聚合物环带球晶的结晶机理

聚合物环带球晶作为一类特殊的球晶结构,其结晶机理一直倍受关注.经过几十年的研究,对于环带球晶形成机理的认识在不断深入,但是仍有许多问题尚未解决.本文总结了常见聚合物环带球晶的分类,综述了国内外在聚合物环带球晶片晶组织形式和片晶扭转机理研究上的主要进展,力图展示聚合物环带球晶研究的整体概况.根据前期研究结果,总结了手性聚...     

高聚物球晶偏光织态研究中的厚度性消光与补偿机理

以两维聚环氧乙烷（ＰＥＯ）球晶为对象，探讨了偏光显微法的消光机理，尤其是其中的厚度性消光机理，并对于补偿片的作用原理作了细致的理论分析，运用上述手段对ＰＥＯ球晶的形态进行了研究。     

聚环氧乙烷球晶中同心环形纹的形成

聚环氧乙烷 (PEO)是一种易结晶的柔性高聚物 ,它形成的球晶比较大 ,易于观察 ,是研究高聚物结晶的常用材料[1～ 3 ] .有人发现PEO球晶在正交偏振片观察下呈现有明暗相间的同心圆环 ,并指出PEO球晶中的此圆环结构不是普通的消光 ,因为在非偏振光下此结构仍然存在[4,5] ;并认为这种同心环形纹的出现与球晶阶梯式生长或螺旋式生长方式有关 .本文作者利用偏光显微镜在观察PEO单个球晶的生长过程中 ,并未发现有这种同心环形纹的出现 ;为了进一步认识环形纹的形成原因 ,本文作者对PEO的结晶过程进行了全程跟踪观察 ,对同心环形纹的形成给予…     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.     

原子力显微镜原位观察球晶界面上片晶的生长

当结晶聚合物由熔融冷却或从浓溶液中析出结晶时 ,在不存在应力和流动的情况下 ,一般形成球晶 .球晶在一定的生长时期内呈现球形外观 ,在偏光显微镜下通常呈现Maltese黑十字消光图样 .球晶作为一种常见的结晶形态 ,由片晶堆积而成[1,2 ] .Keith和Padden认为形成球晶的体系包含杂质和聚合物链 ,由于杂质在片晶生长界面的富集导致片晶产生小角度分叉 ,这样片晶能填满球状的空间[1,2 ] .近年来的研究表明球晶是由一个片晶开始生长 ,片晶在生长过程中不断的诱导成核使片晶分叉 ,首先形成片晶捆束 ,然后片晶向各个方向发散生长 ,最终形成球晶[3…     

聚3-羟基丁酸酯从熔体薄膜及溶液中形成的球晶结构及生长机理

研究了聚3-羟基丁酸酯（PHB）分别从熔体薄膜和溶液中结晶时的球晶结构和形态,提出了在两种不同结晶条件下环带球晶的形成机理．当PHB从熔体薄膜中结晶时,由于二维生长的限制,晶体的不连续生长是球晶形成环带结构的主要原因,而当PHB从溶液中结晶时,片晶生长的扭曲取向导致了球晶环带结构的形成．     

聚羟基丁酸酯环带球晶的形貌研究

聚羟基丁酸酯 ( PHB)是一种由细菌合成的手性高分子材料 ,其分子结构具有高度的规整性 [1] ,球晶比较大 (直径可达几毫米 ) ,是研究高分子结晶行为和形态的理想材料 [2 ] .在偏光显微镜下 ,Bauer[3]和 Martinez- Salazar等 [4 ] 曾在 PHB球晶上观察到消光带和同心的环线 .在聚环氧乙烷 [5] 和小分子液晶4-氰基 - 4 -癸氧基联苯的球晶上 [6 ] 也观察到了同心环线 .但这些工作都把同心环线归结为裂缝 ,并未提供证据 .事实上 ,偏光显微镜的低分辨率及其透视特点 [7] ,使之无法真实反映材料的表面形貌 ,因而也无法区分裂缝和台阶 .我们对光…     

高压结晶PET/PC共混体系中生长在伸直链晶体内部球晶形态的观察

自从Wundedich等报道聚乙烯（PE）在高压结晶时可以生成伸直链晶体以来,相继很多有关聚合物体系的高压结晶行为方面的研究已见报道．研究结果表明,聚合物在高压下经历相转变时可产生非常丰富的微观结构,而球晶及伸直链晶体是其中最常见的两种结晶形态．但是,所观察到的这两种聚合物晶体都是分别存在,且独立生长的．到目前为止,尚未见到关于高压下球晶可以在伸直链晶体内部存在的报道．     

聚对苯甲酰胺液晶态球晶生长机理

本文用热台偏光显微镜和透射电子显微镜研究了聚对苯甲酰胺(PBA)/H_2SO_4液晶态生长球晶的形态结构和结晶机理。结果表明,PBA/H_2SO_4向列型液晶相具有过冷状态,可达30—40℃左右,并可生长球晶结构,一般直径可达5毫米左右。20Wt％溶液在不同的过冷态结晶时,可以生成三种形态的球晶结构,这是由于构成球晶的基本结构单元——有序微区结构在不同过冷条件下堆砌排列的规整程度不同的缘故。球晶的形态结构只与过冷程度有关,而与溶液的浓度无关。同时还研究了变温和剪切应力下结晶的球晶形态。     

聚氨酯硬链段球晶生长与软硬链锻混容性的关系

线型可溶性聚氨酯的硬链段结晶难以长成球晶 ,然而本实验室已经证明即使从熔体结晶硬链段也是能够长成球晶的 .研究了聚酯与聚醚型聚氨酯硬链段长球晶的规律 ,并发现聚氨酯硬链段长球晶的难易与聚氨酯软硬链段混容性密切相关 .动态力学分析 (DMA)与示差扫描量热 (DSC)实验表明聚ε 已内酯 (PCL)、聚已二酸丁二醇酯 (PTMA)、聚四氢呋喃 (PTMO)及聚环氧丙烷 (PPO)型聚氨酯的软硬链段混容性从前至后递减 .从熔体退火结晶时 ,聚氨酯硬链段长成球晶的退火温度范围是有限的 ,软硬链段混容性越好 ,聚氨酯硬链段能长成球晶的温度范围越窄 ,所需长的时间越长 .聚氨酯硬链段长球晶的下限温度取决于软硬链段间所存在的氢键作用 ,聚氨酯硬链段长球晶的上限温度与软硬链段混容性直接相关 .     

Observation of banded spherulites and lamellar structures by atomic force microscopy

Spherulites are common structures of semi-crystalline polymers. It has been known that semi-crystalline polymers can form spherulites when crystallized from solution or from melt. A dark Maltese cross of a spherulite could be easily observed under the polarized optical microscopy (POM). Moreover, some spherulites show an additional alternating dark and bright concentric ring structure that is attributed to the regular twisting of the radial crystallite ribbons as they grow from the spherulit…     

CRYSTALLINE MORPHOLOGY IN A SERIES OF CH3-SUBSTITUTED THERMOTROPIC AROMATIC POLYESTERS WITH EVEN AND ODD FLEXIBLE SPACERS*

 Crystalline morphology in a series of CH₃-substituted main chain thermotropic aromatic polyesters with even and odd numbered methylene spacers has been studied by polarizing optical microscopy (POM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). On crystallization from solution evaporation spherulites of radial structure were observed in the polymers with even numbered spacers, but spherulites with concentric rings form in the polymer with odd numbered spacers. Both spherulites have a lamellar structure, which is about 10 nm in thickness. On crystallization from nematic glassy state spherulites can not be grown; lamellar structure was only observed around disclinations in a specimen during crystallization. In the case of crystallization from nematic melt two types of spherulites can be observed for the sample with even numbered spacers. For the sample with odd numbered spacers spherulites can not be formed, but only irregular crystallites.     

Correlation of crack patterns and ring bands in spherulites of low molecular weight poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid)

Only a single type of circular circumferential crack is conventionally reported for poly(l-lactic acid) (PLLA). In this study, PLLA samples were found to exhibit as many as four crack types of different directions and patterns, which cannot be feasibly explained simply by the directional difference in coefficients of thermal expansion. Depending on crystallization temperature (T _c), PLLA crystallizes into ringless or ring-banded spherulites, whereas the crack patterns are dramatically different in these two types of spherulites. In ring-banded spherulites of PLLA crystallized at intermediate T _c, two uniquely different crack types are present: (1) twin circumferential cracks coinciding with the dark–bright and bright–dark boundary and (2) radial short-segmental voids coinciding on the bright bands in spherulites. The radial short-segmental cracks on the bright band of ring-banded spherulites may be caused by PLLA crystals of radial direction with various twisting that contract laterally upon cooling. Only circumferential cracks are present in PLLA crystallized into ringless spherulites, where concentric continuous circumferential cracks are present in the ringless spherulites at low T _c with finer lamellae, but discontinuous and irregular circumferential cracks are present in the ringless spherulites at high T _c with coarse lamellae. Although all cracks are triggered by cooling from T _c, all evidences indicate that the crack patterns and types are highly associated with the lamellar orientation, patterns, and coarseness in spherulites.     

Surface and interior views on origins of two types of banded spherulites in poly(nonamethylene terephthalate)

Top-surface and three-dimensional views of Type-1 and Type-2 of ring-banded spherulites in poly(nonamethylene terephthalate) (PNT) in thicker bulk crystallized on a nucleating potassium bromide (KBr) substrate were examined using various microscopy techniques: scanning electron microscopy (SEM), polarized-optical microscopy (POM), and atomic-force microscopy (AFM). In PNT crystallized at higher crystallization temperature (T(c)) with heterogeneous nucleating substrate, typically two types of ring-banded spherulites are present that differ significantly in patterns and ring spacings: Type-1 Type-2 (single- and double-ring-banded spherulites). Three-dimensional view on fractured spherulites in bulk PNT samples reveals that the single-ring-banded spherulite (Type-1) tends to be well-rounded spheres as they are nucleated homogeneously from bulk; the double-ring-banded spherulite (Type-2) is concentric hemisphere or truncated sphere shells owing to be nucleated from bottom. With confined thickness of films, the 3-D hemispheres in PNT may become truncated into multi-shell annular cones or arcs when thickness or growth is restricted. Based on the top-surface vs. interior views of banded lamellar assembly, origins and inner structures of dual types of ring bands in PNT were examined in greater details.     

Concentric-ringed structures in polymer thin films

Novel polymer crystalline structures containing micrometer-sized concentric rings (or bands) were observed in thin poly(bisphenol A hexane ether) (BA-C6) films. The origin of the banded structures was found to be different from that of traditional banded spherulites in polymer systems. Analyses based on optical microscopy (OM) and atomic force microscopy (AFM) revealed that the banded structures contained alternating ridge and valley bands of polymer crystals in the flat-on orientation. No lamellar twisting was observed within the concentric-ringed structures, which were developed as a result of the formation of a depletion zone during crystallization. The formation of a depletion zone was determined to be caused by the specific volume decrement between the crystal and the melt and by the diffusion of polymer chains to the fold surfaces of the flat-on lamellae. The height of the ridges and the interband widths could be adjusted by controlling the diffusion rate. Time-of-flight secondary ion mass spectrometry ion images showed higher concentrations of low-molecular-weight polymer chains on the surfaces of the ridges than in the valleys.     

Ring‐banded spherulite surface structure of poly(ε‐caprolactone) in its miscible mixtures with poly(styrene‐co‐acrylonitrile)

The surface structure of the ring‐banded spherulites in polymer blends PCL/SAN (90/10) was studied by optical microscopy, SEM, and TEM, respectively. It is interesting to find that the surface structure of the ring‐banded spherulites in polymer blends PCL/SAN (90/10) is made up of the convex bands. The landscape of the convex bands on the surface has been little emphasized before. Radial fibrils are arranged on the bands. Details of the radial fibrils on the bands can be observed by TEM. The landscape of the convex bands on the surface and twisting of lamellae in the convex bands for PCL/SAN blends may be useful to explain the formation mechanism of the ring banded spherulites in polymer blends or even in homopolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2682–2691, 1999     

THE MORPHOLOGY AND STRUCTURE OF POLYETHYLENE TEREPHTHALATE SPHERULITES

The morphology and structure of three types of normal and abnormal spherulites of polyethylene terephthalate cast from solution in dimethylphthalate were studied by polarizing microscopy, transmission electron microscopy and electron diffraction techniques. In the normal negative spherulites the [0]~* direction is parallel to the radius direction. In the normal positive spherulites the radius direction is parallel to the [6]~*. In the abnormal PET spherulites the Maltese cross extinction pattern in the polarizing microscope under crossed polars is oriented at 45°to the polars and there are concentric extinction rings around the center of the spherulite. Electron diffraction pattern indicates that [2]~* is parallel to the radius of the spherulite and this explains the observed extinction pattern, in the abnormal spherulite.     

Periodic extinction bands composed of all flat‐on lamellae in poly(dodecamethylene terephthalate) thin films crystallized at high temperatures

Using in‐house synthesized poly(dodecamethylene terephthalate) (P12T) as a model, periodic extinction‐banded spherulites melt‐crystallized at high T_cs (100–115 °C) are expounded in terms of growth mechanism. The extinction‐banded spherulites wildly differing from the usual blue/orange double ring‐banded spherulites are composed of all flat‐on discrete single‐crystalline lamellae packed like roof shingles (or fish scales) along the circularly curved bands and the lamellae in the extinction bands are flat with a lozenge shape with no continuous twisting at all. For P12T films of more than 10 µm crystallized at T_c = 105–115 °C, no periodic bands were seen, and all spherulites were ringless, where periodic growth precipitation of crystals to extinction does not occur until impingement. Extinction bands in the P12T spherulites with the inter‐ring spacing steadily decrease with decreasing film thickness, because for thinner films (submicrons to 2 µm), draining or depletion of available molten species takes place more frequently, leading to bands of smaller inter‐ring spacing. The petal‐like extinction bands are discussed and analyzed in detail using 3D AFM imaging. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 601–611