Oligomer-assisted self-assembly of bisurea in organic solvent media.

We report on molecular dynamics simulation evidence revealing that an oligomer additive can be used to greatly facilitate the self-assembly of a bisurea in organic solvent media, through the initial regular packing and the subsequent stiffening of the self-assembly filament. The underlying physics is attributed to the substantially reduced diffusivities of the solute and, in particular, solvent molecules, featuring a generally weakened (thermal) Brownian force under ambient conditions. Without such oligomer-induced molecular cooling-in contrast to the usual external cooling, the original solvent medium is noted to foster instead more stabilized and disordered aggregates and, in particular, it would require a temperature reduction that is practically inaccessible in order to sustain similar stiffness of the self-assembly filament. These features, in accord with recent experimental observations, highlight the open opportunity of promoting the self-assembly of small functional molecules in general solvent media without requiring substantial changes of the system temperature, as is crucial for many practical applications including the biological/biomedical ones.

Effects of Calcium and pH on Rheological Thermal Resistance of Composite Xanthan Gum and High-Methoxyl Apple Pectin Matrices Featuring Dysphagia-Friendly Consistency.

High-methoxyl apple pectin (AP) derived from apple was employed as the main ingredient facilitating rheological modification features in developing dysphagia-friendly fluidized alimentary matrices. Xanthan gum (XG) was also included as a composite counterpart to modify the viscoelastic properties of the thickened system under different thermal processes. The results indicate that AP is extremely sensitive to thermal processing, and the viscosity is greatly depleted under a neutral pH level. Moreover, the inclusion of calcium ions echoed the modification effect on the rheological properties of AP, and both the elastic property and viscosity value were promoted after thermal processing. The modification effect of viscoelastic properties (G' and G″) was observed whne XG was incorporated into the composite formula. Increasing the XG ratio from 7:3 to 6:4 (AP:XG) triggers the rheological transformation from a liquid-like form to a solid-like state, and the viscosity value shows that the AP-XG composite system exhibits better thermal stability after thermal processing. The ambient modifiers of pH (pH < 4) and calcium chloride concentration (7.5%) with an optimal AP-XG ratio of 7:3 led to weak-gel-like behavior (G″ < G'), helping to maintain the texture properties of dysphagia-friendly features similar to those prior to the thermal processing.

Multiscale structures and rheology of bisurea-loaded resins for anti-sagging applications.

Four representative bisurea molecules (HDI-BA, MDI-BA, TDI-BA, and IPDI-BA) were synthesized and dispersed simultaneously by reacting benzylamine (BA) with various types of diisocyanates in a polyester/ortho-xylene resin medium to produce bisurea-loaded resins (BLRs) for anti-sagging application with paints and coating materials. These bisurea molecules are symmetric and differ only in the central spacer unit, thereby presenting an ideal and simplest model system to delve into the structure-performance relationship. The multiscale structural features arising from self-assembly in each of the BLRs were scrutinized using the combination of multi-angular dynamic light scattering (DLS), small-angle light/X-ray scattering (SALS/SAXS), rheology, and scanning electron/optical microscopy (SEM/OM) characterization. All four BLRs were revealed to foster micron-sized, mostly sphere-like agglomerates, with distinct hierarchical structures that correlate well with their thixotropic and anti-sagging performances. Three BLRs (HDI-BA, MDI-BA, and TDI-BA) produce similar rod-like packing units (10 × 1 × 1 nm3), with only one exception (IPDI-BA) that produces a spherical packing unit (2 nm in diameter). However, the bulk feature of the agglomeration state, which dictates the thixotropic and anti-sagging properties, cannot be readily foreseen from the chemical structure or elementary packing unit of a bisurea. The present findings, while confirming the importance of optimum molecular design that controls the early-stage self-assembly behavior of a bisurea in resin media, highlight the necessity of resolving detailed (multiscale) structural features in order to establish the full structure-performance relationship imperatively needed for like material systems and applications.

Multiscale structural and rheological features of colloidal low-methoxyl pectin solutions and calcium-induced sol-gel transition.

The multiscale structural and rheological features of a series of dilute and semidilute low-methoxyl (LM) pectin solutions and a representative pectin/calcium sol-gel sample were systematically explored using a comprehensive combination of dynamic (DLS) and static light/X-ray scattering (SALS/SLS/SAXS), rheology, and microscopy (OM/SEM) characterizations. The study focused on the rarely explored colloidal aspect of LM pectin solutions and sol-gel transition, in contrast to the polymeric features extensively explored in previous studies. A highly uniform colloid-like, micron-sized agglomerate species was revealed in dilute solutions, with a progressively increased degree of flocculation in the semidilute regime (≥1.5 wt%). The agglomerate species in these solutions was resolved to be formed by random associations of individual pectin chains (L = 30 nm, r = 0.4 nm). Adding a critical amount of Ca2+ (10 wt%) to a semidilute solution (2 wt%) has an instant and pronounced effect of enhancing the agglomerate flocculation and resulting in a locally jammed state. Meanwhile, the agglomerate interior underwent microstructural transformation, leading to hierarchical structures defined by intermediate (spherical) aggregate species (Rg,aggregate ≈ 150 nm) and its packing cylindrical bundle (d ≈ 4 nm) composed of five pectin chains. Novel rheological features observed during the LM pectin/Ca2+ sol-gel transition include the following: the dynamic modulus data exhibited excellent TTS (gelling time/relaxation time superposition) as previously observed for weakly attractive colloidal gels. Three yield points were noticed for the final gel sample, suggested to mark the bond breaking of the cluster network, cage breaking of the resulting jammed flocculates, and, eventually, breakup of a flocculate into smaller agglomerates with increasing stress amplitude.

Rheological and Textural Properties of Apple Pectin-Based Composite Formula with Xanthan Gum Modification for Preparation of Thickened Matrices with Dysphagia-Friendly Potential.

Modifying the consistency of a given edible fluid matrix by incorporating food thickeners is a common nursing remedy for individuals with dysphagia when adequate water consumption is a concern. As apple pectin (AP) offers nutraceutical benefits, properly formulated apple pectin (AP)-based thickeners featuring xanthan gum (XG) can be superior candidates for preparation of dysphagia-friendly matrices (DFMs). Our recruited DFMs exhibit fluid-like behavior (loss modulus > storage modulus, G" > G') at lower AP concentrations (2 and 5%, w/w); they turn into weak/critical gels (G' ≈ G") as the concentration becomes higher (9%). In contrast, XG-DFMs display gel-like attributes with G' > G", even at rather low concentrations (<1%) and become more resistant to sugar, Na+, and Ca2+ modifications. The composite matrix of AP1.8XG0.2 (constraint at 2%) exhibits a confined viscosity of 278 ± 11.7 mPa∙s, which is considered a DFM, in comparison to only AP- or XG-thickened ones. The hardness measurements of XG0.6 and AP1.2XG0.8 are 288.33 ± 7.506 and 302.00 ± 9.849 N/m2, respectively, which potentially represent a promising formulation base for future applications with DFMs; these textural values are not significantly different from a commercially available product (p > 0.05) for dysphagia nursing administrations.

Rheological and rheo-birefringence features of semidilute ethyl cellulose dispersions under steady shear flow.

We have conducted comprehensive rheological and rheo-birefringence characterizations of a series of semidilute ethyl cellulose (EC)/α-terpineol dispersions under steady shear flow. The EC dispersions investigated have commonly been utilized as a binder agent in fabricating metal/metal-oxide pastes for a number of industrial applications, and were recently demonstrated to foster nearly monodisperse spherical aggregates under dilute conditions. Herein, semidilute EC dispersions are shown to exhibit rheological features practically no different from those known for standard entangled polymer solutions. The corresponding rheo-birefringence responses, however, reveal microstructural features that are reminiscent of general colloidal systems. The steady-state feature reveals a universal stress-birefringence relationship at various EC concentrations, along with a common critical stress (∼200 Pa) at which the EC network breaks into smaller clusters. The transient feature displays prominent and long-persisting periodic oscillations that have previously been observed only for nearly monodisperse rod-like colloids or liquid crystals. The overall findings shed new light on the role of EC serving as a commonplace polymer binder in industry and, from a scientific perspective, raise interesting questions related to the characteristic rheological and microstructural features of general polymer dispersions in overlapped regimes.

Correlation of the hierarchical structure with rheological behavior of polypseudorotaxane gel composed of pluronic and ß-cyclodextrin.

We have identified the hierarchical (primary, secondary, tertiary and quaternary) structures of a polypseudorotaxane (PPR) gel composed of the Pluronic F108 and ß-cyclodextrin system to be ß-cyclodextrin crystalline, lamellar sheets, lamellar stacks and "grains", respectively. The correlation between the rheological properties and the proposed structures under shear flows was rationalized. Alignment of lamellar stacks and reorganization of grain boundaries under shear flows were investigated by rheo-SANS, small angle X-ray scattering and small-angle light scattering. The relaxation of highly aligned lamellar stacks is slow (>2 h) after flow cessation compared to that of the regrouped grains (a few minutes). The main contribution to thixotropic behavior is likely from the faster relaxation of the reorganized grains containing highly oriented lamellar stacks. The comprehensive understanding of structure-function relationship of the PPR gel will facilitate the rational design for its applications.

Hexagonal Superalignment of Nano-Objects with Tunable Separation in a Dilute and Spacer-Free Solution.

Manipulating building-block nanomaterials to form an ordered superstructure in a dilute and spacer-free solution phase challenges the existing 5-nm node lithography and nanorobotics. The cooperative nature of nanocrystals, polymers, and cells can lead to superarrays or colloidal crystals. For known highly ordered systems, the characteristic length of materials, defined as the shortest dimension of objects, is generally larger than their separations. A spacer (small-molecule surfactant or polymer) is typically required to diminish short range van der Waals attraction, which results in a glassy or liquid state. Herein we propose a new concept of achieving highly ordered nano-objects in a dilute and spacer-free system via the synergistic effects of excellent solvation and appropriate constraints on rotational motion. As a proof of concept, this study demonstrates that aluminosilicate nanotubes (AlSiNTs) suspended in water under dilute conditions (e.g., 1.0 wt%) can spontaneously form hexagonal arrays with an intertubular distance as large as tens of nanometers. The separation distance of the ordered superstructure is also tunable via controlling the concentration and length of nanotubes. These superaligned structures are probed using small-angle x-ray scattering and cryo-TEM characterizations, with underlying mechanisms investigated at an atomic level using molecular dynamics simulations. The concept and discovery of this work can open up opportunities to a variety of applications including visible-UV photonics and nanolithography, and may be generalizable to other nano-object systems that fulfill similar requirements.

PBTTT-C16 sol-gel transition by rod associations and networking.

A low-molecular-weight poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (designated as Lw-pBTTT-C16) in a fair solvent (chlorobenzene, CB) displays peculiar structural, mechanical, and electronic features during sol-gel transition. Using comprehensive (multiscale) dynamic/static analysis schemes, the Lw-pBTTT-C16/CB solution (10 mg mL-1) is shown to capitalize on rod associations and networking to form a gel, in stark contrast with its high-molecular-weight companion previously reported to form gels through hierarchical colloidal bridging. The present study reveals, however, that the molecular weight of pBTTT-C16 has a subtle impact on the gelation behaviors through the rarely recognized, contrasting supramolecular conformations (rod-like vs. wormlike) of the aggregate clusters fostered in the pristine solution. The ac conductivity nearly doubles as a result of improved (mesoscale) packing of cylindrical aggregates near the gel state as well as enhanced backbone rigidity of the constituting chains. Other distinguishing features include: (1) there is no real crossover of the dynamic moduli (G' and G'') upon increasing the temperature from gel (T = 15 °C) to solution (T = 80 °C) states. (2) The gel is about a hundredfold softer in dynamic modulus, yet more resilient with a fivefold increase in the yield strain. Both viscoelastic features are expected to greatly benefit the gel processability. (3) The coexistent microgels and cylinder (aggregate) bundles form a peculiar gel network that has not been reported previously with polymer or colloidal gels. The overall findings provide new mechanistic insight into the phenomenological effects of molecular weight for the pBTTT-Cn series in solution, sol, gel, and thin film.

Solvent Effects on Morphology and Electrical Properties of Poly(3-hexylthiophene) Electrospun Nanofibers.

Herein, poly(3-hexylthiophene-2,5-diyl) (P3HT) nanofiber-based organic field-effect transistors were successfully prepared by coaxial electrospinning technique with P3HT as the core polymer and poly(methyl methacrylate) (PMMA) as the shell polymer, followed by extraction of PMMA. Three different solvents for the core polymer, including chloroform, chlorobenzene and 1,2,4-trichlorobenzene, were employed to manipulate the morphologies and electrical properties of P3HT electrospun nanofibers. Through the analyses from dynamic light scattering of P3HT solutions, polarized photoluminescence and X-ray diffraction pattern of P3HT electrospun nanofibers, it is revealed that the P3HT electrospun nanofiber prepared from the chloroform system displays a low crystallinity but highly oriented crystalline grains due to the dominant population of isolated-chain species in solution that greatly facilitates P3HT chain stretching during electrospinning. The resulting high charge-carrier mobility of 3.57 × 10-1 cm2·V-1·s-1 and decent mechanical deformation up to a strain of 80% make the P3HT electrospun nanofiber a promising means for fabricating stretchable optoelectronic devices.

Solution properties of imidazolium-based amphiphilic polyelectrolyte in pure- and mixed-solvent media.

The solution properties of a synthesized imidazolium-based amphiphilic polyelectrolyte dissolved in pure- and mixed-solvent media composed of two aprotic polar solvents (N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP)) having a similar dielectric constant are explored in the semidilute regime (1-4 wt%). Rheological characterizations reveal that the use of mixed-solvent media (e.g., DMAc/NMP with 1 : 1 in volume fraction, designated as 1 : 1 DMAc/NMP) leads to a substantial reduction in the solution viscosity while altering the fluid attribute from gel-like (G' > G'') to critical-gel-like (G' ∼ G'' ∼ ωn, with n ≅ 0.5). To gain insight into these peculiar rheological features, dynamic light scattering analysis of the representative 1 : 1 DMAc/NMP medium indicates that the fraction and mean hydrodynamic radius of the micrometer-sized cluster alter substantially, too. Multiscale static light/X-ray scattering characterizations further reveal that only the NMP and 1 : 1 DMAc/NMP media (and not the DMAc) are capable of producing hierarchical structures of the cluster interior that are beneficial to mesoscale ion conduction, as supported by ac conductivity measurements. Overall, the present findings suggest that an appropriate selection of mixed-solvent media may offer an exceptional opportunity to promote the rheological, structural, and ion-conduction properties of a polyelectrolyte solution beyond the reach of the corresponding pure-solvent media.

Percolation behaviors of model carbon black pastes.

The percolation behaviors of a series of high-structured carbon black (CB) pastes (CB weight fractions 10-25 wt%, ethyl cellulose as the binder, α-terpineol as the solvent) were systematically investigated using analyses of rheology and impedance spectra together with characterization via small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM). When the CB concentration was near the static percolation threshold (∼20 wt%), the permittivity, ac conductance, and elastic modulus of the paste displayed notable increases, whereas the SAXS profile revealed the prevalence of isolated CB aggregates (mean radius of gyration ∼40 nm). Upon further aging at 25 and 40 °C (up to 6 h), two CB pastes near the static percolation threshold (i.e., 20 and 25 wt%) exhibited prominent temporally evolving responses, including more than tenfold increases in their ac conductance and elastic modulus, as well as a pronounced upturn in the low-q SAXS profile (q < 0.03 nm-1) and the formation of a (partially) interconnected cluster network in SEM observations of the morphologies of screen-printed films. In this case, we provide the first evidence of "(aging) Time-(relaxation) Time-Temperature-Concentration Superposition (TTTCS)" for the dynamic modulus data over a frequency range of seven orders of magnitude. This suggests that prolonged aging time imparted to CB aggregate interaction and restructuring (or gelation) may work in tandem with the known effects of the system temperature and concentration to further extend the accessible range of dynamic modulus data, in a similar way to recent reports on the effect of the curing (crosslinking) time on a carbon nanotube suspension and caramel. In combination with existing (three) master curves for two different colloidal materials, we show that there is a reasonable superposition of all the dynamic modulus data over a frequency range of 12 orders of magnitude.

Scalable Wet Deposition of Zeolite AEI with a High Degree of Preferred Crystal Orientation.

Producing zeolite films with controlled preferred orientation on an industrial scale is a long-standing challenge. Herein we report on a scalable approach to the direct wet deposition of zeolite thin films and membranes while maintaining a high degree of control over the preferred crystal orientation. As a proof of concept, thin films comprising aluminophosphate zeolite AEI were cast on silicon wafer or porous alumina substrates. Electrical properties and separation performance of the zeolite thin films/membranes were engineered through controlling degree of preferred crystal orientation.

PBTTT-C16 sol-gel transition by hierarchical colloidal bridging.

A versatile conjugated polymer, poly(2,5-bis(3-hexadecyllthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT-C16, with Mw = 61 309 g mol-1), in a relatively good solvent (chlorobenzene, CB) medium is shown to produce gels through hierarchical colloidal bridging. Multiscale static/dynamic light and X-ray scattering analysis schemes along with complementary microscopy imaging techniques clearly reveal that upon cooling from the solution state at 80 °C to various gelation temperatures (5, 10, and 15 °C), rod-like colloidal pBTTT-C16 aggregates morph into spherical ones, triggering hierarchical colloid formation and bridging that eventually turn the solution into a gel after about one-day aging. A certain fraction of primal packing units-spherical gelators (∼1 nm in mean radius)-constitute the spherical building particles (∼10 nm) noted above, which in turn constitute loose-packing aggregate clusters (∼300 nm) in the sol state. As gelation proceeds, the aggregate cluster interiors tighten substantially, and micrometer-sized clusters (∼3 µm) formed by them begin to take shape and further interconnect to form the gel network (mean porosity size ∼240 nm and spatial inhomogeneity length ∼20 µm). Rheological measurements and kinetic analysis reveal that the gelation temperature can also have a notable impact on gel microstructure, gelation rate, and mechanical strength, resulting in, for instance, a prominently nonergodic and porous structure for the soft gel incubated at a higher temperature T = 15 °C. The ac conductivity exhibits a notable upturn near pBTTT-C16/CB gelation, well above those achieved by the counterpart pBTTT-C14 solutions, which, in interesting contrast, cannot be brought to the gel phase under similar experimental conditions.

Properties of Single-Walled Aluminosilicate Nanotube/Poly(vinyl alcohol) Aqueous Dispersions.

The properties of (synthesized) single-walled aluminosilicate nanotube (AlSiNT; light-scattering characterized length ∼2000 ± 230 nm and diameter ∼35 ± 4 nm) dispersed in an aqueous poly(vinyl alcohol) (PVA) solution (10 wt %) are systematically explored using a comprehensive combination of (polarized/depolarized) dynamic light scattering, rheological, rheo-optical, and scanning electron microscopy analysis schemes. The nanotube/polymer dispersions under investigation are promising for their fair nanotube dispersion in pristine aqueous media (e.g., without salt or acid addition), as well as for the optical transparency that greatly facilitates systematic exploration of structural features and dispersion state that are practically inaccessible for many of their (opaque) companions such as carbon nanotube dispersions. We provide the first in-depth analysis revealing excellent dispersion state of (unmodified) AlSiNT in the PVA matrix, giving rise to (critical) gel-like features and substantially promoted elasticity that can be utilized, as a practical assessment, to produce uniform and defect-free electrospun nanofibers. Additionally, there is unambiguous evidence of nematic liquid crystal-like "wagging" (strain-invariant, periodic oscillation) under steady shear flow, a phenomenon previously unreported for nanotube composite materials. Overall, the present findings suggest that AlSiNT/PVA dispersions possess promising rheological, optical, and electrospinning properties that are highly desirable for current nanotechnological applications, and may serve as an ideal model system for establishing structure-performance relationships for like nanotube/polymer composite materials.

Ethylcellulose Colloids Incubated in Dilute Solution.

This study revealed, for the first time, that dilute solutions made of a representative series of commercial ethylcellulose (EC; molecular weights 77-305 kDa, provided by the manufacturer) and four distinct organic solvents (α-terpineol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TPIB), tetrahydrofuran (THF), and benzene) can be used to foster stabilized, nearly monodisperse, nanoscale (pure) polymer colloid, with no isolated chains present. Using combined light-scattering (dynamic light scattering, static form factor, and Zimm/Berry plots) and intrinsic viscosity (Tanglertpaibul-Rao, Huggins, and Kraemer plots) analyses, the structural features of colloidal EC aggregates, ρ = ⟨Rg⟩/⟨Rh⟩ = 0.67-0.83, were first shown to be described rather well by the theory on colloidal spheres (⟨Rg⟩ and ⟨Rh⟩ being the mean radius of gyration and the hydrodynamic radius, respectively). An empirical scaling law relating the intrinsic viscosity to the mean colloid size can thus be established: [η]H = (1.7 ± 0.2) ×10-3 ⟨Rh⟩(2.1±0.3) ([η]H and ⟨Rh⟩ in units of mL/g and nm, respectively), which may be contrasted with the Zimm model for isolated Gaussian coils, [η]H ∼ ⟨Rh⟩1, and the Einstein equation for isolated solid spheres, [η]H ∼ ⟨Rh⟩0. Optical microscopy images of thin films cast from different EC solutions clearly revealed the abundance of micron EC agglomerates, contrary to the uniform thin-film morphology produced from a dilute polystyrene solution, which serves as a reference solution composed of isolated chains. These observations point to new features and applications of EC dispersions.

Relationships between the solution and solid-state properties of solution-cast low-k silica thin films.

This paper reports on the fabrication of low-k (amorphous) silica thin films cast from solutions without and with two different types of surfactants (TWEEN® 80 and Triton™ X-100) to elucidate the relationships between the structural/morphological features of the casting solutions and the physical properties of the resulting thin films. Cryogenic transmission microscopy (cryo-TEM), static/dynamic light scattering (SLS/DLS), and small-angle X-ray scattering (SAXS) revealed contrasting colloidal dispersion states and phase behavior among the three casting solutions. Casting solution with the Triton™ X-100 surfactant produced stable (>90 days) nanoparticles with good dispersion in solution (mean particle size ∼10 nm) as well as good mesopore volume (characterized by nitrogen physisorption) in powder and thin films of high mechanical strength (characterized by the nanoindentation test). The longer main chain and bulkier side units of the TWEEN® 80 surfactant led to stable micelle-nanoparticle coexisting dispersion, which resulted in the highest mesopore volume in powder and thin films with the lowest dielectric constant (∼3) among the samples in this study. The casting solution without the surfactant failed to produce a stabilized solution or thin films of acceptable uniformity. These findings demonstrate the possibility of fine-tuning low-k silica film properties by controlling the colloidal state of casting solutions.

Mesoscale aggregation properties of C60 in toluene and chlorobenzene.

The mesoscale aggregation properties of C60 in two distinct aromatic solvents (toluene and chlorobenzene) and a practical range of concentrations (c = 1-2 and c = 1-5 mg mL(-1), respectively) were systematically explored by static/dynamic light scattering (SLS/DLS), small angle X-ray scattering (SAXS), depolarized dynamic light scattering (DDLS), and cryogenic transmission electron microscopy (cryo-TEM) analyses. The central observations were as follows: (1) aggregate species of sizes in the range of several hundred nanometers have been independently revealed by SLS, DLS, and DDLS analyses for both solvent systems. (2) DDLS and cryo-TEM measurements further revealed that while C60 clusters are notably anisotropic (rod-like) in chlorobenzene, they are basically isotropic (spherical) in toluene. (3) Detailed analyses of combined SLS and SAXS profiles suggested that varied, yet self-similar, solvent-induced aggregate units were responsible for the distinct (mesoscale) aggregation features noted above. (4) From a dynamic perspective, specially commissioned DLS measurements ubiquitously displayed two relaxation modes (fast and slow mode), with the second (slow) mode being q (wave vector) independent. While the fast mode in both solvent systems was basically diffusive by nature and leads to geometrical features in good agreement with the above static analyses, the slow mode was analyzed and tentatively suggested to reflect the effect of mutual confinement. (5) Micron-scale aggregate morphology of drop-cast thin films displays similar contrasting features for the two solvent media used. Overall, this study suggests that solvent-induced, nanoscale, aggregate units may be a promising factor to control a hierarchy of microscopic aggregation properties of C60 solutions and thin films.

Surface-engineered growth of AgIn5S8 crystals.

The growth of semiconductor crystals and thin films plays an essential role in industry and academic research. Considering the environmental damage caused by energy consumption during their fabrication, a simpler and cheaper method is desired. In fact, preparing semiconductor materials at lower temperatures using solution chemistry has potential in this research field. We found that solution chemistry, the physical and chemical properties of the substrate surface, and the phase diagram of the multicomponent compound semiconductor have a decisive influence on the crystal structure of the material. In this study, we used self-assembled monolayers (SAMs) to modify the silicon/glass substrate surface and effectively control the density of the functional groups and surface energy of the substrates. We first employed various solutions to grow octadecyltrichlorosilane (OTS), 3-mercaptopropyl-trimethoxysilane (MPS), and mixed OTS-MPS SAMs. The surface energy can be adjusted between 24.9 and 50.8 erg/cm(2). Using metal sulfide precursors in appropriate concentrations, AgIn5S8 crystals can be grown on the modified substrates without any post-thermal treatment. We can easily adjust the nucleation in order to vary the density of AgIn5S8 crystals. Our current process can achieve AgIn5S8 crystals of a maximum of 1 µm in diameter and a minimum crystal density of approximately 0.038/µm(2). One proof-of-concept experiment demonstrated that the material prepared from this low temperature process showed positive photocatalytic activity. This method for growing crystals can be applied to the green fabrication of optoelectronic materials.

Reduced colloidal repulsion imparted by adsorbed polymer of particle dimensions.

This work investigated the detailed interparticle interactions in a concentrated polymer-coated colloidal system in which the bare colloidal particles and the adsorbed polymers are of comparable size and, hence, the polymer adsorption cannot be foreseen to induce repulsive or attractive interactions. Specifically, poly(ethylene oxide) (PEO) chains (R(g) approximately 10nm) adsorbed onto fine silica colloidal particles (SAXS-determined radius approximately 7.4nm; width of log-normal size distribution approximately 0.28) were considered as a model system, for which the impact of a small amount of polymer adsorption (0.18mg/m(2)) in controlling the interactions of the PEO-coated silica particles was systematically explored by analyzing the small-angle X-ray scattering (SAXS) data against three interaction potentials-the equivalent hard-sphere (EHS) potential, the Hayter-Penfold-Yukawa (HPY) potential, and the square-well (SW) potential. Moreover, the SAXS analysis was enforced by dynamic light scattering (DLS) for predetermining the adsorption behavior, as well as for evaluating the possibility of polymer bridging. Under a dilute condition, the DLS analysis showed no sign of forming colloidal multiplets. In concentrated dispersions, both the HPY and SW potentials clearly revealed a systematic decrease of colloidal repulsions with increased PEO coverage, ascribed to a partially "screened" electrostatic interaction and/or the formation of PEO-bridged silica doublets. The present findings have interesting implications for controlling the colloidal interactions and microstructures of fine polymer-coated particles in dense or condensed phases.