Ultrasonic velocity measurements in isobutyric acid - water binary mixtures over the temperature range from 300.15 to 313.15 K

We measured the ultrasonic velocity, U, density, ρ, and viscosity, η in Isobutyric acid - water binary liquid mixtures over the entire composition range at temperatures ranging from 300.15 to 313.15 K under atmospheric pressure. The experimental data values were analyzed to determine, various acoustical parameters: adiabatic compressibility, β, acoustic impedance, Z, free length, L_f, free volume, V_f, molar volume, V_m, relaxation time, τ, absorption coefficient, α/f², internal pressure, π_i, Gibb’s free energy, ΔG, cohesive energy, CE, Wada’s constant, W, Rao’s constant, R_m and relative association, R_A. The variation of these parameters versus the mixture composition was explained on the basis of the intermolecular interactions between the components of the mixture.     

Local Turbulent Energy Dissipation Rate in an Agitated Vessel: Experimental and Turbulence Scaling

The hydrodynamics and the flow field in an agitated vessel were measured using 2-D time resolved particle image velocimetry (2-D TR PIV). The experiments were carried out in fully baffled cylindrical flat bottom vessels 300 and 400 mm in inner diameter. The 300 mm inner diameter tank was agitated by a Rushton turbine 100 mm in diameter, and the 400 mm inner diameter tank was agitated by a Rushton turbine 133 mm in diameter. Three liquids of different viscosities were used as the agitated liquid: (i) distilled water (ν = 9.35 × 10^–7 m²/s), (ii) a 28 vol % aqueous solution of glycol (ν = 2 × 10^–6 m²/s), and (iii) a 43 vol % aqueous solution of glycol (ν = 3 × 10^–6 m²/s). The velocity fields were measured at an impeller rotation speed in the range from 300 to 850 rpm, which covers the Reynolds number range from 50000 to 189000. This means that fullydeveloped turbulent flow was reached. The experiments were performed to investigate the applicability of the following relations: ε* = ε/(u⁴/ν) = const, vK/u = const, Λ/ηK = const, τ_Λ/τ_K = const, ε* = ε/((Nd)4/ν) = const, Λ/d ∝ Re^–1, ηK/d ∝ Re^–1, vK/(Nd) = const, Nτ_Λ ∝ R^–1, Nτ_K ∝ Re^–1, and ε/(Nq) ∝ Re. These formulas were theoretically derived in our previous work, using turbulence theory, in particular, using turbulence spectrum analysis. The correctness of the proposed relations is investigated by statistical hypothesis testing.     

Effect of the Density of a Microspherical Catalyst on the Operating Regimes of a Fluidized Bed

An experimental study is performed of a circulating fluidized bed of two types of finely dispersed Geldart A particles with different bulk densities. The first type of particles have bulk density ρ_b = 1200 kg/m³, while the bulk density of the second type of particles is ρ_b = 1300 kg/m³. The studies are performed on a test bench 0.7 m in diameter and 5.75 m tall at room temperature with air used as the fluidizing gas. The velocity of fluidization ranges from 0.1 to 0.75 m/s. The bed is sectioned along its height with a set of horizontal diffuser grids. The results from measuring the fluctuations, the average drops in pressure, and the pressure distribution along the height of the fluidized bed are used to estimate the effect produced by the density of particles on its operational regimes. Velocity of transition U_c, determined from the mean-square deviations of pressure drop fluctuations, is 0.40 m/s for lighter particles and 0.35 m/s for heavier particles. Velocity of transition U_c determined from the power of the energy spectrum of pressure fluctuations Е is 0.45 and 0.40 m/s for lighter and heavier particles, respectively. The results from pressure measurements along the bed height show a linear drop with increasing bed height, and this drop is faster for heavier particles than for lighter particles.     

Ultrasonic study on binary liquid mixtures of propiophenone with anilines and alkyl substituted anilines at T=303.15 to 318.15 K

Densities ‘ρ’, ultrasonic speeds of sound ‘u’ of binary mixtures of propiophenone (PPH) with aniline, N-Methylaniline, N,N-dimethylaniline and N,N-diethylaniline were measured over the entire composition range from 303.15 K to 318.15 K and at atmospheric pressure 0.1 MPa. Experimental data of ultrasonic sound were compared and discussed with the computed values of ‘u’ from various velocity theories like Nomoto’s relation (U_NOM), impedance relation (U_IMP), Van Dael and Vangeel’s ideal mix relation (U_VDV), Rao’s specific velocity relation (U_RAO), Junjie’s theory (U_JUN) and Jouyban-Acree’s (U_JOE) relation for the above binary mixtures over the entire mole fraction range at the studied temperatures. The results are satisfactory and are in agreement between the theoretical and the experimental values. Further, the molecular interaction parameter (α), average percentage error and Chi-square test values were computed by using the values of experimental and theoretical ultrasonic velocities. The Δu values were correlated with Redlich-Kister polynomial equation to compute the coefficients and the standard deviations of the binary mixtures. The results were analyzed in terms of intermolecular interactions.     

Moisture-holding capacity of coals

As a result of a comprehensive study of 63 samples of coal concentrates (from Ukraine, Russia and countries outside the former Soviet Union), it was established that the prediction of the moisture-holding capacity of coals can be appropriately performed according to their values of W ^a, R ₀, O _d ^daf , and O _s ^daf . It was found that the oxidation of coal increased its moisture-holding capacity; however, in this case, the absolute change in this parameter was smaller than the error of its determination (0.5%). Therefore, upon the oxidation of almost 30% of the organic matter of coal, the moisture-holding capacity increased by only 0.4%. There is a close correlation between the maximum moisture capacity of coals and the water pore volume, and this correlation was described by a linear equation in the studies.     

Bioengineering functional copolymers: synthesis and characterization of poly(<Emphasis Type="Italic">N</Emphasis>-isopropyl acrylamide-<Emphasis Type="Italic">co</Emphasis>-3,4-2H-dihydropyran)s

Novel bioengineering copolymers were synthesized by radical copolymerization of N-isopropylacrylamide (NIPA) and 3,4-2H-dihydropyran (DHP) with 2,2′-azobisisobutyronitrile as an initiator in acetone solution at 70 °C under nitrogen atmosphere. Structure, tacticity and compositons of the copolymers prepared in a wide range of monomer feed were confirmed by FTIR, ¹H{¹³C} NMR-DEPT and elemental analyses. The monomer reactivity ratios (r ₁ and r ₂) were detected using known two methods: r ₁ (NIPA)?=?1.25 and r ₂?=?0.035 (DHP), and r ₁ (NIPA) ?=?0.97 and r ₂?=?0.022 (DHP) by Kelen-Tüdös and Jaacks methods, respectively. It was demonstrated that the studied monomer pair has a tendency to form H-bonding beween amide/ether groups through ?NH...O< complexation which played an important role in the stereoselective chain growth, and significant decrease of allyl degradative chain transfer reactions. This phenomenon is also confirmed by the observed relatively high molecular weights of copolymers (M _v ). The synthesized water-soluble stimuli-responsive poly(NIPA-co-DHP)s exhibit thermal stability, higher glass-transition temperature, polyelectrolyte, pH- and temperature-sensitive behavior and can be attributed to the class of bioengineering functional copolymers useful for various bio- and gene-engineering, and drug delivery applications.     

Predicting the classification characteristics of coal. Part 3. Gross calorific value of dry,ash-free coal

For 63 samples of Ukrainian, Russian, and imported coal, equations for predicting the gross calorific value Q_s^daf on the basis of the following coal characteristics are developed: W^a, O_d^daf, Q_s^af, and C_ar. The error is within the standard tolerances (σ ≤ 0.3 MJ/kg). With sufficient accuracy, Q_s^daf may be predicted from equations based on petrographic characteristics such as the vitrinite reflectance, the content of liptinitegroup minerals, and the sum of lean macerals (I + 2Sv/3). In these equations, the coefficients correspond to the heat of combustion of the vitrinite components at different metamorphic stages, the liptinite, and the lean macerals.     

Particle deposition behaviors of monolithic De-NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> catalysts for selective catalytic reduction (SCR)

A major issue when using selective catalytic reduction (SCR) De-NO _x catalysts is the risk of physical deactivation due to particle deposition and plugging of the monolithic catalysts. In the present study, numerical computations were carried out to investigate the particle deposition behaviors in monolithic SCR catalysts. Based on the calculation results, the effects of particle diameter, particle density, gas velocity, turbulent intensity, chemical reaction and channel size on particle deposition were analyzed in detail. Increasing gas velocity and equivalent diameter of channel can mitigate particle deposition. The increases of turbulent intensity and channel length both lead to the rise of particle deposition ratio. For particles with high Stokes number, particle deposition mainly takes place in the inlet section of catalysts. For particles with low Stokes number, sediment can be observed in the middle and outlet sections of catalysts. De-NO _x chemical reaction can mitigate particle deposition, but the effect of chemical reaction on particle deposition is inactive.     

Cure kinetics of cyanate ester resin using microencapsulated dibutyltin dilaurate as catalyst

Dibutyltin dilaurate (DBTDL) catalyst-filled microcapsules (MCs) were used to catalyze the reaction of thermosetting cyanate ester (CE) resins. Dynamic differential scanning calorimetry (DSC) experiments were performed at multiple heating rates (β) to investigate the effects of the MC content (0.125, 0.25, and 0.5 %) on the cure kinetics of CE resins. The kinetic parameters of CE/MC systems, including activation energy (E _a), preexponential factor (A), and reaction order (n), were analyzed using the Flynn–Wall–Ozawa method, Kissinger method, Crane method, Ozawa isoconversional method, and Coats–Redfern method. The results indicate that, as the MC content increases, the reaction temperature of CE/MC system gradually shifts to low temperature owing to the increase of the DBTDL catalyst released from MCs under heating conditions. Compared to the unencapsulated DBTDL, the encapsulated DBTDL can decrease the E _a, A, and the reaction rate constant of CE resins due to the gradual release of DBTDL from MCs and the homogeneous dispersion of the released DBTDL in CE resins. The E _a, A, and the reaction rate constant of CE/MC systems are effectively adjusted by the MC content and heating process. The reaction orders for all CE/MC systems are close to 1. The reaction model of CE/MCs is considered as a two-dimensional nucleation (A ₂).     

SHS of Y<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>-based mineral-like ceramics: Influence of green density

Explored was the influence of compacting pressure (P) and green density (ρ) on the properties of Zr-doped mineral-like pyrochlore ceramics Y₂(Ti_{1 – x} Zr _x )₂O₇ (x ≤ 0.3) prepared by SHS method. The optimal ρ values that provide minimal porosity and maximal mechanical strength of synthesized ceramics were found. An increase in ρ was found to decrease combustion temperature and increase pyrochlore lattice parameter a. Green density was also found to affect phase composition of the SHS-produced ceramics under study.     

IR Spectroscopy in Rank and Group Assignment of Coal

The possibility of express determination of the characteristics V _IR ^daf , R_{o, IR}, y_IR, ΣLC_IR, and A _IR ^d used in the ranking of coal on the basis of IR spectroscopy is assessed for a specific example: Kuznetsk coals of different maceral composition and metamorphic development. The IR characteristics are compared with values obtained by standard methods (V^daf, R_{o, r, y}, ΣLC, and A^d).     

Adsorption and desorption dynamics of CF<Subscript>4</Subscript> on activated carbon beds: Validity of the linear driving force approximation for pressure-changing steps

Adsorption and desorption dynamics of CF₄ on an activated carbon bed were studied experimentally and theoretically, focusing on pressure-changing steps. The theoretical model used the ideal adsorbed solution (IAS) theory and the linear driving force (LDF) approximation as equilibrium and mass transfer models, respectively. Adsorption breakthrough curves of raw CF₄ gas (500, 1,000, and 1,500 ppm) were well predicted by the theoretical model and the diffusion time constant for CF₄ was found to be 3.3×10^?3 s^?1 from breakthrough curve fitting. Changes in the CF₄ concentration during depressurization could be easily predicted using the above mathematical model when the half-cycle time (θ _c ) was above 0.1. However, significant discrepancies were observed between the predicted CF₄ concentrations and the experimental data when θ _c was 0.1. Nakao and Suzuki also reported that proportional constant of LDF approximation (=KD _e /R _p ²) needs to be modified when θ _c is less than 0.1.     

Effects of co-ion initial concentration ratio on removal of Pb<Superscript>2+</Superscript> from aqueous solution by modified sugarcane bagasse

A modified sugarcane bagasse (SCB) fixed bed column was used to remove Pb²⁺ from aqueous solution. To determine the optimal condition for Pb²⁺ separation, Ca²⁺ was chosen as the model interfering ion, and effects of Ca²⁺ and Pb²⁺ initial concentration ratio (C ₀ ^Ca : C ₀ ^Pb ) on the adsorption of Pb²⁺ were investigated. Results showed that adsorption amount ratio of Ca²⁺ and Pb²⁺ (q _e ^Ca : q _e ^Pb ) had a good linear relationship with C ₀ ^Ca : C ₀ ^Pb . Mass ratio of Pb²⁺ absorbed on the modified SCB was higher than 95% at C ₀ ^Ca : C ₀ ^Pb <1.95, illustrating that Pb²⁺ could be selectively removed from aqueous solution. To verify that, simulated waste water containing co-ions of K⁺, Na⁺, Cd²⁺ and Ca²⁺ was treated, and results showed that the equilibrium amount of Pb²⁺, K⁺, Na⁺, Cd²⁺ and Ca²⁺ adsorbed was 134.14, 0.083, 0.058, 1.28, and 1.28mg g^?1, respectively, demonstrating that the modified SCB could be used to remove Pb²⁺ from aqueous solution in the investigated range.     

Optimal prediction of PKS: RSO modified alkyd resin polycondensation process using discrete-delayed observations,ANN and RSM-GA techniques

Alkyd resins are widely used in the paint industry and although they have a long history about 70–100 years, today the developments in alkyds are still welcome and innovations are still needed. Artificial neural network (ANN) and response surface methodology based on a 2^5?1 fractional factorial design were used as tools for simulation and optimization of the polycondensation process for autooxidative drying alkyd resin from palm kernel stearin: rubber seed oil blend of 70:30 ratio. A feed forward neural network model with Levenberg–Marquardt back propagation training algorithm was adapted to predict the responses (conversion Y ₁, viscosity Y ₂, and molecular weight average Y ₃). The studied input variables were reaction time, temperature, catalyst concentration, oil ratio, and stirring rate. The performance of the RSM and ANN model showed adequate prediction of the responses in terms of the process factors, with MRPD of ±4.47% (Y ₁), ±2.08% (Y ₂), ±8.92% (Y ₃) and ±6.50% (Y ₁), ±3.31% (Y ₂), ±10.20% (Y ₃), respectively. The sensitivity analysis showed that while reaction time is the most effective process parameter, the interaction of the five process variables produced the most significant effect on the studied responses with the overall minimum MSE of 0.079. The optimization task performed using a genetic algorithm linked to the RSM model gave a viable, nondominated optimal response and optimum operating conditions regarding the route to high-quality resin at reduced material and operational costs. Overall, coupled RSM-GA was found to be a better tool for modeling and optimization of the alkyd resin production.     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

Amorphous polyamide coating resins from sugar-derived monomers

In this article, the synthesis of bio-based polyamides for powder coating applications and their evaluation in a solventborne coating system are reported. The M _n values of the resins were between 3000 and 4000 g mol^?1 and the resins displayed T _g values from 60 to 80°C. Both amine and carboxylic acid functionalities (total ~0.6 mmol g^?1) were introduced for curing purposes. The resins were cured with triglycidyl isocyanurate (TGIC) or N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide (Primid XL-552). The curing reaction was followed using rheology which indicated that TGIC achieved higher reaction rates and higher gel contents. The DSC analysis of the cured disks showed that all cured samples were amorphous as is desired for the targeted coating application. The resins required a curing temperature higher than 150°C. Aluminum panels were coated using a solventborne approach and the coatings were cured at 180°C during 1 h. Dewetting was observed on all panels. Network formation was adequate for an amine-functional resin cured with TGIC as indicated by solvent resistance testing. In conclusion, the developed bio-based polyamide resins are promising materials to be used as binder resins in powder coating applications.     

Local turbulent energy dissipation rate in an agitated vessel: New approach to dimensionless definition

Using theory of turbulence, particularly using turbulence spectrum analysis, the relations ε^* = ε/(u ⁴/ν) = const., v_K/u = const. and Λ/η_K = const. were derived. Assuming that u ∝ (Nd) from this it follows that the widely used dimensionless local turbulent energy dissipation rate defined as ε/((N ³ d ²) is directly proportional to impeller Reynolds number, i.e. ε/((N ³ d ²) ∝ Re, and length scale ratio Λ/d is indirectly proportional to impeller Reynolds number, i.e. Λ/d ∝ Re^–1, in an agitated vessel at high Reynolds number. The relations obtained by turbulence spectrum analysis were used for estimation of local turbulent energy dissipation rates experimentally measured by Ståhl Wernersson and Trägårdh (1998, 1999) covering the range of Re = 87600–910200 and own experimental data covering the range of Re = 50000–189000. The experiments have been performed in tanks of 300 mm and 400 mm in the inner diameter for three different viscosities and for various impeller rotational speeds.     

Assessing the technological value of coal in coking

Coking coal of the same rank from different countries and fields may be distinguished in terms of use value by rating on the basis of seven technological and petrographic characteristics that determine the coke yield and properties: the ash content A^d; the total sulfur content S_t^d; the yield of volatiles V^daf; the plastic-layer thickness y; the vitrinite reflection coefficient R_o; the content of vitrinite-group macerals Vt; and the basicity index B_b. A range of values and a rating (on a scale from 1 to 10) are established for each of these parameters. Each rating corresponds to a particular score (from 0.1 to 1.0). Ranges of A^d, S_t^d, Vt, and B_b are established for the whole metamorphic series, while ranges of V^daf, y, and R_o are established for individual ranks and groups of ranks. Altogether, 105 coking coals from Ukraine, Russia, the United States, Australia, and Canada that are used at Ukrainian coke plants are investigated. The range of rating scores and their mean values are determined for individual coal ranks and groups. As an example, three bituminous coals from Ukraine, the United States, and Australia are compared by the proposed method. This method permits objective assessment of the technological value of coal within a single rank and the selection of the best purchase option.     

FTIR spectra and elastic properties of Cd-substituted Ni–Zn ferrites

Solid solutions Ni_0.5–x Cd _x Zn_0.5Fe₂O₄ (x = 0, 0.15, 0.30) were prepared by solid-state synthesis and characterized by FTIR spectroscopy. The FTIR spectra of synthesized ferrites showed two absorption bands (ν₁ and ν₂) in the range 400–600 cm^–1 belonging to tetrahedral (A) and octahedral (B) interstitial sites in the spinel lattice. The force constants for tetrahedral (K _t) and octahedral sites (K _o) were determined, as well as Young’s modulus (E), rigidity modulus (G), bulk modulus (B), Debye temperature (Θ_D), and velocity of transverse (V _t) and longitudinal (V _l) elastic waves. The relevant interionic cation–anion, cation–cation distances and bond angles are also reported.     

Parameters of luminescence and the local structure of Eu<Superscript>3+</Superscript> centers in fluorogermanate glasses

The influence of the chemical nature of the local environment of Eu³⁺ ions on the parameters of luminescence of these centers in glasses of the (BaGeO₃)_{1 ? x ? y} (Al₂O₃) _x (0.45CaF₂ · 0.55MgF₂) _y (x = 0.25, y = 0; x = 0.17, y = 0.17; x = 0.15, y = 0.22; x = 0.07, y = 37.00; x = 0, y = 0.45) system is investigated. The oxidation state of europium atoms and the degree of homogeneity of their local environment in the glasses are determined using ¹⁵¹Eu Mössbauer spectroscopy.