Structure development during melt spinning and subsequent annealing of polybutene‐1 fibers

The structural development during the melt spinning and subsequent annealing of polybutene‐1 fibers was studied with in situ wide‐angle X‐ray scattering techniques. The online spinning apparatus consisted of a vertically translating extruder that allowed different distances from the spinneret to the stationary X‐ray beam to be sampled. For all take‐up speeds examined, phase II crystals mainly were formed, with only a small population of phase I crystals existing. As the take‐up speed was increased, the crystallinity also increased, indicating that strain‐induced crystallization prevailed. The crystalline orientations observed online were very close to perfect alignment with the fiber axis. In addition, annealing studies were performed to study aspects of the gradual phase II to phase I transformation as functions of time and prior processing take‐up speed. This transformation was strongly dependent on the take‐up speed. The dependence appears to be connected to local stress enhancement via chains connecting crystallites. The results also seem to indicate that at low take‐up speeds (17 mpm) there is a series connectivity of amorphous and crystalline components in the fiber, whereas at greater take‐up speeds (100 and 250 mpm), the morphology grows into some type of three‐dimensional network, possibly a shish–kebob‐type morphology. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1872–1882, 2000     

Orientation of guest molecules in doped organic crystals

The orientation of guest molecules in the doped systems, naphthalene-in-anthracene, anthracene-in-naphthalene and tetracene-in-anthracene has been obtained by the use of atom-atom (6-1-exp) potentials. The results indicate that the guest molecules assume nearly the same orientation as the replaced host with only small perturbation on the host lattice. The results are in good agreement with recent ESR studies.     

Orientation of anthracene molecules in naphthalene single crystals

The orientation of anthracene in naphthalene matrix has been determined by EPR of the triplet state of the guest molecule. It differs from the host molecule orientation mainly by a rotation of 25° about the z axis.     

Orientation of anthracene molecules in naphthalene and tetracene molecules in anthracene single crystals

The orientation of isolated anthracene and tetracene molecules in naphthalene and anthracene single crystals, respectively, was determined using electron spin resonance. The result indicates only small deviations of less than 60° from that of a molecule in a substitutional position.     

Orientation control of ferroelectric polymer molecules using contact-mode AFM

We have developed an orientation control technique for polymer molecules utilizing contact-mode atomic force microscopy (AFM). In this technique, the molecular chains were directly modified by scanning an AFM cantilever tip in contact with the film surface at the temperature just below its melting point. We call this process “modification scan”. Here, we applied this technique to poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) thin films on graphite and glass. We prepared a 75-nm thick copolymer crystalline film on graphite whose lamellar plane was perpendicular to the substrate (edge-on), and also prepared a film of the same thickness on glass whose lamellar plane was parallel to the substrate (flat-on). After applying this technique on both films, molecular chains were stretched and aligned to the modification scan direction, and new edge-on crystals were obtained, whose lamellar planes were well-aligned perpendicular to the modification scan direction.     

Fiber spinning from the nematic melt. II. Effect of thermal history on spinning of the copolyester of polyethylene terephthalate and p-oxybenzoate

Fibers were spun from the nematic phase of the copolymer of polyethylene terephthalate having 60 mol % of p-oxybenzoate units. A capillary rheometer was used for spinning with a shear rate at the wall of 6.4 sec^?1, and capillary (length/diameter) ratio of 14.1. The spinning temperature was varied from 250° to 300°C and, at each temperature, the spin-draw ratio was examined as a variable. Spinning was performed under two conditions. When spinning from the melt without preheating, the initial modulus of the fibers increased with spin-draw ratio and increased with increasing spinning temperature for a fixed spin-draw ratio. In the second case, the melt was preheated and then cooled to the desired temperature before spinning the fibers. The preheating temperature was 280°C for spinning at 250°C, and 300°C for spinning at 280°C. Preheating increased the fiber modulus to the value obtained by spinning at the preheating temperature. A reduction of the viscosity due to the melting of poly(p-hydroxybenzoic acid) (PHB) crystallites produces better orientation and higher modulus. However, with increasing spin-draw ratio, the modulus of the preheated fibers decreased to the values expected for the spinning temperature. This decrease in modulus is due to recrystallization of PHB in the threadline.     

Recent developments in phase separation of polyolefin melt blends

Saturated hydrocarbon polymers may be differentiated by the relative amount and placement of methylene, methyl, methine, and quaternary carbon moieties. While it has been known or suspected for some time that polyolefins of conventional molecular weight (M_w ≈ 100 kg/mol) with dissimilar chemical microstructures are most often immiscible in the liquid state, recent experiments with binary blends of model polyolefins have increased greatly our understanding of thermodynamic interactions between unlike chains. Model systems with methyl (−CH₃) and ethyl (−C₂H₅) short-chain branches give results, expressed as the Flory-Huggins interaction parameter χ, that are nearly universal; repulsive interactions (χ > 0) are more pronounced at low temperatures, leading to liquid-liquid phase separation at an upper critical solution temperature. Phase behavior of more complex systems (with distributions of chain microstructures and/or molecular weight) is generally consistent with predictions from model systems. An interesting exception is from work at Bristol on blends of lightly branched ethylene − α-olefin copolymers with unbranched polyethylene as the minority species. Here the presence of two liquid phases is inferred under conditions not expected from model studies; effects of copolymer composition and molecular weight are also unusual. Recent theoretical work points to the importance of chain stiffness (established by short-chain branching) in determining the thermodynamics of model blends. Nonrandom mixing of chains with different stiffness gives rise to an enthalpic χ, which may be negative under certain conditions. Other limitations of the Flory-Huggins approach to describing blend energetics are considered. At present there is no theoretical basis for liquid-liquid phase separation reported by the Bristol group. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2329–2353, 1997     

Orientation of mineral crystals by collagen fibers during in vivo bone engineering: An X-ray diffraction imaging study

The mechanism of mineralized bone matrix deposition was investigated taking advantage of a tissue engineering approach in which bone tissue is formed when porous ceramic scaffold is loaded with bone marrow stromal cells and implanted in vivo. The aim of our study is to point out the interaction between the newly formed mineral crystals and the scaffold imposing the three-dimensional desired architecture to the growing bone. High spatial resolution Small Angle X-ray Scattering measurements obtained using synchrotron radiation and X-ray waveguide as optical element allowed a local structural study at the bone–scaffold interface. Using an original methodology for data analysis, we obtained a two-dimensional microscopic map of the mineralization degree, the collagen presence and the mineral orientation degree around the scaffold pore.     

Orientation and anchoring effects in stretched polymer dispersed nematic liquid crystals

The induction of liquid crystal orientation through mechanical stretching was investigated for polymer dispersed liquid crystals (PDLCs) by means of infrared dichroism. Using a nematic liquid crystal BL006 and polyacrylic acid as the polymer matrix, it was possible to stretch the PDLC films with BL006 in either the isotropic or the nematic phase. After cooling the films under strain to room temperature, the molecular orientation of BL006 was found to be much higher for films that contained isotropic liquid droplets of BL006 at the time of stretching than for films that had nematic droplets. Stretching PDLC films with isotropic droplets results in no molecular orientation, but the orientation is induced during the subsequent cooling when BL006 goes through the isotropic-to-nematic phase transition. Interestingly for PAA/BL006, the nematic director orients along the long axes of the elongated droplets despite liquid crystal anchoring perpendicular to the polymer interface.     

Orientation and anchoring effects in stretched polymer dispersed nematic liquid crystals

The induction of liquid crystal orientation through mechanical stretching was investigated for polymer dispersed liquid crystals (PDLCs) by means of infrared dichroism. Using a nematic liquid crystal BL006 and polyacrylic acid as the polymer matrix, it was possible to stretch the PDLC films with BL006 in either the isotropic or the nematic phase. After cooling the films under strain to room temperature, the molecular orientation of BL006 was found to be much higher for films that contained isotropic liquid droplets of BL006 at the time of stretching than for films that had nematic droplets. Stretching PDLC films with isotropic droplets results in no molecular orientation, but the orientation is induced during the subsequent cooling when BL006 goes through the isotropic-to-nematic phase transition. Interestingly for PAA/BL006, the nematic director orients along the long axes of the elongated droplets despite liquid crystal anchoring perpendicular to the polymer interface.     

Deformation mechanisms of constrained polymer chains. II. Deformation energetics of tie molecules

Energy-deformation characteristics for the primary T, S, and U conformational units of tie molecules were obtained from the analysis of data generated from a constrained minimization algorithm. Energy-deformation profiles (covering the range from compact equilibrium defect structures to the fully extended chain) are reported for the S₀ and S₁ members of the S_λ family and for the U₀₀ member of the U_mn family. Estimates of the energy content V⁰ and the elastic modulus E were obtained from the computed energy-deformation data in the vicinity of the equilibrium Structure—S₀ → {60°, 180°, ?60°}, V = 1.7 kcal/mole, E = 60 kcal/cm³ [250 × 10¹⁰ dyn/cm²];S₁ → {60°, 180°, 180°, 180°, ?60°}: V = 1.7 kcal/mole, E = 25 kcal/cm³ [100 × 10¹⁰ dyn/cm²]; and U₀₀ → {60°, 180°, 60°, 180°, 60°}: V = 2.7 kcal/mole, E = 80 kcal/cm³ [340 × 10¹⁰ dyn/cm²]. Although the elastic modulus of the U₀₀ unit is comparable to the elastic modulus of the fully extended chain, the highenergy content of this unit (V₀ = 2.7 Kcal/mole) prohibits a significant population and thereby mitigates an appreciable reinforcing effect from this rigid unit. A model for a surrogate force constant is introduced to generalize the results from this study to any member of the S_λ or U_mn family as well as any combination of S_λ and U_mn units. This generalization provides a basis for estimating the deformation characteristics of tie molecules comprised of various populations of these primary conformational building blocks.     

Orientation mechanisms during biaxial drawing of polymer films

Summary Second drawing of monoaxially drawn PP and PET films perpendicular to the first drawing direction has been investigated. At low draw ratios structural systems having an angle of 45° with regard to the second draw direction are formed. By increasing the draw ratio the structures rotate into the new preferred direction. The results lead to the impression that the structural transformations do not turn out molecule by molecule, but domain by domain.

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Zusammenfassung Die Zweitverstreckung monoaxial verstreckter PP- und PET-Folien senkrecht zur Erstverstreckrichtung wird untersucht. Bei kleinen Verstreckgraden bilden sich Struktursysteme unter 45° zur Zweitverstreckrichtung; bei weiterer Verdehnung drehen sich die Strukturen in die Vorzugsrichtung. Die Ergebnisse vermitteln den Eindruck, daß die Strukturänderung nicht Molekül für Molekül, sondern Bereich für Bereich abläuft.

With 10 figures and 2 tables     

Electrostatic fiber spinning from polymer melts. II. Examination of the flow field in an electrically driven jet

The flow field in an electrically driven jet has been examined and quantitatively analyzed. Using a model fluid, the nature of the streamlines and magnitude of the stream velocities were investigated with the aid of tracer particle photography. It was found that the velocity field is not purely extensional, but contains rotational components as well. Furthermore, the only portion of the jet completely free of any rotational component is the region about the symmetry axis. The extensional strain rate along the symmetry axis increases rapidly with the applied electric field intensity and can attain values in excess of 50 sec^?1. This suggests that it might be possible to draw continuous oriented fibers from polymer melts by this technique if the jet can be operated at sufficiently high electric field intensity.     

Moisture sorption mechanism of aromatic polyamide fibers. V: Growth of crystallites in as-spun wet poly(p-phenylene terephthalamide) fiber during dehydration

Wide-angle x-ray diffraction studies were performed for as-spun wet poly(p-phenylene terephthalamide) fiber. The effects of sorbed water on the equatorial diffractions from the (110) and (200) crystal planes and on the meridional diffractions from the (002), (004), and (006) crystal planes were analyzed during desorption and absorption. There was no significant change in the d-spacing from the respective crystal plane irrespective of the moisture (water) regain. The ratio of the diffracted intensity from the (110) diffraction to that from the (200) diffraction remarkably increased by removing the sorbed water. The crystallite size estimated from the (110) diffraction, L₁₁₀, also increased as the moisture regain decreased, while the L₂₀₀ did not increase. The longitudinal size of paracrystallite, D₀₀₁, also remarkably increased with the decrease in moisture regain with the lattice distortion factor, g_II, kept unchanged. These results strongly suggested the growth of the crystallite via hydrogen bonds in the lateral (b-axis) direction. The growth of the lateral size of crystallite also accompanied the longitudinal growth of crystallite during desorption. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1423–1432, 1997     

Investigation of low mass oligomers and polymer additives from plastics. Part II: Application to polyolefin soxhlet extracts

Polyolefin Soxhlet extracts have been investigated by capillary SFC using flame ionization detection. Separation and detection of every polymer additive (antioxidants, antistatic agents, etc.) present in the plastic were possible, sometimes in a single CSFC run. Identification of coextracted low mass oligomers and certain of the alteration products of Irganox 1010 was confirmed by GC-MS. New methods are presented for the determination of reacted and remaining calcium stearate, used in plastics both as a stabilizer and a lubricant.     

Orientation of molecules in enzyme reactions

It is suggested that a mutual orientation effect exists for molecules in enzyme reactions.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 4, pp. 236–237, July–August, 1994.