聚苯基单醚喹噁啉薄膜的性能与物理老化

研究了物理老化对聚苯基单醚喹啉薄膜的结构与力学性能的影响 .用差示扫描量热计 (DSC)及正电子湮没寿命谱 (PALS)方法表征了两种不同物理老化条件试样的凝聚结构以及自由体积的差别 .结果表明 ,物理老化使聚苯基单醚喹啉薄膜玻璃化转变温度移向高温 ,在其末端出现热焓吸收峰 ,分子链堆砌紧密使自由体积减小 ,分子可动性降低 .用动态力学分析 (DMTA)以及静态拉伸性能测试等方法研究了两类试样的力学性能 ,结果表明 ,物理老化后 ,试样的动态储能模量稍有增加 ,力学损耗降低 .而静态拉伸实验的断裂应变降低 ,屈服应力增加 ,断裂能降低 ,试样在宏观上由韧性断裂变为明显的脆性断裂 .     

聚苯基单醚喹噁啉薄膜的形变机理

非晶聚合物塑性变形机理主要包括银纹化和剪切屈服[1 ,2 ] .银纹化是链段局部排列疏松区域或缺陷在膨胀应力作用下成为银纹核 ,引发银纹 ,银纹 本体界面应变软化 ,银纹微纤拉伸的应变硬化过程 ,使得聚合物银纹微纤沿拉伸方向取向 ,伴随这一过程聚合物的体积增大[3] .剪切屈服是分子链沿拉伸方向的流动以及分子链间的滑移过程 ,这一过程使聚合物形状改变而体积不变 .聚合物的形变机理与聚合物的内在性质如临界缠结分子量 ,缠结密度或硬度等有关[4] .聚苯基单醚喹啉是一种高性能的芳杂环聚合物 ,它的玻璃化转变温度是 2 98℃ ,它具有耐高温…     

含苯并呋喃环的聚苯基单醚喹噁啉

由含苯并呋喃环的芳族四酮与芳族四胺进行溶液缩聚反应，合成了两种新的含苯并呋喃环的聚苯基单醚喹啉，用红外光谱、元素分析、差热及热重分析对聚合物进行了表征，测试了力学性能，并对其在较低温度下形成的多孔薄膜进行了分离、透过性能的研究，实验结果表明，聚合物不仅具有优良的耐热性与力学性能，也具有良好的纯水透过率和截留性能．     

物理老化对聚甲基丙烯酸甲酯薄膜的玻璃化转变、银纹化特征及力学性能的影响

物理老化对聚甲基丙烯酸甲酯薄膜的玻璃化转变、银纹化特征及力学性能的影响沈静姝，叶卫君（中国科学院化学研究所北京１０００８０）关键词聚甲基丙烯酸甲酯，玻璃化转变，银纹化，物理老化银纹化是聚合物中特有的现象，在应力作用下，许多非晶聚合物、一些半结晶性聚合...     

凝聚条件对聚甲基丙烯酸甲酯薄膜银纹化现象的影响

<正> 当玻璃态聚合物受张力作用时,常可以观察到银纹形成,它是聚合物材料内部断裂的先兆,银纹是垂直于拉伸方向的平面缺陷,与正常裂纹不同,银纹的质量不是零,而是由沿拉伸方向排列的高度应变的微纤及孔穴组成,银纹的典型尺寸约为长100μm,宽1—2μm,微纤的直径约5—15nm,微纤的总体积分数约占20—50％,微纤能支撑负荷,因此银纹在控制聚合物屈服以后的力学行为中的作用一直是个重要的研究领域。近年来从聚合物分子缠结网对银纹生长,微纤断裂及银纹稳定性的影响方面做了一些有意义的工作。     

芳杂环高分子分离膜分离、透过性能的研究——聚苯基单醚喹噁啉(PPQ)超滤膜的研制

随着超滤技术应用范围的不断开拓和新技术工业领域的相继出现,极待开发机械强度好并具有优良的耐温性、耐生物侵蚀性、耐酸碱和耐有机溶剂性等高性能的超滤膜材料,以满足在苛刻条件下的分离、提纯、浓缩与富集以及高温灭菌过程的需要。多年来,国内外学者陆续将多种合成高分子材料用于超滤分离技术中,特别是杂环高分子如聚酰亚胺等,其优良的机械性能、耐温性和耐生物侵蚀性颇引人注目。但是,在已开发的合成高分子超滤膜材料中,由于某些分子的主链上含有—CN、—CONH—、—COOR、—CH_2O—、     

含苯并呋喃环的聚苯基单醚喹噁啉

 由含苯并呋喃环的芳族四酮与芳族四胺进行溶液缩聚反应，合成了两种新的含苯并呋喃环的聚苯基单醚喹啉，用红外光谱、元素分析、差热及热重分析对聚合物进行了表征，测试了力学性能，并对其在较低温度下形成的多孔薄膜进行了分离、透过性能的研究，实验结果表明，聚合物不仅具有优良的耐热性与力学性能，也具有良好的纯水透过率和截留性能．     

3种新型聚苯基醚喹噁啉的合成

用4,4′-二氟代二苯甲酰与双酚A的溶液缩聚制得聚醚苯偶酰(PEB),经邻苯二胺改性后,通过两步法得到聚苯基醚喹噁啉（PEQ-1）。 在PEB的改性反应中加入质量分数分别为1.0%和1.3%的3,3′,4,4′-四胺基二苯醚,可有效增加聚苯基醚喹噁啉的相对分子质量,得到PEQ-2和PEQ-3（总收率≥90%）,其质均相对分子质量分别为7.492×104和1.486×105。 并用IR、 NMR等对这些聚合物进行了表征。 该法操作简便,具有潜在的应用价值。     

分子量对聚丙烯银纹形态的影响

<正> 聚合物在拉伸状态下发生脆性破坏和银纹的形成与发展有着密切联系,银纹与其它局部塑性形变的本质区别在于银纹中存在的微纤,它将两个银纹面连接起来,并能在其中传递载荷,在拉伸应力的作用下,银纹微纤断裂发展成为裂纹,最后导致材料破坏。 最近十几年里,对以PS、PMMA、PC为代表的非晶态聚合物中的银纹化现象作了比较广泛、深入的研究(如不同热历史、不同的银纹化环境等),对银纹的引发、增长、微纤的断裂等现象进行了大量的观察,也提出了一些理论模型来解释银纹化的全过程,这是因为非晶态聚合物具有相对简单的三维空间结构。     

The Effects of Physical Aging on Tensile Behavior of Polyphenylquinoxaline Films

Themechanicalpropertiesareaffectedbyphysicalaging'.P0lyphenylquin0xaline(PPQ-E)-anar0maticheter0cyclicpolymer-hasmanyusesduetoitshighperformance2'.Theaimofthepaperistostudytheeffects0fphysicalagingontensilepr0pertyf0rPPQ-Efilms.T0avoidnewphysicalagingeffectduringstretchingl4.tensiletestmeth0df0rnotchedspecimensandDSCmeasurementareusedintheexperiments.ExperimentaIThePPQ-Esynthesizedinthelab0ratorywascastintoafilmO.O5mminthickness,whichwasthencutintorectangularspecimenDf35rnmlongandl.7mm…     

聚合物银纹化的分子机理

本文综述了近年来有关聚合物银纹化分子机理方面研究的进展情况。内容包括银纹的起源、生长、断裂过程以及各种结构关系对银纹的影响，并对几种典型的聚合物银纹形态进行了描述。     

Modulated Differential Scanning Calorimetry Observation of Physical Ageing in Polymers

Modulated-temperature differential scanning calorimetry (M-TDSC) is becoming a useful tool in the characterisation of thermal behaviour of polymers. In this paper, we discuss whether the non-reversing M-TDSC signal can be used, quantitatively and directly, to study the process of physical ageing in polymers. Difference exists between the values of relaxation enthalpy determined by using average heat capacity, <C _p>, signal as for conventional DSC and non-reversing heat capacity, C ⁿ _p, signal. When the signal of reversing heat capacity of unaged sample is considered as baseline for <C _p> and C ⁿ _p signals, the difference disappears. It is concluded that non-reversing M-TDSC signal can be used to observe the process of physical ageing semi-qualitatively and directly. With increasing annealing time, the peak of the imaginary part, C″_p, of the complex heat capacity becomes narrow, but peak area changes little. This indicated that C″_p is not correlated with relaxation enthalpy. It may be related to entropy change during the modulation. However, the entropy change is quite small. This revised version was published online in August 2006 with corrections to the Cover Date.     

高聚物的物理老化和链的凝聚缠结

本文基于高聚物在物理老化和拉伸变形过程中构象弛豫行为的实验结果,进一步阐明了高分子链局部凝聚缠结的观点。     

Ageing of filled polymers

It is tried to examine briefly all the aspects of filler interactions with polymer ageing, including direct chemical (catalysis of degradation, stabilising effects) and physical (screen and thermooptical effects, modification of transport properties) interactions as well as indirect ones such as stabiliser trapping, influence on the rate of mechanical properties change or interfacial phenomena.     

Thickness, Morphology and Structure of Sol-Gel Hybrid Films: I—The Role of the Precursor Solution's Ageing

The physical properties of inorganic-organic sol-gel hybrid films are determined by a large number of processing parameters, as the initial recipe, the catalysis conditions and the film deposition technique. This work focuses on the influence of the precursor solution's ageing on the quality and structure of hybrid silica-polytetrahydrofuran films, prepared by spin coating. The inorganic precursor, tetraethylorthosilicate, was hydrolysed under acid catalysis and using ethanol as co-solvent. The hydrolysis molar ratio (R) was fixed at 4. Different polymer concentrations of two average molecular weights (M _n = 650 and 2900) were added to the initial colloidal solutions. Ageing took place in open containers. The thickness and surface texture parameters of the films were determined by profilometry, and their structures studied by FTIR. It is shown that the films' thickness increases with the ageing of the precursor solution, more steeply for the hybrid films with higher polymer content and higher M _n. The best films obtained, which present the highest thickness and the lowest relative roughness, are those prepared from the most aged solutions. The FTIR results show that the films' porosity increases with the ageing of the precursor solution, and that the distribution of oligomeric species in solution is maintained upon film deposition. Therefore, the structure of the film is essentially determined by the extension of the condensation reactions until the spinning moment.     

Durability of Protective Polymers: The Effect of UV and Thermal Ageing

This paper aimed at studying thermal contribution to the UV ageing process, trying to understand which decisive changes reduce the protective effectiveness of polymer coatings. In this paper the effects on the shielding efficacy of different protective polymers, applied on different low porosity stones have been studied, comparing ageing of a 1000 h simulated solar UV radiation with thermal ageing at about 50 °C, which is the temperature usually reached in UV chambers. The aim of the study has been the evaluation of a possible thermal contribution: the testing methods have been suggested by UNI-Normal Italian protocol and include capillary water absorption, static contact angles and colour variation measurements. A reduction in protective efficacy has been highlighted, probably due to both oxidation and a surface rearrangement of the polymeric material; in most cases chemical degradation of the macromolecules did not occur.     

Effects of Water and Chemical Solutions Ageing on the Physical,Mechanical, Thermal and Flammability Properties of Natural Fibre-Reinforced Thermoplastic Composites

Biocomposites comprising a combination of natural fibres and bio-based polymers are good alternatives to those produced from synthetic components in terms of sustainability and environmental issues. However, it is well known that water or aqueous chemical solutions affect natural polymers/fibres more than the respective synthetic components. In this study the effects of water, salt water, acidic and alkali solutions ageing on water uptake, mechanical properties and flammability of natural fibre-reinforced polypropylene (PP) and poly(lactic acid) (PLA) composites were compared. Jute, sisal and wool fibre- reinforced PP and PLA composites were prepared using a novel, patented nonwoven technology followed by the hot press method. The prepared composites were aged in water and chemical solutions for up to 3 week periods. Water absorption, flexural properties and the thermal and flammability performances of the composites were investigated before and after ageing each process. The effect of post-ageing drying on the retention of mechanical and flammability properties has also been studied. A linear relationship between irreversible flexural modulus reduction and water adsorption/desorption was observed. The aqueous chemical solutions caused further but minor effects in terms of moisture sorption and flexural modulus changes. PLA composites were affected more than the respective PP composites, because of their hydrolytic sensitivity. From thermal analytical results, these changes in PP composites could be attributed to ageing effects on fibres, whereas in PLA composite changes related to both those of fibres present and of the polymer. Ageing however, had no adverse effect on the flammability of the composites.     

Ageing of wet-synthesized oxide powders

Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original sintering properties can be recovered after washing the aged powders with ethanol in a basic medium.     

Thermodynamic Properties and Kinetics of the Physical Ageing of Amorphous Glucose, Fructose, and Their Mixture

The physical ageing characteristics of glucose, fructose, and their mixtures were studied using standard differential scanning calorimetry (DSC). The inflection, onset, midpoint,half-height, and endpoint glass transition temperature (T _g), fictive temperature (T _f), and relaxation enthalpy (H) were measured as a function of ageing time. The relationship between H and T _f was evaluated. The time dependence of H was fit using the Cowie and Ferguson model. The ageing rate was expressed in terms of the average relaxation time (<>) and the entropy production (P). It was found that the fructose component decreased the rate of ageing of the mixtures.This revised version was published online in November 2005 with corrections to the Cover Date.