Magnetic susceptibility, heat capacity, and optical conductivity of LiPc and LiPcI

The magnetic susceptibility, using dc and electron spin resonance (ESR) methods, the specific heat, and the infrared properties of the one-dimensional molecular semiconductors lithium phthalocyanine (LiPc) and the iodinated compound LiPcI have been investigated for temperatures K. LiPc has a half-filled conduction band and is expected to be an organic metal. However, due to the strong Coulomb repulsion the system is a one-dimensional Mott-Hubbard insulator with a Hubbard gap of 0.75 eV as inferred from optical measurements. The localized electrons along the molecular stacks behave like a S = 1/2 antiferromagnetic spin chain. The spin susceptibility, as determined by ESR experiments, and the magnetic contribution to the heat capacity show a Bonner-Fisher type of behavior with an exchange constant K. LiPcI is an intrinsic narrow-gap semiconductor with an optical gap of 0.43 eV. In ESR experiments it is silent, indicating that all the unpaired electrons have been removed from the macrocycle via doping with iodine. Received: 16 June 1998 / Accepted: 14 July 1998     

Focused cryogenic trapping for dynamic headspace and pyrolytic analysis of polymers on a fused silica capillary column

Focused cryogenic trapping has been used to maximize the high resolution capabilities of fused silica capillary columns during dynamic headspace and pyrolytic polymer analyses. Mass spectrometric detection with data system recording/processing provide sensitive, selective, and rapid results. The techniques described herein demonstrate the power of both dynamic headspace and pyrolytic analyses for troubleshooting applications with complex industrial polymer products.     

Corrosion effects of nuclear tracks in polymers

Usually ion tracks are studies ex-situ, i.e. after removal of the ion-irradiated sample from the evacuated irradiation vessel. The exposure to ambient air leads to degradation effects which are frequently neglected and consequently have been studied rarely. They have never been explained consistently. In this work we compile and discuss them in the frame of today's general understanding of ion tracks in polymers. It appears that some pristine polymers such as polyethylene are covered by a surface layer which is badly permeable for gaseous contaminants. Ion irradiation leads to destruction of this protective layer so that oxygen and moisture from the ambient air can easily penetrate through the ion tracks, and eventually even into the surrounding pristine material. Moisture absorption along the tracks gives rise to some faint conductivity. Oxygen uptake adds new trapping centers to the existing ones along the tracks, so that on one hand an increased dopant uptake capability is recorded, and on the other hand oxygen-sensitive mobile dopants are immobilized along the ion tracks. Photooxidation processes contribute to the fading of the optical blackening of irradiated polymers.     

Analysis of volatile organic compounds in polymers by dynamic headspace and gas chromatography/mass spectrometry

An experimental method for the analysis of volatile organic compounds in polymers is described. The technique involves dynamic headspace sampling, collection, and concentration of the volatiles in a cold trap, followed by capillary column gas chromatography/mass spectometry. Flow switching is carried out by the Deans switching technique. Four technical polymers used as pharmaceutical packaging materials have been analyzed in order to demonstrate the method.     

Proof of gridlock in a polymer model

It has been suggested that some lattice models of polymers, especially ones that incorporate more realistic excluded volume interactions extending to further neighbors, may be subject to gridlock. A model is defined to have the property of gridlock if it cannot melt at any temperature unless a density decrease is allowed. Classical theories of polymer melting are incompatible with the property of gridlock. This paper proves rigorously that a two-dimensional square-lattice model of polymer chains that have nearest-neighbor excluded volume interactions (called the X1S model) has the gridlock property. The proof uses elementary concepts from graph theory. Also, different interpretations of the X1S model are given in terms of real polymers. This leads to a discussion of a number of different classes of melting depending upon whether the intramolecular rotameric energies and the attractive intermolecular energies are antagonistic to or supportive of the melting transition.     

Velocity autocorrelation function for the motion of long-chain molecules in the free draining limit

The thermal motion of a long-chain molecule dispersed in a solvent is examined in terms of the velocity autocorrelation, in a reference frame attached to a subunit of the chain.     

High resolution UHV-AFM surface analysis on polymeric materials: Baltic Amber

In this paper we present, for the first time, the results from Atomic Force Microscopy (AFM) surface studies from freshly fractured Baltic Amber samples, carried out under ultrahigh vacuum (UHV) conditions from micrometer to nanometer resolution. The micrometric AFM images provide a structural clue to the birefringent behavior occasionally observed with amber samples. Two-dimensional pair-distance distributions of the nanometric AFM images prove the completely amorphous structure of the material. This, together with the detection of individual motifs such as aromatic rings, supports the notion of amber being an amorphous polymeric organic network, consistent with the accompanying X-Ray Photoelectron spectroscopy (XPS) data. No nanocrystalline inclusions could be found. The results also show that it is possible to obtain atomically resolved AFM images from amorphous dielectric surfaces.     

Laser processing for bio-microfluidics applications (part I)

This paper reviews applications of laser-based techniques to the fabrication of microfluidic devices for biochips and addresses some of the challenges associated with the manufacture of these devices. Special emphasis is placed on the use of lasers for the rapid prototyping and production of biochips in particular for applications in which silicon is not the preferred material base. Part I of this review addresses applications and devices using UV lasers for laser ablation and surface treatment of microchannels, in particular in polymers.