Combinational simulations of free energy of polymer solution

It is conceptually proposed that the total entropy of polymer solution is contributed from two distinct parts: the positional and the oomformational. The former can be represented analytically, while the latter can be simulated with the random self-avoiding walk model on the simple cubic lattice for multichain systems. The obtained results indicated that both the conformational entropy and the mixing heat are consistent with the scaling laws wry well.     

Thermal Analysis of the Conformational Disorder in SCLC Polymers with Rigid Backbone Glass transition studies

Bis [(ω-(4′-cyanobiphenyl)-4-yl)oxy-n-alkyl]norborn-5-ene-2,3-dicarboxylate was polymerised via ring opening metathesis polymerisation (ROMP). Two disubstituted polynorbornene derivatives both of cis configuration with different length of the side-chain were studied. Differential scanning calorimetry (DSC) was used to study the effect of thermal history on the assignment of the glass transition event associated with the biaxial orientation of a smectic phase. Glass transition temperatures, the change of isobaric specific heats at T_g and the enthalpies of isotropisation were calculated. The DSC traces only show the classic step-wise change in T_g in some cases, giving the evidence that the amorphous domains are constrained and highly restricted in movement due to the morphology developed as a result of the biaxial stretching. Based on the literature data of mono- and disubstituted polynorbornene derivatives and our calorimetric experiments, the shape of T_g dependence on number of (CH₂) units is interpreted. The origin of this shape is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

聚合物微腔的研制及其特性分析

采用ＢＭＰＰＶ：ＰＶＫ的混合物作国源介质，将其按一定比例溶于氯仿中，并旋涂在具有９９．５％的反射率的ＤＢＲ上，其上蒸发３００ｎｍ的银膜，形成了面发射型微腔结构，其中ＤＢＲ在入射腔面，银膜为反射腔面，在激发波长３３７．１ｎｍ，频率２０Ｈｚ脉宽１０ｎｓ的氮分子激光器泵浦下，光谱明显等窄化，出现４６０ｎｍ和５３０ｎｍ两个比较强的发光峰，主峰国４６０ｎｍ半宽度为７ｎｍ。     

Structural properties of charged diblock copolymer solutions

Aqueous micellar solutions of ionic/neutral block copolymers have been studied by light scattering, small angle neutron scattering and small angle X-ray scattering. We made use of a polymer comprised of a short hydrophobic block (polyethylene-propylene) PEP and of a long polyelectrolytic block (polystyrene-sulfonate) PSSNa which has been shown previously to micellize in water. The apparent polydispersity of these micelles is studied in detail, showing the existence of a few large aggregates coexisting with the population of micelles. Solutions of micelles are found to order above some threshold in polymer concentration. The order is liquid-like, as demonstrated by the evolution with concentration of the peak observed in the structure factor (), and the degree of order is found to be identical over a large range of concentrations (up to 20 wt%). Consistent values of the aggregation number of the micelles are found by independent methods. The effect of salt addition on the order is found to be weak. Received: 19 June 1997 / Received in final form: 4 September 1997 / Accepted: 9 October 1997     

From dilute to dense self-avoiding walks on hypercubic lattices

A field-theoretic representation is presented to count the number of configurations of a single self-avoiding walk on a hypercubic lattice ind dimensions with periodic boundary conditions. We evaluate the connectivity constant as a function of the fractionf of sites occupied by the polymer chain. The meanfield approximation is exact in the limit of infinite dimensions, and corrections to it in powers ofd ^–1 can be systematically evaluated. The connectivity constant and the site entropy calculated throughout second order compare well with known results in two and three dimensions. We also find that the entropy per site develops a maximum atf1–(2d)^–1. Ford=2 (d=3), this maximum occurs atf~0.80 (f~0.86) and its value is about 50% (30%) higher than the entropy per site of a Hamiltonian walk (f=1).     

一维螺旋状3，6-哒嗪二甲酸镉(Ⅱ)配位聚合物的合成与结构

Using the ligand pyridazine-3，6-dicarboxylate (H₂pzdc)， a coordination polymer [Cd₂(pzdc)₂(H₂O)₄] was synthesized and characterized by elemental analysis， thermal analysis， IR and single-crystal X-ray diffraction. The complex crystallizes in the tetragonal system with space group I4₁/a. The crystallographic data are: a=1.470 6(4) nm， c=1.489 8(6) nm， V=3.222 0(19) nm³， Z=16， μ=2.725 mm^-1， D_c=2.594 g·cm^-3， R₁=0.017 8， wR₂=0.044 6. In the complex， the cadmium(Ⅱ) ions with the eight-coordinated dodecahedral geometry are linked by the pzdc ligands to generate one-dimensional chains， which are associated into the three-dimensional architecture via O-H…O hydrogen bonding. CCDC: 658853.     

取向聚对苯二甲酸乙二酯纤维的非等温结晶动力学

取向聚对苯二甲酸乙二酯纤维的非等温结晶动力学张志英，赵家森（天津纺织工学院材料科学系天津３００１６０）关键词取向高聚物，聚对苯二甲酸乙二酯，非等温结晶，结晶动力学研究高聚物结晶动力学常用的等温方法有光透射法、密度法、显微镜法、Ｘ－射线衍射法、差示扫描...     

PHASE INVERSION AND ITS MECHANICAL MODEL STUDIES FOR THE TWO-PHASE POLYMER BLEND SYSTEMS (Ⅱ)——DYNAMIC VISCOELASTIC RESPONSE

The dynamic viscoelastic response of the two-phase polymer blend systems shows the characteristics of the thermorheologically complex materials. In this paper theoretical equations for describing the dynamic viscoelastic response of such polymer blend systems have been established by means of the mechanical modeling technique. The dynamic viscoelastic response of the blend systems at any blend composition can be predicted theoretically by using the equations established, provided that the dynamic viscoelastic response of the two pure components and the mechanical model parameters are known in advance. Thus, we provide an effective method for studying the dynamic mechanical properties and the molecular relaxation characteristics of the two-phase polymer blend systems.     

具有六重穿插非中心对称金刚石网络结构的Cd(Ⅱ)和Zn(Ⅱ)的配位高聚物(英)

利用1，4-二-(4-羧基吡啶基)丁烷(L)合成了两个新的三维配位聚合物{(CdL₂)·4H₂O·2ClO₄}_n 1和{(ZnL₂)·4H₂O·2ClO₄}_n 2。单晶X-射线结构分析表明，1和2具有相同的计量式，但其晶体属于不同的空间群(1属于P4n2，2属于P4₂22)。两种配合物中，每个金属离子分别由配体与四个相邻的金属离子连接，从而形成具有六重穿插的金刚石网络结构，其网络中大的空腔被高氯酸根离子和(H₂O)₄分子簇所占据。     

Mechanical analysis on rocket propellants

The mechanical properties of solid rocket propellants are very important for good functioning of rocket motors. During use and storage the mechanical properties of rocket propellants are changing, due to chemical and mechanical influences such as thermal reactions, oxidation reactions or vibrations. These influences can result in malfunctioning, leading to an unwanted explosion of the rocket motor. Most of modern rocket propellants consist of a polymer matrix (i.e. HTPB) filled with a crystalline material (i.e. AP, AN). However, the more conventional double base propellants consist of a solid gel matrix with additives, such as stabilizers. Both materials show a mechanical behaviour, quite similar to that of general polymers. To describe the material behaviour of both propellants a linear visco-elastic theory is often used to describe the mechanical behaviour for small deformations. Because the time-temperature dependency is also valid for these materials a mastercurve can be constituted. With this mastercurve the response properties (stiffness) under extreme conditions can be determined. At TNO-PML a mastercurve of a double base propellant was constituted using dynamical mechanical analysis (DMA) and compared with a mastercurve reduced from conventional (static) stress relaxation tests. The mechanical properties of this double base propellant determined by DMA were compared with conventional (quasi-static) tensile test results. This revised version was published online in July 2006 with corrections to the Cover Date.