Bentonite is to be used as a sealing material for long-term storage of radioactive waste. During permafrost periods the buffer may freeze, causing the following: montmorillonite dehydration, ice formation, and pressure build-up that may fracture the surrounding rock. No previous study has been done on freezing of bentonite in saline water. Using small and wide angle X-ray scattering, the present study aimed to increase understanding of the combined impact of salt and temperature on the hydration (swelling) of Wyoming montmorillonite. The basal spacing of the Na-montmorillonite was very dependent on the water content, while this was not the case for the Ca-montmorillonite (after reaching 19 Å). The basal spacing of the free-swelling Na-montmorillonite (34–280 Å) was estimated successfully using simple calculations. During freezing of Na-montmorillonite in NaCl solution, both ice and hydrohalite formed (at -50 and -100ºC). At starting concentrations ≥ 1.5 M the basal spacing was not affected by freezing. During freezing of Ca-montmorillonite in CaCl2 solution, ice formed; antarcticite formed only sporadically. The basal spacing of the Ca-montmorillonite at high NaCl concentrations (>1 M) was greater at -50 and -100ºC (18 Å) than at 20ºC (16 Å). The opposite was observed at low concentrations. This change was attributed to small amounts of salts introduced into the montmorillonite interlayer, hence changing the interlayer water properties. The montmorillonite hydration was also temperature dependent; decreasing temperature increased the hydration (as long as no ice was formed) and increasing the temperature decreased the hydration. This was attributed to the temperature impact on the entropy of the hydration reaction. This observation was also reproduced in an experiment up to 90ºC. A small amount of salt in the groundwater was noted to reduce significantly the potential problem of ice formation in bentonite sealings.

In this article, we reflect on the pernicious nature of rhetoric aimed at soliciting Black community support for predatory urban development schemes. Highlighting recent examples of Urban One Casino + Resort’s development campaign in Richmond, Virginia, and the messaging leveraged by political leaders on behalf of SoFi stadium and the Intuit Dome in Inglewood, California, we find that discursive moves made by public and private stakeholders reflect what we call the “predatory rhetorics of urban development.” We argue that these rhetorics intend to enlist divested Black communities as supporters of development projects that concentrate wealth and power in the hands of economic and political elites. They do so by playing on Black desires for social and economic inclusion into American middle-class community life. Four common threads of predatory rhetoric appear across both contexts. They are 1) seizing the real needs and concerns of stigmatized places, 2) relying on representational politics to mitigate issues of trust, 3) the neoliberal framing of American internal colonization as a problem that requires extractive private development solutions and, finally, 4) dissimulating intra-community class interests to consolidate “Black needs.” We reflect on the outcomes supported by these rhetorics across both development projects and raise several points of further consideration as we hope for more organized responses to such rhetorics in the future.

Small angle neutron scattering (SANS) and dynamic light scattering (DLS) measurements were made on near physiological solutions of a bottlebrush shape polyelectrolyte, aggrecan. Aggrecan is a biologically important molecule whose complexes with hyaluronic acid (HA) provide the osmotic resistance of cartilage. We have investigated the effect of complexation of aggrecan with HA on the structure and dynamic properties of aggrecan solutions. SANS reveals that the supramolecular structure of aggrecan assemblies is only marginally affected by the HA. DLS indicates that the dynamic response of the aggrecan-HA complex is slower than that of the corresponding aggrecan solution. However, addition of calcium ions slightly increases the relaxation rate of the autocorrelation function of the aggrecan solution.

We investigate the insertion energetics of Ca at low concentrations in four promising vanadium oxide phases (α and δ vanadium pentoxide (V2O5) polymorphs as well as rutile- (R) and bronze-type (B) vanadium dioxide (VO2)) using density functional theory (DFT). We find α-V2O5 to be the most suitable material for an application as cathode, driven by a stable coordinative environment, while VO2(R) does not exhibit a stable low-concentration CaxVO2 phase due to severe distortions of the host lattice due to the large calcium ion. The results provide insight into the possibility of employing these phases as active cathode materials of Ca-ion batteries.

Diatoms represent a natural source of mesoporous silica whose applications range from biomedical to photonic fields. Porous hierarchically organized micro structures, the biosilica shells called frustules, can be obtained by removal of the organic biological matter from the unicellular living algae. Diatoms frustules have been investigated as scaffold for bone tissue growth taking advantage of their nanostructured surface and of the possibility to chemically modify the biosilica. Here we report on an easy way to calcium-doped biosilica supports for bone tissue regeneration by in vivo feeding the algae. FTIR and EDX analyses confirmed the incorporation of calcium into the mesopouros biosilica. Cell viability studies showed an ameliorative effect on the Saos-2 cells spreading compared with the cells grown on non-doped biosilica supports.

The present paper examines nanoporous material – carbon fabrics, which is used as electrodes in rechargeable energy storage capacitors (ultracapacitors). The fabrics structure, impurities composition, the influence of impurity types on ultracapacitor characteristics and the influence of thermal treatments on the impurities concentration are studied. The analysis of the ultracapacitor equivalent circuit with the studied material is made and the capacitor charge-discharge characteristics are investigated.

The performed studies resulted in determination of the investigated carbon material structure, determination of impurities composition of carbon material and change of impurities content depending on thermal treatment in vacuum. The optimum temperature range for treatment in vacuum is established. The equivalent circuit of the ultracapacitor is analyzed and its charge-discharge characteristics are investigated. The chosen equivalent circuit makes it possible to estimate the influence of pores different size on the ultracapacitor charge-discharge characteristics that is important for its application in energy storage devices.

Biomineralization is the matrix-directed calcification of tissue in living organisms. The deposition of different polymorphs of calcium phosphate or calcium carbonate is a highly regulated process. It may involve cell-controlled mechanisms with vesicular delivery of inorganic material to the extracellular matrix and cell-independent processes mediated by dedicated matrix proteins. These proteins promote the formation of microscopic crystals of defined size and shape, which combine to form bio-inorganic materials with unique properties. Successful biomineralization is correlated with structural elements, such as matrix proteins involved in the nucleation process. Circular dichroism (CD) is a spectroscopic technique for the determination of a secondary structure of proteins and has therefore been applied for studying numerous biomineralization promoter proteins. This article reviews and compares CD data on matrix proteins from different contexts, such as eggs, seashells, and teeth. It highlights the potential of CD for secondary structure determination and quantification and points out pitfalls that may lead to misinterpretation of CD spectra. The data suggest that most biomineralization promoter proteins contain domains of different secondary structure with predominantly unordered conformation. However, they may acquire a higher degree of order initiated by environmental factors such as pH, presence of cations, or charged surfaces.

Praseodymium doped CaFe2As2 (122 structure) and CaFeAs2 (112 structure) are characterized by modulated Low Magnetic Field Microwave Absorption (LFMA) spectroscopy. In both (Pr,Ca)122 and (Pr,Ca)112 structures, a strong hysteretic LFMA is found, with a TcH of ∼30 K and ∼26 K, respectively. However, in (Pr,Ca)122, measurements also show an unusual Narrow Peak (NP) LFMA signal appearing at higher temperatures, above the lower TcH superconducting state until a TcNP of 49 K. We associate this NP LFMA with interfacial superconductivity, which has been found previously by highly anisotropic magnetization measurements. Furthermore, the absence of NP in (Pr,Ca)112 correlates with the absence of an interfacial phase. These results give useful information about the microwave signature of interfacial superconductivity present in the (Pr,Ca)122 system, and may form a roadmap towards a stabilized high temperature superconducting phase in pnictides.

Calcium sulfide (CaS) nanoparticles are cadmium free fluorescent nanostructures with potential applications in nanomedicine and photovoltaic cells. We report on the synthesis and optical properties of CaS nanoparticles prepared by the reaction of Ca(CH3CO2)2 and DMSO in a microwave. The absorption spectra of CaS prepared from this method consists of a well-defined peak in the UV and a long wavelength tail that extends above 700 nm. Emission bands centered at around 500 nm with a long wavelength tail that extends above 600 nm are observed upon excitation at 405 nm. STM measurements reveal the formation of CaS nanoparticles with an average diameter of (3.2 ± 0.7) nm. The direct and indirect band gaps are estimated to be (0.403 ± 0.003) eV and (4.135 ± 0.006) eV, respectively. Theoretical calculations on small CaS clusters are used to establish the physical properties of calcium sulfide nanoclusters, including the optical absorption spectra. Unique to CaS nanostructures is the absorption of light at wavelengths longer that in the bulk material instead of the blue shift associated with quantum confinement effects in semiconductors. Indeed, the strong absorption bands in the visible region of the spectra of the CaS nanostructures do not have a counterpart in the gas or solid phases. The optical absorption spectra are proposed to have a significant contribution from indirect transitions which are discussed in terms of the dispersion of the phonon frequency.

The conventional process for preparing dry spinnable regenerated silk fibroin (RSF) aqueous solution needs not only an addition of Ca2+ but also an adjustment of pH value. In this work, an RSF dry spinning dope was prepared by using a simplified method with solely adding Ca2+. Compared with the conventional RSF solution, the simply prepared aqueous solution showed similar content of β-sheet conformation and diameter of RSF aggregates but lower viscosity. Furthermore, the posttreated RSF fiber dry-spun from this simply prepared solution showed higher crystallinity and crystalline orientation, smaller crystallite size, and better mechanical properties. It could be concluded that Ca2+ played a much more important role than pH value in improving the structures and properties of RSF spinning solution and fibers. Therefore, the step of adjusting pH value could be excluded in the process of preparing high performance RSF fibers.

Bismuth is an element obtained as a sub-product in lead production; Mexico occupies the second position in the world in production of this element. Bismuth is used as iron, aluminum and copper alloying, in the pharmaceutical industry, in the cosmetics industry, etc. Bismuth is separated from lead by the Kroll-Betterton Process in which a Ca-Mg alloy is added to the melting lead to form the intermetallic compounds Ca3Bi2, Mg3Bi2 and Ca2MgBi2 which float to the surface of the bath. Unfortunately, there is little thermodynamical information of the compounds of the system Ca-Mg-Bi which can be used to study and optimize the Kroll-Betterton process in a theoretical way. In this work there were synthesized the compounds Ca3Bi2, Mg3Bi2 and CaMg2Bi2 using powders of pure elements (Ca, Mg and Bi) in the required amounts and melted under an inert atmosphere. After synthesis, the samples were characterized by X-Ray Diffraction to ensure the formation of the desire compounds. Later, calorimetric technique was used to determine the thermodynamical properties of the compounds. The results obtained by X-Ray Diffraction show the formation of Mg3Bi2 and Mg2CaBi2 species; however, there is no crystallographic information of the compound Ca3Bi2. The heating curves obtained by calorimetry show endothermic peaks, due to the presence of phases changes as is indicated in the Ca-Bi, Mg-Bi and Ca-Mg-Bi phases diagrams.

When a biomaterial is implanted into the body, blood proteins adsorb on its surface and subsequently cells adhere via the protein adlayer. Thus, the understanding of protein adsorption and conformational change on the biomaterial surfaces is of great importance to control the biocompatibility such as antithrombotic properties and cell adhesion behaviors. In this study, we synthesized hydroxyapatite (HAp) and carbonate apatite (CAp) by a wet method. Then we successfully fabricated the HAp and CAp sensors for QCM-R by an electrophoretic deposition method. Adsorption behavior of proteins on the bone substitute material can be monitored by using these apatite sensors. Bovine serum albumin and fibrinogen were employed for the model proteins, and monitored the adsorption behavior on the HAp, CAp and reference gold (Au) sensors by the QCM-R technique. As a result, we revealed that fibrinogen and bovine serum albumin adsorbs on the gold surface by hydrophobic interaction, and adsorbs on the HAp and CAp surfaces mainly by electrostatic force. Besides, we revealed that fibrinogen adsorbs on the Au surface more rigid than on the HAp and CAp surfaces while bovine serum albumin adsorbs on the HAp and CAp surface more rigidly than on the Au surface.

Bisphosphonate (Bp) was adsorbed on the surface of crystalline calcium phosphates (CP); hydroxyapatite (HAp), octacalcium phosphate (OCP) and Dicalcium phosphate dehydrate (DCPD). The amount of Bp adsorbed was the largest for DCPD per unit surface area, while the amount was the largest for HAp per unit weight. The composites of Bp and amorphous calcium phosphate (ACP) were synthesized by titrating calcium acetate solution into phosphate buffer solution containing Bp. The amount of Bp doped in the composites was 366 μg / mg and was approximately 7 times larger than those of Bp adsorbed on the crystalline Calcium phosphates. TG-DTA measurements of a Bp-calcium and the composite indicated exothermic peaks due to Bp combustion, of which temperature were shifted to higher temperature for the composite. Bp in the composites was gradually released into phosphate buffered saline, while Bp was rapidly released into acetate buffer solution accompanied with the dissolution of ACP. This result suggests that the composite of Bp and ACP has potential for a drug-carrier releasing Bp in response to the condition of osteoclastic bone resorption.

Fluorine substitution in CaH2 has been studied by means of experimental and theoretical methods. Samples with various compositions have been prepared by ball milling. In situ X-ray diffraction analysis has been carried out as a function of temperature by synchrotron radiation experiments. An increase of mixing has been observed during heating, suggesting that mixing is thermodynamically favoured but it is kinetically hindered at low temperatures. Ab initio DFT calculations have been performed to estimate the thermodynamic mixing properties of both orthorhombic and cubic solid solutions. On the basis of ab initio results and literature information, a thermodynamic assessment within the CALPHAD framework has been performed and the pseudo binary CaH2-CaF2 phase diagram has been calculated. The formation of orthorhombic and cubic terminal solid solutions in the CaH2-CaF2 system is predicted, in good agreement with experimental findings.

Biomolecules rich in aspartic acid (Asp) are known to play a role in biomineral morphology and polymorph selection, and have been shown to greatly enhance the growth kinetics of calcite. The mechanism by which these compounds favor calcification may be related to their effects upon cation solvation. Using molecular dynamics, we investigated the influence of small carboxylated molecules on the hydration states and water exchange rates of divalent cations. We show that the carboxylate moieties of Asp promote dehydration of Ca2+ and Sr2+ and that contact ion pair (CIP) formation is not required to disrupt the hydration of these cations. Ca2+- Asp and Sr2+ - Asp CIP formation decreases the total inner sphere coordination from an average of 8.0 and 8.4 in bulk water to 7.5 and 8.0, respectively. Water residence times estimated for Mg2+, Ca2+and Sr2+ follow the expected trend of decreasing residence time with increasing ionic radius. In the presence of Asp, both solvent-separated ion pair (SSIP) and CIP formation decrease the residence times of Ca2+and Sr2+ inner sphere water molecules. Comparable impacts on Mg2+ hydration are not observed. Mg2+ - Asp CIP formation is energetically unfavorable and Asp does not affect Mg2+ inner sphere water residence times.

Carbon steel overpack will corrode by consuming oxygen introduced during repository construction after closure of repository, that will keep the environment in the vicinity of repository reducing. The iron corrosion products can migrate in bentonite as ferrous cations (Fe2+) through the interlayer of montmorillonite replacing the exchangeable sodium ions in the interlayer. This replacement of sodium may affect the migration behavior in the altered bentonite not only for redox-sensitive elements but also the other ions. Therefore we have carried out electrochemical analysis, of calcium, strontium or barium with the ferrous ion supplied by anodic corrosion of iron coupons in compacted bentonite. Fifteen micro liters of tracer solution containing 8.6 M of CaCl2 or 3.0 M of SrCl2 or 1.5 M BaCl2 were sspiked on the interface between the iron coupon and bentonite, for which the dry density was in the range of 1.4 to 1.5 Mg/m3, before assembling. The iron coupons were connected as working electrodes to the potentiostat and held at a constant supplied potential between - 500 to +300 mV (vs. Ag/AgCl reference electrode) for up to 7 days. Calcium and strontium could migrate faster and deeper into the bentonite than iron in each condition, while barium could migrate slower than iron. A model using dispersion and electromigration can explain the measured profiles in the bentonite specimens. The fitted value of electromigration velocity was a function of applied electrical potential and 10 to 23 nm/s for calcium, 11 to 19 for strontium, around 4 nm/s for barium and 5 to 15 nm/s for iron, respectively. Alternatively, the fitted value of the dispersion coefficient was not a function of applied potential, and the values were 3 - 8 × 10-12 m2/s for calcium, 2 - 4 × 10-12 m2/s for strontium, 5 - 10 × 10-12m2/s for barium and 3 - 9 × 10-12 m2/s for iron, respectively.

Thermal energy storage with phase change materials is one of the most efficient means of storing available energy because of its advantages such as providing higher thermal storage capacity, lower storage temperature, isothermal operation and less storage space. Thermal energy storage property of a new type of PCM heat exchanger was investigated, in which its main body is based on the traditional structure of a shell-and-tube heat exchanger, and is full of PCMs (CaCl2·6H2O) in the tubes. The hot air at the temperature of 40° was selected as a flow medium, and the temperature measurements of the test points were carried out at the inlet and outlet of this kind of PCM heat exchanger. The experimental results showed that this kind of PCM heat exchanger could store thermal energy from the hot fluid by means of PCMs in the tubes. Its prospect in engineering applications such as the recovery and utilizations of industrial afterheat or waste heat etc was also analyzed and forecasted.