Solution grown isotactic polystyrene crystals. II. Kinetics of thermal changes by x-ray diffraction

The present paper is a study of the annealing, melting, and recrystallization behavior of solution grown isotactic polystyrene crystals in order to elucidate changes both in total lamellar thickness and in the thickness of the crystalline “core” as a function of temperature. The lamellar thickness was obtained from x-ray long spacings and the core thickness from the broadening of appropriate reflections, both assessed by a high sensitivity x-ray detector system able to produce records within a few minutes during time dependent processes. The x-ray results were correlated with differential scanning calorimetry (DSC) measurements. On heating, first the usual annealing effects with little net melting were observed, but on increasing the temperature large changes in long spacing, which were reversible with temperature, were seen accompanied by only small changes in crystal core thickness. The second effect was found to be associated with a substantial degree of melting. Even after heating above the temperature where complete melting was indicated by DSC, the recrystallization rate was found to decrease as the melt temperature was increased and to be much faster than on cooling from the usual melts. Strikingly, this recrystallization was accompanied by a decrease in long period with time even under isothermal conditions. It is inferred that the memory of the preceding crystalline stack is preserved throughout the melting range and even beyond this, far into the molten state. This “seeding” effect is intrinsic to the polymer even if its nature cannot be specified. The principal effects in question can then be explained by envisaging that randomly placed lamellas gradually disappear within the stack on melting and successively reappear on crystallization during cooling. These ideas agree well with previous work on reversible long spacing changes in polyethylene (see ref. 9) and are likely to be of wider generality for melting and recrystallization phenomena in systems having stacked lamellar morphologies.     

Imperfections in polymer crystals

Summary The crystal-defect model of polymer structure is briefly reviewed along with the evidence for the existence, mobility and generation of dislocations. Starting with the hypothesis that a completely crystallizable homopolymer crystallizes one molecule at a time, it is shown that crystallization at temperatures well below the melting point should result in folded-chain crystals. Such crystals represent metastable equilibrium states which can increase their stability by rejecting or excluding the low molecular weight species. The amount of molecular species segregation which occurs is determined by the kinetics of crystallization and thus kinetics controls which metastable state (i. e. fold-period) occurs under a given set of crystallization conditions. As the annealing temperature is increased both molecular species segregation and molecular fold-period increase. If these processes could go to completion the equilibrium crystal at the melting temperature would be the completely segregated, completely extended-chain molecular crystal. In any practical case molecular species segregation is in complete so that the partial melted or unpeeled model represents the crystal which exists in equilibrium with the melt.

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Zusammenfassung Das Kristalldefektmodell polymerer Struktur wird kurz hinsichtlich der Evidenz des Auftretens, der Beweglichkeit und Erzeugung der Dislokationen dargestellt. Ausgehend von der Hypothese, daß vollkommen kristallisierbare Homopolymere kristallisieren, jeweils Molekül für Molekül, wird gezeigt, daß Kristallisation bei Temperaturen weit genug unter dem Schmelzpunkt zu kettengefalteten Kristallen führen sollte. Solche Kristalle repräsentieren metastabile Gleichgewichtszustände, die ihre Stabilität durch Ausscheiden oder Ausschließen von Molekülen niedrigen Molekulargewichts erhöhen können. Der Betrag der Molekulargewichtstrennung, der stattfindet, wird durch die Kinetik der Kristallisation bestimmt, und so kontrolliert die Kinetik, welche metastabilen Zustände, z. B. welche Faltungslänge bei einer gegebenen Zahl von Kristallisationsbedingungen auftritt. Wenn die Temperungstemperatur erhöht wird, steigt beides, die Entmischung und die Faltungsperiode. Wenn die Prozesse vollkommen ablaufen könnten, würde der Gleichgewichtskristall bei der Schmelztemperatur vollkommen entmischt sein und den vollkommen gestreckten molaren Kettenkristall bilden. In praktischen Fällen ist Entmischung unvollständig, so daß das teilweise geschmolzene oder gestörte Modell den Kristall repräsentiert, der im Gleichgewicht mit der Schmelze existiert.

     

Solution grown isotactic polystyrene crystals. I. Degree and distribution of crystallinity; thermal stability

The subject of this paper is the degree of crystallinity and annealing behavior of solution grown single crystals of isotactic polystyrene (IPS) in relation to the fold length, an enquiry which acquires special significance in view of the fact that previously the fold length had been found to be identical over a wide range of crystallization temperatures (T_c). It was found that both crystallinity and thermal stability increase with T_c even over the range of constant fold length thus invalidating the usual assumption that the fold length and crystal properties are uniquely correlated. Further, the crystallinity figures as measured by conventional calorimetry are very low (<50% throughout) which by conventional ideas would require an unrealistically thick amorphous surface layer. However, the “linear crystallinity” (crystal core thickness as determined from x-ray linewidths) is much larger, commensurate with crystallinities in single crystals from other materials. It is suggested that this is the more relevant figure for the subdivision of the lamellas into crystal core and surface layer. The additional amorphous content being otherwise accommodated. Further, this “linear crystallinity” is broadly unaffected by fold length changes induced by heat annealing. The thermal stability (including annealing ability) of the crystals differs markedly whether T_c is above or below ～60°C, a T_c value which is in the range where the fold length is constant, but corresponds to a maximum in the crystallization rate. Possible connections between crystallization conditions and the stability of the resulting crystals (fold length considerations apart) are pointed out.     

In situ characterization of solution–grown polymer single crystals by light scattering and kerr effect

Simultaneous measurements of light scattering and electric birefringence on a crystallizing solution of poly(ethylene oxide) (PEO) are shown to lead to the determination of the radius, thickness, and number of crystals at the early stages of the crystallization process.     

Nonlinear dynamics of polymer crystals

Advances in the contemporary physics have led to the discovery of new elementary mechanisms that determine on the molecular level the progression of many physical processes in crystals and other ordered molecular structures. Early theoretical investigations of nonlinear dynamics of molecular chains^1‐4) considered one‐dimensional (spatially linear) models with the sign‐positive anharmonism, which only took into account the longitudinal displacements of atoms (molecules) in the chain.     

Experimental criterion for the crystallization regime in polymer crystals grown from dilute solution: Possible limitation due to fractionation

By integration of equations previously derived by Frank, the growth rate of polymer crystals is shown to be dependent on their size, provided that the persistence length L_p or the kinetic length L_k = (2g/i)^1/2 are significantly larger than the primary nucleus. A new method of decorating the fold surface (isochronous decoration) allows the measurement of the quasi-instantaneous growth rate of very small crystals obtained from dilute xylene solution of a sharp polyethylene fraction of moderate molecular weight (M_w = 17,000, M_w/M_n = 1.11). Although the theory predicts that the growth rate increases with the size of the crystals as long as its dimension is smaller than the persistence length and/or the kinetic length, such an increase is not observed experimentally with the sharp PE fraction presently used. Therefore it appears that both the kinetic length and the (hypothetical) persistence length are beyond the resolution limit of electron microscopy and that crystallization occurs in the polynucleation regime. An upper bound is obtained for the rate g at which a locally new layer spreads in two directions on the substrate. The rate is lower than is estimated by the commonly Accepted theories. These theories lead also to an abnormally high value for the lateral surface free energy. The possibility that the observed initial linearity of the growth-rate curve may results from a balance of opposite effects (an increase with the size of the crystals on the one hand, a decrease with decreasing concentration and possible fractionation on the other) is thoroughly examined and ruled out. In fact, it must be stressed that at the early beginning of crystallization, negligible parts of the sample are crystallized and it is only at the end of crystallization that these effects appear. The fall in the growth rate as crystallization ends is due neither to progressive exhaustion of the solution alone nor to a depletion of the concentration by diffusion for this sharp fraction of low-molecular-weight PE. The major effect comes from fractionation. This segregation of the various molecular weights is predicted on the basis of a simple model and is verified by gel permeation chromatography (GPC). The fact that in such a sharp fraction significant fractionation occurs precludes any accurate determination of the supercooling and of the concentration of the polymer actually crystallizing. Subtle differences in the molecular weight distributions may result in significant variation of the growth rate. In conclusion, as the data used in the first part of this work were obtained with only a small percentage of the dissolved polymer sample crystallized, the observed constancy of the growth rate does not result from mutual compensation of opposite effects, and our conclusions about crystallization regime, order of magnitude of the kinetic and persistence lengths, and value of the rate of lateral spreading of a secondary nucleus are well founded.     

Active broadband polymer stabilized liquid crystals

We consider the realization and the electro-optical behaviour of a polymer network stabilized liquid crystal whose reflection band has been broadened. We particularly emphasize the reflective properties (mean value of the selective reflection and bandwidth, and the parameters of broadening) and their evolution with voltage. Broadband active films can be obtained under special conditions of polymerization. A mechanism concerning the broadening of the reflection band is put forward based on inhomogeneous consumption of a chiral monomer within the samples.     

Conjugated polymer crystals via topochemical polymerization

<正>The discovery and development of conductive polymers in the 1970 s by Alan J. Heeger, Alan G. Mac Diarmid and Hideki Shirakawa opens the new research field of organic electronics. Over the past decades, conjugated polymers and their applications in various electronic and optoelectronic devices have received considerable attention and studies due to their unique advantages of low cost fabrication methods and mechanical flexibility [1]. With the development of new conjugated polymer materials(to date, maybe hundreds of semiconducting polymers have been synthesized [2,3]) sig-     

Reversible local melting in polymer crystals

The melting of poly(ethylene terephthalate) is analyzed by quasi-isothermal, temperature-modulated differential scanning calorimetry. The measurement is done by sinusoidally changing the temperature in the melting range (± 1.0 K). In the melting range a small portion of the sample melts reversibly. This observation is taken as a direct observation of the reversibility of melting of specific macromolecules as long as they are melting only partially and need no molecular nucleation for recrystallization.     

Lattice imaging of radiation-sensitive polymer crystals

The total end-point dose (i.e., the electron irradiation dose necessary for complete destruction of the crystal lattice) was measured at 120 kV and room temperature for poly(ethylene oxide), polyethylene, isotactic polystyrene (i-PS), poly(p-xylylene), ramie and bacterial cellulose, and lobster chitin. On the basis of the results obtained, the possibility of lattice imaging of polymer crystals is discussed. As reported in an earlier preliminary paper, 1.1- and 0.55-nm lattice fringes were resolved in i-PS single crystals by using a conventional transmission electron microscope equipped with a device for low-dose imaging. In this paper, the detailed procedure for lattice imaging of i-PS crystals is described and various features of the lattice images are discussed.     

Oriented polymer dispersed discotic liquid crystals

Polymer dispersed discotic liquid crystals (PDDLCs) were prepared using the hexa-n-octanoate of rufigallol (RHO) and three polymer matrices: polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The molecular orientation of RHO in stretched PDDLC films was characterized by means of infrared dichroism. It was found that the stretching of films that contain RHO in both the columnar D1 and crystalline phase can effectively align columns of RHO along the stretching direction, with the short axes of the rigid cores lying in the plane of the film. By contrast with stretched polymer dispersed nematic liquid crystals, no orientation of RHO is induced for films stretched with RHO in the isotropic phase, followed by rapid cooling to room temperature. However, if stretched films are cooled under strain into the columnar D1 phase, orientation of RHO can develop with time.     

Liquid crystals stabilized by polymer networks

This review is devoted to the characteristics of a new class of polymer composites, dispersions of chemical polymer networks in LCs. Photopolymerization of various bifunctional monomers in the medium of LCs leads to the formation of a polymer network that stabilizes the structure of crystals. Methods for the preparation of the above composites, their structure, morphology, and optical characteristic are reviewed, and areas of practical application of such materials are described.     

Active broadband polymer stabilized liquid crystals

We consider the realization and the electro-optical behaviour of a polymer network stabilized liquid crystal whose reflection band has been broadened. We particularly emphasize the reflective properties (mean value of the selective reflection and bandwidth, and the parameters of broadening) and their evolution with voltage. Broadband active films can be obtained under special conditions of polymerization. A mechanism concerning the broadening of the reflection band is put forward based on inhomogeneous consumption of a chiral monomer within the samples.     

Oriented polymer dispersed discotic liquid crystals

Polymer dispersed discotic liquid crystals (PDDLCs) were prepared using the hexa-n-octanoate of rufigallol (RHO) and three polymer matrices: polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The molecular orientation of RHO in stretched PDDLC films was characterized by means of infrared dichroism. It was found that the stretching of films that contain RHO in both the columnar D1 and crystalline phase can effectively align columns of RHO along the stretching direction, with the short axes of the rigid cores lying in the plane of the film. By contrast with stretched polymer dispersed nematic liquid crystals, no orientation of RHO is induced for films stretched with RHO in the isotropic phase, followed by rapid cooling to room temperature. However, if stretched films are cooled under strain into the columnar D1 phase, orientation of RHO can develop with time.     

Twinning in macroscopic polymer single crystals

Twinning in macroscopic single crystals of poly(TSHD) has been investigated using scanning electron microscopy. Two particular chain-axis rotation twins have been identified unambiguously. They have K₁ twinning planes of (012) and (212). It is also thought that twins with K₁ planes of (21 2) and (202) may possibly occur. The possible mechanisms of twinning in polymer crystals have been discussed and chain-axis rotation twinning in poly(TSHD) has been compared with a similar type of deformation that has been suggested to take place in polyethylene crystals.     

Sequential functionalization of porous coordination polymer crystals

Crystal extractor: Heterostructured porous coordination polymer crystals fabricated using epitaxial growth have two contradictory porous functions, namely size selectivity and high storage. The crystals not only extract linear petroleum molecules from a mixture with its branched isomer, even at very low concentrations of linear isomer (1?wt?%), but also shows improved accumulation of the molecules in its pores.     

Mechanically activated cholesteric polymer dispersed liquid crystals

In this paper we deal with a cellulose derivative cholesteric dispersed liquid crystal (CCDLC) with mechanically tuneable optical properties. The composite is formed with a matrix of acetoxypropylcellulose with embedded micrometric and submicrometric droplets of a cholesteric mixture. Polarizing optical microscopy and atomic force microscopy (AFM) measurements performed on the system are reported and it is shown that the wavelength of the reflected light can be changed by a temperature variation and it is also changeable through a mechanical deformation. The pitch of the deformed droplets can be measured from AFM photographs and compared with the wavelength reflected by the CCDLC composite material.     

Self-aligning liquid crystals in polymer composite systems

Soft composite materials combined with a holographic photopolymerization process are used for realizing an innovative switchable periodic structure made of slices of almost pure polymer alternated with films of well aligned nematic liquid crystals named POLICRYPS. It exhibits negligible scattering losses, while the effect of the spatial modulation of the refractive index (from polymer to nematic liquid crystal) can be switched on and off by applying a low (few V/μm) electric field. The diffractive properties of the POLICRYPS structure are characterized in terms of cell thickness, impinging probe angle and wavelength revealing a strong correlation between the diffraction efficiency and all the above mentioned parameters. These results are very attractive for many applications such as switchable Bragg gratings for telecom devices, phase modulators, and displays. Other advantages of the technology include absence of an alignment layer, absence of haze, robust structure, and inexpensive manufacturing. In addition, no special alignment layers are required. This is a unique opportunity and a big advantage compared to conventional liquid crystal devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 158–162     

Electrooptic properties of polymer dispersed liquid crystals

An investigation of the electrooptic properties of polymer dispersed liquid crystals (PDLC) is presented. These materials are light modulating systems. They show a reversible optical response from an opaque state to a highly transmitting state under the action of an appropriate electric field which aligns the liquid crystal director. The switching voltage required to establish such an electric field has been monitored as a function of (i) the starting materials used for the preparation of the PDLCs, (ii) the ageing (curing time) of the PDLC cells. Other physical properties, such as the electrical resistivity and the dielectric constant of the materials, have been measured. The correlations between these properties have been studied. The PDLC switching voltage appears to be strongly correlated with the resistivity. Our data suggest that ionic impurities play a dominant role with respect to the electrooptic response of PDLC films.