Dielectric and piezoelectric properties of sol–gel derived Ca doped PbTiO3

Synthesis of Ca doped PbTiO₃ powder by a chemically derived sol–gel process is described. Crystallization characteristics of different compositions Pb_1−xCa_xTiO₃ (PCT) with varying calcium (Ca) content in the range x = 0–0.45 has been investigated by DTA/TGA, X-ray diffraction and scanning electron microscopy. The crystallization temperature is found to decrease with increasing calcium content. X-ray diffraction reveals a tetragonal structure for PCT compositions with x ≤ 0.35, and a cubic structure for x = 0.45. Dielectric properties on sintered ceramics prepared with fine sol–gel derived powders have been measured. The dielectric constant is found to increase with increasing Ca content, and the dielectric loss decreases continuously. Sol–gel derived Pb_1−xCa_xTiO₃ ceramics with x = 0.45 after poling exhibit infinite electromechanical anisotropy (k_t/k_p) with a high d₃₃ = 80 pC/N, ′ = 298 and low dielectric loss (tan δ = 0.0041).     

Investigations of MX and γ′/γ″ precipitates in the nickel-based superalloy 718 produced by electron beam melting

Samples with a composition similar to the nickel-based superalloy Inconel alloy 718 were produced by electron beam melting of prealloyed powder and investigated with respect to type and composition of the strengthening precipitates. The matrix consists of γ grains orientated in nearly the same direction, almost like a single crystal. Coarse precipitates (<2 μm), mostly of the (Ti,Nb)(C,N,B) type with B1 structure, are aligned along the growth direction. TEM and APFIM investigations of the γ matrix revealed very fine γ″ precipitates of around 5–10 nm in size. Additionally, at small angle grain boundaries, coarser γ″ precipitates of 50–100 nm in size have been observed. The 0 01 γ//0 0 1 γ″ and {1 0 0} γ//{1 0 0} γ″ orientation relationship between γ and γ″, known from literature [M. Sundararaman, P. Mukhopadhyay, Mater. Charact. 31 (1993) 191–196], was confirmed. Some γ′ precipitates of 2–5 nm in size were observed by means of FIM.     

Crystal data and indirect optical transitions in Tl2InGaSe4 crystals

The room temperature crystal data and the optical properties of the Bridgman method grown Tl₂InGaSe₄ crystals are reported and discussed. The X-ray diffraction technique has revealed that Tl₂InGaSe₄ is a single phase crystal of monoclinic structure. The unit cell lattice parameters, which were recalculated from the X-ray data, are found to be a = 0.77244 nm, b = 0.64945 nm, c = 0.92205 nm and β = 95.03°. The temperature dependence of the optical band gap of Tl₂InGaSe₄ single crystal in the temperature region of 290–500 K has also been investigated. The absorption coefficient was calculated from the transmittance and reflectance data in the incident photon energy range of 1.60–2.10 eV. The absorption edge is observed to shift toward lower energy values as temperature increases. The fundamental absorption edge corresponds to indirect allowed transition energy gap of 1.86 eV that exhibited a temperature coefficient γ = −3.53 × 10⁻⁴ eV/K.     

Effects of heat treatments on the microstructures and mechanical properties of Mg–3Nd–0.2Zn–0.4Zr (wt.%) alloy

Microstructure and mechanical properties of as-cast and different heat treated Mg–3Nd–0.2Zn–0.4Zr (wt.%) (NZ30K) alloys were investigated. The as-cast alloy was comprised of magnesium matrix and Mg₁₂Nd eutectic compounds. After solution treatment at 540 °C for 6 h, the eutectic compounds dissolved into the matrix and small Zr-containing particles precipitated at grain interiors. Further aging at low temperatures led to plate-shaped metastable precipitates, which strengthened the alloy. Peak-aged at 200 °C for 10–16 h, fine β″ particles with DO₁₉ structure was the dominant strengthening phase. The alloy had ultimate tensile strength (UTS) and elongation of 300–305 MPa and 11%, respectively. Aged at 250 °C for 10 h, coarse β′ particles with fcc structure was the dominant strengthening phase. The alloy showed UTS and elongation of 265 MPa and 20%, respectively. Yield strengths (YS) of these two aged conditions were in the same level, about 140 MPa. Precipitation strengthening was the largest contributor (about 60%) to the strength in these two aged conditions. The hardness of aged NZ30K alloy seemed to correspond to UTS not YS.     

Effects of Sn content on the microstructure, phase constitution and shape memory effect of Ti–Nb–Sn alloys

The effect of Sn content on the microstructure, phase constitution and shape memory effect of Ti–16Nb–xSn (x = 4.0, 4.5, 5.0 at%) alloys were investigated by means of optical microscopy, X-ray diffraction, transmission electron microscopy and bending test. With the increase of Sn content, the β phase becomes stable. The solution-treated Ti–16Nb–4Sn alloy is composed of ″ and β phases at room temperature, whereas the solution-treated Ti–16Nb–5Sn alloy is only composed of β phase at room temperature. TEM observation shows that there is parallel lamellar ″ martensite with the substructure of () type I twin in the Ti–16Nb–4Sn alloy. There exists the dislocation wall inside the single β phase in the Ti–16Nb–5Sn alloy. The shape recovery ratio decreases with increasing the bending strain and the bending temperature, which is in correspondence with the different deformation mechanisms at different temperature ranges. The shape recovery ratio shows a decreasing trend with the increase of Sn content at the same bending strain and temperature. The maximum completely recovery strain is around 4%.     

Ultraviolet emitting (Y1−xGdx)2O3−δ thin films deposited by radio frequency magnetron sputtering: Combinatorial modeling, synthesis, and rapid characterization

Gadolinium-doped, yttrium oxide thin films have been deposited on silicon (001) substrates by radio-frequency (RF) magnetron reactive sputtering that exhibit cathodoluminescence (CL) at ultraviolet frequencies. The maximum CL brightness occurred at λ314–315 nm characteristic of the ⁶P_3 / 2 → ⁸S (λ = 314 nm) transition observed in Gd-doped, yttrium oxide powders. The radiative recombination takes place at the rare earth activator Gd³⁺ site embedded in the Y₂O_3−δ host; the optical transition resides within the band gap of the Y₂O_3−δ host and the transition observed is characteristic of atomic gadolinium. A combinatorial approach to sputtering was used to deposit a film of variable composition from 1 to 23 at.% Gd in Y₂O_3−δ in order to rapidly discern the composition node of optimal CL brightness. A simulation was created for the purpose of predicting the film combinatorial composition for binary and ternary alloys prior to sputtering experiments in order to facilitate our combinatorial thin film synthesis technique. The model prediction varied from the real experimental composition profile by only 2.2 at.% Gd ± 1.6 at.% proving the predictor as a useful aide to complement combinatorial thin film experiments. A film of composition Y_1.56Gd_0.44O_3.25 (8.3 at.% Gd) yielded the maximum CL brightness. CL brightness increased continuously up to the 8.3 at.% Gd composition due to the increased number of activators present in the host. Beyond this composition the brightness drastically decreased. The oxygen composition in the combinatorial film was strongly dependent on the Gd composition; films were sub-stoichiometric δ > 0 below 6 at.% Gd and was over-stoichiometric δ < 0 beyond this composition.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Fabrication of β-Si3N4 whiskers by combustion synthesis with MgSiN2 as additives

β-Si₃N₄ whiskers with diameter of 0.5–2 μm and aspect ratio of 10–15 have been successfully prepared by combustion synthesis under 30–50 atm nitrogen pressure. The addition of MgSiN₂ powder plays a significant role in the growth of β-Si₃N₄ whiskers. The as-prepared products were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Crystal structure and characterization of [2,5-(CH3O)2C6H3NH3]4P4O12·2H2O

The preparation, crystal structure, TG–DTA analysis and spectroscopy investigation are reported for the 2,5-dimethoxy phenyl ammonium cyclotetraphosphate dihydrate [2,5-(CH₃O)₂C₆H₃NH₃]₄P₄O₁₂·2H₂O. This new compound is triclinic P with unit cell dimensions: a = 7.438(5) Å, b = 11.841(7) Å, c = 12.354(4) Å,  = 96.61(4)°, β = 98.35(4)°, γ = 102.60(6)°, Z = 1 and V = 1038.0(1) Å³. Its crystal structure has been determined and refined to R = 0.049, with 5128 independant reflections. The structure can be described by rows of P₄O₁₂ ring anions along the a axis; between these rows are located the organic groups, connected to them by hydrogen bonds.     

Synthesis, structure refinement and characterization of tetrahydrated acid gadolinium diphosphate HGdP2O7·4H2O

Synthesis and single crystal structure are reported for a new gadolinium acid diphosphate tetrahydrate HGdP₂O₇·4H₂O. This salt crystallizes in the monoclinic system, space group P2₁/n, with the following unit-cell parameters: a = 6.6137(2) Å, b = 11.4954(4) Å, c = 11.377(4) Å, β = 87.53(2)° and Z = 4. Its crystal structure was refined to R = 0.0333 using 1783 reflections. The corresponding atomic arrangement can be described as an alternation of corrugated layers of monohydrogendiphosphate groups and GdO₈ polyhedra parallel to the () plane. The cohesion between the different diphosphoric groups is provided by strong hydrogen bonding involving the W4 water molecule.

IR and Raman spectra of HGdP₂O₇·4H₂O confirm the existence of the characteristic bands of diphosphate group in 980–700 cm⁻¹ area. The IR spectrum reveals also the characteristic bands of water molecules vibration (3600–3230 cm⁻¹) and acidic hydrogen ones (2340 cm⁻¹). TG and DTA investigations show that the dehydration of this salt occurs between 79 and 900 °C. It decomposes after dehydration into an amorphous phase. Gadolinium diphosphate Gd₄(P₂O₇)₃ was obtained by heating HGdP₂O₇·4H₂O in a static air furnace at 850 °C for 48 h.     

Crystal structure and spectroscopic studies of NaGd(PO3)4

Single crystals of gadolinium–sodium polyphosphate NaGd(PO₃)₄ were grown for the first time using a flux method and characterized by X-ray diffraction. This phosphate crystallizes in a monoclinic system with P2₁/n space group and with the following unit-cell dimensions: a = 9.767(3) Å, b = 13.017(1) Å, c = 7.160(2) Å, β = 90.564(5)°, V = 910.3(4) Å³ and Z = 4. The crystal structure was solved from 3451 X-ray independent reflections with final R(F²) = 0.0219 and R_w(F²) = 0.056 refined with 164 parameters (). The atomic arrangement can be described as a long chain polyphosphate organization. Two infinite (PO₃)∝ chains with a period of eight tetrahedra run along the [0 1 1] direction. The structure of NaGd(PO₃)₄ consists of GdO₈ polyhedra sharing oxygen atoms with phosphoric group PO₄. Each Na⁺ ion is bonded to eight oxygen atoms.     

Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

Synthesis of MoSi2–Al2O3 nanocomposite by mechanical alloying

MoSi₂–Al₂O₃ nanocomposite was synthesized by mechanical alloying (MA) of MoO₃, SiO₂ and Al powder mixture. The structural evolution of the powders was studied by X-ray diffraction (XRD). Both β-MoSi₂ and -MoSi₂ were obtained after 3 h of milling. The spontaneous formation of β-MoSi₂ during milling proceeded by a mechanically induced self propagating reaction (MSR), analogous to that of the self propagating high temperature synthesis (SHS). After 70 h of milling the β-phase transformed to -phase. The crystallite size of -MoSi₂ and Al₂O₃ after milling for 100 h was 12 and 17 nm, respectively. Residual Mo and Si in the 3 and 70 h milled samples formed β-MoSi₂ and Mo₅Si₃ during heating at 1000 °C, respectively.     

Sol–gel preparation of boron-containing cordierite Mg2(Al4−xBx)Si5O18 and its crystallization

Five cordierite-based powders were investigated regarding their thermal and crystallization behaviors. The powders were obtained from amorphous gels having nominal compositions of 2Mg : xAl : (4 − x)B : 5Si where x = 4 down to 0. Thermal gravimetry analysis of the dry gels showed some absorbed water and decomposition of organic ligands in addition to network condensation. Gradual substitution of B for Al in the dried gel powders showed a new band in their infrared spectra corresponding to triangular BO₃, whereas the bands corresponding to Al vanished. This also showed a noticeable effect on the crystallization trends, type and stability of cordierite. Cordierite crystallized in samples of B/Al ratio up to 1 while protoenstatite predominated in samples of higher B/Al ratios. In addition, some silica minerals, with little amorphous phase, were formed. Incorporation of boron and increase in temperature enhanced the transformation of γ cordierite to its form.     

Characterization of the thorium phosphate-hydrogenphosphate hydrate (TPHPH) and study of its transformation into the thorium phosphate-diphosphate (β-TPD)

The preparation of thorium phosphate-diphosphate (Th₄(PO₄)₄P₂O₇, TPD) was developed through the precipitation of thorium phosphate-hydrogenphosphate hydrate (Th₂(PO₄)₂(HPO₄)·H₂O, TPHPH) at 150–160 °C in closed PTFE container or in autoclaves. From EPMA analyses and SEM observations, the initial precipitate was single phase and multilayered. The behaviour of TPHPH (orthorhombic system with a = 21.368(2) Å, b = 6.695(1) Å and c = 7.023(1) Å) was followed when heating up to 1250 °C. It was first dehydrated leading to the anhydrous thorium phosphate-hydrogenphosphate (TPHP, orthorhombic system with a = 21.229(2) Å, b = 6.661(1) Å and c = 7.031(1) Å at 220 °C) after heating between 180 and 200 °C. This one turned progressively into the new low-temperature variety of TPD (called -TPD, orthorhombic system with a = 21.206(2) Å, b = 6.657(1) Å and c = 7.057(1) Å at 300 °C) correlatively to the condensation of hydrogenphosphate groups into diphosphate entities. These three phases (TPHPH, TPHP and -TPD) exhibit closely related 2D layered structures, therefore different from the 3D structure of the thorium phosphate-diphosphate (high-temperature variety). This latter compound, now called β-TPD, was obtained by heating -TPD above 950 °C. All the techniques involved in this study (XRD, Raman and IR spectroscopy, ¹H and ³¹P NMR) confirmed the successive chemical reactions proposed.     

YNixMn1−xO3 thin films by pulsed laser deposition: Structure and magnetic properties

Highly oriented YNi_xMn_1−xO₃ thin films on SrTiO₃ (100) substrates were achieved by using pulsed laser deposition for x = 0.33 and x = 0.50. We used a combination of X-ray diffraction, scanning electron microscopy, atomic force microscopy, and magnetic-property measurements. The magnetic transition temperatures (T_c) of the as-grown films are higher than the corresponding bulk values (typically 85 K instead of 80 K, for x = 0.5, and 60 K instead of 50 K, for x = 0.33). Our magnetic measurements also suggest a spin-glass characteristic in the x = 0.33 films, while a cluster glasslike behavior is observed for the films with x = 0.5, which is quite different from that of the bulk samples. Finally, the influence of post-deposition heat treatment on the magnetic properties of the as-grown films is discussed.     

Synthesis and crystal structure of [2-NH2-5-CH3C5H4N]4P4O12·6H2O

Chemical preparation, crystal structure, IR absorption and thermal analysis of a new cyclotetraphosphate [2-NH₂-5-CH₃C₅H₄N]₄P₄O₁₂·6H₂O are reported. This compound is triclinic P-1 with unit-cell parameters: a = 10.206(5), b = 11.778(1), c = 9.991(4) Å,  = 110.40(6), β = 117.74(6), γ = 86.41(3)°, V = 989.1(8) Å³, Z = 1, D_x = 1.445 g cm⁻³. The structure has been determined and refined to R = 0.034 and R_w = 0.044, using 3663 independent reflections. The ring anions and water molecules form layers spreading around (a, b + c) planes via OHO hydrogen bonds. Between them are anchored 2-amino-5-methylpyridium cations, which establish H-bonds to interconnect the different adjacent layers and so contribute to the cohesion of the three-dimensional network. Tautomerization of (C₆H₉N₂)⁺ groups was evidenced in the present structure.     

A study on the mechanical properties of cryorolled Al–Mg–Si alloy

The mechanical properties of a precipitation hardenable Al–Mg–Si alloy subjected to cryorolling and ageing treatments are reported in this present work. The severe strain induced during cryorolling of Al–Mg–Si alloys in the solid solutionised state produces ultrafine microstructures with improved mechanical properties such as strength and hardness. The improved strength and hardness of cryorolled alloys are due to the grain size effect and higher dislocation density. The ageing treatment of cryorolled Al–Mg–Si alloys has improved its strength and ductility significantly due to the precipitation hardening and grain coarsening mechanisms, respectively. The reduction in dimple size of cryorolled Al–Mg–Si alloy upon failure confirms the grain refinement and strain hardening mechanism operating in the severely deformed samples.