高分子物理中动态性能指标的教学

动态性能是高分子结构及其运动的重要表现,也是高分子物理教学中的一个难点.本文介绍了高聚物动态力学性能的教学实践,从复数概念的引入着手,理清动态、复数、复数表达等之间的关系,帮助同学更好地理解高聚物的动态性能,同时对教科书中一些概念的说法提出了自己的看法.     

高分子物理课程知识体系的构建革新

高分子物理是高分子材料相关专业的专业基础课,内容丰富,章节间关系复杂,课程主线往往不容易把握。本文从运动对高聚物性质(性能)的决定性作用角度,提出了构建高分子物理课程知识体系的观点:在高分子结构部分,充实原子、键等部分作用的论述,完善高分子结构划分的层次;明确高分子不同结构层次都具有运动与变化能力的认知,重点突出不同高分子结构运动、变化的特征和规律;根据根据每一个结构层次运动特征,综合理解结构、结构的变化对高分子性能的影响。     

高分子多尺度结构与动力学的固体NMR研究

高分子材料中的微观结构和动力学特征决定了材料的最终物理化学性能,并具有典型的时间和空间上的多尺度特性。在不同时空尺度上表征凝聚态下高分子中多尺度的结构、动力学及其动态演变等问题,进而阐明其结构-性能间的关系一直是高分子科学研究中的挑战性课题。目前,固体NMR技术已成为从原子至100nm的空间和10-9～10s的时间尺度上研究固态高聚物体系中多层次结构和复杂运动并阐明其结构与性能关系的有力工具。本文将综述我们近年来系统构建的多尺度固体NMR实验技术,及其在阐明高分子链结构、链间相容性和相互作用、界面相结构及相区尺寸、以及从高频到超慢链运动等问题中的应用。     

高分子结构与性能关系原理-结构层次的意义

高分子结构是高分子性能的重要物质基础,对其结构进行合理的划分,有助于准确把握高分子物理知识体系的内在脉络。高分子结构层次的划分不仅要思考静态时特定质点在空间的堆砌特征,而且也要考虑结构出现运动或是变化的基本单元。按照质点尺度的不同,高聚物的结构可以分为单一高分子结构(链结构)、多个高分子结构(凝聚结构)和多种高分子结构(织态结构)三个主要层次。其中,化学因素所确定的链结构层次包括相对分子质量以及构造、构型等同分异构体形式;物理因素所确定的结构层次为高分子局部质点集合在空间的堆砌和排列;链段是容易被忽视、但又是最为重要的运动(变化)单元。     

对功能高分子课程教学的思考

功能高分子的设计思想是功能高分子课程的灵魂 ,它以高分子物理学所研究的结构与性能之间关系为基础。结构与性能之间的关系是贯穿功能高分子课程始末的主线。功能高分子材料有三种设计途径 ,即化学结构设计、聚集态结构设计和复合结构设计     

高分子间相互作用的特点及意义

高分子间的相互作用与小分子间的相互作用有着显著的区别，导致高分子物质在凝聚态结构和诸多性能上明显地有别于小分子物质。本文就如下七个方面：特别强的高分子间相互作用、特殊的高聚物溶解过程、马克三角形原理、特征温度、特有的单链凝聚态、凝聚缠结和超分子体系来讨论高分子间相互作用的重要性及其对高聚物的结构和性能的影响。     

“高分子物理”及“高分子物理实验”2门精品课程的建设

"高分子物理"(在中国科学技术大学叫"高聚物的结构与性能")和"高分子物理实验"课是该校高分子科学与工程系本科生的必修课。为了讲好和全面建设这两门课,作者倡导并积极开展教学研究,发表39篇教学研究论文,作者把这些研究心得和成果及时引入教学中,先后编写和出版了十几本教材及教学参考书,教学质量不断提高,并逐步形成了有鲜明特色的教学,在国内高校产生了很好的影响。通过多方面的建设,2005年"高聚物的结构与性能"被评为国家级精品课程,2006年"高分子物理实验"被评为安徽省精品课程。     

高分子物理本科教学之我见

高分子物理是一门物理课,其内涵为高分子物质的结构、结构演变与各层次结构单元的运动规律,而非聚合物的"结构与性能"关系.这门课为解释结构与性能关系提供基础概念与理论,但不是"结构与性能"关系本身.这样的定位决定了高分子物理课不应采用系统教学法,而应当采用逻辑教学法,即从一个不证自明的公理(逻辑起点)出发,沿着一条主线,依次导出、建立全部理论体系.在高分子物理中,这个逻辑起点就是长链结构,主线就是熵弹性.故该门课程应按熵弹性这条主线展开.对现行高分子物理课程内容进行分析,大多数内容均可用熵弹性的主线串起来,另外少部分内容也与熵弹性有密切关系.应根据这两点对现行课程体系与教学方法进行改造,为课程各项内容之间建立逻辑关系,方便学生的学习与应用.     

试论高聚物结构与性能关系的三个层次

高分子物理的基本任务之一就是探求高聚物的结构与性能,揭示结构与性能之间的内在联系及其基本规律。高聚物结构与性能的关系应该包含3个层次:通过分子运动联系的"分子结构与材料性能"关系、通过产品设计联系的"凝聚态结构与制品性能"关系和通过凝聚态物理知识联系的"电子态结构与材料功能"关系。传统教材上仅讲授"结构与性能关系",有相当的局限性,需要在研究生阶段补充有关"凝聚态结构与制品性能"关系和"电子态结构与材料功能"关系的课程。     

Mark-Houwink方程中系数的意义及应用探索——K值的意义及对高分子特性的评估

K值是Mark Houwink经验公式 ([η]=KMα)中的两个常数之一 .理解它的意义不仅有利于公式的应用 ,而且有可能有利于从不同的角度认识高分子材料的性质 .考虑到K是由高分子材料和使用的溶剂性质所决定的 ,因此引入溶剂的一些参数对Mark Houwink经验公式中的K的意义进行了初步探讨 .结果显示 ,高聚物的K和溶剂的极性参数 ,如Reichardt的Et(30 )及Kamlet Taft的π 之间有一定的线性关系 ,而根据这些关系外推发现所有这些被引用的高分子材料似乎可以由此被划分成两大类 ,并进一步推导出高分子材料的极性 .此简易方法得出的数据得到文献和近来的有关研究结论的认可 .     

Structural aspects in polymers: interconnections between conformational parameters of the polymers with their physical properties

This article focuses on the influence of the geometric structure of the polymer chain on the physical properties of polymers. It is shown that for polyheteroarylenes the Kuhn segment calculated based on the geometric structure of the polymer chain has a good correlation with the physical properties of those polymers. For aliphatic polymers, a volume factor is suggested that equals the ratio of the Van der Waals volume of pendant substitute to the volume of the whole polymer chain. It is shown that the properties of aliphatic polymers that depend on free volume are well described by this value.     

Unified study of the different physical properties of amorphous polymers

Uptil now it has not been possible to explain the different physical properties of amorphous polymers using a model based on a single conceptual scheme. In this paper, a phenomenological model is proposed which tries to explain the mechanical, optical and thermal properties (both thermal conductivity and expansivity) of amorphous polymers. The model has similarities with the composite model, proposed by the present authors, which has proved to be successful in interpreting the different physical properties of semicrystalline polymers. The present model considers the bulk form of the polymer as an aggregate of microscopic units possessing intrinsic physical properties. On drawing, the development of anisotropy in different physical properties is supposed to be due to the development of preferred orientation of these units. The development of the preferred orientation has been estimated directly from birefringence data. The agreement between the calculated and experimental values of the elastic modulus, thermal conductivity and thermal expansivity of PVC, PMMA and PS is found to be reasonable good.     

Far-infrared studies of microphase separation in sulfonated ionomers

Far-infrared spectra of a series of un-neutralized and neutralized lightly sulfonated polystyrenes with varying sulfonation levels have been investigated to seek spectroscopic evidence for microphase separation known to control the physical properties of these polymers. Broad, strong absorbance bands, not found in the spectrum of unmodified polystyrene, are observed in the spectra of the sulfonated analogs. The effects on the far-infrared spectra both of sulfonation level and of the mass and charge of the neutralizing cation are discussed in terms of cation motion and the formation of ion-rich domains.     

高分子立构复合结晶的研究进展

立构复合结晶是高分子结晶中的一种普遍现象,也是不同高分子之间共结晶的特殊形式.互为立体异构高分子在共混物和立体嵌段共聚物中可形成立构复合结晶.由于这种独特的链凝聚结构,立构复合结晶材料与相应的同质结晶材料的性能显著不同,立构复合结晶通常可提高高分子材料的熔点、耐热性、结晶能力、结晶度、机械力学性能、耐溶剂性能等.通过立构复合结晶,可使一些非晶或难结晶的高分子转变为可结晶或高结晶度的状态,从而实现材料性能的转变.因此,互为立体异构高分子之间的立构复合结晶为聚合物材料的性能优化和调控提供了有效的途径.文献已报道了多类可立构复合结晶的聚合物体系,包括脂肪族聚酯、脂肪族聚碳酸酯、聚甲基丙烯酸酯、聚酰胺和聚酮等.本文根据聚合物化学结构的不同,针对文献已报道的可立构复合结晶的高分子体系,综述了其立构复合结晶的形成条件、结构特征与物理性质.     

Main-chain organometallic polymers: synthetic strategies, applications, and perspectives

Main-chain organometallic polymers utilize transition metal-organic ligand complexes as primary components of their backbones. These hybrid materials effectively integrate the physical and electronic properties of organic polymers with the physical, electronic, optical, and catalytic properties of organometallic complexes. Combined with the rich and continuously growing array of ligands for transition metals, these materials have outstanding potential for use in a broad range of applications. This tutorial review discusses the major classes of main-chain organometallic polymers, including coordination polymers, poly(metal acetylide)s, and poly(metallocene)s. Emphasis is placed on their synthesis, characterization, physical properties, and applications, as well as ongoing challenges and limitations. These discussions are supplemented with highlights from the recent literature. The review concludes with perspectives on the current status of the field, as well as opportunities that lie just beyond its frontier.     

Topological effects of macrocyclic polymers:from precise synthesis to biomedical applications

Polymer chain architectures play a crucial role in the physical properties of polymers and this unique phenomenon has been recognized as the topological effects.As one of the most representative architectures,macrocyclic polymers characterized by the endless topology have received extensive attention due to their distinct physical properties as compared to the linear counterparts.To understand these differences and unravel the underlying mechanisms,there is a long pursuit to efficiently fabricate macrocyclic polymers.To date,both ring-closing and ring-expansion strategies have been developed,which drastically elevates the accessibility of macrocyclic polymers.The improved availability of macrocyclic polymers enables the further investigation of the biomedical applications and the preliminary results suggest that macrocyclic polymers outperform their linear analogs in terms of improving gene delivery efficiency,elevating blood circulation time,and enhancing colloidal stability of nanoparticles.     

Highly stable olefin-Cu(I) coordination oligomers and polymers

Highly stable Cu(I)-olefin coordination oligomers and polymers have been successfully prepared and applied to construct metal-organic frameworks (MOFs) with interesting physical and chemical functions in recent years. In this review, we present the olefin-Cu(I) coordination oligomers and polymers and their novel physical properties. From structure to functions, particular emphasis is placed on the coordination and organometallic chemistry of olefin-Cu(I) coordination oligomers and polymers, their structures and potential applications as solids possessing unusual physical functional properties such as electrochemical, chiral separation, fluorescent sensing and ferroelectricity.     

在“高聚物的结构与性能”课程中讲透高聚物的特点

通过对高分子链的柔性、聚合物独有的熵弹性、显著的粘弹性、特有的描述链段运动的WLF方程,可能实现的大尺寸取向和小尺寸解取向、银纹、单链凝聚态、折叠链片晶和伸直链晶体、分子量的多分散性、高分子溶液特性和高聚物熔体的弹性行为等的讨论,希望能突出“高聚物的结构与性能”课程中高聚物的特点。     

Influence of physical aging on the performance of corona‐charged amorphous polymer electrets

The influence of physical aging on the electret properties before corona charging of three amorphous polymers, polyetherimide (PEI), poly(phenylene ether) (PPE), and polystyrene (PS), as well as with blends of PPE and PS, was investigated. The degree of aging was monitored by determining the enthalpy relaxation Δh using differential scanning calorimetry (DSC). The electret performance was evaluated by isothermal potential decay (ITPD) at elevated temperatures and by thermal stimulated discharge (TSD) measurements. It was demonstrated that physical aging below the glass transition temperature substantially improves the electret performance of amorphous polymers by reducing the free volume and thus hindering charge motion. As an example, the performance of nonaged PEI was improved by physical aging at 200 °C for 4 days from 18 to 95% retained charge after 24 h at 120 °C. A similar beneficial influence of physical aging on the charge storage capability was achieved using blends of PPE with PS. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 990–997, 2010     

The influence of different fillers on mechanical and physical properties of high-molecular-weight biodegradable aliphatic polyesters

Poly(ethylene succinate) and poly(butylene succinate) are synthetic biodegradable polymers, and much attention is paid to study the properties of pure polymers and the polymers modified by different comonomers and filling materials. The literature data on the physical properties of these polymers vary widely depending on their method of preparation and subsequent modifications. Most of the studies deal with low- and moderate-molecular-weight polymers or commercial grade polymers, modified by different comonomers and chain-extension agents. The data on pure high-molecular-weight polymers are scarce. In this work, we have prepared high-molecular-weight (MW range of (1.4–1.8) × 10⁵) poly(ethylene succinate) and poly(butylene succinate) by direct polycondensation at 200°C in a nitrogen flow without chain-extension agents. We have further studied the properties of pure polymers and examined the effect of different fillers (carbon nanotubes, SiO₂, Aerosil®) on the mechanical and physical properties of these polymers. Because of high-molecular-weight, the polymers possess increased tensile and storage moduli and thermostability. Even very low filler contents (up to 1 wt %) have a pronounced influence on the polymer properties: the polymer tensile and the storage modulus increases, the elongation at break decreases, and the thermal stability of the polymers decreases slightly. The effects of fillers are less pronounced compared with those for low- and moderate-molecular-weight polymers. When mixed together, poly(ethylene succinate) and poly(butylene succinate) crystallize independently from each other as evident from the mechanical and thermal analysis data.