Inkjet fabrication and characterization of calcium alginate microcapsules

The present work describes a method for producing calcium alginate hydrogel microcapsules in the size range of 50-70 μm by means of a piezoelectric drop-on-demand inkjet device. Particles were prepared by emitting droplets of 0.5% and 1% (w/w) sodium alginate solutions into a magnetically stirred pool of CaCl₂ solution of variable viscosity ranging from 1 to 100 mPas. The effect of viscosity on the morphology of the resulting microcapsules was systematically investigated — lower viscosity of the receiving solution has lead to the formation of elongated particles, medium viscosities lead to spherical capsules, and for higher viscosities flattened particles were obtained. The applied voltage used for driving the piezoelectric inkjet print-head was found to be the most significant parameter for influencing the droplet size. The duration of the voltage pulse or the droplet viscosity had only minor effects. The release rates of two model substances (methylene blue dye and vitamin B12) from alginate beads were measured and their effective diffusion coefficients determined as function of alginate concentration.     

Aqueous and Nonaqueous Colloidal Processing of Difficult‐to‐Densify Ceramics: Suspension Rheology and Particle Packing

Aqueous and nonaqueous colloidal processing of zirconium diboride (ZrB₂) and boron carbide (B₄C) has been investigated. The aqueous and nonaqueous ZrB₂ and B₄C suspension formulations have been optimized. The suspensions were cast into green bodies using slip casting. The correlation between the state of dispersion with the rheological properties of the suspensions and the resulting packing density was observed in both aqueous and nonaqueous processing. The attractive interactions between powder particles in water were difficult to overcome with electrical double layer or electrosteric repulsion. Reasonably low viscosity aqueous ZrB₂ suspensions up to 45 vol% solids could be prepared. It was not possible to produce low viscosity (viscosity below 1 Pa·s at shear rate of 100 s^?1) aqueous B₄C suspensions with solid content above 30 vol%. Slip casting of the weakly aggregated ZrB₂ suspensions resulted in low packing densities (~55% relative density) of the green bodies. On the other hand, dispersion of powder particles in nonaqueous media (cyclohexane and dodecane) enabled suspensions with lower viscosities and a higher maximum solid concentration (up to 50 vol%) to be prepared. The well‐dispersed nonaqueous suspensions promoted an efficient particle packing, resulting in higher green densities (64% and 62% relative density for ZrB₂ and B₄C, respectively) compared to aqueous processing. The significantly high green densities are promising to allow densification of the materials at lower sintering temperature.     

Extrusion of PE/PS blends with supercritical carbon dioxide

The effects of dissolved supercritical carbon dioxide on the viscosity and morphological properties were investigated for polyethylene/polystyrene blends in a twin-screw extruder. The viscosities of the blend/CO₂ solutions were measured using a wedge die mounted on the extruder. A considerable reduction of viscosity was found when CO₂ was dissolved in the blend. It was observed that the dissolution of CO₂ into PE/PS blends, regardless of the CO₂ content used, led to decreased shear thinning behavior resulting in an increase of the power law index from 0.29 to 0.34. The cell structures of foamed PE/PS blends showed a typical dependence of pressure and CO₂ concentration, with higher operating pressures and CO₂ content leading to a smaller cell size. Also, it was noted that the size of the dispersed PS phase in the PE/PS phase blends decreased by increasing the CO₂ concentration, and that the dispersed PS phase domains were highly elongated in the direction normal to the cell radius.     

Mechanical characterisation of miniaturised direct inkjet printed 3Y-TZP specimens for microelectronic applications

Direct inkjet printing (DIP) allows the production of small ceramic specimens with special geometries starting from high solids content suspensions. In this work, thin (300 μm thickness) 3Y-TZP specimens were produced with the DIP technique as model materials for microelectronic applications. The mechanical strength of the printed specimens was evaluated under biaxial loading, and the results were interpreted within the framework of the Weibull theory. Hot-pressed 3Y-TZP specimens with the same geometry and dimensions were tested for comparison. The fracture surfaces were subsequently examined using scanning electron microscopy (SEM). The inkjet printed materials revealed high mechanical reliability (m ≈ 10 for σ₀ ≈ 1400 MPa), which was ascribed to the uniform and defect free microstructure generated by the DIP technique.     

Effect of NiO content on structural, surface and catalytic characteristics of nano-crystalline NiO/CeO2 system

The NiO/CeO₂ nano-composite catalysts containing different nickel content prepared by impregnation method have been characterized by XRD and TEM. The surface and catalytic properties of Ni/Ce mixed oxide solids were determined by nitrogen adsorption at −196 °C and catalytic conversion of isopropanol at different temperatures. These composites can be described as a mixture of nickel oxide and ceria modified by the insertion of a part of nickel in the ceria lattice. The size of the nickel oxide varies considerably from clusters to a crystallized material, depending on the amount of nickel oxide. From the characterization of the composites, it was concluded: at low Ni loading, the ceria surface is gradually covered with the dispersed NiO species. At higher loading, highly dispersed NiO, well crystalline nickel oxide and Ni-Ce-O solid solution coexist.It was verified that the structural, morphological, surface and catalytic properties could be influenced by nickel loading. This treatment led to a slightly increase in the crystallite size of ceria particles. On the other hand, the augmentation in the nickel content brought about an increase in the crystallite size, lattice constant and unit cell volume of nickel oxide. The nickel loading brought about an increase in the formation of Ni-Ce-O solid solution with subsequent creation of oxygen vacancies.     

Semiconductor water-based inks: Miniaturized NiO pseudocapacitor electrodes by inkjet printing

The formulation, development and optimization of water-based inks of platelet-like nanoparticles are the main objective of this work. As-synthesized Ni(OH)₂ nanoparticles were dispersed and stabilized in aqueous suspension by PEI addition. The combination of DEG (cosolvent) with H₂O shows the ideal values of surface tension and viscosity for piezoelectric inkjet printing, which exhibits a homogeneous jetting flow of the nanoplatelets suspension. The printed nanostructure was sintered at low temperature (325 °C) and the electrochemical overview of NiO electrode behavior was described. These printable pseudocapacitors tested by a three-electrode cell have showed a competitive specific capacitance, leading 92% and 78% of capacitance retention for 2000 cycles at scan rates of 1 and 2 A/g respectively, and a coulombic efficiency of 100%. The initial performance of this printed NiO pseudocapacitor can be compared with others prepared by conventional methods. This new finding is expected to be particularly useful for the designing of micro-pseudocapacitors.     

Macroscopic properties of liquid-solid circulating fluidized bed with viscous liquid medium

Experiments were conducted in a liquid-solid circulating fluidized bed to study the effect of liquid viscosity and solids inventory on pressure gradient, critical transitional liquid velocity, onset average solids holdup, axial solids holdup distribution, average solids holdup and solids circulation rate in circulating fluidization regime with riser operated in fixed inventory mode. The results indicate that critical transitional liquid velocity decreases with increase in liquid viscosity. The onset average solids holdup, on the other hand, increases with increase in either auxiliary liquid velocity or solids inventory. The variation of axial solids holdup distribution, average solids holdup and solids circulation rate with liquid viscosity when solid inventory was 0.15 m was dissimilar with either 0.25 m or 0.35 m solid inventory. Correlations were proposed for estimating the average solids holdup and are satisfactorily compared with experimental values.     

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.     

Solid Freeforming of Silicon Carbide by Inkjet Printing Using a Polymeric Precursor

Preceramic polymers can be dissolved in solvents to form low-viscosity fluids. This makes them suitable for solid freeforming by direct inkjet printing. Two ways of using polycarbosilane (pcs) were investigated. In the first, it was dissolved in n -heptane at up to 30 vol% and printed as a single-phase material. In the second, it was used as an organic binder for silicon carbide powder suspended in an homologous series of hydrocarbon solvents ranging from n -heptane to n -decane. Polyisobutene succinimide was used as a surfactant. In both cases, components could be rendered successfully but pyrolysis of the unfilled pcs resulted in cracking. Components printed with powder suspensions did not crack on pyrolysis, retained overall near net shape, and underwent low shrinkage (8.2 vol%). The molecular weight of the n -paraffin solvents influenced the viscosity and hence the maximum powder loading while the volatility, a property also related to molecular weight, influenced the quiescence time and the drying time needed between layers. Octane gave the best compromise between speed of printing, the quality and knitting of droplet relics, and the avoidance of nozzle blockage caused by too rapid drying.     

Rheology and processing of UV-curable textured alumina inks for additive manufacturing

A UV-curable resin containing alumina (Al₂O₃) powder and platelets was developed and characterized using a proof-of concept tape-casting system and trialed on a commercially available 3D-printing platform (Admatec Admaflex 130). The influence of solids loading and solids platelet fraction on resin viscosity and depth of cure was investigated. Resins containing up to 40 vol% solids loading at platelet fractions up to 50% were found to have sufficiently low viscosity for tape casting and cure depths ranging from 0.29 to 0.39 mm. Alumina platelets were observed to lower ink viscosity but also reduce shear thinning behavior compared to inks containing only powder. Printability of inks was assessed by layered tape casting, and verified with a trial build on an Admaflex 130. Due to the low solids loading of the resin, hot pressing at 1300°C and 66 MPa was employed to sinter specimens containing no platelets and 15% platelet fractions, yielding specimens with near theoretical densities (99.7%) and average grain sizes of 0.96 µm and 0.83 µm, respectively. Alignment before and after sintering was assessed by SEM and XRD, with lotgering factors of 0.045±0.005 and 0.114 measured in the green and sintered specimens, respectively.     

Development of high solid content aqueous 3Y-TZP suspensions for direct inkjet printing using a thermal inkjet printer

An aqueous 3Y-TZP suspension with 24.2 vol.% solid content was developed for “Direct Inkjet Printing” (DIP). The printing unit was a common HP-DeskJet printer. The suspension was adjusted in terms of particle size, viscosity, and pH-value, so that it became compatible with the printing system. Therefore, suspensions of various compositions were prepared and printed two-dimensionally to analyze the influence of several organic additives on printability. The printouts were evaluated and typical printing errors were classified. The composition of the suspension was optimized and successive and error free single layers of 3Y-TZP were printed. The suspension was examined and characterized in terms of particle size and distribution, composition, viscosity, surface tension, pH-value, vapour pressure, and the Ohnesorge number. A printed 3Y-TZP layer of 12 μm thickness was sintered to full density.     

Droplet break-up by in-line Silverson rotor–stator mixer

Silverson high shear in-line rotor–stator mixers are widely applied in industry for the manufacture of emulsion-based products but the current understanding of droplet breakage and coalescence in these devices is limited. The aim of this paper is to increase the understanding of droplet break-up mechanisms and to identify appropriate literature correlations for in-line rotor–stator mixers. Silicone oils with viscosities ranging from 9.4 to 969 mPa s were emulsified with surfactant in an in-line Silverson at rotor speeds up to 11,000 rpm and flow rates up to 5 tonnes/h. The effect of rotor speed, flow rate, dispersed phase fraction up to 50 wt%, inlet drop size and viscosity ratio on droplet size was investigated. It was found that rotor speed and dispersed phase viscosity have a significant effect on the droplet size, while flow rate, inlet droplet size, viscosity ratio and dispersed phase volume have a lesser effect. The results indicate that low viscosity droplets are broken by turbulent inertial stresses, while droplets smaller than the Kolmogorov length scale are broken by a combination of inertial and viscous stresses. It also appears that the weak dependence of drop size on flow rate enables the energy efficiency of an in-line high shear Silverson to be significantly improved by operating at as high a flow rate as possible.     

Effect of supercritical carbon dioxide on morphology development during polymer blending

Supercritical carbon dioxide (scCO₂) was added during compounding of polystyrene and poly(methyl methacrylate) (PMMA) and the resulting morphology development was observed. The compounding took place in a twin screw extruder and a high‐pressure batch mixer. Viscosity reduction of PMMA and polystyrene were measured using a slit die rheometer attached to the twin screw extruder. Carbon dioxide was added at 0.5, 1.0, 2.0 and 3.0 wt% based on polymer melt flow rates. A viscosity reduction of up to 80% was seen with PMMA and up to 70% with polystyrene. A sharp decrease in the size of the minor (dispersed) phase was observed near the injection point of CO₂ in the twin screw extruder for blends with a viscosity ratio, ηPMMA/ηpolystyrene, of 7.3, at a shear rate of 100 s^?1. However, further compounding led to coalescence of the dispersed phase. Adding scCO₂ did not change the path of morphology development; however, the final domain size was smaller. In both batch and continuous blending, de‐mixing occurred upon CO₂ venting. The reduction in size of the PMMA phase was lost after CO₂ venting. The resulting morphology was similar to that without the addition of CO₂. Adding small amounts of fillers (e.g. carbon black, calcium carbonate, or nano‐clay particles) tended to prevent the de‐mixing of the polymer blend system when the CO₂ was released. For blends with a viscosity ratio of 1.3, at a shear rate of 100 s^?1, the addition of scCO₂ only slightly reduced the domain size of the minor phase.     

Particle fluctuations and dispersion in three-phase fluidized beds with viscous and low surface tension media

Particle fluctuations and dispersion were investigated in a three-phase (gas–liquid–solid) fluidized bed with an inside diameter of 0.102 m and height of 2.5 m. Effects of gas and liquid velocities, particle size (0.5–3.0 mm), viscosity (1.0–38×10⁻³ Pa s) and surface tension (52–72×10⁻³ N/m) of continuous liquid media on the fluctuating frequency and dispersion coefficient of fluidized particles were examined, by adopting the relaxation method base on the stochastic model. The fluctuations and dispersion of fluidized solid particles were successfully analyzed by means of the pressure drop variation with time, which was chosen as a state variable, based on the stochastic model. The fluctuating frequency and dispersion coefficient of particles increased with increasing gas velocity, due to the increase of bubbling phenomena and bed porosity in which particles could move, fluctuate and travel. The frequency and dispersion coefficient of particles showed local maximum values with a variation of liquid velocity. The two values of fluctuating frequency and dispersion coefficient of particles increased with increase in particle size, but decreased with increase in liquid viscosity due to the restricted movement and motion of particles in the viscous liquid medium. Both fluctuating frequency and dispersion coefficient of particles increased with decrease in surface tension of liquid phase, due to the increase of bubbling phenomena with decrease in σ_L. The values of obtained particle dispersion coefficient were well correlated in terms of dimensionless groups as well as operating variables.     

Zirconia nano-colloids transfer from continuous hydrothermal synthesis to inkjet printing

Water dispersions of nanometric yttria stabilized zirconia (YSZ) particles synthesized by Continuous Hydrothermal Synthesis are transferred into nano-inks for thin film deposition. YSZ nanoparticles are synthesized in supercritical conditions resulting in highly dispersed crystals of 10 nm in size. The rheology of the colloid is tailored to achieve inkjet printability (Z) by using additives for regulating viscosity and surface tension. Inks with a wide range of properties are produced. A remarkable effect of nanoparticles on the ink printability is registered even at solid load < 1%vol. In particular, nanoparticles hinder the droplet formation at low values of the printability while suitable jetting is observed at high Z values, i.e. Z ≈ 20. For the optimized inks, we achieve high quality printing with lateral and thickness resolutions of 70 μm and ca. 250 nm respectively, as well as self-levelling effect with a reduction of the substrate roughness. Densification is achieved at sintering temperatures below 1200 °C.     

Direct measurement of entrainment in large flotation cells

A key response variable to describe the metallurgical performance in a flotation cell is the concentrate grade. The mineral feed characteristics and conditioning determine the grade of the particles attached directly to the surfaces of the bubbles by true flotation, while the operating conditions, such as gas rate, bubble size, froth depth and others, determine the amount of gangue recovered by entrainment, which finally decreases the concentrate grade.In this paper, the recovery of liquid and solids by entrainment was evaluated by direct measurement of the fraction of liquid and solids reported to the concentrate in a 130 m³ mechanical flotation cell.The liquid and solids entrainment, per size classes (+ 150; − 150 + 45; − 45 µm), was measured by the radioactive tracer technique. The procedure consisted of introducing a tracer impulse at the cell feed entrance. The tracer time response was monitored on-line at the concentrate overflow and at the tailings discharge. Also, in order to obtain the quantitative distribution of the feed, samples were taken periodically from the concentrate and tailings streams, for a period of 4 residence times, during the tracer tests. This allowed the quantification of the mass of tracer reporting to both streams.Experimental results confirmed that solids entrainment with the froth was strongly dependent on particle size, and that the entrainment factor (EF = solid/water recovery ratio) was similar to that reported for smaller size cells under similar operations conditions.     

Additive manufacturing of SiC-Sialon refractory with excellent properties by direct ink writing

Additive manufacturing of SiC-Sialon refractory with complex geometries was achieved using direct ink writing processes, followed by pressureless sintering under nitrogen. The effects of particle size of SiC powders, solid content of slurries and additives on the rheology, thixotropy and viscoelasticity of ceramic slurries were investigated. The optimal slurry with a high solid content was composed of 81 wt% SiC (3.5 µm+0.65 µm), Al₂O₃ and SiO₂ powders, 0.2 wt% dispersant, and 2.8 wt% binder. Furthermore, the accuracy of the structure of specimens was improved via adjustment of the printing parameters, including nozzle size, extrusion pressure, and layer height. The density and flexural strength of the printed SiC-Sialon refractory sintered at 1600 °C were 2.43 g/cm³ and 85 MPa, respectively. In addition, the printed SiC-Sialon crucible demonstrated excellent corrosion resistance to iron slag. Compared to the printed crucible bottom, the crucible side wall was minimally affected by molten slag.     

Dispersion of carbon nanotubes in ethanol by a bead milling process

Carbon nanotubes (CNTs) were dispersed in ethanol by bead milling to form a CNT suspension. The size and shape of the CNTs were not changed after bead milling. The Brownian motion of the CNTs was observed by an optical microscope. It was shown by analysis off the trajectory of individual CNTs that the diffusion coefficient of their translational Brownian motion was 4.5 × 10⁻¹³ m² s⁻¹. The ratio of the particle mobilities due to drift flow and diffusion flow was 2.4, which is almost the same as for a high-molecular-weight protein. Shear thinning occurred in the CNT suspension, which means that the CNTs were oriented in the suspension under a high shear rate at low viscosity. The intrinsic viscosity for shear rates of 0 and ∞ agreed with those calculated using Simha’s equation and Leal and Hinch’s equation, respectively. Based on the experimental results, the CNTs were found to be well dispersed as isolated and nanosized rod-like particles in the suspension. CNT-dispersed Si₃N₄ ceramics were fabricated using the CNT suspensions. As a result, the bead milling improved the bend strength of the CNT Si₃N₄ ceramics compared with the wet ball milling because granules of CNTs were eliminated by the bead milling.     

Low-temperature synthesis of redispersible iron oxide nanoparticles under atmospheric pressure and ultradense reagent concentration

Highly dispersed α-Fe₂O₃ nanoparticles ca. 3 to 8 nm in diameter were prepared at atmospheric pressure, low temperature, and at an ultradense reagent concentration by titrating an aqueous ammonia solution into a dense iron oleate/toluene mixture. A transparent suspension was obtained by redispersing the prepared particles in nonpolar solvents since they were redispersible to primary particles without aggregate formations. The prepared particles were characterized by TEM, XRD, and FT-IR, and their dispersion stability in organic solvents was determined by dynamic light scattering (DLS) and viscosity measurements. In order to analyze the formation process of the highly dispersed α-Fe₂O₃ nanoparticles, time-course measurements of DLS and viscosity during the nanoparticle synthesis in toluene were carried out. A significant increase in the suspension viscosity and the formation of an aggregated structure were observed as soon as the titration of the aqueous ammonia solution. The suspension viscosity and aggregated particle size gradually reduced with continuous vigorous stirring; finally, α-Fe₂O₃ nanoparticles that were completely redispersible in nonpolar solvents were obtained after ca. 24 h. The particle size could be controlled by the synthesis temperature, and such redispersible α-Fe₂O₃ nanoparticles were obtained even when the reagent concentration was increased to 2.8 mol/L.     

Some properties of a thickener for preparing inkjet printing ink for nylon carpet

The properties of a thickener for nylon carpet inkjet printing are presented in this work. A water-based ink was prepared from polyacrylate-based thickener. The physical and chemical properties of the polyacrylate-based thickener used for preparing the inkjet printing ink, as well as its printing effects on carpet, were investigated. Before printing, the properties of the ink, including its surface tension, electrolyte resistance, storage stability, and percentage removal, were investigated. After printing, the efficiency of coloration of printed carpet and the fastness of printed carpet were studied. The results concerning the surface tension and percentage removal of printing ink show that the polyacrylate-based thickener printing ink is suitable for nylon carpet inkjet printing. Meanwhile, its storage stability and electrolyte resistance make it suitable for printing. The efficiency of coloration of printed carpet and the fastness of printed carpet satisfy the requirements of application at appropriate ink concentration and viscosity.