Conformation of polyisobutylene in dilute solution subjected to a hydrodynamic shear field

A new light-scattering experiment which allows a direct determination of the conformation of macromolecules deformed in flow is described. Light-scattering relationships based on the interference function are developed, and results of an experimental study are detailed. The deformed conformation of high molecular weight polyisobutylene was determined in a Couette-type shear field. Decalin was the solvent. Variables investigated were the shear rate (0 to 600 sec^?1), the polymer molecular weight (1.0 × 10⁷ to 1.6 × 10⁷), and the polymer concentration (2.0 × 10^?4 to 8.0 × 10^?4 g/cc). Conformation variables determined were the orientation of the molecule in the shear field and its maximum and minimum extension ratios in the plane defined by the direction of flow and the direction of the shear rate. The deformation of the macromolecule was found to be markedly discrepant when compared to the dynamic macromolecular models which assume complete coil flexibility, and more closely in agreement with the recent theories of Cerf, developed for nonfree-draining coils which exhibit a finite internal viscosity.     

Nonequilibrium dynamics and superfluid ring excitations in binary Bose-Einstein condensates

We revisit a classic study [D. S. Hall, Phys. Rev. Lett. 81, 1539 (1998)10.1103/PhysRevLett.81.1539] of interpenetrating Bose-Einstein condensates in the hyperfine states |F=1,m{f}=-1 identical with |1 and |F=2,m{f}=+1 identical with |2 of 87Rb and observe striking new nonequilibrium component separation dynamics in the form of oscillating ringlike structures. The process of component separation is not significantly damped, a finding that also contrasts sharply with earlier experimental work, allowing a clean first look at a collective excitation of a binary superfluid. We further demonstrate extraordinary quantitative agreement between theoretical and experimental results using a multicomponent mean-field model with key additional features: the inclusion of atomic losses and the careful characterization of trap potentials (at the level of a fraction of a percent).     

Synthesis and characterization of the homologous M-M bonded series Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C6H3-2,6-(C6H3-2,6-Pr(i)2)2) and related arylmetal halides and hydride species

The synthesis and structural characterization of the first homologous, molecular M-M bonded series for the group 12 metals are reported. The compounds Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) were synthesized by reduction of the corresponding arylmetal halides by alkali metal/graphite (Zn or Hg) or sodium hydride (Cd). These compounds possess almost linear C-M-M-C core structures with two-coordinate metals. The observed M-M bonds distances were 2.3591(9), 2.6257(5), and 2.5738(3) A for the zinc, cadmium, and mercury species, respectively. The shorter Hg-Hg bond in comparison to that of Cd-Cd is consistent with DFT calculations which show that the strength of the Hg-Hg bond is greater. The arylmetal halides precursors (Ar'MI)(1 or 2), and the highly reactive hydrides (Ar'MH)(1 or 2), were also synthesized and fully characterized by X-ray crystallography (Zn and Cd) and multinuclear NMR spectroscopy. The arylzinc and arylcadmium iodides have iodide-bridged dimeric structures, whereas the arylmercury iodide, Ar'HgI, is monomeric. The arylzinc and arylcadmium hydrides have symmetric (Zn) or unsymmetric (Cd) mu-H-bridged structures. The Ar'HgH species was synthesized and characterized by spectroscopy, but a satisfactory refinement of the structure was precluded by the contamination of monomeric Ar'HgH by Ar'H. It was also shown that the decomposition of Ar'Cd(mu-H)(2)CdAr' at room temperature leads to the M-M bonded Ar'CdCdAr', thereby supporting the view that the reduction of the iodide proceeds via the hydride intermediate.     

Isomeric forms of heavier main group hydrides: experimental and theoretical studies of the [Sn(Ar)H]2 (Ar = terphenyl) system

A series of symmetric divalent Sn(II) hydrides of the general form [(4-X-Ar')Sn(mu-H)]2 (4-X-Ar' = C6H2-4-X-2,6-(C6H3-2,6-iPr2)2; X = H, MeO, tBu, and SiMe3; 2, 6, 10, and 14), along with the more hindered asymmetric tin hydride (3,5-iPr2-Ar*)SnSn(H)2(3,5-iPr2-Ar*) (16) (3,5-iPr2-Ar* = 3,5-iPr2-C6H-2,6-(C6H2-2,4,6-iPr3)2), have been isolated and characterized. They were prepared either by direct reduction of the corresponding aryltin(II) chloride precursors, ArSnCl, with LiBH4 or iBu2AlH (DIBAL), or via a transmetallation reaction between an aryltin(II) amide, ArSnNMe2, and BH3.THF. Compounds 2, 6, 10, and 14 were obtained as orange solids and have centrosymmetric dimeric structures in the solid state with long Sn...Sn separations of 3.05 to 3.13 A. The more hindered tin(II) hydride 16 crystallized as a deep-blue solid with an unusual, formally mixed-valent structure wherein a long Sn-Sn bond is present [Sn-Sn = 2.9157(10) A] and two hydrogen atoms are bound to one of the tin atoms. The Sn-H hydrogen atoms in 16 could not be located by X-ray crystallography, but complementary M?ssbauer studies established the presence of divalent and tetravalent tin centers in 16. Spectroscopic studies (IR, UV-vis, and NMR) show that, in solution, compounds 2, 6, 10, and 14 are predominantly dimeric with Sn-H-Sn bridges. In contrast, the more hindered hydrides 16 and previously reported (Ar*SnH)2 (17) (Ar* = C6H3-2,6-(C6H2-2,4,6-iPr3)2) adopt primarily the unsymmetric structure ArSnSn(H)2Ar in solution. Detailed theoretical calculations have been performed which include calculated UV-vis and IR spectra of various possible isomers of the reported hydrides and relevant model species. These showed that increased steric hindrance favors the asymmetric form ArSnSn(H)2Ar relative to the centrosymmetric isomer [ArSn(mu-H)]2 as a result of the widening of the interligand angles at tin, which lowers steric repulsion between the terphenyl ligands.     

Numerical modeling of compact high temperature heat exchanger and chemical decomposer for hydrogen production

The present study addresses fluid flow and heat transfer in a high temperature compact heat exchanger which will be used as a chemical decomposer in a hydrogen production plant. The heat exchanger is manufactured using fused ceramic layers that allow creation of channels with dimensions below 1 mm. The main purpose of this study is to increase the thermal performance of the heat exchanger, which can help to increase the sulfuric acid decomposition rate. Effects of various channel geometries of the heat exchanger on the pressure drop are studied as well. A three-dimensional computational model is developed for the investigation of fluid flow and heat transfer in the heat exchanger. Several different geometries of the heat exchanger channels, such as straight channels, ribbed ground channels, hexagonal channels, and diamond-shaped channels are examined. Based on the results, methods on how to improve the design of the heat exchanger are recommended.     

Aluminum combustion in a solid rocket motor environment

A model for prediction of particle radius and oxide cap size/shape versus time for an aluminum particle tracking a stream-tube through a solid rocket motor port has been developed. Following preliminary calculations leading to a postulated flame structure, a quasi-steady model to predict instantaneous consumption of aluminum and generation of condensed oxide (both as a cap on the aluminum particle and as smoke) as a function of instantaneous particle size, ambient conditions, and cumulative amount of oxide in the cap was developed. Finally, this model was imbedded into a framework tracking evolution of particle size, oxide cap size, and ambient conditions, which change as the particle travels along a stream-tube consuming oxidizer and releasing heat. Qualitative agreement was found between predictions and limited observations.     

Admittance as a useful tool for investigation of solute–solvent interactions at the double layer

The application of admittance measurements, an often neglected topic in impedance spectroscopy, to further our understanding of solute–solvent interactions at the double layer is presented by comparing aqueous solutions of sodium acetate and protonated lidocaine acetate. Unlike impedance, the overlap of concentration-dependent hydration cospheres and the potential- and frequency-dependent orientation effects of water molecules around the ions at or near the double layer could be manifested in admittance data. Admittance, but not impedance, also allows identification of interactions between two dipoles, such as amino and carbonyl groups, by changing frequencies and applied potentials. The effects manifest themselves by exhibiting cathodic and anodic shifts with frequency changes. All the admittance data could be reasonably explained by utilizing the concept of “potential induced and water structure-enforced ion-pair formation”.     

Generalized filters, the low-pass condition, and connections to multiresolution analyses

We study generalized filters that are associated to multiplicity functions and homomorphisms of the dual of an abelian group. These notions are based on the structure of generalized multiresolution analyses. We investigate when the Ruelle operator corresponding to such a filter is a pure isometry, and then use that characterization to study the problem of when a collection of closed subspaces, which satisfies all the conditions of a GMRA except the trivial intersection condition, must in fact have a trivial intersection. In this context, we obtain a generalization of a theorem of Bownik and Rzeszotnik.