Dynamics of propylene glycol and its oligomers confined in clay

The dynamics of propylene glycol (PG) and its oligomers 7-PG and PPG, with (about 70 monomers), confined in a Na-vermiculite clay have been investigated by quasi-elastic neutron scattering and dielectric spectroscopy. The liquids are confined to a single molecular layer between the clay platelets, thus giving a true 2D liquid. The results show that the average relaxation time , deduced from neutron scattering at a momentum transfer Q of about , is in perfect agreement with the dielectric -relaxation time, although neutron scattering does not only probe the main ( -) relaxation, but all motions of hydrogens on the experimental time scale. At room temperature is proportional to Q ², indicating that the relaxations are mainly due to ordinary translational diffusion. The most unexpected finding is that (or the dielectric -relaxation time) is almost unaffected by the 2D confinement, in contrast to the dielectrically active normal mode of PPG which is substantially slower in the confinement. Only the 7-mer has a significantly slower segmental translational diffusion in the clay. The results suggest that the interactions to the clay surfaces are weak and that the present 2D confinement has a very small influence on the time scale of all our observed relaxation processes, except the normal-mode relaxation.Received: 1 January 2003, Published online: 8 October 2003PACS: 61.25.Em Molecular liquids - 68.35.Ja Surface and interface dynamics and vibrations - 61.12.-q Neutron diffraction and scattering     

Dielectric relaxation studies of poly(propylene glycol) confined in vermiculite clay

The molecular dynamics of oligomeric poly(propylene glycol) (PPG) liquids (M(w)=1200, 2000 and 4000 g/mol) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy. In addition to the alpha-relaxation, the normal mode relaxation process was studied for all samples both in bulk and confinement. For the normal mode process the relaxation rate in the clay is drastically shifted to lower frequencies compared to that of the bulk material in contrast to the alpha-process whose relaxation time is only slightly affected by the confinement. Also the temperature dependence of the relaxation time for the normal mode process is strongly affected by the confinement. Moreover, in the clay the intensity of the normal mode is stronger than that of the alpha-process, in contrast to the bulk samples where the opposite is observed.     

Does confined water exhibit a fragile-to-strong transition?

The dynamics of supercooled confined water has recently been shown to have a pronounced, apparent fragile-to-strong transition (FST). Here we use broadband dielectric spectroscopy (10^-2–10⁹ Hz) to study the dynamics of water confined in silica matrices MCM-41 C10 and C18, with pore diameter of 21.4 and 36.1 ?, respectively. The local dynamics of water molecules and the dynamics of the hydroxyl groups on the inner wall of the pores are followed up to over 240 K. We argue that the reported FST for confined water is due to the vanishing of the cooperative α relaxation, which implies that it should not be interpreted as a true FST.     

Partially ordered sets,and minimal systems of counterexamples

Given a finite setA with a partial ordering, in which certain order relations are known to hold, there is a least set of non-relations that must be established to conclude that no relations hold other than the known ones. This set of test cases can be cut down further if algebraic structure is involved. These observations generalize arguments used by Pigozzi and others in studying finite semigroups of operators on classes of algebras.Dedicated to Bjarni Jonsson on his 70th birthdayPresented by G. McNulty.This work was done while the author was partly supported by NSF contracts MCS 82-02632 and DMS 85-02330.     

Encapsulation of cationic ruthenium complexes into a chiral self-assembled cage

A chiral supramolecular assembly encapsulates the two cationic ruthenium sandwich complexes [CpRu(eta(6)-C(6)H(6))](+) and [CpRu(p-cymene)](+). The host-guest complexes K(11)[CpRu(eta(6)-C(6)H(6)) subset Ga(4)L(6)] (2) and K(11)[CpRu(p-cymene) subset Ga(4)L(6)] (3) were characterized by one- and two-dimensional NMR techniques as well as by electrospray mass spectrometry. Encapsulation of the prochiral complex [CpRu(p-cymene)](+) by the chiral host renders enantiotopic protons diastereotopic as evidenced by (1)H NMR spectroscopy.     

Proton-catalyzed hydroamination and hydroarylation reactions of anilines and alkenes: a dramatic effect of counteranions on reaction efficiency

The anilinium salt, [PhNH3][B(C6F5)4], has been identified as a catalyst for the hydroamination and hydroarylation of several different types of alkenes with anilines. The weakly coordinating counterion of this acid plays a key role in this transformation. The reaction is facile for styrenes and tolerates norbornene, cyclic alkenes, and cyclohexadiene. Selectivity between hydroamination and hydroarylation products can be tuned using reaction time, temperature, and substrate substitution. Details regarding the substrate scope and selectivity of this hydroamination/hydroarylation reaction are discussed.     

Characterization of the carrot defect in 4H-SiC epitaxial layers

Characterization of the epitaxial defect known as the carrot defect was performed in thick 4H-SiC epilayers. A large number of carrot defects have been studied using different experimental techniques such as Nomarski optical microscopy, KOH etching, cathodoluminescence and synchrotron white beam X-ray topography. This has revealed that carrot defects appear in many different shapes and structures in the epilayers. Our results support the previous assignment of the carrot defect as related to a prismatic stacking fault. However, we have observed carrot defects with and without a visible threading dislocation related etch pit in the head region, after KOH etching. Polishing of epilayers in a few μm steps in combination with etching in molten KOH and imaging using Nomarski optical microscope has been used to find the geometry and origin of the carrot defects in different epilayers. The defects were found to originate both at the epi-substrate interface and during the epitaxial growth. Different sources of the carrot defect have been observed at the epi-substrate interface, which result in different structures and surfaces appearance of the defect in the epilayer. Furthermore, termination of the carrot defect inside the epilayer and the influence of substrate surface damage and growth conditions on the density of carrot defects are studied.     

An efficient iterative method for finding common fixed point and variational inequalities in Hilbert spaces

ABSTRACT

In this paper, we investigate the problem of finding a common solution to a fixed point problem involving demi-contractive operator and a variational inequality with monotone and Lipschitz continuous mapping in real Hilbert spaces. Inspired by the projection and contraction method and the hybrid descent approximation method, a new and efficient iterative method for solving the problem is introduced. Strong convergence theorem of the proposed method is established under standard and mild conditions. Our scheme generalizes and extends some of the existing results in the literature, and moreover, its computational effort is less per each iteration compared with related works.