Untersuchung der druckinduzierten Kristallisation von Polyäthylen mit Hilfe einer neuen Raman-Hochdruckzelle

Es wird eine Raman-Hochdruckzelle vorgestellt, die es gestattet, druck- und temperaturabhangige Ramanstreuexperimente an flussigen und festen Substanzen bis 7 kbar und 300 °C auszufuhren. Die Zelle bietet die Moglichkeit der gleichzeitigen Messung von Volumenanderungen. Die Apparatur wurde zur Untersuchung der durch Druck eingeleiteten Kristallisation von Polyathylen eingesetzt. Unter isotherm-isobaren Bedingungen wurde die Kristallisation anhand der Linienformanderung im CH2-twisting undLAM-Bereich verfolgt und mit den Volumenanderungen verglichen. Die Verschiebung derLAM-Frequenzen spricht fur ein Dickenwachstum der Lamellen nach ihrer Entstehung. Das Ergebnis druckabhangiger Kristallisat…

Zum Mechanismus der Polymerkristallisation

Auf der Grundlage der Ergebnisse von Rontgenkleinwinkel-Streuexperimenten und elektroenenmikroskopischen Untersuchungen an verzweigtem Polyethylen wird ein neues Modell zum Ablauf des partiellen Kristallisierens und Schmelzens entwickelt. Im Modell wird der Aufbau der Lamellarstruktur als sukzessive „Einschubkristallisation“ beschrieben, die durch die Konzentration an nichtkristallisierfahigen Einheiten in den amorphen Bereichen gesteuert wird. Die Kinetik der Einschubkristallisation last sich durch dilatometrische Experimente verfolgen. Aus vergleichenden Rontgenkleinwinkel- und Ramanstreuexperimenten kann auf eine Anreicherung der Cobausteine an den Lamellenoberflachen geschlossen werden.

Die kristallstruktur von cycloalkanen

An X-ray structure analysis was performed on single crystals of the cycloalkane (CH2)36. The lattice belongs to the space group Aa and is arranged in layers. The unit cell has the dimensions α = 1,033 nm, b = 0,824 nm, c = 4,22 nm, β = 107, 1° and contains four molecules. The molecules consist of two stretched stems which are linked by sharp folds at each end. The folds have the conformation …t(g g t g g) t… lying parallel to the b-axis. Raman measurements suggest that the stems are slightly twisted. A comparison of the homologous series (CH2)n, n = 36, 48, 60, and 72 using X-ray powder methods showed that the (CH2)36-structure, including the fold conformation, is also representative for th…

Effect of amorphous sequences on the longitudinal acoustic modes in partially crystalline polymers. I. Transfer matrix method

A novel theoretical scheme is developed which enables the determination of the LAM-like vibrations of polymer chains made up of crystalline and amorphous parts as they occur in partially crystalline structures. The boundary conditions effective at the junction points are formulated in terms of the compliances of the associated amorphous sequences. These compliances can be derived from their eigenfrequencies and eigenvectors in a disconnected state. The treatment uses a matrix formalism which can be extended to include bending and torsional motions in a general state of vibration of the crystalline stem. A first numerical example demonstrates that the LA mode of a crystalline stem can be str…

Raman spectroscopic method for determining the crystallinity of polyethylene

The Raman spectrum of partially crystalline polyethylene can be described as a superposition of three components, which originate from the orthorhombic crystalline phase, a meltlike amorphous phase, and a disordered phase of anisotropic nature, where chains are stretched but have lost their lateral order. The mass fractions involved in the three phases can be derived directly from the integral intensities of characteristic bands without an additional calibration procedure. A comparison of the results obtained for a variety of samples shows agreement with the crystallinities derived from the density, and the small-angle and wide-angle x-ray diagrams. Data indicate that the disordered anisotr…

Pressure induced changes in the Raman spectra of liquidn-alkanes and perfluoro-n-alkanes

The main effect of pressures up to 6 kbar on the Raman spectra of liquidn-alkanes and perfluoro-n-alkanes is a reduction of line widths indicative for a slowing-down of rotational motions about the long axes. There is no evidence for a change in the conformer populations.

Synthese und Eigenschaften molekulareinheitlicher n-Paraffine bis zum C140H282

Die Umsetzung von α,ω-Dihalogenalkanen mit Natrium fuhrt nach anschliesender katalytischer Hydrierung zu einem Paraffingemisch mit diskontinuierlicher Molekulargewichtsverteilung. So enthalt das aus 1.10-Dibromdecan hergestellte Produkt nur Paraffine mit 10, 20, 30 usw. C-Atomen, ein aus 1.20-Dibromeicosan hergestelltes Produkt dagegen nur die Paraffine mit 20, 40, 60 usw. C-Atomen. Diese Paraffingemische wurden gelchromatographisch in die molekulareinheitlichen Verbindungen zerlegt und Paraffine bis C140H282 isoliert. Am Beispiel des C70H142 wurde die Temperaturabhangigkeit der Rontgenkleinwinkelstreuung gemessen. Aus Intensitat und Lage der Langperiodenreflexe liesen sich die Anderungen v…

Molecular Motion, Defect Structures and Phase Transitions in Oligomer Crystals

Defect structures in the high temperature modifications of oligomer crystals can generally be discribed as a superposition of chain rotations, longitudinal shifts of the molecules and the occurrence of conformational defects. Applying a suitable combination of experimental techniques it is possible to discriminate between the different components of disorder. This is demonstrated in a discussion of results obtained on n-alkanes, cycloalkanes and perfluoro-n-alkanes.

Crystallization and melting of fractions of branched polyethylene

Effects of the molecular weight on the crystallization behaviour of branched polyethylene become observable if isothermal crystallization is studied at temperatures near to the melting end. Crystallinities decrease with decreasing molecular weight. Thicknesses of lamellae grown during isothermal crystallization are independent of the molecular weight. They depend only on temperature. Compared to the effect of the branches polydispersity gives only a minor contribution to the broadening of the crystallization and melting range of low density polyethylene.

The fiber patterns of a series of liquid crystalline polymers were analysed. For polymers with smectic phases and for polymers with long spacers and nematic phases, the mesogenic groups orient perpendicularly to the polymer main chains which are parallel to the fiber axis. The fiber pattern indicate a short range order of the mesogenic groups analogous to that in low-molecular weight liquid crystals. For polymers with short spacer groups and nematic phases qualitatively different fiber patterns are found. These fiber patterns are indicative for a special nematic phase formed by ribbon-like molecules.

Die molekularen Grundlagen der anisotropen thermischen Ausdehnung von Paraffinen und Polyäthylen. Eine ramanspektroskopische Untersuchung am Beispiel des N-Tritriacontans

Die an Paraffinen und Polyathylen zu beobachtende thermische Ausdehnung erfolgt auf charakteristisch anisotrope Art und Weise. So wird zum einen festgestellt, und dies ist aufgrund der Bindungsverhaltnisse im Kristall nicht weiter uberraschend, das die thermische Ausdehnung in Kettenrichtung wesentlich geringer als in der dazu senkrechten, lateralen Ebene ist. Des weiteren zeigt sie jedoch auch innerhalb der lateralen Ebene eine sehr deutliche Richtungsabhangigkeit. Bestimmt man rontgenographisch gesondert die Ausdehnungskoeffizienten langs der a- und der b-Achse der orthorhombischen Zelle, so findet man, das sie sich um etwa eine Grosenordnung unterscheiden und die Ausdehnung in erster Lin…

Raman spectrum of the high pressure phase of polyethylene

The Raman spectrum of the hexagonal high pressure phase of polyethylene was measured at 5.2 kbar and 240 °C, using a hydrostatic high pressure cell. The spectrum is largely identical to that obtained for the melt. This result indicates that the conformational short range order in the hexagonal phase remains melt —like and is not modified by the overall straightening of chains.

Analysis of the intensities of the longitudinal acoustic vibrations inn-alkanes and polyethylene

Simple theoretical considerations indicate, that the integral intensity of the „longitudinal acoustic modes” (LAM) in the Raman spectrum ofn-alkanes should be independent of the chain length. The experiment in fact confirms this expectation. Using this property it becomes possible for polyethylene samples, to derive from the measured LAM-intensity the mass fraction of all-turns sequences contributing to this band. For solution crystallized samples this fraction coincides with the crystallinity, whereas in melt crystallized samples it generally turns out as smaller. The observed difference is likely to be due to the occurrence of local conformational defects (kinks, chain torsions) which int…

Dielectric Relaxation Measurements and X-Ray Investigations of Liquid Crystalline Side-Chain Polymers

In the last few years several liquid crystalline side-chain polymers have been synthesized,1 – 4 which combine the properties of low molecular weight liquid crystals with those of polymers.5 – 9

Small-angle x-ray scattering experiments for investigating the validity of the two-phase model

A New method for evaluating SAXS curves of polymer samples with lamellar structure is applied to two typical scattering curves measured with a solution-crystallized linear polyethylene and a melt-crystallized branched polyethylene respectively. The method permits a rigorous check of the validity of the two-phase model and yields, without additional measurement, the volume fractions of the two phases and the difference in their densities. The densities can than be obtained by measuring the overall density of the sample. The results are: ρc = 0.996 g/cm3,ρa = 0.854 g/cm3, wa = 0.20 for the solution-crystallized sample; ρc = 0.967 g/cm3,ρa = 0.850 g/cm3, wa = 0.36 for the melt-crystallized sam…

Model of partial crystallization and melting derived from small-angle X-ray scattering and electron microscopic studies on low-density polyethylene

A temperature-dependent small-angle x-ray scattering and electron microscopic study on a sample of low-density polyethylene affords a determination of the structure changes in a heating and cooling cycle and suggests a new model of partial crystallization and melting. The analysis of SAXS data is based upon some general properties of the electron-density correlation function. Electron micrographs are obtained from stained sections γ irradiated at elevated temperatures and are analyzed quantitatively by statistical means. According to the model proposed here the thickness distribution in the amorphous layers, rather than that of the crystalline regions, is the essential factor governing the …

Kristallisation und schmelzverhalten von fraktionen verzweigten polyethylens, 1. Darstellung und charakterisierung der fraktionen

A branched polyethylene with broad molecular weight distribution was separated into a series of fractions by fractional precipitation from dilute solution. The fractions were characterized by viscometric and density measurements, IR-spectroscopy and calorimetry. The methyl group content and the density turned out as largely constant. Molecular weight effects show up in the melting behaviour. The main range of melting and the end of the melting curve shift to lower temperatures with decreasing molecular weight. Compared to the overall extension of the melting range these shifts are small. One has to conclude that polydispersity gives only a minor contribution to the broadening of the melting…

A raman spectroscopic determination of the interlamellar forces in crystalline n-alkanes and of the limiting elastic modulus Ec of polyethylene

A simple treatment based on continuum mechanics shows that weak interlamellar forces in crystalline n-alkanes should result in a characteristic upward shift of the frequencies of the longitudinal acoustical (LA) modes, which is independent of the chain length and decreases inversely with the mode order. A raman spectroscopic determination of the LA mode frequencies of a series of different n-alkanes confirms the theoretical conclusion and permits a derivation of a force constant characteristic of the interlamellar forces. The discussion results in a new formula valid for the LA mode frequencies of the orthorhombic n-alkanes in the acoustical limit and yields a new determination of the limit…

Direct evaluation of the electron density correlation function of partially crystalline polymers

A discussion of the general properties of the one-dimensional electron density correlation function K(z) of a partially crystalline polymer with lamellar structure shows that application of a graphical extrapolation procedure permits direct determination of the crystallinity, the specific inner surface, and the electron density difference ηc − ηa. The procedure is based upon the occurrence of a straight section in the “self-correlation” range of K(z). Curved and nonparallel lamellae do not invalidate the concept. In the case of heterogeneous samples composed of partially crystalline and totally amorphous regions, some of the parameters of the experimentally obtained correlation function, as…

Structure relaxation after temperature jumps in homogeneous polystyrene/poly(styrene-co-bromostyrene) blends

Concentration fluctuations in polymer blends and their change after a temperature jump were studied by time-dependent small angle X-ray scattering experiments. Measurements were conducted on homogeneous mixtures of polystyrene and a partially brominated derivative. Structure factors in thermal equilibrium show the form given by the random phase approximation, thus enabling a direct determination of theχ-parameter and the mean radius of gyration. TheT-dependence ofχ can be understood as the result of superposed enthalpic contributions and a free volume term. In theT-jump experiments, samples were quenched to temperatures near Tg. Relaxation occurs on the time scale of minutes and is nonexpon…