Sintering Step Research Articles

Compact Layer‐Free Perovskite Solar Cells with Low‐Temperature UVO Photochemical Annealed Mesoporous TiO2 Layers

In recent years, the field of perovskite solar cells (PSCs) has seen rapid development, with most high‐efficiency devices incorporating dense titanium dioxide (TiO2) barrier layers and mesoporous TiO2 layers to enhance selective electron transport. However, the manufacturing process requires high‐temperature sintering steps above 450 °C, leading to significant energy consumption. In addition, this requirement greatly limits the potential applications of PSCs in the field of flexible electronics. This study introduces a new method for preparing dense‐layer‐free mesoporous PSCs using low‐temperature UVO annealing of m‐TiO2. UVO annealing effectively removes residual organic components from m‐TiO2 precursor films, enhances the conductivity and wettability of the films, thereby reducing carrier recombination and improving the performance of PSCs. Research has shown that PSC with a 40 min UVO annealed m‐TiO2 layer exhibits a final photoelectric conversion efficiency of 17.79%, comparable to devices with traditional high‐temperature annealed m‐TiO2 PSCs. In addition, after 7 days at room temperature and ambient humidity, the unpackaged device maintains a maximum conversion efficiency of 84%. These findings indicate that UVO light annealing is a feasible alternative to high‐temperature annealing, providing a simpler, more cost‐effective, and energy‐saving method for the preparation of metal oxide electron transport layer in PSCs.

Sintering Driven Void Formation in PS@WO3 Core-Shell Composites: A Photodegradation Enhancement Strategy

Background: Polystyrene nanospheres are used as a substrate for the hydrothermal coating of tungsten trioxide (WO3) to form a core-shell composite of PS@WO3. The core-shell structure is used for the next sintering step. This produces porous WO3. The focus of this study is on the role of porous WO3 in enhancing photocatalytic performance. Methods: The hydrothermal method was employed for coating, and the surface morphology, as well as the structural properties of WO3-coated PS spheres, were systematically investigated using SEM and XRD analyses. Additionally, the sintering process was introduced to enhance the material by inducing rupture in the PS sphere core, creating voids that significantly increased the material's surface area. Results: The evaluation of the effect of sintering temperature on photodegradation efficiency highlighted the crucial role of sintering temperature. Un-sintered and 300°C sintered WO3, both having a hexagonal crystalline structure, exhibited superior degradation efficiencies compared to samples sintered at higher temperatures (400°C and 500°C). In particular, the 300°C sintered WO3 outperformed its un-sintered counterpart despite identical crystalline structures. The performance of the PS@WO3 composite was assessed to determine the enhanced role of porous WO3. The porous WO3 obtained, in particular by the sintering of the core-shell PS@WO3 composites at 300°C, showed a remarkable improvement in the degradation efficiency. These composite demonstrated over 95% efficiency within 10 minutes and achieved near complete (100%) degradation for a further 10 minutes, surpassing the performance of pure WO3. It is important to clarify that while the final product was predominantly WO3 after the sintering process, the inclusion of PS served a critical purpose in creating voids during sintering. The PS@WO3 composite structure used as a resource for the preparation of porous WO3, even with a potentially reduced PS composition, has been found to play a significant role in influencing the surface area of the material, and consequently the photocatalytic performance. Conclusion: The study has highlighted the importance of crystalline structure and sintering conditions in optimizing the efficiency of photocatalytic materials. The porous WO3 obtained, in particular by the sintering of the core-shell PS@WO3 composites at 300°C, showed promising potential for applications under UV and visible LED light irradiation. These results provide valuable insights for the development of advanced photocatalytic materials with improved performance, highlighting WO3 as the key contributor to the observed improvements.

In-depth approach and establishment from a structural perspective of LiFePO4 cathodes for lithium-ion batteries by a two-step sintering

Most synthesis of olivine LiFePO4 (LFP) studies have emphasized the importance of a two-step sintering process for the formation of a uniform carbon coating. However, in this study, it is found that, as an advantage of the two-step sintering process, stable carbonization not only improves lithium-ion conductivity by forming a coating layer but also increases the uniformity of the internal crystal structure. In addition to basic crystallinity and structure analysis using X-ray diffraction (XRD), in-depth calculations are performed to explain the formation mechanism of crystal structure according to the two-step sintering process and the temperature of the first sintering step. In particular, lattice defects and structural uniformity are closely investigated from the crystal structure perspective by comparing lattice micro-strain and dislocation density. Improvement in lithium-ion conductivity from structural uniformity is also demonstrated through cyclic voltammetry (CV) analysis. As a result, it is confirmed that LFP, which undergoes a high-temperature two-step sintering, has high capacity and excellent cycle retention at high rates. Furthermore, ex-situ XRD analysis demonstrates the performance difference according to lithium-ion mobility by comparing the LiFePO4/FePO4 two-phase transformation reaction of two-step sintered LFP and the plateau stability during charging.

Versatile binder system as enabler for multi-material additive manufacturing of ceramics by vat photopolymerization

Vat photopolymerization is an additive manufacturing process for producing ceramics with high printing resolution. Extending this approach to multi-material additive manufacturing, the aim is to combine two or more different ceramics in a single component to aggregate their advantages. For this, binders for different ceramic materials are required. To enhance the debinding step, this work aimed to develop a versatile binder system suitable for different ceramic materials. Finally, a binder system was developed and qualified for several different ceramic materials. By thermogravimetrical analyses, a suitable temperature curve for debinding was derived. In a final sintering step, the components were densified almost defect-free. Therefore, this work serves as an enabler for multi-material vat photopolymerization.

High-efficiency RbASiF6:Mn4+ (A = K, Cs) phosphors obtained by one-step green synthesis method

Red-emitting Mn4+-doped fluoride phosphors are recognized as promising materials for high-performance warm white light-emitting diodes (WLEDs). However, the extensive use of toxic hydrofluoric acid in traditional synthesis methods hinders their development and commercialization. Furthermore, the traditional solid-phase method often has cumbersome sintering steps, high temperature, long holding time, and certain safety hazards, so it is very necessary to develop a green synthesis method with simple steps and low energy consumption. In this study, a low-temperature solid-state method is proposed to synthesize RbASiF6:Mn4+ (A = K, Cs) phosphors by one step. Optimal emission intensities were observed at Mn4+ concentrations of 1.2 % in RbKSiF6 and 2.1 % in RbCsSiF6. These phosphors demonstrated high thermal stability. At 423 K, the photoluminescence intensities of RbKSiF6:1.2 %Mn4+ and RbCsSiF6:2.1 %Mn4+ reached 114 % and 87 % of their respective values at room temperature. Meanwhile, the chromaticity shifts were almost negligible, and high color purity was achieved for both phosphors. The electro-optical performance of WLED devices utilizing these phosphors, in combination with YAG:Ce3+ and GaN chips, showed high color rendering indices (CRI) and low correlated color temperatures (CCT) across varying currents. Specifically, under a driving current of 20 mA, the device incorporating RbKSiF6:1.2 %Mn4+ exhibited a CRI of 94 and a CCT of 3732 K, with a luminous efficacy of 61 lm/W. These findings highlight the potential of green-synthesized RASFM phosphors in advancing the application of warm WLEDs.

Phase and microstructure formation during reactive spark plasma sintering of AlxCoCrFeNi (x=0.3 and 1) high entropy alloys

This paper is one of the first studies focusing on phase and microstructure formation mechanisms during reactive sintering of AlxCoCrFeNi (x = 0.3, 1) high entropy alloys (HEAs). The alloys have been prepared by mechanical activation followed by spark plasma sintering (SPS). Both powders are subjected to gluing to the milling vials and the phenomenon intensifies with Al content, resulting in a more important mechanical alloying delay for the equiatomic composition. The temperature influence on phase and microstructure formation was investigated by SPS from 550 to 1100 °C. Al0.3CoCrFeNi reactive sintering led to a face-centered cubic (FCC) solid solution with a grain size around hundreds of nanometers with nanometric intergranular B2 precipitates which content and size reduced with the temperature increase. Grain growth was observed at prior particle boundaries due to dynamic recrystallization, a phenomenon that can be controlled through modification of the milling and sintering steps, leading thus to tailored grain sizes. For the AlCoCrFeNi composition, temperature increase favors secondary FCC formation and leads to sigma phase precipitation. A dual homogeneous-heterogeneous microstructure is obtained due to the important gluing leading to insufficient milling. The dynamic recrystallization at prior particle boundaries promotes also body-centered cubic (BCC) to FCC phase transition. Therefore, the proposed reactive sintering route allows to obtain, for the equiatomic composition, alloys exhibiting very fine microstructures, with higher FCC fraction content than by conventional metallurgy processes.

Additively manufactured, long, serpentine submillimeter channels by combining binder jet printing and liquid-phase sintering

Metallic microfluidic devices made from powder-bed additive manufacturing systems have received increasing attention, but their feasible channel geometry and complexity are often limited by lack of an effective approach to removing trapped powder particles within the channels or conduits of the sintered parts. Here, we present an innovative approach to fabricating long serpentine, high-aspect-ratio submillimeter channels made of stainless steel 316L (SS) by binder jet printing (BJP) and liquid-phase sintering. We leverage the unique nature of the BJP process, that is printing and consolidation steps are decoupled, enabling us to join two or more parts during the sintering step. Instead of constructing the channel device as a single part, we print multiple parts for easy powder removal and later join them to form enclosed channels. The key innovation lies in adding sintering additives like boron nitrides (BN) to the SS stock powder—at the SS/BN interfaces, liquid phase is locally generated at temperature much lower than the SS melting temperature, facilitating the bonding of the multiple parts as well as the consolidation of parts for near-full density. We systematically vary the sintering temperature to show how it affects the joining quality and the channel shape distortion. The joining quality such as the fracture strengths of the joined samples is measured by a pull test while the shape distortion is characterized by various imaging techniques. The feasibility of the proposed approach is demonstrated by fabricating a 400-mm-long, fully enclosed serpentine channel with a rectangular cross-section of 0.5 mm in width and 1.8 mm in height. The pressure drop across this 3D-printed SS serpentine channels is measured for air flow and compared to a standard gas flow model, showing that the device is free of leakage or clogs.

Promotional effect of NaNO3/NaNO2 on CO2 adsorption performance of MgO sorbents

The magnesium oxide (MgO) sorbents doped with different NaNO3/NaNO2 molar ratios were prepared to improve their stability over multiple cycles. Regulating the NaNO3/NaNO2 molar ratio effectively improved the CO2 adsorption performance of the sorbent. The MgO sorbent with the NaNO3/NaNO2 molar ratio of 0.8 exhibited outstanding performance and stability. Characterization and density functional theory calculations confirmed the positive effects of the appropriate NaNO3 amount in improving the adsorption activity, whereas the suitable NaNO2 amount slowed the sintering step and improved stability. Notably, the molten salt remained stable during cycling and did not decompose even at high regeneration temperatures, guaranteeing the cyclic stability of the sorbent. Further characterization showed that the CO2 sorption drop in the first few cycles was ascribed to the decline in the active surface owing to the aggregation of MgO particles, incomplete regeneration of sorbents, and segregation of molten salt on the sorbent surface.

Ultrafast high-temperature sintering of polymer-derived ceramic thick film sensors

Polymer-derived ceramics (PDCs) find extensive applications as sensitive materials in in-situ thin/thick film sensors (TFSs) co-fabricated with components. However, the prolonged high-temperature sintering steps of PDCs inevitably lead to severe thermal damage to their co-sintered substrates. In this study, we employed an ultrafast high-temperature sintering (UHS) method, achieving rapid sintering of preceramic polymer slurry sensitive films in just a few minutes. Through direct ink writing technology, we patterned the preceramic polymer slurry, followed by UHS to prepare high-temperature ITO/SiCN TFSs. UHS-ITO/SiCN exhibited high sensitivity of microstructure, composition, and electrical characteristics to UHS parameters. The obtained ITO/SiCN resistance grid showed high electrical conductivity (706.89 S m−1 at room temperature), highly dense surface structure and excellent oxidation resistance. In an air atmosphere, the resistance drift rate of the resistance grid at 900 °C was only 0.54 %·h−1 without any protective layers. Finally, we fabricated an ITO/SiCN heat flux sensor with high sensitivity (78.75 mV/(kW·m−2)), a wide range (94.8 kW m−2), and excellent repeatability. This work has the potential to expand the application of UHS in the manufacturing of novel in-situ TFSs integrated with components.

Tailoring high-entropy alloys via commodity powders for metal injection moulding: A feasibility study

High entropy alloys (HEAs) represent a novel frontier in metallurgical advancements, offering exceptional mechanical properties owing to their unique multicomponent nature. This study explores a novel strategy utilising commodity powders - Ni625, Invar36, and CoCrF75 - to tailor HEAs via metal injection moulding (MIM). The objective is to achieve cost-effective manufacturing while maintaining desired properties. The research involves mixing these powders in a specific proportion, integrating them with a sustainable polyethylene glycol-cellulose acetate butyrate binder system, and characterising the resulting feedstocks for MIM processing. Subsequent debinding and sintering steps were executed to densify and form a single face-centered cubic (FCC) phase HEA, followed by comprehensive analyses to evaluate the suitability of the developed HEA compositions. In addition, all MIM stages were thoroughly characterised to control the porosity of the final parts and to ensure a single FCC solid solution with promising mechanical properties in the developed non-equiatomic CoCrFeNiMox-type HEAs.

One-Step Molten-Salt-Assisted Approach for Direct Preparation and Regeneration of LiNi0.6Co0.2Mn0.2O2 Cathode.

Single-crystal lithium-nickel-manganese-cobalt-oxide (SC-NMC) is attracting increasing attention due to its excellent structural stability. However, its practical production faces challenges associated with complex precursor preparation processes and severe lithium-nickel cation mixing at high temperatures, which restricts its widespread application. Here, a molten-salt-assisted method is proposed using low-melting-point carbonates. This method obviates the necessity for precursor processes and simplified the synthetic procedure for SC-NMC down to a single isothermal sintering step. Multiple characterizations indicate that the acquired SC-LiNi0.6Mn0.2Co0.2O2 (SC-622) exhibits favorable structural capability against intra-granular fracture and suppressive Li+/Ni2+ cation mixing. Consequently, the SC-622 exhibits superior electrochemical performance with a high initial specific capacity (174 mAhg-1 at 0.1C, 3.0-4.3V) and excellent capacity retention (87.5% after 300 cycles at 1C). Moreover, this molten-salt-assisted method exhibits its effectiveness in directly regenerating SC-622 from spent NMC materials. The recovered material delivered a capacity of 125.4 mAhg-1 and retained 99.4% of the initial capacity after 250 cycles at 1 C. This work highlights the importance of understanding the process-structure-property relationships and can broadly guide the synthesis of other SC Ni-rich cathode materials.

In-situ monitoring of sintering and analytical modeling of densification and shrinkage in binder jetted 316 L stainless steel

In binder jetting, shrinkage and deformation occur during the sintering step, both of which are affected by the green density of the binder jetted materials. The study innovatively introduces a cost-effective, practical, and in-process monitoring system for visualizing shrinkage and deformation on larger samples than conventionally observed using small-scale specimens in dillatometry equipment. The powder characteristics and binder jet printing process itself influence the initial green density. The comprehensive analysis of powder flowability and packing density, densification behavior, and shrinkage reveals that the consolidated parts using virgin powder (with a green density of 55 %) can achieve a relative density above 99.9 % with an anisotropic shrinkage in the Z > X > Y direction. In contrast, the used or recycled powder exhibits a lower green density of ∼48 %, higher shrinkage rate in all three dimensions, and a decreased degree of anisotropy. Using in-process imaging and experimental data on the grain size attained through optical microscopy and electron backscatered diffraction imaging, the material's shear and bulk viscosities were determined. The formation of delta-ferrite and its impact on densification were discussed in the context of solid-state and supersolidus liquid phase sintering. The model relied on the continuum sintering theory formulated by Skorohod and Olevsky. The strain evolution from the in-situ imaging of sintering process is correlated with porosity based on the used feedstock and applied sintering temperatures. The outcomes of this study offer valuable perspectives on anisotropic sintering mechanisms, bridging the knowledge gap regarding the relationships between structures produced through binder jetting and subsequent sintering of materials.

Defect evolution and mitigation in metal extrusion additive manufacturing: From deposition to sintering

Material extrusion additive manufacturing of metals has found widespread application and is typically thought of as a facile technique to create metal components. This can be undertaken without the need for energy sources typically used in direct energy deposition and powder bed fusion processes. Despite recent advances in achieving net shape and improvements to material/component integrity, these processes are characterized by performance limiting defects which often emerge as a result of deposition strategy and are retained post sintering. Although the debinding and sintering steps have been investigated for metal injection molding technology, quantitative studies of defect evolution are lacking. This work proposes an approach to study the pore evolution behavior from deposition to sintering through X-ray Computed Tomography (XCT) image processing. Quantitative results of pore shrinking, partial and full closure through backtracking of individual pores from the sintered to the green state are presented. It is shown that where pores are larger than 4 × 10-6 mm3, equals to the D90 of the feedstock metal particles, these cannot be fully closed upon sintering and will survive to limit the performance of the final part. The average pore shrinkage is by a factor of 5.6 and partial closure happens in pores with minimum Feret diameter of 33 μm, equals to 160% of the D90 powder particle, or less. The utilization of overfill as a proposed technique in the literature for the elimination of macro pores is investigated, yielding disparate and unsatisfactory results. This discrepancy can be attributed to the insufficient formation of micro-channels within the pore structure during the deposition process of the aqueous feedstock, leading to regions of weak grain bonding. To evaluate the contribution of these to undermining material integrity, tensile tests of linear and circular deposition strategies are undertaken. Experiments show that track interface length plays a major role in determining elongation to failure and tensile strength. It is concluded that the limitation to the mechanical properties of metal paste extrusion components originates from the emergence of defects and their characteristics after the completion of the processing, as opposed to being influenced by the metallurgy prior or post sintering.

Significantly enhanced transmittance and EO property in PMN-PT via optimized two-step pressure-free sintering

It is a great challenge to prepare Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN-PT) ceramics of very high transparency with only oxygen atmosphere pressureless sintering process. To address this issue, this work proposed an optimal low-cost two-step oxygen atmosphere sintering process with a first step at high temperature (T1) for minutes, followed by a second step at lower temperature (T2) for hours without applied pressure. High transmittance of 70 % in the near-infrared wavelength was achieved by our novel two-step process, which far exceeds the performance of PMN–PT ceramics prepared by only oxygen atmosphere sintering process reported in the past and demonstrates comparable performance compared to the costly hot-pressing sintering process. Meanwhile, it shows a high quadratic electro-optic (EO) coefficient of 42.1 × 10−16 m2 V−2, which is meaningful for applications in EO devices. Furthermore, the effect of the temperature difference between the first and second sintering step on the microstructure, transmittance, domain structure, ferroelectric and dielectric property, and polarization switching were discussed. The enhanced transparency is mainly attributed to the higher relative density, and weaker photoluminescence effect with lesser light absorption loss at optimal T1-T2. The improved EO property is due to greater polarization response originating from the interaction of defect dipoles and nanodomains. Such a process should facilitate the cost-effective preparation of other transparent electro-optic materials for practical applications.

Two-stage repeat sintering: A modified method for fabricating hydroxyapatite scaffolds with enhanced mechano-therapeutic properties

A modified two-stage repeat sintering (TSRS) technique has been used to produce hydroxyapatite (HAp) from non-separated animal bones, and the energy consumption per cycle of the proposed TSRS was calculated. The TSRS technique was compared to the conventional one-step sintering method. The energy consumption per cycle of the proposed TSRS was calculated considering economies of scale and typical energy consumption billing in Nigeria. The synthesized powders from both techniques underwent comprehensive characterization through X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM). The XRD analysis revealed the main reflections of HAp in the (112), (300), and (202) planes. The FT-IR spectra exhibited characteristic bands representative of HAp at all measurement points. Notably, the TSRS-derived sample during the second sintering step showed carbonate bands, suggesting relevance in the bone structure makeup. SEM images unveiled varying crystal morphologies, ranging from irregular shapes in the raw bone (RB) sample to rounded shapes with nucleation in aggregates and agglomerates at micro and macro levels in the TSRS-derived samples. The samples obtained from the TSRS technique demonstrated a high Ca/P ratio that is potentially beneficial for osteoblast adhesion in vivo. The cost analysis of electricity consumption per TSRS cycle, factoring in economies of scale and typical energy consumption billing in Nigeria, amounted to approximately $8 with consideration of the exchange rates at the time of the study. The microhardness measured using the TSRS technique was 0.5 GPa with a 1 MPa compaction pressure, while the samples prepared using the conventional sintering method were too fragile to handle and measure. The obtained microhardness using the modified technique surpassed values reported in various studies. In conclusion, the samples produced using the TSRS technique exhibited promising results regarding energy efficiency, material characteristics, and microhardness compared to the samples produced through conventional sintering. The distinct crystal morphologies observed suggest potential advantages for biomedical applications, particularly in enhancing osteoblast adhesion.

Electrical conductivity upon sintering of pure Cu produced by material extrusion additive manufacturing: Effects of pore, grain size, and impurity

This study investigates the development of pores and microstructures at each processing step and sintering conditions in the material extrusion additive manufacturing process, examining their correlation with related physical properties. This is achieved by fabricating copper parts using material extrusion (MEX) and examining the primary factors that impact the electrical characteristics of the MEX parts. Initially, the application of solvent debinding to MEX-produced Cu parts effectively removes a portion of the binder, forming printing-pattern–induced pores and ineffectual pore channels. Subsequently, thermal debinding eliminates the remaining binder and promotes neck formation between the Cu particles. The process proceeds to a subsequent sintering step, where even after the final sintering, some pores remain. These pores are categorized as sintering-induced and printing-pattern–induced pores. The relatively large pore size due to the printing pattern is identified as the main reason for reduced density of MEX parts, especially those influenced by the contour pattern. As the sintering progresses, the grain size increases, with the overall grain size and shape becoming uniform during extended sintering periods. Impurities, specifically carbon and oxygen, are detected in the sintered part, and their concentrations rise with longer sintering times. After examining the variation in porosity, grain size, and impurity content with respect to sintering time, it becomes evident that porosity plays a pivotal role in influencing electrical conductivity. Consequently, the densest 48 h sintered sample, with a relative density of 95.5 %, achieves the highest electrical conductivity at 94.6 % IACS. This demonstrates that MEX can be effectively employed to craft complex-shaped Cu parts with outstanding electrical properties. In summary, densification is crucial for enhancing the electrical properties of Cu parts produced through MEX, achieved by minimizing printing-pattern–induced pores, the primary contributor to density reduction. This study is poised to advance the manufacturing of high-performance, intricate Cu components by providing insights into the development and locations of primary pores through detailed microstructural investigations.

A Design Strategy for Removing the Debinding and Sintering Gas in Additive Manufactured Samples of a Bronze/Polylactic Acid Filament

To lower the cost of additive manufacturing of metallic components, the goal of this work is to investigate and optimize a multi‐step process by material extrusion (MEX) of a polylactide filament loaded with bronze to remove the gas produced during the debinding and sintering steps. First, by adjusting the infill (10%, 50%, and 100%), and then by designing and constructing internal passages to aid in the expulsion of gases that occur during the debinding, a calibration cube is created. Additionally, the impact of the cooling period during the debinding is examined. To assess how the technique changes shape, sizes, and internal structure, all the samples are ultimately weighed, scanned, and cut. In order to reduce deformation occurred during the debinding and sintering gases, a new design method has been developed. The method consists of the generation of internal channels which connect the voids of the infill and allow gases to flow out through a central channel. As seen, samples with ejection channels and an intermediate infill (i.e., 50%) both exhibit better attributes.

Comparative analysis of binder systems in copper feedstocks for metal extrusion additive manufacturing and metal injection moulding

In the realm of material innovation, the remarkable versatility of thermoplastic-based highly filled composites emerges as a pivotal advantage for fabricating metal parts, seamlessly integrating design flexibility. This study delves into the fusion of design and manufacturing, spotlighting the convergence of material extrusion additive manufacturing (MEX) and metal injection moulding (MIM) processes through the adept utilization of three distinct in-house developed copper-feedstocks. Each feedstock had a different composition that influenced their processability; two feedstocks were for solvent and thermal debinding, and one was only for thermal debinding. The sintering was carried out under the same conditions for all produced specimens to assess the effect of binder composition on the properties of the sintered components. Structural integrity evaluations of sintered specimens encompassed 3-point bending, hardness tests, and metallography. It was possible to perform MEX with all produced filaments and MIM with the pellets of the same feedstocks and to obtain acceptable-quality specimens. Regardless of the shaping method, specimens shaped with binders containing a soluble binder survived the thermal and sintering steps. The specimens produced from the feedstock intended solely for thermal debinding experienced a nearly complete loss of shape during the debinding process. For the specimens that could be debound and sintered without defects, a relative density between ∼88 and 94 % was measured for MEX components and ∼93 and 95 % for MIM components after sintering. All sintered components showed the same diffraction peaks as pure copper powder, confirming that the reductive hydrogen atmosphere provided protection from contamination and reduced the oxides that could have appeared during thermal debinding in air. Moreover, adequate shrinkage of ∼10–18 % was observed in the sintered specimens. Vickers microhardness of the MEX and MIM sintered components were ∼32 HV and ∼36 HV, respectively. Compared to MEX, MIM-produced sintered components showed a higher maximum stress (i.e., σmax = 79 ± 3.2 MPa). These results demonstrate that the binder composition plays a crucial role in determining the success of metal MEX and MIM processes. Having the possibility to choose between MEX and MIM allows for greater design flexibility for copper parts.

Abnormal grain growth inhibition of extrusion-based 3D-Printed 3Y-TZP ceramics sintered by flash sintering

This study investigated the combination of Direct Ink Writing (DIW) and Flash Sintering of zirconia stabilized with 3 mol. % Y2O3 (3Y-TZP). The samples were printed in two stacking configurations, and flash sintering was performed without current ramp control (FS) and using current ramp (CRFS) for comparison purposes. In both conditions, an electric field of 80 V cm−1 and a current density of 150 mA mm−2 were applied. The physical, microstructural, and mechanical properties of the printed samples were evaluated. The stacking configuration influenced both the grain size gradients and mechanical properties. Furthermore, controlling the current density ramp resulted in a slight homogenization of the grains’ size across different regions of the sample (core, edge, and flat surfaces). The presence of zirconia polymorphs, such as ZrO2-t and ZrO2-c, as well as a distorted form of the tetragonal phase (ZrO2-t'), was observed in the samples. These phases were affected by both the printing strategy and the current ramp control during the flash sintering step. In addition, the samples demonstrated typical values of Vickers hardness for 3Y-TZP (ranging from 10.5 to 11.8 GPa) and fracture toughness (ranging from 3.6 to 4.7 MPa m1/2), with a minor current density ramp control influence. Therefore, both FS and CRFS techniques represent viable pathways for producing dense 3D printed ceramic materials.

Photonic post-processing of a multi-material transparent conductive electrode architecture for optoelectronic device integration.

Emerging flexible optoelectronic devices require multi-material processing capabilities to fully enable the use of temperature-sensitive substrates and materials. This report demonstrates how photonic sintering enables the processing of materials with very different properties. For example, charge carrier transport/blocking metal-oxides, and transparent conductive silver nanowire-based electrodes ought to be compatible with low-energy and high-throughput processing for integration onto flexible low-temperature substrates. Compared to traditional post-processing methods, we show a rapid fabrication route yielding highly-stable hybrid electrode architectures on polyethylene terephthalate (PET). This architecture consists of an interconnected silver nanowire network encapsulated with a thin crystalline photo-sensitive titanium dioxide (TiO2) coating, allowing both layers to be treated using independent photonic post-processing sintering steps. The first step sinters the nanowires, while the second completes the conversion of the top metal-oxide layer from amorphous to crystalline TiO2. This approach improves on the fabrication speed compared to oven processing, while delivering optical and electrical characteristics comparable to the state of the art. Optimized transparency values reach 85% with haze values down-to 7% at 550 nm, while maintaining a sheet resistance of 18.1 Ω sq.-1. However, this hybrid architecture provides a much stronger resilience to degradation, which we demonstrate through exposure to harsh plasma conditions. In summary, this study shows how carefully-optimized photonic curing post-processing can provide more-stable hybrid architectures while using a multi-material processing technique suitable for high-volume manufacturing on low-temperature substrates.