Mechanical and thermal properties of hot pressed neodymium-substituted britholite Ca9Nd(PO4)5(SiO4)F2

Neodymium-substituted britholite, a phosphate–silicate apatite Ca₉Nd(PO₄)₅(SiO₄)F₂, is considered as a potential host matrix for specific immobilization of radionuclides. Complementary investigations have been carried out to complete the database concerning this compound. The aim was to establish mechanical and thermal properties of dense britholite. Hot pressing was used to nearly fully densify the material. Low values of mechanical properties were found: 0.75 MPa m^1/2 for the fracture toughness and 95 MPa for the flexural strength. The Young's modulus and the Poisson's ratio were 108 GPa and 0.30, respectively. The specific and the thermal conductivity at 298 K were Cp=0.75 J g⁻¹ K⁻¹ and λ=1.15 W m⁻¹ K⁻¹. The average coefficient of thermal expansion in the 20–1000 °C temperature range was α=21×10⁻⁶ K⁻¹.     

Synthesis and characterization of Al2?xScx(WO4)3 ceramics for low-expansion infrared-transmitting windows

A low thermal-expansion material was synthesized with potential application in thermal-shock-resistant infrared-transmitting windows. The material is derived from a solid solution of Al₂(WO₄)₃, which has positive thermal expansion, and Sc₂(WO₄)₃ with a negative thermal expansion. An optimum composition of Al_0.5Sc_1.5(WO₄)₃ was identified by synthesizing solid solutions, Al_2−x Sc _x (WO₄)₃, by a solid-state route with compositions ranging from x = 0 to 2.0. A single orthorhombic phase was obtained at all compositions. A composition corresponding to x = 1.5 had a low coefficient of thermal expansion of −0.15 × 10⁻⁶/°C in the temperature range 25–700 °C. A low temperature solution combustion process was developed for this optimum composition, resulting in a single-phase powder with a surface area of ~14 m²/g and average particle size (as determined from surface area) of 92 nm. The powder was consolidated by slip-casting, sintering, and hot-isostatic pressing into visibly translucent disks with a peak in-line transmittance of 73 % at 2300 cm⁻¹. Significant infrared absorption in a 1-mm-thick disk of this material begins near 2200 cm⁻¹ and features three absorptions arising from 2-phonon transitions at 2002, 1847, and 1676 cm⁻¹. The infrared and Raman spectra are interpreted in terms of 1-, 2-, and 3-phonon vibrational transitions.     

Negative thermal expansion in Y2W3O12

Neutron diffraction data were collected on polycrystalline Y₂W₃O₁₂ at seven temperatures from 15 to 1373 K. All three cell edges of orthorhombic Y₂W₃O₁₂ decrease with increasing temperature, giving an average linear thermal expansion coefficient of −7.0×10⁻⁶ K⁻¹. Rietveld refinements of the neutron diffraction data show an apparent decrease in the average W–O distance of 0.05 Å from 15 to 1373 K. This apparent decrease causes the decrease in the cell edges, but it is not an actual decrease of average W–O distances. The apparent shrinkage is instead considered to be caused by the transverse thermal motion of oxygen in the Y–O–W linkages.     

Crystal structure and thermal annealing behaviors of high d 33 Aurivillius-phase ceramics Li0.04Ce0.04Na(0.46−x/2)Bi(4.46+x/2)Ti(4−x)Sc x O15 with the Sc3+/Bi3+ co-substitution

Modified Aurivillius-type-structured piezoelectric ceramics, Li_0.04Ce_0.04Na_(0.46?x/2)Bi_(4.46+x/2)Ti_(4?x)Sc _x O₁₅ (LiCe–NBT–Sc?x, x = 0, 0.025, 0.075, 0.125, 0.15, 0.175) were synthesized by using conventional solid-state reaction process. Rietveld refinement for the x = 0.125 modified sample was carried out by using powder X-ray diffraction and LiCe–NBT–Sc?0.125 was confirmed to be a four-layer Aurivillius oxide with orthorhombic space group A2 ₁ am [a = 5.45814(7) Å, b = 5.43029(7) Å, c = 40.8547(4) Å and V = 1,210.902(26) Å³; Z = 4], at room temperature. The Sc³⁺/Bi³⁺ substitution led to an increase in Curie temperatures (T _c) and an enhancement in piezoelectric property, and the LiCe–NBT–Sc?0.125 ceramic with a T _c of 675 °C had a high piezoelectric activity (d ₃₃) of 32 pC/N. Variable thermal-annealing d ₃₃ and resistivity (ρ) of the LiCe–NBT–Sc?0.125 ceramic were investigated; the d ₃₃ of the O₂ annealed sample reached up to 37 pC/N, and its resistivity was about 6.8 × 10⁶ Ω cm at 575 °C and about 6.5 × 10⁵ Ω cm at 650 °C.     

A study on the thermal expansion characteristics of Inconel-82® filler wire by high temperature X-ray diffraction

The lattice parameter (a) change with respect to temperature (T) has been measured by high temperature X-ray diffraction (HT-XRD) technique for Inconel-82®¹ filler wire used in the TIG welding of a dissimilar joint involving Inconel-600® and commercially pure iron. By taking proper precautions to minimise the temperature gradient across the sample thickness, and by suitably calibrating the shift in 2θ produced as a result of sample buckling at high temperatures, we could obtain fairly reliable estimates of lattice parameter in the temperature range 300–1200 K. The lattice parameter and the coefficient of mean linear thermal expansion at 300 K, have been found to be 3.546(2)×10⁻¹⁰ m and 11.03×10⁻⁶ K⁻¹, respectively.     

Tuning of crystal phase and luminescence properties of Gd2(MoO4)3:Dy3+ phosphors

The orthorhombic and monoclinic Gd₂(MoO₄)₃:Dy³⁺ were successfully synthesized by a hydrothermal process with a subsequent annealing treatment at 800 °C for 4 h. The crystal phase of Gd₂(MoO₄)₃:Dy³⁺ was controlled as a function of the pH value of the solution. The crystallization and microstructures of the samples were characterized by Powder X-ray diffraction (XRD) and scanning electron micrograph (SEM). Furthermore, the optical properties were investigated by the diffuse reflection, excitation and emission spectra. The mechanisms of different crystal phases affected on the luminescence properties of Gd₂(MoO₄)₃:Dy³⁺ were discussed. The electric dipole–dipole interaction between Dy³⁺ ions was identified as the main mechanism for the concentration quenching of the two structures. Finally, the chromatic natures of all the samples were analyzed in detail. The results indicate that the orthorhombic phosphor Gd_1.84(MoO₄)₃:Dy_0.16³⁺ can be considered as a suitable candidate for white light emitting diodes (W-LEDs).     

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.     

A zinc phosphate, [NH3(CH2)3NH3][Zn4(PO4)2(HPO4)2], possessing alternate inorganic and organic layers

A new zinc phosphate of the formula, [NH₃(CH₂)₃NH₃][Zn₄(PO₄)₂(HPO₄)₂], has been synthesized hydrothermally starting from a zinc amine complex. It crystallizes in the monoclinic space group C2/c; a=17.279(1), b=5.193(1), c=20.115(1) Å, β=92.6(1)°; V=1803.1(2) ų; Z=4; D_calc=2.05 g cm⁻³; μ (MoKα)=5.62 mm⁻¹. The final R, and wR₂=0.037, 0.093 obtained for 136 observed data [I>2σ(I)]. The structure consists of macroanionic sheets of interconnected ZnO₄ and PO₄ tetrahedra in the ab plane. The sheets are held together by hydrogen bond interactions with the organic structure-directing amine, forming alternate inorganic–organic layers in this material. Hydrogen bond interactions between the inorganic layers, via the terminal –OH group, leads to the formation of pseudo one-dimensional channels.     

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.     

Phase equilibria in the Tl2MoO4-Pr2(MoO4)3-Hf(MoO4)2 system and crystal structure of TlPr(MoO4)2

Subsolidus (450–480°C) phase relations in the Tl₂MoO₄-Pr₂(MoO₄)₃-Hf(MoO₄)₂ system have been studied by X-ray diffraction. The system has been shown to contain molybdates with the compositions Tl₅PrHf(MoO₄)₆ (5: 1: 2), TlPrHf_0.5(MoO₄)₃ (1: 1: 1), and Tl₂PrHf₂(MoO₄)_6.5 (2: 1: 4). Single crystals of the double molybdate TlPr(MoO₄)₂ have been grown for the first time from high-temperature solutions through spontaneous nucleation, and their crystal structure has been determined: tetragonal symmetry, sp. gr. P4/nnc, a = 6.3170(1) Å, c = 9.5529(2) Å, V = 381.204(12) ų, Z = 2.     

Hygroscopicity and bulk thermal expansion in Y2W3O12

Negative thermal expansion material, Y₂W₃O₁₂ has been synthesized by the solid-state method and bulk thermal expansion of the material has been investigated from 300 to 1100 K. The material reversibly forms a trihydrate composition whose X-ray diffraction pattern can be indexed to an orthorhombic unit cell with a = 10.098(1) Å, b = 13.315(3) Å, c = 9.691(4) Å. The cell volume of the hydrated pattern is 7% smaller than the unhydrated cell volume. According to the dilatometric studies, the material shows a 3-6% increase in the linear strain at about 400 K, which can be attributed to the removal of water. Sintering the material at 1473 K leads to large grain size of >100 μm, which results in a large hysteresis in the bulk thermal expansion behavior. Hot pressing at 1273 K under a uniaxial pressure of 25 MPa results in a fine-grained (2-5 μm) ceramic. Glazing the ceramic prevents moisture pick up and a linear thermal expansion over the entire temperature range 1100-300 K and an average linear thermal expansion co-efficient of −9.65 × 10⁻⁶/K is observed. The effect of water on the thermal expansion behavior of this system is discussed.     

Synthesis and properties of actinide dimolybdate complexes M<Subscript>2</Subscript>[AnO<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>]·H<Subscript>2</Subscript>O (M = Rb,Cs; An = Np,Pu)

New Np(VI) and Pu(VI) dimolybdates Rb₂NpO₂(MoO₄)₂·H₂O (I), Cs₂NpO₂(MoO₄)₂·H₂O (II), Cs₂PuO₂(MoO₄)₂·H₂O (III), and Rb₂PuO₂(MoO₄)₂·H₂O (IV) were synthesized under hydrothermal conditions. The crystal structures of the compounds were determined, and their absorption spectra in the UV, visible, and IR ranges were measured. The compounds crystallize in the monoclinic system. Their crystal structure is based on [AnO₂(MoO₄)₂]_n^2n– anionic layers (An = Np, Pu) formed by (AnO₂)O₅ pentagonal bipyramids and MoO₄ tetrahedra, sharing common vertices. Each An atom in the layer is bonded to other five An atoms via MoO₄ tetrahedra with the formation of a 4343² network. The effect of the ionic radius of the outer-sphere cation on the parameters of the crystal structure and features of the absorption spectra is discussed.     

Intense red-emitting phosphors for LED solid-state lighting

The phosphors Gd_2−xEu_x(MoO₄)₃ (x = 0.20, 0.40, 0.60, 0.80, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0), Gd_0.8−xY_xEu_1.2(MoO₄)₃ (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8) and Gd_0.2Y_0.6−xEu_1.2Sm_x(MoO₄)₃ (x = 0.02, 0.024, 0.028, 0.032, 0.036, 0.04) were prepared by solid-state reaction technique at 950 °C. The presence of the Y³⁺ and Sm³⁺ ions strengthen and broaden the absorption of the phosphors at ∼400 nm. The intense red-emitting phosphor Gd_0.2Y_0.572Eu_1.2Sm_0.028(MoO₄)₃ with orthorhombic structure was obtained. Both Eu³⁺ and Sm³⁺ f-f transition absorptions are observed in the excitation spectra, the main emission line is at 616 nm (⁵D₀ → ⁷F₂ transition of Eu³⁺) and the chromaticity coordinates (x = 0.66, y = 0.33) is very close to the NTSC standard values (x = 0.67, y = 0.33). It is considered to be an efficient red-emitting phosphor for GaN-based light emitting diode (LED).     

Oxygen nonstoichiometry, thermal expansion and high-temperature electrical properties of layered NdBaCo2O5+δ and SmBaCo2O5+δ

Layered LnBaCo₂O_5+δ (Ln = Nd, Sm) with the cation-ordered double perovskite structure were synthesized by the solid-state reaction route and characterized by X-ray diffraction, thermogravimetric analysis and dilatometry. For NdBaCo₂O_5.73 and SmBaCo₂O_5.61 equilibrated with atmospheric oxygen at low temperatures, tetragonal and orthorhombic polymorphs were found to form, respectively. The oxygen content at 300-1300 K decreases with decreasing rare-earth cation size, whilst δ variations and chemical contribution to the apparent thermal expansion in air are substantially lower compared to the disordered (Ln, A)CoO_3−δ (A = Ca, Sr) analogues. The average thermal expansion coefficients are 23.1 × 10⁻⁶ K⁻¹ for NdBaCo₂O_5+δ and 20.8 × 10⁻⁶ K⁻¹ for SmBaCo₂O_5+δ at 300-1370 K and atmospheric oxygen pressure. These values are comparable to those of Bi₂O₃-based ionic conductors, but are incompatible with common electrolytes such as stabilized zirconia or doped ceria. The oxygen partial pressure dependencies of the total conductivity and Seebeck coefficient, studied in the P(O₂) range from 10⁻¹⁰ to 1 atm, confirm predominant p-type electronic conductivity.     

Preparation of Eu3+-Y3+ co-doping red-emitting phosphors for white-light emitting diodes (W-LEDs) application and investigation of their optical characteristics

Eu³⁺-Y³⁺ co-doping Ca_0.54Sr_0.34?1.5x Eu_0.08Y _x (MoO₄) _y (WO₄)_1?y (x = 0.01, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20. y = 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0), have been prepared and their luminescent properties are investigated to seek a new red-emitting phosphor for ultraviolet-light emitting diodes chips. In absorption efficiency, luminescent intensity and chromaticity coordinates, Ca_0.54Sr_0.22(MoO₄)_0.2(WO₄)_0.8:0.08Eu³⁺, 0.08Y³⁺ phosphor is better than commercial Y₂O₂S:Eu³⁺ phosphor excited by 390?C405 nm light emitting diodes chip.     

Synthesis and properties of dielectric (HfO2)1 − x (Sc2O3) x films

(HfO₂)_{1 ? x} (Sc₂O₃) _x films have been grown by chemical vapor deposition (CVD) using the volatile complexes hafnium 2,2,6,6-tetramethyl-3,5-heptanedionate (Hf(thd)₄) and scandium 2,2,6,6-tetramethyl-3,5-heptanedionate (Sc(thd)₃) as precursors. The composition and crystal structure of the films containing 1 to 36 at % Sc have been determined. The results demonstrate that, in the composition range 9 to 14 at % scandium, the films are nanocrystalline and consist of an orthorhombic three-component phase, which has not been reported previously. Using Al/(HfO₂)_{1 ? x} (Sc₂O₃) _x /Si test structures, we have determined the dielectric permittivity of the films and the leakage current through the insulator as functions of scandium concentration. The permittivity of the films with the orthorhombic structure reaches k = 42–44, with a leakage current density no higher than ～10^?8 A/cm².     

Microwave dielectric properties of Bi(Sc<Subscript>1/3</Subscript>Mo<Subscript>2/3</Subscript>)O<Subscript>4</Subscript> ceramics for LTCC applications

A novel microwave dielectric ceramics Bi(Sc_1/3Mo_2/3)O₄ with low firing temperature were prepared via the solid reaction method. The specimens have been characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy and DC conductivity. The Bi(Sc_1/3Mo_2/3)O₄ ceramics showed B-site ordered Scheelite-type structure with space group C2/c. Raman analysis indicated that prominent bands were attributed to the normal modes of vibration of MoO₄ ^2? tetrahedra. The dielectric loss of Bi(Sc_1/3Mo_2/3)O₄ ceramics can be depended strongly the bulk conductivity by DC measurement. The superior microwave dielectric properties are achieved in the Bi(Sc_1/3Mo_2/3)O₄ ceramic sintered at 875 °C/4 h, with dielectric constant?~?25, Q?×?f ~?51,716 GHz at 6.4522 GHz and temperature coefficient of resonance frequency ~???70.4 ppm/°C. It is a promising microwave dielectric material for low-temperature co-fired ceramics technology.     

New data on rubidium vanadium phosphate: Structure determination of the disordered (VV–PV) compound Rb6(V2O3)2(VO)2(PO4)4(HP2−xVxO7) with x∼0.6

Brownish crystals of Rb₆(V₂O₃)₂(VO)₂(PO₄)₄(HP_2−xV_xO₇) were prepared hydrothermally. The structure was solved from single crystal X-ray diffraction data in the non centrosymmetric orthorhombic space group Pmn2₁ (No. 31) a=13.5505(2) Å, b=7.1407(2) Å, c=14.7040(2) Å. (R₁(Fo)=0.048, wR₂(Fo²)=0.111). The structure of Rb₆(V₂O₃)₂(VO)₂(PO₄)₄(HP_2−xV_xO₇) is closely related to the previously reported M₃(V₂O₃)(VO)(PO₄)₂(HPO₄) (M=K⁺, Tl⁺) with a disordered occupation of the tetrahedral voids by V^V and P^V atoms.     

Combined structural refinement of Bi4Ti3O12 using X-ray and neutron powder diffraction data

The combined structural refinement using X-ray and neutron powder diffraction data was carried out to determine the crystal system and to get the structural information of Bi₄Ti₃O₁₂. Of the two crystal systems, monoclinic and orthorhombic, the monoclinic system was more suitable than the orthorhombic one as a crystal system of Bi₄Ti₃O₁₂ at room temperature. The final weighted R-factor, R_wp, on the all data was 7.02% (R_wp=15.03% and 4.97% for X-ray and neutron powder diffraction data, respectively) and the goodness-of-fit indicator, S (=R_wp/R_e), was 1.16. The structural parameters of Bi₄Ti₃O₁₂, such as lattice parameters, atomic coordinates and isotropic thermal parameters, were successfully determined on the basis of the monoclinic crystal system. The lattice parameters obtained from the combined structural refinement were a=5.4483(1) Å, b=5.4092(1) Å and c=32.8111(4) Å. The remnant polarization (P_r) of Bi₄Ti₃O₁₂, 2P_r, showed 19.24 μC/cm².     

Dissociation energy of a Sc<Subscript>2</Subscript> molecule

The–(G°(T)–H°(0))/T Gibbs energy functions have been calculated for Sc₂ at Т = 2000 K in the context of recent data on the low-lying electron states for this kind of molecules. In particular, some recent experimental results on the vapor composition over scandium are presented in this study. The data on the measured scandium vapor composition have been processed using the evaluated Gibbs energy function values. The advised dissociation energy value for Sc₂ is found to be D°₀(Sc₂) = 7750 ± 1750 cm^–1.