Sintering kinetics and properties of NiFe2O4-based ceramics inert anodes doped with TiN nanoparticles

Sintering kinetics of NiFe₂O₄-based ceramics inert anodes for aluminum electrolysis doped 7 wt% TiN nanoparticles were conducted to investigate densification and grain growth behaviors. The linear shrinkage increased gradually with the increasing sintering temperature between 1000 and 1450°C, whereas the linear shrinkage rate exhibited a broad peak. The maximum linear shrinkage rate was obtained at 1189.4°C, and the highest densification rate was achieved at the relative density of 75.20%. Based on the pressureless sintering kinetics window, the sintering process was divided into the initial stage, the intermediate stage, and the final stage. The grain growth exponent reduced with increased sintering temperature, whereas the grain growth activation energy decreased by increasing sintering temperature and shortening dwelling time. The grain growth was mainly controlled by atomic diffusion. NiFe₂O₄-based ceramics possessed high-temperature semiconductor essential characteristics. The electrical conductivity of NiFe₂O₄-based ceramics first increased and then decreased with increasing sintering temperature, reached their maximum value (960°C) of 33.45 S/cm under 1300°C, mainly attributed to the relatively dense and uniform microstructure. The thermal shock resistance of NiFe₂O₄-based ceramic was improved by a stronger grain boundary bonding strength and lower coefficient of linear thermal expansion.     

Fabrication of high-density NiFe2O4 ceramics by slip casting and pressureless sintering

High-density NiFe₂O₄ ceramics with homogeneous microstructure were produced by slip casting and pressureless sintering. The slurry stability, sintering behavior, and microstructure of NiFe₂O₄ ceramics were investigated. A stable slurry can be obtained by adding 12.5 wt% NiFe₂O₄ nanoparticle and 5 wt% nano-binder at a slurry pH around 11.0. The linear shrinkage and linear shrinkage rate for both NiFe₂O₄ ceramic green bodies shaped by cold press molding and slip casting showed nearly the same trends. The temperature associated with the maximum linear shrinkage rate of slip casted green body was 1263.5°C, which was lower than that of cold press molded sample (1272.0°C). The sintering activation energy of slip casted green body was also lower than that of cold press molded sample (279.18 vs 288.47 kJ mol⁻¹), owing to high density and homogeneity of slip-casted green compact. A high-density NiFe₂O₄ ceramics with uniform grain size distribution can be produced by slip casting and pressureless sintering at 1350°C for 6 hours, attributed to the ability of slip casting to minimize agglomerates and micropores. It demonstrated that slip casting was more suitable to prepare high-density NiFe₂O₄ ceramics with good homogeneity.     

Effect of MnO2 addition on properties of NiFe2O4-based cermets

The impact of MnO₂ as an additive on the properties of NiFe₂O₄-based cermets prepared by the two-steps sintering method has been investigated. The new material was characterized in terms of the crystal structure, microstructure, linear shrinkage, relative density and porosity. Moreover, the bending strength of NiFe₂O₄-based cermets was measured. Differential scanning calorimetry (DSC) and X-ray diffraction analysis (XRD) shows that the addition of MnO₂ has no obvious influence on the crystal structure of the cermets. Scanning electron microscope (SEM) studies reveals that the grain sizes of cermets decreases slightly with doped MnO₂. The results show that the linear shrinkage, relative density and bending strength increase at first and then decrease slightly. A high-density (99.56%) and high-strength (84.28 MPa) NiFe₂O₄-based cermets has been obtained by adding 0.50 wt% MnO₂ into the matrix.     

Influence of yttrium oxide addition and sintering temperature on properties of alumina-based ceramic cores

Al₂O₃-based ceramic cores with a uniform microstructure were fabricated successfully by a traditional pressing forming method, in which Al₂O₃ powders were used as matrix and yttrium oxide as additive. The influences of yttrium oxide content and sintering temperature on properties of ceramic cores were studied carefully. Results indicated that a higher sintering temperature benefited the preparation of ceramic cores with excellent properties. As the temperature was above 1400°C, the reaction of Al₂O₃ and yttrium oxide occurred, leading to the formation of YAG phases. And, YAG was uniformly adhered on the surface of Al₂O₃ particles, exerting a good role in connecting Al₂O₃ particles. Based on XRD analyses, it was found that the increase in the sintering temperature could promote the formation of more YAG phases. When sintering temperature was adjusted to 1600°C, with the increase in the yttrium oxide content, their relative density developed a trend of decreasing first and then increasing, while the apparent porosity had an opposite change tendency. With the increase in the sintering temperature, the line shrinkage and bending strength of Al₂O₃-based ceramic cores both increased gradually. In our research, their bending strength reached to 53.5 MPa and apparent porosity was 33.9% when the ceramic cores were prepared with 9 wt% yttrium oxide at 1600°C.     

Effect of Li2CO3–Bi2O3 doping on the low-temperature sintering,structure, and dielectric and mechanical properties of MgO–TiO2(w) ceramics

Dense MgO–12% TiO₂(w) ceramics containing 12 wt% TiO₂, which were doped with Li₂CO₃–Bi₂O₃ composite sintering aids, were prepared at a low sintering temperature of 950 °C in this study. The effects of sintering additives on the sintering characteristics, phase composition, microstructure, and dielectric and mechanical properties of the ceramic samples were systematically investigated, and the influences of their phase composition and microstructure on the dielectric and mechanical properties were examined. The introduction of sintering aids produced a new Bi₄Ti₃O₁₂ phase in the sample structure, while the residual Bi₂O₃ mixed with the newly formed Mg₂TiO₄ and Bi₄Ti₃O₁₂ phases distributed at MgO grain boundaries formed a structure surrounding MgO grains. This structure filled the pores in the ceramic sample, which increased its density and enhanced the mechanical properties. At a Li₂CO₃–Bi₂O₃ content of 15 wt%, the density, flexural strength, and Vickers hardness of the ceramic samples reached their maximum values of 3.4 g/cm³, 218.9 MPa, and 778.7 HV, respectively. However, the further increase in the Li₂CO₃–Bi₂O₃ content deteriorated their dielectric properties although the dielectric constant and dielectric loss remained below 13.4 and 2.1 × 10⁻³, respectively. The findings of this work indicate that Li₂CO₃–Bi₂O₃ sintering aids can significantly lower the sintering temperature of MgO–12% TiO₂(w) ceramics and control their dielectric and mechanical properties through microstructural changes.     

Dielectric and magnetic properties of Nickel ferrite ceramics using crystalline powders derived from DL alanine fuel in sol–gel auto-combustion

Dielectric and magnetic properties of NiFe₂O₄ ceramics prepared with powders using DL-alanine fuel in the sol–gel auto combustion technique are studied. DL-alanine fuel yields crystalline as-burnt powders, and when used for ceramic processing yields varying microstructure at different sintering temperatures. The dielectric properties are influenced by the resulting microstructure and the magnetic properties show slight change in saturation magnetization M_s (~44 – 46 emu/g). The coercive fields, dielectric losses and dispersion are reduced considerably at higher sintering temperatures (1200–1300 °C). The influence of changing microstructure is analyzed through dielectric response, complex impedance analysis and electrical modulus spectroscopy in the frequency range (10⁻²–10⁷ Hz) to understand the interactions from the grain and grain boundary phases. Sintering at 1200 °C, is found to be optimum, yields lower losses & reduced dielectric dispersion, and high resistivity (3.4×10⁸ Ω cm).     

Fabrication and mechanical properties of short ZrO2 fiber reinforced NiFe2O4 matrix composites

Short ZrO₂ fibers (ZrO_2(f)) reinforced NiFe₂O₄ ceramic composites were fabricated by cold pressing process. The phase composition, microstructure, mechanical properties and fiber/matrix interface of the composites were investigated by X-ray diffraction, scanning electron microscopy and mechanical testing machines. ZrO_2(f) show good thermodynamic and chemical compatibility with NiFe₂O₄ ceramic matrix and effectively enhanced the mechanical properties. The toughening mechanisms are fiber bridging, interfacial debonding, fiber pullout, phase transformation and the matrix constraint effect. By incorporation of 3 wt% fibers with the average length of 5～6 mm, the bending strength and fracture toughness of the composites reached 88.92 MPa and 4.62 MPa m^1/2, respectively, while the strength conservation ratio after thermal shock increased from 48.85% to 75.86%. The weak interface bonding built up between ZrO_2(f) and NiFe₂O₄ facilitates the reinforcing effects of the fibers to operate.     

Improved magnetic and electromagnetic absorption properties of xSrFe12O19/(1−x)NiFe2O4 composites

xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites (0 ≤ x ≤ 1.0) were synthesized by using a conventional solid-state synthetic route. The results show that magnetic hysteresis loops of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are similar to those of individual component ferrites, except for the 0.1SrFe₁₂O₁₉/0.9NiFe₂O₄ and 0.3SrFe₁₂O₁₉/0.7NiFe₂O₄, suggesting that the hard/soft magnetic phases are well exchange-coupled. The saturation magnetization, coercivity, and remanent magnetization of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are increased with increasing content of SrFe₁₂O₁₉, with maximal values of 42.1 Am² kg⁻¹, 78.7 kA m⁻¹, 17.2 Am² kg⁻¹, respectively, as the content x is about 0.5. They are higher than those of the individual components, implying that interface coupling is present in the magnetic composites. The coercivity and remanent magnetization of the composites are increased initially with increasing sintering temperature and then show a downward tendency. For the component SrFe₁₂O₁₉ and NiFe₂O₄, the minimum reflection losses are −12.5 dB and −18.3 dB at match thicknesses of 2.5 mm and 2 mm, respectively. Compared with those of the component SrFe₁₂O₁₉ and NiFe₂O₄, the microwave absorption performances of the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites are improved remarkably, especially for the samples of x = 0.3 and x = 0.9. The minimum reflection losses values of the 0.3SrFe₁₂O₁₉/0.7NiFe₂O₄ composite are −31.6 dB (12.7 GHz) and −20.2 dB (13 GHz), while those of the 0.9SrFe₁₂O₁₉/0.1NiFe₂O₄ composites are −23.7 dB (16.3 GHz) and −33.5 dB (15.8 GHz), as the matching thicknesses are 2.5 mm and 2 mm, respectively. Therefore, the xSrFe₁₂O₁₉/(1−x)NiFe₂O₄ composites could be used as potential microwave absorption materials.     

Enhanced grain boundary ionic conductivity of LiTa2PO8 solid electrolyte by 75Li2O-12.5B2O3-12.5SiO2 sintering additive

LiTa₂PO₈(LTPO) has low electrolyte density and many pores at grain boundaries, and it is easy to precipitate dielectric phase LiTa₃O₈ at grain boundaries. The performance can be improved by adding 75Li₂O-12.5B₂O₃-12.5SiO₂ (LBS) sintering additive with low melting point during sintering. The effects of LBS addition on the microstructure and grain boundary ionic conductivity of LTPO electrolytes were studied. The results showed that the addition of LBS sintering additives reduced the sintering temperature, improved the density and stability of LTPO electrolyte samples, effectively inhibited the precipitation of LiTa₃O₈ phase, reduced the grain boundary impedance of samples, and improved the total ionic conductivity of electrolytes. When LBS was added at 0.4 wt%, the relative density of LTPO reached 93.54%, the grain boundary impedance decreased from 1243 Ω to 248.2 Ω, the total ionic conductivity increased from 1.55 × 10⁻⁴ S cm⁻¹ to 6.51 × 10⁻⁴ S cm⁻¹, and the ionic activation energy was 0.137 eV.     

Effect of MgAl2O4 nanoparticles addition on the densification and properties of MgO-CaO refractories

MgAl₂O₄nanoparticles were added to MgO–CaO refractory ceramic composites in the range of 0–8 wt%. Refractory specimens were obtained by sintering at 1650 °C for 3 h in an electric furnace. Refractory specimens were characterized by measurements of bulk density, apparent porosity, hydration resistance, cold crushing strength, crystalline phase formation, and microstructural analysis. Results show that with additions of MgAl₂O₄ nanoparticles the bulk density of the samples increased. But the apparent porosity and cold crushing strength decreased and increased, respectively with addition MgAl₂O₄ nanoparticles up to 6 wt% and for further MgAl₂O₄ nanoparticles, due to the thermal expansion mismatch, the results is reversed. Also, the hydration resistance of the samples was appreciably improved by the addition of MgAl₂O₄ nanoparticles due to its effect on decreasing the amount of free CaO in the refractory composite and promotion of densification by creating a dense microstructure.     

NiFe-NiFe2O4/rGO composites: Controlled preparation and superior lithium storage properties

Binary transition-metal oxides with spinel structure have great potential as advanced anode materials for lithium-ion batteries (LIBs). Herein, NiFe-NiFe₂O₄/ reduced graphene oxide (rGO) composites are obtained via a facile cyanometallic framework precursor strategy to improve the lithium storage performance of NiFe₂O₄. In the composites, NiFe-NiFe₂O₄ nanoparticles with adjustable mass ratios of NiFe₂O₄ to NiFe alloy are homogeneously deposited on rGO sheets. As anode material for LIBs, the optimized NiFe-NiFe₂O₄/rGO composite displays remarkably enhanced lithium storage performance with an initial specific capacity as high as 1362 mAh g⁻¹ at 0.1 A g⁻¹ and a decent capacity retention of ca. 80% after 130 cycles. Besides, the composite delivers a reversible capacity of 550 mAh g⁻¹ at 1 A g⁻¹ after 300 cycles. During the charge–discharge cycles, the aggregation of the NiFe-NiFe₂O₄ nanoparticles and the structural collapse of the electrode can be well alleviated by rGO sheets. Moreover, the conductivity of the electrode can be significantly improved by the well-conductive NiFe alloy and rGO sheets. All these contribute to the improved lithium storage performance of NiFe-NiFe₂O₄/rGO composites.     

Microstructure and properties of mullite–ZrO2 ceramics with silicon nitride additive prepared by spark plasma sintering

The process of densification and development of the microstructure of mullite–ZrO₂/Y₂O₃ ceramics from mixture of Al₂O₃, SiO₂, ZrO₂ and Y₂O₃ by gradually adding of α–β Si₃N₄ nanopowder from 1 to 5 wt% by traditional and spark plasma sintering were investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and some ceramic and mechanical properties. The processes of DTA for all samples are characterised by a low-pitched endo-effect, when gradual mullite formation and noticeable densification at temperatures of 1200–1400 °C is started. It is testified by shrinkage and density both for traditionally and by SPS-sintered samples. The influence of the Si₃N₄ additive on the density characteristics is insignificant for both sintering cases. For SPS samples, the density reaches up to 3.33 g/cm³, while for traditionally sintered samples, the value is 2.55 g/cm³, and the compressive strength for SPS grows with Si₃N₄ additives, reaching 600 N/mm². In the case of traditional sintering, it decreases to approximately 100 N/mm². The basic microstructure of ceramic samples sintered in a traditional way and by SPS is created from mullite (or pseudo-mullite) crystalline formations with the incorporation of ZrO₂ grains. The microstructure of ceramic samples sintered by SPS shows that mullite crystals are very densely arranged and they do not have the characteristic prismatic shape. The traditional sintering process causes the creation of voids in the microstructure, which, with an increasing amount of Si₃N₄ additive, are filled with mullite crystalline formations.     

Effect of TiO2 Doping on the Sintering Process,Mechanical and Magnetic Properties of NiFe2O4 Ferrite Ceramics

TiO₂‐doped NiFe₂O₄ samples were prepared via ball‐milling and two‐step sintering processes. Besides NiFe₂O₄ phase, two new phases, NiTiO₃ and Fe₂TiO₅, formed in TiO₂‐doped samples. The temperature of sintering onset for 1.0 wt% TiO₂‐doped samples is 230°C lower than that of undoped samples. Early‐stage synthesis process of TiO₂‐doped NiFe₂O₄ ceramics is controlled by grain boundary diffusion mechanism. Increasing TiO₂ content from 0 to 1.0 wt%, the apparent activation energy decreased from 813.919 KJ/mol to 639.361 KJ/mol. The values of relative density and bending strength reached their maximum value with 1.0 wt% TiO₂. Saturation magnetization, residual magnetization ratio and coercivity decrease with increasing TiO₂ content.     

The sintering behavior,microstructure, and electrical properties of gallium-doped zinc oxide ceramic targets

The properties of sputtering targets have recently been found to affect the performances of sputtered films and the sputtering process. To develop high-quality GZO ceramic targets, the influences of Ga₂O₃ content and sintering temperature on the sintering behavior, microstructure, and electrical properties of GZO ceramic targets were studied.The results showed that the increase in Ga₂O₃ content from 3 wt% (GZO-3Ga) and 5 wt% (GZO-5Ga) not only inhibited the densification but retarded grain growth. During sintering, ZnGa₂O₄ phase formed before 800 °C, and Zn₉Ga₂O₁₂ phase was found after sintering at 1000 °C. Moreover, after sintering at 1200 °C, the number of Zn₉Ga₂O₁₂ precipitates increased at the expense of ZnGa₂O₄ and ZnGa₂O₄ disappearing completely. The relative density, grain size, and resistivity of GZO-3Ga sintered at 1400 °C in air were 99.3%, 3.3 μm, and 2.8 × 10⁻³ Ω cm, respectively. These properties of GZO ceramics are comparable to properties reported in the literature for AZO sintered in air.     

Strengthening and toughening of TiN-based and TiB2-based ceramic tool materials with HfC additive

Effects of HfC addition on the microstructures and mechanical properties of TiN-based and TiB₂-based ceramic tool materials have been investigated. Their pore number decreased gradually and relative densities increased progressively when the HfC content increased from 15 wt% to 25 wt%. The achieved high relative densities to some extent derived from the high sintering pressure and the metal phases. HfC grains of about 1 µm evenly dispersed in these materials. Both TiN and TiB₂ grains become smaller with increasing HfC content from 15 wt% to 25 wt%, which indicated that HfC additive can inhibit TiN grain and TiB₂ grain growth, leading to the formation of a fine microstructure advantageous to improve flexural strength. Especially, TiB₂-HfC ceramics exhibited the typical core-rim structure that can enhance flexural strength and fracture toughness. The toughening mechanisms of TiB₂-HfC ceramics mainly included the pullout of HfC grain, crack deflection, crack bridging, transgranular fracture and the core-rim structure, while the toughening mechanisms of TiN-HfC ceramics mainly included pullout of HfC grain, fine grain, crack deflection and crack bridging. Besides, HfC hardness had an important influence on the hardness of these materials. Higher HfC content increased Vickers hardness of TiN-HfC composite, but lowered Vickers hardness of TiB₂-HfC composite, being HfC hardness higher than for TiN while HfC hardness is lower than for TiB₂. The decrease of fracture toughness of TiN-HfC ceramic tool materials with the increase of HfC content was attributed to the formation of a weaker interface strength.     

Preparation,sintering and electrochemical performance of novel Fe2N-TiN nanocomposites

Transition metal nitrides (TMNs) hold great promises as electrode materials in energy devices like supercapacitors, lithium ion batteries and solar cells. However, the poor electrochemical stability severely limits their real-life applications. In this study, we prepared electrochemically stable Fe₂N-TiN nanocomposite with varied TiN contents by the nitridation of oxide precursors by ammonia. The formation mechanism consists of the solid reaction between TiO₂ and Fe₂O₃. A protective sintering (PS) technique has been developed for the first time to fabricate pure Fe₂N-TiN nanocomposite ceramics after comparing different sintering methods including spark plasma sintering (SPS). Porous microstructures formed by homogenous distribution of ultrafine TiN nanoparticles within large Fe₂N micro-grains skeleton were obtained after sintering. The electrochemical performances of the Fe₂N-TiN nanocomposites by PS have been investigated in different electrolytes. The mechanism of charge storage is mainly due to the double layer capacitance. The composites with 15 wt% TiN loading show the highest specific capacitance of 58.4 F g⁻¹ in 7.5 M KOH. Furthermore, excellent cycling stability with zero degradation after 1000 cycles was proved for such nanocomposite electrodes, confirming their potential for energy storage.     

Impact of synthesis route on the microstructure and energy-storage properties of (Bi1/2K1/2)TiO3–SrTiO3 relaxor ferroelectric ceramics: Solid-state and hydrothermal approaches

Bismuth potassium titanate (Bi_1/2K_1/2)TiO₃-based relaxor ferroelectrics are promising materials for high-energy-density ceramic capacitors. Herein, we compare the microstructure and energy-storage properties of (Bi_1/2K_1/2)_0.5Sr_0.5TiO₃ (BKST50) ceramics fabricated via two different routes: solid-state and hydrothermal reactions. A BKST50 fine powder composed of well-dispersed cubic nanoparticles was obtained via the hydrothermal reaction, whereas the conventional solid-state reaction resulted in the aggregation of primary particles. The grain size of the ceramics prepared from the hydrothermal powder could be controlled between 273 ± 24 and 936 ± 69 nm while maintaining a relative density of over 95% by simply varying the sintering temperature. On the other hand, ceramics prepared via the solid-state reaction could not be fully densified even at 1200 °C (the highest tested sintering temperature). The hydrothermally derived ceramics withstood higher electric field owing to dense and fine-grained microstructure, leading to a high recoverable energy-storage density of 2.25 J cm⁻³ at 240 kV cm⁻¹.     

One-step solvothermal synthesis of spherical spinel type NiFe2−xMnxO4-RGO as high-performance supercapacitor electrodes

A facile route for the synthesis of spinel type NiFe_2−xMn_xO₄-RGO as supercapacitor electrodes is reported and the microstructure, elemental composition/content, morphology and thermal stability of NiFe_1.7Mn_0.3O₄-RGO₁₀ were characterized by XRD, FTIR, ICP, XPS, TEM, and TGA. Uniform NiFe_1.7Mn_0.3O₄ nanospheres were deposited densely on the reduced graphene oxide (RGO) sheets. The as prepared NiFe_1.7Mn_0.3O₄-RGO₁₀ composite showed better electrochemical performance than the corresponding binary metal systems. The spinel structure and the doping of Mn as the third component provided the composite with high specific capacitance of 1214.7 F g⁻¹ at 0.5 A g⁻¹ in a three-electrode system along with good cycling stability.     

Influence of Gd2O3 on the microstructure and properties of transparent MgAl2O4: Cr3+ ceramic

In this work, MgAl₂O₄: Cr³⁺ transparent ceramics have been synthesized by the hot press sintering techniques, and the effect of the sintering aid Gd₂O₃ and its content on the densification, microstructure, and optical, photoluminescence was studied and discussed. The relative density reached 99.29% with 0.8 wt% Gd₂O₃ as a sintering aid, and the optical transmittance at 686 nm and 1446 nm were approximately 76%. As Gd₂O₃ content continued to increase, the grain size of the ceramics became smaller and uniform, accompanied by some pores with the size of ～1 μm. The ceramics with 4.0 wt% Gd₂O₃ showed a higher transmittance, of 82% at 1446 nm. Additionally, Gd₂O₃ was helpful for Cr³⁺ in the sites of octahedral symmetry, which increased the quantum yield. The quantum yield of MgAl₂O₄: Cr³⁺ with 0.8 wt% Gd₂O₃ was about 0.175, which was 36% higher than that of ceramic without Gd₂O₃. In short, the sintering aid Gd₂O₃ not only contributed to improving the densification, homogenizing the grain size, and heightening the optical transmittance but also enhanced the quantum yield of Cr³⁺.     

TiN modified SiC with enhanced strength and electrical properties

SiC based composites were manufactured with varying TiN content (0–50 V%) using Al₂O₃ and Y₂O₃ sintering aids. Basic dilatometry measurements were performed to determine when densification begins within the composite system. Samples were consolidated via uni-axial hot pressing at 1900 °C to produce ceramic composites with >98% theoretical density. Electrical measurements show increasing TiN additions reduce resistivity and begin to plateau at 40–50V%. Resistivity decreased from 2.0 × 10⁵ Ω − cm (0% TiN) to 2.0 × 10⁻⁴ Ω − cm (50V% TiN). Flexural strengths were characterized and compared against a baseline (0% TiN) SiC. Strengths increased gradually with TiN content. A maximum strength 921 MPa was observed at 40V% TiN content vs. 616 MPa for the baseline SiC. This was a gain of 50% over baseline. Additions beyond that range did not produce further gains in strength.