Low-temperature preparation of porous SiC ceramics using phosphoric acid as a pore-forming agent and a binder

Porous SiC ceramics combine the properties of both SiC ceramics and porous materials. Herein, we design a facile method via pressureless sintering at relatively low temperatures for the synthesis of porous SiC ceramics. In the synthesis process, phosphoric acid was used as the sintering additive that reacted with SiO₂ on the surface of SiC to form phosphates. The formed phosphates acted as a binder to connect the SiC particles. At a fixed temperature, the phosphates were partially decomposed and released a large amount of gas. This changed the pore structure of the ceramics and greatly improved their porosity. Finally, we obtained the porous SiC ceramics with high porosity and high strength. We investigate the effects of H₃PO₄ content on the phase composition, microstructure, porosity, mechanical properties and thermal expansion coefficient of the prepared porous SiC ceramics. It was shown that at the sintering temperature of 1200 °C, the highest porosity of the samples can reach 70.42% when the H₃PO₄ content is 25 wt%, and their bending strength reaches 36.11 MPa at room temperature when the H₃PO₄ content is 15 wt%. In addition, the porous SiC ceramics show good high-temperature stability with a bending strength of 42.05 MPa at 1000 °C and the thermal expansion coefficient of 3.966 × 10⁻⁶/°C.     

Development of compositions of highly refractory mortars

A composition of corundum mortar with a binder of technical Na(PO₃)_n or a composite binder of aqueous solutions of technical Na(PO₃)_n and Na₃PO₄ · 12H₂O is suggested. A mortar with a basic composition with a sintering additive of Na₅P₃O₁₀ is presented. Translated from Ogneupory i Tekhnicheskaya Keramika, No. 4, pp. 36–38, April, 2000.     

Preparation of porous SiC-Al2O3 ceramics via gelcasting utilising a shrinkable pore-forming agent and oxidised coarse-grained SiC

By utilising soaked millet as a shrinkable pore-forming agent, porous silicon carbide-alumina (SiC-Al₂O₃) ceramics were prepared via gelcasting. The fabrication of SiC-Al₂O₃ ceramics based on oxidised and unoxidised coarse-grained SiC was also studied. The water swelling, drying shrinkage, and low-temperature carbonisation of the millet were investigated. We found that the shrinkage of the soaked millet was greater than that of gel body during drying, which left large gaps that prevented shrinkage stresses from destroying the gel body. Low-temperature carbonisation of the millet should be performed slowly at 220–240?°C because its expansion rate increases to 45% at 250?°C, resulting in the cracking of samples. At a constant sintering temperature, the flexural strength of the SiC-Al₂O₃ ceramics prepared with SiC powders oxidised at 1000?°C was the highest, indicating that oxidised powders can successfully decrease the required sintering temperature and improve the flexural strength of composite ceramics. Based on our optimised process, porous SiC-Al₂O₃ ceramics were sintered at 1500?°C for 2?h. When their skeletons were fully developed, their pore sizes were in the range of 1.5–2?mm. Their porosity and flexural strength were 60.2–65.1% and 8.3–10.5?MPa, respectively.     

An economic and environment friendly way of recycling boron carbide waste to prepare B4C/Al composite ceramic

Recently, with the rapid growth of sapphire wafer applications, boron carbide as abrasive, has shown an increasing demand. Great amounts of boron carbide waste (low purity and small grain size with D₅₀ ≈ 1 μm) are therefore produced during the production of boron carbide abrasives and barely recovered and utilized. This paper is aimed at developing an economic and environment friendly process to recycle the boron carbide waste through adding a certain amount of Al powder to prepare B₄C/Al composite ceramic. Prior to the sintering process, samples were firstly mixed with different Al powder and then pelleted and dehydrated. The effects of the pelletizing factors on performances of the pellets and the ceramics were optimized as binder hydroxypropyl methylcellulose addition 0.4%, pelleting pressure 30 MPa, Al addition 9 wt%, sintering time 90 minutes. Under these conditions, the apparent porosity, bulk density, compressive strength and flexural strength of the sintered B₄C/Al are 19.08%, 1.84 g/cm³, 246.88 MPa and 71.10 MPa respectively. Al addition can not only attribute to the low-temperature liquid sintering and densification of the product, but also generation of some stable phases including AlB₁₂, AlB₁₂C₂ and Al₃BC, which in turn increase the performance of the ceramic composite.     

Low-temperature sintering of Al2O3 ceramics doped with 4CuO-TiO2-2Nb2O5 composite oxide sintering aid

Dense alumina ceramics doped with 5 wt% 4CuO-TiO₂-2Nb₂O₅ composite sintering aids were obtained at low sintering temperatures of 950∼975 °C. The ceramic sintered at optimal condition shows good microwave dielectric properties (ε_r = 12.7, Q × f = 7400 GHz), high thermal conductivity (18.4 W/m K) and high bending strength (320 MPa). TEM and EDS analysis revealed that amorphous Cu-Ti-Nb-O interfacial films with nanometer thickness formed at the grain boundaries, which could provide paths of mass transportation for densification. Al³⁺ ions may be involved in mass transportation through substitution by Ti³⁺ and Ti⁴⁺ ions near the grain boundary during the sintering process. The accumulation of copper ions at the trigeminal grain boundary was observed. The migration and reaction of copper ions in grain boundaries may also play an important role in promoting mass transportation and low-temperature densification of alumina ceramics.     

Direct ink writing of aluminum-phosphate-bonded Al2O3 ceramic with ultra-low dimensional shrinkage

Three-dimensional (3D) printing of ceramics has attracted increasing attention in various fields. However, the pyrolysis of organic components used for binding or polymerization in 3D printing commonly causes a large shrinkage (up to 30 %–40 %), high porosity, and cracking or deformation, severely limiting practical applications. In this study, 3D printing of Al₂O₃ ceramic architectures with ultra-low shrinkage is realized by introducing inorganic binder aluminum dihydrogen phosphate (Al(H₂PO₄)₃, AP) as a ceramic precursor. Compared to organic binders, the inorganic AP binder can undergo crystallization conversion, which reduces mass loss during sintering at high temperatures, resulting in low shrinkage. Moreover, AP can be used as a rheological modifier to regulate the printability of the ceramic ink for direct ink writing of Al₂O₃ ceramic architectures, such as wood-piled scaffolds, honeycomb structures, and tubes with high fidelity. The resultant Al₂O₃ structural ceramics sintered at 1250 °C exhibit good mechanical performance and structural integrity. Most importantly, the linear shrinkage of the printed ceramics is less than 5 %, which is several times lower than that of ceramics with organic binders. This study provides a viable strategy for fabricating high-performance ceramic architectures with good dimensional fidelity for practical applications.     

Phase evolution and microstructure of new Sr0.5Zr2(PO4)3-NdPO4 composite ceramics prepared by one-step microwave sintering

Sodium Zirconium Phosphate (NaZr₂(PO₄)₃, hereinafter NZP) and monazite are both potential materials for immobilization of nuclear waste. In this work, novel (1-x)Sr_0.5Zr₂(PO₄)₃-xNdPO₄ composite ceramics (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) for simultaneously immobilizing the simulated fission product (FP) Sr and trivalent minor actinide (MA) Nd were prepared by one-step microwave sintering technique, in which Sr and Nd were immobilized into NZP and monazite type structures, respectively. The phase evolution and microstructure of the samples were investigated by X-ray diffraction (XRD), Raman, and backscattering scanning electron microscopy (BSE). The results showed that the expected composite ceramics were successfully obtained by one-step microwave sintering at 1050 °C for 2 h. The as-prepared samples consisted of Sr_0.5Zr₂(PO₄)₃ and NdPO₄ phases, and the content of the two phases varied regularly as x changed, generally conforming to the designed nominal chemical composition. Importantly, the composite ceramics presented the homogenous and dense microstructure. The relative density of the composite ceramics was more than 95%, meanwhile, the Vickers-hardness of the samples was higher than 600 MPa. It was indicated that NZP-monazite type composite ceramics could be a potential matrix for the simultaneous immobilization of actinide and fission product.     

Facile preparation of BN coatings on graphite substrates and their binding strength

To decrease the curing temperature and achieve excellent binding strength of BN coatings on graphite substrates, a proper Al(H₂PO₄)₃ binder has been carefully designed where MgAl₂O₄ and poly vinyl alcohol (PVA) were used as the curing agent and the dispersant, respectively. XRD, SEM, TEM and DSC showed that the desired binding phase AlPO₄ had been successfully obtained, where MgAl₂O₄ and PVA worked synergistically to lower the curing temperature down to 70–100 °C and promote the formation of AlPO₄. Such optimized binder might have formed hydrogen bond with –NH₂ and –OH groups on the BN flakes. It might also form hydrogen bond with-OH and –COOH groups on graphite substrates to ensure an optimal binding strength of 5.5 N (～22 MPa) as suggested by the scratch tests. This work affords a better understanding on the curing chemistry of Al(H₂PO₄)₃ and the binding mechanism between BN flakes, AlPO₄ binding phases and graphite substrates.     

Silicon Nitride Ceramics Prepared by Vibratory Casting of Self-Reinforced Mixtures: Testing for Crack Resistance

Technological factors capable of influencing the structure, physicomechanical properties, and crack resistance of silicon nitride ceramics intended for fabrication of component of complex shape are considered. The effect of a composite sintering aid Al₂O₃ + Y₂O₃ and an ethyl silicate binder on strength and crack resistance of raw and sintered ceramics subjected to hydrostatic compression is discussed. It is shown that the ceramics in question can be tested for crack resistance by the indentation method.     

Influence of co-doped alumina on the microstructure and radioluminescence of SrHfO3:Ce ceramics

SrHfO₃:Ce and SrHfO₃:Ce,Al powders were prepared by the solid-state synthesis using the commercial HfO₂, SrCO₃, CeO₂ and α-Al₂O₃ as the starting materials. All the SrHfO₃:Ce and SrHfO₃:Ce,Al powders calcined at different temperatures within 1100 °C–1300 °C for 8 h in air exhibited a pure SrHfO₃ phase. Meanwhile, the effects of different calcination temperatures and co-doped alumina on the microstructure of SrHfO₃:Ce,Al powders were discussed. SrHfO₃:Ce and SrHfO₃:Ce,Al ceramics were successfully fabricated via the vacuum sintering at 1800 °C for 20 h. The alumina acted as the sintering aid, which promoted the densification and eliminated the intragranular pores of SrHfO₃:Ce,Al ceramics. The charge disbalance was effectively compensated by co-doped alumina. SrHfO₃:Ce,Al ceramics exhibited a higher light yield of 5700 ph/MeV compared with 4600 ph/MeV obtained in SrHfO₃:Ce ceramics. The charge traps in ceramics and their effects on scintillation properties were also investigated by thermoluminescence measurement.     

Fabrication of translucent alumina ceramics from pre-sintered bodies infiltrated with sintering additive precursor solutions

Translucent alumina ceramics were fabricated by infiltrating aqueous solutions containing sintering dopant ions (Mg²⁺/Y³⁺/La³⁺) into pre-sintered alumina compacts and sintering in H₂ atmosphere. The improved microstructural homogeneity, finer grain size and enhanced transmission properties of infiltration processed samples over those processed by conventional ball-milling method were corroborated by experimental results. Triple doping via infiltration appears to be significantly beneficial for achieving enhanced transmission (36.3% at wavelength 800 nm for sample thickness of 0.75 mm). This study indicates that infiltration technique can be used to fabricate translucent alumina ceramics with improved performance.     

Pressure-less joining of alumina ceramics by the reaction-bonded aluminum oxide (RBAO) method

The present work demonstrates a pressure-less and reliable joining technique for alumina ceramics through a reaction-bonded aluminum oxide (RBAO) method. Effective joining relies on the RBAO mechanism, in which Al particles are converted to alumina through oxidation and bond with alumina particles from the parts to be joined upon sintering. Alumina ceramics in a green state were successfully joined with the use of an Al/Al₂O₃ powder mixture as an interlayer. The oxidation behavior of the Al particles was confirmed by thermogravimetry and X-ray diffraction analyses. Joining was performed in ambient air at 1650 °C for 2 h without applying any external pressure. Microstructural observations at the joining interfaces indicated a compact joining. The joining strengths were assessed by determining the biaxial strengths at room temperature, and the joined samples exhibited no fractures at the joining interfaces. Moreover, the joints had a strength of almost 100 % when compared with those of the parent alumina ceramics.     

Fabrication of magnesium aluminate (MgAl2O4) spinel foams

This paper reports on a novel-processing route for fabricating magnesium aluminate (MgAl₂O₄) spinel (MAS) foams from aqueous suspensions containing 30–35 vol.% solids loading. A stoichiometric MAS powder formed from alumina (71.8%) and magnesia (28.2%) at 1400 °C was surface passivated against hydrolysis in an ethanol solution of H₃PO₄ and Al(H₂PO₄)₃ at 80 °C for 24 h. Stable aqueous suspensions with 30–35 vol.% solids loading were prepared using the surface passivated MAS powder with the help of tetra-methylammonium hydroxide (TMAH) and an ammonium salt of polyacrylic acid (Duramax D-3005) employed as dispersing agents. An aqueous solution of N-cetyl-N,N,N-trimethylammonium bromide (CTMAB) was utilized to create foam in aqueous MAS suspensions by mechanical frothing. Liquid foam was then consolidated in non-porous moulds by introducing a polymerization initiator and a catalyst under ambient conditions. Dried (at >90 °C for 24 h) MAS foams were then sintered for 1 h at 1650 °C. For comparison purposes, dense MAS bodies out of an un-passivated stoichiometric MAS powder, and, dense as well as foams out of alumina were also prepared in this study. The sintered properties of MAS and alumina ceramics were characterized by various means and thus obtained results are presented and discussed in this paper. The sintered MAS foams exhibited a porosity of about 74–76% and a compressive strength of about 4–7.2 MPa inline to values reported for other ceramic foams in the literature.     

Tensile strength and corrosion resistance properties of porous Al2O3/Ni composites prepared with rice husk pore-forming agent

The mechanical performance and chemical stability of porous alumina materials operating under harsh service conditions are of utmost importance in understanding their operational behavior if they are to stand the test of time. In the present study, the joint effect of nickel (Ni) reinforcement and rice husk (RH) pore-forming agent (PFA) on the tensile strength and the corrosion resistance properties of composite porous alumina ceramics was studied. To exploit the potential of this new porous alumina system, plain and Ni-reinforced porous alumina samples (Al₂O₃-xNi-RH; x?=?2, 4, 6 and 8?wt%) were developed through the powder metallurgy technique. Comprehensive investigation on the tensile strength properties of the developed porous alumina ceramics showed that relative to the plain sample (tensile strength and elastic modulus; 6.1?MPa and 1201?MPa), the presence of highly stable Ni₃Al₂SiO₈ spinelloid promoted the tensile strength enhancement (12.6–6.4?MPa) and the elastic modulus decline (897–627?MPa) of the composite samples. Similarly, corrosion resistance test was performed on the composite porous alumina samples in both 10?wt% NaOH and 20?wt% H₂SO₄ hot aqueous solutions. Overall, the composite samples demonstrated superior chemical stability in NaOH solution as compared with the plain sample. On the other hand, the composites were more prone to attack in H₂SO₄ solution, except for the Al₂O₃-2Ni-10RH composite sample which maintained its superiority over the plain counterpart.     

Preparation and Performance Study of Sialon‐Si3N4‐SiC Composite Ceramics for Concentrated Solar Power

For lowering the sintering temperature of silicon carbide ceramics used for solar thermal energy storage technology, O'‐Sialon and silicon nitride were employed as composite phases to construct Sialon‐Si₃N₄‐SiC composite ceramics. The composite ceramics were synthesized using SiC, Si₃N₄, quartz, and different alumina sources as starting materials with noncontact graphite‐buried sintering method. Influences of alumina sources on the physical properties and thermal shock resistance of the composites were studied. The results revealed that the employment of O'‐Sialon and silicon nitride could decrease the sintering temperature greatly to 1540°C. The optimum formula G2 prepared from mullite as alumina source achieved the best performances: 66.7 MPa of bending strength, 10.0 W/(m·K) of thermal conductivity. The composition parameter x = 0.4 of O'‐Sialon decreased to 0.04 after 30 cycles thermal shock, and the bending strength increased with a rate of 11.0% due to the increase of O'‐Sialon grain size, and the optimization of microstructure caused by the transformation of O'‐Sialon grains and densification within the samples. The good thermal shock resistance makes the composites suitable for the use as thermal storage materials of concentrated solar power generation.     

Synthesis and sintering of a monazite–brabantite solid solution ceramics using metaphosphate

In order to improve monazite-based ceramics, to be used as actinides waste-form, a procedure for synthesis and sintering of a monazite–brabantite solid solution (ssMB) using metaphosphate La(PO₃)₃ is described. Using LaPO₄, CeO₂, ThO₂, CaCO₃ and La(PO₃)₃ as precursors, the gaseous emissions are strongly reduced, compared to a process using (NH₄)H₂PO₄. Detailed dilatometric studies show sintering of that product is a two-steps process: coalescence and boundary diffusion. From X-ray diffraction, electron microprobe analyses, SEM observation, dilatometric study and TG–DTA, the reaction scheme is identified and the thermal treatment for synthesis and sintering is optimized to obtain homogeneous, dense, reproducible and well-crystallized pellets of La_0.73Ce_0.09Th_0.09Ca_0.09PO₄ and La_0.91Ce_0.09PO₄.     

Non-shrinkage porous ceramics by In-situ hollow sphere method based on the Kirkendall effect of Al particle

The significant shrinkage of porous ceramics after sintering has produced a number of issues with their use and development. As a result, we proposed an in-situ hollow sphere method for producing non-shrinkage alumina porous ceramics. The obtained green samples were made up of Al₂O₃ and Al powders, with pores emerging inside the materials due to the Kirkendall effect of Al particles after sintering. The expansion of hollowing particles exactly offsets the shrinkage generated by sintering throughout the process. When 50 vol. % Al powder (10 µm) is added, the linear shrinkage rate of the sample after sintering at 1500 °C can reach −3.47 %, and its apparent porosity and flexural strength are 30.69 % and 44.03 MPa, respectively. According to approximate calculations, the pores formed by the oxidation of Al powder are smaller than the initial size of Al powder. This method suggests a novel approach for producing controlled shrinkage porous ceramics.     

Fabrication of high strength Li-rich 2Li2TiO3–Li4SiO4 composite breeding ceramics at low-temperature by two-step sintering

In this study, Li-rich 2Li₂TiO₃–Li₄SiO₄ composite breeding ceramics were prepared for the first time through a two-step low-temperature sintering route to meet the increasingly stringent performance requirements of tritium breeding materials. The effects of excess Li addition and sintering atmosphere on the phase composition, mechanical properties, and microstructure of the composite breeding ceramics were systematically studied. A two-step low-temperature sintering method was proposed to integrate the advantages of different sintering environments. The results show that moderate Li addition can significantly enhance the crushing load of composite ceramics while maintaining the nanostructure. However, further increasing the amount of Li addition does not continue to increase the crushing load, and will even affect the structural uniformity of the composite breeding ceramics. Most importantly, the S2.5 (2Li_2.5TiO₃–Li₄SiO₄, molar ratio) composite breeding ceramics sintered at 750 °C in an air-vacuum environment exhibited a grain size of ～86 nm and a crushing load of ～66.9 N, which has not been achieved by previous studies.     

Ultrafine-grained β-Sialon fabricated by two-stage sintering and study on diffusion toughening of Ti–22Al–25Nb

The ultrafine-grained β-Sialon ceramics were fabricated by spark plasma sintering at different temperatures with inorganic Al₂O₃–Y₂O₃ and Ti–22Al–25Nb intermetallic powder as composite additives. The research showed that β-Sialon ceramics achieve two-stage sintering densification. Al₂O₃–Y₂O₃ inorganic additives promoted the synthesis and densification of β-Sialon ceramics at 1125–1215°C. Ti–22Al–25Nb intermetallic powder diffused Ti and Nb elements at 1240–1425°C, thereby improving the fracture toughness of β-Sialon ceramics. The maximum fracture toughness (∼9.69 MPa m^1/2) under 19.6 N was obtained for β-Sialon ceramics sintered at 1600°C.