Chain folding and the structure of nylon 6.6 spherulites

Following the assignment of the 1329 and 1224 cm^?1 infrared bands to chain-folded conformations in nylon 6.6 by Koenig et al. examination of the infrared spectra of positively birefringent and negatively birefringent spherulitic films has been made. The spectra indicate extensive regular folding in negative spherulites but fewer folds or less regular folding in the positive spherulite structure.

The assignment of the infrared fold bands to modes of vibration of the repeat unit is discussed with reference to the spectra of films with varying extents of N deuteration (normal 6.6, disordered regions deuterated, N deutero 6.6, disordered regions hydrogenated).

Electron micrographs of negative spherulites are analyzed with the infrared and previous evidence. We suggest they are built up of single-crystal lamellae of 0.2 to 0.3 μ lateral dimensions packed with a preferential orientation of the lamellae planes parallel to the radial direction but otherwise randomly oriented.     

Structure and mechanical properties of nylon 6.12 prepared by temperature slope crystallization. II. Rolling deformation and microhardness of the oriented negative spherulite

Oriented negative spherulites of nylon 6.12 were crystallized by the temperature slope method. Rolling deformation of the negative texture was performed in three directions. The deformation mechanism of the negative spherulites was investigated by x-ray diffraction and microhardness measurements. Slip deformation between crystalline lamellae (interlamellar slip) was observed in the first stage of deformation. The results are compared with the rolling deformation of other polymer textures such as the positive spherulites of nylon 6.12 and β-phase isotactic polypropylene. In the rolling deformation of nylon 6.12, hydrogen-bonded (010) planes play an important role. For large deformations (λ > 1.5), preferential slip between (010) planes appears, resulting in a lamellar inclination of 60° and a decrease of the lamellar thickness. Microhardness measurements after rolling deformation of the oriented negative texture show good agreement with the structural analysis. The rapid decrease in the microhardness with increasing deformation can be explained by the lamellar thickness decrease brought about by the preferential slip between the (010) planes.     

Scanning and transmission electron microscopy studies on a model series of spherulitic segmented polyurethanes

Scanning (SEM) and transmission (TEM) electron microscopy studies were made on a model series of four segmented polyurethanes. The morphologies of both the homopolymers and of their mixtures were made by SEM while TEM was utilized to study only ultrathin films of the homopolymers. It was found that well-structured spherulitic morphologies could be induced in these systems and their mixtures, and that control over the textures could be maintained by solution casting conditions. The domains were observable via TEM, and the general orientation of this structure within the spherulites was noted. Deformation studies of the spherulitic textures were followed by both SEM and small-angle light scattering. It was concluded that, in general, the spherulites deform in a nonaffine manner–this is particularly true for the systems possessing a porous texture.     

The development of spherulite morphology in polymers

Morphology of polyethylene spherulites has been investigated by the low-dose technique using transmission electron microscopy (TEM) in a scanning mode for dark field and microdiffraction. Specimens were prepared by solvent casting and subsequent recrystallization at different temperatures. The dark-field studies provide spatial information on the lamellar morphology. Two major types of spherulite morphology have been observed: At high temperatures (low crystallization rate) the dark fields show a preferred orientation of the lamellae along the 020 axis. At low temperatures the preferred orientation is 110. The microdiffraction patterns confirm the dark-field results and also show that for intermediate temperatures, regular alteration of regions with 020 and 110 growth planes is responsible for the ringed spherulite appearance. The twisted lamellae model cannot be excluded, but it is shown that it is not responsible for the regular changes in contrast. A model of dendritic growth of spherulite lamellae is used in which the plane of crystal growth is temperature dependent and, for intermediate temperatures, results in regular fluctuation in the mode of crystal growth, branching, and ringed spherulites appearance.     

On the morphology and structure of poly(p-phenylene terephthalamide) single crystals and spherulites

Poly(p-phenylene terephthalamide) (PPTA) single crystals and negative spherulites obtained from concentrated sulfuric acid solution were studied by polarizing microscopy, transmission electron microscopy, electron diffraction, and infrared spectroscopy techniques. Electron microscopy shows that the single crystals with nearly pyramidal shape are composed of rectangular platelets which are packed in parallel with the same orientation. The long edge of the platelet is parallel to [avec]?, while the macromolecular chains are located in the plane of the platelet and perpendicular to the long edge. The width of the platelet is dependent on the molecular weight. The radius direction of PPTA negative spherulites is [avec]?. Electron diffraction patterns indicate that the unit cell parameters of PPTA single crystals and spherulites are not the same as those of Kevlar fibers. For the former c = 11.5 Å, while for the latter c = 12.9 Å. This indicates that the molecular conformation of PPTA molecules in the single crystals and spherulites is different from the conformation of PPTA molecules in the fibers. Infrared absorption spectra show large shifts of the amide I and amide II bands between the two conformations.     

Miscibility,Crystallization, and Morphology of the Double-Crystalline Blends of Insulating Polyethylene and Semiconducting Poly(3-Butylthiophene)

A series of crystalline semiconducting poly(3-butylthiophene) (P3BT)/crystalline insulating polyethylene (PE) blends were prepared and the miscibility, crystallization, and structure/morphology were investigated. Even though phase separation was observed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS), several pieces of evidence indicated that limited miscibility should be present in PE/P3BT blends: small changes in both T_m and crystallinity of PE phase and a small portion of PE being dissolved in P3BT. The study of PE isothermal crystallization kinetics revealed that the introduction of P3BT significantly influenced the nucleation mechanism and growth geometry, i.e., PE was transformed from three-dimensional (3D) spherulitic to two-dimensional (2D) disc crystals. A striking reduction of nucleation density and an obvious ringed morphology of PE spherulites (2D) in PE/P3BT blends were also observed by polarized optical microscopy; it is proposed that the limited miscibility between PE and crystalline P3BT favors the formation of ringed PE spherulite in the blends. Additionally, preferred orientation of PE lamellae, with their b-axis largely constrained to the thin film plane, was observed by X-ray diffraction in PE/P3BT blend films. It is evidenced that the PE orientation was due to the b-axis being the crystal growth direction, which can only be in film plane.     

Mechanism of formation of texture and its influence on the strength of thermoelectric <Emphasis Type="Italic">p</Emphasis>-Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript>

It is established that, in preparing p-Bi_0.5Sb_1.5Te₃ by vertical zone melting, in addition to the directional texture (characteristic of materials exhibiting a highly anisotropic growth rate) in which the cleavage planes of crystal grains are parallel to the direction of propagation of the crystallization front, other texture types can arise, in which the orientation of grain cleavage planes is ordered in a cross-sectional plane of the ingot. Two types of such textures, “radial” and “circular,” were observed. In a radial texture, the lines of intersection of grain cleavage planes with a cross-sectional plane of the ingot are oriented along radii of this cross section and, in a circular texture, these lines of intersection are oriented approximately perpendicular to a radius crossing the grain. The formation of a radial texture is associated with rotation of the ampoule with the crystallizing substance about its vertical axis causing centrifugal flows of the melt. The formation of a circular texture is associated with the orientation effect of the ampoule walls and with circular motion of the melt during torsional oscillations of the ampoule about the vertical axis. Ingots with a radial texture exhibit much lower resistance to splitting along their axis than ingots with a circular texture do. An explanation is provided for this fact.     

Determine mechanical properties of particulate composite using ultrasound spectroscopy

It is known that microscopic spherulite growth plays an important role in macroscopical properties such as elastic moduli of some semicrystalline polymers. Ultrasonic spectroscopy can be used to quantitatively determine the role of spherulites. As a first approximation, spherulitic polymers are modeled as a material with spherical inclusions in an amorphous matrix. This two-phase composite model is then physically realized by embedding glass micro-spheres in an epoxy. The dynamic mechanical properties of these composites are experimentally determined by measuring their acoustic properties such as phase velocity and attenuation. Acoustic scattering theories are then applied to this model to test their predictive capabilities for the real composite's mechanical properties.     

Multimolecule glasses and crystals of isotactic polystyrene

When spreading dilute solutions of isotactic polystyrene (iPS) on water, it was observed that different concentrations produce different morphologies in the resulting amorphous films. From 10^?1 to 10^?2 wt% solutions, ribbonlike films and circular platelets of multimolecule aggregates were obtained. After isothermal crystallization of these amorphous films, lamellae, incipient spherulites, and single-molecule crystals were observed. The formation of lamellar crystals lying flat on the substrate is an indication of the absence of epitaxy by the substrate, which would require the molecular chains to be in the surface plane and thus yield lamellae normal to the substrate. The dense packing in the center of sheaflike spherulites is caused by screw-dislocation growth, and it produces structures similar to shish kebabs. It was also observed that the lamellae grown from the center develop secondary growth spirals, causing the branching and splaying of the structure typical for spherulitic growth.     

CRYSTALLIZATION OF A LOW MOLECULAR WEIGHT POLYETHYLENE AND PARAFFINS UNDER A TEMPERATURE GRADIENT

A low molecular weight polyethylene (PE) and even-number paraffins were crystallized under a temperature gradient. Highly oriented crystalline textures were developed by the temperature slope crystallization. The in situ crystallizing surface was observed by an optical microscope and X-ray diffraction. Polyethylene has a b-axis orientation in which the lamellar normal and crystalline c-axis are perpendicular to the temperature gradient. On the contrary, in the even-number paraffins, both axes are parallel to the temperature gradient. The results of the in situ measurements and the crystalline orientation are compared and discussed for both cases.     

A possibility to produce elliptically polarized transition radiation

Transition radiation produced when a charged particle successively crosses two anisotropically conducting planes is considered. The first plane has the form of a two-dimensional array (grating) made of thin metal wires parallel to the x and y axes. The second plane is a one-dimensional array whose wires are parallel to the y axis. The planes are parallel to each other and perpendicular to the particle trajectory. Transition radiation is shown to be elliptically polarized, the degree of ellipticity and rotation direction being dependent on the direction of radiation, the distance between the arrays, and the particle velocity.     

Compatibilization of Poly(Trimethylene Terephthalate)/Polycarbonate Blends by Epoxy. Part 2. Melting Behavior and Spherulite Morphology

The melting behaviors of poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends, compatibilized by epoxy, and PTT spherulite morphology in the blends were investigated. When epoxy was present during blending, the melting behaviors of PTT/PC blends changed substantially; glass transition temperatures (T_g's) and cold crystallization temperature (T_cc's) of the PTT‐rich phase shifted to higher temperatures, while T_m's shifted slightly to lower temperatures, indicating that epoxy suppressed considerably all processes of dynamic movements pertinent to molecular (or segmental) movements. The cold crystallization process responded sensitively to thermal history. Changes of T_cc's with composition suggested that the epoxy's compatibilization effect was pronounced when PTT and PC were in near equal content.

Recrystallization or reorganization exotherms appeared before melting for isothermally crystallized PTT/PC and PTT/PC epoxy (E) blends. A wide angle X‐ray diffraction (WAXD) analysis showed that, although the perfection of PTT crystallites was influenced either by PC content and the presence of compatibilizer or by the crystallization temperature and crystallization time, PTT's crystal structure was independent of these variables.

The polarized light microscopy (PLM) observations showed that PTT spherulite morphology was very sensitive to blend composition. Epoxy addition interfered severely with the growth of PTT spherulites, causing them to be much less developed. When the spherulites grew under a condition of varied composition, they would exhibit diversified spherulite morphology, though in one spherulite.     

Angle-resolved photoemission of chain-like molecules: the electronic band structure of sexithiophene and sexiphenyl

Here we report the electronic π-band structure of sexithiophene obtained from 6T(010) oriented films. The angle-resolved valence band photoemission results taken parallel and perpendicular to the molecular axis are compared to those of sexiphenyl and interpreted in terms of intra- and inter-molecular band dispersion. We show that the strong photoemission intensity variations with emission angle parallel to the molecular axis are well reproduced by the Fourier transforms of the molecular orbitals of the isolated molecules. These results imply that ARUPS can yield quite detailed information about molecular geometry, both in terms of molecular orientation and internal structure.     

Active Control of Cellular Orientation through In-Situ Stress in the Substrate

We investigate the orientation of cells on substrates to find possible methods for controlling the cellular orientation. The force dipole model is employed in our modelling and simulation. The elastic interaction between cells as well as the elastic interaction between the cell and in-situ stress field in the substrate are found to be the two main physical mechanisms to control the cellular orientation. The former interaction dominates the cellular orientation when the in-situ stress is small, while the later dominates when the in-situ stress is large enough. Two cells tend to align perpendicularly on a free substrate, but the cellular orientation varies with the increasing in-situ stress. Two cells tendto align in parallel when the normal stress is large enough. Their direction is perpendicular to the extension stress direction or parallel to the compression stress direction. When the positive in-situ shear stress is large enough, the two cells tend to align at -45°. Based on this theoretical simulation, it is believed that the cellular orientation on substrates can be controlled by thein-situ stresses.     

Miscibility Determination in Poly(ε-caprolactone)/Poly(Vinyl Formal) Blend by Equilibrium Melting Temperature and Spherulite Morphology

Miscibility of poly(ε-caprolactone), (PCL), containing 1, 5, and 10 wt.% poly(vinyl formal) (PVF) blends was investigated by polarized optical microscopy (POM), atomic force microscopy (AFM), and differential scanning calorimetry (DSC) for spherulitic morphology and equilibrium melting temperature (T°_m, via Hoffman-Weeks plot). The T°_m of PCL in the blends was similar to that of pure PCL, indicating immiscibility. Isothermally, melt crystallized virgin PCL between 30°C and 50°C showed spherulitic morphology with negative birefringence, Maltese cross, and without extinction rings. The nucleation and growth rates of PCL spherulites were found to be dramatically reduced with the addition of PVF. Extinction rings and a change in the sign of the birefringence of the PCL spherulites were observed and were found to be dependent on blend composition and crystallization temperature. The presence of a ring pattern in spherulites was an indication of miscibility between the two polymers that had failed to be detected by thermal methods. The formation of a ring pattern is discussed in terms of lamella twisting originating from a change in the crystallization mechanism.     

Spherulitic crystallization of holmium tartrates in silica gels

Spherulites of holmium tartrate trihydrate and holmium nitro-tartrate monohydrate have been grown in silica gel medium by making holmium nitrate to react with tartaric acid at high supersaturations. The mechanism of spherulitic growth of holmium tartrates is discussed. The spherulitic crystallization is shown to be due to heterogeneous nucleation. In the early stages of growth an amorphous spherical mass gets nucleated inside the gel. Crystal fibers diverge radially from the surface of the spherical mass giving rise to a spherical polycrystalline holmium tartrate. Thermal stability of the two types of spherulites grown in the silica gel shows that the holmium tartrate trihydrate is more stable than holmium nitro-tartrate monohydrate. The surface morphology and internal structure of the spherulites of holmium tartrates have been studied by using scanning electron microscopy. The results on growth kinetics are given by studying the variation of radius of spherulites as a function of time. A non-linear time–size relations under several conditions of growth have been observed, which suggests a non-uniform solute concentration at the crystal surface.     

X-ray diffraction studies of the structure of nanocrystals in Fe<Subscript>73.5</Subscript>Si<Subscript>13.5</Subscript>B<Subscript>9</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript> soft magnetic alloys before and after thermomechanical treatment

The structure of the Fe_73.5Si_13.5B₉Nb₃Cu₁ soft magnetic alloy has been investigated using X-ray diffraction in transmission geometry. The initial alloy prepared by rapid quenching from the melt has a short-range order (∼2 nm) in the atomic arrangement, which is characteristic of the Fe-Si structure with a body-centered cubic lattice. The alloy subjected to annealing contains Fe-Si nanocrystals with sizes as large as 10–12 nm. The annealing under a tensile load leads to an extension of the nanocrystal lattice so that, after cooling, a significant residual deformation is retained. This can be judged from the relative shifts of the (hkl) peaks in the X-ray diffraction patterns measured for two orientations of the scattering vector, namely, parallel and perpendicular to the direction of the load applied. The deformation is anisotropic: within the accuracy of the experiment, no distortions in the [111] direction are observed and the distortions in the [100] direction are maximum. It is known that crystals with a composition close to Fe₃Si exhibit a negative magnetostriction; i.e., their magnetization induced under a load (Villari effect) applied along the [100] direction is perpendicular to this direction along one of the easy magnetization ([010] or [001]) axes. In the alloy, the orientation of the nanocrystal axes is isotropic and the majority of the nanocrystals have a composition close to Fe₃Si. The direction of magnetization of these nanocrystals is determined by the residual deformation of their lattice and lies near the plane perpendicular to the direction of the tensile load applied during heat treatment. This is responsible for the appearance of transverse magnetic anisotropy of the easy-plane type in the Fe_73.5Si_13.5B9Nb₃Cu₁ alloy.     

Growth Rate of Spherulites in Thin Films: Direct Evidence of Failure of Traditional Growth Theory

Growth rates of PPS and PVDF spherulites in very thin films were measured. The growth rates change by about four orders of magnitude within the crystallization temperature ranges examined in this work. Film thickness at the position of the spherulite for which growth rates were determined was measured; the film thickness was deduced from retardation in the spherulite. In the light of the criterion we proposed, film thicknesses more than several tens of microns are required for the growth rate to change by four orders of magnitude. However, the thickness of the thinnest film examined experimentally was less than 1 μm. This discrepancy between theory and experiment is large and violates the framework of the traditional growth model unrecoverably.     

Surface diffusion of Pd and Au on W single crystal planes: II. Anisotropy of Pd surface diffusion due to the influence of substrate structure

Large anisotropy effects have been observed for the spreading of Pd on W single crystal planes exhibiting regular step structures. The spreading rate was studied as function of step density and step direction at temperatures around 1000 K. The terraces had always (110) orientation. Step densities as low as 3.3 × 10⁴cm^?1 corresponding to an average terrace width of 3000 Å already cause enhanced spreading rates parallel to the step direction. Steps parallel to the [001] direction showed the largest promoting action. The rate perpendicular to steps does not depend markedly on step density. The diffusion behaviour on the “step free” (110) plane turned out to be isotropic. A model is proposed which assumes the mass transport to occur in the second Pd layer. The increase of the diffusion rate along steps is correlated with the much larger density of diffusing atoms in step sites as compared to terrace sites due to the difference in binding energy.     

Spherulite Growth of cis-1,4-Polyisoprene Isolated from Natural Rubber

The crystallization behavior of cis-1,4-polyisoprene, isolated from natural rubber, was investigated by polarized light microscopy. Natural rubber was purified by deproteinization followed by transesterification to remove protein, phospholipid, and fatty acids present in the rubber. The purified rubber was fractionated into seven fractions. For the fractionated rubbers, spherulite growth was observed during the course of crystallization. The size of the spherulites increased linearly with crystallization time, and thus, growth rate was estimated. The growth rate was proportional to TΔT, where ΔT is supercooling. Because the slope of the line was independent of the molecular weight, the growth rate was confirmed to be a function of diffusion of the rubber.