AN ATOMIC FORCE MICROSCOPY STUDY ON THE AGGREGATION OF ISOTACTIC POLY(METHYL METHACRYLATE)

Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95 ± 0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.

Impact of Annealing on the Melt Recrystallization of a-PDLA/α-PLLA Double-layered Films

Poly(lactic acid)(PLA) as a bio-based polymer with biodegradability and biocompatibility has attracted much attention. To manipulate its properties for different applications, regulation of crystal structure and crystalline morphology becomes an attractive research topic. In this work, the structure evolution of layered samples containing an amorphous poly(D-lactide)(PDLA) layer and a crystalline poly(L-lactide)(PLLA)layer with highly oriented edge-on α lamellar crystals after annealing at 150 ℃ or/and after melt-recrystallization has been studied by AFM, FTIR,and TEM combined with electron diffraction. The results demonstrate that melt recrystallization of the as-prepared sample leads to the formation of abundant randomly oriented PLA stereo-complex(PLA SC) crystals. Annealing at 150 ℃ results in the formation of a small amount of oriented PLA SC crystals at the interface. These PLA SC crystals show great impact on the recrystallization behavior of sample after melting at 190 ℃ and then crystallizing at 90 ℃. First, they impede the mutual diffusion of the overlying PDLA and underlying PLLA, and thus reduce their stereocomplexation ability as manifested by the decreased amount of PLA SC crystals. Second, they act as substrate to initiate the epitaxial crystallization of the overlying PDLA and underlying PLLA, which ensures the production of a highly oriented structure of PDLA and PLLA after melt recrystallization again.

Effect of Phase Separation Size on the Properties of Self-healing Elastomer

Regulation of phase structure has been recognized as one of the most effective ways to fabricate self-healing polymers with high mechanical strength.The mechanical properties of the resultant polymers are certainly affected by the size of separated phase domain.However,the study on this aspect is absence,because it can hardly exclude the influence of variation in monomer proportion required for tuning the separated phase size.Here,we report the first study on tuning the phase size through reversible addition-fragmentation chain transfer(RAFT)polymerization without changing the proportion of monomers.As expected,the size of separated phase has been successfully mediated from 15 nm to 9 nm by tuning the molecular weight of the chain transfer agent.It is found that the mechanical strength and the self-healing efficiency of the resultant polymers increase simultaneously with the decrease of phase size.The study on the formation kinetics of hydrogen bonds reveals that the decrease of phase size can facilitate the re-bonding rate of hydrogen bonds,even if the migration of polymer chains is restricted.

Influence of Freezing Layer on the Crystallization Kinetics of PCL on Oriented PE Film

The effect of freezing layer on the crystallization kinetics of poly(ε-caprolactone)(PCL)thin and ultrathin films was investigated by monitor the growth process of it on oriented polyethylene(PE)and CaF_(2)with and without freezing layer,respectively.It was found that the PCL films with similar thicknesses crystallize much faster on oriented PE than on CaF_(2)substrate.For example,the crystallization rate constant of a 102 nm thick PCL film decreases tremendously by 3 orders of magnitude from 1.1×10^(-1) on PE substrate at 50℃to 7×10^(-4)on CaF_(2)surface at 40℃.Moreover,the crystallization of PCL accelerates on CaF_(2)surface while slows down at PE surface with increasing film thickness.The ultrathin films of PCL with thickness less than 14 nm exhibits the fastest crystallization rate on oriented PE with a rate constant of about 3.5×10^(-1),which is 3 times higher than that of a ca.50 nm thick film.This illustrates the great influence of freezing layer on the crystallization process of PCL.The freezing layer thickness of PCL on PE is estimated to be in the range of 14-17 nm.Taking the radius of gyration(R_(g)~15.6 nm)of the used PCL material into account,the obtained results may imply the existence of a correlation between the R_(g)of PCL and its freezing layer thickness at PE substrate.

中国改革开放以来的高分子物理和表征研究

本综述介绍了改革开放四十多年来中国大陆学者在高分子物理和表征领域所取得的部分成就.按照时间顺序,分别从概念的突破、理论的发展和技术的创新三个方面选取具有代表性研究成果进行简短的介绍,以期展示当代中国学者在这一基础研究领域所表现出来的拼搏意志和创新精神,激励新一代学者共同努力,勇攀科学高峰,为国民经济和社会发展作出更大的贡献.

聚合物热激活延迟荧光材料的分子设计与器件性能

聚合物热激活延迟荧光(TADF)材料应用于有机发光二极管(OLEDs)中以来,取得了飞速发展,迄今为止已经报道了多种不同分子结构及性能优异的聚合物TADF发光材料.它们具有不含重金属的化学结构、100%的理论内量子效率和易于通过溶液加工进行大面积制造的优势.本文从分子结构和发光颜色2个角度总结了不同结构TADF聚合物的研究进展,重点介绍了我们课题组在长链型TADF聚合物设计与OLEDs器件性能方面的研究工作,探究TADF聚合物颜色调控与效率提升的途径,论述了TADF聚合物存在的问题与未来发展.

聚合物限域和预有序熔体的结晶行为及结构调控

高分子物理领域的挑战性难题之一是调控高分子的结晶行为.高分子结构具有多尺度的特点,且易受到各种本征因素以及加工过程中引入的外场与受限作用的影响.高分子的结晶过程复杂多变,为避免最终产品性能的良莠不齐,促进高分子材料的实际生产和应用,需要建立高分子结构与性能的直接关系并实现对高分子结晶结构的精细化调控.本文以几种典型高分子为例,重点阐述了我们课题组在有关薄膜和纳米孔道构筑的限域空间与分子链预有序熔体对高分子结晶行为的影响、相关结晶结构调控机制以及结构-性能关系等方面的研究工作,阐明了聚合物多层次结构调控领域存在的科学问题,并展望了其未来发展方向.

Direct Comparison of Crystal Nucleation Activity of PCL on Patterned Substrates

A sample containing different regions with poly(ε-caprolactone)(PCL), oriented polyethylene (PE), and oriented isotactic polypropylene (iPP) films in contact with glass slide has been prepared to be observed in the same view field in an optical microscope and the crystallization of PCL in different regions during cooling from 80 °C down to room temperature at a rate of 1 °C·min^-1 was studied. The results showed that the crystallization of PCL started first at the PE surface and then at the iPP surface, while its bulk crystallization occured much later. This indicates that though both PE and iPP are active in nucleating PCL, the nucleation ability of PE is stronger than that of iPP. This was due to a better lattice matching between PCL and PE than that between PCL and iPP. Moreover, since lattice matching existed between every (hk0) lattice planes of both PCL and PE but only between the (100)PCL and (010)iPP lattice planes, the uniaxial orientation feature of the used PE and iPP films resulted in the existence of much more active nucleation sites of PCL on PE than on iPP. This led to the fact that the nucleation density of PCL at PE surface was so high that the crystallization of PCL at PE surface took place in a way like the film developing process with PCL microcrystallites happened everywhere with crystallization proceeding simultaneously. On the other hand, even though iPP also enhanced the nucleation density of PCL evidently, the crystallization of PCL at iPP surface included still a nucleation and crystal growth processes similar to that of its bulk crystallization.

Enhanced αγ′ Transition of Poly(vinylidene fluoride) by Step Crystallization and Subsequent Annealing

Poly（vinylidene fluoride）（PVDF） exhibits pronounced polymorphs. Its γ phase is attractive due to the electroactive properties. The γ-PVDF is however difficult to obtain under normal crystallization condition. In a previous work, we reported a simple melt-recrystallization approach for producing γ-phase rich PVDF thin films through selective melting and subsequent recrystallization. We reported here another approach for promoting the αγ′ phase transition to prepare γ-phase rich PVDF thin films. To this end, a stepwise crystallization and subsequent annealing process was used. The idea is based on a quick generation of a large amount of α-PVDF crystals with some of their γ-PVDF counterparts at suitable crystallization temperature and then annealing at a temperature above the crystallization temperature for enhancing the molecular chain mobility to overcome the energy barrier of phase transition. It was found that crystallizing the PVDF melt first at 152 °C for 4 h, then quenching to room temperature and finally annealing the sample at 160 °C for 100 h was the most efficient to produce γ-PVDF rich films. This is related to the melting and recrystallization of the α-PVDF crystals produced during quenching in the annealing process at 160 °C, which favors the formation of γ-PVDF crystals for triggering the αγ′ phase transition.

PREFACE

Crystalline polymers exhibit their strong connections to our practical world. In synthetic polymer materials, crystallization brings fiber orientation-strengthening, rubber strain-hardening and plastic neck-toughening Important properties such as hardness, thermal stability, anisotropic structures, etc. are endowed to the polymeric materials. In natural polymer materials, crystallization provides proteins of skins, hairs, wools and silks as well as carbohydrates like celluloses, starches and chitins with the necessary strength to support versatile living activities. On the other hand,

Crystallizability of Poly(ε-caprolactone) Blends with Poly(vinylphenol) under Different Conditions

The intermolecular interaction between poly（vinylphenol） （PVPh） and polycaprolactone （PCL） and the crystallization behavior of PCL in PCL/PVPh blends with different compositions and under different conditions were investigated by Fourier transform infrared spectra （FTIR） and differential scanning calorimetry （DSC）. It has been shown that the PCL in the blends with different blend ratios all exists in crystalline state after solution casting, even though the crystallinity decreases with increasing PVPh content. For the melt crystallized samples, PCL in its 80/20 PCL/PVPh sample can still crystallize. The crystallinity is, however, lower than that of the solution cast sample. For blends containing 50% or 20% PCL, the as-cast samples are semicrystalline and can change to compatible amorphous state after heat treatment process. FTIR analysis shows the existence of hydrogen bonding between PCL and PVPh and the fraction of hydrogen bonds increases remarkably after heat treatment process.

The Effect of Substrate on the Properties of Non-volatile Ferroelectric P(VDF-TrFE)/P3HT Memory Devices

Ferroelectric poly(vinylidene fluoride-trifluoroethylene)(P(VDF-TrFE))/semiconducting poly(3-hexyl thiophene)(P3HT)blend systems have drawn great attention with their potential use for electronic applications,particularly non-volatile memory devices.It is essential to grasp a full understanding of the crystallization habits of the two polymers on different substrates for purposeful control of the structures of the blend and therefore the properties of the devices.Here,the effects of structure and morphology of the blend films generated at different substrate surfaces on the ferroelectric and switching properties of related devices are reported.It is identified that P(VDF-TrFE)/P3HT blend films prepared on graphene substrate show not only an obvious optimization in the ferroelectric behavior of P(VDF-TrFE),but also an enhancement of the charge transport within P3HT domains.By employing sandwich structure constructed by silver electrode and P3HT/P(VDF-TrFE)blend film on graphene substrate,high-performance ferroelectric memory devices have been obtained,which exhibit a great electrical switching behavior with high ON/OFF ratio of about 1000 and low coercive voltage of approximately 5 V.These findings provide useful guidance for fabricating highperformance ferroelectric memory devices.

Effects of Interface on the Dynamic Hysteresis Loss and Static Mechanical Properties of Illite Filled SBR Composites

Despite growing interest in nano-sized fillers,micro-sized fillers with desired compatibility are still used for reinforcing rubbers,owing to their lower production cost and easier processing relative to nano-sized fillers.Especially,the abundant and eco-friendly clay minerals are recognized as the materials of the twenty-first century.Herein,illite,a naturally occurring clay having dimension in micrometric scale,has been selected as filler to reinforce the SBR.To improve the compatibility of illite with SBR,the illite was modified by either bis[3-(triethoxysilyl)propyl]tetrasulfide(Si69-illite)or 3-mercaptopropyltriethoxysilane(KH580-illite).The interfacial interactions of SBR composites filled with pristine illite(illite/SBR)and Si69-illite(Si69-illite/SBR),or KH580-illite(KH580-illite/SBR)were characterized by bound rubber content and Payne effect measurements,while dynamic hysteresis losses of these uncured and cured composites were also analyzed under various strain amplitudes.It was found that the filler-rubber interactions were greatly improved for Si69-illite/SBR and KH580-illite/SBR systems compared to the illite/SBR composite.This leads to an increment of modulus at 300%strain of the composites from 3.46 MPa for illite/SBR to 7.70 MPa for Si69-illite/SBR and12.96 MPa for KH580-illite/SBR.Moreover,lower rolling resistance and better wear resistance without compromising wet traction of Si69-illite/SBR and KH580-illite/SBR have been achieved.This demonstrates the high possibility of Si69 and KH580 modified illites as promising alternative fillers for reinforcing rubbers.

How Temperatures Affect the Number of Dislocations in Polymer Single Crystals

The influence of crystallization temperature （Tc） on the number of spiral growths on poly（butylene succinate） （PBS） single crystals, obtained by self-seeding method, was systematically studied. The studies show that the statistical average number of spiral growths formed on the PBS single crystals decays exponentially with respect to the To. Inspired by BCF （Bruton, Cabrera and Frank） theory and L-H （Lauritzen and Hoffman） theory, a thermodynamic model has been proposed, in which the origin of spiral growth was treated as a nucleation process. The model suggests that the nucleation rate of spiral growth depends on the inverse square of super-cooling degree, which predicted the density of spiral growth formed on lamellae, and was consistent with the experiments very well.

Erratum to “The Effect of Substrate on the Properties of Non-volatile Ferroelectric P(VDF-TrFE)/P3HT Memory Devices”

We are sorry for the misuploading of Fig.1(a)as Fig.2(b),which makes Fig.2(b)the same as Fig.1(a).The correct Fig.2(b)is presented below.It should be noted that the replacement of Fig.2(b)does not influence the discussion and conclusion.

Ordered Organization of Long Chain Polymers:Advances and Challenges

Due to the long chain character and entanglement feature,polymer chains were initially believed incapable of organizing into ordered structures.However,X-ray studies in the 1920s demonstrated unequivocally the existence of ordered structures of celluloses and their derivatives,which has thus opened a new field of polymer physics.

A Special Issue of Chinese Journal of Polymer Science:Ordered Structure of Polymers

The property and functionality of polymers are basically related to their chain structures.However,the aggregation of molecular chains in condensed state is vital to bring them into fullest play.For example,ordered structures,widely seen in natural and synthetic polymers and macromolecules,can endow them unique thermodynamics,kinetics and mechanical performance.