ALBERT

Description: Herein, we report on the crystal structures of Nb 2 AlC and TiNbAlC—actual composition (Ti 0.45 ,Nb 0.55 ) 2 AlC—compounds determined from Rietveld analysis of neutron diffraction patterns in the 300–1173 K temperature range. The average linear thermal expansion coefficients of a Nb 2 AlC sample in the a and c directions are, respectively, 7.9(5) × 10 −6 and 7.7(5) × 10 −6  K −1 on one neutron diffractometer and 7.3(3) × 10 −6 and 7.0(2) × 10 −6  K −1 on a second diffractometer. The respective values for the (Ti 0.45 ,Nb 0.55 ) 2 AlC composition—only tested on one diffractometer—are 8.5(3) × 10 −6 and 7.5(5) × 10 −6  K −1 . These values are relatively low compared to other MAX phases. Like other MAX phases, however, the atomic displacement parameters (APDs) show that the Al atoms vibrate with higher amplitudes than the Ti and C atoms, and more along the basal planes than normal to them. When the predictions of the APDs obtained from density functional theory are compared to the experimental results, good quantitative agreement is found for the Al atoms. In case of the Nb and C atoms, the agreement was more qualitative.

Description: In this study, lithium disilicate (LS 2 ) glass samples with different particle sizes ranging from less than 105 to 850 μm were prepared. These specimens were inserted in a Pt-Rh DSC crucible and heated to 850°C at different rates (ϕ = 0.5–30 K/min) to identify their crystallization peaks. The activation energies for the overall crystallization ( E ) and the Avrami coefficient ( n ) were evaluated using different nonisothermal models. Specifically, n was evaluated using the Augis–Benett model and the Ozawa method, and E was evaluated using the Kissinger and Ligero methods. As expected, the coarse particles mainly crystallized in the volume, while surface crystallization was predominant in the samples with particle sizes of less than 350 μm. This result was confirmed through SEM analysis of the double stage heat-treated samples. In contrast with previous studies, our results demonstrated that the activation energy decreased as the particle size increased. In addition, no clear correlation between the peak intensity (δ T p ) and the particle size was observed.

Description: The possibility of predicting the droplet size distribution from the particle size distribution was investigated. For that purpose, suspensions of different types of materials were dried in a laboratory-scale spray drier. Drying of suspensions was performed with different sizes of two-fluid nozzles. Droplet size distribution was evaluated from the data obtained for spray drying of bismuth molybdate suspension. The method was validated experimentally with other tested materials. Investigated systems involve processes of drying, crystallization, and coating. The proposed methodology can be applied when nonagglomerated particles, spherical particles, or spherical agglomerates were obtained by spray drying. Spray drying is a unique drying process since formation of solid phase and drying occur simultaneously. Droplet size distribution produced by a two-fluid nozzle during spray drying of bismuth molybdate suspension was evaluated simply from the particle size distribution. The proposed methodology enables prediction of the particle size distribution obtained by spray drying.

Description: The influence of vibration parameters on the segregation phenomenon of a binary mixture in a vibration fluidized bed is investigated. Initially, the mixture composed of spherical balls with different densities but same diameter is in a perfect mixing state in the bed. The motion of particles is simulated based on the discrete element method. The effects of friction coefficient, vibration frequency, amplitudes, and gas velocity are analyzed. The coefficient of segregation to the degree of particle segregation is calculated for different operating conditions. The segregation degree in the vibration fluidized bed is found to be higher than that in the bed without vibration. The curve for the segregation degree exhibits a single peak value which represents the optimal segregation result. The impact of vibration on gas phase- and particle flow is not yet clarified due to the complex motion of particles in vibrated fluidized beds. Discrete particle simulation is used to investigate the segregation behavior of binary mixtures in a fluidized bed. The effect of vibration parameters and suitable operating conditions for segregation, particle distribution, and particle motion are evaluated.

Description: The effects of a turbulence-generating grid on fluid mixing and a passive chemical reaction are experimentally investigated in a liquid shear mixing layer under a nonpremixed condition. The grid is installed at three streamwise locations to find the optimal location to promote the chemical reaction. The results show that the grid generates disturbances at small scales that enhance fluid mixing and the chemical reaction. However, the turbulence intensity and mass diffusion in the mixing layers with the grid decrease rapidly and become even smaller than those in the mixing layer without the grid in a downstream region. Therefore, in the present study, the chemical production is maximized when the grid is installed at where the flow is turning to a developed mixing layer. Installation of a turbulence-generating grid is advantageous to promote fluid mixing and chemical reaction in a free shear flow in which the reactive fluids are introduced under a nonpremixed condition. Special attention is needed regarding the location of the grid to maximize the promotion effect since it could be better to install it in the downstream region rather than the upstream region.

Description: Bubble splitting in 2D gas-solid freely bubbling fluidized beds is experimentally investigated using digital image analysis. The quantitative results can be applied for the development of a new breakage model for bubbly fluidized beds, especially discrete bubble models. The variation of splitting frequency with bubble diameter, new resulting bubble volumes, positions, and also the assumptions of mass and momentum conservation for bubbles after breakage are studied in detail. Small bubbles are found to be more stable than large ones and nearly all mother bubbles split into two almost equally sized daughter bubbles. The momentum of gas bubbles in the vertical direction remains approximately constant after breakage, whereas that of bubbles in the horizontal direction changes with no clear trend. The effect of fluidizing gas velocity in breakage frequency is also examined. The behavior of gas bubbles plays a key role in heat- and mass-transfer operations in fluidized beds. Bubble splitting for Geldart B-type particles under varying conditions was investigated in a pseudo-2D gas-solid fluidized bed by digital image analysis. The quantitative results can facilitate the development of new breakage models for bubbly fluidized beds and are particularly relevant for discrete bubble modeling.

Description: For the application of microreactors in industrial processes, more scaling-up strategies are still required except of the original concept, the numbering-up. A more maneuverable and economic approach, combining both similarity-up and numbering-up, is introduced as an example for an innovative strategy. CFD simulation is also applied to assist analysis and optimization of fluid distribution. Based on this concept, named similarity-up + numbering-up + simulation, a pilot-plant microsieve dispersion minireactor used to proceed the reaction of cyclohexanecarboxylic acid and oleum is designed and tested experimentally. With the contribution of similarity-up, the treating capacity of the core unit is significantly increased. Ten parallel units are integrated to form a correspondingly enhanced capacity of the microreactor which exhibits low pressure drop, stable operating performance, and excellent main product selectivity. For industrial applications of microreactors, more flexible and economic scaling-up strategies are required. A scale-up approach for a microsieve dispersion reactor is proposed, combining similarity-up and numbering-up of the core unit with CFD simulation-based device structure optimization. Low fabrication cost, low pressure drop, and excellent main product selectivity can be achieved by this strategy.

Description: A new design of conjugated heat transfer in double-pass parallel-plate laminar countercurrent operations of power law fluids under wall isoflux was investigated experimentally and theoretically. The analytical solutions were obtained with a superposition model by introducing an eigenfunction expansion in terms of a power series for the homogeneous part and an asymptotic solution for the inhomogeneous part. The influence of the power law index on the average Nusselt numbers with the various design and operating parameters is also delineated. The theoretical predictions of the experimental results are represented graphically. The heat transfer performance was considerably improved when compared with a single-pass parallel-plate heat exchanger (without inserting a solid separator sheet). Suitable adjustments of the solid separator sheet position can effectively enhance the heat transfer efficiencies for such a recycling double-pass device, as compared with the efficiencies of single- and double-pass devices.

Description: In this letter, 2-μm Pb 0.97 La 0.02 (Zr 0.75 Sn 0.18 Ti 0.07 )O 3 antiferroelectric thick film with tetragonal structure was prepared. The effects of operating electric field, temperature, and frequency on the thermal–electrical energy harvesting capacity of the film were studied by using the Olsen cycle. The results demonstrated that giant energy harvesting effect could be realized in the antiferroelectric thick film. The maximum harvestable energy density per cycle of the film was about 7.8 J/cm 3 at 1 kHz, which was the largest reported value to date. The corresponding energy harvesting efficiency was 0.53%. Moreover, the film had a low leakage current density (about 7.3 × 10 −7 and 3.9 × 10 −5  A/cm 2 at 25 and 200°C, respectively), which was favorable for its application in the devices of the thermal–electrical energy harvesting.

Description: Discharged energy properties of PbO–SrO–Na 2 O–Nb 2 O 5 –SiO 2 glass-ceramics with crystallization time from 1 to 1000 min were investigated by measuring their hysteresis loops (described as quasi-static measuring method) and pulse-discharge current-time curves (described as dynamic measuring method). The results show the same trend for both measuring methods: With the increment of crystallization time, the discharged energy density increases gradually, while the energy efficiency decreases. The highest energy efficiencies were obtained in the sample with crystallization time of 1 min, which are 96.3% and 82.4%, corresponding quasi-static and dynamic measurement, respectively. The reduction of energy efficiency with crystallization time is attributed to combined effect of ferroelectric polarization and interfacial polarization, and part of the corresponding energy could not release in the pulse-discharge process.

Description: In order to study emulsification phenomena, devices generating well-defined flow conditions are essential. Thus, emulsification of drop collectives under laminar shear flow is commonly performed in cylindrical Couette or Searle devices. In these devices, the flow conditions in the shear gap and in the volume underneath the rotor are often different, which can lead to inhomogeneous product properties and may complicate sample taking. Here, a novel cone-cone shear cell is presented to study emulsification processes. The flow inside the device is examined using numerical simulations. The numerical simulations indicate that simple shear flow is realized all over the sample volume in the cone-cone shear cell. The experimental results show that the drop breakup in the cone-cone shear cell is equivalent to the breakup under simple shear realized in the shear gap of a conventional device, i.e., the Searle device. Critical capillary numbers are calculated from the experimental data and show breakup behavior as predicted by single-drop experiments. Thus, the cone-cone shear cell proved to be suitable to study emulsification mechanisms in simple shear flow. Emulsion-based products are widely used in the food, chemical, and pharmaceutical industries. A novel cone-cone shear cell to study emulsification characteristics is described. The flow conditions inside the shear cell are validated via numerical simulations and experimental results.

Description: Hydrocracking of a bitumen-derived asphaltene over NiMo/ γ -Al 2 O 3 was investigated in a microbatch reactor at varying temperatures. The molar kinetics of asphaltene cracking reaction was examined by fitting the experimental data. Below a defined temperature, the molar reaction showed the first-order kinetic feature while at higher temperatures secondary reactions such as coke formation became significant, causing deviation of the reaction behavior from the proposed first-order kinetic model. Selectivity analysis proved that dominant products varied from gases to liquids to gases with increasing temperature, shifting the dominant reaction from C–S bonds cleavage to C–C bonds cleavage. Catalytic hydrocracking could be a proper choice for asphaltene upgrading but the reaction conditions still need to be optimized. Hydrocracking of a bitumen-derived asphaltene over a NiMo/ γ -Al 2 O 3 catalyst in a microbatch reactor at varying temperatures was analyzed. The molar kinetics of asphaltene cracking reaction was evaluated by fitting the experimental data.

Description: Two different types of metals (Cu and Ni) and the effect of CeO 2 addition to produce a CeO 2 -ZrO 2 co-supporter were investigated through the water-gas shift (WGS) reaction. It was found that the WGS activity could be enhanced with CeO 2 addition. At relatively high temperature, Ni-loaded catalysts exhibited higher CO conversion while Cu-loaded catalysts demonstrated better performance at low temperatures. The stability and yield of the CO 2 and H 2 products of the Cu catalysts were higher than those of the Ni catalysts. These results may be caused by an irreversible adsorption of CO on Ni and the reverse WGS reaction occurring on the Ni catalysts. In situ diffuse-reflection infrared Fourier transform spectroscopy data suggests that the WGS mechanism likely proceeded via formate species. The water-gas shift reaction (WGS), as an alternative way to produce H 2 and convert poisonous CO into CO 2 , was carried out using Cu and Ni loaded onto CeO 2 -ZrO 2 as catalysts. The Ni-loaded catalysts exhibited higher CO conversion at high temperature while the Cu-loaded catalysts performed better at low temperature. The WGS reaction was found to occur via the formation of formate species.

Description: Power ultrasound is applied for cooling crystallization to control and modify the particle size and crystal habit of an active pharmaceutical ingredient, phenacetin. Operating parameters including sonication intensity and duration, solution concentration, and cooling rate are studied and compared. With respect to mean particle size, the effect of sonication intensity is most significant. In addition, the crystal habit of recrystallized phenacetin is modified substantially and shows an elliptic shape. Recrystallized phenacetin also provides an enhanced dissolution rate compared with the original sample. These results prove that ultrasonic crystallization is an efficient tool for controlling the solid-state properties of an active pharmaceutical ingredient. Ultrasonic crystallization is a promising process for controlling the different stages of crystallization. Cooling crystallization applying power ultrasound is adopted for recrystallization of a nonsteroidal anti-inflammatory drug, phenacetin. The mean particle size can be managed by adjusting sonication intensity and duration. Phenacetin crystals with a regular crystal habit and an elliptic shape are obtained.

Description: In a variety of reactions in the chemical industry, eggshell catalysts with a thin active layer are applied; they are often crushed for laboratory testing. The destruction of the shell can be avoided by a special reactor design. The presented advanced TEMKIN reactor is a further development of the reactor system for testing eggshell catalysts on the laboratory scale published by Temkin and Kul'kova in 1969. It is suitable for kinetic studies and for the detailed investigation of deactivation processes, as shown on the example of selective hydrogenation of acetylene. The advanced TEMKIN reactor is well suitable for testing of uncrushed industrial eggshell catalysts because of its defined flow pattern and excellent mass and heat transport properties. Because of its simple and robust design, all technical requirements are fulfilled for a fast, competitive, and accurate optimization of prototypes as well as already established catalysts for industrial applications.

Description: A bench-scale submerged membrane bioreactor (SMBR) was employed to treat vegetable oil plant wastewater with complete sludge retention. Treatment performance and membrane fouling of the SMBR were investigated. The system stably removed high amounts of total organic carbon, oil, and ammonia from vegetable oil wastewater and reduced the chemical oxygen demand, demonstrating the great potential of the SMBR in removing pollutants. The membrane fouling layer was not only governed by deposition of organic substances composed of extracellular polymeric substances like proteins, polysaccharides etc., and oil substances but also by inorganic elements. Organic foulants coupled to inorganic precipitation enhanced the formation of a gel layer and triggered severe membrane fouling in the SMBR. Treatment and disposal of vegetable oil wastewaters (VOWs) represents one of the principal problems for vegetable oil producing countries. A bench-scale submerged membrane bioreactor was applied to treat VOWs with complete sludge retention. Treatment performance and membrane fouling were investigated. The experimental results demonstrated the great potential of this membrane bioreactor in removing pollutants.

Description: Adsorption processes are frequently applied to separate traces of hazardous and toxic substances from gas streams. Hence, knowledge of sorption characteristics of these substances on standard adsorbents is essential. Sorption of hexanal and acetaldehyde from a nitrogen gas stream in trace concentrations on activated carbon and ordered mesoporous carbon-based adsorbents (CMK) is studied. A magnetic suspension balance and an attached gaschromatograph-mass spectrometer were used to analyze the sorption process both gravimetrically and spectrometrically. Both types of adsorbents show a higher capacity for hexanal than acetaldehyde. The activated carbon exhibits considerable differences in regard to desorption of hexanal compared to the mesoporous CMK. Information on sorption characteristics of hazardous substances is essential to design separation processes. Adsorption and desorption of the toxic acetaldehyde and the intensely odorous hexanal on activated carbon and periodic mesoporous carbon were studied. Magnetic suspension balances were used to analyze the sorption processes. Both adsorbents exhibit a higher capacity for hexanal than acetaldehyde.

Description: High-solids biomass slurries exhibit non-Newtonian behavior with a yield stress and require high power input for mixing. The goals were to determine the effect of scale and geometry on power number P 0 , and estimate the power for mixing a pretreated biomass slurry in a 3.8 million L hydrolysis reactor of conventional design. A lab-scale computational fluid dynamics model was validated against experimental data and then scaled up. A pitched-blade turbine and A310 hydrofoil were tested for various geometric arrangements. Flow was transitional; laminar and turbulence models resulted in equivalent P 0 which increased with scale. The ratio of impeller diameter to tank diameter affected P 0 for both impellers, but impeller clearance to tank diameter affected P 0 only for the A310. At least 2 MW is required to operate at this scale. High-solids biomass slurries are characterized by non-Newtonian behavior with a yield stress and high power input demand for mixing. A computational fluid dynamics model was developed to predict power requirements of non-Newtonian lignocellulosic slurry in an industrial-scale hydrolysis reactor with conventional mixing impellers. The lab-scale model was validated against experimental data and then scaled up.

Description: The effect of NaCl added in different quantities on thermodynamic properties, granulometric characteristics, and structure of glycine in a crystallization process was investigated. Solubilities of α - and γ -polymorphs in the presence of varying amounts of NaCl were analyzed. In order to examine the impact of the additive on granulometric properties of glycine, crystal morphology was examined by observing crystals under a scanning electron microscope. Crystal size distribution was determined by sieve analysis. By X-ray diffraction analysis, the critical concentration of NaCl at which the structure of glycine changed, could be defined. The purity of obtained polymorphs was confirmed by Fourier transform infrared spectroscopy. Interactions between additives and crystallizing phase influence crystallization processes. Batch-cooling crystallization of glycine with different amounts of added NaCl is described, causing changes in solubility, metastable zone width, supersaturation, final mass of crystals, granulometric properties, and structure. Process conditions for a conversion of α- into a γ- glycine structure are defined.

Description: Cryogenic air separation as the most important part of an integrated gasification combined cycle is a widely used operation unit for producing large quantities of high-purity oxygen and nitrogen. However, cryogenic distillation requires a large amount of energy due to the work needed to compress the air feed. An improved heat-integrated air separation column (HIASC) is proposed. The requirements of high-purity separation in the industrial cryogenic air separation process are achieved. An optimization model of the heat transfer coefficient ( UA ), a key parameter in column structure design and operation, is presented. The optimized UA value is obtained within the accepted value range reported in the international open literature, which ensures the practicability of the improved HIASC. An improved heat-integrated air separation column is proposed. With the new heat-integrated and thermally coupled structure, the pressure of the high-pressure column and the energy consumption decrease significantly compared with the conventional air separation column. The mathematic model and parameter analysis are presented. An optimization model for the heat transfer coefficient is proposed.

Description: Functional mesoporous Mo–SiO 2 materials were synthesized by a one-pot and facile room-temperature procedure, and characterized by X-ray diffraction, TEM, Raman spectroscopy, FT-IR, diffuse reflectance spectra, and BET analysis. The experimental results demonstrated that the mesoporous materials presented a high dispersion of molybdenum species and excellent catalytic activity for the removal of dibenzothiophene (DBT) without organic solvents as extractants. The catalytic performance on different sulfur-containing compounds was also investigated in detail. After recycling for eight times, the removal of the oxidation desulfurization system could still reach high values. GC-MS analysis detected the oxidation product of DBT. A mechanism was proposed for the absorptive oxidation process of sulfur compounds. The removal of sulfur compounds from petroleum is of utmost importance for stringent fuel specifications and environment pollution. Functional mesoporous Mo–SiO 2 materials were synthesized by a facile procedure and were characterized by a high dispersion of molybdenum species and excellent catalytic activity for the removal of dibenzothiophene under mild conditions without organic solvents as extractants.

Description: The level set method is combined with the concentration transformation method to solve the interphase mass transfer process. However, the artificial diffusion generated in the mass transfer convection term across the interface is inevitable, especially when large shape deformation is encountered at high Reynolds numbers. A semi-Lagrangian advection scheme is introduced to overcome this disadvantage. The methyl isobutyl ketone (MIBK)-acetic acid-water system is adopted to study the unsteady mass transport process accompanied with the Marangoni effect of a single deformable drop ascending in the infinite continuous phase. The predicted overall mass transfer coefficients agree with experimental data very well. The configuration of Marangoni convection is revealed and its effect on the interphase mass transfer process is investigated. The solute-induced Marangoni effect on an ascending drop driven by buoyancy is numerically simulated based on the level set method. The semi-Lagrangian convection scheme is introduced to eliminate the artificial diffusion. Compared with literature data, the present algorithm with the semi-Lagrangian convection scheme significantly suppressed the numerical diffusion and achieved much better predictions.

Description: The surface properties of solvent-based (SB) and water-based (WB) coatings and their impact on fouling during convective heat transfer of CaSO 4 solutions were investigated. Experiments demonstrated that the SB coatings had generally better non-adhesive characteristics, especially at higher values of the electron donor component since the deposits could easily be washed away. For the SB coatings, a longer induction period compared to those of untreated surfaces was observed and a significant reduction of the fouling rate could be achieved. Further analysis of surfaces revealed that SB coatings enhanced the acid-base repulsive force and thus reduced the deposit/solid adhesion energy. For the WB coatings, the Liftshitz-van der Waals attractive force plays a decisive role in the adhesion process due to the higher apolar component of the surface energy. Recent technological advances have given impetus in altering surface properties to mitigate fouling of heat transfer surfaces. The attempted coatings in this study demonstrated that they can extend the induction period of the fouling processes of CaSO 4 deposits by four times. This was but mostly due to their higher electron donor component of the surface energy compared to stainless-steel substrate.

Description: New lead-free perovskite solid solution ceramics of (1  − x )( Bi 1/2 Na 1/2 ) TiO 3 – x Ba ( Ni 1/2 Nb 1/2 ) O 3 [(1− x )BNT– x BNN, x  =   0.02–0.06) were prepared and their dielectric, ferroelectric, piezoelectric, and electromechanical properties were investigated as a function of the BNN content. The X-ray diffraction results indicated that the addition of BNN has induced a morphotropic phase transformation from rhombohedral to pseudocubic symmetry approximately at x  =   0.045, accompanying an evolution of dielectric relaxor behavior as characterized by enhanced dielectric diffuseness and frequency dispersion. In the proximity of the ferroelectric rhombohedral and pseudocubic phase coexistence zone, the x  =   0.045 ceramics exhibited optimal piezoelectric and electromechanical coupling properties of d 33 ~121 pC/N and k p ~0.27 owing to decreased energy barriers for polarization switching. However, further addition of BNN could cause a decrease in freezing temperatures of polar nanoregions till the coexistence of nonergodic and ergodic relaxor phases occurred near room temperature, especially for the x  =   0.05 sample which has negligible negative strains and thus show the maximum electrostrain of 0.3% under an external electric field of 7 kV/mm, but almost vanished piezoelectric properties. This was attributed to the fact that the induced long-range ferroelectric order could reversibly switch back to its original ergodic state upon removal of external electric fields.

Description: Light transmission in polycrystalline magnesium fluoride was studied as a function of the mean grain size at different wavelengths. The mean grain size was varied by annealing hot-pressed billets in argon atmosphere at temperatures ranging from 600°C to 800°C for 1 h. The grain-size and grain-orientation distributions were characterized by electron back scatter diffraction. The scattering coefficients were calculated from the in-line transmittance measured at various wavelengths. The scattering coefficient of polycrystalline magnesium fluoride increased linearly with the mean grain size and inversely with the square of the wavelength of light. It is shown that these trends are consistent with theoretical models based on both a limiting form of the Raleigh–Gans–Debye (RGD) theory of particle scattering and light retardation theories that take refractive index variations along the light path. Quantitative predictions of the theories are, however, subject to uncertainly due to the restrictive assumptions made in the theories and difficulties in representing the microstructure in the theoretical models. In particular, grain-size distribution has a significant influence on the scattering coefficient calculated using particle scattering models.

Description: Determining the absolute chronology of ceramic artifacts has significant implications for archeological and historical research. Wilson, Hall et al . recently suggested a new technique for direct absolute dating of archeological ceramics based on a moisture-induced chemical reaction, called rehydroxylation (RHX) dating. RHX dating proceeds by measuring the mass of chemically combined water in the ceramics in the form of OH hydroxyls, and the mass gain rate at the Effective Lifetime Temperature (ELT) that the ceramics experienced over its lifetime. To date, ELT determinations have been based on estimates of the ceramic's lifetime temperature history; taking into account weather and climate data and the depth at which the artifact was found. The uncertainty in determining the ELT can be a major component of the overall dating uncertainty. Here, we propose an alternative method which relies minimally on weather and climate data, and provides more precise determinations of the ELT and the ceramic age . The proposed method (SAS: Same Age Samples) involves a minimum of four measurements of the RHX mass gain rate constant for two ceramic samples of the same age at two temperatures. We show via simulations that the proposed SAS method can determine the ELT with a precision of 0.2 K which is comparable to the best ELT determination based on lifetime temperature history, and also comparable to available microbalance temperature resolutions of around 0.1 K. The corresponding percent age error is then 1.4%, or 43 yr for a 3000-yr-old ceramic. The proposed SAS method should be tested with ceramic samples of different ages, whose ELT are well-known.

Description: Glasses in the Na 2 O–CaO–SrO–ZnO–SiO 2 system have previously been investigated for suitability as a reagent in Al-free glass polyalkenoate cements (GPCs). These materials have many properties that offer potential in orthopedics. However, their applicability has been limited, to date, because of their poor strength. This study was undertaken with the aim of increasing the mechanical properties of a series of these Zn-based GPC glasses by doping with nitrogen to give overall compositions of: 10Na 2 O–10CaO–20SrO–20ZnO–(40−3 x )SiO 2 – x Si 3 N 4 ( x is the no. of moles of Si 3 N 4 ). The density, glass-transition temperature, hardness, and elastic modulus of each glass were found to increase fairly linearly with nitrogen content. Indentation fracture resistance also increases with nitrogen content according to a power law relationship. These increases are consistent with the incorporation of N into the glass structure in threefold coordination with silicon resulting in extra cross-linking of the glass network. This was confirmed using 29 Si MAS-NMR which showed that an increasing number of Q 2 units and some Q 3 units with extra bridging anions are formed as nitrogen content increases at the expense of Q 1 units. A small proportion of Zn ions are found to be in tetrahedral coordination in the base oxide glass and the proportion of these increases with the presence of nitrogen.

Description: Ultrasonic hot embossing of polymers is an alternative to reduce fabrication costs of microreactors. An ultrasonic welding machine is used to melt a stack of thermoplastic foils and adapting them to a short-time milled aluminum mold showing the inversed design of the desired microfluidic cavities. Two micromixers were fabricated this way providing a low degree of axial dispersion and pressure loss. Stability analysis is successfully performed for a wide temperature range and high pressure. Mixing of colored aqueous solutions and neutralization reactions are implemented to both systems for defined volume flow rates and optically investigated via microscope. Reaction progress is automatically determined with a MATLAB script by reference to the consequential color change of the neutralization reaction with a color indicator. Typical mixing characteristics are identified for both mixers. Ultrasonic hot embossing of chemically resistant polymers as a simple and cost-effective fabrication method of microstructures and an optical analysis tool for tracing the progress of chemical reactions are introduced and evaluated. The simplicity of the fabrication method itself and good similarities of produced polymer micromixers with conventional ones made of other materials are pointed out.

Description: The existing screening and characterization systems for biocatalysts operate in batch mode, which could make catalyst selection and process development inaccurate when continuous operation mode is required in industry. A significant improvement of an innovative screening system based on miniaturized multiple membrane reactors formerly presented by the author is outlined, which enables continuous feeding of substrates and continuous removal of products. Although the presented screening system was originally designed for homogeneous enzymatic reactions, it can be used without further modifications for continuous catalysis with polymer-bound chemical catalysts or for quasi-homogeneous systems like reverse micelles. Currently available screening and characterization systems for biocatalysis are not sufficiently suitable for process description and scale-up of results to pilot- or full-scale reactors often operated in continuous mode. Hydrolysis of N -acetyl- L -methio-nine served as model reaction for an innovative continuous characterization system, implementing a precise dosing system.

Description: The synthesis of n -butyl levulinate, one of the most important biodiesel additives, by catalytic esterification of biomass-derived levulinic acid (LA) with n -butanol over modified H-ZSM-5 (micro/meso-HZ-5) in a closed-batch system is reported for the first time. The optimization of the reaction conditions such as the reactant molar ratio, the catalyst loading, the reaction time and the temperature was performed in view to maximize the yield of n -butyl levulinate. Micro/meso-HZ-5 was found to be the most efficient catalyst, with 98 % yield of n -butyl levulinate and a reusability for six cycles, which is higher than reported in the literature. A possible catalytic mechanism for the esterification reaction is also proposed. A second-order pseudo-homogeneous model with R 2  〉 0.97 confirmed that the esterification reaction is performed in the kinetic regime due to the high activation energy of 23.84 kJ mol −1 . The modified zeolite catalyst H-ZSM-5 (micro/meso-HZ-5) was used as heterogeneous acid catalyst in the esterification of renewable levulinic acid with n -butanol to produce n -butyl levulinate in a closed system. Micro/meso-HZ-5 turned out to be an efficient catalyst with 98 % yield of n -butyl levulinate and high reusability.

Description: This study presents a thermodynamic analysis to predict the type of initial, amorphous oxide overgrowth (i.e., am - Al 2 O 3 or am - SiO 2 ) on bare Al – Si alloy substrates. This analysis have taken into account the energies associated with both its interfaces (interface between the Al – Si alloy substrate and the thin oxide film and interface between the thin oxide film and vacuum) along with the bulk Gibbs free energy of oxide formation. This developed analysis is then applied for various parameters, such as, Si alloying element content at the substrate/oxide interface, the growth temperature, the oxide film thickness (up to 1 nm), and various low-index crystallographic surfaces of the substrate. It is found that am - SiO 2 overgrowth is thermodynamically preferred for a combination of lower oxide film thickness, lower growth temperature, and lower Si alloying content at the alloy/oxide interface. This is because of the overcompensation of the lower energies of both the interfaces over the bulk Gibbs free energy. Furthermore, it is found that for all cases, am - Al 2 O 3 forms a more stable interface with Al – Si alloy than am - SiO 2.

Description: Robot in Laboratory. Copyright: Max Tactic – Fotolia.com.

Description: Sintered nanoceramics of Pr -doped lanthanum hafnate, La 2 Hf 2 O 7 : Pr , were prepared by means of a high-pressure sintering technique using nanopowders made by Pechini method. Structure, morphology, and spectroscopic properties of the ceramics compared to the starting powder are presented and discussed. Emission and excitation spectra recorded at room temperature as well as at 7 K using synchrotron radiation are presented together with results of luminescence kinetics measurements. In ceramics, at 7 K, the Pr 3+ luminescence from 3 P 0 (blue-green, green, and red region) and 1 D 2 (red) levels is accompanied by a broad-band emission located in the 380–530 nm range of wavelengths, whereas powders gives only the Pr 3+ -related luminescence. Depending on the excitation wavelength, the broad-band emission maximum moves between 430 and 470 nm indicating superposition of at least two components. In sintered nanoceramics, the lifetimes of Pr 3+ emissions from 3 P 0 and 1 D 2 levels were by 10%–20% shorter compared to the powder. The existence of different luminescence centers was proved by the selective emission decays examination. The fast 5 d → 4 f luminescence of Pr 3+ was not observed from either of the two types of La 2 Hf 2 O 7 :Pr materials.

Description: We have investigated the electromechanical response of potassium sodium niobate ( K 0.5 Na 0.5 NbO 3 or KNN) thick films. The high-field strain hysteresis loops and weak-field converse piezoelectric d 33 coefficient of the films were measured and compared with those of KNN bulk ceramics under the same electric field conditions. The converse d 33 values of the thick films and bulk ceramics were equal to 82.5 and 138 pm/V, respectively, at 0.4 kV/mm. The fundamental difference between the piezoelectric response of the KNN films and the ceramics was studied in terms of the effective (“clamped”) piezoelectric d 33 coefficient. The reduction in the piezoelectric d 33 coefficient of the KNN films, resulting from the clamping by the substrate, was compared to lead-based ferroelectric thick films, including Pb ( Zr , Ti ) O 3 (PZT) and (1 −  x ) Pb ( Mg 1/3 Nb 2/3 ) O 3 − x PbTiO 3 (PMN-PT). We propose a possible explanation, based on the particular elastic properties of KNN, for the small relative difference observed between the “clamped” and “unclamped” (“bulk”) d 33 of KNN, in comparison with lead-based systems.

Description: Lead zirconate titanate (PbZr 1 −  x Ti x O 3 , PZT)/epoxy composites with one- dimensional epoxy in PZT matrix (called 3-1 type piezocomposites) have been fabricated by tert-butyl alcohol (TBA)-based directional freeze casting of PZT matrix and afterward infiltration of epoxy. The composites with PZT volume fraction ranging from 0.36 to 0.69 were obtained by adjusting initial solid loading in freeze-casting slurry. The effect of poling voltage on piezoelectric properties of the composites was studied for various volume fraction of PZT phase. With the increasing of PZT volume fraction, relative permittivity (ε r ) increased linearly and piezoelectric coefficient ( d 33 and d 31 ) increased step by step. The resultant composites with 0.57 PZT volume fraction possessed the highest hydrostatic piezoelectric strain coefficient ( d h ) value (184 pC/N), voltage coefficient ( g h ) value (13.6 × 10 −3  V/m Pa), and hydrostatic figure of merit (HFOM) value (2168 × 10 −15  Pa −1 ).

Description: Multiphase borosilicate glass-ceramics represent one candidate to contain radioactive nuclear waste separated from used nuclear fuel. In this work, the thermophysical properties from room temperature to 1273 K were investigated for four different borosilicate glass-ceramic compositions containing waste loadings from 42 to 60 wt% to determine the sensitivity of these properties to waste loading, as-fabricated microstructure, and potential evolutions in microstructure brought about by temperature transients. The thermal expansion, specific heat capacity, thermal diffusivity, and thermal conductivity are presented. The impact of increasing waste loading is shown to have a small but measurable effect on the thermophysical properties between the four compositions, contrasted to a much greater impact observed when transitioning from predominantly crystalline to amorphous systems. Thermal cycling below 1273 K was not found to measurably impact the thermophysical properties of the compositions investigated here.

Description: We report a novel oscillatory pressure-assisted hot-pressing process for preparing high-quality ceramics. Compared with the samples prepared by conventional pressureless sintering (PS) and hot-pressing (HP), the zirconia ceramic prepared by oscillatory pressure-assisted hot-pressing (OPAHP) exhibited a higher density, smaller grain size, and more homogeneous structure. More remarkably, the strength of the OPAHP sample reached 1556 MPa, which is much higher than the samples prepared by other two techniques. The results suggest that OPAHP is a more effective technique for preparing high-quality zirconia, which is likely applicable to other material systems.

Description: The formation of a homogeneous Bi 8 TiO 14 phase was successfully achieved in a specimen calcined at 600°C. However, a Bi 4 Ti 3 O 12 secondary phase also developed in specimens calcined at temperatures higher than 600°C, probably because of Bi 2 O 3 evaporation. For specimens sintered above 800°C, a small amount of the Bi 8 TiO 14 phase melted during sintering, with the liquid phase contributing to the densification of the specimens; however, Bi 4 Ti 3 O 12 and Bi 12 TiO 20 secondary phases were still formed in these specimens. The microwave dielectric properties of the Bi 8 TiO 14 phase were considerably affected by variations in the microstructure of the specimens. When the sintering temperature exceeded 825°C, the amount of secondary phases increased, and this decreased the density and Q×f values of the specimens. Bi 8 TiO 14 ceramics sintered at 825°C exhibited promising microwave dielectric properties, with ε r = 47.4, Q×f  =   5370 GHz, and τ f = −16.01 ppm/°C.

Description: A new solid solution of (1− x ) Pb ( Mg 1/2 W 1/2 ) O 3 – x Pb ( Zn 1/2 W 1/2 )O 3 has been prepared in the form of ceramics by solid-state reaction with composition x up to 30%. It is found that with the substitution of Zn 2+ for Mg 2+ on the B site of the of complex perovskite structure the antiferroelectric (AFE) Curie temperature T C of PMW increases from 40°C ( x  = 0) to 67°C ( x  = 30%), indicating an enhancement of antiferroelectric order, whereas, at the same time, the phase transition becomes more diffuse due to a higher degree of chemical inhomogeneity. X-ray diffraction analysis indicates that the crystal structure adopts an orthorhombic space group ( Pmcn ) with a decrease in lattice parameter a, but an increase in b and c as the Zn 2+ concentration increases. The low dielectric constant (~ 10 2 ), low dielectric loss (tanδ ≈ 10 −3 ), linear-field-induced polarization, and significantly high breakdown field (~ 125 kV/cm) at room temperature make this family of dielectric materials a promising candidate for ceramic insulators.

Description: Polyethersulfone (PES) was blended with poly( D,L -lactide) (PDLLA) to prepare asymmetric membranes using the phase inversion method. The effects of the blend ratios and poly(ethylene glycol) (PEG) as additive on the membrane structure, properties, and performance were investigated. The membranes were characterized by contact angle determination, scanning electron microscopy, porosity measurement, thermogravimetric analysis, degradation tests in compost, and dynamic tests for pure water flux and bakery product wastewater treatment. PES and PEG slightly reduced the membrane contact angle. Increasing the PDLLA concentration in the blend membranes enhanced the membrane degradation in compost and also the membrane porosity. The permeate flux of the membranes was improved, but the rejection of pollution indices did not change noticeably. Porous membranes have been widely applied in the fields of dialysis, clarification, and purification. The composition of membranes prepared by blending polyethersulfone with poly( D,L -lactide) (PDLLA) affected their characteristics. Increases in the concentrations of PDLLA and the additive poly(ethylene glycol) led to more porous structures, causing higher fluxes.

Description: The separation efficiency of a pilot-scale zigzag apparatus is investigated numerically using computational fluid dynamics simulations and discrete particle modeling in a coupled manner. The effects of various process variables, like particle size and air flow velocity, and of turbulence models were analyzed. The resulting changes concerning the process performance expressed by separation function and sharpness are discussed. Moreover, the residence time distribution was found to differ for fine and coarse particle discharges. Small particles are easily carried away by the fluid and respond immediately to almost every change in flow velocity. Therefore, they are affected by vortices, which increase their residence times compared to bigger particles. Zigzag air classifiers are superior to simple sieves for the separation of particles and are used in many industrial processes. The separation efficiency of a pilot-scale zigzag apparatus is studied using combined computational fluid dynamics simulations and discrete particle modeling. The process performance is discussed with respect to the chosen modeling approach and the operating conditions.

Description: In order to observe the impact of different water compositions on sludge dewaterability, assessments of floc sizes using a particle size analyzer and of sludge dewaterability based on the capillary suction time (CST) test were carried out. Synthetic raw water had small floc sizes, and synthetic domestic wastewater had both larger median floc sizes and a better correlation between sludge dewaterability and median floc sizes. The floc size distribution results showed that synthetic raw water is associated with a narrow particle size distribution. In comparison, synthetic domestic wastewater produced a wider distribution. However, the CST values were similar for both waters. Compared to synthetic wastewater, natural wastewater had the largest distribution with generally larger particle sizes. In order to observe the impact of different water compositions on sludge dewaterability, assessments of floc sizes and sludge dewaterability tests were carried out. The particle distribution results show that synthetic raw water is associated with a very narrow range of particles. In comparison, synthetic domestic wastewater produced a larger distribution. The capillary suction times were similar.

Description: The direct-ignition technology of an entrained-flow coal-water slurry gasifier with hot-oxygen burner (HOB) is presented. Experimental tests were carried out using diesel oil and coal-water slurry in a bench-scale entrained-flow opposed multi-burner (OMB) gasifier. Using a CCD camera equipped with high-temperature endoscope, flame images inside the gasifier were recorded and subsequently processed. The results show that the HOB diesel flame is more stable than the normal two-channel burner flame typically used. Entrained-flow coal-water slurry gasifiers can start up using the HOB directly without a higher preheated wall temperature. An HOB can potentially save gasifier preheating time and operation costs and enables a wide range of future applications. Entrained-flow gasification offers one of the cleanest ways to obtain energy from coal. The direct-ignition technology of an entrained-flow coal-water slurry gasifier with a new type of hot-oxygen burner (HOB) was extensively studied to prove the feasibility of the gasifier startup with this setup. The HOB permits to effectively decrease the gasifier preheating time and the system operation costs.

Description: Different approaches were analyzed to combine the tuneable micropore structure of carbide-derived carbons with a foam-like secondary porosity. The resulting structured catalyst supports were characterized in detail and applied in the model reaction of ethene hydrogenation. Preparation methods studied were dip-coating using polytetrafluoroethylene as binder on cellular metal structures, a chemical vapor deposition coating of the metal structures with thin carbide layers and subsequent conversion to carbide-derived carbon, and the partial or full conversion of carbide foams to carbon/carbide composites. For the binder method, optimal parameters for stable slurry preparation as well as for calcination of the slurry were obtained. It could further be demonstrated that the conversion of carbide foams into carbon/carbide composites leads to an appreciation between decreasing mechanical strength and increasing specific surface area. Structured catalysts are advantageous to conventional fixed-bed systems. Carbide-derived carbons with tuneable microporous structure were combined with a foamlike catalyst structure. The three preparation methods studied resulted in highly active catalysts. Optimal conditions for the easy-to-apply dip-coating method to stabilize the slurry for successful coating were determined and evaluated.

Description: An opposed multi-burner (OMB) entrained-flow gasifier with coal water slurry feeding is developed by the East China University of Science and Technology. A 3D model is employed to numerically simulate the gas flow field, motion of char particles, and distributions of temperature and gaseous components in an OMB gasifier and in a conceptual two-stage gasifier modified from the OMB gasifier (TS-OMB gasifier). Results show that the TS-OMB gasifier produces higher concentration and productivity of the effective gases (CO+H 2 ) with a slightly higher carbon conversion than the OMB gasifier. The reasons for the differences between these two types of gasifier are discussed by means of numerical simulation. This information is valuable for guiding the design of an advanced OMB gasifier. With an increasing demand for syngas, entrained-flow gasifiers for coal conversion are installed at the fastest pace due to advantages such as low pollutant emission. Simulations of the gas component distribution, amongst other key factors, in an opposed multi-burner (OMB) gasifier and modified two-stage OMB gasifier were compared. The results are valuable for future design of an advanced OMB gasifier.

Description: Direct coagulation casting of alumina suspension via controlled release of high valence counter ions (DCC–HVCI) using calcium citrate as coagulating agent was reported. Hydrolysis of glycerol diacetate shifts the pH of suspension to weakly acidic region which helps to decompose calcium citrate and release calcium ions. The effect of concentration of glycerol diacetate and calcium citrate on the pH and viscosity of alumina suspension was investigated at 25°C and 60°C, respectively. The pH of suspensions with glycerol diacetate and calcium citrate decreases to 8.6 and 7.5 treated at 25°C and 60°C, respectively. It is indicated that high viscosity is achieved by adding 2 vol% glycerol diacetate and 0.5 wt% calcium citrate which is enough to coagulate the suspension. Green body with compressive strength of 1.0 MPa is obtained by treating the alumina suspension with 2 vol% glycerol diacetate and 0.5 wt% calcium citrate at 60°C for 1 h. The alumina ceramics sintered at 1550°C have homogeneous microstructure with relative density above 99.0%.

Description: A series of lead-free perovskite solid solutions of (1 −  x ) Na 0.5 Bi 0.5 TiO 3 (NBT)— x BaSnO 3 (BSN), for 0.0 ≤  x  ≤ 0.15 have been synthesized using a high-temperature solid-state reaction route. The phase transition behaviors are studied using dielectric and Raman spectroscopic techniques. The ferroelectric to relaxor phase transition temperature ( T FR ) and the temperature corresponding to maximum dielectric permittivity ( T m ) are estimated from the temperature-dependent dielectric data. Dielectric studies show diffuse phase transition around ~335°C in pure NBT and this transition temperature decreases with increase in x . The disappearance of x -dependence of A 1 mode frequency at ~134 cm −1 for x  ≥ 0.1 is consistent with rhombohedral-orthorhombic transition. In situ temperature dependence Raman spectroscopic studies show disappearance and discontinuous changes in the phonon mode frequencies across rhombohedral ( x  〈 0.1)/orthorhombic ( x  ≥ 0.1) to tetragonal transition.

Description: Two mole percentage Er -doped ( K 0.5 Na 0.5 ) 1 −  x Li x NbO 3 ceramics have been prepared and their dielectric, ferroelectric, and photoluminescence (PL) properties have been investigated. Under an excitation of 980 nm, the ceramics exhibit intense up-conversion luminescent emission at 548 nm (green), weak emission at 660 nm (red) as well as strong down-conversion luminescent emission in near-infrared (NIR) (1.40–1.65 μm) and mid-infrared (2.60–2.85 μm) regions. Probably due to the induced structure distortion and reduced local symmetry, the PL intensities of the green, red as well as mid-infrared emissions are enhanced by the doping of Li + . Our results show that the Li-doping is effective in establishing a dynamic circulatory energy process to further enhance the PL intensity of the mid-infrared emission at the expense of the NIR emission. At the optimum doping level of Li + (~6 mol%), the full bandwidth at half maximum of the mid-infrared emission reaches a very large value of ~250 nm. The ceramics also exhibit good ferroelectric properties, and thus they should have great potential for multifunctional optoelectronic applications.

Description: We report a power conversion efficiency of ~0.01% in multistacking of BiFeO 3 /BiCrO 3 bilayer thin films used as active layers in a photovoltaic (PV) device. The films were epitaxially deposited by pulse laser deposition onto (100) oriented CaRuO 3 -coated LaAlO 3 substrates and were subsequently illuminated with 1 sun (AM 1.5). The fill factor is determined to be 0.31%, a remarkable value for ferroelectric- and multiferroic-based PV devices. Our results demonstrate that photocurrent density and photovoltage can be tuned by varying the thickness and number of respective bilayers in the improvement of PV properties of multiferroic heterostructures. The maximum photocurrent is generated at an optimal multilayer thickness of 60 nm, with its origin being mainly ascribed to the contribution of ferroelectric polarization.

Description: Temperature dependences of thermal and elastic properties, such as the Grüneisen parameters, thermal expansion, bulk modulus, and heat capacity of Ti 2 AlC and Cr 2 AlC , are studied by combining first-principles method and lattice dynamic calculation based on the quasi-harmonic model. Experimental thermal expansion coefficient is also measured for comparison. Thermal expansion coefficients of Ti 2 AlC and Cr 2 AlC show different trends: Ti 2 AlC exhibits anisotropic thermal expansion while Cr 2 AlC shows generally isotropic character. The mechanism is explored by investigating the isotropy or anisotropy of Grüneisen parameters (phonon anharmonicity and thermal pressure) and elastic stiffness (response to thermal pressure) of Ti 2 AlC and Cr 2 AlC . In addition, the calculated bulk modulus of Cr 2 AlC is higher at ambient temperature but decreases faster than the value of Ti 2 AlC as temperature increasing.

Description: The effects of process parameters on thermal barrier coating (TBC) formation and microstructural properties have been studied. Further understanding of the evolution of properties such as porosity and hardness is an important aspect in the design of efficient TBCs. Plasma-sprayed yttria-stabilized zirconia was coated onto mild steel substrates. The torch was held perpendicular to the substrate to form cone-shaped deposits. Standoff distance (SOD) (80, 90, and 120 mm) and time (15, 30, and 60 s) were altered to investigate the microstructural property relationships of the coatings. Shape characteristics of the coatings were measured via a coordinate measuring machine, and surface roughness measurements were acquired using a 3D optical profiler. The deposition efficiency and coating roughness were affected by SOD and the evolving contour of the underlying surface. Hardness and porosity profiles were mapped to display the effect of process parameters. Dynamic parameters such as particle trajectory, evolving impact angle and dwell time affected changes in porosity, hardness, and density for each coating profile.

Description: Wear resistance of ceramics can be improved by suppressing fracture, which can be accomplished either by decreasing the grain size or by reducing the size of the deformation zone. We have combined these two strategies with the goal of understanding the atomistic mechanisms underlying the plasticity-controlled friction and wear in nanocrystalline (nc) silicon carbide ( SiC ). We have performed molecular dynamics simulations of nanoscale wear on nc- SiC with 5 nm grain diameter with a nanoscale cutting tool. We find that grain-boundary (GB) sliding is the primary deformation mechanism during wear and that it is accommodated by heterogeneous nucleation of partial dislocations, formation of voids at the triple junctions, and grain pull-out. We estimate the stresses required for heterogeneous nucleation of partial dislocations at triple junctions and shear strength of GBs. Pile up in nc- SiC consists of grains that were pulled out during deformation. We compare the wear response of nc- SiC to single-crystal (sc) SiC and show that scratch hardness of nc- SiC is lower than that of sc- SiC . Our results demonstrate that the higher scratch hardness in sc- SiC originates from nucleation and motion of dislocations, whereas nc- SiC is more pliable due to additional mechanism of deformation via GB sliding.

Description: A composite geopolymeric material was synthesized from Bayer red mud combined with granulated blast-furnace slag. Thermal pretreatment was applied to improve the solubility of red mud in alkaline solution to promote geopolymerization. The dissolution efficiencies of alumina and silica reached a maximum when red mud was calcined at 800°C, resulting in the highest compressive strength of binders. It was demonstrated that a higher solubility of calcined red mud led to a higher strength of the composite binders. The characteristic microstructures of hydration products were studied to illustrate the geopolymerization process by XRD, FTIR and SEM. The results showed that aluminosilicates were dissolved in the alkaline solution to form nanostructural particulates during the early dissolution process, and then accumulated to form highly dense geopolymeric matrices through solidification reaction. The coexistence of geopolymer and C–(A)–S–H is suggested to contribute to the good performance of the composite binders.

Description: The crystals Gd 2 SiO 5 and Yb -doped Gd 2 SiO 5 were grown by Czochralski method successfully. Dielectric properties of the two crystals were investigated in the temperature range from 100 to 1100 K and the frequency range from 20 Hz to 10 MHz. Our results revealed that these crystals show intrinsic dielectric behavior in the temperature below room temperature, whereas in above room temperature, a relaxor-like dielectric anomaly and a metal–insulator transition were observed. It was found that the relaxor-like anomaly contains two dielectric relaxations. Impedance analysis showed that the low- and high-temperature relaxations are dipolar- and Maxwell–Wagner-type relaxation, respectively. The transition was found to be strongly related to oxygen vacancies, which leads to positive temperature coefficient of resistance and an abnormal dielectric behavior contrary to the conventional thermally activated behavior at temperatures near the transition temperature.

Description: Sol–gel-derived TiO 2 films were prepared by dip-coating from Ti (OC 3 H 7 i ) 4 –CH 3 COCH 2 COCH 3 –HNO 3 – H 2 O – C 2 H 5 OH solutions, and the effect of the H 2 O content in solutions on the crystallization of TiO 2 films during the heat treatment at 800°C was discussed. The crystalline phase, crystallite size, grain size, and refractive index of the TiO 2 films depended on the H 2 O / Ti (OC 3 H 7 i ) 4 mole ratios ( x ) in the coating solutions. Highly dense and crystalline rutile films were obtained at x  = 0.5–10, where the crystallites and grains became larger with increasing x . The further increase in x from 10 to 50 reduced the crystallite size and refractive index of the films, where anatase phase appeared at x  = 30–50.

Description: Dy 3+ -doped Li 8 Bi 2 ( MoO 4 ) 7 (LBM: Dy 3+ ) white-emitting phosphors have been prepared by sol-gel method at about 400~550°C low temperature. The electronic structure of Li 8 Bi 2 ( MoO 4 ) 7 is also calculated using density functional theory. The calculation results show that Li 8 Bi 2 ( MoO 4 ) 7 has a direct band gap with 2.63 eV, the top of the valence band and the bottom of the conduction band are dominated by O 2 p and Mo 4 d , respectively. The effect from Bi 3+ ions is so weak that it could be neglected, which is also be proved by the experimental results. The crystal structure and luminescent properties of the obtained phosphors are characterized by powder X-ray diffraction and photoluminescence spectrum, respectively. Photoluminescence results showed that the obtained phosphors can be excited efficiently by near-UV 387 nm and generated white light emission. The yellow/blue ratio and Commission International de I'Eclairage color coordinates could be tuned by adjusting the concentration of Dy 3+ . Results demonstrated that Li 8 Bi 2 ( MoO 4 ) 7 : Dy 3+ was a potential white light-emitting phosphor candidate for NUV-based w-LEDs.

Description: In this paper, the phase compositions and the dielectric properties of 3 ZnO –2 B 2 O 3 glass-ceramic prepared by solid-state method were investigated. The X-ray diffraction patterns show that all sintered samples consist of Zn 3 B 2 O 6 and α- Zn (BO 2 ) 2 . The dielectric properties changed significantly with the sintering temperature. After sintering at 650°C for 30 min, the glass-ceramic exhibits optimum dielectric properties: a dielectric constant of 7.5 and a dielectric loss of 0.6 × 10 −3 at 10 MHz. The chemical compatibility with Ag electrode under the co-fired process illustrates a potential application in low temperature co-fired ceramic field for the glass-ceramic.

Description: A novel technique was utilized to fabricate fine-scaled piezoelectric ceramic/polymer 2-2 composites for high-frequency ultrasonic transducers. Lead zirconate titanate (PZT) was used as raw material. Tape-casted acetylene black tapes were used to define kerfs after sintering. A one-directional supporter was utilized to avoid distortion of PZT elements. PZT elements with 20 ± 2 μm width exhibited good consistency in longitudinal direction. A resonant method was utilized to evaluate the piezoelectric and dielectric properties of the composites. A 72-μm-thick composite with an aspect ratio of ~3.6 exhibited a k t of 0.61 with satisfied piezoelectric and dielectric properties. A prototype high-frequency ultrasonic transducer was fabricated and evaluated by an underwater pulse-echo test. The center frequency was found to be 23.75 MHz, with −6 dB bandwidth of 5.5 MHz.

Description: The 0.45 Bi ( Mg 0.5 Ti 0.5 ) O 3 –(0.55 −  x ) PbTiO 3 – x ( Bi 0.5 Na 0.5 ) TiO 3 (BMT–PT– x BNT) ternary solid solution ceramics were prepared via a conventional solid-state reaction method; the evolution of dielectric relaxor behavior and the electrostrain features were investigated. The XRD and dielectric measurements showed that all studied compositions own a single pseudocubic perovskite structure and undergo a diffuse-to-relaxor phase transition owing to the evolution of the domain from a frozen state to a dynamic state. The formation of the above dielectric relaxor behavior was further confirmed by a couple of measurements such as polarization loops, polarization current density curves, as well as bipolar strain loops. A large strain value of ~0.41% at a driving field of 7 kV/mm (normalized strain d 33 * of ~590 pm/V) was obtained at room temperature for the composition with x  = 0.32, which is located near the boundary between ergodic and nonergodic relaxor. Moreover, this electric field-induced large strain was found to own a frequency-insensitive characteristic.

Description: Factory. Copyright: Dmitry Lavrenyuk – Fotolia.com .

Description: AgNbO 3 is a weak ferroelectric with antiferroelectricity due to Ag displacements at room temperature. A dielectric anomaly at 250 K, which has not been observed previously, reveals a transition between the weak ferroelectric phase (M1 phase) at the higher temperature and a new ferroelectric phase (M0 phase) at the lower temperature in AgNbO 3 . This transition was further verified by the pyroelectric current and differential scanning calorimetry measurements. The spontaneous polarization value is found to be much larger in the M0 phase than that of the M1 phase. A well-defined saturating ferroelectric hysteresis loop can also be observed at 77 K, showing a remnant polarization value of 2.4 μC/cm 2 and a coercive field of 25 kV/cm. All the above results indicate that the larger polarization of the M0 phase mainly comes from the alignment of the antiferroelectric displacements of the Ag atoms.

Description: Steel pipe line. Copyright: supakitmod – Fotolia.com.

Description: Light olefin and paraffin are commonly separated by energy-intensive cryogenic distillation. Membrane/distillation hybrid systems constitute an economical alternative separation process. Different configurations of this hybrid system are studied for olefin-paraffin separation with emphasis on C 3 separation. An approach based on the McCabe-Thiele method is applied to analyze different process configurations. A facilitated transport membrane is considered as membrane type. Both new column design and augmentation of an existing distillation column by a membrane module are considered. Numerical examples are considered for the separation of propane from propylene through different hybridization shapes with facilitated transport membranes. The energy requirement can be halved using hybrid systems. Membrane/distillation hybrid systems represent an economical alternative separation process compared to the commonly applied energy-intensive cryogenic distillation for separation of light olefin and paraffin. Different process configurations of such a hybrid system are evaluated. Under optimum conditions the energy requirement could be halved.

Description: The oxidation kinetics of ZrB 2 -30 vol% SiC were analyzed statistically with the goal of understanding the underlying mechanisms for observed variability. A box furnace was used to oxidize specimens for times between 30 s and 100 h at temperatures of 1300°C–1550°C in air. The specimens were characterized to determine weight change, scale thickness, and scale composition to quantify the oxidation behavior. Weight gain measurements of different specimens after 100 min of exposure showed differences of up to 2 mg/cm 2 for the same testing conditions where the average weight gain was 2.54 mg/cm 2 . Variation of 30%–80% was observed in the average thickness of each layer of the oxide within a single specimen. Viscous glass flow was ruled out as a potential mechanism. Glass bubble formation was proposed as the main cause for oxidation kinetics variability.

Description: Phase equilibria in the La 1− x Ca x FeO 3−δ (LCF) system were assessed at temperatures below 1350°C in both simulated air and argon atmospheres using a combination of differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and high-temperature X-ray diffraction. The solubility limit of Ca in the perovskite structure was determined to be 38% A-site substitution. A high-temperature orthorhombic to rhombohedral transition was identified and the dependence on oxygen partial pressure and effect on thermal expansion were characterized. A partial, pseudobinary LaFeO 3 –CaFeO 2.5 phase diagram is presented that is based on these analyses combined with data available in the open literature.

Description: TiB 2 powders were synthesized by borothermal reduction in nanoscale TiO 2 with boron under vacuum. Reaction processes were investigated, and the effect of by-product B 2 O 3 was evaluated. Results showed that TiO 2 was firstly reduced by boron to form TiBO 3 and Ti 2 O 3 , and then to produce TiB 2 and B 2 O 3 with increasing temperature. The reaction processes of TiB 2 powders synthesis included two-step reduction in TiO 2 by boron and the removal of B 2 O 3 . The presence of B 2 O 3 , which was previously reported as the most important factor in promoting the coarsening of ZrB 2 and HfB 2 powders by borothermal reduction, did not lead to significant coarsening of TiB 2 powders. Due to the minor effect of B 2 O 3 , TiB 2 powders with small particle size and low oxygen content could be prepared by direct heat treatment of TiO 2 and boron at 1550°C under vacuum for 1 h. The particle size and oxygen content of synthesized TiB 2 powders were ~0.9 μm and ~1.7 wt%, respectively.

Description: In this work, a low-firing microwave dielectric ceramic PbMoO 4 with tetragonal structure was prepared via a solid-state reaction method. The sintering temperature ranges from 570°C to 670°C. Ceramic samples with relative densities above 97% were obtained when sintering temperature was around 600°C. The best microwave dielectric properties were obtained in the ceramic sintered at 650°C for 2 h with a permittivity ~26.7, a Q  ×  f value about 42 830 GHz (at 6.2 GHz) and a temperature coefficient value of 6.2 ppm/°C. From the X-ray diffraction, backscattered electron imaging results of the cofired sample with 30 wt% silver and aluminum additive, the PbMoO 4 ceramic was found not to react with Ag and Al at 630°C. The microwave dielectric properties and low sintering temperature of PbMoO 4 ceramic make it a candidate for low-temperature cofired ceramic applications.

Description: Commercial EIA-Y5V base-metal-electrode multilayer ceramic capacitors (BME-MLCCs) made of ( CaO + ZrO 2 )-doped BaTiO 3 are analyzed for the microstructure and investigated for its relation to dielectric properties. The characteristic diffuse scattering (DS) intensities observed in BaTiO 3 ceramics and the featureless “solid-solution” grains in Y5V capacitor chips are originated from multiple Ti sites in the dynamic BaTiO 3 structure. The pseudo-cubic ( PC )-grains retaining the overall cubic ( C -) symmetry metastably at room temperature are embedded with polar nanoregions (PNRs) in the ferroelectric (FE) tetragonal ( T -), and rhombohedral ( R -) phases, as revealed by high-resolution transmission electron microscopy (HRTEM). The presence of PNRs contributes effectively to large relative permittivity ε r  ≈ 13 200 at 25°C. The FE T -domains grow from within PC -grains at the expense of embedded PNRs after prolonged annealing by extending “oxidizing firing” at 950°C in p O 2  = 10 −7  atm. These domains contain less Zr with otherwise homogeneously distributed solutes in PNR-dispersed PC -grains. Although preserving the relaxors characteristics, ε r is reduced to ~11 000 after 12 h, and then to ~9000 after 24 h annealing. The reduction in ε r is attributed to the annealing-induced FE T -domains grown at the expense of PNRs in PC -grains. The Vögel–Fulcher analysis indicates that Y5V ceramics are in the relaxor FE category, containing PNRs derived from polarization frustration.

Description: The progresses of the relative density, average grain size (GS), and maximum pore size entering into the final sintering stage are investigated in 3 mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) compacts in the range of 87%~99% theoretical density. It is found that during conventional pressureless sintering, the pores in the compact enlarged dramatically, which appears to be the major obstacle for preparing fully dense nanoceramics. Transparent 3Y-TZP nanoceramics with an average GS of 87 nm were prepared by exploiting microstructural refinement on nanoscale. The yields a maximal optical transmittance of 67% and shows no noticeable low-temperature degradation after 100 h aging at 134°C under a hydrothermal pressure of two bars.

Description: Porous β- Si 3 N 4 ceramics are sintered at 1600°C in N 2 and postheat treated at 1500°C under vacuum using Li 2 O and Y 2 O 3 as the sintering additives. The partial sintering and phase transformation are promoted at low temperature by the addition of Li 2 O . The addition of Y 2 O 3 is advantageous for the formation of high aspect ratio β- Si 3 N 4 grains. After postheat treatment, a large amount of intergranular glassy phase is removed, and the Li content in the samples is decreased. By this method, the β- Si 3 N 4 porous ceramic with a porosity of 54.1% and high flexural strength of 110 ± 8.1 MPa can be prepared with a small amount of sintering additives, 0.66 wt% Li 2 O and 0.33 wt% Y 2 O 3 , and it is suitable for high-temperature applications.

Description: To solve the heavy mass problem of the traditional spinel ferrite using as the microwave absorber, the Co x Zn (1− x ) Fe 2 O 4 ( x  =   0.2, 0.4, 0.6, 0.8) ferrite nanofibres were synthesized by electrospinning method. The phase composition, morphology, and electromagnetic properties were analyzed. The results showed that all the as-prepared Co x Zn (1− x ) Fe 2 O 4 ferrites exhibited the homogeneous nanofibrous shape. The saturation magnetization and coercivity were enhanced by tuning the Co 2+ content. The electromagnetic loss analysis indicated that the Co 0.6 Zn 0.4 Fe 2 O 4 ferrite nanofiber performed the strongest microwave attenuation ability. The microwave absorbing coating containing 15 wt% of Co 0.6 Zn 0.4 Fe 2 O 4 ferrite nanofiber showed the reflection loss less than −10 dB in the whole X -band and 80% of the Ku -band frequencies. Meanwhile, the surface density was only 2.4 Kg/m 2 .

Description: The kinetics of the cristobalite transformation are reported for sintered silica glass from 1200°C to 1650°C and plotted as a time–temperature–transformation diagram. The 1200°C–1350°C transformation data were fit to the Johnson–Mehl–Avrami–Kolmogorov expression with an time exponent of 3.0 ± 0.6 and an apparent activation energy of 555 ± 24 kJ/mol for the kinetic constant. The temperature of maximum transformation rate was found to fall between 1500°C and 1600°C. Seeding amorphous silica powder with cristobalite resulted in accelerated transformation kinetics. Silica glass powder containing residual quartz had faster transformation kinetics than fully amorphous powder seeded with cristobalite.

Description: The morphology and crystal growth of devitrite crystals nucleated heterogeneously on glass surfaces have been studied. The crystals grow as fans of needles, with each needle having a characteristic [100] growth direction with respect to the centrosymmetric triclinic unit cell. An analysis of crystal growth data reported here and a reappraisal of crystal growth data reported in prior studies suggests a best estimate of 260 kJ/mol for the activation enthalpy for the crystal growth of devitrite along [100], higher than the values previously reported.

Description: Single crystal (1  − x ) Pb ( Mg 1 / 3 Nb 2 / 3 ) O 3 – x PbTiO 3 [ PMN – x PT] ( x  = 0.32) is a relaxor-ferroelectric material known to exhibit ‘giant’ piezoelectric behavior, with achievable strains in excess of 1% for samples of certain particular crystallographic orientations and chemical compositions close to the morphotropic phase boundary. In this study, we investigate the electric field-induced structural phase transitions in single crystal PMN –0.32 PT with time-of-flight neutron diffraction and macroscopic electrical polarization measurements, and show that both the frequency of the applied ac field and the temperature of the sample are critical factors in determining these phase transition fields.

Description: Glass nanocomposites, fabricated using borosilicate glass microspheres and antimony tin oxide (ATO) nanoparticles, were previously reported to have formed segregated networks at the boundaries of the glass particles. This resulted in an electrically conducting composite at low volume fractions (~0.5–0.8 vol%) of ATO nanoparticles. The wide range of electrical response in these borosilicate glass composites containing networks of varying concentration of ATO was examined using impedance spectroscopy. The electrical resistance of these composites varied over a range of around 12 orders of magnitude and exhibited several different types of insulator and conductor behavior. The formation of the ATO network was identified and tracked by scanning electron microscopy images and energy dispersive X-ray spectroscopy (EDS) scans. Detailed impedance spectroscopy analysis using all of the dielectric functions (impedance, permittivity, electric modulus, and admittance) was found to be an excellent method for detecting the development of the network and the effect that processing variables can have on its formation and the overall electrical properties of the nanocomposites.

Description: By combining the concept of defect chemistry and the small-polaron hopping conduction model, the present work takes an intensively considering of the electron conduction mechanism in the nonstoichiometric SnO 2 nanocrystalline film. The temperature-dependent and atmosphere-dependent relationship between the electrical conductivity and the defect reaction is outlined. To investigate the influence of temperature and atmosphere on the electrical properties of the SnO 2 nanocrystalline film, a temperature-programmed system integrated with the high-throughput screening platform of gas-sensing materials (HTSP-GM) is developed as the test tool in this work. With this platform, the temperature-dependent conductivity of SnO 2 nanocrystalline film in different atmosphere (dry air, nitrogen, and formaldehyde) was conducted. A good fit between the theoretical deductions and experimental results is achieved.

Description: We demonstrate a facile synthesis of monodisperse magnetite ( Fe 3 O 4 ) nanoparticles (NPs) via a simple wet chemical route at 180°C using oleylamine ( C 18 H 37 N ), which serves as a solvent, ligand, and surfactant. The particles have a narrow size distribution centered at about 10 nm. To provide better electron conductivity and structural stability, the as-synthesized particles are given a carbon nanocoating by pyrolysis of the residual surfactant on their surface. This pyrolysis forms a uniform thin nanocoating on each particle, and a core/shell Fe 3 O 4 /carbon NP network was thus obtained. The core/shell Fe 3 O 4 /carbon electrode shows better reversible capacity, cycle life, and rate capability than a bare Fe 3 O 4 NP electrode because of its efficient electron transport and stress relaxation provided by the thin carbon layer.

Description: Nickel ferrite (NiFe 2 O 4 ) is a major constituent of the corrosion deposits formed on the exterior of nuclear fuel cladding tubes during operation. NiFe 2 O 4 has attracted much recent interest, mainly due to the impact of these deposits, known as CRUD, on the operation of commercial nuclear reactors. Although advances have been made in modeling CRUD nucleation and growth under a wide range of conditions, the thermophysical properties of NiFe 2 O 4 at high temperatures have only been approximated, thereby limiting the accuracy of such models. In this study, samples of NiFe 2 O 4 were synthesized to provide the thermal diffusivity, specific heat capacity, and thermal expansion data from room temperature to 1300 K. These results were then used to determine thermal conductivity. Numerical fits are provided to facilitate ongoing modeling efforts. The Curie temperature determined through these measurements was in slight disagreement with literature values. Transmission electron microscopy investigation of multiple NiFe 2 O 4 samples revealed that minor nonstoichiometry was likely responsible for variations in the Curie temperature. However, these small changes in composition did not impact the thermal conductivity of NiFe 2 O 4 , and thus are not expected to play a large role in governing reactor performance.

Description: Boron carbide thin films have been synthesized via pulsed laser deposition process using Spark Plasma Sintered (SPSed) and dual-targets, respectively. Two kinds of structural evolutions have been found by investigation of bonding environments in as-deposited thin films via X-ray photoelectron spectroscopy study. With decreasing of B/C ratio, films deposited from SPSed-target show the transformation of B 11 C -CBB → B 11 C -CBC. In contrast, the films deposited from dual-target present the B 11 C -CBB → B 10 C 2 -CBB structural change.

Description: The SrTiO 3 (STO) thin films were directly grown on Si (111) substrates without buffer layer by an electron-cyclotron-resonance ion beam sputter deposition. The growth temperature was varied from 700°C to 850°C, while other parameters were kept unchanged. X-ray structural analysis demonstrates that the growth temperature has a strong influence in tuning degree of (100) orientation. The STO film grown at 800°C is found to be the highest degree of (100) orientation (98%) and a strong (100) fiber texture. For the surface morphology, the development of plate-shaped grains reveals a good correlation with the change in the degree of (100) orientation. Moreover, the leakage current–voltage characteristics of the Au /STO/ Si (111) metal-insulator-semiconductor capacitors are investigated and discussed in considerable detail.

Description: The effect of combined substitution of Sm 3+ and O 2− with Ca 2+ and F − , respectively, on the structural and superconducting properties of SmFeAsO system is investigated. It is observed that the binary doping using CaF 2 causes considerable structural as well as microstructural changes wherein the preferred orientation of (00  l ) planes and enhancement of grain size are quite interesting. Moreover, a maximum T C of 53.8 K and a transport J C of 880 A/cm 2 (12 K) are achieved in the codoped samples. The achievement of preferred orientation, enhanced T C , and the subsequent increase in J C of the modified SmFeAsO system are particularly significant for high current conductor development.

Description: Lead free piezoelectric ceramics of Y 3+ -doped Ba 1− x Ca x Zr 0.07 Ti 0.93 O 3 with x  = 0.05, 0.10, and 0.15 were prepared. Composition and temperature-dependent structural phase evolution and electrical properties of as-prepared ceramics were studied systematically by X-ray diffraction, Raman spectroscopy, impedance analyzer, ferroelectric test system, and unipolar strain measurement. Composition with x  = 0.10 performs a good piezoelectric constant d 33 of 363 pC/N, coercive field E c of 257 V/mm, remanent polarization P r of 14.5 μC/cm 2 , and a Curie temperature T m of 109°C. High-resolution X-ray diffraction was introduced to indicate presence of orthorhombic phase. Converse piezoelectric constant d 33 * of x  = 0.10 composition performed better temperature stability in the range from 50°C to 110°C. That means decreasing orthorhombic–tetragonal phase transition temperature could be an effective way to enlarge its operating temperature range.

Description: TiO 2 -doped Y 2 O 3 -stabilized ZrO 2 compounds with low thermal conductivity have been considered as a promising thermal barrier coating material. In the present research, a series of TiO 2 -doped Y 2 O 3 -stabilized ZrO 2 compounds have been synthesized and investigated. Lattice distortion and disordering caused by TiO 2 doping were observed and their effects on mechanical properties, such as fracture toughness, elastic modulus, and coefficient of thermal expansion (CTE), were also investigated. Lattice distortion enhanced the ferroelastic toughening and the fracture toughness, whereas the variation in elastic modulus and CTE is due to the lattice disordering. The combination of thermal and mechanical properties bodes well for the potential application as thermal barrier coating materials.

Description: The influence of second phase zirconia particles on the electrical properties and fracture behavior of various polycrystalline soft Pb ( Zr 1− x Ti x ) O 3 (PZT) compositions was investigated. PZT composites with yttria-stabilized tetragonal zirconia particles exhibited enhanced crack resistance in comparison to monolithic compositions, regardless of the PZT composition. The addition of zirconia, however, was found to change the PZT composition through the diffusion of zirconium, resulting in variations in the observed piezoelectric and ferroelectric responses. Through the tailoring of the PZT matrix composition, the large electromechanical response and enhanced fracture toughness could be retained. The variation in both small and large signal properties is contrasted to fracture results and crystal structure changes, as determined by X-ray diffraction.

Description: A novel method is employed for the formation of rare earth phosphate solid solution compounds with unique mesoscopic structures. Europium- and lanthanum-doped sodium borate glass microspheres and particles, ranging in sizes from 50 to 300 μm, were reacted in 0.25 M K 2 HPO 4 solution to form hollow spheres of nanocrystalline rare earth phosphate compounds by dissolution–precipitation reactions. The initially X-ray amorphous precipitated rare earth phosphate materials were heat-treated at 700°C for 2 h to form nanocrystalline compounds. Differential thermal analysis (DTA) experiments yield an average activation energy for crystallization of 394 ± 26 kJ/mol. X-ray diffraction (XRD) data indicate that samples crystallized to the monazite structure (monoclinic P2 1 /n) with unit cell volumes ranging from 306.5 Å 3 for LaPO 4 to 282.5 Å 3 for EuPO 4 and with crystallite grain sizes of 56 ± 14 nm. Compositions containing both rare earth elements formed solid solutions with the composition La (1− x ) Eu x PO 4 . Raman spectroscopy indicates that the P–O symmetric stretching vibrations (ν 1 ) change systematically from 963 cm −1 for LaPO 4 to 986 cm −1 for EuPO 4 , consistent with a systematic decrease in average P–O bond length. Photoluminescence measurements show maximum emission intensity for the La 0.65 Eu 0.35 PO 4 composition.

Description: A single crystal of α- Ca 2 [ HSiO 4 ](OH) (α- C 2 SH) was repeatedly imaged at room temperature with synchrotron mid-infrared microscopy after heating to 310°C, 340°C, 370°C, and 400°C respectively. The mechanisms of the observed phase transformations are discussed on the basis of a modular concept of the crystal structures. All images show domains of dellaite, Ca 6 [ Si 2 O 7 ][ SiO 4 ](OH) 2 , which are predominantly formed in the core of the crystal. In the crystal rim area α- C 2 SH persists in higher abundance. The mechanism of the phase transformation of α- C 2 SH into dellaite includes the following: (1) Partial formation of killalaite ( Ca 3 [ HSi 2 O 7 ](OH)) as nuclei according to the isochemical reaction 2 Ca 2 [ HSiO 4 ](OH) → Ca 3 [ HSi 2 O 7 ](OH) +  Ca (OH) 2 probably induced by anisotropic thermal expansion, local chemical fluctuations, structural (proton) disorder, and different bond strengths of the OH groups in the α- C 2 SH structure. (2) Further dehydration of killalaite and α- C 2 SH domains results in the formation of dellaite according to Ca 3 [ HSi 2 O 7 ](OH) + Ca(OH) 2  + Ca 2 [ HSiO 4 ](OH) – 2 H 2 O → Ca 6 [ Si 2 O 7 ][ SiO 4 ](OH) 2 . The results suggest that the polymerization of two isolated [ HSiO 4 ] tetrahedra takes place without dehydration according to reaction (1) rather than through condensation with simultaneous H 2 O release: 2[ HSiO 4 ] → [ Si 2 O 7 ] +  H 2 O . We suggest that reaction (1) cannot be completed at ambient pressure. Thus in the regions close to the rim of the crystals we expect the formation of x - C 2 S , which starts along the crystal edges according to Ca 2 [ HSiO 4 ](OH) → Ca 2 SiO 4  +  H 2 O . Based on a modular concept, a structural relationship between α- C 2 SH, killalaite, dellaite, and x - C 2 S has been established. Similarities and differences in the thermal behavior of α- C 2 SH and afwillite have been highlighted.

Description: The oxygen permeability of polycrystalline α-alumina wafers, which served as models for alumina scales on alumina-forming alloys, under steep oxygen potential gradients ( ) was evaluated at 1873 K. Oxygen permeation occurred by the grain-boundary (GB) diffusion of oxygen from the higher-oxygen-partial-pressure ( ) surface to the lower- surface, along with the simultaneous GB diffusion of aluminum in the opposite direction. The fluxes of oxygen and aluminum at the outflow side of the wafer were significantly larger than at the inflow side. Furthermore, Lu and Hf segregation at the GBs selectively reduced the mobility of oxygen and aluminum, respectively. A wafer with a bilayer structure, in which a Lu-doped layer was exposed to a lower and an Hf-doped layer was exposed to a higher , decreased the oxygen permeability. When the sign of was reversed, however, the oxygen permeability of the wafer was comparable to that of a nondoped wafer. Co-doping with both Lu and Hf markedly increased the oxygen permeation, presumably because the Lu-stabilized HfO 2 particles that were segregated at the GBs acted as extremely fast diffusion paths for oxygen through the large number of oxygen vacancies introduced by the solid solution of Lu in the particles.

Description: Scandium fluoride ( ScF 3 ) belongs to one of the rare compounds which exhibit isotropic negative thermal expansion. Here, a facile and environmentally friendly hydrothermal synthesis method has been presented. High-quality single-crystalline ScF 3 cubes, with an average size of 200 nm, can be easily fabricated in a large scale. Sc (NO 3 ) 3 and NH 4 HF 2 were used as precursors. The as-prepared ScF 3 demonstrates cubic symmetry ( Pm -3  m ), which was confirmed by X-ray diffraction and selected-area electron diffraction. Its uniform morphology and size were characterized by high-resolution transmission electron microscopy. Furthermore, thermal analysis was also performed in argon gas atmosphere to investigate its thermal stability.

Description: Results of the spectroscopic characteristics and upconversion luminescence in Er 3+ doped yttria ( Y 2 O 3 ) transparent ceramics prepared by a modified two-step sintering method are presented. The near-infrared (1.5 μm) luminescence properties were evaluated as a function of Er 3+ concentration. Judd–Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were determined and compared with results reported for Er 3+ -doped Y 2 O 3 single crystal and nanocrystals. Following pumping at 1.532 μm, weak blue (~0.41 μm, 2 H 9/2 → 4 I 15/2 ), strong green (~0.56 μm, 2 H 11/2 , 4 S 3/2 → 4 I 15/2 ), and red (~0.67 μm, 4 F 9/2 → 4 I 15/2 ) emission bands were observed as well as weak near-infrared emissions at 0.8 μm ( 4 I 9/2 → 4 I 15/2 ) and 0.85 μm ( 4 S 3/2 → 4 I 13/2 ) at room temperature. The upconversion luminescence properties under ~1.5 μm pumping were further investigated through pump power dependence and decay time studies. Sequential two-photon absorption leads to the 4 I 9/2 upconversion emission, whereas energy-transfer upconversion is responsible for the emission from the higher excited states 2 H 9/2 , 2 H 11/2 , 4 S 3/2 , and 4 F 9/2 . The enhanced red emission with increasing Er 3+ concentration most likely occurred via the cross-relaxation process between ( 4 F 7/2 → 4 F 9/2 ) and ( 4 I 11/2 → 4 F 9/2 ) transitions, which increased the population of the 4 F 9/2 level.

Description: Zirconia phase transformation is usually studied on surface. For in-depth study, three methods were proposed using Raman microspectroscopy quantitative evaluation: direct measurement on sample cross section, confocal Raman spectroscopy (CRS), and progressive pinhole aperture enlargement (PPAE). The aim of this study was to compare transformation profiles obtained with these three methods on the same sample. Three 3Y-TZP samples were aged, respectively, for 25, 72, and 90 h in artificial saliva. Transformation profiles were determined with cross-sectional measurement, CRS and PPAE. A transformation profile simulation model based on PPAE measurements is proposed, using the convolution of the excitation intensity profile and the Beer–Lambert law (optical properties of zirconia). The simulation model was validated with the determination of 3Y-TZP transformation factor, T  = 1.15 μm −1 , identical for the three aging durations. Both cross section and PPAE measured similar in-depth transformation decrease, but with a 10 μm-shift: transformed zirconia layer is more important in cross-sectional protocol (36 μm with PPAE and 46 μm with cross-sectional after 90 h aging). Complementary measurements on a 10 h aged sample, where transformation is initiated by Low-Temperature Degradation, showed that sample preparation and polishing, necessary in the cross-sectional method, were responsible for the higher transformation. PPAE method enables noninvasive in-depth measurements with limited optical and mechanical biases.

Description: New cementitious materials based on calcium hydrosilicate hydrates were recently developed as potential substitutes for ordinary portland cement, but with a reduced CO 2 footprint. The materials are produced by hydrothermal processing of SiO 2 and Ca ( OH ) 2 , giving rise to calcium silicate hydrates, followed by mechanical activation of the latter via cogrinding with various siliceous materials. Thus, the chemical composition in terms of C/S ratio could be adjusted over a broad range (1–3). In this study the synthesis of a previously unknown cementitious material produced via the combination of mechanical activation in a laboratory mill and thermal treatment of a mixture of quartz and hydrothermally synthesized calcium silicate hydrates: α- Ca 2 [ HSiO 4 ]( OH ) (α- C 2 SH ) and Ca 6 [ Si 2 O 7 ]( OH ) 6 (jaffeite) are reported. It forms independently of the type of mill used (eccentric vibrating mill, vibration grinding mill) after thermal treatment of the ground materials at 360°C–420°C. The new material is X-ray amorphous and possesses a CaO / SiO 2 ratio of 2. A characteristic feature in regards to the silicate anionic structure is the increased silicate polymerization (up to 27% Si 2 O 7 dimers) as revealed by the trimethylsilylation method. Infrared (IR) spectra show a very broad absorption band centered at about 935 cm −1 . Another characteristic feature is the presence of ~2.5 wt% H 2 O as shown by thermogravimetry (TG) coupled with IR spectroscopy. As this water is bound mostly as hydroxyl to Ca, we refer to this new cementitious material as calcium-oxide–hydroxide–silicate ( C – CH – S ). Calorimetric measurements point to a very high hydraulic reactivity which is beyond that for typical C 2 S materials. The influence of the type of grinding on the thermal behavior of α- C 2 SH upon its transformation into water-free Ca 2 SiO 4 modifications is discussed.