Self-organization of interlaced network lamellar crystals of trans-1,4-polybutadiene (TPBD) on an amorphous surface

A novel morphology of TPBD crystals consisting of a three-dimensional interlaced network was obtained by casting the self-seeded 0.1% benzene solution onto carbon-boated mica. Both the transmission electron microscopy (TEM) and electron diffraction (ED) analyses showed that the network was composed of well-developed lamellae. It is imagined this interesting morphology is the results of asymmetrical growth of the original TPBD lamellae on the amorphous interface, and that their preferred orientation changed when they encountered each other.

Helical single-lamellar crystals thermotropically formed in a synthetic nonracemic chiral main-chain polyester

Phase structures and transformation mechanisms of nonracemic chiral biological and synthetic polymers are fundamentally important topics in understanding their macroscopic responses in different environments. It has been known for many years that helical structures and morphologies can exist in low-ordered chiral liquid crystalline (LC) phases. However, when the chiral liquid crystals form highly ordered smectic liquid crystal phases, the helical morphology is suppressed due to the crystallization process. A double-twisted morphology has been observed in many liquid crystalline biopolymers such as dinoflaggellate chromosomes (in Prorocentrum micans) in an in vivo arrangement. Helical crystals grown from solution have been reported in the case of Bombyx mori silk fibroin crystals having the beta modification. This study describes a synthetic nonracemic chiral main-chain LC polyester that is able to thermotropically form helical single lamellar crystals. Flat single lamellar crystals can also be observed under the same crystallization condition. Moreover, flat and helical lamellae can coexist in one single lamellar crystal, within which one form can smoothly transform to the other. Both of these crystals possess the same structure, although translational symmetry is broken in the helical crystals. The polymer chain folding direction in both flat and helical lamellar crystals is determined to be identical, and it is always along the long axis of the lamellae. This finding provides an opportunity to study the chirality effect on phase structure, morphology, and transformation in condensed states of chiral materials. [S0163-1829(99)01042-5].

Lamellar single crystals of nylon-10,10 crown from a dimethylformamide solution

A new solvent, dimethylformamide (DMF), and the traditional solvent, 1,4-butanediol, were used to prepare single crystals of nylon-10,10 from a dilute solution. The lamellae grown from DMF inhabited a more perfect structure and regular shape than those crystals crystallized from traditional solvents such as 1,4-butanediol and glycerin. These thin and perfect lamellar crystals demonstrated patterns of variation in spacing different from those of melt-crystallized spherulites on heating. Specifically, the two main spacings slightly separated rather than continuously approaching each other when the temperature was greater than 180 degreesC. This is a novel phenomenon observed in nylons. Nevertheless, the usual pattern of change in spacing was observed during the cooling process. These lamellar crystals showed more compact spacing of the (002) and (010/100) planes than spherulites at room temperature. (C) 2001 John Wiley & Sons, Inc.

Morphology and structure of poly(di-n-butylsilane) single crystals prepared by controlling kinetic process of solvent evaporation

The silicon backbone conformation in poly(di-n-butylsilane) (PDBS) has been shown to be a 7/3 helix at ambient conditions, which is in marked contrast to the near-planar conformation of its homologous polymers with side chain lengths of one to three or six to eight carbon atoms. In this work, both the 7/3 helical and near-planar chain conformations are achieved by controlling the solvent evaporation rate around room temperature. The chain conformation and crystal structure obtained in this method have been correlated to the crystal morphology by wide-angle X-ray diffraction, transmission electron microscopy, electron diffraction, optical microscopy, atomic force microscopy, and UV absorption spectrum. The lath-shaped single crystals obtained at 12 degreesC correspond to an orthorhombic form with near-planar chain conformation whereas the lozenge-shaped single crystals obtained at 30 degreesC (in coexistence with the lath-shaped crystals) are orthohexagonal with a 7/3 helix.

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone.

Morphology and structure of nylon-2,14 single crystals from dilute solution

A perfect single crystal of nylon-2,14 was prepared from 0.02% (w/v) 1,4-butanediol solution by a "self-seeding" technique and isothermal crystallization at 120 and 145 degreesC. The morphology and structure features were examined by transmission electron microscopy with both image and diffraction modes, atomic force microscopy, and wide-angle X-ray diffraction (WAXD). The nylon-2,14 single crystal grown from 1,4-butanediol at 145 degreesC inhabited a lathlike shape with a lamellar thickness of about 9 nm. Electron diffraction and WAXD data indicated that nylon-2,14 crystallized in a triclinic system with lattice dimensions a = 0.49 nm, b = 0.51 nm, c = 2.23 nm, alpha = 60.4degrees, beta = 77degrees, and gamma = 59degrees. The crystal structure is different from that of nylon-6,6 but similar to that of other members of nylon-2Y.

Liquid crystalline phases, microtwinning in crystals and helical chirality transformations in a main-chain chiral liquid crystalline polyester

A main-chain nonracemic chiral liquid crystalline polymer was synthesized from (R)-(-)4'-{w-[2-(p-hydroxy-o-nitrophenyloxy)-1-propyloxy]-1-decyloxyl-4-biphenylcarboxylic acid. This polymer contained 10 methylene units in each chemical repeating unit and was abbreviated PET(R*-10). On the basis of differential scanning calorimetry, wide-angle X-ray diffraction, and polarized light microscopy experiments, chiral smectic C (S-C*) and chiral smectic A (S-A*) phases were identified. Both flat-elongated and helical lamellar crystal morphologies were observed in transmission electron microscopy. Of particular interest was the flat-elongated lamellar crystals were constructed via microtwinning of an orthorhombic cell with dimensions of a = 1.42 nm, b = 1.28 nm, and c = 3.04 nm. On the other hand, the helical lamellar crystals were exclusively left-handed, which was opposite to the right-handed helical crystals grown in PET(R*-9) and PET(R*-11) (having 9 and 11 methylene units, respectively). Note that these three polymers had identical right-handed chiral centers (R*-). Therefore, a single methylene unit difference on the polymer backbones on an atomic length scale substantially changed the chirality of the crystals in the micrometer length scale. Furthermore, aggregates of these helical crystals in PET(R*-10) did not generate banded spherulites in polarized light microscopy. Possible reasons for this change and loss of helical senses (handedness) on different length scales in chirality transferring processes were discussed.

Double twist in helical polymer "soft" crystals

In natural and synthetic materials having non-racemic chiral centers, chirality and structural ordering each play a distinct role in the formation of ordered states. Configurational chirality can be extended to morphological chirality when the phase, structures possess low liquid crystalline order. In the crystalline states the crystallization process suppresses the chiral helical morphology due to strong ordering interactions, In this Letter, we report the first observation of helical single lamellar crystals of synthetic non-racemic chiral polymers. Experimental evidence shows that the molecular chains twist along both the long and short axes of the helical lamellar crystals, which is the first time a double-twist molecular orientation in a helical crystal has been observed.

The Study of Electroactive Block Copolymer Containing Aniline Pentamer Isolated from Different Solvents

For the films and powder of polymers containing conductive oligomer are usually obtained from solution, the choice of better solvents for the regular arrangement of oligomers is very important for the higher conductivity. Because of the poor solubility of the oligomers, it is difficult to study the arrangement directly in most common solvents, so, we synthesized a triblock copolymer, mPEG2k-aniline pentamer-mPEG2k, as the model to investigate the arrangement-solvent relationship. For the poor solubility of the AP block in common solvents, the copolymer self-assembled into spheric micelles in toluene and into lamellar crystals in water and THF. The crystallinity (X-c) and crystallization temperature (T-c) values of mPEG blocks in powders prepared from different solvents differed obviously, which may be the effect of different self-assembled structures. From the two-phase model of one-dimensional electron density correlation function of SAXS, the long period of copolymer prepared from THF was presumably equal to the long period of pure mPEG plus the chain length of AP, which demonstrates that the AP blocks arrange regularly in the noncrystalline regions.

Crystal Growth Transition from Flat-On to Edge-On Induced by Solvent Evaporation in Ultrathin Films of Polystyrene-b-Poly(ethylene oxide)

The transition of lamellar crystal orientation from flat-on to edge-on in ultrathin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) via solvent vapor (toluene) treatment Was investigated. When the as-prepared film was treated in saturated solvent vapor, breakout crystals could form quickly, and then they transformed from square single crystals (flat-on lamellae) to dendrites and finally to nanowire crystals (edge-on lamellae). Initially, heterogeneous nucleation tit the polymer/substrate interface dominated the structure evolution, leading to flat-on lamellar crystals orientation. And the transition from faceted habits to dendrites indicated a transition of underlying mechanism from nucleation-controlled to diffusion-limited growth. As the solvent molecules gradually diffused into the polymer/substrate interface, it will subsequently weaken the polymer-substrate interaction.

High mobility vanadyl-phthalocyanine polycrystalline films for organic field-effect transistors

The organic films of vanadyl-phthalocyanine (VOPc) compounds showed weak epitaxy growth (WEG) behavior on thin ordered para-sexiphenyl (p-6P) layer with high substrate temperature. The WEG of VOPc molecules standing up on the p-6P layer leaded to high in-plane orientation and their layer-by-layer growth behavior. In consequence, high quality VOPc films were obtained, which were consisted of lamellar crystals. Organic field-effect transistors with VOPc/p-6P films as active layers realized high mobility of above 1 cm(2)/V s. This result indicated that nonplanar compounds can obtain a device performance better than planar compounds, therefore, it may provide a rule to find disklike organic semiconductor materials.

Crystallization kinetics and morphology of nylon 1212

The isothermal and non-isothermal crystallization processes of nylon 1212 were investigated by polarized optical microscopy. The crystal growth rates of nylon 1212 measured in isothermal conditions at temperatures ranged from 182 to 132 degreesC are well comparable with those measured by non-isothermal procedures (cooling rates ranged from 0.5 to 11 degreesC/min). The kinetic data were examined with the Hoffman-Lauritzen nucleation theory on the basis of the obtained values of the thermodynamic parameters of nylon 1212. The classical regime I --> II and regime II --> III transitions occur at the temperatures of 179 and 159 degreesC, respectively. The crystal growth parameters were calculated with (100) plane assumed to be the growth plane. The regime I --> II --> III transition is accompanied by a morphological transition from elliptical-shaped structure to banded spherulite and then non-banded spherulite. The development of morphology during isothermal and non-isothermal processes shows a good agreement.

Primary and secondary crystallization kinetic analysis of nylon 1212

The isothermal and non-isothermal melt-crystallization kinetics of nylon 1212 were investigated by differential scanning calorimetry. Primary and secondary crystallization behaviors were analysed based on different approaches. The results obtained suggested that primary crystallization under isothermal conditions involves three-dimensional spherulite growth initiated by athermal nucleation, while under non-isothermal conditions, the mechanism of primary crystallization is more complex. Secondary crystallization displays a lower-dimensional crystal growth, both in the isothermal and non-isothermal processes. The crystallite morphology of nylon 1212, isothermally crystallized at various temperatures, was observed by polarized optical microscopy. The activation energies of crystallization under isothermal and non-isothermal conditions were also calculated based on different approaches.

Melting behaviors, isothermal and non-isothermal crystallization kinetics of nylon 1212

Isothermal crystallization, subsequent melting behavior and non-isothermal crystallization of nylon 1212 samples have been investigated in the temperature range of 160-171 degreesC using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited three melting endotherms. The commonly used Avrami equation and that modified by Jeziorny were used, respectively, to fit the primary stage of isothermal and non-isothermal crystallizations of nylon 1212. The Avrami exponent n was evaluated, and was found to be in the range of 1.56-2.03 for isothermal crystallization, and of 2.38-3.05 for non-isothermal crystallization. The activation energies (DeltaE) were determined to be 284.5 KJ/mol and 102.63 KJ/mol, respectively, for the isothermal and non-isothermal crystallization processes by the Arrhenius' and the Kissinger's methods.