Search

The large-scale implementation of renewable energy systems necessitates the development of energy storage solutions to effectively manage imbalances between energy supply and demand. Herein, we investigate such a scalable material solution for energy storage in supercapacitors constructed from readily available material precursors that can be locally sourced from virtually anywhere on the planet, namely cement, water, and carbon black. We characterize our carbon-cement electrodes by combining correlative EDS–Raman spectroscopy with capacitance measurements derived from cyclic voltammetry and galvanostatic charge-discharge experiments using integer and fractional derivatives to correct for rate and current intensity effects. Texture analysis reveals that the hydration reactions of cement in the presence of carbon generate a fractal-like electron-conducting carbon network that permeates the load-bearing cement-based matrix. The energy storage capacity of this space-filling carbon black network of the high specific surface area accessible to charge storage is shown to be an intensive quantity, whereas the high-rate capability of the carbon-cement electrodes exhibits self-similarity due to the hydration porosity available for charge transport. This intensive and self-similar nature of energy storage and rate capability represents an opportunity for mass scaling from electrode to structural scales. The availability, versatility, and scalability of these carbon-cement supercapacitors opens a horizon for the design of multifunctional structures that leverage high energy storage capacity, high-rate charge/discharge capabilities, and structural strength for sustainable residential and industrial applications ranging from energy autarkic shelters and self-charging roads for electric vehicles, to intermittent energy storage for wind turbines and tidal power stations.

The ancient Egyptian blue pigment was developed over 5000 years ago and was used extensively for around four millennia until its use mysteriously declined dramatically during the Early Middle Ages. It recently attracted a lot of attention along with some related materials, leading to a fast-growing number of applications in fields, such as sensors, solar concentrators, energy-saving, and medicine. The new surge in interest began in 1996 with the discovery of their intense NIR photoluminescence that surprisingly can be triggered even by visible light. In 2013, the possibility of exfoliating them and producing NIR luminescent nanosheets was established, expanding the family of 2D nanomaterials. More recently, the discovery of their high antibacterial effects and biocompatibility, and very promising optical, electric and magnetic properties, has further boosted their applications. The characteristics of Egyptian blue are due to its main component: the very stable crystalline compound CaCuSi4O10. This tetragonal sheet silicate is the synthetic analogous of the rare cuprorivaite mineral. In Part A of this review, we summarize the historical uses and main properties (i.e., composition, structure, color, stability, luminescence, and biological activity) of cuprorivaite and related 2D silicates, i.e., BaCuSi4O10 (the main constituent of the ancient pigment Chinese Blue), BaCuSi2O6 (the main constituent of the ancient pigment Chinese Purple), SrCuSi4O10 (synthetic analogous of wesselsite) and BaFeSi4O10 (synthetic analogous of gillespite). The Part B of the review will focus on the modern rediscovery of these materials, their modern synthesis and exfoliation, and the innovative applications based on their properties.

Microcalcifications, primarily biogenic apatite, occur in cancerous and benign breast pathologies and are key mammographic indicators. Outside the clinic, numerous microcalcification compositional metrics (e.g., carbonate and metal content) are linked to malignancy, yet microcalcification formation is dependent on microenvironmental conditions, which are notoriously heterogeneous in breast cancer. We interrogate multiscale heterogeneity in 93 calcifications from 21 breast cancer patients using an omics-inspired approach: For each microcalcification, we define a “biomineralogical signature” combining metrics derived from Raman microscopy and energy-dispersive spectroscopy. We observe that (i) calcifications cluster into physiologically relevant groups reflecting tissue type and local malignancy; (ii) carbonate content exhibits substantial intratumor heterogeneity; (iii) trace metals including zinc, iron, and aluminum are enhanced in malignant-localized calcifications; and (iv) the lipid-to-protein ratio within calcifications is lower in patients with poor composite outcome, suggesting that there is potential clinical value in expanding research on calcification diagnostic metrics to include “mineral-entrapped” organic matrix.

Ancient Roman concretes have survived millennia, but mechanistic insights into their durability remain an enigma. Here, we use a multiscale correlative elemental and chemical mapping approach to investigating relict lime clasts, a ubiquitous and conspicuous mineral component associated with ancient Roman mortars. Together, these analyses provide new insights into mortar preparation methodologies and provide evidence that the Romans employed hot mixing, using quicklime in conjunction with, or instead of, slaked lime, to create an environment where high surface area aggregate-scale lime clasts are retained within the mortar matrix. Inspired by these findings, we propose that these macroscopic inclusions might serve as critical sources of reactive calcium for long-term pore and crack-filling or post-pozzolanic reactivity within the cementitious constructs. The subsequent development and testing of modern lime clast–containing cementitious mixtures demonstrate their self-healing potential, thus paving the way for the development of more durable, resilient, and sustainable concrete formulations.

© 2019 Maragh et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. There has been significant progress in recent years aimed at the development of new analytical techniques for investigating structure-function relationships in hierarchically ordered materials. Inspired by these technological advances and the potential for applying these approaches to the study of construction materials from antiquity, we present a new set of high throughput characterization tools for investigating ancient Roman concrete, which like many ancient construction materials, exhibits compositional heterogeneity and structural complexity across multiple length scales. The detailed characterization of ancient Roman concrete at each of these scales is important for understanding its mechanics, resilience, degradation pathways, and for making informed decisions regarding its preservation. In this multi-scale characterization investigation of ancient Roman concrete samples collected from the ancient city of Privernum (Priverno, Italy), cm-scale maps with micron-scale features were collected using multi-detector energy dispersive spectroscopy (EDS) and confocal Raman microscopy on both polished cross-sections and topographically complex fracture surfaces to extract both bulk and surface information. Raman spectroscopy was used for chemical profiling and phase characterization, and data collected using EDS was used to construct ternary diagrams to supplement our understanding of the different phases. We also present a methodology for correlating data collected using different techniques on the same sample at different orientations, which shows remarkable potential in using complementary characterization approaches in the study of heterogeneous materials with complex surface topographies.

This paper explores the use of the meshfree computational mechanics method, the Material Point Method (MPM), to model the composition and damage of typical renal calculi, or kidney stones. Kidney stones are difficult entities to model due to their complex structure and failure behavior. Better understanding of how these stones behave when they are broken apart is a vital piece of knowledge to medical professionals whose aim is to remove these stone by breaking them within a patient’s body. While the properties of individual stones are varied, the common elements and proportions are used to generate synthetic stones that are then placed in a digital experiment to observe their failure patterns. First a more traditional engineering model of a Brazil test is used to create a tensile fracture within the center of these stones to observe the effect of stone consistency on failure behavior. Next a novel application of MPM is applied which relies on an ultrasonic wave being carried by surrounding fluid to model the ultrasonic treatment of stones commonly used by medical practitioners. This numerical modeling of Extracorporeal Shock Wave Lithotripsy (ESWL) reveals how these different stones failure in a more real-world situation and could be used to guide further research in this field for safer and more effective treatments.

Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). The miraculously preserved 2000-year-old Dead Sea Scrolls, ancient texts of invaluable historical significance, were discovered in the mid-20th century in the caves of the Judean desert. The texts were mainly written on parchment and exhibit vast diversity in their states of preservation. One particular scroll, the 8-m-long Temple Scroll is especially notable because of its exceptional thinness and bright ivory color. The parchment has a layered structure, consisting of a collagenous base material and an atypical inorganic overlayer. We analyzed the chemistry of the inorganic layer using x-ray and Raman spectroscopies and discovered a variety of evaporitic sulfate salts. This points toward a unique ancient production technology in which the parchment was modified through the addition of the inorganic layer as a writing surface. Furthermore, understanding the properties of these minerals is particularly critical for the development of suitable conservation methods for the preservation of these invaluable historical documents.

© 2017 Elsevier Inc. Microcalcifications (MCs) are routinely used to detect breast cancer in mammography. Little is known, however, about their materials properties and associated organic matrix, or their correlation to breast cancer prognosis. We combine histopathology, Raman microscopy, and electron microscopy to image MCs within snap-frozen human breast tissue and generate micron-scale resolution correlative maps of crystalline phase, trace metals, particle morphology, and organic matrix chemical signatures within high grade ductal carcinoma in situ (DCIS) and invasive cancer. We reveal the heterogeneity of mineral-matrix pairings, including punctate apatitic particles (<2 µm) with associated trace elements (e.g., F, Na, and unexpectedly Al) distributed within the necrotic cores of DCIS, and both apatite and spheroidal whitlockite particles in invasive cancer within a matrix containing spectroscopic signatures of collagen, non-collagen proteins, cholesterol, carotenoids, and DNA. Among the three DCIS samples, we identify key similarities in MC morphology and distribution, supporting a dystrophic mineralization pathway. This multimodal methodology lays the groundwork for establishing MC heterogeneity in the context of breast cancer biology, and could dramatically improve current prognostic models.

© 2020 Meanwell et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This study presents evidence of two tuyères, or blowpipe tips, used in metalworking at the Postclassic period city of Mayapán. Blowpipe technology has long been hypothesized to be the production technique for introducing oxygen to furnaces during the metal casting process on the basis of ethnohistorical depictions of the process in ancient Mesoamerica. To our knowledge, the tuyères recovered at Mayapán are the first archaeologically documented tuyères for pre-Hispanic Mesoamerica. The dimensions, internal perforation, vitrification, and presence of copper prills within the ceramic fabric, suggest that they were used in pyrotechnological production, likely metalworking, and is consistent with previous evidence for small-scale metalworking at Mayapán. Blowpipe use in metallurgical production is a logical extension of a much longer tradition of blowgun use in hunting, which was likely already present in Mesoamerica by the time metal was introduced to West Mexico from South America. Furthermore, the dimensions of the Mayapán tuyères are consistent with the internal diameter of ethnohistorically-documented blowguns from Jacaltenango in the southwest Maya region. We conducted replication experiments that suggest that when combined with wooden blowpipes, the Mayapán tuyères would have been ideal for small-scale, furnace-based metallurgy, of the type identified at Mayapán from Postclassic period contexts.

This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. The ancient pigment Egyptian blue has long been studied for its historical significance; however, recent work has shown that its unique visible induced luminescent property can be used both to identify the pigment and to inspire new materials with this characteristic. In this study, a multi-modal characterization approach is used to explore variations in ancient production of Egyptian blue from shabti statuettes found in the village of Deir el-Medina in Egypt (Luxor, West Bank) dating back to the New Kingdom (18th-20th Dynasties; about 1550-1077 BCE). Using quantitative SEM-EDS analysis, we identify two possible production groups of the Egyptian blue and demonstrate the presence of multiple phases within samples using cluster analysis and ternary diagram representations. Using both macroscale non-invasive (X-rays fluorescence and multi-spectral imaging) and micro-sampling (SEM-EDS and Raman confocal microspectroscopy) techniques, we correlate photoluminescence and chemical composition of the ancient samples. We introduce Raman spectroscopic imaging as a means to capture simultaneously visible-induced luminesce and crystal structure and utilize it to identify two classes of luminescing and non-luminescing silicate phases in the pigment that may be connected to production technologies. The results presented here provide a new framework through which Egyptian blue can be studied and inform the design of new materials based on its luminescent property.