Application of Deep Learning Workflow for Autonomous Grain Size Analysis.

Traditional grain size determination in materials characterization involves microscopy images and a laborious process requiring significant manual input and human expertise. In recent years, the development of computer vision (CV) has provided an alternative approach to microstructural characterization with preliminary implementations greatly simplifying the grain size determination process. Here, an end-to-end workflow to measure grain size in microscopy images without any manual input is presented. Following the ASTM standards for grain size determination, results from the line intercept (Heyn's method) and planimetric (Saltykov's method) approaches are used as the baseline. A pre-trained holistically nested edge detection (HED) model is used for CV-based edge detection, and the results are further compared to the classic Canny edge detection method. Post-processing was performed using open-source image processing packages to extract the grain size. In optical microscope images, the pre-trained HED model achieves much higher accuracy than the Canny edge detection method while reducing the image processing time by one to two orders of magnitude compared to traditional methods. The effects of morphological operations on the predicted grain size accuracy are also explored. Overall, the proposed end-to-end convolutional neural network (CNN)-based workflow can significantly reduce the processing time while maintaining the same accuracy as the traditional manual method.

Electroactive Ionic Polymer of Intrinsic Microporosity for High-Performance Capacitive Energy Storage.

Here, we report an ionic polymer of intrinsic microporosity (PIM) as a high-functioning supercapacitor electrode without the need for conductive additives or binders. The performance of this material is directly related to its large accessible surface area. By comparing electrochemical performance between a porous viologen PIM and a non-porous viologen polymer, we reveal that the high energy and power density are both due to the ability of ions to rapidly access the ionic PIM. In 0.1 M H2SO4 electrolyte, a pseudocapacitve energy of 315 F g-1 is observed, whereas in 0.1 M Na2SO4, a capacitive energy density of 250 F g-1 is obtained. In both cases, this capacity is retained over 10,000 charge-discharge cycles, without the need for stabilizing binders or conductive additives even at moderate loadings (5 mg cm-2). This desirable performance is maintained in a prototype symmetric two-electrode capacitor device, which had >99% Coloumbic efficiency and a <10 mF capacity drop over 2000 cycles. These results demonstrate that ionic PIMs function well as standalone supercapacitor electrodes and suggest ionic PIMs may perform well in other electrochemical devices such as sensors, ion-separation membranes, or displays. This article is protected by copyright. All rights reserved.

Nonlinear active materials: an illustration of controllable phase matchability.

For a crystal to exhibit nonlinear optical (NLO) activity such as second-harmonic generation (SHG), it must belong to a noncentrosymmetric (NCS) space group. Moreover, for these nonlinear optical (NLO) materials to be suitable for practical uses, the synthesized crystals should be phase-matchable (PM). Previous synthetic research into SHG-active crystals has centered on (i) how to create NCS compounds and/or (ii) how to obtain NCS compounds with high SHG efficiencies. With these tactics, one can synthesize a material with a high SHG efficiency, but the material could be unusable if the material was nonphase-matchable (non-PM). To probe the origin of phase matchability of NCS structures, we present two new chemically similar hybrid compounds within one composition space: (I) [Hdpa]2NbOF5·2H2O and (II) HdpaNbOF4 (dpa = 2,2'-dipyridylamine). Both compounds are NCS and chemically similar, but (I) is non-PM while (II) is PM. Our results indicate--consistent with organic crystallography--the arrangement of the organic molecule within hybrid materials dictates whether the material is PM or non-PM.

The role of polar, lamdba (Λ)-shaped building units in noncentrosymmetric inorganic structures.

A methodology for the design of polar, inorganic structures is demonstrated here with the packing of lambda (Λ)-shaped basic building units (BBUs). Noncentrosymmetric (NCS) solids with interesting physical properties can be created with BBUs that lack an inversion center and are likely to pack into a polar configuration; previous methods to construct these solids have used NCS octahedra as BBUs. Using this methodology to synthesize NCS solids, one must increase the coordination of the NCS octahedra with maintenance of the noncentrosymmetry of the bulk. The first step in this progression from an NCS octahedron to an inorganic NCS solid is the formation of a bimetallic BBU. This step is exemplified with the compound CuVOF(4)(H(2)O)(7): this compound, presented here, crystallizes in an NCS structure with ordered, isolated [Cu(H(2)O)(5)](2+) cations and [VOF(4)(H(2)O)](2-) anions into Λ-shaped, bimetallic BBUs to form CuVOF(4)(H(2)O)(6)·H(2)O, owing to the Jahn-Teller distortion of Cu(2+). Conversely, the centrosymmetric heterotypes with the same formula MVOF(4)(H(2)O)(7) (M(II) = Co, Ni, and Zn) exhibit ordered, isolated [VOF(4)(H(2)O)](2-) and [M(H(2)O)(6)](2+) ionic species in a hydrogen bond network. CuVOF(4)(H(2)O)(7) exhibits a net polar moment while the heterotypes do not; this demonstrates that Λ-shaped BBUs give a greater probability for and, in this case, lead to NCS structures.

Connectomic analysis of Alzheimer's disease using percolation theory.

Alzheimer's disease (AD) is a severe neurodegenerative disorder that affects a growing worldwide elderly population. Identification of brain functional biomarkers is expected to help determine preclinical stages for targeted mechanistic studies and development of therapeutic interventions to deter disease progression. Connectomic analysis, a graph theory-based methodology used in the analysis of brain-derived connectivity matrices was used in conjunction with percolation theory targeted attack model to investigate the network effects of AD-related amyloid deposition. We used matrices derived from resting-state functional magnetic resonance imaging collected on mice with extracellular amyloidosis (TgCRND8 mice, n = 17) and control littermates (n = 17). Global, nodal, spatial, and percolation-based analysis was performed comparing AD and control mice. These data indicate a short-term compensatory response to neurodegeneration in the AD brain via a strongly connected core network with highly vulnerable or disconnected hubs. Targeted attacks demonstrated a greater vulnerability of AD brains to all types of attacks and identified progression models to mimic AD brain functional connectivity through betweenness centrality and collective influence metrics. Furthermore, both spatial analysis and percolation theory identified a key disconnect between the anterior brain of the AD mice to the rest of the brain network.

Palm readings: Manicaria saccifera palm fibers are biocompatible textiles with low immunogenicity.

Plant-based fibers are a potential alternative to synthetic polymer fibers that can yield enhanced biocompatibility and mechanical properties matching those properties of tissue. Given the unique morphology of the bract of the Manicaria saccifera palm, being an interwoven meshwork of fibers, we believe that these fibers with this built-in structure could prove useful as a tissue engineering scaffold material. Thus, we first investigated the fiber's in vitro biocompatibility and immunogenicity. We cultured NIH/3T3 mouse fibroblasts, human aortic smooth muscle cells, and human adipose-derived mesenchymal stem cells on the fiber mats, which all readily attached and over 21 days grew to engulf the fibers. Importantly, this was achieved without treating the plant tissue with extracellular matrix proteins or any adhesion ligands. In addition, we measured the gene expression and protein secretion of three target inflammatory cytokines (IL-1ß, IL-8, and TNFα) from THP-1 human leukemia monocytes cultured in the presence of the biotextile as an in vitro immunological model. After 24 h of culture, gene expression and protein secretion were largely the same as the control, demonstrating the low immunogenicity of Manicaria saccifera fibers. We also measured the tensile mechanical properties of the fibers. Individual fibers after processing had a Young's modulus of 9.51 ± 4.38 GPa and a tensile strength of 68.62 ± 27.93 MPa. We investigated the tensile mechanical properties of the fiber mats perpendicular to the fiber axis (transverse loading), which displayed upwards of 100% strain, but with a concession in strength compared to longitudinal loading. Collectively, our in vitro assessments point toward Manicaria saccifera as a highly biocompatible biotextile, with a range of potential clinical and engineering applications.

Complex ceramic structures. I. Weberites.

The weberite structure (A2B2X7) is an anion-deficient fluorite-related superstructure. Compared with fluorites, the reduction in the number of anions leads to a decrease in the coordination number of the B cations (VI coordination) with respect to the A cations (VIII coordination), thus allowing the accommodation of diverse cations. As a result, weberite compounds have a broad range of chemical and physical properties and great technological potential. This article summarizes the structural features of weberite and describes the structure in several different ways. This is the first time that the stacking vector and stacking angle are used to represent the weberite structure. This paper also discusses the crystallographic relationship between weberite, fluorite and pyrochlore (another fluorite-related structure). The cation sublattices of weberite and pyrochlore are correlated by an axial transformation. It has been shown that the different coordination environment of anions is due to the alternating layering of the AB3 and A3B close-packed cation layers. A stability field of weberite oxides is proposed in terms of the ratio of ionic radius of cations and relative bond ionicity. In addition, a selection of weberite compounds with interesting properties is discussed.

Evaluation of the computational capabilities of a memristive random network (MN3) under the context of reservoir computing.

This work presents the simulation results of a novel recurrent, memristive neuromorphic architecture, the MN3 and explores its computational capabilities in the performance of a temporal pattern recognition task by considering the principles of the reservoir computing approach. A simple methodology based on the definitions of ordered and chaotic dynamical systems was used to determine the separation and fading memory properties of the architecture. The results show the potential use of this architecture as a reservoir for the on-line processing of time-varying inputs.

Memristive nanowires exhibit small-world connectivity.

Small-world networks provide an excellent balance of efficiency and robustness that is not available with other network topologies. These characteristics are exhibited in the Memristive Nanowire Neural Network (MN3), a novel neuromorphic hardware architecture. This architecture is composed of an electrode array connected by stochastically deposited core-shell nanowires. We simulate the stochastic behavior of the nanowires by making various assumptions on their paths. First, we assume that the nanowires follow straight paths. Next, we assume that they follow arc paths with varying radii. Last, we assume that they follow paths generated by pink noise. For each of the three methods, we present a method to find whether a nanowire passes over an electrode, allowing us to represent the architecture as a bipartite graph. We find that the small-worldness coefficient increases logarithmically and is consistently greater than one, which is indicative of a small-world network.

Unexpectedly high piezoelectricity of Sm-doped lead zirconate titanate in the Curie point region.

Large piezoelectric coefficients in polycrystalline lead zirconate titanate (PZT) are traditionally achieved through compositional design using a combination of chemical substitution with a donor dopant and adjustment of the zirconium to titanium compositional ratio to meet the morphotropic phase boundary (MPB). In this work, a different route to large piezoelectricity is demonstrated. Results reveal unexpectedly high piezoelectric coefficients at elevated temperatures and compositions far from the MPB. At temperatures near the Curie point, doping with 2 at% Sm results in exceptionally large piezoelectric coefficients of up to 915 pm/V. This value is approximately twice those of other donor dopants (e.g., 477 pm/V for Nb and 435 pm/V for La). Structural changes during the phase transitions of Sm-doped PZT show a pseudo-cubic phase forming ≈50 °C below the Curie temperature. Possible origins of these effects are discussed and the high piezoelectricity is posited to be due to extrinsic effects. The enhancement of the mechanism at elevated temperatures is attributed to the coexistence of tetragonal and pseudo-cubic phases, which enables strain accommodation during electromechanical deformation and interphase boundary motion. This work provides insight into possible routes for designing high performance piezoelectrics which are alternatives to traditional methods relying on MPB compositions.

Biocompatibility evaluation of porous ceria foams for orthopedic tissue engineering.

Ceria ceramics have the unique ability to protect cells from free radical-induced damage, making them materials of interest for biomedical applications. To expand upon the understanding of the potential of ceria as a biomaterial, porous ceria, fabricated via direct foaming, was investigated to assess its biocompatibility and its ability to scavenge free radicals. A mouse osteoblast (7F2) cell line was cultured with the ceria foams to determine the extent of the foams' toxicity. Toxicity assessments indicate that mouse osteoblasts cultured directly on the ceria scaffold for 72 h did not show a significant (p > 0.05) increase in toxicity, but rather show comparable toxicity to cells cultured on porous 45S5 Bioglass. The in vitro inflammatory response elicited from porous ceria foams was measured as a function of tumor necrosis factor alpha (TNF-α) secreted from a human monocytic leukemia cell line. Results indicate that the ceria foams do not cause a significant inflammatory response, eliciting a response of 27.1 ± 7.1 pg mL(-1) of TNF-α compared to 36.3 ± 5.8 pg mL(-1) from cells on Bioglass, and 20.1 ± 2.9 pg mL(-1) from untreated cells. Finally, we report cellular toxicity in response to free radicals from tert-butyl hydroperoxide with and without foamed ceria. Our preliminary results show that the foamed ceria is able to decrease the toxic effect of induced oxidative stress. Collectively, this study demonstrates that foamed ceria scaffolds do not activate an inflammatory response, and show potential free radical scavenging ability, thus they have promise as an orthopedic biomaterial.

Investigation of Bismuth Triiodide (BiI3) for Photovoltaic Applications.

Guided by predictive discovery framework, we investigate bismuth triiodide (BiI3) as a candidate thin-film photovoltaic (PV) absorber. BiI3 was chosen for its optical properties and the potential for "defect-tolerant" charge transport properties, which we test experimentally by measuring optical absorption and recombination lifetimes. We synthesize phase-pure BiI3 thin films by physical vapor transport and solution processing and single-crystals by an electrodynamic gradient vertical Bridgman method. The bandgap of these materials is ∼1.8 eV, and they demonstrate room-temperature band-edge photoluminescence. We measure monoexponential recombination lifetimes in the range of 180-240 ps for thin films, and longer, multiexponential dynamics for single crystals, with time constants up to 1.3 to 1.5 ns. We discuss the outstanding challenges to developing BiI3 PVs, including mechanical and electrical properties, which can also inform future selection of candidate PV absorbers.

Biocompatible evaluation of barium titanate foamed ceramic structures for orthopedic applications.

The potential of barium titanate (BT) to be electrically active makes it a material of interest in regenerative medicine. To enhance the understanding of this material for orthopedic applications, the in vitro biocompatibility of porous BT fabricated using a direct foaming technique was investigated. Characterization of the resultant foams yielded an overall porosity between 50 and 70% with average pore size in excess of 30 µm in diameter. A mouse osteoblast (7F2) cell line was cultured with the BT to determine the extent of the foams' toxicity using a LDH assay. After 72 h, BT foams showed a comparable cytotoxicity of 6.4 ± 0.8% to the 8.4 ± 1.5% of porous 45S5 Bioglass®. The in vitro inflammatory response elicited from porous BT was measured as a function of tumor necrosis factor alpha (TNF-α) secreted from a human monocytic leukemia cell line (THP-1). Results indicate that the BT foams do not cause a significant inflammatory response, eliciting a 9.4 ± 1.3 pg of TNF-α per mL of media compared with 20.2 ± 2.3 pg/mL from untreated cells. These results indicate that porous BT does not exhibit short term cytotoxicity and has potential for orthopedic tissue engineering applications.

Heat treatments modify the tribological properties of nickel boron coatings.

The effects of annealing temperature on the tribological properties of electroless nickel-boron coatings have been investigated. The coatings were annealed in a tube furnace under a flow (0.0094 N m(3)/min) of oxygen gas at temperatures of 250, 400, 550, and 700 °C for 3 h. Using scanning electron microscopy, images of the annealed coatings documented changes in surface morphology. From this it was seen that the higher annealing temperatures produced marked changes, moving from the nodular structure of nickel-boron coatings to a flaked surface morphology. The chemical effect of the annealing temperature was studied via X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data indicated that after annealing at the temperatures of 550 and 700 °C, an accumulation of boron oxide species could be seen at the surface as well as a complete loss of nickel signal. An analysis of Raman spectra collected across the surface further identified the predominant species to be boric acid. The tribological response of the coatings was studied with a pin-on-disk tribometer with 440C stainless steel balls run against the coatings in ambient air. It was seen that the as received sample and the sample annealed at 250 °C samples exhibited modest friction properties, while the 400 °C sample had increased friction due to wear debris from the ball. The 550 and 700 °C samples showed remarkably low friction coefficients between 0.06 and 0.08, attributable to the presence of boric acid. The wear tracks were analyzed using scanning white light interferometry and from this data wear rates were obtained for the coatings ranging from 10(-8) to 10(-7) mm(3)/Nm.

Interfacial reactivity of Au, Pd, and Pt on BiI3 (001): implications for electrode selection.

Understanding the contact-semiconductor interface is important in determining the performance of a semiconductor device. This study investigated the contact chemistry of BiI(3) single crystal with Au, Pd, and Pt electrodes using X-ray photoelectron spectroscopy (XPS), a technique widely used to probe the interfacial chemistry of many materials. Chemical reactions were identified on the BiI(3) surface for the case of Pd and Pt contacts, while Au showed no reactivity with BiI(3). The difference in reactivities correlated with different surface morphologies of the contact on the BiI(3) surface, which was evidenced by atomic force microscopy (AFM) characterization. The dark resistivity of the BiI(3) crystal with above contact materials was measured by I-V characterization. The highest resistivity was obtained when Au was employed as the contact. These results suggest that Au is better than Pd and Pt as the contact material for BiI(3) single crystal.