High‐pressure behavior of (Cs,K)Al4Be5B11O28 (londonite): A single‐crystal synchrotron diffraction study up to 26 GPa

The compressional behavior and the P‐induced deformation mechanisms at the atomic scale of (Cs,K)Al₄Be₅B₁₁O₂₈ (londonite, a ~7.31 Å and space group P3m) were investigated by in situ single‐crystal synchrotron X‐ray diffraction with a diamond anvil cell up to 26 GPa. No phase transition was observed within the P‐range investigated: this material exhibits isotropic compression (i.e., with cubic symmetry) in response to the applied pressure. Fitting the P–V data with a Birch‐Murnaghan isothermal equation of state, we obtained: V₀=390.8(3) ų, K_P0=212(7) GPa (β₀=1/K_P0=0.0047(1) GPa^?1) and K′=4.6(6). A series of structural refinements, based on the high‐pressure intensity data, were performed. The stiffness of londonite (similar to that of carbides) is governed by its close‐packing structure, and in particular by the very low compressibility of B‐ and Be‐tetrahedra and the modest compressibility of the Al‐octahedra. The Cs‐polyhedra are the most compressible units of the structure. The effects of pressure can be accommodated by intrapolyhedral compression or deformation, leading to a modest bulk compression. The high amount of boron in londonite (B₂O₃ ~50 wt%) makes its synthetic counterpart a potential neutron absorber. In addition, the high content of Cs makes londonite‐type materials as potential hosts for nuclear waste.     

Synthesis,Crystal Structure,and Thermal Behavior of 3‐(4‐Aminofurazan‐3‐yl)‐4‐(4‐nitrofurazan‐3‐yl)furazan (ANTF)

The energetic material 3‐(4‐aminofurazan‐3‐yl)‐4‐(4‐nitrofurazan‐3‐yl)furazan (ANTF) with low melting‐point was synthesized by means of an improved oxidation reaction from 3,4‐bis(4′‐aminofurazano‐3′‐yl)furazan. The structure of ANTF was confirmed by ¹³C NMR spectroscopy, mass spectrometry, and the crystal structure was determined by X‐ray diffraction. ANTF crystallized in monoclinic system P2₁/c, with a crystal density of 1.785 g cm⁻³ and crystal parameters a=6.6226(9) Å, b=26.294(2) Å, c=6.5394(8) Å, β=119.545(17)°, V=0.9907(2) nm³, Z=4, μ=0.157 mm⁻¹, F(000)=536. The thermal stability and non‐isothermal kinetics of ANTF were studied by differential scanning calorimetry (DSC) with heating rates of 2.5, 5, 10, and 20 K min⁻¹. The apparent activation energy (E_a) of ANTF calculated by Kissinger's equation and Ozawa's equation were 115.9 kJ mol⁻¹ and 112.6 kJ mol⁻¹, respectively, with the pre‐exponential factor lnA=21.7 s⁻¹. ANTF is a potential candidate for the melt‐cast explosive with good thermal stability and detonation performance.     

Synthesis,Crystal Structure,and Thermal Behaviors of 3‐Nitro‐1,5‐bis(4,4′‐dimethylazide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP)

The energetic material, 3‐nitro‐1,5‐bis(4,4′‐dimethyl azide)‐1,2,3‐triazolyl‐3‐azapentane (NDTAP), was firstly synthesized by means of Click Chemistry using 1,5‐diazido‐3‐nitrazapentane as main material. The structure of NDTAP was confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopy; mass spectrometry, and elemental analysis. The crystal structure of NDTAP was determined by X‐ray diffraction. It belongs to monoclinic system, space group C2/c with crystal parameters a=1.7285(8) nm, b=0.6061(3) nm, c=1.6712(8) nm, β=104.846(8)°, V=1.6924(13) nm³, Z=8, μ=0.109 mm⁻¹, F(000)=752, and D_c=1.422 g cm⁻³. The thermal behavior and non‐isothermal decomposition kinetics of NDTAP were studied with DSC and TG‐DTG methods. The self‐accelerating decomposition temperature and critical temperature of thermal explosion are 195.5 and 208.2 °C, respectively. NDTAP presents good thermal stability and is insensitive.     

γ‐FOX‐7: Structure of a High Energy Density Material Immediately Prior to Decomposition

1,1‐Diamino‐2,2‐dinitroethene, C₂H₄N₄O₄ (FOX‐7), is a novel high energy density material with low friction and impact sensitivity and a high activation barrier to detonation. In this study, the previously unknown crystal structure of the γ‐polymorph of trimorphic FOX‐7 is reported. γ‐FOX‐7 is stable from ∼435 K until the compound decomposes just above 504 K. A single crystal of α‐FOX‐7 (P2₁/n, Z=4, a=694.67(7) pm, b=668.87(9) pm, c=1135.1(1) pm, β=90.14(1)°, T=373 K) was first transformed into a single crystal of β‐FOX‐7 (P2₁2₁2₁, Z=4, a=698.6(1) pm, b=668.6(2) pm, c=1168.7(3) pm, T=423 K) and then into a single crystal of γ‐FOX‐7 at 450 K. The γ‐FOX‐7 crystal was then subsequently quenched to 200 K. The structure of γ‐FOX‐7 (P2₁/n, Z=8, a=1335.4(3) pm, b=689.5(1) pm, c=1205.0(2) pm, β=111.102(8)°, T=200 K) consists of four planar layers, each containing two crystallographically independent FOX‐7 molecules found in the asymmetric unit.     

High-pressure behavior and phase stability of Na2B4O6(OH)2·3H2O (kernite)

The high-pressure behavior of kernite [ideally Na₂B₄O₆(OH)₂·3H₂O, a ~ 7.02 Å, b ~ 9.16 Å, c ~ 15.68 Å, β = 108.9°, Sp Gr P2₁/c, at ambient conditions], an important B-bearing raw material (with B₂O₃ ≈ 51 wt%) and a potential B-rich aggregate in radiation shielding materials, has been studied by single-crystal synchrotron X-ray diffraction up to 14.6 GPa. Kernite undergoes an iso-symmetric phase transition at 1.6-2.0 GPa (to kernite-II). Between 6.6-7.5 GPa, kernite undergoes a second phase transition, possibly iso-symmetric in character (to kernite-III). The crystal structure of kernite-II was solved and refined. The isothermal bulk modulus (K_V0 = β^-1_P0,T0, where β_P0,T0 is the volume compressibility coefficient) of the ambient-pressure polymorph of kernite was found to be K_V0 = 29(1) GPa and a marked anisotropic compressional pattern, with K(a)₀: K(b)₀: K(c)₀~1:3:1.5., was observed. In kernite-II, the K_V0 increases to 43.3(9) GPa and the anisotropic compressional pattern increases pronouncedly. The mechanisms, at the atomic scale, which govern the structure deformation, have been described.     

Synthesis and Characterization of 3,4,5‐Triamino‐1,2,4‐Triazolium 5‐Nitrotetrazolate

3,4,5‐Triamino‐1,2,4‐triazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 3,4,5‐triamino‐1,2,4‐triazole (guanazine) ( 1 ) and ammonium 5‐nitrotetrazolate. The new compound 2 was characterized by vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N), elemental analysis and single crystal X‐ray diffraction (triclinic, P(‐1), a=0.7194(5), b=0.8215(5), c=0.8668(5) nm, α=75.307(5), β=70.054(5), γ=68.104(5)°, V=0.4421(5) nm³, Z=2, ϱ=1.722 g cm⁻¹, R₁=0.0519 [F>4σ(F)], wR₂(all data)=0.1154). The ¹⁵N NMR spectrum and X‐ray crystal structure (triclinic, P‐1, a=0.5578(5), b=0.6166(5), c=0.7395(5) nm, α=114.485(5)°, β=90.810(5)°, γ=97.846(5)°, V=0.2286(3) nm³, Z=2, ϱ=1.658 g cm⁻¹, R₁=0.0460 [F>4σ(F)], wR₂(all data)=0.1153) of 1 were also determined.     

Gel‐spinning of partially saponificated poly(vinyl alcohol)

DMSO/water (80/20 volume ratio) solutions of commercial poly(vinyl alcohol)s (a‐PVA₉₉, a‐PVA₈₈) with degrees of saponification of 99.3 and 88 mol % were gel‐spun into methanol (−20 and −70°C). The dry filaments obtained were drawn at 200°C (a‐PVA₉₉) and 150–180°C (a‐PVA₈₈). The maximum draw ratio and Young's modulus were 26 and 34 GPa for a‐PVA₉₉ and 21 and 24 GPa for a‐PVA₈₈ (drawing temperature: 160°C). So, at first, the dry filaments obtained for a‐PVA₈₈ were drawn at 150–180°C until 10 times their original length. Moreover, the predrawn a‐PVA₈₈ filaments were perfectly saponificated under fixing at the both ends and then the filaments were redrawn at 200°C. The maximum draw ratio and Young's modulus for the filaments (a‐PVA_88→99) predrawn at 150°C were 28 and 39 GPa, respectively. The a‐PVA_88→99 filaments had two melting peaks (228 and 236°C). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2872–2876, 2000     

Near‐Zero Thermal Expansion in In(HfMg)0.5Mo3O12

In(HfMg)_0.5Mo₃O₁₂, which can be considered as a 1:1 mole ratio solid solution of the low‐positive thermal expansion material HfMgMo₃O₁₂ and the low‐negative thermal expansion (NTE) material In₂Mo₃O₁₂ was prepared. From DSC and XRPD results, we show that In(HfMg)_0.5Mo₃O₁₂ exists in a monoclinic (P2₁/a) structure at low temperature and undergoes a phase transition at ~425 K to an orthorhombic phase (Pnma), with an associated enthalpy change of 0.89 kJ mol^?1. Thermal expansion is large and positive in the low‐temperature monoclinic phase (average α_? = 16 × 10^?6 K^?1 and 20 × 10^?6 K^?1, from dilatometry and XRPD, respectively). Remarkably, this material has a near‐zero thermal expansion (ZTE) coefficient over the temperature range ~500 to ~900 K in the high‐temperature orthorhombic phase, both intrinsically and for the bulk sample. The average linear intrinsic (XRPD) value is α_? = ?0.4 × 10^?6 K^?1, and the average bulk (dilatometric) value is α_? = 0.4 × 10^?6 K^?1 with an uncertainty of ± 0.2 × 10^?6 K^?1. The slight difference between intrinsic and bulk thermal expansion is attributed to microstructural effects. XRPD results show that the thermal expansion is more isotropic than for the parent compounds HfMgMo₃O₁₂ and In₂Mo₃O₁₂.     

Preparation and Molecular Structure of {[Ca(CHZ)2(H2O)](NTO)2⋅3.5H2O}n

The title compound {[Ca(CHZ)₂(H₂O)](NTO)₂⋅3.5H₂O}_n was synthesized by using an aqueous solution of calcium 3‐nitro‐1,2,4‐triazol‐5‐onate and carbohydrazide (CHZ, NH₂NHCONHNH₂). Its molecular structure was determined by X‐ray diffraction and its crystals have monoclinic form, with space group C2/c, where a=2.4483(4) nm, b=1.2581(2) nm, c =1.6269(3) nm, β=121.168(12)°, V=4.2879(13) nm³, Z=8, d_c=1.727 g⋅cm⁻³, μ (Mo K_α)=3.9 cm⁻¹, M=557.47, F(000)=2312. The coordination polyhedron is a tricapped trigonal prism in a tetradecahedron with a coordination number of nine. The whole molecule has many long chains formed through the carbohydrazide bridges, and every long chain is unlimited along the c axis. The long chains are linked by hydrogen bonds to form the crystal structure.     

Triazidotrinitro Benzene: 1,3,5‐(N3)3‐2,4,6‐(NO2)3C6

Triazidotrinitro benzene, 1,3,5‐(N₃)₃‐2,4,6‐(NO₂)₃C₆ ( 1 ) was synthesized by nitration of triazidodinitro benzene, 1,3,5‐(N₃)₃‐2,4‐(NO₂)₂C₆H with either a mixture of fuming nitric and concentrated sulfuric acid (HNO₃/H₂SO₄) or with N₂O₅. Crystals were obtained by the slow evaporation of an acetone/acetic acid mixture at room temperature over a period of 2 weeks and characterized by single crystal X‐ray diffraction: monoclinic, P 2₁/c (no. 14), a=0.54256(4), b=1.8552(1), c=1.2129(1) nm, β=94.91(1)°, V=1.2163(2) nm³, Z=4, ϱ=1.836 g⋅cm⁻³, R_all =0.069. Triazidotrinitro benzene has a remarkably high density (1.84 g⋅cm⁻³). The standard heat of formation of compound 1 was computed at B3LYP/6‐31G(d, p) level of theory to be ΔH°_f=765.8 kJ⋅mol⁻¹ which translates to 2278.0 kJ⋅kg⁻¹. The expected detonation properties of compound 1 were calculated using the semi‐empirical equations suggested by Kamlet and Jacobs: detonation pressure, P=18.4 GPa and detonation velocity, D=8100 m⋅s⁻¹.     

Synthesis of Al2O3/SiO2 nano‐nano composite ceramics under high pressure and its inverse Hall–Petch behavior

We report the synthesis of alumina/stishovite nano‐nano composite ceramics through a pressure‐induced dissociation in Al₂SiO₅ at a pressure of 15.6 GPa and temperatures of 1300°C‐1900°C. Stishovite is a high‐pressure polymorph of silica and the hardest known oxide at ambient conditions. The grain size of the composites increases with synthesis temperature from ~15 to ~750 nm. The composite is harder than alumina and the hardness increases with reducing grain size down to ~80 nm following a Hall–Petch relation. The maximum hardness with grain size of 81 nm is 23 ± 1 GPa. A softening with reducing grain size was observed below this grain size down to ~15 nm, which is known as inverse Hall–Petch behavior. The grain size dependence of the hardness might be explained by a composite model with a softer grain‐boundary phase.     

Synthesis,Thermal Decomposition,and Properties of [Mn(CHZ)3][C(NO2)3]2

A new coordination compound, [Mn(CHZ)₃][C(NO₂)₃]₂, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was determined by X‐ray single crystal diffraction. The crystal belongs to the triclinic system and space group with a=0.88737(18) nm, b=1.1804(2) nm, c=1.1936(2) nm, β=83.73(3)°, V=1.1121(4) nm³, Z=2, D_c=1.867 g cm⁻³. Every Mn(II) ion is six‐coordinated to three CHZ molecules through three carbonyl oxygen atoms and three terminal nitrogen atoms to form a distorted octahedral structure. Mn(II) ions, carbohydrazide ligand molecules, and trinitromethanide anions are jointed to a complicated three‐dimensional netted structure through coordination bonds, electrostatic forces, and extensive hydrogen bonds. The thermal decomposition character and mechanism was studied by DSC, TG‐DTG, and FTIR techniques. The non‐isothermal kinetics has also been studied on the exothermic decomposition by using Kissinger's method and Ozawa–Doyle's method. In addition, the impact, friction, and flame sensitivity data were determined. All properties data observed show that the title complex has high energy, good thermal stability, and moderately friction sensitivity.     

High temperature‐insensitive ferro‐/piezoelectric properties and nanodomain structures of Pb(In1/2Nb1/2)O3–PbZrO3–Pb(Mg1/3Nb2/3)O3–PbTiO3 relaxor single crystals

For rhombohedral (R) Pb(In_1/2Nb_1/2)O₃–PbZrO₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PZ–PMN–PT) relaxor single crystal, high temperature‐insensitive behaviors under different external stimuli were observed (remnant polarization P_r from 30°C to 180°C and piezoelectric strain d₃₃* from 30°C to 116°C). When electric field E ≥ 50 kV/cm in the case of an activation field E_a = 40‐50 kV/cm was applied, it was found that the domain switching was accompanied by a phase transition. The high relaxor nature of the R phase PIN–PZ–PMN–PT was speculated to account for the large E_a and high piezoelectric response. The short‐range correlation lengths extracted from the out‐of‐plane (OP) and in‐plane (IP) nanodomain images, were 64 nm and 89 nm, respectively, which proved the high relaxor nature due to In³⁺ and Zr⁴⁺ ions entering the B‐site in the ABO₃‐lattice and enhancing the disorder of B‐site cations in the R phase PIN–PZ–PMN–PT. The switching process of R nanodomain variants under the step‐increased tip DC voltage was visually revealed. Moreover, the time‐dependent domain evolution confirmed the high relaxor nature of the R phase PIN–PZ–PMN–PT single crystal.     

Synthesis and Characterization of 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) and silver 5‐nitrotetrazolate. Both new compounds ( 1, 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁴N, ¹⁵N), elemental analysis and single crystal X‐ray diffraction. 1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) represents the first example of an energetic material which contains both a tetrazole based cation and anion. Compound 2 is hydrolytically stable with a high melting point of 190 °C (decomposition). The impact sensitivity of compound 2 is very low (30 J), it is not sensitive towards friction (>360 N). The molecular structure of 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) in the crystalline state was determined by X‐ray crystallography: orthorhombic, F_ddd, a=1.3718(1) nm, b=1.4486(1) nm, c=1.6281(1) nm, V=3.2354(5) nm³, Z=16, ρ=1.979 g cm⁻¹, R₁=0.0169 (F>4σ(F)), wR₂ (all data)=0.0352.     

Low‐firing and temperature stable microwave dielectric ceramics: Ba2LnV3O11 (Ln = Nd,Sm)

Low‐firing and temperature stable microwave dielectric ceramics of Ba₂LnV₃O₁₁ (Ln = Nd, Sm) were prepared by solid‐state reaction. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate the phase purity, crystal structure, sintering behavior, and microstructure. The XRD patterns indicated that Ba₂LnV₃O₁₁ (Ln = Nd, Sm) ceramics belong to monoclinic crystal system with P2₁/c space group in the whole sintering temperature range (800°C ‐900°C). Both ceramics could be well densified at 880°C for 4 hours with relative densities higher than 96%. The Ba₂LnV₃O₁₁ (Ln = Nd, Sm) samples sintered at 880°C for 4 hours exhibited excellent microwave dielectric properties: ε_r = 12.05, Q × f = 23 010 GHz, τ_f = ?7.7 ppm/°C, and ε_r = 12.19, Q × f = 27 120 GHz, τ_f = ?16.2 ppm/°C, respectively. Besides, Ba₂LnV₃O₁₁ (Ln = Nd, Sm) ceramics could be well co‐fired with the silver electrode at 880°C.     

Microwave Dielectric Properties of Ultralow‐Temperature Cofirable Ba3V4O13 Ceramics

Ultralow‐temperature sinterable Ba₃V₄O₁₃ ceramics have been prepared through solid‐state ceramic route. Structural properties of the ceramic material are studied using powder X‐ray diffraction. Ba₃V₄O₁₃ ceramic has monoclinic structure and the existence of [V₄O₁₃]^6? polyhedra is confirmed through Laser Raman studies. The sample sintered at 600°C for 1 h shows dense microstructure with microwave dielectric properties of ε_r = 9.6, Q × f = 56 100 GHz, and τ_f = ?42 ppm/°C. The ceramics under study show good chemical compatibility with aluminum during cofiring.     

Enhanced Piezoelectric Properties of Praseodymium‐Modified Lead‐Free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 Ceramics

The role of Pr₆O₁₁ addition on the structure, microstructure, electrical, and electromechanical properties of lead‐free (Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ piezoelectric ceramics has been systemically investigated. Addition of praseodymium (Pr) results in improved ferroelectric and piezoelectric properties. XRD analysis revealed the co‐existence of rhombohedral (R) and tetragonal (T) phases at room temperature. High remanent polarization values (2P_r ~17 μC/cm²) and loop squareness of nearly 0.87 were obtained for the BCZT‐0.04 wt%Pr ceramic, along with high piezoelectric coefficient (d₃₃ = 435 pC/N) and transduction coefficient [(d₃₃·g₃₃) = 11589 × 10^?15 m²/N]. Results are correlated with the crystal structure and microstructure that significantly influence the ferroelectric and piezoelectric properties near the R–T phase transition point. This material seems to be especially suitable for energy harvesting applications, exhibiting outstanding figure of merit.     

Study on Crystal Structure and Thermal Decomposition Mechanism of a Novel Coordination Compound [Zn(DAT)2(H2O)4](PA)2⋅2H2O

A novel coordination compound [Zn(DAT)₂(H₂O)₄](PA)₂⋅2H₂O has been synthesized using 1,5‐diaminotetrazole (DAT) as ligands. It crystallizes in the monoclinic space group C2/c, with a=1.51973(19) nm, b=0.67904(9) nm, c=3.0712(4) nm, β=90.507(2)°, V=3.1692(7) nm³, Z=4, and μ=0.888 mm⁻¹. With the intermolecular hydrogen bonds, molecules are linked together to form a three‐dimensional net structure. Thermal decomposition mechanism of the title compound was predicted based on DSC, TG‐DTG, and FT‐IR analyses. The kinetic parameters of the first exothermic process of the title compound were studied applying the Kissinger's and Ozawa–Doyle's methods.