Densification of copper oxide doped alumina toughened zirconia by conventional sintering

The effect of copper oxide doping (0.05–1 wt%) on the densification, microstructure evolution and mechanical characteristics of alumina toughened zirconia (ATZ: 80 wt% Y-TZP + 20 wt% Al₂O₃) ceramic composites was investigated. Green samples were pressureless sintered using a short hold time of 12 min at temperatures varying from 1250 °C to 1500 °C. The incorporation of up to 0.2 wt% copper oxide was beneficial in promoting densification at low sintering temperature and improving the mechanical properties of ATZ without affecting the tetragonal phase stability. It was found that 0.2 wt% copper oxide addition was most efficacious, and the samples could attain a relative density of approximately 92% at 1250 °C, approximately 97% dense at 1350 °C and above 99% dense at 1450–1500 °C. This approach was also accompanied by an improvement in the Vickers hardness (12.7 GPa) and fracture toughness (6.94 MPam^1/2) when consolidated at 1450 °C/12 min. In comparison, the undoped composite exhibited relative densities of approximately 80% at 1250 °C, 87% at 1350 °C and approximately 97%–98% at 1450 °C-1500 °C. However, the study also found that higher dopant levels (0.5 wt% and 1 wt%) was not beneficial because the tetragonal zirconia phase was disrupted upon cooling from sintering, resulting in the monoclinic phase formation. In addition, low densification and poor mechanical properties were obtained.     

Fine grained Al2O3/SiC composite ceramic tool material prepared by two-step microwave sintering

Fine-grained Al₂O₃/SiC composite ceramic tool materials were synthesized by two-step microwave sintering. The effects of first-step sintering temperature (T1), content and particle size of SiC on the microstructure and mechanical properties were studied. It was found that the sample with higher content of SiC was achieved with finer grains, and the incorporation of SiC particles could bridge, branch and deflect the cracks, thus improving the fracture toughness. Higher T1 was required for the densification of the samples with higher content of SiC (>5?wt%). The sample containing 3?wt% SiC particles with the mean particle size of 100?nm, which was sintered at 1600?°C (T1) and 1100?°C (T2) for 5?min had the fine microstructure and optimal properties. Its relative density, grain size, Vickers hardness and fracture toughness obtained were 98.37%, 0.78?±?0.31?μm, 18.40?±?0.24?GPa and 4.97?±?0.30?MPa?m^1/2, respectively. Compared to the sample prepared by single-step microwave sintering, although near full densification can be achieved in both two methods, the grain size was reduced by 36% and the fracture toughness was improved by 28% in two-step microwave sintering.     

Analysis of reactions during sintering of CuO-doped 3Y-TZP nano-powder composites

3Y-TZP (yttria-doped tetragonal zirconia) and CuO nano powders were prepared by co-precipitation and copper oxalate complexation–precipitation techniques, respectively. During sintering of powder compacts (8 mol% CuO-doped 3Y-TZP) of this two-phase system several solid-state reactions clearly influence densification behaviour. These reactions were analysed by several techniques like XPS, DSC/TGA and high-temperature XRD. A strong dissolution of CuO in the 3Y-TZP matrix occurs below 600 °C, resulting in significant enrichment of CuO in a 3Y-TZP grain-boundary layer with a thickness of several nanometres. This “transient” liquid phase strongly enhances densification. Around 860 °C a solid-state reaction between CuO and yttria as segregated to the 3Y-TZP grain boundaries occurs, forming Y₂Cu₂O₅. This solid-state reaction induces the formation of the thermodynamic stable monoclinic zirconia phase. The formation of this solid phase also retards densification. Using this knowledge of microstructural development during sintering it was possible to obtain a dense nano–nano composite with a grain size of only 120 nm after sintering at 960 °C.     

Densification behaviour and properties of manganese oxide doped Y-TZP ceramics

The effect of employing a short sintering holding time of 12 min as compared to that of the commonly employed holding time of 120 min (2 h) on the properties of undoped and 1 wt% manganese oxide (MnO₂)-doped Y-TZP ceramics were studied. Sintering studies was conducted over the temperature range of 1150-1600 °C. Bulk density, Young's modulus, Vickers hardness and fracture toughness tests were carried out on the sintered samples. The results revealed that the 12 min sintering holding time was effective in promoting densification of the 1 wt% MnO₂-doped Y-TZP without sacrificing tetragonal phase stability or mechanical properties and incurring grain growth. Microstructure investigation by using the scanning electron microscope (SEM) of the fracture MnO₂-doped Y-TZP samples which was subjected to rapid quenching in liquid nitrogen revealed distinct microstructural features believed to be associated with the presences of a transient liquid phase during sintering. A sintering mechanism was subsequently proposed to explain the densification behaviour of MnO₂-doped Y-TZP ceramics.     

Effect of manganese oxide on the sintered properties and low temperature degradation of Y-TZP ceramics

The sinterability of yttria-tetragonal zirconia polycrystals (Y-TZP) containing small amounts of MnO₂ as sintering aid was investigated over the temperature range of 1250–1500 °C. Sintered samples were evaluated to determine bulk density, Young's modulus, Vickers hardness and fracture toughness. In addition, the tetragonal phase stability of selected samples was evaluated by subjecting the samples to hydrothermal ageing in superheated steam at 180 °C/10 bar for up to 24 h. The results showed that the addition of MnO₂, particularly ≥0.3 wt% was effective in aiding densification, improving the matrix stiffness and hardness when compared to the undoped Y-TZP sintered at temperatures below 1350 °C. On the other hand, the fracture toughness of Y-TZP was unaffected by MnO₂ addition except for the 1 wt% MnO₂-doped Y-TZP samples sintered above 1400 °C. The hydrothermal ageing resistance of Y-TZP was significantly improved with the additions of MnO₂ in the Y-TZP matrix.     

Microwave Sintering of Zirconia Materials: Mechanical and Microstructural Properties

Commercially, 3 mol% Y₂O₃‐stabilized tetragonal zirconia (70–90 nm) compacts were fabricated using a conventional and a nonconventional sintering technique; microwave heating in a resonant mono‐mode cavity at 2.45 GHz, at temperatures in the 1100–1400°C range. A considerable difference in the densification behavior between conventional (CS) and microwave (MW) sintered materials was observed. The MW materials attain a full density of 99.9% of the theoretical density (t.d.) at 1400°C/10 min, whereas the CS reach only 98.0% t.d. at the same temperature and 1 h of dwelling time. Therefore, the MW materials exhibit superior Vickers hardness values (16.0 GPa) when compared with CS (13.4 GPa).     

Sintering behaviour and properties of manganese-doped alumina

The effect of manganese (0.1, 0.5 and 1.0?wt%) on the sintering and mechanical properties of alumina was studied. Sintering was carried out by the conventional heating method in a box furnace and in a hybrid multimode microwave furnace. XRD analysis revealed the precipitation of a spinel second phase (MnAl₂O₄) in manganese-doped samples as a result of manganese limited solubility in the corundum lattice. The addition of 0.1?wt% manganese was most beneficial in enhancing the densification of alumina (97.5% relative density when compared to 94.2% for the undoped sample), hindered grain growth, and improved the hardness of the ceramic when sintered at 1500?°C. The study also revealed that microwave sintering was effective in suppressing grain growth of alumina. In addition, the hardness was dependent on the sintered bulk density and that grain coarsening ensued as the density of the sintered alumina exceeded 95% of theoretical.     

Effect of nano CuO addition on the tribo-mechanical behavior of alumina ceramics in non-conformal contact

Sintering of alumina from 1500°C to 1650°C and tribo-mechanical properties at room temperature had been investigated using nano CuO as a sintering aid. Bulk density gradually increases with sintering temperature from 1500°C to 1600°C and is optimized at 1600°C, beyond this, bulk density does not significantly increase at 1650°C. The addition of 2 wt% CuO showed the best result on densification. Densification of about 97.74% was attained at 1600°C with the incorporation of 2 wt% CuO. Nano CuO at grain boundaries forms CuAl₂O₄ liquid which modifies the morphology of the grain and improves mechanical properties. The formation of self-lubricating tribo-film on the wear track results in a low coefficient of friction <0.2 and reduces specific wear rate. 4 wt% CuO addition increases contact tensile stress (σ_max) by 51.2% and high Hertzian contact pressure (P_max≈1.51 GPa) causes plastic deformation of wear track. The re-solidified strengthening bond phase on the wear track simultaneously increases in friction coefficient and wear resistance with CuO addition. The optimizing effect of CuO addition shows that 2 wt% significantly decreases wear rate, and increases hardness and fracture toughness.     

Sintering behavior of anorthite-based composite ceramics produced from natural phosphate and kaolin

In the present work anorthite-TCP composite ceramics was produced for the first time by the solid-state sintering process involving the mixture of local natural materials of phosphate and kaolin. Various samples were prepared by varying the kaolin content from 47 to 57 wt%. The composite ceramics were sintered in air at various temperatures ranging from 1250 °C to 1325 °C and characterized to determine the phase present, relative density, Vickers microhardness, chemical bonding of molecules and microstructural development. In general, all the samples exhibited a hybrid structure, comprising of anorthite and β-TCP as the major phases with a concomitant minor phases such as TTCP and/or gehlinite depending on the temperature and kaolin content. In addition, increasing kaolin content and sintering temperature were found to be effective in improving the densification and hardness of the sintered body. In particular, sample containing 57 wt% kaolin exhibited excellent densification at 1300 °C and 1325 °C, achieving above 97% dense bodies and highest hardness of about 6.5 ± 0.7 GPa. Microstructural investigation revealed that a dense structure was evident for these samples due mainly to enhanced particle coalescence during the liquid phase sintering, resulting in pore elimination and grain coarsening.     

Sintering behaviour of fluorapatite–silicate composites produced from natural fluorapatite and quartz

In this work, the sintering behaviour of fluorapatite (FAp)–silicate composites prepared by mixing variable amounts of natural quartz (2.5 wt% to 20 wt%) and FAp was studied. The composites were pressureless sintered in air at temperatures from 1000 °C to 1350 °C. The effects of temperatures on the densification, phase formation, chemical bonding and Vickers hardness of the composites were evaluated. All the samples exhibited mixed phase, comprising FAp and francolite as the major constituents along with some minor phases of cristobalite, wollastonite, dicalcium silicate and/or whitlockite dependent on the quartz content and sintering temperature. The composite containing 2.5 wt% quartz exhibited the best sintering properties. The highest bulk density of 3 g/cm³ and a Vickers hardness of >4.2 GPa were obtained for the 2.5 wt% quartz–FAp composite when sintered at 1100 °C. The addition of quartz was found to alter the microstructure of the composites, where it exhibited a rod-like morphology when sintered at 1000 °C and a regular rounded grain structure when sintered at 1350 °C. A wetted grain surface was observed for composites containing high quartz content and was believed to be associated with a transient liquid phase sintering.     

Microwave-sintering preparation and densification behavior of sodium zirconium phosphate ceramics with ZnO additive

The dense NaZr₂(PO₄)₃ (NZP) ceramics were successfully prepared by a microwave sintering process with x wt.% ZnO as a sintering aid (where x = 0, 0.5, 1.0, 2.0 and 3.0). The effects of ZnO additive on the crystal structure, microstructure and sintering behavior of as-prepared NZP ceramics were systematically investigated. The single NZP phase can be achieved in the wide temperature range of 900–1200 °C holding for 2 h by microwave-sintering technology. The addition of ZnO sintering aid would not noticeably change the crystal structure of NZP. Importantly, ZnO additive significantly promoted the densification and 1.0 wt% ZnO-added sample possessed the maximum relative density of 96.5% after sintering at 1100 °C, considerably higher than that of pure NZP sample. Besides, the Vickers hardness of the above sample could attain near 800 MPa, which is about four times as hard as the pure NZP ceramics without ZnO additive. It was suggested that the combination of microwave sintering with appropriate addition of ZnO sintering aid would provide a convenient and efficient method for rapid fabrication of dense NZP ceramics.     

Influence of sintering pressure on the microstructure and tribological properties of low temperature fast sintered hot-pressed Y-TZP

Contrarily to conventional sintering (CS) method where longer cycles and high temperature (1400–1500?°C) are applied to sinter yttria-stabilized tetragonal zirconia polycrystalline (Y-TZP) ceramics, this work presents a faster and low temperature (1175?°C) way through hot pressing (HP) to produce full densified zirconia with good mechanical and tribological properties. This work is concerned with the influence of sintering pressure on the microstructure and tribological properties of hot-pressed Y-TZP. For this purpose, four sintering pressures 5, 20, 60 and 100?MPa were tested. The wear tests were carried out by reciprocating ball-on-plate as a simplified test for tooth-to-restorative material contact under 37?°C using artificial saliva to mimic oral conditions. The results demonstrated that density, hardness and tribological properties are strongly influenced by the sintering pressure, namely an improvement with pressure increase was achieved. The highest density, hardness values and wear resistance were achieved for Y-TZP samples produced at P?=?100?MPa. Furthermore, it was revealed that a smaller grain size for Z100 samples (full densification condition) was achieved comparatively to conventional-sintered Y-TZP. This work proves that it is possible to produce dense Y-TZP materials under low sintering temperature and faster cycles with reduced grain size without compromise mechanical and tribological properties.     

Comparison of a laboratorial scale synthesized and a commercial yttria-tetragonal zirconia polycrystals ceramics submitted to microwave sintering

Conventional sintering techniques of yttria-tetragonal zirconia polycrystals (Y-TZP) ceramics have presented limitations regarding the sintering time and temperature, increasing the cost of the final dental and biomedical products. Herein, microwave sintering comes to be an interesting alternative by providing fast heating, high densification, and grain-size control. The aim of this study was to compare the effect of microwave sintering of Y-TZP dental ceramics prepared from a pre-sintered commercial block and produced from powders synthesized in a laboratorial scale by the precipitation route. The synthetized and commercial discs were submitted to microwave sintering at 1450°C and 1350°C for 15, 30, and 60 minutes. Densification, fracture toughness, grain size, and crystalline phase quantification of the sintered groups were evaluated. Both synthetized and commercial groups sintered at 1450°C for 15 and 30 minutes showed the higher densification results (98% TD). XRD quantitative phase analysis indicates that samples present 89% tetragonal and 11% cubic phases, except for the group prepared from coprecipitated powders sintered at 1450°C for 30 minutes, that presented 79% and 21% of tetragonal and cubic phases. The microwave sintering at 1450°C allows hardness and fracture toughness values comparable to conventional sintering.     

In situ synthesis,mechanical properties,and microstructure of reactively hot pressed WB4 ceramic with Ni as a sintering additive

In this study, tungsten tetraboride (WB₄) ceramics were synthesized in situ from powder mixtures of W and amorphous B with Ni as a sintering aid by reactive hot pressing method. The as-synthesized ceramics exhibited porosity as low as 0.375% and ultra-high Vickers hardness (H_v), as much as 49.808?±?1.683?GPa (for the low load of 0.49?N). It was seen that the addition of Ni greatly improved the sinterability of WB₄ ceramic. Besides, the flexural strength and fracture toughness of WB₄ ceramic were measured for the first time to be 332.857?±?36.763?MPa and 4.136?±?0.259?MPa?m^1/2, respectively, suggesting that the ceramic has good mechanical properties. The effects of sintering temperature and holding time on the densification, Vickers hardness, and mechanical properties of WB₄ ceramics were also investigated systematically as part of our study. The results indicated that increasing the sintering temperature can obviously improve the densification and mechanical properties of the ceramics. The bulk density and Vickers hardness of WB₄ ceramic sintered at 1650?°C for 60?min under 30?MPa revealed the highest values of 6.366?g?cm^?3 and 27.948?±?0.686?GPa (for the high load of 9.8?N), respectively. The flexural strength increased to the highest value of 332.857?±?36.763?MPa for sintering temperature up to 1550?°C, but decreased slightly as the sintering temperature further increased to 1650?°C. On the other hand, the fracture toughness increased gradually with increasing temperature. It was also found that Vickers hardness showed a similar trend as the densification of the samples with increasing temperature and holding time. Besides, no obvious improvements in the densification, mechanical properties, and Vickers hardness of the samples with sintering time were observed in this study. The microstructure and fracture behaviours of the as-synthesized WB₄ ceramic were also revealed, and the toughening mechanism has been discussed.     

Enhanced mechanical properties of 3 Y2O3 stabilized tetragonal ZrO2 incorporating tourmaline particles

The current study reports on the improvement of mechanical properties of 3?mol% Y₂O₃ stabilized tetragonal ZrO₂ (3Y-TZP) by introduction of tourmaline through ball milling and subsequent densification by pressureless sintering at 800, 1200, 1300, 1400?°C. Findings demonstrate that no matter which sintering temperature the 3Y-TZP ceramic containing 2?wt% tourmaline reach a maximum value in flexural strength and fracture toughness as compared to other composite ceramics. As the tourmaline content is 2?wt% and the sintering temperature is 1300?°C, the flexural strength and fracture toughness of the composite ceramics are the highest, increases of 36.2% and 36.6% over plain 3Y-TZP ceramic respectively. The unique microstructure was systematically investigated through X-ray diffraction, scanning electron microscopy, energy dispersive spectrum, and flourier transform-infrared. The strengthening and toughening mechanism of tourmaline in 3Y-TZP ceramic were also discussed.     

Dielectric,mechanical and thermal properties of ZrO2–TiO2 materials obtained by microwave sintering at low temperature

The sinterability of 3Y-TZP/TiO₂ materials using micrometre-sized ZrO₂ and nanometre-sized TiO₂ (16 wt%) by one-step fast microwave sintering at low temperature (1200–1300 °C) was investigated. Firstly, in situ detailed analysis of the dielectric properties of the material with temperature was carried out in order to measure the capacity of the material to transform microwave energy into heat. Another related parameter associated to microwave sintering is the penetration depth of the microwave radiation into the material, which showed great homogeneity from 400 °C. Secondly, the effect of sintering conditions on microstructure, density, hardness and coefficient of thermal expansion was evaluated. The X-ray diffraction study and microstructural characterization demonstrate that it is possible to obtain fully dense pieces (>99%) by microwave sintering, a condition yielding to a coarse-grained (~1–2 μm), quite hard (~13.7 GPa) 3Y-TZP/TiO₂ material. However, the most important feature is the significant reduction of the thermal expansion coefficient (8·10⁻⁶ K⁻¹) as compared to that of 3Y-TZP. In addition, the results from conventional sintering at 1400–1500 °C with 2 and 6 h of dwell time are examined and compared. The materials obtained at 1500 °C showed high density with grain size and hardness similar to those obtained by microwave but with a dramatic difference in the power consumption of the sintering cycle, since the materials obtained by microwave used a maximum absorbed power of 120 W and a heating cycle of only 40 min.     

Sintering Behavior of 0.8 mol%-CuO-Doped 3Y-TZP Ceramics

In recent years, 3 mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) doped with copper oxide has obtained increasing interest due to its enhanced superplastisity and good potential in tribological applications. In this work, the effect of addition of small amounts (0.8 mol%) of copper oxide on the sintering behavior of 3Y-TZP was studied using a dilatometer and high-temperature X-ray diffraction (XRD). A qualitative sintering model was established based on several reactions during sintering as indicated by thermal analysis and XRD. Some of these reactions remarkably retard densification and consequently result in low final density (86%) of the sample sintered at 1400°C in air. The reaction between molten Cu₂O and yttria as segregated to the Y-TZP grain boundaries at around 1180°C leads to the depletion of yttria from Y-TZP grains, which results in the formation of monoclinic phase during cooling. A relatively higher oxygen partial pressure can inhibit the dissociation of CuO to Cu₂O. This inhibition in dissociation is one of the reasons why a dense (>96%) 0.8 mol% CuO-doped 3Y-TZP ceramic can be obtained after sintering at 1400°C in flowing oxygen.     

Microstructure and properties of a graphene platelets toughened boron carbide composite ceramic by spark plasma sintering

A kind of B₄C/SiC composite ceramic toughened by graphene platelets and Al was fabricated by spark plasma sintering. The effects of graphene platelets and Al on densification, microstructure and mechanical properties were studied. The sintering temperature was decreased about 125–300?°C with the addition of 3–10?wt% Al. Al can also improve fracture toughness but decrease hardness. The B₄C/SiC composite ceramic with 3?wt%Al and 1.5?wt% graphene platelets sintered at 1825?°C for 5?min had the optimal performances. It was fully densified, and the Vickers hardness and fracture toughness were 30.09?±?0.39?GPa and 5.88?±?0.49?MPa?m^1/2, respectively. The fracture toughness was 25.6% higher than that of the composite without graphene platelets. The toughening mechanism of graphene platelets was also studied. Pulling-out of graphene platelets, crack deflection, bridging and branching contributed to the toughness enhancement of the B₄C-based ceramic.     

3D printing of high solid loading zirconia feedstock via screw-based material extrusion

Zirconia ceramic (3Y-TZP) feedstocks with solid loadings from 50 vol% to 68 vol%, in a 60:40 paraffin wax to LDPE ratio binder system, were prepared and printed using a screw-based material extrusion printer. A two-step debinding process involving solvent debinding (cyclohexane + ethanol) and thermal debinding (140 °C–600 °C at 0.2 °C/min) followed by sintering at 1500 °C for 2 h was employed. Tests performed include TGA, density test, Vickers hardness and fracture toughness, XRD, and SEM. The TGA result showed two significant drops in weight starting at 180 °C and 380 °C, which corresponds to the decomposition of paraffin wax and LDPE, respectively. A minimum of 40 wt% of soluble binder was removed from the green sample after solvent immersion for 3 h at 40 °C for solid loadings ≥55 vol%. High solid loading feedstocks produced samples with comparable density, Vickers hardness and fracture toughness, which are 97.5%, ∼12.3 GPa, and ∼5.5 MPa m^1/2, respectively; while XRD and SEM shows no adverse tetragonal to monoclinic phase transformation and grain growth, respectively. This study demonstrates that 3D printing of granular 3Y-TZP ceramic feedstock via screw-based material extrusion technique is feasible even with high solid loadings, which is usually difficult to fabricate into flexible filaments and print due to high viscosity.     

Effects of metal phases on microstructure and mechanical properties of microwave-sintered Ti(C,N)-based cermet tool

A kind of Ti(C, N)-based cermet tool material was prepared by microwave sintering. The influence of metal phases (Ni, Co, and Mo) on densification and mechanical properties was studied by orthogonal test. The results indicated that Co was more significant in improving relative density and fracture toughness than Ni, while Ni and Co had the similar effects on increasing the hardness of Ti(C, N)-based cermet. Mo can improve fracture toughness but decrease hardness. Ti(C, N)-based cermet with 6 wt% Ni, 6 wt% Co and 6 wt% Mo (TN6C6M6) had the optimal comprehensive mechanical performances, and its fracture toughness and hardness were better than that of Ti(C, N)-based cermet prepared by conventional sintering. The increasing of sintering temperature promoted the uniformity of microstructure and significantly improved densification and hardness of the Ti(C, N)-based cermet. The highest fracture toughness of TN6C6M6 (12.41 ± 0.33 MPa·m^1/2) was achieved when sintered at 1600°C. For the microwave-sintered Ti(C, N)-based cermet, heat preservation period had little effect on densification. The relative density can reach up to 98.6% even though the heat preservation period was 0 minute.