Production of a stable and homogeneous colloid dispersion of nano CoAl2O4 pigment for ceramic ink-jet ink

Different types of nano-CoAl₂O₄ pigments were prepared by controlling concentration of cetyltrimethylammonium bromide (CTAB) and polyvinyl pyrrolidone (PVP) as double capping agents in a co-precipitation process. The prepared nano-CoAl₂O₄ pigments were characterized by TGA, UV spectroscopy, and XRD. The optimum synthesized nano pigment was well dispersed into de-ionized water to form the ink. Rheology, surface tension and DLS of the prepared ink were examined. The prepared ink was printed onto a ceramic substrate. The printing process was repeated 1, 3 and 5 times in order to evaluate variations in the optical properties by changing thicknesses of the printed film. Appearance of the printed image and morphology of the prepared nano-pigments were observed by SEM. Moreover, shape and size of the nano-particles in the prepared ink were investigated by TEM. The obtained results revealed that the ink-jet printing method can be used to produce a nano-film of pigments on the ceramic.     

Solubility of blue CoAl2O4 ceramic pigments in water and diethylene glycol media

The chemical stability of blue CoAl₂O₄ ceramic pigment in aqueous and non-aqueous suspension was investigated. Distilled water and diethylene glycol (DEG) were used as media. The isoelectric points (IEP) for the commercial and synthesised CoAl₂O₄ pigment were determined to be 4.9 and 8.5, respectively. The IEP shifts toward acidic pH values for the commercial pigment with respect to the synthesised pigment due to the existence of the quartz phase. In water, the cobalt ion concentration was low (2.5 mg dm⁻³), and this concentration did not change with time. However, the aluminium ion concentration was initially high and then decreased to ∼10 mg dm⁻³ at pH 9 and 11 due to the precipitation of Al³⁺ ions as an Al(OH)₃ phase. In DEG, the dissolution of pigment particles with higher ion concentrations (>800 mg dm⁻³) was more significant than that of the aqueous medium, implying that CoAl₂O₄ pigment has insufficient chemical stability in DEG medium with respect to aqueous suspensions.     

Synthesis and properties of blue zirconia ceramic based on Ni/Co doped Ba0.956Mg0.912Al10.088O17 blue pigments

Novel blue pigments based on Ba_0.956Mg_0.912Al_10.088-xNi_xO₁₇ (0 ≤ x ≤ 0.3) and Ba_0.956Mg_0.912Al_10.088-xCo_xO₁₇ (0 ≤ x ≤ 0.3) solid solutions were successfully synthesized by solid state method. The XRD results confirmed the structure of the as-synthesized sample belongs to hexagonal β-alumina structure with the space group of P6₃/mmc. The d-d electron transitions in Ni²⁺/Co²⁺ tetrahedral sites in the visible light range are the reason for the blue colors. Then, the as-prepared blue oxides were sintered with ZrO₂ powders at 1400 °C to prepare blue zirconia ceramic materials. Based on XRD and SEM analysis, the pigment phase is stable after high-temperature sintering with ZrO₂, and a clear grain boundary is observed. The XCT results indicate the prepared blue ceramics are dense and very small pores are rarely distributed inside the blue zirconia ceramic body. Additionally, the mechanical properties of the fabricated blue ceramics were maintained compared to pure ZrO₂ ceramic.     

Air plasma-sprayed Y2O3 coatings for Al2O3/Al2O3 ceramic matrix composites

Al₂O₃/Al₂O₃ ceramic matrix composites (CMC) are candidate materials for hot-gas leading components of gas turbines. Since Al₂O₃/Al₂O₃ CMC are prone to hot-corrosion in combustion environments, the development of environmental barrier coatings (EBC) is mandatory. Owing to its favorable chemical stability and thermal properties, Y₂O₃ is considered a candidate EBC material for Al₂O₃/Al₂O₃ CMC. Up to 1 mm thick Y₂O₃ coatings were deposited by means of air plasma spraying (APS) on Al₂O₃/Al₂O₃ CMC with a reaction-bonded Al₂O₃ bond-coat (RBAO). APS Y₂O₃ coatings exhibit a good adherence in the as-deposited state as well as upon isothermal annealing up to 1400 °C. Moreover, furnace cyclic testing performed at 1200 °C revealed an excellent durability. This is explained by the formation of a continuous, approximately 1 μm thick reaction zone at the APS Y₂O₃/RBAO interface. The reaction zone between Y₂O₃ and Al₂O₃ comprises three layers of thermodynamically stable yttrium-aluminates exhibiting strong bonding, respectively.     

Physico-chemical properties of ceramic pigments for high-temperature application

Heat resistant coatings are required primarily for stacks, exhaust pipes, reactors, space crafts and similar equipments that are permanently or occasionally exposed to elevated temperatures. High-temperature coatings are generally based on silicone resin with ceramic and metallic pigments. In this study, iron oxide, cobalt oxide (thermo chromic compound) and aluminum oxide are used for the preparation of four new types of coloured pigments. The thermal resistant characteristics of these ceramic pigments were studied by differential thermal analysis, thermo gravimetric analysis and differential scanning calorimetric analysis. These ceramic pigments are found to be thermally stable up to 400 °C.     

Synthesis and color properties of the TiO2@CoAl2O4 blue pigments with low cobalt content applied in ceramic glaze

The TiO₂@CoAl₂O₄ complex blue pigments with low cobalt content were synthesized through calcinations of the precursor obtained from coprecipitating Co²⁺ and Al³⁺ to form Co‐Al LDHs (layered double hydroxides) on the surface of TiO₂ particles. The structure and the properties of the synthesized pigments were characterized by XRD, SEM, TEM, UV‐Vis spectroscopy, XPS, and colorimeter. The precursors of the blue TiO₂@CoAl₂O₄ complex pigments were consisted of LDHs shell layer encapsulated TiO₂ microsphere. After calcinations at 1100°C, the LDHs shell layer were absolutely transformed to the spinel CoAl₂O₄, and the pigments presented a core‐shell structure and uniform sphere morphology (the diameter of microsphere was about 780 nm). The absorption bands at around 547, 584, and 624 nm in the Uv‐Vis absorption spectra of the TiO₂@CoAl₂O₄ complex pigments were corresponded to the characteristic absorption bands of the spinel CoAl₂O₄, revealed the pigments with a bright blue hue. In addition, as the mass ratio of CoAl₂O₄/TiO₂ increased to 0.4, the blue component of the pigments reached to 27.89 and slight color variation with the increase in the CoAl₂O₄ content in a range, possessed low cobalt content and exhibited a stabile performance in commercial low‐temperature ceramic glazes. The XGT results showed that the TiO₂@CoAl₂O₄ complex pigments with low cobalt content presented bright color in ceramic glaze. Especially, the synthesized pigments reduced the usage and toxicity of cobalt, which were efficiency for economy and environmental protection.     

Conformal coatings of NiCo2O4 nanoparticles and nanosheets on carbon nanotubes for supercapacitor electrodes

NiCo₂O₄ is a promising electrode material for supercapacitors and it has been widely investigated. However, its low conductivity restricts the reaction kinetics. Combining it with carbon materials can efficiently overcome the issue. But, very limited research about the homogenous coatings of NiCo₂O₄ nanocrystals on carbon nanotubes (CNTs) is reported. In this work, thin nanosheets and small nanoparticles of NiCo₂O₄ densely coated on CNTs are synthesized by tuning the annealing time with a hybrid of metal hydroxide@CNTs as a precursor. In the precursor, core−shell structures are formed by conformally coating 2D metal hydroxides on CNTs. After annealing it at 300 °C for different time, NiCo₂O₄ nanosheets or nanoparticles are then obtained and the core−shell structure is remained. Due to the reduced crystal size of NiCo₂O₄ and the high conductivity of CNTs, the composites have large specific capacitances, excellent rate performances, and good stability. The composite of NiCo₂O₄ nanoparticles on CNTs has a higher specific capacitance, about 1786 F g⁻¹ at 0.5 A g⁻¹, than the hybrid of NiCo₂O₄ nanosheets on CNTs due to their different morphologies. Using the composite as positive electrode and activated carbon as negative electrode, a hybrid capacitor cell can work in a voltage of 1.6 V, delivering an energy density of 32.5 Wh kg⁻¹ at 800 W kg⁻¹, showing a large potential for supercapacitors.     

微波水热合成纳米CoAl2O4色料的工艺研究

以CoCl2·6H2O和AlCl3为起始原料,NaOH为沉淀剂,用微波水热法合成了纳米CoAl2O4钴蓝色料.分别研究了填充度、pH值、nCo/nAl、起始原料浓度等对合成色料物相组成、颗粒大小与形貌和呈色的影响.用XRD、TEM和色度仪对样品进行了表征.结果表明:CoCl2·6H2O和AlCl3的浓度分别为0.15 mol/L和0.30 mol/L,在填充度为50％、pH值为13、nCo/nAl为1∶2的条件下,230℃微波水热反应3h可制得呈色较好的尖晶石型钴蓝色料;其形态为八面体,晶型完整、发育良好,粒径多为70～80 nm左右.     

Synthesis of Y(Al,Cr)O3 red pigments by co-precipitation method and their interactions with glazes

New red pigment based on the system YAl_1−yCr_yO₃ (y = 0.01–0.1) was synthesized by co-precipitation method. The precipitant was attained by mixing solutions of yttrium, aluminum and chromium nitrates, respectively, and addition of ammonia as the precipitator. The effects of chromium as dopant and glaze composition on the color shade of resulting pigments were studied. EDX analysis of the prepared pigment particles, which was embedded in glaze, showed the occurrence of reactions between some glaze constituents and pigment particles. Accordingly, a glaze which was enriched in Al₂O₃ and poor in ZnO was more suitable in point of achieving a reddish shade. The resulting pigments were characterized by using X-ray diffraction (XRD), SEM and UV–vis spectrophotometer.     

Wettability and interfacial reactions of a low Hf-containing nickel-based superalloy on Al2O3-based,SiO2-based,ZrSiO4, and CoAl2O4 substrates

To understand the wetting behavior and interfacial phenomena between molten superalloys and ceramic materials, the wettability and interfacial reactions of a low Hf-containing Nickel-based superalloy on the Al₂O₃-based, SiO₂-based, ZrSiO₄, and CoAl₂O₄ substrates were studied using the sessile drop method at 1773 K. The wetting angles of the alloy on the Al₂O₃-based, SiO₂-based, ZrSiO₄, and CoAl₂O₄ substrates were 141.4°, 143.5°, 135.7°, and 128.4°, respectively. This indicated that the wettability of the alloy on the Al₂O₃-based substrate was comparable to that on the SiO₂-based substrate, and the wettability of the CoAl₂O₄ system was the best among the four systems. The microstructure characteristics of the interface implied that Hf has a strong tendency to react with ceramic substrates, even at low contents. Additionally, the interfacial reactions transformed the Al₂O₃-based, SiO₂-based, ZrSiO₄, and CoAl₂O₄ ceramic substrates into (Al₂O₃ + HfO₂), (Al₂O₃ + HfO₂), (Al₂O₃ + HfO₂ + ZrO₂), and (Al₂O₃ + HfO₂ + Co), respectively, which were in contact with the alloys. The experimental results demonstrated that the wettability of the system was governed by the properties of the reaction products.     

Preparation of high-porosity Al2O3 ceramic foams via selective laser sintering of Al2O3 poly-hollow microspheres

In this paper, high-porosity Al₂O₃ ceramic foams called Al₂O₃ PHM ceramics were fabricated through selective laser sintering (SLS) via Al₂O₃ poly-hollow microspheres (Al₂O₃ PHMs). SLS parameters were optimized by an orthogonal experiment as to be laser power = 6 W, scanning speed = 1800 mm/s, and scanning space = 0.15 mm. The effect of sintering temperature on microstructure, shrinkage, porosity, phase composition, mechanical properties and pore size distribution of Al₂O₃ PHM ceramics were investigated. When sintering temperature increased, Al₂O₃ PHM ceramics contained only Al₂O₃ phase and were gradually densified. With the raise of sintering temperature, the porosity of Al₂O₃ PHM ceramics decreased gradually from 77.09% to 72.41%, but shrinkage in H direction and compressive strength of Al₂O₃ PHM ceramics increased from 6.63% and 0.18 MPa to 13.10% and 0.72 MPa, respectively. Sintering temperature had little effect on pore size distribution of Al₂O₃ PHM ceramics, which only declined from 24.2 to 21.4 μm with the increase of sintering temperature from 1600 to 1650 °C. This method can not only directly prepare ceramic foams with complex shapes, but also control properties of ceramic foams. It provides a simple preparation method for many kinds of ceramic foams with complex structure and high porosity by using PHMs with different composition.     

Theoretical analysis and synthesis of Al4O4C and Al2CO phase in the resin bonded Al-Al2O3 refractory in N2-flowing

In flowing nitrogen, Al₄O₄C and Al₂CO bonded Al₂O₃-based composite was successfully prepared by a gaseous phase mass transfer pathway at 1600 °C for 3 h after an Al-AlN core-shell structure was formed in the resin bonded Al-Al₂O₃ refractory at 580 °C for 8 h. The formation mechanism of Al₄O₄C and Al₂CO phase is as follows. An Al-AlN core–shell structure is built at 580 °C for 8 h and broken at higher temperatures, and then, Al(g) reacts with C from the resin and N₂ to form Al₄C₃ and AlN, respectively. Owing to the exothermic reaction of the Al₄C₃ and AlN formation, the reaction temperature in the resin bonded Al-Al₂O₃ refractory is above the practical environmental temperature; for instance, the reaction temperature is above 1715 °C at 1600 °C in this work. Therefore, Al₄C₃ reacts with Al₂O₃ to generate Al₄O₄C and then Al₄O₄C is transformed into Al₂OC by the reaction ${\mathrm{Al}}_4{\mathrm{O}}_{\mathrm{4}}{C(s)+\text{Al}}_4{\mathrm{C}}_{\mathrm{3}}(s)\to {\mathrm{4Al}}_{\mathrm{2}}\text{OC}(s)$ at elevated temperatures. Al₂OC solid solution is finally formed through the dissolution of AlN into Al₂OC.     

Fe2O3-MnO-Cr2O3-La2O3系统紫色颜料的制备及表征

采用溶胶均匀共沉淀法于低温下合成了含少量稀土氧化物La2O3的紫色颜料，并采用颜色测定、SEM、XRD等手段对颜料的颜色、检度及结晶构造等进行了表征。     

Calcium Cl/OH-apatite,Cl/OH-apatite/Al2O3 and Ca3(PO4)2 fibre nonwovens: Potential ceramic components for osteosynthesis

Polycrystalline calcium phosphate ((Cl/OH)Ap = Ca₅(PO₄)₃(OH/Cl); TCP = Ca₃(PO₄)₂) fibres were prepared from aqueous solutions of calcium chloride and phosphoric acid using poly(ethylene oxide) (PEO) as spinning aid. Generation of nonwoven materials was accomplished via rotary jet spinning. Polycrystalline (Cl/OH)Ap fibres 10–25 μm in diameter were obtained with 37% ceramic yield by pyrolysis of the green fibres followed by sintering at 1150 °C in air. X-ray diffraction (XRD) analysis provided evidence for apatite formation starting at 650 °C while (Cl/OH)Ap ceramic fibres were obtained at 1100 °C via transformation through intermediate dicalcium dichloride hydrogen phosphate (Ca₂Cl₂(HPO₄)) and calcium pyrophosphate (Ca₂P₂O₇) phases. A glass-forming Al-based additive was applied to enhance the mechanical properties of the Cl/OH)Ap ceramic fibres and indeed resulted in the formation of (Cl/OH)Ap/Al₂O₃ fibres with improved mechanical stability. Finally, TCP, (Cl/OH)Ap and (Cl/OH)Ap/Al₂O₃ fibres were subjected to seeding with mesenchymal stem cells. Negligible cytotoxicity is observed.     

Ternary ZnO/ZnAl2O4/ Al2O3 composite nanofiber as photocatalyst for conversion of CO2 and CH4

Electrospinning is a flexible synthesis method which not only facilitates the preparation of the nanofibers with dramatically improved surface area, but also takes advantage of the structural defects to form heterojunctions with photocatalytic activities. In this study for the first time, a continuous layer of composite ceramic nanofiber was fabricated by employing two-nozzle electrospinning method to make the nanofiber from a 12: 3: 3: 13: 87 (percent ratio) solution of aluminum acetate: boehmite nanoparticle: zinc acetate: polyacrylonitrile: dimethylformamide respectively. The step by step thermal post-processing was performed on the nanofiber to decompose the polymeric part and achieve a pure ceramic phase. Characterization of the ceramic nanofiber was conducted using Fe-SEM, FTIR, XRD, TGA-DTA, BET and UV–Vis techniques. The SEM and XRD results confirmed that the ceramic nanofiber with average diameter of 160 nm was composed of ZnO, Al₂O₃ and ZnAl₂O₄ phases. The resultant nanofiber was used as a photocatalyst for conversion of CO₂ in presence of CH₄ as the reductant and UV–A irradiation under mild conditions. The maximum conversion percentages of CO₂ and CH₄ after 240 min were 20% and 11.7% respectively.The present study proposes a method for preparing a ternary nanofiber of Al₂O₃, ZnO, and ZnAl₂O₄ with the potential to be used as a photocatalyst for conversion of CO₂ in presence of CH₄.     

A Novel Catalyst Pt/CoAl2O4/Al2O3 for Combination CO2 Reforming and Partial Oxidation of CH4

Pt/CoAl₂O₄/Al₂O₃, Pt/CoO_x/Al₂O₃, CoAl₂O₄/Al₂O₃ and CoO_x/Al₂O₃ catalysts were studied for combination CO₂ reforming and partial oxidation of CH₄. The results indicate that Pt/CoAl₂O₄/Al₂O₃ is the most effective, and XRD results indicate that Pt species are well dispersed over the Pt/CoAl₂O₄/Al₂O₃. High dispersion is related to the presence of CoAl₂O₄, formed during calcining at high temperature before Pt addition. In the presence of Pt, CoAl₂O₄ in the catalyst could be reduced partially at 973 K. Based on these results, it appears that zerovalent platinum with high dispersion and zerovalent cobalt resulting from CoAl₂O₄ reduction are responsible for high activity in the Pt/CoAl₂O₄/Al₂O₃ catalyst.     

凝胶成型Al2O3-(30vol%)MgO·1.35Al2O3泡沫陶瓷的研制

以板状刚玉和富铝尖晶石为主原料,采用泡沫浸浆凝胶工艺制备了Al2O3-(30 vol%)MgO@1.35Al2O3泡沫陶瓷.研究了分散剂AN-2000与pH值对Al2O3-(30vol%)MgO@1.35Al2O3混合浆料流变特性的影响.在pH值=9.5、AN-2000添加量为0.4 mL@m-2的条件下制备的粘度为O.14 Pa@s,固相体积分数为55%的Al2O3-(30vol%)MgO@1.35Al2O3混合浆料,通过有机泡沫浸浆、引发凝胶反应、湿坯干燥、排胶和烧结,制备出了气孔率为89.3%,强度为5.2 MPa的Al2O3-(30vol%)MgO@1.35Al2O3泡沫陶瓷.     

矿化剂对Al2O3-SiO2质陶瓷辊棒性能的影响

研究了含MgO的单一型矿化剂及含MgO和TiO2 的复合型矿化剂对Al2 O3-SiO2 质陶瓷辊棒性能的影响。结果表明 :基质中Al2 O3与SiO2 的质量比 (Al2 O3/SiO2 )为 2 .33时 ,引入 0 .6 %的复合型矿化剂可促进莫来石的发育和基质的烧结 ,明显改善了陶瓷辊棒的抗热震性和机械强度。     

Synthesis, through pyrolysis of aerosols, of YIn1−xMnxO3 blue pigments and their efficiency for colouring glazes

Mn-doped YInO₃ blue pigments have been synthesised at a much lower temperature (1100 °C) than that required by the traditional solid state method (1400 °C). The developed procedure, which is based on the pyrolysis at 600 °C of aerosols generated from aqueous solutions of Y, In and Mn nitrates followed by an annealing treatment at 1100 °C, yields spherical pigments particles with heterogeneous size in the optimum range required for ceramic applications (<10 μm). The amount of Mn introduced in the YInO₃ matrix has been systematically varied in order to evaluate the effects of the Mn content on the colour properties of the pigments. It has been found that the optimum pigment composition (bluer colour with the lowest Mn content) is given by the formula YIn_0.90Mn_0.10O₃. The technological performance of these YIn_1−xMn_xO₃ blue pigments has also been evaluated by testing their efficiency for colouring ceramic glazes of different composition (boracic and plumbic) and properties, aiming to find a less toxic alternative for the Co-based pigments commonly used by the ceramic industry.     

Power prediction for laser engineered net shaping of Al2O3 ceramic parts

Laser-aided additive manufacturing technique is a competitive method for direct fabrication of ceramic components. However, the optimal processing parameters are difficult to find because defects are easy to generate for ceramic parts. This paper proposes a mathematical model for predicting required laser power in direct fabrication of Al₂O₃ ceramic parts by laser engineered net shaping (LENS). The laser power model, which is derived based on energy balance of one deposition layer, reveals the relationship between laser power and other process conditions, such as powder flow rate, nozzle travel speed and physical properties of deposited material. The proposed model was then verified through a fabrication experiment of several single-bead wall Al₂O₃ ceramic parts with different laser power. Experimental results indicate that the laser power predicted by the model is accurate for different processing conditions. This model provides a new yet simple method for predicting required laser power accurately during LENS processes.