On the dynamics of polymers in dense systems – Results of neutron spin echo spectroscopy

One of the basic problems in the dynamics of polymers concerns the importance of geometrical or topological interactions which are directly related to the large scale molecular structures. In the famous reptation model these constraints are pictured in terms of a tube of localization following the average chain profile and confining the chain motion to the curve‐linear tube. Recently studying the dynamic structure factor of a single labeled chain in a polymer melt by means of neutron spin echo spectroscopy (NSE) led to a direct observation of these tube constraints. Here I shall summarize these neutron spin echo experiments. I shall address the NSE technique, present results on the entropy driven segmental chain dynamics, discuss the dynamics of single chains in the melt where the chain length is increased through the transition to “reptation” dynamics and display NSE measurements on long chain systems which revealed the molecular existence of the entanglement distance. Their magnitudes agree very well with tube diameters derived from dynamical mechanical measurements on the basis of the reptation model proving thereby the basic assumption of this Nobel Price winning concept. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of dimethylditritiogermane Me<Subscript>2</Subscript>GeT<Subscript>2</Subscript>

A microsynthetic procedure for preparing tritium-labeled alkyl-substituted germanes is developed. The resulting dimethylditritiogermane can be used as a source of dimethylgermylium ions. The synthesis was performed by the reduction of dibromodimethylgermane with lithium tritide in presence of AlBr₃.     

Radio-Frequency Hexamethyldisiloxane Plasma Deposition: A Comparison of Plasma- and Deposit-Chemistry

This study reports on the effect of input power to hexamethyldisiloxane (HMDSO) plasmas. The power dependence of the plasma-phase species and of the surface chemistry (of the deposits) has been investigated. Neutral and positive molecular species were detected within the plasma using mass spectrometry (MS). Secondary ion mass spectrometry (SIMS) was used to probe the molecular structure of the deposits. The elemental composition of the surface was determined by XPS and the deposition rate was monitored using a vibrating quartz crystal microbalance. Neutral and cationic molecules of mass greater than HMDSO were detected in the plasma. Their formation through ion-molecule reactions is proposed. Changes in the relative concentration of plasma-phase species follow those seen in molecular species detected at the deposit surface. Thus, we believe that the molecular structure of the deposits can be related to the species present in the plasma. While traditionally the dominant mechanism in deposit formation is assumed to be free radical combinations, we propose other possibilities involving cations with the aim of putting forward a new perspective on plasma polymerization mechanisms and thereby stimulating discussion.     

Spectroscopic investigation of 4f correlations in CeAg; comparison between LDA and many-body descriptions

High resolution photoemission and bremsstrahlung isochromat spectroscopy experiments have been carried out on CeAg and LaAg. From a comparison between these two compounds, we extract the cerium 4f spectral function, we compare it with band structure calculations and with many-body model simulations based on the single-impurity Anderson Hamiltonian. We show that the localized 4f charge estimated from previous band structure calculations cannot be identified with the 4f occupation number deduced from the Anderson model.     

Static polarizabilities for the ne-isoelectronic series using Harbola–Sahni potential

The recently proposed Harbola–Sahni local potential in its exchange-only version [Phys. Rev. Lett. 62 , 689 (1989)] is found to give the static dipole and quadrupole polarizabilities for the Neisoelectronic series in excellent agreement with the corresponding Hartree–Fock estimates. © 1992 John Wiley & Sons, Inc.     

A novel approach to thermal Analysis of Thin films

A novel instrument is described called the Thin film Analyser (TFA) which quantitatively measures changes in mechanical and rheological properties of drying films in-situ on a test panel. It is based around a simple force-sensing device, capable of carrying various probes, which can be positioned in anX-Y plane over the panel. Temperature control is achieved by means of a heating block under the sample. By imposing a thermal gradient along the block, measurements can be obtained at a series of temperatures in a single experiment. Several applications of the TFA to the drying of curable and latex-based coatings are discussed, as well as some more specialized uses. The TFA concept represents a novel approach to the thermal analysis of thin films.The authors gratefully acknowledge the design, engineering and software development work of the Instrument Group at ICI Paints, in particular John Hayton, Neil Burrows, Tony Evans and Ian Francis, who have now built three versions of the TFA.     

Synthesis of sterically hindered aromatic dialdehydes

A study was carried out on the formylation of a series of aromatic compounds containing two mesitylene or durene residues [dimesityl (I), dimesitylmethane (II), 1,2-dimesitylethane (III), 1,6-dimesitylhexane (IV), dimesityl sulfide (V), 1,1-dimesitylethylene (VI), 1,1-dimesityl-1-butene (VII), and didurylmethane (VIII)] by the action of dichloromethyl methyl ether (DCM) in the presence of A1C1₃ and TiCl₄. The corresponding dialdehydes are the major products. The formylation products when the reaction is carried out in the presence of A1C1₃ in the case of (I) and (V) contain significant amounts of monoaldehydes, while partial cleavage of the substrates with the formation of products containing only one benzene ring is observed in the case of (II) and (VIII) in addition to formylation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1700–1703, July, 1991.     

Multiparameter Polynomial Adaptive Stabilizers

In 1983 Morse proved, for unknown scalar one-dimensional linearsystems, the nonexistence of rational or polynomial universalstabilizers (UAS). In 1983, Nussbaum gave an example of an analyticUAS. In our paper, it is shown that there exist time-invariantpolynomial UAS's with multidimensional gain adaptation. Thedesign procedure is developed for linear, minimum-phase systemsof relative degree one. Convergence of the closed-loop systemis proved. Some numerical simulations are provided.