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The post-processing treatment plays an important role in tailoring the mechanical and biological properties of the three-dimensional powder-printed porous scaffolds. Depending on scaffold material composition, a combination of post-processing treatments can be used to tailor these properties. This work probes into the impact of post-processing on the microstructure and deformation behavior of 3D-printed scaffolds. In this study, we have chosen CaSO4·xH2O (POP), a system for 3D powder printing and two different post-processing methodologies, namely chemical conversion and polymer infiltration. POP-based scaffolds were fabricated using water-based binder with up to 55% interconnected microporosity and moderate compressive strength of 1.5 MPa. Microcomputed tomography (µCT) is extensively utilized to determine the accuracy and efficacy of the adopted printing and post-processing approach. It was shown that the reproducibility of the fine features depends not only on the size but also on the presence of neighboring features. Crucially, µCT-based microstructure modeling and finite elemental simulation were attempted to computationally capture the compression behavior, in silico. Finally, in situ compression coupled with µCT imaging provided us an insight into fracture behavior of 3D powder-printed scaffolds.
Seeking to improve the wear resistance of the Ti6Al4V (Ti64) alloy for biomedical applications, carbon nanotubes (CNTs) and calcium phosphate (CaP) ceramics were added to Ti64 powder and successfully 3D-printed using a commercial laser engineered net shaping (LENS™) system. It was hypothesized that CNTs would allow for in situ carbide formation during laser processing, resulting in increased surface hardness. It was also hypothesized that CaPs would allow for protective tribofilm formation during wear, reducing material loss from wear-induced damage. Scanning electron microscopy images reveal defect-free microstructures with fine carbides evenly distributed, while X-ray diffraction confirms the presence of carbides without additional unwanted intermetallic phases. Vickers microhardness shows an increase in surface hardness in coatings containing both CNTs and CaPs. In vitro tribological studies found reduced coefficient of friction, reduced wear rates, and reduced metal ion-release concentrations in coatings containing both CNTs and CaPs. This study demonstrates the efficacy of CNTs and CaPs to improve wear resistance of Ti64 for potential applications in articulating surfaces of load-bearing implants.
Single-phase polycrystalline samples of RBa2Cu2.9Zn0.1Oy (R = Y, Nd, Gd, Er, and Tm) (ZnR123) were synthesized using the standard solid-state reaction method. They were characterized by X-ray powder diffraction (XRD) and scanning electron microscope. XRD shows that all samples consist essentially of a single phase and retain the orthorhombic structure. The structure of the samples was refined by the Rietveld method with the help of the bond valence sum method. The variation of the lattice parameters and some meaningful bond angles and lengths with the ionic radius are discussed. In these compounds, the variations of the buckling angles Cu2–O(2,3)–Cu2 and Cu2–Cu2–O(2,3) are unique: the bond angles Cu2–O3–Cu2 and Cu2–Cu2–O2 increase, whereas the bond angles Cu2–O2–Cu2 and Cu2–Cu2–O3 decrease. The variation of these bond angles brings about a strong curvature of the Cu2O plane. Furthermore, we have found tree fixed triangles formed by the Cu2, O2, and O3 atoms in addition to another fixed triangle O1–Ba–O1 observed for the first time. BVS of Cu2 atom shows a specific and unique variation compared with other compounds.
This contribution presents a comprehensive analysis of the low temperature deformation behavior of CoCrFeMnNi on the basis of quasistatic tensile tests at temperatures ranging from room temperature down to 4.2 K. Different deformation phenomena occur in the high-entropy alloy in this temperature range. These include (i) serrated plastic flow at certain cryogenic temperatures (4.2 K/8 K), (ii) deformation twinning (4.2 K/8 and 77 K), and (iii) dislocation slip (active from 4.2 K up to room temperature). The importance of deformation twinning for a stable work-hardening rate over an extended stress range as well as strain range has been addressed through the use of comprehensive orientation imaging microscopy studies. The proposed appearance of ε-martensite as well as a previously uninvestigated route of analysis, essentially a quantitative time-dependent, strain-dependent, and stress-dependent evaluation of the serrated plastic flow in CoCrFeMnNi is provided.
The National Institute of Standards and Technology (NIST) certifies a suite of Standard Reference Materials (SRMs) to address specific aspects of the performance of X-ray powder diffraction instruments. This report describes SRM 1879b, the third generation of this powder diffraction SRM. SRM 1879b is intended for use in the preparation of calibration standards for the quantitative analyses of cristobalite by X-ray powder diffraction in accordance with National Institute for Occupational Safety and Health (NIOSH) Analytical Method 7500, or equivalent. A unit of SRM 1879b consists of approximately 5 g of cristobalite powder bottled in an argon atmosphere. It is certified with respect to crystalline phase purity, or amorphous phase content, and lattice parameter. Neutron powder diffraction, both time-of-flight and constant wavelength, was used to certify the phase purity using SRM 676a as an internal standard. A NIST-built diffractometer, incorporating many advanced design features was used for certification measurements for lattice parameters.
In this study, the effects of 3D-printed SiO2 and ZnO-doped tricalcium phosphate (TCP) scaffolds with interconnected pores were evaluated on the in vivo bone formation and healing properties of a rabbit tibial defect model. Pure and doped TCP scaffolds were fabricated by a ceramic powder-based 3D printing technique and implanted into critical sized rabbit tibial defects for up to 4 months. In vivo bone regeneration was evaluated using chronological radiological examination, histological evaluations, SEM micrographs, and fluorochrome labeling studies. Radiograph results showed that Si/Zn-doped samples had slower degradation kinetics than the pure TCP samples. 3D printing of TCP scaffolds improved bone formation. The addition of dopants in the TCP scaffolds improved osteogenic capabilities when compared to the pure scaffolds. In summary, our findings indicate that the addition of dopants to the TCP scaffolds enhanced bone formation and in turn leading to accelerated healing.
Novel cerium-loaded MnTiOx/attapulgite (Ce/MnTiOx/ATP) and cerium-doped MnTiOx/attapulgite (Ce–MnTiOx/ATP) catalysts for low-temperature selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) were synthesized by co-precipitation methods. The results of catalytic activity testing for the as-prepared Ce–MnTiOx/ATP and Ce/MnTiOx/ATP indicated that the Ce–MnTiOx/ATP catalyst exhibited better catalytic performance with over 80% NOx conversion within a wide temperature window between 170 and 350°, and the highest NOx conversion attained for the Ce–MnTiOx/ATP catalyst was 97.5%. A series of characterization illustrated that the Ce–MnTiOx/ATP catalyst exhibited a higher specific surface area, oxygen vacancy, redox ability, and acid site as compared to that of the Ce/MnTiOx/ATP catalyst. The performance tests showed that the Ce–MnTiOx/ATP catalyst exhibited not only better SO2 & H2O resistance but also higher N2 selectivity and good stability. Therefore, the Ce–MnTiOx/ATP catalyst was testified to be a promising catalyst for NH3-SCR.
An efficient representative volume element generation strategy is developed in modeling nanoporous materials. It uses periodic 3D beam finite element (FE) models derived from skeletonization of spinodal-like stochastic microstructures produced by a leveled random field. To mimic stiffening with agglomeration of the mass at junctions, an increased Young’s modulus is assigned to the elements within the junction zone. The effective Young’s modulus, Poisson’s ratio, and universal anisotropy index are computed. A good agreement of the Young’s modulus predictions with those obtained from experimental results for phase volume fractions $0.20 \lt {\phi _{\cal B}} \lt 0.50$ is observed. Moreover, the elastic anisotropy index of the generated beam networks shows sufficient proximity to isotropy. Finally, it is demonstrated that, as compared to the simulation statistics of voxel-FE models, for the beam-FE models over 500-fold computational acceleration with 250-fold less memory requirement is provided.
Two series of binuclear metal phthalocyanine complexes M2(PcTN)2Nap and M2(PcTA)2Nap (M = Mn2+, Fe2+, Co2+, Cu2+) were designed and synthesized through the liquid solvent method and amination reaction. Elemental analysis, IR, and UV-vis spectroscopy were applied to characterize the compounds. To evaluate their catalytic performance, all the compounds were respectively added into the electrolyte of Li/SOCl2 battery systems as well as three-electrode systems for cyclic voltammetry (CV) measurements. The research studies indicate that the average discharge voltage and discharge time of the battery could be effectively enhanced by 0.2440 V and 810.7 s when compared with the battery in the absence of the compounds. As for capacities of the batteries containing catalysts, they were also found to have an improvement of 51.78–91.62%. Among the effects of diverse metal ions on the catalytic performance of phthalocyanines, the complexes whose center metal ions were Mn2+ or Co2+ exhibited relatively high catalytic performance. Meanwhile, combined with experimental results of CV analyses, the suggested catalytic mechanism of binuclear phthalocyanines for catalyzing Li/SOCl2 batteries had been proposed.
A thorough investigation of nanoindentation response of fiber/matrix composites by using a Berkovich indenter and its equivalent conical counterpart was carried out. Three-dimensional finite element models were developed to study how fiber orientations and the axial distance between the fiber and nanoindenter affect the nanoindentation response of fiber/matrix composites. This demonstrates that the indenter geometry and its orientation have little effect on the nanoindentation response when the fiber is horizontally aligned to the surface. However, when the fiber is vertically embedded in the matrix, the apparent modulus measured by using the Berkovich indenter (depending on the indenter orientation) can be significantly different from its conical counterpart. The results demonstrate that when the ratio of fiber-to-indenter distance over fiber diameter is relatively small, nanoindentation response strongly depends on fiber orientation and distance between fiber and indenter as well as indenter geometry.
Recently, significant progress in the field of grain boundary segregation was achieved, for example, in better understanding and modeling the stabilization of nanocrystalline structures by grain boundary segregation, searching for more advanced approaches to theoretical calculation of segregation energies and development of the complexion approach. Nevertheless, with each progress, new important questions appear which need to be solved. Here, we focus on two basic questions appearing recently: How can be the experimental results on the grain boundary segregation compared reliably to their theoretical counterparts? Is the preferred segregation site of a solute in the grain boundary core substitutional or interstitial? We also show that the entropy of grain boundary segregation is a very important quantity which cannot be neglected in thermodynamic considerations as it plays a crucial role, for example, in prediction of thermodynamic characteristics of grain boundary segregation and in the preference of the segregation site at the boundary.
A transmission surface plasmon resonance image (TSPRi) obtained with a plasmonic grating structure was investigated in combination with a smartphone camera. A substrate of a gold-coated CYTOP grating/glass slide showed the TSPR excitation wavelength of 675 nm at the incident light angle of 30°. The TSPRi acquired from a smartphone camera assembled with liquid crystal tunable filters corresponded with spectroscopic results. The sensitivity of this technique was 282/RIU. Due to changes in the sensitivity of the TSPRi intensity to the refractive index of the environment, this technique can be further developed for portable devices for sensor applications.
Developing metallic materials with a good combination of strength and ductility has been an unending pursuit of materials scientists. The emergence of high/medium-entropy alloys (HEA/MEA) provided a novel strategy to achieve this. Here, we further strengthened a strong-and-ductile MEA using a traditional solid solution strengthening theory. The selection of solute elements was assisted by mechanical property and microstructure predictive models. Extensive microstructural characterizations and mechanical tests were performed to verify the models and to understand the mechanical behavior and deformation mechanisms of the designated CoCrNi–3W alloy. Our results show good experiment-model agreement. The incorporation of 3 at.% W into the ternary CoCrNi matrix increased its intrinsic strength by ∼20%. External strengthening through microstructural refinement led to a yield strength nearly double that of the parent alloy, CoCrNi. The increase in strength is obtained with still good ductility when tested down to 77 K. Nanoscale twin boundaries are observed in the post-fracture microstructure under 77 K. The combination of strength and ductility after W additions deviate from the traditional strength-ductility-trade-off contour.
The selectivity of catalyst is an essential factor in direct methanol fuel cells (DMFCs) and plays an important role to improve their performance. To this end, platinum (Pt)-based low-cost trimetallic catalysts have been developed. The catalyst comprising ultra-low Pt-decorated NiCu bimetallic alloys nanoparticles fabricated on reduced graphene oxide (rGO). The series of Pt-NiCu/rGO nanocomposites were synthesized with different compositions to obtain the optimal conditioned material. The electrochemical results showed good performance for the electro-oxidation of methanol at anodic end of DMFCs. These outcomes opened up a broad avenue for developing lower cost-active catalysts with better performance for DMFCs.
The effects of misorientation on the quasi-static and dynamic mechanical behaviors of a second generation Ni-based single crystal superalloy DD5 were investigated. A Split-Hopkinson pressure bar system was used to perform dynamic compression. The crystallographic misorientation between the stress axis and the [001] direction was characterized through rotating orientation X-ray diffraction. The results demonstrated that the flow stress was closely related to the misorientation. It decreased first and consequently increased as the misorientation increased from 0° to 45°. The dynamic flow stress was significantly higher than the quasi-static stress. Moreover, the flow stress under dynamics was more sensitive to the misorientation. A constitutive model was used to illustrate the misorientation effect on the mechanical behavior. Finally, the effect of strain rate on the crystal orientation was also investigated. It was discovered that the orientation deviation change following quasi-static compression could be neglected. By contrast, the orientation changed by 3–9° subsequently to dynamic compression.
Frequency-dependence and magnitude of second harmonic generation (SHG) from ~4 × 105 nm2 molybdenum disulfide (MoS2) monolayers was examined in presence of single 150 nm plasmonic gold@silica shell@core nanoantenna monomer and dimers. Quantitative agreement between discrete dipole approximation-calculated fields and measured SHG enhancements was found. SHG from MoS2 was enhanced up to 1.88 × upon deposition of a plasmonic nanoantenna-dimer with 170 nm gap, reaching maximal normalized SHG conversion efficiency of 0.0250%/W. Pump losses attributable to plasmonic damping, e.g., scattering and/or hot-electron injection into MoS2, were apparent. Linear and nonlinear optical activity of MoS2 and nanoantenna controls were compared with literature values.
To overcome the limited feasibility of various refractory high-entropy alloys (HEAs) due to the presence of (i) very dense elements (W and Ta), (ii) costly elements (Hf and Ta), and (iii) oxidation prone elements (V) in them, AlxCryMozNbTiZr HEAs were prepared via arc-melting. Considering the critical nature of oxidation resistance in high-temperature applications, HEAs were characterized to form a combinatorial library of microstructural and oxidation behavior. AlxCryMozNbTiZr HEAs revealed multiphase microstructures consisting of intermetallic phases along with BCC matrices. Mass loss and porous microstructures were obtained in Mo-rich HEAs after oxidation at 1000 °C for 1 h. The presence of Al enhanced the oxidation resistance and developed a protective oxide layer on the HEAs. Al30Cr10-NTZ exhibited promising potential for use in high temperature applications, as it showed an oxidation time exponent of ∼0.5 and a dense and continuous oxide layer.