烷基苯类化合物结构-热力学性质定量构效关系研究

计算并研究了烷基苯类化合物拓扑指数 N、J、Ij 与其热力学性质 ΔHc (g)、ΔHf (g)、S (g)、ΔGf (g)、log Kp 之间的相关性和选择性 ,结果显示 ,本文所构建经验公式其相关性和选择性均优于文献 [13]、[15 ]。

控制生胶-预聚物硫化胶结构和性能的原则(一)

用结构-热力学分析研究了模型生胶-预聚物共混物的硫化胶形态与起始混合料相结构的关系。主要研究了相区数及粒子尺寸(纳米、微米及大粒子尺寸)与硫化胶强度的关系。所提出的原理适于探讨硫化胶结构参数与超始生胶-预聚物体系的热力学特性的关系,从而可根据相图来预知所得复合物的形态组成,并用一般工艺方法来控制其性能及提高硫化胶的最大强度。文章还列举实例加以说明。

控制生胶-预聚物硫化胶结构和性能的原则(二)

用结构-热力学分析研究了模型生胶-预聚物共混物的硫化胶形态与起始混合料相结构的关系。主要研究了相区数及粒子尺寸(纳米、微米及大粒子尺寸)与硫化胶强度的关系。所提出的原理适于探讨硫化胶结构参数与超始生胶-预聚物体系的热力学特性的关系,从而可根据相图来预知所得复合物的形态组成,并用一般工艺方法来控制其性能及提高硫化胶的最大强度。文章还列举实例加以说明。

First principles investigation of binary intermetallics in Mg-Al-Ca-Sn alloy:Stability,electronic structures,elastic properties and thermodynamic properties

The structural stability, electronic structures, elastic properties and thermodynamic properties of the main binary phases Mg_（17）Al_（12）, Al_2Ca, Mg_2 Sn and Mg_2 Ca in Mg-Al-Ca-Sn alloy were determined from the first-principles calculation. The calculated lattice parameters are in good agreement with the experimental and literature values. The calculated heats of formation and cohesive energies show that Al_2Ca has the strongest alloying ability and structural stability. The densities of states（DOS）, Mulliken electron occupation number, metallicity and charge density difference of these compounds are given. The elastic constants of Mg_（17）Al_（12）, Al_2Ca, Mg_2 Sn and Mg_2 Ca phases are calculated, and the bulk moduli, shear moduli, elastic moduli and Poisson ratio are derived. The calculations of thermodynamic properties show that the Gibbs free energies of Al_2Ca and Mg_2 Sn are lower than that of Mg_（17）Al_（12）, which indicates that Al_2Ca and Mg_2 Sn are more stable than Mg_（17）Al_（12） phase. Hence, the heat resistance of Mg-Al-based alloys can be improved by adding Ca and Sn additions.

Effect of heat treatment on microstructure and tensile strength of NiCoCrAl alloy sheet fabricated by EB-PVD

The NiCoCrAl alloy sheet was fabricated by electron beam physical vapor deposition technique and the effects of the heat treatment on the microstructure and tensile strength of the NiCoCrAl alloy sheet were investigated. The heat treatment at 1050 °C is favorable to improve the interface bonding between the columnar structures due to the disappearance of the intergranular gaps. Comparing with the thin NiCoCrAl alloy sheet before heat treatment, the Ni3Al phase appears in the NiCoCrAl alloy sheet after heat treatment, which is favorable to improve the interface bonding between the columnar structures. The increase in the tensile strength and elongation is attributed to the improvement of the interface bonding between the columnar structures. The residual stress in the NiCoCrAl alloy sheet after heat treatment is reduced significantly, which also confirms that the interface bonding is improved by the heat treatment.

Study on structural,mechanical and thermodynamic properties of TiAl alloy under high pressure based on first-principles

The effect of pressure on structural, mechanical properties as well as the temperature dependence of thermodynamic properties of TiAl alloy are investigated by implementing first-principles calculations. The results show that the volume decrea-ses with the pressure increasing. We calculated the CtJ at various pressures and all the results satisfy mechanical stability crite-ria, thus the TiAl alloy is mechanically stable. The elastic constants？ bulk modulus and shear modulus calculated are well in a-greement with the calculated values at zero the pressure. The bulk modulus and shear modulus increase with the pressure in-creasing, which reflects the deformation resistance, and accordingly, deformation resistance can be strengthened with the in-crease of pressure. The brittle nature of TiAl alloy turns to ductile nature in 10 - 20 GPa . The Debye temperature, linear ther-mal expansion and heat capacity are calculated using the quasi-harmonic Debye model under the pressure ranging from 0 to 50 GPa and the temperature ranging from 0 to 1 000 K, which are useful to investigate the effect of temperature and pressure on thermodynamic parameters. Finally, electronic structure is calculated at various pressures,and it can be found that the peak intensity decreases with increasing pressure and the the strength of d-d orbital of Ti is weakened but the ductility is enhanced.

Transformation of microstructure and phase of disodium guanosine 5′-monophosphate: Thermodynamic perspectives

Microstructure and phase transformation of disodium guanosine 5′-monophosphate(5′-GMPNa_2) are extremely important for controlling the process and understanding the mechanism of crystallization. In this work, the thermodynamic properties of polymorphous 5′-GMPNa_2 especially the solubility were studied, the solubility results show that 5′-GMPNa_2 is more soluble in ethanol–water(E–W) than in isopropanol–water(I–W). The amorphous form of 5′-GMPNa_2 is more soluble than the crystalline form at the same mole fraction and temperature. Meanwhile, the crystalline forms and morphologies of the residual solids were characterized by PXRD and SEM. The results indicate that solid forms of 5′-GMPNa_2 transformed spontaneously from amorphous to crystalline when the ethanol proportion is ≥20%. In addition, increasing the pH facilitates the dissolution of 5′-GMPNa_2 and helps to maintain the crystalline form. The associated Gibbs free energy values were calculated to verify the trend of transformation from amorphous to crystalline 5′-GMPNa_2. These results should help to guide the industrial crystallization process and to obtain the crystalline form of 5′-GMPNa_2.

Density Functional Theory Study of Selectivity of Crown Ethers to Li^+ in Spent Lithium-Ion Batteries Leaching Solutions

It is a challenge to recover lithium from the leaching solution of spent lithium-ion batteries,and crown ethers are potential extractants due to their selectivity to alkali metal ions.The theoretical calculations for the selectivity of crown ethers with different structures to Li ions in aqueous solutions were carried out based on the density functional theory.The calculated results of geometries,binding energies,and thermodynamic parameters show that 15C5 has the strongest selectivity to Li ions in the three crown ethers of 12C4,15C5,and 18C6.B15C5 has a smaller binding energy but more negative free energy than 15C5 when combined with Li^+,leading to that the lithium ions in aqueous solutions will combine with B15C5 rather than 15C5.The exchange reactions between B15C5 and hydrated Li^+,Co^2+,and Ni^2+were analyzed and the results show that B15C5 is more likely to capture Li^+from the hydrated ions in an aqueous solution containing Li^+,Co^2+,and Ni^2+.This study indicates that it is feasible to extract Li ions selectively using B15C5 as an extractant from the leaching solution of spent lithium-ion batteries.

Microstructures and properties of porous TiAl-based intermetallics prepared by freeze-casting

Preparation of porous Ti Al-based intermetallics with aligned and elongated pores by freeze-casting was investigated. Engineering Ti-43 Al-9V-1Y powder(D50=50 μm), carboxymethyl cellulose, and guar gum were used to prepare the aqueous-based slurries for freeze-casting. Results showed that the porous Ti Al was obtained by using a freezing temperature of -5 ℃ and the pore structure was tailored by varying the particle content of slurry. The total porosity reduced from 81% to 62% and the aligned pore width dropped from approximately 500 to around 270 μm, with increasing the particle content from 10 to 30 vol.%. Furthermore, the compressive strength along the aligned pores increased from 16 to 120 MPa with the reduction of porosity. The effective thermal conductivities of porous Ti Al were lower than 1.81 W/(m·K) and showed anisotropic property with respect to the pore orientation.

Effects of solution heat treatment on microstructure and mechanical properties of AZ61-0.7Si magnesium alloy

The effects of solution heat treatment on the microstructure and mechanical properties of AZ61-0.7Si magnesium alloy were investigated.The results indicate that the solution heat treatment can modify the Chinese script shaped Mg2Si phases in the AZ61-0.7Si magnesium alloy.After being solutionized at 420℃ for 16-48 h,the morphology of the Mg2Si phases in the AZ61-0.7Si alloy changes from the Chinese script shape to the short pole and block shapes.Accordingly,the tensile and creep properties of the AZ61-0.7Si alloy are improved.After being solutionized at 420℃ for 24 h and followed by aging treatment at 200℃ for 12 h,the heat-treated alloy exhibits relatively high tensile and creep properties than those of the as-cast alloy.

2024 aluminum alloy ultrahigh-strength sheet due to two-level nanostructuring under cryorolling and heat treatment

The effect of rolling to a total effective strain of 2 at the liquid nitrogen temperature and subsequent natural and artificial aging on the structure and service properties of the pre-quenched hot-pressed 2024 aluminum alloy was investigated.Using optical and electron microscopy,and X-ray analysis,it was found that the cryorolling did not qualitatively change the type of the initial coarse-fibered microstructure,but produced a well-developed nanocell substructure inside fibers.Further aging led to decomposition of the preliminary supersaturated and work-hardened aluminum solid solution and precipitation of strengthening phases in the statically recovered and/or recrystallized matrix.As a result,the rolled and naturally aged alloy demonstrated the yield and ultimate tensile strengths(YS=590 MPa,UTS=640 MPа)much higher than those in the pressed andТ6-heat treated alloy at equal elongation to failure(El^6%).Artificial aging at a temperature less than conventional T6 route could provide the extra alloy strengthening and the unique balance of mechanical properties,involving enhanced strength(YS=610 MPa,UTS=665 MPа)and ductility(El^10%),and good static crack resistance(the specific works for crack formation and growth were 42 and 18 k J/m^2,respectively)and corrosion resistance(the intensity and depth of intercrystalline corrosion were 23%and 50μm,respectively).

Process optimization,microstructures and mechanical/thermal properties of Cu/Invar bi-metal matrix composites fabricated by spark plasma sintering

An orthogonal experiment scheme was designed to investigate the effects of the Cu content,compaction pressure,and sintering temperature on the microstructures and mechanical and thermal properties of(30−50)wt.%Cu/Invar bi-metal matrix composites fabricated via spark plasma sintering(SPS).The results indicated that as the Cu content increased from 30 to 50 wt.%,a continuous Cu network gradually appeared,and the density,thermal conductivity(TC)and coefficient of thermal expansion of the composites noticeably increased,but the tensile strength decreased.The increase in the sintering temperature promoted the Cu/Invar interface diffusion,leading to a reduction in the TC but an enhancement in the tensile strength of the composites.The compaction pressure comprehensively affected the thermal properties of the composites.The 50wt.%Cu/Invar composite sintered at 700℃ and 60 MPa had the highest TC(90.7 W/(m·K)),which was significantly higher than the TCs obtained for most of the previously reported Cu/Invar composites.

Low Temperature One-Step Synthesis of Barium Titanate:Thermodynamic Modeling and Experimental Synthesis

A thermodynamic model has been developed to determine the reaction conditions favoring low temperature direct synthesis of barium titanate (BaTiO3). The method utilizes standard-state thermodynamic data for solid and aqueous species and a 0ebye-Huckel coefficients model to represent solution nonideality. The method has been used to generate phase stability diagrams that indicate the ranges of pH and reagent concentrations, for which various species predominate in the system at a given temperature. Also, yield diagrams have been constructed that indicate the concentration, pH and temperature conditions for which different yields of crystalline BaTiO3 can be obtained. The stability and yield diagrams have been used to predict the optimum synthesis conditions (e.g., reagent concentrations, pH and temperature). Subsequently, these predictions have been experimentally verified. As a result, phase-pure perovskite BaTiO3 has been obtained at temperature ranging from 55 to 85℃ using BaCl2, TiCl4 as a source for Ba and Ti, and NaOH as a precipitator.

Gravitational Collapse of a Spherical Star with Heat Flow as a Possible Energy Mechanism of Gamma-Ray Bursts

We investigate the gravitational collapse of a spherically symmetric, inhomogeneous star, which is described by a perfect fluid with heat flow and satisfies the equation of state p = p/3 at its center. In the process of the gravitational collapse, the energy of the whole star is emitted into space. And the remaining spacetime is a Minkowski one without a remnant at the end of the process. For a star with a solar mass and solar radius, the total energy emitted is at the order of 10^54 erg, and the time-scale of the process is about 8 s. These are in the typical values for a gamma-ray burst. Thus, we suggest the gravitational collapse of a spherical star with heat flow as a possible energy mechanism of gamma-ray bursts.

Ruppeiner Geometry of (2+l)-Dimensional Spinning Dilaton Black Hole

In this paper, we study the geometrothermodynamics of （2 ＋ 1）-dimensional spinning dilaton black hole. We show that the Ruppeiner curvature vanishes, which implies that there exist no phase transitions and thermodynamic interactions. However when the thermodynamics fluctuation is included, the geometry structure is reconsidered. The non-vanishing Ruppeiner curvature is obtained, which means the phase space is non-flat. We also study the phase transitions and show that it can indeed take D/ace at some points.

Effect of heat treatment on microstructures and mechanical properties of Al-6Zn-2Mg-1.5Cu-0.4Er alloy

The microstructures and mechanical properties of Al-6Zn-2Mg-1.5Cu-0.4Er alloy under different treatment conditions were investigated by transmission electron microscopy （TEM） observation, and tensile properties and hardness test, respectively. The relationship between mechanical properties and microstructures of the alloys was discussed. With trace Er addition to A1-Zn-Mg-Cu alloy, Er and Al interact to form Al3Er phase, which is coherent with a（A1） matrix. The results show that Al-Zn-Mg-Cu alloy after retrogression and re-ageing （RRA） heat treatment exhibits higher tensile strength, ductility and conductivity.

Crystal structure and thermal decomposition kinetics of1-(pyridinium-1-yl)propane-(1-methylpiperidinium)bi[bis(trifluoromethanesulfonyl)imide], [PyC_3Pi][NTf_2]_2

The structure of a room temperature asymmetrical dicationic ionic liquid （ADIL）, 1-（pyridinium-l-yl） propane- （1-methylpiperidinium） bi[bis（tfifluoromethanesulfonyl）imide] （[PyC3Pi][NTf2]2）, was studied by the X-ray difo fraction method. Meanwhile, thermal analysis of [PyC3Pi][NTf2]2 was also studied using non-isothermal thermo- gravimetric analysis （TGA）. The title crystal belongs to the triclinic with space group Pi and unit-cell parameters a ： 0.95217 （8） nm, b = 1.05129 （11 ） nm, c = 1.70523 （14） nm, ct = 89,759 （8）°,β = 80.657 （7）°, γ=68.007 （9）°, and F（000） = 792. Thermal stability and thermal decomposition kinetics of the title compound were also investigated using TGA under the atmosphere of highly pure nitrogen. Heating curves at different rates were cor- related with kinetic equations Friedman and ASTM （also called iso-conversion method）. The values of average activation E （kJ·mol^-1 ） and pre-exponential constant lgA are 149.58 kJ. mol- 1 and 8.83, respectively, which were obtained by the two methods. The kinetic model function, activation energy and pre-exponential constant of this reaction using the multivariate non-linear-regression method were f（a） = （1 -a）（1 ＋ 4.1870a）, 151.04 kJ·mol^-1 and 8.81, respectively, which were basically consistent with iso-conversion methods.

First-principles calculation of structural and thermodynamic properties of titanium boride

The equilibrium lattice parameters, electronic structure, bulk modulus, Debye temperature, heat capacity and Gibbs energy of TiB and TiB2 were investigated using the pseudopotential plane-wave method based on density functional theory (DFT) and the improved quasi-harmonic Debye method. The results show that the total density of states (DOS) of TiB2 is mainly provided by the orbit hybridization of Ti-3d and B-2p states, and the total DOS of TiB is mainly provided by the hybrids bond of Ti-3d and B-2p below the Fermi level and Ti—Ti bond up to the Fermi level. The Ti—B hybrid bond in TiB2 is stronger than that in TiB. Finally, the enthalpy of formation at 0 K, heat capacity and Gibbs free energy of formation at various temperatures were determined. The calculated results are in excellent agreement with the available experimental data.

Structural, thermodynamics and elastic properties of Mg_(17)Al_(12), Al_2Y and Al_4Ba phases by first-principles calculations

Structural stabilities, thermodynamics stabilities, elastic properties and electronic structures of Mgl7Al12, Al2Y and AlaBa phases were analyzed by first-principles calculations with Castep and Drool3 program based on the density functional theory. The calculated results of heat of formation indicate that AI2Y phase has the strongest alloying ability. The calculated thermodynamic properties show that the thermal stability of these compounds gradually increases in the order ofMgl7Al12, A12Y and Al4Ba phases. Y or Ba addition to the Mg-Al alloys could improve the heat resistance. The calculated bulk modulus B, shear modulus G, elastic modulus E and Poisson ratio v show that the adding Y or Ba to Mg-Al alloys could promote the brittleness and stiffness, and reduce tenacity and plasticity by forming Al4Ba and Al2Y phases. The calculated cohesive energy and density of state （DOS） show that Al2Y has the strongest structural stability, then AlaBa and finally Mg17Al12. The calculated electronic structures show that Al2Y has the strongest structure stability because of the strong ionic bonds and covalent bonds combined action.

Local structure of calcium silicate melts from classical molecular dynamics simulation and a newly constructed thermodynamic model

The distributions of local structural units of calcium silicate melts were quantified by means of classical molecular dynamics simulation and a newly constructed structural thermodynamic model. The distribution of five kinds of Si-O tetrahedra Qi from these two methods was compared with each other and also with the experimental Raman spectra, an excellent agreement was achieved. These not only displayed the panorama distribution of microstructural units in the whole composition range, but also proved that the thermodynamic model is suitable for the utilization as the subsequent application model of spectral experiments for the thermodynamic calculation. Meanwhile, the five refined regions mastered by different disproportionating reactions were obtained. Finally, the distributions of two kinds of connections between Qi were obtained, denoted as Qi-Ca-Qj and Qi-[Ob]-Qj, from the thermodynamic model, and a theoretical verification was given that the dominant connections for any composition are equivalent connections.