Negative thermal expansion in silicalite-1 and zirconium silicalite-1 having MFI structure

In situ high temperature X-ray diffraction (HTXRD) studies on monoclinic silicalite-1 (S-1, silica polymorph of ZSM-5) and an orthorhombic metallosilicate molecular sieve, zirconium silicalite-1 (ZrS-1) with MFI structure (Si/Zr = 50) have been carried out using a laboratory X-ray diffractometer with an Anton Parr HTK 1600 attachment. While the structure of the S-1 collapsed at 1123 K forming α-cristobalite. S-1 and ZrS-1 showed a complex thermal expansion behavior in the temperature range 298–1023 K, ZrS-1 was stable. Powder X-ray diffraction (PXRD) data taken in this region have shown strong negative lattice thermal expansion coefficient, α_V = −6.75 × 10⁻⁶ and −17.92 × 10⁻⁶ K⁻¹ in the temperature range 298–1023 K⁻¹ for S-1 and ZrS-1 samples, respectively. The thermal expansion behavior of S-1 and ZrS-1 is anisotropic, with the relative strength of contraction along a axis is more than that along b and c axes. Three different thermal expansion regions could be identified in the overall temperature range (298–1023 K) studied, corroborating with the three steps of weight loss in the TG curve of ZrS-1 sample. While the region between 298 and 423 K, displays positive thermal expansion coefficient with α_V = 2.647 × 10⁻⁶ and 4.24 × 10⁻⁶ K⁻¹, the second region between 423 and 873 K shows strong negative thermal expansion (NTE) coefficient α_V = −7.602 × 10⁻⁶ and −15.04 × 10⁻⁶ K⁻¹, respectively, for S-1 and ZrS-1 samples. The region between 873 and 1023 K, shows a very strong NTE coefficient with α_V = −12.08 × 10⁻⁶ and −45.622 × 10⁻⁶ K⁻¹ for S-1 and ZrS-1, respectively, which is the highest in the whole temperature range studied. NTE seen over a temperature range 298–1023 K could be associated with transverse vibrations of bridging oxygen atoms in the structure which results in an apparent shortening of the Si–O distances.     

Flux growth and thermal properties of LiBaB9O15 single crystal

A large LiBaB₉O₁₅ single crystal has been grown by the top-seeded solution growth (TSSG) method using a Li₂Mo₃O₁₀ flux system. The crystal obtained exhibits (1 1 0), (1 1 3) and (1 0 2) faces. For the first time, thermal properties of the as-grown crystal, including thermal expansion, specific heat and thermal conductivity, have been investigated as a function of temperature. The specific heat of the LiBaB₉O₁₅ crystal was measured to be 0.663–1.110 J g^?1 K^?1 over the temperature range of 20–400 °C. The crystal exhibits thermal expansion along the a- and b-axis, coupled with thermal contraction along the c-axis, over the measured temperature range of 25–500 °C. The average thermal expansion coefficients along the a- and c-axis of the LiBaB₉O₁₅ crystal from 25 to 500 °C are calculated to be α_a = 6.56 × 10^?6 K^?1 and α_c = ?4.82 × 10^?6 K^?1, respectively.     

Spectroscopic properties of HoAl3(BO3)4 single crystal

The Judd–Ofelt theory has been applied to analyze absorption spectra of Ho³⁺ ion in HoAl₃(BO₃)₄ measured in spectral range 300–700 nm at room temperature. The Judd–Ofelt spectroscopic parameters have been determined as: Ω₂ = 18.87 × 10⁻²⁰ cm², Ω₄ = 17.04 × 10⁻²⁰ cm², Ω₆ = 9.21 × 10⁻²⁰ cm². These parameters have been used to calculate radiative lifetimes and branching ratios of the luminescence manifolds. Three luminescent bands were found in the spectral range 450–700 nm ascribed to transitions from the ⁵F₅, (⁵F₄, ⁵S₂) and ³K₈ states to the ground state ⁵I₈. Experimental intensities of these luminescence transitions were compared with those calculated by using Judd–Ofelt theory and the system of kinetic equations for populations of starting luminescing states. Probabilities of radiativeless transitions were evaluated from this comparison.     

Structure and magnetism in Pr3RuO7

The crystal structure of the ordered fluorite, Pr₃RuO₇, was refined from powder neutron diffraction data in Cmcm. An interesting structural feature is the presence of relatively well separated zig-zag chains of corner sharing RuO₆ octahedra, Ru–Ru interchain distance 6.61 Å vs. Ru–Ru intrachain distance of 3.76 Å. Magnetic susceptibility data show a Curie–Weiss behavior for T>225 K with C=5.96(4) emu K mol⁻¹ and θ_c=+11(2) K. In an attempt to separate the contributions of Pr(3+) and Ru(5+), the properties of isostructural Pr₃TaO₇ were also measured, yielding C=4.63(3) emu K mol⁻¹. Thus, the contribution of Ru(5+), 4d³, S=3/2, to the measured Curie constant is estimated to be 1.33 emu K mol⁻¹, not far from the spin-only value of 1.87 emu K mol⁻¹. This supports the view that the Ru 4d electrons are localized and magnetic, not itinerant. A susceptibility maximum at about 50 K is attributed to long-range magnetic order and this is substantiated by neutron diffraction data. There is little evidence for one-dimensional antiferromagnetic correlations in this material but behavior characteristic of short-range ferromagnetic correlations attributed to Pr–Ru exchange interactions are found in the temperature range 50–200 K, consistent with the positive θ_c.     

High-temperature electrical resistivity and heat capacity studies on nano-crystalline geikielite

We report here for the first time the temperature dependence of the electrical resistivity and heat capacity of nano-crystalline MgTiO₃ geikielite of up to 1000 K. The temperature dependence of heat capacity of nano-crystalline geikielite expressed as C_p = 46.44(5) + 0.0502(2)T − 4.56 × 10⁶T² + 1.423 × 10³T^− 0.5 − 8.672 × 10^− 6T^− 2, where C_p = is specific heat expressed in J/mol. K and T is the temperature in K. Both the electrical resistivity and heat capacity behaviour show that the geikielite (both the natural and synthetic nano-crystalline samples) are stable and remains electrically insulating up to 1000 K.     

Growth,thermal and optical properties of Yb:GdYAl3(BO3)4 crystal

Single crystal of Yb:GdYAl₃(BO₃)₄(Yb:GdYAB) has been grown by the flux method. The structure of Yb:GdYAB crystal has been determined by X-ray diffraction analysis. The experiment show that the crystal has the same structure as that of YAl₃(BO₃)₄ crystal and its unit cell constants have been measured to be a = 9.30146 Å, c = 7.24164 Å, Vol = 542.59 Å³. The absorption and fluorescence spectrum of Yb:GdYAl₃(BO₃)₄ crystal have also been measured at room temperature. In the absorption spectra, there are two absorption bands at 938 nm and 974 nm, respectively, which is suitable for InGaAs diode laser pumping. In the fluorescence spectra, there are two fluorescence peaks at 992 and 1040 nm. The thermal properties of Yb:GdYAl₃(BO₃)₄ crystal have been studied for the first time. The thermal expansion coefficient along c-axis is almost 5.4 times larger than that along a-axis. The specific heat of the crystal has been measured to be 0.77 J/g °C at room temperature. The calculated thermal conductivity is 5.26 Wm⁻¹ K⁻¹ along a-direction.     

Synthesis,crystal structure refinement,electrical and magnetic properties of BaV13O18 and SrV13O18

Polycrystalline samples of BaV₁₃O₁₈ and SrV₁₃O₁₈ were prepared by solid-state reaction of BaCO₃, SrCO₃, V₂O₅ and V at 1773–2073 K in flowing Ar. The crystal structures of BaV₁₃O₁₈ (R-3, a_h=12.6293(10) Å, c_h=7.0121(4) Å) and SrV₁₃O₁₈ (a_h=12.5491(7) Å, c_h=6.9878(3) Å) were refined by the Rietveld method using X-ray diffraction data. BaV₁₃O₁₈ exhibited semiconducting behavior with electrical resistivity from 5.8×10⁻³ to 2.7×10⁻³ Ω cm at 100–300 K. Electrical resistivity of SrV₁₃O₁₈ ranged from 1.5×10⁻³ to 1.8×10⁻³ Ω cm, and it increased slightly up to around 250 K and decreased above 250 K with increasing temperature. Negative Seebeck coefficients of both compounds at 100–300 K indicated that electron was the dominant carrier. BaV₁₃O₁₈ and SrV₁₃O₁₈ showed paramagnetism with the effective magnetic moment of 0.11μ_B and 0.15μ_B, respectively, at 10–100 K.     

Low energy implantation to inhibit wear in N+ ions implanted WC–Co composite

This work discusses the influence of nitrogen ion (N⁺) implantation on wear resistance of WC–Co composite. The WC–Co samples were bombarded at low N⁺ ions energies of 20 and 30 keV and doses of 10¹⁷ and 2 × 10¹⁷ ions cm⁻². Tribological tests were conducted against cylindrical 100Cr6 pin at 200 N load and 180 mm s⁻¹ speed. The tests use water lubrication and four sample types with Co binder content ranging in 6.5–25%. The X-ray spectra reveal that implantation is able to transform the original [CFC] Co structure of virgin surface to harder amorphous phase. However, it was found that excessive low binder content alters the wear behavior on non-implanted samples since it causes wear rate transition from 0.59 × 10⁻⁷ to 2.1 × 10⁻⁷ mm³/(mm² s) imposing hence instable wear regime. The SEM micrographs confirm the formation of transferred film within the implanted worn surface owing to (i) an enhancement in Co flow and (ii) a generation of oxides (Fe₂O₃, Fe₃O₄, Co₂O₃, WO₂). While the formed film acts to inhibit severe abrasion, the material removal process combining cobalt flow and carbide grains pull-out seems to be associated with oxidation mechanisms to be accentuated with energy increase. The most improvements in wear resistance were observed on samples with the highest Co content and the results were found more sensitive to N⁺ ions implantation energy than dose.     

An innovative process to fabricate copper/diamond composite films for thermal management applications

Diamond dispersed copper matrix (Cu/D) composite films with strong interfacial bonding were produced by tape casting and hot pressing without carbide forming additives. The tape casting process offers an original solution to obtain laminated materials with accurate thickness control, smooth surface finish, material net-shaping, scalability, and low cost. This study presents an innovative process of copper submicronic particles deposition onto diamond reinforcements prior to densification by hot pressing. Copper particles act as chemical bonding agents between the copper matrix and the diamond reinforcements during hot pressing, thus offering an alternative solution to traditionnal carbide-forming materials in order to get efficient interfacial bonding and heat-transfer in Cu/D composites. It allows high thermal performances with low content of diamond, thus enhancing the cost-effectiveness of the materials. Microstructural study of composites by scanning electron microscopy (SEM) was correlated with thermal conductivity and thermal expansion coefficient measurements. The as-fabricated films exhibit a thermal conductivity of 455 W m^?1 K^?1 associated to a coefficient of thermal expansion of 12 × 10^?6 °C^?1 and a density of 6.6 g cm^?3 with a diamond volume fraction of 40%, which represents a strong enhancement relative to pure copper properties (λ_Cu = 400 W m^?1 K^?1, α_Cu = 17 × 10^?6 °C^?1, ρ_Cu = 8.95 g cm^?3). The as-fabricated composite films might be useful as heat-spreading layers for thermal management of power electronic modules.     

Temperature influence on the voltage-controlled diffractive property of Mn-doped potassium sodium tantalate niobate crystal

We report the temperature influence on the voltage-controlled diffractive property of Mn-doped potassium sodium tantalate niobate crystal. The crystal was grown by the top seeded solution growth method. Its quadratic electro-optic coefficients achieved as high as R₁₁ = 3.50 × 10⁻¹⁵ m²/V² and R₁₂ = −0.44 × 10⁻¹⁵ m²/V² near the Curie temperature, while they declined with the increasing temperature. The external electric field which correspond to the maximum diffraction efficiency of photorefractive grating moved from 166 V/mm to 512 V/mm as the temperature increased from 25 °C to 32.5 °C. The maximum diffraction efficiencies all reached the maximum value of 60% at different temperatures. The results were discussed and compared with the theoretical equations.     

Investigation on third order nonlinear optical,electrical and surface properties of organic stilbazolium crystal of 4-N,N-dimethylamino-N′-methylstilbazolium p-methoxybenzenesulfonate

The third order nonlinear optical, electric and dielectric properties of an organic stilbazolium derivative of 4-N,N-dimethylamino-N′-methylstilbazolium p-methoxybenzenesulfonate (DSMOS) crystal are reported. The nonlinear refractive index (n₂), two photon absorption coefficient (β) and third order optical susceptibility χ⁽³⁾ have been measured by Z-scan technique using Gaussian beam from the Nd:YAG laser at 1064 nm. The results show a large negative nonlinear refractive index (n₂ = −1.122 × 10−9 cm²/W) with a molecular two photon absorption coefficient β value of 3.625 × 10⁻⁶ cm/W. The low dielectric constant observed in the high frequency region indicates the suitability of the sample for electro-optic applications. The surface features are also investigated by atomic force microscopy (AFM).     

EPR and optical absorption studies of Cr3+ doped lithium potassium sulphate single crystals

X-band electron paramagnetic resonance (EPR) studies of Cr³⁺ doped lithium potassium sulphate single crystals have been done at room temperature. The Cr³⁺ crystal field and spin Hamiltonian parameters have been evaluated by employing resonance line positions observed in the EPR spectra for different orientations of external magnetic field. The evaluated g, D and E values are: g_x = 2.0763 ± 0.0002, g_y = 1.9878 ± 0.0002, g_z = 1.8685 ± 0.0002 and D = 549 ± 2 × 10^?4 cm^?1, E = 183 ± 2 × 10^?4 cm^?1. Using EPR data the site symmetry of Cr³⁺ ion in the crystal is discussed. Cr³⁺ ion enters the lattice substitutionally replacing K⁺ site. The optical absorption study of the single crystal is also done in 195–925 nm wavelength range at room temperature. By correlating optical and EPR data the nature of bonding in the crystal is discussed. The calculated values of Racah parameters (B and C), crystal field parameter (D_q) and nephelauxetic parameters (h and k) are obtained as: B = 697, C = 3247, D_q = 2050 cm^?1, h = 1.146 and k = 0.21.     

Structural,optical, thermal,photoconductivity, laser damage threshold and fluorescence analysis of an organic material: β-P-amino benzoic acid single crystal

β-P-amino benzoic acid, an organic single crystal was grown by slow evaporation technique. Single crystal X-ray diffraction studies show that the grown crystal has β-polymorph of P-amino benzoic acid [β-PABA] form and the lattice parameters are a = 6.30 Å, b = 8.61 Å, c = 12.43 Å α = γ = 90° and β = 100.20°. FTIR analysis confirms that bands at 1588 cm⁻¹, 1415 cm⁻¹ are assigned to ring skeletal vibrations of title compound. The molecular structure of the grown crystal has been identified by Nuclear Magnetic Resonance spectral study. The optical absorbance spectrum from 200 to 1100 nm shows that there is an edge absorbance in UV region. Optical band gap of the crystal has been assessed from the absorbance spectrum. The thermal properties of crystals were evaluated from TG-DTA analysis, it exhibits that there is no weight loss up to 187 °C. Laser damage threshold indicates that the grown crystal has no surface damage up to 35 mJ. Photoconductivity and fluorescence spectral experiments are also carried out and the results are discussed.     

New quaternary alkali metal,rare earth (3+) thiophosphate,K2SmP2S7 with both [P2S6]4− and [PS4]3− anions

A new quaternary alkali metal, rare earth thiophosphate was synthesized by the ceramic method and characterized by single crystal X-ray diffraction: K₂SmP₂S₇ crystallizes in the monoclinic space group C2 (no. 5) with the unit cell parameters a = 22.746(5) Å, b = 6.7362(13) Å, c = 8.9004(18) Å, β = 99.68(3)°, V = 1344.3(5) Å³ and Z = 2. The phase K₂SmP₂S₇ can be better described as K₄Sm₂[PS₄]₂[P₂S₆] because it contains in the crystal structure both discrete anions [PS₄]^3? and [P₂S₆]^4?. The crystal structure consists of infinite chains of ¹_∞[SmPS₄] that are linked together through the ethane-like [P₂S₆]^4? anions to form two-dimensional layers. The packing of K₂SmP₂S₇ is formed by layers of ²_∞[Sm₂[PS₄]₂[P₂S₆]]^4? separated by K⁺ cations. K₂SmP₂S₇ was characterized by Raman and Fourier transform infrared (FTIR) spectroscopy and SEM-EDX microprobe analyses. The optical band gap of K₂SmP₂S₇ was determined by UV–vis diffuse reflectance measurements to be 2.59 eV.     

Friction and wear behavior of polytetrafluoroethene composites filled with Ti3SiC2

In this work, polytetrafluoroethylene (PTFE) composites filled with Ti₃SiC₂ or graphite were prepared through powder metallurgy. The effects of different filling components, loads and sliding velocities on the friction performance of Ti₃SiC₂/PTFE composites were studied. Ti₃SiC₂/PTFE composites exhibit better wear resistance than graphite/PTFE composites due to the better mechanical properties of Ti₃SiC₂. The wear resistance was found to improve around 100× over unfilled PTFE with the addition of 1 wt.% Ti₃SiC₂. In addition, the 10 wt.% sample had the lowest wear rate of K = 2.1 × 10⁻⁶ mm³/Nm and the lowest steady friction coefficient with μ = 0.155 at the condition of 90 N–0.4 m/s. Ti₃SiC₂ was proved to promote the formation of a thin and uniform transfer film on counterpart surface and a protection oxide film on worn surface, which are the key roles for improving wear resistance.     

Biopolymer-clay nanoparticles composite system (Chitosan-laponite) for electrochemical sensing based on glucose oxidase

Nanocomposite matrix based on chitosan/laponite was successfully utilized to construct a new type of amperometric glucose biosensor. This hybrid material combined the merits of organic biopolymer, chitosan, and synthesized inorganic clay, laponite. Glucose oxidase (GOD) immobilized in the material maintained its activity well as the usage of glutaraldehyde was avoided. The composite films were characterized by Fourier transform infrared (FT-IR). The parameters affecting the fabrication and experimental conditions of biosensors were optimized. The sensitivity of the proposed biosensor (33.9 mA M^− 1 cm^− 2) permitted the determination of glucose in the concentration range of 1 × 10^− 6–5 × 10^− 5 M with a detection limit of 0.3 μM based on S/N = 3. The apparent Michaelis–Menten constant (K_M^app) for the sensor was found to be 15.8 mM.     

Investigation of La3 + Doped Yb2Sn2O7 as new thermal barrier materials

Low thermal conductivity is one of the key requirements for thermal barrier coating materials. From the consideration of crystal structure and ion radius, La^3 + Doped Yb₂Sn₂O₇ ceramics with pyrochlore crystal structures were synthesized by sol–gel method as candidates of thermal barrier materials in aero-engines. As La^3 + and Yb^3 + ions have the largest radius difference in lanthanoid group, La^3 + ions were expected to produce significant disorders by replacing Yb^3 + ions in cation layers of Yb₂Sn₂O₇. Both experimental and computational phase analyses were carried out, and good agreement had been obtained. The lattice constants of solid solution (La_xYb_1 − x)₂Sn₂O₇ (x = 0.3, 0.5, 0.7) increased linearly when the content of La^3 + was increased. The thermal properties (thermal conductivity and coefficients of thermal expansion) of the synthesized materials had been compared with traditional 8 wt.% yttria stabilized zirconia (8YSZ) and La₂Zr₂O₇ (LZ). It was found that La^3 + Doped Yb₂Sn₂O₇ exhibited lower thermal conductivities than un-doped stannates. Amongst all compositions studied, (La_0.5Yb_0.5)₂Sn₂O₇ exhibited the lowest thermal conductivity (0.851 W·m^− 1·K^− 1 at room temperature), which was much lower than that of 8YSZ (1.353 W·m^− 1·K^− 1), and possessed a high coefficient of thermal expansion (CTE), 13.530 × 10^− 6 K^− 1 at 950 °C.     

Investigation of traps in AlGaN/GaN HEMTs by current transient spectroscopy

Deep levels in AlGaN/GaN HEMTs on Si substrate are known to be responsible for trapping processes like: threshold voltage shift, leakage current, degradation in saturation current and hysteresis effect. The related deep levels are directly characterized by Conductance Deep Level Transient Spectroscopy (CDLTS) method. Hereby we have detected four carrier traps with activation energy of 0.83, 0.50, 0.20 and 0.07 eV and capture cross-section respectively of σ = 3.14 × 10^− 14 cm², σ = 2.57 × 10^− 15 cm², σ = 3.03 × 10^− 17 cm² and σ = 2.65 × 10^− 15 cm². All these traps are located between the substrate and the two-dimensional electron gas (2DEG) channel.     

Electrical and thermal conductivity in Mg–5Sn Alloy at different aging status

The electrical conductivity, thermal conductivity and its relationship with the microstructure in Mg–5Sn alloy aged at 513 K for different aging times were investigated systematically in this paper. The results show that the electrical conductivity and thermal conductivity obviously increase with the increasing aging time, and its values increase from 10.25 × 10⁶ S·m^− 1 to 13.7 × 10⁶ S·m^− 1, 87.5 W·m^− 1·K^− 1 to 122 W·m^− 1·K^− 1 after aging treatment for 120 h, respectively. Meanwhile, it is found that there exist quite different relationships between unit cell volume and thermal conductivity in early and later aging stages.     

Structural and spectroscopic characteristics of Eu3+-doped tungsten phosphate glasses

Tungsten based phosphate glasses are interesting non-crystalline materials, commonly known for photochromic and electrochromic effects, but also promising hosts for luminescent trivalent rare earth ions. Despite very few reports in the literature, association of the host́s functionalities with the efficient emissions of the dopant ions in the visible and near-infrared spectra could lead to novel applications. This work reports the preparation and characterization of glasses with the new composition 4(Sb₂O₃)96−x(50WO₃ 50NaPO₃)xEu₂O₃ where x = 0, 0.1, 0.25, 0.5 and 1.0 mol%, obtained by the melt quenching technique. The glasses present large density (∼4.6 g cm⁻³), high glass transition temperature (∼480 °C) and high thermal stability against crystallization. Upon excitation at 464 nm, the characteristic emissions of Eu³⁺ ions in the red spectral region are observed with high intensity. The Judd–Ofelt intensity parameters Ω₂ = 6.86 × 10⁻²⁰, Ω₄ = 3.22 × 10⁻²⁰ and Ω₆ = 8.2 × 10⁻²⁰ cm² were calculated from the emission spectra and found to be higher than those reported for other phosphate glass compositions. An average excited state lifetime value of 1.2 ms, was determined by fitting the luminescence decay curves with single exponential functions and it is comparable or higher than those of other oxide glasses.