Thermal expansion of oriented poly(methyl methacrylate)

The thermal expansivities along (α∥) and perpendicular (α_⊥) to the draw direction of poly(methyl methacrylate) (PMMA) with extrusion draw ratios 1 ≤ λ ≤ 4 have been measured between 150 and 298 K. As λ was increased from 1 to 4, α∥ decreased 2–3 times, whereas α_⊥ increased only 20–35%. The orientation function f calculated from thermal expansivity using the aggregate model is found to change linearly with birefringence, indicating that each property provides a sensitive measure of molecular orientation. For PMMA, however, only thermal expansivity can give an absolute f, with results at 150 K in reasonable agreement with previous studies using other techniques. At higher temperature, i.e., above ambient, PMMA side-group motions are excited, expanding volume, and calculations based on the aggregate model may not be valid.     

Thermal conductivity and thermal expansivity of thermotropic liquid crystalline polymers

The thermal conductivity and thermal expansivity of a thermotropic liquid crystalline copolyesteramide with draw ratio λ from 1.3 to 15 have been measured parallel and perpendicular to the draw direction from 120 to 430 K. The sharp rise in the axial thermal conductivity K_par; and the drastic drop in the axial expansivity α_∥ at low λ, and the saturation of these two quantities at λ > 4 arise from the corresponding increase in the degree of chain orientation revealed by wide-angle x-ray diffraction. In the transverse direction, the thermal conductivity and expansivity exhibit the opposite trends but the changes are relatively small. The draw ratio dependences of the thermal conductivity and expansivity agree reasonably with the predictions of the aggregate model. At high orientation, K_par; of the copolyesteramide is slightly higher than that of polypropylene but one order of magnitude lower than that of polyethylene. In common with other highly oriented polymers such as the lyotropic liquid crystalline polymer, Kevlar 49, and flexible chain polymer, polyethylene, α_par; of the copolyesteramide is negative, with a room temperature value differing from those of Kevlar 49 and polyethylene by less than 50%. Both the axial and transverse expansivity show transitions at about 390 and 270 K, which are associated with large-scale segmental motions of the chains and local motions of the naphthalene units, respectively. ©1995 John Wiley & Sons, Inc.     

Thermal expansion of ultradrawn polystyrene

Measurements on the linear thermal expansivities α∥ and α⊥ parallel and perpendicular to the extrusion direction, respectively, have been carried out between ?160 and 30°C for atactic polystyrene (aPS) with extrusion ratio 1 ≤λ≤ 15 and isotactic polystyrene (iPS) with 1 ≤λ≤ 7.5. For both aPS and iPS, α∥ decreases sharply with increasing λ whereas α⊥ shows only a slight increase. Below λ = 5 the anisotropy α⊥/α∥ is nearly the same for both, but α⊥/α∥ for iPS becomes much larger at higher λ. This is accompanied by an abrupt rise in crystallinity and probably results from the increase in the number and tautness of intercrystalline tie molecules. The birefringences of aPS and iPS increase with λ and have nearly the same values for λ < 5. At higher λ, however, there is a sharp rise in the birefringence of iPS which is probably associated with the sudden increase in crystallinity. With an aggregate model, the chain orientation function for aPS calculated from thermal expansivity is found to be in reasonable agreement with the corresponding value obtained from birefringence.     

Viscosities of dilute polymer solutions in nematic liquids

A nematic fluid is characterized by five friction coefficients. When dilute polymer coils are added to the fluid, all these coefficients are modified. Three Miesowicz viscosities (measured under an aligning magnetic field) and two coupling coefficients between orientation and flow are discussed. In our calculation, elastic dumbbells are used to model the flexible polymer chains. The results are written in terms of two size parameters R_∥ and R_⊥ and two chain friction coefficients λ_∥ and λ_⊥ (the label ∥ refers to a direction parallel to the nematic axis). This could be compared to other experiments (such as translational diffusion) which measure λ_∥ and _⊥ directly. They may give useful estimates of coil conformation in nematic solvents.     

Negative thermal expansion in oriented crystalline polymers

Measurements on the thermal expansivity α_∥ and α_? (along and normal to the draw direction, respectively) have been carried out for a series of oriented polymers with widely different crystallinities (0.36–0.81) and draw ratios (1–20) and over large temperature ranges covering the major amorphous transitions in each case. While α_? increases with temperature, α_∥ tends to decrease sharply above the transition temperature. For highly crystalline polymers, α_∥ decreases to values typical of polymer crystals (?1 × 10^?5 K^?1) and this can be attributed to the constraining effect of the crystalline bridges connecting the crystalline blocks. However, for polymers of lower crystallinity, α_∥ may become an order of magnitude more negative and this remarkable phenomenon is attributed to the rubber–elastic contraction of taut tie-moleucles. Since taut tie-molecules and bridges have drastically different effects on α_∥ at high temperatures, this allows a rough determination of their relative fractions.     

Thermal conductivity of oriented crystalline polymers

Thermal conductivities of six oriented semicrystalline polymers which range from 0.37 to 0.63 in crystallinity and 1 to 5 in draw ratio λ (up to about 15 for two polymers) have been measured between 100 and 340 K. It was found that for increasing λ the conductivity K_∥ (along the draw direction n?) increases rapidly while K_⊥ (normal to n?) decreases slightly; K_∥ also increases with temperature, but K_⊥ shows no simple pattern in temperature dependence. These general features can be reproduced reasonably well at low draw ratio (λ < 5) by the modified Maxwell model, and the discrepancy in details may be attributed to the fact that the model does not take into account the possible anisotropy of the amorphous phase of the oriented polymers. At high draw ratio the intercrystalline bridge effect becomes important, and one must resort to the Takayanagi model, but the lack of corroborating x-ray data has rendered a detailed comparison impossible.     

Ultrasonic measurements of the elastic moduli of ultradrawn polyoxymethylene

We have employed an ultrasonic method to measure from ?40 to 60°C the five independent elastic moduli C₁₁, C₁₃, C₃₃, C₄₄, and C₆₆ of polyoxymethylene with draw ratio λ from 1 to 26 prepared by continuous drawing under microwave heating. The elastic moduli are controlled by three major factors: molecular orientation in the crystalline regions, fraction of noncrystalline taut tie molecules, and void content. The steep rise in the axial extensional modulus C₃₃ and axial Young's modulus E₀ with increasing draw ratio results from the alignment of chains in the crystalline blocks and an increase in the number of disordered taut tie molecules. Below the γ relaxation (located at 0°C at our measurement frequency of 10 MHz), these two factors also give rise to a slight decrease in the transverse extensional modulus C₁₁, Young's modulus E₉₀ and shear modulus C₆₆. At high temperature where the amorphous regions have very low modulus, the stiffening effect of taut tie molecules becomes dominant, leading to an increase in all moduli as λ increases from 1 to 10. At higher λ the void fraction increases appreciably, causing small decreases in E₉₀, C₁₁, and C₆₆ at all temperatures.     

Diffusion of Rod-Like Polypeptides in the Liquid Crystalline and Isotropic Phases as Studied by High Field-Gradient NMR Spectroscopy

In this lecture the measurements and analyses of the isotropic and anisotropic diffusion coefficients(D) of rod-like polypeptide such as poly(γ-L-glutamate)(PLG) with n-alkyl side chains, of which the main chain takes the α-helical conformation, as a function of the main chain length in the thermotropic and lyotropic liquid crystalline phases over a wide range of temperatures from 30 to 80°C by means of pulse high field-gradient spin echo ¹H NMR method have been introduced. In the anisotropic diffusion, the D_∥ value in direction parallel to the α-helical chain axis is found to be much larger than the D_⊥ value in direction perpendicular to the α-helical chain axis. The diffusion process is followed by the Kirkwood theory. Further, it is described that the diffusion in the nematic liquid crystalline phase is much slower than that in the isotropic phase.     

Extra‐Large Mechanical Anisotropy of a Hydrogel with Maximized Electrostatic Repulsion between Cofacially Aligned 2D Electrolytes

In our previous work, we have shown that “electrostatic forces”, when generated anisotropically in aqueous media by 2D electrolytes upon cofacial orientation, enable the formation of a hydrogel with an anisotropic parameter, as defined by the ratio of elastic moduli E_⊥/E_∥, of 3.0. Herein, we successfully developed the design strategy for a hydrogel with an anisotropic parameter of no less than 85. This value is not only 28 times greater than that of our previous anisotropic hydrogel but also 6 times larger than the current champion record in synthetic hydrogels (E_⊥/E_∥～15). Firstly, we simply lowered ionic contaminants in the hydrogel and were able to enhance the anisotropic parameter from 3.0 to 18. Then, we chose a supporting polymer network allowing the hydrogel to carry a higher interior permittivity. Consequently, the anisotropic parameter was further enhanced from 18 to 85. Owing to the enhanced mechanical anisotropy, our new hydrogel displayed a superb ability of seismic isolation.     

Orientation behavior of high-modulus polyoxymethylene produced by microwave heating drawing

The orientation behavior of high-modulus polyoxymethylene tapes produced by tensile drawing with microwave heating has been investigated over the draw ratio range 10–29. Young's modulus E increases monotonically with draw ratio λ and reaches 55 GPa. The volume fraction of taut tie molecules (TTMs) in the amorphous phase has been estimated by using a Takayanagi model for oriented tapes. The increase in E at draw ratios of less than 10 is mainly due to the increase in crystalline orientation (crystalline orientation function, 0.00 → 0.99). The increase in E at draw ratios of more than 10 is due to the increase both in crystallinity (volume-fraction crystallinity, 0.84 → 0.95) and in TTM (TTM fraction, 0.14 → 0.40). The maximum Young's modulus obtainable by this method of drawing is estimated to be ca. 72 GPa from the relation between 1/E and 1/λ².     

Thermal expansion of polyoxymethylene

The thermal expensivities of polyoxymethylene crystals in the direction parallel (α_|^c) and perpendicular (α_‖^c) to the chain axis have been measured from 160 to 400 K using wide-angle x-ray diffraction. Although polyoxymethylene has a helical chain structure, it exhibits a thermal expansion behavior similar to that of polymer crystals with planar zigzag chains, namely that α_‖^c is negative while α_|^c is positive and larger by an order of magnitude. The negative α_‖^c arises from the shortening along the chain axis caused by the torsional and bending motions of the chain, whereas the large and positive α_|^c reflects the weak interaction across the chains. Combining the crystal data with dilatometric measurements on semicrystalline samples, the thermal expansivity is found to vary linearly with crystallinity, thus allowing the expansivity of the amorphous phase to be derived by extrapolation. With the thermal expansivities of the crystalline and smorphous phases known, the draw ratio dependence can be calculated in terms of existing models and is found to agree reasonably with experimental data.     

Oscillatory shear‐induced alignment of ketjen black conductive particles in polylactic acid and its effect on the electrical anisotropy

This study aligned Ketjen black (KB) particles along one preferred direction in a polylactic acid (PLA) matrix using an oscillatory shear flow and investigated the effect of aligned KB on the electrical anisotropy. Under the oscillatory shear, the KB particles are aligned along the flow direction in the PLA matrix, resulting in an oriented conductive network. When the concentration of KB is in the range of 0.88–1.56 vol %, the electrical volume resistivity along the flow direction (ρ_∥) decreases to ～3 × 10⁴ Ω m and that perpendicular to the flow direction (ρ_⊥) remains at ～1 × 10¹⁰ Ω m, showing an extremely large electrical anisotropy, and the ρ_⊥/ρ_∥ value is 3–4 orders of magnitude higher than that of previously reported carbon‐nanotube‐based electrical anisotropic composites. This strong anisotropy is attributed to the preferential alignment of KB particles with lower percolation threshold for conductive path along the flow direction. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 369–373     

Uniaxial Draw Of Poly(aryl-ether-ether-ketone) by solid-state extrusion

Poly(aryl-ether-ether-ketone) (PEEK) films and rods have been solid-state extruded at 154 and 310°C, respectively. The crystal orientation functions, melting behavior, density, and tensile properties of the drawn PEEK films (EDR ≤ 3.7) and rods (EDR ≤ 5.5) have been measured. As extrusion draw ratio (EDR) was increased, the c-axis orientation function, melting temperature, and tensile modulus and strength increased. Moduli up to 6.5 GPa and the strengths up to 600 MPa, 3 and 6 times the values of undrawn films, respectively, were obtained for the drawn films. The thermal expansivities along (α_‖) and perpendicular (α_?) to the draw direction of PEEK rods were measured from ?40 to +10°C. As EDR was increased, α_? increased, but α_‖ decreased. At EDRs of 3.8 and 5.5, α_‖ even exhibited negative values (about ?5 × 10^?6°C^?1), probably due to reversible contraction of elongated tie-molecules.     

Chain orientation and anisotropies in optical and dielectric properties in thin films of stiff polyimides

Thin films of poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by optical waveguide, ultraviolet-visible (UV-VIS), infrared (IR), and dielectric spectroscopies. The polyimide films exhibit an extraordinarily large anisotropy in the refractive indices with the in-plane index n_∥ = 1.806 and the out-of-plane index n_⊥ = 1.589 at 1064 nm wavelength. No discernible effect of the film thickness on this optical anisotropy is found between films of ca. 2.1 and ca. 7.8 μm thickness. This large birefringence is attributed to the preferential orientation of the biphenyltetracarboximide moieties with their planes parallel to the film surface, coupled with the strong preference of BPDA-PDA chains to align along the film plane. The frequency dispersion of the in-plane refractive index n_∥ is consistent with the results calculated by the Lorentz–Lorenz equation from the UV-visible spectrum exhibiting several absorption bands in the 170–500 nm region. The contribution from the IR absorption in the range 7000–400 cm,^?1 computed by the Spitzer-Kleinmann dispersion relations from the measured spectra, adds ca. 0.046 to the in-plane refractive index n_∥. Tilt-angle–dependent polarized IR results indicate nearly the same increase for the out-of-plane index n_⊥. Application of the Maxwell relation then leads to the out-of-plane dielectric constant ε^⊥ ? 2.7 at 1.2 × 10¹³ Hz, as compared with the measured value of ca. 3.0 at 10⁶ Hz. Assuming this small difference to remain the same for the in-plane dielectric constants ε_∥, we obtain a very large anisotropy in the dielectric properties of these polyimide films with the estimated in-plane dielectric constant ε_∥ ? 3.4 at 1.2 × 10¹³ Hz, and ε_∥ ? 3.7 at 10⁶ Hz. © 1992 John Wiley & Sons, Inc.     

Optical anisotropy of polymeric films measured by waveguide propagation mode determination

Extruded thin films of a liquid-crystalline charge-conjugated rigid-rod polymer poly(p-phenylenebenzobisthiazole), PBT, and a semicrystalline thermoplastic polyethylene-terephthalate (Mylar) were fabricated and examined for film thickness, refractive index, and linear attenuation coefficient. Optical waveguide modes were successfully induced on the polymeric films using a prism coupler at λ = 633 and 1300 nm. Highly consistent thickness values were obtained for the polymeric films. In addition, the anisotropic nature of the optical properties was determined using TE and TM propagation modes. A refractive index as high as 2.3 was observed on PBT film. The refractive index data suggested that the PBT and Mylar films were optically anisotropic with refractive indices n? (out-of-plane) invariably smaller than n∥ (in-plane). Large anisotropy was also discovered in the linear attenuation coefficient α, with α_∥/α_? ≈ 50 for the Mylar films. Complementary polarimetric and spectroscopic interference measurements were also applied to investigate the optical anisotropy of the extruded polymeric films. © 1992 John Wiley & Sons, Inc.     

Fourier-transform infrared studies of polypropylene during mechanical deformation

Quantitative Fourier-transform infrared (FTIR) measurements of frequency shifts Δν and absorbance profile asymmetry are reported for various polypropylene samples as a function of uniaxial stress σ. Generally, it was found that the frequency shift coefficient α_χ, defined by Δν = α_χσ, depended on stress rate \documentclass{article}\pagestyle{empty}\begin{document}$\dot \sigma$\end{document}, draw ratio, λ, molecular orientation f, tensile modulus E, and annealing conditions. With annealing, α_χ decreased with increasing shrinkage in the case of highly oriented isotactic PP. The α_χ values for the “helix bands” were less affected than those for the “liquid bands.” With increasing \documentclass{article}\pagestyle{empty}\begin{document}$\dot \sigma$\end{document}, generally α_χ increased to an apparent asymptotic limit. With increasing λ, f, or E, α_χ also increased from α_χ ? 0 for λ = 1 (spherulitic) to maximum values for highly oriented isotactic PP. The observed variations in α_χ can be interpreted in terms of the changes in the peak position and shape of the nonuniform molecular stress distribution. Analogous behavior with x-ray diffraction peaks obtained for polymers under stress is discussed.     

Photochemical reactions. 137th communication. Preparation and photolysis of (E/Z)-7-methyl-β-ionone

The title compounds (E/Z)- 7 were prepared in 66% overall yield by reaction of β-ionone ((E)-( 1 ) with lithium dimethylcuprate, trapping of the intermediate enolate with benzeneselenenyl bromide and oxidation with H₂O₂. Analogously, (E/Z)-7-methyl-α-inone ((E/Z)- 12 ) was obtained in 65% yield from α-ionone ((E)- 11 ). ¹n, π^*- Excitation (λ > 347 nm, pentane) of (E)-7 causes rapid (E/Z)-isomerization and subsequent reaction of (Z)- 7 to 15 (66%). The formation of 15 is explained by twisting of the dienone chromophore due to repulsive interaction of the 7-CH₃-group with the CH₃-groups of the cyclohexene ring. On the other hand, irradiation λ > 347 nm, Et₂O) of (E)- 7 in the presence of acid leads to (Z)- 7 (5%) and to the novel compound 16 (88%).     

Relationship between piezoelectricity and superstructure in highly oriented poly(vinylidene fluoride) film prepared by zone drawing

The oriented superstructure of poly(vinylidene fluoride) is controlled by using a forced-quenching type of zone drawing apparatus. Systematic variation of the weight fraction χ(I) of form-I crystals and the orientation function f_a of amorphous chains shows that the piezoelectricity increases with increasing χ(I) and f_a. A change in the state of molecular aggregation during poling is also effective in increasing the piezoelectricity and the orientation of the crystal b axis along the poling direction. Equations relating piezoelectricity to the form-I crystallinity, the orientation of amorphous chains, and the orientation of the crystal b axis along the poling direction are derived. These are based on a mechanical model having regions of taut tie molecules in parallel with composite regions consisting of crystalline and amorphous blocks in series.     

On the refractive indexes and birefringence of nylon 6 yarns as a function of draw ratio and strain

A systematic study of the dispersion curves of the refractive indexes of nylon 6 yarns was made. The parameters were the draw ratio and strain. The measurements show that the dispersions of the refractive indexes n_∥ and n_⊥, parallel and perpendicular to the fiber axis, are equal, independently of draw ratio and strain. The average dispersion equals n_F ? n_C = 109 × 10^?4. Consequently, the birefringence is, within experimental accuracy, independent of the wavelength. The refractive indexes and the birefringence show a change in trend at 10–12% strain. This point corresponds to the yield strain in the stress–strain diagrams. The inference is that beyond the yield point the overall molecular orientation must increase less strongly with strain than before. An analysis shows that the Lorentz–Lorenz relation holds for the average refractive index n? = ? (n_∥ + 2n_⊥). So the change in n? versus draw ratio is mainly due to the change in density. By applying the Lorentz–Lorenz relation to the change of n? on straining, a value of Poisson's ratio (μ) could be derived. The average value found for nylon 6 yarns was μ = 0.48, which means that the density hardly changes with strain.