Effect of the Interparticle Pair Potential on the Rheological Behavior of Zirconia Powders: I, Electrostatic Double Layer Approach

Aqueous slurries containing 20 vol% ZrO₂ powder doped with 3 mol% Y₂O₃ were prepared by first dispersing the powder at pH 11, then adding 0.1 M to 1.0 M tetramethylammonium chloride (TMACl), or 1.0 M of TPACl, CsCl, and LiCl to produce different, weakly attractive particle networks. The particle pair potentials in the slurries were investigated by viscosity versus shear rate measurements. Slurries exhibited increasing viscosities (at a given shear rate) with increasing salt concentration and decreasing (unhydrated) counterion size. The viscosities for these weakly attractive networks were intermediate to dispersed (pH 11 without added salt) and flocced (isoelectric point, pH 7.5) slurries. Cylindrical bodies were consolidated from these slurries by pressure filtration at different applied pressures. The bodies consolidated from slurries formulated with TMACl had the highest packing densities relative to those consolidated from a flocculated slurry, but the relative densities were much lower than those achieved from bodies consolidated from a dispersed slurry. The plastic or brittle nature of these bodies was determined in uniaxial compression. Powder compacts consolidated from flocced slurries and slurries coagulated with 1 M TMACl, CsCl, and LiCl showed plastic behavior for filtration pressures ≤7.5 MPa. Results for ZrO₂ will be compared with those previously obtained for Al₂O₃, which produces plastic, consolidated bodies over a much broader range of slurry conditions.     

Morphologies and properties of NiO particles prepared from NiCl<Subscript>2</Subscript>·6H<Subscript>2</Subscript>O by spray pyrolysis

Nickel oxide particles were prepared by spray pyrolysis of aqueous solution of NiCl₂·6H₂O. In the reactor the salt droplets were first converted to hollow particles by drying and then they were collapsed by oxidation to reduce their size. Each oxide particle was composed of many small nuclei with voids among them due to extremely low rate of sintering. The particle size decreased with the temperature as the sintering and crystallization proceeded. The size as well as the crystallinity of the particles increased with the initial salt concentration. When the salt droplets were preliminarily dried in diffusion dryer before entering the reactor, the collapse of the particles was considerably reduced, resulting in lower hollowness and higher sphericity. Numerical simulation on the drying of the droplets provided insight on the initial stage of spray pyrolysis.     

Chemisorption of Organofunctional Silanes on Silicon Nitride for Improved Aqueous Processing

Different chem-adsorbed silane molecules have been used to produce weakly attractive silicon nitride particle networks for aqueous colloidal processing. Silanes with diamino and poly(ethylene glycol) hydrophilic heads yielded slurries with the lowest viscosity, longest sedimentation stability, and highest packing density. Chem-adsorbed silane molecules protected silicon nitride and yttrium oxide, a common processing aid, from hydrolysis at pHs between 5.5 and 11. A novel approach was used to produce short-range repulsive potentials necessary to yield the weakly attractive networks. Addition of salt to dispersed silicon nitride slurries with particles coated with poly(ethylene glycol)-silane caused the collapse of the 22-atom-long chains and residual electrical double layer. This produced a weakly attractive network which persisted during consolidation to yield a plastic body with a flow stress that was dependent on the counterion size. When 0.5 M tetramethylammonium chloride was used at pH 10, plastic bodies had a flow stress similar to clay, whereas lithium counterions produced bodies with a much higher flow stress.     

Increasing Wet Green Strength of Alumina Body During Microfabrication by Colloidal Isopressing

Colloidal Isopressing involves formulating a slurry with a weakly attractive particle network that can be pre-consolidated to a high relative density by pressure filtration and still retain fluid-like characteristics. The pre-consolidated slurry is injected into an elastomeric mold and isopressed. Isopressing rapidly converts the slurry into an elastic body that can be removed from the mold without shape distortion. Not only is this process rapid, but since the water saturated compact produced by this method does not shrink during drying, it can also be converted into a green body without a long drying period. It is demonstrated that micron-size surface features, such as 5 μm wide channels with a depth/width ratio of 2, can be rapidly produced on the surface of alumina powder compacts. The fracturing of thin vertical portions of a micro-patterned surface during pressure release and demolding has been an obstacle to obtaining micron-sized features with high aspect ratios. A method is shown here that enables the fabrication of such features by strengthening the saturated isopressed body. It is shown that concentration controlled gelation of a poly(vinyl alcohol)–Tyzor^® Triethanolamine Tritanate (TE) additive effectively increases the strength of the elastic, isopressed body, saturated with water, while maintaining the low viscosity of the pre-consolidated slurry, which is required for transferring the pre-consolidated slurry into a rubber mold prior to isopressing.     

Experimental investigation of the morphology of salt deposits from drying sessile droplets by white‐light interferometry

This study presents a new approach to investigate the drying behavior and the structure of deposit resulting from drying of solid containing micro droplets. It is shown that deposit structure (porosity and “footprint”) depends on drying conditions. This dependency may contribute to better understanding of particle‐forming processes, such as fluidized bed coating. In the framework of this study, sessile droplets containing sodium benzoate dissolved in water were dried on thin glass plates in a small drying chamber. The drying conditions (temperature, moisture content and flow rate of drying gas) and material parameters (solid content of solution) were systematically varied. The drying rate of droplets was determined from the moisture balance of the drying gas. The final three‐dimensional shape of dried sessile droplets was measured using white‐light interferometry and transformed into a two‐dimensional profile using a Monte Carlo method. Moreover the mean porosity of dried droplets was calculated. By comparison of structural information and process conditions it is shown that the drying process may have a large influence on deposit structure. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2002–2016, 2018     

Influence of Particle Size on the Drying Kinetics of Single Droplets Containing Mixtures of Nanoparticles and Microparticles: Modeling and Pilot-Scale Validation

The particle size of the primary particles is an important parameter influencing the drying behavior of droplets. In this work, the influence of particle size on the drying kinetics and grain properties was analyzed for droplets containing silica nanoparticles, microparticles, and mixtures of the two. The presence of microparticles was found to increase the drying rate and shrinkage of the droplet. The drying curves were modeled using a reaction engineering approach (REA) model. Finally, different suspensions were dried in a pilot-scale spray dryer in order to prove the influence of the particle size obtained in the levitator tests.     

Plastic-to-Brittle Transition of Saturated, Alumina Powder Compacts

Alumina slurries, in which different particle pair potentials were produced by adjusting ρH and salt concentration, were used to form cylindrical, consolidated bodies by pressure filtration, at applied pressures between 0.25 and 100 MPa. The mechanical properties of these bodies were investigated by uniaxial compressive loading at a specific rate. Saturated bodies formed from flocced slurries (ρH 9) were plastic at low relative densities (<0.54, formed at filtration pressures < 40 MPa) but were brittle (fractured prior to flow) at higher relative densities. Bodies formed from the dispersed slurries (ρH 4) were always brittle. When initially stressed, plastic bodies consolidated from the coagulated slurries (ρH 4, 5, and 6 with additions of NH₄C1) produced a stress-strain behavior characterized by a peak stress, followed by a much lower flow stress. The peak stress reduced to the flow stress upon several reloading cycles. The peak stress observed during the initial loading rapidly increased with consolidation pressure. These bodies exhibited a transition from plastic to brittle behavior at large consolidation pressures (∼65 MPa), with little change in relative density. It was reasoned that the plastic-to-brittle transition occurred for bodies formed from coagulated slurries when a sufficient fraction of the particles were pushed into their primary minimum to form a touching particle network. The reduction of the peak stress to the flow stress was reasoned to occur once the touching network was broken apart to reestablish the weakly attractive, but nontouching, network that existed in the slurry state. This can only occur when the fraction of particles in the touching network is less than that necessary for fracture. It was also noted that the flow stress for certain bodies formed from the coagulated slurry had a nearly identical flow stress as measured for a commercial, throwing clay.     

Formation and Control of Agglomerates in Alumina Powder

High-purity alumina powder with submicrometer particle size was colloidally dispersed and classified in either water or ethanol to remove agglomerates from as-received powder. After the slurries were dried, fine alumina particles cohered to form agglomerates, which were "hard" when formed in a water slurry, and "soft" in an ethanol slurry. Firing of the powder compacts with "hard" agglomerates resulted in inhomogeneous microstructures, and homogeneous microstructures were formed with "soft" agglomerates. The reasons for their formation are discussed and experimentally confirmed. In the case of water slurry, a small amount of transition alumina reacted with water at low pH. After drying, alumina gels were formed and acted as a strong binder between α-alumina particles to form "hard" agglomerates.     

Spray-dried ceramic powders: A quantitative correlation between slurry characteristics and shapes of the granules

The characteristics and consequently the properties of ceramic coatings performed using plasma spraying means depend not only on the operating conditions but also on the powder feedstock. Oxide powders are commonly prepared in one stage or in a combination of stages of fusing, crushing, agglomerating and sintering. The spray drying process (which corresponds to the agglomerating route) is a technique in which small constituent particles dispersed in water (which is called slurry) are sprayed in hot air and granulated thanks to a binder (latex or PVA). Spray drying is carried out for a variety of reasons, two major motivations being the production of composite and shape controlled powders for thermal spray applications. The aim of the present work was to establish a correlation between the slurry formulation and the characteristics of the spray dried granules for two oxide ceramics: Al₂O₃ and Y₂O₃-ZrO₂. Detailed studies on the dispersion and stability of the slurries were performed using sedimentation tests, electrophoretic mobility measurements as well as adsorption isotherms experiments. Then, a drying experimental test based on the drying of a suspended droplet was developed to assess the drying mechanisms, identify the correlation between the slurry characteristics and the morphology of the dried granules and finally to predict the shapes of the spray-dried powders. It was shown that there is a qualitative relation between the sedimentation behaviour (as measured by the sediment ratio) and the granule shape (solid or hollow) and a quantitative relation between the thickness of the shell (for hollow granule) and the state of dispersion and the nature of the binder used. Finally, several powder batches were prepared in the spray-dryer which confirm the reliability of the drying simulation test.     

Formation of Particle Layer Within Coated Slurry Characterized by Thickness Variation

An understanding of the conversion process from slurry to particle layer on a substrate is required for the precise control of the particle alignment and the material distribution in the coated slurry. In this work, variation of coated slurry thickness during drying was applied to evaluate drying and particle layer formation simultaneously. The slurry used consisted of micron-sized silica or poly (methyl methacrylate) particles and an aqueous solution of poly-vinyl alcohol (PVA) possessing differing degrees of hydrolysis. During the drying process, initially the thickness of the coated slurry was observed to decrease at a constant rate in the concentration stage, and subsequently it began to show large fluctuations due to the emergence of particles on the drying surface in the packing stage. In the final fixing stage, the fluctuation of film thickness was restricted because particles were immobilized by highly viscous concentrated PVA or by PVA molecule bridging. Based on the variation and fluctuation of film thickness, we introduced two characteristic dimensionless time ratios: (a) void fraction in a packed particle layer at the end of concentration stage; and (b) the time required to fix particle position after the end of the packing stage. We concluded that the dispersed state and settling velocity of the particle determines the space between particles in a loose packing layer, and we found that the distribution of polymers in a particle layer has a strong influence on the mobility of particles in a tightly packed layer.     

Development of Short-Range Repulsive Potentials in Aqueous, Silicon Nitride Slurries

The properties of aqueous, dispersed, silicon nitride slurries, with an isoelectric point of pH 5.5, can be changed with additions of NH₄CI. At pH 10 the effect of adding NH₄Cl is similar to that suggested by DLVO theory; namely, for concentrations .0.5 M , the viscosity vs shear rate behavior, the elastic modulus, and the relative packing density are identical to those for slurries prepared at the isoelectric point. On the other hand, the effect of salt on dispersed slurries prepared at pH 2 differs from the behavior implied by classic DLVO theory; i.e., measurement of the same properties showed that the attractive interparticle potential was much weaker relative to that produced at the isoelectric point. As previously reported for alumina slurries, the results suggest that a short-range, repulsive interparticle potential is developed in salt-added slurries prepared at pH 2 which prevents attractive particles in the slurry from touching and aids particle packing. The same short-range potential apparently is not developed with salt additions at pH 10. The difference between silicon nitride and alumina slurries is apparent when the slurries are consolidated. Bodies consolidated from any silicon nitride slurry are elastic (i.e., they fracture before they flow) unlike salt-added alumina slur-ries, which are plastic.     

A one-dimensional plug-flow model of a counter-current spray drying tower

A one-dimensional numerical model for a detergent slurry drying process in a counter-current spray drying tower is developed for the prediction of the gas and droplet/particle temperature profiles within the tower. The model accommodates droplets/particles over a range of sizes. A semi-empirical slurry droplet drying model is integrated with a counter-current tower simulation based on mass, energy and particulate phase momentum balances in order to calculate the drying rate and the particle residence time within the tower. The coupled first order ordinary differential equations for the two phases are solved numerically using the iterative shooting method in an algorithm developed within MATLAB. The predictions of the numerical model are compared with industrial pilot plant data. The results are found to vary significantly with the specified size distribution of the droplets. Despite the simplicity of the model in ignoring the coalescence, agglomeration, wall deposition and re-entrainment, the model gives reasonable agreement with the experimental data.     

The effect of the slurry formulation upon the morphology of spray-dried yttria stabilised zirconia particles

A study has been performed to determine how the characteristics of spray-dried granules prepared from aqueous yttria doped zirconia slurries can be affected by the spray-drying process parameters: dispersant amount, pH and binder type. First, the colloidal stability of aqueous zirconia suspensions as a function of polyacrylic acid content, pH and binder nature has been investigated in order to establish a stability map. The concentration of dispersant required to stabilise the zirconia suspensions decreases with increasing pH (for instance Γ_max=0.93 mg m⁻² at pH 4 and 0.1 mg m⁻² at pH 10). The addition of a binder may modify the state of dispersion. The stability map makes it possible to define regions of stable (dispersed) and unstable (flocculated) suspensions. Then, dried granules have been produced by means of a single droplet drying method. Granules prepared from a dispersed slurry (low Ratio Sediment Height—RSH <53%) result in hollow shapes that contain a single large open pore. Changing the nature of the binder from latex to an hydrosoluble compound (polyvinyl alcohol) has an effect on the wall thickness of the hollow granules. Conversely, granules obtained from a flocculated slurry (high RSH>62%) result in full granules. The sedimentation volume, which represents the state of dispersion of the suspension, is the major factor controlling the droplet drying mechanism.     

Mathematical Modeling of Drying of Liquid/Solid Slurries in Steady State One-Dimensional Flow

A mathematical model of simultaneous mass, heat and momentum transfer for two-phase flow of a gas and a solid/liquid slurry was developed. The model was applied to calculation of the drying process of coal-water slurry droplets in a gas medium in a steady one-dimensional flow. The model was based on the well-known two-stage drying process for slurry droplets. After the first period of drying, in which the evaporation rate is controlled by the gas phase resistance, the evaporating liquid diffuses through the porous shell (crust) and then, by convection, into the gas medium. Inside the dry external crust of the drop, a wet central core forms, which shrinks as evaporation proceeds. The temperature of the slurry droplet rises. The process ends when the temperature of the dry outer crust reaches the coal ignition temperature in the case of combustion or when the moisture of the particle reaches the final required moisture. The developed model was based on one-dimensional balance equations of mass, energy and momentum for the liquid/solid and gas phases. The system of governing equations was represented by first-order differential equations and solved simultaneously. The numerical solution of the governing equations was obtained using Gear's method. The model permitted calculation     

Measurements of the Size Distribution of Aerosols Produced by Ultrasonic Humidification

Aerosol number and mass distributions produced by an ultrasonic room humidifier and an ultrasonic medical nebulizer were examined in a limited-scale study. Rapid droplet drying occurred at room humidities and under near saturated conditions. A model was tested describing the diameter of dried particles as a function of the dissolved mineral content of the water and the transducer frequency. Water containing 102 mg/L of dissolved minerals in a humidifier with a 1.6 MHz transducer produced droplets with a mass median diameter of 2.9 μm. The number median diameter of particles after drying was computed to be 0.11 μm. The distribution of particles in a nebulizer tube using a NaCl solution was shown to consist of a mixture of dried salt particles and droplets which included coagulated multiplets.     

Flame spray drying: Droplet and particle flow dynamics

ABSTRACT

The work presents the fundamental research of dispersed phase flow during flame spray drying. Particle dynamics analysis and laser Doppler anemometry technique were applied to determine particle size distribution and particle velocity distribution. Results of the study showed that stable combustion and longer length of the flame were observed for coarse spray (large droplets, low atomization pressure, small spraying angle, and low concentration of droplets in spray). Particle residence time in the combustion zone is the main factor affecting the increase in particle diameters due to puffing. Complex flow dynamics of dispersed phase observed at the outward regions of the flame in recirculation zones results in the formation of particle agglomerates.     

"Alumina" Surface Modification of Silicon Nitride for Colloidal Processing

Two different methods are used to coat silicon nitride particles with an alumina precursor to make Si₃N₄ behave like Al₂O₃ in aqueous slurries. The first method involves the precipitation of an aluminum hydroxycarbonate from dissolved Al(NO₃)₃ during the decomposition of urea. In the second method, dry silicon nitride powder is reacted with aluminum tri- sec -butoxide in hexane at room temperature. Both methods produce a coated powder in which the electrophoretic and rheological properties of aqueous slurries mimic those of alumina. When salt is added to slurries consisting of coated Si₃N₄ powder, all rheological evidence suggests the presence of a short-range repulsive potential that produces a weakly attractive particle network similar to that previously reported for Al₂O₃ powder. Although electrophoretic and rheological data showed that the coated powder behaved like Al₂O₃, consolidation data indicated that slurries of coated powder with added salt did not pack to high density. In addition, these bodies were not plastic as found for bodies consolidated from dispersed and salt-added Al₂O₃ slurries.     

Rheological Control of the Coffee Stain Effect for Inkjet Printing of Ceramics

The rheology of inkjet printing inks must be well controlled in order to be able to form small droplets. One solution is to use low volume fraction dispersed suspensions, but this leads to a common problem during drying called the coffee stain effect. It is caused by particle migration from the center to the edge of a drying drop and leads to nonuniform printed structures. This article describes an approach, to suppress the coffee stain effect by a sufficiently fast increase in viscosity after deposition. Due to the viscosity limitations during printing, inks with tailored rheology and drying behavior need to be developed. Ceramic inks were prepared and printed. First, a binder was added to study the influence of viscosity on printability and the coffee stain effect. Second, the use of a high vapor pressure solvent for faster drying was investigated. Eventually, an ink with the combination of binder and fast drying agent was prepared. This ink showed a considerable decrease in drying time as well as a rapid increase in viscosity after deposition and was suitable to completely suppress the coffee stain effect. Plateau‐like structures were achieved by adapting the drying temperature to permit particle movement to a certain degree.     

Mathematical Modeling of Drying of Liquid/Solid Slurries in Steady State One-Dimensional Flow

ABSTRACT

A mathematical model of simultaneous mass, heat and momentum transfer for two-phase flow of a gas and a solid/liquid slurry was developed. The model was applied to calculation of the drying process of coal-water slurry droplets in a gas medium in a steady one-dimensional flow. The model was based on the well-known two-stage drying process for slurry droplets. After the first period of drying, in which the evaporation rate is controlled by the gas phase resistance, the evaporating liquid diffuses through the porous shell (crust) and then, by convection, into the gas medium. Inside the dry external crust of the drop, a wet central core forms, which shrinks as evaporation proceeds. The temperature of the slurry droplet rises. The process ends when the temperature of the dry outer crust reaches the coal ignition temperature in the case of combustion or when the moisture of the particle reaches the final required moisture. The developed model was based on one-dimensional balance equations of mass, energy and momentum for the liquid/solid and gas phases. The system of governing equations was represented by first-order differential equations and solved simultaneously. The numerical solution of the governing equations was obtained using Gear's method. The model permitted calculation