Viscoelastic Drag of Particles Settling in Wormlike Micellar Solutions of Varying Surfactant Concentration

Wormlike micellar octadecyl trimethyl ammonium chloride (OTAC) solution is a self-assembled fracturing fluid used to carry proppants into fractures in oil recovery. Slow settling velocity of proppant is desirably resulted from the viscoelastic drag with low viscosity of fracturing fluids for fracturing work. Steel spheres, as a substitute for proppants, fall into three semi-dilute OTAC solutions. The steady rheology demonstrates that OTAC solutions are divided into shear-thickening and shear-thinning regimes by the critical shear rate. The applied steel spheres always lie in the shear-thickening regime of the 2.8 wt% OTAC solution with aggregated micelles as their characteristic shear rates are less than the critical shear rate of the solution. Strong shear-thickening viscous drag results in lower settling velocity of steel spheres. Most of the applied steel spheres, on the other hand, lie in the shear-thinning regime of the 4 wt% OTAC solution with orientated micelles. Although the latter solution has small dissipation coefficient, high Weissenberg number, and consequently high elastic effect, the shear-thinning viscosity results in higher settling velocity of steel spheres.     

Wall-retardation effects on particles settling through non-Newtonian fluids in parallel plates

Walls can exert a retardation effect on particles settling in bounded fluid media. In this work, the parallel plate retardation effect was studied for particles falling in non-Newtonian fluids along the centreline of parallel plate ducts. The eccentric effect was also investigated for those particles which approached the wall. For spheres settling in sodium carboxymethylcellulose (CMC) solutions, the variation in wall factors against the size ratio of the sphere’s diameter to the parallel plate wall spacing shows a non-linear trend; the particle settling velocity is independent at small size ratio, and then decreases quickly with increase in size ratio. A new correlation was presented covering a wider range of size ratios (0.02 < λ < 0.83) in the flow region of 0.0011 < Re < 9.75. When particles settle in polyacrylamide solutions, the fluid elasticity reduces the wall-retardation effect and it can be deduced that the drag reduction mechanism of some polyacrylamide solutions may weaken the wall retardation effect. As the spheres settling in the CMC solutions approach the wall, the neighbouring wall exerts no retardation effect at small size ratios (≤ 0.8). Then the settling velocity reduces sharply, while the effect is negligible for polyacrylamide solutions. In comparison with cylinders, the actuating range of the neighbouring wall is smaller for parallel plates.     

Mixing time of a non-Newtonian liquid in an unbaffled agitated vessel with an eccentric propeller

Experimental study of mixing time of non-Newtonian shear-thinning fluids within the transitional regime (3 × 10² < Re < 3 × 10³) of liquid flow is presented. The purpose of this study was to analyze the effect of eccentricity and pumping mode of the impeller as well as of position of the tracer dosage point into the agitated liquid on mixing time. The measurements were conducted in an unbaffled agitated vessel with inner diameter D = 0.7 m equipped with an up-or down-pumping propeller located centrically (e/R = 0) or eccentrically (e/R ≠ 0) in the vessel. Experiments were carried out by means of computer-aided unsteady-state thermal method for three positions of the tracer dosage point. The experimental data show that eccentric position of the propeller in an unbaffled vessel causes a decrease of the mixing time compared to that obtained in a vessel with a centrically located propeller. Mixing time depends also on the pumping mode of the propeller as well as on the position of the tracer dosage point. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Rheological behavior and particle suspension capability of guar gum: sodium tetraborate decahydrate gels containing cellulose nanofibrils

Guar gum (GG) fracturing fluids were studied by incorporating cellulose nanofibrils (CNFs) in anhydrous borax crosslinked guar gum gels. To fully understand the impact of CNF on the proppant suspension capability of developed fracturing fluids, their shear rate-dependent viscosity and viscoelasticity were investigated. The shear rate dependencies of fluids was fitted to the Carreau model. The zero shear rate viscosity and elasticity of fracturing fluids increased significantly by incorporating CNF in guar gum gels. On the other hand, the viscosity at high shear rates (>100 s^?1) decreased as desired. The proppant settling velocities through fracturing fluids were evaluated by modeling the terminal falling velocity of proppants moving through a Carreau model fluid. The experimental results of the rheological behavior and the modeling results of the proppant settling rate indicated that the fracturing fluids containing CNF had better suspension capabilities. In addition, the lower viscosities of CNF formulated GG gels at higher shear rates will make them more pumpable.     

Synthesis,liquid crystalline mesophases and morphologies of diblock copolymers composed of a poly(dimethylsiloxane) block and a nematic liquid crystalline block

In this study, a series of liquid crystalline diblock copolymers, composed of a soft poly(dimethylsiloxane) (PDMS) block with a de?ned length and a side-on liquid crystalline poly(3??-acryloyloxypropyl 2,5-di(4?-butyloxybenzoyloxy) benzoate) (P3ADBB) block with different lengths, are synthesised by the atom transfer radical polymerisation. The macromolecular structures, liquid crystalline properties and the microphase-separated morphologies of the diblock copolymer are investigated by ¹H NMR, FT-IR, GPC, POM, DSC and TEM. The results show that the well-de?ned diblock copolymers (PDMS_n-b-P3ADBB_m) possess four different soft/rigid ratios (n = 58, m = 10, 25, 42, 66) and relatively narrow molecular distributions (PDI ≤ 1.30). P3ADBB blocks of the copolymers show nematic sub-phases, which are identical to the mesomorphic behaviour of the homopolymer P3ADBB. After being annealed at 90°C in a vacuum oven for 48 h, the copolymers form a lamellar morphology when m = 10 and morphologies of PDMS spheres embedded in P3ADBB matrix when m = 25, 42 and 66.     

Development and Validation of a Liquid Chromatographic Method Useful for the Determination of Amino Acids in New and Commercial Alimentary Supplements

In this study, a new liquid chromatographic method with pre-column derivatization was developed and validated for the simultaneous quantification of acetylcarnitine taurinate, asparagine, potassium aspartate, asparagine and carnosine in new and commercial alimentary supplements. The effect of complex matrices was evaluated by the study of the amino acid derivatization reaction with 2,5-dimethyl-1H-pyrrole-3,4-dicarbaldehyde in placebo solutions (DPD). Experimental parameters affecting the derivatization and chromatographic separation were investigated. The reaction was carried out at room temperature for 10 min. The adducts were separated on a Synergi Hydro-RP 80 Å column using a mobile phase consisting of 11 mM aqueous tetrapropylammonium bromide (pH 3.5)/methanol by gradient elution conditions at a flow rate of 0.8 mL/min. UV absorbance detection was set at λ = 320 nm. The validation parameters such as linearity, sensitivity, accuracy, precision, specificity and ruggedness were highly satisfactory. Linear responses were obtained by placebo solutions (determination coefficient ≤ 0.9994). Intra-day precision (RSD) was ≤1.06 % for corrected peak area and ≤1.14 % for retention times (t _R) without significant differences between intra- and inter-day data. Recovery studies showed good results for all the examined compounds (from 97.72 to 101.5 %) with RSD ≤1.30 %.

     

The stability of Tenax TA thermal desorption tubes in simulated field conditions on the HAPSITE® ER

Due to the growing need to monitor aircraft cabin, cockpit and breathing-line air quality, functional assessment of sampling equipment for the specialised field conditions of flight need to be established for both in-flight and ground safety. In this article, we assess the reliability of Tenax TA thermal desorption tubes to perform under various relevant field sampling conditions, such as storage temperature, loading temperature, vibrational velocity, gravitational force (G Force) and altitude pressure with semi-real-time gas chromatograph-mass spectrometer (GC-MS) analysis on the field portable HAPSITE^® ER (Hazardous Air Pollutants on Site Extended Range) instrument. First, we show that Tenax TA thermal desorption tubes can handle storage under extreme environmental conditions, 4–77°C, over numerous analytical test cycles. Next, we confirm that extreme loading temperature, both hot (77°C) and cold (4°C), does not affect the analytical reliability of Tenax TA thermal desorption tubes. Then, we illustrate that G Force may have a significant (p ≤ 0.0364) effect on Tenax TA performance while vibrational velocity (p ≤ 0.7265) and low ambient air pressure (p ≤ 0.1753), such as that found at high altitude, do not. Finally, several Tenax TA thermal desorption tubes were flight-tested, demonstrating that the durability of these tubes maybe insufficient for use on military cargo aircraft (p = 0.0107). The results presented here provide a rationale for additional testing of Tenax TA thermal desorption tubes for flight suitability.     

Isolation and X-ray structure analysis of citreohybridonol from marine-derived Penicillium atrovenetum

The anti-neuroinflammatory meroterpenoid citreohybridonol was isolated for the first time from a sponge-derived fungus Penicillium atrovenetum. In this study, in addition to isolation and structure featuring, its unambiguous absolute configuration was determined exclusively by single crystal X-ray diffraction. The C-17-keto tautomer was clearly observed in X-ray analysis. The substance crystallises in the monoclinic space group P2₁ with a = 10.7496(5) Å, b = 14.3286(7) Å, c = 17.4909(8) Å, β = 103.235(2)°, V = 2622.5(2) Å³, Z = 2, D_calcd = 1.280 g/cm³. The chirality of the asymmetric carbon atoms was as follows: C3 (S), C5 (R), C6 (S), C8 (S), C9 (R), C10 (R), C13 (R), C14 (R).     

Development and Validation of a Liquid Chromatographic Method Useful for the Determination of Amino Acids in New and Commercial Alimentary Supplements

In this study, a new liquid chromatographic method with pre-column derivatization was developed and validated for the simultaneous quantification of acetylcarnitine taurinate, asparagine, potassium aspartate, asparagine and carnosine in new and commercial alimentary supplements. The effect of complex matrices was evaluated by the study of the amino acid derivatization reaction with 2,5-dimethyl-1H-pyrrole-3,4-dicarbaldehyde in placebo solutions (DPD). Experimental parameters affecting the derivatization and chromatographic separation were investigated. The reaction was carried out at room temperature for 10 min. The adducts were separated on a Synergi Hydro-RP 80 Å column using a mobile phase consisting of 11 mM aqueous tetrapropylammonium bromide (pH 3.5)/methanol by gradient elution conditions at a flow rate of 0.8 mL/min. UV absorbance detection was set at λ = 320 nm. The validation parameters such as linearity, sensitivity, accuracy, precision, specificity and ruggedness were highly satisfactory. Linear responses were obtained by placebo solutions (determination coefficient ≤ 0.9994). Intra-day precision (RSD) was ≤1.06 % for corrected peak area and ≤1.14 % for retention times (t _R) without significant differences between intra- and inter-day data. Recovery studies showed good results for all the examined compounds (from 97.72 to 101.5 %) with RSD ≤1.30 %.     

Synthesis,crystal structures,and antimicrobial activities of hydrazone complexes of vanadium(V)

Two hydrazone ligands, (E)-N′-(3-bromo-2-hydroxybenzylidene)-2-methoxybenzohydrazide (HL^a) and (E)-N′-(2-hydroxy-3-methylbenzylidene)-2-methoxybenzohydrazide (HL^b), were prepared and characterized by IR, UV–vis, and ¹H NMR spectroscopy. The corresponding vanadium(V) complexes, 2[VOL^aL]·CH₃OH (1) and [VOL^bL] (2), where L is the monoanionic form of benzohydroxamic acid (HL), were prepared and characterized by IR and UV–vis spectroscopy, and single-crystal X-ray diffraction. Complex 1 crystallizes as the monoclinic space group P2₁/c, with unit cell dimensions a = 14.4161(16) Å, b = 14.0745(16) Å, c = 24.069(2) Å, β = 96.247(2), V = 4854.5(9) Å³, Z = 4, R₁ = 0.0541, wR₂ = 0.1423, Goof = 1.032. Complex 2 crystallizes in the orthorhombic space group Pbca, with unit cell dimensions a = 13.5906(6) Å, b = 18.1865(11) Å, c = 18.4068(11) Å, V = 4549.5(4) Å³, Z = 8, R₁ = 0.0549, wR₂ = 0.1397, Goof = 1.054. X-ray analysis indicates that the complexes are mononuclear octahedral vanadium(V) complexes. The thermal behavior of the complexes was investigated. The hydrazone ligands and their complexes were also evaluated for their antibacterial (Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence) and antifungal (Candida albicans and Aspergillus niger) activities using the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assay. The two complexes have moderate to good activities against B. subtilis and S. aureus, and 1 has moderate activity against E. coli.     

Transient molecular dynamics simulations of liquid viscosity for nonpolar and polar fluids

A transient molecular dynamics (TMD) method for obtaining fluid viscosity is extended to multisite, force-field models of both nonpolar and polar liquids. The method overlays a sinusoidal velocity profile over the peculiar particle velocities and then records the transient decay of the velocity profile. The viscosity is obtained by regression of the solution of the momentum equation with an appropriate constitutive equation and initial and boundary conditions corresponding to those used in the simulation. The transient velocity decays observed appeared to include both relaxation and retardation effects. The Jeffreys viscoelastic model was found to model accurately the transient responses obtained for multisite models for n-butane, isobutane, n-hexane, water, methanol, and 1-hexanol. TMD viscosities obtained for saturated liquids over a wide range of densities agreed well for the polar fluids, both with nonequilibrium molecular dynamics (NEMD) results using the same force-field models and with correlations based on experimental data. Viscosities obtained for the nonpolar fluids agreed well with the experimental and NEMD results at low to moderate densities, but underpredicted experimental values at higher densities where shear-thinning effects and viscous heating may impact the TMD simulations.     

Rheology and high-temperature stability of novel viscoelastic gemini micelle solutions

To broaden the application of clean fracturing fluid based on surfactant, a gemini cationic C₂₅-tailed surfactant, called FL-25, was synthesized. FL-25 can form a wormlike viscoelastic fluid in aqueous solution without adding any organic or inorganic salts. The rheological properties and thermal stability of the novel gemini micelle solutions were further investigated. The results show that the gemini micelle solution possesses viscoelasticity, thixotropy, and shear-thinning properties. The apparent viscosity of the viscoelastic gemini micelle solution at a shear rate of 170?s^?1 remains approximately 69?mPa?·?s at 110°C for 90 minutes, showing good high-temperature-resistance property. FL-25 may be a novel gemini surfactant applied in clean viscoelastic surfactant fracturing fluids in the oil and gas field.     

Contraceptive studies of isolated fractions of Cuminum cyminum in male albino rats

The contraceptive efficacy of Cuminum cyminum isolated fractions (CcFr) in male albino rats was investigated. Oral dose of CcFr at 50 mg/rat/day for 60 days revealed no significant changes in body weight, while marked abnormalities in spermatogenesis were observed with decreased counts (P ≤ 0.001) in round spermatids, preleptotene spermatocytes and secondary spermatocytes. Cross sectional surface area of Sertoli cells as well as number of mature Leydig cell were decreased significantly (P ≤ 0.001). Testicular as well as accessory sex organ biochemical parameters were significantly changed (P ≤ 0.001). Sperm motility, density and morphology were resulted in 100% negative fertility. Testosterone levels were declined significantly. In conclusion, Cuminum cyminum inhibited spermatogenesis in rats, indicating the possibility of developing an herbal male contraceptive.     

Impacts of delignification and hot water pretreatment on the water induced cell wall swelling behavior of grasses and its relation to cellulolytic enzyme hydrolysis and binding

The relationships between biomass composition, water retention value (WRV), settling volume and enzymatic glucose yield and enzyme binding is investigated in this work by employing grasses pretreated with combinations of alkaline hydrogen peroxide (AHP) delignification and liquid hot water pretreatment that result in significant alterations of cell wall properties and subsequent enzymatic hydrolysis yields. Specifically, these cell wall treatments are performed on corn stover and switchgrass to generate material with a range of lignin (6–35 %) and xylan (2–28 %) contents as well as a range of other properties such as carboxylic acid content, water binding affinity and swellability. It was determined that WRV and settling volume are predictors of glucose yield (R² = 0.900 and 0.895 respectively) over the range of materials and treatment conditions used. It was also observed that mild AHP delignification can result in threefold increases in the WRV. Dynamic vapor sorption isotherms demonstrated that AHP-delignified corn stover exhibited an increased affinity for water sorption from the vapor phase relative to untreated corn stover. These results indicate that these water properties may be useful proxies for biomass susceptibility to enzymatic deconstruction.     

Magnetic field effects on natural convection flow of a non-Newtonian fluid in an L-shaped enclosure

The effect of magnetic field on natural convection heat transfer in an L-shaped enclosure filled with a non-Newtonian fluid is investigated numerically. The governing equations are solved by finite-volume method using the SIMPLE algorithm. The power-law rheological model is used to characterize the non-Newtonian fluid behavior. It is revealed that heat transfer rate decreases for shear-thinning fluids (of power-law index, n?<?1) and increases for shear-thickening fluids (n?>?1) in comparison with the Newtonian ones. Thermal behavior of shear-thinning and shear-thickening fluids is similar to that of Newtonian fluids for the angle of enclosure α?<?60° and α?>?60°, respectively.     

Conformations of Alternating Partially Fluorinated Copolymers in Dilute Ethanol Solutions

Equimolar copolymers of N-vinyl pyrrolidone with 1,1,1-3,3,3-hexafluoroisopropyl-α-fluoroacrylate were obtained by reversible addition-fragmentation chain transfer radical (RAFT) polymerization and by conventional radical polymerization (RAD). The copolymer conformation and compositional heterogeneity were analyzed by dynamic and static light scattering. RAFT copolymers of 41,000 ≤ M _w  ≤ 68,000 g/mol were shown to adopt cylindrical all-trans conformation. RAD copolymer of higher molecular mass (M_w = 390,000 g/mol) exhibited less extended conformation, thus indicating that the statistical Kuhn segment is less than RAD copolymer length.     

Interaction between Two Similar Plane Parallel Double Layers for Al2(SO4)3 Type Asymmetric Electrolytes at Positive Surface Potential

The interaction between two similar plane double-layers for Al₂(SO₄)₃ type asymmetric electrolytes was investigated with the aid of λ parameter method. The interaction energies for the system at positive surface potential were expanded in the power series at low and high potential, respectively. The high potential formula can be applied to 0.2 ≤ y_e  < y ₀ ≤ 20. This almost covers with the bounds of all potential, and that the calculative method is relative simple. The accurate numeral results and V′?ξ_d curves were given for y ₀ ≤ 20. When y ₀ ≥ 5, V′ hardly change with y ₀. The interaction energies between two similar plane parallel double layers for the different type electrolytes at y ₀ = 1 were compared. The present results are also fit for Mg₃(PO₄)₂ type electrolytes at negative surface potential.     

Comparison of the Rheological Behavior of Solutions and Formulated Oil-in-Water Emulsions Containing Carboxymethylcellulose (CMC)

In this study, it was aimed to compare the rheological properties of carboxymethylcellulose (CMC) in aqueous solutions and their corresponding emulsions containing 0.05, 0.1, 0.25, and 0.5% CMC in the aqueous phase. Samples with 0.05 and 0.1% CMC showed Newtonian behavior, but shear-thinning behavior was observed in CMC solutions and emulsions with increasing CMC concentrations to 0.25% and 0.5%. Rheological behavior of all samples were modeled by Power law (R ² = 0.986–197) and Casson models (R ² = 0.968–1). According to the Ostwald–de Waele model, the consistency index of all samples was increased and the flow behavior index decreased with increasing CMC concentration. Comparison of our data with four predicting models (Einstein, Larson, Pal, and Dougherty-Krieger equations) showed that the viscosity of continuous phase controls the viscosity of emulsions with high CMC concentrations and these models are not applicable for such situations. Addition of CMC increased the emulsion stability of O/W emulsions. This stability was increased with increasing CMC concentrations.     

Physical adsorption of gases

Summary Theoretically derived isotherms for monolayer and multilayer adsorption are used to interpret some earlier published experimental data. A satisfactory agreement is found in nearly all cases. To check the validity of the theoretical constant b it is plotted versus l/√T and this results in a straight-line dependence as it is foreseen by the theory. The b values found for the adsorption of n-butane on glass spheres are used to calculate the average settling times τ _L at different temperatures and subsequently τ _0(L) which is estimated to be ∼ 10⁻¹³ sec. It seems that the constant b is quasi-independent of the adsorbent properties which permits to obtain a characteristic plot for nitrogen isotherms.