In situ study on microwave sintering of ZTA ceramic: Effect of ZrO2 content on densification,hardness, and toughness

Better understanding of the effect of multimode‐microwave sintering of zirconia‐toughened alumina (ZTA) was investigated. A comparative dilatometric analysis was conducted between conventional and microwave heating processes, to clarify the influence of zirconia on the densification of ZTA under electromagnetic field. The thermal gradient on sample measurements indicates the change to the microwave volumetric heating is improved by zirconia which adsorbs microwave energy better, thus acting as a susceptor. The most beneficial effect on microstructure, toughness, and hardness were observed at the optimal zirconia content of 10 vol%. The results with both microwave and conventional sintering illustrate the strengthening effect on the composite by zirconia. Of special interest, multimode microwave sintering creates a finer homogeneous microstructure, with resulting hardness and toughening comparable to those obtained for conventional sintering, as well as improved densification, and at lower cost.     

Consolidation of undoped,monoclinic zirconia polycrystals by flash sintering

Consolidated, monoclinic ZrO₂ polycrystal was produced from undoped ZrO₂ powders in air by flash sintering at the sintering temperature of 1350°C for 5 minutes or 3 hours under an applied DC electric field of 175 V/cm. When the ZrO₂ was heated under the applied DC field, the electric current of the specimen steeply increased at the furnace temperature of 1335°C below the sintering temperature of 1350°C. When the furnace temperature was decreased from the sintering temperature of 1350°C to room temperature, volumetric expansion associated with tetragonal‐to‐monoclinic phase transformation gradually took place at the furnace temperature from 1000°C to 750°C, and monoclinic ZrO₂ body was remained consolidated even at room temperature in both specimens. In contrast, conventionally sintered ZrO₂ without applying DC field exhibited the abrupt volumetric expansion at about 1000°C, and shattered. SEM observation revealed the presence of grain‐boundary second phase in the flash‐sintered specimen for 3 hours, which is a possible origin of keeping a bulk body at room temperature. The thinner second phase is considered to be formed also in the flash‐sintered specimen for 5 minutes, although the formation of the phase could not be observed clearly by SEM observation. On the other hand, XRD measurements showed that <001> directions of the monoclinic ZrO₂ grains were oriented along the applied DC field after the isothermal flash sintering for 3 hours while the grain alignment could not be observed in flash‐sintered specimen for 5 minutes. The alignment of ZrO₂ grains observed in the isothermal flash sintering is considered to be closely related to the preferential direction of oxygen ionic conduction and the second phase formed along grain boundaries.     

Flash sintering of yttria-stabilized zirconia powders coated with nanoscale films of alumina by atomic layer deposition

The addition of small quantities of aluminum oxide (Al₂O₃) to 8 mol% yttria-stabilized zirconia (8YSZ) benefits conventional sintering by acting as a sintering aid and altering grain growth behavior. However, it is uncertain if these benefits observed during conventional sintering extend to flash sintering. In this work, nanoscale films of Al₂O₃ are deposited on 8YSZ powders by particle atomic layer deposition (ALD). The ALD-coated powders were flash sintered using voltage-to-current control and current rate experiments. The sintering behavior, microstructural evolution, and ionic conductivities were characterized. The addition of Al₂O₃ films changed the conductivity of the starting powder, effectively moving the flash onset temperature. The grain size of the samples flashed with current rate experiments was ~65% smaller than that of conventionally sintered samples. Measurement of grain size and estimates of sample density as a function of temperature during flash sintering showed that small quantities of Al₂O₃ can enhance grain growth and sintering of 8YSZ. This suggests that Al₂O₃ dissolves into the 8YSZ grain boundaries during flash sintering to form complexions that enhance the diffusion of species controlling these processes.     

In-operando synchrotron experiments of flash sintering carried out in current rate mode

We report first-time results for in-operando flash sintering synchrotron experiments carried out in current rate mode where the specimen, held at a constant temperature, is fed current that is increased at a constant rate. These experiments are unique because the time dependence of the sintering behavior can be stretched out over a longer period (by changing the current rate) than in voltage-to-current experiments in which sintering occurs in a burst at the onset of the flash. Two results are presented: (i) A comparison of temperatures measured with the platinum standard to those predicted by the black body radiation model leading to estimates of the emissivity as a function of porosity whereby emissivity increases from 0.65 to 0.9 as the sample sinters from its green state to full density, and (ii) measurements of the excess lattice expansion as a function of density as the sample sinters continuously while the current is increased. The present work highlights the promise of current rate experiments to obtain results while the sample sinters gradually from its green density to full density (somewhat akin to conventional sintering) for gaining further insights into the mechanisms of flash sintering.     

Onset of selective laser flash sintering of AlN

Flash sintering uses a combination of heating and electric fields to rapidly densify ceramics. Previously, it has been shown that a scanning laser can be used to initiate flash sintering in localized regions on an yttria-stabilized zirconia (YSZ) sample in a process known as selective laser flash sintering (SLFS). In this work, we show using a combination of measurements of electric current flowing through the sample and observations of necks formed between powder particles that aluminum nitride (AlN) can also undergo SLFS. Scan conditions required to initiate SLFS are characterized over a range of laser powers and laser scan speeds in a dry nitrogen environment. It is shown that initiation of SLFS in AlN is governed by both the local input energy density per scan and heat dissipation and a numerical model is developed to predict temperatures during SLFS. Assuming the minimum temperature along the conductive path determines the onset of SLFS, the minimum temperature and time required is 450–670 K in 2–0.25 s for the pressed AlN pellets used in this study for laser scan speeds of 33–300 m/s, laser powers of 10–30 W, and an applied electric field of 3000 V/cm.     

Thermochemical model on the carbothermal reduction of oxides during spark plasma sintering of zirconium diboride

Carbon was used to reduce oxides in spark plasma sintered ZrB₂ ultra-high temperature ceramics. A thermodynamic model was used to evaluate the reducing reactions to remove B₂O₃ and ZrO₂ from the powder. Powder oxygen content was measured and carbon additions of 0.5 and 0.75 wt% were used. A C–ZrO₂ pseudo binary diagram, ZrO₂–B₂O₃–C pseudo ternaries, and Zr–C–O potential phase diagrams were generated to show how the reactions can be related to an open system experiment in the tube furnace. Scanning transmission electron microscopy identified impurity phases composed of amorphous Zr–B–O with lamellar BN and a Zr–C–O ternary model was calculated under SPS sintering conditions at 1900°C and 6 Pa to understand how oxides can be retained in the microstructure.     

Densification kinetics of boron carbide with medium entropy alloy as a sintering aid during spark plasma sintering

The high sintering temperature of pure B₄C considerably limits its widespread application, thus searching an effective sintering aid is critical. In this work, B₄C-based ceramic with 1 vol.% nonequiatomic Fe₅₀Mn₃₀Co₁₀Cr₁₀ medium entropy alloy as a sintering aid were fabricated at 1900-2000°C by spark plasma sintering (SPS) under applied pressure, and their mechanical properties were examined and compared with pure B₄C ceramic sintered at same condition. The maximal flexural strength of 255.59 MPa, microhardness of 2297.6 Hv_0.2 and fracture toughness of 3.62 MPa m^1/2 could be obtained at optimized SPS pressure of 50 MPa, which were all higher than those of pure B₄C ceramic. To better understand the densification kinetics mechanisms, the densification ratio as a function of SPS temperature and pressure was theoretically analyzed using steady creep model. It was found that densification controlled by grain-boundary sliding at lower pressure transferred to power law creep regime at higher pressure, which were proved by the dislocation net shown in transmission electron microscopy image.     

In‐situ measurements of lattice expansion related to defect generation during flash sintering

We report results from in‐situ measurements of lattice expansion during flash sintering of 3 mol% yttria stabilized tetragonal zirconia taken at the Advanced Photon Source, Argonne National Laboratory. The expansion is anisotropic, with the relative expansion of the a‐lattice constant exceeding that of the c‐lattice constant. The anisotropic expansion cannot be explained by thermal expansion and is consistent with predictions from ab‐initio calculations based upon the generation of vacancy‐interstitial pairs of zirconium and oxygen.     

Ultra-fast densification of boron carbide ceramics under high heating rate and high pressure

Boron carbide ceramics were obtained in 2 min by a method based on self-propagating high-temperature synthesis plus quick pressing (SHS/QP). The samples were densified to 98% of theoretical density under a large mechanical pressure (120 MPa) and a fast heating rate (2300 °C/min). The microstructure and mechanical properties were studied. The sample obtained at this heating rate presents an average grain size of 3 μm and a hardness of 34 ± 0.2 GPa.     

Pressureless sintering and properties of boron carbide composite materials

Boron carbide and Tantalum boride composites were prepared by pressureless sintering of B₄C with addition of TaC powder. The effect of TaC addition on the sinterability of boron carbide was studied. High densified ceramic with a relative density of 98.7% was obtained at sintering temperature of 2250°C. The composition and the microstructure of the dense composites are characterized by means of x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive x-ray spectroscopy (EDX). The studies show that the composites contain boron carbide, TaB₂, and carbon phases with a homogeneous structure. In addition, the correlation between the composition and the electrical conductivity was investigated. The electrical conductivity of the composite increased with increasing addition of TaC, and a change in conduction behavior from semiconducting to metallic was observed. High hardness value of 28.49 ± 1.33 GPa was obtained by the sample with 30 wt% TaC addition.     

Fabrication of ZrO2/rGO nanocomposites by flash sintering under AC electric fields

Ceramic matrix nanocomposites containing graphene possess superior mechanical properties. However, these nanocomposites are very difficult to be prepared using the conventional methods due to severe grain growth and simultaneous degradation of the graphene at high sintering temperatures and long dwell time. Herein, the dense ZrO₂/rGO (reduced graphene oxide) nanocomposites are successfully fabricated by flash sintering of the green compacts consisting of ZrO₂ nanoparticles and graphene oxide (GO) at 893–951℃ in merely 5 seconds under the alternating current (AC) electric fields of 130–150 V cm⁻¹. The GO can be in situ thermal reduced during the flash sintering. The as-prepared ZrO₂/rGO nanocomposites exhibit excellent mechanical properties. This study presents a green and simple approach to fabricate the dense ceramic matrix nanocomposites reinforced with graphene at low temperatures in a short time.     

Processing and properties of Bi0.98R0.02FeO3 (R = La,Sm, Y) ceramics flash sintered at ~650°C in <5 s

We show that flash sintering produces single-phase, nanograin-sized polycrystals of isovalent-substituted multiferroic ceramics of complex compositions. Single-phase polycrystals of Bi_0.98R_0.02FeO₃ (R = La, Sm, Y) were produced at a furnace temperature of ~650°C in a few seconds by the application of an electric field of 50 V cm⁻¹, with the current limit set to 40 mA mm⁻². The dielectric and insulating properties compared favorably with expected values. Impedance spectroscopy suggests electrically homogenous microstructure, except for the sample Bi_0.98La_0.02FeO₃ that shows a small grain boundary contribution to the impedance. These results reinforce the enabling nature of flash sintering for ceramics which pose difficulties in conventional sintering because they contain low melting constituents or develop secondary phases during the sintering protocol.     

Microstructure development and optical properties of Fe:ZnSe transparent ceramics sintered by spark plasma sintering

Fe:ZnSe transparent ceramics were prepared by spark plasma sintering. Fe:ZnSe powders synthesized via co-precipitation yielded well-dispersed particles with an average particle size of 550 nm. These powders were in the cubic phase Fe:ZnSe, indicating the successful substitution of Fe²⁺ for Zn²⁺. The highest relative density, 99.4%, was obtained by increasing the pressure and sintering time. The effects of sintering temperature, pressure, and time on the microstructure of SPS prepared ceramics were presented by micrographs. With increasing sintering temperature, from 600°C to 900°C, the average grain size increased from < 1 to 10 μm. The intergranular fracture indicated no neck formation in the sintering process. High pressure was essential for the densification process. The average grain size deceased from approximately 10 to 5 μm when the pressure was increased. Increasing the sintering time from 10 to 120 minutes lead to a change in the microstructure, from inter- to transgranular fracture, and eliminated the micropores. The as-prepared Fe:ZnSe ceramics were composed of single-phased cubic ZnSe. The sample sintered at 900°C under a pressure of 90 MPa for 120 minutes yielded a transmittance of approximately 60% at 1.4 μm and 68% at 7.5 μm and had residual micropores as its main scattering source. There was a strong characteristic absorption peak of Fe²⁺ ions at around 3 μm, which was red-shifted compared to Fe:ZnS transparent ceramics. Fe:ZnSe transparent ceramics have a reddish-brown color and it could be a promising mid-infrared laser material.     

Flame‐assisted flash sintering: A noncontact method to flash sinter coatings on conductive substrates

We present a novel and effective method for sintering ceramic coatings onto metallic substrates. This new technique, called Flame‐assisted flash sintering (FAFS), utilizes a flame as both a heating source and a conformal, current‐carrying top electrode to facilitate flash sintering. Using this method, Yttria‐stabilized Zirconia (8 mol% Y, 8YSZ) coatings are sintered onto stainless steel substrates to controlled degrees of porosity in rapid fashion. Flame‐assisted flash sintering utilizes a dynamic soft electrode for flash sintering and has commercial potential to sinter ceramic coatings on complex‐shaped substrates for a variety of applications including tribological or thermal protection coatings.     

In-situ synthesis and densification of boron carbide and boron carbide-graphene nanoplatelet composite by reactive spark plasma sintering

Simultaneous synthesis and densification of boron carbide and boron carbide- graphene nano platelets (GNP) were carried out by reactive spark plasma sintering of amorphous boron and graphene nano platelets at temperature ranging from 1200 to 1600?°C, pressure of 50?MPa and heating rate of 50?°C/min and 100?°C/min. X-ray diffraction and Raman spectroscopy confirmed the formation of required phases. Electron microscopic images revealed the formation of sub-micron and nano sized grains of plate like morphology. Sintered product with high relative density of 96%TD was achieved at a temperature of 1600?°C and heating rate of 50?°C/min for B₄C stoichiometric composition and also exhibited maximum hardness of 21.10?GPa.     

Highly textured and strongly anisotropic TiB2 ceramics prepared using magnetic field alignment (9T)

Highly textured TiB₂ ceramics were prepared by slip casting an aqueous suspension in a magnetic field of 9 T, followed by sintering using Field Assisted Sintering Technology (FAST). Particle size refinement by ball milling improved both the degree of texturing and densification of the material (RD > 98 %). The sintered material exhibited a Lotgering orientation factor of 0.90, with the c-axis of TiB₂ oriented parallel to the magnetic field and FAST pressing direction. The texturing effect induced by the uniaxial pressing was negligible. The textured TiB₂ material exhibited a significant anisotropy in mechanical properties; the values of hardness and indentation elastic modulus measured along directions transverse to the c-axis of TiB₂ were 37 % and 13 % higher than the ones measured along the c-axis direction. Moreover, the specific wear rate of a surface of textured TiB₂ parallel to the field was one order of magnitude lower than a surface perpendicular to the field.     

Spark plasma sintering of boron nitride micron tubes reinforced boron carbide ceramics with excellent mechanical property

In this paper, the novel boron nitride micron tubes (BNMTs) were used to reinforce commercial boron carbide (B₄C) ceramics prepared via spark plasma sintering technology. The effects of the sintering parameters, sintering temperature, the holding time, and the BNMTs content on the microstructure and mechanical properties of B₄C/BNMTs composite ceramics were studied. The results indicated that adding a proper amount of BNMTs could inhibit the grain growth of B₄C and improve the fracture toughness of the B₄C/BNMTs composite ceramics. The prepared composite ceramic sample with 5 wt% BNMTs at 1850°C, 8 min and 30 MPa displayed the best mechanical properties. The relative density, hardness, fracture toughness, and bending strength of the samples were 99.7% ± .1%, 35.62 ± .43 GPa, 6.23 ± .2 MPa m^1/2, and 517 ± 7.8 MPa, respectively. Therein, the corresponding value of hardness, fracture toughness, and bending strength was increased by 10.3%, 43.59%, and 61.5%, respectively, than that of the B₄C/BNMTs composite ceramic without BNMTs. It was proved that the high interface binding energy and bridging effect between boron carbide and BNMTs were the toughening principle of BNMTs.     

Effect of monomers content in enhancing solid-state densification of silicon carbide ceramics by aqueous gelcasting and pressureless sintering

The possibility of obtaining solid-state sintered silicon carbide (SiC) through aqueous gelcasting using commercial SiC powders was demonstrated. Green bodies were prepared from thixotropic SiC slurries in aqueous medium with optimized pH and solid-loading. The monomer system in gelcasting provides strength to the green bodies through formation of a gel network by polymerization and the carbon from polymeric gel enhances the densification of SiC, thereby avoiding addition of carbon externally to the gelcasting batches. Maximum bulk density of 3.16 g/cm³ (98.4% of relative density) was achieved in gelcast SiC on sintering at 2150 °C in argon atmosphere. The effect of carbon on SiC densification is evinced from the changes in microstructure of sintered SiC with increase in carbon content. The density and microstructure of gelcast and sintered SiC was comparable to that obtained from dry pressing and sintering of additive mixed SiC powders.     

Fabrication of carbon-coated boron carbide particle and its role in the reaction bonding of boron carbide by silicon infiltration

To tackle the dissolution problem of boron carbide particles in silicon infiltration process, carbon-coated boron carbide particles were fabricated for the preparation of the reaction-bonded boron carbide composites. The carbon coating can effectively protect the boron carbide from reacting with liquid Si and their dissolution, thus maintaining the irregular shape of boron carbide particles and preventing the growth of boron carbide particles and reaction formed SiC regions. Furthermore, the nano-SiC particles, originated from the reaction of the carbon coating and the infiltrated Si, uniformly coated on the surfaces of boron carbide particles, thus forming a ceramic skeleton of the nano-SiC particles-coated and -bonded boron carbide particles. The Vickers hardness, flexural strength and fracture toughness of the composites can be increased by 26 %, 45 %, and 37 % respectively, by using carbon-coated boron carbide particles as raw materials.     

Shrinkage rate control during a flash state by current-ramping for 3 mol% Y2O3-doped ZrO2 polycrystals

3 mol% Y₂O₃-doped ZrO₂ green compacts with rectangular shapes were sintered by maintaining the shrinkage rates at constant values under alternating electric fields by ramping the electric current during flash states. Green compacts were furnace-heated under 40-100 V_rms/cm until current hits an initial current limit of 100 mA_rms. After then, current-ramping was started to keep the shrinkage rates constant by increasing the limit current value using a programmable power supply operating in a current control mode. Highly densified 3 mol% Y₂O₃-doped ZrO₂ polycrystals with a density of 6.05 g/cm³ as a bulk density and a grain size of about 0.4 μm were obtained at a furnace temperature of about 930℃, 50 V_rms/cm with 1000 Hz and shrinkage rate of about 120 μm/min (0.8%/min against initial lengths of green compacts). The Vickers hardness and indentation fracture toughness of the compact exhibit similar values to those obtained from thermally sintered compacts.