Optical studies of the stress-induced crystallization of rubber

The low-angle light scattering by films of stretched natural and synthetic rubbers was investigated. Intense V_v scattering is found under conditions when crystallization occurs which is characteristic of the scattering from aggregates of dimensions comparable with the wavelength of visible light. These were identified with the γ fibrils described by Andrews. The dependence of scattering was studied as a function of light polarization direction, orientation direction, elongation, temperature, degree of swelling, type of swelling liquid, and degree of crosslinking. It was concluded that the scattering unit consists of an assembly of crystals with their chain axes parallel to the stretching direction, but (in the case of natural rubber at high elongations) with the fibril axis at a slight angle to the stretching direction. The scattering is not affected much by swelling but is decreased upon increasing the temperature. Upon recooling the scattering returns, but does so over several hours, indicating that much of the scattering arises from secondary crystallization.     

Morphology of a liquid-crystalline polyester film

Morphological studies are reported for a thermotropic liquid crystalline polyester. Small angle light scattering studies were carried out as a function of temperature using H_v and V_v polarization with photographic as well as photometric techniques. No scattering was observed from a thin film cast from a dilute solution of the polymer in a highly volatile solvent. When the film was heated, scattering of light was observed above the glass transition temperature of the polyester. The scattering was found to be azimuthally dependent with V_v intensities being much higher than the corresponding H_v intensities. The size of the morphological features responsible for SALS patterns were calculated and were found not to change significantly with temperature ranging from glass transition temperature to the solid-nematic transition temperature of the polyester. The WAXS pattern of solution cast polymer was representative of an amorphous structure. Solution cast films heat treated under various conditions (all above the T_g of the polymer) contained crystalline as well as amorphous structures. The maximum apparent crystallinity for annealed samples was of the order of 30%.     

Stress-induced crystallization of poly(ethylene terephthalate)

Quenched amorphous films of poly(ethylene terephthalate) (PET) are stretched at temperatures less than T_g; changes in density, wide-angle x-ray diffraction, and small-angle light scattering are observed. The density increase upon stretching is attributed to an increase in crystallinity accompanied by an increase in the intensity of somewhat diffuse wide-angle x-ray diffraction and of both V_V and H_V small-angle light scattering patterns. The formation of oriented rodlike superstructure may be discerned from small-angle light scattering. Annealing of these samples increases the crystallinity as measured from density and leads to an increase in the perfection of crystalline and supercrystalline structure as measured by wide-angle x-ray diffraction and small-angle light scattering. The rodlike morphology changes to form spherulitelike aggregates as observed by small-angle light scattering and light micrographs. A model is proposed to explain the observations. Studies are extended to stretching films of PET above their T_g and observing changes in birefringence, density, wide-angle x-ray diffraction and small-angle light scattering as a function of elongation and stretching temperature. The formation of defomed spherulitelike superstructure may be discèrned from light micrographs. Results are compared with those obtained upon stretching films below T_g.     

Small-angle light scattering by random assemblies of incomplete spherulites. II. Truncated spherulites

Previous theoretical calculations of the scattering from spherulites are for isolated complete spheres, whereas most spherulitic polymer samples contain truncated spherulites as a result of impingement by other spherulites. The effect of such truncations on the scattering patterns for two-dimensional spherulites is explored as a function of the size, number and location of the truncations. The scattering of severely truncated spherulites is modified, particularly with regard to the enhancement of the H_V scattering at small angles. However, reasonable amounts of truncation corresponding to experimentally observed structures do not produce appreciable modification of the pattern so that the neglect of truncation will not lead to appreciable error in the estimated spherulite size from light scattering.     

Synthesis of ferrocenyl-containing silicone rubbers via platinum-catalyzed Si–H self-cross-linking

Self-cross-linkable ferrocenyl-containing polymethylhydrosiloxanes were synthesized. Karstedt's catalyst and cis-[PtCl₂(BnCN)₂] were examined as cross-linking catalysts at room temperature for the reaction between Si–H groups of the ferrocenyl-containing polymethylhydrosiloxanes. Cis-[PtCl₂(BnCN)₂] is an effective catalyst that allows cross-linked ferrocenyl-containing silicones (silicone rubbers) to be obtained with no visible mechanical defects (bubbles or cracks) compared with Karstedt's catalyst. The ferrocene content of the ferrocenyl-containing silicone rubbers was found to be approximately 50 wt.% by energy-dispersive X-ray analysis. Compared with cross-linked non-modified polymethylhydrosiloxanes, the ferrocenyl-containing silicone rubbers exhibited improved tensile properties (the tensile strength increased from 0.47 to 0.75 MPa) and a 1.5–2.5 times lower cross-linking degree. The surface resistivity of the ferrocenyl-containing silicone rubbers (50 wt.% ferrocenyl units) was approximately 7 × 10⁹ Ω/□, which was 10,000 times lower than that of pure polymethylhydrosiloxane. The obtained flexible electroactive ferrocenyl-containing silicone rubbers can potentially be applied as coatings for electronic and electrostatic-sensitive devices, interfaces, and sensors.     

Changes in light scattering from poly(ethylene terephthalate) and nylon 6 films upon stretching in relation to the deformation mechanism

Unoriented T-die flat films of nylon 6 and PET films annealed at 90°C were stretched in water at 80°C. Amorphous PET films were stretched in water at 65–75°C. Changes in the light scattering patterns from these samples upon stretching were investigated. One of the observed LS patterns from the stretched samples is the H_v eight-leaf pattern consisting of four lobes and streaks. In the nylon 6 and heat-treated PET showing this pattern, spherulitic patterns can be seen in polarization microscopy. The microscopic spherulitic superstructure may possibly be the factor responsible for producing the lobe-and-streak pattern. On the other hand, many microscopic eight-leaf patterns can be observed in amorphous unannealed PET showing the lobe-and-streak pattern. These microscopic patterns are due to retardation at stress concentrations around impurities and nuclei. The superstructure giving these microscopic patterns must be the origin of the lobe-and-streak pattern from unannealed PET. Another scattering pattern, the V_v cruciform pattern, was observed in both stretched nylon 6 and unannealed PET. This pattern is due to an orientation change across the slip lines observed under a polarizing microscope. It is noted (1) that the appearance of the slip lines in PET coincides with the occurrence of oriented crystallization on stretching, (2) that the lobe-and-streak pattern from PET in which orientation crystallization has taken place is fairly stable to heat treatment and does not disappear until just before melting, and (3) that the superstructures produced at low stretching seem to be deformed on further stretching, in accordance with affine deformation theory.     

Relation of initial supermolecular organization in crystalline polymer systems to the organization produced by stretching

An investigation of small-angle scattering produced by polarized light from stretched and annealed polymer systems containing spherulites yields information on the supermolecular transitions that occur during such treatment. A series of semicrystalline polymer systems (films, fibers) show that stretching leads to deformation of spherulites and subsequent transformation to an orientational supermolecular order. The size of the single element C₂ of the supermolecular order in the direction of stretching, determined from the distance between the layer lines of the scattering pattern, is related to the diameter D₀ of the initial spherulites by the relation C₂ = KD₀λ_s, where λ, is the draw ratio of the macrosystem and K is a parameter determining the deformability of the spherulites. For polyethylene at room temperature K is unity and for polychloroprene it is 1.2. Changes of C₂ after annealing and restretching of the systems also obey this ratio.     

The scattering of light from thin polymer films: Multiple scattering. II. Effect of depolarization

A procedure is described to include the effect of depolarization of the originally plane-polarized incident light beam as it passes through a thin polymer sample on the intensity of multiple light scattering. The multiple scattering gives rise to “polarization scrambling” in which, for example, H_v scattering measurements involve multiple scattered rays which may have undergone some V_v scattering. These phenomena reduce the angular dependence of scattering since large intensities originally occurring at small values of θ are rescattered so as to enhance intensities at other angles. Correction factors for both H_v and V_v scattering are presented.     

Light scattering from swollen textured polymer network composites

Light scattering from a swollen textured heterogeneous polymer network is discussed using example of a network composite filled by spherical inclusions anisotropically distributed in the matrix. The dependence of the scattering intensity on the Fourier transform of the correlation function dry-state shear moduli fluctuations has been established. H_v scattering patterns from uniaxial textures and their ratio with the composite anisotropy parameter are analyzed. The sensitivity of the H_v scattering pattern on restrictions during the swelling is emphasized. © 1993 John Wiley & Sons, Inc.     

Supramolecular structure investigation of poly(γ-benzyl, α-l-glutamate)-benzyl alcohol system by static light scattering

The cholesteric mesophase of the PBLG-BA system in concentrated solutions and in the gel phase has been investigated by static laser light scattering. The observed ‘distortion’ of the patterns in terms of their dependence on the azimuthal angle was studied. Effect of form-optical rotation on the pattern is discussed. The manner of distortion in the H_v pattern determines the sense of cholesteric twisting. The observed scattering patterns are analogous to those obtained by previous investigators in other solvents. Quantitative measurements of the intensity as a function of scattering vector provide information on the sense and pitch of the cholesteric twisting, as a function of temperature and concentration. Optical microscopy studies reveal onset and build-up of the cholesteric structure. Optical rotation and differential scanning calorimetry (DSC) studies support the conclusions obtained from light-scattering experiments.     

Conformation of linear polyethylene in 1-chloronaphthalene: Light scattering characterization of polymers. IV

Light scattering measurements were carried out on a linear polyethylene sample NBS 1475 in 1-chloronaphthalene at 135 and 115°C to determine the weight-average molecular weight, the second virial coefficient A₂, and the z-average mean-square radius of gyration. By use of these results, the system is analyzed in terms of the interpenetration function Ψ for A₂. Observed values of A₂ are rather large but the excluded volume is nevertheless relatively small. Such behavior seem to be similar to that of semiflexible polymers. The characteristic ratio C_n,LS as determined by light scattering is found to be almost twice the literature value of 6.7, which was obtained from viscosity measurements. This discrepancy is explained by comparing the theoretical value of the Flory viscosity parameter Φ at the nondraining limit with values calculated from the light scattering results.     

Light scattering from spherulitic materials

The azimuthal angular dependence of the depolarized component of the light scattered from spherulitic materials is derived by an algebraic method that avoids the difficult angular integrations of the usual approach. The result appears as a sum of products of two factors, a molecular factor, that depends only on the structure and the scattering angle θ, and a geometrical factor that depends only on the azimuthal angle ? and the scattering angle θ. The molecular factors are evaluated for models of spherulitic structure that assume a constant tilt of the optical polarizability tensor. The radial distribution, in principle, is arbitrary, and an evaluation for the layered spherulite is made. If the tilt angle is ω when the azimuthal patterns depend only on a linear combination of P₂(cos ω) and P₄(cos ω), where P_n(x) is the Legendre polynomial of order n. In our theory the V_H scattering pattern is a four-leaf clover whose axes are restricted by the theory to be at either 0 or 45° to the polarization directions.     

Rodlike/flexible polyimide composite films prepared from soluble poly(amic diethyl ester) precursors: Miscibility,structure, and properties

Homogeneous precursor/precursor solutions with various compositions were obtained with appreciably high solid contents in N-methyl-2-pyrrolidone from soluble poly(amic diethyl ester) precursors of rodlike poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA) and flexible poly(4,4′-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA), which are hydrolytically more stable as well as more soluble than the corresponding poly(amic acid)s being equilibrated with the constituent monomers. Both optical microscopic and light scattering measurements showed that the dried precursor blend films and resultant polyimide composite films were optically transparent, regardless of compositions and process conditions. The composite films showed a single T_g behavior. However, for the composite of 30 wt % BPDA-PDA dispersed in the matrix of 70 wt % BPDA-ODA, a smectic crystalline-like aggregation of the BPDA-PDA component was detected on wide-angle x-ray diffraction patterns, indicative of microscopic phase separation between the two components. This phase separation was not detected on the optical microscopy, light scattering, and dynamic mechanical thermal analysis because of their resolution limits: Optical microscopy has a resolution of submicrometers, whereas dynamic mechanical thermal analysis and light scattering have a resolution of ca. 50 Å. Therefore, it is speculated that in the composite films BPDA-PDA and BPDA-ODA polyimide molecules have demixed on the scale of a few nanometers. The mean long periodicity, which was estimated from the small-angle x-ray scattering pattern, varied from 134 to 170 Å as the content of BPDA-ODA component increased. In addition, mechanical properties of the composite films were characterized. ©1995 John Wiley & Sons, Inc.     

Dynamic and electrophoretic light scattering of poly(dimethyldiallylammonium chloride) in salt-free solutions

Dynamic and electrophoretic light scattering were used to study the diffusion and electrophoretic mobility of poly(dimethyldiallylammonium chloride) as a function of polymer molecular weight in salt-free solutions. Two relaxation modes characterized as fast diffusion (D_f) and slow diffusion (D_s) were obtained from dynamic light scattering. Although the slow diffusion coefficient D_s strongly depends on molecular weight (M_w), the fast diffusion coefficient D_f was found to be independent of M_w over the range in the study. The fast diffusion was considered as the diffusion of a part of the polymer chain; the slow diffusion was interpreted by multichain diffusion. Electrophoretic light scattering results in the salt-free solution show that the electrophoretic mobility of the polymer is independent of M_w. © 1996 John Wiley & Sons, Inc.     

A new spectral memory of filled rubbers

We recently discovered that shearing particle‐reinforced rubbers in oscillation at a frequency f_a at a small strain γ_a (e.g., ～1% strain) for time t_a can often produce a spectrum hole or drop in the strain‐dependent dissipation spectra of the materials. The location of the hole (or localized perturbation in the loss modulus or loss tangent) depends on the aging strain amplitude γ_a. The depth of this hole is influenced by both the oscillatory aging frequency f_a and the aging duration t_a, and follows a simple power relationship of the product of f_a and t_a. The exponent for the power relationship is a function of filler concentration. These attributes of the spectral hole in filled rubbers are not sensitive to the frequency used to postanalyze the hole. This new memory effect occurs at very small strains and involves material stiffening during the strain aging, and both of those features are quite different from the Mullins effect in filled elastomers. We interpret this newly discovered memory character of filled rubbers from a much broader concept of structure pinning in a condensed frustrated system and consider that the agglomeration of filler particles in rubber matrix shares common physics with granular materials and glass‐forming materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 859–869, 2010     

Statistical approach to light scattering from deformed textured heterogeneous polymer materials

A statistical theory of light scattering from deformed isotropic and textured heterogeneous polymer materials is formulated. Two types of textured structures are analyzed: assemblies of optically isotropic and anisotropic rods and a spatially anisotropic distribution of isotropic spherical inclusion centers. The small-angle H_v light-scattering patterns are calculated. The appearance of scattering from isotropic rods and spheres in deformed materials has been demonstrated. The changes of the H_v scattering patterns as a function of elongation and strucuture parameters are discussed. © 1993 John Wiley & Sons, Inc.     

Crystal orientation in a semicrystalline polymer in relation to deformation of polymer spherulites. III. Small-angle light scattering

Small-angle polarized light scattering from a deformed three-dimensional spherulite is formulated on the basis of the deformation model proposed in Part II of this series. The intensity distribution of scattered light is discussed chiefly for the cross-polarization condition, the so-called H_v polarization, as a function of elongation of the spherulite. In the undeformed state, the scattered intensity distribution forms the typical fourleaf clover pattern, and the intensity decreases with increasing fraction of crystals oriented randomly (type R crystals) within the crystal lamellae of the spherulites. In a system composed of type R crystals and folded-chain crystals (type B crystals) within the lamellae, the four-leaf pattern moves to the horizontal zone near the equator with increasing elongation of the spherulite, and, simultaneously, extends to some extent to the vertical zone near the meridional direction as a parameter measuring the ease of lamellar untwisting increases. In a system composed, in addition to type R and type B crystals, of crystals transformed from type B to type C_a and type C_r due to tilting and unfolding of polymer chains, respectively, within the crystal lamellae an eight-leaf pattern appears, even at small elongation up to about 30%. Each lobe of the eight-leaf pattern undergoes a characteristic change with increasing elongation. In both systems, the scattered intensity increases with sharpening of orientation distribution of crystals within the crystal lamellae.     

Phase Behavior in Blends of Ethylene Oxide–Propylene Oxide Copolymer and Poly(ether sulfone) Studied by Modulated-Temperature DSC and NMR Relaxometry

The state diagram of a blend consisting of a copolymer containing ethylene oxide and propylene oxide, P(EO-ran-PO), and poly(ether sulfone), PES, is constructed by using modulated-temperature differential scanning calorimetry (MTDSC), T₂ NMR relaxometry, and light scattering. The apparent heat capacity signal in MTDSC is used for the characterization of polymer miscibility and morphology development. T₂ NMR relaxometry is used to detect the onset of phase separation, which is in good agreement with the onset of phase separation in the apparent heat capacity from MTDSC and the cloud-point temperature as determined from light scattering. The coexistence curve can be constructed from T₂ values at various temperatures by using a few blends with well-chosen compositions. These T₂ values also allow the detection of the boundary between the demixing zones with and without interference of partial vitrification and are in good agreement with stepwise quasi-isothermal MTDSC heat capacity measurements. Important interphases are detected in the heterogeneous P(EO-ran-PO)/PES blends.