聚酰亚胺/功能化石墨烯复合材料力学性能及玻璃化转变温度的分子动力学模拟

应用分子模拟方法,建立了聚酰亚胺(polyimide,PI),石墨烯及羧基、氨基、羟基功能化石墨烯模型,探究了聚酰亚胺和石墨烯,聚酰亚胺和功能化石墨烯共混后复合材料的力学性能和玻璃化转变温度(T_g).研究结果表明,羧基修饰的石墨烯与PI复合后材料力学性能增加显著,其杨氏模量和剪切模量分别为4.946 GPa和1.816 GPa.不同官能团修饰的石墨烯引入PI后材料的T_g均有不同程度下降;未修饰的石墨烯与PI复合后,其T_g(559.30 K)较纯PI的T_g(663.57 K)降幅最大;而羧基修饰的石墨烯与PI复合后T_g(601.61 K)降幅最小.计算比较了PI/石墨烯复合材料体系密度、溶解度参数、相互作用能、弹性系数和氢键平均密度,研究发现羧基修饰石墨烯/PI复合材料的密度为1.396 g·cm~(-3),溶解度参数为23.51 J~(1/2)·cm~(-3/2),其相互作用能与氢键平均密度最大,弹性系数显示羧基修饰石墨烯与PI组成的复合材料内部最均匀.计算结果表明,羧基功能化石墨烯可以大幅度提高PI的力学性能,增强石墨烯与PI之间的相互作用可以减少复合材料T_g的降幅程度.此基体间相互作用的研究方法可以作为预测聚合物基纳米复合材料结构与性能的有效工具,以期为材料的设计与应用提供理论指导.     

Numerical study on the gas heating mechanism in pulse-modulated radio-frequency glow discharge

The gas heating mechanism in the pulse-modulated radio-frequency(rf) discharge at atmospheric pressure was investigated with a one-dimensional two-temperature fluid model. Firstly, the spatiotemporal profiles of the gas temperature(T_g)in both consistent rf discharge and pulse-modulated rf discharge were compared. The results indicated that T_gdecreases considerably with the pulse-modulated power, and the elastic collision mechanism plays a more important role in the gas heating change. Secondly, the influences of the duty cycle on the discharge parameters, especially on the T_g, were studied.It was found that T_gdecreases almost linearly with the reduction of the duty cycle, and there exists one ideal value of the duty cycle, by which both the T_gcan be adjusted and the glow mode can be sustained. Thirdly, the discharge mode changing from α to γ mode in the pulse-modulated rf discharge was investigated, the spatial distributions of T_gin the two modes show different features and the ion Joule heating is more important during the mode transition.     

Ge20Sb15Se65薄膜的热致光学特性变化研究

采用磁控溅射法制备了Ge₂₀Sb₁₅Se₆₅薄膜, 研究热处理温度(150—400 ℃)对薄膜光学特性的影响. 通过分光光度计、X射线衍射仪、显微拉曼光谱仪对热处理前后薄膜样品 的光学特性和微观结构进行了表征, 并根据Swanepoel方法以及Tauc公式分别计算了薄膜折射率色散曲线和光学带隙等参数. 结果表明当退火温度(T_a)小于薄膜的玻璃转化温度(T_g)时,薄膜的光学带隙(E_g^opt)随着退火温度的增加由1.845 eV上升至1.932 eV, 而折射率由2.61降至2.54; 当退火温度大于薄膜的玻璃转化温度时,薄膜的光学带隙随退火温度的增加由1.932 eV降至1.822 eV, 折射率则由2.54增至2.71. 最后利用Mott和Davis提出的非晶材料由非晶到晶态的结构转变模型对结果进行了解释, 并通过薄膜XRD和Raman光谱进一步验证了结构变化是薄膜热致变化的重要原因. 关键词： 20Sb₁₅Se₆₅薄膜')" href="#">Ge₂₀Sb₁₅Se₆₅薄膜 热处理 光学带隙 折射率     

Anomalous temperature dependence of magnetization in single-crystal Fe65Ni35 alloy

Magnetization (0–10 Oe) and magnetic relaxation measurements were carried out in the temperature range between 4.2 and 300 K for three picture-frame samples of Fe₆₅Ni₃₅ alloy whose edges were parallel to 100, 110 and 111, respectively. The typical temperature T_g and the magnetic field H_g which correspond to the anomalous temperature in the χ-T curve and inflection field in the σ-H curve, respectively are summarized and H-T_g and H_g-T diagrams are obtained. A strong magnetic relaxation is observed along the H_g-T line. The dependence of H_g on the crystallographic direction and on the temperature are discussed by the thermal activation process of the 180° domain wall which is pinned strongly by the antiferromagnetic clusters below T_g. The anomaly of magnetization of Fe₆₅Ni₃₅ alloy can be interpreted by the macroscopic picture of the coexistence of ferromagnetic and antiferromagnetic-like regions which may be caused by a statistical fluctuation of alloy composition.     

Anomalous temperature dependence of magnetization in polycrystalline Fe65Ni35 alloy

Magnetization at 0.3 and 140 Hz (0–10 Oe) and magnetic relaxation measurements were carried out in detail in the temperature range between 4.2 and 300 K for a polycrystalline Fe₆₅Ni₃₅ alloy. The typical temperature T_g and the magnetic field H_g which correspond to the anomalous temperature in χ-T curves and inflection field in σ-H curves, respectively, are summarized and a H-T diagram is obtained. A strong magnetic relaxation is observed along the H_g-T line. The temperature dependence of H_g is discussed by the thermal activation of 180° domain wall which is pinned strongly by the antiferromagnetic-like clusters below T_g. It is find that H _g is a linear function of T .     

Effects of crystallographic ordering on the magnetic behaviour of (AgIn)1-zMn2zTe2 and (CuIn)1-zMn2zTe2 alloys

Measurements of magnetic susceptibility in the temperature range 4.2–300 K were made on polycrystalline samples of the (AgIn)_{1 - z}Mn_2zTe₂ and (CuIn)_{1 - z}Mn_2zTe₂ alloys, and the data used to give values of spin-glass transition te mperature T_g and Curie-Weiss paramagnetic temperature θ. For any sample for which the X-ray powder photograph indicated an apparently single phase condition, either zinc-blende or chalcopyrite, the susceptibility data could show up to three separate T_g values. These different magnetic conditions are attributed to crystallographic ordering of the Mn ions on the chalcopyrite and zinc-blende lattices, the three observed T_g values corresponding to disordered zinc-blende, ordered zinc-blende and ordered chalcopyrite. The value of θ obtained from the 1/χ vs. T plot is shown to be a weighted mean of the separate values of θ for the phases present. The relative sizes of the T_g peaks and the values of θ for any given sample gives an indication of the amount of each phase present. These amounts were varied by using different methods of heat treatment and it was shown that the magnetic behaviour was consistent with the T(z) phase diagram for the two alloy systems.     

Temperature range for critical scaling behavior in YBCO thin films

The magnetic and transport properties of thin films and single crystals of YBa₂Cu₃O_7−δ are compared. For measurements on thin films, the apparent critical scaling behavior is observed to exist over a temperature range from 87 K down to the vortex-glass transition T_g = 84.2 K at 2.5 kOE and from 83 K to T_g = 70.4 K at 50 kOe. The inflection point (T_inf) in temperature dependent resistivity measurements R(T) coincides with the highest temperature at which current-voltage (I–V) characteristics are found to scale. The region between T_g and T_inf shows a behavior characteristics of thermally activated flux motion, while above T_inf I–V curves show ohmic behavior. No similar scaling region is observed in some single crystal results, supporting recent claims that the phase transition in some single crystals may not be critical in nature (of order greater than one).     

快凝过程中液态Cu64Zr36合金二十面体团簇遗传与演化跟踪

采用分子动力学方法模拟研究了液态Cu₆₄Zr₃₆合金在冷速50 K/ns下 的快速凝固过程, 并通过双体分布函数、Honeycutt-Andersen (H-A) 键型指数和团簇类型指数对其微结构演变特性进行了分析. 液态与快凝玻璃合金的主要原子组态都是二十面体(12 0 12 0)及其变形结构 (12 8/1551 2/1541 2/1431), 其中比例最高的是Cu芯Cu₈Zr₅基本原子团, 其次是Cu₇Zr₆和Cu₉Zr₄团簇; 并且由这些二十面体基本原子团铰链形成的中程序, 其尺寸分布在液相和固相中分别呈现出13, 19, 25,···和13, 19, 23, 25, 29, 37,···的幻数特征. 团簇的演化与跟踪分析发现: 没有任何团簇能从液态直接遗传到固态合金, 遗传的起始温度出现在T_m–T_g过冷液相区. 二十面体团簇的遗传主要以完全和直接遗传为主, 并且一个明显的增加发生在T_g附近. 在玻璃化转变温度T_g以下, (12 0 12 0) 二十面体比 (12 8/1551 2/1541 2/1431) 变形二十面体具有更高的结构遗传能力, 但仅有少部分在遗传过程中能保持化学成分的恒定. 通过部分遗传, 某些二十面体中程序甚至也能从过冷液体中被遗传到玻璃合金. 关键词： 快速凝固 分子动力学 二十面体团簇 遗传     

Determination and analysis of the dispersive optical constants of the 5,5′,6,6′-tetraphenyl-2,2′-bi([1,3]dithiolo[4,5-b][1,4]dithiinylidene)–DDQ complex thin film

The synthesis and optical properties of the 5,5′,6,6′-tetraphenyl-2,2′-bi([1,3]dithiolo [4,5-b] [1,4]dithiinylidene)–2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) complex thin film were investigated by the optical characterization. The optical constants such as refractive index, extinction coefficient and absorption coefficient were determined using the transmittance T(λ) and reflectance R(λ) spectra and the refractive index dispersion was analyzed using single oscillator of Wemple–Didomenico model. The single oscillator energy E₀ and the dispersion energy E_d were calculated. The effect of temperature on refractive dispersion and optical band gap E_g is also discussed. As a result, the annealing temperatures have an important effect on refractive index of thin film.     

Characterization of elastomeric materials by NMR-microscopy

This review reflects a long experience with the application of NMR-imaging methods to elastomeric materials. The experimental techniques, used to obtain parameter selective NMR-images (T₁,T₂, T_1ρ-images), are described in detail and the methods required for the data analysis are explained. A special emphasis is put on the analysis of experimental errors within the framework of NMR-imaging.

In order to make parameter selective images generally useful their information should be correlated to material properties, so that images of the material properties can be obtained. This is demonstrated for the case of crosslink density, which is certainly one of the molecular properties in rubber materials, exhibiting the main influence on mechanical and other material properties.

Sulfur cured and carbon black filled technical rubbers with different degree of crosslink density and oxidative aging were investigated using parameter selective imaging techniques. The image data were analyzed by means of gaussian and multiexponential fitting procedures, revealing spatially resolved NMR relaxation parameters. The further interpretation of these parameters was based on physical models describing molecular motions in crosslinked polymers.     

The effect of Magic Angle Spinning on proton spin–lattice relaxation times in some organic solids

Proton spectra of solids are usually broadened by strong proton homonuclear dipolar interactions. However, substantial line narrowing may be achieved by Magic Angle Spinning (MAS) in systems of low proton density or in systems in which rapid molecular motions occur. In such conditions, T₁(H) measurements are often used to characterise the dynamics of each resolved proton site. We show that T₁(H) values measured for solid organic compounds with high proton abundance, such as adamantane and glycine, may be strongly dependent on the spinning rate employed, so that care is required when values are compared. The effects of molecular motion and proton density on T₁(H) and its dependence on spinning rate were investigated. We found that an increase in molecular motion leads to an increase of T₁(H) at higher spinning rates. The opposite is found for systems with low proton densities which show relatively lower T₁(H), at higher spinning rates. A possible interpretation is suggested in terms of the reduced spin diffusion efficiency at higher spinning rates.     

Effects of phosphorus doping on the physical properties of axion insulator candidate EuIn2As2

We report an investigation on the single crystal growth, magnetic and transport properties of EuIn₂(As_1-xP_x)₂ (0≤x≤ 1). The physical properties of axion insulator candidate EuIn₂As₂ can be effectively tuned by P-doping. With increasing x, the c-axis lattice parameter decreases linearly, the magnetic transition temperature gradually increases and ferromagnetic interactions are enhanced. This is similar to the previously reported high pressure effect on EuIn₂As₂. For x=0.40, a spin glass state at T_g=10 K emerges together with the observations of a butter-fly shaped magnetic hysteresis and slow magnetic behavior. Besides, magnetic transition has great influence on the charge carriers in this system and negative colossal magnetoresistance is observed for all P-doped samples. Our findings suggest that EuIn₂(As_1-xP_x)₂ is a promising material playground for exploring novel topological states.     

Dynamical spin susceptibility of the d–p model in the over doping region

Dynamical spin susceptibility χ^s(q,ω) of the d–p model in the over doping region is investigated by using the auxiliary boson technique. It includes higher order terms of the 1/N-expansion within the random phase approximation (RPA) of the local vertex, where frequency dependence of the quasi-particle interaction is taken into account. The incommensurate spin fluctuation is obtained due to the nesting effect in the low energy region (ωω^*), whereas the commensurate one in the high energy region (ωω^*), the characteristic energy ω^* is estimated to be about 30 meV. Both of the spin–lattice relaxation rate 1/T₁ and the spin–spin relaxation rate 1/T_g monotonically increase as T decreases, while the spin Knight shift K is almost independent of T.     

Chemical pressure effect on the superconductor MgCNi3

In order to investigate the positive and negative pressure effects on superconducting properties for MgCNi₃, chemical pressure was applied by means of Zn-doping to Mg site (Mg_1−xZn_xCNi₃) and by substituting Mg with Cd (CdCNi₃). The lattice constant decreases (increases) with increasing Zn (Cd) content. In the magnetic measurements, superconducting transition temperature (T_c) is decreasing with increasing Zn content and disappears at x > 0.3. While for CdCNi₃, T_c also decreases down to 3.4 K. The result seems not to be fully understandable in the case of CdCNi₃ since T_c seems to rise owing to the increase of density of states at Fermi energy caused by lattice expansion.     

Selection of pulse sequences producing maximum tissue contrast in magnetic resonance imaging

The importance of spin density [N(H)] and spin-lattice (T₁) and spin-spin (T₂) relaxation in the characterization of tissue by nuclear magnetic resonance (NMR) is clearly recognized. This work considers which optimized pulse sequences provide the best tissue discrimination between a given pair of tissues. The effects of tissue spin density and machine-imposed minimum rephasing echo times (TE_MIN) for achieving maximum signal tissue contrast are discussed. A long TE_MIN sacrifices T₁-dependent contrast in saturation recovery (SR) and inversion recovery (IR) pulse sequences so that spin-echo (SE) becomes the optimum sequence to provide tissue contrast, due to T₂ relaxation. Pulse sequences providing superior performance may be selected based on spin density and T₁ and T₂ ratios for a given pair of tissues. Selection of the preferred pulse sequence and interpulse delay times to produce maximum tissue contrast is strongly dependent on knowledge of tissue spin densities as well as T₁ and T₂ characteristics. As the spin density ratio increases, IR replaces SR as the preferred sequence and SE replaces IR and SR as the pulse sequence providing superior contrast. To select the optimal pulse sequence and interpulse delay times, an accurate knowledge of tissue spin density, T₁ and T₂ must be known for each tissue.     

非自治物质畸形波的传播操控

研究了(1+1)维的变系数Gross-Pitaevskii方程, 获得了该方程的精确畸形波解. 基于该精确畸形波解, 深入研究了非自治物质畸形波在随时间指数变化的相互作用下的传播动力学行为, 发现非自治畸形波除具有“来无影、去无踪”的不可预测特性外, 也可实现完全激发、抑制激发以及维持激发等操控. 研究表明, 畸形波操控的关键是对累积时间的最大值T_max 与峰值位置T₀ (或T_I,T_II)值大小关系的调节. 当T_max > T₀ (或T_I,T_II)时畸形波被快速地完全激发, 热原子团中的原子增加到凝聚体中. 当T_max = T₀ (或T_I,T_II) 时畸形波激发到最大振幅, 可以维持相当长的时间而不消失, 热原子团中的原子增加到凝聚体中. 当T_max < T₀ (或T_I,T_II)时畸形波没有充足的时间来激发而被抑制甚至消失, 凝聚体中的原子减少. 这些结果在理论和实际应用上具有启迪意义.     

Electronic and magnetic properties of single-layer and double-layer VX_2(X=Cl,Br) under biaxial stress

First-principles calculations and Monte Carlo simulations reveal that single-layer and double-layer VX_2(X = Cl, Br)can be tuned from antiferromagnetic(AFM) semiconductors to ferromagnetic(FM) state when biaxial tensile stress is applied. Their ground states are all T phase. The biaxial tensile stress at the phase transition point of the double-layer VX_2 is larger than that of the single-layer VX_2. The direct band gaps can be also manipulated by biaxial tensile stress as they increases with increasing tensile stress to a critical point and then decreases. The Néel temperature(TN) of double-layer VX_2 are higher than that of single-layer. As the stress increases, the TNof all materials tend to increase. The magnetic moment increases with the increase of biaxial tensile stress, and which become insensitive to stress after the phase transition points.Our research provides a method to control the electronic and magnetic properties of VX_2 by stress, and the single-layer and double-layer VX_2 may have potential applications in nano spintronic devices.     

广义不确定性原理下费米气体低温热力学性质

在考虑到广义不确定性原理时, 统计物理中的态密度必须做出修正, 这导致对传统统计物理的所有结果都有不同程度的修正. 在高能、高温条件下, 此修正是颠覆传统观念的, 在低温条件下, 也有一定的修正. 研究了低温条件下考虑到广义不确定性原理时, 理想费米气体和具有弱相互作用费米气体的热力学性质, 分别给出理想费米气体和弱相互作用费米气体的化学势、内能和定容热容的解析表达式, 并以铜电子气体为例进行了具体数值计算, 将计算结果与不考虑广义不确定性原理时的费米气体的热力学性质进行了比较, 探讨了广义不确定性原理对系统热力学性质的影响. 考虑到广义不确定性原理后费米气体的化学势、费米能和基态能增大, 热容减少, 内能随温度的增加先增大, 到某一温度(对于铜电子气体, T/T_F0～0.3)时, 增值为零, 温度再增加内能减少. 这些修正的具体数值主要由粒子数密度决定, 粒子数密度越大, 修正越大.     

Phase transition and chemical decomposition of liquid carbon dioxide and nitrogen mixture under extreme conditions

Thermodynamic and chemical properties of liquid carbon dioxide and nitrogen(CO_(2~–)N_2) mixture under the conditions of extremely high densities and temperatures are studied by using quantum molecular dynamic(QMD) simulations based on density functional theory including dispersion corrections(DFT-D). We present equilibrium properties of liquid mixture for 112 separate density and temperature points, by selecting densities ranging from ρ = 1.80 g/cm~3 to 3.40 g/cm~3 and temperatures from T = 500 K to 8000 K. In the range of our study, the liquid CO_(2~–)N_2 mixture undergoes a continuous transition from molecular to atomic fluid state and liquid polymerization inferred from pair correlation functions(PCFs)and the distribution of various molecular components. The insulator–metal transition is demonstrated by means of the electronic density of states(DOS).     

Influence of alkali metal superoxides on structure,electronic,and optical properties of Be_(12)O_(12) nanocage:Density functional theory study

The effect of alkali metal superoxides M_3O(M = Li,Na,K) on the electronic and optical properties of a Be_(12)O_(12) nanocage was studied by density functional theory(DFT) and time-dependent density functional theory(TD-DFT).The energy gaps(Eg) of all configurations were calculated.Generally,the adsorption of alkali metal superoxides on the Be_(12)O_(12) nanocage causes a decrease of Eg.Electric dipole moment μ,polarizability α,and static first hyperpolarizability β were calculated and it was shown that the adsorption of alkali metal superoxides on Be_(12)O_(12) increases its polarizability.It was found that the absorption of M_3 O on Be_(12)O_(12) nanocluster improves its nonlinear optical properties.The highest first hyperpolarizability(β≈ 214000 a.u.) is obtained in the K_3O–Be_(12)O_(12)nanocluster.The TD-DFT calculations were performed to investigate the origin of the first hyperpolarizabilities and it was shown that a higher first hyperpolarizability belongs to the structure that has a lower transition energy.