Solid Oxide Fuel Cells (SOFCs) are a promising technology that can provide efficient and clean energy production. The general barriers hindering their market entry are durability, i.e. resistance to aging, and costs. In parallel to the deeper insight into the different degradation sources and improved understanding of ageing factors and their interactions, work towards higher accuracy for the assessment and monitoring of real-world fuel cell ageing in necessary. The requirements for operational stability formulate the parameter “degradation rate” (DR). Most often long term durability tests are performed at constant current load and the decrease of the voltage is used for its definition. In this work a new approach based on analysis of the volt-ampere characteristics, named Differential Resistance Analysis (DRA), is presented. It operates with the differential resistance, i.e. with the derivative of the voltage in respect to the current (dU/dI = Rd) which is more sensitive to small deviations and thus increases the sensitivity of the analysis. Two performance indicators are derived (Rd, min and ∆U*) with differing selectivity: ∆U* is more sensitive to activation losses and Rd, min - to transport hindrances. The application of the DRA is demonstrated on examples from measurements in fuel cell and in reverse (fuel cell/electrolyzer) mode, as well as on modeling data. The results show that the method is at least 10 times more sensitive to DR evaluation in comparison with the classical approach.

A simple and scalable method is developed to prepare highly wrinkled graphene sheets – carbon nanospheres (WG-CN) composite for ultra high energy density supercapacitor application. Here, we introduce a novel simple paraffin wax candle flame technique for the simultaneous reduction of graphene oxide (GO) and deposition of carbon nanospheres on the graphene sheets. This is followed by introducing permanent wrinkles to the composite. The WG-CN composite exhibit the high specific capacitance values of 290 F g-1 and 253.7 F g-1 (138.5 F cm-3) for 6M KOH and EMIMBF4 ionic liquid electrolytes respectively. The ultra high energy density values of 108 Wh Kg-1 and 58.9 Wh L-1 has been obtained at the power density of 3955 W Kg-1 and 2157 W L-1 simultaneously. These attractive performances exhibited by the WG-CN composite supercapacitor electrode make them potential candidate for future energy storage devices. The key to success of this composite is the ability to make full utilization of the high intrinsic specific surface area of the nanocomposite.

Bandelier National Monument (BNM) was created to protect an extraordinary inventory of archaeological resources carved in the Tshirege Member of the Bandelier Tuff. These include more than one thousand excavated chambers, called cavates, used for dwelling, storage, and textile production. The glass-rich tuffs at the base of the Tshirege Member are poorly consolidated and susceptible to erosion by wind, rain, and mechanical abrasion, with resultant loss of cultural material. However, rock surfaces develop protective weathering rinds that are resistant to erosion. Using optical microscopy, SEM-EDS, XRD, and electron microprobe analysis, we determined that this rind consists of clay and silt sediments colonized by lichens and other surface biota, accompanied by the precipitation of secondary minerals in the near-surface pore space. Scoping experiments focused on glass-organic acid interactions indicate that oxalic acid excreted by microbial crust constituents catalyzes biogeochemical reactions that lead to the preferential dissolution of Si, Al, and Fe components of the volcanic glass; these cations become available for precipitation of opal, and smectite and sepiolite clays. Enzyme assays that quantify biological activity at outcrop surfaces indicate that microbial populations initially thrive as they derive nutrients from the dissolution reactions of the glass, but activity starts to decline as precipitation of secondary minerals limits access to new sources of nutrients, so that alteration processes are self-limiting. As case hardening progresses, imbibition rates at the surface decrease, and the erosion resistance of the altered surfaces is substantially improved. This article presents summary results of research conducted over a period of five years to characterize the roles of lichens and other microflora in rind formation, and the resulting contributions to tuff stability. The interaction of lichens and other microflora with rock surfaces in archaeological sites and monuments is usually explored in terms of biodeterioration and consequent damage. However, this study shows that, under some circumstances, lichens and microflora provide a level of erosion protection to relatively porous and unconsolidated rock strata that outweighs their biodeteriorative effects.

Eleven ancient Chinese ceramics from the early Bronze Age Qijia culture (c. 2200 – 1600 BCE) in the collection of the Harvard Art Museums were the subject of an interdisciplinary research project to explore questions about manufacturing techniques, specifically details of formation and decoration. While the Qijia culture, centered in the Gansu and Qinghai provinces of northwest China, is historically important as one of the earliest metalworking cultures of China and as a center of intercultural communication between China and central Asia, detailed scholarship about the culture is still emerging. Qijia ceramics have been categorized by typology, but little has been done regarding methods of manufacture. This study used visual examination and digital X-radiography to investigate ceramic production, especially the use of a wheel. In addition, the ceramic paste, including natural inclusions and temper, was examined. While film radiography has often been used to study ceramics, digital radiography presented new capabilities as well as challenges. Experimentation through the making of test vessels and tiles at the Harvard Ceramics Program provided additional insights into Qijia ceramics’ manufacture and surface decoration techniques, often described as cord-impressed.

The local chemistry of technetium-99 (99Tc) in oxide glasses is important for understanding the incorporation and long-term release of Tc from nuclear waste glasses, both those for legacy defense wastes and fuel reprocessing wastes. Tc preferably forms Tc(VII), Tc(IV), or Tc(0) in glass, depending on the level of reduction of the melt. Tc(VII) in oxide glasses is normally assumed to be isolated pertechnetate TcO4- anions surrounded by alkali, but can occasionally precipitate as alkali pertechnetate salts such as KTcO4 and NaTcO4 when Tc concentration is high. In these cases, Tc(VII) is 4-coordinated by oxygen. A reinvestigation of the chemistry of alkali-technetium-oxides formed under oxidizing conditions and at temperatures used to prepare nuclear waste glasses showed that higher coordinated alkali Tc(VII) oxide species had been reported, including those with the TcO5- and TcO6- anions. The chemistry of alkali Tc(VII) and other alkali-Tc-oxides is reviewed, along with relevant synthesis conditions.

Additionally, we report attempts to make 5- and 6-coordinate pertechnetate compounds of K, Na, and Li, i.e. TcO5- and TcO6-. It was found that higher coordinated species are very sensitive to water, and easily decompose into their respective pertechnetates. It was difficult to obtain pure compounds, but mixtures of the pertechnetate and other phase(s) were frequently found, as evidenced by x-ray absorption spectroscopy (XAS), neutron diffraction (ND), and Raman spectroscopy. Low temperature electron paramagnetic resonance (EPR) measurements showed the possibility of Tc(IV) and Tc(VI) in Na3TcO5 and Na5TcO6 compounds.

It was hypothesized that the smaller counter cation would result in more stable pertechnetates. To confirm the synthesis method, LiReO4 and Li5ReO6 were prepared, and their Raman spectra match those in the literature. Subsequently, the Tc versions LiTcO4 and Li5TcO6 were synthesized and characterized by ND, Raman spectroscopy, XANES, and EXAFS. The Li5TcO6 was a marginally stable compound that appears to have the same structure as that known for Li5ReO6. Implications of the experimental work on stability of alkali technetate compounds and possible role in the volatilization of Tc are discussed.

Interference lithography has proven to be a useful technique for generating periodic sub-diffraction limited nanostructures. Interference lithography can be implemented by exposing a photoresist polymer to laser light using a two-beam arrangement or a one-beam configuration based on a Lloyd’s Mirror Interferometer. For typical photoresist layers, an anti-reflection coating must be deposited on the substrate to prevent adverse reflections from cancelling the holographic pattern of the interfering beams. For silicon substrates, such coatings are typically multilayered and complex in composition. By thinning the photoresist layer to a thickness well below the quarter wavelength of the exposing beam, we demonstrate that interference gratings can be generated without an anti-reflection coating on the substrate. We used ammonium dichromate doped polyvinyl alcohol as the positive photoresist because it provides excellent pinhole free layers down to thicknesses of 40 nm, and can be cross-linked by a low-cost single mode 457 nm laser and etched in water. Gratings with a period of 320 nm and depth of 4 nm were realized, as well as a variety of morphologies depending on the photoresist thickness. This simplified interference lithography technique promises to be useful for generating periodic nanostructures with high fidelity and minimal substrate treatments.

As the scaling of the device dimensions in CMOS devices runs into physical limitations, new materials beyond Si with high electron and hole mobilities such as Ge, SiGe, and III-V materials are introduced. Challenges of CMP for these materials are reviewed in this paper. First we discussed the challenge of the new integration schemes to CMP. Loading effects can result in different growth rates for varying feature sizes, which results in a critical dimension dependent overburden. This makes it more difficult to meet the targets of the CMP process with respect to oxide loss and Ge/SiGe/III-V dishing. Secondly we discuss the challenge for the reduction of the defects during CMP for these new materials. Finally the challenge that is relevant especially for the introduction of III-V materials is studied. During the polishing of III-V materials, toxic gases as well as III-V containing liquid waste will be created. The chemical mechanism of the waste control is discussed.

Initial results en route toward construction of complex magnetic core-shell silica and organosilica nanotheranostics are presented. Magnetite nanoparticles are synthesized by three different methods and embedded within mesoporous silica and organosilica frameworks by different surfactant-templated procedures to produce three types of core-shell nanoparticles. Magnetite nanoparticles (15 nm in diameter) are embedded within mesoporous silica nanoparticles to produce cell-like material with predominantly one magnetite nuclei-resembling core per nanoparticle, with final particle diameter of ca. 150 nm, specific surface area of 573 m2/g and hexagonally structured tubular pores (2.6 nm predominant diameter), extended throughout the volume of nanoparticles. Two forms of spherical core-shell nanoparticles composed of magnetite cores embedded within mesoporous organosilica shells are also obtained by employing ethylene and ethane bridged organobisalkoxysilane precursors. The obtained nanomaterials are characterized by high surface area (978 and 820 m2/g), tubular pore morphology (2 and 2.8 nm predominant pore diameters), different diameters (386 and 100-200 nm), in case of ethylene- and ethane-composed organosilica shells, respectively. Different degree of agglomeration of magnetite nanoparticles was also observed in the obtained materials, and in the case of utilization of surfactant-pre-stabilized magnetite nanoparticles for the syntheses, their uniform and non-agglomerated distribution within the shells was noted.

Using Density Functional Theory based modeling, we compare sodium attachment to disodium terephthalate (Na2Tph) and a related molecule disodium pyridine dicarboxylate (Na2PDC). We predict that substitution of the Na2Tph’s aromatic ring with pyridine will lead to an increased voltage by about 0.4 V vs Na2+xTph up to Na2+1PDC and a similar voltage to the terephthalate between Na2+1PDC and Na2+2PDC, i.e. a two-plateau behavior vs. a single plateau for Na2+xTph.

Perovskite solar cells (PSCs) based on organometal halide light absorbers have hit the limelight in recent years owing to their low temperature solution processability, material abundance and rapidly rising efficiency. To rival the leading photovoltaic technologies, efficiency and long-term stability of PSCs represent two prime facets of the challenges currently facing the research community. Herein we summarize the strategies for improving efficiency and stability of PSCs by drawing on our recent work. Emphasis is given to the importance of perovskite film growth, electron/hole transport materials and interface materials in cell performance. We also discuss possible degradation mechanisms of PSCs.

We use cyclic charge-discharge experiments to evaluate the capacity retention rates of two quinone-bromide flow batteries (QBFBs). These aqueous QBFBs use a negative electrolyte containing either anthraquinone-2,7-disulfonic acid (AQDS) or anthraquinone-2-sulfonic acid (AQS) dissolved in sulfuric acid, and a positive electrolyte containing bromine and hydrobromic acid. We find that the AQS cell exhibits a significantly lower capacity retention rate than the AQDS cell. The observed AQS capacity fade is corroborated by NMR evidence that suggests the formation of hydroxylated products in the electrolyte in place of AQS. We further cycle the AQDS cell and observe a capacity fade rate extrapolating to 30% loss of active species after 5000 cycles. After about 180 cycles, bromine crossover leads to sufficient electrolyte imbalance to accelerate the capacity fade rate, indicating that the actual realization of long cycle life will require bromine rebalancing or a membrane less permeable than Nafion® to molecular bromine.

Peptide nanotubes based on short dipeptide diphenylalanine (FF) attract a lot of attention due to their unique physical properties ranging from strong piezoelectricity to extraordinary mechanical rigidity. In this work, we present the results of high-resolution Piezoresponse Force Microscopy (PFM) measurements in FF microtubes prepared from the solution. First in-situ temperature measurements show that the effective shear piezoelectric coefficient d15 (proportional to axial polarization) significantly decreases (to about half of the initial value) under heating up to 100 oC. The piezoresponse becomes inhomogeneous over the surface being higher in the center of the tubes. Further, PFM study of a composite consisting of FF microtubes and reduced graphene oxide (rGO) was performed. We show that piezoelectric properties of peptide microtubes are significantly modified and radial (vertical) piezoresponse appears in the presence of rGO as confirmed via PFM analysis. The results are rationalized in terms of molecular approach in which π – π molecular interaction between rGO and dipeptide is responsible for the appearance of radial component of polarization in such hybrid structures.

Providing magnetite nanoparticles with saccharide coatings has been found to significantly increase the interactions of the nanoparticles with cells. Glucose (Glc) or N-acetylglucosamine (GlcNAc) coated magnetic nanoparticles (MNPs) were used to magnetically label 3T3 fibroblast cells, and the response of the labelled cells to external magnetic fields was studied. It was found that cells incubated with Glc- or GlcNAc-coated nanoparticles were much more likely to move towards an external magnet than those incubated with uncoated nanoparticles. Furthermore, cells in suspension moved much faster than those in contact with the surface of polystyrene well plates, with stronger magnets increasing the speed of movement. Cells that were adhering to the floor of the cell culture well and did not move in the x-y plane could still be rotated about the z-axis by moving the external magnet around the cell.

Gas detecting and sensing is a largely studied field of knowledge, but total understanding is not yet achieved and the ideal device is still far in the future. Many experimental efforts have been devoted to find the minimum optimal temperature and operational conditions for SnO2 to sense hydrocarbons; different methods to build gas-detecting devices keep being developed all around the world, from paste-based bulk devices to nanostructured thick and thin films, but little effort has been aim to characterize the reactions by calculating their related enthalpies. Computational methods have been widely used to characterize, understand and model many physicochemical interactions. In this regard, three main courses can be followed: Ab initio (first principles of quantum mechanics), DFT (Density Functional Theory) and MD (Molecular Dynamics) simulation. In this research, DFT modelling tool is employed to understand and characterize the gas-sensing reactions of Tin Oxide when exposed to an atmosphere with Methane. In CASTEP, a robust DFT module of the Materials Studio suite, one SnO2 (110) crystal plane is exposed to CH4 and the structure is optimized many times for each possible step of the reaction, recording the energies related with each optimization stage, in sum giving us the Transition State (TS) of the reaction. Based on the data, a promising reaction-path is proposed and analyzed for the (110) surface.

ZnO films were fabricated by RF magnetron sputtering with nitrogen mediated crystallization (NMC) under various gas pressures. X-ray diffraction measurements show that the NMC-ZnO films are highly crystalline regardless of the gas pressure, and the full width at half maximum values of the (0002) rocking curves range from 0.032 to 0.044°. In contrast, atomic force microscopy (AFM) reveals that the gas pressure plays an important role in determining the surface morphology of the films. The root-mean-square (RMS) roughness decreases monotonically from 1.05 to 0.60 nm with increasing pressure from 0.2 to 0.7 Pa. However, the RMS roughness increases with further increases in the pressure, reaching 2.15 nm at 2.1 Pa. The height distribution of the NMC-ZnO films derived from the AFM images is narrowest at 0.7 Pa, indicating that the smooth surface obtained at 0.7 Pa can be attributed to spatially uniform nucleation occurring in a short time period. These results indicate that the sputtering gas pressure is a key parameter for controlling the surface morphology of NMC-ZnO films.

The focus of this paper is on analysis, comparison and research on the colorful low-temperature, lead-containing overglazes on glazed porcelain body and on the enamel glazes on the metal body of the Qing Dynasty by adopting several analytical methods. Analysis and tests on the element, boron in overglaze on glazed porcelain body and enamel glaze on metal body, were performed using laser induced breakdown spectroscopy (LIBS), and the results showed that Cloisonné enamel, painted enamel and Falangcai samples contained boron, while Famille Rose (Fencai) samples did not contain boron. Meanwhile, such analysis methods as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), energy dispersive X-ray spectroscopy (EDXRF), Micro-Raman, stereomicroscope and Confocal laser scanning microscopy (CLSM) were used to test and observe the element composition, crystal composition and microstructure of the samples. The results illustrated that matrix glaze of Cloisonné enamel, painted enamel and Falangcai was the same. The yellow glaze was a lead-alkali glass and other color glazes were boron-lead-alkali glass, while all color glazes of Famille Rose were lead-alkali glass. Colorful low-temperature overglaze on glazed porcelain body and enamel glaze on metal body had a common practice and technology in the use of opacifiers and colorants. Compared to painted enamel, the painting technique of Famille Rose was more complicated, and effect was apparently praised as being superior.

This work investigates a diesel engine operating with different blends of diesel fuel, biodiesel and anhydrous ethanol. Anhydrous ethanol (99.8% purity) was added to diesel oil with 7% (B7) and 20% of biodiesel (B20), with the concentrations of 5% (E5), 10% (E10) and 15% (E15) and 20% (E20). The experiments were conducted on a naturally aspirated, four-stroke, four-cylinder, direct injection 44 kW diesel engine, operating at a constant speed of 1800 RPM and at the fixed load of 27.5 kW to attain the lowest specific fuel consumption (SFC). The results were compared with the standard B7 operation, and showed that ethanol addition (B7E5) reduced up to 7% carbon dioxide (CO2) emissions, associated with the decrease of the cylinder gas temperature, due to the ethanol high latent heat of evaporation, and to the ethanol lower carbon-to-hydrogen ratio and oxygen content. Total hydrocarbons (THC) emissions were reduced up to 14% with ethanol addition (B7E15), indicating higher fuel burn efficiency when ethanol is added to the fuel, as the oxygen available in ethanol molecule improves the burning during combustion. On the other hand, increasing biodiesel content in the fuel from 7% to 20% increased CO2 and THC emissions, both mitigated with the use of ethanol. Carbon monoxide (CO) and oxides of nitrogen (NOX) emissions showed different behavior, depending on ethanol and biodiesel concentration. Both biodiesel and ethanol increased SFC, due to the reduction of fuel lower heating value (LHV), although ethanol addition slightly increased fuel conversion efficiency.

AlGaN based multiple quantum wells (MQWs) were grown on 8° vicinal 4H p-SiC substrates by plasma-assisted molecular beam epitaxy. The MQWs were designed to emit near 300 nm using the wurtzite k.p model. The MQW periodicity and strain state were measured with X-ray diffraction. The optical properties were characterized with temperature dependent photoluminescence (PL). The internal quantum efficiency was estimated from the ratio of room temperature to 18K integrated PL intensity. Internal quantum efficiency up to 48% was achieved. These data are encouraging for future vertical and inverted ultraviolet light emitting diodes grown on p-SiC substrates.

The growth mechanism and the barrier performance of Al2O3, SiO2 and a binary Si-Al oxide (SiAlxOy) deposited by spatial atomic layer deposition (SALD) were investigated. Alumina and silica were deposited by TMA and BDEAS with growth-per-cycles (GPC) of 0.16 and 0.013 nm, respectively. Interestingly a significant higher GPC of 0.225 nm was found for SiAlxOy. Although alumina in principle has excellent barrier properties, the films easily degraded and lose their barrier performance if exposed to water vapor at elevated temperatures. Therefore, the barrier performances of these films were investigated under harsh environment conditions. We found that the barrier performance of 100 nm Al2O3 failed in less than one day at 70 °C with 70 % relative humidity, whereas 100 nm SiAlxOy sustained for approximately one week. However, the resistivity of those barrier systems was significantly improved by inserting a single 3.3 nm SiO2 layer into the barrier films. In this way the barrier system withstands up to 5 months and the intrinsic water vapor transition rate was reduced by two to three orders of magnitude to ∼10-4 g/m2/day at these tough aging conditions.

Emissive PbS/CdS core/shell nanosheets are synthesized using a cation-exchange method. A significant blue-shift of the photoluminescence is observed, indicating a stronger quantum confinement in the PbS core as its thickness is reduced to eight atomic layers. High resolution transmission-electron-microscopy images of the cross-sections of the core/shell nanosheets show atomically sharp interfaces between PbS and CdS. Accurate analysis of the thickness of each layer reveals the relationship between the energy-gap and the thickness in the extremely one-dimensionally confined nanostructure.