Effects of heating rate on microstructure and transparency of spark-plasma-sintered alumina

Commercial alumina powder was densified by spark plasma sintering (SPS) at 1150 °C. During SPS processing, the effects of the heating rate were examined on microstructure and transparency. With decreasing heating rate, the grain size and the residual porosity decreased, while the transparency increased. At a heating rate of 2 °C/min, the grain size was 0.29 μm, and the in-line transmission was 46% for a wavelength of 640 nm. The mechanisms for the fine microstructure and low porosity at slow heating, which are conflicting with some existing results, were explained by considering the role of defect concentration and grain-boundary diffusion during densification.     

Distribution of carbon contamination in oxide ceramics occurring during spark-plasma-sintering (SPS) processing: II - Effect of SPS and loading temperatures

Carbon contamination during the SPS processing was investigated in the spinel, alumina and zirconia. The carbon contamination changes with the SPS conditions and the target materials. At the high heating rate of 100?°C/min, the contamination occurred over the entire area in the spinel, but only around the surface areas in the alumina and zirconia. For the spinel, the contamination is sensitive to the SPS parameters, such as the heating rate and loading conditions, but less sensitive to the sintering temperature. This suggests that the carbon contamination was caused by evaporation of CO gas from the carbon paper/dies. At the high heating rates, the carbon evaporation is enhanced due to the rapid heating, and then, the evaporated CO gases are encapsulated into the closed pores during the heating process and remain in the matrix. The carbon contamination can be suppressed by a high temperature loading even at the high heating rate.     

Mechanical Properties and Microstructure of Nano-SiC–Al2O3 Composites Densified by Spark Plasma Sintering

Heterogeneous precipitation method has been used to produce 5 vol% SiC–Al₂O₃ powder, from aqueous suspension of nano-SiC, aqueous solution of aluminium chloride and ammonia. The resulting gel was calcined at 700°C. Nano-SiC–Al₂O₃ composites were densified using spark plasma sintering (SPS) process by heating to a sintering temperature at 1350, 1400, 1450, 1500 and 1550°C, at a heating rate of 600 °/min, with no holding time, and then fast cooling to 600°C within 2–3 min. High density composites could be achieved at lower sintering temperatures by SPS, as compared with that by hot-press sintering process. Bending strength of 5 vol% SiC–Al₂O₃ densified by SPS at 1450°C reached as high as 1000 MPa. Microstructure studies found that the nano-SiC particles were mainly located within the Al₂O₃ grains and the fracture mode of the nanocomposites was mainly transgranular fracture.     

Fabrication of sub-micrometer MgO transparent ceramics by spark plasma sintering

Transparent MgO ceramics were fabricated by spark plasma sintering (SPS) of the commercial MgO powder using LiF as the sintering additive. Effects of the additive amount and the SPS conditions (i.e., sintering temperature and heating rate) on the optical transparency and microstructure of the obtained MgO ceramics were investigated. The results showed that LiF facilitated rapid densification and grain growth. Thus, the MgO ceramics could be easily densified at a moderate temperature and under a low pressure. In addition, the transparency and microstructure of the MgO ceramics were found to be strongly dependent on the temperature and heating rate. For the MgO ceramics sintered at 900 °C for 5 min with the heating rate of 100 °C/min and the pressure of 30 MPa from the powders with 1 wt% LiF, the average in-line transmittance reached 85% in the range of 3 – 5 μm, and the average grain size is ∼0.7 μm.     

Heating rate effects on the crystallization behavior of isotactic polypropylene from mesophase – A de-polarized light transmission study

It was ever reported in a communication of this journal that the large crystal grains having “bamboo leaf-like (BL)” morphology were produced by a rapid heating of isotactic polypropylene (iPP) from the mesophase. In order to optimize the condition to generate the BL crystals, heating rate effects on the crystallization behavior from the mesophase of iPP have been studied by utilizing a de-polarized light transmission (DPLT) method. The DPLT sensitively detected not only the cold crystallization from the mesophase around 100–120 °C but also the crystal grain growth in a narrow temperature region just below the melting temperature. With increasing the heating rate, both the temperature regions of the cold crystallization and the crystal grain growth shifted toward the higher temperatures. When the heating rate is slow (<20 °C/min), the crystal grain growth was not conspicuous. With increasing the heating rate, the rate of the crystal grain growth increased and showed a maximum when the heating rate is approximately 60–80 °C/min. However, excessively fast heating (>100 °C/min) also suppressed the crystal grain growth.     

Bending strength and microstructure of Al2O3 ceramics densified by spark plasma sintering

Al₂O₃ ceramics were superfast densified using spark plasma sintering (SPS) by heating to a sintering temperature between 1350 and 1700°C at a heating rate of 600°C/min, without holding time, and then fast cooling to 600°C within 3 min. High-density Al₂O₃ ceramics could be achieved at lower sintering temperatures by SPS, as compared with that by conventional pressureless sintering (PLS). The bending strength of Al₂O₃ superfast densified by SPS in the range of sintering temperature between 1400 and 1550°C reached values as high as 800 MPa, almost twice that obtained by the PLS. SEM observations indicated that intragranular fracture was the preponderant fracture mode in these samples, resulting in these excellent bending strength values.     

Sintered glass-ceramics from Municipal Solid Waste-incinerator fly ashes—part I: the influence of the heating rate on the sinter-crystallisation

A glass composition, made by mixing 70% of MSW ashes and 30% of waste from feldspar production, was studied. The batch was melted at 1350 °C and the melt was quenched in water. The chemical stability of the glass was investigated by TCLP leaching test. DTA experiment, at 10 °C/min heating rate in the 20–1200 °C range, showed that the glass has a high crystallisation trend with a gehlenite (2CaO.Al₂O₃.SiO₂) formation at 935 °C. The percentage of crystal phase formed as a function of the heat treatment was measured by density variation and XRD. In order to obtain sintered glass ceramics, the frit was heat treated in Al₂O₃ moulds at 950, 1000 and 1050 °C by 2 and 20 °C/min heating rates. At high heating rate predominantly surface crystallisation occurred with fibre-like crystals growing perpendicularly from the surface; at low heating rate bulk crystallisation took place. At low rate, the sintering was inhibited by the crystallisation process. Non porous sintered samples were obtained by a 30 °C/min heating rate and a 40 min isothermal step at 1120 °C, near the liquidus temperature.     

Transparent LiOH-doped magnesium aluminate spinel produced by spark plasma sintering: Effects of heating rate and dopant concentration

The effects of LiOH doping of magnesium aluminate spinel powders and various Spark Plasma Sintering (SPS) schedules on densification behavior and final transparency of polycrystalline magnesium aluminate spinel were studied. Two commercial magnesium aluminate spinel powders, with different specific surface areas, were doped with up to 0.6 wt% of LiOH and consolidated using SPS with slow (2.75 °C/min) and fast (100 °C/min) heating rates. The slow heating rate was optimal for undoped magnesium aluminate spinel (LiOH-free) with the best real in-line transmittance (RIT) of 84.8% (measured at 633 nm on a disc 0.8 mm thick). For the magnesium aluminate spinel doped with 0.3 wt% of LiOH, the fast heating rate was beneficial, and an RIT of 76.5% was achieved. μ-Raman analysis confirmed that the addition of LiOH suppressed carbon contamination.     

Distribution of carbon contamination in MgAl2O4 spinel occurring during spark-plasma-sintering (SPS) processing: I – Effect of heating rate and post-annealing

Carbon contamination from the carbon paper/dies during spark-plasma-sintering (SPS) processing was examined in the MgAl₂O₄ spinel. The carbon contamination sensitively changes with the heating rate during the SPS processing. At the high heating rate of 100 °C/min, the carbon contamination having organized structures occurred over almost the entire area from the surface to deep inside the SPSed spinel disk. In contrast, at the slow heating rate of 10 °C/min, the carbon contamination having disordered structures occurred only around the surface area. The carbon phases transform into high pressure CO/CO₂ gases by post-annealing in air and lead to pore formation along the grain junctions. The pore formation significantly occurs at the high heating rate due to the large amount of the contaminant carbon phases. This suggests that if once the carbon contamination was formed in the materials, it is very difficult to remove the carbon phases from the materials.     

Rapid pressure-less and spark plasma sintering of (Ba0.85Ca0.15Zr0.1T0.9)O3 lead-free piezoelectric ceramics

This work shows for the first time the possibility to sinter BCZT powder compacts by rapid heating rates within one hour of sintering, while achieving good piezoelectric properties. The sintering was performed by rapid (heating rates 100 and 200 °C/min) pressure-less sintering (PLS) at 1550 °C/5-60 min and by SPS sintering (100 °C/min, 1450 °C/5?60 min and 1500 °C/15?45 min). The rapid PLS samples reached a relative density up to 94 % and grain sizes of 17–36 μm acquiring d₃₃ up to 414 pC/N. Although the SPS samples reached full density at 1450 °C, their piezoelectric properties worsened due to smaller grains (10?15 μm) as well as formation of cracks at dwell times > 30 min. At elevated SPS temperature of 1500 °C/30 min, the d₃₃ increased to 360 pC/N sustaining full density. Even higher increase in d₃₃ (424 pC/N) of SPS samples was achieved by post-rapid PLS at 1550 °C/60 min resulting from further expansion in grain size.     

Spark plasma sintering of ultra-porous γ-Al2O3

Nanocrystalline gamma alumina (γ-Al₂O₃) powder with a crystallite size of ~10 nm was synthesized by oxidation of high purity aluminium plate in a humid atmosphere followed by annealing in air. Spark plasma sintering (SPS) at different sintering parameters (temperature, dwell time, heating rate, pressure) were studied for this highly porous γ-Al₂O₃ in correlation with the evolution in microstructure and density of the ceramics. SPS sintering cycles using different heating rates were carried out at 1050–1550 °C with dwell times of 3 min and 20 min under uniaxial pressure of 80 MPa. Alumina sintered at 1550 °C for 20 min reached 99% of the theoretical density and average grain size of 8.5 µm. Significant grain growth was observed in ceramics sintered at temperatures above 1250 °C.     

Influence of Spark Plasma Sintering (SPS) Conditions on Transmission of MgAl2O4 Spinel

The effects of the spark plasma sintering (SPS) parameters, such as heating rate α, temperature T and soak time t_s, and impurities on in‐line transmission T_in were examined in MgAl₂O₄ spinel. The SPS processing at T = 1300°C for t_s = 20 min with a low heating rate of α = 10°C/min is a preferable condition for attaining higher T_in. For the higher T or the longer t_s, grain coarsening enhanced the coalescence of residual pores and second phase precipitation, resulting to the limited T_in even at the slow α. Although the lower T and longer t_s attained fine and dense microstructure simultaneously, the maximum T_in was limited to about 50%. The limited transmission, particularly in the visible range, can be ascribed to the discoloration caused by the carbon contamination. The carbon contamination arose from the preexisting trace CO₃ impurities, irrespective of the SPS conditions. For the higher α, which is the primary advantage of the SPS technique, the additional carbon contamination occurred from the paper/die and remained as glassy carbon in the matrix. To attain higher T_in by the SPS technique, the lower α and T, and the shorter t_s should be utilized after removing the impurities.     

Spark plasma sintering of combustion-synthesized β-SiAlON powders

In this paper, the sintering behavior of β-Si_6−zAl_zO_zN_8−z (z=1) powder prepared by combustion synthesis (CS) was studied using spark plasma sintering (SPS). The CSed powder was ball milled for various durations from 0.5 to 20 h and was then sintered at different temperatures with heating rates varying from 30 °C/min to 200 °C/min. The effects of ball milling, sintering temperature, and heating rate on sinterability, final microstructure, and mechanical property were investigated. A long period of ball milling reduced the particle size and subsequently accelerated the sintering process. However, the fine powder was easily agglomerated to form secondary particles, which accordingly decreased the densification of the SPS product. The high sintering temperature accelerated the densification process, whereas the high heating rate reduced the grain growth and increased the relative density of the sintered product.     

High-pressure spark plasma sintering (SPS) of transparent polycrystalline magnesium aluminate spinel (PMAS)

A high pressure SPS (spark plasma sintering) process was applied for consolidation of un-doped polycrystalline magnesium aluminate spinel. This approach allows fabricating a fully dense transparent ceramic with submicron grain size and high hardness values at a relatively low temperature (1200 °C). The light transmittance of the specimens increases with increasing applied pressure, while the hardness gradually decreases. The optimal combination of properties was achieved after sintering at 1200 °C at a heating rate of 5°/min, a holding time of 15 min and an applied pressure of 350–400 MPa. The specimens display the level of transmittance in the visible wavelengths and hardness values comparable with the best results reported in the literature for the two-stage fabrication process (pressureless sintering and hot isostatic pressing).     

Fabrication and properties of diatomite ceramics with hierarchical pores based on direct stereolithography

Porous diatomite ceramics with hierarchical pores and high apparent porosity (50.29–56%) were successfully fabricated via direct stereolithography. The pre-ball-milling time, dispersant type and dispersant concentration were systematically investigated to prepare diatomite pastes with high solid loading, low viscosity and a self-supporting effect. The results showed that a pre-ball-milling time of 24 h was more suitable to prepare diatomite pastes with high solid loading, and Span80 at 2 wt% was the optimal dispersant to obtain 40 vol% diatomite paste with a low viscosity and a self-supporting effect. To restrain the formation of defects, a heating rate as low as 0.2 °C/min was allowed to control the pyrolysis rate in the multistage debinding process. At sintering temperatures ranging from 900 °C to 1000 °C, porous diatomite ceramics exhibited a typical bimodal porosity, high apparent porosity and great flexural strength.     

Pressureless spark plasma–sintered Bioglass® 45S5 with enhanced mechanical properties and stress–induced new phase formation

Commercial Bioglass^® 45S5 powder was sintered using spark plasma sintering (SPS) technique without the assistance of mechanical pressure with heating and cooling rate of 100 °C/min, dwell temperature of 1050 °C and dwell time of 30 min. Such route enabled the production of samples exhibiting superior mechanical properties in comparison with Bioglass^® sintered in furnace. In particular, flexural strength and fracture toughness reached values close to those of apatite-wollastonite bioceramics, already widely used in clinical applications. The residual stresses implemented by indentation promoted the formation of a new phase in samples sintered by SPS. Complementary use of Raman and energy dispersive spectroscopy (EDS) indicated the phase as sodium carbide and a formation mechanism was proposed.     

Spark-Plasma-Sintering Condition Optimization for Producing Transparent MgAl2O4 Spinel Polycrystal

By controlling the heating rate at <10°C/min during spark-plasma-sintering (SPS) processing, transparent polycrystalline spinel with an in-line transmission of 50% and 70% in the visible- and infrared-wavelengths, respectively, can be successfully fabricated for only a 20-min soak at 1300°C. The high transmission can be attained by reducing the residual porosity and pore size, which was achieved by the low-heating rate. At high heating rates, many closed pores are formed due to the high densification rate during the heating process and remain as large pores around grain junctions. At temperatures >1300°C, the coalescence of the residual pores and the precipitation of second phases, which are caused by rapid grain growth, degrade the transparency. The present study demonstrates that although the high heating rates have been regarded as a primary advantage for the SPS processing, the low heating rate is highly effective in attaining a high transparency in the spinel even at low temperatures and for short sintering times.     

Biodiesel (FAME) Productivity,Catalytic Efficiency and Thermal Stability of Lipozyme TL IM for Crude Palm Oil Transesterification with Methanol

Crude palm oil (CPO) transesterification with methanol at room temperature is an important factor for optimizing biodiesel processing costs with respect to energy input; in addition, good stability of expensive lipase activity was ensured and is reported in this study. The enzyme loading, agitation speed and reaction time at a constant operating temperature of 30 °C were studied to find favourable operational conditions using a factorial design. Statistical analysis was used to assist the enzymatic transesterification so that a reduced mass transfer effect was achieved to obtain high FAME yields. The combination of optimum enzyme loading of 6.67 wt% and 150 rpm agitation speed for the system at 30 °C gave 81.73% FAME yield at 4 h and a production rate of 85.86% FAME yield/h. The high viscosity of CPO observed at 30 °C compared to 40 °C hindered the achievement of 96.15% FAME yield at room temperature. It was found that an increase of 10 °C invariably deactivated the lipase, but was compensated by the enhanced FAME production rate with 96.15% FAME yield after only 4 h reaction time. Thus, 40 °C was considered the most suitable operating temperature for lipozyme TL IM to catalyze CPO transesterification.     

Microstructural characterization of spark plasma sintered boron carbide ceramics

Fully dense boron carbide specimens were fabricated by the spark plasma sintering (SPS) technology in the absence of any sintering additives. Densification starts at 1500 °C and the highest densification rate is reached at about 1900 °C. The microstructure of the ceramic sintered at 2200 °C, with heating rates in the 50–400 °C/min range, displays abnormal grain growth, while for a 600 °C/min heating rate a homogeneous distribution of finely equiaxed grains with 4.05 ± 1.62 μm average size was obtained. TEM analysis revealed the presence of W-based amorphous and of crystalline boron-rich B₅₀N₂ secondary phases at triple-junctions. No grain-boundary films were detected by HRTEM. The formation of a transient liquid alumino-silicate phase stands apparently behind the early stage of densification.     

MoSi2-based cylindrical susceptor for rapid high-temperature induction heating in air

Conductive susceptors are necessary for heating non-conductive materials in induction heating systems. Susceptor materials should have sufficient electrical conductivity and thermal/chemical stability under a range of environmental conditions. However, many susceptor materials oxidize in high-temperature environments, resulting in degradation and poor durability. Here, we used intermetallic MoSi₂ ceramics as a susceptor material and designed a cylindrical susceptor to apply to rapid high-temperature induction heating in an oxidizing environment. MoSi₂ was prepared by self-propagating high-temperature synthesis (SHS), and then used to fabricate cylindrical susceptors by slip casting. The optimal thickness of the susceptor was controlled by modelling. A MoSi₂-based cylindrical susceptor with SiO₂ protective layer showed higher heating rate (4.2–26.8 °C/s at 0.5–2.5 kW) than a commercial rod-type susceptor (7.7–13.6 °C/s at 1.0–2.5 kW) of the same material. In addition, our susceptor endured high temperatures below 1700 °C and severe thermal cycle (700–1600 °C, heating for 2min and cooling for 1min) during 36 cycles. In general, these results demonstrate that the MoSi₂-based susceptor can be applied to a rapid induction heating furnace that can be used in air at a high temperature of 1600 °C (equal to the available temperature of a commercial graphite susceptor in H₂).