Automated light-scattering apparatus for studying polymer films

The design and operation of an automated light-scattering apparatus for studying structures in polymer films are described. The apparatus has angular resolution of 0.02 and 1.0° in radial and azimuthal angles, respectively. The radial scan can be made over the range of 0.5 (or less) to 90° and the azimuthal scan covers 180°. Time resolution is in the order of milliseconds. The operation, data collection, and reduction are fully automatic. Illustrative data on the crystallization of a low density polyethylene are described.     

Depolarized light-scattering spectroscopy and polymer characterization

Light scattering has long been established as a technique for measuring the molecular weight and radius of gyration of polymer molecules. Depolarized light scattering can be studied accurately with lassers. The theory of static and dynamic depolarized light-scattering spectroscopy is presented and illustrated with two examples of novel particles in solution. From the static intensity measured as a function of angle, the length of rod-like molecules can be evaluated. More complicated geometrical measures are obtained in the eneral case. From the dynamic light scattering, the translational self-diffusion coefficient and the rotational diffusion coefficient are obtained. These quantities can be interpreted in terms of a major semi-axis length and an axial ratio for the molecule or particle by using the Perrin equations.     

Interaction via diffusion of polymer crystals in growing spherulites

Previous calculations of how diffusion ranges should be averaged when polymer molecules of various lengths are segregated at crystal growth fronts have been extended. Crystals of acicular or lamellar habit are addressed directly, necessarily using more approximate methods, and earlier conclusions regarding appropriate averaging are reaffirmed. Results also lead to a better understanding of why crystalline texture in polyethylene spherulites appears to scale with the averaged diffusion range at crystallization temperatures within regime II but not at higher temperatures within regime I.     

Formation of interpenetrated spherulites based on miscible crystalline polymer blends

The morphology and formation process of interpenetrated spherulites of poly(butylene succinate)/poly(vinylidene choloride‐co‐vinyl chloride) (PBSU/PVDCVC) blends were investigated by confocal laser scanning microscopy (CLSM). CLSM images showed that the dense fibrils of PBSU spherulites penetrated into the sparse PVDCVC spherulites. For a blend with PBSU content 50% and crystallization temperature T_c = 368 K, the simultaneous growth of PBSU and PVDCVC spherulites was observed. After PBSU fibrils collided with PVDCVC spherulites, they kept growing through PVDCVC spherulites. For a blend with PBSU content 30% and T_c = 363 K, PBSU started to nucleate after PVDCVC spherulites filled the whole space.     

Crystal orientation in a semicrystalline polymer in relation to deformation of spherulites

A mathematical development interrelating the orientation distribution functions of three kinds of orientation units for a polymer spherulite (i.e., a crystal lamella, a crystallite, and a given reciprocal lattice vector of the crystallite) is formulated on the basis of series expansions of the distribution functions in generalized spherical harmonies. Two types of uniaxial deformation models of a polyethylene spherulite, taking account of micronecking and untwisting of crystal lamellae, and of chain tilting and untwisting of crystal lamellae, respectively, both in addition to affine deformation of the lamellae are discussed. The models are tested by comparison of the theoretical orientation distribution functions of some reciprocal lattice vectors of the crystallite with the results of x-ray diffraction experiments.     

Effect of molecular weight on the radial growth rates of polymer spherulites

Data existing in the literature for the spherulitic growth rate of molecular weight fractions of linear polyethylene, poly-(tetramethyl-p-silphenylene)siloxane, and trans-1,4-polyisoprene have been analyzed according to nucleation theory on taking into account the influence of chain length on the free energy of fusion. All three polymers display very similar behavior in that the interfacial free energy reaches an asymptotic value at high molecular weights, decreases as the molecular weight is lowered, and appears to also reach an asymptotic value at low molecular weights. Although the changes in the interfacial energy with molecular weight are quite distinct, the relative change is much less than has been previously reported when a molecular crystal analysis is used. The same general behavior observed points out the dominating influence of the chain-like character of the molecules in governing the growth rate.     

Effect of birefringence on low-angle light-scattering patterns from oriented polymer films

The effect of birefringence of a polymer film upon its photographic light-scattering pattern is considered for the case of a single, anisotropic, two-dimensional spherulite imbedded in a birefringent matrix. It is shown that for the case of a polarizer and analyzer crossed at +45° and ?45° to the analyzer, the scattering pattern is modified in a manner agreeing with experimental observation.     

以“偏光显微镜观察高聚物的球晶”为例的高分子物理实验项目改革

本文对高分子物理实验教学改革进行了思考,提出实验项目的建设应当成为实验教学改革的核心,而实验项目的改革不应当局限在将最新的科研成果引入到实验教学中。以"偏光显微镜观察聚合物的球晶"这一传统实验为例,更为有效的办法可以是通过系统化的设计扩展实验项目内容,注重实验项目实施过程中多知识点的串联以及实验结果获取过程的思维过程培养,从而将传统的验证性实验项目转化为综合性实验项目,有力提升实验教学的效果。     

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.     

Mechanism for twisting in polyethylene spherulites

A model is proposed to account for the regular twisting of radial ribbons in certain polymer spherulites. The model assumes that the ribbons have crystallographically regular fold surfaces and that growth of the ribbons is nucleation-controlled. The model leads directly to a possible mechanism of spherulitic growth in some polymers.     

An electrically controlled light-scattering device based on liquid crystal/polymer microsphere composites

ABSTRACT

There is a widely applied prospect of electrical controlled liquid crystal (LC) light-scattering device. Numerous electrical controlled LC light-scattering technologies have been studied, but each technology has its own shortcomings, such as high driving voltage, high hysteresis, complex electrode structure, and serious heating. In this work, the composite of LC and polymer microspheres are used to fabricate light-scattering devices. This device is operated by the vertical electric field and does not require complex preparation process. LC/polymer microsphere composite has the advantages of low driving voltage and zero hysteresis. The role of microspheres in the composites is to change the size and density of a refractive-index-mismatched micro-domain. The effects of the ratio, particle size, and refractive index of microspheres on the optical characteristics of a composite are studied. The normal directional light transmittance at the transparent state and light-scattering state decreases with an increasing weight ratio of microspheres. The particle size of microspheres has negligible influence on the electro-optical properties of composites when the weight ratio of microspheres is small. The LCs doped with Polymethylsilsesquioxane (PMSQ) microspheres or polymethyl methacrylate (PMMA) microspheres are compared, and the mismatched refractive index and density of micro-domain show the influence on the electro-optical properties of the composites.     

A light-scattering study of deformation of liquid-crystalline spherulites of poly(γ-benzyl-L-glutamate) in an electric field

The deformation of liquid-crystalline spherulites of poly(γ-benzyl-L -glutamate) (PBLG) in an electric field was investigated by light scattering, polarized-light microscopy, and birefringence measurements. Under the polarizing microscope, the deformation was found to be dependent upon the field strength. The spherulites deformed perpendicular to the field. Above 75 V/cm in N,N-dimethylformamide or 120 V/cm in 1,1,2-trichloroethane, the deformed spherulites were transformed to rodlike textures. With increasing voltage, the rods gradually oriented parallel to the electric field. On the basis of the experimental results, models for affine deformation are proposed. With these models, light-scattering patterns are calculated. The calculated and experimental patterns agree semiquantitatively.     

Surface light-scattering at the air-liquid interface: from newtonian to viscoelastic polymer solutions

The dynamics of the liquid-air interface of aqueous solutions of a tensioactive triblock copolymer (Pluronic F-68) has been studied using surface quasielastic light scattering over a broad range of concentrations and temperatures. Ancillary surface tension and bulk rheometry data have been obtained for the same system. The results show that the classical theoretical spectrum for monolayers on a Newtonian fluid can be applied only for concentrations below 4.10(-2) mM. For concentrations above c = 14 mM a clear peak centered at zero frequency appears in the spectrum. This feature is incompatible with the classical theoretical spectrum. The SQELS spectra have been described in terms of the theory of Wang and Huang [Wang, C. H.; Huang, Q. R. J. Chem. Phys. 1997, 107, 5898] considering that the loss modulus of the concentrated solutions shows the existence of two relaxation modes even at low frequencies. The theory is able to explain the existence of a peak centered at zero frequency in the spectra, and the theoretical spectra point out the existence of an elastic peak together with the capillary one. There is a reasonable agreement between the relaxation times and the product Gtau obtained from the fits of the SQELS spectra to the theory of Wang and Huang and those obtained from bulk rheology.     

Effect of birefringence on low-angle light-scattering patterns from oriented polymer films. II

A quantitative theoretical calculation is made of the effect of birefringence of the surrounding medium on the light-scattering pattern from a two-dimensional anisotropic spherulite. The calculated modification of the light-scattering pattern is in accord with the prediction previously made on the basis of qualitative considerations and model experiments.     

Scattering from truncated spherulites

A general two-dimensional theory is derived to explain the light scattering from truncated spherulites. The severity of the truncation is expressed by a statistical parameter σ²/ā² which is the ratio of the variance σ² of the size of the spherulite to the square of its average size ā. The H_v light-scattering patterns are calculated for different values of the truncation parameter. It is observed that the truncation decreases the position of maximum scattering intensity of the pattern. It also increases the scattering intensity at small and large angles, but reduces it at intermediate angles. For a spherulitic polyethylene sample, the truncation parameter is found to equal 0.100 ± 0.030 as measured microscopically. The theory can also be used to calculate light-scattering patterns from row-nucleated spherulites. If it is assumed that the interference effect averages out to zero when a large number of spherulites is involved, a single “sliced” spherulite model can be used. Then, the scattering intensity per unit area decreases as the “slice” becomes very thin.     

Low-angle light scattering of ionotropic gels

Low-angle light-scattering patterns were obtained on ionotropic gels formed by the diffusion of Ca⁺⁺ into a polygalacturonate sol. Near the sol–gel boundary, diffraction patterns were obtained which indicated organized structures with repeating units of 1100, 250, and 12.5 μ. Microscopic investigations confirmed that at this gel boundary capillaries run parallel to each other and perpendicular to the direction of diffusion. The diameter of capillaries was 12 μ while their length was in the 1000 μ range. Short interconnecting capillaries were about 200–300 μ in length. Inside the gel, in the more highly crosslinked parts, a disorientation occurs during the aging process with the partial disappearance of capillaries. However, at the gel–sol and gel–semipermeable membrane boundaries, the highly organized structures remain even during prolonged aging. The kinetics of the gel formation was also investigated.     

Cracking in polylactide spherulites

A polylactide of high optical purity was crystallized between 100 and 140 °C, in‐between two glass slides, and its morphology was investigated by polarizing optical microscopy, scanning electron microscopy, and atomic force microscopy, during subsequent heating and cooling cycles between ?15 °C and the crystallization temperature. It was found that dark circular rings show up on cooling on top of the spherulites and represent cracks of about 300 nm in width. This phenomenon is completely reversible, and the heating–cooling curves are centered at about 56 °C, which coincide with the T_g of polylactide. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3308–3315, 2005     

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.     

Deformation of elastomeric polyolefin spherulites

The ethylene‐octene block copolymers in this study consist of long crystallizable sequences with low comonomer content alternating with rubbery amorphous blocks with high comonomer content. The crystallizable blocks form lamellae that organize into space‐filling spherulites even when the fraction of crystallizable block is so low that the crystallinity is only 7%. These unusual spherulites are highly elastic and recover from strains as high as 300%. This new class of thermoplastic elastomers is fundamentally different from conventional elastomeric olefin copolymers that depend on isolated, fringed micellar‐like crystals to provide the junctions for the elastomeric network. The elastomeric block copolymers are shown to be unique in that a hierarchical organization of space‐filling lamellar spherulites provides the junctions for the elastomeric network. The deformation of the elastic spherulites is readily studied with small angle light scattering, wide angle X‐ray diffractograms, and atomic force microscopy. At strains in excess of 300%, the spherulites break up into a fibrillar structure following lamellar deformation processes that are similar to those established for high density ethylenic polymers. The crystalline transformation produces a stiffer elastomer that exhibits complete recovery on subsequent loadings. Similar experiments on elastomeric random ethylene‐octene copolymers where fringed micellar crystals provide the physical crosslinks that connect the rubbery, amorphous chain segments reveal significant differences. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1313–1330, 2009