Mechanical properties and structures of bulk nanomaterials based on carbon nanopolymorphs

Bulk nanomaterials based on sp² carbon nanopolymorphs are promising candidates for supercapacitors due to their unique properties such as extremely high specific surface area, high conductivity and stability against graphitization. However, the mechanical response of such materials to external loading is not understood well. This Letter studies the effect of hydrostatic pressure on the mechanical properties and structures of these materials via molecular dynamics simulations. Three types of nanopolymorphs‐based nanomaterials that are composed of bended graphene flakes, short carbon nanotubes and fullerenes are considered. It is found that these three materials show a distinct relation between the pressure and volume strain. Moreover, their resistance to graphitization depends on the structure of their constituent components. The phenomena are explained by analysing the radial distribution function and coordination numbers of the atoms. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electronic properties of phenanthrimidazoles as hole transport materials in organic light emitting devices and in photoelectron transfer to ZnO nanoparticles

Phenanthrimidazoles as hole transport materials have been synthesized, characterized, and applied as nondoping emitters in organic light emitting devices. The synthesized molecules possess high fluorescent quantum yield and thermal properties and display film forming abilities. The highest occupied molecular orbital (HOMO) energies of these materials are shallower than the reported tris(8‐hydroxyquinoline)aluminum (Alq₃), which enables the hole transport ability of these phenanthrimidazoles. Taking advantage of the thermal stability and hole transporting ability, these compounds can be used as a functional layer between NPB [4,4‐bis(N‐(1‐naphthyl)‐N‐phenylamino)biphenyl] and Alq₃ layers and show that these phenanthrimidazoles can be alternatively used as novel hole transport materials and to improve the device performances. Geometrical, optical, electrical, and electroluminescent properties of these molecules have been probed. Further, natural bond orbital, nonlinear optical materials (NLO), molecular electrostatic potential, and HOMO–lowest unoccupied molecular orbital (LMO) energy analysis have been made by density functional theory (DFT) method to support the experimental results. Hyperpolarizability analysis reveals that the synthesized phenanthrimidazoles possess NLO behavior. The chemical potential, hardness, and electrophilicity index of phenanthrimidazoles have also been computed by DFT method. Photoinduced electron transfer explains the enhancement of fluorescence by nanoparticulate ZnO, and the apparent binding constant has been obtained. Adsorption of the fluorophore on ZnO nanoparticle lowers the HOMO and LUMO energy levels of the fluorophore. The strong adsorption of the phenanthrimidazoles on the surface of ZnO nanocrystals is likely due to the chemical affinity of the nitrogen atom of the organic molecule to Zn(II) on the surface of nanocrystal. Copyright © 2013 John Wiley & Sons, Ltd.     

Shape‐Tunable Selective Synthesis of Bismuth Fluoride Nanostructures for Versatile Applications

A facile approach for shape‐tunable synthesis of bismuth fluoride nanoparticles is reported. The approach is based on the homogeneous precipitation of precursor materials in mixed solvents (H₂O and ethylene glycol) and only ethylene glycol. The influencing factors on the morphology of the particles, i.e., solvent ratio, F/Bi ratio, and ethylenediaminetetraacetic acid, are studied in detail, and are schematically illustrated. The morphology, crystallinity, structure, and optical properties of the prepared samples are characterized by using a field‐emission scanning electron microscope, transmission electron microscope, X‐ray diffractometer, Fourier transform infrared spectrometer, and spectrofluorometer, respectively. The hollow sphere‐shaped nanoparticle doped with Eu³⁺ ions exhibit reddish orange emission under ultraviolet illumination due to the symmetric environment around the dopant ions. Subsequently, the effect of dopant concentration on the optical properties is also evaluated. The temperature‐dependent photoluminescence emission spectra reveal good thermal stability. The obtained results provide an efficient strategy for synthesizing the shape‐tunable nanoparticles with excellent optical properties.     

High‐temperature thermoelectric properties of p‐type skutterudites Ybx Co3FeSb12

Partially filled polycrystalline p‐type skutterudites of nominal compositions Yb_x Co₃FeSb₁₂ were synthesized and their thermoelectric properties characterized. The compositions and filling fractions were confirmed with a combination of Rietveld refinement and elemental analysis. The thermoelectric properties were evaluated from 300 K to 810 K. The Seebeck coefficient and resistivity increase while the thermal conductivity decreases with increasing Yb content. A maximum ZT value of 0.85 was obtained at 810 K. This work is part of a continuing effort to enhance the thermoelectric properties of p‐type skutterudites, as this class of materials continues to be of interest for thermoelectrics applications. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical design study on multifunctional triphenyl amino‐based derivatives for OLEDs

The use of triphenyl amino‐based derivatives in organic light‐emitting diodes (OLEDs) can significantly improve their efficiency and stability and especially their electroluminescence characteristics – most of the new hole‐transport materials have this feature. In this study, a series of triphenyl amino‐based compounds were computed, including two newly designed molecules. They can function as charge transport materials and emitters with high efficiency and stability. To reveal the relationship between the properties and structures of these bifunctional and multifunctional electroluminescent materials, the ground and excited state geometries were optimized at the B3LYP/6‐31G(d), HF/6‐31G(d), TD‐B3LYP/6‐31G(d), and CIS/6‐31G(d) levels, respectively. The ionization potentials (IPs) and electron affinities (EAs) were computed. The lowest excitation energies, the maximum absorption, and emission wavelengths of these compounds were calculated by employing the time‐dependent density functional theory (TD‐DFT) method. Also, the mobilities of holes and electrons were studied computationally based on the Marcus electron transfer theory. The CH₂Cl₂ solvent effect on the absorption spectra of N,N′‐di‐1‐naphthyl‐N,N′‐diphenylbenzidine ( NPB ) was considered by polarizable continuum model (PCM). The results obtained for these compounds are in good agreement with the experimental values. These data show that the proposed compounds 1 and 2 (N,B‐di‐1‐naphthyl‐N,B‐diphenylbenzidine and Mes₂N[p‐4,4′‐biphenyl‐NPh(1‐naphthyl)]), are multifunctional and bifunctional materials similar to Mes₂B[p‐4,4′‐biphenyl‐NPh(1‐naphthyl)] ( BNPB ) and NPB , respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis,Morphological Control,and Properties of Silver Nanoparticles in Potential Applications

Nanostructured materials, especially nanoparticles (NPs), of noble metal NPs such as silver (Ag) have been the focus of research in recent decades because of their distinct physical, chemical, and biological properties. These materials have attracted considerable attention because of their potential applications, such as catalysis, biosensing, drug delivery, and nanodevice fabrication. Previous studies on Ag NPs have clearly demonstrated that their electromagnetic, optical, and catalytic properties are strongly influenced by their shape, size, and size distribution, which can be varied by using different synthetic methods, reducing agents, and stabilizers. The valuable optical properties of Ag NPs have allowed for new approaches in sensing and imaging applications, offering a wide range of detection modes, such as colorimetric, scattering, and surface‐enhanced Raman scattering techniques, at extremely low detection limits. Here, an overview of the various chemical, physical, and biological properties of Ag NP fabrication approaches to obtain the various shapes and sizes is presented.     

Preparation and Characterization of Linear Low Density Polyethylene/Carbon Nanotube Nanocomposites

Linear low‐density polyethylene (LLDPE)/multiwalled carbon nanotube (MWNT) nanocomposites were prepared via melt blending. The morphology and degree of dispersion of nanotubes in the polyethylene matrix were investigated using scanning electron microscopy (SEM). Both individual and agglomerates of MWNTs were evident. The rheological behavior and mechanical and electrical properties of the nanocomposites were studied using a capillary rheometer, tensile tester, and Tera ohm‐meter, respectively. Both polyethylene and its nanocomposites showed non‐Newtonian behavior in almost the whole range of shear rate. Addition of carbon nanotubes increased shear stress and shear viscosity. It was also found that the materials experience a fluid‐solid transition below 1 wt% MWNT. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. With increasing nanotube content, the activation energy of flow increases. A decrease of about 7 orders of magnitude was obtained in surface and volume resistivity upon addition of 5 wt% MWNT. In addition, a difference between electrical and rheological percolation thresholds was observed. The results confirm the expected nucleant effect of nanotubes on the crystallization process of polyethylene. A slight increase in Young's modulus was also observed with increasing MWNT content.     

Probing the paramagnetic interactions between the unpaired electronic spins of carbon atoms and the nuclear spins of hydrogen molecules with Raman spectroscopy

Carbon materials typically have a high density of unpaired electronic spins but the exact nature of the defect sites that give rise to their magnetic properties are not yet well understood. In this work, the paramagnetic interactions between the unpaired electronic spins of carbon atoms and the nuclear spins of hydrogen molecules were probed with Raman spectroscopy by monitoring the relative population of H₂ rotational states. For H₂, the symmetries of nuclear spin and rotational wave functions are correlated. Because of the weak interactions between H₂ nuclear spins, the transitions between odd and even rotational states are normally hindered. The magnetic field generated by unpaired electronic spins relaxes the selection rules and promotes transitions between H₂ rotational levels of different symmetry. This affects the rotational levels' relaxation kinetics toward equilibrium and makes H₂ molecules useful to study unpaired electrons in paramagnetic materials. It is suggested that simultaneous electron paramagnetic resonance and Raman measurements on carbon materials interacting with hydrogen molecules could result in a better understanding of the nature of paramagnetic defects in carbon materials, which could have a substantial impact on Li‐ion batteries or for understanding the graphene electronic properties. Copyright © 2011 John Wiley & Sons, Ltd.     

Giant Auxetic Behaviour in Engineered Graphene

Graphene monolayers engineered to adopt a corrugated conformation are found to exhibit very pronounced lateral expansion characteristics upon uniaxial stretching in specific directions, i.e. giant negative Poisson's ratio (auxeticity). Such anomalous properties are manifested in‐plane and may be controlled through the shape and amplitude of the wave‐like pattern of the corrugation, which in the case of graphene may be controlled through the introduction of patterned ‘defects’. This confirms that auxeticity via corrugation can be achieved even at the nanoscale, as demonstrated here for graphene with patterned ‘defects’, suggesting that this mechanism should be operational at different scales of structures, thus providing a new blueprint for the design or manufacture of auxetic materials and metamaterials which can have tailor‐made giant negative Poisson's ratio properties.     

Direct femtosecond laser surface nano/microstructuring and its applications

This paper reviews a new field of direct femtosecond laser surface nano/microstructuring and its applications. Over the past few years, direct femtosecond laser surface processing has distinguished itself from other conventional laser ablation methods and become one of the best ways to create surface structures at nano‐ and micro‐scales on metals and semiconductors due to its flexibility, simplicity, and controllability in creating various types of nano/microstructures that are suitable for a wide range of applications. Significant advancements were made recently in applying this technique to altering optical properties of metals and semiconductors. As a result, highly absorptive metals and semiconductors were created, dubbed as the “black metals” and “black silicon”. Furthermore, various colors other than black have been created through structural coloring on metals. Direct femtosecond laser processing is also capable of producing novel materials with wetting properties ranging from superhydrophilic to superhydrophobic. In the extreme case, superwicking materials were created that can make liquids run vertically uphill against the gravity over an extended surface area. Though impressive scientific achievements have been made so far, direct femtosecond laser processing is still a young research field and many exciting findings are expected to emerge on its horizon.     

Investigation of some Chinese jade artifacts (5000 BC to 771 BC) by confocal laser micro‐Raman spectroscopy and other techniques

The study on material properties of ancient stone or jade artifacts is essential to trace the trade routes of raw materials, the tools used to making them, and moreover the social function of the artifacts. In present research, we focused on 23 intact samples that were made of versatile rocks. These samples dated from 5000 bc to 771 bc were unearthed from the Yellow River and Yangtze River basins in China. Based on the analytical results of confocal laser micro‐Raman spectroscopy, 14 minerals consisted of these rocks such as muscovite, antigorite, calcite, quartz, diopside, turquoise, corundum, and sillimanite were identified. The obtained scientific information about their primary material properties helps us to better understand their social functions and technologically related issues. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrical conductivity and dielectric properties of nanofibrillated cellulose thin films from bagasse

Nanocelluloses are potential candidates for applications in flexible electronic due to their unique physical and mechanical properties. However, electrical properties of these materials have not investigated thoroughly to study their electrical properties. In the current work, electrical properties of nanocellulose films prepared from bagasse pulp were studied and compared with those of bagasse pulp fibers. Two kinds of nanocelluloses were used in the current study: microfibrillated cellulose (MFC) and TEMPO‐oxidized nanofibrillated cellulose (NFC). The crystallinity, grain size, and morphology of the different nanocelluloses were studied using X‐ray diffraction and transmission electron microscopy techniques. The dc‐, ac‐ electrical conductivity, dielectric constant ?′, and dielectric loss ?″ of non‐plasticized and glycerol‐plasticized nanocellulose films were studied in the temperature range from 298 to 373 K and in the frequency range from 0.1 KHz to 5 MHz. The results showed that the dc‐ electrical conductivity verifies Arrhenius equation and the activation energies varied in the range of 0.9 to 0.42 eV. Ac‐electrical conductivity increased with frequency and fitted with power law equation, which ensures that the conduction goes through hopping mechanism. The dielectric constant decreased with increasing frequency and increased with increasing temperature, probably due to the free movement of dipole molecular chains within the cellulose fiber. Glycerol‐plasticized NFC (NFC‐G) film had the highest dielectric constant and ac‐electrical conductivity values of 79 800 and 2.80× 10^?3ohm^?1 cm^?1, respectively. The high values of dielectric constant and conductivity of the prepared films support their use in electronic components.     

Measurement of the bulk acoustic properties of fibrous materials at high temperatures

It is common for fibrous porous materials to be used in high temperature applications such as automotive and gas turbine exhaust silencers. Understanding the effect of temperature on the acoustic properties of these materials is crucial when attempting to predict silencer performance. This requires knowledge of the bulk acoustic properties of the porous materials and so this article aims to quantify the effect of temperature on the bulk acoustic properties of three fibrous materials: rock wool, basalt wool and an E-glass fibre. Measurements are undertaken here using a standard impedance tube that has been modified to accommodate temperatures of up to 500 °C. It is shown that measured data for the bulk acoustic properties may be collapsed using a standard Delany and Bazley curve fitting methodology provided one modifies the properties of the material flow resistivity and air to account for a change in temperature. Moreover, by using a previously proposed power law describing the dependence of the flow resistivity with temperature, one may successfully collapse data measured at every temperature and obtain the Delany and Bazley coefficients in the usual way. Accordingly, to predict the bulk acoustic properties of a fibrous material at elevated temperatures it is necessary only to measure these properties at room temperature, and then to apply the appropriate temperature corrections to the properties of the material flow resistivity and air when using the Delany and Bazley formulae.     

Modeling the Effect of Thermophysical Properties on Pyrolysis of Intumescent Fire-retardant Materials

Thermophysical properties of intumescent fire-retardant (IFR) materials are important input parameters to simulate the pyrolysis process of IFR materials in fire scenarios. In this article, the effects of the thermophysical properties on pyrolysis of IFR materials are simulated based on a pyrolysis model of IFR materials. The selected thermophysical properties here are the specific heat capacity of the virgin material, thermal conductivity of the virgin material and char layer, heat of decomposition, density of virgin material, intumescent temperature, and surface emissivity of virgin material and char layer. Simulated mass loss rates (MLR) for the IFR materials at an incident heat flux of 50 kW/m² are investigated for the varied thermophysical parameter values. The results show that changes in these property values can affect the pyrolysis behavior of materials profoundly. Comparison with experimental results indicates that the simulations of MLR are in reasonably good agreement with the experiments.     

Theoretical insights on a series of difluoramino group–based energetic molecules

A series of difluoramino group–based energetic molecules was designed and the relative properties were investigated by density functional theory. The results show that all the designed molecules have high positive heat of formation which ranges from 479.48 to 724.02 kJ/mol, detonation velocity ranges from 8.01 to 11.26 km/s, detonation pressure ranges from 28.03 to 63.46 GPa, and impact sensitivity ranges from 18.2 to 54.5 cm. Then, compounds D2, D3, D5, E4, E5, E6, and F2 were selected as the potential high energy density materials based on detonation properties and sensitivities. Natural bond orbital charges, electronic density, frontier molecular orbital, electrostatic potential on the surface, and thermal dynamic parameters of the screened molecules (compounds D2, D3, D5, E4, E5, E6, and F2) were also predicted at B3LYP/6‐31G(d,p) level to give a better understanding on the chemical and physical properties of them.     

Pressure‐induced incompressibility and point singularity of mechanical properties of TaC in NiAs‐type structure

The structural and elastic properties of TaC in NiAs‐type structure under high pressure have been investigated using first principles calculations based on density functional theory. Results indicate that the incompressibility along the c‐axis of TaC exceeds that of diamond under higher pressure. Particularly, an interesting point singularity exists in its mechanical properties as the pressure increases from 20 GPa to 40 GPa. The minimal shear modulus, Young's modulus, Debye temperature, and maximum Poisson ratio of TaC are simultaneously obtained at 28 GPa. The calculations of hardness indicate that the NiAs‐type TaC crystal possesses excellent mechanical properties. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of Molecular Structure and Packing on Sorption and Transport Properties of Dichloromethane in Polyetherimides

The effects of thermal history on dichloromethane vapor sorption and transport properties of polyetherimides were studied. Films were prepared by solution casting at room temperature and heat treated for 24 h at different temperatures below the corresponding glass transition temperature of each material. Changes of the transport properties due to heat treatment were observed and are correlated to changes in density, free volume, and thermal transitions. Deviation from Fick's and Henry's laws was observed for all the samples studied. Without heat treatment and at low activities of the penetrant, the materials studied show sorption kinetics similar to the Fickian behavior. On the other hand, sorption measurements tests for the heat‐treated films at high activities of dichloromethane show kinetics similar to Case II diffusion. Equilibrium sorption data obtained at different penetrant concentrations show deviation from Henry's law behavior depending on the thermal history of the sample.     

Nanocrystalline materials – Current research and future directions

Nanocrystalline materials, with a grain size of typically <100 nm, are a new class of materials with properties vastly different from and often superior to those of the conventional coarse-grained materials. These materials can be synthesized by a number of different techniques and the grain size, morphology, and composition can be controlled by controlling the process parameters. In comparison to the coarse-grained materials, nanocrystalline materials show higher strength and hardness, enhanced diffusivity, and superior soft and hard magnetic properties. Limited quantities of these materials are presently produced and marketed in the US, Canada, and elsewhere. Applications for these materials are being actively explored. The present article discusses the synthesis, structure, thermal stability, properties, and potential applications of nanocrystalline materials. This revised version was published online in July 2006 with corrections to the Cover Date.     

Magnetic properties of lithium intercalation compounds

Magnetic experiments are powerful tools to study fundamental properties and to check the qualities of samples. Temperature, stress, and impurities of materials can all affect magnetic properties and play an important role in the utilization of these materials for engineering applications. The estimation and analysis of the spontaneous magnetization can reveal ferromagnetic particles as impurities in samples. The shape of the temperature dependence of magnetization is indicative of the origin of the magnetic properties. However, it is necessary to correlate the χ _m (T) curves and isothermal M(H) plots to achieve a complete analysis of the electronic properties of the materials. Highlights of magnetic properties of lithium intercalation compounds are briefly described. Intrinsic and extrinsic properties are considered as useful parameters to determine the purity of electrode materials for rechargeable Li-ion batteries.     

Effects of Mn‐doping on surface acoustic wave properties of ZnO films

Surface acoustic wave (SAW) filters based on Mn‐doped ZnO films have been fabricated and effects of Mn‐doping on SAW properties are investigated. It is found that the electromechanical coupling coefficient (K²) of Zn_0.913Mn_0.087O films is 0.73 ± 0.02%, which is 73.8% larger than that of undoped ZnO films (0.42 ± 0.02%). Zn_0.913Mn_0.087O film filters also exhibit a lower absolute value of insertion loss (|IL|) of 16.1 dB and larger bandwidth (BW) of 5.9 MHz compared with that of undoped ZnO film filter. However, Zn_0.952Mn_0.048O film filters exhibit a smaller K² of 0.34 ± 0.02%, larger |IL| of 26.9 dB and smaller BW of 3.5 MHz. It is suggested that the SAW properties can be improved by appropriate Mn‐doping and Mn–ZnO/Si multilayer structure with large d₃₃ is promising for wide‐band and low‐loss SAW applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)