A resistive switching (RS) phenomenon, namely reversible transitions between the low and high resistance states after forming process, is caused by the formation and rupture of a conductive filament. We confirmed that conductive filaments including a quantum point contact (QPC) in Pt/NiO/Pt RS cells were formed by semiforming, the first step of the forming process. In this study, we examine correlation between microscopic structures in NiO layers and forming characteristics in the Pt/NiO/Pt cells. The appearance condition of the quantized conductance is considered to be associated with the composition ratio of O to Ni of either equivalent to or larger than a critical value. Furthermore, we proposed a RS model based on the forming characteristics especially obtained from the RS cells with different size. Defects which act as the source of a conductive filament including a QPC by semiforming may be randomly distributed in a NiO layer according to Poisson statistics.

The advent of containerless processing techniques has opened the possibility of high quality measurements of equilibrium and metastable liquids. This review focuses on the structure and dynamics of metallic liquids at high temperature. A clear connection between structure, viscosity, and fragility has emerged from recent containerless experiments and molecular dynamics simulation studies. The temperature-dependent changes of liquid structures are smaller for the stronger liquids. The onset of cooperativity usually occurs above the liquidus temperature at a characteristic temperature T A, where the dynamics change from Arrhenius to non-Arrhenius behavior; this is accompanied by the onset of development of more spatially extended structural order in the liquids. Several metrics for fragility, consistent with the traditional fragility parameter, can be developed from the structural and dynamical properties at high temperature. It is becoming increasingly evident from theory and experiments that the fundamental properties that determine fragility are the repulsive part of the interatomic potential and the anharmonicity.

A CrMnFeCoNi high-entropy alloy was investigated by nanoindentation from room temperature to 400 °C in the nanocrystalline state and cast plus homogenized coarse-grained state. In the latter case a 〈100〉-orientated grain was selected by electron back scatter diffraction for nanoindentation. It was found that hardness decreases more strongly with increasing temperature than Young’s modulus, especially for the coarse-grained state. The modulus of the nanocrystalline state was slightly higher than that of the coarse-grained one. For the coarse-grained sample a strong thermally activated deformation behavior was found up to 100–150 °C, followed by a diminishing thermally activated contribution at higher testing temperatures. For the nanocrystalline state, different temperature dependent deformation mechanisms are proposed. At low temperatures, the governing processes appear to be similar to those in the coarse-grained sample, but with increasing temperature, dislocation-grain boundary interactions likely become more dominant. Finally, at 400 °C, decomposition of the nanocrystalline alloy causes a further reduction in thermal activation. This is rationalized by a reduction of the deformation controlling internal length scale by precipitate formation in conjunction with a diffusional contribution.

Using very long molecular dynamics simulations of duration up to a microsecond of physical time, temperature protocols spanning up to five orders of magnitude in time are performed to investigate thermally activated structural relaxation in a model binary amorphous solid. The simulations demonstrate significant local structural excitations (LSE) as a function of increasing temperature and show that enthalpy rather than internal potential energy is primarily responsible for relaxation. At low temperatures these LSE involve atoms whose displacements are smaller than a typical bond length, whereas at higher temperatures approaching that of the glass transition regime, bond-length displacements occur in the form of string-like motion where one atom replaces the position of another. Such thermally activated excitations are observed to mainly involve the smaller atom type. The observed enthalpy changes can be correlated with the level of internal hydrostatic stress homogenization and icosahedral content within the glassy solid.

Metallic glasses (MGs) are known to have high strength, but poor ductility. Prior studies have shown that plasticity in MG can be enhanced by significantly reducing their dimension to nanoscale. Here we show that, via the introduction of certain types of crystalline/amorphous interfaces, plasticity of MG can be prominently enhanced as manifested by the formation of ductile “dimples” in a 2 μm thick amorphous CuNb film. By tailoring the volume fraction and architecture of crystalline/amorphous multilayers, tensile fracture surface of MG can evolve from brittle featureless morphology to containing ductile dimples. In situ micropillar compression studies performed inside a scanning electron microscope show that shear instability in amorphous layers can be inhibited by interfaces. The mechanisms for improving plasticity and fracture resistance of MG via interface and size effect are discussed.

In this study, the influence of an externally applied elastic strain on the electrochemical activity of metal film catalysts during the oxygen reduction reaction (ORR) was examined. A novel three-layer specimen, composed of a 10 nm-thick Pt or Pd surface film on a 20 nm-thick Pd70Zr30 metallic glass film that was first deposited on a polymer substrate was used. The intermediate metallic glass layer is instrumental in allowing the top-layer catalytic film to be elastically deformed to a large elastic strain, (up to 2%), enabling a strain effect to be clearly observed. The results consistently show that an applied compressive strain improves the ORR catalytic activity of the Pd and Pt surface layer, while a tensile strain degrades it. These experimental findings are consistent with the prediction of the d-band model, and provide an opportunity to improve the catalytic response during ORR.

Perovskite solar cells are promising for realizing high power conversion efficiency (PCE) with low manufacturing costs, but efficient coating methods are needed for commercialization. Here, a gas blowing method was used to fabricate perovskite solar cells and was found to create a smooth perovskite layer and to prevent voids in large-area cells, when organic materials were used as scaffolds for forming the perovskite. A PCE of 13% in a 1 cm2 active area is achieved by tuning the band-gap energy of MAPbX3 via substitution of Br for I ions in X sites. Incorporation of a poly(3,4-ethylenedioxythiophene) hole transport layer with a higher work function increased the open circuit voltage of the solar cells. All layers of the cells were fabricated at low temperatures (<140 °C), which makes it possible to incorporate a polymer substrate for producing flexible solar cells and high-throughput fabrication.

Diketopyrrolopyrrole (DPP) is a critically important building block that has gained importance in the organic electronics community because of its wide applicability in various devices. In this work, the thiophene flanked DPP moiety attached to alkyl chains of various lengths (this includes straight octyl and branched ethyl hexyl units) has been used as the monomer for electropolymerization. This paper focuses on the study of optical, thermal, solid state ordering and electrochemical properties of these electron deficient monomers using various characterization techniques such as UV–Vis spectrometry (UV), photo-luminescence spectroscopy (PL), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), cyclic voltammetry (CV), as well as ab initio modeling. These monomers exhibit broad absorption spectra from the ultraviolet (280–400 nm) to visible (400–600 nm) regions and emission spectra between 560 and 610 nm. The band gaps of these monomers were calculated to be in the range of 2.00–2.20 eV. These monomers were electropolymerized by scanning the potential between −0.5 and 2.0 V versus ferrocene for up to 50 cycles on a glassy carbon electrode.

Biological hydrogel is important in drug delivery system and tissue engineering. In this paper, we prepared a series of biological hydrogels with N,O-carboxymethyl chitosan (CS) and oxidized safflower and ligusticum wallichii polysaccharide-II (oxidized SLWP-II). Morphological analysis indicated the N,O-carboxymethyl CS/oxidized SLWP-II hydrogels (CSLHs) had porous interior structures, pore diameter ranged from tens to hundreds of micrometers. In vitro release test showed, with proportion of N,O-carboxymethyl CS to oxidized SLWP increasing from 1:1 to 1:3, cumulative release of bovine serum albumin decreased from 99 to 82%. In vitro cytotoxicity study showed that the developed hydrogels were not cytotoxic during one week of culturing with WI-38 cells, and they have a role in promoting cell proliferation. So the N,O-carboxymethyl CS/oxidized safflower and ligusticum wallichii polysaccharide-II hydrogels might have potential application in the drug delivery system and tissue engineering.

Organic molecular crystals are often noncubic and contain significant steric hindrance within their structure to resist dislocation motion. Plastic deformation in these systems can be imparted during processing (tableting and comminution of powders), and the defect density impacts subsequent properties and performance. This study measured the elastic and plastic properties of representative monoclinic, orthorhombic, and triclinic molecular crystalline structures using nanoindentation of as-grown sub-mm single crystals. The variation in modulus due to in-plane rotational orientation, relative to a Berkovich tip, was approximately equal to the variation of a given crystal at a fixed orientation. The onset of plasticity occurs consistently at shear stresses between 1 and 5% of the elastic modulus in all three crystal systems, and the hardness to modulus ratio suggests conventional Berkovich tips do not generate fully self-similar plastic zones in these materials. This provides guidance for mechanical models of tableting, machining, and property assessment of molecular crystals.

The thermal expansion behavior of polymer carbon nanotube (CNT) nanocomposites was investigated, and a micromechanical model was proposed to explain the highly nonlinear dependence of the coefficient of thermal expansion of the nanocomposite with CNT content for the CNT/polyimide nanocomposite. The microscopic analysis of CNT/polyimide matrix showed homogeneous dispersion of bundles composed of CNTs. Therefore, the proposed model to predict the thermal expansion behavior of the nanocomposite considered a random, homogeneous distribution of CNT bundles with a hierarchical arrangement of helical CNTs within the polymeric matrix. The CNT bundle morphology influenced the thermal expansion response of the nanocomposite through (i) bundle volume fraction and (ii) degree of helicity, affecting thermo-mechanical properties of the bundle. The effective, homogenized, properties of CNT bundles were determined by the elasticity based solution of the layered cylinder model. Bundle effective properties were used in the micromechanical model implementing the homogenized strain rule of the mixture expression to predict the thermal expansion behavior of nanocomposite in a wide range of CNT volume contents. The proposed micromechanical analytical model was found to correlate closely with the experimental results for polyimide/CNT nanocomposite films as measured using a digital image correlation method.

The oxidation behavior of nonstoichiometric Ti2AlC x (x = 0.69) powders synthesized by combustion synthesis was investigated in flowing air by means of simultaneous thermal gravimetric analysis-differential thermal analysis, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscope/energy dispersive spectroscopy, with an effect of powder size. The oxidation of the fine Ti2AlC powders with the size of about 1 μm starts at 300 °C and completes at 980 °C, while with increasing the powder size around 10 μm the corresponding temperature increases to 400 and 1040 °C, respectively. The oxidation of nonstoichiometric Ti2AlC x (x = 0.69) powders is controlled by surface reaction in 400–600 °C, and mainly diffusion in 600–900 °C, with the corresponding oxidation activation energy of 2.35 eV and 0.12 eV, respectively. In other words, the critical temperature of changing oxidation controlling step is around 600 °C. The oxidation products were mainly rutile-TiO2 and α-Al2O3. The tiny white flocculent particles of α-Al2O3 appeared on the surface of fine Ti2AlC powders and increased with increasing the oxidation temperature.

The exaggerated grain growth, anisotropic crystallite morphology, and thermal expansion are the main reasons for the microcracking of sintered TiB2, wherein grain coarsening and anisotropic crystallite morphology are believed to be controlled by the surface stabilities of TiB2. To deeply understand the grain growth mechanism, the anisotropic stability and bonding features of TiB2 surfaces, including $\left( {11\bar 20} \right)$ , two types of (0001), and three types of $\left( {10\bar 10} \right)$ , are investigated by first-principles calculations. By employing the two-region modeling method, surface energies are calculated and the $\left( {11\bar 20} \right)$ surface is found to be more stable than (0001) and $\left( {10\bar 10} \right)$ surfaces. Hexagonal plate-like grain morphology is predicted. The different bonding conditions of surface Ti and B atoms contribute to the difference of surface structure relaxation between surfaces with Ti- and B-termination, which lead the B-terminated ones to be more stable. It is also found that the surface energies of TiB2 are much higher than those of ZrB2 with a similar structure, which may be responsible for the easy coarsening of TiB2.

Recently, solution combustion synthetic approach has emerged as a potential route to synthesize a wide range of catalytic oxides. Nano TiO2 was synthesized by solution combustion methods using glycine, urea, and oxalyldihydrazide as fuels. X-ray diffraction and field emission scanning electron microscopy analyses revealed the structural and morphological differences of TiO2 synthesized with different fuels. The oxidizer to fuel ratio from lean to rich conditions also played a crucial role in determining the polymorphic percentage concentration in the synthesized TiO2 powders. However, diffuse reflectance spectroscopy and photoluminescence spectroscopy studies did not show any significant differences in the electronic properties of the synthesized TiO2. As the polymorphic composite phases synergistically influence the catalytic performances, photodegradation of methylene blue (MB) and photo hydrogen production were studied with the synthesized catalysts. The synergistic role crucially depended on the specific reaction. The presence of different TiO2 polymorphs due to difference in fuels during combustion controlled the photocatalytic efficiency of the catalysts toward MB degradation and hydrogen production.

Two novel porphyrins (5,10,15,20-tetra(3-(carboethoxymethyleneoxy)phenyl)porphyrin, H2TEPp and 5,10,15,20-tetra(3-(carboxymethyleneoxy)phenyl)porphyrin, H2TCPp) and their copper(II) porphyrins (CuTEPp, CuTCPp) were synthesized. With these porphyrins, four new porphyrin-sensitized TiO2 nanorod composites (H2TEPp/TiO2, H2TCPp/TiO2, CuTEPp/TiO2, and CuTCPp/TiO2) were prepared and characterized by methods of XRD, SEM, TEM, FT-IR, UV-vis DRS, nitrogen adsorption–desorption and fluorescence spectra. Besides, the photocatalytic activity and stability of the composites were assessed in the degradation of 4-nitrophenol (4-NP). The results indicate that the morphologies and structures of these composites are less influenced by the loaded porphyrins or copper porphyrins compared with the nanorods TiO2 (anatase). The porphyrin or copper porphyrin molecules are confirmed to bond on the surface of TiO2 through carboxyl group, which is beneficial to the electron transfer between porphyrin and TiO2. All composites exhibit enhanced photoactivities compared with the bare TiO2 nanorods. The possible reason is that the recombination of photoproduced electron–hole has been controlled effectively in these composites, which can be seen from their decreased fluorescence emission. The stability results of composites show that they still hold considerable photocatalytic activities after six cycling experiments.

{001} facets dominant TiO2 nanosheets have attracted intensive attention in the photocatalytic field, due to their undercoordinated Ti5c centers, higher surface energy, and photocatalytic activity than those of any other low-energy facet. However, a fluorine-rich (001) surface is controversial to the photocatalytic activity of TiO2 nanocrystals. We have removed the surface F atoms bonding with Ti by hydrogenation method successfully, and found that {001} facets dominant TiO2 nanosheets without the terminated F atoms showed dramatic enhancement in the photocatalytic activity. Moreover, the clean (001) surface was more in favor of the deposition of PdO than the fluorine-rich surface, and the amorphous structure from the hydrogenation is beneficial to the reduction of PdCl4 2− to Pd nanoparticles. The PdO attached on {001} facets and the amorphous structure promoted the separation of charge carriers, and Pd nanoparticles transferred plasmonic-induced electrons to the conduction band of hydrogenated TiO2 under simulated solar irradiation. Thus, a significantly enhanced photocatalytic activity of Pd–H–TiO2 is achieved on degrading organic environmental pollution, due to the synergy of palladium species and hydrogenation on {001} facets exposed TiO2.

A series of self-assembled WO3–BiVO4 nanostructured thin films with 17, 25, 50, 67, and 100 mol% WO3 were grown on the (001) yttria-stabilized zirconia (YSZ) substrate by pulsed laser deposition method. The microstructures including crystalline phases, epitaxial relationship, interface structures, and chemical composition distributions were investigated by a combination of various electron microscopy techniques including scanning electron microscopy, transmission electron microscopy, and X-ray energy dispersive spectroscopy. The monoclinic BiVO4 formed the matrix, in which WO3 nanopillars were embedded with specific epitaxial relationships. In BiVO4-rich sample, orthorhombic Bi2WO6 was formed. However, metastable hexagonal WO3 phase and orthorhombic WO3 phase coexisted in other composite samples. The thin amorphous layer at the film/substrate interface indicated that the mismatch strain between films and substrate is released. The hydrostatic tensile strain due to thermal expansion mismatch between BiVO4 and WO3 as well as the diffusion of Bi into the WO3 stabilized the metastable h-WO3. A WO3–BiVO4 pseudobinary phase diagram was proposed based on the magnitude of the thermal expansion mismatch and the distance of Bi diffusion, which can be applied to design the microstructures of WO3–BiVO4 heterojunctions and optimize their photoelectrochemical properties.

A highly sensitive impedance sensor operating at room temperature has been developed for the quantitative determination of formaldehyde vapor. Nanostructured zinc oxide (ZnO) was synthesized by chemical reduction and used, in the form of a pellet, as the sensing material. Its performance was compared to that of the pellet made from commercial ZnO. Both samples were characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, ultraviolet–visible spectroscopy, and atomic force microscopy techniques. Changes in impedance caused by formaldehyde in the concentration range from 100 to 800 ppm were measured and Nyquist plots revealed a systematic variation in impedance. The sensor response and formaldehyde concentration are exponentially correlated for both the laboratory synthesized and commercial ZnO samples. However, the lab-synthesized sample displays a better performance in terms of sensitivity, response, recovery, and stability. In addition, the response of the lab-synthesized sample is less sensitive to interferences by reducing gases such as ammonia, ethanol, methanol, and propanol.

Alumina gel-cast foams were manufactured in a broad total porosity range (43–86%) by using agarose or ovalbumin as gelling agents. The foams were examined in terms of microstructural, permeability, and mechanical properties. For the achieved open porosity level (19–85%), the mean cell size (19–375 µm), and mean window size (8–77 µm) of the alumina foams manufactured using ovalbumin were slightly wider than those obtained using agarose (34–262 µm and 18–33 µm, respectively). By using different contents of agarose (0.3–1 wt%) or albumin (5 wt%) and solids (30–45.9 wt%), it was possible to vary the foaming yield from 1.6 to 4.4 and produce bodies with a very wide permeability level that included several classes of porous ceramics. Darcian (k 1) and non-Darcian (k 2) permeability coefficients displayed values in the range 3.2 × 10−18 to 4.3 × 10−9 m2 and 1.8 × 10−18 to 6.5 × 10−5 m respectively. Compressive strength of bodies was dependent upon the porosity level, with a variation of 8.5–149.7 MPa.

Due to the increasingly severe environmental pollution problems, the development of semiconductor photocatalysts is being extensively carried out because they have exhibited high activities for the degradation of many organic and inorganic pollutants. In this study, waxberry-like Ni11(HPO3)8(OH)6 microball photocatalysts with a diameter of 10–20 μm have been successfully synthesized via a solvothermal route by using NiSO4 as a Ni-source and NaH2PO2 as a P-source in a mixture of ethylene glycol and water under the optimized conditions with a Ni:P molar ratio of 1:2 at 200 °C for 16 h. The as-prepared photocatalysts were characterized by powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, Brunauer–Emmett–Teller N2 adsorption, zeta potential, ultraviolet-visible (UV–vis) absorption, and photocatalysis tests. The decolourization of organic dyes, methylene blue and rhodamine B, under ultraviolet light over the as-prepared products reveals an excellent photocatalytic performance due to the good absorption for ultraviolet light.