Freeze gelcasting of hydrogenated vegetable oil-in-aqueous alumina slurry emulsions for the preparation of macroporous ceramics

Freeze gelcasting of hydrogenated vegetable oil-in-aqueous alumina slurry (HVO-in-AAS) emulsions has been studied for the preparation of macroporous ceramics. The emulsions with HVO to AAS volume ratios in the range of 1.34–2.69 prepared from a 30 vol.% AAS containing carrageenan using sodium dodecyl sulphate emulsifying agent at 85 °C undergo gelation on cooling to room temperature due to the solidification of HVO and physical cross-linking of carrageenan. Macroporous ceramics obtained by drying, HVO removal followed by sintering at 1500 °C of the gelled emulsion bodies had porosity in the range of 70.7–84% and contain cells of spherical to polygonal shape. The average cell size (13.24–3.6 μm) decreased and the cell interconnectivity increased with an increase in HVO to AAS volume ratio and mixing speed. The macroporous alumina bodies had high compressive strength (6.5–39.6 MPa) and Young's modulus (350–2352 MPa).     

Influence of solution composition on sprayed ZnO nanorods properties and formation process: Thermoanalytical study of the precursors

ZnO is an important inorganic material for numerous applications. Different physical and chemical methods have been applied to deposit ZnO. Spray pyrolysis method being simple, rapid and low-cost is amongst the many options and has been chosen for this study. Fabrication of ZnO nanorods crystals by chemical spray pyrolysis was performed using an acidic solution of ZnCl₂1 or a basic ammonia-containing solution of ZnCl₂2. All layers were studied using X-ray diffractometry and Scanning Electron Microscopy. The formation of ZnO nanorods from 2 appeared at 450?°C, whereas spraying acidic solution 1 yielded ZnO nanorods like morphology at 550?°C.Thermal decomposition of precursors for ZnO layers prepared by de-watering of acidic aqueous solution of ZnCl₂ with pH =?3 (1) and basic solution of ZnCl₂ and NH₄OH with pH =?10 (2) was monitored by simultaneous thermogravimetric and differential thermal analysis (TG/DTA) in air coupled online with evolved gas analyses by Fourier transformed infrared spectroscopy (FTIR).The precursor (1) is ZnCl₂ *nH₂O; the precursor (2) is a mixture of (NH₄)₃(ZnCl₄)Cl, Zn(NH₃)₂Cl₂, NH₄Cl(NH₃)₃ and Zn(OH)₂ phases. The thermal decomposition of (1) and (2) in the temperature range of 30–700?°C consists of two steps with total mass losses of 86.2% and 93.8%, respectively. The main evolved gases from (1) are H₂O and HCl, whereas the main evolved gases from (2) are H₂O, NO_x and NH₃. Degradation of (1) and (2) is completed by 670 and 620?°C, respectively. The final decomposition product of (1) and (2) at 700?°C is ZnO.This study shows that the use of basic solutions enables to decrease the temperature of ZnO formation and the deposition temperature of ZnO nanorods layers.     

Processing of low-density alumina foam

A novel method for synthesizing low-density alumina foam has been developed. The alumina foam with 98.5% porosity was synthesized by an unconventional route from an aqueous aluminum nitrate–sucrose solution. The resin formed by heating this solution underwent foaming and set into solid green foam, which was sintered at 1873 K. The thermogram of the green foam showed mass loss in four stages. The foam exhibited interconnected porous network with window size in the range 103–226 and 167–311 μm for foams sintered at 1223 and 1873 K, respectively. The alumina foam sintered at 1223 K exhibited gamma phase and that sintered at 1873 K exhibited alpha phase.     

Fabrication of magnesium aluminate (MgAl2O4) spinel foams

This paper reports on a novel-processing route for fabricating magnesium aluminate (MgAl₂O₄) spinel (MAS) foams from aqueous suspensions containing 30–35 vol.% solids loading. A stoichiometric MAS powder formed from alumina (71.8%) and magnesia (28.2%) at 1400 °C was surface passivated against hydrolysis in an ethanol solution of H₃PO₄ and Al(H₂PO₄)₃ at 80 °C for 24 h. Stable aqueous suspensions with 30–35 vol.% solids loading were prepared using the surface passivated MAS powder with the help of tetra-methylammonium hydroxide (TMAH) and an ammonium salt of polyacrylic acid (Duramax D-3005) employed as dispersing agents. An aqueous solution of N-cetyl-N,N,N-trimethylammonium bromide (CTMAB) was utilized to create foam in aqueous MAS suspensions by mechanical frothing. Liquid foam was then consolidated in non-porous moulds by introducing a polymerization initiator and a catalyst under ambient conditions. Dried (at >90 °C for 24 h) MAS foams were then sintered for 1 h at 1650 °C. For comparison purposes, dense MAS bodies out of an un-passivated stoichiometric MAS powder, and, dense as well as foams out of alumina were also prepared in this study. The sintered properties of MAS and alumina ceramics were characterized by various means and thus obtained results are presented and discussed in this paper. The sintered MAS foams exhibited a porosity of about 74–76% and a compressive strength of about 4–7.2 MPa inline to values reported for other ceramic foams in the literature.     

Kinetic analysis for crystal growth rate of NH4Cl in the NaCl‐MgCl2‐H2O system with a thermodynamic approach

A growth kinetic model has been developed from a rigorous thermodynamic perspective to describe the crystal growth rates of NH₄Cl on the basis of the difference of chemical potentials of NH₄Cl at solid–liquid interface in aqueous NH₄Cl, NH₄Cl‐NaCl, and NH₄Cl‐MgCl₂ solutions. The solid–liquid equilibrium and activity coefficient of NH₄Cl are calculated by the newly developed accurate Pitzer model with aid of Aspen Plus? platform. The predictions of the resulting model are in good agreement with the experimental data published in literature and determined in this work at 283.15–333.15 K within the supersaturation up to 0.1. The kinetic model was subsequently used to analyze the effect of several operation variables, including temperature (283.15–333.15 K), supersaturation (up to 0.1), and NaCl or MgCl₂ concentration (0～2.5 mol kg^?1), on the crystal growth rate of NH₄Cl. The crystal growth rate of NH₄Cl, with activation energy of 39 kJ mol^?1, is strongly temperature‐dependent and increases with increasing temperature in the three systems investigated. The advantage of MgCl₂ over NaCl on the recovery of NH₄Cl is theoretically and experimentally illustrated from the thermodynamic and kinetic perspectives with the aid of the established model. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Multihollow nanocomposite microspheres with tunable pore structures by templating Pickering double emulsions

Micrometer-sized dual nanocomposite polymer microspheres with tunable pore structures were fabricated using a simple and straightforward method based on Pickering double emulsions. First, a primary water-in-styrene (oil) emulsion (w₁/o) was prepared using the hydrophobic silica nanoparticles as a particulate emulsifier without any molecular surfactants. Then, a water-in-styrene-in-water (w₁/o/w₂) Pickering emulsion was produced by the emulsification of the primary w₁/o emulsion into water using Fe₃O₄ nanoparticles as external emulsifier. The big styrene droplets containing small water droplets were polymerized after the formation of the double emulsions. Nanocomposite polystyrene microspheres with a multihollow structure were obtained and their morphological structures were studied by scanning electron microscopy (SEM). The pore structure of the microspheres could be tuned by the volume ratio of the internal water phase to the medium oil phase (w₁:o) of the primary emulsions. With increasing w₁:o from 1:8 to 4:1, the amount of the pores in one microsphere increased gradually and the pore structures changed from close to interconnected. The resulting multihollow microspheres had a responsive ability to magnetic stimulus due to the existence of Fe₃O₄ nanoparticles. This kind of multihollow hybrid polymer microspheres is expected to have a wide potential application in materials science and biotechnology.     

Aqueous core polystyrene microspheres fabricated via suspension polymerization basing on a multiple pickering emulsion

Multi‐hollow or hollow polymer particles are of great interest in many fields. Here we successfully fabricate polystyrene microspheres with aqueous cores through w/o/w Pickering emulsion stabilized by modified SiO₂ nanoparticles. The final structure and constituents of the microspheres is investigated via SEM, X‐ray photoelectron spectra, and thermo‐gravimetric analysis. The results demonstrate that the size and amount of aqueous cores in the microspheres can be tuned by the original structure of the multiple emulsions: when the volume fraction of inner water is 0.2, the inner structure of the microspheres obtained is porous and each pore is not interconnected; when the volume fraction of inner water is increased to 0.7, the resulting products are hollow microspheres and when 0.3% wt/vol of salt is added to the inner aqueous phase, the inner pores of the resulting microspheres enlarge or even coalesce. The multi‐hollow or hollow polystyrene microspheres with aqueous cores are expected to be candidates for encapsulation in biotechnology. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39761.     

The effects of different synthetic conditions on the porous properties of carbon cryogel microspheres

Carbon cryogel microspheres (CC microspheres) are synthesized through the inverse emulsion polymerization of a resorcinol-formaldehyde (RF) aqueous solution in cyclohexane using SPAN80 as an emulsifier. The conditions of the inverse emulsion polymerization, specifically the volume ratio of SPAN80 to cyclohexane, the temperature of the emulsification, T_gel, and the holding time after the emulsification, are examined. It is revealed that the RF aqueous solution is dehydrated by cyclohexane containing SPAN80 during the inverse emulsion polymerization, and that the degree of dehydration can be changed by varying T_gel. In the case of a T_gel lower than 313 K, this dehydration leads to the formation of ultramicroporous surfaces on the CC microspheres. Conversely, a T_gel higher than 323 K results in the suppression of dehydration, which in turn leads to mesoporous CC microspheres. The mesoporosity of the microspheres synthesized at T_gel = 333 K can be changed by varying the amount of basic catalyst used in the preparation of the RF aqueous solution.     

Preparation of titania-coated alumina film by electrolysis of TiCl4-containing solution

Direct current in the range from 50 to 390 mA/cm² was flowed between alumina/tin-doped indium oxide (indium tin oxide, ITO) composite (cathode) and carbon (anode) electrodes in an aqueous solution containing TiCl₄ and (NH₄)₂SO₄ at pH 0.5. The composite electrode dissolved in the solution and was precipitated again on the surface of the electrode. The thickness of precipitated layer increased at a higher applied charge. During the electrolysis, TiO₂ was also deposited on the surface of precipitated layer. The amorphous TiO₂ heated at 300 °C and sintered Al₂O₃–ITO composite showed a good adsorption property of electromagnetic energy in the wide wavelength of 200–800 nm.     

A physical route to porous ethyl cellulose microspheres loaded with TiO2 nanoparticles

Porous ethyl cellulose (EC) microspheres were prepared via a physical method in oil‐in‐water (O/W) emulsions. The morphologies and pore structures of the resulting porous microspheres were investigated by scanning electron microscopy (SEM), mercury porosimeter and spectrometer equipped with an integrating sphere. The increase of EC amount in oil phase will increase the size of the microspheres. All the microspheres possess open macropores in the shell and interconnected pores inside the microspheres by means of phase separation. The saturation of the Ethyl acetate (EA) in external phase has an effect on the morphology of the EC particles obtained. Using EA unsaturated aqueous solution as the external water phase in the emulsion process results in the formation of porous EC particles with irregular shape. The loaded TiO₂ nanoparticles uniformly disperse in EC matrix, and slightly deceases the size and volume of interconnected pores inside the microspheres. The addition of TiO₂ nanoparticles is also proved to increase the light‐scattering power of the porous EC microspheres. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40822.     

Modeling solid–liquid equilibrium of NH4Cl‐MgCl2‐H2O system and its application to recovery of NH4Cl in MgO production

A new method to recover NH₄Cl from NH₄Cl‐rich aqueous solutions generated in the magnesia (MgO) production is developed on the basis of modeling the solid–liquid equilibrium (SLE) for the NH₄Cl‐MgCl₂‐H₂O system with the Pitzer model embedded in Aspen Plus? platform. The SLE values for the ternary system were determined from 278.15 to 348.15 K. The new standard‐state chemical potentials of NH₄Cl and MgCl₂·6H₂O were judicially obtained. The resulting equilibrium constants were used to determine new interaction parameters for the NH₄Cl‐H₂O and MgCl₂‐H₂O systems. These new parameters, together with the mixing parameters determined from correlating the experimental values, were used to correlate the equilibrium constant for NH₄MgCl₃·6H₂O, which plays a key role in NH₄Cl recovery. The results could extend SLE calculation for the NH₄Cl‐MgCl₂‐H₂O system from 278.15 to 388.15 K, satisfying the process identification and simulation requirement involved in the recovery process. The phase‐equilibrium diagram generated by modeling was illustrated to identify the process alternatives for recovering NH₄Cl. The resulting course to recover NH₄Cl by three fractional crystallization operations was finally proved feasible. © 2010 American Institute of Chemical Engineers AIChE J, 2011.     

Facile fabrication of polystyrene/halloysite nanotube microspheres with core–shell structure via Pickering suspension polymerization

In this article, a facile method for fabrication of core–shell nanocomposite microspheres with polystyrene (PS) as the core and halloysite nanotubes (HNTs) as the shell via Pickering suspension polymerization was introduced. Stable Pickering emulsions of styrene in water were prepared using HNTs without any modification as a particulate emulsifier. The size of the Pickering emulsions varied from 195.7 to 26.7?μm with the water phase volume fraction increasing from 33.3 to 90.9?%. The resulting Pickering emulsions with the water phase volume fraction of above 66.7?% were easily polymerized in situ at 70?°C without stirring. HNTs played an important role during polymerization and effectively acted as building blocks for creating organic–inorganic nanocomposite microspheres after polymerization. The sizes of PS/HNTs microspheres were roughly in accord with that of the corresponding emulsion droplets before polymerization. The effect of the water phase volume fraction on the stability of Pickering emulsions and the morphologies of nanocomposite microspheres was investigated by optical microscopy, confocal laser scanning microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and so on.     

Integrated utilization of high alumina fly ash for synthesis of foam glass ceramic

Due to the numerous increase of the building energy consumption and huge volume of industrial wastes produced in China, the development of thermal insulation materials is quite needed. Herein, foam glass ceramic, a kind of thermal insulation materials, was fabricated by using solid wastes high alumina fly ash and waste glass as the main raw materials. First, in this study the proportion scheme of this research was designed by using Factsage 7.1 and the foaming agent was CaSO₄. Secondly, the decomposition of calcium sulfate and the influence of process parameters, namely the sintering temperature and the foaming agent additive amount, on the microstructure and mechanical properties of foam glass ceramic were investigated. The experimental results showed that when the proposed foam glass ceramic was sintered at between 1180 and 1220?°C, it exerted excellent macro and micro properties. The optimum parameters were 2% CaSO₄ addition and sintering temperature of 1200?°C, and the corresponding bulk density and compress strength values were 0.98?g/cm³ and 9.84?MPa, respectively. Overall these results indicated that the preparation of foam glass ceramic made up a promising strategy for recycling industrial waste into new kind of building insulation materials.     

The first transition-metal metal–organic framework showing cation exchange for highly selectively sensing of aqueous Cu(II) ions

The anionic metal–organic framework (MOF), [NH₄]₂[ZnL]·6H₂O(1, L = 1,2,4,5-benzenetetracarboxylate), featuring the PtS-type net allows for [NH₄]⁺-to-(metal ions) cation exchange, and thus performs the potential of luminescent sensing of aqueous metal ions. To our best knowledge, polymer 1 presents the first transition-metal MOF suitable for luminescent sensing and the first MOF solid material for aqueous luminescent sensing.     

Tensile strength and corrosion resistance properties of porous Al2O3/Ni composites prepared with rice husk pore-forming agent

The mechanical performance and chemical stability of porous alumina materials operating under harsh service conditions are of utmost importance in understanding their operational behavior if they are to stand the test of time. In the present study, the joint effect of nickel (Ni) reinforcement and rice husk (RH) pore-forming agent (PFA) on the tensile strength and the corrosion resistance properties of composite porous alumina ceramics was studied. To exploit the potential of this new porous alumina system, plain and Ni-reinforced porous alumina samples (Al₂O₃-xNi-RH; x?=?2, 4, 6 and 8?wt%) were developed through the powder metallurgy technique. Comprehensive investigation on the tensile strength properties of the developed porous alumina ceramics showed that relative to the plain sample (tensile strength and elastic modulus; 6.1?MPa and 1201?MPa), the presence of highly stable Ni₃Al₂SiO₈ spinelloid promoted the tensile strength enhancement (12.6–6.4?MPa) and the elastic modulus decline (897–627?MPa) of the composite samples. Similarly, corrosion resistance test was performed on the composite porous alumina samples in both 10?wt% NaOH and 20?wt% H₂SO₄ hot aqueous solutions. Overall, the composite samples demonstrated superior chemical stability in NaOH solution as compared with the plain sample. On the other hand, the composites were more prone to attack in H₂SO₄ solution, except for the Al₂O₃-2Ni-10RH composite sample which maintained its superiority over the plain counterpart.     

Hydrolysis control of alumina and AlN mixture for aqueous colloidal processing of aluminum oxynitride

AlN powder, surface modified by phosphoric acid treatment was employed for the aqueous colloidal processing of Aluminum Oxynitride (AlON). The hydrolysis of AlN leads to the formation of Al(OH)₃ and NH₃. On mixing of alumina to the phosphoric acid treated AlN in aqueous medium this reaction reoccurred. The phosphoric acid shield around AlN particles is ruptured by alumina addition thus exposing AlN surface to hydrolysis reactions. Hence hydrolysis can be effectively controlled by providing a phosphoric acid treatment to the alumina, prior to its addition to AlN. AlON precursor mixture thus obtained can be successfully shaped by an aqueous slip casting process and sintered to phase pure AlON at 1925 °C for 2 h. Viscosity, pH, SEM, FTIR, and XRD measurements are employed to elucidate the effect of Al₂O₃ addition on surface modified AlN for colloidal processing of AlON.     

Formation of aluminium nitride whiskers by direct nitridation

This work describes novel results on the growth of aluminium nitride (AlN) whiskers by direct nitridation of Al–NH₄Cl starting mixtures. The nitridation experiments were carried out in a horizontal tube furnace at 1000 °C for 1 h in 1 l/min N₂ gas flow. It is found that the growth of AlN whiskers was principally promoted by NH₄Cl which provided a different reaction pathway depends on vapor-phase reactions mechanism instead of normal liquid–gas mechanism. The thermodynamic analysis of possible intermediate reactions in the operating temperatures range confirmed that the AlN whiskers could be grown through spontaneous vapor-phase chlorination–nitridation sequences. The SEM observation revealed that depending on NH₄Cl concentration homogeneous AlN nanowhiskers of <150 nm in diameters can be obtained as well as composites of particles-whiskers of AlN which may be potential for preparing useful sintered AlN materials.     

Reversible nitro–nitrito inter-conversion in a simple mono-nuclear nickel(II) complex [NiII{C6H4(NH2)2}2(NO2)2] in the solid state

A simple mono-nuclear nickel(II) complex [Ni^II{C₆H₄(NH₂)₂}₂(NO₂)₂] (1) has been synthesized from an aqueous solution containing nickel chloride, sodium nitrite and ortho-phenylenediamine (opda). When crystals of compound 1 are heated in the temperature range of 110–120 °C for 5 min, their brown color changes to blue, that is accompanied by the conversion of nitro group (N-coordinated) in compound 1 into nitrito group (O-coordinated) in compound [Ni^II{C₆H₄(NH₂)₂}₂(ONO)₂] (2). On cooling, the nitrito compound 2 goes back to parent nitro-compound 1.     

Effect of oxygen donor alcohol on nonaqueous precipitation synthesis of alumina powders

Monodispersed alumina powders were prepared via nonaqueous precipitation process using aluminum powders as aluminum source, acetic acid as precipitant. Effect of oxygen donor and solvent alcohol such as methanol, ethanol, isopropanol on the preparation of ultrafine alumina powders and the precursor reaction mechanism have been investigated by XRD, FT-IR, TEM, FE-SEM and performance tests of sintered bodies. The intermolecular condensation of methanol with the catalysis of Lewis acid aluminum methoxide leads to hydrolysis of aluminum methoxide, forming amorphous precipitates, dehydration polycondensation of aluminum hydroxide and resulting in serious agglomeration of precipitates and alumina powders, the worst morphology and properties of sintered body. The pulling electron effect and steric hindrance of isopropyl group make the structure of aluminum isopropoxide overwhelmingly stable and relatively arduous to be replaced by precipitant acetic acid, which results in underdeveloped crystallinity and agglomeration of both precipitates and alumina powders, poor morphology and properties of sintered body. The optimized oxygen donor and solvent alcohol is ethanol. Monodispersed, high crystallinity C₄H₇AlO₇ precipitates and alumina powders can be obtained when ethanol is used as oxygen donor and solvent, and the highest relative density, mechanical properties and the most homogeneous microstructure was obtained. The density, flexural strength, volume resistivity, breakdown voltage and thermal expansion coefficient are 99.1% of TD, 128.0?±?2.2?MPa, 9.8?×?10¹⁶ Ω?cm, 45.2?kV/mm and 7.6?×?10^?6 °C^?1, respectively. Precursor reaction mechanism is deduced that aluminum powders react with oxygen donor alcohol to form aluminum alkoxide with the catalyst iodine, and then react with acetic acid to form crystal C₄H₇AlO₇ precipitates. Nonaqueous precipitation method is expected to become a promising candidate for mass production of alumina powders.     

Effects of Inorganic Salts and Polymers on the Foam Performance of 1-Tetradecyl-3-methylimidazolium Bromide Aqueous Solution

The foaming performance of 1-tetradecyl-3-methylimidazolium bromide (C₁₄mimBr) aqueous solution, in the presence of polymers (PEG or PVA) or inorganic salts (NaBr, MgCl₂, NaNO₃, Na₂SO₄ or Na₃PO₄), was investigated at 25.0?°C by using the self-made apparatus and the conductivity method. The experimental results show that the foaming ability and foam stability of the ternary aqueous systems of C₁₄mimBr coexisting with PEG or PVA are stronger than those of the C₁₄mimBr solutions in the absence of a polymer, and both the efficiency of foaming ability and foam stability of the surfactant solutions are evidently enhanced with an increase in polymer concentration. However, the addition of inorganic salts can decrease the foaming ability and foam stability of C₁₄mimBr solution. Especially, the inorganic salts, with high valence state of the anion (SO₄ ^2? and PO₄ ^3?), are good antifoam agents which can remove and inhibit foam quickly. For the aqueous solution of the surfactant, the effect of temperature on foaming properties was also examined. The results show that both the foaming ability and stability of the foams of the surfactant solutions decrease with an increase in the temperature within the range from 25.0 to 45.0?°C.