Preparation and properties of thin films of hyperbranched polyesters with different end groups

Hyperbranched polyesters (HBP) with different end groups were prepared as thin films. They were characterized with regard to their chemical composition, thickness, optical constants and morphology using infrared spectroscopy, spectroscopic ellipsometry, and atomic force microscopy. The surface properties of the films were determined by zeta‐potential and contact angles measurements. The differences in the molecular structure and surface energetic and acid‐base properties between HBP materials with carboxylic, hydroxy and acetoxy end groups result in differences in their swelling behavior in atmospheric humidity. The swelling behavior at different atmospheric humidity was observed in situ using spectroscopic ellipsometry and reflectometric interference spectroscopy. From the results it can be concluded that HBP films can be used potentially as sensoric materials.     

Light scattering and dielectric relaxation studies of glass forming liquids

Extended Abstract: Glass forming organic liquids and polymers exhibit long range density fluctuations with correlation length ξ in the range of 10–300 nm at temperatures above T_g (1 - 6). This follows from dynamic and static light scattering experiments revealing some unexpected features, which cannot be explained on the basis of conventional liquid state theories: (i) In static light scattering the intensity I(q → 0) is no longer proportional to the isothermal compressibility, (ii) This excess scattering I_exc shows a strong q-dependence (q = (4π/Λ.)sin(θ/2)) corresponding to a correlation length ξ in the above mentioned range, (iii) The Landau-Placzek ratio I_Rayleigh/2I_Brillouin is much too high compared with the results of light scattering theories, (iv) In photon correlation spectroscopy a new ultraslow hydrodynamic mode (Γ ˜ q²) is detected with relaxation rates Γ about 10⁻⁶ to 10⁻⁹ lower than those of the α-process at a given temperature. In order to explain these observations, a two-state fluid model is proposed, which starts from the coexistence of “liquid-like” and “aperiodic solid-like” regions within the liquids. Such ideas have been discussed many times before, so for example A.R. Ubbelohde (7) speculates about “anticrystalline” clusters in liquids. Molecular dynamics simulations of atomic liquids showed that long range orientational fluctuations appear upon supercooling (8). A preferred icosahedral ordering is observed (9) and the number of icosahedral clusters increases with decreasing temperature (10). In connection with the interpretation of the dynamics of supercooled liquids different “two-state” models have been proposed (11 - 15). For the explanation of the light scattering results we propose that the molecules in the different dynamic states (“liquid” or “solid”) aggregate during annealing of the liquid at temperatures above T_g. Experiments showed that the equilibration times can be rather long (3 - 5), but nevertheless the liquids exhibiting long range density fluctuations are in the state of lowest free energy. We claim that our observations are the first experimental proof of the existence of such different dynamic states, which have been discussed many times before. The extended secondary clusters can also be detected by ultra small angle X-ray scattering.     

Isolation and Characterization of Wax Esters in Fennel and Caraway Seed Oils by SPE-GC

A rapid method for the isolation and quantitative determination of wax esters in vegetable oils was developed. For the first time wax esters in oils were separated from the triglyceride matrix by means of solid-phase extraction, which allows rapid sample preparation in parallel and therefore a high sample throughput. The thus obtained wax ester fractions of fennel and caraway seed oils were analyzed by high temperature gas chromatography. GC-MS analyses were carried out using electron impact ionization in order to characterize the wax ester fraction. With respect to the results of the GC-MS analyses different isomers of saturated wax esters with the same carbon number were observed. Additional monounsaturated wax esters with an unsaturated fatty acid moiety were identified.     

Linking numbers in local quantum field theory

Linking numbers appear in local quantum field theory in the presence of tensor fields, which are closed two-forms on Minkowski space. Given any pair of such fields, it is shown that the commutator of the corresponding intrinsic (gauge-invariant) vector potentials, integrated about spacelike separated, spatial loops, are elements of the center of the algebra of all local fields. Moreover, these commutators are proportional to the linking numbers of the underlying loops. If the commutators are different from zero, the underlying two-forms are not exact (i.e. there do not exist local vector potentials for them). The theory then necessarily contains massless particles. A prominent example of this kind, due to J.E. Roberts, is given by the free electromagnetic field and its Hodge dual. Further examples with more complex mass spectrum are presented in this article.

     

Enhancing nucleation and controlling crystal orientation by rubbing/scratching the surface of a thin polymer film

We used the tip of an atomic force microscope (AFM) in the contact mode to scratch/rub the surface of a glassy polymer thin film, i.e., isotactic polystyrene (i-PS) at room temperature. After subsequent isothermal crystallization, an extremely high nucleation density of edge-on crystals within the rubbed region or at the edge of the scratched area was observed. Furthermore, a transition from edge-on to flat-on lamellae occurred beyond a certain distance from the edge of the scratched region. Our results demonstrate that both, soft rubbing or hard scratching, allow to lower the nucleation barrier for polymer crystallization and to control the orientation of the resulting crystalline lamellae. The role of scratching/rubbing on chain deformation and its relation to nucleation and crystal orientation in polymer thin films is discussed.     

Ultra-low background measurements of decayed aerosol filters

Aerosol samples collected on filter media were analyzed using HPGe detectors employing varying background-reduction techniques in order to experimentally evaluate the opportunity to apply ultra-low background measurement methods to samples collected, for instance, by the Comprehensive Test Ban Treaty International Monitoring System (IMS). In this way, realistic estimates of the impact of low-background methodology on the sensitivity obtained in systems such as the IMS were assessed. The current detectability requirement of stations in the IMS is 30 μBq/m³ of air for ¹⁴⁰Ba, which would imply ~10⁶ fissions per daily sample. Importantly, this is for a fresh aerosol filter. One week of decay reduces the intrinsic background from radon daughters in the sample allowing much higher sensitivity measurement of relevant isotopes, including ¹³¹I. An experiment was conducted in which decayed filter samples were measured at a variety of underground locations using Ultra-Low Background (ULB) gamma spectroscopy technology. The impacts of the decay and ULB are discussed.