有序结构氟聚合物压电驻极体的制备和压电性研究

描述了一种有序微孔结构压电聚合物功能膜的制备方法,利用模板的高度有序实现薄膜微孔结构的精确控制.将此制备方法用于氟聚合物压电驻极体薄膜的制备,通过扫描电子显微镜(SEM)对其微观结构的观察表明薄膜具有理想的有序结构.对氟聚合物压电驻极体压电性的研究则是利用正压电效应测量准静态压电系数d₃₃,通过等温衰减和压强依赖性的测量考察其压电性能.结果表明:有序结构氟聚合物压电驻极体的准静态压电系数d₃₃可高达300 pC/N;与无序结构氟聚合物     

氟聚合物压电驻极体的压电性及其电荷的动态行为

描述了一种可控微结构的多孔聚合物压电功能膜的制备方法,讨论了采用该工艺制备的聚四氟乙烯(PTFE)和全氟乙丙烯共聚物(FEP)复合膜压电驻极体的压电性能及其热稳定性.通过等温压电系数衰减和短路热刺激放电(TSD)方法,研究了氟聚合物复合膜压电活性热稳定性改善的根源,以及脱阱电荷输运和复合的特性.结果表明,这类氟聚合物压电驻极体膜的准静态压电系数d₃₃可高达2200pC/N;压电系数d₃₃的压强特性在直到20kPa的压强范围内呈现良好的 关键词： 氟聚合物 压电驻极体 热稳定性 电荷动态特性     

Wetting and Phase Separation in Polymer Blend Films: Identification of Four Thickness Regimes with Distinct Morphological Pathways

Using forward recoil spectrometry and atomic force microscopy, the phase evolution of a critical blend thin film of deuterated poly(methyl methacrylate) (dPMMA) and poly(styrene-ran-acrylonitrile) (SAN) is found to depend on film thickness. Four regimes are identified as film thickness l ₀ decreases from semi-infinite to below the radius of gyration, R _g. In the semi-infinite limit or regime IV (l ₀ R _g), surface directed spinodal decomposition is observed and found to agree with cell dynamic simulations. In regime III (10 R _g < l ₀ < 150 R _g), three stages of evolution are observed. During the early stage, wetting dominates and produces a dPMMA-rich/SAN-rich/dPMMA-rich structure. During the intermediate stage, the surface phase flows back into the middle layer inducing lateral phase coarsening. During the late stage, capillary fluctuations rupture the middle layer by spinodal dewetting, resulting in a final morphology with SAN-rich droplets encapsulated by dPMMA-rich wetting layers. Although regime II (R _g < l ₀ < 10 R _g) films also exhibit a tri-layer early stage, correlated holes in the middle layer spontaneously grow suggesting that this layer is too thin to support fully developed capillary fluctuations. Three stages of roughening are observed with a final morphology similar to regime III. In regime I (l ₀ < R _g), films roughen almost immediately after annealing in contrast to the other regimes. Initially, the surface roughness increases logarithmically with time before reaching a constant value of 2 R _g. The final average droplet height, 29.5 nm, is in good agreement with a simple interfacial energy model. Whereas the final morphology for regimes I, II and III are identical, the pathways by which films roughen are distinct suggesting that erroneous conclusions can be made by simply analyzing the final morphology.     

Existence of enantiomeric phase separation in a three-dimensional lattice gas model

A three-dimensional lattice gas model for enantiomeric phase separation is introduced. The enantiomeric molecules (d andl) are the two nonsuperimposable mirror images having the molecular structure C(AB)₂, where C is a tetrahedrally bonded carbon atom with one bond to each end of two AB groups. The lattice gas model consists of a body-centered cubic lattice, each site of which can be either vacant or occupied by a molecule oriented so that the A and B groups point toward neighboring lattice sites. Pairs of molecules interact with short-range, orientationally-dependent interactions. For a domain of interaction parameters, the Pirogov-Sinai extension of the Peierls argument is used to prove thatd-rich andl-rich phases exist in the model at sufficiently low temperature. For another domain of interaction parameters, at sufficiently high chemical potential there is an infinite number of ground states, each containing a racemic mixture ofd andl molecules.     

Abscheidung von Glimmpolymerschichten in einem weiten Metallrezipienten und Untersuchungen zur Struktur

Investigations are reported of growth rate, chemical structure (IR-spectroscopy, mass-spectrometry), thermal stability, surface structure (scanning electron microscopy) of thin polymeric films grown in a gas (Ar-hexamethyldisiloxane-mixture) discharge with a heated cathode, which is situated in the centre of a cylindrical metallic vessel (l = 50 cm, 2r = 30 cm). The discharge conditions are the following: I = 0,25 – 4 A, U = 30 – 100 V, p = 6 – 40 Pa, argon flow rate = 3,8 · 10^?5 mol/min, Ar/HMDS = 1 : 0,7 – 1 : 2,4. The growth rate changes from 2 to 18 nm/min, depending on the discharge conditions. The reproducibility of the growth rate shows deviations smaller than 10%. The films consist of a highly cross linked polymeric material and are stable up to 260°C, the solubility in n-hexane being smaller than 2%. The surface of the thin film (d ～ 10² nm) is smooth. Corrosion resistance to soda lye (0,2% NaOH) has been proved.     

SIMS depth profiling of polymer blends with protein based drugs

We report the results of the surface and in-depth characterization of two component blend films of poly(l-lactic acid) (PLLA) and Pluronic surfactant [poly(ethylene oxide) (A) poly(propylene oxide) (B) ABA block copolymer]. These blend systems are of particular importance for protein drug delivery, where it is expected that the Pluronic surfactant will retain the activity of the protein drug and enhance the biocompatibility of the device. Angle dependant X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) employing an SF₅⁺ polyatomic primary ion source were both used for monitoring the surfactant's concentration as a function of depth. The results show an increased concentration of surfactant at the surface, where the surface segregation initially increases with increasing bulk concentration and then remains constant above 5% (w/w) Pluronic. This surface segregated region is immediately followed by a depletion region with a homogeneous mixture in the bulk of the film. These results suggest the selection of the surfactant bulk concentration of the thin film matrices for drugs/proteins delivery should achieve a relatively homogeneous distribution of stabilizer/protein in the PLLA matrix. Analysis of three component blends of PLLA, Pluronic and insulin are also investigated. In the three component blends, ToF-SIMS imaging shows the spatial distribution of surfactant/protein mixtures. These data are reported also as depth profiles.     

Surface segregation of InGaAs films by the evolution of reflection high-energy electron diffraction patterns

Surface segregation is studied via the evolution of reflection high-energy electron diffraction (RHEED) patterns under different values of As 4 BEP for InGaAs films. When the As 4 BEP is set to be zero, the RHEED pattern keeps a 4×3/(n×3) structure with increasing temperature, and surface segregation takes place until 470 C. The RHEED pattern develops into a metal-rich (4×2) structure as temperature increases to 495 C. The reason for this is that surface segregation makes the In inside the InGaAs film climb to its surface. With the temperature increasing up to 515 C, the RHEED pattern turns into a GaAs(2×4) structure due to In desorption. While the As 4 BEP comes up to a specific value (1.33×10 4 Pa–1.33×10 3 Pa), the surface temperature can delay the segregation and desorption. We find that As 4 BEP has a big influence on surface desorption, while surface segregation is more strongly dependent on temperature than surface desorption.     

人工调控微结构压电驻极体的热稳定性和电荷动态特性

利用表面带有周期性结构的硬质模板,通过冷压工艺将周期结构图案复制到多孔聚四氟乙烯(PTFE)薄膜表面,再经过热黏合工艺与致密氟化乙丙烯共聚物(FEP)薄膜复合,制备出了高度有序的微孔结构复合膜,并用电晕充电的方法对复合膜进行极化处理,最终获得氟聚合物复合膜压电驻极体.借助对这类复合膜压电驻极体介电谐振谱的测量,得到了材料的杨氏模量.并利用等温热老化工艺对它们的压电系数d33的热稳定性进行了考察.最后通过短路热刺激放电谱的测量和分析,讨论了该复合膜在热老化处理后的电荷动态 关键词： 有序结构 压电驻极体 压电性 电荷动态特性     

Lifshitz points in ising systems

Phase diagrams of Ising systems with competing interactions are calculated using (a) the method of Müller-Hartmann and Zittartz to determine the transition temperature via the vanishing of an interface free energy (b) a Migdal-Kadanoff bond-moving scheme and (c) Monte Carlo simulations. It is shown that in two-dimensional Ising systems a uniaxial Lifshitz point can exist at non-zero temperatures, whereas the lower critical dimensiond _l for a Lifshitz point in a system with identical competing interactions along each of its cartesian axis isd _l 2.     

Properties of the skeleton of aggregates grown on a Cayley tree

We discuss and analyze a family of trees grown on a Cayley tree, that allows for a variable exponent in the expression for the mass as a function of chemical distance, M(l)l ^dl . For the suggested model, the corresponding exponent for the mass of the skeleton,d _l ^s , can be expressed in terms ofd _l asd _l ^s = 1,d _l d _l ^c = 2;d _l ^s = d _l –1,d ₁ d _l ^c = 2, which implies that the tree is finitely ramified ford _l 2 and infinitely ramified whend _l 2. Our results are derived using a recursion relation that takes advantage of the one-dimensional nature of the problem. We also present results for the diffusion exponents and probability of return to the origin of a random walk on these trees.     

Ferromagnetic order and critical behavior at surfaces of ultrathin epitaxial films

The critical behavior, ferromagnetic order and magnetic anisotropies of ultrathin, epitaxial, magnetic films is studied using electron capture spectroscopy (ECS), which is capable of probing the long-ranged and short-ranged electron spin polarization (ESP) at the topmost surface layer of uncoated and coated magnetic structures. For all systems [Ni(100)/Cu(100), Ni(100)/NaCl(100), fcc Fe(111)/Cu(111), Fe(100)/Ag(100), Tb/Fe(100)/Ag(100), Fe(100)/Au(100), hcp Tb(0001)/W(110), Fe(110)/W(110), V(100)/Ag(100), Pd(100)/Ag(100), Pd/W(110)] investigated so far, ferromagnetic order is detected. It is found that the surface Curie temperatureT _Cs depends on film thicknessd. ECS data obtained at the surface of various systems reveal the existence ofT- andd-dependent magnetic anisotropies. Although for V(100)/Ag(100) the measured critical exponent=0.128 agrees very well with=1/8 predicted for the two-dimensional Ising model, for other systems, such as Fe(100)/Au(100), the measured value (0.25) is in disagreement with theoretical predictions. The experimental results are discussed within the framework of presently available experimental and theoretical data.     

Delocalization transition of two-dimensional disordered systems in a strong magnetic field

The delocalization transition in two-dimensional systems and a strong magnetic field is investigated with respect to its dependence on the Landau band indexj and on the type of disorder. The generation of random potentials according to a given correlation functionf and for a chosen correlation lengthd is described. The spectral properties of random eigenvalue sequences are examined as measures for the extension of wavefunctions and indicate a nonuniversal delocalization behaviour in higher Landau bands for short ranged correlated potentials. The critical exponents of the localization length of wavefunctions are determined for rapidly varying potentials in the second lowest Landau band (j=1) and depend on the correlation lengthd of the disorder. This different critical behaviour compared to that in the lowest band is confirmed by calculations for the density-density correlations of wavefunctions at the centers of the Landau levels. Calculations in different geometries also show that the critical systems of delocalized states are conformal invariant in the case of the nonuniversal delocalization transition (dl ₀), whereas such local rescaling properties cannot be expected for slowly varying potentials.     

Surface modification of PDMS using atmospheric glow discharge polymerization of tetrafluoroethane for immobilization of biomolecules

In this study an atmospheric glow discharge with a fluorocarbon gas as precursor was used to modify the surface of polydimethyl siloxane (PDMS -[(CH₃)₂SiO]_n-). The variation in protein immobilizing capability of PDMS was studied for different times of exposure. It was observed that the concentration of proteins adsorbed on the surface varied in an irregular manner with treatment time. The fluorination results in the formation of a thin film of fluorocarbon on the PDMS surface. The AFM and XPS data suggest that the film cracks due to stress and regains its uniformity thereafter. This Stranski-Krastanov growth model of the film was due to the high growth rate offered by atmospheric glow discharge.     

Oscillating Dependence of the Acoustic Attenuation Coefficient in Thin Metal Layers

Dimensional and frequency dependences of the energy absorption coefficient of a longitudinal sound wave in a plane parallel metal layer are theoretically investigated for arbitrary relationship between the layer thickness d and the electron free path l. Exact and asymptotic (for thick (d >> l) and thin (d << l) metal layers) formulas are derived for the coefficient for an arbitrary angular dependence of the probability of specular reflection of charge carriers from the sample surface q(). A square-root dependence of the acoustic absorption coefficient on the thin film thickness is predicted. If the direction of sound wave propagation is perpendicular to the thin metal layer boundary, the acoustic absorption coefficient becomes an oscillating function of the layer thickness; its amplitude decreases with increasing kd, where k is the acoustic wave number.     

Sr/Si界面沉积SrTiO3初始生长阶段的扫描遂道显微术研究

本文工作利用脉冲激光沉积术(PLD)和超高真空扫描隧道显微术(UHV-STM),研究了在Sr/Si(001)-(2×1)衬底表面上真空室温沉积几个单层SrTiO₃薄膜的初始生长过程.经660 ℃退火处理后,Sr/Si衬底表面上形成了纳米岛状结构.经分析,这些纳米小岛为C49-TiSi₂和 C54-TiSi₂.实验结果表明,在没有氧气的情况下退火,Sr/Si界面无法有效阻止SrTiO₃薄膜与Si衬底之间的相互作用. 关键词： 脉冲激光沉积术(PLD) 扫描隧道显微镜(STM) 3')" href="#">SrTiO₃ 2')" href="#">C54-TiSi₂     

超薄溶液LPE技术生长GaInAsP/InP超晶格的理论与实验

本文由有限厚度溶液及自由表面浓度和恒定表面浓度二种模型出发对LPE生长动力学过程进行了理论分析,并导出了实现薄层生长的参数控制条件,根据这一条件用LPE技术实际生长了GaInAsP/InP超晶格,570℃下用突冷法及被压缩到200μm～500μm的薄层溶液在0.2s的驻留时间内分别重复长出了5nm(Ga0.40In0.60As0.89P0.11)和10nm(InP)的超晶格,证明了用重复推拉舟的LPE系统在一定的参数条件下可以生长MQW结构.     

类镍等电子系列离子M1,M2,E2禁戒跃迁特性的理论研究

利用基于全相对论框架下的多组态Dirac-Fock理论方法发展起来的程序包GRASP92和新发展的处理辐射跃迁过程的程序REOS99，计算了类镍等电子系列离子(Z=45—95)的基组态3s²3p⁶3d¹⁰¹S₀以及低激发组态3s²3p⁶3d⁹4l,3s²3p⁵3d¹⁰4l和3s3p⁶3d¹⁰4l(l=s,p,d,f)的能级及其向基态的M1,M2,E2禁戒跃迁概率.通过分析高离化类镍离子在特定的原子序数范围内由于存在能级交叉而产生的强组态相互作用，解释了高离化类镍离子禁戒跃迁概率的反常变化现象，探讨了禁戒跃迁概率受强组态相互作用影响而变化的一般规律.     

Computational studies on non-succinimide-mediated stereoinversion mechanism of aspartic acid residues assisted by phosphate

ABSTRACT

Although nearly all of the amino acids that constitute proteins are l-amino acids, d-amino acid residues in human proteins have been recently reported. d-amino acid residues cause a change in the three-dimensional structure of proteins, and d-aspartic acid (Asp) residues are considered to be one of the causes of age-related diseases. The stereoinversion of Asp residues in peptides and proteins is thought to proceed via a succinimide intermediate; however, it has been reported that stereoinversion can occur even under conditions where a succinimide intermediate cannot be formed. In order to elucidate the non-succinimide-mediated stereoinversion pathway, we investigated the stereoinversion of l-Asp to d-Asp catalysed by phosphate and estimated the activation barrier using B3LYP/6?31+G(d,p) density functional theory (DFT) calculations. For the DFT calculations, a model compound in which the Asp residue is capped with acetyl and methyl-amino groups on the N- and C-termini, respectively, was used. The calculated activation barrier was not excessively high for the stereoinversion to occur in vivo. Therefore, this stereoinversion mechanism may compete with the succinimide-mediated mechanism.     

Crystallization Kinetics of Lamellar Crystals Confined in Polymer Thin Films

We used dynamic Monte Carlo simulations to investigate the crystallization kinetics of flat-on lamellar polymer crystals in variable thickness films. We found that the growth rates linearly reduced with decreasing film thickness for the films thinner than a transition thickness d_t , while they were constant for the films thicker than d_t . Moreover, the mean stem lengths (crystal thickness) we calculated decreased with film thickness in a similar way to the growth rates, and the intramolecular crystallinities we calculated confirmed the film thickness dependence of the crytsal thickness. Besides, the crystal melting rates in thin films were calculated and increased with decreasing film thickness. We proposed a new interpretation on the film thickness dependence of the crystal growth rate in thin films, suggesting that it is dominated by the crystal thickness in terms of the driving force term (l–l _min) expressed by Sadler, rather than the chain mobility based on experiments. The crystal thickness can determine whether a crystal grows or melts in a thin film at a fixed temperature, indicating the reversibility between the crystal growth and melting.     

Heterogenization of supercritical fluids and nonvariant critical equilibria in ternary systems with one volatile component (for water-salt systems as examples)

The phase equilibria in ternary systems with one volatile component and a homogeneous supercritical fluid (SCF) region in one of the binary subsystems (with two critical end-points p and Q) were analyzed. Heterogenization of SCFs, extending from the 2d′ boundary subsystem into a ternary system, starts with monovariant critical phenomena in saturated solutions (l₁ = l₂-s) or (g = l−s), which pass through the extremal parameters of the temperature or composition to form special critical equilibria such as double critical end-points DCEs (l₁ = l₂-s, g = l-s, l₁ = l₂-g) or double homogeneous points DHPs (l₁ = l₂-s ↔ g = l-s). Ternary nonvariant critical points (l₁ = l₂ = g, l₁ = l₂-g-s, and l₁ = g-l₂-s) appear at the intersections of the monovariant critical and noncritical curves.