XPS studies of directly fluorinated HDPE: problems and solutions

X-ray photoelectron spectroscopy (XPS) applied to the study of fluorinated polymer surfaces presents several problems related both to peak assignment and to degradation. In this work, we analyse extensively the question of XPS peak assignments in this kind of surfaces. We conclude that in this kind of surfaces using binding energy differences between fluorine and carbon is better than using absolute binding energies. Also a useful relation between fluorine photoelectron energy vs. polymer composition expressed through the atomic ratio fluorine/carbon (F/C) was found. A protocol for data treatment is proposed and applied to a XPS study of the degradation induced by X-ray on high-density polyethylene surfaces modified by direct fluorination. Results obtained for the degradation, namely the atomic ratio F/C obtained by two different methods, combined with angle resolved X-ray photoelectron spectroscopy (ARXPS) were used to study the fluorine concentration profile in depth, producing self-consistent results.     

膨润土凝胶调剖剂XJF的研制及应用

介绍了调剖剂XJF的配方,讨论了影响调剖剂性能的配方因素(膨润土含量、HPAM溶液浓度、XJ用量及添加剂Fc的浓度),考察了封堵能力和应用范围,简介了在火烧山油田现场试验的结果。     

深井重泥浆弱凝胶工艺技术初探

重泥浆强凝胶体系对钴井会产生不利影响。笔者结合川东地区的实际情况,分析了重泥浆强凝胶形成的原因和重泥浆弱凝胶的形成机制,提出了形成重泥浆弱凝胶体系的核心和设计原则,总结出了一套以正确使用泥浆添加剂并配合强有力的固控措施为主的成套深井重泥浆弱凝胶工艺技术,介绍了这套技术在川东地区的应用情况。实践证明,少用甚至不用泥浆降粘剂就可获得并维持尽可能低的静切力,使τ_s,10s为0.5—6Pα、τ_s,10min为2—12.5Pα。     

塑料合金用反应型相容剂

反应型相容剂含有反应基团,可与含相应基团的聚合物起化学反应,因而在混炼过程中增容。本文系统地介绍各种反应型相容剂的设计、合成、品种和应用。     

Studies of the positron lifetime and Doppler-broadened annihilation radiation of polypropylene-polystyrene alloys

Positron annihilation lifetime spectroscopy and Doppler-broadened annihilation radiation (DBAR) experiments were performed on polypropylene-polystyrene (PP-PS) alloys (0-100% styrene) prepared by in situ polymerisation of styrene in a PP host matrix. The mean size of free-volume holes estimated from the ortho-positronium lifetime τ₃ shows a continuous decrease from 0.119 nm³ in PP to 0.095 nm³ in PS. The intensity of the o-Ps component, I₃, the average positron lifetime τ_av, the curve-shape parameter S and the peak height H of the DBAR spectra increase linearly with the styrene concentration. This is attributed to a linear superposition of the Ps yields of PP and PS in the PP-PS alloys. The DBAR spectra were fitted by a sum of three Gaussians, the narrowest of them is attributed to self-annihilation of para-positronium confined within holes. After its subtraction, a ‘broad component’ is obtained which represents the momentum distribution of electrons bound to molecules. Its normalised peak height does not show any change with the composition which reflects the fact that both constituents of the PP-PS alloys contain only hydrogen and carbon atoms in their chemical units. Immersing of PP into styrene liquid leads to a very pronounced increases in the lifetime parameters which is attributed to the plasticisation of PP.     

用微机计算电子衍射径向分布函数

本文介绍用微机计算非晶态高聚物电子衍射径向分布函数(RDF)。运用二次样条函数分段拟合及傅氏积分的数学方法,通过 BASIC 程序,只要输入初始实验数据即可自动解算且连续得到与各运算阶段相应的曲线图及其运算结果.     

Telechelic polydimethylsiloxanes with terminal acetylenic groups prepared by phase-transfer catalysis

Telechelic, hydroxyalkyl terminated polydimethylsiloxanes were obtained under mild conditions via hydrosilylation of allyl alcohol or ethylene glycol monoallyl ether by oligomeric αω-hydride terminated polydimethylsiloxanes, with the use of a platinum catalyst. They were subsequently modified in a phase transfer catalyzed reaction by propargyl bromide, to give telechelic polysiloxanes terminated by acetylenic groups. The synthetic pathway is described and the characterization of the obtained products is presented.     

High performance LDPE/thermoplastic starch blends: a sustainable alternative to pure polyethylene

Thermoplastic starch (TPS), as opposed to dry starch, is capable of flow and hence when mixed with other synthetic polymers can behave in a manner similar to conventional polymer-polymer blends. This paper presents an approach to preparing polyethylene/thermoplastic starch blends with unique properties. A one-step combined twin-screw/single screw extrusion setup is used to carry out the melt-melt mixing of the components. Glycerol is used as the starch plasticizer and its content in the TPS is varied from 29 to 40%.Under the particular one-step processing conditions used it is possible to develop continuous TPS (highly interconnected) and co-continuous polymer/TPS blend extruded ribbon which possess a high elongation at break, modulus and strength in the machine direction. The PE/TPS (55:45) blend prepared with TPS containing 36% glycerol maintains 94% of the elongation at break and 76% of the modulus of polyethylene. At a composition level of 71:29 PE/TPS for the same glycerol content, the blend retains 96% of the elongation at break and 100% of the modulus of polyethylene. These excellent properties are achieved in the absence of any interfacial modifier and despite the high levels of immiscibility in the polar-nonpolar TPS-PE system. The 55:45 blend possesses a 100% continuous or fully interconnected TPS morphology, as measured by hydrolytic extraction. This highly continuous TPS configuration within the blend should enhance its potential for environmental biodegradation. The elongation at break in the cross direction of these materials, although lower than the machine direction properties, also demonstrates ductility at high TPS concentrations. At a glycerol content of 36% in the TPS, the blends demonstrate only very low levels of sensitivity to moisture. A high degree of transparency is maintained over the entire concentration range due to the similar refractive indices of PE and TPS and the virtual absence of interfacial microvoiding.Effective control of the glycerol content, TPS concentration and processing conditions can result in a wide variety of morphological structures including spherical, fiber-like, highly continuous and co-continuous morphologies. These various blend morphologies are shown to be the determining parameters with respect to the observed mechanical properties.This material has the added benefit of containing large quantities of a renewable resource and hence represents a more sustainable alternative to pure synthetic polymers.     

Phase equilibria of quasi-binary systems consisting of multicomponent polymers 1 and 2. IV: Poly(ethylene oxide)/poly(propylene oxide) systems

To confirm the reliability of the theory of phase equibria of multicomponent polymer 1/multicomponent polymer 2 systems (i.e. quasi-binary systems) and the method of computer experiment based on this theory (Brit. Polym. J., 23 (1990)285; 23 (1990)299; Polym. Int., 29 (1992)219), could point curves (CPC), two-phase volume ratios ( R ) and critical solution points (CSP) have been determined experimentally for the quasi-binary mixtures of poly(ethylene oxide) (M¯_w = 647, M¯_w/M¯_n = 1.15; M¯_w and M¯_n, the weight-average and numberaverage molecular weights, respectively) and poly(propylene oxide) (M¯_w = 2028, M¯_w/M¯_n = 1.08; and M_w = 2987, M_w/M_n = 1.13). The hydroxyl end groups of both polymers were methoxylated in advance by the Cooper & Booth method (Polymer, 18 (1977)164). The thermodynamic interaction parameter between both polymers, χ₁₂, and the concentration dependence parameters for the above quasi-binary systems were determined by the method proposed in a previous paper (Brit. Polym. J., 23 (1990)299). CPC, R and CSP values calculated on the basis of the theory are in good agreement with the values determined experimentally.