The characteristic curvature (Cc) definition and its use in assessing Cc for single ionic surfactants

The hydrophilic–lipophilic-difference (HLD) is a set of empirical equations that correlate the formulation conditions at phase inversion (HLD = 0). Based on partition studies for nonionic surfactants, the HLD can be interpreted as a normalized chemical potential difference between the surfactant dissolved in water and oil. The net-average curvature (NAC) model extrapolates this interpretation into a curvature form that has been used to fit and predict the phase behavior of surfactant-oil–water (SOW) systems. The curvature interpretation led to renaming the HLD surfactant parameter, sigma (σ), as the characteristic curvature (Cc). This work tests the validity of the curvature interpretation of the HLD, and the Cc concept, for single ionic surfactants and the use of this concept as a method to assess the Cc without the use of reference surfactants or alcohols. To this end, the net curvature of six anionic and two cationic surfactants was evaluated from solubilization data at the characteristic condition of 25°C, no added cosolvent, in the presence of an oil mixture with equivalent alkane carbon number (EACN) of zero, and as a function of salinity. These studies showed that the original HLD equation for ionic surfactant could not be interpreted as chemical potential or curvature because a salinity prefactor (coefficient) “bi” was missing. The revised equation, HLD_bi = bi∙ln(S)-k_bi∙EACN+Cc_bi -a_Tbi∙(T-25°C), could now be interpreted as a curvature expression, and it was demonstrated that Cc could be obtained from curvature using the expression Cc = Cc_bi/bi. This single surfactant method produces uncertainties that, for most surfactants, ranged from 0.2 to 1 Cc units, similar to the uncertainty obtained with the conventional method of Cc determination using mixtures of test and reference surfactants.     

Synthesis and Characterization of Novel Surfactants based on 2-Hydroxy-4-(Methylthio)Butanoic Acid Part 3: Microemulsions from Nonionic Sulfoxide Ester Surfactants

In this work, ester sulfoxide (ESO) surfactants based on 2-hydroxy-4-(methylthio) butyric acid are shown to have temperature-sensitive microemulsion phase behaviors. Both C10 (C₁₀ESO) and C12 (C₁₂ESO) surfactants studied contained one sulfoxide unit in the structure. Phase inversion temperatures (PIT) and interfacial tensions (IFT) between water-rich and oil-rich phases have been measured for ternary systems of water, oil, and sulfoxide surfactants. Hydrophilic–lipophilic deviation (HLD) parameters of these surfactants were obtained by fitting the experimental data to a semiempirical HLD equation. The characteristic surfactant parameter and temperature sensitivity of C₁₀ESO and C₁₂ESO surfactants were obtained and compared with similar ethoxylated alcohol surfactants. By comparing the characteristic parameters of these surfactants with those of ethoxylated alcohol surfactants, it was shown that one sulfoxide ester moiety is equally hydrophilic as approximately 5 ethylene oxide groups. The temperature sensitivity of the ESO was roughly a factor of four less than ethoxylated surfactants based on the temperature coefficient of the HLD equation.     

Correlation between Detergency of Different Oily and Solid Non-Particulate Soils and Hydrophilic–Lipophilic Deviation

This research examined the correlation between the detergency of soils with varying equivalent alkane carbon numbers (EACN) and hydrophilic–lipophilic deviation (HLD) values. The detergency of oily soils with EACN ranging from 5.2 to 16.6 was evaluated using C₁₀-4PO-SO₄Na as a primary surfactant system and a 1:1 binary mixture of C₁₀-4PO-SO₄Na and AOT as a confirmatory surfactant system (with 65/35 polyester/cotton at 25°C). These surfactant systems were characterized using HLD concepts which showed that C₁₀-4PO-SO₄Na was more hydrophilic (had a higher negative Cc value) than that of the mixed surfactant system. Detergency of the selected soils was evaluated at different salinities corresponding to HLD ranging from negative to positive values. The results showed that detergency of all soils increased with increasing salinity (starting with an HLD = −3.0 (Winsor Type I microemulsion)), reached the maximum at widely different optimum salinity (S*) but at an identical HLD value of zero (optimum Type III), and then decreased with further increasing salt levels corresponding to positive HLD values (Type II). The preferred HLD range from −3.0 to 0.0 showed detergency levels exceeding 80% removal with interfacial tension values (IFT) below 1 mN m⁻¹ for all oily soils studied. Detergency of octadecane (EACN = 18, solid at 25°C) was further conducted and demonstrated that performing detergency at HLD = −3.0 to 0.0 likewise revealed superior soil removal (over 80%) versus systems with HLD values outside this range. Thus, this work highlighted the utility of using the HLD approach in designing surfactant formulations for detergency of soils with widely varying EACN.     

Effect of Ethylene Oxide Group in the Anionic–Nonionic Mixed Surfactant System on Microemulsion Phase Behavior

The phase behavior of microemulsions stabilized by a binary anionic–nonionic surfactant mixture of sodium dihexyl sulfosuccinate (SDHS) and C12-14 alcohol ethoxylate (C_{12 − 14}E_j) that contains an ethylene oxide (E_j) group number, j, of either 1, 5, or 9 was investigated for oil remediation. The oil–water interfacial tension (IFT) and optimal salinity of the microemulsion systems with different equivalent alkane carbon numbers (EACN) were examined. The anionic–nonionic surfactant ratio was found to play a pivotal role in the phase transition, IFT, and optimal salinity. The minimum IFT of mixed SDHS − C_{12 − 14}E_j systems were about three times lower than those of neat SDHS systems. A hydrophilic–lipophilic deviation (HLD) empirical model for the mixed anionic–nonionic surfactant system with the characteristic parameter was proposed, as represented in the excess free energy term . The results suggested that the mixed system of SDHS − C_{12 − 14}E₁ was more lipophilic, while SDHS − C_{12 − 14}E₉ was more hydrophilic than the ideal mixture (no excess free energy during the microemulsion formation), and the SDHS − C_{12 − 14}E₅ system was close to the ideal mixture. The findings from this work provide an understanding of how to formulate mixed anionic–nonionic microemulsion systems using the HLD model for oils that possess a wide range of EACN.     

Densification mechanisms of UO2 consolidated by spark plasma sintering

Despite the growing interest in the spark plasma sintering (SPS) of uranium dioxide, its sintering mechanisms have yet to be studied in great detail. Herein we propose a direct method to calculate the apparent activation energy for densification, Q_act, and the stress exponent, n, for SPS of nearly stoichiometric UO₂. A set of experiments performed at different heating rates (CHR) and different pressures levels allowed us to calculate Q_act and n, respectively, though we were limited to a theoretical density between 50% to 75 %. The master sintering curve was employed as a complementary method to compare Q_act. The average values were Q_act =96 kJ/mol (CHR), Q_act = 100 kJ/mol (MSC) and n = 1.4. We have therefore proposed grain boundary diffusion coupled with grain boundary sliding as the densification mechanism. The activation energy in SPS tends to be lower compared with that in other processes like conventional sintering (250?450 kJ/mol), creep (350?550 kJ/mol) and hot pressing (222 kJ/mol and 480 kJ/mol).This decrease could be due to the effect of the electric field combined with the higher heating rates, typical of SPS.     

Catalytic Synthesis of Higher Aliphatic Amines from the Corresponding Alcohols

Abstract

Aliphatic amines are of considerable industrial importance and find application in almost every field of modern technology, agriculture, and medicine [1], Lower aliphatic amines (C₁ to C₆) are important intermediates for the chemical and pharmaceutical industries. A large number of drugs, herbicides, pesticides, dyes, and other chemicals contain amino pups which originate from reactions with such intermediates, Many important applications of higher aliphatic amines (fatty amines) and their derivatives (most important derivatives are quarternary ammonium compounds) are based on their cationic surface activity. Relatively small amounts of such compounds are usually required to achieve the desired changes in surface and colloidal properties. Thus, not surprising, one of the first applications of fatty amines was in the flotation separation of nonmetallic materials such as potash, feldspar, phosphate, and mica. Today, probably the biggest demand for fatty amines lies in the production of fabric softeners. There are other important applications for aliphatic amines in the plastics and protective coat industries as emulsion stabilizers, mold release agents, pigment dispersers, and flushing agents. They are used as catalysts for polyurethane production. For granular products, alkylamines are used as anticaking and antidusting agents. In the rubber industry they are used as oxidation inhibitors and catalysts for accelerating vulcanization. Aliphatic amines find also many applications in the petroleum industry, especially as corrosion inhibitors and as components of lubricating oils, greases, and fuel oil where they act as sludge dispersants and stabilizers. They are added to gasoline as corrosion inhibitors.     

Water solubilization in microemulsions containing amines as cosurfactant

Water-in-oil microemulsions were produced by mixing different combinations of the cationic surfactants cetyltrimethylammonium bromide and cetylpyridinium chloride,n-alkanes (C₅–C₇) and benzene as oils,n-alkylamines (C₆ and C₈) and cyclohexylamine as cosurfactants with water. The influence of chainlength of the alkanes and amines on water solubilization behavior of these systems has been investigated. The solubilization of water in a particular microemulsion is governed by the partitioning of amines among oil, water and interfacial phases, depending on the chainlength and nature of oil and amine, and their interaction with the surfactant. The molar ratio of amine to surfactant at the droplet interface increased with the length of the oil chain. The free energy changes accompanying cosurfactant adsorption at the interface have also been computed.     

Laboratory investigation of reinforcement corrosion initiation and chloride threshold content for self-compacting concrete

Time-to-corrosion (T_i) of reinforcement in concrete and chloride threshold content (C_th) are important service life determinants for reinforced concrete structures in chloride-laden environments. In this study, the two determinants of a series of self-compacting concretes (SCC) and regular concretes were experimentally investigated. A new sampling approach for C_th determination (milling powder from corrosion active site at the rebar/concrete interface) was adopted to accurately express chloride content resulting in corrosion occurrence. It is found that the T_i and C_th follow the 3-parameter Weibull distribution. The results indicate that the corrosion initiation of rebar in concrete slabs depends upon both cement alkalinity and superplasticizer. Rebar, embedded in high alkalinity cement SCC, exhibits better corrosion resistance as indicated by the longer T_i, higher C_th and larger Weibull modulus, m. A larger Weibull modulus indicates that anti-corrosion performance of rebar in slabs is more stable and less scattered. The effects of specific superplasticizer on rebar corrosion resistance are discussed from the viewpoint of air void amount and size distribution at the rebar/concrete interface.     

Improved cold-water detergency of malodourous soil correlating with hydrophilic–lipophilic deviation concept

The persistence of sebum after low-water-temperature washing can contribute to malodor and microbial growth during subsequent use; thus, this work focuses on improved sebum removal. The detergency of sebum at various hydrophobic–lipophilic deviation (HLD) values was performed using 0.1 w/v% C_12-13-8PO-SO₄Na and C₈-4PO-1EO-SO₄Na at 1:1 molar ratio. The detergency of synthetic sebum on 87/13 polyester/spandex was relatively poor (70% removal) at HLD = 0. Various additives (heptanol, dipropylene glycol n-butyl ether, decyltrimethyl ammonium bromide or sodium benzoate) were explored and it was found that none of them could facilitate sebum removal on the 87/13 polyester/spandex surface. On the other hand, adding low molecular weight primary amines (ethylene diamine, or monoethanolamine [MEA]) in the surfactant system without salt showed sebum removal of 70%–80% depending on the amine molecule. Adding MEA as a detergency additive with salt appeared to achieve good detergency (>80% removal) at all studied HLD numbers between −1.0 and 1.1 and the maximum detergency (approximately 90% removal) was observed at the optimum formulation (HLD = 0). The formulation pH with added MEA decreased from 11 to roughly 9. Detergency performance with added MEA was not dependent on pH within the studied basic conditions. The principal cold water sebum removal mechanism was found to be detachment of solid sebum fractions, dispersed in the detergent bath or floating on the bath surface.     

Design,Synthesis, and Biological Evaluation of Novel 6H-Benzo[c]chromen-6-one Derivatives as Potential Phosphodiesterase II Inhibitors

Urolithins (hydroxylated 6H-benzo[c]chromen-6-ones) are the main bioavailable metabolites of ellagic acid (EA), which was shown to be a cognitive enhancer in the treatment of neurodegenerative diseases. As part of this research, a series of alkoxylated 6H-benzo[c]chromen-6-one derivatives were designed and synthesized. Furthermore, their biological activities were evaluated as potential PDE2 inhibitors, and the alkoxylated 6H-benzo[c]chromen-6-one derivative 1f was found to have the optimal inhibitory potential (IC₅₀: 3.67 ± 0.47 μM). It also exhibited comparable activity in comparison to that of BAY 60-7550 in vitro cell level studies.     

Synthesis and Characterization of Privileged Monodentate Phosphoramidite Ligands and Chiral Brønsted Acids Derived from d-Mannitol

The synthesis of several novel chiral phosphoramidite ligands (L1–L8) with C₂ symmetric, pseudo C₂ symmetric secondary amines and chiral Brønsted acids 1a,b has been achieved. These chiral auxiliaries were obtained from commercially available d-mannitol, and secondary amines in moderate to excellent yields. Excellent diastereoselectivites of ten chiral auxiliaries were obtained. The chiral phosphoramidite ligands and chiral Brønsted acids were fully characterized by spectroscopic methods.     

A polyacrylonitrile-based gelled electrolyte: electrochemical kinetic studies

The bulk and interfacial properties of thin films of a polyacrylonitrile-based (PAN-based) gelled electrolyte, which was tested in conjunction with lithium electrodes, were evaluated at room temperature. The typical composition of the gelled electrolyte (GE) studied was PAN (9.13 wt %); propylene carbonate, or PC (84.87 wt %); and LiBF₄ (6 wt %). A.c. and d.c. measurements were used to determine the bulk conductivity and the interfacial apparent charge-transfer resistance (R _act) of the GE. While the bulk conductivity remains stable at around 10^–3 S cm^–1, the R _act varies initially before reaching a steady value. The steady R _act value obtained from the electrochemical measurements is near 1000 cm². The plating/stripping efficiency of lithium, from potentiostatic and galvanostatic measurements, is 70 to 80%.     

Classification of Fragrances and Fragrance Mixtures Based on Interfacial Solubilization

In the present study, the influence of perfumes on the interfacial curvature of microemulsions is investigated. The hydrophilic-lipophilic deviation (HLD) concept was applied to nonionic Winsor I type systems (O/W microemulsions in equilibrium with an oil excess phase) containing a mixture of oils with isopropyl myristate as supporting oil and a variety of liquid solutes as co-oil for which an Equivalent Alkane Carbon Number of the mixture (EACN_mix) was defined. Temperature was used as a formulation variable and the phase inversion temperature change, provoked by the solubilization of different solutes, was determined. The hydrodynamic radius of the droplet and the interfacial solubilization of fragrances were measured subsequently and correlated to the EACN_mix. In a first step, selected perfumery raw materials (PRMs) were used as solutes and were studied separately. It was demonstrated that the PRMs can be classified in interfacial solubility according to their chemical functionalities and they follow the order alcohols > aldehydes > terpenes > aromatics > alkanes. Solutes that lead to low EACN_mix values (<6) have preferential interfacial solubility and provoke strong curvature changes, whereas those leading to higher EACN values (>6) typically do not change the curvature significantly. The HLD method was also applied to complex fragrances and it was demonstrated that they can be considered as single, non-polar entities, and studied as such instead of investigating each raw material included in the composition separately. Determination of the dimensionless number EACN_mix offers the possibility of classifying perfumes in an environment similar to surfactant formulations of typical consumer products and to predict the interaction with the surfactant base according to the rules established on the basis of the individual raw materials.     

Monitoring the degradation of a high solids epoxy coating by means of EIS and EN

This paper reports a study of the degradation processes suffered by steel samples painted with a high solid content epoxy coating. Because this coating shows a high resistance when exposed to NaCl solutions, HCl solutions were employed to accelerate the corrosion processes. Macroscopic images were used to observe the coating degradation. Then electrochemical techniques, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) were employed to monitor the corrosion behaviour of the system studied. A close correlation was found between EIS and EN data. Several parameters were estimated using these techniques: R_po, R_ct, C_c, C_dl and Z_0.1 Hz using EIS, and R_n using EN. In addition, a new parameter estimated by means of EN was employed, Z_0.1 Hz(EN). The evolution of all these parameters with time enabled the effective monitoring of the degradation stage of the coating.     

Non-Arrhenius temperature dependence of direct-current conductivity in amorphous carbon (a-C:H) above room temperature

The temperature dependence of the direct-current (DC) electrical conductivity (σ) of hydrogenated amorphous carbon (a-C:H) does not exhibit Arrhenius-type behavior at and above room temperature. By increasing the temperature the actual activation energy, E_act, defined as the local gradient in a plot of ln σ versus reciprocal temperature, increases continuously by a rate depending on the material properties. This sort of temperature dependence of DC conductivity is expected when the distribution of tail states is very broad and the mobility edge is not sharp. In such a case the energy at which the dominant transport process takes place may change drastically with temperature. This argument gains strong support from our present results: thermal annealing and higher deposition self-bias decrease those potential barriers which localize the π electrons and result in a much weaker dependence of E_act on temperature. After annealing the actual activation energy decreases and, for samples deposited at −700 V self-bias, E_act becomes nearly constant. The structural changes caused by thermal treatment and by deposition voltage were monitored by Raman scattering measurements.     

Determination of the glass transition temperature of poly(styrene-co-divinylbenzene) by inverse gas chromatography

Inverse gas chromatography (i.g.c.) was used to characterize the supermolecular structure of modified, moderately crosslinked poly(styrene-co-divinylbenzene) (5–20 wt%) and to determine the interactions with normal alcohols (C₁C₆). For all copolymers a decrease of retention time with increasing molecular weight of alcohols from C₁ to C₃ followed by an increase for C₄ to C₆ alcohols was observed. It was found that with propanol or butanol the measured T_g values were close to those measured by d.s.c. The T_g values for poly(styrene-co-divinylbenzene) containing 5, 10 and 20 wt% divinylbenzene were: 102°C, 116°C and 133°C respectively. The highest alcohols (C₅ and C₆) acted as plasticizers and reduced the apparent T_g value. The relationship between the isosteric heat of adsorption and the number of carbon atoms in the alcohols was nonlinear with a minimum corresponding to butanol.     

Radical polymerization of butyl acrylate and random copolymerization of styrene and butyl acrylate and styrene and methyl methacrylate mediated by monospiro- and dispiropiperidinyl-N-oxyl radicals

Radical polymerization of butyl acrylate (BA) and random copolymerizations of styrene (St) and BA and St and methyl methacrylate (MMA) in the presence of 7-aza-15-hydroxydispiro[5.1.5.3]hexadecane-7-yloxyl (1) and 1-aza-2,2-dimethyl-4-hydroxyspiro[5.6]dodecane-1-yloxyl (2) were carried out. Radical polymerization of BA at 120 °C in the presence of 1 gave poly(BA) with M_n=20200 and M_w/M_n=1.30 at 23% conversion. The termination of polymerization observed around ∼20% conversion was solved to a certain extent by an addition of small amounts of dicumyl peroxide, and poly(BA) with M_n=37400 and M_w/M_n=1.33 was obtained in 46% yield. Random copolymerizations of St and BA and St and MMA in the presence of 1 and 2 at 80 °C gave the corresponding random copolymers with narrow polydispersities of 1.12-1.38 at the molar fraction above 0.30 of St in feed. The kinetic study for the NO-C bond homolysis of the corresponding alkoxyamines prepared from 1 and 2 were carried out, and evaluation of the preexponential factors (A_act) and the activation parameters (E_act) showed that the steric factors of the nitroxides are reflected mainly on E_act.     

Protective abilities of nanocomposite coatings containing Al2O3 nano-particles loaded by CeCl3

The protective ability of hybrid nano-composite oxysilane coatings, deposited via sol–gel method on AA2024-T3 – aluminium alloy, were studied by linear voltammetry (LVA) and electrochemical impedance spectroscopy (EIS) methods in 0.05 M solution of NaCl. Cerium chloride (CeCl₃) was incorporated as an inhibitor into a sol–gel hybrid matrix in two different routes: directly and via filled porous Al₂O₃ nano-particle aggregates with diameters up to 500 nm. The influences of the inhibitor concentration, as well as the influence of nano-particles on the barrier properties and the susceptibility against corrosion, were evaluated and EIS spectra were fitted by appropriated equivalent circuits. The values for C_coat, R_coat, C_oxy and R_oxy were achieved and their evolution over time was investigated. The investigated coatings possess highly expressed barrier properties (10⁶ to 10⁷ Ω cm²). Despite of the chloride ions inside of the matrix, some samples illustrated a significant durability of over 4000 h during exposure to the corrosion medium before first signs of corrosion appeared. The electrochemical results were compared with the neutral salt spray test. Thus, it was proved that the potential of these coatings is to be used as anticorrosive protective materials and are candidate to replace Cr(VI)-based anti-corrosion coatings.     

CFD simulation of gas–liquid flow in a high-pressure bubble column with a modified population balance model

In this study, based on the Luo bubble coalescence model, a model correction factor C_e for pressures according to the literature experimental results was introduced in the bubble coalescence efficiency term. Then, a coupled modified population balance model (PBM) with computational fluid dynamics (CFD) was used to simulate a high-pressure bubble column. The simulation results with and without C_e were compared with the experimental data. The modified CFD-PBM coupled model was used to investigate its applicability to broader experimental conditions. These results showed that the modified CFD-PBM coupled model can predict the hydrodynamic behaviors under various operating conditions.     

Drag on a single fluid sphere translating in power-law liquids at moderate Reynolds numbers

A numerical investigation has been carried out to obtain the steady state drag coefficients and flow patterns of a single Newtonian fluid sphere sedimenting in power-law liquids. A finite difference method based simplified marker and cell (SMAC) algorithm has been implemented on a staggered grid arrangement to solve the continuity and momentum equations. For both phases, the convective terms have been discretized using the quadratic upstream interpolation for convective kinematics (QUICK) scheme, and diffusive and non-Newtonian terms with central differencing scheme. An exponential transformation has been applied in the radial direction for the continuous phase computational domain. In order to ensure the accuracy of the solver, extensive validation has been carried out by comparing the present results with the existing literature values for a few limiting cases. Further, in this study the effects of the Reynolds number (Re_o), internal to external fluid characteristic viscosity ratio (k) and power-law index (n_o) on the continuous phase flow field, pressure drag (C_dp), friction drag (C_df) and total drag (C_D) coefficients have been analyzed over the range of parameters: 5?Re_o?500, 0.1?k?50 and 0.6?n_o?1.6. Based on numerical results obtained in this work, a simple correlation has been proposed for the total drag coefficient, which can be used to predict the rate of sedimentation of a fluid sphere in power-law liquids.