Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)]

A new iron phosphonate-oxalate [Fe(O₃PCH₃)(C₂O₄)_0.5(H₂O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO₆ octahedra and O₃PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.851(2) Å, b = 16.803(7) Å, c = 7.941(4) Å, β = 107.516(6)°, V = 617.2(5) Å³, Z = 4, R₁ = 0.0337 and wR₂=0.0874 for 1251 reflections [I > 2σ(I)]. Mössbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T_N = 30 K due to a weak spin canting.     

Effect of aggregate size on the fracture and mechanical properties of a simple concrete

The influence of the aggregate size on the fracture energy, tensile strength and elasticity modulus in different types of concrete are analyzed. For this purpose, nine simple cement-based composites have been designed, manufactured and tested, with one objective to provide experimental results that can be used as a benchmark for checking numerical models of concrete fracture, as this simple composite (a matrix, spherical aggregates of the same radius, and two types of matrix-aggregate interface) is amenable to modelling. All in all, 44 specimens were tested. From notched beam tests, values of the fracture energy and modulus of elasticity were obtained. The tensile stress was deduced from indirect standard tensile test. Data for bilinear softening functions extracted from the experimental measurements are also provided. Comparison with available experimental data is also included and discussed.     

Structural, thermal, magnetic and electrical studies of the iron oxophosphate Rb7Fe7(PO4)8O2·2H2O

A new iron oxophosphate of composition Rb₇Fe₇(PO₄)₈O₂·2H₂O has been synthesized and studied by X-ray diffraction, TG and DTA analysis, magnetic susceptibility, neutron diffraction, Mössbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic system with the P2₁/c space group and the unit cell parameters a = 8.224(8) Å, b = 22.162(6) Å, c = 9.962(6) Å and β = 109.41(8)°. Its structure is built up from Fe₇O₃₂ clusters of edge- and corner-sharing FeO₅ and FeO₆ polyhedra. Neighboring clusters are connected by the phosphate tetrahedra to form a three-dimensional framework. The Rb⁺ cations and the water molecules are occupying intersecting tunnels parallel to a and c. The presence of water molecules was confirmed by TG and DTA analysis. The magnetic susceptibility measurements have shown the existence of antiferromagnetic ordering below 22 K with a weak ferromagnetic component. Additionally, these measurements show evidence for a strong magnetic frustration characterized by |θ/T_N| ≈ 12. Powder neutron diffraction study confirms the presence of a long range antiferromagnetic order coupled to a weak ferromagnetic component along the b-axis. The strongly reduced magnetic moments extracted from the refinement support the existence of a magnetically frustrated ground state. The Mössbauer spectroscopy results confirmed the presence of only Fe³⁺ ions in both five and six coordination. The ionic conductivity measurements led to activation energy of 0.81 eV, a value that agrees with the obtained for other rubidium phosphates.     

Fracture behavior and mechanism of 2D C/SiC-BCx composite at room temperature

2D C/SiC composite was modified with partial BC_x matrix by low pressure chemical vapor infiltration technique (LPCVI), which was named as 2D C/SiC-BC_x composite. The flexural fracture behavior, mechanism, and strength distribution of 2D C/SiC-BC_x composite are investigated. The results indicate that the flexural strength, fracture toughness, and fracture work are 442.1 MPa, 22.84 MPa m^1/2, and 19.2 kJ m⁻², respectively. The flexural strength of C/SiC-BC_x composite decrease about 20% than that of C/SiC composite. However, the fracture toughness and fracture work increase about 19% and 18.5%, respectively. The properties varieties between C/SiC-BC_x composite and C/SiC composite can be attributed to the weak-bonding interface between BC_x/SiC matrices according to the results of detailed microstructure analysis. The strength distribution of 2D C/SiC-BC_x composite follows as Normal distribution or Weibull distribution with σ_u = 0, and m = 8.1393. The mean value of flexural strength for 2D C/SiC-BC_x composite is 443 MPa obtained by theory calculation, which is consistent with experiment result (442.1 MPa) very well.     

Modeling motivation and habit in driving behavior under lifetime driver's license revocation

The purpose of the present study was to verify the motivational factors underlying the theory of planned behavior (TPB) predicting the driving behavior of lifetime driving license revoked offenders. Of a total of 639 drivers whose licenses had been permanently revoked, 544 offenders completed a questionnaire constructed to measure attitudes toward behaviors, subjective norms, perceived behavioral control, behavioral intentions (the key constructs of the TPB), and previous driving habit strength. The finding of the study revealed that an offenders’ driving behavior after a lifetime license revocation was significantly correlated to behavioral intention (R = 0.60, p < 0.01), perceived behavioral control (R = 0.61, p < 0.01), previous driving habit (R = 0.44, p < 0.01), and attitude (R = 0.41, p < 0.01). There was no evidence that subjective norms including road regulation, society ethics, and people important to offenders had an influence on driving behavior (R = 0.03). Low driving habit strength offenders are motivated to drive because of behavioral intention, whereas strong driving habit strength offenders are motivated to drive because of perceived behavioral control. Previous driving habit strength is a moderator in the intention–behavior relationship. The model appeared successful when previous habits were weak, but less successful when previous habits were strong.     

2D-network of inorganic-organic hybrid material built on Keggin type polyoxometallate and amino acid: [L-C2H6NO2]3[(PO4)Mo12O36]·5H2O

A new inorganic-organic hybrid material based on polyoxometallate, [L-C₂H₆NO₂]₃[(PO₄)Mo₁₂O₃₆]·5H₂O, has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2₁/c_, with a = 12.4938 (8) Å, b = 19.9326 (12) Å, c = 17.9270 (11) Å, β = 102.129 (1)°, V = 4364.8 (5) Å³, Z = 4 and R₁(wR₂) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/∞ [(PO₄)Mo₁₂O₃₆]³⁻) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO₄)Mo₁₂O₃₆]³⁻ appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 °C.     

Co0.5TiOPO4: Crystal structure, magnetic and electrochemical properties

The new titanium oxyphosphate Co_0.5TiPO₅ has been prepared by solid state reaction. Its structure has been determined by single crystal X-ray diffraction and was further investigated by FT-IR spectroscopy and magnetic measurements. The compound crystallizes in the monoclinic system, S.G: P2₁/c [a = 7.358(1) Å, b = 7.378(2) Å, c = 7.383(3) Å, β = 119.66(3)°, Z = 4, R₁ = 0.0142, wR₂ = 0.0429]. The structure can be described as a network of very distorted TiO₆ octahedra, in which the Ti⁴⁺ ions are displaced from the centres of the octahedra, and slightly distorted PO₄ tetrahedra. Half of the octahedral cavities are occupied by Co atoms. The other half of octahedral sites is vacant and favourable for the electrochemical insertion of lithium. The insertion of lithium was studied by galvanostatic charging and discharging between different voltage limits.     

Hypervelocity penetration of concrete

Experiments have been conducted with 6.25 mm diameter tungsten rods striking concrete at 2.2 km/s. Three concretes were used—one was 2.35 g/cm³ and the other two were 2.27 g/cm³. The erosion rates were measured to be T/ΔL = 2.4–3.1 depending on the density of the concrete. This is greater than the hydrodynamic value, which shows that the strength of the penetrator is affecting the penetration. The cratering efficiency was computed (which included surface spall) and was found to be commensurate with the strength of the concrete, 28–34 MPa. CTH calculations were conducted using the brittle fracture kinetics (BFK) and Holmquist–Johnson–Cook (HJC) material models for concrete. Density in the calculations was 2.25 g/cm³. It was not possible to match erosion rates at 2.2 km/s, which were too high in the calculations. Also, computed crater volumes were much too small, mainly due to spall in the experiments that was not shown in the computations. Another significant inaccuracy of the calculations was the damage extent, which became unrealistically widespread as time increased in the BFK model.     

Evaluation of elastic/mechanical properties of some glasses and nanocrystallized glass by cube resonance and nanoindentation methods

Elastic and mechanical properties of 10La₂O₃·30Bi₂O₃·60B₂O₃ (LaBiB) glass, 15K₂O·15Nb₂O₅·68TeO₂·2MoO₃ (KNbTeMo) glass and a transparent KNbTeMo nanocrystallized (particle size: ∼40 nm) glass were examined using cube resonance and nanoindentation methods. The values of Poisson’s ratio, Young’s modulus (E), Debye temperature (θ_D), fractal bond connectivity, Martens hardness, indentation hardness, indentation Young’s modulus, elastic recovery, Vickers hardness, fracture toughness (K_c) and brittleness for the samples were evaluated, and the relation with the structure and nanocrystallization were clarified. LaBiB glass containing high oxygen-coordinated La³⁺ ions and two-dimensional BO₃ structural units shows excellent properties of E=90.6 GPa, θ_D=404 K and K_c=0.72 MPa m^1/2 and a high resistance against deformation during Vickers indentation. KNbTeMo glass with the three-dimensional network structure and consisting of weak Te-O bonds has small values of E=51.4 GPa and K_c=0.29 MPa m^1/2. It was demonstrated that the elastic and mechanical properties of KNbTeMo precursor glass are largely improved by nanocrystallization, e.g., E=69.7 GPa and K_c=0.32 MPa m^1/2. The nanocrystallization also induces a high resistance against deformation during Vickers indentation.     

Structural phase evolution in Bi7/8Ln1/8FeO3 (Ln = La-Dy) series

Regularities of the structural phase evolution associated with changing ionic radius of the A-site dopants in Bi_7/8Ln_1/8FeO₃ (Ln = La-Dy) series were investigated by X-ray diffraction technique at room temperature. A strong tendency to the structural phase separation was found. Initial polar rhombohedral R3c structure characteristic of pure bismuth ferrite is retained only for La-doped compound. For most other samples, intrinsic polar-antipolar R3c + Pnam (Ln = Pr, Nd, Sm), antipolar-nonpolar Pnam + Pnma (Ln = Gd), or polar-nonpolar R3c + Pnma (Ln = Tb, Dy) phase coexistence was revealed. Investigation of temperature evolution of crystal structure of La-doped compound performed with a neutron powder diffraction technique found that its high-temperature paraelectric phase had the orthorhombic Pnma symmetry.     

Synthesis and characterization of a new 2,4,6-triaminopyridinium dihydrogendiphosphate dihydrate (C4H8N5)2H2P2O7·2H2O

Structural properties of the 2,4,6-triaminopyridinium dihydrogendiphosphate dihydrate are discussed on the basis of an X-ray structure investigation. (C₄H₈N₅)₂H₂P₂O₇·2H₂O is monoclinic, C2/c, with a = 10.414(1) Å, b = 13.365(1) Å, c = 13.736(2) Å, β = 98.39(4)°, and Z = 4. The structure has been solved by a direct method and refined to a reliability R factor of 0.0375 (R_w = 0.0961) using 2751 independent reflections. The structural arrangement can be described as inorganic infinite ribbons, , spreading along the c direction; the organic groups, [C₄H₈N₅]⁺, link the precedent ribbons, via their hydrogen bonds, to form a three-dimensional network. The present work, deals with crystal structure, thermal behavior and IR analysis of this new compound.     

Synthesis and characterization of a new monophosphate (5-Cl-2,4-(OCH3)2C6H2NH3)H2PO4

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation 5-chloro(2,4-dimethoxy)anilinium monophosphate H₂PO₄ are given. This new compound crystallizes in the monoclinic system, with the space group P2₁/c and the following parameters: a = 5.524(2) Å, b = 9.303(2) Å, c = 23.388(2) Å, β = 90.66(4), V = 1201.8(2) Å³, Z = 4 and D_x = 1.573 g cm⁻³. Crystal structure has been determined and refined to R = 0.031 and R_w = 0.080 using 1702 independent reflections. Structure can be described as an infinite (H₂PO₄)_nⁿ⁻ corrugated chains in the a-direction. The organic groups (5-Cl-2,4-(OCH₃)₂C₆H₂NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. This compound is also investigated by IR, thermal, and solid-state, ¹³C, ³¹P MAS NMR spectroscopies.     

Crystal growth and structure refinement of monoclinic Li2TiO3

Colorless platelet crystals of monoclinic Li₂TiO₃ with a maximum size of 5.0 mm × 5.0 mm × 0.5 mm were successfully grown by a flux method at 1373 K using a LiBO₂-Li₂O system flux. The stoichiometric chemical composition of Li₂TiO₃ was determined by the SEM-EDX, ICP-AES and density measurement using the single crystal samples. The thermal conductivity of the Li₂TiO₃ single crystals was evaluated using hot-disk method. A single-crystal X-ray diffraction study confirmed the monoclinic Li₂SnO₃-type structure, space group C2/c and the lattice parameters of a = 5.0623(5) Å, b = 8.7876(9) Å, c = 9.7533(15) Å, β = 100.212(11)°, and V = 427.01(9) Å³. The crystal structure was refined to the conventional values of R = 2.4% and wR=3.3% for 2187 independent observed reflections. The cationic arrangement of (LiTi₂) layers in Li₂TiO₃ was precisely revealed by the structure analysis.     

Transformation of Dion-Jacobson phase to Aurivillius phase: synthesis of (PbBiO2)MNb2O7 (M = La, Bi)

We describe transformations of the Dion-Jacobson (D-J) phases, KLaNb₂O₇ and RbBiNb₂O₇, to the Aurivillius (A) phases, (PbBiO₂)LaNb₂O₇ (1) and (PbBiO₂)BiNb₂O₇ (2), in a metathesis reaction with PbBiO₂Cl. Oxide 1 adopts centrosymmetric tetragonal structure (a = 3.905(1) Å, c = 25.66(1) Å), whereas oxide 2 crystallizes in a noncentrosymmetric orthorhombic (A2₁am) (a = 5.489(1) Å, b = 5.496(2) Å, c = 25.53(1) Å) structure. Oxide 2 shows a distinct SHG response towards 1064 nm laser radiation. The role of La³⁺ versus Bi³⁺ in the perovskite slabs for the occurrence of noncentrosymmetric structure/ferroic property in these materials is pointed out.     

Evaluation of fracture parameters of concrete from bending test using inverse analysis approach

In this study, an inverse analysis approach is developed to obtain the fracture parameters of concrete, including stress–crack opening relationship, cracking and tensile strength as well as fracture energy, from the results of a three-point bending test. Using this approach, the effects of coarse aggregate size (5–10, 10–16, 16–20 and 20–25 mm) and matrix strength (compressive strength of 40 and 80 MPa, respectively) on the fracture parameters are evaluated. For normal strength concrete, coarse aggregate size and cement matrix strength significantly influence the shape of σ–w curve. For a given total aggregate content, small aggregate size leads to a high tensile strength and a sharp post-peak stress drop. The smaller the coarse aggregate, the steeper is the post-peak σ–w curve. By contrast, in high strength concrete, a similar σ–w relationship is obtained for various aggregate sizes. The post-peak stress drop for high strength concrete is more abrupt than that for normal strength concrete. Also, the smaller the coarse aggregate size, the higher is the flexural strength. For both normal and high strength concrete, fracture energy and characteristic length are found to increase with increase of coarse aggregate size.     

Compressive fracture behavior of Cu-based bulk amorphous alloys

The mechanical properties of newly developed Cu_52.5 − xTi₃₀Zr_11.5Ni₆Al_x (x = 0, 1, 1.5, 2 at.%) bulk amorphous alloys were investigated under compressive condition. They exhibit high fracture strength of 2212 MPa, 2165 MPa, 2209 MPa and 2286 MPa, respectively. Three distinct vein patterns corresponding to the different zones can be observed on the fracture surfaces of the samples. Fracture propagation along two different directions and formation of striated vein patterns may contribute to the higher compressive fracture strength of the tested Cu-based bulk amorphous alloys.     

Structural characterization, thermal, spectroscopic and magnetic studies of the (C3H12N2)0.75[Mn1.50Fe1.50(AsO4)F6] and (C3H12N2)0.75[Co1.50Fe1.50(AsO4)F6] compounds

The (C₃H₁₂N₂)_0.94[Mn_1.50Fe_1.50^III(AsO₄)F₆] and (C₃H₁₂N₂)_0.75[Co_1.50Fe_1.50^III(AsO₄)F₆] compounds 1 and 2 have been synthesized using mild hydrothermal conditions. These phases are isostructural with (C₃H₁₂N₂)_0.75[Fe_1.5^IIFe_1.5^III(AsO₄)F₆]. The compounds crystallize in the orthorhombic Imam space group. The unit cell parameters calculated by using the patterns matching routine of the FULPROOF program, starting from the cell parameters of the iron(II),(III) phase, are: a = 7.727(1) Å, b = 11.047(1) Å, c = 13.412(1) Å for 1 and a = 7.560(1) Å, b = 11.012(1) Å, c = 13.206(1) Å for 2, being Z = 8 in both compounds. The crystal structure consists of a three-dimensional framework constructed from edge-sharing [M^II(1)₂O₂F₈] (M = Mn, Co) dimeric octahedra linked to [Fe^III(2)O₂F₄] octahedra through the F(1) anions and to the [AsO₄] tetrahedra by the O(1) vertex. This network gives rise two kinds of chains, which are extended in perpendicular directions. Chain 1 is extended along the a-axis and chain 2 runs along the c-axis. These chains are linked by the F(1) and O(1) atoms and establish cavities delimited by eight or six polyhedra along the [1 0 0] and [0 0 1] directions, respectively. The propanediammonium cations are located inside these cavities. The thermal study indicates that the structures collapse with the calcination of the organic dication at 255 and 285 °C for 1 and 2, respectively. The Mössbauer spectra in the paramagnetic state indicate the existence of two crystallographically independent positions for the iron(III) cations and a small proportion of this cation in the positions of the divalent Mn(II) and Co(II) ones. The IR spectrum shows the protonated bands of the H₂N- groups of the propanediamine molecule and the characteristic bands of the [AsO₄]³⁻ arsenate oxoanions. In the diffuse reflectance spectra, it can be observed the bands characteristic of trivalent iron(III) cation and divalent Mn(II) and Co(II) ones in a distorted octahedral symmetry. The calculated Dq and B-Racah parameters for the cobalt(II) phase are 710 and 925 cm⁻¹, respectively. The ESR spectra of compound 1 maintain isotropic with variation in temperature, being g = 1.99. Magnetic measurements for both compounds indicate that the main magnetic interactions are antiferromagnetic in nature. However, at low temperatures small ferromagnetic components are detected, which are probably due to a spin decompensation of the two different metallic cations. The hysteresis loops give values of the remnant magnetization and coercive field of 84.5, 255 emu/mol and 0.01, 0.225 T for phases 1 and 2, respectively.     

Preparation and crystal structure of a new bismuth vanadate, Bi3.33(VO4)2O2

Single crystals of a new bismuth vanadate, Bi_3.33(VO₄)₂O₂ was prepared by hydrothermal reaction using a hydrated sodium bismuthate, NaBiO₃·nH₂O as one of the starting compounds. The crystal structure was determined by using single crystal X-ray diffraction data. This compound crystallizes in the triclinic space group (#2) with a = 7.114(1), b = 7.844(2), c = 9.372(2) Å, α = 106.090(7), β = 94.468(7) and γ = 112.506(8)°, Z = 2 and the final R factors are R1 = 0.052 and wR2 = 0.14 for 2085 unique reflections. The crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO₄ tetrahedra, and one of four bismuth atoms is statistically distributed in the splitting sites with the distance of 0.83 Å. This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation and its activity was less than that of monoclinic BiVO₄.     

J integral solution for semi-elliptical surface crack in high density poly-ethylene pipe under bending

The goal of this work is to analyse the severity of semi-elliptical crack defects and to study the degree of damage in the poly-ethylene pipe in bending during the crack propagation. The semi-elliptical cracks are considered in this work located in different position in the wall of the pipe. The three finite element method based on the computation of the J integral was used to analyse the fracture behaviour of these structures. The effect of the position, shape and size of the crack on the J integral values was highlighted. The effects of strain rate and the temperature on the J integral values were also examined. The obtained results show that the strain rates have a strong influence on the J integral values especially for circumferential crack at higher bending moment. However, the energy for circumferential crack is more important compared to axial crack. The effect of the depth of the crack becomes important when the ratio (a/t) reaches a critical value of 0.6 (a/t = 0.6), especially when the ratio a/c is weak (semi-elliptical crack, a/c = 0.2) where the J integral values becomes independently of the crack depth, this conclusion is opposite to the above for the poly-ethylene pipe subjected to internal pressure. We recall finally, that the temperature effect on circumferential cracks behaviour is more important compared to the axial cracks at critical crack size (a/c = 0.2 and a/t = 0.6). It is also shown that in the wall of pipe, the internal cracks are more dangerous than the external cracks.     

BaZr(BO3)2: a non-centrosymmetric dolomite-type superstructure

The investigation of the ternary phase diagram for BaOZrO₂B₂O₃ has allowed single crystals to be grown by the flux method with formula BaZr(BO₃)₂. As this composition has been already announced in the literature, but without any structural data, the structure of BaZr(BO₃)₂ has been solved using X-ray data collected on a Kappa CCD diffractometer.This borate crystallizes in the trigonal symmetry with non-centrosymmetric space group R3c (no. 161): a=b=5.167(1) Å and c=33.913(7) Å; Z=6. The structure derived from the dolomite-type with a doubling of the c parameter. Along the c-axis, alternated layers of Ba atoms and Zr atoms are separated by planes of BO₃ groups. BaO₆ and ZrO₆ octahedra so formed are linked by their corners and each Ba(Zr) octahedron is linked to six Zr(Ba) octahedra and to six borate groups. The small deviation from centrosymmetry is attested by considering refinement agreement for the (weak) reflections (h k l) with odd value of l, and positive response of the powder second harmonic generation (SHG) test.A new J.C.P.D.S.-I.C.D.D. card is proposed for this compound.