Nanophase separation in segmented polyurethane elastomers: Effect of specific interactions on structure and properties

Polyurethanes were prepared from 4,4′-methylenebis (phenyl isocyanate) (MDI), 1,4-butanediol (BD) and poly (tetrahydrofurane) polyether polyol (PTHF). The -OH functional group ratio of polyol/total diol was kept constant at 0.4 in all experiments, while the ratio of the isocianate and hydroxyl groups (NCO/OH) changed between 0.940 and 1.150. Melt polymerization was carried out in an internal mixer. The polymers were characterized with a number of methods including GPC, FTIR, WAXS, DSC, DMA and tensile testing. Changing stoichiometry modifies molecular weight as expected, but the relative concentration of end-groups also changes at the same time. The respective end-groups preferentially associate with each other leading to phase separation. -OH end-groups enter into weaker interactions with each other than urethane and amine groups. The extent of phase separation, as well as the size and properties of the dispersed phase depend on composition. Each property of the polymer is affected differently by molecular weight and phase separation. Melt viscosity depends mostly on the length of the molecules, ultimate tensile properties are influenced also by interactions, while stiffness is determined almost exclusively by phase structure.     

氮化铂在高压下的相变及弹性性质的第一原理计算

用PBE形式下的广义梯度近似（GGA）赝势平面波方法研究了氮化铂的结构相变以及弹性性质,计算了氮化铂的氯化钠（B1）、氯化铯（B2）、闪锌矿（B3）、纤维矿（B4）等四种结构并应用高压下的焓与压强的关系,得出在常温常压下B4结构是最稳定的结构,这与Yu 等人得的结果一致,且 B4→B1及B1→B2的相变压强分别发生在36.7 GPa和 185.4 GPa,同时,研究了B4结构在高压的弹性性质,发现弹性常数、体模量、剪切模量、压缩波速、剪切波速以及德拜温度均随着压强的增大而单调增大     

The behavior of a many-particle electrode in a lithium-ion battery

We study a rechargeable lithium-ion battery that uses a many-particle FePO₄ electrode to reversibly store lithium atoms. This process is accompanied by a phase transition and charging/discharging run along different paths, so that hysteretic behavior is observed.Although there are experimental studies suggesting that the overall behavior of the battery is a many-particle effect, most authors exclusively describe the phase transition within a single particle model of the electrode.In this work, we study in detail a many-particle model for the electrode. The model is capable to describe a kind of phase transition where each individual particle of the electrode is homogeneous. It will be shown that the particles are either in the first phase or in the second phase. This phenomenon is due to the non-monotone relation between the chemical potential and the lithium mole fraction of a single particle.The pressure-radius relation of a spherical elastic rubber balloon also exhibits non-monotone behavior. In fact, a system of many interconnected balloons behaves correspondingly to an electrode consisting of many storage particles. The analogy between the two systems is important, because the predictions of the many-particle model can easily be tested with rubber balloons of macroscopic size than with an ensemble of microscopically small (FePO₄) particles.     

Synthesis and Characterization of 2d Ferromagnetic (RNH3)2CrX4 Containing Mixed-Halides,R = CnH2n+1, X = Br,C1

The bis(benzylammonium)tetrahalogenochromate(II), (C₆H₅CH₂NH₃)₂CrBr₃. ₃Cl₀. 7, has been synthesized and characterized. The crystal structure is related to that of K₂NiF₄. The compound is ferromagnetic and the Curie temperature T_C (T_C= 49 K) has been measured by a mutual inductance technique. The susceptibility increases sharply at T_C and then shows a drop-off below T_C, typical of a single-domain powder sample. The compound is found to behave as a typical 2D easy plane ferromagnet.     

First principles calculation of L21+A2 coherent equilibria in the Fe–Al–Ti system

By combining first-principles density functional total energy calculations and statistical mechanics the ground state and the phase equilibria at finite temperatures of the ternary system Fe–Al–Ti have been investigated. Total energy calculations have been performed by means of the Wien 2k code to establish the ground state energetic. A cluster expansion method was therewith used to describe solid solutions. At several chosen finite temperatures the cluster variation method in the irregular tetrahedron approximation was employed in order to calculate the iron rich ternary bcc equilibria. It is confirmed that there are two kinds of phase separations of the bcc phase, A2+L2₁ and B2+L2₁.     

Core/Shell Structured PCM Nanocapsules Obtained by Resin Fortified Emulsion Process

Phase change material (PCM, octadecane) nanocapsules were successfully prepared by resin fortified emulsion (RFE) polymerization using the alkali soluble resin (ASR) of poly(ethylene‐co‐acrylic acid) (EAA) and poly(styrene‐co‐acrylic acid) (SAA). Stable PCM nanocapsules were obtained by resin fortified emulsion polymerization, which could be attributed to the prevention of Ostwald ripening due to PCM being hydrophobic. Analysis of online FTIR measurements throughout the reaction confirmed that the nanocapsules contained octadecane as a PCM. TEM imaging of the PCM nanocapsules showed spherical and core/shell morphology. The characteristics of PCM nanocapsules can be controlled by process parameters. As a result, the particle size and particle size distribution (i.e., polydispersity index (Dw/Dn)) of the PCM nanocapsules were created by adjusting manufacturing conditions. The PCM nanocapsules exhibited thermal energy storage (～49.8 J/g) and release (～47.9 J/g) behavior.     

Structural transitions of NaAlH4 under high pressure by first-principles calculations

First-principles calculations have been performed on NaAlH₄ using the generalized gradient approximation pseudopotential method. The predicted β-NaAlH₄ (α-LiAlH₄-type) structure is energetically more favorable than α-NaAlH₄ for pressures over 15.9 GPa, which is apparently correlated with the experimental transition pressure 14 GPa. This transition is identified as first-order in nature with volume contractions of 1.8%. There is no pressure-induced softening behavior from our calculated phonon dispersion curves near the phase transition pressure. Based on the Mulliken population analysis, the β-NaAlH₄ structure is expected to be the most promising candidate for hydrogen storage.     

Metastable states at low temperature in spin crossover compounds in the framework of the atom-phonon coupling model

In the current study we report on the unusual results obtained in the framework of the atom-phonon coupling model: two metastables states at low temperatures. These results can explain the experimental results reported by Ould Moussa et al. [9] and Matsumoto et al. [10]. This type of SCO behavior is due to the competition between the Light-Induced Excited Spin State Trapping (LIESST) effect, the elastic interaction between the molecules and the thermal activation. In order to determine the stability of the states founded at low temperature, the free energy F is presented for the case of the two step spin transition of a SCO compound.     

Magnetic phase transitions in transition-metal complexes with triazole derivatives

Three divalent transition-metal (Co, Ni and Cu) complexes with the organic anion, 1,2,4-triazolato (tr), as a ligand molecule were prepared by means of hydrothermal syntheses and their magnetic properties were investigated by SQUID magnetometry. The Co(tr)₂ and Cu(tr)₂ complexes exhibit long range ordering below 8 and 30 K, respectively, while the Ni(tr)₂ complex does not show any magnetic phase transition down to 1.8 K. The magnetization isotherms of Co(tr)₂ and Cu(tr)₂ measured at 2.0 K show hysteresis loops with the coercive fields of 0.5 and 4.7 kOe, respectively. At temperatures higher than about 50 K, the temperature dependence of the magnetic susceptibility of Co(tr)₂, Ni(tr)₂ and Cu(tr)₂ follows the Curie-Weiss law with the Curie constants of 2.95, 0.945 and 0.420 emu K mol⁻¹ and the Weiss temperatures of −62, −74 and −97 K, respectively. These results suggest that the magnetically ordered phases observed in Co(tr)₂ and Cu(tr)₂ at low temperatures come from antiferromagnetic interactions resulting in canted arrangements of magnetic moments of the transition-metal cations. We discuss here the magnetic interactions in these transition-metal complexes by referring the results of the magnetization measurements.     

Structural properties of rutherfordium: An ab-initio study

The structural and electronic properties of rutherfordium, the latest group IV B element, have been evaluated by first principles density functional theory in scalar relativistic formalism with and without spin-orbit coupling and compared with its 5d homologue Hf. It is found that Rf will crystallize in the hexagonal close packed structure as in Hf. However, under pressure, it will have different sequence of phase transitions than Hf: hcp→bcc instead of hcp→ω→bcc. An explanation is offered for this difference in terms of the competition between the band structure and the Ewald energy contributions.