Development of a Continuous Segmented Flow Tubular Reactor and the “Scale‐out” Concept – In Search of Perfect Powders

The synthesis of powders with controlled shape and narrow particle size distributions is still a major challenge for many industries. A continuous Segmented Flow Tubular Reactor (SFTR) has been developed to overcome homogeneity and scale‐up problems encountered when using batch reactors. Supersaturation is created by mixing the co‐reactants in a micromixer inducing precipitation; the suspension is then segmented into identical micro‐volumes by a non‐miscible fluid and sent through a tube. These micro‐volumes are more homogeneous when compared to large batch reactors leading to narrower size distributions, better particle morphology, polymorph selectivity and stoichiometry. All these features have been demonstrated on single tube SFTR for different chemical systems. To increase productivity for commercial application the SFTR is being “scaled‐out” by multiplying the number of tubes running in parallel instead of scaling‐up by increasing their size. The versatility of the multi‐tube unit will allow changes in type of precipitate with a minimum of new investment as new chemistry can be researched, developed and optimised in a single tube SFTR and then transferred to the multi‐tube unit for powder production.     

Polymer–nanofiller prepared by high‐energy ball milling and high velocity cold compaction

High‐energy ball milling using comilling in a solid state by low‐temperature mechanical alloying to prepare nickel‐ferrite (NiFe₂O₄) nanopowders and ultrafine poly(methyl methacrylate) (PMMA), dispersing nanoparticles in a polymer matrix, and a uniaxial high‐velocity cold compaction process using a cylindrical, hardened steel die and a new technique with relaxation assists have been studied. The focus has been on the particle size distributions of the nanocomposite powder during the milling and on the surface morphology of the nanocomposite‐compacted materials after compaction with and without relaxation assists. Experimental results for different milling systems are presented showing the effects of milling time and material ratio. It was found that a longer mixing time give a higher degree of dispersion of the nanopowder on the PMMA particle surfaces. Furthermore, with increasing content of NiFe₂O₄ nanopowder, the reduction of the particle size was more effective. Different postcompacting profiles, i.e. different energy distributions between the upper and lower parts of the compacted powder bed, lead to different movements of the various particles and particle layers. Uniformity, homogeneity, and densification on the surfaces in the compacted powder are influenced by the postcompacting magnitude and direction. It was found that the relaxation assist device leads to an improvement in the polymer powder compaction process by reducing the expansion of the compacted volume and by reducing the different opposite velocities, giving the compacted composite bed a more homogeneous opposite velocity during the decompacting stage and reducing the delay time between the successive pressure waves. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Study on Ultrasound‐ and Spray‐Assisted Precipitation of CL‐20

Ultrafine hexanitrohexaazaisowurtzitane (CL‐20) samples were prepared by a ultrasound‐ and spray‐assisted precipitation method. Raw CL‐20 and ultrafine CL‐20 samples were characterized by SEM, FT‐IR spectroscopy, XRD, and particle size analysis. The impact sensitivity and thermal stability of two CL‐20 samples were also tested and compared. The results indicate that by this recrystallization process, the mean particle size of CL‐20 is 470 nm, and the particle size distribution was in the range from 400–700 nm. The particle morphology is nearly spheric with a smooth surface. Compared with raw CL‐20, the impact sensitivity of the ultrafine sample is significantely reduced and the drop height (H₅₀) is increased from 12.8 to 37.9 cm. The critical explosion temperature of ultrafine CL‐20 decreased from 235.6 to 229.0 °C, which suggests that the thermal stability of ultrafine CL‐20 is lower than that of raw CL‐20.     

Particle size and distribution of biodegradable poly‐D,L‐lactide‐co‐poly(ethylene glycol) block polymer nanoparticles prepared by nanoprecipitation

A biodegradable block copolymer, poly‐D ,L ‐lactide (PLA)‐co‐poly(ethylene glycol) (PEG), was prepared by the ring‐opening polymerization of lactide with stannous caprylate [Sn(Oct₂)] as a catalyst; then, the PLA–PEG copolymer was made into nanoparticles by nanoprecipitation under different conditions. The average molecular weight and structure of PLA–PEG were detected by ¹H‐NMR and gel permeation chromatography. The sizes and distributions of the nanoparticles were investigated with a laser particle‐size analyzer. The morphologies of the nanoparticles were examined by transmission electron microscopy. The effects of the solvent–nonsolvent system, operation conditions, and dosage of span‐80 on the sizes and distributions of the nanoparticles are discussed. The results show that acetone–water was a suitable solvent–nonsolvent system and the volume ratio of the nonsolvent phase to the solvent phase (O/W) (v/v), the concentration of PLA–PEG in the solvent phase, and the dosage of span‐80 had important effects on the particle sizes and distributions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1884–1890, 2005     

Experimental Investigation into the Influence of Mixing on Nanoparticle Precipitation

Precipitation is a promising method for the economic production of commercial amounts of nanoparticles because it is fast, and operable at ambient temperature. However, process control – due to the rapidity of the involved processes of mixing, nucleation, growth, and agglomeration – and stabilization against agglomeration represent challenges. This paper shows how these challenges can be successfully handled. The focus of this work is therefore set on how to tailor the particle‐size distribution in continuous precipitation. Precipitation experiments with barium sulfate in a T‐mixer are presented. It was found that the size of the precipitated primary particles is strongly dependent on the mixing intensity. On increasing the mixing intensity, it was possible to generate particles of approximately 50 nanometers in diameter. The second challenge, to stabilize the particles against agglomeration, was successfully met by adsorbing potential‐determining ions on the particle surfaces, i.e., by increasing repulsive particle interactions. Thus, stable suspensions of barium sulfate nanoparticles were obtained.     

Predictive simulation of nanoparticle precipitation based on the population balance equation

Nanoparticle precipitation is an interesting process to generate particles with tailored properties. In this study we investigate the impact of various process steps such as solid formation, mixing and agglomeration on the resulting particle size distribution (PSD) as representative property using barium sulfate as exemplary material. Besides the experimental investigation, process simulations were carried out by solving the full 1D population balance equation coupled to a model describing the micromixing kinetics based on a finite-element Galerkin h-p-method. This combination of population balance and micromixing model was applied successfully to predict the influence of mixing on mean sizes (good quantitative agreement between experimental data and simulation results are obtained) and gain insights into nanoparticle precipitation: The interfacial energy was identified to be a critical parameter in predicting the particle size, poor mixing results in larger particles and the impact of agglomeration was found to increase with supersaturation due to larger particle numbers. Shear-induced agglomeration was found to be controllable through the residence time in turbulent regions and the intensity of turbulence, necessary for intense mixing but undesired due to agglomeration. By this approach, however, the distribution width is underestimated which is attributed to the large spectrum of mixing histories of fluid elements on their way through the mixer. Therefore, an improved computational fluid dynamics-based approach using direct numerical simulation with a Lagrangian particle tracking strategy is applied in combination with the coupled population balance-micromixing approach. We found that the full DNS-approach, coupled to the population balance and micromixing model is capable of predicting not only the mean sizes but the full PSD in nanoparticle precipitation.     

Synthesis of CaCO3 nanoparticles by controlled precipitation of saturated carbonate and calcium nitrate aqueous solutions

Calcium carbonate nanoparticles (CCNP) were synthesised by precipitation from saturated sodium carbonate and calcium nitrate aqueous solutions. The effect of agitation rate, mixing time, calcium/carbonate ions concentration and temperature on particle size and morphology were investigated. Particles were characterised using X‐ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Increasing the mixing time from 30 to 180 min resulted in a decrease in particles size. Mixing rate variation between 300 and 14 000 rpm decreased the particle size. Temperature increase favoured a significant growth in particle size and in the formation of aragonite beginning from 80°C. Calcium and carbonate ion concentrations are key parameters controlling the CCNP particle size. Calcite is the main polymorph obtained as revealed by XRD analysis. © 2011 Canadian Society for Chemical Engineering     

Enhanced thermal conductivity of boron nitride epoxy‐matrix composite through multi‐modal particle size mixing

Castable particulate‐filled epoxy resins exhibiting excellent thermal conductivity have been prepared using hexagonal boron nitride (hBN) and cubic boron nitride (cBN) as fillers. The thermal conductivity of boron nitride filled epoxy matrix composites was enhanced up to 217% through silane surface treatment of fillers and multi‐modal particle size mixing (two different hBN particle sizes and one cBN particle size) prior to fabricating the composite. The measurements and interpretation of the curing kinetics of anhydride cured epoxies as continuous matrix, loaded with BN having multi‐modal particle size distribution, as heat conductive fillers, are highlighted. This study evidences the importance of surface engineering and multi‐modal mixing distribution applied in inorganic fillered epoxy‐matrix composite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of solvent contents on the rubber‐phase particle size distribution of high‐impact polystyrene

High‐impact polystyrene (HIPS) was prepared by the bulk or low‐solvent polymerization of styrene in the presence of dissolved rubber and characterized to measure the dispersed particle size of the rubber phase. Before preparation, the prepolymerization time was established by measuring the evolution of particle size distribution of the dispersed phase as a function of reaction time. The measurement technique by laser light scattering was found to be efficient enough not only to lead to the right prepolymerization time but also to predict rubber‐phase particle size distribution. Polymerization experiments were then conducted to investigate the effect of solvent contents on the particle size distribution of the rubber phase, in which ethylbenzene was introduced as a solvent at levels of 0, 3, 10, and 15%. As the solvent content increased, the size of rubber‐phase particles initially increased, reaching a maximum, and then decreased. It is speculated that a decrease in the molecular weight of the matrix, a decrease in the viscosity ratio between polybutadiene to polystyrene phases, and a change in rubber morphology all contributed to the change in the rubber particle size of HIPS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3672–3679, 2003     

Influence of Different Silica Nanoparticles on Drop Size Distributions in Agitated Liquid‐Liquid Systems

The impact of different silica nanoparticles on rheology, interfacial tension and drop size distributions in liquid‐liquid systems is determined experimentally. The particles vary in wettability and specific surface area. In contrast to commonly used high‐energy devices for Pickering emulsion preparation, low energy input by stirring allows to quantify drop breakage and coalescence in steady state and dynamic conditions. The experiments can provide essential information for drop size model development in nanoparticle‐stabilized emulsions.     

Nanoenergetic Composites of CuO Nanorods,Nanowires, and Al‐Nanoparticles

This paper reports on the synthesis of the nanoenergetic composites containing CuO nanorods and nanowires, and Al‐nanoparticles. Nanorods and nanowires were synthesized using poly(ethylene glycol) templating method and combined with Al‐nanoparticles using ultrasonic mixing and self‐assembly methods. Poly(4‐vinylpyridine) was used for the self‐assembly of Al‐nanoparticles around the nanorods. At the optimized values of equivalence ratio, sonication time, and Al‐particle size, the combustion wave speed of 1650 m s⁻¹ was obtained for the nanorods‐based energetics. For the composite of nanowires and Al‐nanoparticles the speed was increased to 1900 m s⁻¹. The maximum combustion wave speed of 2400 m s⁻¹ was achieved for the self‐assembled composite, which is the highest known so far among the nanoenergetic materials. It is possible that in the self‐assembled composites, the interfacial contact between the oxidizer and fuel is higher and resistance to overall diffusional process is lower, thus enhancing the performance.     

Preparation of raspberry‐shaped styrene‐butadiene‐methyl acrylate‐acrylic acid latex particles by emulsion polymerization followed by alkali/heating method

Monodispersed raspberry‐shaped polystyrene‐butadiene‐methyl acrylate‐acrylic acid particles were made by semi‐batch emulsion polymerization followed by alkali and heat treatment. The particle sizes and size distributions were studied by hydrodynamic chromatography and transmission electronic microscopy. The morphology of the particles was observed by SEM, cryo‐SEM, and TEM. Treatment temperature was found to have a significant impact on the particle size and morphology of the treated latexes. Higher temperatures lead to larger particle sizes and more discernible raspberry domains with sizes around 50 nm on the particle surfaces. Higher levels of alkali did not significantly change the particle size but did increase the total titratable acid amount, presumably due to the hydrolysis of methyl acrylate during the treatment. GPC results showed that higher amount of oligomers or polymers are produced in the serum for the heat‐treated latexes. Divinylbenzene crosslinking agent at the levels of 0.05–3% limited the particle expansion and decreased the serum acid. A possible mechanism of raspberry particle formations was proposed, which involves migration of hydrophilic and hydrophobic species during the heat treatment. Lastly, potential applications for raspberry particles in paper coating were explored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystal Growth in Drowning‐Out Crystallization using a T‐Mixer

The kinetics of nucleation and crystal growth in drowning‐out crystallization using a T‐mixer were estimated using crystal size distribution, taking into account a size‐independent growth. At the conditions of the feed compositions investigated, the product weight mean size changed from 7–29 μm when the residence time varied between 0.32 and 0.61 s. Nucleation and growth rates were expressed simply as a function of the residence time. The T‐mixer can be used to generate high levels of supersaturation due to inducing micro‐mixing effects. The particle size correlated well with the ratio of growth rate to nucleation rate. Finally, the particle size obtained in drowning‐out crystallization using a T‐mixer was found to be proportional to the 1.69^th power function of the residence time.     

Synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid

Poly(styrene‐co‐divinylbenzene) microspheres with size ranging from 1.6 to 1.8 μm were prepared in acetic acid by precipitation polymerization. The particle size and particle size distribution were determined by laser diffraction particle size analyzer, and the morphology of the particles was observed with scanning electron microscope. Besides, effects of various polymerization parameters such as initiator and total monomer concentration, divinylbenzene (DVB) content, polymerization time and polymerization temperature on the morphology and particle size were investigated in this article. In addition, the yield of microspheres increased with the increasing total monomer concentration, initiator loading, DVB concentration and polymerization time. In addition, the optimum polymerization conditions for synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Optimization of Continuous Synthesis of Cross‐Linked Chitosan Nanoparticles Using Microreactors

A process for continuous synthesis of cross‐linked chitosan‐sodium tripolyphosphate (CS‐TPP) nanoparticles is optimized using microreactors for its comparison with a batch stirred reactor. The effect of various parameters including residence time, concentration of CS, pH of the CS solutions, and stabilizing surfactant concentration was modeled by population balance equations (PBEs) to determine size, growth, and nucleation rates of the CS‐TPP nanoparticles. The smallest particle size was obtained at lower residence time, lower concentration of CS, pH 5, and using a surfactant concentration above its critical micellar concentration. The particles obtained from the microreactors are agglomerated but are smaller in size as compared to those obtained from the batch reactor. The system was also optimized for the minimum particle size applying the estimated growth rate and the PBEs.     

Effects of Sand Fraction on Toluene‐diluted Heavy Oil in Water Emulsions in Turbulent Flow

The impact of the presence of sand on emulsification of toluene‐diluted heavy oil in simulated process water was systematically studied as a function of agitation time, in a stirred tank. Droplet size distributions were measured by light scattering technique. Optical microscopy and high‐speed video micrography were used to visually monitor agitation and emulsion stability. Results showed that the Sauter mean diameters of the droplets decreased with increasing sand content. Droplet breakage followed a first‐order kinetic model for all mixing speeds. Plots of droplet volume percent frequency versus droplet size followed lognormal distribution. The distribution span broadened into lower sizes with increased sand content. Emulsions were stable for over 48 h after formation.     

The Influence of Shear Stress on Crystallization in an Ultrasound Levitator

Industrial precipitation processes often use chemical agents to influence crystal morphology and size distribution. This experimental study deals with the investigation of physical parameters including an alternative method to affect crystal growth, thus, avoiding the presence of additives as intrinsic impurities. The influence of shear stress acting on growing crystals within a droplet is investigated in an ultrasound levitator. An ultrasound levitator enables the suspension of a single droplet against gravity and the study of containerless precipitation with specific mechanical forces acting on crystals. The levitator is used as a three‐phase reactor with precipitation from the gas and liquid, and as a reactor for precipitation from two different solutions. Calcium carbonate is used as a model system. The variation of temperature and the amount of applied shear stress leads to different amounts of calcium carbonate morphologies. An increase in the shear stress results in more rounded or spherical crystals. The intensity of the shear stress also influences the particle size distributions of the precipitated crystals, i.e., with increasing shear stress, particle size distributions are shifted to smaller sizes.     

A general compartment‐based population balance model for particle coating and layered granulation

In this work, a general multidimensional population balance (PB) model is developed to predict the coating volume distribution on polydisperse particles as a function of time during particle coating in a paddle mixer. The model adopts a compartmental approach to account for coating variation caused by particle flow heterogeneity. Simulations show that for a realistic range of seed particle size polydispersity and coating mass applied, the coating volume distribution depends on the growth rate exponent and seed particle size distribute on, with the coating volume coefficient of variance (CoV) approaching an asymptotic value as the coating‐to‐particle volume ratio increases. These effects cannot be predicted by simpler one‐dimensional models. However, the full two‐dimensional PB and simpler one‐dimensional models such as Mann's equation do predict similar sensitivity of coating volume CoV to the variation in the compartment model parameters, i.e., to changes in the particle mixing behavior in the vessel. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Nanoparticle formation through solid‐fed flame synthesis: Experiment and modeling

The preparation of silica nanoparticles through solid‐fed flame synthesis was investigated experimentally and theoretically. Monodispersed submicrometer‐ and micrometer‐sized silica powders were selected as solid precursors for feeding into a flame reactor. The effects of flame temperature, residence time, and precursor particle size were investigated systematically. Silica nanoparticles were formed by the nucleation, coagulation, and surface growth of the generated silica vapors due to the solid precursor evaporation. Numerical modeling was conducted to describe the mechanism of nanoparticle formation. Evaporation of the initial silica particles was considered in the modeling, accounting for its size evolution. Simultaneous mass transfer modeling due to the silica evaporation was solved in combination with a general dynamics equation solution. The modeling and experimental results were in agreement. Both results showed that the methane flow rate, carrier gas flow rate, and initial particle size influenced the effectiveness of nanoparticle formation in solid‐fed flame synthesis. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Applying a Thermodynamic Model to the Non‐Stoichiometric Precipitation of Barium Sulfate

Thermodynamic models for aqueous Ba²⁺‐SO₄^2–‐Na⁺‐Cl^–‐solutions are compared in their accuracy to predict ion activities in saturated and supersaturated solutions. The Pitzer and the Bromley model are employed, taking into account ion pair formation of barium sulfate. Such models are then used to describe particle nucleation and growth, and finally they are imbedded in a mechanistic mixing‐precipitation model for a single feed semibatch process. The effect of the key operating parameters on the mean particle size is analyzed through simulations. The results are compared with previous experimental data, thus highlighting the significance of a proper choice of the thermodynamic model.