Y-TZP,Ce-TZP and as-synthesized Ce-TZP/Al2O3 materials in the development of high loading rate digital light processing formulations

Y-TZP, Ce-TZP and Ce-TZP/Al₂O₃ materials are widely investigated in dentistry. Digital Light Processing (DLP) is considered as a breakthrough technology for the dental field to fine print Y-TZP green parts. High loading photocurable formulations (>45 vol%) with Y-TZP, Ce-TZP commercial powders and Ce-TZP/30 vol% Al₂O₃ as-synthesized powder suitable to DLP printing were achieved in this study. A low specific surface area (5–13 m²/g) of particles without any pores and 1 wt% to 2 wt% of steric dispersant are required to obtain high loading formulations. The as-synthesized composites provide these properties by increasing the calcination temperature from 800 °C to 1200 °C. The as-prepared ceramic formulations based on the same photocurable resin exhibit a curing behavior suitable to DLP process for Y-TZP formulations (thickness > 50 μm in few seconds with a high conversion rate) in comparison with ceria ceramic. The ceria is a strongly UV absorbing material and a specific formulation is developed to obtain 80% of conversion and a cured thickness of 75 μm in 0.5 s.     

Digital light processing stereolithography of zirconia ceramics: Slurry elaboration and orientation-reliant mechanical properties

Digital Light Processing (DLP) is a promising technique for the preparation of ceramic parts with complex shapes and high accuracy. In this study, 3 mol% yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) UV-curable slurries were prepared and printed via DLP. Two different solid loadings (40.5 and 43.6 vol%, respectively) and printing directions were investigated to assess the influence of these parameters on physical and mechanical properties of the sintered parts. Zirconia samples were sintered at 1550 °C for 1 h, achieving a very high relative density (99.2%TD), regardless of solid loading and printing direction. FE-SEM micrographs shown a homogeneous and defect-free cross section with an average grains size of 0.56 ± 0.19 µm. Finally, mechanical properties were influenced by printing direction and zirconia vol%. Indeed, the composition with the higher solid loading (i.e. 43.6 vol%) had the highest three-point flexural strength (751 ± 83 MPa) when tested perpendicular to the printing plane.     

Flexural strength and Weibull analysis of Y-TZP fabricated by stereolithographic additive manufacturing and subtractive manufacturing

Digital light processing (DLP) is a relatively mature technology of ceramic additive manufacturing and is promising for fabricating zirconia-based dental restorations. It allows for manufacturing ceramic components with nearly unlimited geometries compared to traditional subtractive manufacturing technology. In order to explore its potential for fabricating dental prosthesis and determine its clinical indications, it is essential to investigate its microstructural characteristics and mechanical behavior. In this study, yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) fabricated by stereolithographic additive manufacturing, namely DLP acquired favorable flexural strength close to that of conventional subtractive-manufactured Y-TZP as indicated by uniaxial (three-point bending) and biaxial (ring on ring) tests, though the Weibull modulus of DLP-manufactured zirconia was lower than that of subtractive-manufactured zirconia. The strength predicting approach that uses effective area calculations was found to be applicable for both DLP-manufactured zirconia and subtractive-manufactured zirconia. Though both materials showed similar microstructures considering grain size and phase composition, significant differences in critical defects were observed.     

3D printing of zirconia via digital light processing: optimization of slurry and debinding process

Digital light processing (DLP) is regarded as one of the most promising 3D printing technologies to process ceramics, however the precise composition of the slurry and the optimisation of the debinding process are still challenges that need to be overcome. In this work, both the dispersion and rheological behaviour of the zirconia slurry were studied using rheometery and UV-vis spectroscopy, and optimising the dispersant concentration was found to have significant benefits. Zirconia green parts were fabricated with zirconia slurry based on DLP technology, which exhibited good dimensional resolution under an exposure energy dose of 15 mJ cm^-2. In addition, the debinding process was studied using TGA and an optimised approach was designed and developed. Dye penetration and SEM results showed that debinding under argon, rather than flowing air, could lead to crack-free parts at heating rates of either 0.2 or 0.5 °C min^-1, though the former yielded slightly better results overall.     

Additive manufacturing of electrofused mullite slurry by digital light processing

Mullite, one of the main refractory materials, has several applications that may demand tiny structures with complex geometries, and digital light processing (DLP) can produce such parts with outstanding dimensional precision and surface quality. In this work, electrofused mullite powder was used as a raw material for additive manufacturing by DLP. Photosensitive mullite suspensions were developed and their rheological behavior, stability, and thermal decomposition were investigated. Mullite parts were printed from suspensions with different ceramic loadings, debound, and sintered at different temperatures (from 1500 to 1650 °C). Density and strength increased with an increase in both solid loading and sintering temperature. Printed parts from slurry with 50 vol% of solid loading sintered at 1650 °C reached a relative density of 97.7 ± 0.3 % and flexural strength of 95.2 ± 5.0 MPa.     

Effects of ZrSiO4 content on properties of SiO2-based ceramics prepared by digital light processing

SiO₂-based ceramic cores are widely used in the preparation of gas turbine engine hollow blades due to their excellent chemical stability and easy removal after casting. In this paper, ZrSiO₄ reinforced SiO₂-based ceramics were fabricated using digital light processing (DLP) technology. The results showed that the addition of ZrSiO₄ reduced the cure depth due to its high UV light absorptivity and refractive index. When the content of ZrSiO₄ increased to 15 wt%, the cristobalite content reached the maximum, and radial shrinkage reached the minimum of 1.4%. ZrSiO₄ grains could hinder the propagation of cracks, enhancing the room-temperature flexural strength. At 1550 °C, fracturing across SiO₂ grains in SiO₂-based ceramics led to the great improvement of high-temperature flexural strength. When the content of ZrSiO₄ reached 15 wt%, the flexural strength at room temperature and high temperature was 11.5 MPa and 36.7 MPa, respectively. Therefore, the SiO₂-based ceramics prepared using DLP technology have good room temperature and high temperature properties, and are expected to be used for hollow blade casting.     

High-performance 0.9Al2O3-0.1TiO2 microwave dielectric ceramics prepared by digital light processing

In this work, the 0.9Al₂O₃-0.1TiO₂ ceramic sample with good microwave dielectric properties and complex structures can be well fabricated by digital light processing (DLP). A relationship between dispersant content and rheological behavior of 0.9Al₂O₃-0.1TiO₂ slurry was explored. When dispersant content was 3.0 wt%, 0.9Al₂O₃-0.1TiO₂ slurry with high solid loading (50 vol%) and low viscosity (2.9 Pa s) could be obtained. 0.9Al₂O₃-0.1TiO₂ ceramic parts with high accuracy were fabricated successfully by adding 3.0 wt% photoinitiator under 600 mJ/cm² exposure energy. With the increase of sintering temperature from 1400 °C to 1600 °C, relative density, dielectric constant (ε_r), and quality factor (Q × f) of 0.9Al₂O₃-0.1TiO₂ ceramic sample increased first and then decreased, and all reached the maximum value at 1550 °C due to the uniformity and densification of microstructures. The temperature coefficient of resonant frequency (τ_f) value showed an almost monotonous increase, changing from negative to positive, and near-zero τ_f value at 1550 °C. In addition, 0.9Al₂O₃-0.1TiO₂ ceramic samples sintered at 1550 °C fabricated by DLP method presented much better microwave dielectric properties: ε_r = 11.30 ± 0.02, Q × f = 35,345 ± 143 GHz (@～12 GHz), τ_f = 2.16 ± 0.21 ppm/°C than that of by dry pressing method: ε_r = 11.16 ± 0.11, Q × f = 30,195 ± 257 GHz (@～12 GHz), τ_f = 4.45 ± 0.13 ppm/°C, especially the Q × f value achieved a 17% increase. Accordingly, DLP technique, which has advantages of producing relatively high properties and complex geometry of microwave dielectric ceramics as well as without extra high-cost mold, greatly satisfies application requirements.     

Sintering of lunar regolith structures fabricated via digital light processing

Architectural and functional structures composed of lunar regolith-simulant CLRS-2 were fabricated via digital light processing and sintered at 1100 °C and 1150 °C under an air or argon atmosphere. This work is to investigate effects of atmosphere and temperature on mechanical properties, microstructure, and chemical composition of lunar regolith products. Samples sintered at 1150 °C in air underwent the highest sintering shrinkage and showed the best mechanical properties, likely due to the formation of glassy phase and dense structure following sintering. Conversely, argon-sintered samples exhibited lower density resulting from the lack of glassy phase. Phase analysis revealed varying chemical composition and therefore different underlying reaction mechanisms under two sintering atmospheres, indicating that sintering atmosphere significantly influences the microstructure and macroscopic properties of lunar regolith products.     

Composite bioceramic scaffolds with controllable photothermal performance fabricated by digital light processing and vacuum infiltration

Photothermal scaffolds can help clear bone tumor cells after resection. In this work, hydroxyapatite-akermanite-Fe₃O₄ (HA-AK-FE) bioceramic scaffolds were fabricated by infiltrating digital light processing (DLP)-printed HA-AK scaffolds in nano-Fe₃O₄ solution. The prepared HA-AK-FE samples exhibited excellent and controllable photothermal performance under the irradiation of 808 nm near-infrared light. By controlling nano-Fe₃O₄ concentration, irradiation power and infiltration time, temperature of HA-AK-FE samples could be regulated in a wide range from room temperature to 150 °C within 15 s. Photothermal temperature remained stable after 4 times repeated irradiations. In SBF solution and under subcutaneous tissue, the heating rate and photothermal temperature decreased obviously compared with in air, but they could still meet the needs of killing tumors (41–48 °C). The Fe release concentration of wafers after immersing in SBF for 1 day was 0.037 mg/L and non-venomous. These results confirm the feasibility and controllability of fabricating photothermal scaffolds by coating nano-Fe₃O₄ with vacuum infiltration, and the prepared HA-AK-FE scaffolds are hopeful to be used in photothermal therapy of bone tumors.     

Influence of particle size on 3D-printed piezoelectric ceramics via digital light processing with furnace sintering

To improve the properties of BaTiO₃ piezoelectric ceramics fabricated by 3D printing, effects of particle size were investigated on the properties of ceramic slurries and the electrical properties of BaTiO₃ fabricated by Digital light processing (DLP) 3D printing method. It was found that the curing ability of the slurries decreased significantly when the particle size is close to the ultraviolet wavelength, while the viscosity kept decreasing with the increase of particle size. When the particle size in a range of submicron (d₅₀<1 μm), the grain size of sintered ceramics decreased from 13.27 to 6.84 μm as particle size increasing. Moreover, the piezoelectric constant and relative permittivity of sintered ceramics were measured, and it turns out to reach 168.1 pC/N and 1512, respectively, while using the BaTiO₃ powder with particle size of 993 nm. Finally, a cellular structural BaTiO₃ ceramics was fabricated by using optimized powder and process parameters and packaged as a piezoelectric sensor, showing a good function of force-electricity conversion. These results demonstrate the feasibility of fabricating high-quality functional ceramics with designed geometry by DLP.     

Densification and grain growth of nanocrystalline 3Y-TZP during two-step sintering

Two-step sintering (TSS) was applied on nanocrystalline yttria tetragonal stabilized zirconia (3Y-TZP) to control the grain growth during the final stage of sintering. The process involves firing at a high temperature (T1) followed by rapid cooling to a lower temperature (T2) and soaking for a prolonged time (t). It is shown that for nanocrystalline 3Y-TZP (27 nm) the optimum processing condition is T1 = 1300 °C, T2 = 1150 °C and t = 30 h. Firing at T1 for 1 min yields 0.83 fractional density and renders pores unstable, leading to further densification at the lower temperature (T2) without remarkable grain growth. Consequently, full density zirconia ceramic with an average grain size of 110 nm is obtained. XRD analysis indicated that the ceramic is fully stabilized. Single-step sintering of the ceramic compact yields grain size of 275 nm with approximately 3 wt.% monoclinic phase. This observation indicates that at a critical grain size lower than 275 nm, phase stabilization is induced by the ultrafine grain structure.     

Crystal structure and morphology of CeO2 doped stabilized zirconia ceramics under high-frequency microwave field sintering

Under high-frequency microwave irradiation, zirconia ceramics were prepared by sintering nano-CeO₂ (Ce = 7 mol%) doped zirconia powder. The different effects of temperature environment on the phase structure transformation, surface functional groups, microstructure, growth process, and density of doped zirconia were analyzed, and the optimized microwave sintering process for zirconia was determined. The experimental results reveal that the tetragonal phase of zirconia is positively correlated with the temperature when the temperature reaches about 1100 °C in the studied range. The reason is that the grain grows with the increase of sintering temperature, and the surface energy of grain decreases, which leads to the fluctuation of tetragonal phase content. The density of zirconia reaches 98.03% at 1300 °C, and the growth activation energy is 27.40 kJ/mol. There is no abnormal growth of zirconia particles, and the phase transition temperature decreases, which is attributed to the efficient heating of microwave and the incorporation of nano-ceria stabilizer.     

Aluminum borate whisker-based lattices with a hierarchical pore structure obtained via digital light processing

To satisfy the ever-increasing demand for aluminum borate porous ceramics with complex shapes and tunable pore structures in a diverse set of fields, aluminum borate whisker-based lattices with hierarchical pore structures were fabricated by a combination of in situ reaction and digital light processing three-dimensional (3D) printing. The optimal dispersant concentration and exposure parameters for 3D printing were determined based on analyses of the rheological properties and working curves of the Al₂O₃–B₂O₃ photosensitive slurries. The effects of the B₂O₃/Al₂O₃ molar ratio on the morphology and properties of aluminum borate lattices were investigated. The results showed that the addition of an excess of B₂O₃ was beneficial to the growth of aluminum borate whiskers. When the B₂O₃/Al₂O₃ molar ratio was set to 6:9, the resultant aluminum borate lattices exhibited a typical hierarchical pore structure, including inherent large pores in the lattices and small pores formed by interlocked aluminum borate whiskers generated in situ within the struts. This unique hierarchical pore structure endowed the ceramic lattices with a high compressive strength (1.18 MPa) and porosity (82.58%), as well as non-brittle fracture characteristics. Owing to these outstanding properties, aluminum borate whisker-based lattices are promising candidates for high-temperature thermal insulation, catalyst supports, acoustic absorption, and particle filtration.     

Three-dimensional printing of high-flux ceramic membranes with an asymmetric structure via digital light processing

In this study, a novel method was proposed for preparing high-flux ceramic membranes via digital light processing (DLP) three-dimensional (3D) printing technology. Two different alumina powders were well dispersed in a photosensitive resin to form a UV-curable slurry for DLP 3D printing. The effects of the grading ratio on the viscosity of the slurry and the porosity, pore size distribution, mechanical strength, roughness, and permeability of the ceramic membranes were systematically investigated. The thermal treatment conditions were also studied and optimized. The obtained ceramic membranes exhibited a uniform pore size distribution, a high porosity, a low tortuosity factor, and an asymmetric structure. The combination of these factors led to a high flux for the 3D-printed ceramic membranes. DLP 3D printing exhibited a good potential to be a strong candidate for the next generation of ceramic membrane fabrication technology.     

Optimisation of two-step sintering parameters to produce bioactive and dense zirconia-hydroxyapatite composite ceramics

3Y-TZP along with Hydroxyapatite (HAp) are common bioceramics used in bone tissue engineering scaffolds to yield better patient outcomes and faster healing times. However, significant differences in thermal expansion of these ceramics result in challenges to co-sintering these materials without losing functionality and strength. In this work, a two-step sintering (TSS) process was utilised to co-sinter composites using (1-x)3Y-TZP and xHAp where x varies between 20 and 80 wt%. A peak temperature of 1300 °C, a plateau temperature of 1175 °C, a holding time of 600 min and heating rate of 10 °C/min were the optimum TSS conditions for all compositions. The TSS process produced specimens with grain sizes between 0.5 and 1.2 µm and a compression strength between 88 and 176 MPa. The similarity in compression strength of these zirconia-hydroxyapatite composites with natural bone and the retention of HAp make them suitable for bone tissue engineering applications in load bearing areas.     

Yellow resistant photosensitive resin for digital light processing 3D printing

Digital light processing (DLP) has been studied and developed in the field of three-dimensional (3D) printing in recent years due to its fast curing rate and high resolution. To reduce the cost and viscosity of the resin system, the aromatic polyurethane acrylates (PUAs) were used as oligomer. The matrix resin called PUH₂ consists of oligomers (PUA, bisphenol A polyoxyethylene ether dimethyl acrylate) and active diluents (hydroxyethyl acrylate, hydroxyethyl methacrylate). However, the photosensitive resin containing aromatic isocyanate groups was easily yellowed under ultraviolet light. In this article, we developed a resin for DLP 3D printing with yellowing resistance, excellent mechanical properties and high heat resistance. The optimal ratio of 3DP-PUH₂ resin was PUH₂/TPO/RYOJI-292/dye/nanosilica = 100/5/0.4/0.01/0.1, and its viscosity was 500 cp, which is suitable for DLP 3D printing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48369.     

Mechanical properties and biocompatibility of MgO / Ca3(PO4)2 composite ceramic scaffold with high MgO content based on digital light processing

Magnesium oxide-calcium phosphate (MgO/Ca3(PO4)2) composite ceramic materials are considered a promising class of bioactive materials, expected to be used in artificial bone scaffolds. However, there are few pieces of research on the content of magnesium oxide in composite ceramic scaffolds. To study the effect of magnesium oxide content on the biocompatibility and mechanical properties of magnesium oxide-calcium phosphate composite ceramic scaffolds, six groups of scaffolds with magnesium oxide content of 10 wt%, 20 wt%, 30 wt%, 40 wt%, 100 wt%, and 0 wt% were produced by digital light processing (DLP) printing technology. And scaffolds’ pores size and porosity percentage were 0.6–1 mm and 50%, respectively. The compressive strength of the scaffold increased with the magnesium oxide proportion, and the 40 wt% group was almost twice that of the 0 wt% magnesium oxide group. The 40 wt% and 0 wt% magnesium oxide groups performed better for biocompatibility. Comprehensive analysis of the biocompatibility and mechanical properties of the scaffold confirmed that the 40 wt% magnesium oxide group was the best. The results show that high magnesium oxide content enhanced the mechanical properties and achieved well biocompatibility of the composite scaffolds, broadening the scope of future experimental research.     

Complex mullite structures fabricated via digital light processing of a preceramic polysiloxane with active alumina fillers

By taking advantage of the multi-functional properties of preceramic polymers, their transformation into ceramic material at low sintering temperatures and the processing capabilities of polymer manufacturing processes, mullite components were fabricated by additive manufacturing. A photocurable silicone preceramic polymer resin containing alumina particles was shaped into complex structures via Digital Light Processing. Dense and crack-free, highly complex porous mullite ceramics were produced by firing a mixture of a commercially available photosensitive polysiloxane as the silica source, containing alumina powder as active filler, in air at a low sintering temperature (1300 °C). In particular, the developed formulations, coupled with the additive manufacturing approach, allow for precise control of the architecture of the porous ceramic components, providing better properties compared to parts with stochastic porosity.     

Impact strengthening of 3Y-TZP dental ceramic root posts

3Y-TZP ceramics are commonly used in restorative dentistry for fixed partial dentures, implants, abutments and root posts. The stress-induced transformation-toughening mechanism leads to improved mechanical properties advocating 3Y-TZP to be ground or sandblasted for better clinical performance. Such invasive mechanical treatments facilitate the additional surface strengthening as a result of the residual compressive stresses, but the exact origin is not completely understood. This study evaluated the effect of continuous impacting between 3Y-TZP root posts during 500 -h-long shaking on the extent of (sub)surface microstructural changes affecting the fracture strength. With an increase of the shaking time the surface roughness decreased, where the grains were flattened and partially spalled. The observed 6-micrometre-thick altered subsurface region containing compressive residual stresses contributed to a systematic increase in the forces of fracture within the sample population; however, only for those containing the surface type of critical flaws that were in the form of mould imprints.