Two high-temperature pore generators (porogens) have been used to study the effect of porogen structure on moisture uptake and k-value in methylsilsesquioxane/porogen hybrid films and their corresponding porous films in a postintegration porogen removal scheme. Poly(styrene-b-4-vinylpyridine) containing di-block structure and pyridine polar group leads to higher moisture uptake and k-value in the hybrid films as compared to poly(styrene-block-butadiene-block-styrene) with symmetrical structure and nonpolar groups. Moreover, the moisture uptake behavior in both as-prepared hybrid films is in physical sorption mode based on their reversible adsorption–desorption curve measured by quartz crystal microbalance. After porogen removal, the k-values of porous films are favorably not influenced by porogen structures, and their moisture uptake is as low as 1.78 wt% even at 40 vol.% porosity. However, based on the simulation of the modified-Rayleigh model, the porous films are found to possess 0.4 vol.% chemisorbed moisture on the pore surface, resulting in 17–23% deviation from the ideal k-values.

We report a detailed study of the structural, chemical, electrical, and magnetic properties of undoped ZnO thin films grown under different conditions and the films that were annealed in various environments and irradiated with an ultraviolet laser. Samples prepared in low oxygen pressure or subsequently annealed in vacuum have always been strongly magnetic. Oxygen-annealed films displayed a sequential transition from the ferromagnetic to the diamagnetic state as a function of the annealing temperature. Reversible switching of room temperature ferromagnetism and n-type conductivity have been demonstrated either by annealing in different environments or by a novel laser irradiation treatment. Enhancements in both the electrical conductivity and magnetic moment have been controlled precisely with laser pulses, without altering the crystal structure. Electron paramagnetic resonance data were found to be in good agreement with the magnetization and conductivity measurements. Our secondary ion mass spectrometer and electron energy loss spectrometer studies conclusively rule out the presence of any external ferromagnetic impurities.

A facile, efficacious, and practical multifunctional paradigm has been developed for imparting corrosion resistance to low carbon steel based on the direct in situ growth of carbon nanofibers (CNF) onto steel substrates followed by infusion of a polymer matrix. The polymer layer locks into place between the nanofibers, simultaneously preventing coating delamination and imparting unprecedented surface passivation properties. The novel hybrid nanocomposite coatings maintain structural integrity even after 30 days of exposure to saline corrosive environments, indicating unprecedented corrosion protection derived from the redox-active nature of the CNF fillers and their excellent dispersion within the polymer matrix. These remarkable coating properties are further enhanced by the strong adhesion of the host polymer to the underlying steel substrate.

We investigated a simple and low-cost route for the formation of metallic nanodots on Si substrates ordered in size and position and laterally isolated by SiO2. The method was based on a two-step process: (i) the formation of a nanopattern of ordered cylindrical pores on oxidized Si substrates through self-assembly of diblock copolymers, and successive oxide dry etching down to the Si; (ii) the deposition of gold nanodots and thermal diffusion over the nanopatterned oxide substrates. After diffusion, the nanodot density outside the nanopores was found to decrease, and most of the nanodots were found to saturate the nanopores. The process was followed in situ by transmission electron microscopy (TEM) and ex situ by scanning electron microscopy (SEM) analysis for different thermal budgets. This patterned substrate can be used for catalyst mediated growth, for example, through vapor-liquid-solid (VLS), of nanowires for the formation of absorber materials in novel photovoltaic architectures.

We exploit a facile synthetic route to fabricate dendritic SnO2/TiO2 nanodentrites with a twofold point symmetry by a combination of vapor transport deposition method for the SnO2 nanowire backbones and subsequent hydrothermal heteroepitaxial growth of TiO2 nanorod branches. As a result of the good lattice matching and same rutile crystal structures between SnO2 and TiO2, an interface epitaxy is established accounting for the high symmetry. Proof-of-principle demonstration of the function in photoelectrochemical water splitting is presented.

Polycrystalline BaTiO3 thin films have been prepared by hydrothermal reaction with sputter-deposited nanostructured reactive Ti templates designed to control net diffusion direction and distance. Templates were prepared in two morphologies, i.e., planar and nanopillar. The samples produced from flat templates showed sluggish transformation kinetics and an eventual termination of reaction without fully consuming the Ti metal. Templates with pillar morphology, on the other hand, could be transformed to phase-pure BaTiO3, independent of the template thickness. In the as-precipitated state, those films revealed a permittivity of ~1000 and loss tangent values around 0.1 with mild dispersion in the kilohertz frequency range. Annealing these films under forming gas containing 1 vol% H2 balance N2 for 3 h at 200 °C decreased high-field losses to 0.06 and reduced dispersion. Mn incorporation as an in situ acceptor dopant was also explored. Addition of Mn during hydrothermal treatment further improved the electrical properties. Annealing under the same postgrowth conditions virtually eliminated the frequency dispersion in the range of 1 kHz to 1 MHz, while maintaining permittivity values in the range of 350.

A facile ethylene glycol–based solvothermal method was developed for the synthesis of lanthanide orthovanadate LnVO4 (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu) nanoparticles with relatively uniform size and morphologies. The LnVO4 nanoparticles ranged from 100 to 500 nm and changed from spheres to ellipses and platelet–shaped particles depending on the ionic size. Radius of the Ln ions affected crystal structure. The particles with larger ions form monoclinic-type structure for LaVO4 and with smaller ions form zircon-type structure for LnVO4 (Ln = Pr-Yb). A nucleation and aggregates formation mechanism of LnVO4 nanomaterials was proposed to illustrate the crystal growth. The morphologies of LnVO4 nanoparticles could be turned by pH value and molar ratio of reactants. Spherical LaVO4 and PrVO4 nanoparticles were obtained at pH 6, whereas elliptical nanoparticles were obtained at pH 3. Eu3+-, Dy3+-, and Sm3+-doped zircon-type YVO4 nanoparticles exhibit strong luminescence typical of doped ions.

We have synthesized single- and polycrystal Ba8AlxSi46−x clathrates to compare their thermoelectric properties. Single-crystal sample was prepared by Czochralski method in an argon atmosphere. Polycrystal sample was prepared by arc melting and annealed at 850 °C for 100 h in an argon atmosphere. The Seebeck coefficients of single- and polycrystal Ba8Al12Si34 at 500 °C were 44.5 and 53.0 μV/K, respectively. The Seebeck coefficients of both samples were almost the same because the Seebeck coefficients depend on carrier concentration, which is related to aluminum content. The electrical resistivity of the single-crystal sample with 0.49 mΩcm was lower than that of the polycrystal sample with 0.95 mΩcm because of the reduction of electron scattering. Therefore, the power factor of the single-crystal sample with 4.0 × 10−4 V2/K2Ωm was higher than that of the polycrystal sample with 3.0 × 10−4 V2/K2Ωm at 500 °C. It is suggested that single crystallization is efficient for improvement of the thermoelectric property in the Ba8AlxSi46−x clathrate.

The cathodic electrodeposition of crystalline ZnO nanowires and amorphous FeO(OH) nanotubes in polycarbonate track-etched membranes with pore diameters of 50–200 nm is reported. Nitrate was used as a sacrificial precursor for the electrochemical generation of hydroxyl ions that raised the pH of the interior of the nanopore, leading to precipitation of a metal oxide or hydroxide phase. The crystalline and semiconducting ZnO phase formed directly above 60 °C at sufficiently high pH and led to the formation of dense nanowires with preferential (0001) orientation. The morphology of the wire could be influenced by the deposition temperature. Axially segmented gold–ZnO and silver–ZnO nanowires were made. In contrast, the iron hydroxide phase deposited inside the pore as a permeable gel that collapsed and transformed into hollow FeO(OH) tubes during drying. The as-formed nanotubes were amorphous and could be filled with nickel in a subsequent electrodeposition step, yielding core-shell nickel iron-oxohydroxide nanowires. The cathodic efficiency of nitrate reduction was low in both cases, suggesting that diffusional supply of metal ions may be the rate-determining step.

Equilibrium thermodynamic calculations, coupled to a kinetic model for the dissolution rates of clinker phases, have been used in recent years to predict time-dependent phase assemblages in hydrating cement pastes. We couple this approach to a 3D microstructure model to simulate microstructure development during the hydration of ordinary portland cement pastes. The combined simulation tool uses a collection of growth/dissolution rules to approximate a range of growth modes at material interfaces, including growth by weighted mean curvature and growth by random aggregation. The growth rules are formulated for each type of material interface to capture the kinds of cement paste microstructure changes that are typically observed. We make quantitative comparisons between simulated and observed microstructures for two ordinary portland cements, including bulk phase analyses and two-point correlation functions for various phases. The method is also shown to provide accurate predictions of the heats of hydration and 28 day mortar cube compressive strengths. The method is an attractive alternative to the cement hydration and microstructure model CEMHYD3D because it has a better thermodynamic and kinetic basis and because it is transferable to other cementitious material systems.