间同立构聚丙烯的结晶行为和形态结构的研究

通过在不同温度下等温结晶,我们得到了sPP (ttgg)_2 螺旋构象的三种晶型(晶型I、晶型II和晶型III）。 晶型I和晶型II结构的晶体是亚稳态结构的晶体，在提高退火温度的条件下，能转变成稳定的晶型III结构的晶体。在室温下进行单轴拉伸时，无论是从玻璃态还是从螺旋构象的晶体，当拉伸比超过100%时，我们可以清楚地观察到(ttt)全反式构象晶体的生成。以上的实验结果在熔体取向薄膜的再拉伸中得到了证实。当由拉伸制得的(ttt)全反式构象晶体在不同温度下进行退火时，当退火温度超过46℃时，这种全反式构象的晶体能转变成(ttgg)_2螺旋构象的晶体。如果固定样品的长度进行退火时，这种转变直到退火温度超过100℃时才发生。提高退火温度有利于(ttgg)_2螺旋构象晶体的生成，而张力则有利于全反式构象的保持。根据已有的实验结果，我们提出了合理的转变机理。在不同温度下等温结晶，无论从玻璃态还是从熔体，我们都得到了不同形态结构的晶体，从球晶，孪晶到单层规则的长方形单晶，以及一种较少见球晶的生成过程，并分析了它的结晶机理。另外还研究了结晶温度对电子衍射中h10衍射条纹强度变化的影响。对比熔体结晶和玻璃态结晶，发现二者没有本质的差别，只是从玻璃态结晶所需的时间较长、结晶不够完善。这是由于处于玻璃态中的分子链活动能力较差的缘故。本文利用DSC等手段系统地研究了两种间同立构聚丙烯的结晶行为。利用Avrami方程作图求得 Avrami指数 n、结晶速率常数k;作图求得整体熔体结晶活化能ΔE；通过Hoffman-Weeks 和Thomson-Gibbs方程，作图求得平衡熔点T_m~o; 利用Hoffman和 Lauritzen的球晶生长速率方程作图求得成核常数K_g,发现 sPP1的结晶生长过程分成两个阶段，阶段III和阶段II，其K_g(III)/ K_g(II) = 1.9, 与理率基本吻合。同时也计算出折叠表面自由能σ_e和侧表面自由能σ以及链折叠功q。最后本文利用DSC分析了熔融双峰现象，研究了结晶速度，结晶温度和升温速率对熔融双峰的影响，提出了可能的解释。

Applicatioo of Pade Approximation in Simulating Photonic Crystals

To save finite-difference time-domain(FDTD) computing time, several methods are proposed to convert the time domain FDTD output into frequency domain. The Padé approximation with Baker's algorithm and the program are introduced to simulate photonic crystal structures. For a simple pole system with frequency 160THz and quality factor of 5000,the intensity spectrum obtained by the Padé approximation from a 28-item sequence output is more exact than that obtained by fast Fourier transformation from a 220-item sequence output. The mode frequencies and quality factors are calculated at different wave vectors for the photonic crystal slab from a much shorter FDTD output than that required by the FFT method,and then the band diagrams are obatined. In addition,mode frequencies and Q-factors are calculated for photonic crystal microcavity.

Design of spectrometer based on volume phase grating for near infrared range

In order to design and fabricate a spectrometer for the infrared range widely used in the different applications, Volume Phase Grating (VPG) with. low Polarization Dependence Loss (PDL) and high efficiency has been adopted as the dispersion element. VPG is constructed by coating an optical substrate with a thin film of dichromated. gelatin and exposing the film to two mutually coherent laser beams to form index modulation. The diffraction efficiency for a VPG is governed by Bragg effects. The depth (d) and index modulation contrast of the grating structure control the efficiency at which the light is diffracted when the Bragg condition is satisfied. Gradient index lens with high performance and low aberration are used as collimating system instead of standard lens. The spot diagrams and MTF curve of the collimating lens are shown in the paper. The receive system is InCaAs photodiode (PD) array including 512 pixels with 25 mum pitch. The spectrum resolution of the spectrometer reaches to 0.2nm and wavelength accuracy is 40pm.

Josephson dynamics of a Bose-Einstein condensate trapped in a double-well potential

The Josephson equations for a Bose-Einstein Condensate gas trapped in a double-well potential are derived with the two-mode approximation by the Gross-Pitaevskii equation. The dynamical characteristics of the equations are obtained by the numerical phase diagrams. The nonlinear self-trapping effect appeared in the phase diagrams are emphatically discussed, and the condition EcN > 4E(J) is presented.

Separation of ethyl acetate-ethanol azeotropic mixture using hydrophilic ionic liquids

The separation of ethyl acetate and ethanol (EtOH) is important but difficult due to their close boiling points and formation of an azeotropic mixture. The separation of the azeotropic mixture of ethyl acetate and EtOH using the hydrophilic ionic liquids (ILs) 1-alkyl-3-methylimidazolium chloride (alkyl = butyl, hexyl, and octyl) ([C(n)mim]Cl, n = 4, 6, 8) and 1-allyl-3-methylimidazolium chloride and bromide ([Amim]Cl and [Amim]Br) has been investigated. Triangle phase diagrams of five ILs with ethyl acetate and EtOH were constructed, and the biphasic regions were found as follows: [Amim]Cl > [Amim]Br > [C(4)mim]Cl > [C(6)mim]Cl > [C(8)mim]Cl. The mechanisms of the ILs including cation, anion, and polarity effect were discussed.

Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

Hybridization of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine) aggregates in dioxane/water solution

Self-assembly of binary blends of two triblock copolymers of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine), i.e., P4VP(43)-b-PS260-b-P4VP(43) (P1) and P4VP(43)-b-PS366-b-P4VP(43) (P2), in dioxane/water solution was studied. These two triblock copolymers individually tend to form vesicles (P2) and cylindrical micelles (P1) in dilute solution. It was found that copolymer components in the blend, sample preparation method, and annealing time had significant effect on hybridization aggregate morphology. By increasing P1 content in the copolymer blends, fraction of looped and stretched cylinders increased, while fraction of bilayers decreased. Nearly no bilayer was observed when P1 content was above 85 wt%.

Studies of the intermolecular DNA triplexes of C+center dot GC and T center dot AT triplets by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry

Formation and stabilities of four 14-mer intermolecular DNA triplexes, consisting of third strands with repeating sequence CTCT, CCTT, CTT, or TTT, were studied by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the gas phase. The gas-phase stabilities of the triplexes were compared with their CD spectra and melting behaviors in solution, and parallel correlation between two phases were obtained. In the presence of 20 mm NH4+ (pH 5.5), the formation of the TTT triplex was not detected in both solution and the gas phase.

Study of morphology and phase diagram of the H-shaped (AC)B(CA) ternary block copolymers using self-consistent field theory

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymer systems, the micro-phase morphologies of the H-shaped (AC)B(CA) ternary block copolymer system are studied in three-dimensional (3D) space. By systematically varying the volume fractions of the components A, B, and C, six triangle phase diagrams of this H-shaped (AC)B(CA) ternary block copolymer system with equal interaction energies among the three components are constructed from the weaker segregation regime to the strong segregation regime, In this study, thirteen 3D micro-phase morphologies for this H-shaped ternary block copolymer system are identified to be stable and seven 3D microphase morphologies are found to be metastable.

Microphase Separation of Mixed Polymer Brushes: Dependence of the Morphology on Grafting Density, Composition, Chain-Length Asymmetry, Solvent Quality, and Selectivity

Microphase separation of binary mixed A/B polymer brushes exposed to different solvents is studied using Single-Chain-in-Mean-Field simulations. Effects of solvent quality and selectivity, grafting density, composition, and chain-length asymmetry are systematically investigated, and diagrams of morphologies in various solvents are constructed as a function of grafting density and composition or chain-length asymmetry. The structure of the microphase segregated morphologies lacks long-range periodic order, and it is analyzed quantitatively Using Minkowski measures.

Effect of Solvent Molecular Size on the Self-Assembly of Amphiphilic Diblock Copolymer in Selective Solvent

Real-space self-consistent field theory (SCFT) is employed to study the effect of solvent molecular size on the self-assembly of amphiphilic diblock copolymer in selective solvent. The phase diagrams in wide ranges of interaction parameters and solvent molecular size were obtained in present study. The results indicate that the solvent molecular size is a key factor that determines the self-assembly of amphiphilic diblock copolymer. The self-assembled morphology changes from circle-like micelle to line-like micelle, then to loop-like micelle by decreasing the solvent molecular size in a wide range of solvent selectivity. We analyze and discuss this change in terms of the solvent solubility and the entropy contribution.

Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments.

Phase diagram data for several salt plus salt aqueous biphasic systems at 298.15 K

Phase diagrams corresponding to aqueous biphasic systems of salt (the organic ionic liquid of salts [C(4)mim]Cl, [C(6)mim]Cl, and [C(8)mim]Cl) + salt (K3PO4, K2CO3) + water were determined at 298.15 K. The binodal curve was fitted to the Merchuk equation. Tie lines assigned from mass phase ratios according to the lever arm rule were satisfactorily described using the Othmer-Tobias and Bancroft equations.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.

Characterization of non-covalent complexes of rutin with cyclodextrins by electrospray ionization tandem mass spectrometry

Electrospray ionization tandem mass spectrometry (ESI-MSn) and the phase solubility method were used to characterize the gas-phase and solution-phase non-covalent complexes between rutin (R) and alpha-, beta- and gamma-cyclodextrins (CDs). The direct correlation between mass spectrometric results and solution-phase behavior is thus revealed. The order of the 1:1 association constants (K-c) of the complexes between R and the three CDs in solution calculated from solubility diagrams is in good agreement with the order of their relative peak intensities and relative collision-induced dissociation (CID) energies of the complexes under the same ESI-MSn condition in both the positive and negative ion modes. Not only the binding stoichiometry but also the relative stabilities and even binding sites of the CD-R complexes can be elucidated by ESI-MSn. The diagnostic fragmentation of CD-R complexes, with a significant contribution of covalent fragmentation of rutin leaving the quercetin (Q) moiety attached to the CDs, provides convincing evidence for the formation of inclusion complexes between R and CDs. The diagnostic fragment ions can be partly confirmed by the complexes between Q and CDs. The gas-phase stability order of the deprotonated CD-R complexes is beta-CD-R > alpha-CD-R > gamma-CD/R; beta-CD seems to bind R more strongly than the other CDs.