On the origin of the hole pressure

Summary One wall of a slit die apparatus contains a slot filled with the test liquid. Photographs of marked streamlines near the slot mouth show a pronounced curvature. A 0.5% aqueous solution of Separan AP 30 and molten polystyrene and polyethylene were investigated at low values of Reynolds number (Re < 1.0). In each case, streamlines are convex towards the slot mouth. This supports the hypothesis ofTanner andPipkin which attributes hole pressures in flowing viscoelastic liquids to the combined effect of holegenerated streamline curvature and shear-generated normal stress differences.

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Zusammenfassung In einer der Wände einer Schlitzdüsenvorrichtung ist eine mit Testflüssigkeit gefüllte Quernut angebracht. Es wurde die Strömung einer 0,5%-igen wässerigen Separan AP 30-Lösung, sowie einer Polystyrol- und einer Polyäthylenschmelze bei kleinen Reynoldszahlen (Re < 1.0) untersucht. In allen Fällen waren die Stromlinien konvex, also zur Schlitzmündung hin gekrümmt. Dadurch wird die Hypothese vonTanner andPipkin unterstützt, wonach die Lochdrücke in strömenden viskoelastischen Flüssigkeiten als Wirkung der durch die Scherung erzeugten Normalspannungsdifferenzen auf die gekrümmten Stromlinien erklärt werden.

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Department of Engineering Mechanics.

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Material Science Program.

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With 4 figures     

Flow development of xanthan solutions in capillary rheometers

Flow experiments through capillaries with 0.2% xanthan in aqueous solution and 0.1 N NaCl brine were carried out to study the influence of the molecular conformation on the flow development at relatively low shear rates, from 20s^–1 to 400s^–1. Capillaries with a wide range of length-to-diameter ratios, L/D = 4.5 to 1015 were used.The apparent viscosity as a function of L/D at a constant shear rate shows a continuous decrement of the viscosity as L/D increases, until an asymptotic value is reached. The decrement in the apparent viscosity is partially explained in terms of slip. It was found that slip is a function of L/D as well as shear stress, i.e., slip develops during flow, thus inducing spatial anisotropy in the fluid until a stable state is reached. However, the substantial difference in apparent viscosity between short capillaries and capillaries longer than 300 D may be attributed to dominant elongational flow due to the contraction in the small capillaries and slip in long capillaries.The flow in a sufficiently long capillary can be divided in four regions rather than three, as is usually assumed. In the first region, which corresponds to the entry, elongational and shear flow coexist and elongational flow dominant. In the second region, end effects and slip development are coupled. In the third region the flow is fully developed and end effects are negligible. However, the fluid shows physical characteristics different from those of the fluid at rest, as a consequence of prior slip development. The fourth zone is the exit region in which the velocity rearranges due to the change of boundary conditions. The length of each region depends on the conformation of the macromolecules and shear rate. In addition, it was found that the stiffness of xanthan increases with the increase of the ionic strength.Finally, a performance of Bagley's analysis in the whole range of L/D studied showed that the use of the Bagley correction is not a reliable way to correct for end effects when the flow is not fully developed and/or in the presence of slip.Dedicated to Arthur S. Lodge at the occasion of his 70th birthday and his retirement from the University of Wisconsin.     

Identification of a Lead Candidate in the Search for Carbene‐Stabilised Homoaromatics

The effect of carbenes as Lewis donor groups on the homoaromaticity of mono‐ and bicyclic organic molecules is surveyed. The search for viable carbene‐stabilised homoaromatics resulted in a large amount of rejected candidates as well as nine promising candidates that are further analysed for their homoaromaticity by using a number of metrics. Of these, five appeared to show modest homoaromaticity, whereas another compound showed a level of homoaromaticity comparable with the homotropylium cation benchmark compound. Isoelectronic analogues and constitutional isomers of the lead compound were investigated, however, none of these showed comparable homoaromaticity. The implications of these calculations on the design of donor‐stabilised homoaromatics are discussed.     

Ethanol Production from Residual Wood Chips of Cellulose Industry: Acid Pretreatment Investigation,Hemicellulosic Hydrolysate Fermentation,and Remaining Solid Fraction Fermentation by SSF Process

Current research indicates the ethanol fuel production from lignocellulosic materials, such as residual wood chips from the cellulose industry, as new emerging technology. This work aimed at evaluating the ethanol production from hemicellulose of eucalyptus chips by diluted acid pretreatment and the subsequent fermentation of the generated hydrolysate by a flocculating strain of Pichia stipitis. The remaining solid fraction generated after pretreatment was subjected to enzymatic hydrolysis, which was carried out simultaneously with glucose fermentation [saccharification and fermentation (SSF) process] using a strain of Saccharomyces cerevisiae. The acid pretreatment was evaluated using a central composite design for sulfuric acid concentration (1.0–4.0 v/v) and solid to liquid ratio (1:2–1:4, grams to milliliter) as independent variables. A maximum xylose concentration of 50 g/L was obtained in the hemicellulosic hydrolysate. The fermentation of hemicellulosic hydrolysate and the SSF process were performed in bioreactors and the final ethanol concentrations of 15.3 g/L and 28.7 g/L were obtained, respectively.     

Intramolecular N to N acyl migration in conformationally mobile 1′-acyl-1-benzyl-3′,4′-dihydro-1′<Emphasis Type="Italic">H</Emphasis>-spiro[piperidine-4,2′-quinoline] systems promoted by debenzylation conditions (HCOONH<Subscript>4</Subscript>/Pd/C)

We report an efficient and useful synthesis of new attractive spiropiperdine scaffolds 4 based on an intramolecular acyl transfer process in 1′-acyl-1-benzyl-3′,4′-dihydro-1′H-spiro[piperidine-4,2′-quinolines] 3 using simple and mild debenzylation reaction conditions (HCOONH₄/Pd/C). The compounds 3 were prepared by acylating 1-benzyl-4′-methyl-3′,4′-dihydro-1′H-spiro[piperidine-4,2′-quinolines] 2 that are easily available from 1-benzyl-4-piperidone 1. The intramolecular character of this process was proven primarily through a crossover experiment technique. Through an examination of all spectroscopic information (¹H, ¹³C NMR, VT-¹H NMR, and ²D NMR) it was possible to correctly predict amide configurations and piperidine ring conformations of starting and final spiropiperidine compounds.      

Invariant Measures for Cherry Flows

We investigate the invariant probability measures for Cherry flows, i.e. flows on the two-torus which have a saddle, a source, and no other fixed points, closed orbits or homoclinic orbits. In the case when the saddle is dissipative or conservative we show that the only invariant probability measures are the Dirac measures at the two fixed points, and the Dirac measure at the saddle is the physical measure. In the other case we prove that there exists also an invariant probability measure supported on the quasi-minimal set, we discuss some situations when this other invariant measure is the physical measure, and conjecture that this is always the case. The main techniques used are the study of the integrability of the return time with respect to the invariant measure of the return map to a closed transversal to the flow, and the study of the close returns near the saddle.     

Electrical conductivity relaxation in PVOH+LiH2PO4+Al2O3 polymer composites

Low-frequency conductivity measurements have been performed in solid polymer electrolyte composites based on the anhydrous PVOH–LiH₂PO₄–Al₂O₃ system. A typical power law dependency in the real part of the conductivity, at higher frequencies, of the form ω ⁿ is observed, with an exponent n that depends on the alumina content and nearly independent of temperature. An analysis of the frequency dependence of the electrical susceptibility is conducted to obtain relaxation functions of the form exp[?(t/τ) ^β ], with an exponent β?≈?n???1. Correlation times, τ, and parameters characterizing the electrical relaxation in time and frequency domains are compared to show the equivalence of these representations. The anhydrous dc conductivity of the electrolytes increases with increasing lithium salt content, becoming of the order of 10^?5 S/cm for a salt molar fraction of x?=?0.14. This conductivity value increased by about one order of magnitude by addition of nanoporous particles of Al₂O₃. The temperature dependence of the samples conductivity was well described by the Vogel–Tammann–Fulcher’s equation indicating the effect of the polymer chains flexibility on ion migration. Although all membranes exhibited a “universal dynamic response” associated to the random hopping of the mobile carriers, variations in the measured relaxation parameters with alumina content indicate an increase of ionic correlations when adding the nonporous particles to the polyelectrolyte.     

On the use of the photoacoustic technique for the measurement of the thermomechanical properties of semiconductor two-layer systems

The photoacoustic technique is used in semiconductor two-layer systems for the determination of thermal properties and thermal expansion coefficient. The two-layer systems studied were amorphous silicon-glass and Al_0.2Ga_0.8As---GaAs. Our results show that the proposed method is a reliable technique for the characterization of other semiconductor two-layers systems.