Polarized IR Spectroscopy Research Articles

Interpolymer Complexes of Poly(methacryloyloxyethyl phosphorylcholine) and Polyacids.

It has been shown that macromolecules of poly(methacryloyloxyethyl phosphorylcholine) can form hydrogen bonded interpolymer complexes with homo- and copolymers of carboxylic acids and with poly(vinylphosphonic) acid in aqueous solutions. Polarized luminescence and IR spectroscopy were applied in the investigation. Nanosecond relaxation times characterizing the mobility of the chain fragments for the initial luminescent labeled polymers were determined and their changes by a factor of 2–50 were established during the formation of an interpolymer complex. Hydrogen bonds play a dominant role in the formation of these complexes. Hydrophobic interactions serve as an additional stabilizing factor. It is established that poly(methacryloyloxyethyl phosphorylcholine)/poly(vinylphosphonic acid) complex forms a looser structure in comparison with those for polycarboxylic acids as result of electrostatic repulsion between charged groups.

In-Situ Infrared Spectra of OH in Pakistan Forsterite at High Temperature

The hydroxyl of the gem-grade forsterite from Pakistan was measured by the polarized spectra at room temperature to 1000 °C, showing four unambiguous absorption bands at 3612, 3597, 3579, and 3566 cm−1. Here, we report angle-resolved polarized IR spectroscopy of the crystal-oriented forsterite, which were heated at 1 bar up to 1000 °C in situ to investigate the hydrogen diffusion character. The peak positions of the IR absorbance at 3579 cm−1, 3597 cm−1, and 3566 cm−1 of forsterite decreased linearly depending on the temperature, while the 3612 cm−1 is stable. We discuss that the dipole orientation of the hydroxyl is analyzed by a pleochroic scheme of the integrated absorbance vs. sample to polarizer angle. Our data suggest that the temperature effect cannot be ignored since the absorption coefficients and absorbance band positions of OH may alter.

The nature of hydrogen-bonding interactions in nonsteroidal anti-inflammatory drugs revealed by polarized IR spectroscopy

The influence of hydrogen-bonding interactions in the solid phase on the IR spectroscopic pattern of the νOH band of nonsteroidal anti-inflammatory drugs (NSAIDs) was studied experimentally by IR spectroscopy with the use of polarized light at two temperatures (293K and 77K) and in isotopic dilution. The neat and deuterated crystals of (S)-naproxen ((S)-NPX), (R)-flurbiprofen ((R)-FBP), (RS)-flurbiprofen ((RS)-FBP) and (RS)-ketoprofen ((RS)-KTP) were obtained by melt crystallization between the two squeezed CaF2 plates. The vibrational spectra of selected α-aryl propionic acid derivatives (2APAs) reflected the characteristics of their hydrogen-bond networks, i.e., 2APAs were characterized by the chain ((S)-NPX, (R)-FBP) and by dimeric ((RS)-FBP, (RS)-KTP) arrangement of hydrogen bonds in the crystal lattice. Spectroscopic results showed that the interchain (through-space) exciton coupling, between two laterally-spaced hydrogen bonds, dominates in the crystals of four NSAIDs. The same exciton coupled hydrogen bonds were also responsible for the H/D isotopic recognition mechanism in the crystalline spectra of deuterated 2APAs. The presented spectral results may help to predict the hydrogen bond motifs in the crystalline NSAIDs, which structures are not yet known, based on their IR spectra of hydrogen bond in the crystals.

Polymorphism in the 1:1 Charge-Transfer Complex DBTTF-TCNQ and Its Effects on Optical and Electronic Properties.

The organic charge-transfer (CT) complex dibenzotetrathiafulvalene - 7,7,8,8-tetracyanoquinodimethane (DBTTF-TCNQ) is found to crystallize in two polymorphs when grown by physical vapor transport: the known α-polymorph and a new structure, the β-polymorph. Structural and elemental analysis via selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), and polarized IR spectroscopy reveal that the complexes have the same stoichiometry with a 1:1 donor:acceptor ratio, but exhibit unique unit cells. The structural variations result in significant differences in the optoelectronic properties of the crystals, as observed in our experiments and electronic-structure calculations. Raman spectroscopy shows that the α-polymorph has a degree of charge transfer of about 0.5e, while the β-polymorph is nearly neutral. Organic field-effect transistors fabricated on these crystals reveal that in the same device structure both polymorphs show ambipolar charge transport, but the α-polymorph exhibits electron-dominant transport while the β-polymorph is hole-dominant. Together, these measurements imply that the transport features result from differing donor-acceptor overlap and consequential varying in frontier molecular orbital mixing, as suggested theoretically for charge-transfer complexes.

Elucidating the Davydov-coupling mechanism in hydrogen bond dimers: Experimental and theoretical investigation of the polarized IR spectra of 3-thiopheneacetic and 3-thiopheneacrylic acid crystals.

Monocrystals of the 3-thiopheneacetic and 3-thiopheneacrylic acid dimers were investigated by polarized IR spectroscopy at 77 and 293K in the υO‒H and υO‒D band frequency ranges. We propose to elucidate the strong difference between spectra of the two individual systems, expressed by the corresponding band shapes and by the temperature effects characterizing the bands. The experimental results are compared to predictions obtained with theoretical calculations based on a model for a centrosymmetric hydrogen-bonded dimer that treats the high-frequency OH stretches harmonically and the low-frequency intermonomer stretches anharmonically. It was found that the vibronic coupling mechanism involving the hydrogen bond protons and the electrons on the π-electronic systems in the molecules determines the way in which the vibrational exciton coupling between the hydrogen bonds in the carboxylic acid dimers occurs.

Inter-hydrogen bond coupling in crystals with molecular chains in their lattices investigated by polarized IR spectroscopy: 4-Bromo-3,5-dimethylpyrazole and 3,4-dimethoxyphenylacetic acid

We report the results of the experimental and theoretical studies of the polarized IR crystalline spectra of 4-bromo-3,5-dimethylpyrazole (4Br35DMPz) and 3,4-dimethoxyphenylacetic acid (34DMPAA) as well as the spectra of their deuterium-bonded analogues. The results of model calculations of the temperature impact exerted on to the band shapes measured in the X–H- and X–D bond stretching vibration regions, performed on the basis of the “strong-coupling” model, are also shown. These studies confirm a direct relationship between the spectral properties in IR and the electronic structure of the associating molecules in the crystals. Two different competing exciton coupling mechanisms involving hydrogen bonds, the “tail-to-head” (TH) in 4Br35DMPz and the “side-to-side” coupling in 34DMPAA, were recognized. The molecular electronic structure determines the relative contribution of each individual vibrational exciton coupling mechanism in the spectra generation. It also strongly influences the temperature-induced evolution of the Davydov-splitting effects in the crystalline spectra. Dynamical co-operative interactions responsible for a non-random distribution of protons and deuterons in the crystal hydrogen bonds can also be identified in the investigated systems.

Inter-hydrogen bond coupling in crystals of 3-phenylpyrazole polymorphs investigated by polarized IR spectroscopy

The remarkably strong differences in the fine structure patterns of the νN–H and νN–D bands, temperature and H/D isotopic effects in crystals of two 3-phenylpyrazole (3PhPz) polymorphs, with tetrameric and hexameric hydrogen bond aggregates, were examined by polarized IR spectroscopy, aided by the calculations utilizing the “strong-coupling” model. Experimental and theoretical approaches have suggested that the anti-co-operativity of hydrogen bonds is the main factor responsible for the differences in the spectral properties of both polymorphs. This interaction affects hydrogen-bond geometry of the associates constituting the lattices and in consequence decides about the relative contribution of two different exciton coupling mechanism, “through-space” (SS) and “tail-to-head” (TH), in the spectra generation. The relative contribution of each individual exciton coupling mechanism in the spectra generation is temperature-dependent. In tetramers the TH coupling mechanism dominates at low temperatures, whereas the role of the SS mechanism increases at higher temperatures. For the hexamers the SS mechanism dominates in the wide temperature range. The two types of 3PhPz associates exhibit two different ways of occurring of the H/D isotopic recognition in the crystal hydrogen bonds. In the tetrameric polymorph identical hydrogen isotope atoms exist in entire hydrogen-bonded cycle of 3PhPz. In the case of 3PhPz hexamers, the H/D isotopic recognition mechanism involves pairs of the closely-spaced hydrogen bonds in a cycle.

Temperature, H/D isotopic and Davydov-splitting effects in the polarized IR spectra of hydrogen bond chain systems: 1,2,4-Triazole and 3-methyl-2-oxindole crystals

The spectral properties of two different hydrogen-bonded crystalline systems, 1,2,4-triazole and 3-methyl-2-oxindole, containing molecular chains in their lattices, were examined by polarized IR spectroscopy, aided by the calculations utilizing the “strong-coupling” model. The experimental and theoretical approaches have shown that the individual crystal spectral properties in IR remain in a close relation with the electronic structure of the individual molecular systems. A vibronic coupling mechanism involving the hydrogen bond protons and the electrons occupying the π-electronic orbitals in the molecules determines the way in which the vibrational exciton coupling between the hydrogen bonds in the crystals occurs. For the associating systems, which molecules contain large delocalized π-electronic systems coupled directly with H-bonds, strong exciton interactions involving the vibrationally excited hydrogen bonds in the chains prefer a “tail-to-head”–type Davydov-coupling widespread via the π-electrons. A weak through-space exciton coupling involves two closely-spaced hydrogen bonds belonging to two different adjacent chains in the case, when large π-electronic systems in the molecules are absent. The relative contribution of each exciton coupling mechanism in the chain system spectra generation is temperature-dependent. The two competing individual Davydov-coupling mechanism are responsible for the appearance in the polarized spectra of temperature-dependent Davydov-splitting effects differentiating the spectral properties of the two crystalline systems. The H/D isotopic ‘‘self-organization’’ phenomenon, depending on a non-random distribution of protons and deuterons in the crystal hydrogen bridges was also analyzed.

Anisotropic Optical Properties of Thin-Film Thiacarbocyanine Dye Aggregates

Optical properties of thin films of aggregated thiacarbocyanine (TCC) dyes have been studied by means of spectroscopic ellipsometry and polarized IR spectroscopy. The experimental results reveal a strongly anisotropic response of the films, as quantified in the reported anisotropic dielectric functions over a wide range of frequencies. The studied TCC films exhibit both J-aggregate and H-aggregate absorption bands with different polarization properties. A strong dielectric resonance arising from the J-aggregate electronic excitations was found to be polarized along the film. The observations are consistent with the preferential orientation of aggregate filaments along the films. We have also used the measured anisotropic properties in model calculations of energy transfer into thin films of J-aggregates to illustrate the potential importance of accurate optical characterization in engineering aggregate-based hybrid nanostructures for optoelectronic applications.

Luminescent Amphiphilic 2,6‐Bis(1,2,3‐triazol‐4‐yl)pyridinePlatinum(II) Complexes: Synthesis, Characterization, Electrochemical, Photophysical, and Langmuir–Blodgett Film‐Formation Studies

A new series of platinum(II) complexes with tridentate ligands 2,6-bis(1-alkyl-1,2,3-triazol-4-yl)pyridine and 2,6-bis(1-aryl-1,2,3-triazol-4-yl)pyridine (N7R), [Pt(N7R)Cl]X (1-7) and [Pt(N7R)(CCR')]X (8-17; R=n-C4 H9 , n-C8 H17 , n-C12 H25 , n-C14 H29 , n-C18 H37 , C6 H5 , and CH2 -C6 H5 ; R'=C6 H5 , C6 H4 -CH3 -p, C6 H4 -CF3 -p, C6 H4 -N(CH3 )2 -p, and cholesteryl 2-propyn-1-yl carbonate; X=OTf(-) , PF6 (-) , and Cl(-) ), has been synthesized and characterized. Their electrochemical and photophysical properties have also been studied. Two amphiphilic platinum(II)2,6-bis(1-dodecyl-1,2,3-triazol-4-yl)pyridine complexes (3-Cl and 8) were found to form stable and reproducible Langmuir-Blodgett (LB) films at the air/water interface. These LB films were characterized by the study of their surface-pressure-molecular-area (π-A) isotherms, XRD, and IR and polarized-IR spectroscopy.

Strain-Induced Crystallization and Conformational Transition of Poly(trimethylene terephthalate) Films during Uniaxial Deformation Probed by Polarized Infrared Spectroscopy

The structure development during the drawing of PTT films immediately above the glass transition temperature at two different strain rates (8.33 × 10–3 and 8.33 × 10–4 s–1) has been investigated using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. It was found that both the melting temperature and the crystallinity development are dependent on the strain rate. The cold crystallization peak decreases with increasing draw ratio and disappears completely beyond a draw ratio of 2.5. DSC results showed that the decreasing strain rate delays crystallization and reduces the rate of crystallization. The bands at 1358 and 976 cm–1 were chosen to determine the gauche and trans conformations of methylene segments in PTT as a function of the draw ratios and strain rates. It was found that the crystalline gauche conformation increases at the expense of the amorphous trans conformation during the strain-induced crystallization of PTT. The conversion of the amorphous trans conformation into the crystalline gauche conformation is also delayed at lower strain rate, which is consistent with our DSC observation. Polarized IR spectroscopy was used to measure the crystalline and the amorphous orientation functions separately with draw ratios and strain rates, and it was demonstrated that the crystalline orientation develops rapidly with strain-induced crystallization and that the amorphous orientation stays constant up to draw ratio of 2.5 and increases slowly above a draw ratio of 2.5, which is typical behavior for flexible chain polymers.

Polarized Infrared Studies on Charge Transport in 4-Hydroxycyanobenzene Single Crystals

4-Hydroxycyanobenzene (4HCB) semiconducting single crystals have been probed by polarized IR radiation under various conditions. Linearly polarized IR spectroscopy was found to be sufficient to identify the main crystal axes, provided that crystallographic and electrical analyses have been carried out at least once on the crystal. Moreover, a 2D anisotropic hydrogen bonding degree, which results to be higher along the axis a (one of the two planar axes), has been found. Static electrical polarization induces a rather large and anisotropic rotation of the 3D electric dipole vector of the crystal (p), which increases its component along the axis a and decreases the one along b (the other planar axis). When the crystal is probed under actual charge transport conditions in a field effect transistor (FET) structure, the IR radiation is more effectively screened along axis a (which presents the highest carrier mobility) than along axis b.

Impact of initial solvent on thermal stability and mechanical properties of recombinant spider silk films

Spider silk fibers are one of the most remarkable biopolymers displaying a unique combination of mechanical properties, biocompatibility and biodegradability. The recombinant production of spider silk proteins now allows the processing of silk proteins into novel materials with the aim of future applications. Here, we analyzed films made of a recombinantly produced, engineered spider silk protein with a sequence derived from the dragline silk protein ADF4 of the European garden spider Araneus diadematus. An influence of different initial solvents (aqueous buffer, hexafluoro-2-propanol and formic acid) on certain film properties was identified in as cast as well as methanol post-treated films: while no significant effects on the films' thermal stability were observed, a significant influence on their mechanical properties could be shown. Interestingly, solvent-induced effects were sustained after methanol post-treatment and could be correlated with the presence and arrangement of secondary structure elements. Insights into molecular orientation of individual structural elements within the films upon applied load were revealed by combined polarized IR spectroscopy and mechanical measurements.

Luminescent Amphiphilic 2,6‐Bis(1‐alkylpyrazol‐3‐yl)pyridyl Platinum(II) Complexes: Synthesis, Characterization, Electrochemical, Photophysical, and Langmuir–Blodgett Film Formation Studies

Two series of novel platinum(II) 2,6-bis(1-alkylpyrazol-3-yl)pyridyl (N5Cn) complexes, [Pt(N5Cn)Cl][X] (1-9) and [Pt(N5Cn)(C[triple bond]CR)][X] (10-13) (X=trifluoromethanesulfonate (OTf) or PF(6); R=C(6)H(5), C(6)H(4)-p-CF(3) and C(6)H(4)-p-N(C(6)H(5))(2)), with various chain lengths of the alkyl groups on the nitrogen atom of the pyrazolyl units have been successfully synthesized and characterized. Their electrochemical and photophysical properties have been studied. Some of their molecular structures have also been determined by X-ray crystallography. Two amphiphilic platinum(II) 2,6-bis(1-tetradecylpyrazol-3-yl)pyridyl (N5C14) complexes, [Pt(N5C14)Cl]PF(6) (7) and [Pt(N5C14)(C[triple bond]CC(6)H(5))]PF(6) (13), were found to form stable and reproducible Langmuir-Blodgett (LB) films at the air-water interface. The characterization of such LB films has been investigated by the study of their surface pressure-area (pi-A) isotherms, UV/Vis spectroscopy, XRD, X-ray photoelectron spectroscopy (XPS), FTIR, and polarized IR spectroscopy. The luminescence property of 13 in LB films has also been studied.

Noncentrosymmetric Crystals with Marked Nonlinear Optical Properties

The crystal structures and optical properties of the novel (1R,2R)-(-)-1,2-diammoniumocyclohexane squarate trihydrate (1) and bis(hydrogen squarate) (2) were elucidated and reported. Physical methods, single crystal X-ray diffraction, UV-vis-NIR, polarized IR spectroscopy of oriented colloids, mass spectrometry, and thermal methods were used. Quantum chemical DFT calculations were performed with a view to predict the optical and NLO properties of the systems (1) and (2). Both compounds are characterized with the noncentrosymmetric orthorhombic space groups C222(1) (1) and P2(1)2(1)2(1) (2), indicating nonlinear optical properties in the bulk. These organic salts are thermal stable up to 400 degrees C and transparent over the range from 270 to 1100 nm.

2-(Phenylethyl)ammonium hydrogensquarate hemihydrate: crystal structure, solid-state IR-spectroscopic and theoretical characterization

The title compound, 2-(phenylethyl)ammonium hydrogensquarate hemihydrate, was synthesized and structurally and spectroscopically characterized by a single crystal X-ray diffraction and solid-state polarized IR spectroscopy of oriented colloids in a nematic host. The crystal structure consists of two crystallographically independent 2-(phenylethyl)ammonium cations, joined in a 2D hydrogen-bonded network with hydrogensquarate anions and solvent water molecules. Surprisingly, the crystallographically non-equivalent cations exhibit differing pseudo T and G trans configurations.

Comment on ''Behaviour of H2 O and OH in lawsonite: a single-crystal neutron diffraction and Raman spectroscopic investigation'' by B. A. Kolesov et al.

Low-temperature phase transitions of the high-pressure low-temperature silicate lawsonite, CaAl2(Si2O7)(OH)2·H2O, were discovered by Libowitzky & Armbruster (1995) using single-crystal X-ray diffraction and optical microscopy. The space group symmetry is changed in two steps from Cmcm (>273 K) via Pmcn (<273 K) to P 21 cn (<155 K) as a consequence of different H2O and OH arrangements in the cavities of an almost unchanged framework that consists of chains of edge-sharing AlO6 octahedra interconnected by di-silicate groups. The phase transitions were interpreted using polarized IR spectroscopy of oriented single-crystal sections as dynamic order-disorder transitions, involving hopping motions of H2O and OH groups at ambient temperature, freezing in at low temperatures, thus leading to an enhanced hydrogen bond system (Libowitzky & Rossman, 1996). Later studies, using a number of different techniques confirmed the phase transitions, and revealed their tricritical ( Cmcm to Pmcn ) and second-order ( Pmcn to P 21 cn ) character, as well as an additional displacive component in the framework of the lawsonite structure ( e.g. , Sondergeld et al. , 2000a and b; Carpenter et al. , 2003; McKnight et al. , 2007, and references therein). A recent paper of Kolesov et al. (2008) presents single-crystal neutron diffraction and Raman spectroscopic data from 20 and 4 K, respectively, to ambient temperature to further examine the H positions and the hydrogen bond system during the phase transitions. These experimental data are in excellent agreement with the previous single-crystal X-ray diffraction and IR spectroscopic results (Libowitzky & Armbruster, 1995; Libowitzky & Rossman, 1996). The interpretation of the Raman data, however, contradicts a number of observations, which will be elucidated in the present comment. At ambient temperature, the crystal structure of lawsonite appears to …

Incorporation of Transmembrane Peptides from the Vacuolar H+-ATPase in Phospholipid Membranes: Spin-Label Electron Paramagnetic Resonance and Polarized Infrared Spectroscopy

Peptides were designed that are based on candidate transmembrane sequences of the V o-sector from the vacuolar H (+)-ATPase of Saccharomyces cerevisiae. Spin-label EPR studies of lipid-protein interactions were used to characterize the state of oligomerization, and polarized IR spectroscopy was used to determine the secondary structure and orientation, of these peptides in lipid bilayer membranes. Peptides corresponding to the second and fourth transmembrane domains (TM2 and TM4) of proteolipid subunit c (Vma3p) and of the putative seventh transmembrane domain (TM7) of subunit a (Vph1p) are wholly, or predominantly, alpha-helical in membranes of dioleoyl phosphatidylcholine. All three peptides self-assemble into oligomers of different sizes, in which the helices are differently inclined with respect to the membrane normal. The coassembly of rotor (Vma3p TM4) and stator (Vph1p TM7) peptides, which respectively contain the glutamate and arginine residues essential to proton transport by the rotary ATPase mechanism, is demonstrated from changes in the lipid interaction stoichiometry and helix orientation. Concanamycin, a potent V-ATPase inhibitor, and a 5-(2-indolyl)-2,4-pentadienoyl inhibitor that exhibits selectivity for the osteoclast subtype, interact with the membrane-incorporated Vma3p TM4 peptide, as evidenced by changes in helix orientation; concanamycin additionally interacts with Vph1p TM7, suggesting that both stator and rotor elements contribute to the inhibitor site within the membrane. Comparison of the peptide behavior in lipid bilayers is made with membranous subunit c assemblies of the 16-kDa proteolipid from Nephrops norvegicus, which can substitute functionally for Vma3p in S. cerevisiae.

Stretched PEO–LiCF 3SO 3 films: Polarized IR spectroscopy and X-ray diffraction

The effect of tensile stretching on pure PEO and P(EO) x LiCF 3SO 3 ( x = 10 and 20) films was studied using polarized FTIR spectroscopy, wide angle scattering X-ray scattering (WAXS) and small angle X-ray scattering (SAXS). The polarization effects observed in the spectra are readily explained by the selection rules governing IR transitions and symmetry-based vibrational mode assignments of PEO and the 3:1 compound, P(EO) 3LiTf. The degree of polymer chain orientation in the stretched samples as measured by the average of the second Legendre polynomial was calculated from the dichroic ratio for the PEO helices in both pure PEO and the 20:1 film. The degree of chain orientation was markedly higher in the 20:1 film than in the pure PEO film; however it was difficult to calculate the degree of orientation in the 10:1 film. The addition of LiTf causes a slight increase in the fractional crystallinity of the samples as determined from the WAXS data. Orientation of the films did not significantly affect the fractional crystallinity for the 10:1 and 20:1 samples, whereas a slight decrease in the fractional crystallinity was noted for pure PEO upon stretching. The SAXS data suggested that the average crystal size becomes smaller with the addition of lithium triflate to PEO. The SAXS data also indicated that substantial morphological changes occur upon stretching, since the Bragg peak due to the crystalline–amorphous phase separation disappeared upon stretching. These data, taken together, suggest that in the 10:1 film, the tensile stress tends to form small, unoriented domains of the 3:1 compound.

Molecular structure and orientation of gel‐spun polyethylene fibers

AbstractCharacterization of molecular structure and orientation of six commercially available gel‐spun polyethylene fibers have been carried out using infra‐red and Raman spectroscopy, thermal and X‐ray diffraction analysis, together with optical microscopy techniques. Thermal and X‐ray diffraction analysis revealed the existence of highly oriented orthorhombic and monoclinic crystallites together with a highly oriented intermediate phase known as pseudohexagonal mesophase structure. The results suggest the existence of a three‐phase structure consisting, at room temperature, of orthorhombic and monoclinic polymorphic crystallites, oriented noncrystalline and un‐oriented noncrystalline (amorphous) phases, respectively. The crystallinity measurements have been carried out using density, thermal and X‐ray diffraction analysis together with infra‐red and Raman spectroscopy techniques whereas the molecular orientation measurements have been carried out using birefringence and polarized IR spectroscopy, respectively. The results obtained from density, thermal analysis, and Raman spectroscopy based on a simple two‐phase modeling approach lead to the overestimated amorphous fractions and appears to ignore the presence of an intermediate phase known as oriented noncrystalline structure. X‐ray analysis has also been used for the measurement of the apparent crystallite sizes. The birefringence values have been used to determine the overall orientation parameters whereas the dichroic measurements of IR bands have been used to determine the crystalline and oriented noncrystalline orientation parameters. The results show that the orthorhombic and monoclinic phases are more highly oriented than the oriented pseudohexagonally packed noncrystalline chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1317–1333, 2006