Investigation of thermal expansion,phase diagrams,and barocaloric effect in the (NH4)2WO2F4 and (NH4)2MoO2F4 oxyfluorides

The thermal expansion along the principal crystallographic axes of the (NH₄)₂WO₂F₄ and (NH₄)₂MoO₂F₄ oxyfluorides has been studied. The anomalous behavior of α _i (T) due to the phase transitions has been revealed at T ₁ = 271.4 K and T ₂ ≈ 180 K for the molybdate and at T ₁ = 201.5 K and T ₂ ≈ 161 K for the tungstate. The quantities dT/dp and dT/dσ _i , which characterize the dependence of the phase transition temperatures on the hydrostatic and uniaxial pressures, have been determined from analyzing the results of studies of the thermal expansion and heat capacity with the use of the Pippard relations. The p-T and α _i -T phase diagrams reflect different characters of the influence of the pressure on the stability of the initial and distorted phases of the oxyfluorides. The magnitudes of the extensive and intensive barocaloric effects determined in the vicinity of the structural phase transitions are as follows: ΔS _BCE varies from approximately −10 to −17 J/mol K and ΔT _AD ≈ 8−17 K for the molybdate and ΔS _BCE varies from approximately −10 to −17 J/mol K and ΔT _AD ≈ 8−13 K for the tungstate.     

Structure-property and composition-property relationships for poly(ethylene terephthalate) surfaces modified by helium plasma-based ion implantation

The surfaces of untreated and helium plasma-based ion implantation (He PBII) treated poly(ethylene terephthalate) (PET) samples were characterised by reflectance colorimetry, contact angle studies and measurements of surface electrical resistance. The results were related to the structural and compositional data obtained by the authors earlier on parallel samples by XPS and Raman spectroscopy. Inverse correlations between lightness and I_D/I_G ratio and between chroma and I_D/I_G ratio were obtained, suggesting that the PBII-treated PET samples darken and their colourfulness decreases with the increase of the portion of aromatic sp² carbon rings in the chemical structure of the modified layer. Direct correlation between water contact angle and the I_D/I_G ratio and inverse correlations between surface energy and I_D/I_G ratio and between dispersive component of surface energy and I_D/I_G ratio were found, reflecting that surface wettability, surface energy and its dispersive component decrease with the formation of surface structure, characterised again by enhanced portion of aromatic sp² carbon rings. The surface electrical resistance decreased with the increase of the surface C-content determined by XPS and also with the increase of the surface concentration of conjugated double bonds, reflected by the increase of the π → π* shake-up satellite of the C 1s peak.     

The a-type rotational spectrum of isocyanic acid,HNCO, in the excited bending states

Rotational transitions of HNCO in the v₄ = 1, v₅ = 1, and v₆ = 1 vibrational states have been measured. The assignment of the a-type ^qR_K and ^qQ₁ branches has been made with the help of a qualitative discussion of the vibration-rotation interactions. Effective rotational and centrifugal distortion constants have been determined precisely for each vibrational K_a-rotational state, up to K_a = 4 for the lowest excited state and K_a = 3 for the other two excited states. The K_a dependence of the effective rotational constants B and D was observed to be quite anomalous for some of the transitions because of the a-type Coriolis interactions and accidental b-type Coriolis resonances. From a discussion of the selection rules and the effect on B and D of the interactions, the first excited state of the out-of-plane vibration, ν₆, has been assigned definitely to the second lowest excited vibrational state of HNCO.     

Superhyperfine structure of the EPR spectra of Nd<Superscript>3+</Superscript> and U<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The superhyperfine structure of the EPR spectra of impurity Nd³⁺ and U³⁺ ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals has been observed and discussed. In LiYF₄: Nd (g _| = 1.987, g _⊥ = 2.554) and LiTmF₄: Nd, the superhyperfine structure is observed at the orientation of the external magnetic field B in parallel to the c axis of the crystals and consists of nine components with a splitting of ∼15.4 MHz. In LiYF₄: U (g _| = 1.149, g _⊥ = 2.508) and LiLuF₄: U, the superhyperfine structure is observed at both B | c and B ⊥ c and consists of nine and eleven components, respectively, with a splitting of ∼21.5MHz. It should be noted that the resolution of the superhyperfine structure of the EPR spectrum of LiLuF₄: U³⁺ becomes significantly higher with a deviation from the orientation B ⊥ c.     

Structure, phase transitions, 55Mn NMR, and magnetoresistive properties of La0.6Sr0.2Mn1.2 ? yCryO3 ± δ

The structure and properties of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 − y} Cr _y O_{3 ± δ} (y = 0–0.3) sintered at 1430°C have been studied by X-ray, resistive, and magnetic (χ_ac and ⁵⁵Mn NMR) methods. The parameter of the rhombohedrally distorted (R $ \bar 3 $ \bar 3 c) perovskite structure decreases with increasing y. The real perovskite structure contains point (anion and cation vacancies) and cluster-type nanostructure defects. The analysis of asymmetrically broadened ⁵⁵Mn NMR spectra has confirmed the high-frequency electron-hole exchange Mn³⁺ ↔ Mn⁴⁺ and local inhomogeneity of their surrounding by other ions and point and cluster-type defects. An increase in the Cr content leads to an increase in the resistivity and the magnetoresistive effect and a decrease in the metal-semiconductor and ferromagnetic-paramagnetic phase transition temperatures (T _ms and T _c ) due to the distortion of the exchange interactions Mn³⁺ ↔ Mn⁴⁺ by chromium ions, vacancies, and clusters. Introduction of Cr decreases the ferromagnetic component and increases the activation energy. The magnetoresistive effect near T _ms and T _c is caused by scattering of charge carriers from intercrystallite nanostructure inhomogeneities of the lattice, and the low-temperature effect is associated with the tunneling on mesostructural intercrystallite boundaries.     

New features of a smectic-A-crystal-B phase transition in a homologous series of liquid crystals

The components L _j of the Lorentz tensor and the polarizability density of molecules G in the smectic-A and crystalline-B phases have been determined for homologues of the series of alkyl-p-(4-alkoxybenzylideneamino-)cinnamates. The quantity L _j (G) in both phases is a linear (quadratic) function of the orientational order parameter of molecules S, which is invariant (noninvariant) with respect to the A-B transition, which is manifested in the form of jumps δL _j and δG and enhancement of the G(S) dependence. An increase in the length of terminal molecular chains and weakening of interlayer correlation of molecules are accompanied by strengthening of the A-B transition of the first order and G(S) dependences in both phases together with an increase in δL _j and δG. Change δG and dependence G(S) in the B phase are related to change in the conformation (flattening) of aromatic molecular cores.     

Stability of Zn–Ni–TiO<Subscript>2</Subscript> and Zn–TiO<Subscript>2</Subscript> nanocomposite coatings in near-neutral sulphate solutions

Zn–Ni–TiO₂ and Zn–TiO₂ nanocomposites were prepared by galvanostatic cathodic square wave deposition. X-ray diffraction analysis and scanning electron microscopy revealed that the occlusion of TiO₂ nanoparticles (spherical shaped with diameter between 19.5 and 24.2 nm) promotes the formation of the γ-Ni₅Zn₂₁ phase, changes the preferred crystallographic orientation of Zn from (101) and (102) planes to (002), and decreases the particle size of the metallic matrices. The stability of the nanocomposites immersed in near-neutral 0.05 mold m⁻³ Na₂SO₄ solution (pH 6.2) was investigated over 24 h. The initial open circuit potential for the Zn–Ni–TiO₂ and Zn–TiO₂ coatings were −1.32 and −1.51 V (vs. Hg/Hg₂SO₄), respectively, and changed to −1.10 and –1.49 V (vs. Hg/Hg₂SO₄) after 24 h of immersion. Data extracted from the steady state polarization curves demonstrated that the metal–TiO₂ nanocomposites have, with respect to the metal coatings, a higher corrosion potential in the case of the Zn–Ni alloy composite; a lower corrosion potential in the case of Zn-based nanocomposite albeit the predominant (002) crystallographic orientation; and a lower initial corrosion resistance due to the smaller grain size and higher porosity in the Zn–Ni–TiO₂ and Zn–TiO₂ nanocomposites. Morphological and chemical analyses showed that a thicker passive layer is formed on the surface of the Zn–Ni–TiO₂ and Zn–TiO₂ deposits. After 24 h of immersion in the sulphate solution, the Zn–Ni–TiO₂ coating has the highest corrosion stability due to the double-protective action created by the deposit’s surface enrichment in Ni plus the higher amount of corrosion products.     

Intensities of rotational lines in first overtone bands for axially symmetric molecules of the group C3v

The interaction of vibration and rotation is considered in the computation of the intensities of rotational lines in the first overtone bands of axially symmetric molecules of the group C_3v. The calculation utilizes the contact transformation method through first order of approximation as outlines by Hanson and Nielsen. General formulas for the intensities of the lines in the first overtone bands 2ν_n and 2ν_m are obtained, where n and m denote normal modes of species A₁ and E, respectively. It is found that to this order of approximation the usual selection rules ΔJ = 0, ±1 and ΔK = 0 are observed for the parallel overtone band 2ν_n. For the overtone band 2ν_m, the selection rules are more complicated, being ΔJ = 0, ±1; Δl_m = 0 and ΔK = 0, Δl_m = ±2 and $\text{Δ}\text{K = ?1}$, or Δl_m = ±2 and ΔK = ±2.     

Studies of interface phonons

The vibrational modes localized at the interface between two distinct crystals have been studied for a simple crystal model obeying all of the invariance conditions required for models used in studies of dynamical properties of crystal surfaces, and giving rise to Rayleigh surface waves. The two crystals are assumed to be semi-infinite simple cubic and to have the same lattice parameter a. They differ by their mass (M and M_A) and the central force interactions between first (K and K_a) and second nearest neighbors $\text{1}\text{2}\text{K}$ and $\text{1}\text{2}\text{K}{}_{\mathrm{A}}$. The interface is obtained by coupling the (001) free surfaces of these distinct crystals by central force intractions (K^'). We find that the variation of the interaction conditions (K^') at the interface and of the $\text{(}\text{K}\text{M}\text{)}\text{(}\text{K}{}_{\mathrm{A}}\text{M}{}_{\mathrm{A}}\text{)}$ parameter has the following qualitative effects on the properties of surface and bulk phonons. When (K^') increases from zero to a finite value, the frequencies of the surface phonons increase and are splitted in the case of two identical crystals. One can say that the surface phonons are transformed into interface modes. For some values of $\text{K}{}^{\mathrm{\text{'}}}\text{K}$ and $\text{(}\text{K}\text{M}\text{)}\text{(}\text{K}{}_{\mathrm{<mtext>A</mtext>}}\text{M}{}_{\mathrm{<mtext>A</mtext>}}\text{)}$ parameters these interface phonons may be admixed with bulk phonons and thus become virtual interface states.     

High Resolution Study of Deuterated Hydrogen Sulfide in the Region 2400-3000 cm

High resolution Fourier transform spectra of deuterated hydrogen sulfide have been recorded in the region 2400-3000 cm⁻¹. Rotational structures of the ν₁ + ν₂, ν₂ + ν₃ bands of D₂³²S, of the ν₃ and ν₁ + ν₂ bands of HD³²S, and of the ν₁ + ν₂ band of HD³⁴S were analyzed. Band centers and rotational, centrifugal distortion, and resonance parameters were obtained, which reproduce the initial values of the upper energy levels within a mean accuracy of 1.39 × 10⁻⁴ cm⁻¹ for the states (110) and (011) of D₂³²S, 1.61 × 10⁻⁴ cm⁻¹ and 1.82 × 10⁻⁴ cm⁻¹ for the states (001) and (110) of HD³²S, and 2.09 × 10⁻⁴ cm⁻¹ for the state (110) of HD³⁴S, respectively.     

Magnetic and structural properties of the electrochemically deposited arrays of Co and CoFe nanowires

Magnetic and structural properties of the arrays of 18 nm diameter nanowires of Co and Co₉₀Fe₁₀ electrodeposited in the pores of anodic alumina are investigated. Arrays of Co and Co₉₀Fe₁₀ nanowires show perpendicular magnetic anisotropy and textured crystallographic behaviour. Coercivity H_c (⊥) and remanence M_r/M_s (⊥) values of 2275 Oe (Co₉₀Fe₁₀); 1188 Oe (Co) and 96% (Co₉₀Fe₁₀), 81% (Co) are observed. The continuous films of Co and Co₉₀Fe₁₀ on Cu substrates show in plane magnetic anisotropy and coercivity values between 109 and 288 Oe.     

Beam quality of radial Gaussian Schell-model array beams

Taking the Rayleigh range z_R and the M²-factor as the characteristic parameters of beam quality, the beam quality of radial Gaussian Schell-model (GSM) array beams is studied. The analytical expressions for the z_R and the M²-factor of radial GSM array beams are derived. It is shown that for the superposition of the cross-spectral density function z_R is longer and the M²-factor is lower than that for the superposition of the intensity. For the two types of superposition, z_R increases and the M²-factor decreases with increase in beam coherence parameter, and both z_R and the M²-factor increase with increase in inverse radial fill-factor. For the superposition of the cross-spectral density function, z_R increases and the M²-factor decreases with increase in beam number, while for the superposition of the intensity both the z_R and M²-factor are independent of the beam number.     

Hard magnetic properties in Pr2Fe14B/α-Fe nanocomposite magnets with a combined addition of V and C

Nanostructured Pr₈Fe_86−xV_xB_6−yC_y (x=0, 1; y=0, 1) ribbons composed of Pr₂Fe₁₄B and α-Fe phases with a high coercivity are fabricated by direct melt spinning. The effects of a single addition of V and a combined addition of V and C on the structures and magnetic properties of melt-spun Pr₈Fe₈₆VB_6−xC_x (x=0 and 1) ribbons have been investigated. Compared with addition-free ribbons, 1 at% V addition is found to reduce the grain sizes of the samples and improve their magnetic properties due to a strong exchange coupling between the hard and the soft phase. A remanence ratio of 0.82, a coercive field of 6.2 kOe and a maximum energy product of 23.4 MGOe in melt-spun Pr₈Fe₈₅VB₆ ribbons are obtained at room temperature. The combined addition of V and C is found to lead to the formation of an intermediate phase of VC at grain boundaries, which appears as a pinning barrier during magnetization and results in an increase of the coercivity value to 6.9 kOe for melt-spun Pr₈Fe₈₅VB₅C ribbons.     

Surface modification of Mg2B2O5 whisker and its effect on the mechanical properties and thermostability of polycarbonate/Mg2B2O5w composites

The Mg₂B₂O₅ whiskers (Mg₂B₂O₅w) were modified by boric acid ester (BE) coupling agent and used to prepare polycarbonate (PC) composites. Surface wettability test and evaluation of dispersibility of BE-modified Mg₂B₂O₅w (BE-Mg₂B₂O₅w) in n-heptane were carried out by water contact angle measurement and polarizing microscopy, respectively. The surface chemical characteristics of BE-Mg₂B₂O₅w and estimation of the amount of tightly bonded organic modifier were examined by Fourier transform infrared spectrometry (FT-IR) and thermogravimetric analysis (TGA), respectively. The influence of BE-Mg₂B₂O₅w on the mechanical property, morphology and thermostability of PC composites was investigated by using universal testing machine, scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and TGA, respectively. It was found that BE was successfully grafted to the surface of Mg₂B₂O₅w, and the hydrophobic BE-Mg₂B₂O₅w leads to high ratio of adhesion work to interfacial tension between PC and BE-Mg₂B₂O₅w, and its better dispersibility in n-heptane. Furthermore, the incorporation of BE-Mg₂B₂O₅w into PC matrix resulted in higher tensile properties of PC/BE-Mg₂B₂O₅w than that of PC/Mg₂B₂O₅w composites and lower maximum weight loss rate than that of PC. The storage modulus of the PC/Mg₂B₂O₅w composites increased obviously as a function of whisker content, especially for the composites with BE-Mg₂B₂O₅w, but the T_g value changed little.     

Dependence on substrate bias of the effective mass and dingle temperature of electrons in the surface inversion layer of silicon

The amplitude of the quantum oscillations in the magnetoconductance of a silicon inversion layer has been studied as a function of gate voltage V_g, for different values of the temperature T, applied magnetic field strength H and substrate bias V_s. By analyzing the amplitude of the oscillations at fixed V_g and V_g as a function of T and H, the dependence of the cyclotron effective mass m¹ and the Dingle temperature T_D on V_g and V_s can be obtained. The dependence of m¹ on V_g for different values of V_s is compared with the prediction of theory.     

Theoretical investigation of the conduction and valence band offsets of GaAs1−x Nx/GaAs1−yNy heterointerfaces

Theoretical investigations of the conduction band offset (CBO) and valence band offset (VBO) of the relaxed and pseudo-morphically strained GaAs_1−xN_x/GaAs_1−yN_y heterointerfaces at various nitrogen concentrations (x and y) within the range 0-0.05 and along the [0 0 1] direction are performed by means of the model-solid theory combined with the empirical pseudopotential method under the virtual crystal approximation that takes into account the effects of the compositional disorder. It has been found that for y < x, the CBO and VBO have negative and positive signs, respectively, whereas the reverse is seen when y > x. The band gap of the GaAs_1−xN_x over layer falls completely inside the band gap of the substrate GaAs_1−yN_y and thus the alignment is of type I (straddling) for y < x. When y > x, the alignment remains of type I but in this case it is the band gap of the substrate GaAs_1−yN_y which is fully inside the band gap of the GaAs_1−xN_x over layer. Besides the CBO, the VBO and the relaxed/strained band gap of two particular cases: GaAs_1−xN_x/GaAs and GaAs_1−xN_x/GaAs_0.98N_0.02 heterointerfaces have been determined.     

Effect of Mn on the magnetic properties of Fe3B/Nd2Fe14B nanocomposites

The magnetic properties of Nd_4.5Fe_77−xMn_xB_18.5 (x=0, 1 and 2) nanocomposites prepared by the crystallization of amorphous precursors were investigated. Addition of Mn is found to decrease the crystallization temperature of the amorphous ribbons. The intrinsic coercivity _iH_c and maximum energy product (BH)_max increase from 2.6 kOe and 9.1 MGOe for x=0 to 3.1 kOe and 10.3 MGOe for x=1, respectively, and the remanence ratio M_r/M_s increases from 0.70 to 0.72. The effect of Mn on Curie temperature T_C and the thermal stability of M_r and _iH_c were also studied. ⁵⁷Fe Mössbauer spectra have been recorded for x=0, 1 and 2 ribbons at room temperature and site preference of the Mn atoms in Fe₃B and Nd₂Fe₁₄B phases is discussed using the Mössbauer spectroscopy.     

Symmetry enforced gauge invariance of nuclear magnetic shielding constants

E.S.R. experiments performed at 1·3 K by optical detection are reported for the photo-excited triplet state of palladiumporphin in a single crystal of n-octane, and the observation of a level anticrossing signal is described.

In the crystal the orbital degeneracy of the ³ E _u state of the free molecule is lifted by the crystal field and in n-octane the energy difference between the two orbital components |x> and |y> is found to be 58 ± 2 cm^-1. The spinorbit coupling (SOC) and the orbital Zeeman interaction couple the triplet manifolds of |x> and |y>, and for a proper understanding of the magnetic properties of these states it is necessary to work in the basis of the six spin-orbit functions deriving from the ³ E _u state of the free molecule. It is shown that either of the two triplet states can be described by an effective spin hamiltonian of the common form and expressions for the zero-field parameters D and E and the principal values of the g tensor are given. The experimental values of the parameters in the lowest triplet state are D = -24·38 ± 0·03 GHz, |E| = 320 ± 60 MHz, g _‖ = 1·677 ± 0·001 and g _⊥ = 1·989 ± 0·002. The matrix element of the SOC connecting the |x> and |y> triplet manifolds amounts to qZ = 15 ± 3 cm^-1 and the vibronic orbital angular momentum (in units of ?) in the ³ E _u state of the free molecule to qΛ = 1·5 ± 0·3. A tentative value of 0·63 for the orbital reduction factor q is obtained by comparison with a theoretical estimate of Λ. The value of q is indicative of weak Jahn-Teller coupling.