Twenty‐one new theoretically based cubic equations of state for athermal hard‐sphere chain pure fluids and mixtures

Eight new hard‐sphere equations of state (EOS's) were obtained from molecular simulation data for the pair correlation function g_HS(σ) vs. packing fraction η and combined with three theoretical schemes to obtain 21 new cubic EOS's for athermal hard‐sphere chains (AHSC's). The eight new hard‐sphere EOS models successfully reproduced isotropic fluid compressibility factor Z_HS and g_HS(σ) vs. η simulation data and predicted metastable liquid Z_HS vs. η and virial coefficients up through B₁₀. Moreover, calculated Z vs. η and reduced second‐virial coefficient vs. chain length m were compared with molecular simulation data for chains up to m = 201 for a set of representative (eight of twenty‐one) chain equations. Z vs. η for three AHSC binary mixtures was also successfully predicted. The results indicate that the new cubic EOS's give a satisfactory representation of simulation data for chain fluids and can be used to develop theoretically based cubic EOS's for “real” fluids including attractive effects. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1677–1690, 2015     

Attaining a controlled graded distribution of particles in polymerizing fluid for functionally graded materials

The precise control on concentration profile of dispersion in functionally graded material (FGM) is essential for obtaining a desired material. A suitable simulation of parameters and an appropriate model that describes the motion of particles in the fluid can predict various aspects those are needed to produce FGM, by gravity sedimentation or centrifugation technique. Simulation was conducted to observe the changes in concentration profile, while using the following equations applicable to polymerizing fluid, and to determine the terminal velocities (V_m) of particles; V_m = {D²(ρ_s ? ρ_l)g*(1 ? ?_s)^4.65}/(18μ₀e) for gravity sedimentation and V_m = {D²(ρ_s ? ρ_l)rω²(1 ? ?_s)^4.65}/(18μ₀ e) for centrifugation, where D is the diameter of the spherical particle, ρ_s the density of solid particles, ρ_l the density of fluid, μ the viscosity of fluid, g* the acceleration due to gravity, ?_s is the volume fraction of particles, and t_c is the elapsed time of curing of thermosetting resin. b is a constant, r is the radius, and ω is the angular velocity. This simulation demonstrates that the time of centrifugation/sedimentation, particle size, distribution of particle size, and centrifugal/gravitational forces can be effectively utilized to attain a desired concentration profile in graded materials. Simulation also revealed that there exist the possibility of two graded profiles, namely low concentration profile and high concentration profile, in one sample of graded material, made either by centrifugation or sedimentation. Low concentration profile is more sensitive to particle size distribution as compared to high concentration profile. The present simulation method is also sensitive to concentration‐measuring methods. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Estimates of the Properties of Liquids

An equation which relates the volume term (V=M/_(ρL-ρg)) of unassociated liquids to pressure P and temperature T has been obtained by the combination of (a) 03V(?I/?V)_P→0=T_x-T for the effect of temperature on V at low (atmospheric) pressure and (b) - V(?P/?V)_T = P_x V_x/⁶/V⁶ _p→0+9(P-p) for the effect of pressure on volume at constant temperature. In the equations, p is the vapour pressure; pL the density of the liquid and pg the vapour density. Often pg can be neglected compared with pL and p is small compared with the large pressures required to affect the densities of liquids appreciably. There are three constants: Tx, Px, which equals 4.455 × 10⁹ N m², and Vx which can be calculated by the addition of atomic values for all the atoms in the molecule and subtraction of a value (6.56 × 10⁶ m³ mol¹) for each bond. When V approximates to M/ρL, the molar volume, the equation can be integrated to give the work and heat of isothermal compression. The viscosity of a liquid is related to the work of compression and solubilities in a liquid to the work required to bring the solute to the compressibility of the liquid. Many relationships can be derived and can be used to estimate properties of unassociated liquids.     

Densities,ultrasonic speeds,refractive indices,and COSMO analysis for binary mixtures of dichloromethane with acetone and dimethylsulfoxide at T = (298.15, 303.15, and 308.15) K

Experimental densities (ρ), ultrasonic speeds (u), and refractive indices (n_D) of binary mixtures of dichloromethane (DCM) with acetone (ACT) and dimethylsulfoxide (DMSO) were measured over the whole composition range at T?=?298.15, 303.15, and 308.15?K. From the experimental data, excess molar volume (V^E), deviations in isentropic compressibility (Δk_s), deviations in intermolecular free length (ΔL_f), deviations in refractive index (Δn_D), and deviations in ultrasonic speed (Δu) were calculated. Moreover, the Benson–Kiyohara theory was applied to the binary mixtures to obtain the theoretical Δk_s values. The COSMO calculations depending on density functional theory were utilized to estimate the σ-profiles for the DCM, ACT, and DMSO. The interpreted σ-profile trends were found supportive with the experimental findings. Applicability of different empirical and semi-empirical relations of refractive index data were tested against the measured results, and good agreement has been obtained. The possible results of intermolecular molecular interactions among mixture components were interpreted.     

A Method for Determining Bulk Density,Material Density,and Porosity of Melter Feed During Nuclear Waste Vitrification

Glassmelting efficiency largely depends on heat transfer to reacting glass batch (melter feed), which in turn is influenced by the bulk density (ρ_b) and porosity (?) of the reacting feed as functions of temperature (T). Neither ρ_b(T) nor ?(T) functions are readily accessible from direct measurements. For the determination of ρ_b, we monitored the profile area of heated feed pellets and calculated the pellet volume using numerical integration. For the determination of ?, we measured the material density of feeds quenched at various stages of conversion via pycnometry and then computed the feed density at heat‐treatment temperature using thermal expansion values of basic feed constituents.     

Physicochemical studies of globular proteins—Bovine serum albumin,egg albumin,and lysozyme—In some aqueous iodide salts solutions of IA group and cetyltrimethyl ammonium bromide systems

Densities (ρ, kg m^?3), and viscosities (η, 0.1 kg m^?1 s^?1) of Bovine Serum Albumin (BSA), Egg Albumin, and Lysozyme in aqueous iodide salts of lithium, sodium, and potassium, along with cationic surfactant‐cetyltrimethyl ammonium bromide (CTAB) were measured at a temperature of 303.15 K. The 0.0010–0.0018 g %, w/v of each protein at an interval of 0.0002 mol L^?1 in 0.2, 0.4, and 0.8 millimol L^?1 of salt and CTAB are studied. Data are used for apparent molar volumes (V_?, 10^?6 m³ mol^?1) and intrinsic viscosities ([η], dL kg^?1), respectively. Data are regressed and extrapolated to zero concentrations for ρ⁰, η⁰, and limiting values and S_d, S_η and S_V corresponding slopes for protein–salt structural interactions. With size of cations, the densities decrease as CTAB > LiI > NaI > KI and increase with salts concentrations, with salts the densities are as Lysozyme > BSA > Egg Albumin, viscosities and V_? as BSA > Egg–Albumin > Lysozyme. The ρ and η values with CTAB higher and [η] are lower and converse at around 0.4 mmol L^?1 salt and is effective for greater stability of proteins. The [η] in CTAB are higher than other salts and decreases with size of cations with stronger intermolecular forces. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Failure criterion for brittle materials with U-notches: Unification of characteristic length-based and grain size-based criteria

Here, the limitations of characteristic length-based (L_chb) and grain size-based (G_b) criteria with two or three parameters were pointed out employing the apparent toughness tests of 12 different ceramics at a large span range of U-notch root radius (ρ) values. After comprehensively considering the potential influencing factors of stress intensity factor (K_c), ρ divided by critical notch tip radius (ρ_c) was proposed as the independent variable, and the data of 21 materials (covering ceramics, plastics, resins, rocks, and metals) was summarized and discussed to establish a simple and more applicable K_c prediction model. Results indicated that K_c/K_Ic was a power function of ρ/ρ_c with a power exponent n of 0.5 for ideal materials and less than 0.5 for actual materials. It was also found that ρ_c can be calculated simply by K_Ic²/(πσ₀²), where σ₀ represented the inherent strength. This semiempirical criterion succeeded in unifying the L_chb and G_b criteria without introducing more parameters to increase the prediction accuracy of the K_c at the U-notch root for brittle materials like ceramics.     

Copolymerization of styrene. IV. Copolymerization with esters of benzylidenecyanoacetic acid

Styrene was copolymerized in bulk with a number of esters of benzylidenecyanoacetic acid. The kinetic scheme of all pairs fitted the improved scheme of copolymerization, taking into account the effect of the penultimate unit. The Alfrey-Price Q and e values were calculated. Using the modified Taft equation, log (1/r₁) = ρ^*σ^* + δE_s, it was found that the relative reactivities of the ester monomers toward the polystyryl radical were correlated by the polar substituent constants σ^* of the ester alkyl groups (ρ^* = 0.14) and not by their steric substituent constants E_s (δ = 0.008).     

Systematic study on heat transfer and surface hydrodynamics of a vertical heat tube in a fluidized bed of FCC particles

Bed‐to‐wall heat transfer properties of a vertical heat tube in a fluidized bed of fine fluid catalytic cracking (FCC) particles are measured systematically using a specially designed heat tube. Two important surface hydrodynamic parameters, i.e. the packet fraction (δ_pa) and mean packet residence time (τ_pa) based on the packet renewal theory, are determined by an optical fiber probe and a data processing method. The experimental results successfully reveal the axial and radial profiles of heat‐transfer coefficient, the effects of superficial gas velocity, and static bed height on heat‐transfer coefficient, most of which can be explained successfully by the measured τ_pa, an indicator of packet renewal frequency. τ_pa is found to play a more dominant role than δ_pa on bed‐to‐wall heat transfer. With a fitted correction factor, the modified Mickley and Fairbanks model is able to predict the heat‐transfer coefficients with enough accuracy based on the determined packet parameters. © 2014 American Institute of Chemical Engineers AIChE J, 61: 68–83, 2015     

Tomography images to analyze the deformation of the cavern in the continuous‐flow mixing of non‐Newtonian fluids

Tomography, an efficient nonintrusive technique, was employed to visualize the flow in continuous‐flow mixing and to measure the cavern volume (V_c) in batch mixing. This study has demonstrated an efficient method for flow visualization in the continuous‐flow mixing of opaque fluids using two‐dimensional (2‐D) and 3‐D tomograms. The main objective of this study was to explore the effects of four inlet‐outlet configurations, fluid rheology (0.5–1.5% xanthan gum concentration), high‐velocity jet (0.317–1.660 m s^?1), and feed flow rate (5.3 × 10^?5?2.36 × 10^?4 m³ s^?1) on the deformation of the cavern. Dynamic tests were also performed to estimate the fully mixed volume (V_{fully mixed}) for the RT, A310, and 3AM impellers in a continuous‐flow mixing system, and it was found that V_{fully mixed} was greater than V_c. Incorporating the findings of this study into the design criteria will minimize the extent of nonideal flows in the continuous‐flow mixing of complex fluids and eventually improve the quality of end‐products. © 2013 American Institute of Chemical Engineers AIChE J, 60: 315–331, 2014     

Electrochemical study of β-diketonatobis(triphenylphosphite)rhodium(I) complexes

The electrochemical behaviour of the series of ten [Rh(RCOCHCOR′)(P(OPh)₃)₂] complexes with R, R′ = CF₃, CF₃ (1), CF₃, CH₃ (2), CF₃, Ph (C₆H₅) (3), CF₃, Fc (ferrocenyl = (C₅H₅)Fe(C₅H₄)) (4), CH₃, Ph (5), CH₃, CH₃ (6), Ph, Ph (7), Fc, CH₃ (8), Fc, Ph (9) and Fc, Fc (10) were studied in acetonitrile containing 0.100 mol dm⁻³ tetra-n-butylammonium hexafluorophosphate as supporting electrolyte utilizing a glassy carbon working electrode. Results are consistent with Rh(I) being first oxidized in an electrochemically irreversible two-electron transfer process at peak anodic potentials ranging E_pa(Rh) = 0.124–0.881 V vs. Fc/Fc⁺. For the ferrocene-containing complexes (4), and (8)–(10) the rhodium oxidation was followed by the electrochemically reversible oxidation of the ferrocenyl group in a one-electron transfer process at a slightly more positive potential. Relationships were established between the electrochemical quantity E_pa(Rh) and kinetic parameter log k₂ as well the sum of experimental group electronegativities (Gordy Scale) of the R and R′ groups (χ_R + χ_R′), the Hammett σ values (σ_R + σ_R′) and the Lever ligand parameter E_L for the [Rh(RCOCHCOR′)(P(OPh)₃)₂] complexes: E_pa(Rh) (vs. Fc/Fc⁺/V) = 0.31 (χ_R + χ_R′)–1.09 = 0.56 (σ_R + σ_R′) + 0.28 = S_M (ΣE_L) + (I_M − 0.66 V) = −0.23 log k₂ − 0.03 (k₂ = second order rate constant for the oxidative addition of methyl iodide to rhodium). A profound shift of E_pa(Rh) to a more positive potential was observed for Rh(I) substrates containing β-diketonato ligands with increasing electronegative substituents R and R′. An exponential dependence of E_pa(Rh) on the pK_a of the β-diketone was obtained.     

Permanent antistatic polypropylene based on polyethylene wax/polypropylene wax grafting sodium acrylate

Two types of permanent antistatic agents, polyethylene wax grafted with sodium acrylate (PEW‐g‐AAS) and polypropylene (PP) wax grafted with sodium acrylate (PPW‐g‐AAS), were prepared using a solution grafting method and applied to PP for enhancing antistatic properties. The grafting degree was determined using back titration method and structures were confirmed by Fourier transform infrared spectroscopy. The antistatic properties of PEW‐g‐AAS/PP blends and PPW‐g‐AAS/PP blends were characterized by surface resistivities (ρ_s) and volume resistivities (ρ_v), and a combination of contact angle measurements, scanning electron microscope, permittivity, and dielectric loss were used to investigate the surface and inner structures of the blends. Results showed ρ_s and ρ_v of PEW‐g‐AAS/PP blends dropped significantly (4–7 magnitudes) above a critical addition at 10%, where a electrostatic dissipative network formed; PPW‐g‐AAS revealed an inferior antistatic performance than PEW‐g‐AAS due to its better compatibility and smaller dispersed phase in the matrix. Further, the antistatic blends treated in 80°C water, 80°C air, and room temperature were investigated, and the results were interpreted from surface energy. Moreover, the addition of antistatic agent had little impact on tensile strength of the PP matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Integral equation study of the residual chemical potential in infinite‐dilution supercritical solutions

A new method for solving the integral equation based on the Ornstein‐Zernike equation for binary mixture is proposed. Then the radial distribution function obtained for both the Percus‐Yevick and the hypernetted chain closure equations are used to calculate the residual chemical potential at infinite‐dilution and at reduced temperatures T^* = 2, 1.5 (supercritical isotherms) over a varying range of reduced densities ρ^* = 0.1 to 0.6 for various types of the Lennard‐Jones mixture in terms of size ratios D and energy ratios C. To examine the ability of the integral equation approach for the residual chemical potential calculations, the results are compared with the Monte‐Carlo simulation data and the van der Waals I results (Shing et al., 1988). It is seen that at ρ^* = 0.1 to 0.5, the deviation of the integral equation results from the MC simulation data is less than the reported statistical fluctuation.     

Expansion characteristics of an anaerobic fluidized bed reactor with internal biogas production

More realistic dynamic bed‐expansion experiments using a three‐phase anaerobic fluidized bed reactor (AFBR) with and without internal biogas production were conducted for the establishment of correlation equations for the mean volume ratio of wakes to bubbles (k). A predictive model was also developed for the expansion characteristics of the three‐phase AFBR with internal biogas production. The predicted bed‐expansion heights (H_GLS) deviated by only ±10% from the experimental measurements for the three‐phase AFBR. According to the modeling results, if a three‐phase AFBR is loaded into a carrier with low specific gravity (dry density of carrier, ρ_md = 1.37 g cm^?3; wet density of carrier, ρ_mw = 1.57 g cm^?3) and operated at a high superficial liquid velocity (u_l = 4.0 cm s^?1), the ratio of H_GLS to H_LS at a high superficial gas velocity (u_g = 1.5 cm s^?1) can reach as high as 271%. A higher fluidized‐bed height has a greater effect on the bed‐expansion behavior because of the decrease in liquid pressure (surrounding gas bubbles) along the fluidized‐bed height. From parametric sensitivity analyses, H_GLS is most sensitive to the parameter reactor width (X), especially within a small ΔX/X₀ range of ±10%; sensitive to ρ_mw, diameter of the carrier, ρ_md and total mass of carrier and least sensitive to u_l, biofilm thickness and u_g. Copyright © 2005 Society of Chemical Industry     

Glass Formation and Characterization Studies in the TeO2–WO3–Na2O System

Glass formation behavior of the TeO₂–WO₃–Na₂O system was studied by using conventional melt‐quenching technique. A wide glass formation range was determined for the first time in the literature and thermal, physical, and structural characterization of sodium‐tungsten‐tellurite glasses were realized using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy techniques. Glass transition (T_g) and crystallization (T_c/T_p) temperatures, glass stability (?T), density (ρ), molar volume (V_M), oxygen molar volume (V_O), and oxygen packing density (OPD) values and structural transformations in the glass network were investigated according to the equimolar substitution of TeO₂ by Na₂O+WO₃ and changing Na₂O or WO₃ at constant TeO₂.     

Stability of electrical properties of vanadium dioxide based ceramics

The influence of thermocycling process at VO₂ phase transition temperature (T_t≈68°C) on the resistivity temperature dependences and dielectric constant (ε) of ceramics on a basis of VO₂ and V₂O₅–P₂O₅ glasses has been studied. The differential thermal analysis and dilatometric measurements for tested ceramics has been made. Vanadium dioxide based ceramics exhibits a variation of electrical properties with thermocycling. The resistivity increases, ε and electrical resistivity jump ρ_s/ρ_m in the vicinity of T_t decrease with a growth of a number of thermocycles. The reason of such behavior is microcracks formation due to a sharp variation of thermal expansion in the vicinity of T_t. After some repetition of thermocycling process the stabilization of ceramics electrical properties has been observed, but the resistivity jump ρ_s/ρ_m has been disappeared practically. Possible reasons of the stabilization have been discussed. The stabilization of electrical resistivity jump ρ_s/ρ_m (ρ_s/ρ_m∼10²–10³) after thermocycling for thin ceramic samples (a thickness ∼0·4 mm or less) has been shown. ©     

Preparation and characterisation of BaTiO3 based PTC ceramics with high performance

Abstract

The nanocrystalline BaTiO₃ based PTC powders had been prepared by a simple sol–gel method starting from comparatively cheap raw materials. The powders and ceramics were characterised by thermogravimetry–differential scanning calorimetry, X-ray diffraction and scanning electron microscopy, while electronic properties of the ceramics were also studied. The good material electronic properties were obtained, including a Curie temperature (T _C) of 100°C, a resistivity at room temperature (ρ _25°C) of 18 Ω cm, a high resistivity step ratio (ρ _max/ρ _min) of 1·2×10⁶, a temperature coefficient of resistivity (α ₃₀) of 17% °C^?1 and a withstand voltage intensity (V _b) of 196 V mm^?1.     

Characterization of nanosilica‐filled epoxy composites for electrical and insulation applications

We report in this article the results of nanosilica (SiO₂)‐filled epoxy composites with different loadings and their electrical, thermal, mechanical, and free‐volume properties characterized with different techniques. The morphological features were studied by transmission electron microscopy, and differential scanning calorimetry was used to investigate the glass‐transition temperature (T_g) of the nanocomposites. The properties of the nanocomposites showed that the electrical resistivity (ρ), ultimate tensile strength, and hardness of the composites increased with SiO₂ weight fraction up to 10 wt % and decreased thereafter; this suggested that the beneficial properties occurred up to this weight fraction. The temperature and seawater aging had a negative influence on ρ; that is, ρ decreased with increases in the temperature and aging. The free‐volume changes (microstructural) in the composite systems correlated with seawater aging but did not correlate so well with the mechanical properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Electrically conductive nanocomposites of polyaniline with poly(vinyl alcohol) and methylcellulose

Electrically conductive nanocomposites of HCl‐doped polyaniline (PANI–HCl) nanocolloid particles with water‐soluble and film‐forming polymers such as poly(vinyl alcohol) (PVA) and methylcellulose (MC) were prepared by the redispersion of preformed MC‐coated submicrometric PANI–HCl particles in PVA and MC solutions under sonication for 1 h and the casting of the films from the dispersions followed by drying. The submicrometric polyaniline (PANI) particles were prepared by the oxidative dispersion polymerization of aniline in an acidic (1.25M HCl) aqueous ethanol (30 : 70) medium with MC as a steric stabilizer. The particles contained 4.7 wt % MC and had a conductivity of 7.4 S/cm. They had an oblong shape of 203 nm (length) and 137 nm (breadth). Sonication broke the oblong‐shaped particles to sizes of ～10 nm in the PVA matrix and ～60 nm in the MC matrix. The electrical conductivity of these films was measured, and the percolation threshold was determined. The composites had the characteristics of a low percolation threshold at a volume fraction of PANI of 2.5 × 10^?2 in the PVA matrix and at a volume fraction of 3.7 × 10^?2 in the MC matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure and electrical properties of grafted polypropylene/graphite nanocomposites prepared by solution intercalation

A novel process was developed to prepare electrically conducting maleic anhydride grafted polypropylene (gPP)/expanded graphite (EG) nanocomposites by solution intercalation. The conducting percolation threshold at room temperature (Φ_c) of the nanocomposites was 0.67 vol %, much lower than that of the conventional conducting composites prepared by melt mixing (Φ_c = 2.96 vol %). When the EG content was 3.90 vol %, the electrical conductivity (σ) of the former reached 2.49 × 10^?3 S/cm, whereas the σ of the latter was only 6.85 × 10^?9 S/cm. The TEM, SEM, and optical microscopy observations confirmed that the significant decrease of Φ_c and the striking increase of σ might be attributable to the formation of an EG/gPP conducting multiple network in the nanocomposites, involving the network composed of particles with a large surface‐to‐volume ratio and several hundred micrometers in size, and the networks composed of the boards or sheets of graphite with high width‐to‐thickness ratio and particles of fine microscale or nanoscale sizes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1864–1869, 2003