Morphology Transformation of Supramolecular Structures in Aqueous Mixtures of Two Oppositely Charged Amphiphiles.

The co-assembly of oppositely charged amphiphiles provides a fascinating approach for forming complex supramolecular structures, which are interesting from both fundamental and technological viewpoints. Here, we report a stepwise morphology transformation of co-assembled supramolecular structures in the aqueous mixture of lithocholic acid (LCA) and cetyltrimethylammonium bromide (CTAB) at mixed molar ratios of 1:1 and 2:1. The co-assembly of LCA and CTAB initially forms multilamellar vesicles followed by the spontaneous growth of membrane tubes from the vesicles. The vesicle-to-tube transition is accompanied by a fluidic-to-crystalline phase transition. After being aged, the membrane tubes twist into left-handed helices, which then intertwine into left-handed double helices and multihelix bundles. The single handedness of these supramolecular structures is a reflection of the amplification of the chirality of LCA. An understanding of the co-assembly mechanism and pathway is a key step toward producing supramolecular structures with distinguished morphologies.

Structural evolutions in polymer-derived carbon-rich amorphous silicon carbide.

The detailed structural evolutions in polycarbosilane-derived carbon-rich amorphous SiC were investigated semiquantitatively by combining experimental and analytical methods. It is revealed that the material is comprised of a Si-containing matrix phase and a free-carbon phase. The matrix phase is amorphous, comprised of SiC4 tetrahedra, SiCxOx-4 tetrahedra, and Si-C-C-Si/Si-C-H defects. With increasing pyrolysis temperature, the amorphous matrix becomes more ordered, accompanied by a transition from SiC2O2 to SiCO3. The transition was completed at 1250 °C, where the matrix phase started to crystallize by forming a small amount of ß-SiC. The free-carbon phase was comprised of carbon nanoclusters and C-dangling bonds. Increasing pyrolysis temperature led to the transition of the free carbon from amorphous carbon to nanocrystalline graphite. The size of the carbon clusters decreased first and then increased, while the C-dangling bond content decreased continuously. The growth of carbon clusters was attributed to Ostwald ripening and described using a two-dimensional grain growth model. The calculated activation energy suggested that the decrease in C-dangling bonds is directly related to the lateral growth of the carbon clusters.

Emission evolution of alpha-silicon nitride nanowires with temperature.

The photoluminescence and temperature dependent emission spectra of silicon nitride nanowires were investigated by using femtosecond pulse laser. Three discrete sharp emission peaks were observed in photoluminescence, which were significantly different from that pumping by low excitation intensity laser. The temperature effects on emission peak energy were extracted using Gauss function, and should be attributed to volume-temperature effect and phonon effect.

Hot Oscillatory Pressing of Carbon Nanotube-Reinforced Copper Matrix Nanocomposite.

Carbon nanotube reinforced copper matrix nanocomposites have great potential in machinery, microelectronics, and other applications. The materials are usually prepared by powder metallurgy processes, in which consolidation is a key step for high performance. To improve the density and mechanical properties, the authors explored the use of hot oscillatory pressing (HOP) to prepare this material. A carbon nanotube reinforced copper matrix nanocomposite was synthesized by both HOP and hot pressing (HP) at various temperatures, respectively. The samples prepared by HOP exhibited significantly higher density and hardness than those prepared by HP at the same temperature, and this was because the oscillatory pressure of HOP produced remarkable plastic deformation in copper matrix during sintering. With the decrease of sintering temperature in HOP, the amount of deformation defect increased gradually, playing a key role in the increasing hardness. This work proves experimentally for the first time that HOP can produce much more plastic deformation than HP to promote densification, and that HOP could be a very promising technique for preparing high-performance carbon nanotube reinforced copper matrix nanocomposites.

Al-doped single-crystalline SiC nanowires synthesized by pyrolysis of polymer precursors.

Al-doped 6H-SiC nanowires are synthesized by catalyst-assisted pyrolysis of polymer precursors. The obtained nanowires were characterized using scanning electron microscopy, X-ray diffraction, transmission electron microscopy and selective area electron diffraction. We demonstrate that doping concentrations can be controlled by tailoring the Al concentrations in the precursors. We also find that Al-doping has a profound effect on the morphology and emission behavior of the SiC nanowires. The current results suggest a simple technique for synthesizing Al-doped SiC nanomaterials in a controlled manner, which are promising for applications in optical and electronic nanodevices.

Single-crystal AlN nanonecklaces.

Distinct single-crystal aluminum nitride nanonecklaces with uniform [1011] faceted beads are synthesized via catalyst-assisted nitriding of Al. The detailed morphology and structure of the nanonecklaces have been characterized. The growth process has been investigated by comparing the products obtained at different synthesis times. The results reveal that the formation of the nanonecklaces is via a process consisting of facet formation and bead unification. The formation of the [1011] facets is due to the presence of a liquid phase that lowers the surface tension of otherwise high-energy [1011] planes. The bead unification is driven by minimizing the energy contributed by surface energy and electrostatic energy. The unique morphology of the nanonecklaces could be useful for studying fundamental physical phenomena and fabricating nanodevices.

Buckling instability of lipid tubules with multibilayer walls under local radial indentation.

The mechanical behavior of self-assembled lipid tubules is an important property which determines their suitability for technological applications. We study the instability of multibilayer lipid tubules (with wall thickness t and external radius R(ext)) beyond elastic response under local radial atomic force microscopy indentations. A discontinuity in force-distance curves associated with the buckling instability of lipid tubules is observed. The critical force at which lipid tubules undergo a buckling transition linearly scales as t/R(ext). In addition, a reduced critical buckling force is found to extend a distance of approximately 1 microm from the end of lipid tubules.

Catalyst and temperature dependent growth of silicon nitride micro/nanoribbons.

One-dimensional micro/nanostructured silicon nitrides have attracted significant interests because they are potentially important for many applications due to its high stability, chemical inertness and capability for high-concentration doping. In this paper, single crystalline Si3N4 micro/nanoribbons were synthesized by catalyst-assisted pyrolysis of a polymeric precursor. The effects of catalyst and processing temperature on the morphology of the ribbons were investigated. The results revealed that both parameters can significantly influence the morphology of the ribbons, suggesting one-dimensional Si3N4 can be grown in a controllable manner by tailoring the processing conditions.

Effect of Nd-doping on the optical properties of yttrium aluminum garnet nanopowders.

Nd-doped and Nd/Si-codoped yttrium aluminum garnet powders were synthesized via a solvothermal method using ethanol as the solvent. The photoluminescence spectra of the powders revealed that the intensity of the emission increased with Nd-doping concentration initially and then decreased with further increase in Nd concentration. The powder containing 3.5 atm% Nd exhibited the highest light emission intensity. The fluorescence lifetime of the yttrium aluminum garnet powders was also measured as a function of Nd-doping concentration. The results were fitted with an empirical equation.

Effect of mechanical milling on photoluminescence of gamma-alumina nanoparticles.

The effect of mechanical alloying on the photoluminescence behavior of gamma-Al2O3 nanopowder was studied. Two emission peaks centered at 343 and 378 nm and a broad emission band ranging between 400-600 nm have been observed. It is found that the intensity of the two emission peaks decreases with ball-milling time, while that the broad band remains un-change. These results suggested that the two peaks are resulted from the surface defects that analogs of F+ centers, while the broad band is resulted from impurity.

Controlled Al-doped single-crystalline silicon nitride nanowires synthesized via pyrolysis of polymer precursors.

Al-doped single-crystalline Si(3)N(4) nanowires were synthesized by catalyst-assisted pyrolysis of polymeric precursors. The doping levels can be controlled by tailoring the Al concentration in the precursors. It is found that the Al concentration has a significant effect on the shape, sizes, and phase compositions of the synthesized Si(3)N(4) low-dimensional nanomaterials. The photoluminescence measurements revealed that the Al dopants have a profound effect on the emission behavior. The current study provides a simple way to realize the controlled doping in Si(3)N(4) nanomaterials, which could be useful for applications in optoelectronic nanodevices.

Coalescence of nanobranches: a new growth mechanism for single crystal nanobelts.

We report a fundamentally new growth mechanism for single crystalline nanobelts, namely, the growth and coalescence of nanobranches. The growth process of the nanobelts includes four typical steps such as nucleation and growth of the stem, nucleation and growth of the nanobranches at the expense of the stem, widening and geometrical coalescence of the nanobranches, and finally having nanobelts with perfect structure. The unique widening growth process of the nanobranches is apparently driven by the lattice distortion within the surface area of the stem. The continuous geometrical coalescence between the neighboring branches leads to the formation of the beltlike structures.

Abnormal behavior of silica doped with small amounts of aluminum.

Silica is the most abundant mineral in the crust of the Earth. It has been demonstrated that the aluminum concentration in silica plays a key role in determining many properties of silica-based components. Although the alumina-silica system has been intensely studied, the effect of very small amounts of aluminum on the structure and properties of silica remains unclear. We report results of first principles calculations showing that small amounts of aluminum could be metastable when located in the center of Si-O rings without breaking the silica network. In contrast, higher aluminum contents will result in the destruction of the Si-O bonds, leading to the formation of triclusters and a 4-, 5-, and 6-fold Al-O coordination, as observed in previous studies. Based on the silica structure obtained through geometric optimization, the properties of silica doped with small amounts of aluminum were calculated. The results can account for many 'abnormal' phenomena experimentally observed. The results benefit most areas such as geosciences, microelectronics, glass industry, and ceramic materials.

Facilitating Anion Transport in Polyolefin-Based Anion Exchange Membranes via Bulky Side Chains.

Highly anion-conductive polymer electrolyte membranes with excellent alkaline stabilities for fuel cell applications were prepared. Thus, a series of polyolefin copolymers with poly(4-methyl-1-pentene) (PMP) moieties containing bulky side chains and side-chain quaternary ammonium (QA) groups were prepared through copolymerization with a Ziegler-Natta catalyst and subsequent quaternization. The separation of hydrophilic microphase and hydrophobic microphase was induced by PMP bulky side chains, and then well-connected ionic domains were formed. This result was confirmed by AFM (atomic force microscopy) and SAXS (small-angle X-ray scattering) analyses. It was discovered that well-defined ionic domains of the PMP-TMA-x (TMA, trimethylamine) membranes depended on the content of PMP moieties. The well-defined ionic domains enhanced the hydroxide conductivity of the PMP-TMA-x membranes despite their lower water uptake (WU) as compared to polypropylene (PP)-containing membranes (PP-TMA-x). The PMP-TMA-41 membrane showed the highest ionic conductivity value (43 mS/cm) while maintaining low WU (29.2 wt %) at room temperature. The membranes mostly preserved (>93.0%) their initial hydroxide conductivity after alkaline treatment (10 M aqueous NaOH, 80 °C, 700 h), thereby revealing desirable alkali stability characteristics. Presumably, the nucleophilic attack from hydroxide or water in the cationic center is inhibited by long alkyl spacers (-CH2-)n (n = 9) which are located between the cation groups and the polymer backbone.

Comparative study of flexural strength test methods on CAD/CAM Y-TZP dental ceramics.

Clinically, fractures are the main cause of computer-aided design and computer-aided manufacturing (CAD/CAM) 3 mol%-yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) all-ceramic dental restorations failure because of repetitive occlusal loading. The goal of this work is to study the effect of test methods and specimen's size on the flexural strength of five ceramic products. Both bi-axial flexure test (BI) and uni-axial flexure tests (UNI), including three-point flexure test (3PF) and four-point flexure test (4PF), are used in this study. For all five products, the flexural strength is as follows: BI > 3PF > 4PF. Furthermore, specimens with smaller size (3PF-s) have higher values than the bigger ones (3PF). The difference between BI and UNI resulted from the edge flaws in ceramic specimens. The relationship between different UNI (including 3PF-s, 3PF and 4PF) can be explained according to Weibull statistical fracture theory. BI is recommended to evaluate the flexural strength of CAD/CAM Y-TZP dental ceramics.

Soluble and meltable hyperbranched polyborosilazanes toward high-temperature stable SiBCN ceramics.

High-temperature stable siliconborocarbonitride (SiBCN) ceramics produced from single-source preceramic polymers have received increased attention in the last two decades. In this contribution, soluble and meltable polyborosilazanes with hyperbranched topology (hb-PBSZ) were synthesized via a convenient solvent-free, catalyst-free and one-pot A2 + B6 strategy, an aminolysis reaction of the A2 monomer of dichloromethylsilane and the B6 monomer of tris(dichloromethylsilylethyl)borane in the presence of hexamethyldisilazane. The amine transition reaction between the intermediates of dichlorotetramethyldisilazane and tri(trimethylsilylmethylchlorosilylethyl)borane led to the formation of dendritic units of aminedialkylborons rather than trialkylborons. The cross-linked hb-PBSZ precursors exhibited a ceramic yield higher 80%. The resultant SiBCN ceramics with a boron atomic composition of 6.0-8.5% and a representative formula of Si1B(0.19)C(1.21)N(0.39)O(0.08) showed high-temperature stability and retained their amorphous structure up to 1600 °C. These hyperbranched polyborosilazanes with soluble and meltable characteristics provide a new perspective for the design of preceramic polymers possessing advantages for high-temperature stable polymer-derived ceramics with complex structures/shapes.

Hierarchically porous Co3O4 hollow spheres with tunable pore structure and enhanced catalytic activity.

Co3O4 hollow spheres with two-level hierarchical pores and high surface area are synthesized, and the shell thickness and the mesoporous structure are well-tuned through pre-treatment of the carbon spheres with alkali/acid. Evaluation of the Co3O4 hollow spheres for the combustion of CH4 reveals that they exhibit excellent catalytic activity and durability.

Magnetoceramics from the bulk pyrolysis of polysilazane cross-linked by polyferrocenylcarbosilanes with hyperbranched topology.

In this contribution, we report a novel strategy for the synthesis of nanocrystal-containing magnetoceramics with an ultralow hysteresis loss by the pyrolysis of commercial polysilazane cross-linked with a functional metallopolymer possessing hyperbranched topology. The usage of hyperbranched polyferrocenylcarbosilane offers either enhanced ceramic yield or magnetic functionality of pyrolyzed ceramics. The ceramic yield was enhanced accompanied by a decreased evolution of hydrocarbons and NH3 because of the cross-linking of precursors and the hyperbranched cross-linker. The nucleation of Fe5Si3 from the reaction of iron atoms with Si-C-N amorphous phase promoted the formation of α-Si3N4 and SiC crystals. After annealing at 1300 °C, stable Fe3Si crystals were generated from the transformation of the metastable Fe5Si3 phase. The nanocrystal-containing ceramics showed good ferromagnetism with an ultralow (close to 0) hysteresis loss. This method is convenient for the generation of tunable functional ceramics using a commercial polymeric precursor cross-linked by a metallopolymer with a designed topology.

Polymer-derived ceramic composite fibers with aligned pristine multiwalled carbon nanotubes.

Polymer-derived ceramic fibers with aligned multiwalled carbon nanotubes (MWCNTs) are fabricated through the electrospinning of polyaluminasilazane solutions with well-dispersed MWCNTs followed by pyrolysis. Poly(3-hexylthiophene)-b-poly (poly (ethylene glycol) methyl ether acrylate) (P3HT-b-PPEGA), a conjugated block copolymer compatible with polyaluminasilazane, is used to functionalize MWCNT surfaces with PPEGA, providing a noninvasive approach to disperse carbon nanotubes in polyaluminasilazane chloroform solutions. The electrospinning of the MWCNT/polyaluminasilazane solutions generates polymer fibers with aligned MWCNTs where MWCNTs are oriented along the electrospun jet by a sink flow. The subsequent pyrolysis of the obtained composite fibers produces ceramic fibers with aligned MWCNTs. The study of the effect of polymer and CNT concentration on the fiber structures shows that the fiber size increases with the increment of polymer concentration, whereas higher CNT content in the polymer solutions leads to thinner fibers attributable to the increased conductivity. Both the SEM and TEM characterization of the polymer and ceramic fibers demonstrates the uniform orientation of CNTs along the fibers, suggesting excellent dispersion of CNTs and efficient CNT alignment via the electrospinning. The electrical conductivity of a ceramic fibers with 1.2% aligned MWCNTs is measured to be 1.58 x 10(-6) S/cm, which is more than 500 times higher than that of bulk ceramic (3.43 x 10(-9) S/cm). Such an approach provides a versatile method to disperse CNTs in preceramic polymer solutions and offers a new approach to integrate aligned CNTs in ceramics.

Aligned ultra-long single-crystalline α-Si(3)N(4) nanowires.

We report the synthesis of aligned ultra-long single-crystalline α-Si(3)N(4) nanowires by pyrolysis of a polymeric precursor without any template. The length of the wires is up to several centimeters, which is significantly longer than that of any Si(3)N(4) wires reported previously. Microscopy characterization reveals that the wires are single crystals, with a uniform diameter of ∼200 nm. Intense visible photoluminescence was observed between 1.3 and 3.7 eV. The wires could be useful in the fabrication of optoelectronic nanodevices and nanocomposites.