Dilute solution properties of methyl methacrylate—acrylonitrile copolymer (MA2)

This article deals with studies of the dilute solution properties of methyl methacrylate-acrylonitrile (MMA-AN) copolymer of 0.415 mole fraction (mf) of acrylonitrile composition. Mark—Houwink parameters for this copolymer have been evaluated in acetonitrile (MeCN), 2-butanone (MEK), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL). The Mark-Houwink exponent a in all four solvents at all temperatures is larger than the corresponding values of the parent homopolymers. The solvent power is in the order of DMF < γ–BL < MEK < MeCN; [η] decreases with an increase in temperature, which is behavior characteristic of polymers in good solvent. The unperturbed dimensions (K0) values, obtained by the Stockmayer–Fixman method, are lower than those for the parent homopolymers and depend on solvent as well as temperature. The solute—solvent interaction parameter X1 values are close to 0.5; X1 is independent of temperature. The excess interaction parameter XABvalues are negative. The results for this copolymer system in regard to low second virial coefficient A2, large X1, and high a values suggest that the large extension of these copolymer chains is due to the unusual short-range interactions.

The effect of structure on the dilute solution properties of branched polysaccharides studied with SEC and AsFlFFF

Cereal arabinoxylans, guar galactomannans, and dextrans produced by lactic acid bacteria(LAB) are a structurally diverse group of branched polysaccharides with nutritional and industrial functions. In this thesis, the effect of the chemical structure on the dilute solution properties of these polysaccharides was investigated using size-exclusion chromatography(SEC) and asymmetric flow field-flow fractionation (AsFlFFF) with multiple-detection. The chemical structures of arabinoxylans were determined, whereas galactomannan and dextran structures were studied in previous investigations. Characterization of arabinoxylans revealed differences in the chemical structures of cereal arabinoxylans. Although arabinoxylans from wheat, rye, and barley fiber contained similar amounts of arabinose side units, the substitution pattern of arabinoxylans from different cereals varied. Arabinoxylans from barley husks and commercial low-viscosity wheat arabinoxylan contained a lower number of arabinose side units. Structurally different dextrans were obtained from different LAB. The structural effects on the solution properties could be studied in detail by modifying pure wheat and rye arabinoxylans and guar galactomannan with specific enzymes. The solution characterization of arabinoxylans, enzymatically modified galactomannans, and dextrans revealed the presence of aggregates in aqueous polysaccharide solutions. In the case of arabinoxylans and dextrans, the comparison of molar mass data from aqueous and organic SEC analyses was essential in confirming aggregation, which could not be observed only from the peak or molar mass distribution shapes obtained with aqueous SEC. The AsFlFFF analyses gave further evidence of aggregation. Comparison of molar mass and intrinsic viscosity data of unmodified and partially debranched guar galactomannan, on the other hand, revealed the aggregation of native galactomannan. The arabinoxylan and galactomannan samples with low or enzymatically extensively decreased side unit content behaved similarly in aqueous solution: lower molar mass samples stayed in solution but formed large aggregates, whereas the water solubility of the higher-molar-mass samples decreased significantly. Due to the restricted solubility of galactomannans in organic solvents, only aqueous galactomannan solutions were studied. The SEC and AsFlFFF results differed for the wheat arabinoxylan and dextran samples. Column matrix effects and possible differences in the separation parameters are discussed, and a problem related to the non-established relationship between the separation parameters of the two separation techniques is highlighted. This thesis shows that complementary approaches in the solution characterization of chemically heterogeneous polysaccharides are needed to comprehensively investigate macromolecular behavior in solution. These results may also be valuable when characterizing other branched polysaccharides.

Solubility of sulfur dioxide at low partial pressures in dilute sulfuric acid solutions

Equilibrium of dissolution of sulfur dioxide at ppm levels in aqueous solutions of dilute sulfuric acid is analyzed, and a general expression is derived relating the total concentration of sulfur dioxide in the liquid phase to the partial pressure of SO2 in the gas and to the concentration of sulfuric acid in the solution. The equation is simplified for zero and high concentrations of the acid. Experiments at high concentrations of sulfuric acid have enabled the direct determination of Henry’s constant and its dependency on temperature. Heat of dissolution is -31.47 kJ/mol. Experiments in the absence of sulfuric acid and the related simplified expression have led to the determination of the equilibrium constant of the hydrolysis of aqueous sulfur dioxide and its temperature dependency.The heat of hydrolysis is 15.69 kJ/mol. The model equation with these parameters predicts the experimental data of the present work as well as the reported data very well.

Non-Linear effects of membrane fluctuations in the dilute lamellar phase

The static structure factor of the dilute sterically stabilised lamellar phase is calculated and found to have an Ornstein-Zernike form with a correlation length that diverges at infinite dilution. The relaxation time for concentration fluctuations at large wave number q is shown to go as q-3 with a coefficient independent of the membrane bending rigidity. The membrane fluctuations also give rise to strongly frequency-dependent viscosities at high frequencies.

Correlation of resistivity and microstructure in dilute titaniulll–nitrogen alloy

The precipitation kinetics of the quenched dilute Ti-1.6 at.-%N alloy has been followed by resistivity measurements at 77 K using the four probe method. Resistivity behaviour has been studied for various durations for the alloys aged in the temperature range 273-373 K. The resistivity behaviour has been explained on the basis of the growth and decay of interfacial strain fields associated with the precipitation process. In addition, the resistivity changes have been correlated with transmission electron microscopy observations. (C) 1995 The Institute of Materials.

Stereospecific construction of stereogenic vicinal quaternary carbon atoms. Enantiospecific synthesis of (+)-valerane

Stereo- and enantiospecific synthesis of (+)-valerane starting from R-carvone utilising orthoester Claisen rearrangement and intramolecular diazo ketone cyclopropanation reactions for the construction of the two vicinal quaternary carbon atoms is described. Copyright (C) 1996 Elsevier Science Ltd.

The concentration dependent cooperative friction coefficient of dilute polymer solutions at the theta point

We combine multiple scattering and renormalization group methods to calculate the leading order dimensionless virial coefficient k(s) for the friction coefficient of dilute polymer solutions under conditions where the osmotic second virial coefficient vanishes (i.e., at the theta point T-theta). Our calculations are formulated in terms of coupled kinetic equations for the polymer and solvent, in which the polymers are modeled as continuous chains whose configurations evolve under the action of random forces in, the velocity field of the solvent. To lowest order in epsilon=4-d, we find that k(s) = 1.06. This result compares satisfactorily with existing experimental estimates of k(s), which are in the range 0.7-0.8. It is also in good agreement with other theoretical results on chains and suspensions at T-theta. Our calculated k(s) is also found to be identical to the leading order virial coefficient of the tracer friction coefficient at the theta point. We discuss possible reasons for the difficulties encountered when attempting to evaluate k(s) by extrapolating prior renormalization group calculations from semidilute concentrations to the infinitely dilute limit. (C) 1996 American Institute of Physics.

Discontinuous shear thickening in confined dilute carbon nanotube suspensions

A monotonic decrease in viscosity with increasing shear stress is a known rheological response to shear flow in complex fluids in general and for flocculated suspensions in particular. Here we demonstrate a discontinuous shear-thickening transition on varying shear stress where the viscosity jumps sharply by four to six orders of magnitude in flocculated suspensions of multiwalled carbon nanotubes (MWNT) at very low weight fractions (approximately 0.5%). Rheooptical observations reveal the shear-thickened state as a percolated structure of MWNT flocs spanning the system size. We present a dynamic phase diagram of the non-Brownian MWNT dispersions revealing a starting jammed state followed by shear-thinning and shear-thickened states. The present study further suggests that the shear-thickened state obtained as a function of shear stress is likely to be a generic feature of fractal clusters under flow, albeit under confinement. An understanding of the shear-thickening phenomena in confined geometries is pertinent for flow-controlled fabrication techniques in enhancing the mechanical strength and transport properties of thin films and wires of nanostructured composites as well as in lubrication issues.

Velocity distribution function for a dilute granular material in shear flow

The velocity distribution function for the steady shear flow of disks (in two dimensions) and spheres (in three dimensions) in a channel is determined in the limit where the frequency of particle-wall collisions is large compared to particle-particle collisions. An asymptotic analysis is used in the small parameter epsilon, which is naL in two dimensions and na(2)L in three dimensions, where; n is the number density of particles (per unit area in two dimensions and per unit volume in three dimensions), L is the separation of the walls of the channel and a is the particle diameter. The particle-wall collisions are inelastic, and are described by simple relations which involve coefficients of restitution e(t) and e(n) in the tangential and normal directions, and both elastic and inelastic binary collisions between particles are considered. In the absence of binary collisions between particles, it is found that the particle velocities converge to two constant values (u(x), u(y)) = (+/-V, O) after repeated collisions with the wall, where u(x) and u(y) are the velocities tangential and normal to the wall, V = (1 - e(t))V-w/(1 + e(t)), and V-w and -V-w, are the tangential velocities of the walls of the channel. The effect of binary collisions is included using a self-consistent calculation, and the distribution function is determined using the condition that the net collisional flux of particles at any point in velocity space is zero at steady state. Certain approximations are made regarding the velocities of particles undergoing binary collisions :in order to obtain analytical results for the distribution function, and these approximations are justified analytically by showing that the error incurred decreases proportional to epsilon(1/2) in the limit epsilon --> 0. A numerical calculation of the mean square of the difference between the exact flux and the approximate flux confirms that the error decreases proportional to epsilon(1/2) in the limit epsilon --> 0. The moments of the velocity distribution function are evaluated, and it is found that [u(x)(2)] --> V-2, [u(y)(2)] similar to V-2 epsilon and -[u(x)u(y)] similar to V-2 epsilon log(epsilon(-1)) in the limit epsilon --> 0. It is found that the distribution function and the scaling laws for the velocity moments are similar for both two- and three-dimensional systems.

Rearrangement approaches to sesquiterpenes containing multiple contiguous quaternary carbon atoms. Total synthesis of (+/-)-myltayl-8(12)-ene and (+/-)-6-epijunicedranol

Details of the first total syntheses of the sesquiterpenes myltayl-8(12)-ene and 6-epijunicedran-8-ol are described. The aldehyde 13, obtained by Claisen rearrangement of cyclogeraniol, was transformed into the dienones 12 and 18. Boron trifluoride-diethyl ether mediated cyclization and rearrangement transformed the dienones 12 and 18 into the tricyclic ketones 16 and 17, efficiently creating three and four contiguous quaternary carbon atoms, respectively. Wittig methylenation of 16 furnished (+/-)-myltayl-8(12)-ene (11), whereas reduction of the ketone 17 furnished (+/-)-6-epijunicedranol (23).

Velocity distribution for a dilute vibrated granular material

The velocity distribution for a vibrated granular material is determined in the dilute limit where the frequency of particle collisions with the vibrating surface is large compared to the frequency of binary collisions. The particle motion is driven by the source of energy due to particle collisions with the vibrating surface, and two dissipation mechanisms-inelastic collisions and air drag-are considered. In the latter case, a general form for the drag force is assumed. First, the distribution function for the vertical velocity for a single particle colliding with a vibrating surface is determined in the limit where the dissipation during a collision due to inelasticity or between successive collisions due to drag is small compared to the energy of a particle. In addition, two types of amplitude functions for the velocity of the surface, symmetric and asymmetric about zero velocity, are considered. In all cases, differential equations for the distribution of velocities at the vibrating surface are obtained using a flux balance condition in velocity space, and these are solved to determine the distribution function. It is found that the distribution function is a Gaussian distribution when the dissipation is due to inelastic collisions and the amplitude function is symmetric, and the mean square velocity scales as [[U-2](s)/(1 - e(2))], where [U-2](s) is the mean square velocity of the vibrating surface and e is the coefficient of restitution. The distribution function is very different from a Gaussian when the dissipation is due to air drag and the amplitude function is symmetric, and the mean square velocity scales as ([U-2](s)g/mu(m))(1/(m+2)) when the acceleration due to the fluid drag is -mu(m)u(y)\u(y)\(m-1), where g is the acceleration due to gravity. For an asymmetric amplitude function, the distribution function at the vibrating surface is found to be sharply peaked around [+/-2[U](s)/(1-e)] when the dissipation is due to inelastic collisions, and around +/-[(m +2)[U](s)g/mu(m)](1/(m+1)) when the dissipation is due to fluid drag, where [U](s) is the mean velocity of the surface. The distribution functions are compared with numerical simulations of a particle colliding with a vibrating surface, and excellent agreement is found with no adjustable parameters. The distribution function for a two-dimensional vibrated granular material that includes the first effect of binary collisions is determined for the system with dissipation due to inelastic collisions and the amplitude function for the velocity of the vibrating surface is symmetric in the limit delta(I)=(2nr)/(1 - e)much less than 1. Here, n is the number of particles per unit width and r is the particle radius. In this Limit, an asymptotic analysis is used about the Limit where there are no binary collisions. It is found that the distribution function has a power-law divergence proportional to \u(x)\((c delta l-1)) in the limit u(x)-->0, where u(x) is the horizontal velocity. The constant c and the moments of the distribution function are evaluated from the conservation equation in velocity space. It is found that the mean square velocity in the horizontal direction scales as O(delta(I)T), and the nontrivial third moments of the velocity distribution scale as O(delta(I)epsilon(I)T(3/2)) where epsilon(I) = (1 - e)(1/2). Here, T = [2[U2](s)/(1 - e)] is the mean square velocity of the particles.

Nature and strength of C-H center dot center dot center dot O interactions involving formyl hydrogen atoms: computational and experimental studies of small aldehydes

Structural and electronic properties of C-H center dot center dot center dot O contacts in compounds containing a formyl group are investigated from the perspective of both hydrogen bonding and dipole-dipole interactions, in a systematic and graded approach. The effects of a-substitution and self-association on the nature of the formyl H-atom are studied with the NBO and AIM methodologies. The relative dipole-dipole contributions in formyl C-H center dot center dot center dot O interactions are obtained for aldehyde dimers. The stabilities and energies of aldehyde clusters (dimer through octamer) have been examined computationally. Such studies have an implication in crystallization mechanisms. Experimental X-ray crystal structures of formaldehyde, acrolein and N-methylformamide have been determined in order to ascertain the role of C-H center dot center dot center dot O interactions in the crystal packing of formyl compounds.

Quasichemical equations for oxygen and sulphur in liquid binary alloys

An equation has been derived for predicting the activity coefficient of oxygen or sulphur in dilute solution in binary alloys, based on the quasichemical approach, where the metal atoms and the oxygen atoms are assigned different bond numbers. This equation is an advance on Alcock and Richardson's earlier treatment where all the three types of atoms were assigned the same coordination number. However, the activity coefficients predicted by this new equation appear to be very similar to those obtained through Alcock and Richardson's equation for a number of alloy systems, when the coordination number of oxygen in the new model is the same as the average coordination number used in the earlier equation. A second equation based on the formation of “molecular species” of the type XnO and YnO in solution is also derived, where X and Y atoms attached to oxygen are assumed not to make any other bonds. This equation does not fit experimental data in all the systems considered for a fixed value of n. Howover, if the strong oxygen-metal bonds are assumed to distort the electronic configuation around the metal atoms bonded to oxygen and thus reduce the strength of the bonds formed by these atoms with neighbouring metal atoms by approximately a factor of two, the resulting equation is found to predict the activity coefficients of oxygen that are in good agreement with experimental data in a number of binary alloys.

Solubility and activity of oxygen in liquid gallium and gallium copper alloys

The solubility of oxygen in liquid gallium in the temperature range 775 –1125 °C and in liquid gallium-copper alloys at 1100 °C, in equilibrium with β-Ga2O3, has been measured by an isopiestic equilibrium technique. The solubility of oxygen in pure gallium is given by the equation log (at.% O) = −7380/T + 4.264 (±0.03) Using recently measured values for the standard free energy of formation of β-Ga2O3 and assuming that oxygen obeys Sievert's law up to the saturation limit, the standard free energy of solution of oxygen in liquid gallium may be calculated : View the MathML sourceΔ°298 = −52 680 + 6.53T (±200) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which the activity is equal to atomic per cent. The effect of copper on the activity of oxygen dissolved in liquid gallium is found to be in good agreement with that predicted by a recent quasichemical model in which it was assumed that each oxygen is interstitially coordinated to four metal atoms and that the nearest neighbour metal atoms lose approximately half their metallic cohesive energies.