Stress-optical coefficients of swollen polymer networks

Stress-optical coefficients have been determined for crosslinked samples of polyethylen (PE) and polystyrene (PS) at high temperatures, i.e., in the rubberlike state, and when swollen in a variety of liquids. For PE, swelling liquids with long straight molecules gave large values of optical anisotropy whereas liquids with more symmetrical molecules gave minimum values, as found previously for cis- polyisoprene and trans-polyisoprene. This solvent effect is attributed to short-range orientational order in molecularly asymmetric media. Sizes of the equivalent random link for unperturbed molecules of these three polymers were deduced from the minimum values of optical anisotropy. Measures of shape asymmetry were also obtained by matching the optical anisotropy of samples when unswollen with that observed when swollen with a liquid of known molecular asymmetry. Reasonable agreement was found to hold between the two methods. In contrast, the optical anisotropy of swollen PS was found to be substantially independent of the swelling liquid. The apparent absence of a molecular ordering effect in this case is attributed to the bulky nature of the PS molecule. A marked reduction in optical anisotropy on swelling is ascribed to increased phenyl group motion.     

Polyethylene/Poly(Butyl Methacrylate-co-Styrene) Copolymers Interpenetrating-Like Networks. I. Influence of the Copolymer Composition on Interpenetrating Polymer Network Properties

Abstract

IPN-like systems, consisting of low-density polyethylene (PE) and poly[butyl methacrylate (BMA)-co-styrene (S)] copolymer networks, were prepared in situ by a procedure described in previous papers. The initial PE/copolymer molar ratio was kept equal to 1 for all samples. The initial molar BMA/S ratio of the copolymer was varied over a composition range from pure S to pure BMA in order to investigate its influence on IPN properties. The samples obtained were analyzed by DSC; WAXS; tensile mechanical, dynamic-mechanical, and impact tests; swelling in CCl₄; and by some optical and electronic observations. The materials, became more and more brittle after undergoing mechanical and impact tests, even in the rubbery state, with increasing copolymer BMA content. The morphology consisted of a two-phase system. Good optical properties were obtained for the transparent specimens at relatively high BMA molar contents in the copolymer (70–80% BMA). Reversible changes of the optical properties were induced by temperature variations. A matching/mismatching of the refractive indexes of PE and the copolymer was found to be the cause of the optical behavior of these materials. Work is in progress to improve the mechanical behavior of these systems.     

聚乙烯与聚顺-1,4-丁二烯共混材料的结构与性能

聚乙烯(PE)用顺-1,4-丁二烯(PB)增韧改性以获得耐卷绕的被复线(一种野外用电话线)。采用光学显微镜、电子显微镜、X-射线衍射、光学解偏振等技术研究不同共混组成对序态结构的影响,以及序态结构与耐折性能之间的关系。结果表明,当PB由分散相开始转变成连续相以前,PB用量愈多,共混材料的耐折性能愈好。不论是线型、支化或分子量不同的PB,经用PB增韧后,其耐折性能可提高7.6—11.5倍左右。     

Two-dimensional circularly polarized IR photon echo spectroscopy of polypeptides: four-wave-mixing optical activity measurement

A coherent two-dimensional (2D) optical spectroscopy utilizing circularly polarized (CP) beams, which was shown to be useful in studying molecular chirality in condensed phases, was theoretically proposed recently [Cho et al. J. Chem. Phys. 2003, 119, 7003]. A photon echo (PE) version of 2D optical activity spectroscopy is discussed in this paper. Considering various dipeptide and polypeptide systems, where the amide I local modes constitute the set of basis modes used to describe exciton and biexciton states as linear combinations of those basis modes, we present numerically simulated 2D circularly polarized IR PE spectra. It is shown that this novel spectroscopic method can provide additional information on the angles between the transition magnetic dipole and the transition electric dipole of two different vibrationally excited states, which are highly sensitive to the 3D structure and chirality of a given polypeptide. Also, a hierarchical relation of IR absorption, vibrational circular dichroism, 2D IR PE, and 2D CP-IR PE is discussed to show advantages of 2D optical activity spectroscopy in general.     

Biofunctionalisation of colloidal gold nanoparticles via polyelectrolytes assemblies

Bioapplications of gold nanoparticles (Au NPs) have received significant attention due to their sensitive optical characteristics which depend on particle size and shape, state of aggregation and to surrounding (bio)chemical environment. In this review, we present an overview of several methods to synthesise stable colloidal Au NPs with focus on the use of the electrostatic assembly method of polyelectrolytes (PE) to functionalise Au NPs. This versatile method allows adjusting the thickness, chemical functions and the surface charge of the shells surrounding the Au NPs, thus the relevance of these features for the bioapplications of Au NPs involving surface-mediated processes is discussed. Moreover, because the PE used can be functionalised with organic fluorophores, drugs or antibodies yielding multifunctional nanocomposites useful for those applications, this review also provides an overview of the electrostatic assembly of functionalised PE onto Au NPs and their bioapplications.     

The Photoelectron Spectra of Ni,Pd, Pt-Diallyl

The He (I) photoelectron (PE.) spectra of bis (π-allyl)palladium (2a) , bis (π-allyl)platinum (3a) , bis (π-methallyl)palladium (2b) and bis (π-methallyl)-platinum (3b) have been recorded and compared with the PE. spectra of bis (π-allyl)nickel (1a) and bis (π-methallyl)nickel (1b) . By use of the He (II) PE. spectra 2a, 2b and 3b and correlations between the PE. spectra of 1–3 it is possible to assign the first seven to eight transitions in the PE. spectra of 1–3 . In contrast to previous assignments it is shown that the first band in the PE. spectrum of 1a corresponds to the ejection of an electron from 7a_u, a pure ligand orbital. The assignment proposed is supported by semiempirical calculations of the INDO-type by considering the relaxation effects explicitly using the ΔSCF and transition operator method.     

熔体结晶聚乙烯晶体的高分辨电子显微学研究

聚乙烯在一定的不良溶剂中或在熔融结晶的条件下可以得到具有弧形生长边缘的单晶,对于具有弧形边的（200）晶面的形成机理,已有一些研究报道,但由于高分子链具有成千上万个结构单元,使其结晶过程很复杂,可能会导致弧形边的成因有所不同,因此对于弧形边的形成机理有不同的解释。     

Time-resolved optical absorption spectroscopy of molten polyethylene blends

By means of pulse radiolysis and laser photolysis experiments with detection by optical absorption spectroscopy short-living radical transients in pure PE and in PE doped with additives (e.g. di->tert-butyl-p-cresol, diphenylamine, benzophenone and carbon tetrachloride) were characterized by their optical absorption spectra and kinetics. It was found that the additive radicals were formed in a very fast process probably via exciton migration and subsequent energy transfer and dissociation reactions.     

Induced crystallization behavior of poly(ethylene adipate) by highly oriented polyethylene

The crystallization behavior of poly(ethylene adipate) (PEA) on highly oriented high-density polyethylene (PE) substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edge-on lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the (00l) PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00l} lattice planes.     

Engineering of layer-by-layer coated capsules with the prospect of materials for efficient and directed electron transfer

Intermolecular electron transfer is investigated in a dye-doped polyelectrolyte (PE) multilayer film. Hollow PE capsules, with a mean diameter of 2 microm, were prepared by stepwise adsorption of a pyrene (PY)-labeled polyanion and various polycations onto charged colloids and subsequent dissolution of the colloidal core. The high concentration of dye molecules within the capsule wall and the control of the medium polarity on a nanometer length scale are proposed to facilitate light-induced charge separation over distances of a few nanometers. In particular, a PY-labeled poly(styrene sulfonate) (PSS-PY) has been synthesized and used as polyanion for the polyelectrolyte capsule preparation. A polarity gradient across the wall of the PE shells is assumed to be achieved by adsorbing diverse polycations at different film positions. The high effective film area followed by high optical density of the PE capsule solution enables time-resolved optical spectroscopy. Using pulsed excited state absorption (ESA) the transient absorption peaks of the radical anion and cation state of pyrene were measured, respectively. In the presence of additional electron donor (or acceptor) molecules in the capsule solution the pyrene anion (cation) is observed in the ESA spectra, while both transient states are seen if no additional molecules are present. These results are interpreted as an electron transfer from pyrene to the donor (acceptor) molecule or between two pyrene molecules. An asymmetry of the electron donor and electron acceptor efficiency was observed when multilayer shells were used that are supposed to carry an internal polarity gradient.     

Photochromic composites based on porous stretched polyethylene filled by nematic liquid crystal mixtures

A number of the novel photochromic polyethylene (PE)‐based liquid crystal composites were prepared and studied. The oriented stretched porous polyethylene films were used as the polymer matrices. Commercial liquid crystals doped with new photochromic compounds were introduced into PE films and photo‐optical properties of the obtained composites were investigated. It was shown that a director of nematic liquid crystals is highly oriented along the stretching axis of PE films resulting in noticeable linear dichroism of the PE composite films. New approaches for reversible or irreversible image recording on PE LC composites by UV irradiation were demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.     

The effect of nucleating agents on the crystallization kinetics of polypropylene

Compositions of neat polyproylene (PP), PP–PE (polyethylene) blend and PP–PE–DBS (dibenzylidene sorbitol) were studied with respect to their crystallization kinetics by means of differential scanning calorimetry in isothermal mode. A modified Avrami equation was applied to obtain the crystallization parameters of PP, PP–PE and PP–PE–DBS. Optical and hot-stage microscopy and dynamical analysis were used for structure determination. Experimental results have indicated that PE addition inhibits PP crystallization rate and acts as a plasticizer, while addition of DBS changes the crystallization kinetics. A detailed study of the DBS nucleation effects indicates that owing to the high surface energy, nuclei are formed during primary crystallization, leading to a fine PP crystalline structure and improved mechanical properties.     

HALS和抗氧剂对PE辐射致色的影响

聚乙烯;稳定剂;HALS和抗氧剂对PE辐射致色的影响     

Structure and Shape Control of Hydrothermally Synthesized PbTiO3--Effects of pH and Complexing Agents

Tabular PE-PbTiO3,spherical PY-PbTiO3,and acicular PX-PbTiO3 powders were hydrothermally synthesized from triethanolamine(TEA)-complexed precurso;clubbed PE-PbTiO3 powders were obtained from diethanolamine(DEA)-complexed precursor,The effects of pH of the hydrolyzation as well as complexing agents including TEA,DEA,and MEA(monoethanolamine) on the structure and the morphology of PbTiO3 powders are discussed.The optimal conditions for hydrothermal Synthese of acicular and clubbed PbTiO3 powders have been established.The products were characterized by means of XRD.TEM and other techniques.     

Interplay between solid state microstructure and photophysics for poly(9,9‐dioctylfluorene) within oriented polyethylene hosts

We present a study of isotropic and uniaxially oriented binary blend films comprising ≤1 wt % of the conjugated polymer poly(9,9‐dioctylfluorene) (PFO) dispersed in both ultra‐high molecular weight (UHMW) and linear‐low‐density (LLD) polyethylene (PE). Polarized absorption, fluorescence and Raman spectroscopy, scanning electron microscopy, and X‐ray diffraction are used to characterize the samples before and after tensile deformation. Results show that blend films can be prepared with PFO chains adopting a combination of several distinct molecular conformations, namely glassy, crystalline, and the so‐called β‐phase, which directly influences the resulting optical properties. Both PFO concentration and drawing temperature strongly affect the alignment of PFO chains during the tensile drawing of the blend films. In both PE hosts, crystallization of PFO takes place during drawing; the resulting ordered chains show optimal optical anisotropy. Our results clarify the PFO microstructure in oriented blends with PE and the processing conditions required for achieving the maximal optical anisotropy. © 2014 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 22–38     

Eigen-line in welded structures of thermoplastic polymers

Welding is widely used as a joining method for thermoplastics, and it is imperative to ensure the joining quality, particularly for critical applications. In a previous work by the authors, an Eigen-line was found in the electrofusion joint of polyethylene (PE) pipes based on ultrasonic tests and it could be used to detect and assess cold welding defects. However, the nature of the Eigen-line and reasons for the Eigen-line's existence in ultrasonic images have not yet been fully understood, which limited its applications. In this paper, Eigen-lines were observed in other thermoplastics including polypropylene (PP), polyamide 6 (PA 6), polyoxymethylene (POM) and polyethylene terephthalate (PET), suggesting that Eigen-lines have common existence. Microindentation tests were conducted on specimens cut from electrofusion joints and butt joints of PE pipes. It was found that a significant change of elastic modulus exists around the Eigen-line, which can partly explain the appearance of an Eigen-line in ultrasonic images. Scanning electron microscopy (SEM) and reflective optical microscopy were also employed to explore the nature of the Eigen-line. The results showed that an Eigen-line is a thin layer with polymer chain orientation between base material and welded zone.     

Plastically deformable polyethylene with excellent transparency and stress whitening resistance properties fabricated by constructing massive chain entanglement

Stress whitening is one of the most prominent macroscopic defects for polyethylene (PE), which greatly affects the appearance and quality of its commodity. In order to eliminate the stress whitening defects of PE, ultrahigh molecular weight polyethylene (UHMWPE) was blended with PE to fabricated PE/UHMWPE, and the enhanced intermolecular entanglement and stretchability was achieved, which greatly suppressed and impeded the occurrence of heterogeneous plastic deformation and fibrillar bundle structure during applying tensile stress, resulting in the sharply deceased of the nanoscale cavities defects for the sample. And thus, the elimination of stress whitening defects and high-light transmittance in the visible region with excellent optical transparency performance were successfully achieved for PE/UHMWPE. Moreover, introduction of UHMWPE chains significantly improved the orientation degree and formed a dense oriented crystalline network with fine lamellae for the sample, which highly enhanced the mechanical strength of PE/UHMWPE after applying stress. This work provided a new strategy for developing stress whitening eliminating polyolefin materials with high performance, which was of great significance for sustainable development and environmental friendliness.     

Crystallization behavior of polylactide on highly oriented polyethylene thin films

The crystalline structure and morphology of the PLA crystallized isothermally from the glassy state on highly oriented PE substrates at 130℃were investigated by means of optical microscopy,AFM and X-ray diffraction.The results indicate that the PE substrate influences the crystallization behavior of PLA remarkably,which leads to the growth of PLA crystals on PE substrate always in edge-on form rather than the twisted lamellar crystals from edge-on to flat-on when crystallizing the PLA on glass surface under the same condition.The edge-on PLA lamellae on the PE substrate are preferentially arranged with their long axes in the chain direction of the PE substrate crystals.It is further demonstrated that except for the different crystal orientation,the PE does not influence the crystalline modification and crystallinity of the PLA.     

Comparative height measurements of dip-pen nanolithography-produced lipid membrane stacks with atomic force, fluorescence, and surface-enhanced ellipsometric contrast microscopy

Dip-pen nanolithography (DPN) with phospholipids has been shown to be a powerful tool for the generation of biologically active surface patterns, but screening of the obtained lithographic structures is still a bottleneck in the quality control of the prepared samples. Here we performed a comparative study with atomic force microscopy (AFM), fluorescence microscopy (FM), and surface-enhanced ellipsometric contrast (SEEC) microscopy of phospholipid membrane stacks consisting of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) with high admixing of 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-[6-[(2,4-dinitrophenyl)amino]hexanoyl] (DNP Cap PE) produced by DPN. We present a structural model of membrane stacking based on the combined information gained from the three microscopic techniques. Domains of phase-separated DNP Cap PE can be detected at high DNP Cap PE admixing that are not present at medium or low admixings. While the optical methods allow for a high-throughput screening of lithographic structures (compared to AFM), it was found that, when relying on FM alone, artifacts due to phase-separation phenomena can be introduced in the case of thin membrane stacks.     

Inhibition of radiation degradation of polyolefins by hydroaromatics

Heavy hydroaromatics from petroleum (HHAP) which has evident inhibiting ability toward deterioration of hydrocarbon oils was added to high density polyethylene (PE) and isotactic polypropylene (PP), and the additive effects were examined. After the confirmation of the prominent effects to thermal oxidation of PE and PP, the additive effects to radiation degradation were tested by γ-ray and electron beam irradiations in air. The addition of HHAP was obviously effective in radiation degradation, and the crosslinking of PE was distinctly suppressed by HHAP.