Dried particle plasma spray in-flight synthesis of spinel coatings

Powder particle diameters currently used for spraying are generally between 5 and 100 μm with a preferred size range around 40–60 μm. Future trends in plasma spraying involve the use of fine or ultrafine powders and the reduction of the number of steps between raw material preparation and coating. The use of non-sintered spray dried ceramic aggregates as feedstock material for plasma spraying has accordingly been investigated. Al₂O₃ based coatings were prepared by this route of dried particle plasma spray (DPPS). The microstructure and crystallographic phases of these deposits were characterised using scanning electron microscopy (SEM) equipped with energy dispersive spectrometry (EDS) and X-ray diffraction (XRD). Given the intimate mixing of the starting oxides, reactions occur during spraying leading to the formation of spinel (MgAl₂O₄ and/or ZnAl₂O₄) and zinc aluminum oxide (Zn₄Al₂₂O₃₇). The layered structure of the deposit is characteristic of conventional plasma-sprayed coatings but the features are smaller in size. Depending on the operating conditions (plasma characteristics and powder injection), two different melting modes of the particles were identified; the first leads to individual well-melted droplets that splash regularly even if generating some fingers and the second leads to aggregates that are well-melted on their outer parts and strengthened in their cores.     

Synthesis and characterization of MgAl2O4–ZrO2 composites

Different types of dense 5–97% ZrO₂–MgAl₂O₄ composites have been prepared using a MgAl₂O₄ spinel obtained by calcining a stoichiometric mixture of aluminium tri-hydroxide and caustic MgO at 1300 °C for 1 h, and a commercial yttria partially stabilized zirconia (YPSZ) powder as starting raw materials by sintering at various temperatures ranging from 1500 to 1650 °C for 2 h. The characteristics of the MgAl₂O₄ spinel, the YPSZ powder and the various sintered products were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area, particle size analysis, Archimedes principle, and Vickers indentation method. Characterization results revealed that the YPSZ addition increases the sintering ability, fracture toughness and hardness of MgAl₂O₄ spinel, whereas, the MgAl₂O₄ spinel hampered the sintering ability of YPSZ when sintered at elevated temperatures. A 20-wt.% YPSZ was found to be sufficient to increase the hardness and fracture toughness of MgAl₂O₄ spinel from 406 to 1314 Hv and 2.5 to 3.45 MPa m^1/2, respectively, when sintered at 1600 °C for 2 h.     

Ion beam assisted electron beam vacuum deposition of antireflective SiO2 coating on MgAl2O4 spinel

In this paper, the electron beam vacuum coating method was used to coat a SiO₂ film on an MgAl₂O₄ spinel substrate. The thickness of the coating was aimed to be 925 nm based on the physics of the antireflection coatings. Atomic force microscope images revealed that the coated silica was 880 nm thick, which is close to the aimed theoretical thickness and had 2.11 nm roughness. It could enhance the transparency of the spinel substrate by being coated on it. The infrared transmittance of the sample coated with SiO₂ film in the range of 3700 nm-4800 nm was measured by a Fourier transform infrared spectrometer and reached 92.5% to 78.5%, which was about 2%–4% higher than that of MgAl₂O₄ spinel. In addition, it was discovered that the bonding force between the coating and the substrate is determined to be about 200 MPa. The results of this study can be used for further precise design and production of antireflection coatings on the transparent materials that need more transparency.     

Synthesis andcharacterisation of nanocrystalline MgAl2O4 ceramic powders by use of molten salts

Abstract

Nanocrystalline MgAl₂O₄ powders were prepared by a thermal decomposition method, i.e. by use of molten salts. This method involves co-melting stoichiometric amounts of magnesium nitrate hydrate Mg(NO₃)₂.6H ₂O and aluminium nitrate hydrate Al(N O₃) ₃.9H₂O at 500°C. The spinel content of the co-melted and calcined powders at different firing temperatures up to 1000°C was determined by chemical analysis and the powders were characterised with respect to spinel formation, crystallite and particle sizes by X RD, T EM , and IR spectroscopy. The results obtained revealed that the co-melted materials were amorphous. After heat treatment of the amorphous materials at up to 1000°C, pure spinel powder was obtained, reaching over 98% spinel content. During calcination at different firing temperatures up to 1000°C the amorphous material progressively crystallised, forming nanocrystalline spinel with a maximum crystallite size of about 10 nm and particle size of around 300 nm. Bands in IR spectra were observed corresponding to the ex istence of AlO₆ groups prior to magnesium spinel formation, which was the only crystalline phase at 1000°C.     

Europium(III)‐Doped MgAl2O4 Spinel Nanophosphor Prepared by CO2 Laser Co‐Vaporization

Photoluminescent nanoparticles (NPs) are of specific interest for biomedical applications, bioimaging, and cell tracking. Here, we report on the synthesis of europium(III)‐doped MgAl₂O₄ spinel NPs by the CO₂ laser co‐vaporization of a homogeneous raw powder mixture consisting of micrometer‐sized MgAl₂O₄ and Eu₂O₃ (2 and 4 mol%, respectively). The resulting NPs are spherically shaped, show a narrow size distribution (mean diameter: ~30 nm), and are well dispersed. The as‐prepared NPs are highly crystalline and consist of MgAl₂O₄ with small amounts of the secondary phases MgO (~10 mass%) and Eu₂O₃ (<0.5 mass%). The photoluminescence spectra of the doped spinel nanopowders show an intense red emission (λ_em = 615 nm) resulting from the ⁵D₀→⁷F₂ transition with a maximum intensity at an excitation wavelength of 470 nm.     

Formation mechanism of Al2O3-YAG amorphous ceramic coating deposited via atmospheric plasma spraying

Al₂O₃-YAG (Al₅Y₃O₁₂) amorphous ceramic coatings exhibit excellent crack propagation resistance under harsh wear services due to the amorphous phase contributing to the plastic deformation performance of the coating. However, the formation mechanism of the amorphous phase is ambiguous. This study mainly investigated the formation mechanism of Al₂O₃-YAG amorphous coating prepared by atmospheric plasma spraying from the perspective of crystallization chemistry. Nano and microsized powders with low eutectic point ratio were selected as feedstock for comparison. X-ray diffraction, scanning electron microscope, and electron backscattered diffraction were used to analyze the phase composition, morphologies, phase distribution, and structure of the coating. It is concluded that the significant thermodynamically stable structure of polycompound with high coordination numbers of cations prioritized crystallizing in the Al₂O₃-YAG melt, but it needed more time to crystallize and hardly crystallized in the limited time during plasma spraying. Therefore, the selection of as-sprayable powder should also be considered the critical factor for preparing amorphous coatings. The nanoscale or submicro scale powder distributed uniformly with low eutectic point ratio was chosen as the feedstock to ensure the powder droplets diffuse sufficiently during deposition.     

Gel-casting of MgAl2O4 transparent ceramics using a common dispersant

The ethanolaminic salt of citric acid (commercial name Dolapix CE 64) has commonly been used as a dispersant for colloidal based ceramic forming process. In this paper, a surprise was presented that MgAl₂O₄ spinel slurries consisting of MgAl₂O₄ spinel nanoparticles and Dolapix CE 64 gelled in air at room temperature spontaneously. The MgAl₂O₄ spinel slurries with high solid loading (54 vol%) were prepared with Dolapix CE 64 and the green body with up to 57% relative density was obtained. MgAl₂O₄ transparent ceramics with small grain size (0.92 μm) and high transmittance (81.7% at 600 nm) were fabricated after pre-sintering at 1500°C and hot-isostatic sintering at 1550°C.     

Preparation and properties of MgAl2O4 spinel ceramics by double-doped CeO2 and La2O3

Magnesium aluminate spinel (MgAl₂O₄) ceramics are high-performance and carbon-free materials widely used in both military and civilian fields. However, it is usually challenging to densify during the solid-state sintering process. The excellent properties of some rare earth oxides have been proved to promote the densification of MgAl₂O₄ spinel ceramics. But the mechanism of promoting sintering is not clear. In the present work, MgAl₂O₄ spinel ceramics have been successfully fabricated by co-doping CeO₂ and La₂O₃ via a single-stage solid-state reaction sintering. The effects of addition amounts of CeO₂ and La₂O₃ on phase compositions, microstructures, sintering characteristics, cold compressive strength, and thermal shock resistance of as-prepared MgAl₂O₄ spinel ceramics were systematically investigated. The results show that by co-doping CeO₂ and La₂O₃ can increase the defect concentration due to the lattice distortion. This could promote the movement of Al³⁺ and Mg²⁺ at high temperature, which is beneficial to the formation of more secondary MgAl₂O₄ spinel. t-ZrO₂ with more Ce⁴⁺ filling between spinel grains could prevent the growth of grains and promote the densification, besides the new-formed LaAlO₃ that was mainly distributed along the grain boundary of the MgAl₂O₄ phase, both of which were favorable for the formation of dense microstructure of MgAl₂O₄ spinel materials. At the same time, the formation of more secondary MgAl₂O₄ spinel and sintering densification also improve the mechanical properties of spinel ceramics. La³⁺ will segregate to the spinel grain boundary, preventing grain boundary movement and absorbing the main crack's fracture energy. With 3 wt% CeO₂ and 3 wt% La₂O₃ co-doping, the bulk density of the sample increased from 3.02 g∙cm⁻³ to 3.55 g∙cm⁻³; the apparent porosity decreased from 12.21% to 9.97%; the cold compressive strength increased from 172.88 MPa to 189.54 MPa; and the residual strength retention ratio after thermal shock increased from 84.92% to 89.15%.     

Characterisation of plasma-sprayed SrFe12O19 coatings for electromagnetic wave absorption

SrFe₁₂O₁₉ coatings, intended as electromagnetic wave absorbers, were produced by atmospheric plasma spraying (APS) using two different kinds of feedstock powders: spray-dried agglomerates of micrometric SrFe₁₂O₁₉ particles (type-A) or spray-dried agglomerates of raw materials (SrCO₃, Fe₂O₃), reactively sintered at 1100 °C (type-B).During spraying, type-A agglomerates either remain unmelted, producing porous coating regions where crystalline hexaferrite is retained, or are disrupted into smaller granules which melt completely, resulting in dense coating regions with no crystalline hexaferrite.The sintered type-B agglomerates possess higher cohesive strength and do not fall apart: the finer ones melt completely, whereas, in the larger ones, the outer region melts and infiltrates the porous unmelted core which retains crystalline hexaferrite. Dense coatings can therefore be obtained while preserving high amounts of crystalline hexaferrite even inside the dense areas. Such coatings show magnetic properties that are promising for electromagnetic wave absorption applications.     

Effect of TiO2 on phase evolution and microstructure of MgAl2O4 spinel in different atmospheres

The effect of TiO₂ on the formation and microstructure of magnesium aluminate spinel (MgAl₂O₄) at 1600 °C in air and reducing conditions were investigated. Under reducing conditions, stoichiometric MgAl₂O₄ spinel shifted toward alumina-rich types owing to volatilization of MgO, resulting in an increase in the porosity of fired samples. Addition of graphite to mixtures of MgO and Al₂O₃ intensified the reducing conditions and accelerated the formation of non-stoichiometric MgAl₂O₄. For TiO₂-containing samples on addition of MgAl₂O₄, magnesium aluminum titanium oxide (Mg_xAl_2(1−x)Ti_(1+x)O₅, x = 0.2 or 0.3) was detected as a minor phase. Under reducing conditions, XRD peak shifts were smaller for TiO₂-containing samples than for samples without TiO₂ owing to the formation of a solid solution of TiO₂ in MgAl₂O₄ and establishment of alumina-rich spinel, which have opposite effects on increasing the lattice parameter. In bauxite-containing samples, MgAl₂O₄ spinel, corundum, magnesium orthotitanate spinel (Mg₂TiO₄) and amorphous phases were identified. Mg₂TiO₄ spinel formed a complete solid solution with MgAl₂O₄ spinel but Mg₂TiO₄ remained as a distinct phase owing to the heterogeneous microstructure of bauxite-containing samples. Also dense microstructure established in air fired TiO₂ containing samples. The results are discussed with emphasis on the application and design of alumina-magnesia-carbon refractory materials, which are used in the steel industry.     

Preparation,characterisation, and growth mechanism of mesoporous petal-like MgAl2O4 spinel

Petal-like MgAl₂O₄ spinel was successfully prepared using a novel inorganic salt-assisted nonhydrolytic sol-gel method without a template and was employed as absorbent in the removal of the Congo red (CR). The effects of the inorganic salt type, heat-treatment temperature, and dwelling time on the morphology and phase composition of the petal-like MgAl₂O₄ spinel were investigated systematically. Results indicated that when Na₂MoO₄ was employed as the salt and the heat-treatment temperature and dwelling time were 600 °C and 5 h, respectively, the as-obtained petal-like MgAl₂O₄ spinel exhibited a highly uniform morphology with a thickness of 19–23 nm and a length of 240–280 nm. The N₂ adsorption-desorption results revealed that the petal-like MgAl₂O₄ exhibited a large BET specific surface area of 161 m²g^-1 with a pore volume of 0.24 cm³g^-1. The growth mechanism of the petal-like MgAl₂O₄ is believed to be the formation of a two-dimensional layered network structure by the coordination between the condensation product of the magnesium aluminium bimetallic alkoxides and the ions in the salt. The as-prepared MgAl₂O₄ petal exhibited an effective adsorption capacity toward anionic dyes CR. The maximum adsorption capacity of CR onto the mesoporous MgAl₂O₄ petal was found to be 572.01 mg/g, it is showed the petal-like MgAl₂O₄ exhibit huge potential of application in the field of environmental remediation.     

Hercynite and magnesium aluminate spinels acting as a ceramic bonding in an electrofused MgO–CaZrO3 refractory brick for the cement industry

Innovative chrome-free basic refractory bricks have been design based on electrofused magnesia–calcium zirconate (MgO-CaZrO₃) technology using as ceramic bonding magnesium aluminate spinel (MgAl₂O₄) and hercynite spinel (FeAl₂O₄) in order to improve their properties. Industrial refractory bricks have been manufactured by solid state sintering of magnesium and calcium zirconate aggregates with MgAl₂O₄ and FeAl₂O₄ spinels at 1650 °C in a tunnel kiln. Physical and microstructural characteristics of new refractory bricks have been characterised in terms of density, porosity, crystalline phases, phase distribution and morphology. X-ray diffraction (XRD) analyses and scanning electron microscopy (SEM) with microanalysis (using energy dispersive spectroscopy analysis -EDS) have been used. The mechanical behaviour has been evaluated in terms of cold crushing strength (CCS) at room temperature and three point bending modulus of rupture (MOR) at 25 and 1260 °C. Static and dynamic resistance test by chemical attack of clinker raw meal constituents have been carried out at 1450 °C. Results have shown that thermo-mechanical properties of new refractory bricks significantly improved with increasing both type of spinel in content. Microstructural analysis revealed that spinel phases aided to develop a strong bond between the magnesia and calcium zirconate refractory aggregates. Finally, these refractory matrixes exhibit a good thermal stability and an excellent chemical resistance against clinker raw meal.     

Preparation of a thick sponge-like structured amorphous silica ceramic coating on 6061 aluminum alloy by plasma electrolytic oxidation in TEOS solution

Plasma electrolytic oxidation (PEO) was performed on 6061 aluminum alloy in organosilicon electrolyte using a stepwise constant potential control method for 23 min. The resulting coating was a sponge-like structured amorphous silica ceramic with a thickness of about 130 μm. Its exceptional wear resistance was attributed to the high hardness of the silica ceramic and the low elastic modulus of the sponge-like structure. The corrosion resistance was enhanced by a dense layer of approximately 2 μm between the coating and the substrate. Impressively, the indentation depth of the PEO coating during nano-indentation tests was only 50–60% of that of 6061 aluminium alloy under varying loads, while the recovery depth of the PEO coating after unloading was 2.5–3.1 times greater than that of 6061 aluminium alloy. Due to its special composition and structure, the PEO coating caused serious wear to the high hardness Si₃N₄ friction balls during the friction and wear test. In the electrochemical tests, the coating reduced the corrosion current density from 1.056 × 10⁻⁵A·cm⁻² to 1.239 × 10⁻⁷A·cm⁻², while extending the passivation region from 0.322 V to 1.032 V.     

Preparation of nanostructured Gd2Zr2O7-LaPO4 thermal barrier coatings and their calcium-magnesium-alumina-silicate (CMAS) resistance

Nanostructured 30 mol% LaPO₄ doped Gd₂Zr₂O₇ (Gd₂Zr₂O₇-LaPO₄) thermal barrier coatings (TBCs) were produced by air plasma spraying (APS). The coatings consist of Gd₂Zr₂O₇ and LaPO₄ phases, with desirable chemical composition and obvious nanozones embedded in the coating microstructure. Calcium-magnesium-alumina- silicate (CMAS) corrosion tests were carried out at 1250 °C for 1–8 h to study the corrosion resistance of the coatings. Results indicated that the nanostructured Gd₂Zr₂O₇-LaPO₄ TBCs reveals high resistance to penetration by the CMAS melt. During corrosion tests, an impervious crystalline reaction layer consisting of Gd-La-P apatite, anorthite, spinel and tetragonal ZrO₂ phases forms on the coating surfaces. The layer is stable at high temperatures and has significant effect on preventing further infiltration of the molten CMAS into the coatings. Furthermore, the porous nanozones could gather the penetrated molten CMAS like as an absorbent, which benefits the CMAS resistance of the coatings.     

Mechanical and tribological properties of nano/micro composite alumina coatings fabricated by atmospheric plasma spraying

Adding nano particles can significantly improve the mechanical properties and wear resistance of thermal sprayed Al₂O₃ coating. However, it still remains a challenge to uniformly incorporate nano particles into traditional coatings due to their bad dispersibility. In the present work, nanometer Al₂O₃ (n-Al₂O₃) powders modified by KH-560 silane coupling agent were introduced into micrometer Al₂O₃ (m-Al₂O₃) powders by ultrasonic dispersion to afford nano/micro composite feedstock, and then four resultant coatings (weight fraction of n-Al₂O₃: 0%, 3%, 5% and 10%) were fabricated by atmospheric plasma spraying. The features and constitutes of feedstock and as-sprayed coatings, as well as their porosity, bonding strength, microhardness and frictional behaviors were investigated in detail. Results show that the nano/micro composite feedstock with uniform microstructure can be better melted in the spraying process, thereby obtaining coatings with denser microstructure, higher hardness and bonding strength. Added n-Al₂O₃ has no obvious effect on the friction coefficient of composite coatings, whereas can improve their wear-resistant and reduce the worn degree of counterpart. The wear mechanism of traditional coating is brittle fracture and lamellar peeling, while that of composite coating with weight fraction of n-Al₂O₃ of 10% is adhesive wear.     

The influence of multilayer structure on mechanical behavior of TiN/TiAlSiN multilayer coating

Nitride coatings have been generally applied on light alloys like titanium and aluminium to promote their multiple performances, including hardness, thermal stability and wear resistance. In this work, TiAlSiN/TiN multilayered (ML) coating and TiAlSiN single-layer (SL) coating were deposited on TC18 (Ti5Al5Mo5V1CrFe) alloy by Multi-arc ion plating technique. The microstructure and chemical composition of the coatings were evaluated by SEM, XRD and XPS. Additionally, hardness, adhesion and wear resistance were measured through nanoindentation, scratch spectrometer and ball-on-disk tribometer. The results present that both ML and SL coating contain three main phases of TiN, Al₂O₃ and Si₃N₄. Nevertheless, the adhesion of ML coating is 62.4 N, compared to that of the SL coating is 51.8 N. The parameter H³/E² as an indication of plastic deformation to evaluate wear resistance shows that the ML coating has high hardness and high toughness concurrently. The tribological study indicated that the wear rate of the ML coated specimen was 1/7 of the SL coated counterpart.     

Microstructural effects on the sliding wear of transparent magnesium-aluminate spinel

Grain size effects have been investigated in the lubricated sliding wear of three transparent magnesium aluminate (MgAl₂O₄) spinel materials with different grains sizes identified as: Nano, Fine, and Coarse. Only Fine spinel shows classical wear behavior, which is characterized by initial mild wear followed by a sharp transition to severe fracture-controlled wear. Worn surfaces of Fine spinel show extensive grain pullout, consistent with intergranular mode of fracture found in that spinel. Nano and Coarse spinels both show gradual transition from mild wear to severe wear, and both have significantly lower overall wear rates compared to Fine spinel. Worn surfaces in both Nano and Coarse spinels show transgranular fracture and material removal, which is reminiscent of lateral-crack induced chipping. The transgranular fracture mode in Nano spinel can be attributed to stronger grain boundaries in that spinel, which could be due to the Y₂O₃ sintering additive used for grain refinement. Whilst the large scale of the grains in Coarse spinel could be responsible for the transgranular fracture observed in that spinel.     

Development of MgAl2O4 spinel coating on graphite surface to improve its water-wettability and oxidation resistance

Low water-wettability and oxidation resistance of graphite have limited its application in carbon containing refractory castables. The aims of this study are the improvement of water-wettability and the oxidation resistance of natural flaky graphite by applying an oxide coating on its surface. To develop the coating, magnesium aluminate spinel sol was formulated via a citrate–nitrate route and graphite powder was then added to the sol. The mixture was heat treated in appropriate temperature and atmosphere to get the polycrystalline MgAl₂O₄ coating on graphite particles surface. The microstructure of coating was studied by X-ray diffractometer, SEM and TEM. The water-wettability was evaluated by measuring the water drop contact angle and plotting the zeta potential vs. pH. The results showed the development of a stable nanocrystalline MgAl₂O₄ spinel coating which improved the water-wettability and oxidation resistance of graphite significantly. Also, characterization of the coating is explained with emphasis on its application importance.     

Preparation of MgAl2O4 solar thermal storage ceramics from different magnesium sources

In order to study the performance and feasibility of magnesia-alumina spinel (MgAl₂O₄) ceramics for thermal storage in solar thermal power generation, MgAl₂O₄ was prepared by theoretical composition using α-Al₂O₃ as aluminium source, fused magnesia, magnesite, and light burned magnesia as different magnesium sources and kaolin as additive. The effects of magnesium source and the additive on sintering properties, thermal shock resistance and thermal properties of MgAl₂O₄ ceramics were researched. The results shown sample A1 (with fused magnesia) sintered at 1670°C possessed the optimum comprehensive properties, the bending strength increased by 7.71% after 30 thermal shock times (room temperature-1000°C, air cooling), the specific heat capacity was 1.05 J/ (g·K). Therefore, the MgAl₂O₄ ceramics exhibited great potential in high-temperature thermal storage material.     

Sintering behavior and microstructure of (1-x)MgAl2O4-xMg2TiO4 spinel solid solutions prepared by isostructural heterogeneous nucleation

Magnesium aluminate (MgAl₂O₄) spinel has grasped considerable attention in high-temperature application by right of its excellent properties. However, the poor sintering behavior of MgAl₂O₄ is detrimental to its further development. In the present work, the application of isostructural heterogeneous nucleation method provides a novel idea for optimizing the sintering behavior of refractory materials. A series of (1-x)MgAl₂O₄-xMg₂TiO₄ (x = 0, 0.02, 0.04, 0.06, 0.08, and 0.1) spinel solid solutions with a present ration of components were fabricated from light calcined magnesia, reactive alumina and pre-preparation Mg₂TiO₄. The effect of Mg₂TiO₄ heterogeneous nucleating agent on the crystalline phase, densification, and microstructure evolution of MgAl₂O₄–Mg₂TiO₄ spinel solid solutions was studied. The XRD, XPS, and EDS results showed that Mg₂TiO₄ entered the lattice of MgAl₂O₄ to form a spinel solid solution, and the heterovalent substitution process was identified, where Ti⁴⁺ and Mg²⁺ ions of larger radius in the Mg₂TiO₄ replaced the Al³⁺ of smaller radius in the MgAl₂O₄. For the sample at x = 0.08, the spinel solid solutions exhibited the optimized densification with a relative density of 93.3%, an apparent porosity of 1.2%, and a compressive strength of 84.5 MPa. A significant increase in densification was related to the lattice distortion induced by ion size mismatch during the heterovalent substitution, thus accelerating the diffusion rate of Mg²⁺ and Al³⁺ ions in the spinelisation state. Moreover, the solid solubility content of Ti⁴⁺ in the MgAl₂O₄–Mg₂TiO₄ spinel solid solutions had a significant effect on the grain morphologies. The Mg₂TiO₄ heterogeneous nucleating agent significantly increased the spinelisation rate of MgAl₂O₄ spinel with negligible effect on densification.