The structure of 12-(tetrathiafulvenyl)-11-dodecenoic acid at 120 K

The structure of C₁₈H₂₄O₂S₄ (TTF---C₁₁H₂₀COOH) has been determined at 120 K. TTF---C₁₁H₂₀COOH, M_r = 400.65, crystallizes in the monoclinic space group P2₁/c with a = 18.117(5), b = 9.152(4), c = 12.100(3) Å, ß = 102.68(2)°, V = 1957(1) ų, Z = 4 andD_c = 1.361 g cm⁻³. Least-squares refinement gave R = 0.0898 for 788 observed unique reflections. The TTF parts of the molecules are not stacked, but are coupled into pairs with the usual overlap, double bond over ring. The high R-value reflects the disorder around the double bond in the aliphatic chain.     

Microstructure Evolution of Primary γ'Phase in Ni3Al-Based Superalloy

In this work, water cooling, air cooling (AC) and furnace cooling (FC) were applied to investigate the effect of cooling rate on microstructure evolution of primary γ′ in a newly designed Ni₃Al-based alloy. The results showed that nucleation rate of primary γ′ increased with increasing cooling rate. In addition, higher cooling rate shortened growth period of primary γ′, which made its morphology close to the initial precipitated γ′. For AC and FC specimens, due to the lower cooling rate, primary γ′ possessed longer growth period and its morphology was mainly due to the evolution of lattice misfit between γ and primary γ′. Meanwhile, growth of primary γ′ depended on lattice misfit distribution between its corner and edge area. Moreover, primary γ′ morphologies of sphere, cube and concave cube with tip corners were illustrated by considering interaction between elemental diffusion and elastic strain energy.     

Crystallographic Texture Evolution of ■-Fe_4N and Its Influences on Tribological Property of Nitrided Steel

The crystallographic texture of ■-Fe4 N in compound layer and its influences on the tribological properties of nitrided steel 38 Cr Mo Al are investigated in the study. The preferred orientation of(200)■ is produced by low-temperature nitriding in atmosphere with low nitrogen–hydrogen ratio and increases with the nitriding time. The preferred orientation of(220)■ appears after 72 h cyclic nitriding. The orientation relationships(0001)_ε//(101)_■ and [110]_ε//[111]_■,(111)_■//(0001)_ε and 011_■//[1■10]_g,(200)■//(110)_■ and [011]_■//[111]_■, as well as (1■03)_ε //(220)_■ and [0100]_ε//[1■0]_■ are established by first-principles method. The misfit of interatomic distance(δ), determining the phase transition resistance, is calculated. Accordingly, two reaction pathways during nitriding, ■→■ and ■→ε→■, are assumed, which determines the preferred orientations of ■-Fe_4 N. Results of wear tests demonstrate that the specimen with preferred orientation of(200)■ exhibits lower frictional coefficient and lower wear rate in comparison with the specimen with(220)■ preferred orientation.(111)■ texture usually relates to the lower frictional coefficient but higher wear rate due to the main slip system parallel to the sliding plane. Therefore, the(200)■ preferred orientation has a positive significance in improving the wear properties of steels.     

Structural chemistry and magnetism of dicyclopentadienidehalides of lanthanides Part 8: terbiumdicyclopentadienidebromide [Tb(C5H5)2Br]2

A single-crystal X-ray structural investigation of [Tb(C₅H₅)₂Br]₂ revealed the [Sc(C₅H₅)₂Cl]₂-type structure, space group P2₁/c, with a = 1407.6(2) pm, b = 1644.7(2) pm, c = 1370.6(9) pm, β = 93.46(3)°, V = 3167(2) × 10⁶ pm³, D_c = 2.322 g cm⁻³ and Z = 6 dimers (R = 0.036 for 4627 reflections with I > 3σ(I)). The metal centres have the pseudosymmetry C_2v. Magnetic susceptibility data show Curie-Weiss behaviour between 213 and 6 K with θ_p = −4.5(3) K and a magnetic moment μ = 9.8(1) μ_B close to the Tb³⁺ free-ion value (9.72 μ_B). Below 6 K, deviations from Curie-Weiss behaviour are observed, and at 5.3 K a maximum in the susceptibility is detected which may be caused by intradimer antiferromagnetic spin coupling. The magnetic properties are compared with the prediction of various models, starting from cubic crystal fields and isotropic intramolecular exchange interactions, followed by extension to lower crystal field symmetry (orthorhombic) and anisotropic contributions to the spin coupling. However, a reasonable agreement between the measured and calculated data was not obtained. As in [Gd(C₅H₅)₂Br]₂, the low-temperature behaviour is governed by effects which cannot be described by spin coupling models in the generally accepted form.     

Effect of Cooling Rate on Microstructure and Mechanical Properties of Sand-Casted Al-5.0Mg-0.6Mn-0.25Ce Alloy

This study examines the relationship among cooling rate, microstructure and mechanical properties of a sand-casted Al-5.0Mg-0.6Mn-0.25Ce (wt%) alloy subjected to T4 heat treatment (430 °C × 12 h + natural aging for 5 days), and the tested alloys with wall thickness varying from 5 to 50 mm were prepared. The results show that as the cooling rate increases from 0.22 to 7.65 K/s, the average secondary dendritic arm spacing (SDAS, λ₂) decreases from 94.8 to 27.3 μm. The relation between SDAS and cooling rate can be expressed by an equation: $\lambda_{2} = 53.0R_{\text{c}}^{ - 0.345}$. Additionally, an increase in cooling rate was shown not only to reduce the amount of the secondary phases, but also to promote the transition from Al₁₀Mn₂Ce to α-Al₂₄(Mn,Fe)₆Si₂ phase. Tensile tests show that as the cooling rate increases from 0.22 to 7.65 K/s, the ultimate tensile strength (UTS) increases from 146.3 to 241.0 MPa and the elongation (EL) increases sharply from 4.4 to 12.2% for the as-cast alloys. Relations of UTS and EL with SDAS were determined, and both the UTS and EL increase linearly with (1/λ₂)^0.5 and that these changes can be explained by strengthening mechanisms. Most eutectic Al₃Mg₂ phases were dissolved during T4 treatment, which in turn further improve the YS, UTS and EL. However, the increment percent of YS, UTS and EL is affected by the cooling rate.     

Preparation and crystal structure of a new barium silicon nitride, Ba5Si2N6

Single crystals of a new ternary nitride, Ba₅Si₂N₆, were synthesized by slow cooling from 750°C using a starting mixture of Ba, Si, Na and NaN₃, where Na and NaN₃ were a flux and a nitrogen source respectively. It crystallizes with orthorhombic symmetry: space group P2₁2₁2₁ (No. 19), A = 6.159, B = 10.305, C = 15.292 Å, and Z = 4. The crystal structure was determined from single-crystal data and refined to R1 = 0.0495 for all 1637 observed reflections and 89 variables. A pair of SiN₄ tetrahedra contained in the structure forms a nitridometallate anion of [Si₂N₆]¹⁰ by edge sharing.     

Crystal structure and magnetism of the Y2Pd14B5 compound

The crystal structure of the ternary boride Y₂Pd₁₄B₅, space group I4₁/amd, a=8.484(2) Å, c=16.490(3) Å, V=1186.98 ų, Z=4, was refined down to R=0.0475, wR2=0.1276 from single crystal X-ray diffraction data. Two types of coordination for boron atoms were observed: the coordination sphere for the B1 atom is a trigonal prism with one additional atom; the B2 atom has only four neighboring atoms which form a square. No boron–boron contact was observed. Analysis of the Y₂Pd₁₄B₅ crystal structure shows the existence of a correlation between this structure and the Sc₄Ni₂₉B₁₀ structure type. Magnetization and AC susceptibility measurements indicate that there is no superconducting or magnetic transition in Y₂Pd₁₄B₅ down to 2 K.     

Element Segregation and Solidification Behavior of a Nb,Ti, Al Co-Strengthened Superalloy ЭК151

The as-cast microstructure, element segregation and solidification behavior of a multi-alloyed superalloy ЭК151 have been investigated. The results show that the severe element segregation leads to the complicated precipitations at the inter-dendritic region, including η-Ni_3(Ti, Nb), eutectic(γ + γ') and Laves, which shows the characteristics of both Ti, Al-strengthened and Nb-strengthened alloys. Differential thermal analysis, heating and quenching tests reveal the solidification sequence as follows: Liquids →γ matrix →(Nb, Ti)C →η-Ni 3(Ti, Nb) →eutectic( γ+γ') → Laves. The melting points are between 1250 and 1260 °C for(Nb, Ti)C, between 1200 and 1210 °C for η phase, between 1180 and 1190 °C for eutectic(γ+γ') and Laves. γ' initially precipitates from matrix at 1150 °C and achieves the maximum precipitation at 1130 °C. According to the microstructure evolution captured during solidification and composition analysis by an energy dispersive spectrometer and electron probe microanalyzer,(Nb, Ti)/Al ratio is put forward to explain the formation of η-Ni_3(Ti, Nb) and eutectic( γ+γ'). The solidification of γ matrix increased the Nb, Ti concentration in the residual liquids, so the high(Nb, Ti)/Al ratio would result in the formation of η-Ni_3(Ti, Nb); the precipitation of the phase consumed Nb and Ti and decreased the(Nb, Ti)/Al ratio in the liquid, which led to the precipitation of eutectic(γ + γ'). Laves formed by the sides of η-Ni_3(Ti, Nb) and in front of the eutectic( γ + γ') after Al, Ti were further depleted by the two phases and Cr, Co, Mo were rejected to liquids.     

Ba3YB3O9: phase transition and crystal structure

A new modification of the compound Ba₃YB₃O₉, β phase, has been attained through solid phase transition from phase at 1125–1134 °C. β-Ba₃YB₃O₉ crystallizes in the hexagonal space group with cell parameters a=13.0529(8) Å, c=9.5359(9) Å. The crystal structure of -Ba₃YB₃O₉ has been determined from powder X-ray diffraction (XRD) data. The refinement was carried out using the Rietveld methods and the final refinement converged with R_p=8.8%, and R_wp=11.8% with R_exp=5.65%. In its structure, the isolated [BO₃]³⁻ anionic groups are parallel to each other and distributed layer upon layer along the c-axis. The Y atoms are six-coordinated by the O atoms to form octahedra. The result of IR spectrum confirmed the existence of [BO₃]³⁻ triangular groups.     

Improvement of critical current density in Y---Ba---Cu---F---O compounds by addition of platinum

Platinum added Y---Ba---Cu---F---O compounds with nominal composition YBa₂Cu₃F_0.4O_xPt_y {y=0, 0.3, 0.5} were prepared by a partial melt process performed at lower temperature than the conventional melt process. Optical micrograph observations showed that Y₂BaCuO₅ (211) particles increase in density and are dispersed finely when increasing the doping of Pt up to 0.3 wt%. For the 0.5 wt% Pt sample, however, the size of the 211 particles became larger than in the samples containing less than 0.3 wt% Pt. The magnetization was measured using a SQUID magnetometer in the temperature range 20–77 K under magnetic fields B_e up to 1 T. The magnetization M also increased with increasing quantity of platinum up to 0.3 wt%. The J_c values estimated from the width of the magnetization curves were 9.8×10⁷ A/m² for the 0.3 wt% Pt sample and 5.4×107 A/m² for the undoped sample at 77 K and B_e=0.8 T. In addition, the whereabouts of the platinum in the quenched samples was investigated by using electron spectroscopy for chemical analysis (ESCA).     

Re-recognition of the Effects of Phosphorus and Boron on the γ’’ and γ’ Phases in IN718 Alloy

The effects of P and B on the matrix strength and precipitations of γ’ and γ’’ phases in the grain interior were re-recognized in this study. The combination addition of P and B markedly accelerated the precipitations of γ’ and γ’’ phases and strengthened the matrix of IN718 alloy when air-cooled from high temperature, while made no difference when waterquenched from high temperature. The effect of single addition of P on the precipitations of γ’’ and γ’ phases was the same with that of the combination addition of P and B, while the single addition of B had no effect on the precipitations of the two phases. Therefore, it was P rather than B which accelerated the precipitations of γ’ and γ’’ phases. P could take part in the precipitations of γ’ and γ’’ phases, which was revealed by electrochemical extraction and quantitative analysis of chemical composition. It also revealed that P atoms were dissolved in the c matrix to a relatively high degree at the temperature that γ’ and γ’’ phases began to precipitate, and consequently the precipitations of γ’ and γ’’ phases were accelerated. The first-principle calculation indicated that P decreased the formation enthalpies of γ’ and γ’’ phases when it occupied the Ni lattice sites in the two phases, which explained the effect of P on the γ’ and γ’’ phases.     

Cr、V合金化弹簧钢腐蚀产物的相组成与转化

采用中性盐雾腐蚀实验对不同Cr与V含量的合金弹簧钢进行了24~288 h的腐蚀实验，用光学显微镜(OM) 观察腐蚀样品的表面宏观形貌，通过扫描电镜 (SEM) 观察腐蚀产物 (简称锈层) 截面情况，用能谱仪(EDS) 分析确定了腐蚀产物中Cr、V和Cl含量与分布情况，用X射线衍射 (XRD) 和Rietveld分析确定了腐蚀产物各锈层相的相对含量。结果表明：当腐蚀时间达到288 h时，钢表面逐渐形成内层 (30~50 μm) 和外层 (100~180 μm) 的两层结构锈层。其中外层主要是由γ-FeOOH组成，很容易剥落；而内层包含α-FeOOH和Fe₃O₄，结构较致密，与基体结合比较牢固。Cr和V在内层锈层中明显富集，而没有Cl^-，说明在内层锈层区域Cl^-侵入受到阻止；而外层锈层中Cr和V基本没有富集，且含有一定量的Cl^-；通过XRD分析腐蚀的不同阶段和不同部位的锈层成分图谱及相对含量关系，分析了γ-FeOOH形成和γ-FeOOH转化为α-FeOOH的过程。基于上述分析构建了不同相的转化模型。     

Structural investigation of ternary RIr3B2 compounds (R=Ce and Pr)

Structural studies were performed for the ternary RIr₃B₂ compounds (R=Ce and Pr) from as cast samples. The crystal structure of the ternary boride CeIr₃B₂ (CeCo₃B₂ structure type, space group P6/mmm, a=5.520(3) Å, c=3.066(2) Å, Z=1, V=80.91 ų, ρ_x=15.154 g cm⁻³) was refined to R₁=0.0470, wR₂=0.1240 from single-crystal X-ray diffraction data. The new ternary boride PrIr₃B₂ was found to be isostructural with the CeIr₃B₂ compound. Its lattice parameters a=5.5105(2) Å, c=3.1031(1) Å were obtained from a Rietveld refinement of X-ray powder diffraction data.     

Hydrothermal synthesis and characterization of a new layered compound Li2VGeO5

The new compound Li₂VGeO₅ with a layered structure has been synthesized at 580 °C via the hydrothermal method. The compound crystallizes in the space group P4/n of the tetragonal system with two formula units in a cell of dimensions a=6.5187(9) Å, c=4.5092(9) Å (T=298 K), V=191.61(5) Å³. The structure is composed of layers made of repeating [(VO₅)(GeO₄)]¹⁻ units. Li⁺ ions reside between the layers. The magnetic susceptibility data show an antiferromagnetic coupling below 5 K with C=0.47 emu K mol⁻¹, and θ=−13 K with μ_eff=1.89μ_B for each Li₂VGeO₅ unit.     

The YbNi2−xSn compound, a new structure type of ternary stannides

The crystal structure of the new ternary stannide YbNi_2−xSn [space group P6₃/mmc (N 194), z=4] was investigated using single crystal X-ray diffraction data (automatic single crystal diffractometers Philips PW1100 and Bruker SMART CCD, Mo K radiation). Three crystals with different composition YbNi_1.695Sn [a=4.424(4) Å, c=15.232(6) Å, V=258.2(4) ų, ρ=10.066 g cm⁻³, μ=57.32 mm⁻¹], YbNi_1.705Sn [a=4.424(5) Å, c=15.179(7) Å, V=257.3(4) ų, ρ=10.116 g cm⁻³, μ=57.59 mm⁻¹] and YbNi_1.745Sn [a=4.303(6) Å, c=16.001(9) Å, V=256.7(5) ų, ρ=10.199 g cm⁻³, μ=58.00 mm⁻¹] were refined to R=0.0494, wR²=0.1330, to R=0.0782, wR²=0.1916 and to R=0.0643, wR²=0.1460, respectively. The compounds belongs to a new structure type of intermetallic compounds and are formed from two hypothetical structures YbNi_1.5Sn (space group P6₃/mmc, z=4) and YbNi₂Sn (space group P6₃/mmc, z=4) containing segments of the MnCu₂Al, ZrBeSi and ZrPt₂Al structures.     

Chiroptical activity of holmium pyrogermanate: tetragonal Ho2Ge2O7

Chiroptical luminescence and circular dichroism measurements are reported for single crystals of Ho₂Ge₂O₇. These crystals belong to the tetragonal space group P4,2,2 (or P4₃2₁2) with Z=4. Each Ho³⁺ ion in the crystal structure is coordinated to seven oxygens to form a distorted pentagonal bipyramid. The Ho³⁺ ions exhibit luminescence from several excited multiplet levels; chiroptical luminescence spectra are reported for ⁶I₈ → ⁶F₆, ⁶S₂, and ⁶F₃ at a sample temperature of 10 K. Room-temperature absorption and circular dichroism measurements are reported for the ⁶I₈ → ⁶F₆, ⁵S₂, ⁶F₄, and ⁶F₃ transition regions.     

Na3As revisited II. Space group confirmation and structure refinement at 150, 210 and 240 K

The crystal structure of Na₃As at 150 K, 210 K and 240 K was refined in space group P6, cm to R1(F) = 0.0197, 0.0182, 0.0171 for F_σ >σ(F_σ), R1(F) = 0.0322, 0.0322, 0.0318, 0.0309 and wR2(F²) = 0.0518, 0.0954, 0.0978 for all data respectively. It has been found that refinement on F² gives much better results than refinement on F, particularly with respect to the U_ν and U_eq values, which are by far better balanced after using the F² refinement strategy. There is a gradual decrease of the U_ν values towards lower temperatures, as expected. In addition, the refinement in P6, cm was straightforward, regarding R-values and convergence. In contrast, refinement in space group P321, proposed by Cardoso Gil (Dissertation. University of Stuttgart, 1994) for Na₃As, was symmetry from hexagonal to trigonal, i.e. to change from space group P6,cm to its maximal subgroup P3cl. It can thus be concluded with good confidence that space group P6,cm, proposed earlier by us, is indeed the correct one for Na₃As.     

Effect of Co on Microstructure and Stress Rupture Properties of K4750 Alloy

The effects of substituting Co for Fe on the microstructure and stress rupture properties of K4750 alloy were studied.The microstructure of the alloy without Co(K4750 alloy) and the alloy containing Co(K4750-Co alloy) were analyzed.Substitution of Co for Fe inhibited the decomposition of MC carbide and the precipitation of η phase during long-term aging treatment.In K4750-Co alloy,the morphology of MC carbide at the grain boundary(GB) remained dispersed blocky shape and no η phase was observed after aging at 750℃for 3000 h.However,in K4750 alloy,almost all the MC carbides at GBs broke down into granular M_(23)C_6 carbide and needle-like η phase.The addition of cobalt could delay the decomposition of MC carbides,which accordingly restricted the elemental supply for the formation of η phase.The stress rupture tests were conducted on two alloys at 750℃/430 MPa.When Co is substituted for Fe in K4750 alloy,the stress rupture life increased from 164.10 to 264.67 h after standard heat treatment.This was mainly attributed to increased concentration of Al,Ti and Nb in γ' phase in K4750-Co alloy,which further enhanced the strengthening effect of γ' phase.After aging at 750℃for 3000 h,substitution of Co for Fe can also cause the stress rupture life at 750℃/430 MPa to increase from 48.72 to 208.18 h.The reason was mainly because MC carbide degradation and η phase precipitation in K4750 alloy,which promoted the initiation and propagation of micro-crack during stress rupture testing.     

Typical Microstructural Characteristics of Ti-5Al-5Mo-5V-3Cr-1Fe Metastable βTi Alloy Forged in α+β Region

In this study, typical microstructural characteristics of a metastable β Ti alloy (Ti-5Al-5Mo-5V-3Cr-1Fe) forged in a dual-phase region (strain of 54% at 820 °C) were investigated in detail by the combined use of X-ray diffraction, energy dispersive spectroscopy, electron channeling contrast imaging and electron backscatter diffraction techniques. Results show that the microstructure of the forged alloy is composed of bulk α grains, α plates and β matrix. The bulk α grains correspond to retained primary α phase (α_p, average grain size~2.4 μm), while the α plates are secondary α phase (α_s, width~70 nm) precipitated from the β matrix during air cooling. During forging, the β matrix experiences dynamic recovery with many subgrains and significant orientation gradients formed. Analyses of the orientation relationship between the α and β phases show that the Burgers orientation relationship is not maintained between some α_p and β phases, which should be related to thermal deformation-induced changes of their orientations. In contrast, all of the α_s plates are found to maintain well the Burgers orientation relationship with the β phase.     

Single crystal preparation and crystal structure of the Cu2Zn/Cd,Hg/SnSe4 compounds

Single crystals of Cu₂Zn/Cd/SnSe₄ were grown using a solution-fusion method. The crystal structure of the Cu₂Zn/Cd,Hg/SnSe₄ compounds were investigated using X-ray powder diffraction. These compounds crystallize in the stannite structure (space group I 2m) with the lattice parameters: a=0.56882(9), c=1.13378(9) nm, c/a=1.993 (Cu₂ZnSnSe₄), a=0.58337(2), c=1.14039(4) nm, c/a=1.955 (Cu₂CdSnSe₄) and a=0.58288(1), c=1.14179(2) nm, c/a=1.959 (Cu₂HgSnSe₄). Atomic parameters were refined in the isotropic approximation (R_I=0.0517, R_I=0.0511 and R_I=0.0695 for Cu₂ZnSnSe₄, Cu₂CdSnSe₄ and Cu₂HgSnSe₄, respectively).