Advances and challenges in direct additive manufacturing of dense ceramic oxides

Ceramic oxides,renowned for their exceptional combination of mechanical,thermal,and chemical properties,are indispensable in numerous crucial applications across diverse engineering fields.However,conventional manufacturing methods frequently grapple with limitations,such as challenges in shaping intricate geometries,extended processing durations,elevated porosity,and substantial shrinkage deformations.Direct additive manufacturing(dAM)technology stands out as a state-of-the-art solution for ceramic oxides production.It facilitates the one-step fabrication of high-performance,intricately designed components characterized by dense structures.Importantly,dAM eliminates the necessity for post-heat treatments,streamlining the manufacturing process and enhancing overall efficiency.This study undertakes a comprehensive review of recent developments in dAM for ceramic oxides,with a specific emphasis on the laser powder bed fusion and laser directed energy deposition techniques.A thorough investigation is conducted into the shaping quality,microstructure,and properties of diverse ceramic oxides produced through dAM.Critical examination is given to key aspects including feedstock preparation,laser-material coupling,formation and control of defects,in-situ monitoring and simulation.This paper concludes by outlining future trends and potential breakthrough directions,taking into account current gaps in this rapidly evolving field.

Thermodynamic analysis of interactions between Ti-Al alloys and oxide ceramics

The thermodynamics of interactions between various oxides（CaO,MgO,Al2O3 and Y2O3） and molten Ti and Ti alloys was investigated.The dissolution mechanism of oxides in molten Ti alloys was provided and the stability of oxides in molten Ti alloys was investigated and predicted by thermodynamic analysis.Interactions between oxides and Ti-Al melts were studied by oxide crucible melting experiments.By quantitative analysis,it is indicated that impurity contents in alloys are proportionally decreased with increasing the Al content in alloys and decreasing the melt temperature,which is in agreement with the results of the predicting thermodynamic stability.

Microstructure and Oxidation Behavior of ZrB_(2)-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration

ZrB_(2)-based ceramics typically necessitate high temperature and pressure for sintering,whereas ZrB_(2)-SiC ceramics can be fabricated at 1500℃using the process of reactive melt infiltration with Si.In comparison to the conventional preparation method,reactive synthesis allows for the more facile production of ultra-high temperature ceramics with fine particle size and homogeneous composition.In this work,ZrSi_(2),B4C,and C were used as raw materials to prepare ZrB_(2)-SiC via combination of tape casting and reactive melt infiltration herein referred to as ZBC ceramics.Control sample of ZrB_(2)-SiC was also prepared using ZrB_(2) and SiC as raw materials through an identical process designated as ZS ceramics.Microscopic analysis of both ceramic groups revealed smaller and more uniformly distributed particles of the ZrB_(2) phase in ZBC ceramics compared to the larger particles in ZS ceramics.Both sets of ceramics underwent cyclic oxidation testing in the air at 1600℃for a cumulative duration of 5 cycles,each cycle lasting 2 h.Analysis of the oxidation behavior showed that both ZBC ceramics and ZS ceramics developed a glassy SiO_(2)-ZrO_(2) oxide layer on their surfaces during the oxidation.This layer severed as a barrier against oxygen.In ZBC ceramics,ZrO_(2) is finely distributed in SiO_(2),whereas in ZS ceramics,larger ZrO_(2) particles coexist with glassy SiO_(2).The surface oxide layer of ZBC ceramics maintains a dense structure because the well-dispersed ZrO_(2) increases the viscosity of glassy SiO_(2),preventing its crystallization during the cooling.Conversely,some SiO_(2) in the oxide layer of ZS ceramics may crystallize and form a eutectic with ZrO_(2),leading to the formation of ZrSiO_(4).This leads to cracking of the oxide layer due to differences in thermal expansion coefficients,weakening its barrier effect.An analysis of the oxidation resistance shows that ZBC ceramics exhibit less increase in oxide layer thickness and mass compared to ZS ceramics,suggesting superior oxidation resistance of ZBC ceramics.

Oxidation behavior of amorphous and nanocrystalline SiBCN ceramics–Kinetic consideration and microstructure

In this study,the structural evolution of SiBCN ceramics during crystallization and its effects on oxidation behavior involving different atomic units or formed phases in amorphous or crystalline SiBCN ceramics were analyzed.The amorphous structure has exceptionally high oxidation activity but presents much better oxidation resistance due to its synchronous oxidation of atomic units and homogeneous composition in the generated oxide layer.However,the oxidation resistance of SiBCN ceramic will degrade during the continual crystallization process,especially for the formation of the nanocapsule-like structure,due to heterogeneous oxidation caused by the phase separation.Besides,the activation energy and rate-controlling mechanism of the atomic units and phases in SiBCN ceramics were obtained.The BNCx(Ea=145 kJ/mol)and SiC(2-x)(Ea=364 kJ/mol)atomic units in amorphous SiBCN structure can be oxidized at relatively lower temperatures with much lower activation energy than the corresponding BN(C)(Ea=209 kJ/mol)and SiC(Ea=533 kJ/mol)phases in crystalline structure,and the synchronous oxidation of the SiC(2-x)and BNCx units above 750C changes the oxidation activation energy of BNCx(Ea=332 kJ/mol)to that similar to SiC(2-x).The heterogeneous oxide layer formed from the nanocapsule-like structure will decrease the activation energy SiC(Ea=445 kJ/mol)and t-BN(Ea=198 kJ/mol).

Influence of Metal Additives on the Electrical Conductivities of the Oxide Ceramics as an Electrode Material

The electrical conductivities are reported for various oxide ceramics and cermets at 1000°C.Adding metal can greatly enhance the electrical condnctivities of the oxide materials.The conductivity of the ceramic added with metal depends on:(1)the conductivity σ_o of the oxides;(2)the content of metal additives;(3)the dispersion of the metal phase among oxide phase.The conductivity of the metal added does not affect the con- ductivity of the metal-containing ceramic.Although the metal-containing ceramic has much higher conductivi- ty than oxide ceramic,the change rate of their conductivities with temperature is similar and is controlled by E_g of the oxide.

MICROSTRUCTURE AND INFRARED EMISSIVITY AT NORMAL TEMPERATURE IN TRANSITIONAL METAL OXIDES SYSTEM CERAMICS

The fabrication of Fe2O3-MnO2-Co2O3-CuO system ceramics, and the composite system ceramics of transitional metal oxides-cordierite and transitional metal oxides-kaolinit are presented in this work. The research was carried out with the main attention to the infrared emissivity in the band of 8 similar to 14 mu m at room temperature, the microstructure of the ceramics and the relation between them. High infrared emissivities exceeding 0.9 in the band of 8 similar to 14 mu m at room temperature were gained in the transitional metal oxide ceramics and the composite system ceramics. It is suggested that the formation of inverse spinels and partially inverse spinels, such as Fe3O4, CoFe2O4, CuFe2O4 and CuMn2O4, is beneficial to the enhancement of the infrared emissivity of the transitional metal oxide ceramics. The transitional metal oxides play an important role in determining the infrared emissivity of the composite system ceramics.

Effects of Dysprosium Oxide Doping on Microstructure and Properties of Barium Titanate Ceramic

Different amounts of dysprosium oxide were incorporated into barium titanate powders synthesized by hydrothermal method. Relations of substitution behaviors and lattice parameters with solid-solubility were studied. Furthermore, the influences of dysprosium oxide doping fraction on grain size and dielectric properties of barium titanate ceramic, including dielectric constant and breakdown electric field strength , were investigated via scanning electron microscope, X-ray diffraction and electric property tester. The results show that dysprosium oxide can restrain abnormal grain growth during sintering and that fine-grained and high density of barium titanate ceramic can result in excellent dielectric properties. As mass fraction of dysprosium oxide is 0.6%, the lattice parameters of grain increase to the maximum because of the lowest vacancy concentration. The electric property parameters are cited as following： dielectric constant （25 ℃ ） reaches 4100, the change in relative dielectric constant with temperature is - 10% to 10% within the range of - 15 - 100 ℃, breakdown electric field strength （alternating current） achieves 3.2 kV·mm^-1, which can be used in manufacturing high voltage ceramic capacitors

High-Entropy Perovskite Oxide: A New Opportunity for Developing Highly Active and Durable Air Electrode for Reversible Protonic Ceramic Electrochemical Cells

Reversible proton ceramic electrochemical cell(R-PCEC)is regarded as the most promising energy conversion device,which can realize efficient mutual conversion of electrical and chemical energy and to solve the problem of large-scale energy storage.However,the development of robust electrodes with high catalytic activity is the main bottleneck for the commercialization of R-PCECs.Here,a novel type of high-entropy perovskite oxide consisting of six equimolar metals in the A-site,Pr_(1/6)La_(1/6)Nd_(1/6)Ba_(1/6)Sr_(1/6)Ca_(1/6)CoO_(3−δ)(PLN-BSCC),is reported as a high-performance bifunctional air electrode for R-PCEC.By harnessing the unique functionalities of multiple ele-ments,high-entropy perovskite oxide can be anticipated to accelerate reaction rates in both fuel cell and electrolysis modes.Especially,an R-PCEC utilizing the PLNBSCC air electrode achieves exceptional electrochemical performances,demonstrating a peak power density of 1.21 W cm^(−2)for the fuel cell,while simultaneously obtaining an astonishing current density of−1.95 A cm^(−2)at an electrolysis voltage of 1.3 V and a temperature of 600℃.The significantly enhanced electrochemical performance and durability of the PLNBSCC air electrode is attributed mainly to the high electrons/ions conductivity,fast hydration reactivity and high configurational entropy.This research explores to a new avenue to develop optimally active and stable air electrodes for R-PCECs.

Graphene oxide membranes supported on the ceramic hollow fibre for efficient H2 recovery

The special channels and intrinsic defects within GO laminates make it a very potential candidate for gas separation in recent years. Herein, the gas separation performance of GO membranes prepared on the surface of ceramicα-Al_2O_3 hollow fibre was investigated systematically. The microstructures of ceramic hollow fibre supported GO membranes were optimized by adjusting operation conditions. And, the GO membrane fabricated at 30 min exhibited great promising H_2 recovery ability from H_2/CO_2 mixture. At room temperature, the H_2 permeance was over 1.00 × 10^(-7)mol·m^(-2)·s^(-1)·Pa^(-1)for both single gas and binary mixture. The corresponding ideal selectivity and mixture separation factor reached around 15 and 10, respectively. In addition, humility, operation temperature, H_2 concentration in the feed and the reproducibility were also studied in this work.

Characteristic Analysis of the Solid Oxide Fuel Cell with Proton Conducting Ceramic Electrolyte

An electrolyte model for the solid oxide fuel cell (SOFC) with proton conducting perovskite electrolyte is developed in this study, in which four types of charge carriers including proton, oxygen vacancy (oxide ion), free electron and electron hole are taken into consideration. The electrochemical process within the SOFC with hydrogen as the fuel is theoretically analyzed. With the present model, the effects of some parameters, such as the thickness of electrolyte, operating temperature and gas composition, on the ionic transport (or gas permeation) through the electrolyte and the electrical performance, i.e., the electromotive force (EMF) and internal resistance of the cell, are investigated in detail. The theoretical results are tested partly by comparing with the experimental data obtained from SrCe0.95M0.05O3-α, (M=Yb, Y) cells.

Interfacial reaction between zirconium alloy and graphite mold/yttrium oxide ceramic mold

Zirconium alloys are active in the molten state and tend to react with the mold during casting. The casting technology of zirconium is not yet well established; especially in selecting the mold materials, which are difficult to determine. In the present work, the interfacial reactions between zirconium casting and casting mold were studied. The zirconium alloy was melted in a vacuum arc skull furnace and then cast into the graphite mold and ceramic mold, respectively. The zirconium casting samples were characterized using SEM, EDS and XRD with an emphasis on the chemical diffusion of elements. A reaction layer was observed at the casting surface. Chemical analysis shows that chemical elements C, O and Y from the mold are diffused into the molten zirconium, and new phases, such as ZrC, Zr30, YO1.335 and Y6ZrO11, are formed at the surface. In addition, an end product of zirconium valve cast in a yttria mold has a compact structure and good surface quality.

Adsorption and Desorption Mechanisms of Methylene Blue Removal with Iron-Oxide Coated Porous Ceramic Filter

Adsorption and desorption mechanisms of methylene blue (MB) removal with iron-oxide coated porous ce-ramics filter (IOCPCF) were investigated in batch and column mode. The results revealed that MB removal mechanisms included physical adsorption and chemical adsorption, of which chemical adsorption by surface ligand complex reaction played a dominant role after infrared spectrum analysis. Recycling agents were se-lected from dilute nitric acid (pH=3), sodium hydroxide solution (pH=12) and distilled water. Among three agents, dilute metric acid (pH=3) was the best recycling agent. Regeneration rate of IOCPCF arrived at 82.56% at batch adsorption and regeneration was finished in 75min at column adsorption. Adsorp-tion-desorption cycles of IOCPCF after batch and column adsorption were four and three times, respectively. Further, compared with fresh IOCPCF, MB removal rate with these desorbed IOCPCF adsorption only slightly decreased, which suggested that IOCPCF should be used repeatedly.

Ab initio energetic study of oxide ceramics with rare-earth elements

Ab initio energetic calculations based on the density functional theory （DFF） and the projector augmented wave method （PAW） for determining the polymorphisms of lanthanide sesquioxides Ln2O3 （where Ln = rare-earth element, Y, and Sc）, LnMO3 perovskites （where M = AI and Ga）, and Ln2B207 pyrochlores （where B = Ti, Zr, and Hf） were reported. The relative lattice stabilities agreed well with the critically assessed results or the experimental results except the C-type Ln2O3 with a cubic structure, for which the calculated total energies were considerably more negative. With the increase of the Ln^3＋-cation radius, the polymorphic structures showed a degenerative tendency. The tendencies and quantities of the enthalpies of formation of the ternary oxide ceramics synthesized from their constituent binary oxides reasonably agreed with the available experimental results, and valuable thermodynamic properties were afforded to the compound, for which no experimental data is available. The enthalpies of formation of both perovskites and pyrochlores tend to become more negative with the increase of the Ln^3＋-cation radius.

Spectral properties of Ce^(3+) doped yttrium lanthanum oxide transparent ceramics

Ce3＋-doped yttrium lanthanum oxide （Y0.9La0.1）2O3 transparent ceramics is fabricated with nanopowders and sintered in H2 atmosphere. The spectral properties of Ce：（Y0.9La0.1）2O3 transparent ceramics are investigated. There appear two characteristic absorption peaks of Ce3＋ ions at 230~nm and 400~nm, separately. It is found that Ce3＋ ions can efficiently produce emission at 384~nm from （Y0.9La0.1）2O3 transparent ceramic host, while the emission is completely quenched in Re2O3 （Re=Y, Lu, La） host materials.

Fabrication and Characterization of Glass-Ceramics Doped with Rare Earth Oxide and Heavy Metal Oxide

Cordierite-based glass-ceramics with non-stoichiometric composition doped with rare earth oxide (REO_2) and heavy metal oxide (M_2O_3) respectively were fabricated from glass powders. After sintering and crystallization heat treatment, various physical properties, including compact density and apparent porosity, were examined to evaluate the sintering behavior of cordierite-based glass-ceramics. Results show that the additives both heavy metal oxide and rare earth oxide promote the sintering and lower the phase temperature from μ- to α-cordierite as well as affect the dielectric properties of sintered glass-ceramics. The complete-densification temperature for samples is as low as 900 ℃. The materials have a low dielectric constant (≈5), a low thermal expansion coefficient ((2.80～3.52)×10^(-6) ℃^(-1)) and a low dissipation factor (≤0.2%) and can be co-fired with high conductivity metals such as Au, Cu, Ag/Pd paste at low temperature (below 950 ℃), which makes it to be a promising material for low-temperature co-fired ceramic substrates.

On the Atomic Kinetic Energies in Ceramic Oxides

We calculated the mean atomic kinetic energy, , of the X atom (X = Si, Ti, Hf, O) in some ceramic oxides, SiO2, TiO2 and HfO2 using the published partial vibrational density of states (PVDOS). These were simulated by means of lattice dynamics, molecular dynamics and density functional theory. The predicted values are compared to those recently obtained by electron Compton scattering (ECS), with an overall good agreement of ~4%. In accord with calculations, the ECS measurements reveal a small, but detectable, dependence of on the fine structural details of the oxide, e.g. whether it is in a crystalline or amorphous form, and whether it exhibits surface or bulk characteristics. This study illustrates the limitations and the potential of PVDOS simulations in predicting experimental atomic kinetic energies, and can be viewed as a promising approach for elucidating valuable structural and dynamical information of ceramic oxides and other materials.

Simultaneous generation of electricity, ethylene and decomposition of nitrous oxide via protonic ceramic fuel cell membrane reactor

Ethylene,one of the most widely produced building blocks in the petrochemical industry,has received intense attention.Ethylene production,using electrochemical hydrogen pump-facilitated nonoxidative dehydrogenation of ethane(NDE)to ethylene,is an emerging and promising route,promoting the transformation of the ethylene industry from energy-intensive steam cracking process to new electrochemical membrane reactor technology.In this work,the NDE reaction is incorporated into a BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)electrolyte-supported protonic ceramic fuel cell membrane reactor to co-generate electricity and ethylene,utilizing the Nb and Cu doped perovskite oxide Pr_(0.6)Sr_(0.4)Fe_(0.8)Nb_(0.1)Cu_(0.1)O_(3-δ)(PSFNCu)as anode catalytic layer.Due to the doping of Nb and Cu,PSFNCu was endowed with high reduction tolerance and rich oxygen vacancies,showing excellent NDE catalytic performance.The maximum power density of the assembled reactor reaches 200 mW cm^(-2)at 750℃,with high ethane conversion(44.9%)and ethylene selectivity(92.7%).Moreover,the nitrous oxide decomposition was first coupled in the protonic ceramic fuel cell membrane reactor to consume the permeated protons.As a result,the generation of electricity,ethylene and decomposition of nitrous oxide can be simultaneously obtained by a single reactor.Specifically,the maximum power density of the cell reaches 208 mW cm^(-2)at 750℃,with high ethane conversion(45.2%),ethylene selectivity(92.5%),and nitrous oxide conversion(19,0%).This multi-win technology is promising for not only the production of chemicals and energy but also greenhouse gas reduction.

A robust fluorine-containing ceramic cathode for direct CO_(2) electrolysis in solid oxide electrolysis cells

Stro ntium-doped lanthanum ferrite(LSF)is a potential ceramic cathode for direct CO_(2) electrolysis in solid oxide electrolysis cells(SOECs),but its application is limited by insufficient catalytic activity and stability in CO_(2)-containing atmospheres.Herein,a novel strategy is proposed to enhance the electrolytic performance as well as chemical stability,achieved by doping F into the O-site of the perovskite LSF.Doping F does not change the phase structure but reduces the cell volume and improves the chemical stability in a CO_(2)-rich atmosphere.Importantly,F doping favors oxygen vacancy formation,increases oxygen vacancy concentration,and enhances the CO_(2) adsorption capability.Meanwhile,doping with F greatly improves the kinetics of the CO_(2) reduction reaction.For example,kchem increases by 78%from3.49×10^(-4) cm s^(-1) to 6.24×10^(-4) cm s^(-1),and Dchem doubles from 4.68×10^(-5) cm^(2) s^(-1) to 9.45×10^(-5)cm^(2) s^(-1).Consequently,doping F significantly increases the electrochemical performance,such as reducing R_(p) by 52.2%from 0.226Ωcm^(2) to 0.108Ωcm^(2) at 800℃.As a result,the single cell with the Fcontaining cathode exhibits an extremely high current density of 2.58 A cm^(-2) at 800℃and 1.5 V,as well as excellent durability over 200 h for direct CO_(2) electrolysis in SOECs.

Photostimulated Luminescence and Optical Storage in Eu ^(2+)-Doped Fluoride-Oxide Glass Ceramics

Photostimulated luminescence (PSL) phenomenon was observed in a fluoride-oxide glass ceramics doped with Eu 2+. When the UV light irradiated glass ceramic was stimulated by a longer wavelength light, PSL at 447 nm due to the 5d-4f transition of Eu 2+ was observed. The PSl excitation band peaking at 543 nm is due to the electron trap centers which are located either in the Eu 2+-doped crystallites or in the glass; where exactly they are located in is not yet known. The optical storage properties of this kind of glass ceramic were also studied. By comparing with the investigations on PSL phosphor Eu 2+ doped alkali halides, PSL mechanism in glass ceramics which is still an open question and has to be investigated in further experiments was explained.

Effects of current density on microstructure and properties of plasma electrolytic oxidation ceramic coatings formed on 6063 aluminum alloy

Plasma electrolytic oxidation (PEO) ceramic coatings were fabricated in a silicate-based electrolyte with the addition of potassium fluorozirconate (K2ZrF6) on 6063 aluminum alloy, and the effects of current density on microstructure and properties of the PEO coatings were studied. It was found that pore density of the coatings decreased with increasing the current density. The tribological and hardness tests suggested that the ceramic coating produced under the current density of 15 A/dm2showed the best mechanical property, which matched well with the phase analysis. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves proved that the coating obtained under 15 A/dm2 displayed the best anti-corrosion property, which was directly connected with morphologies of coatings.