Single-chain single crystals

Single-chain single crystals of isotactic polystyrene and poly(ethylene oxide) were studied by using transmission electron microscopy, high resolution electron microscopy, electron diffraction. Single-chain single crystals were prepared by spreading a dilute solution of polymers on a water surface and collecting the resulting single-chain particles on copper grids, followed by isothermal crystallization. A statistical analysis of the sizes of single-chain crystals was found to match with the known molecular weight distribution of original sample, indicating the particles to be composed of single chain. Observation of the morphology and electron diffraction gave evidence of the single crystal nature. Regular-shaped single-chain crystals were obtained after isothermal crystallization for a longer time. By close observation, several types of morphologies were found for single-chain crystals of isotactic polystyrene and poly(ethylene oxide); in addition to the conventional morphologies observed for multi-chain crystals, new morphologies were observed in both cases. The morphologies of poly(ethylene oxide) were explained according to the crystal structure and twin modes. Tent-like single-chain crystals were often observed. Because of the small size of the crystals, they can avoid collapse on the substrate. The crystalline c-axis of single-chain crystals were found to orient preferably in the direction normal to the substrate. The investigation of electron diffraction and high resolution electron microscopy revealed that the structure of the single-chain crystals of isotactic polystyrene is the same as for multi-chain crystals. A reasonable explanation is given for the unusual resistance to electron irradiation and the missing of lower-index reflections. Regular periodic stripes were found on the top surface of single-chain crystal of isotactic polystyrene with an average periodic length in accordance with (220) spacing. In addition, a statistical thermodynamics theory was developed for single-chain crystal. It is found that the equilibrium dimensions are related to molecular weight and annealing temperature, while the equilibrium melting temperature depends on molecular weight.     

Single-molecule single crystals

Various approaches to the preparation and verification of single-molecule single crystals are discussed for polyethylene and poly (oxyethylene). Analytic tools are electron microscopy, electron diffraction, and differential scanning calorimetry. The main difficulty in producing a single-molecule single crystal is to keep crystals from joining during growth.     

Polymer networks formed in liquid crystals

Monomers with reactive double bonds were mixed with liquid crystals and polymerized under UV irradiation. The polymer networks formed are anisotropic and consist of fibrils. The orientation of the polymer networks depend on the orientation of the liquid crystals during polymerization. Optical and scanning electron microscopy (SEM) were used to study the polymer networks.     

Structural properties of nonionic surfactant/glycerol/paraffin lyotropic liquid crystals

Lamellar lyotropic liquid-crystalline systems are thermodynamically stable, optically isotropic and are formed spontaneously. New possibilities for the development of controlled drug delivery systems are inherent in these systems in consequence of their stability and special, skin-friendly structure. The aim was to formulate and study two-component or multicomponent compositions with a relatively low Brij 96V content, liquid paraffin, glycerol and water for therapeutic purposes. The liquid crystals were examined by polarizing light microscopy and transmission electron microscopic observation of replicas produced by the freeze–fracture technique to demonstrate the presence of lamellar liquid-crystalline domains. The existence of a regular structure was determined by X-ray diffraction.     

Synthesis and characterization of naphthalene-substituted triphenylene discotic liquid crystals

A series of naphthalene-substituted triphenylene liquid crystals (LCs), viz. triphenylene-2,3,6,7,10,11-hexayl hexakis(6-alkenyloxy-2-naphthoate)s (HTPnN compounds) were synthesized and characterized. Alkenyloxy groups containing three to eleven carbon atoms were used as peripheral spacers in these liquid crystals. The discotic liquid crystals synthesized trap one to three water molecules depending on the length of their peripheral spacers. Differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction measurements confirm both nematic (N_d) and rectangular disordered columnar (Col_rd) phases for most of the synthesized discotic LCs. The clearing temperatures of these discotic LCs increase with increasing peripheral spacer length. A hybrid aligned HTP9N sample was investigated to evaluate its optical performance. Retardation values of this hybrid sample decrease with increasing wavelength and increase with increasing measuring angle.     

Organic lyotropic lamellar liquid crystals

X-ray diffraction experiments on smectic A and C forming thermotropic liquid crystals reveal that the smectic layer spacing increases with the addition of organic solvents to the host material. The rate of this increase indicates the formation of an organic lyotropic lamellar liquid crystal phase in which the solvent is intercalated between the smectic layers of the host liquid crystal.     

Single-Molecule single crystals of isotactic polystyrene

Single-molecule single crystals were grown from amorphous droplets of fractionated isotactic polystyrene. The crystals were analyzed by electron microscopy and electron diffraction. The molecular mass distribution could be matched with a statistical analysis of single-molecule particles (amorphous and crystals). Proof was brought that single molecules of isotactic polystyrene do not reach equilibrium dimensions on crystallization, rather assume the lamellar morphology with chain-folded macroconformation, also known from crystallization of polymolecular crystals. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America. US Government contract No. DE-AC05-840R-21400.

     

Single crystals of cellulose IVII: Preparation and properties

Lamellar single crystals of cellulose were obtained from dilute solutions of low-DP cellulose triacetate, by deacetylation followed by precipitation. At temperatures between 150 and 160°C, pure cellulose IV_II crystals were obtained whereas at temperatures between 90 and 150°C, hybrid crystals, having cellulose II and cellulose IV_II domains cocrystallized in syntaxy were obtained. In both cases, the crystals were identified and characterized by electron diffraction. When the solutions leading to cellulose IV_II were seeded with native cellulose microfibrils, a shish-kebab structure resulted with the microfibrils decorated by cellulose II lamellae.     

Molecular lattice resolution of single faceted crystals of a thermotropic liquid crystalline poly(aryl ether ketone) using atomic force microscopy

Communication: The surfaces of single faceted crystals of a thermotropic liquid crystalline poly(aryl ether ketone) copolymer containing chloro‐side group are investigated by atomic force microscope. The molecular lattice resolution images of the single faceted crystals indicate that the surfaces of the crystals consist of molecular chain ends of the copolymer, and the crystals exhibit orthorhombic packing with the unit cell dimensions of a = 0.787 ± 0.020 nm and b = 0.625 ± 0.010 nm, respectively. The data are further confirmed by electron diffraction results.     

Structure of single-molecule single crystals of isotactic polystyrene and their radiation resistance

The structure of single-molecule single crystals of isotactic polystyrene (i-PS) was investigated by electron diffraction (ED). The nanoscale single-molecule single crystals were found to be more resistant to electron irradiation when compared to the larger crystals of many molecules, as indicated by both observation of ED and high-resolution electron microscopy with increasing radiation dose. It is proposed that since the single-molecule single crystals are very small, the secondary electrons escape more frequently from the crystal so that the radiation damage is reduced. Lattice imaging was achieved at room temperature in the case of single-molecule single crystals because of their stability to electron irradiation. Published 1998 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

J Polym Sci B: Polym Phys 36 : 105–112, 1998     

Discotic liquid crystals at the air water interface

The monolayer properties of two types of discotic liquid crystals, hexasubstituted triphenylenes 1 and azo derivatives of phloroglucinol 5, were examined. First investigations show that these discotic liquid crystals form stable monolayers. It could be shown that electron acceptors insert into the monolayer of 1. Azo discs display a packing behaviour at the monolayer that is ascribed to a side-on packing of the molecules.     

Freeze fracture TEM investigations in liquid crystals

This review describes the results obtained in the determination of the nanometric structures of liquid crystal systems using the technique of freeze fracture transmission electron microscopy (FF-TEM). I focus the review on two types of major results that were obtained with this technique in respectively lyotropic and thermotropic liquid crystals systems.     

Application of electron diffraction in the structure characterization of polymer crystals

The dependence of properties on the structure and morphology of semicrystalline polymers offers an effective way to tailor the properties of these materials through structure control. To this end, establishing the structure and property relationship is of great importance. For a right characterization of the crystal structure, several techniques can be used. Among these techniques, electron diffraction has its advantage for determining the crystal structure related to specific formation condition since it can combine with bright and dark fields observation of the sample. This feature article describes the application of electron diffraction in determining the crystal structure of semicrystalline polymers with elaborately selected examples. We focus on how the electron diffraction can be used to disclose the crystal structure, mutual orientation of different crystals, as well as the disorders included in the polymer crystals.     

Synthesis and characterization of single-layer silver-decanethiolate lamellar crystals

We report the synthesis of silver-decanethiolate (AgSC10) lamellar crystals. Nanometer-sized Ag clusters grown on inert substrates react with decanethiol vapor to form multilayer AgSC10 lamellar crystals with both layer-by-layer and in-plane ordering. The crystals have strong (010) texture with the layers parallel to the substrates. The synthesis method allows for a precise control of the number of layers. The thickness of the lamellae can be manipulated and systematically reduced to a single layer by decreasing the amount of Ag and lowering the annealing temperature. The single-layer AgSC10 lamellae are two-dimensional crystals and have uniform thickness and in-plane ordering. These samples were characterized with nanocalorimetry, atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray reflectivity (XRR), Fourier transform infrared spectroscopy (FTIR), and Rutherford backscattering spectroscopy (RBS).     

Morphology of poly(phthalocyaninatogermoxane) crystals

The morphology of fully and partially polymerized poly(phthalocyaninatogermoxane), [Ge(Pc)O]_n, crystals was studied by both scanning and transmission electron microscopy. It was found that the morphological units are lath-like crystals which aggregate into particles. Generally speaking, the thickness, width, and length of the laths are in the range of 1000–2000 Å, 2000–10,000 Å, and 1–5 μm, respectively. Each lath may possess a mosaic substructure. Selected-area electron diffraction patterns indicate that the rigid, extended [Ge(Pc)O]_n chains are parallel to the large surface of the lath, and in most crystals the chains lie parallel to the lengthwise direction of the lath. However, in several cases, the chain orientation is at an angle of about 60° with respect to the long edge of the lath. The electron diffraction results are in accord with a tetragonal crystal structure (P4/m).     

Microscopic investigations of the indium nitride crystals with flower-like morphology grown by means of halide chemical vapour deposition under atmospheric pressure

Indium nitride prepared under atmospheric pressure using a halide chemical vapour deposition method has been examined by means of a variety of analytical techniques. From the scanning electron microscopic observations of the crystals deposited onto a Si(100) substrate, it was found that they have flower-like morphology. Based on the electron diffraction and X-ray photoelectron spectroscopic analyses, it was deduced that the flower-like InN crystals have a stoichiometry close to In:N=1:1. Transmission electron diffraction and selected area electron diffraction images showed that each petal and a style constituting the flower are of single crystals form with staggered hexagonal bipyramidal structure.     

Structure of fibers drawn from polyethylene single crystals

Transmission electron microscopy and electron diffraction were used to study the molecular structure of fibers drawn from polyethylene single crystals at 77, 293, and 383°K. The results suggest that the formation of the fibers occurs by a two-step process. The first step is the breaking off of single blocks of folded chains from the single crystals so that a “string-of-pearls” structure is obtained. If the temperature is sufficiently high this process is followed by the thermally activated rearrangement of the molecules in the drawn fibers so that a “bamboo” structure results.     

Crystal structure, thermal behavior and enzymatic degradation of poly(tetramethylene adipate) solution-grown chain-folded lamellar crystals

Solution-grown chain-folded lamellar single crystals of poly(tetramethylene adipate) (PTMA) were prepared from a dilute solution of 2-methyl-1-propanol by isothermal crystallization. PTMA crystals were hexagonal-shaped and polyethylene decoration of the crystals resulted in a "six cross-sector" surface morphology and showed that the average direction of chain folding is parallel to the crystal growth planes of [110] and [010]. Chain-folded lamellar crystals gave well-resolved electron diffraction diagrams corresponding to all the equatorial reflections of the X-ray fiber diagram obtained from stretched PTMA melt-quenched film (beta structure). The unit cell parameters of the beta structure of PTMA were determined as a = 0.503 nm, b = 0.732 nm and c (fiber axis) = 1.442 nm with an orthorhombic crystal system. The fiber repeat distance is appropriate for an all-trans backbone conformation for the straight stems. The setting angle, with respect to the a axis, is +/-46 degrees for the corner and center chains. Thermal behavior of lamellar crystals has been investigated by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM). The lamellar thickness at the edges of the crystal increased after thermal treatment with taking the molecular chains into recrystallization parts; the holes then opened up at the thickening front of the crystal. The morphological changes of lamellar crystals after enzymatic degradation by Lipase type XIII from Pseudomonas sp. and water-soluble products were characterized by TEM, AFM, gel permeation chromatography, high performance liquid chromatography and fast atom bombardment mass spectrometry. The degradation progressed mainly from the edges of the lamellar crystals without decreasing the molecular weights and the lamellar thicknesses. The central portion of single crystals was often degraded by enzymatic attacks. This result combined with thermal behavior indicates that the loosely chain-packing region exists inside the single crystal, and that molecular chains in this region have higher mobility against thermal and enzymatic treatments.     

Transient holographic grating in azo-dye-doped liquid crystals with off-resonant light

Holographic gratings in nematic liquid crystals doped with Disperse Red 1 (DR1) were investigated using a linearly polarised He–Ne laser. Although the electric transitions of the samples were almost off-resonant, the diffraction of the transient holographic grating was found to exhibit a sinusoidal feature with changing the polarisation of recording beams, and the diffraction intensities and response time of the gratings were strongly dependent on DR1 concentration. The results revealed that the diffraction of holographic grating depends on the rate of trans–cis isomerisation of DR1 molecules. Moreover, the temperature dependence of diffraction indicated that the grating formation mechanism was attributed to photoinduced reorientation of photoisomerisation effect.