LDH–dye hybrid material as coloured filler into polystyrene: Structural characterization and rheological properties

The organic–inorganic hybrid assembly composed of a dye molecule of large size, direct yellow^®50, as interleaved anionic molecule and layered double hydroxide host was investigated by X-ray diffraction. Upon hydrothermal post-synthesis treatment, the basal spacing is strongly decreased, explained by a drastic change in the orientation of the organic molecule against the LDH sheets, from perpendicular to parallel. The interactions were studied by ¹³C CPMAS NMR technique. Dispersed into polystyrene, the coloured filler was found to behave better in the viscoelastic domain than conventional surfactant LDH filler, maintaining similar rheological properties to filler-free PS. We demonstrate here that an intercalated nanocomposite polymer structure, providing an additional function as colour, is not preposterous.     

H and C NMR studies of molecular orientation and dynamics in liquid crystal 6BA

The dynamics and orientation of dimers accompanying the formation and destruction of hydrogen bonds in the nematic phases of 4-n-hexylbenzoic acid (6BA) were studied by ¹³C and ²H NMR. The orientational order parameter S in the nematic phase was estimated from the quadrupole splitting of the ²H NMR spectrum. The intermolecular interaction energy for the molecular order in the nematic phase decreased with increasing temperature. The flexibility of dimers due to the destruction of the hydrogen bond is closely related to a decrease in the intermolecular interaction energy. The proportion of ²H NMR spin-lattice relaxation time (T₁) to S, which reveals the coupling of the orientational fluctuations with the hydrogen bonding processes, was observed.     

Thermal properties and structures of chlorocadmate, bromocadmate, and bromochlorocadmate glasses

Glass transition temperatures (T_g), crystallization temperatures (T_x), and ¹¹³Cd magic-angle spinning (MAS) NMR spectra of the chlorocadmate, bromocadmate, and bromochlorocadmate glasses and the CdCl₂, CdBrCl, and CdBr₂ crystals have been measured. The T_g and T_x, and thermal stabilities (T_x−T_g) decreased with increasing Br-content. No enhancement of (T_x−T_g) of bromochlorocadmate glasses by anion-mixing was observed. The CdCl₂ and CdBr₂ crystals gave the isotropic chemical shifts of 183 and −24 ppm, which are assigned to the CdCl₆ and CdBr₆ octahedra, respectively. The isotropic chemical shifts of CdBrCl crystal (186, 166, 135, 101, 63, 25 and −21 ppm) were assigned to CdBr_nCl_(6−n) (n=0-6) octahedra, respectively. It was found that the Br and Cl atoms in CdBrCl randomly occupy chlorine sites in the CdCl₂ structure. The ¹¹³Cd MAS NMR spectra revealed that the chlorocadmate, bromocadmate, and bromochlorocadmate glasses are composed of the CdCl₆, CdBr₆ and CdBr_nCl_(6−n) octahedra (n=0-6), respectively, and that the Cd²⁺ in all the bromochlorocadmate glasses was more preferentially bonded to Br⁻ than Cl⁻. The relationship between the thermal properties and the anion coordination environments around Cd²⁺ in these glasses is discussed.     

Preparation, characterization and application of a nanostructured composite: Octakis(cyanopropyldimethylsiloxy)octasilsesquioxane

Octakis(cyanopropyldimethylsiloxy)octasilsesquioxane was prepared and characterized by ¹³C, ²⁹Si NMR (MAS), SEM, FT-IR, XRD and thermogravimetric techniques. The four groups α, β, γ, κ (to the terminal silicon atom), associated with an acrylonitrile, were clearly seen in the ¹³C NMR (α-CH₂ at 17.9; β-CH₂ at 31.3; γ-CH₂ at 50.4; κ-CN at 59.0 ppm). The ²⁹Si NMR spectrum of the final product, exhibits only Q type silicon signal, ascribed to Q⁴ (−118.0 ppm). The presence of acrylonitrile substituted for octameric cube confers a relative change phase and thermal stability to the material. With regard to the applications for this new material, it was intended, in this case, to react with Na₂[Fe(CN)₅NH₃] by chemical substitution. This composite was incorporated into a carbon paste electrode and the electrochemical studies were performed by cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode, showed one redox couples with formal potential () = 0.24 V versus SCE.     

Identification of optical nonlinearities of dye-doped nematic and polymer-dispersed liquid crystals using Z-scan technique

This study investigates the nonlinear optical properties of azo-dye-doped nematic and polymer-dispersed liquid crystal (ADDPDLC) films with nano-sized LC droplets using the Z-scan technique, which is a simple but powerful technique for measuring the optical Kerr constants of materials. The results indicate that the optical Kerr constant (n₂) of the azo-dye-doped nematic LC (ADDLC) film is large because of the photoisomerization effect and the thermal effect. Therefore, the optical Kerr constant of this material can be modulated by varying the temperature of the sample and the direction of polarization of incident laser. The range of n₂ modulated is from −5.26 × 10⁻³ to 1.62 × 10⁻³ cm²/W. The optical Kerr constants of ADDPDLC films at various temperatures are also measured. The experimental results reveal that liquid crystals in the ADDPDLC film strengthen the nonlinearity. The n₂ of the ADDPDLC film is maximal at ∼35 °C, because of the decrease in the clearing temperature of the ADDPDLC films. The clearing temperatures of the liquid crystals (E7), and the ADDPDLC film used in this work were found to be 61 °C and 43 °C, respectively.     

Rigid lattice NMR spectra of proton conductors H(H2O)nSbO3

The “rigid lattice” ¹H NMR spectra of H(H₂O)_nSbO₃ have been interpreted for n=0.20, 0.92 and 1. For n?0.92 the compounds contain deformed H₃O⁺ ions and OH groups. For n=1 the real formula is (H₃O)_0.7H_0.3SbO₃,0.3 H₂O. The results are discussed in relation to the level of proton conductivity.     

A density functional theory study on the H2S molecule adsorption onto small gold clusters

An all-electron scalar relativistic calculation on Au_nH₂S (n = 1-13) clusters has been performed by using density functional theory with the generalized gradient approximation at PW91 level. The small gold cluster would like to bond with sulfur in the same plane and the H₂S molecule prefers to occupy the on-top and single fold coordination site in the cluster. The Au_n structures and H₂S molecule in all Au_nH₂S clusters are only slightly perturbed and still maintain their structural integrity. After adsorption, the S-H, H-H bond-lengths and most Au-Au bond-lengths are elongated, only a few Au-Au bond-lengths far from H₂S molecule are shortened. The reactivity enhancement of H₂S molecule is obvious and the strong gold-sulfur bond is observed expectedly. The most favorable adsorption takes place in the case that the H₂S molecule is adsorbed by an even-numbered Au_n cluster and becomes Au_nH₂S cluster with even number of valence electrons. It is believed that the strong scalar relativistic effect is favorable to H₂S molecule adsorption onto small gold clusters and is also one of the important reasons for the strong gold-sulfur bond.     

Electronic structure and conduction properties of copolymers of silole based donor-acceptor polymers: effect of multi-neighbour interaction

Using the ab initio band structure results of two novel silole based donor-acceptor polymers PSICF (A)_x and PSICN (B)_x, the electronic structures and conduction properties of their various quasi-one-dimensional superlattices (copolymers) (A_mB_n)_x, belonging to the class of type-II staggered superlattices, have been investigated using negative factor counting method taking into account multi-neighbour interaction. Both PSICF and PSICN consist of a bicyclopentadisilole unit bridged by an electron-accepting group Y (Y=CCF₂ in PSICF and Y=CC(CN)₂ in PSICN). The trends in the electronic structures and conduction properties of these copolymers (A_mB_n)_x as a function of the (i) block sizes m and n; (ii) composition (m/n) and (iii) arrangement of blocks (periodic or aperiodic) in the copolymer chain are discussed. The results obtained are important guidelines for designing copolymers with tailor-made conduction properties.     

Dilute magnetic semiconductors based on wide bandgap SiO2 with and without transition metal elements

Material designs based on the first principle calculations of electronic structures are proposed for α-quartz SiO₂-based dilute magnetic semiconductors. The incorporation of transition metals (TMs) into Si sites and of the non-TM atoms into O sites are treated for various concentrations. At temperatures higher than room temperature, most of the TM-doped SiO₂ have no magnetism, yet Si_1−xMn_xO₂ might achieve the ferromagnetism. The substitution of O by non-TM atoms as C or N also induces the magnetism in the host. However, while the N's substitution induces the ferromagnetism, C's substitution causes an anti-ferromagnetic behavior in the host material SiO₂.     

Magnetic contribution to heat capacity and entropy of nickel ferrite (NiFe2O4)

The heat capacity of nickel ferrite was measured as a function of temperature from 50 to 1200 °C using a differential scanning calorimeter. A thermal anomaly was observed at 584.9 °C, the expected Curie temperature, T_C. The observed behavior was interpreted by recognizing the sum of three contributions: (1) lattice (vibrational), (2) a spin wave (magnetic) component and (3) a λ-transition (antiferromagnetic-paramagnetic transition) at the Curie temperature. The first was modeled using vibrational frequencies derived from an experimentally-based IR absorption spectrum, while the second was modeled using a spin wave analysis that provided a T^3/2 dependency in the low-temperature limit, but incorporated an exchange interaction between cation spins in the octahedral and tetrahedral sites at elevated temperatures, as first suggested by Grimes [15]. The λ-transition was fitted to an Inden-type model which consisted of two truncated power law series in dimensionless temperature (T/T_C). Exponential equality (m=n=7) was observed below and above T_C, indicating symmetry about the Curie temperature. Application of the methodology to existing heat capacity data for other transition metal ferrites (AFe₂O₄, A=Fe, Co) revealed nearly the same exponential equality, i.e., m=n=5.     

Magnetoelectricity in multiferroically composed multilayers and multiglasses

Single-crystalline magnetoelectric (ME) antiferromagnetic Cr₂O₃ exchange coupled to a ferromagnetic multilayer (Pt/Co/Pt)_n, n?1, represents a multiphase multiferroic material with sophisticated multifunctional properties. They comprise the possibility of switching the exchange bias (EB) of the ferromagnetic hysteresis loop via the linear ME effect of Cr₂O₃, and to design MERAM and logic cells operating at room temperature. Quadratic and cubic ME effects - promoted by soft-mode quantum fluctuations - are observed at lowest order in ceramic Sr_0.98Mn_0.02TiO₃ at low temperatures. Dipolar and spin glass orders occur simultaneously on the Mn²⁺ subsystem and form a multiglass by analogy with conventional multiferroics.     

H, C NMR and JCH coupling constants investigation of 4-Phenylpyridine: A combined experimental and theoretical study

Proton coupled and uncoupled ¹³C, ¹H, DEPT, COSY and HETCOR NMR spectra of 4-Phenylpyridine (4-Phpy) have been reported for the first time except for its ¹H NMR spectrum. In order to provide a precise structural elucidation for carbon atoms those have very close chemical shifts to each other, the magnitude of ⁿJ_CH (n=1,2,3) coupling constants of 4-Phpy (C₁₁H₉N) have also been investigated. ¹³C, ¹H NMR chemical shifts and ^1-3J_CH coupling constants of 4-Phpy have been calculated by means of B3LYP density functional method with 6-311++G(d,p) basis set. Moreover, the optimized parameters (bond lengths, bond and torsion angles) of 4-Phpy have been calculated with B3LYP at 6-31G(d) level in methanol (ε=32.63). Comparison between the experimental and the theoretical results indicates that density functional B3LYP method is able to provide satisfactory results for predicting NMR properties.     

Electrical and electromechanical properties of lead-potassium-yttrium-niobate ceramics—piezoelectric applications

Tungsten bronze (TB)-type oxide ceramic Pb_0.74K_0.13Y_0.13Nb₂O₆ (PKYN) has been synthesized by the standard solid state reaction method. Single phase formation, orthorhombic crystal structure was confirmed by X-ray diffraction (XRD). The substitution of Y³⁺ in Pb_0.74K_0.52Nb₂O₆ (PKN) decreased the unit cell volume and T_C=260 °C. PKYN exhibited the remnant polarization, P_r=8.5 μC/cm², and coercive field, E_c=28.71 kV/cm. Electrical spectroscopy studies were carried out over the temperature (35-595 °C) and frequency (45 Hz-5 MHz) ranges, and the charge carrier phenomenon, grain-grain boundary contribution and non-Debye-type relaxation were analyzed. The relaxation species are immobile charges in low temperature and oxygen vacancies at higher temperature. The theoretical values computed using the relations, ε′=ε_∞+sin(n(T)π/2)(a(T)/ε₀)(ω^n(T)−1); σ(ω)=σ_dc+Aωⁿ are fitted with the experimental one. The n and A parameters suggested that the charge carrier's couple with the soft mode and become mobile at T_C. The activation enthalpy, H_m=0.38 eV, has been estimated from the hopping frequency relation ω_p=ω_e exp(−H_m/k_BT). The piezoelectric constants K_t=35.4%, d₃₃=69×10⁻¹² C/N, d₃₁=−32×10⁻³ mV/N, S₁₁^E=17.8 pm²/N, etc., achieved in PKYN indicate the material is interesting for transducer applications. The activation energies from different formalisms confirmed the ionic-type conduction.     

UV laser induced desorption of CsI and RbI ion clusters

Experimental results of laser sputtering of cesium and rubidium iodide secondary ions are presented. A TOF mass spectrometer, operating in linear mode, continuous extraction for positive or negative ions, was used for the analysis of (CsI)_nCs⁺, (CsI)_nI⁻, (RbI)_nRb⁺ and (RbI)_nI⁻ ion emission as a function of the laser irradiance. Experimental data show that the cluster ion emission yields decrease exponentially with n, for all the laser irradiances applied. Theoretical analysis of the clusters structure was performed using density functional theory at the B3LYP/LACV3P level, for the positive and negative cluster series. A quasi-equilibrium evolution of the clusters is proposed to extract a parameter characteristic of the cluster recombination process: the effective temperature. The hypothesis of the atomic species’ recombination (during the expansion of a high density highly ionized cloud) leading to cluster formation is confirmed to some extent in a second set of experiments: the UV laser ablation of a mixed and non-mixed cesium iodide and potassium bromide targets. These experiments show that the emission yields contain contributions from both the recombination process and from the sample stoichiometry, even for high laser irradiances.     

Mössbauer study of the HgBa2Ca n−1CunO2n+2 ceramics

The parameters of the electric-field gradient tensor at the copper, barium, and mercury sites in the HgBa₂Ca _n?1Cu_nO_2n+2 lattices (n=1,2,3) have been determined by Mössbauer emission spectroscopy on the ⁶⁷Cu(⁶⁷Zn), ¹³³Ba(¹³³Cs), and ¹⁹⁷Hg(¹⁹⁷Au) isotopes, and calculated in the point-charge approximation. An analysis of these results combined with available ⁶³Cu NMR data showed that the experimental and theoretical data can be reconciled by assuming that the holes originating from defects in the material are localized primarily on the sublattice of the oxygen lying in the copper plane [for HgBa₂Ca₂Cu₃O₈, in the plane of the Cu(2) atoms].     

Structure, phase transitions and molecular dynamics in 4-methylpyridinium tetrachloroantimonate(III), [4-CH3C5H4NH][SbCl4]

Crystal structure of the 4-methylpyridinium tetrachloroantimonate(III), [4-CH₃C₅H₄NH][SbCl₄], has been determined at 240 K by X-ray diffraction as monoclinic, space group, P2₁/n, Z=8. Differential scanning calorimetry and dilatometric studies indicate the presence of two reversible phase transitions of first order type, at 335/339 and 233/289 K (cooling/heating) with ΔS=0.68 and 2.2 J mol⁻¹ K⁻¹, respectively. Crystal dynamics is discussed on the basis of the temperature dependence of the ¹H NMR spin-lattice relaxation time T₁ and infrared spectroscopic studies. The low temperature phase transition at 233 K of an order-disorder type is interpreted in terms of a change in the motional state of the 4-methylpyridinium cations. The phase transition at 335 K, probably of a displacive type, is characterised by a complex mechanism involving the dynamics of both the cationic and anionic sublattice. The ¹H NMR studies show that the low temperature phase III is characterised only by the dynamics of the CH₃ groups.     

NMR Study of proton transport in crystalline antimonic acid

Pulsed ¹H NMR measurements are reported for polycrystalline antimonic acid (Sb₂O₅·nH₂O) in the temperature range 145 K<T<330 K at 60 MHz. Motional narrowing occurs at T>220 K and the relaxation behaviour is compatible with fast proton transport with a distribution of activation energies.     

Galvanomagnetic properties of air-stable and highly conductive potassium-intercalated graphite sheet

Magnetoresistance and Hall coefficient of air-stable potassium-intercalated graphite sheets (hereafter abbreviated as K-PGS) were determined at room temperature. The magnitude of the magnetoresistance and the absolute value of Hall coefficient of K-PGS decreased with increasing potassium content of K-PGS, n_K/n_C. Two-carrier model was used for calculating carrier density and mobility. The electron density increased with increasing n_K/n_C: 3.07×10²⁰ cm⁻³ (n_K/n_C=0.005), 5.67×10²⁰ cm⁻³ (n_K/n_C=0.008) and 6.40×10²⁰ cm⁻³ (n_K/n_C=0.011). The value of the electron density of K-PGS with n_K/n_C=0.011 (nominal composition KC₉₁) was about 80% of the reported value, 7.8×10²⁰ cm⁻³, for KC₄₈ (n_K/n_C=0.021) prepared from HOPG (highly oriented pyrolytic graphite). The mobility decreased with increasing n_K/n_C: 2.11×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.005), 1.42×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.008) and 1.34×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.011). The value of the mobility of K-PGS with n_K/n_C=0.011 was about 60% of the reported value (2300 cm² V⁻¹ s⁻¹) for KC₄₈ prepared from HOPG.     

Crystal structure,NMR study,dielectric relaxation and AC conductivity of a new compound [Cd3(SCN)2Br6(C2H9N2)2]n

The crystal structure, the ¹³C NMR spectroscopy and the complex impedance have been carried out on [Cd₃(SCN)₂Br₆(C₂H₉N₂)₂]_n. Crystal structure shows a 2D polymeric network built up of two crystallographically independent cadmium atoms with two different octahedral coordinations. This compound exhibits a phase transition at (T=355±2 K) which has been characterized by differential scanning calorimetry (DSC), X-rays powder diffraction, AC conductivity and dielectric measurements. Examination of ¹³C CP/MAS line shapes shows indirect spin–spin coupling (¹⁴N and ¹³C) with a dipolar coupling constant of 1339 Hz. The AC conductivity of this compound has been carried out in the temperature range 325–376 K and the frequency range from 10⁻² Hz to 10 MHz. The impedance data were well fitted to two equivalent electrical circuits. The results of the modulus study reveal the presence of two distinct relaxation processes. One, at low frequency side, is thermally activated due to the ionic conduction of the crystal and the other, at higher frequency side, gradually disappears when temperature reaches 355 K which is attributed to the localized dipoles in the crystal. Moreover, the temperature dependence of DC-conductivity in both phases follows the Arrhenius law and the frequency dependence of σ(ω,T) follows Jonscher's universal law. The near values of activation energies obtained from the conductivity data and impedance confirm that the transport is through the ion hopping mechanism.