Manufacturing B4C parts with Ti-Al intermetallics by aqueous colloidal processing

The aqueous colloidal processing of submicrometre B₄C powder (∼0.6 μm) with coarse Ti-Al powder (∼40 μm) as sintering additive was investigated. Firstly, by measuring the zeta potential, pHs were identified that promote the individual colloidal stability of the B₄C and Ti-Al particles as well as their co-dispersion in water with two different deflocculants (one anionic and the other cationic). It was found that the anionic and cationic deflocculants shift the isoelectric points of B₄C and Ti-Al to more acidic and more basic pHs, respectively, making their co-dispersion possible at neutral pH. And secondly, by means of rheological studies, conditions were identified (sonication time, deflocculant type, and deflocculant content) that at quasi-neutral pH yield B₄C + Ti-Al shear-thinning concentrated suspensions (30 vol.% total solids) with low viscosity and small hysteresis loop. Interestingly, those deflocculated with the cationic polyelectrolyte had better rheological behaviour, being also less viscous and almost non-thixotropic. These suspensions were freeze-dried, obtaining powder mixtures that were compacted by conventional spark plasma sintering (SPS), and also slip-cast, obtaining robust green pieces that were densified by pressureless SPS. The two B₄C composites thus obtained are superhard, with Vickers hardnesses greater than 30 GPa.     

Pressureless ultrafast sintering of near-net-shaped superhard isotropic B4C/rGO composites with Ti-Al additives

Superhard composites of B₄C reinforced with randomly-oriented reduced graphene oxide (rGO) nanoplatelets are manufactured by a near-net-shape fabrication route based on three successive steps. Firstly, aqueous colloidal processing is used for the environmentally-friendly preparation of a semi-concentrated multi-component slurry (B₄C as main component, Ti-Al as sintering additive, and rGO as toughening reinforcement), whose suitability for wet shaping is demonstrated by rheological measurements. Secondly, slip casting is used to produce robust green parts with shapes on demand and microstructures free of macro- and micro-defects. And thirdly, pressureless spark-plasma sintering (PSPS) is used for the ultrafast and energy-efficient densification of the green parts with shape retention. Measurements of shrinkage and hardness, as well as the microstructural observations, are used to identify suitable PSPS temperatures leading to obtaining isotropic B₄C/rGO composites that are superhard and almost twice as tough as the monolithic B₄C ceramics.     

Mechanical Properties of Gd‐CeO2 Electrolyte for SOFC Prepared by Aqueous Tape Casting

Mechanical properties of gadolinium‐doped ceria (Ce_0.9Gd_0.1O_1.95, 10GDC) green tape prepared by aqueous‐based tape casting process were characterized by tensile test and shear punch test (SPT). SPT was found to be a useful method for characterizing mechanical properties of green tapes. Microstructures and mechanical properties such as flexural modulus, bending strength, and microhardness of tapes sintered at 1,300–1,500 °C have been evaluated. Indentation fracture toughness was also determined by the method of Palmqvist cracks at different applied loads for tapes sintered at 1,500 °C. Grain size measurements showed that excessive grain growth occurred during sintering despite using 10GDC nanopowders as the starting material. However, mechanical properties of sintered tapes improved by increasing sintering temperature and the results are comparable with those reported for 10GDC in literature.     

Aqueous tape casting of B4C ceramics

B₄C green tapes are prepared by aqueous tape casting and a spark plasma sintering (SPS) process using polyethylenimine (PEI) as dispersant, hydroxypropyl methyl cellulose (HPMC) as binder and polyethylene glycol (PEG) as plasticiser. The influences of solid content, dispersant content, mass ratio of plasticiser to binder (R value) and milling time on the slurry viscosity are studied. The samples are characterised by means of hardness tester, universal testing machine and scanning electron microscopy. The results indicate that the solid content of B₄C slurry achieves 47.5?wt-% with milling time of 12?h when the content of PEI, HPMC and PEG is 1.5, 5 and 5?wt-%, respectively. The relative density of B₄C ceramics subject to SPS at 1600°C and 50?MPa for 8?min is up to 97.2%. The Vickers hardness, flexural strength and fracture toughness of B₄C ceramics reach 36.5?±?0.7?GPa, 510.3?±?19.4?MPa and 5.04?±?0.29?MPa?m^?1/2, respectively.     

Fabrication of B4C ultrafiltration membranes on SiC supports

The fabrication of B₄C ultrafiltration membranes is described. Firstly, a semi-dilute B₄C slurry was environmentally-friendly prepared by aqueous colloidal processing, optimizing its dispersion by sonication, and used to deposit B₄C membranes onto SiC macro-porous supports by dip-coating. Secondly, the resulting green membranes were characterised microstructurally by scanning electron microscopy (SEM), and pressureless sintered within the intermediate sintering regime. Thirdly, the sintered membranes were calcined in air to clean them from possible free carbon in the smallest pores, with the optimal calcination conditions having been identified by thermogravimetry coupled with mass spectrometry. Next, the calcined, sintered membranes were characterised microstructurally by SEM, tested mechanically against scratching, and characterised texturally by capillary flow porometry, thus identifying the optimal among them. Lastly, as a complement to the fabrication study, the filtration permeability of the optimal membrane was evaluated using deionized water. This work thus paves the way towards the fabrication of ceramic membranes based on B₄C, lighter and potentially more durable than others, for filtration applications.     

Processing of orthotropic and isotropic superhard B4C composites reinforced with reduced graphene oxide

A fabrication route based on aqueous colloidal processing plus transient liquid-phase assisted spark-plasma-sintering (SPS) with Ti-Al additives is described for the environmentally friendly obtention of superhard B₄C composites reinforced with reduced graphene oxide (rGO) having orthotropic and isotropic microstructures. It is shown that the former, which have coarse rGO platelets preferentially aligned perpendicular to the SPS pressing direction, can be prepared from mixtures of B₄C and Ti-Al particles with a source of thick, large rGO nanoplatelets by imposing smooth co-dispersion conditions to avoid platelet re-exfoliation and fragmentation. The latter, which have fine rGO platelets randomly oriented, can be fabricated from mixtures of B₄C and Ti-Al particles with a source of thin, small rGO nanoplatelets by applying intensive sonication to promote platelet re-exfoliation and fragmentation during co-dispersion. Finally, it is shown that these orthotropic and isotropic B₄C/rGO composites are equally superhard, and that, as expected, their microstructures interact differently with the cracks. Finally, this processing route is simple, and easily adaptable/extensible to make other ceramic/rGO composites with orthotropic and isotropic microstructures.     

Transient liquid-phase assisted spark-plasma sintering and dry sliding wear of B4C ceramics fabricated from B4C nanopowders

With the motivation of developing B₄C composites with superior wear resistance for tribological applications, an ultrafine-grained (～200?300 nm) B₄C composite was fabricated, characterized microstructurally, and tested mechanically and tribologically. First, a well-dispersed powder mixture of B₄C nanopowders (～40 nm) with coarse Ti-Al powders (～38 μm) as transient liquid-phase sintering additives was environmentally-friendly prepared by aqueous colloidal processing, optimized by measurements of the zeta potential of dilute suspensions and rheological studies of concentrated suspensions. Second, the powder mixture obtained by freeze-drying was densified by spark-plasma sintering (SPS), identifying the optimal SPS temperature (1850°C) by measurements of density, hardness, and toughness. Third, the dry sliding-wear behaviour of the optimal superhard B₄C composite (～31.5 GPa) was investigated by pin-on-disk tests and observations of the worn surface, determining its specific wear rate (～4.4·10^?8 mm³/(N·m)) as well as wear mode (two-body abrasion) and mechanism (plastic deformation). And lastly, the wear behaviour of the ultrafine-grained B₄C composite was compared with that of a reference fine-grained (～0.7?0.9 μm) B₄C composite, finding that both have the same mode and mechanism of wear but with the former being more resistant than the latter (～2.3·10⁷ vs 1.9·10⁷ (N·m)/mm³). Implications for the fabrication of B₄C tribocomponents with greater superior wear resistance are discussed.     

Aqueous and Nonaqueous Colloidal Processing of Difficult‐to‐Densify Ceramics: Suspension Rheology and Particle Packing

Aqueous and nonaqueous colloidal processing of zirconium diboride (ZrB₂) and boron carbide (B₄C) has been investigated. The aqueous and nonaqueous ZrB₂ and B₄C suspension formulations have been optimized. The suspensions were cast into green bodies using slip casting. The correlation between the state of dispersion with the rheological properties of the suspensions and the resulting packing density was observed in both aqueous and nonaqueous processing. The attractive interactions between powder particles in water were difficult to overcome with electrical double layer or electrosteric repulsion. Reasonably low viscosity aqueous ZrB₂ suspensions up to 45 vol% solids could be prepared. It was not possible to produce low viscosity (viscosity below 1 Pa·s at shear rate of 100 s^?1) aqueous B₄C suspensions with solid content above 30 vol%. Slip casting of the weakly aggregated ZrB₂ suspensions resulted in low packing densities (~55% relative density) of the green bodies. On the other hand, dispersion of powder particles in nonaqueous media (cyclohexane and dodecane) enabled suspensions with lower viscosities and a higher maximum solid concentration (up to 50 vol%) to be prepared. The well‐dispersed nonaqueous suspensions promoted an efficient particle packing, resulting in higher green densities (64% and 62% relative density for ZrB₂ and B₄C, respectively) compared to aqueous processing. The significantly high green densities are promising to allow densification of the materials at lower sintering temperature.     

Near-net shape manufacture of B4C–Co and ZrC–Co composites by slip casting and pressureless sintering

Fabrication of near-net shaped B₄C–Co and ZrC–Co composites by slip casting and pressureless sintering is described. It is shown how B₄C–Co and ZrC–Co concentrated suspensions can be prepared by aqueous colloidal processing, and optimized (in terms of pH, deflocculant contents, and sonication time) to have a shear-thinning rheological behaviour suitable for the near-net shaping of the corresponding cermet compacts by slip casting. It is also demonstrated that the robust, highly-dense compacts so obtained have a uniform green microstructure without macro-defects or gradient density, and which can be fully densified by pressureless sintering. Specifically, it is shown that B₄C–Co compacts densify by reactive and transient liquid-phase sintering, thus resulting in multi-component ceramics. ZrC–Co compacts densify however by persistent liquid-phase sintering, thus resulting in cermets. An explanation is given for these observations, and general implications are discussed for the near-net shape manufacture of these and similar carbide-metal composites for use in engineering applications.     

Improving the dry sliding-wear resistance of B4C ceramics by transient liquid-phase sintering

A critical comparison is made between the dry sliding-wear resistance of a B₄C composite fabricated by transient liquid-phase sintering with Ti-Al intermetallic additive and two reference monolithic B₄C ceramics fabricated by solid-state sintering. It is shown that, as a consequence of its full densification and super-hardness, the B₄C composite is, despite containing secondary phases, markedly more wear resistant (significantly lower coefficient of friction, specific wear rate, worn volume, and wear damage) than the reference monolithic B₄C ceramic fabricated under identical spark-plasma-sintering (SPS) conditions, and at least as wear resistant as the reference monolithic B₄C ceramic fabricated at much higher SPS temperature. In all materials, wear is nonetheless mild and occurred by two-body abrasion dominated by plastic deformation at the micro-contact level plus, in the porous reference monolithic B₄C ceramic, three-body abrasion dominated by fracture. Implications for the lower-cost manufacture of superhard B₄C tribocomponents are discussed.     

Colloidal Processing of Glass–Ceramics for Laminated Object Manufacturing

Green tapes of Li₂O–ZrO₂–SiO₂–Al₂O₃ (LZSA) parent glass were produced by aqueous tape casting as the starting material for the laminated object manufacturing (LOM) process. The rheological behavior of the powder suspensions in aqueous media, as well as the mechanical properties of the cast tapes, was evaluated. According to ξ potential measurements, the LZSA glass powder particles showed acid surface characteristics and an IEP of around 4 when in aqueous media. The critical volume fraction of solids was about 72 wt% (27 vol%), which hindered the processability of more concentrated slurries. The glass particles also showed an anisometric profile, which contributed to an increase in the interactions between particles during flow. Therefore, the suspensions could not be processed at high solids loadings. Aqueous-based glass suspensions were also characterized by shear thickening after the addition of dispersants. Three slurry compositions were formulated, suitable green tapes were cast, and tapes were successfully laminated by LOM to a gear wheel geometry. A higher tensile strength of the green tapes corresponded to a higher tensile strength of the laminates. Thermal treatment was then applied to the laminates: pyrolysis at 525°C, sintering at 700°C for 1 h, and crystallization at 850°C for 30 min. A 20% volumetric shrinkage was observed, but no surface flaws or inhomogeneous areas were detected. The sintered part maintained the curved edges and internal profile after heat treatment.     

Fabrication of textured B4C ceramics with oriented tubal pores by strong magnetic field-assisted colloidal processing

Highly structure-controlled B₄C ceramics were prepared via strong magnetic field-assisted slip casting of a slurry, containing B₄C base particles and pore-forming agents with a fiber shape. To achieve gas release at a lower porosity for maintaining its mechanical strength, these B₄C ceramics had a structure in which a large number of oriented tubal pores were dispersed in a crystallographically-aligned and dense B₄C matrix phase. The B₄C microstructure, such as structuration and orientation degree distributions of the B₄C grains and tubal pores, was characterized by SEM observation, EBSD analysis, and X-ray CT. Among the investigations, it was found that the oxidic impurities, as an inhibitor of sintering, which existed on the B₄C surface, can be removed by ethylation and azeotropy due to an ethanol treatment followed by vacuum drying. Thus, an ethanol treatment of a green compact before sintering was significantly effective for the fabrication of the B₄C ceramics, including the microstructure that coexisted with a dense matrix phase with tubal pores. The resultant ceramic specimens showed the remarkable three-point bending strength of 459?554 MPa, which is two times higher when compared to conventional B₄C pellets with a similar porosity.     

Influences of Solid Loadings on the Microstructures and the Optical Properties of Yb:YAG Ceramics

Transparent Y_2.85Yb_0.15Al₅O₁₂ ceramics were prepared using an aqueous tape casting and vacuum sintering method. The rheological properties were measured by a rheometer. The results indicate high quality tapes, and ceramics can be obtained by increasing the solid loading of the corresponding slurries. The densities of the tapes increase from 2.42 to 2.69 g/cm³ by increasing the solid loadings from 35 to 50 vol%. The corresponding green body densities range from 52.7 to 57.1% of the theoretical. The solid loading suitable for fabricating transparent Yb:YAG ceramics should be higher than 45 vol%.     

Tape casting of PLZST tapes via aqueous slurries

A well-dispersed aqueous slurry for tape casting of PLZST (Pb_0.97La_0.02Zr_0.66Sn_0.23Ti_0.11) was prepared. Properties of PLZST slurries with and without polyelectrolyte dispersant were characterized by zeta potential, sedimentation etc. The experimental results show that the pH value of the slurries is changing with ball-milling time, and that the polyelectrolyte dispersant has a significant effect on the isoelectric point of PLZST. TGA analysis indicates that the organic additives in the green tapes can be completely removed by heat treatment at 600 °C. The density of PLZST ceramics is tightly related to the plasticizer and the sintering temperature. However, the results demonstrated that it is possible to prepare a dense PLZST thick film through aqueous slurry tape casting.     

Sintering behavior,microstructure and thermoelectric properties of calcium cobaltite thick films for transversal thermoelectric multilayer generators

The sintering behavior and the thermoelectric performance of Ca₃Co₄O₉ multilayer laminates were studied, and a multilayer thermoelectric generator was fabricated. Compacts and multilayer samples with anisotropic microstructure and residual porosity were obtained after conventional sintering at 920 °C, whereas dense and isotropic multilayer samples were prepared by firing at 1200 °C and reoxidation at 900 °C. A hot-pressed sample has a dense and anisotropic microstructure. Samples sintered at 920 °C exhibit low electrical conductivity due to the low density, whereas the Seebeck coefficient is not sensitive to preparation conditions. However, thermal conductivity of multilayers is very low, and, hence acceptable ZT values are obtained. A transversal multilayer thermoelectric generator (TMLTEG) was fabricated by stacking layers of Ca₃Co₄O₉ green tapes, AgPd conductor printing, and co-firing at 920 °C. The TMLTEG has a power output of 3 mW at ΔT = 200 K in the temperature interval of 25 °C to 300 °C.     

Production of Si3N4/Glass Composites for LTCC Substrate by Aqueous Tape Casting Process

In this work, Si₃N₄/glass sheets were prepared by aqueous tape casting, and the preparation process and properties of green and sintered tapes were discussed thoroughly. The effect of Si₃N₄ content on the rheological behavior of the slurries was investigated, and the results showed that the viscosity of the slurry increased with the solid loading and all the slurries exhibited shear‐thinning behavior within the entire range of shear rate. Green tapes were fabricated successfully by aqueous tape casting which have excellent properties such as uniform pore distribution, low porosity, and high bulk density. The sintered samples exhibited low shrinkage, and low dielectric constant and loss.     

The wear resistance of Ni alumina and NiAl2O4 alumina nanocomposites

The influence of metallic Ni or NiAl₂O₄ as a reinforcing particle on grain growth and wear resistance in alumina matrix composites was evaluated. Alumina composites with various Ni or NiAl₂O₄ concentrations were prepared by multiple-infiltrations of Ni-nitrate into bisque-fired (necked) alumina green bodies followed by heat treatment and sintering at 1600 °C for 2 h. Sintering in a reducing environment resulted in composites with metallic Ni nanoparticles, while NiAl₂O₄ alumina composites were formed when sintering in air. The addition of Ni or NiAl₂O₄ resulted in a reduction in alumina grain size after sintering. The material response to abrasive wear was estimated by measuring the time to section samples of a defined area using a diamond wafering saw and was compared to the wear resistance of undoped alumina. In both cases, reinforcing alumina with Ni or NiAl₂O₄ particles resulted in a significant increase in wear resistance, correlated to the reduced grain size.     

Porous YbB6 Ceramics Prepared by In Situ Reaction between Yb2O3 and B4C Combined with Partial Sintering

Porous YbB₆ ceramic, a member of the ultrahigh‐temperature (UHT) family, is successfully prepared from Yb₂O₃ and B₄C powders by in situ synthesis combined with partial sintering method. Due to the fact that pores can be produced using the gases such as B₂O₃ and CO generated in reaction between Yb₂O₃ and B₄C, phase‐pure porous YbB₆ ceramics are obtained after sintering the Yb₂O₃/B₄C green bodies at 1750°C for 2 h in a flowing argon atmosphere under ambient pressure without addition of pore‐forming agent. Using this new and simple method, the porosity and volume shrinkage of porous YbB₆ ceramics are controllable by changing the green density. The prepared porous YbB₆ ceramic has homogeneous pore structure with very narrow pore diameter distribution. Furthermore, the porous YbB₆ possesses high compressive strength of ~21.34 MPa when the porosity is ~58.7% and the density is ~2.27 g/cm³. The combination of these favorable properties renders porous YbB₆ ceramic being a light‐weight structural and functional component for UHT applications.     

Pressureless sintering of high-entropy boride ceramics

High-entropy boride ceramics were densified by pressureless sintering. Green densities of the ceramics varied by composition with the highest green density of 53.6 % for (Hf, Nb, Ta, Ti, Zr)B₂. After pressureless sintering, relative densities up to ∼100 % were obtained for (Cr, Hf, Ta, Ti, Zr)B₂ and (Hf, Ta, Ti, V, Zr)B₂. Two compositions, (Hf, Ta, Ti, W, Zr)B₂ and (Hf, Mo, Ti, W, Zr)B₂ contained secondary phases and did not reach full density. All compositions had average grain sizes less than 10 µm and less than 2 vol % of residual B₄C. This is the first report of conventional pressureless sintering of high-entropy boride ceramics powder compacts without evidence of liquid phase formation.     

Microstructure and properties of aluminum nitride ceramics prepared by aqueous gelcasting method with nontoxic curdlan as gelling agent

Aluminum nitride ceramics were prepared by aqueous gelcasting method and pressureless sintering technique in N₂ atmosphere using Y₂O₃ as sintering additives with nontoxic curdlan as gel system. The solidification mechanism of curdlan was studied. The effects of curdlan content and solid content on the microstructure, relative density and flexural strength of green bodies were investigated. The influences of Y₂O₃ content and sintering soaking time on the microstructure and properties of sintered bodies were also studied. The results show that, as the temperature increases to 80 °C, the ceramic powders solidify through three-dimensional gel networks of curdlan during gelling process. The green bodies can be successfully fabricated through aqueous gelcasting method with modified powder as original materials. Suitable curdlan content and solid content contribute to fabricating green body with uniform microstructures and high flexural strength. The relative density and flexural strength of sintered bodies enhance as the Y₂O₃ content and soaking time increase. The flexural strength and thermal conductivity are about 107.5∼172.3 MPa and 75.2∼112.5 W/(m·K), respectively. The sintered body with 4 wt% Y₂O₃ soaking for 3 h exhibits the highest thermal conductivity because of appropriate relative density, uniform microstructure and reasonable intergranular phase distribution. The mechanical property and thermal conductivity of sintered bodies can be improved by optimizing the gelcasting process parameter, Y₂O₃ content, and soaking time. The nontoxic gelling system will have wide application for aqueous gelcasting ceramic with complex shape.