Viscoelasticity and birefringence of polyisobutylene

The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), were measured for polyisobutylene (PIB) over a wide temperature range near and above its glass transition temperature. The master curves could be constructed well for each function with the method of reduced variables. The shift factor, a_T, for E*(ω) is the same as that for O*(ω). The ratio of the imaginary parts of O*(ω) and E*(ω), O″(ω)/E″(ω), takes an extremum, which has never been observed for other polymers. The relation between O*(ω) and E*(ω) cannot be described by a modified stress-optical rule (MSOR) which has been found valid for various polymers. The basic concept of the MSOR. i.e., the chain orientation and the orientation of flat monomer units in the stretch direction, is not sufficient to describe the behavior of PIB and another origin of stress, presumably due to the fluctuation of local stress, should be included. This term does not contribute to the birefringence. The main maximum of tan δ is ascribed to the relaxation of the chain orientation in contrast with many other polymers, such as polyisoprene and polycarbonate, for which the maximum of tan δ is ascribed to the rotational relaxation of monomer units. © 1995 John Wiley & Sons, Inc.     

Electric birefringence and streaming-electric birefringence of synthesized imogolite: the anisotropy of electric polarizability

Imogolite synthesized from sodium orthosilicate and aluminum trichloride was fractionated into four fractions by centrifuging at 12,000 x g (1h). The supernatant, which did not deposit by three times centrifugations, was used for all measurements. The signal of birefringence under a reversing electric pulse showed that the permanent dipole moment is negligibly small at low fields. The electric birefringence under a rectangular electric pulse is positive. The saturated value is proportional to the concentration of imogolite in the range of 0-0.1mg/ml and decreases rapidly with an increase of added salt concentration for NaCl and AgNO(3). It slightly depends on the pH of solution and is biggest in pure water. Then we have determined the anisotropy of electric polarizability (Deltaalpha) for imogolite in pure water at 0.05 mg/ml. Deltaalpha we obtained from the method decreases rapidly at low fields and slowly at high fields as shown in references [M. Matsumoto, Colloids Surf. A 148 (1999) 75, M. Matsumoto, Biophys. Chem. 58 (1996) 173]. It is approximately shown by the following expression, Deltaalpha=Deltaalpha(infinity)+(Deltaalpha(0)-Deltaalpha(infinity))/(1+KE), (Deltaalpha(0):Deltaalpha at E=0, Deltaalpha(infinity):Deltaalpha at E=infinity). Using this relation we can draw the curve of electric birefringence as a function of electric field and compare it with experimental values. The results, when Deltaalpha(0)=1.17x10(-28)Fm(2), Deltaalpha(infinity)=0.005x10(-28)Fm(2) and K=0.00031 m/V, are in good agreement with each other. In order to explain the reason why the anisotropy of electric polarizability rapidly decreases with an increase of electric field we propose that the difference of electrophoretic mobility between parts of colloidal particle causes the orientation of a rod like particle. The theoretical electric birefringence as a function of electric field we obtained is considerably in good agreement with the experimental values.     

Strain birefringence in ethylene-propylene copolymers

A series of polymeric networks were prepared by the γ-radiation crosslinking of two ethylene-propylene copolymers containing 62 and 69 mol % ethylene units. The elastomeric materials thus obtained were studied in elongation, both swollen and unswollen, over the temperature range ?30 to 95°C. The experiments involved measurements of both the elastic force and birefringence, using primarily changes in temperature at constant length (rather than changes in length at constant temperature). There is evidence for crystallization in these networks, as manifested by marked decreases in force and increases in birefringence at relatively low elongations and at temperatures as high as 70°C. As expected, the birefringence and related quantities were found to be more sensitive to crystallization than the force, with the stress-optical coefficient showing the greatest sensitivity. The results obtained in the elongation-temperature regions presumably free from effects of network crystallization were used to calculate values of the temperature coefficient of the unperturbed dimensions of the chains, and values of the optical-configuration parameter. Both are widely used to characterize (spatial) configurations of chain molecules. Values of the former quantity are in very good agreement with those predicted some years ago using a rotational isomeric state model for ethylene-propylene chains of various chemical and stereochemical compositions. The extension of these theoretical calculations to include the stress-optical coefficient should provide further information on crystallization in ethylene-propylene elastomers and the configurational characteristics of these copolymeric chains.     

Optical anisotropy of absorbing particles: Light scattering depolarization,electric- and flow birefringence and dichroism of suspensions of carbon blacks

Summary The use of a rather: elongated spheroid, the compacity of which decreases with its weight, equivalent to the aggregates allows to explain the effects of depolarized light scattering and of birefringence. In particular, a very unusual negative macroform birefringence has been found. Moreover the theoretical expressions concerning the absorbing particles which simultaneously exhibit an electric dichroism and birefringence have been written. They were tested by means of suspensions of carbon blacks.

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Zusammenfassung Die Effekte der Depolarisation von Streulicht und der Str?mungsdoppelbrechung k?nnen mit Hilfe des Modells von relativ gestreckten Rotationsellipsoiden erkl?rt werden. Insbesondere wurde die Existenz eines ganz ungew?hnlichen Ph?nomens wahrscheinlich gemacht, n?mlich eine negative Formdoppelbrechung. Weiter wurden theoretische Beziehungen entwickelt, die Suspensionen von absorbierenden Teilchen betreffen, die zugleich Doppelbrechung und Dichroismus zeigen. Diese Gleichungen werden anhand von Ru?-Suspensionen verifiziert.

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Résumé Les effets de dépolarisation de la lumiére diffusée et de la biréfringence d'écoulement peuvent être expliqués á l'aide de modéles d'ellipsoídes de révolution équivalents relativement allongés. En particulier, on a mis en évidence l'existence d'un phénoméne tout-á-fait inhabituel: celui d'une biréfringence de macroforme négative. De plus, on a développé des relations théoriques concernant des suspensions de particules absorbantes, présentant à la fois de la biréfringence et du dichroisme. Ces expressions ont été vérifiées á l'aide de suspensions de noirs de carbone.

     

Optical anisotropy of nanotube suspensions

A semimacroscopic model of an optically anisotropic nanotube suspension is derived perturbatively from Maxwell's equations in a dielectric medium. We calculate leading-order expressions, valid in the dilute and semidilute limits, for the intrinsic and form contributions to the complex dielectric tensor in terms of the volume fraction, mean orientation, aspect ratio, optical anisotropy, and optical contrast of the nanotubes. The birefringence and dichroism are derived explicitly to leading order in fluctuations, and the connection with depolarized light scattering is established. The results are generalized to include tube deformation.     

High birefringence and large negative dielectric anisotropy phenyl-tolane liquid crystals

Two phenyl-tolane compounds with two pairs of (2,3) lateral difluoro substitutions were synthesized and their properties evaluated. These compounds exhibit a high birefringence (Δn ∼ 0.35) and a large negative dielectric anisotropy (Δε∼ -8). These two important features make the phenyl-tolane compounds useful as a dopant in a negative Δε liquid-crystal mixture to enhance the performance of the host mixture, or as a negative component in a dual-frequency liquid-crystal mixture to improve the dielectric anisotropy and birefringence and lower the crossover frequency.     

Flow birefringence and optical anisotropy of poly(N-vinylpyrrolidone) molecules

Concentration dependences of flow birefringence and viscosity of poly(N-vinylpyrrolidone) solutions in water and benzyl alcohol are investigated. The intrinsic anisotropy for a poly(N-vinylpyrrolidone) macromolecular segment, (α₁ ? α₂) = ?(82 ± 8) × 10^?25 cm³, is determined from the results of birefringence measurements in benzyl alcohol. For aqueous solutions, a strong concentration dependence of the specific anisotropy of solution is obtained, a result that may be explained by the heterogeneity of coils. A model allowing for this heterogeneity is suggested. It makes it possible to fit the concentration dependence to a hyperbolic function, to separate contributions of heterogeneity anisotropy and form anisotropy to the birefringence of a solution, and to estimate the segment asymmetry parameter as p = 3.0 ± 0.5.     

Optical birefringence and dichroism in physical steroid organogels

Optical birefringence and dichroism have been studied in physical steroid organogels. We have used two complementary derivatives (SNH and SNO*) in cyclohexane: the former has no chromophoric group in the 220-800 nm wavelength range studied, in contrast with the latter. The dichroism is mainly due to linear contributions. The amplitude of the signal is correlated with the growth of fibrillar structures and specially with the heterogeneities of the gel network which was assumed to be chiral fibrillar junction zones. The characteristic SNO* dichroic absorptions (for C ≈ 2.0 × 10^-2 M) are λ_max = 250nm, |Δε| ≈ 6.0 (mainly a linear contribution) and λ_max = 450 nm, Δε = +0.45 (mainly a circular contribution). These preliminary observations provide strong evidence for a helical stacking of the steroid molecules within the fibres of the gel samples. The optical dichroic absorption can be a valuable technique to monitor the orientational order of the microdomains crossed by the light beam.     

Strain birefringence studies on poly(vinyl acetate) networks

Atactic poly(vinyl acetate) prepared in a free-radical polymerization was crosslinked by means of benzoyl peroxide. The resulting elastomeric networks were studied in elongation, both unswollen and swollen with triethylbenzene, over the range 0–90°C. The most important experimental results obtained were values of the network birefringence, which is negative, as was recently also found to be the case for networks of atactic poly(methyl acrylate).Calculations carried out to interpret the birefringence were based on Monte Carlo simulations of the atactic structure, and on the rotational isomeric-state theory of chain configurations. The agreement between theory and experiment was very good, in fact much better than has usually been observed for other polymers studied to date.     

Optical anisotropy in solution-cast film of cellulose triacetate

The out-of-plane birefringence and its wavelength dispersion are studied employing solution-cast films of cellulose triacetate (CTA). In solution-cast process, CTA molecules are induced to align in the film plane. Although refractive index is the lowest in the oriented direction for the CTA films stretched more than 110 %, refractive index is found to be the lowest in the normal direction for the unstretched cast film. Attenuated total reflection measurements reveal that in-plane alignment of the acetyl group which provides strong polarizability anisotropy is responsible for the phenomenon. Furthermore, the out-of-plane birefringence is found to increase with increasing wavelength, i.e. extraordinary wavelength dispersion, whereas a stretched CTA film shows ordinary wavelength dispersion. The level of the out-of-plane birefringence in cast films depends on the preparation conditions, which is predictable considering the evaporation rate. Moreover, it is demonstrated for the first time that the out-of-plane birefringence and its wavelength dispersion can be modified by addition of a certain plasticizer such as tricresyl phosphate (TCP). During the evaporation, TCP molecules orient in the film plane accompanying the orientation of CTA chains by intermolecular orientation correlation, called nematic interaction. This technique will widen the scope of material design of retardation films because there are numerous liquid compounds having strong polarizability anisotropy.     

Functionalization of polyisobutylene and polyisobutylene oligomers via the ritter reaction

The Ritter reaction, that is, reaction of a carbocation with a nitrile, was carried out on polyisobutylene (PIB) using a variety of reaction conditions. End quenching of PIB carbocations with acrylonitrile under living polymerization conditions (methyl chloride (MeCl)/hexane 60/40 (v/v) solvent mixtures at −70 °C) resulted in either tert‐chloride end groups or loss of chain‐end fidelity via carbocation rearrangement, as evidenced by NMR spectroscopy. Exo‐olefin functionalized PIB substrates were also reacted with nitriles under a variety of reaction conditions including various acid and solvent medium combinations. In all cases, the result was either no reaction or PIB that had undergone severe backbone degradation, as determined via NMR spectroscopy and gel permeation chromatography. Finally, the Ritter reaction was performed on a series of exo‐olefin functionalized oligoisobutylenes using acrylonitrile as the nitrile and either 60/40 dichloromethane/hexane or excess acrylonitrile as the solvent. In 60/40 dichloromethane/hexane, significant carbocation rearrangement and/or degradation resulted in a variety of isomeric, acrylamide‐functionalized oligomers. In excess acrylonitrile, the desired Ritter reaction was the only reaction observed, resulting in the smooth formation of the terminal acrylamide. The various N‐oligoisobutylacrylamides thus obtained represent new hydrophobic monomers useful for the introduction of hydrophobic moieties into acrylamide‐based water‐soluble polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 840–852     

Electrically induced anisotropy in a colloidal dispersion of nanospheres as measured by electric birefringence

Electrically induced birefringence experiments were performed on dispersions consisting of sulfate latex nanospheres of two different sizes and charges dispersed in an electrolyte solution, at various ionic strengths. The induced birefringence was found to have an important contribution increasing as a quadratic power law of the volume fraction of the spheres. This shows that interparticle interactions play a role in the observed birefringence. The data were analyzed, using a theory from Hafkenscheid and Vlieger [Physica 75 (1974) 57], in terms of the changes of the interparticle separations in the directions parallel and perpendicular to the applied electric field.     

Optical anisotropy of molecules of pyromellite-dianilic amido acid polyesters

The optical anisotropy of molecules of pyromellite-dianilic amido acid polyesters has been studied by the method of flow birefringence. Positive flow birefringence, which depends on the isomeric composition of the repeating unit, is detected. The thermodynamic rigidity of pyromellite-dianilic amido acid polyester molecules is calculated in terms of the valence-optical scheme. On passage from 100% para isomers of pyromellite-dianilic amido acid polyesters to macromolecules with a predominant content of meta isomers, optical anisotropy and equilibrium rigidity decrease by a factor of ～2.     

Optical anisotropy of excimer emission from solutions of polystyrene

The optical anisotropy of excimer emission from polystyrene dissolved in dichloromethane is found to vary with concentration and molecular weight. It is concluded that the time constant for rotation of the dimeric structure increases with increasing both concentration and molecular weight. It is proposed that intermolecular interactions cause this, and such interactions occur well below the concentration corresponding to overlap of macromolecules.     

Optical birefringence and molecular orientation of electrospun polycaprolactone fibers by polarizing-interference microscopy

The potential of polarizing-interference Pluta microscope for determination of optical birefringence of individual nanofibers formed by electrospinning was shown. This technique can be applied for measurements of fiber birefringence, practically at diameter above 300 nm. The molecular orientation of individual polycaprolactone (PCL) nanofibers was determined from birefringence assuming the same orientation of both phases, crystal and amorphous. The molecular orientation was determined using DSC crystallinity, crystal intrinsic birefringence calculated for the first time for PCL from bond polarizabilities as well as estimated value of amorphous intrinsic birefringence. Our results indicate that the birefringence and thus molecular orientation are strongly inhomogeneous along the nanofibers, reflecting a complex nature of forces acting during electrospinning process. The average molecular orientation is weak if any, being dependent together with fiber thickness and crystallinity on electrospinning parameters, like applied voltage, concentration and type of solvent. The obtained results indicate that the average molecular orientation displays similar dependence on applied voltage as fiber diameter. Relatively low melting temperature of electrospun nanofibers suggests low crystal size and/or high concentration of defects in crystals. This observation corresponds with low crystallinity and molecular orientation, indicating together relatively low degree of crystal ordering due to high rate of cooling and solvent evaporation during electrospinning, limiting thus crystallization process.     

Crystal structure of polyisobutylene

The crystal structure of polyisobutylene was determined by x-ray analysis. The orthorhombic cell, with a = 6.88 Å, b = 11.91 Å, c (fiber axis) = 18.60 Å (space group: P2₁2₁2₁ ? D), contains two molecular chains each consisting of eight monomeric units in the fiber identity period. The chain conformation is essentially an (8/3) helix, but deviates appreciably from the exact (8/3) helix symmetry. The symmetry of the molecular chain is only a twofold screw axis in exact sense, and a crystallographic asymmetric unit consists of four monomeric units. The torsional angles are where M denotes the methyl group. The averaged skeletal C? CH₂? C and C? CM₂? C bond angles are 128° and 110°, respectively. The large C? CH₂? C bond angles may be due to steric respulsion between the adjacent methyl groups, giving intramolecular distances larger than 3.09 Å.     

Molecular orientation in stretched poly(vinyl alcohol). I. NMR anisotropy and birefringence

The second and fourth moments of the proton resonance line in stretched poly(vinyl alcohol) samples have been measured by a pulse technique. Their anisotropy has been analyzed at different elongation ratios λ. The use of the second and fourth moments gives an interesting cross-check on the reliability of the results. Despite the fact that the lattice sums required for absolute determination of the orientation cannot be calculated, coefficients related to the second and fourth moments of the orientation distribution function can be compared to the prediction of the quasiaffine orientation scheme for the crystalline phase and to the experimental values of the birefringence as a function of λ. It is shown that NMR clearly detects the onset of the orientation of the amorphous chains above λ ≈ 4.     

Optical anisotropy of a thermotropic liquid-crystalline polymer in transient shear

A rheo-optical apparatus, based on a linear shear rheometer, has been constructed to study the deformation of liquid–crystalline polymers. This apparatus uses optical techniques such as flow birefringence, small-angle light scattering, and optical microscopic image analysis. The rheological responses were simultaneously measured under varying temperatures and deformation conditions. The modified Debye-Bueche equation for scattering, in the nonspherically symmetrical form, was adapted to analyze small-angle light-scattering data. The orientation correlation lengths, determined by this method, reveal the deformation mechanism in nematic melts. Flow birefringence results are in agreement with the proposed mechanism.     

Optical anisotropy and liquid-crystal alignment properties of rubbed polyimide layers

The relation between the optical anisotropy of rubbed polyimide layers and the rubbing process is investigated using the recently developed polarization-conversion guided mode technique. Results indicate that the effective optical anisotropy of the polyimide layers may be substantially changed by the rubbing process, although this does not significantly influence the ability of the polyimide layers to align liquid crystals.