Morphology of nascent polyolefins prepared by Ziegler-Natta catalysis

The morphology of nascent (i.e., as-polymerized) Ziegler-Natta polymers was studied by optical and electron microscopy and x-ray and electron diffraction. Observations were made on six polyolefins: polyethylene, polybutene, polypropylene, polystyrene, poly-4-methylpentene-1, and polyisoprene. These polymers were synthesized by using conventional techniques by polymerizing the undiluted monomer or monomer–diluent mixtures with a preformed heterogeneous catalyst obtained by reacting a titanium halide and aluminium alkyl. After the reactions were terminated the polymers were subjected to suitable purification treatments and stored in the wet state. Observations in the optical microscope revealed that, in most cases, the polymers is formed as discrete hollow particles with a fibrous texture, but in a few instances, depending upon experimental conditions, it could also form as fibrous sheets or webs. More detailed observations in the electron microscope showed that the polymer is composed of a profusion of fibrils 200–1000 A. in width and of indefinite length. The fibrils themselves have a fine structure as indicated by the presences of lamellae running prependicular to their length. Various interpretations of this appaerent structure are discussed. The x-ray and electron diffraction studies show that the molecular chain axis is oriented prependicular, or nearly so, to the plane of fibril lamellae and suggest that the molecules are folded within the lamellae in a manner analogous to conventional polymer single crystals. As fibril formation is observed under most conditions of polymerization it is considered to be basic to the mechanism of Ziegler-Natta catalysis. It is proposed that the fibrils are formed by the crystallization of polymer chains growing from the active sites on the catalyst surface. The process is likened to root growth in whiskers, new materials being added at the base or root. The detailed mechanism of fibril formation and of the organization of the fibrils into larger structural formations are obscure, but several possibilities are discussed.     

Real-time AFM study of lamellar growth of semi-crystalline polymers

Atomic force microscopy (AFM) has been used to study the lamellar development during the crystallization and melting processes of poly(bisphenol A-co-alkyl ether) (BA-Cn) films. High-resolution and real-time AFM phase imaging enables us to observe the detailed growth process of the lamellae. At the early stage of the lamellar growth, embryos appeared firstly and some disappeared on the film surface after a period of time. The stable embryo developed into a single lamella. Then the lamella developed into a lamellar sheaf through branching and splaying. Our results revealed that the branches of the lamellae were formed by induced nucleation and it was also dependent on the crystallization temperature. Real-time AFM study of the melting, recrystallization and remelting processes of lamellae indicated that the thermal stability of different segments of a single lamella is different and that the thermal stability of the different lamellae is also different even if they develop at the same annealing temperature. The orientation and the development of the lamellae at the characteristic eyes and boundaries of the spherulites are observed in details.     

On the development of special positive isotactic polypropylene spherulites

A new type of positive α‐iPP spherulites has been developed by self‐seeding process. The growth process of these positive α‐iPP spherulites is just like “photographic development process,” which is very different from the conventional growth process of polymer spherulites. Scanning electron microscopy (SEM) was used to explore the morphologies of these positive α‐iPP spherulites on a lamellar level. The results show that these spherulites are composed of a large number of lamellae having interwoven structures, which result in different optical character, special melting behavior, and different contrast under SEM as compared with the conventional melt‐crystallized spherulites. The development of these interwoven lamellar structures has been considered because in the sites of the original spherulites, a large number of self‐nuclei are formed because of the incomplete melting of the original spherulites and these induce nearly equal number of radial and tangential lamellae at rather high temperatures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1114–1121, 2006     

分级聚丙烯的取向结晶过程

聚丙烯熔体在剪切或应变应力作用下 ,分子链发生取向形成伸直链纤维晶 ,这些先取向形成的纤维晶成为其后结晶的晶核 .这种线形排列的特殊自晶核被称作排核 ( Row nuclei) [1] .排核诱导的结晶温度高于异相核和均相核 .折叠链片晶在排核上附生生长 ,形成具有柱状对称性的超分子结构 ,称为柱状晶 ( Cylindrite) [2 ,3] .聚合物的分子量 ,剪切温度和剪切速度等因素对柱状晶的生成有很大影响 [4 ,5] .本文选用不同级分的聚丙烯样品 ,利用高分子 (特别是取向结晶 )的记忆效应 [6,7] ,研究了剪切后薄膜试样在熔融重结晶过程中柱状晶的形成和发展…     

Melting behavior of lamellae of isotactic polypropylene studied using hot-stage atomic force microscopy

The α- and β-form lamellae of isotactic polypropylene were developed at different temperatures. The melting behaviors of the lamellae were observed in real time at elevated temperatures using a hot-stage atomic force microscopy. The melting behavior of the α-form lamellae was determined by the lamellar defects. For the α-form lamellae developed at different undercoolings, the larger the undercoolings, the relatively higher amount of defect in the lamellae was observed. The lamellae with defects were melted into lamellar segments, and recrystallization took place during the heating process. The β-form lamellae had lower thermal stability, and they melted firstly and separately from that of α-form.     

一个低分子量聚氧化乙烯从亚稳态的折叠链片晶向稳态的伸直链片晶转化增厚过程的研究

报道分子量为5000的聚氧化乙烯(PEO)从熔融态淬火到液氮温度后形成的两次链折叠(2-FC)片晶增厚过程的研究结果.在升温和恒温条件下,采用小角X射线散射(SAXS)在位地跟踪了2-FC片晶增厚成一次链折叠(1-FC)和进一步成为伸直链(EC)片晶的增厚过程.通过对SAXS数据以及它们的一维相关函数的数据的分析,发现在52℃以下,2-FC片晶主要增厚为1-FC片晶;在52℃以上,2-FC片晶则主要增厚为EC片晶;在58℃到EC片晶的熔点的温度区域里,已经形成的1-FC片晶还会熔融,完全转化为EC片晶.利用偏光显微镜(PLM)和扫描电子显微镜(SEM)观察晶体的形貌,比如球晶,获得的研究结果表明,没有发生大范围的晶体破坏后再形成的变化,也就是说片晶的增厚过程是一个发生在球晶内部的薄片晶熔融后转化为厚片晶的过程.     

Interfacial Banded Transcrystallization of Polyoxymethylene/Poly(butylene succinate) Blends Induced by the Polyamide 6 Fiber

Interfacial crystallization of polyoxymethylene/poly(butylene succinate) blends induced by the polyamide 6 (PA6) fiber was investigated. Due to strong heterogeneous nucleating ability, dense nuclei were generated on the surface of the PA6 fiber, which compelled the growth of twisted lamellae perpendicular to the PA6 fiber. As a result, unique interfacial banded transcrystallization was formed, which is rarely found before. Crystallization temperature was dominant in determining the nucleation activity of the PA6 fiber, further affecting the architecture of banded transcrystallization. With the increase of crystallization temperature, the nucleation density decreased to give more growth space for the twisted lamellae around the fiber. The wave-like banded stripes were transformed into fan-like stripes. Accordingly, band spacing and eccentricity respectively showed positive and negative correlation with crystallization temperature. These meaningful results shed light on regulating the architecture of banded crystals in polymer composites.

     

The deformation behaviour of polyethylene shish-kebabs produced by stirring-induced crystallization

Polyethylene mats of shish-kebab fibrils were prepared from solution by stirring-induced crystallization, and subjected to deformation. A morphological study by scanning electron microscopy showed that the elementary shish-kebabs are elongated during drawing. For low draw ratios, the average distance between the lamellae on the fibrils increases proportionally to the draw ratio. The invariance of the fibril diameter upon drawing indicates a transformation of lamellar into fibrillar material. The molecular topology which underlies this deformation mode is discussed and related to the crystallization process.     

New understanding on the memory effect of crystallized iPP

In this study, recovery processes of isotactic polypropylene(iPP) melted spherulites at 135 °C after melting at higher temperatures(170 °C–176 °C) were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 °C and 174 °C, the melted spherulite could recover back to the origin spherulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.     

THE CRYSTALLIZATION BEHAVIOR OF URETHANE SUBSTITUTED POLYDIACETYLENE

The crystalline behavior of urethane substitute polydiacetylene was studied by using pohrized light and electron microscopy. The lamellar morphological structure was observed in the crystallized films. The thickness of lamellae is about 300A, being independent of the crystalline temperature. But the size and density of lamellae were dependent on the crystallization temperature. If the molten film was sheared during the crystallzation process the oriented lamellae grew with their long axes perpendicular to the direction of shear and the chain direction was normal to the lamellar surface.     

Effect of shear on vesicle and lamellar phases of DDAB/lecithin ternary systems

The influence of shear flow on bilayer structures (vesicle and planar lamellar phases, L(α)), formed in DDAB/lecithin ternary systems, is studied by means of conventional rheology, Rheo NMR, and optical microscopy. The vesicles in the diluted (Lam(1)) phase are polydisperse multilamellae which turn into smaller monodisperse vesicles under shear. The concentrated (Lam(2)) phase is formed by non-oriented lamellae that do not surprisingly exhibit any pronounced shear-induced alignment prior to the transition into giant multilamellar vesicles. The biphasic region (Lam(1)+Lam(2)) shows a mosaic texture with a powder pattern indicating the prevalence of lamellae that transform into onions under shear.     

Quiescent and strain-induced crystallization of poly(p-phenylene terephthalamide) from sulfuric acid solution

Quiescent and strain-induced crystallization of poly(p-phenylene terephthalamide) (PPTA) from sulfuric acid solution has been studied. Negative spherulites (SA-PPTA spherulites) are formed from hot concentrated solutions by cooling. The spherulite consists of radiating fibrous lamellae several hundred angstroms wide. The electron diffraction pattern indicates that PPTA molecules are oriented perpendicular to the long axes of the fibrous lamellae and that the [010] or [110] direction of the modification I crystal and [010] direction of the modification II crystal are parallel to the long axes of the fibrous lamellae. The width of the lamellae is much smaller than the chain length of the starting PPTA. It appears that hydrolysis of PPTA during melting crystallization determines the chain length, i.e., the width of the fibrous lamella. Stacked, lamellar structures like “row structures” are formed under shear. The longer axes of the fibrous lamellae are oriented perpendicular to the shear direction. It is confirmed by electron diffraction studies that the PPTA molecules are oriented parallel to the shear direction. Well-developed fibrils with the PPTA molecules oriented to the fibril axis, are formed by adding the SA-PPTA spherulites to water with vigorous stirring.     

聚环氧乙烷的双层片晶

聚环氧乙烷(M_n=7000)的双层片晶形态用透射电镜和差示扫描量热计进行了研究。在结晶温区54—56℃,现察到双层片晶,高于这个温区,同时看到双层片晶及单层片晶,低于这个温区,只看到单层片晶。双层片晶的熔点稍高于单层片晶。根据非整数次折迭链晶向整数次折迭链晶的转变,讨论了双层片晶和单层片晶的生长过程。在双层片晶界面上的H键降低了表面自由能,这是形成双层片晶的主要原因。     

Influence of the order of polymer melt on the crystallization behavior: I. Double melting endotherms of isotactic polypropylene

The influence of the order of polymer melt on the subsequent crystallization and melting has been carefully studied. The experimental data show that the order of isotactic polypropylene (iPP) melt decreases with increases in the fusion temperature. For an iPP sample isothermally crystallized at 130 °C for half an hour, the degree of order of melt is higher when the fusion temperature is lower than about 170.5 °C, hence the lamellae formed in a rapid cooling process are perfect. If the fusion temperature is not higher than 167 °C, some thicker lamellae can exist in the melt. The melting of these unmelted lamellae and those lamellae recrystallized in the cooling process result in double endotherms. On the other hand, when the fusion temperature is higher than 170.5 °C, the order of the iPP melt decreases greatly; thus, the lamellae formed in the following cooling process are imperfect. At a lower heating rate, the recrystallization or reorganization of these imperfect lamellae also leads to double melting endotherms. Received: June 16, 2000 Accepted: October 16, 2000     

A Salt Controlled Scalable Approach for Formation of Polyelectrolyte Complex Fiber†

A new scalable approach is reported here for producing the polyelectrolyte complex (PEC) fiber of alginate (ALG) and poly(diallyldimethylammonium chloride) (PDDA). Salt (LiBr, NaBr, or KBr) is used to restrict the complexation of negatively charged ALG and positively charged PDDA in solution to obtain spinnable fluid that can be directly extruded into the coagulation bath to form nascent fiber. A water washing step is adopted right after the formation of nascent fiber to eliminate the defects in fiber. Morphology and mechanical properties of the as‐prepared ALG/PDDA complex fiber are found to be greatly affected by the water washing, as well as the amount and the type of salt used. As the reported approach is similar to the wet‐spinning process which is a commonly used method for industrial production of fibers, it is promising to be applied in larger scale production of PEC fibers.     

尼龙66盐固态缩聚反应的研究

采用测定转化率和特性粘数、红外光谱、偏光显微镜、扫描电镜和DSC等方法,研究了结晶尼龙66盐固态缩聚过程的反应历程、初生态尼龙66的结晶形态及其热行为与热历史的关系。实验结果表明,在缩聚过程中尼龙66盐结晶的缺陷可以诱发大分子相的成核,并出现外延结晶过程。发现,初生态尼龙66呈现出原纤状结构状态,且原纤的取向取决于反应条件;讨论了初生态尼龙66在DSC谱上所出现的熔融双峰现象。     

Imaging Nanocarbon Materials: Soot Particles in Flames are Not Structurally Homogeneous

For the first time, nascent soot particles are probed by using helium‐ion microscopy (HIM). HIM is a technique that is similar to scanning electron microscopy (SEM) but it can achieve higher contrast and improved surface sensitivity, especially for carbonaceous materials. The HIM microscope yields images with a high contrast, which allows for the unambiguous recognition of smaller nascent soot particles than those observed in previous transmission electron microscopy studies. The results indicate that HIM is ideal for rapid and reliable probing of the morphology of nascent soot, with surface details visible down to approximately 5 nm, and particles as small as 2 nm are detectable. The results also show that nascent soot is structurally and chemically inhomogeneous, and even the smallest particles can have shapes that deviate from a perfect sphere.     

Lamellar morphology of polyethylene: Electron microscopy of a melt-crystallized sharp fraction

The morphology of linear polyethylene of M_w/M_n 1.19 crystallized isothermally from the melt has been investigated. Electron microscopy (EM) of stained thin sections gave exceptionally well-defined images. There were no qualitative differences between Regime I and Regime II crystallization, but the lamellae grown at lower supercooling were thicker, larger, and had fewer spiral growths per unit area of fold surface. Small-angle x-ray scattering indicated a much sharper distribution of lamellar thicknesses than EM and Raman LAM did. This is evidence of the complementary nature of the techniques and not a contradiction. EM also revealed nonrepresentative features in detail. There were extremely thin lamellae formed on cooling, indicating molecular weight segregation even in this fractionated material, and there were extremely thick lamellae, attributed to isothermal thickening. As the representative lamellae are also supposed to have thickened isothermally, this raises the issue of when and how the lamellae which are the primary products of crystallization can be identified.     

STM imaging of a heptanuclear ruthenium(II) dendrimer, mono-add layer on graphite

Scanning tunneling microscopy (STM) and molecular mechanics calculations were used to investigate the long-range packing and the structure of an heptanuclear ruthenium (II) dendritic species, as a PF6- salt. STM imaging was carried out on a mono-add layer of the ruthenium dendrimer formed by physisorption from a 1,2,4-trichlorobenzene solution at the liquid-graphite interface. The packing of the molecules on the surface was visualised by the formation of ordered patterns and a distance of 27 +/- 2 A was measured between two adjacent lamellae. The comparison of this dimension with the molecular-modelling data indicates that the lamellae were formed by rows of dendrimer molecules in which the counterions (PF6-) were strongly associated with the Ru atoms. The images acquired with higher spatial resolution revealed the presence of repeating units within the lamellae. The comparison of the STM images with the modelling results allowed the attribution of the repeating units observed in the imaged pattern to the STM signature of single dendrimer molecules.     

Crystal structure and thermal behavior of cold-crystallized poly(trimethylene terephthalate)

The structure and thermal behavior of cold-crystallized poly(trimethylene terephthalate) (PTT) are revealed in detail by DSC, AFM, TEM, and WAXD as well as in situ FTIR and SAXS techniques. There is no effect of crystallization temperature and initial state on the crystal modification, yet the morphology is strongly affected by these two factors. First, the small rod-like lamellae for PTT are obtained during the cold crystallization instead of the spherulites formed in the melt crystallization. Second, the edge-on lamellar orientation in thin films is identified during the cold crystallization. The thickness and the lateral width of rod-like lamellae get larger and larger with increasing crystallization temperature. Thin lamellar crystals assemble randomly when the cold-crystallization temperature is lower, while lamellar stacks composed of thicker lamellae are observed when the PTT was annealed at elevated temperature. Moreover, for the cold-crystallized PTT, the final melting temperature does not vary with the crystallization temperature. This phenomenon is explained by the structural improvement during the heating process. For the cold-crystallized PTT sample at lower temperature, three transitions occur when it is heated again: the relaxation of the rigid amorphous phase, the reorganization of molecules in the intermediate phase, and then the melt–recrystallization behavior. Those transitions finally lead to thicker lamellae besides a higher crystallinity before the final fusion. Therefore, the final melting peak of these lamellae is at the same temperature.