Vergleich des Koaleszenzverhaltens ruhender und umströmter Wasser‐in‐Öl‐in‐Wasser‐Einzeltropfen

Phase inversion of a water‐in‐oil emulsion to a water‐in‐oil‐in‐water double emulsion is practically used for liquid/liquid separation. For successful separation in the water leg the coalescence of the internal droplets with the surrounding continuous water phase is decisive. The determination of this coalescence phenomenon is applied for the process design. Therefore, single water‐in‐oil‐in‐water drops are investigated under static and dynamic conditions by means of high speed imaging. The influence of physical and geometrical parameters on the coalescence time and partial coalescence is determined.     

Study of Binary‐Solid Liquid Fluidized Beds

A proper characterization of the hydrodynamics of binary‐solid liquid fluidized beds is an important first step in its effective utilization. Of particular importance in this connection is to be able to predict the unique hydrodynamic phenomenon of the layer‐inversion, which is associated with the change of the stratification pattern of the two solid species in the fluidized bed brought about due to a change either in the liquid velocity or the bed composition. Past few years have witnessed the development of several models for the prediction of the layer‐inversion phenomenon. It is, therefore, important to analyze their predictions in the light of the growing wealth of the literature data. Such an exercise is important to examine the underlying assumptions and propose modifications to improve their predictive capability. Predictions of well‐known layer‐inversion models are compared with the experimental data reported in the literature including our own which comprises of solid species of widely different size, and therefore, provide an important test of predictive capability of models.     

Experimental investigation of phase inversion in a stirred vessel using LIF

A non-intrusive dye tracing technique, laser-induced fluorescence (LIF), has been applied to investigate phase inversion in concentrated immiscible organic-aqueous liquid dispersions. The phase inversion process from oil-in-water (o/w) dispersion to water-in-oil (w/o) dispersion has been recorded by a high-speed video camera. Apart from phase inversion, secondary dispersion, drop coalescence and breakup mechanisms, have also been observed in great detail. The experimental results demonstrate that phase inversion is a gradual phenomenon: the process occurs only over 1-2 s, may not occur globally and depends on the local phase distribution. During phase inversion, two opposing pairs of processes, namely drop coalescence and break-up, and the inclusion and escape of small drops in larger drops, play a key role in phase inversion. The structure of the dispersion is extremely complex and a great number of secondary dispersions and multi-dispersions appear during phase inversion, which include water-oil-water secondary dispersions.     

Prediction of Layer‐Inversion Behavior of Down‐Flow Binary Solid‐Liquid Fluidized Beds

The layer‐inversion behavior of down‐flow binary solid‐liquid fluidized beds is predicted using the property‐averaging approach. The binary pair in this case consists of a larger solid species which is also heavier than its smaller counterpart, while both are lighter than the fluidizing medium. The model is based on using the generalized Richardson‐Zaki correlation for evaluation of the bed void fraction wherein mean values of particle properties are used. However, unlike the maximum bulk density condition for the conventional up‐flow binary solid fluidized bed, the model is based on a minimum bulk density condition for occurrence of layer inversion. This is due to the fact that the volume contraction phenomenon associated with the mixing of unequal solid species leads to a decrease in bulk density of the bed. Model predictions are also compared using the limited data available in the literature. Predictions are consistent with the observed mixing behavior.     

Phase Inversion and Associated Phenomena in Oil‐Water Vertical Pipeline Flow

Phase inversion and its associated phenomena are experimentally investigated in co‐current upward and downward oil‐water flow in a vertical stainless steel test section (38 mm I.D.). Oil (ρ_o=828 kg/m³, µ_o=5.5 mPa s) and tap water are used as test fluids. Two inversion routes (w/o to o/w and o/w to w/o) are followed in experiments where either the mixture velocity is kept constant and the dispersed phase fraction is increased (type I experiments), or the continuous phase flow rate is kept constant and that of the dispersed phase is increased (type II experiments). By monitoring phase continuity at the pipe centre and at the wall it was found that phase inversion does not happen simultaneously at all locations in the pipe cross‐section. In type I experiments, the velocity ratios (U_o/U_w) where complete inversion appeared acquired the same constant value in both flow directions, although the phase inversion points, based on input phase fractions, were different. In contrast to previous results in horizontal flows, frictional pressure gradient was found to be minimum at the phase inversion point. The interfacial energies of the two dispersions before and after phase inversion, calculated from the measured drop sizes, were found to be different in contrast to the previously suggested criterion of equal energies for the appearance of the phenomenon. In type II experiments the phase inversion point was found to depend on mixture velocity for low and medium velocities but not for high ones. In all cases studied an ambivalent region, commonly reported for inversion in stirred vessels, was not observed.     

Physical and electrochemical characterizations of poly(vinylidene fluoride‐co‐hexafluoropropylene)/SiO2‐based polymer electrolytes prepared by the phase‐inversion technique

Highly porous poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF–HFP)‐based polymer membranes filled with fumed silica (SiO₂) were prepared by a phase‐inversion technique, and films were also cast by a conventional casting method for comparison. N‐Methyl‐2‐pyrrolidone as a solvent was used to dissolve the polymer and to make the slurry with SiO₂. Phase inversion occurred just after the impregnation of the applied slurry on a glass plate into flowing water as a nonsolvent, and then a highly porous structure developed by mutual diffusion between the solvent and nonsolvent components. The PVdF–HFP/SiO₂ cast films and phase‐inversion membranes were then characterized by an examination of the morphology, thermal and crystalline properties, absorption ability of an electrolyte solution, ionic conductivity, electrochemical stability, and interfacial resistance with a lithium electrode. LiPF₆ (1M) dissolved in a liquid mixture of ethylene carbonate and dimethyl carbonate (1:1 w/w) was used as the electrolyte solution. Through these characterizations, the phase‐inversion polymer electrolytes were proved to be superior to the cast‐film electrolytes for application to rechargeable lithium batteries. In particular, phase‐inversion PVdF–HFP/SiO₂ (30–40 wt %) electrolytes could be recommended to have optimum properties for the application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 140–148, 2006     

Liquid velocity in a high‐solids‐loading three‐phase external‐loop airlift reactor

BACKGROUND: Airlift reactors are of interest for many different processes, especially for three‐phase systems. In this study the behavior of a high‐loading three‐phase external‐loop airlift reactor was examined. In particular, the effect of parameters such as airflow rate (riser superficial gas velocities between 0.003 and 0.017 m s^?1), solids loading (up to 50%, v/v) on liquid circulation velocity in the air‐water‐alginate beads system as a crucial hydrodynamic parameter was studied. RESULTS: It was observed that increase of the airflow rate resulted in increase of the liquid velocity in the system. The same result but less pronounced was observed by introducing small amounts of solid particles up to 7.5% v/v. However, further introduction of solids caused decrease of the liquid velocity. Laminar regime for the liquid circulation was observed for low gas velocities. Minimum gas velocities for recirculation initiation in the reactor were determined for all solid loadings and linear dependence on the solid content was found. Gas holdups for the three‐phase system were larger than for the two‐phase system in all experiments. A simple model for predicting the liquid circulation velocity in the three‐phase system with high solid loading of low‐density particles was developed. This model is based on the viscosity of integrated medium (solid + liquid) which is a new aspect to analyze this phenomenon. CONCLUSIONS: The developed model shows very good agreement with the experimental results for all solid loadings. It also includes the influence of reactor geometry on the liquid circulation velocity thus enabling optimization. Copyright © 2012 Society of Chemical Industry     

Neue Untersuchungen zum Phänomen Aussalzen mit einem nahekritischen Gas

Investigations on gas‐induced phase split, i.e., salting out by a nearcritical gas, were carried out for several aqueous solutions (including an ionic liquid). The research aimed to verify and characterize high‐pressure multiphase equilibria that might be suitable for technical applications. The respective criteria are occurrence at relatively low pressures and the existence of the phase equilibrium phenomenon over a significant region of both composition and pressure, which is related to a pressure‐induced significant alteration of the compositions of the coexisting liquid phases. The employed ionic liquids revealed the expected phase behavior but without full compliance of all criteria. In anticipation of an application, the partitioning of an amphiprotic, high‐molecular biomolecule to the coexisting liquid phases was successfully administered via a pH variation.     

Laboratory investigation of inversion of heavy oil emulsions

Laboratory investigations have been undertaken to assess the suitability of heavy oil‐in water emulsions for pipeline transportation. The emulsions contained 65% oil in water and were prepared using polyethoxy nonylphenol surfactants. Two methods were employed for simulating the shear process which accompanies pipeline flow: a bench scale stirred vessel and a rotated pipe toroid. The progress of the emulsions towards inversion, at which point the oil becomes the continuous phase, was followed by measuring the surfactant concentration in the aqueous phase using liquid chromatography. At inversion the surfactant concentration falls below the threshold level required to sustain an oil‐in‐water emulsion. The experiments showed that the lifetime of the emulsion depends upon the initial surfactant dosage, the solids content of the oil, the intensity of shear and the nature of the shear process. Laminar flow was found to be less desirable than turbulent flow.     

Droplet size and viscosity of tackifier emulsions formed via phase inversion

Tackifier dispersions used in pressure‐sensitive adhesives are made by phase inverting an aqueous rosin ester emulsion. The recipe also includes rosin acid and potassium hydroxide which react to form a surfactant. The amount of surfactant available plays a key role in determining dispersion properties. As the surfactant concentration increases, the point of phase inversion is delayed to larger dispersed phase concentrations. This also results in excess dispersant in the liquid phase and a narrower particle size distribution, even though the droplet size remains relatively unchanged.     

Effect of mixed solvents on phase inversion of polymeric membranes

The thermodynamics of phase inversion of polyvinylidene fluoride membrane with mixed solvents (N,N‐dimethyl formamide (DMF) and acetone) were modeled using Flory–Huggins theory. The kinetics of phase inversion were studied by measuring solvent concentration in the precipitation bath. A model was proposed to predict the time‐dependent solvent concentration profile in the precipitation bath. Depending on solvent volatility, the duration of the kinetics‐dominated regime and the evaporation‐dominated regime varies. A comparative analysis of thermodynamic and kinetic factors was used to predict membrane morphology and it was observed that the system under consideration was thermodynamics dominated. The membrane porosity exhibited decreasing porosity up to the Ac60 membrane (acetone to DMF ratio 60) and thereafter the membrane sublayer showed small pores. Addition of acetone resulted in increased crystallinity and surface hydrophilicity. The mean flow pore diameter measured using a liquid–liquid porometer decreased from 105 nm for an Ac0 membrane (acetone to DMF ratio 0) to 17 nm for an Ac60 membrane. Correspondingly, the molecular weight cut‐off of the membranes decreased from 135 kDa (for the Ac0 membrane) to 104 kDa (for the Ac60 membrane). The model proposed in this work can be used as a tool to predict the properties of intermediate compositions and prepare tailor‐made membranes with desired properties. © 2020 Society of Chemical Industry     

Role of operating conditions in determining droplet size and viscosity of tackifier emulsions formed via phase inversion

Water‐based pressure‐sensitive adhesives are formulated by combining a polymer latex with a tackifier emulsion. The latter is an oil‐in‐water emulsion made by the process of phase inversion. The phase inversion itself is carried out in a stirred tank fitted with a heating jacket by progressively adding water to a water‐in‐oil emulsion. The point of onset of phase inversion and the characteristics of the emulsion that is formed depend on process conditions; these include temperature, rate of water addition, and agitation speed. The role of these operating conditions is elucidated here. Increasing temperature delayed the onset of phase inversion slightly, but it did not affect emulsion particle size, provided it remained below a critical value. Agitation speed had to be increased upon increasing the water flow rate to prevent increasing the particle size. Finally, the point of onset of phase inversion could be predicted reasonably well using a model available in the literature. © 2010 American Institute of Chemical Engineers AIChE J, 57: 96–106, 2011     

相态逆转及其密度波的不稳定性

在长度／直径比为1250的水平管内研究了液液相态逆转现象及其对油水两相流和油气水多相流水动力特性的影响．以双流体模型为基础,考虑悬浮相所受的雷诺应力,提出了描述气液两相流和液液两相流中密度波不稳定性的通用模型．模型计算结果表明,“水包油”流型与“油包水”流型之间的相态逆转在悬浮相体积分数为0.3左右发生,与经验性结论相吻合,揭示了相态逆转的机理．     

Mass transfer dynamics of the evaporation step in membrane formation by phase inversion

A ternary diffusion model has been developed for the evaporation step of the phase inversion process. The model is applied to the analysis of mass transfer dynamics of the evaporation step for the methanol–acetone–cellulose acetate (CA) ternary casting system. The combined analysis of quantitatively computational results from the ternary evaporation model and qualitative dynamic results during the quench process has shown that the evaporation step is essentially necessary to prepare the defect‐free, ultrathin skinned asymmetric CA membrane for the separation of CO₂/CH₄. The skin layer of high CA concentration obtained by evaporation has an ability to suppress liquid–liquid phase separation. And the skin layer with high tensile strength can resist the interfacial tension caused by spinodal decomposition from the substructure. Although the CA concentration in the skin layer increases considerably because of the evaporation step and the following delay time during the quench process, the substructure can still induce the spinodal decomposition because the strong coagulant, methanol, can diffuse rapidly across the ultrathin skin layer. Hence the defect‐free, ultrathin‐skinned asymmetric membrane for gas separation can be prepared from methanol–acetone–CA casting system by evaporation step and the wet phase inversion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1564–1571, 2002     

Morphology,nanomechanical and thermodynamic surface characteristics of nylon 6/feather keratin blend films: an atomic force microscopy investigation

The surface structure and nanomechanical properties of solution‐cast nylon 6 (NY6)/feather keratin (FK) blend films were investigated using a combination of tapping‐mode atomic force microscopy (AFM) phase imaging and nanoscale indentation. A tendency for a nanoscale phase separation between NY6 and FK in their various blends was judged based on the blend phase images. The surface topography and roughness analysis of the AFM height images revealed that FK‐rich blends had coarser surfaces than NY6‐rich ones, possibly due to the heterogeneous nature of the FK chemical structure. Amplitude–phase–distance measurements involving the assignment of the darker and brighter regions of the phase images to NY6‐rich and FK‐rich, respectively, or vice versa led to the recognition of a phase inversion in the blend containing 40 wt% FK. The occurrence of the phase inversion phenomenon was related to the significant difference between the molecular weights of the blend constituents. Analysis of nanoindentation data showed that blending FK and NY6 at various ratios resulted in mixtures with modified mechanical and adhesion features. On the one hand, the NY6 component was responsible for an enhanced elastic modulus and stiffness of the blends, and on the other hand, the FK component provided higher pull‐off force and work of adhesion for the samples. A new approach is also proposed to directly determine the surface energy (γ) values of samples from the nanoindentation data. The excellent consistency between the calculated γ values and the results obtained from contact angle measurements lends credence to the proposed approach. Copyright © 2012 Society of Chemical Industry     

Phase inversion and mass transfer during liquid–liquid dispersed flow through mini-channel

The present study aims to identify means of process intensification during liquid–liquid flow through a mini-channel. During liquid–liquid flow, depending on the flow conditions either the organic or the aqueous phase can be dispersed and with increase in flow velocity the dispersed phase can spontaneously invert to form the continuous phase or vice-versa. The present study aims to investigate the phenomena of phase inversion and its influence on mass transfer during toluene/acetic acid-water flow in a 1.98 mm glass mini-channel. It is observed that for organic phase as dispersed regime, higher mass transfer efficiency is achieved when the liquid–liquid mixture is in the phase inversion zone which marks the transition from organic to aqueous phase dispersion. The mixture velocities as well as the inlet concentration of diffusing species influence mass transfer characteristics in this zone. The results have indicated some interesting observations which can be exploited for process intensification in monolith and micro-reactor.     

Novel phase inversion process for symmetric membrane formation through thermal quenching of polymer solution in same solvent

A new and useful form of phase inversion for the formation of porous polymeric membranes is presented herein. As in the case of thermally induced phase separation (TIPS), this new form involves only two components (polymer and solvent) and a thermal quench; here the quench is accomplished via immersion in a cold bath of the micromolecular component (solvent) of the dope. Ιn terms of a fixed‐pressure two‐component phase diagram the quench is a non‐vertical one. We will refer to the new method as cold‐solvent induced phase separation (CIPS). In the present work we study mainly the poly(ethylene‐co‐vinyl alcohol)/1,3‐propanediol system which leads to bi‐continuous structures stemming from a combination of liquid‐liquid demixing and crystallization. In addition, we compare with the case of the Nylon‐l2/formic acid system that we have briefly considered before and study further herein; the consequences of the TIPS to CIPS shift of method are different for the two systems, and the two situations are representative of two general possibilities. We also report general properties such as porosity, tensile strength, water permeation flux, and crystallinity of the produced poly(ethylene‐co‐vinyl alcohol) membranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42282.     

Formation of poly‐vinyl‐alcohol structures by supercritical CO2

Poly‐vinyl‐alcohol (PVA) porous structures have been prepared using a supercritical phase inversion process in which supercritical carbon dioxide (SC‐CO₂) acts as the nonsolvent. First, we tested the versatility of the SC‐CO₂ phase inversion process, forming PVA/dimethylsulfoxide (DMSO) solutions with polymer concentrations ranging from 1 to 35% (w/w) and changing the process parameters. We worked at temperatures from 35 to 55°C and pressures from 100 to 200 bar obtaining different membranes morphologies: dense films, membranes with coexisting morphologies, and microparticles. However, we did not produce symmetric or asymmetric porous membranes. To obtain this result, we used casting solutions formed by adding acetone to DMSO with the aim of modifying the affinity between SC‐CO₂ and the liquid solvent. In this series of experiments, we obtained asymmetric membranes with skin layer thicknesses lower than 10 μm. The results obtained in this work have been explained considering that the membranes formation mechanism is related to the kinetics of the process; i.e. the affinity between the solvent (mixture of solvents) and SC‐CO₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of temperature on the phase inversion of chlorinated polypropylene

In this study, the maleic anhydride modified chlorinated polypropylene (MCPP) resin was emulsified by mixed ionic surfactants comprising sodium dodecyl sulfate (SDS) and sulfonated castor oil (SCO). The influence of temperature on the morphology of emulsion was studied through transitional and catastrophic inversion methods. The transitional inversion of emulsion from water‐in‐oil (W/O) to oil‐in‐water (O/W) was triggered by decreasing the temperature and the catastrophic inversion was achieved by increasing the weight fraction of water. The results of transitional and catastrophic inversion both indicated that the phase inversion of “ionic surfactant–MCPP–water” system is easier to trigger at low temperatures than at high temperatures, which could be interpreted by the thermodynamic and hydrodynamic theory. Incomplete phase inversion occurred at low temperatures when the volume of water phase was small and emulsions with small particle size and narrow particle size distribution could only be obtained at an intermediate temperature. These results are of great importance for the preparation of stable polymer emulsions in food, cosmetics and paints industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40325.     

Understanding and guiding the phase inversion process for synthesis of solvent resistant nanofiltration membranes

Since its introduction in membrane technology in the 1960's, phase inversion by means of immersion precipitation has been widely studied for the preparation of membranes to be applied in the fields of microfiltration (MF) and ultrafiltration (UF). However, much less knowledge is available about this process in terms of integrally skinned asymmetric nanofiltration membranes, especially for more hydrophobic polymers applied in solvent resistant nanofiltration (SRNF). This review focuses on the preparation aspects of integrally skinned asymmetric membranes to be applied in the field of SRNF via phase inversion. It starts with the explanation of the basic principles of the phase inversion process, covering both thermodynamic and kinetic aspects. Further, it summarizes the parameters that significantly influence final membrane performance and morphology, including polymer type and concentration, casting solvent, additives, evaporation time, and temperature, humidity, membrane thickness, composition, and temperature of coagulation bath and post‐treatment. Literature contained within this review constitutes the core references in the field of SRNF, but also several references on preparation of MF, UF, aqueous NF, and reverse osmosis (RO) membranes have been included to better clarify or illustrate certain aspects of the process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42130.