In this study, the authors report the production of nanocomposite-enhanced phase-change materials (NEPCMs) using the direct-synthesis method by mixing paraffin with alumina (Al2O3), titania (TiO2), silica (SiO2), and zinc oxide (ZnO) as the experimental samples. Al2O3, TiO2, SiO2, and ZnO were dispersed into three concentrations of 1.0, 2.0, and 3.0 wt.%. Through heat conduction and differential scanning calorimeter experiments to evaluate the effects of varying concentrations of the nano-additives on the heat conduction performance and thermal storage characteristics of NEPCMs, their feasibility for use in thermal storage was determined. The experimental results demonstrate that TiO2 is more effective than the other additives in enhancing both the heat conduction and thermal storage performance of paraffin for most of the experimental parameters. Furthermore, TiO2 reduces the melting onset temperature and increases the solidification onset temperature of paraffin. This allows the phase-change heat to be applicable to a wider temperature range, and the highest decreased ratio of phase-change heat is only 0.46%, compared to that of paraffin. Therefore, this study demonstrates that TiO2, added to paraffin to form NEPCMs, has significant potential for enhancing the thermal storage characteristics of paraffin.
Several Mousterian sites in France have yielded large numbers of small black blocs. The usual interpretation is that these ‘manganese oxides’ were collected for their colouring properties and used in body decoration, potentially for symbolic expression. Neanderthals habitually used fire and if they needed black material for decoration, soot and charcoal were readily available, whereas obtaining manganese oxides would have incurred considerably higher costs. Compositional analyses lead us to infer that late Neanderthals at Pech-de-l'Azé I were deliberately selecting manganese dioxide. Combustion experiments and thermo-gravimetric measurements demonstrate that manganese dioxide reduces wood’s auto-ignition temperature and substantially increases the rate of char combustion, leading us to conclude that the most beneficial use for manganese dioxide was in fire-making. With archaeological evidence for fire places and the conversion of the manganese dioxide to powder, we argue that Neanderthals at Pech-de-l'Azé I used manganese dioxide in fire-making and produced fire on demand.
The Mg-Si-O system is the major Earth and rocky planet-forming system. Here, through quantum variable-composition evolutionary structure explorations, we have discovered several unexpected stable binary and ternary compounds in the Mg-Si-O system. Besides the well-known SiO2 phases, we have found two extraordinary silicon oxides, SiO3 and SiO, which become stable at pressures above 0.51 TPa and 1.89 TPa, respectively. In the Mg-O system, we have found one new compound, MgO3, which becomes stable at 0.89 TPa. We find that not only the (MgO)x·(SiO2)y compounds, but also two (MgO3)x·(SiO3)y compounds, MgSi3O12 and MgSiO6, have stability fields above 2.41 TPa and 2.95 TPa, respectively. The highly oxidized MgSi3O12 can form in deep mantles of mega-Earths with masses above 20 M⊕ (M⊕:Earth’s mass). Furthermore, the dissociation pathways of pPv-MgSiO3 are also clarified, and found to be different at low and high temperatures. The low-temperature pathway is MgSiO3 ⇒ Mg2SiO4 + MgSi2O5 ⇒ SiO2 + Mg2SiO4 ⇒ MgO + SiO2, while the high-temperature pathway is MgSiO3 ⇒ Mg2SiO4 + MgSi2O5 ⇒ MgO + MgSi2O5 ⇒ MgO + SiO2. Present results are relevant for models of the internal structure of giant exoplanets, and for understanding the high-pressure behavior of materials.
Abstract Aggregation of metal oxide nanoparticles in aqueous media complicates interpretation of in vitro studies of nanoparticle-cell interactions. We used dynamic light scattering to investigate the aggregation dynamics of iron oxide and zinc oxide nanoparticles. Our results show that iron oxide particles aggregate more readily than zinc oxide particles. Pretreatment with serum stabilises iron oxide and zinc oxide nanoparticles against aggregation. Serum-treated iron oxide is stable only in pure water, while zinc oxide is stable in water or cell culture media. These findings, combined with zeta potential measurements and quantification of proteins adsorbed on particle surface, suggest that serum stabilisation of iron oxide particles occurs primarily through protein adsorption and resulting net surface charge. Zinc oxide stabilisation, however, also involves steric hindrance of particle aggregation. Fluid shear at levels used in flow experiments breaks up iron oxide particle aggregates. These results enhance our understanding of nanoparticle aggregation and its consequences for research on the biological effects of nanomaterials.
The synthesis of highly-crystalline porous TiO(2) microspheres is reported using ultrasonic spray pyrolysis (USP) in the presence of colloidal silica as a template. We have exploited the interactions between hot SiO(2) template particles surface and TiO(2) precursor that occur during reaction inside the droplets, to control the physical and chemical properties of the resulting particles. Varying the SiO(2) to titanium precursor molar ratio and the colloidal silica dimension, we obtained porous titania microspheres with tunable morphology, porosity, BET surface area, crystallite size, band-gap, and phase composition. In this regard, we have also observed the preferential formation of anatase vs. rutile with increasing initial surface area of the silica template. The porous TiO(2) microspheres were tested in the photocatalytic degradation of nitrogen oxides (NO(x)) in the gas phase. USP prepared nanostructured titania samples were found to have significantly superior specific activity per surface area compared to a commercial reference sample (P25 by Evonik-Degussa).
Reactive dynamics simulations with the reactive force field (ReaxFF) were performed in NVE ensembles to study the sintering of two solid calcium oxide (CaO) particles with and without CO(2) chemisorption. The simulated sintering conditions included starting adsorption temperatures at 1000 K and 1500 K and particle separation distances of 0.3 and 0.5 nm. The results revealed that the expansion of sorbent particles during CO(2) chemisorption was attributed to the sintering of two CaO-CaO particles. Increasing the adsorption temperature resulted in more particle expansion and sintering. The shorter the distance between two particles, the faster the rate of sintering during CO(2) adsorption. A detailed analysis on atom spatial variations revealed that the sorbent particles with a larger separation distance had a larger CO(2) uptake because of less sintering incurred. The chemisorptions of CO(2) on CaO particles sintered at high adsorption temperatures were also simulated to mimic the process of sorbent regeneration. It was found that regeneration would be more difficult for sintered particles than for fresh particles. In addition, a possible sintering barrier, magnesium oxide (MgO), was introduced to prevent CaO particles from sintering during CO(2) chemisorption. It was found that the MgO particles could reduce the sintering of CaO particles during CO(2) chemisorption. Simulation results from this study provided some guidelines on synthesizing or selecting sorbents with less sintering effect for multiple CO(2) adsorption-regeneration cycles.
A highly stable high-temperature CO2 sorbent consisting of scaffold-like Ca-rich oxides (CaAlO) with rapid absorption kinetics and a high capacity is described. The Ca-rich oxides were prepared by annealing CaAlNO3 layered double hydroxide (LDH) precursors through a sol-gel process with Al(O(i) P)3 and Ca(NO3 )2 with Ca(2+) /Al(3+) ratios of 1:1, 2:1, 4:1, and 7:1. XRD indicated that only LDH powders were formed for Ca(2+) /Al(3+) ratios of 2:1. However, both LDH and Ca(OH)2 phases were produced at higher ratios. Both TEM and SEM observations indicated that the CaAlNO3 LDHs displayed a scaffold-like porous structure morphology rather than platelet-like particles. Upon annealing at 600 °C, a highly stable porous network structure of the CaO-based CaAlO mixed oxide (CAMO), composed of CaO and Ca12 Al14 O33 , was still present. The CAMO exhibited high specific surface areas (up to 191 m(2) g(-1) ) and a pore size distribution of 3-6 nm, which allowed rapid diffusion of CO2 into the interior of the material, inducing fast carbonation/calcination and enhancing the sintering-resistant nature over multiple carbonation/calcination cycles for CO2 absorption at 700 °C. Thermogravimetric analysis results indicated that a CO2 capture capacity of approximately 49 wt % could be obtained with rapid absorption from the porous 7:1 CAMO sorbents by carbonation at 700 °C for 5 min. Also, 94-98 % of the initial CO2 capture capability was retained after 50 cycles of multiple carbonation/calcination tests. Therefore, the CAMO framework is a good isolator for preventing the aggregation of CaO particles, and it is suitable for long-term cyclic operation in high-temperature environments.
This study explored the potential for engineered nanoparticles (ENPs) to contaminate the UK drinking water supplies and established the significance of the drinking water exposure route compared to other routes of human exposure. A review of the occurrence and quantities of ENPs in different product types on the UK market as well as release scenarios, their possible fate and behaviour in raw water and during drinking water treatment was performed. Based on the available data, all the ENPs which are likely to reach water sources were identified and categorized. Worst case concentrations of ENPs in raw water and treated drinking water, using a simple exposure model, were estimated and then qualitatively compared to available estimates for human exposure through other routes. A range of metal, metal oxide and organic-based ENPs were identified that have the potential to contaminate drinking waters. Worst case predicted concentrations in drinking waters were in the low- to sub-µg/l range and more realistic estimates were tens of ng/l or less. For the majority of product types, human exposure via drinking water was predicted to be less important than exposure via other routes. The exceptions were some clothing materials, paints and coatings and cleaning products containing Ag, Al, TiO2, Fe2O3 ENPs and carbon-based materials.
We use dark field spectroscopy to monitor the dissociation of hydrogen on single gold nanoparticles embedded in metal oxide supports. Individual gold nanorods were monitored in real-time to reveal the peak position, the full width at half maximum and the relative intensity of the surface plasmon resonances during repeated N2-H2-N2 and air-H2-air cycles. Shifts in the spectra are shown to be due to changes in electron density and not to refractive index shifts in the environment. We demonstrate that hydrogen does not dissociate on gold nanorods (13 nm × 40 nm) at room temperature when in contact with silica and that electrons or hydrogen atoms migrate from Pt nanoparticles to Au nanoparticles through the supporting metal oxide at room temperature. However, this spillover mechanism only occurs for semiconducting oxides (anatase TiO2 and ZnO) and does not occur for Au and Pt nanoparticles embedded in silica. Finally, we show that hydrogen does dissociate directly on anatase surfaces at room temperature during air-H2-air cycles. Our results show that hydrogen spillover, surface dissociation of reactants and surface migration of chemical intermediates can be detected and monitored in real time at the single particle level.
We report a novel betavoltaic device with significant conversion efficiency by using electrochemically reduced graphene oxide (ERGO) on TiO2 nanotube arrays (TNTAs) for enhancing the absorption of beta radiation as well as the transportation of carriers. ERGO on TNTAs (G-TNTAs) were prepared by electrochemical anodization and subsequently cyclic voltammetry techniques. A 10 mCi of 63Ni/Ni source was assembled to G-TNTAs to form the sandwich type betavoltaic devices (Ni/63Ni/G-TNTAs /Ti). By I-V measurements, the optimum betavoltaic device exhibits a significant effective energy conversion efficiency of 26.55% with an open-circuit voltage of 2.38 V and a short-circuit current of 14.69 nAcm-2. The experimental results indicate that G-TNTAs are a high-potential nanocomposite for developing betavoltaic batteries.