Effect of boiling on deposition of metallic colloids

In this study the relationship between heterogeneous nucleate boiling surfaces and deposition of suspended metallic colloidal particles, popularly known as crud or corrosion products in process industries, on those heterogeneous sites is investigated. Various researchers have reported that hematite is a major constituent of crud which makes it the primary material of interest; however the models developed in this work are irrespective of material choice. Qualitative hypotheses on the deposition process under boiling as proposed by previous researchers have been tested, which fail to provide explanations for several physical mechanisms observed and analyzed. In this study a quantitative model of deposition rate has been developed on the basis of bubble dynamics and colloid-surface interaction potential. Boiling from a heating surface aids in aggregation of the metallic particulates viz. nano-particles, crud particulate, etc. suspended in a liquid, which helps in transporting them to heating surfaces. Consequently, clusters of particles deposit onto the heating surfaces due to various interactive forces, resulting in formation of porous or impervious layers. The deposit layer grows or recedes depending upon variations in interparticle and surface forces, fluid shear, fluid chemistry, etc. This deposit layer in turn affects the rate of bubble generation, formation of porous chimneys, critical heat flux (CHF) of surfaces, activation and deactivation of nucleation sites on the heating surfaces. Several problems are posed due to the effect of boiling on colloidal deposition, which range from research initiatives involving nano-fluids as a heat transfer medium to industrial applications such as light water nuclear reactors. In this study, it is attempted to integrate colloid and surface science with vapor bubble dynamics, boiling heat transfer and evaporation rate. Pool boiling experiments with dilute metallic colloids have been conducted to investigate several parameters impacting the system. The experimental data available in the literature is obtained by flow experiments, which do not help in correlating boiling mechanism with the deposition amount or structure. With the help of experimental evidences and analysis, previously proposed hypothesis for particle transport to the contact line due to hydrophobicity has been challenged. The experimental observations suggest that deposition occurs around the bubble surface contact line and extends underneath area of the bubble microlayer as well. During the evaporation the concentration gradient of a non-volatile species is created, which induces osmotic pressure. The osmotic pressure developed inside the microlayer draws more particles inside the microlayer region or towards contact line. The colloidal escape time is slower than the evaporation time, which leads to the aggregation of particles in the evaporating micro-layer. These aggregated particles deposit onto or are removed from the heating surface, depending upon their total interaction potential. Interaction potential has been computed with the help of surface charge and van der Waals potential for the materials in aqueous solutions. Based upon the interaction-force boundary layer thickness, which is governed by debye radius (or ionic concentration and pH), a simplified quantitative model for the attachment kinetics is proposed. This attachment kinetics model gives reasonable results in predicting attachment rate against data reported by previous researchers. The attachment kinetics study has been done for different pH levels and particle sizes for hematite particles. Quantification of colloidal transport under boiling scenarios is done with the help of overall average evaporation rates because generally waiting times for bubbles at the same position is much larger than growth times. In other words, from a larger measurable scale perspective, frequency of bubbles dictates the rate of collection of particles rather than evaporation rate during micro-layer evaporation of one bubble. The combination of attachment kinetics and colloidal transport kinetics has been used to make a consolidated model for prediction of the amount of deposition and is validated with the help of high fidelity experimental data. In an attempt to understand and explain boiling characteristics, high speed visualization of bubble dynamics from a single artificial large cavity and multiple naturally occurring cavities is conducted. A bubble growth and departure dynamics model is developed for artificial active sites and is validated with the experimental data. The variation of bubble departure diameter with wall temperature is analyzed with experimental results and shows coherence with earlier studies. However, deposit traces after boiling experiments show that bubble contact diameter is essential to predict bubble departure dynamics, which has been ignored previously by various researchers. The relationship between porosity of colloid deposits and bubbles under the influence of Jakob number, sub-cooling and particle size has been developed. This also can be further utilized in variational wettability of the surface. Designing porous surfaces can having vast range of applications varying from high wettability, such as high critical heat flux boilers, to low wettability, such as efficient condensers.

Contactless Spectral-Dependent Measurement of Bulk Lifetime and Surface Recombination Velocity in Silicon Photovoltaic Materials

Charge carrier lifetime measurements in bulk or unfinished photovoltaic (PV) materials allow for a more accurate estimate of power conversion efficiency in completed solar cells. In this work, carrier lifetimes in PV- grade silicon wafers are obtained by way of quasi-steady state photoconductance measurements. These measurements use a contactless RF system coupled with varying narrow spectrum input LEDs, ranging in wavelength from 460 nm to 1030 nm. Spectral dependent lifetime measurements allow for determination of bulk and surface properties of the material, including the intrinsic bulk lifetime and the surface recombination velocity. The effective lifetimes are fit to an analytical physics-based model to determine the desired parameters. Passivated and non-passivated samples are both studied and are shown to have good agreement with the theoretical model.

DopSCAT: A mission concept for simultaneous measurements of marine winds and surface currents

A radar scatterometer operates by transmitting a pulse of microwave energy toward the ocean's surface and measuring the normalized (per-unit-surface) radar backscatter coefficient (σ°). The primary application of scatterometry is the measurement of near-surface ocean winds. By combining σ° measurements from different azimuth angles, the 10 m vector wind can be determined through a Geophysical Model Function (GMF), which relates wind and backscatter. This paper proposes a mission concept for the measurement of both oceanic winds and surface currents, which makes full use of earlier C-band radar remote sensing experience. For the determination of ocean currents, in particular, the novel idea of using two chirps of opposite slope is introduced. The fundamental processing steps required to retrieve surface currents are given together with their associated accuracies. A detailed description of the mission proposal and comparisons between real and retrieved surface currents are presented. The proposed ocean Doppler scatterometer can be used to generate global surface ocean current maps with accuracies better than 0.2 m/s at a spatial resolution better than 25 km (i.e., 12.5 km spatial sampling) on a daily basis. These maps will allow gaining some insights on the upper ocean mesoscale dynamics. The work lies at a frontier, given that the present inability to measure ocean currents from space in a consistent and synoptic manner represents one of the greatest weaknesses in ocean remote sensing.

Color stability and surface roughness of artificial teeth brushed with an experimental Ricinus communis toothpaste

Aim: To evaluate, in vitro, the effect of brushing with a Ricinus communis -based experimental toothpaste on color stability and surface roughness of artificial teeth. Methods: Ninety artificial teeth (maxillary central incisors) in different shades, light and dark (NatusDent Triple Pressing, Dentbras) were used. Initial color (Spectrophotometer Easyshade, VITA) and surface roughness (Rugosimeter Surfcorder SE 1700, Kosakalab) readouts were performed. After baseline measurements, samples were assigned to 10 groups (n=9) according to the artificial tooth shade and type of toothpaste used during the mechanical brushing test (Pepsodent, MAVTEC): Sorriso Dentes Brancos – SDB, Colgate Luminous White - CLW (Colgate-Palmolive), Close up White Now - CWN (Unilever), Trihydral - THL (Perland Pharmacos) and Ricinus communis - RCE (Experimental). After 29,200 cycles of brushing, corresponding to 2 years of brushing by a healthy individual, new color and roughness readouts of the specimens were performed. Data (before and after the tests) were statistically analyzed (2-way repeated measures ANOVA, Tukey, p<0.05). Results: RCE toothpaste produced the greatest color stability for dark tooth shade and the second best color stability for light tooth shade. For surface roughness alteration, there was no difference (p>0.05) for any tested toothpaste regardless of tooth shade. Conclusions: The experimental Ricinus communis toothpaste did not cause color and surface roughness alteration in the artificial teeth, and it may be considered a suitable option for denture cleaning.

Usefulness of clinical observations and blood chemistry values for predicting clinical outcomes in dairy goats with pregnancy toxaemia

Background Pregnancy toxaemia (PT) is a disease that affects pregnant goats during their last month of gestation and is characterized by a high case fatality rate. This study involved 32 does maintained on a commercial dairy goat farm that were diagnosed with PT. A physical examination was performed on and haematology parameters obtained from each doe, at the time of diagnosis. The data from the 24 PT goats that died was compared with the corresponding data from the 8 PT goats that survived. Results Polypnea, swollen limbs, anorexia with absence of ruminal motility, recumbency, nervous signs and drooping ears were the most frequently observed clinical manifestations. Nineteen out of 21 recumbent goats died. Sixteen out of 17 goats with anorexia and absence of ruminal motility died. Mean beta-hydroxybutyric acid (BHBA) values in the goats that died were not significantly different from those in goats that survived. The blood values for pH and pCO2 (p < 0.005) as well as for HCO3 −, BE and K+ (p < 0.001) were significantly lower in the goats that died than in those that survived. Conclusions The clinical signs most indicative of a poor prognosis are anorexia with absence of ruminal motility and recumbency. Among the blood parameters to be considered, hypokalaemia and metabolic acidosis are the most relevant. Goats with PT have a high mortality and their condition can deteriorate very fast. Based on the authors’s experience, a good strategy to minimize the economic losses caused by PT is to focus on the offspring survival rate since an early decision (induction of kidding or caesarian surgery) can increase the number of alive kids.

Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering

We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500–1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.

From spent Mg/Al layered double hydroxide to porous carbon materials

Adsorption has been considered as an efficient method for the treatment of dye effluents, but properdisposal of the spent adsorbents is still a challenge. This work attempts to provide a facile methodto reutilize the spent Mg/Al layered double hydroxide (Mg/Al-LDH) after the adsorption of orange II(OII). Herein, the spent hybrid was carbonized under the protection of nitrogen, and then washedwith acid to obtain porous carbon materials. Thermogravimetric analysis results suggested that thecarbonization could be well achieved above 600◦C, as mass loss of the spent hybrid gradually stabilized. Therefore, the carbonization process was carried out at 600, 800, and 1000 ◦C, respectively. Scanning electron microscope showed that the obtained carbon materials possessed a crooked flaky morphology. Nitrogen adsorption–desorption results showed that the carbon materials had large BET surface area and pore volume, e.g., 1426 m2/g and 1.67 cm3/g for the sample carbonized at 800 ◦C. Moreover, the pore structure and surface chemistry compositions were tunable, as they were sensitive to the temperature. Toluene adsorption results demonstrated that the carbon materials had high efficiency in toluene removal. This work provided a facile approach for synthesizing porous carbon materials using spent Mg/Al-LDH.

Fabrication of fused silica phase gratings with inductively coupled plasma technology

Inductively coupled plasma (ICP) technology is a new advanced version of dry-etching technology compared with the widely used method of reactive ion etching (RIE). Plasma processing of the ICP technology is complicated due to the mixed reactions among discharge physics, chemistry and surface chemistry. Extensive experiments have been done and microoptical elements have been fabricated successfully, which proved that the ICP technology is very effective in dry etching of microoptical elements. In this paper, we present the detailed fabrication of microoptical fused silica phase gratings with ICP technology. Optimized condition has been found to control the etching process of ICP technology and to improve the etching quality of microoptical elements greatly. With the optimized condition, we have fabricated lots of good gratings with different periods, depths, and duty cycles. The fabricated gratings are very useful in fields such as spectrometer, high-efficient filter in wavelength-division-multiplexing system, etc..

Sorting nanoparticles by centrifugal fields in clean media

The on-demand availability of nanomaterials with selected size and well-defined chemical/physical properties is of fundamental importance for their widespread application. We report two clean, rapid, and non-destructive approaches for nanoparticle (NP) size selection in centrifugal fields. The first exploits rate zonal separation in a high viscosity gradient. The second exploits selective sedimentation of NPs with different sizes. These methods are here applied to metallic nanoparticles (MNPs) with different compositions and surface chemistry, dispersed either in water or organic solvents. The approach is general and can also be exploited for the separation of NPs of any material. We selectively sort both Au and AgNPs with sizes in the 10-30 nm range, achieving chemical-free MNPs with low polydispersivity. We do not use solutes, thus avoiding contamination, and only require low centrifugal fields, easily achievable in benchtop systems. © 2013 American Chemical Society.

Complex molecule formation in grain mantles

Context. Complex molecules such as ethanol and dimethyl ether have been observed in a number of hot molecular cores and hot corinos. Attempts to model the molecular formation process using gas phase only models have so far been unsuccessful. Aims. To demonstrate that grain surface processing is a viable mechanism for complex molecule formation in these environments. Methods. A variable environment parameter computer model has been constructed which includes both gas and surface chemistry. This is used to investigate a variety of cloud collapse scenarios. Results. Comparison between model results and observation shows that by combining grain surface processing with gas phase chemistry complex molecules can be produced in observed abundances in a number of core and corino scenarios. Differences in abundances are due to the initial atomic and molecular composition of the core/corino and varying collapse timescales. Conclusions. Grain surface processing, combined with variation of physical conditions, can be regarded as a viable method for the formation of complex molecules in the environment found in the vicinity of a hot core/corino and produce abundances comparable to those observed.

Nanoparticle Platform to Modulate Reaction Mechanism of Phenothiazine Photosensitizers

Herein, we report on the synthesis of photosensitizing nanoparticles in which the generation of different oxidizing species, i.e., singlet oxygen ((1)O(2)) or radicals, was modulated. Sol gel and surface chemistry were used to obtain nanoparticles with specific ratios of dimer to monomer species of phenothiazine photosensitizers (PSs). Due to competition between the reactions involving electron transfer within dimer species and energy transfer from monomer triplets to oxygen, the efficiency of (1)O(2) generation could be controlled. Nanoparticles with an excess of dimer have an (1)O(2) generation efficiency (S(Delta)) of 0.01 while those without dimer have a S, value of 0.4. Furthermore, we demonstrate that the PS properties of the nanoparticles are not subjected to interference from the external medium as is commonly the case for free PSs, i.e., PS ground and triplet states are not reduced by NADH and ascorbate, respectively, and singlet excited states are less suppressed by bromide. The modulated (1)O(2) generation and the PS protection from external interferences make this nanoparticle platform a promising tool to aid in performing mechanistic studies in biological systems. Also, it offers potential application in technological areas in which photo-induced processes take place.

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.