Mechanism and microstructural evolution of combustion synthesis of ZrB2–Al2O3 composite powders

Mechanism of combustion synthesis (CS) of ZrB₂–Al₂O₃ composite powders was systematically analyzed by a combustion front quenching method (CFQM). The microstructural evolution during the CS process was investigated by field-emission scanning electron microscopy (FESEM) equipped with energy dispersive X-ray spectrometer (EDS). The combustion temperature and wave velocity were measured by the data acquisition system. Moreover, the phase constituents of the final product were examined by X-ray diffraction (XRD). The thermal behaviors of the stoichiometic powders under the thermal exposure were characterized using differential scanning calorimetry (DSC) and thermogravimetric (TG). The results showed that the combustion reaction started from the melting of the B₂O₃ and Al particles, which was followed by the formation of ZrO₂–B₂O₃–Al solution. The ignition temperature of this system was determined to be around 800 °C. B and Al₂O₃ were then precipitated from the solution. As the CS reaction proceeded, Zr and Al₂O₃ were produced by the reaction between ZrO₂ particles and Al and precipitated from the solution. ZrB₂ could then be formed by the direct reaction between Zr and B. Finally, the ZrB₂–Al₂O₃ composite powders were obtained. Furthermore, a model corresponding to the dissolution–precipitation mechanism was proposed.     

The effect of Si–Bi2O3 on the ignition of the Al–CuO thermite

The ignition temperature of the Al–CuO thermite was measured using DTA at a scan rate of 50 °C min^?1 in a nitrogen atmosphere. Thermite reactions are difficult to start as they require very high temperatures for ignition, e.g. for Al–CuO thermite comprising micron particles it is ca. 940 °C. It was found that the ignition temperature is significantly reduced when the binary Si–Bi₂O₃ system is added as sensitizer. Further improvement is achieved when the reagents are nano-sized powders. For the composition Al + CuO + Si + Bi₂O₃ (65.3:14.7:16:4 wt.%), with all components nano-sized, the observed ignition temperature is ca. 613 °C and a thermal runaway reaction is observed in the DTA.     

SnO2–polyaniline composites for the desensitization of Al/SnO2 thermite composites

Nanothermites consisting of a reducing metal and a metal oxide nanopowder represent a new generation of energetic materials in pyrotechnics due to their impressive reactive properties. However, their extreme sensitivity regarding electrostatic discharge appears to be detrimental to their future practical applications. Herein, the mitigation of the sensitivity thresholds of the aluminium/tin (IV) oxide energetic nanocomposite is successfully achieved by using a conducting polymer, polyaniline (PAni). PAni was introduced within the thermite by the chemical polymerization of an oxidizer/PAni hybrid matrix. The SnO₂–PAni composites were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, electrical conductivity measurements, and transmission electron microscopy. The derived Al/SnO₂–PAni thermites were investigated in terms of sensitivities and reactivity. Results revealed gradual desensitization of the Al/SnO₂ thermite as a function of the concentration of PAni for both the electrostatic discharge (0.14–1212 mJ) and friction (216–360 N) tests while maintaining reactive energetic composites. This work presents a way for the preparation of insensitive and reactive energetic formulations. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48947.     

Electrical resistivity of Cr–Al2O3 and ZrxAly–Al2O3 composites with interpenetrating microstructure

AC and DC resistivity of Cr–Al₂O₃ and Zr_xAl_y–Al₂O₃ composites with varying metal content were measured. A strong percolation behavior was observed in the Cr–Al₂O₃ system, where the AC resistivity varied nine orders of magnitude close to the percolation threshold of 28 vol.%. AC measurements were less dependant on the contact resistance than DC measurements. The best reproducibility was obtained at a frequency of 100 kHz. AC resistivity values of insulating composites differed from DC values and may also be frequency-dependant. DC measurements up to 600 °C indicate that the intermetallic phases ZrAl₃ and ZrAl are PTC conductors. The electrical properties of Zr_xAl_y–Al₂O₃ samples with a metal content of 29 vol.% were anisotropic, with a much higher resistivity in the pressing direction.     

Characterization of MoO3–V2O5/Al2O3 catalysts for selective catalytic reduction of NO by NH3

MoO₃–V₂O₅/Al₂O₃ catalysts were characterized by B.E.T., XRD, LRS, XPS and TPR and the effect of MoO₃ addition to alumina supported vanadia catalysts on the catalytic activity for the selective catalytic reduction of NO by ammonia was investigated. Upon the addition of MoO₃, catalytic activity was enhanced and the particle size of V₂O₅ which is shown by the results of B.E.T., XRD and Raman spectroscopy decreased. This was one reason for increased catalytic activity. The results obtained by XPS and TPR showed that MoO₃ addition to alumina supported vanadia catalysts increased the reducibility of vanadia and this was the another reason for synergy effect between MoO₃ and V₂O₅ in MoO₃–V₂O₅/Al₂O₃ catalysts.     

Fabrication and microstructure of Al2O3–ZrO2(3Y)–SiC nanocomposites

Al₂O₃–ZrO₂(3Y)–SiC composite powder was prepared by the heterogeneous precipitation method. Calcinating temperature of the powder was important to obtain dense sintered body. The nanocomposites were got by hot-pressing, and addition of ZrO₂ did not raise the sintering temperature. Some Al₂O₃ grain shape was elongated, and Al₂O₃ grain size was about μm. Nano SiC particles were observed uniformly distributing throughout the composites, and most of them were located within the matrix grains. Because SiC particles located within ZrO₂ grains influenced the phase transformation of ZrO₂, the sintering of nanocomposites, which controlled grain size and transformable ZrO₂ amount, become important to get high performance. The strength of 80 wt% Al₂O₃–15 wt% ZrO₂–5 wt% SiC nanocomposites was 555 MPa, and toughness was 3·8 MPa m^1/2, which were higher than those of monolithic Al₂O₃ ceramics. ©     

Pressure-less joining of SiCf/SiC composites by Y2O3–Al2O3–SiO2 glass: Microstructure and properties

In this study, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass was prepared from Y₂O₃, Al₂O₃, and SiO₂ micron powders. Thermal expansion coefficient of as-obtained YAS glass was about 3.9 × 10⁻⁶, matching-well with that of SiC_f/SiC composites. SiC_f/SiC composites were then brazed under pressure-less state by YAS glass and effects of brazing temperature on microstructures and properties of resulting joints were investigated. The results showed that glass powder in brazed seam sintered and precipitated yttrium disilicate, cristobalite, and mullite crystals after heat treatment. With the increase in temperature, joint layer gradually densified and got tightly bonded to SiC_f/SiC composite. The optimal brazing parameter was recorded as 1400 °C/30 min and shear strength of the joint was 51.7 MPa. Formation mechanism of glass-ceramic joints was proposed based on combined analysis of microstructure and fracture morphology of joints brazed at different temperatures. Thermal shock resistance testing of joints was also carried out, which depicted decline in shear strength with the increase of thermal shock times. The strength of the joint after three successive thermal shock cycles at 1200 °C was 35.6 MPa, equivalent to 69% of that without thermal shock.     

Load-dependence of Knoop hardness of Al2O3–TiC composites

Nine samples of Al₂O₃–30 wt.% TiC composites were prepared by hot-pressing the Al₂O₃ powder mixed with TiC particles. The average sizes of the TiC particles used for preparing the nine samples were different with each other. Knoop hardness measurements were conducted on these nine samples, respectively, in the indentation load range from 1.47 to 35.77 N. For each sample, the measured Knoop hardness decreases with the increasing indentation load. The classical Meyer's power law and an empirical equation proposed originally by Bückle were verified to be sufficiently suitable for describing the observed load-dependence of the measured hardness. Analysis based on Meyer's law can not provide any useful information about the cause of the observed ISE while true hardness values, which are load-independent, can be deduced from the Bückle's equation. It was found that the deduced true hardness increases with the average size of TiC particles existing in the sample.     

Effects of in situ synthesis of CNTs/SiCw on microstructure and properties of Al2O3–SiC–C composites

Al₂O₃–SiC–C composites were prepared using tabular corundum, ball pitch and silicon carbide as the main raw materials. The carbon nanotubes (CNTs) and SiC whiskers (SiC_w) were in situ synthesized and their effects on the thermo–mechanical properties of Al₂O₃–SiC–C composites have been studied. The experimental results indicated that the high yield of SiC_w and CNTs with large aspect ratio could be obtained due to addition of Ni(NO₃)₂·6H₂O as catalyst in the composites. The cold modulus of rupture values were increased by 24% to 7.2 MPa, and the flexural modulus was increased from 19 GPa to 24 GPa. Additionally, the hot modulus of rupture reached a maximum value of 3.6 MPa, which presented a 71% increase over that of composites without catalyst. After three thermal shock cycles, the residual cold crush strength was improved from 57.1% to 76.9%. It is believed that the enhancement in the thermo-mechanical properties of Al₂O₃–SiC–C composites could be attributed to the reinforcement effect of SiC_w and CNTs.     

Synthesis of Camphene by α-Pinene Isomerization Using W2O3–Al2O3 Catalysts

W₂O₃–Al₂O₃ catalysts prepared by “sol–gel” and impregnation methods were characterised by XRD, FTIR and nitrogen adsorption. Both catalysts were tested in the isomerization of α-pinene in a batch reactor at atmospheric pressure and 150 °C. Conversion of α-pinene and selectivity to camphene was superior for the “sol–gel” catalyst than that observed for the impregnated catalyst.     

Fabrication and mechanical properties of Al2O3–TiC ceramic composites synergistically reinforced with multi-walled carbon nanotubes and graphene nanoplates

In this study, Al₂O₃–TiC composites synergistically reinforced with multi-walled carbon nanotubes (MWCNTs) and graphene nanoplates (GNPs) were prepared via spark plasma sintering (SPS). The effects of the MWCNT and GNP contents on the phase composition, mechanical properties, fracture mode, and toughening mechanism of the composites were systematically investigated. The experimental results indicated that the composite grains became more refined with the addition of MWCNTs and GNPs. The nanocomposites presented high compactness and excellent mechanical properties. The composite with 0.8 wt% MWCNTs and 0.2 wt% GNPs presented the best properties of all analysed specimens, and its relative density, hardness, and fracture toughness were 97.3%, 18.38 ± 0.6 GPa, and 9.40 ± 1.6 MPa m^1/2, respectively. The crack deflection, bridging, branching, and drawing effects of MWCNTs and GNPs were the main toughening mechanisms of Al₂O₃–TiC composites synergistically reinforced with MWCNTs and GNPs.     

Composite W–Cu powders by joint reduction of oxides in combustion mode

Composite powders W–Cu were prepared via joint reduction of WO₃ and CuO oxides with Mg?C combined reducer in a combustion mode by using the method of coupled reactions. Combustion phenomenology and the processes of phase and microstructure formation were investigated by thermocouple and copper- wedge techniques combined with XRD, SEM, and EDS analyses. Thermal conditions of combustion and phase composition and microstructure of products were found to depend on a Mg/C ratio in green mixtures. It was established that the magnesiothermic reaction was preceded by the stage of low-caloric carbothermal reduction. Slow propagation of combustion wave was found to favor the complete reduction of oxides and formation of target W–Cu composite nanopowder.     

Synthesis of Si3N4–TiN–SiC composites by combustion reaction under high nitrogen pressures

Si₃N₄–TiN–SiC composites were synthesized from TiSi₂ and SiC mixtures via the combustion reaction under high nitrogen pressure. The nitridation mechanism of TiSi₂ was analyzed. The results show that the nitridation of TiSi₂ produced TiN and Si firstly, and Si₃N₄ phase was formed by the further nitriding of Si. The molten eutectic phase and its agglomeration between Si and TiSi₂ formed one core-shell structure and affected the nitridation process. Under higher nitrogen pressure, the nitridation reaction was complete and the relatively dense Si₃N₄–TiN–SiC composites obtained. TEM observation revealed inhomogeneous Si₃N₄ grain size, amorphous phase, cavities, microcracks and dislocations, and graphite from the nitridation of SiC in the microstructure.     

Preparation and characterization of Al2O3–25 mol% ZrO2 composites

Al₂O₃–ZrO₂ (AZ_x), with 25 mol% ZrO₂ content, was prepared using the co-precipitation method. Synthesized powders were characterized by thermal reaction using a differential thermal analysis technique (TG–DTA) and were investigated by phase formation using X-ray diffraction. It indicated that the reaction occurred at 850 °C; cubic (c)-ZrO₂ phase and Al₂O₃ were obtained. By increasing temperature to 1100 °C, tetragonal (t)-ZrO₂ phase was detected. The Al₂O₃–25 mol% ZrO₂ was sintered for 2 h in the temperature range of between 1300 and 1600 °C. The majority phases of ceramics were m-ZrO₂ and α-Al₂O₃, although a t-ZrO₂ phase also appeared as a minor phase and decreased with higher temperature. Moreover, morphology and particle size evolution have been determined via the SEM technique. SEM showed that the particles of powder are agglomerated and basically irregular in shape. An SEM micrograph of ceramics exhibits uniform microstructure without abnormal grain growth.     

Preparation of AlN–Al2O3 composites exhibiting antibacterial and water purification properties

This study aimed to develop new antibacterial and water purification materials without heavy metal contamination. Herein, AlN–Al₂O₃ composites were prepared by changing the content of AlN in raw material. The results showed that AlN, Al₂O₃, aluminum oxynitride, and yttrium aluminum garnet phases were generated by adjusting the AlN: Al₂O₃ ratio. The difference in the ability of AlN and aluminum oxynitride to release substances such as ammonium ions and aluminum hydroxide when reacting with water resulted in remarkably different pH values of the sample immersion solution, which led to an increase in the material antibacterial efficiency with the addition of AlN. Similar results were also obtained with zinc ion absorption. Therefore, AlN–Al₂O₃ composite ceramics can potentially be used as novel antibacterial and water purification materials without heavy metal contamination through the release of ammonium ions for conferring antibacterial effects and of aluminum hydroxide for absorbing heavy metals and suspended impurities.     

Enhancing the sinterability and fracture toughness of Al2O3–TiN0.3 composites

We introduce a new and effective method for improving the fracture toughness of Al₂O₃-based composites through the addition of a nonstoichiometric material. Al₂O₃–TiN_0.3 composites were sintered by spark plasma sintering with different TiN_0.3 content at temperatures between 1300 and 1600 °C for 10 min and a micro-region diffusion phenomenon was observed at the Al₂O₃–TiN_0.3 interface. Ti atoms from TiN_0.3 diffused into Al₂O₃ to occupy Al sites, which led to the formation of Al vacancies that enabled the transport of aluminum by a vacancy mechanism. The optimal densification temperature of the Al₂O₃–30vol% TiN_0.3 composite was approximately 1400 °C. The maximum fracture toughness measured was 6.91 MPa m^1/2, from the composite with 30 vol% TiN_0.3 sintered at 1500 °C.     

Ultrafast formation of Al2O3–Y3Al5O12 eutectic ceramic by flash sintering

In this study, a dense Al₂O₃–Y₃Al₅O₁₂ (YAG) ceramic was synthesized by flash sintering a powder mixture of Al₂O₃ and Y₂O₃ in less than 150 seconds at a furnace temperature of 1350°C. The resultant ceramic has a well-defined eutectic structure consisting of alternating Al₂O₃ and YAG layers. The hardness and fracture toughness of the ceramic were measured to be 18.5 GPa and 4.3 MPa.m^1/2, respectively. These values are comparable to those of similar eutectic ceramics made by directional solidification techniques. The results suggest a new method for making high-performance eutectic ceramics, which could be applied in other systems.     

Y3Al5O12-α-Al2O3 composites with fine-grained microstructure by hot pressing of Al2O3-Y2O3 glass microspheres

Yttrium aluminate glass microspheres with the eutectic composition 76.8 mol. % Al₂O₃ and 23.2 mol. % Y₂O₃ were prepared by combining the sol-gel Pechini method with flame synthesis. The sol-gel method was applied to achieve the desired composition homogeneity of the prepared glass and hence, improve the microstructure homogeneity and mechanical properties of bulk polycrystalline materials. The latter were prepared by hot pressing, more specifically pressure assisted sintering, at 1050 °C, 1300 °C and 1600 °C using pressures of 30 MPa and 80 MPa and holding times between 0 and 30 min. This also led to the crystallization of the glass. A composite with the Vickers hardness 18.0 ± 0.7 GPa and an indentation fracture toughness 4.9 ± 0.3 MPa.m^1/2 was obtained by sintering at 1600 °C, at the pressure of 80 MPa and with 30 min isothermal heating at the maximum temperature. Improved mechanical properties were observed when increasing the temperature of sintering and the holding time. This can be attributed to the formation of a unique microstructure consisting of α-Al₂O₃ grains in the μm-scale embedded in a YAG (yttrium-aluminium garnet) matrix in the hot-pressed samples.     

3D microstructure and crack pathways of toughened CaO–Al2O3–SiO2 glass by precipitation of hexagonal CaAl2Si2O8 crystal

We investigated CaO–Al₂O₃–SiO₂ glass partially crystallized with molybdenum particles as nucleating agents. Microstructure of the material was characterized as a house-of-cards structure composed of plate-like crystals. Microcracks propagated along the crystal plane parallel to the double layer of SiO₄/AlO₄ tetrahedrons separated by layers of calcium atoms. To investigate the fracture behavior of the hexagonal CaAl₂Si₂O₈ crystals, molecular dynamics simulations were performed, which demonstrated that a crack can be easily triggered by shear deformation along the calcium layer. Additionally, once a crack was generated in the calcium layer, it propagated rapidly, whereas the crack perpendicular to the calcium layer hardly propagated. This simulated behavior is consistent with the experimentally observed cleavage behavior of the hexagonal CaAl₂Si₂O₈ crystal. The experimental and simulation results effectively explained the non-elastic fracture behavior of the material.     

The role of residual stresses in layered composites of Y–ZrO2 and Al2O3

Laminar composites, containing layers of Y–TZP and either Al₂O₃ or a mixture of Al₂O₃ and Y–ZrO₂ have been fabricated using a sequential centrifuging technique of water solutions containing suspended particles. Controlled crack growth experiments with notched beams of composites were done and showed the significant effect of barrier layer thickness and composition on crack propagation path during fracture. Distinct crack deflection in alumina layers was observed. The increase of crack deflection angle with the alumina layer thickness was also found. In the case of the barrier layer made of a mixture, crack deflection did not occur independently on layer thickness. The observed changes have been correlated with the radial distribution of residual stresses in barrier layers created during cooling of sintered composites from fabrication temperature. The stresses found were the result of the difference in the thermal expansion and sintering shrinkage of alumina and zirconia and the crystallographically anisotropic thermal expansion of the alumina. The residual stress distribution has been measured by piezo-spectroscopy based on the optical fluorescence of Cr⁺³ dopants in alumina.