Prediction of flow stress of metallic material and interfacial friction condition at high temperature using inverse analysis

Inverse analysis is a method for determining material parameters by minimizing the difference between experimental and the finite element (FE) simulated results, such as the load-stroke curve and barreling shape of a deformed specimen using an optimum design technique. In this study, ring compression tests were conducted to predict the flow stress of materials and interfacial friction conditions. Cylinder compression tests were conducted under the same process conditions to estimate the validity of the data obtained from the ring compression tests. By comparing the experimental results with the FE simulated results, it was confirmed that flow stress and the interfacial friction condition obtained from the ring compression tests, as well as their inverse analysis, are quite reasonable. The validity of both the flow stress function and the interfacial friction condition using the above procedures was verified by the experiments.     

Dissolution of Soap Scum by Surfactant. Part II: Effects of NaCl and Added Chelant on Equilibrium Solubility and Dissolution Rate of Calcium Soap Scum in Amphoteric Surfactant Solutions

The effects of solution pH and NaCl on the equilibrium solubility and dissolution rate of a model soap scum (calcium octadecanoate or calcium stearate) in aqueous solutions of dimethyldodecylamine oxide surfactant (DDAO) with and without chelant disodium ethylenediaminetetraacetate are reported. The equilibrium solubility and dissolution rate of soap scum increased with increasing solution pH when the chelant was added in the DDAO system while in the chelant-free systems the opposite trend was observed. The added NaCl has an ambiguous effect on the solubility and dissolution rate of soap scum in the absence of chelant, but a small level of added NaCl reduces both solubility and the dissolution rate constant in the presence of chelant. Both equilibrium and kinetics of dissolution are maximized at high pH with DDAO/chelant and no added salt.     

Dissolution Study of Salt of Long Chain Fatty Acids (Soap Scum) in Surfactant Solutions. Part II: Kinetics of Dissolution

A study of the dissolution kinetics of soap scum, calcium octadecanoate (Ca(C₁₈)₂), by aqueous solutions was carried out by measuring the rate of dissolution of Ca(C₁₈)₂ using a flow cell apparatus. These solutions contained three different types of surfactants: dimethyldodecylamine oxide (DDAO), sodium dodecyl sulfate (SDS), or octyl polyglycoside (C₈APG), in the presence of a chelating agent, disodium ethylenediaminetetraacetate (Na₂EDTA). The resulting rate of dissolution corresponds well with the equilibrium solubility obtained in the part I of this series even though the dissolution is rate limited (far from equilibrium). High rates of Ca(C₁₈)₂ dissolution are achieved in solutions of zwitterionic DDAO or nonionic C₈APG with Na₂EDTA at high pH. From rate analysis, the Ca(C₁₈)₂ dissolution was found to be surface-reaction limited rather than limited by solution processes or wettability.     

Dissolution Study of Salt of Long Chain Fatty Acids (Soap Scum) in Surfactant Solutions. Part I: Equilibrium Dissolution

Dissolution of calcium salt of a long chain fatty acid or soap scum is a major challenge for hard surface cleaners since soap scum forms when soap is exposed to hard water and has very low water solubility. In this paper, the aqueous equilibrium solubility of calcium octadecanoate (or calcium stearate) was measured as a function of pH as well as chelating agent (ethylenediaminetetraacetate disodium salt) and surfactant concentrations. Anionic, nonionic, and amphoteric surfactants were studied. The highest soap scum solubility was observed at high pH with an amphoteric surfactant. Under this condition, the chelant effectively binds calcium, and the stearate anion forms mixed micelles well with the amphoteric surfactant, which is in zwitterionic form at high pH.     

Interaction Between an Anionic and an Amphoteric Surfactant. Part I: Monomer–Micelle Equilibrium

A mixture of anionic and amphoteric surfactants is composed of three components at intermediate pH levels: anionic, cationic (protonated amphoteric), and zwitterionic (unprotonated amphoteric). Knowledge of the composition of each surfactant in both monomer and micellar forms (monomer–micelle equilibrium) is important in applications using this mixture. Hydrogen ion titration of the mixed surfactant solution as a function of surfactant composition is combined with the pseudophase separation model and regular solution theory for the three-surfactant mixture to calculate the concentration of each surfactant in monomer and in micelle forms at different pH levels. The specific systems studied here contain sodium dodecyl sulfate (SDS) and dimethyldodecylamine oxide (DDAO), which are used in a wide range of consumer products. The degree of protonation of monomeric DDAO is not affected by the presence of SDS, indicating an insignificant formation of ion pairs between these monomers. However, the presence of SDS in micelles shifts the micellar pK _a of DDAO protonation significantly and the method used here allows the quantification of partial fugacities of each individual surfactant in micelle form. The composition in the monomer phase at each pH will aid in understanding and predicting solution compositions corresponding to anionic/amphoteric surfactant precipitation boundaries, which is the focus of the subsequent paper in this series.

Mechanism of antifoam behavior of solutions of nonionic surfactants above the cloud point

Aqueous solutions of nonionic surfactants exhibit low foaming above their cloud point, a temperature above which the homogeneous solutions separates into two phases: a dilute phase containing a low surfactant concentration and coacervate phase containing a very high surfactant concentration (e.g., 20 wt% surfactant). In this work, foam formation was measured for the dilute phase, the coacervate, and the mixed solution using the Ross-Miles method for nonylphenol polyethoxylates with 8, 9, or 10 ethylene oxide moieties per molecule. The dilute phase showed no antifoam effect above the cloud point if the coacervate phase was not present, and the coacervate phase foamed little in the absence of the dilute phase. The coacervate phase acts as an oil droplet antifoam to the dilute phase. From surface and interfacial tension data, entering, spreading, and bridging coefficients for this system make it appear probable that the coacervate phase is forming bridges across the film lamellae of the dilute-phase foam and acting to suppress foam formation through the bridging mechanism.     

Dissolution of Soap Scum by Surfactant Part I: Effects of Chelant and Type of Soap Scum

The equilibrium solubilities of two model soap scums [calcium stearate and magnesium stearate: Ca(C₁₈)₂ and Mg(C₁₈)₂] were measured in aqueous solutions containing three different types of surfactants: methyl ester sulfonate (MES) as an anionic; alcohol ethoxylate (EO9) as a nonionic; and dimethyldodecylamine oxide (DDAO) as an amphoteric with and without a chelating agent [disodium ethylenediaminetetraacetate (Na₂EDTA)]. The solubility of calcium soap scum was generally higher than that of magnesium soap scum, the exception being some DDAO systems. The use of the DDAO surfactant with the Na₂EDTA chelating agent at high pH gives the highest solubilities of both studied soap scums. The soap scum solubility is on the order of 2,000 times that in water at high pH. The DDAO is the most effective surfactant under all conditions. The MES is more effective than the EO9 at low pH with the opposite trend observed at high pH. The synergism from added chelant is generally greater at higher pH and is greatest for DDAO followed by EO9.     

Use of a Nonionic Surfactant to Inhibit Precipitation of Anionic Surfactants by Calcium

One synergism of using surfactant mixtures is the reduction in the equilibrium extent of and rate of precipitation. The overall time required for calcium-induced precipitation of mixed sodium dodecyl sulfate (SDS) and sodium octylbenzene sulfonate (SOBS) over a particular range of ratios has been found to increase dramatically when compared to either SDS or SOBS alone. In this study, light transmission and isoperibol calorimetry were used to measure the delay in the precipitation reaction, while scanning electron and optical micrographs of crystals formed give insight into the precipitation mechanism. The smaller the difference in the supersaturation ratio of the two precipitating surfactants, the longer the induction time is. The delay in the extent of precipitation is due to the interruption of crystal formation from dissimilar precipitating surfactants.     

Relation of Supersaturation Ratio in Mixed Anionic Surfactant Solutions to Kinetics of Precipitation with Calcium

One synergism of using surfactant mixtures is the reduction in the equilibrium extent of and rate of precipitation. The overall time required for calcium-induced precipitation of mixed sodium dodecyl sulfate (SDS) and sodium octylbenzene sulfonate (SOBS) over a particular range of ratios has been found to increase dramatically when compared to either SDS or SOBS alone. In this study, light transmission and isoperibol calorimetry were used to measure the delay in the precipitation reaction, while scanning electron and optical micrographs of crystals formed give insight into the precipitation mechanism. The smaller the difference in the supersaturation ratio of the two precipitating surfactants, the longer the induction time is. The delay in the extent of precipitation is due to the interruption of crystal formation from dissimilar precipitating surfactants.     

Dissolution of Soap Scum by Surfactants. Part III. Effect of Chelant Type on Equilibrium Solubility and Dissolution Rate of Calcium and Magnesium Soap Scums in Various Surfactant Systems

Soap scum can be effectively removed by using an appropriate surfactant with a chelating agent at a high solution pH. The equilibrium solubilities and dissolution rates of two model soap scums [calcium stearate and magnesium stearate: Ca(C₁₈)₂ and Mg(C₁₈)₂] were investigated in aqueous solutions containing three different types of surfactants [methyl ester sulfonate (MES) as an anionic surfactant; alcohol ethoxylate (EO9) as a nonionic surfactant; and dimethyldodecylamine oxide (DDAO) as an amphoteric surfactant] in the presence of different biodegradable chelants: trisodium ethylenediamine disuccinic acid (Na₃EDDS) and tetrasodium glutamate diacetic acid (Na₄GLDA) compared with disodium ethylenediamine tetraacetate (Na₂EDTA), a chelant with poor biodegradability. The highest equilibrium solubility and dissolution rate of either soap scum were observed at high pH in the DDAO system with Na₄GLDA. In addition, the calcium soap scum had a similar to higher equilibrium solubility and a higher dissolution rate constant as compared with the magnesium soap scum.