimental results.

Size-dependent phase transfer of gold nanoparticles from water into toluene by tetraoctylammonium cations: A wholly electrostatic interaction

In this study, it is demonstrated that the tetraoctylammonium cation can be used directly as a phase-transfer reagent of negatively charged water-based gold nanoparticles. The transference is size-dependent and is based on a wholly electrostatic interaction.

Ordered pattern formation from dewetting of polymer thin film with surface disturbance by capillary force lithography

The dewetting process of thin polystyrene (PS) film with built-in ordered disturbance by capillary force lithography (CFL) has. been investigated in situ by AFM. Two different phenomena are observed depending on the excess surface energy (DeltaF(gamma)) of the system. When DeltaF(gamma) is less than a certain critical value (i.e., the disturbance amplitude is under a critical value), the PS film would be flattened and become stable finally by heating above T-g. While, if the size of the disturbance amplitude is larger than the critical value, ordered PS liquid droplets form by further dewetting. The pattern formation mechanisms and influencing factors have been discussed in detail.

Brittle-ductile transition of polypropylene/ethyllene-propylene-diene monomer blends induced by size, temperature, and time

To study the brittle-ductile transition (BDT) of polypropylene (PP)/ethylene-propylene-diene monomer (EPDM) blends induced by size, temperature, and time, the toughness of the PP/EPDM blends was investigated over wide ranges of EPDM content, temperature, and strain rate. The toughness of the blends was determined from the tensile fracture energy of the side-edge notched samples. The concept of interparticle distance (ID) was introduced into this study to probe the size effect on the BDT of PP/EPDM blends, whereas the effect of time corresponded to that of strain rate. The BDT induced by size, temperature, and time was observed in the fracture energy versus ID, temperature, and strain rate. The critical BDT temperatures for various EPDM contents at different initial strain rates were obtained from these transitions. The critical interparticle distance (IDc) increased nonlinearly with increasing temperature, and when the initial strain rate was lower, the IDc was larger. Moreover, the variation of the reciprocal of the initial strain rate with the reciprocal of temperature followed different straight lines for various EPDM contents. These straight lines were with the same slope.

Hydrodynamic radius characterization of a vinyl-type polynorbornene by size-exclusion chromatography with a static and dynamic laser light scattering detector

Both absolute molecular weight and molecular sizes (radius of gyration and hydrodynamic radius) of a vinyl-type polynorbornene eluting from size-exclusion chromatography columns were determined by combined with a static and dynamic laser light scattering detector. The hydrodynamic radius of polymer fraction eluting from size-exclusion chromatography columns was obtained from dynamic laser light scattering measurements at only a single angle of 900 by introducing a correction factor. According to the scaling relationship between molecular sizes and molecular weight and the ratio between radius of gyration and hydrodynamic radius, the vinyl-type polynorbornene took a random coil conformation in 1,2,4-trichlorobenzene at 150 degreesC.

How does solvent molecular size affect the microscopic structure in polymer solutions?

Monte Carlo simulation has been used to investigate the effects of linear solvent molecular size on polymer chain conformation in solutions. Increasing the solvent molecular size leads to shrinkage of the polymer chains and increase of the critical overlap concentrations. The root-mean-square radius of gyration of polymer chains (R-g) is less sensitive to the variation of polymer concentration in solutions of larger solvent molecules. In addition, the dependency of R-g on polymer concentration under normal solvent conditions and solvent molecular size is in good agreement with scaling laws. When the solvent molecular size approaches the ideal end-to-end distance of the polymer chain, an extra aggregation of polymer chains occurs, and the solvent becomes the so-called medium-sized solvent. When the size of solvent molecules is smaller than the medium size, the polymer chains are swollen or partially swollen. However, when the size of solvent molecules is larger than the medium size, the polymer coils shrink and segregate, enwrapped by the large solvent molecules.

Syntheses of Ag, PbSe, and PbTe nanocrystals and their binary self-assembly exploration at low size-ratio

Nanocrystals of Ag, PbSe, and PbTe were prepared via a high-temperature organic solution approach, respectively. Using a size-selection technique, the size-distribution of each set of nanocrystals could be fine-tuned and finally monodisperse products were achieved. Superlattice structure of binary self-assemblies in low size-ratio were also explored and characterized by transmission electron microscopy. It is realized that a success of achieving binary self-assembly pattern is greatly dependent on several key factors including particle size-distributions, relative concentrations of both components, as well as the size-ratios between Ag and PbSe (or PbTe) nanocrystals.

Surface and interface morphology of polystyrene/poly(methyl methacrylate) thin-film blends and bilayers

The surface and interface morphologies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) thin-film blends and bilayers were investigated by means of atomic force microscopy (AFM) and X-ray photoelectron spectroscopy. Spin-coating a drop of a PS solution directly onto a PMMA bottom layer from a common solvent for both polymers yielded lateral domains that exhibited a well-defined topographical structure. Two common solvents were used in this study. The structure of the films changed progressively as the concentration of the PS solution was varied. The formation of the blend morphology could be explained by the difference in the solubility of the two polymers in the solvent and the dewetting of PS-rich domains from the PMMA-rich phase. Films of the PS/PMMA blend and bilayer were annealed at temperatures above their glass-transition temperatures for up to 70 h. All samples investigated with AFM were covered with PS droplets of various size distributions. Moreover, we investigated the evolution of the annealed PS/PMMA thin-film blend and bilayer and gave a proper explanation for the formation of a relatively complicated interface inside a larger PS droplet.