聚乙烯-碳酸钙复合材料的光氧化降解及沿深度的分布

研究了聚乙烯-碳酸钙复合材料薄膜和厚试样的自然光氧化降解.结果表明,碳酸钙含量对复合材料的氧化程度影响不大,但羟基指数随碳酸钙含量增大而增大.不同的表面处理对复合材料的氧化降解影响很大,用钛酸酯进行表面处理,可大大促进聚乙烯的氧化降解,其它的偶联剂则没有明显的影响.用显微红外研究厚试样中氧化程度随深度的变化,发现从表面到中心,不同体系的羰基指数表现出不同程度的衰减,断面呈不同的老化形貌.含钛酸酯的体系,羰基指数沿深度方向明显下降,曲线的转折点与断面上的裂纹深度相对应.填充碳酸钙以及碳酸钙的表面处理会明显降低聚乙烯的结晶度.结合氧化程度分布、裂纹以及结晶度对复合材料的光氧化机理进行了讨论.     

液态氧化法处理超高分子量聚乙烯纤维

用液态氧化法对超高分子量聚乙烯纤维进行了表面处理,研究了处理介质、处理时间对超高分子量聚乙烯／环氧复合材料层间剪切强度的影响,用扫描电子显微镜、ＸＰＳ表面元素分析、毛细浸润法测接触角等方法探讨了纤维表面性能处理前后的变化,以及纤维与树脂的界面结合情况。     

聚乙烯光引发交联过程中的表面光氧化和光稳定

通过测定凝胶含量并利用红外-光声光谱和光电子能谱对光交联聚乙烯表面氧化程度和氧化产物进行了研究.结果表明,聚乙烯光交联过程中随着光照时间的增加,表面光氧化加剧,氧化产物主要是氢过氧化物和含羰基的化合物.考察了预辐照和添加受阻胺型光稳定剂对聚乙烯光交联过程的影响,发现这两种方法都能有效地降低光交联聚乙烯(XLPE)的表面氧化,但有些光稳定剂会降低XLPE的交联度.     

乙烯等离子体处理的云母表面结构及表面性质

用元素分析、色-质谱、裂解气相色谱和顺磁共振等方法研究了经乙烯等离子体处理的云母表面化学结构及处理过程。结果表明,云母颗粒表面形成了厚数十埃的等离子体聚乙烯膜,其化学结构与反应体系中无云母时得到的等离子体聚乙烯膜相同。通过扫描电镜观察到云母片表面的聚合膜具有规则的海星状花样,随处理时间的延长花样按比例长大。水与云母表面的接触角数据说明,乙烯等离子体处理使云母表面的疏水性提高到聚乙烯的水平,比氩气等离子体、硅烷偶联剂及钛酸酯偶联剂处理的效果均更为显著。     

聚丙烯/凹凸棒石纳米复合材料的制备与性能研究

以聚丙烯(PP)为聚合物基体,天然凹凸棒石(ATP)为无机组分,经过氧化聚乙烯对ATP表面进行包覆处理,用熔融共混的方法制备了PP/ATP纳米复合材料.扫描电镜结果显示,经本方法处理后的ATP在PP基体中分散较为均匀.ATP棒晶簇直径最佳分散尺寸能达到20~40 nm,比未处理ATP在基体中的棒晶簇直径小10 nm以上;XRD测试表明,未处理ATP和处理后的ATP均有使PP晶粒细化的作用,同时不改变PP的α晶型;DSC结果显示,ATP的加入提高了PP的结晶温度和结晶度,说明ATP有一定的成核作用.通过对复合材料的力学性能测试发现,经过处理的ATP制备的复合材料力学性能优于未处理ATP复合材料对PP力学性能的改善.其中ATP与氧化聚乙烯固含量的质量比为2∶1,ATP含量为3 wt%时复合材料力学性能达到最好.缺口冲击强度比纯PP最高提高了83%,提高幅度显著;经过处理的ATP制备的复合材料拉伸强度提高了6%~11%;弯曲强度提高了33%~45%;弯曲模量提高了90%~106%.     

硼酰化钴在橡胶与镀锌钢丝粘合中的应用研究

研究硼酰化钴的用量变化对丁苯橡胶／天然橡胶与镀锌钢丝粘合的影响,通过表面分析对其粘合机理进行了研究。研究表明：硼酰化钴对丁苯橡胶／天然橡胶与镀锌钢丝粘合的粘合增强作用十分明显。硼酰化钴添加2phr左右,粘合性能最佳,同时硫化胶的物理性能得到改善。X-射线光电子能谱分析表明,粘合物镀锌钢丝界面中存在ZnO、ZnS、CoS2,说明粘合时发生了Zn的硫化反应,硼酰化钴中的钴向钢丝表面迁移,继而在锌层中扩散,提高了ZnO和ZnS晶格的缺陷浓度,这两种行为的共同作用,使橡胶与镀锌钢丝的粘合强度显著提高。     

纳米Ni-Co-B非晶态合金抗氧化行为的原位XPS研究

采用原位XPS手段研究了纳米非晶态Ni-Co-B合金中B和Co的抗氧化行为、表面组成与氧化处理条件之间的关系以及各元素含量随深度的变化趋势.结果发现,氧优先氧化表面的元素B物种,在元素态B被完全耗尽后才开始氧化表面的元素态Co物种,在元素态B和Co均被完全氧化后,元素态Ni才开始被氧化.另外,研究还发现,在氧化过程中,B和Co的氧化物具有在表面富集的倾向.正是由于B和Co的优先被氧化才保护了催化加氢反应中的活性中心--元素态Ni.     

石墨纤维氧化表面处理对环氧树脂界面粘合影响的研究

<正> 由于石墨纤维表面能较低,因此石墨纤维/树脂复合材料的界面粘合情况极为重要,为了阐明界面的粘合机理,需要对石墨纤维的表面特性如表面活化能、浸润性、表面积、表面化学基团等方面进行研究,为了提高复合材料的层间剪切强度,常常用各种方法对石墨纤维的表面进行处理,以期改变纤维表面的物理和化学结构来增加纤维和环氧树脂     

木粉/聚乙烯复合材料的等离子体表面处理——等离子体处理时间对复合材料表面特性的影响

为改善木粉/聚乙烯复合材料的表面粘接性,实现木粉/聚乙烯复合材料的无缝连接,利用低温等离子体处理技术,对木粉/聚乙烯复合材料进行了表面处理.采用接触角测试、傅立叶变换红外光谱分析(FTIR)以及X射线光电子能谱分析(XPS)研究了等离子体处理前后复合材料表面性能的变化.试验结果表明,经等离子体处理后,复合材料表面的接触角减小,表面润湿性得以改善;FTIR分析结果表明,经等离子体处理后,复合材料表面有—OH、—C=O和—O—C=O基团生成;XPS分析表明,经等离子体处理后,复合材料表面含氧基团的含量增加,在较短的时间内表面氧元素含量增加会达到平衡,且生成大量的—O—C=O基团。     

碳纤维负载Wacker催化剂的X-射线光电子能谱研究

研制了一种在常温下对一氧化碳氧化具有高活性多相的 Wacker催化剂。活性组份负载于经活化处理的聚丙烯腈基(PAN)的碳纤维上。PAN碳纤维经活化处理后表面上形成一些含氧官能团(-COOH,C=O,—OH),并使其比表面积增大到～1000m~2/go上述催化剂在常温下(20—40℃)对浓度为数千ppm的一氧化碳的氧化显示出良好的催化活性。     

Adhesive Contact in Surface Layers of Low-Density Polyethylene Irradiated in Air

The formation of adhesive bond was studied for bulk low-density polyethylene irradiated in air. It was shown that the amount of the gel fraction over the depth of the surface layer is a signature of the relative contribution of degradation and crosslinking to the structure of the material at a given depth and makes it possible to determine its minimal depth below which the polymer has a sufficient strength required for the formation of an adhesive joint.     

Anilinium 5-sulfosalicylate electropolymerization on mild steel from an aqueous solution of sodium 5-sulfosalicylate/disodium 5-sulfosalicylate

Aniline is electropolymerized on bare and chemically pretreated mild steel from an aqueous solution of 0.10 M anilinium 5-sulfosalicylate in 0.20 M sodium 5-sulfosalicylate/0.20 M disodium 5-sulfosalicylate buffer as the supporting electrolyte, at room temperature. At constant anodic potential black poly(anilinium 5-sulfosalicylate) (PANISSA) films are obtained on bare mild steel and characterized by IR spectroscopy, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). IR spectroscopic analysis confirms typical polyaniline structure with 1,4-disubstituted aromatic nuclei and incorporation of sulfosalicylate anions as dopants. Adhesion of PANISSA films is significantly improved when the mild steel electrode surface is chemically pretreated by 0.10 M ammonium peroxydisulfate aqueous solution. The IR spectra of the films obtained on chemically pretreated mild steel surface indicate an interaction between PANISSA and products of the mild steel oxidation by peroxydisulfate. The SEM images show differences in morphology between PANISSA films synthesized on bare and chemically pretreated mild steel surface. The efficient anticorrosion behavior of adherent PANISSA film on chemically pretreated mild steel is proved by EIS. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 12, pp. 1497–1504. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes.” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Template‐free synthesis of polyaniline nanobelts as a catalytic counter electrode in dye‐sensitized solar cells

Polyaniline (PAn) nanobelts were synthesized by simply mixing aniline and hydrochloric acid aqueous solution with ammonium peroxydisulfate and hydrochloric acid aqueous solution at room temperature without any templates. The PAn nanobelt paste with polytetrafluoroethylene as binder is proper for low‐cost and efficient casting processes such as doctor blade method, screen printing, spin‐casting, and even roll‐to‐roll painting. The porous network structure of the PAn nanobelt counter electrode was obtained after drying the paste on the conductive glass. The as‐prepared PAn nanobelt counter electrode showed nearly equivalent electrochemical catalytic activity as that of thermal decomposed Pt counter electrode, owing to the well‐connected conductive network and high active surface area. The power conversion efficiency of dye‐sensitized solar cell with PAn nanobelt counter electrode attained 90% of the value of the cell with Pt counter electrode. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical oxidative polymerization of aminodiphenylamines

The course of oxidation of 4-aminodiphenylamine with ammonium peroxydisulfate in an acidic aqueous ethanol solution as well as the properties of the oxidation products were compared with those of 2-aminodiphenylamine. Semiconducting oligomers of 4-aminodiphenylamine and nonconducting oligomers of 2-aminodiphenylamine of weight-average molecular weights 3700 and 1900, respectively, were prepared by using an oxidant to monomer molar ratio of 1.25. When this ratio was changed from 0.5 to 2.5, the highest conductivity of oxidation products of 4-aminodiphenylamine, 2.5 x 10 (-4) S cm (-1), was reached at the molar ratio [oxidant]/[monomer] = 1.5. The mechanism of the oxidative polymerization of aminodiphenylamines has been theoretically studied by the AM1 and MNDO-PM3 semiempirical quantum chemical methods combined with the MM2 molecular mechanics force-field method and conductor-like screening model of solvation. Molecular orbital calculations revealed the prevalence of N prim-C10 coupling reaction of 4-aminodiphenylamine, while N prim-C5 is the main coupling mode between 2-aminodiphenylamine units. FTIR and Raman spectroscopic studies confirm the prevalent formation of linear N prim-C10 coupled oligomers of 4-aminodiphenylamine and suggest branching and formation of phenazine structural units in the oligomers of 2-aminodiphenylamine. The results are discussed with respect to the oxidation of aniline with ammonium peroxydisulfate, leading to polyaniline, in which 4-aminodiphenylamine is the major dimer and 2-aminodiphenylamine is the most important dimeric intermediate byproduct.     

Freezing transition of wetting film of tetradecane on tetradecyltrimethylammonium bromide solutions

We have performed ellipsometry and surface tensiometry at tetradecyltrimethylammonium bromide (TTAB) aqueous solution surface coexisting with tetradecane lens as a function of the molality of TTAB and the temperature under atmospheric pressure. From the theoretical analysis of the coefficient of ellipticity, it was clarified that the liquid monolayer comprising the surfactant and alkane is formed at higher surfactant concentrations by the wetting transition of tetradecane lens on the aqueous solution, and the solid monolayer is formed by lowering temperature (freezing transition). The results of the surface tension measurement support the occurrence of wetting transition and the freezing transition. A phase diagram of the wetting film was constructed by ellipsometry and surface tensiometry, of which the mixed solid monolayer had never been reported before. From the thermodynamic analysis of the phase diagram, it is also demonstrated that the TTAB surface density decreases accompanied with the freezing transition, which agrees with surface densities of TTAB calculated from surface tension vs. concentration curves.     

ABSORPTION SPECTRA AND ACID-BASE DISSOCIATION OF THE 4-ALKYL DERIVATIVES OF 7-HYDROXYCOUMARIN IN SELF-ASSEMBLED SURFACTANT SOLUTION: COMMENTS ON THEIR USE AS ELECTROSTATIC SURFACE POTENTIAL PROBES

Abstract— The absorption spectra of the un-ionized and ionized forms of 4-heptadecyl-7-hydroxycoumarin (HHC) in aqueous self-assembled surfactant solution have been investigated. From a comparison with the absorption spectra of 7-hydroxycoumarin, 7-hydroxy-4-methylcoumarin (MHC) and HHC in neat organic solvents and organic solvent/water mixtures it is shown that the 7-hydroxycoumarin chromophore of HHC in self-assembled surfactant solution resides, on average, in an interfacial microenvironment which has a lower effective dielectric constant than that of the bulk aqueous solution. The absorption spectrum of the ionized form of HHC in aggregates of self-assembled surfactant molecules with cationic quaternary ammonium headgroups is found to be consistent with there being specific molecular interaction between the anionic chromophore and the quaternary ammonium headgroup. pH titrations performed with MHC in pure water and in four molar aqueous solutions of sodium chloride and tetra-methylammonium chloride indicate that the acid-base dissociation of HHC in charged micelles and vesicles should not be substantially influenced by any interfacial salt-effects, and that the acid-base dissociation of HHC in cationic micelles and vesicles with quaternary ammonium headgroups should not be markedly affected by the specific molecular interaction that exists. Estimates of the electrostatic surface potentials of a number of self-assembled surfactant aggregates are made by utilising the acid-base dissociation of HHC and assuming that the nonionic micelles of n -dodecyl octaoxyethylene glycol monoether (C₁₂E₈) can serve as a reference state of zero surface potential. The validity of this assumption in relation to both micelles and vesicles is discussed in detail.     

In‐depth diffusion of oxygen into LDPE exposed to an Ar–O2 atmospheric post‐discharge: a complementary approach between AR‐XPS and Tof‐SIMS techniques

The in‐depth oxygen diffusion into a low density polyethylene film is performed in the post‐discharge of an atmospheric plasma torch, supplied in argon as carrier gas and with or without oxygen as reactive gas. The chemical and structural properties of the polymer surface and bulk are studied in terms of plasma parameters (treatment time, power, and reactive gas flow rate). A good correlation between XPS and Fourier transform infrared spectroscopy analyses is demonstrated. The penetration depth of oxygen into the bulk of the polymer is investigated by angle resolved‐XPS and time‐of‐flight SIMS. It is shown that, depending on the plasma conditions, oxygen could penetrate up to 20–40 nm into the low density polyethylene during the atmospheric plasma treatment. Copyright © 2014 John Wiley & Sons, Ltd.     

Application of polyaniline/bacterial extracellular polysaccharide nanocomposite for removal and detoxification of Cr(VI)

Polyaniline/bacterial extracellular polysaccharide (Pn/EPS) nanocomposite was prepared by in situ polymerization of aniline using ammonium peroxydisulfate as oxidant. Transmission electron micrograph showed that the surface of the nanocomposite was rough, providing good possibility for adsorption of Cr(VI). Under optimized conditions, the nanocomposite removed 97.3 % (25 mg L^?1) of Cr(VI) from aqueous solution. The Freundlich isotherm model and pseudo-first order rate expression better described the adsorption equilibrium of Pn/EPS nanocomposite. X-ray diffractogram peak for Cr₂O₃ (2θ = 24.5) in the nanocomposite confirmed the reduction of Cr(VI). Fourier transform infrared spectroscopy pattern of the nanocomposite confirmed the ionic interaction between Cr species and surface functional groups. The results of the study indicate that Pn/EPS nanocomposite could be used for the removal and detoxification of Cr(VI) from aqueous solution.     

Polymer analysis: Molecular structure and properties of industrial polymers

Low density polyethylenes made by the known high pressure processes show significantly different molecular structures. The physical and technological properties are closely related to molecular structure and morphology. For example, the adhesive strength of a laminate consisting of an ozone treated low density polyethylene film and an aluminum foil depends strongly on the synthesis conditions. The molecular structures and dilute solution properties of many fully aromatic thermotropic liquid crystalline copolyesters can now be determined using the new solvent 3,5-bis(trifluoromethyl)phenol. A typical random copolyester was fractionated by precipitation from solution, and the fractions were studied in detail by viscometry, integrated and dynamic light scattering, and size exclusion chromatography. From the structure data thus obtained the molecular mass distribution and the persistence length were calculated. Polymer blends, block copolymers, and graft copolymers can be characterized by fractionation procedures using demixing solvents in an ultracentrifuge and subsequent analysis of the fractions.     

Crystallization of aqueous ammonium sulfate particles internally mixed with soot and kaolinite: crystallization relative humidities and nucleation rates

Using optical microscopy, we investigated the crystallization of aqueous ammonium sulfate droplets containing soot and kaolinite, as well as the crystallization of aqueous ammonium sulfate droplets free of solid material. Our results show that soot did not influence the crystallization RH of aqueous ammonium sulfate particles under our experimental conditions. In contrast, kaolinite increased the crystallization RH of the aqueous ammonium sulfate droplets by approximately 10%. In addition, our results show that the crystallization RH of aqueous ammonium sulfate droplets free of solid material does not depend strongly on particle size. This is consistent with conclusions made previously in the literature, based on comparisons of results from different laboratories. From the crystallization results we determined the homogeneous nucleation rates of crystalline ammonium sulfate in aqueous ammonium sulfate droplets and the heterogeneous nucleation rates of crystalline ammonium sulfate in aqueous ammonium sulfate particles containing kaolinite. Using classical nucleation theory and our experimental data, we determined that the interfacial tension between an ammonium sulfate critical nucleus and an aqueous ammonium sulfate solution is 0.064 +/- 0.003 J m(-2) (in agreement with our previous measurements), and the contact angle between an ammonium sulfate critical nucleus and a kaolinite surface is 59 +/- 2 degrees. On the basis of our results, we argue that soot will not influence the crystallization RH of aqueous ammonium sulfate droplets in the atmosphere, but kaolinite can significantly modify the crystallization RH of atmospheric ammonium sulfate droplets. As an example, the CRH50 (the relative humidity at which 50% of the droplets crystallize) ranges from about 41 to 51% RH when the diameter of the kaolinite inclusion ranges from 0.1 to 5 microm. For comparison, the CRH50 of aqueous ammonium sulfate droplets (0.5 microm diameter) free of solid material is approximately 34.3% RH under atmospheric conditions.