Migration,transformation and solidification/stabilization mechanisms of heavy metals in glass-ceramics made from MSWI fly ash and pickling sludge

In consideration of recycling solid waste to achieve high value-added products, glass-ceramics have been fabricated from municipal solid waste incineration (MSWI) fly ash, pickling sludge (PS), and waste glass (WG) by melting at 1450 °C firstly to achieve parent glass and then crystallizing at 850 °C. Results demonstrated that heavy metals have been well solidified in the prepared glass-ceramics, and relatively/extremely low leaching concentrations of heavy metals have been detected. The synthetic toxicity index of heavy metals has been greatly reduced from 7-18 to <3.2 after crystallization treatment, and the leaching concentrations of Cr, Ni, Zn, Cu, and Pb are 0.15, 0.05, 0.26, 0.12, 0.19 mg L^-1 respectively. Chemical morphology analysis, principal component analysis, TEM and EPMA were utilized to clarify the migration, transformation, and solidification mechanism of heavy metals from the as-received solid wastes. The major heavy metals, Cr and Ni which is responsible for the most toxicity, mainly exist in form of the oxidation state and residual state in parent glass, while the residual state in the glass-ceramics. The solidification performance was mostly positively correlated with the form of residue state, which the stability of heavy metals in glass-ceramics is improved. The solidification mechanism of heavy metals in glass-ceramics could be explained by the combination of chemical solidification/stabilization and physical coating. The TEM and EPMA confirmed that Cr and Ni mainly exist in the spinel crystalline (NiCr₂O₄, Fe_0.99Ni_0.01Fe_1.97Cr_0.03O₄) by solid solution or chemical substitution, and a small amount of Cr in the diopside phase. Pb, Cu, and Zn are homogenously dispersed in the glass-ceramics, which is considered as physical coating solidification.     

A comprehensive exploration on the development of nano Y2O3 dispersed in AA 7017 by mechanical alloying and hot-pressing technique

The main objective of the present study is to develop AA 7017 alloy matrix reinforced with yttrium oxide (Y₂O₃, rare earth element) nanocomposites by mechanical alloying (MA) and hot pressing (HP) techniques for armor applications. AA 7017+10 vol % Y₂O₃ nanocomposites were synthesized in a high-energy ball mill with different milling times (0, 5, 10, and 20 h) to explore the structural refinement effect. The phase analysis and homogeneous dispersion of Y₂O₃ in AA 7017 nanocrystallite matrix were investigated by X-ray diffraction (XRD), various electron microscopes (HRSEM, and HRTEM), Particle Size Analyzer (PSA), and Differential Thermal Analysis (DTA). The nanostructured powders were hot-pressed at 500 MPa pressure with a temperature of 673k for 1hr. The consolidated sample results revealed significant grain refinement and the enhanced mechanical properties with the function of milling time in which the 20h sample exhibited improvement in the hardness (142 VHN - 260 VHN) and ultimate compressive strength (514 MPa–906.45 MPa) due to effective dispersion of Y₂O₃. The various strengthening mechanisms namely, grain boundary (27.02–32.69 MPa), solid solution (57.21 MPa), precipitate (189.79–374.62 MPa), Orowan (135.68–206.92 MPa), and dislocation strengthening (84.99–149.82 MPa) were determined and correlated to the total strength.     

Carbon doped with binary heteroatoms (N,X–C,where X = P,B, or S) derived from polypyrrole for enhanced electromagnetic wave absorption at microwave frequencies

Dual heteroatom-doped carbon materials show great promise as electromagnetic wave absorbers. However, synthesizing carbons containing multiple heteroatoms at controlled heteroatom doping levels has provided challenges to date. Herein, we report a simple method for manufacturing dual heteroatom doped carbons (N,X–C, where X = P, B, or S) by direct carbonization of polypyrrole synthesized in the presence of H₃PO₄, H₃BO₃, or H₂SO₄, respectively. The heteroatom content of the N,X–C products could be precisely tuned by varying amounts of acid dopant used in the polypyrrole synthesis. The N,X–C materials showed excellent electromagnetic wave absorption properties, especially N,S₁–C (prepared using equimolar amounts of pyrrole and H₂SO₄) which offered a wide absorption bandwidth up to 6.6 GHz (11.38–18 GHz), and a RL_min of ?32.3 dB (14.2 GHz) at 2.5 mm at a ?ller loading of 9.0 wt%. The outstanding electromagnetic wave absorption performance of N,S₁–C was attributed to the presence of N dopant species, defects, C–S, and C–SO_x groups, which optimized dipole polarization and conduction loss in the dielectric loss leading to excellent impedance matching.     

Oxygen-ion conductivity and mechanical properties of Lu2O3-doped ZrO2 as a solid electrolyte

The characteristics of Lu₂O₃-doped ZrO₂ as a solid electrolyte material were investigated in terms of its oxygen ion conductivity and flexural strength to realize its electrolytic function at intermediate and high temperatures. The effect of doping Lu³⁺, which has a high nuclear charge electric field strength, was examined through impedance spectroscopy, open-circuit potential measurements, and bending tests. The results with Lu₂O₃ dopant were compared with those obtained with a widely used dopant, Y³⁺, having a similar ionic radius with Lu³⁺, as well as a dopant that provides high ionic conduction, Sc³⁺, having a smaller ionic radius with Zr⁴⁺. The results revealed that, at the same dopant concentration, both the ionic conductivity and the flexural strength of Lu₂O₃-doped ZrO₂ are higher than those of the widely used Y₂O₃-doped ZrO₂. The conductivity of 8 mol% Lu₂O₃-doped ZrO₂ surpassed that of 8 mol% Sc₂O₃-doped ZrO₂ in the range of 800–950 °C (0.153 S/cm vs. 0.121 S/cm at 900 °C). These results indicate the potential of Lu³⁺ as a dopant for enhancing the performance of ZrO₂ solid electrolytes.     

Interface properties of Ti3SiC2/Al2O3 ceramics: Combined experiments and first-principles calculations

The synthesis, characterization, and first-principles calculations of Ti₃SiC₂/Al₂O₃ ceramics were reported. X-ray diffraction measurements showed that the composite ceramics were highly pure. Scanning electron microscopy and transmission electron microscopy were used to characterize the interface information for Ti₃SiC₂ and Al₂O₃ crystals. Surface energies and interface properties were calculated using the first-principles method. The results suggested that Ti₃SiC₂ with Ti terminations and Al₂O₃ with O terminations are more stable than other terminations crystals. Thus powerful attraction between the coordinatively unsaturated Ti and O atoms on the Ti₃SiC₂∥Al₂O₃ interface would result in higher work of adhesion (Wad) and shorter boundary distance, demonstrating the intercrystalline strengthening of Ti₃SiC₂/Al₂O₃ composite ceramics.     

Non-isothermal nitridation kinetics of Ti6Al4V in Al2O3-based refractories

To establish a kinetic model of nitridation of Ti6Al4V in Al₂O₃-based refractories, the non-isothermal nitridation of Ti6Al4V–Al₂O₃ composite refractories at various heating rates was investigated using a thermogravimetric (TG) analyzer for large samples. The activation energy (E) and kinetic model (G(α)) for the nitridation of Ti6Al4V were determined using the isoconversional and master plots methods, respectively. The nucleation and growth of nitriding products of the TiN solid solution was the controlling step in the nitridation of Ti6Al4V in Al₂O₃-based refractories. The Avrami-Erofeev kinetic model, depicted by the G(α) = [-ln (1-α)]⁴ equation, is the most rational kinetic model. The values of E and A for the nitridation of Ti6Al4V were calculated to be 214.99 kJ/mol and 1.46 × 10⁷ (S^?1), respectively.     

Tuning the electronic and thermal transport behaviors of metal-dispersed Ti2O3 composites derived by metal–insulator transition

Thermal management requires an understanding of the relations among the thermal energy transfer, electronic properties, and structures of thermoconductive materials. Here, we enhanced the metal–insulator transition (MIT)-induced effect on the thermal conductivities of microstructure-controlled Ti₂O₃ composites containing W as a thermal conductive filler at approximately 450 K. To change the electronic and thermal transport properties, we varied the particle radii of the conductive phases in the raw material. The change in the calculated electronic thermal conductivity relative to the electrical conductivity of the W_x(Ti₂O₃)_1?x composite was enhanced by compounding the material. When x was reduced from 50 vol% to 20 vol% and the W particle diameter was reduced from 150 μm to 5 μm, the variation in the estimated electronic thermal conductivity of the W_x(Ti₂O₃)_1?x composite was increased by a factor of 2.01. The total thermal conductivity was also changed by the MIT. At x = 50 vol% and a W particle diameter of 5 μm, the maximum thermal conductivity change was 6.34 times larger than that of pure Ti₂O₃. The detailed relation between the MIT-induced changes in thermal transport and the microstructure were elucidated in classical effective medium approximations.     

Sintering characteristics and microwave dielectric properties of ultralow-loss SrY2O4 ceramics

A SrY₂O₄ microwave dielectric ceramic suitable for 5G systems is synthesised via a solid-state reaction in a sintering temperature range of 1425–1525 °C. X-ray diffraction patterns and Rietveld refinement analysis show that the ceramic has an antispinel orthorhombic crystal structure belonging to the Pnma space group. Scanning electron microscopy images show that the ceramic particles are closely connected, the grain boundaries are clear, and the particles are uniform at the optimal sintering temperature of 1475 °C. The optimal microwave dielectric performances are ε_r = 14.78, Q × f = 84090 GHz, τ_? = ?14.98 ppm/°C. The relatively low dielectric constant, high Q × f value, low τ_? value, and easily available raw materials indicate that it is a good choice for 5G equipment.     

Fabrication of in situ elongated β-Sialon grains bonded to tungsten carbide via two-step spark plasma sintering

In order to reduce the difficulty of preparing binder-less cemented carbide and further broaden its application prospects, tungsten carbide toughened by in situ elongated β-Sialon grains was developed via sintering ball-milled WC and α-Si₃N₄ powders using Al₂O₃–ZrO₂ as a sintering aid and transformation additive. The two-step spark plasma sintering of the mixture at 1650 °C with dwelling at 1500 °C for 10 min was conducted under 30 MPa uniaxial pressure, and the densification behaviors, phase transformations, mechanical properties, and microstructures of the produced composites were investigated. The addition of Al₂O₃–ZrO₂ reduced the initial temperature of the densification process by approximately 100 °C and its final temperature by 200 °C (compared with the densification temperatures of pure WC and Si₃N₄ materials) and fully transformed α-Si₃N₄ to Sialon (Si–Al–O–N) phases. Microstructural characterization data showed that the WC matrix contained homogeneously distributed equiaxed and elongated β-Si₅AlON₇ grains. The WC composites containing in situ elongated β-Sialon grains exhibited an optimal hardness of 18.93 ± 0.03 GPa and enhanced fracture toughness of 10.43 ± 0.27 MPa m^1/2. The toughening mechanism of the β-Sialon phase involved the pull-out of elongated grains and crack bridging.     

Al2O3 coated glass by aerosol deposition with excellent mechanical properties for mobile electronic displays

Al₂O₃ thin film was deposited on Gorilla glass using an aerosol deposition method to improve the mechanical property of cover glass for mobile electronic device. The deposited Al₂O₃ film (approximately 1 μm thick) was a polycrystalline structure and showed a high light transmittance of approximately 90% in the visible light region. The CIE color space (L*a*b) measurement also showed a characteristic corresponding to the acceptable optical range of the cover glass. Further, it was confirmed that the bending strength improved by 10 %, as compared with bare Gorilla glass (from 6970 kgf/cm² to 7704 kgf/cm²), and the Vickers hardness increased to approximately 1700–2000 HV, as compared with that of Gorilla glass (<700 HV). Owing to the improved mechanical properties, the Al₂O₃ thin film exhibited good anti-scratch properties and is expected to be applied to the cover glass of various display products.     

Tuning specific loss power of CoFe2O4 nanoparticles by changing surfactant concentration in a combined co-precipitation and thermal decomposition method

New synthetic approaches of nanoparticles (NPs) can be used for magnetic hyperthermia, destroying malignant cells without damaging healthy tissues. Here, a combination of co-precipitation and thermal decomposition techniques was employed to synthesize monodisperse CoFe₂O₄ NPs. A mixture of oleylamine and oleic acid with different concentrations was utilized as a surfactant, significantly changing magnetic, morphological and structural properties of the NPs. Increasing the surfactant concentration from 1 to 7.5 mmol resulted in maximum and minimum coercivity and saturation magnetization of 420.0 Oe 73.6 emu/g, and 67.2 Oe and 48.3 emu/g, respectively, arising from the prevention of agglomeration and reduction in crystallite size. The first-order reversal curve analysis was employed to clarify the role of the surfactant in magnetic distributions and detailed characteristics. The specific loss power of the NPs was found to be tuned for the different surfactant concentrations, achieving a maximum of 268.5 W/g at 7.5 mmol for CoFe₂O₄ NPs with enhanced superparamagnetic contribution in Néel and Brownian mechanisms. MTT assay of the NPs was also carried out, indicating their low cytotoxicity.     

Direct ink writing of Pd-Decorated Al2O3 ceramic based catalytic reduction continuous flow reactor

Continuous flow reactor, due to the characteristics of safety and stability, faster reaction, less solvent demand, smaller occupied area and less energy requirements, is a satisfactory selection for heterogeneous catalysis compared with the traditional intermittent and non-intermittent reactors. Herein, the emerging 3D printing is employed to build the all-Al₂O₃ ceramic based continuous flow reactor (Pd/Al₂O₃ CFR) with the direct ink writing technique, where the outer wall is the dense Al₂O₃ ceramic and the inner is the Pd immobilized porous Al₂O₃ ceramic carrier for catalytic hydrogenation reaction. Polymethylmethacrylate (PMMA) microspheres are used to realize the inside micro-/nanometer porous structures during calcination, which offer plentiful sites for Pd anchoring via the vacuum self-assembly. The Pd/Al₂O₃ CFR therefore exhibits outstanding catalytic performance in the reduction of 4-nitrophenol (4-NP). Importantly, the continuous flow reactor is programmable in diameter, length and shape, and reusable as well. A 3 cm length Pd/Al₂O₃ CFR can be reused for a period of 4 cycles consecutively and still achieve 93.87% catalytic efficiency at 90 s for the reduction of 4-NP with no any post-treatment but washing. Combining the freeform fabrication 3D printing and the porous Al₂O₃ ceramic, the present direct ink writing continuous flow reactor is promising in practical application due to the stability, reusability, and designability etc.     

Effects of oxygen sources on properties of atomic-layer-deposited ferroelectric hafnium zirconium oxide thin films

Orthorhombic Hf_xZr_1-xO₂ (HZO) is a promising ferroelectric material for realizing ferroelectric devices in the modern semiconductor industry because of its excellent CMOS compatibility and scalability. Atomic layer deposition (ALD) facilitates the growth of robust ferroelectric HZO films that can be used in nanoelectronic devices. Herein, we provide a comprehensive understanding of the effects of the oxygen source, either H₂O or O₃, on the properties of ALD-grown HZO films. Although the growth per cycle promoted by ALD does not change with the type of oxygen source, the impurity content of the HZO film grown with H₂O are higher than that with O₃. The low impurity content of the HZO film grown with O₃ results in low leakage current. The ALD process with O₃ further suppresses the emergence of the nonferroelectric monoclinic phase in the ferroelectric orthorhombic HZO matrix. Consequently, the HZO film grown with O₃ exhibits a small coercive field for ferroelectric domain switching and high electrical reliability. This study demonstrates that O₃ is more favorable for growing high-quality HZO films via ALD by using metal precursors comprising tetrakis(ethylmethylamino) ligands.     

Fabrication of Al2O3/AlN composite ceramics with enhanced performance via a heterogeneous precipitation coating process

To improve the thermal and mechanical properties of Al₂O₃/AlN composite ceramics, a novel heterogeneous precipitation coating (HPC) approach was introduced into the fabrication of Al₂O₃/AlN ceramics. For this approach, Al₂O₃ and AlN powders were coated with a layer of amorphous Y₂O₃, with the coated Al₂O₃ and AlN powders found to favor the formation of an interconnected YAG second phase along the grain boundaries. The interconnected YAG phase was designed to act as a diffusion barrier layer to minimize the detrimental interdiffusion between Al₂O₃ and AlN particles. Compared with samples prepared by a conventional ball-milling method, the HPC Al₂O₃/AlN composites exhibited less AlON formation, a higher relative density, a smaller grain size and a more homogeneous microstructure. The thermal conductivity, bending strength, fracture toughness and Weibull modulus of the HPC Al₂O₃/AlN composite ceramics were found to reach 34.21 ± 0.34 W m⁻¹ K⁻¹, 475.61 ± 21.56 MPa, 5.53 ± 0.29 MPa m^1/2 and 25.61, respectively, which are much higher than those for the Al₂O₃ and Al₂O₃/AlN samples prepared by the conventional ball-milling method. These results suggest that HPC is a more effective technique for preparing Al₂O₃/AlN composites with enhanced thermal and mechanical properties, and is probably applicable to other composite material systems as well.     

Mechanical properties and microstructure evolution of MgO–Al–C slide plate refractories in presence of Al powder-modified magnesia aggregates

MgO–Al–C slide plate refractories were fabricated using sintered magnesia and modified sintered magnesia as aggregates, fused magnesia aggregates and fines, Al powder and carbon black (N220) as fines, and thermosetting phenolic resin as the binder. Al powder-modified magnesia aggregates were prepared and characterized and were introduced into the MgO–Al–C slide plate refractories. The effects of the modified aggregates on the properties, phase composition, and microstructure were investigated. 1) The Al powder-modified magnesia aggregates exhibited considerably high bonding strengths and low Al powder shedding ratios, thus meeting the preparation requirements of MgO–Al–C slide plate refractories. 2) At high temperatures, more needle-like and fibrous Al₄C₃, AlN and octahedral MgAl₂O₄ were generated on the surface of the modified magnesia aggregates, which enhanced the bond between the matrix and the aggregates and increased the hot modulus of rupture of the material. 3) Non-oxide Al₄C₃ and AlN phases were formed in situ and had high thermal conductivity and low coefficient of expansion; this could relieve the internal thermal stress of the material and create a toughening effect, improving the thermal shock resistance of the material.     

Effect of grain boundary state and grain size on the microstructure and mechanical properties of alumina obtained by SPS: A case of the amorphous layer on particle surface

The work was aimed at the investigation of kinetics of Spark Plasma Sintering (SPS) of the α-Al₂O₃ particles with amorphous surface layers and investigation of the effect of the amorphous layers on the grain growth and on the mechanical properties of alumina. The objects of investigations comprised:(i) submicron α-Al₂O₃ powder, (ii) submicron α-Al₂O₃ powder with the amorphous layers on the particles' surfaces, and (iii) the fine-grained α-Al₂O₃ powder. The submicron powders (i) and (ii) were used to analyze the effect of the amorphous layers on the sintering kinetics. Powders (i) and (iii) were used to analyze the effect of the initial particle sizes on the shrinkage kinetics. The effect of the temperature regime and of the rate (V_h) on the shrinkage kinetics of the submicron and fine alumina powders has been studied. The shrinkage curves were analyzed using the Young–Cutler and Coble models. The sintering kinetics was shown to be determined by the intensity of grain boundary diffusion for the submicron powders and by simultaneous lattice diffusion and grain boundary one for the fine powders. The amorphous layers on the surfaces of the submicron α-Al₂O₃ particles were found to affect the grain boundary migration rate and the Coble equation parameters at the final stages of SPS. The abnormal characteristics of the alumina ceramics sintered from the submicron powder with the amorphous layers on the particles’ surfaces were suggested to originate from the increased concentration of the defects and of the excess free volume at the grain boundaries formed during crystallization of the amorphous layers.     

Preparation of spherical and porous strontium titanate particles by hot water and hydrothermal conversion of hydrous titania

Uniform, micron-sized SrTiO₃ particles do not tend to aggregate, and the low surface area of larger particles can be improved by incorporating porous structures, thus offering superior performance for a range of applications. In this study, submicron-to micron-sized SrTiO₃ particles were prepared using hot water or hydrothermal conversion of spherical hydrous titania (TiO₂·nH₂O) and porous hydrous titania. When spherical hydrous titania particles were employed as the starting material, spherical SrTiO₃ particles of hydrous titania were obtained via treatment at 120 °C for 24 h. Similarly, the use of porous hydrous titania particles treated at 90 °C for 48 h resulted in spherical porous SrTiO₃ particles with macropores of porous hydrous titania. These porous SrTiO₃ particles have a specific surface area of ~115 m²/g, which is one of the largest among micron-sized SrTiO₃ particles, thereby making them suitable for use as catalysts or photocatalysts.     

Mechanical and dielectric properties of porous magnesium aluminate (MgAl2O4) spinel ceramics fabricated by direct foaming-gelcasting

Porous ceramic materials have been broadly applied in various fields due to their multifunctional properties. Optimization of their microstructural characteristics, such as pore morphology, total porosity, and pore size distribution, which determine various properties of the final products, is crucial to improve their performances and thus extend their applications. In this study, single-phase porous MgAl₂O₄ materials were fabricated by direct foaming–gelcasting. With an increase in the foam volume from 260 to 350 mL, the total porosity and pore size of the porous ceramic increased, and its microstructure varied from mostly closed cells to open cells containing interconnected large pores (40–155 μm) and small circular windows (10–40 μm) in the ceramic skeleton. The total porosity could be tailored from 84.91% to 76.08% by modulating the sintering temperature and foam volume and the corresponding compressive strengths were in the range of 2.8–15.0 MPa. The compressive strength exhibited a power-law relationship with the relative density with indices of approximately 3.409 and 3.439, respectively. Porous MgAl₂O₄ ceramics exhibited low dielectric constants in the range of 1.618–1.910 at room temperature, which are well matched with theoretical calculations on account of a modified Bruggeman model. The porous MgAl₂O₄ ceramics with good mechanical and dielectric properties controlled easily by various sintering temperatures and foam volumes are promising for practical applications.     

Preparation of pod-like 3D Ni0.33Co0.67Fe2O4@rGO composites and their microwave absorbing properties

The ferrite/reduced graphene oxide (rGO) composites have attracted increasing attention due to the combination of the dielectric loss of rGO and the magnetic loss of ferrites. In this paper, pod-like 3D Ni_0.33Co_0.67Fe₂O₄@rGO composites were prepared using a solvothermal reaction followed by cold quenching. The structures and morphologies of as obtained composites were characterized using X-ray diffractometer, Raman microscope, photoelectron spectroscopy, scanning electron microscope and transmission electron microscope. The Ni_0.33Co_0.67Fe₂O₄ microspheres with a diameter of 100–150?nm were wrapped in rGO rolls due to the shrinkage of rGO in liquid nitrogen. The rGO sheets with ferrite microspheres wrapped in form the pod-like 3D network morphology. The minimum reflection loss of as-prepared composites reaches ?47.5?dB and the absorption bandwidth (RL<?10?dB) is 5.02?GHz. The composites show much better absorbing performances than pure Ni_0.33Co_0.67Fe₂O₄ microspheres and Ni_0.33Co_0.67Fe₂O₄-rGO mixture formed by mechanically blending of cold quenched pure rGO and ferrite microspheres.