Transport properties of mesomorphic syndiotactic polystyrene

Amorphous syndiotactic polystyrene (sPS) films were annealed at 110° and 115°C for 24 h. The annealing at the higher temperature produced the mesomorphic form of sPS, characterized by conformational order, as shown both by the presence of the zigzag band in the infrared spectrum and by the presence of characteristic peaks in the x-ray diffractogram. The crystalline form was not formed at the investigated temperatures. Differential scanning calorimetry of the mesomorphic sample shows that the transformation of the mesophase into the crystalline phase occurs during the heating run. The transport properties of dichloromethane show that the mesophase is impermeable to the vapors at low activity and becomes permeable at higher activities. At low activity it is therefore possible to derive the fraction of impermeable phase, which corresponds to the fraction of mesophase. This fraction was about 50%.     

Annealing of the delta form of syndiotactic polystyrene

The effects of thermal treatments on the phase organization in some polymorphic forms of syndiotactic polystyrene have been investigated. In particular the thermal stability of the delta form was studied using x-ray diffraction and infrared spectroscopy as analytical techniques. The obtained results show that this form, characterized by chains in helix conformation, is affected by non-equilibrium phenomena. Moreover, the transition from the delta to the gamma form occurs through an intermediate form which maintains the helix chain conformation but partially loses the crystalline order.     

Normal vibrations and their dispersion in syndiotactic polystyrene

Normal modes and their dispersion are obtained for syndiotactic polystyrene (sPS) in the planar zigzag and s(2/1)2 helical conformations. Comparison is made with the spectra of isotactic polystyrene (ips) to identify the conformation-sensitive modes; for example, the 1221 cm^?1 mode is identified as a skeletal mode sensitive to chain structure and it also shows maximum dispersion. Bunching of dispersion curves and their intersection are among the characteristic features which are discussed. A check on the dispersion curves below 400 cm^?1 is made from the spectra of polystyrene oligomers.     

Effect of thermal treatments on the structure of syndiotactic polystyrene

Syndiotactic polystyrene films were prepared from the melt with different thermal treatments. Amorphous or crystalline films were obtained; x-ray analysis shows that in the crystalline samples two crystalline forms can be present and that the phase composition depends on the thermal conditions. The two forms show a different stability to liquid methylene chloride, one being stable while the other can be dissolved or transformed to a completely different crystalline structure. In all the analyzed samples the study of transport properties of CH₂ Cl₂ at low activity indicates that the amorphous component behaves as atactic polystyrene. This allows the determination of the crystallinity in the different samples.     

The mechanisms of recrystallization after melting in syndiotactic polypropylene and isotactic polystyrene

Several semicrystalline polymers show a recrystallization after melting during a heating scan. We have studied the mechanisms of such recrystallization processes for two different polymers, namely syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS). This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multi-stage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we have observed such a mechanism which resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though, when crystallization sets in an entangled polymer melt, it follows the multi-stage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism. Received 23 July 2001 and Received in final form 4 October 2001     

Aging phenomena in polystyrene thin films

The aging behavior is investigated for thin films of atactic polystyrene through measurements of complex electric capacitance. During isothermal aging process the real part of the electric capacitance increases with aging time, while the imaginary part decreases with aging time. This result suggests that the aging time dependence of the real and imaginary parts are mainly associated with change in thickness and dielectric permittivity, respectively. In thin films, the thickness depends on thermal history of aging even above the glass transition. Memory and `rejuvenation' effects are also observed in the thin films.     

Order-disorder transitions in atactic polystyrene films

The results of the electron microscopy investigation of the surface topology of the films obtained from solutions of linear atactic polystyrene in chloroform are presented. It has been shown that the distribution of density fluctuations in the films can be described using the model of a fractal percolation cluster of macromolecular coils. A decrease in the local packing density of particles upon going from θ-coils to blobs is associated with mutual penetration of the coils. An increase in density fluctuations and a decrease in the relative area and fractal surface of the cluster of the particles are associated with a decrease in the short-range order caused by the formation of the percolation cluster, which reflects portions of the chains not involved in the blobs.     

氘代聚合物膜靶制备技术与性能研究

 氘代聚合物膜是快点火基础物理实验的一种重要靶型。通过氘代苯乙烯单体的本体自由基聚合反应制备氘代聚苯乙烯，并利用流延法和浇铸法制备出厚度从几十nm到数百μm的膜靶。溶剂挥发过程中的随机扰动对膜厚均匀性造成影响，采用清洁的基片和在涂沫基片或模具外加防护罩可以降低这种影响。采用PVA作脱膜剂有利于获得较薄的聚合物薄膜。DSC分析表明薄膜的玻璃化转变温度与热处理过程有关，缓慢退火有利于提高Ｔ-g和储能模量。     

Thickness induced structural changes in polystyrene films

Changes to the structure of polystyrene melt films as measured through the spectrum of density fluctuations have been observed as a function of film thickness down to the polymer radius of gyration (Rg). Films thicker than 4Rg show bulklike density fluctuations. Thinner films exhibit a peak in S(q) near q=0 which grows with decreasing thickness. This peak is attributed to a decreased interpenetration of chains resulting in an enhanced compressibility. Measurements were made using small angle x-ray scattering in a standing wave geometry designed to enhance scattering from the interior of the film compared to interface scattering.     

聚苯乙烯多孔薄膜的密度梯度控制

利用单分散的SiO2微球自组装制备了含一种尺寸微球的SiO2胶体晶体和含多种尺寸微球的多层异质结构。对含一种尺寸微球的SiO2胶体晶体进行煅烧和刻蚀处理后,胶体晶体中空隙所占比例大于立方密堆结构的26%,形成了非密堆结构,而且刻蚀时间越长,空隙比例越大。在同样的热处理和刻蚀条件下,微球尺寸越小的胶体晶体被刻蚀的程度越高,结构中空气空隙所占的比例越大。对SiO2多层异质结构经过煅烧和刻蚀处理后,得到了空隙梯度变化的多层结构,以此为模板制备了密度梯度变化的聚苯乙烯多孔薄膜。薄膜各层之间形成了平滑的过渡,没有显示出明显的层间缺陷,且孔与孔之间没有出现3维有序多孔结构中常见的大的连通孔道。     

聚苯乙烯多孔薄膜的密度梯度控制

利用单分散的SiO2微球自组装制备了含一种尺寸微球的SiO2胶体晶体和含多种尺寸微球的多层异质结构。对含一种尺寸微球的SiO2胶体晶体进行煅烧和刻蚀处理后,胶体晶体中空隙所占比例大于立方密堆结构的26%,形成了非密堆结构,而且刻蚀时间越长,空隙比例越大。在同样的热处理和刻蚀条件下,微球尺寸越小的胶体晶体被刻蚀的程度越高,结构中空气空隙所占的比例越大。对SiO2多层异质结构经过煅烧和刻蚀处理后,得到了空隙梯度变化的多层结构,以此为模板制备了密度梯度变化的聚苯乙烯多孔薄膜。薄膜各层之间形成了平滑的过渡,没有显示出明显的层间缺陷,且孔与孔之间没有出现3维有序多孔结构中常见的大的连通孔道。     

Light scattering by polystyrene films containing carbon nanoparticles

Laser (λ = 0.63 μm) Mueller polarimetry at different angles of incidence and detection is used to measure the elements of the Mueller matrices of polystyrene films, as well as of polystyrene films modified by adding carbon nanoparticles (fullerenes or nanotubes). The complex index of refraction, depolarization index, and polarizance (degree of polarization) of the test samples are determined. It is shown that adding even a small amount (1.0–3.5 mass %) of fullerenes or carbon nanotubes changes the depolarization properties of the modified polystyrene films. Depending on the illumination and observational geometry, these films are found to have different depolarization properties.     

High energy electron irradiation effects on polystyrene films

The effect of an 8 MeV electron-beam on the structural, optical and dielectric properties of polystyrene films has been investigated respectively by means of Fourier transform infrared (FTIR) spectroscopy, ultraviolet–visible (UV–VIS) spectroscopy and electrical impedance (LCR) analysis over a radiation dose in the range of 50–250 kGy using a Microtron accelerator. The FTIR spectral analysis shows no change in the overall structure of the irradiated polystyrene films, except a minor change in the intensity of a few peaks in the FTIR spectrum, indicating that polystyrene is resistant to electron-beam irradiation over the range of radiation doses investigated. The optical band gap analysis using the UV–VIS absorption spectra of the polystyrene shows a small decrease in the optical band gap (E _g) and the activation energy with an increase in electron doses. Further, the dielectric measurements over a frequency range of 100 Hz to 1 MHz for the electron-beam-irradiated polystyrene films show that both the dielectric constant and the dielectric loss increase with an increase in electron radiation dose, which may be ascribed to the formation of defect sites in the band gap of polystyrene as a consequence of molecular chain scission in the polymer films upon irradiation.     

孔径梯度变化的聚苯乙烯多孔薄膜的制备

为了对聚合物多孔材料的微观孔结构进行控制,利用垂直沉积技术,制备了蛋白石结构和多层异质结构的SiO2胶体晶体,并通过模板导向前驱物填充手段,获得了反蛋白石结构和孔径梯度变化的聚苯乙烯多孔薄膜。扫描电镜分析表明,聚苯乙烯多孔结构精确复制了原始模板的反结构。光学透射谱显示,填充聚苯乙烯后复合蛋白石光子禁带位置相对原始模板发生红移,除去模板后,光子禁带位置发生蓝移。根据布拉格衍射方程,计算出胶体晶体模板空隙的填充分数。     

Quasi-molecular angle dependence of photoemission from thin films of polystyrene

Angle-resolved photoelectron spectra from thin films of randomly oriented polystyrene show a pronounced angular dependence of the emission for several peaks derived from benzene molecular orbitals in the valence band region. The analysis yields a clear molecular behaviour for the angular distribution of the uppermost π-band (1e_1g) which can be described by a β parameter of β = 0.6 for hν = 31 eV. These results support, for polystyrene, the notion of weak intermolecular interaction in a randomly oriented “condensed gas”.     

Influence of surface cleaning on dewetting of thin polystyrene films

Thin polystyrene (PS) films on top of silicon substrates are a frequently investigated model system in the framework of unstable films. However, with respect to stability the various experiments yielded contradictory results. Focussing on the influence of preparation conditions such as the surface cleaning solves these contradictions. By applying different surface cleans the PS film can be changed from a stable homogeneous one into a completely dewetted one. In addition to the type of clean applied, the time between cleaning the surface and spin-coating the polymeric layer on top turned out to be an important experimental parameter.Received: 1 August 2003PACS: 68.55.-a Thin film structure and morphology - 68.15. + e Liquid thin films - 68.47.Mn Polymer surfaces     

Fabrication of anatase titania inverse opal films using polystyrene templates

High-performance titania inverse opal films have been derived from a sol–gel procedure using polystyrene colloidal crystals as templates. By carefully controlling the synthetic procedures, the titania inverse opal films display a uniform color over centimeter dimensions. Scanning electron microscopy is employed to characterize the qualities of the titania inverse opal films. Electron diffraction pattern shows a polycrystalline anatase structure of TiO₂.     

Physical properties and elemental composition of starlike fullerene-containing polystyrene films

The elemental composition of starlike fullerene-containing polystyrene films has been determined by the Rutherford backscattering, ion x-ray spectrum analysis, and nuclear reaction method. The physical properties of the films are investigated by ellipsometric, photoluminescence, and dc electrical conductivity techniques. The complex refractive index of the films is equal to 1.7?i(0.05?0.10). It is found that a maximum in the photoluminescence spectrum of the fullerene-containing polystyrene film is shifted toward the high-energy range as compared to that of the C₆₀ film. The energy shift is directly proportional to the number N of polymer chains chemically bonded to the fullerene molecule and can be described by the empirical formula ΔE [eV]=0.04N. The electrical conductivity of the films increases proportionally with the molar concentration of C₆₀.