Enhancing the dehydrogenation properties of LiAlH4 using K2NiF6 as additive

Lithium alanate (LiAlH₄) is a material that can be potentially used for solid-state hydrogen storage due to its high hydrogen content (10.5 wt%). Nevertheless, a high desorption temperature, slow desorption kinetic, and irreversibility have restricted the application of LiAlH₄ as a solid-state hydrogen storage material. Hence, to lower the decomposition temperature and to boost the dehydrogenation kinetic, in this study, we applied K₂NiF₆ as an additive to LiAlH₄. The addition of K₂NiF₆ showed an excellent improvement of the LiAlH₄ dehydrogenation properties. After adding 10 wt% K₂NiF₆, the initial decomposition temperature of LiAlH₄ within the first two dehydrogenation steps was lowered to 90 °C and 156 °C, respectively, that is 50 °C and 27 °C lower than that of the аs-milled LiAlH₄. In terms of dehydrogenation kinetics, the dehydrogenation rate of K₂NiF₆-doped LiAlH₄ sample was significantly higher as compared to аs-milled LiAlH₄. The K₂NiF₆-doped LiAlH₄ sample can release 3.07 wt% hydrogen within 90 min, while the milled LiAlH₄ merely release 0.19 wt% hydrogen during the same period. According to the Arrhenius plot, the apparent activation energies for the desorption process of K₂NiF₆-doped LiAlH₄ are 75.0 kJ/mol for the first stage and 88.0 kJ/mol for the second stage. These activation energies are lower compared to the undoped LiAlH₄. The morphology study showed that the LiAlH₄ particles become smaller and less agglomerated when K₂NiF₆ is added. The in situ formation of new phases of AlNi and LiF during the dehydrogenation process, as well as a reduction in particle size, is believed to be essential contributors in improving the LiAlH₄ dehydrogenation characteristics.     

Topological homogenization of metamaterial variability

With the proliferation of additive manufacturing and 3D printing technologies, a broader palette of material properties can be elicited from cellular solids, also known as metamaterials, architected foams, programmable materials, or lattice structures. Metamaterials are designed and optimized under the assumption of perfect geometry and a homogeneous underlying base material. Yet in practice real lattices contain thousands or even millions of complex features, each with imperfections in shape and material constituency. While the role of these defects on the mean properties of metamaterials has been well studied, little attention has been paid to the stochastic properties of metamaterials, a crucial next step for high reliability aerospace or biomedical applications. In this work we show that it is precisely the large quantity of features that serves to homogenize the heterogeneities of the individual features, thereby reducing the variability of the collective structure and achieving effective properties that can be even more consistent than the monolithic base material. In this first statistical study of additive lattice variability, a total of 239 strut-based lattices were mechanically tested for two pedagogical lattice topologies (body centered cubic and face centered cubic) at three different relative densities. The variability in yield strength and modulus was observed to exponentially decrease with feature count (to the power −0.5), a scaling trend that we show can be predicted using an analytic model or a finite element beam model. The latter provides an efficient pathway to extend the current concepts to arbitrary/complex geometries and loading scenarios. These results not only illustrate the homogenizing benefit of lattices, but also provide governing design principles that can be used to mitigate manufacturing inconsistencies via topological design.     

Predictive process mapping for laser powder bed fusion: A review of existing analytical solutions

One of the main challenges in the laser powder bed fusion (LPBF) process is making dense and defect-free components. These porosity defects are dependent upon the melt pool geometry and the processing conditions. Power-velocity (PV) processing maps can aid in visualizing the effects of LPBF processing variables and mapping different defect regimes such as lack-of-fusion, under-melting, balling, and keyholing. This work presents an assessment of existing analytical equations and models that provide an estimate of the melt pool geometry as a function of material properties. The melt pool equations are then combined with defect criteria to provide a quick approximation of the PV processing maps for a variety of materials. Finally, the predictions of these processing maps are compared with experimental data from the literature. The predictive processing maps can be computed quickly and can be coupled with dimensionless numbers and high-throughput (HT) experiments for validation. The present work provides a boundary framework for designing the optimal processing parameters for new metals and alloys based on existing analytical solutions.     

Microstructure and mechanical behavior of laser aided additive manufactured low carbon interstitial Fe49.5Mn30Co10Cr10C0.5 multicomponent alloy

Laser aided additive manufacturing(LAAM)was used to fabricate bulk Fe49.5Mn30Co10Cr10C0.5 interstitial multicomponent alloy using pre-alloyed powder.The room temperature yield strength(σy),ultimate tensile strength(σUTS)and elongation(εUST)were 645 MPa,917 MPa and 27.0％respectively.The as-built sample consisted of equiaxed and dendritic cellular structures formed by elemental segregation.These cellular structures together with oxide particle inclusions were deemed to strengthen the material.The other contributing components include dislocation strengthening,friction stress and grain bound-ary strengthening.The high εUTS was attributed to dislocation motion and activation of both twinning and transformation-induced plasticity(TWIP and TRIP).Tensile tests performed at-40℃and-130℃demonstrated superior tensile strength of 1041 MPa and 1267 MPa respectively.However,almost no twinning was observed in the fractured sample tested at-40℃and-130℃.Instead,higher fraction of strain-induced hexagonal close-packed(HCP)ε phase transformation of 21.2％were observed for fractured sample tested at-40℃,compared with 6.3％in fractured room temperature sample.     

Direct writing of textured ceramics using anisotropic nozzles

Direct writing is a unique means to align anisotropic particles for the fabrication of textured ceramics by templated grain growth (TGG). We show that alignment of tabular barium titanate (BT) template particles (20–40 μm width and 0.5–2 μm thickness) in a PIN-PMN-PT matrix powder (d₅₀ = 280 nm) is significantly improved during direct writing using anisotropic nozzles at high printing rates. The particle orientation distribution in as-printed filaments, and the texture orientation distribution in sintered ceramic filaments are shown to directly correlate with COMSOL Multiphysics-predicted torque distributions for direct writing with aspect ratio 2, 3 and 5 oval nozzles. Electromechanical strain properties of the textured piezoelectric ceramics significantly improved relative to random ceramics when printed with anisotropic nozzles. Simulations of aspect ratio 20 nozzles and nozzles with interior baffles demonstrate significantly increased torque and near elimination of constant shear stress cores (i.e. plug flow).     

Binder jetting additive manufacturing of aluminum nitride components

In this work, we report on the novel fabrication of aluminum nitride (AlN) components using Binder Jetting (BJT) additive manufacturing (AM). The AlN constructs were subjected to post-fabrication thermal treatment by hot isostatic pressing (HIPing) for 8 hours at a pressure of 206 MPa and temperature of 1900 °C. This treatment resulted in a 60.1% relative density maximum densification for AlN. The BJT printed AlN specimens were analyzed using various characterization techniques. The purity, microstructure, and polycrystallinity of the AlN phase formed were confirmed by techniques that included x-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), and high-resolution transmission electron microscopy (HRTEM). Second harmonic generation (SHG) microscopy showed polarization dependence and second harmonic signal at 470 nm, indicating the potential to produce thermal and optical-mechanical devices. Mechanical properties obtained by nanoindentation resulted in an elastic modulus of ~251 GPa when measured in fully dense, contiguous crystalline regions, corresponding to an apparent, porous bulk stiffness of ~90 GPa for the final, 60.1 % dense products. Finally, the laser flash method (LFM) was used to measure the thermal conductivity of the material as a function of temperature resulting in values from 4.82 W/mK to 3.17 W/mK for the temperature range from 23 °C to 500 °C, respectively.     

Additive manufacturing of zirconia ceramics by material jetting

The possibility of additive manufacturing of ceramics has been reported widely in scientific literature. This study investigates the potential of direct inkjet printing or material jetting of 3Y-TZP ceramics by assessing the microstructure and mechanical properties of the sintered printed parts. The technique allows to print in layers of 10.5 μm, with an as-printed green density of 58 % and nearly fully sintered density of 6.03 ± 0.1 g/cm³ (99.7 % TD). The dimensions of the green and sintered parts were highly accurate but showed an anisotropic roughness in function of the building direction, mainly due to the support structures. The biaxial bending and 4-point bending strength of the sintered material was found to be substantially higher in the XY direction than in the building (Z) direction. SEM and X-Ray computed tomography revealed the presence of delamination cracks, agglomerates and spherical pores, which were identified as fracture origins on fractured surfaces.     

Feasibility of manufacturing of Al2O3–Mo HTCC by hybrid additive process

Additive manufacturing processes make it possible to produce increasingly complex 3D parts. In addition, these numerical processes can be usefully used to manufacture ceramic/metal parts of high dimensional resolution with thermal, electrical and electronic properties of interest for applications in the field of power electronics.In this context, a hybrid additive machine was developed to manufacture ceramic/metal parts. This machine consists in the combination of two additive manufacturing processes: stereolithography and robocasting.Using this hybrid process, the feasibility of HTCC components has been demonstrated by building dielectric alumina by stereolithography and molybdenum conductive network by robocasting. Molybdenum-based metallic formulation adapted to the process and allowing to obtain a high conductive metallic network has been developed. The co-debinding and co-sintering cycles have been optimized to minimize the content of residual carbon and to prevent the oxidation of molybdenum. The alumina/molybdenum interface has also been observed to conclude about a possible delamination between these two materials with different thermal expansion coefficients (CTE). Sintered HTCC parts have been characterized in the domain of hyperfrequency. The frequency responses deviate from the simulation due to a lack of dimensional accuracy of the metallic network.     

The effect of particle size distribution on the microstructure and properties of Al2O3 ceramics formed by stereolithography

Stereolithography (SL) shows advantages for preparing alumina-based ceramics with complex structures. The effects of the particle size distribution, which strongly influence the sintering properties in ceramic SL, have not been systematically explored until now. Herein, the influence of the particle size distribution on SL-manufactured alumina ceramics was investigated, including bending strength at room temperature, post-sintering shrinkage, porosity, and microstructural morphology. Seven particle size distributions of alumina ceramics were studied (in μm/μm: 30/5, 20/3, 10/2, 5/2, 5/0.8, 3/0.5, and 2/0.3); a coarse:fine particle ratio of 6:4 was maintained. At the same sintering temperature, the degree of sintering was greater for finer particle sizes. The particle size distribution had a larger influence on flexural strength, porosity and shrinkage than sintering temperature when the particle size distribution difference reached 10-fold but was weaker for 10 μm/2 μm, 5 μm/2 μm and 5 μm/0.8 μm. The sintering shrinkage characteristics of cuboid samples with different particle sizes were studied. The use of coarse particles influenced the accuracy of small-scale samples. When the particle size was comparable to the sample width, such as 30 μm/5 μm and 5 mm, the width shrinkage was consistent with the height shrinkage. When the particle size was much smaller than the sample width, such as 2 μm/0.3 μm and 5 mm, the width shrinkage was consistent with the length shrinkage. The results of this study provide meaningful guidance for future research on applications of SL and precise control of alumina ceramics through particle gradation.     

Direct additive manufacturing of melt growth Al2O3-ZrO2 functionally graded ceramics by laser directed energy deposition

Functionally graded ceramics (FGC), which combine properties of different ceramics in one part, usually have better comprehensive function and structural efficiency. In this study, four different gradient transition Al₂O₃-ZrO₂ FGC samples were prepared by laser directed energy deposition (LDED) method. The results show that there is an obvious interface in direct transition sample. The transition section bears tensile stress caused by difference of thermophysical properties of materials, resulting in significant longitudinal cracks. Element transition in interface region shows a step sharp transition. The direct transition sample shows intergranular fracture and the bonding strength is very low. Gradient transition mode can effectively suppress cracks, and avoid the step transition of microstructure and elements. Elements, microhardness of 25, 20 wt% FGC samples realized a nearly linear smooth transition. The interface fracture of FGC samples changed to transgranular fracture, bonding strength was significantly improved, and the maximum flexural strength reached 160.19 MPa.