In situ mass-suspension polymerisation

In situ mass-suspension polymerisation of MMA was carried out in a single reactor. The mass polymerisation was carried out in a gently agitated monomer layer of a two stratified layers of monomer and water in the reactor. The degree of conversion at which mass polymerisation changed to suspension polymerisation, by increasing the rate of agitation, was altered systematically. The polymer content of the monomer/polymer solution, formed during the mass polymerisation stage, significantly affected the evolution of the particle size distribution. Mass-suspension polymerisation was found to be more vulnerable to drop coalescence and process failure than conventional suspension polymerisation. The results indicate the importance of the transition stage in a typical suspension polymerisation during which the rate of polymerisation is very low and the adsorption of stabiliser on the surface of drops is completed. The polymer beads from the mass-suspension polymerisation had a very broad size distribution with a large contribution from satellite particles.     

Drop mixing in suspension polymerisation

In suspension polymerisation, monomer is suspended as liquid droplets in a continuous water phase by means of strong agitation and the presence of a suspending agent. As the suspension polymerisation proceeds, the viscosity of a monomer-polymer droplet increases with conversion. Hence, the physical behaviour of the droplet changes during the process. When new dispersible material is added to the existing suspension drops, the new material and existing drops can remain segregated for significant amounts of time. The aim of this project was to study the behaviour of drop mixing when new material is added to the existing suspension polymerisation. This study concentrated on the effect of the dispersed phase viscosity on drop mixing. The results show that viscosity affects drop size and that may then affect the rate of coalescence between drops. A critical drop size exists which determines the coalescence efficiency effect. Above the critical drop size, mixing rate increases as the drop viscosity decreases. While below the critical drop size, drop size of the dispersion determines the coalescence rate; as the drop size increases, coalescence rate also increases. The investigation of the effect of suspending agent shows that Tween 20 is more efficient in stabilising and protecting the drops, based on a weight basis, than PVA as the coalescence rate is lower with Tween 20.     

Two‐stage stabilizer addition protocol as a means to reduce the size and improve the uniformity of polymer beads in suspension polymerization

A two‐stage stabilizer addition protocol is suggested for reducing the size and improving the uniformity of polymer beads resulting from conventional suspension polymerization. The stabilizer load was divided into an initial charge and a secondary addition. The use of a low concentration of stabilizer in the initial charge served to assist drop rupture while avoiding significant reduction in drop size and production of too many satellite droplets. The secondary addition time of stabilizer occurred just before the onset of the growth stage when drops were vulnerable to coalescence but robust against break up due to their high viscosity. The secondary addition of stabilizer served to provide stability to monomer drops during the growth stage and as a result the drops underwent limited coalescence. This resulted in the formation of smaller and more uniform polymer beads in comparison to beads obtained by conventional suspension polymerization at the same overall concentration of stabilizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45671.     

Online monitoring of drop/particle size and size distribution in liquid–liquid dispersions and suspension polymerizations by optical reflectance measurements

Evolutions of drop/particle size and size distribution in liquid–liquid dispersions and suspension polymerizations of methyl methacrylate (MMA) were monitored by using an online optical reflectance measurement (ORM), and effects of operating parameters such as the agitation rate, concentration of poly(vinyl alcohol) (PVA) dispersant, and initial concentration of poly(methyl methacrylate) (PMMA) in MMA monomer on the Sauter mean diameter (d₃₂) and size distribution of drop/particle were investigated. According to the variations of d₃₂ of drops/particles with time, four characteristic particle formation stages can be identified for suspension polymerization process. The factors that lead to increase the rate of drop break up, such as increasing of concentration of PVA and decreasing of viscosity of dispersed phase, would postpone the particle growth stage. The d₃₂ and size distribution breadth of drops/particles were significant increased when the liquid–liquid dispersions or suspension polymerizations were conducted at low PVA concentrations or MMA/PMMA solutions with high PMMA contents were used as the dispersed phase, in consistent with the scanning electron micrograph observation on final PMMA particles. It is clear that ORM can be effectively applied in online monitoring of size and size distribution of drops/particles in the liquid–liquid dispersions and suspension polymerizations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43632.     

Electric Field-Enhanced Coalescence of Liquid Drops

Abstract

A fundamental understanding of drop coalescence and growth is of importance to separations and materials processing. Under external driving forces, drops dispersed in an immiscible fluid collide and coalesce with each other due to their relative motion. As a result of drop coalescence, the average drop size in the dispersion increases over time, improving the separation process. Collision and coalescence of spherical, conducting drops bearing no net charge in dilute, homogeneous dispersions are considered theoretically under conditions where drop motion results from gravity settling and electric field-induced attraction. A trajectory analysis is used to follow the relative motion of two drops and predict pairwise collision rates. A population dynamics equation is then solved to predict the time evolution of the size distribution and the average size of drops. The results show that the rate of drop collision and growth can be increased significantly by applying an electric field, in accord with fundamental experiments and patents on electrocoalescence.     

Acrylic latices stabilized by polymerizable non-ionic surfactant

The final latex particle size is controlled by the concentration of polymerizable non-ionic surfactant NE-40 in the emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The particle size decreases with increasing NE-40 concentration and increases with increasing persulphate initiator concentration. The dependence of particle size on the initiator concentration does not follow conventional Smith–Ewart theory, which is attributed to the bridging flocculation process during the particle nucleation period. The differences in the particle nucleation and growth stages and colloidal stability observed in the NE-40 and nonyl phenol-40 mol ethylene oxide adduct (NP-40) stabilized systems can be attributed to the different distribution patterns of surfactant molecules in the particles. Experimental data also indicate that the particle size decreases with increasing electrolyte concentration, or agitation speed. The total scrap, presumably caused by the bridging flocculation process, increases rapidly with increase in the NaCl concentration The amount of large flocs formed during polymerization is generally greater for the run operated at higher agitation speed. As expected, the latex products stabilized by non-ionic surfactants show excellent stability toward added sodium salt.     

A Combined Mass Transfer Coefficient Model for Liquid‐Liquid Systems under Simultaneous Effect of Contamination and Agitation

The simultaneous effect of contamination and agitation was investigated using a pilot rotating disc contactor and mass transfer in both directions with single drops in the absence of drop break‐up and coalescence. It is ideally required to account for the extent of contamination in a quantitative manner and in both phases with a single parameter. In this work, a combined mass transfer model is applied and an improvement is made using an empirical coefficient and having mathematical consistency. Based on 120 experimental data series obtained for each mass transfer direction, a correlation is proposed for the coefficient of this model.     

Solving dynamic equations for the collection and evaporation of an aerosol

We investigate the coalescence of drops undergoing random Brownian motion and evaporation. The evolution of the drop size spectrum is determined by solving a partial integro-differential equation with a kernel that describes the pairwise coalescence of drops. Numerical results for fuel injection with n-octane suggest that the size distribution of drops is determined by two competing processes, namely coalescence and evaporation.     

Evolution of the morphology of HIPS particles

The formation and evolution of the particle morphology during the production of high impact polystyrene in bulk were investigated. Evidence about the morphology of the system during phase inversion and the subsequent evolution of the particle morphology was obtained by transmission electron microscopy in reactions in which the type and concentration of initiator, agitation speed and polybutadiene content were varied.     

Blending of immiscible polymers in a mixing zone of a twin screw extruder—effects of compatibilization

The dependence of the morphology development of physical as well as of reactive compatibilized polypropylene/polyamide 6 (PP/PA6) blends in a mixing zone of a co‐rotating twin screw extruder on blend composition and screw rotational speed was investigated. A special process analytical set‐up based on a co‐rotating twin screw extruder was used, which allowed melt sampling from different positions along the operating extruder in time periods less than 10 seconds. It has been shown that the disperse particle sizes in physical blends depend crucially on the blend composition because of the increasing influence of coalescence with an increasing concentration of the disperse phase. Furthermore, the morphology of physical PP/PA6 blends depends strongly on their rheological properties. In contrast, the influence of the screw rotational speed on the morphology is minor. The resulting particle size in a mixing zone is achieved already after a short screw length. The particle size of compatibilized blends is significantly smaller than in physical blends because of the better conditions for drop break‐up and the suppression of coalescence effects. Due to this, compatibilization has a stronger influence on the blend morphology than a variation of process or rheological conditions with physical blends. Furthermore, the compatibilization leads to a concurrent crystallization of the PA6 phase with the PP phase.     

Monte Carlo Simulation of Coalescence Processes in Oil Sands Slurries

Conditioning of an oil sand slurry is a critical step in the extraction of bitumen from oil sand ore. To model the conditioning process, a constant‐number Monte Carlo algorithm is used to simulate the mean‐field kinetics of coalescing bitumen drops and air bubbles. The coalescence rate of drops and bubbles is described by the model of Coulaloglou and Tavlarides (1977). Simulations yield results that are consistent with aerated bitumen drop sizes and conditioning times reported in the literature. The effects of turbulent energy, bitumen concentration, and initial bitumen drop size on the evolution of drop size distributions are investigated.     

Semibatch emulsion copolymerization of butyl acrylate and glycidyl methacrylate: Effect of operating variables

Semibatch emulsion copolymerization was carried out to prepare poly(butyl acrylate‐co‐glycidyl methacrylate) latexes at 75°C, using potassium persulfate as an initiator, sodium dodecylbenzene sulfonate as an emulsifier and sodium bicarbonate as a buffer. The reaction was conducted in three stages; a further stage (called the steady stage, 2 h) was added to the traditionally stages (i.e., feed and seed stages) to improve considerably the monomer conversion. The monomer conversion and particle size distribution were studied by gravimetric and laser light scattering methods, respectively. The effects of variables such as agitation speed, emulsifier concentration, initiator concentration, feeding rate and comonomers ratio were fully investigated based on the monomer conversion‐time profiles and the particle size distribution to find the optimized copolymerization conditions. Increasing the agitation speed had a negative effect on the monomer conversion, but reduced coagulation of polymer particles. Monomer conversion could be improved by increasing the initiator or emulsifier contents. Feeding rate increased the polymer particle size sharply; however, it showed no significant effect on conversion. The final conversions were as high as 97–99% and they were recognized to be independent of the comonomers ratios employed. Morphological studies by scanning electron microscopy showed nano‐sized isolated particles which were partially aggregated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development of polymer blend morphology during compounding in a twin-screw extruder. Part II: Theoretical derivations

In Part II of the work, the intermeshing twin-screw extruder is briefly described and the theoretical procedures used to model its operation are summarized. Based on the microrheological considerations discussed in Part I, a predictive procedure of the morphology evolution during compounding of two immiscible polymers is proposed. In this first generation model, only the shear flow effects are considered. Furthermore, to avoid complications due to coalescence a low concentration of the dispersed phase was assumed. In the procedure, two drop breakup mechanisms are discussed. The first assumes that the drops do not break under flow while the second postulates that breakup occurs under flow. Two dispersion mechanisms are considered, the first postulating continuously increasing polydispersity of drop size and the second postulating that drop polydispersity is inversely proportional to deformation strain. The influence of the screw configuration and operating conditions on blend morphology evolution is studied. It is expected that the computed drop size distribution provides limiting values for the experimental data. Dependency of predicted morphology on operating conditions is also investigated. Increasing screw rotating speed (resulting in increasing energy consumption) and decreasing throughput (resulting in decreasing productivity) lead to prediction of finer drop size. In practice, therefore, a compromise would be required. The proposed procedure is limited to melt flow (excluding the die region) within the region of large capillary parameter values, k > 4k_crit.     

Break-up of a drop in a stirred tank

The drop break-up mechanism was studied in a stirred tank containing two immiscible liquids. The daughter drops formed by break-up of a single drop of known size were recorded photographically. From the experiments at constant agitator speed the following results were obtained. There is a critical drop size under which drops do not break up under given conditions. The break-up frequency increases approximately linearly with increase in drop volume. The number of daughter drops, v, is a random variable with a mean v > 2 which increases with the volume of the mother drop. The relative volume of a daughter drop has a β-distribution.     

Modeling the effect of drop charge on coalescence in turbulent liquid—liquid dispersions

In this work, a mechanistic model of drop coalescence based upon a stochastic film-drainage analysis is developed. The coalescence model accounts for previously considered factors, such as turbulence intensity, drop size, and drop deformability, while additionally describing the dual effects of drop surface potential and system electrolyte concentration. Model results indicate that electrostatic repulsion may strongly inhibit small drop coalescence, as well as coalescence between larger deformable drops. Comparison of model predictions to data from several transient coalescence experiments shows good agreement in most cases.     

Particle Nucleation in Semi-batch Surfactant-free Emulsion Polymerization of Acrylic Monomers

Based on the coagulative particle nucleation mechanism, a two-step model has been developed for the semi-batch surfactant-free emulsion polymerization of butyl acrylate, or butyl acrylate in the presence of a small amount of acrylic acid. During Stage 1, precursor particles are first formed by phase separation of the oligomeric radicals in the aqueous phase. These precursor particles are extremely unstable and tend to aggregate until a stable (primary) particle size is achieved. The size of the newly formed particles is controlled mainly by limited coagulation among the precursor particles in this stage. During the early part of Stage 2, the rate of aggregation of these precursor particles to form a primary particle may be slower than the rate of coagulation of the primary particles. This factor would lead to a decrease in the particle concentration with time. Later on, the particle concentration starts to level off and finally reaches a steady value due to the effect of limited coagulation. In this stage, the particle growth is achieved mainly by polymerization of the feed monomer inside the particles. This model has been assessed by a number of experiments. The reaction variables selected for this purpose are the concentrations of initiator, acrylic acid and NaHCO₃, and the agitation speed. The proposed model predicts the experimental data of the particle concentration and particle size reasonably well. © of SCI.     

Effect of an unsteady agitation method on drop coalescence characteristics in suspension polymerization of styrene

A tracer dye technique was used to investigate the effect of the co‐reverse rotational of impeller method, the agitation speed and periodic time interval on the coalescence rate in the suspension polymerization of styrene. The results showed that the extent of coalescence decreased with the use of the co‐reverse rotational method and with the decrease in the periodic time interval or agitation speed. The results also showed that the final particle sizes became small and the particle size distributions became uniform with the use of the co‐reverse rotational method and with a decrease in the periodic time interval.     

Dynamic behaviour of drops in oil/water/oil dispersions

The dynamic behaviour of drops of oil/water/oil (O/W/O) and water/oil (W/O) in abnormal polymer/water/surfactant systems was investigated. The size of internal oil droplets continuously decreased with time until it reached a steady-state value. Whereas the size of multiple water drops showed a minimum. After the minimum, the size of multiple water drops either reached a steady-state value or continued enlarging until phase inversion occurred. The phase inversion occurred because inclusion of oil droplets into water drops resulted in a continuous increase in effective volume fraction of dispersed phase. The time evolution of the size of multiple drops was described in terms of a balance between (a) drop break-up and escape and (b) drop coalescence and inclusion. The inclusion events retarded the initial decrease in the size of multiple water drops with time and increased the drop size after the minimum. By reducing the surfactant concentration, the ability of the dispersed phase to entrain the continuous phase decreased so that no minimum was achieved for the size of multiple drops with time, similar to conventional systems with simple drops. The size distribution of the multiple water drops initially narrowed and then widened again, whereas the size distribution of internal oil droplets continuously narrowed with time until it reached a constant value. Generally, the size distribution of drops narrowed as the average size of drops decreased. The possible mechanisms for complex drop formation were discussed and drop deformation was suggested as the main cause for inclusion at a low dispersed phase ratio.     

滴状冷凝传热机理的研究 (Ⅱ)液滴分布、液滴生长速率及液滴脱离直径的研究

采用高速摄影方法,实时记录水蒸气在铜基合金表面上的滴状冷凝情况,利用数字图象分析系统对所得图片进行分析,研究了不同条件下的液滴分布函数、液滴生长速率及液滴脱离直径.     

湍流分散系统中的液滴聚并

主要分析各向同性湍流中的液滴聚并过程且建立了一个模型,用以预测表面活性剂系统和纯净系统中的最小稳定液滴直径,该模型不含任何可调参数或经验参数．在此基础上,进一步研究了液滴尺寸分布和聚并效率．