Academic literature on the topic 'Active Nucleation Site Density'

It has been well established that the rate of heat transfer associated with boiling systems is strongly dependent on the nucleation site density. Over many years attempts have been made to predict nucleation site density in boiling systems using a variety of techniques. With the exception of specially prepared surfaces, these attempts have met with little success. This paper presents an experimental investigation of nucleation site density measured on roughly polished brass and stainless steel surfaces for gas nucleation and pool boiling over a large parameter space. A statistical model used to predict the nucleation site density in saturated pool boiling is also investigated. The fluids used for this study, distilled water and ethanol, are moderately wetting and highly wetting, respectively. Using distilled water it has been observed that the trends of nucleation site density versus the inverse of the critical radius are similar for pool boiling and gas nucleation. The nucleation site density is higher for gas nucleation than for pool boiling. An unexpected result has been observed with ethanol as the heat transfer fluid, which casts doubt on the general assumption that heterogeneous nucleation in boiling systems is exclusively seeded by vapor trapping cavities. Due to flooding, few sites are active on the brass surface and at most two are active on the stainless steel surface during gas nucleation experiments. However, nucleation sites readily form in large concentration on both the brass and stainless steel surfaces during pool boiling. The pool boiling nucleation site densities for ethanol on rough and mirror polished brass surfaces are also compared. It shows that there is not a significant difference between the measured nucleation site densities on the smooth and rough surfaces. These results suggest that, in addition to vapor trapping cavities, another mechanism must exist to seed vapor bubble growth in boiling systems.

Abstract. Mineral dust particles are thought to be an important type of ice-nucleating particle (INP) in the mixed-phase cloud regime around the globe. While K-rich feldspar (K-feldspar) has been identified as being a particularly important component of mineral dust for ice nucleation, it has been shown that quartz is also relatively ice-nucleation active. Given quartz typically makes up a substantial proportion of atmospheric desert dust, it could potentially be important for cloud glaciation. Here, we survey the ice-nucleating ability of 10 α-quartz samples (the most common quartz polymorph) when immersed in microlitre supercooled water droplets. Despite all samples being α-quartz, the temperature at which they induce freezing varies by around 12 ∘C for a constant active site density. We find that some quartz samples are very sensitive to ageing in both aqueous suspension and air, resulting in a loss of ice-nucleating activity, while other samples are insensitive to exposure to air and water over many months. For example, the ice-nucleation temperatures for one quartz sample shift down by ∼2 ∘C in 1 h and 12 ∘C after 16 months in water. The sensitivity to water and air is perhaps surprising, as quartz is thought of as a chemically resistant mineral, but this observation suggests that the active sites responsible for nucleation are less stable than the bulk of the mineral. We find that the quartz group of minerals is generally less active than K-feldspars by roughly 7 ∘C, although the most active quartz samples are of a similar activity to some K-feldspars with an active site density, ns(T), of 1 cm−2 at −9 ∘C. We also find that the freshly milled quartz samples are generally more active by roughly 5 ∘C than the plagioclase feldspar group of minerals and the albite end member has an intermediate activity. Using both the new and literature data, active site density parameterizations have been proposed for freshly milled quartz, K-feldspar, plagioclase and albite. Combining these parameterizations with the typical atmospheric abundance of each mineral supports previous work that suggests that K-feldspar is the most important ice-nucleating mineral in airborne mineral dust.

Abstract. Deposition nucleation experiments with Arizona Test Dust (ATD) as a surrogate for mineral dusts were conducted at the AIDA cloud chamber at temperatures between 220 and 250 K. The influence of the aerosol size distribution and the cooling rate on the ice nucleation efficiencies was investigated. Ice nucleation active surface site (INAS) densities were calculated to quantify the ice nucleation efficiency as a function of temperature, humidity and the aerosol surface area concentration. Additionally, a contact angle parameterization according to classical nucleation theory was fitted to the experimental data in order to relate the ice nucleation efficiencies to contact angle distributions. From this study it can be concluded that the INAS density formulation is a very useful tool to decribe the temperature and humidity dependent ice nucleation efficiency of ATD particles. Deposition nucleation on ATD particles can be described by a temperature and relative humidity dependent INAS density function ns(T, Sice) with ns(xtherm) = 1.88 × 105 · exp(0.2659 · xtherm) [m−2] (1) where the thermodynamic variable xtherm is defined as xtherm = −(T − 273.2) + (Sice−1) × 100 (2) with Sice>1 and within a temperature range between 226 and 250 K. For lower temperatures, xtherm deviates from a linear behavior with temperature and relative humidity over ice. Two different approaches for describing the time dependence of deposition nucleation initiated by ATD particles are proposed. Box model estimates suggest that the time dependent contribution is only relevant for small cooling rates and low number fractions of ice-active particles.

Abstract. Deposition nucleation experiments with Arizona Test Dust (ATD) as a surrogate for mineral dusts were conducted at the AIDA cloud chamber at temperatures between 220 and 250 K. The influence of the aerosol size distribution and the cooling rate on the ice nucleation efficiencies was investigated. Ice nucleation active surface site (INAS) densities were calculated to quantify the ice nucleation efficiency as a function of temperature, humidity and the aerosol surface area concentration. Additionally, a contact angle parameterization according to classical nucleation theory was fitted to the experimental data in order to relate the ice nucleation efficiencies to contact angle distributions. From this study it can be concluded that the INAS density formulation is a very useful tool to describe the temperature- and humidity-dependent ice nucleation efficiency of ATD particles. Deposition nucleation on ATD particles can be described by a temperature- and relative-humidity-dependent INAS density function ns(T, Sice) with ns(xtherm) = 1.88 ×105 · exp(0.2659 · xtherm) [m−2] , (1) where the temperature- and saturation-dependent function xtherm is defined as xtherm = −(T−273.2)+(Sice−1) ×100, (2) with the saturation ratio with respect to ice Sice >1 and within a temperature range between 226 and 250 K. For lower temperatures, xtherm deviates from a linear behavior with temperature and relative humidity over ice. Also, two different approaches for describing the time dependence of deposition nucleation initiated by ATD particles are proposed. Box model estimates suggest that the time-dependent contribution is only relevant for small cooling rates and low number fractions of ice-active particles.

A model to describe the effect of wettability on nucleation site density is presented. First, from Helmholtz free energy analysis, a criterion for the entrapment condition in a uniform temperature field is developed. Second, the stability condition of preexisting gas/vapor nuclei during the heating process and the minimum superheat required to initiate nucleation are determined. The prediction of the entrapment condition and the incipient temperature are consistent with the experimental observations made on surfaces having naturally existing cavities. Third, a naturally formed cavity on a heater surface is modeled as a spherical cavity. The cumulative active nucleation site density for a specified contact angle is expressed in terms of the cumulative density of cavities existing on the surface as Na = Pas · Nas where Nas is the heater surface cumulative cavity density with cavity mouth angles less than a specified value and Pas is a function of contact angle and cavity mouth angle. The model successfully predicts active site densities for different contact angles.

An experimental method was further developed to quantify the anisotropy of multi-site fatigue crack initiation behaviors in high strength Al alloys by four-point bend fatigue testing under stress control. In this method, fatigue crack initiation sites (fatigue weak-links, FWLs) were measured on the sample surface at different cyclic stress levels. The FWL density in an alloy could be best described using a three-parameter Weibull function of stress, though other types of sigmoidal functions might also be used to quantify the relationship between FWL density and stress. The strength distribution of the FWLs was derived from the Weibull function determined by fitting the FWLs vs. stress curve experimentally obtained. As materials properties, the FWL density and strength distribution could be used to evaluate the fatigue crack nucleation behaviors of engineering alloys quantitatively and the alloy quality in terms of FWL density and strength distribution. In this work, the effects of environment, types of microstructural heterogeneities and loading direction on FWLs were all studied in detail in AA7075-T651, AA2026-T3511, and A713 Al alloys, etc. It was also found that FWLs should be quantified as a Weibull-type function of strain instead of stress, when the applied maximum cyclic stress exceeded the yield strength of the tested alloys. In this work, four-point bend fatigue tests were conducted on the L-T (Rolling-Transverse), L-S (Rolling-Short transverse) and T-S planes of an AA7075-T651 alloy plate, respectively, at room temperature, 20 Hz, R=0.1, in air. The FWL populations, measured on these surfaces, were a Weibull-type function of the applied maximum cyclic stress, from which FWL density and strength distribution could be determined. The alloy showed a significant anisotropy of FWLs with the weak-link density being 11 mm-2, 15 mm-2 and 4 mm-2 on the L-T, L-S and T-S planes, respectively. Fatigue cracks were predominantly initiated at Fe-containing particles on the L-T and L-S planes, but only at Si-bearing particles on the T-S plane, profoundly demonstrating that the pre-fractured Fe-containing particles were responsible for crack initiation on the L-T and L-S planes, since the pre-fracture of these particles due to extensive deformation in the L direction during the prior rolling operation could only promote crack initiation when the sample was cyclically stressed in the L direction on both the L-T and L-S planes. The fatigue strengths of the L-T, L-S and T-S planes of the AA7075 alloy were measured to be 243.6, 273.0 and 280.6 MPa, respectively. The differences in grain and particle structures between these planes were responsible for the anisotropy of fatigue strength and FWLs on these planes. Three types of fatigue cracks from particles, type-I: the micro-cracks in the particles could not propagate into the matrix, i.e., type-II: the micro-cracks were fully arrested soon after they propagated into the matrix, and type-III: the micro-cracks became long cracks, were observed in the AA7075-T651 alloy after fatigue testing. By cross-sectioning these three-types of particles using Focused Ion Beam (FIB), it was found that the thickness of the particles was the dominant factor controlling fatigue crack initiation at the particles, namely, the thicker a pre-fractured Fe-containing particle, the easier it became a type-III crack on the L-T and L-S planes. On the T-S plane, there were only types-I and III Si-bearing particles at which crack were initiated. The type-I particles were less than 6.5 μm in thickness and type-III particles were thicker than 8.3 μm. Cross-sectioning of these particles using FIB revealed that these particles all contained gas pores which promoted crack initiation at the particles because of higher stress concentration at the pores in connection with the particles. It was also found that fatigue cracks did not always follow the any specific crystallographic planes within each grain, based on the Electron Backscatter Diffraction (EBSD) measurement. Also, the grain orientation did not show a strong influence on crack initiation at particles which were located within the grains. The topography measurements with an Atomic Force Microscope (AFM) revealed that Fe-containing particles were protruded on the mechanically polished surface, while the Si-bearing particles were intruded on the surface, which was consistent with hardness measurements showing that Si-bearing particles were softer (4.030.92 GPa) than Fe-containing ones (8.9 0.87 GPa) in the alloy. To verify the 3-D effects of the pre-fractured particles on fatigue crack initiation in high strength Al alloys, rectangular micro-notches of three different types of dimensions were fabricated using FIB in the selected grains on the T-S planes of both AA2024-T351 and AA7075-T651 Al alloys, to mimic the three types of pre-fractured particles found in these alloys. Fatigue testing on these samples with the micro-notches verified that the wider and deeper the micro-notches, the easier fatigue cracks could be initiated at the notches. In the AA2024-T351 samples, cracks preferred to propagate along the {111} slip plane with the smallest twist angle and relatively large Schmid factor. These experimental data obtained in this work could pave a way to building a 3-D quantitative model for quantification of fatigue crack initiation behaviors by taking into account the driving force and resistance to short crack growth at the particles in the surface of these alloys.

Catalysis has a responsibility to provide solutions to the growing grand challenge of sustainability in the fuels and chemical industry to help combat climate change. These changes; however, cannot be realized without a more fundamental understanding of the active sites that catalyze chemical reactions, and how they can be tuned to control rates and selectivities. Four specific examples of active site modification will be considered in this work: the speciation of isolated metals in zeolite frameworks, solvent thermodynamics and structure at defects in zeolite frameworks, the electronic modification of platinum through alloying in well-defined intermetallic nanoparticles, and the mobility and shape of gold nanoparticles in zeolite channels. Each will highlight how quantum chemistry calculations can provide a fundamental understanding of how these active site modifications influence the kinetics of chemical reactions, and how they can be controlled to pursue solutions to the reduction of carbon through sustainable utilization of shale gas as well as renewable chemicals production through biomass upgrading.

Zeolites exchanged with metal heteroatoms can behave as solid Lewis or Brønsted acids depending on heteroatom identity. Lewis acid heteroatoms can adsorb water and hydrolyze to speciate into “open sites” which have been shown to differ in their ability to catalyze reactions such as glucose isomerization as compared to “closed sites” which are fully coordinated to the zeolite framework. The structure and catalytic properties of these sites are interrogated by a gas phase reaction, ethanol dehydration, in Sn-Beta by a combined Density Functional Theory (DFT) and experimental study. DFT is used to map the possible reaction mechanisms for ethanol dehydration, including the speciation of Sn sites into hydrolyzed configurations from water or ethanol. A microkinetic model for ethanol dehydration including unselective and inhibitory intermediates is constructed. This microkinetic model predicts the population of reactants and products on the catalyst surface as well as the sensitivity of individual elementary steps to the total rates. Powerful anharmonic entropy methods using ab-initio molecular dynamics (AIMD) is used to capture the entropy of confined reactive intermediates, which is shown to be necessary to compare with experiment. Results on closed and hydrolyzed open zeolite sites can then be compared with ethanol dehydration on “defect open” sites which were shown experimentally to occur at material stacking faults. A grain boundary model is constructed of zeolite Beta, where unique sites have similar ligand identity as hydrolyzed open sites. These defect open sites are found to not contribute to the observed reaction rate as they cannot stabilize the same transition state structures that were observed in internal Beta sites.

Intuition about the ethanol dehydration reaction in Sn-Beta was then used to map a more expansive and diverse chemical network, the synthesis of butadiene from acetaldehyde and ethanol. For elementary reactions in this mechanism, which included aldol condensation, MPV reduction, and crotyl alcohol dehydration in addition to ethanol dehydration, the hydrolyzed open sites were found to be crucial reactive intermediates. Hydrolyzed sites were necessary to stabilize favorable transition states, which requires reconstruction of the local framework environment. Methods to preferentially stabilize hydrolyzed sites were then explored, using a screening algorithm developed to consider all possible sites in each zeolite framework. It was found that the stability of these hydrolyzed sites could be correlated to the local strain exerted by the surrounding silica matrix. This provides a new descriptor that stabilizes intermediates relevant to the synthesis of butadiene and ethanol dehydration.

Next, the structure and thermodynamic stability of water networks around Sn-Beta defects and heteroatom active sites was considered using AIMD. As many biomass reactions occur in the presence of water, the interactions of water with hydrophobic and hydrophilic functionalized defects dictate how the stability of reactive intermediates and transition states is affected by a solvating environment. Locally stable and strongly nucleated clusters of water were observed to form at Sn defects, with less densely packed water structures stable at hydrophilic defects. This is in comparison to defect-free siliceous Beta, where significantly less water uptake is observed. These local clusters are in equilibrium with the less dense liquid-like phase that extends between defects. These results motivate localized cluster models around active sites in Lewis acids, as well as advance the fundamental understanding of hydrophobic/hydrophilic interactions in microporous materials. The local cluster models are then applied to the ethanol dehydration reaction in protonated aluminum Beta zeolites where experimentally observed non-unity coefficient ratios are rationalized by quantifying a different degree of solvation for the ethanol reactant state as opposed to the transition state, validated by a thermodynamic phase diagram.

Changes in the electronic energy levels of d electrons upon alloying was studied in conjunction with a new spectroscopic technique being performed at Argonne National Laboratory to develop new descriptors to predict the degree of coking for different alloys. Resonant Inelastic X-ray Scattering (RIXS) simultaneously probes the occupied and unoccupied valence states of platinum in nanoparticles at ambient conditions. The specific excitation process of this spectroscopy is particularly amendable to DFT modeling, which was used to provide richer chemical insight into how changes in observed RIXS signature related to the electronic structure changes of platinum upon alloying. From a suite of multiple 3d alloy promoter catalysts synthesized, a quantitative comparison with DFT modeled spectroscopy was developed. The stability of DFT calculated coke precursors, relevant to dehydrogenation catalysts to convert light alkanes into olefins, was then correlated to DFT modeled RIXS spectra, which is a better descriptor for adsorption of unsaturated chemical intermediates that used previously, as well as being a descriptor accessible to direct experimental usage.

Finally, the diffusion of gold nanoparticles in the TS-1 catalyst was studied using AIMD to help understand what structural motifs of gold are present under reaction conditions and how the shape and binding sites of gold is strongly influenced by deformation by the zeolite framework. This is used to help predict new zeolites for use in direct propylene epoxidation using molecular oxygen and hydrogen. The optimization of this catalyst is environmentally relevant to reduce the usage of inorganics and reduce the cost associated with production of hydrogen peroxide. Following these discussions, the role of computation in the prediction of active site structures and kinetics in conjunction with experiment was included. The broader impact of these findings will also be considered, which span beyond these specific reactions and materials.

Selective catalytic reduction (SCR) of NO_x using NH₃ as a reductant (4NH₃+ 4NO + O₂ 6H₂O + 4N₂) over Cu-SSZ-13 zeolites is a commercial technology used to meet emissions targets in lean-burn and diesel engine exhaust. Optimization of catalyst design parameters to improve catalyst reactivity and stability against deactivation (hydrothermal and sulfur poisoning) necessitates detailed molecular level understanding of structurally different active Cu sites and the reaction mechanism. With the help of synthetic, titrimetric, spectroscopic, kinetic and computational techniques, we established new molecular level details regarding 1) active Cu site speciation in monomeric and dimeric complexes in Cu-SSZ-13, 2) elementary steps in the catalytic reaction mechanism, 3) and deactivation mechanisms upon hydrothermal treatment and sulfur poisoning.

We have demonstrated that Cu in Cu-SSZ-13 speciates as two distinct isolated sites, nominally divalent Cu^II and monovalent [Cu^II(OH)]⁺ complexes exchanged at paired Al and isolated Al sites, respectively. This Cu site model accurately described a wide range of zeolite chemical composition, as evidenced by spectroscopic (Infrared and X-ray absorption) and titrimetric characterization of Cu sites under ex situ conditions and in situ and operando SCR reaction conditions. Monovalent [Cu^II(OH)]⁺ complexes have been further found to condense to form multinuclear Cu-oxo complexes upon high temperature oxidative treatment, which have been characterized using UV-visible spectroscopy, CO-temperature programmed reduction and dry NO oxidation as a probe reaction. Structurally different isolated Cu sites have different susceptibilities to H₂ and He reductions, but are similarly susceptible to NO+NH₃ reduction and have been found to catalyze NO_x SCR reaction at similar turnover rates (per Cu^II; 473 K) via a Cu^II/Cu^I redox cycle, as their structurally different identities are masked by NH₃ solvation during reaction.

Molecular level insights on the low temperature Cu^II/Cu^I redox mechanism have been obtained using experiments performed in situand in operando coupled withtheory. Evidence has been provided to show that the Cu^II to Cu^I reduction half-cycle involves single-site Cu reduction of isolated Cu^II sites with NO+NH₃, which is independent of Cu spatial density. In contrast, the Cu^I to Cu^II oxidation half-cycle involves dual-site Cu oxidation with O₂ to form dimeric Cu-oxo complexes, which is dependent on Cu spatial density. Such dual-site oxidation during the SCR Cu^II/Cu^I redox cycle requires two Cu^I(NH₃)₂sites, which is enabled by NH₃solvation that confers mobility to isolated Cu^I sites and allows reactions between two Cu^I(NH₃)₂ species and O₂. As a result, standard SCR rates depend on Cu proximity in Cu-SSZ-13 zeolites when Cu^I oxidation steps are kinetically relevant. Additional unresolved pieces of mechanism have been investigated, such as the reactivity of Cu dimers, the types of reaction intermediates involved, and the debated role of Brønsted acid sites in the SCR cycle, to postulate a detailed reaction mechanism. A strategy has been discussed to operate either in oxidation or reduction-limited kinetic regimes, to extract oxidation and reduction rate constants, and better interpret the kinetic differences among Cu-SSZ-13 catalysts.

The stability of active Cu sites upon sulfur oxide poisoning has been assessed by exposing model Cu-zeolite samples to dry SO₂ and O₂ streams at 473 and 673 K, and then analyzing the surface intermediates formed via spectroscopic and kinetic assessments. Model Cu-SSZ-13 zeolites were synthesized to contain distinct Cu active site types, predominantly either divalent Cu^II ions exchanged at proximal framework Al (Z₂Cu), or monovalent [Cu^IIOH]⁺ complexes exchanged at isolated framework Al (ZCuOH). SCR turnover rates (473 K, per Cu) decreased linearly with increasing S content to undetectable values at equimolar S:Cu ratios, consistent with poisoning of each Cu site with one SO₂-derived intermediate. Cu and S K-edge X-ray absorption spectroscopy and density functional theory calculations were used to identify the structures and binding energies of different SO₂-derived intermediates at Z₂Cu and ZCuOH sites, revealing that bisulfates are particularly low in energy, and residual Brønsted protons are liberated at Z₂Cu sites as bisulfates are formed. Molecular dynamics simulations also show that Cu sites bound to one HSO₄^- are immobile, but become liberated from the framework and more mobile when bound to two HSO₄^-. These findings indicate that Z₂Cu sites are more resistant to SO₂poisoning than ZCuOH sites, and are easier to regenerate once poisoned.

The stability of active Cu sites on various small-pore Cu-zeolites during hydrothermal deactivation (high temperature steaming conditions) has also been assessed by probing the structural and kinetic changes to active Cu sites. Three small-pore, eight-membered ring (8-MR) zeolites of different cage-based topology (CHA, AEI, RTH) have been investigated. With the help of UV-visible spectroscopy to probe the Cu structure, in conjunction with measuring differential reaction kinetics before and after subsequent treatments, it has been suggested that the RTH framework imposes internal transport restrictions, effectively functioning as a 1-D framework during SCR catalysis. Hydrothermal aging of Cu-RTH results in complete deactivation and undetectable SCR rates, despite no changes in long-range structure or micropore volume after hydrothermal aging treatments and subsequent SCR exposure, highlighting beneficial properties conferred by double six-membered ring (D6R) composite building units. Exposure aging conditions and SCR reactants resulted in deleterious structural changes to Cu sites, likely reflecting the formation of inactive copper-aluminate domains. Therefore, the viability of Cu-zeolites for practical low temperature NO_x SCR catalysis cannot be inferred solely from assessments of framework structural integrity after aging treatments, but also require Cu active site and kinetic characterization after aged zeolites are exposed to low temperature SCR conditions.

Although Cu-SSZ-13 zeolites are used commercially in diesel engine exhaust after-treatment for abatement of toxic NO_x pollutants via selective catalytic reduction (SCR) with NH₃, molecular details of its active centers and mechanistic details of the redox reactions they catalyze, specifically of the Cu(I) to Cu(II) oxidation half-reaction, are not well understood. A detailed understanding of the SCR reaction mechanism and nature of the Cu active site would provide insight into their catalytic performance and guidance on synthesizing materials with improved low temperature (< 473 K) reactivity and stability against deactivation (e.g. hydrothermal, sulfur oxides). We use computational, titration, spectroscopic, and kinetic techniques to elucidate (1) the presence of two types of Cu²⁺ ions in Cu-SSZ-13 materials, (2) molecular details on how these Cu cations, facilitated by NH₃ solvation, undergo a reduction-oxidation catalytic cycle, and (3) that sulfur oxides poison the two different types of Cu²⁺ ions to different extents at via different mechanisms.

Copper was exchanged onto H-SSZ-13 samples with different Si:Al ratios (4.5, 15, and 25) via liquid-phase ion exchange using Cu(NO₃)₂ as the precursor. The speciation of copper started from the most stable Cu²⁺ coordinated to two anionic sites on the zeolite framework to [CuOH]⁺ coordinated to only one anionic site on the zeolite framework with increasing Cu:Al ratios. The number of Cu²⁺ and [CuOH]⁺ sites was quantified by selective NH₃ titration of the number of residual Brønsted acid sites after Cu exchange, and by quantification of Brønsted acidic Si(OH)Al and CuOH stretching vibrations from IR spectra. Cu-SSZ-13 with similar Cu densities and anionic framework site densities exhibit similar standard SCR rates, apparent activation energies, and orders regardless of the fraction of Z₂Cu and ZCuOH sites, indicating that both sites are equally active within measurable error for SCR.

The standard SCR reaction uses O₂ as the oxidant (4NH₃ + 4NO + O₂ -> 6H₂O + 4N₂) and involves a Cu(I)/Cu(II) redox cycle, with Cu(II) reduction mediated by NO and NH₃, and Cu(I) oxidation mediated by NO and O₂. In contrast, the fast SCR reaction (4NH₃ + 2NO + 2NO₂ -> 6H₂O + 4N₂) uses NO₂ as the oxidant. Low temperature (437 K) standard SCR reaction kinetics over Cu-SSZ-13 zeolites depend on the spatial density and distribution of Cu ions, varied by changing the Cu:Al and Si:Al ratio. Facilitated by NH₃ solvation, mobile Cu(I) complexes can dimerize with other Cu(I) complexes within diffusion distances to activate O₂, as demonstrated through X-ray absorption spectroscopy and density functional theory calculations. Monte Carlo simulations are used to define average Cu-Cu distances. In contrast with O₂-assisted oxidation reactions, NO₂ oxidizes single Cu(I) complexes with similar kinetics among samples of varying Cu spatial density. These findings demonstrate that low temperature standard SCR is dependent on Cu spatial density and requires NH₃ solvation to mobilize Cu(I) sites to activate O₂, while in contrast fast SCR uses NO₂ to oxidize single Cu(I) sites.

We also studied the effect of sulfur oxides, a common poison in diesel exhaust, on Cu-SSZ-13 zeolites. Model Cu-SSZ-13 samples exposed to dry SO₂ and O₂ streams at 473 and 673 K. These Cu-SSZ-13 zeolites were synthesized and characterized to contain distinct Cu active site types, predominantly either divalent Cu²⁺ ions exchanged at proximal framework Al sites (Z₂Cu), or monovalent CuOH+ complexes exchanged at isolated framework Al sites (ZCuOH). On the model Z₂Cu sample, SCR turnover rates (473 K, per Cu) catalyst decreased linearly with increasing S content to undetectable values at equimolar S:Cu molar ratios, while apparent activation energies remained constant at ~65 kJ mol^-1, consistent with poisoning of each Z₂Cu site with one SO₂-derived intermediate. On the model ZCuOH sample, SCR turnover rates also decreased linearly with increasing S content, yet apparent activation energies decreased monotonically from ~50 to ~10 kJ mol^-1, suggesting that multiple phenomena are responsible for the observed poisoning behavior and consistent with findings that SO₂ exposure led to additional storage of SO₂-derived intermediates on non-Cu surface sites. Changes to Cu²⁺ charge transfer features in UV-Visible spectra were more pronounced for SO₂-poisoned ZCuOH than Z₂Cu sites, while X-ray diffraction and micropore volume measurements show evidence of partial occlusion of microporous voids by SO₂-derived deposits, suggesting that deactivation may not only reflect Cu site poisoning. Density functional theory calculations are used to identify the structures and binding energies of different SO₂-derived intermediates at Z₂Cu and ZCuOH sites. It is found that bisulfates are particularly low in energy, and residual Brønsted protons are liberated as these bisulfates are formed. These findings indicate that Z₂Cu sites are more resistant to SO₂ poisoning than ZCuOH sites, and are easier to regenerate once poisoned.

Enzymes catalyze the biochemical reactions in cells of all organisms. These reactions constitute the chemical basis of life. Most enzymes are proteins—a few are ribonucleic acids or ribonucleoproteins—and the catalytic machinery is located in a relatively small active site, where substrates bind and are chemically processed into products. Illustrations of the molecular structure of chymotrypsin, a typical enzyme, and the location of its active site appear in figs. 1-1A and B. The polypeptide chain is shown as a ribbon diagram, and the active site is the region in which an inhibitor, the black ball-and-stick model, is bound. The gray ball-and-stick structures are amino acid side chains at the active site that participate in catalysis. The ribbon diagram shows the individual chains and the α-helices and β-strands as if there were vacant spaces between them; however, very little free space exists in the interior of an enzyme. The packing density in the interior of a protein is typically 0.7 to 0.8, meaning that 70% to 80% of the space is filled and only 20% to 30% is interstitial space (Richards, 1974). That the packing density in hexagonally closest packed spheres is 0.75, similar to a protein, conveys a concept of the interior. The free space inside a protein is so little that in a space-filling model, the polypeptide chain cannot be discerned, and interactions between active sites and substrate or inhibitors cannot be seen. For this reason, we display structures as ribbon diagrams to facilitate the discussion of ligand binding interactions within an active site. Chymotrypsin is the most widely studied and one of the best-understood enzymes. It catalyzes the hydrolysis of proteins at the carboxamide groups of hydrophobic amino acid residues, principally phenylalanyl, tyrosyl, and tryptophanyl residues. It also catalyzes the hydrolysis of small substrates, such as acetyltyrosine ethyl ester (ATEE) or acetyltyrosine p-nitroanilide (ATNA). These reactions are practically irreversible, their rates can be measured spectrophotometrically, and they behave kinetically as one-substrate enzymatic reactions. The overall reaction of ATEE can be written as ATEE → Acetyltyrosine + Ethanol, where the participation of water as a substrate is understood.

This chapter looks at sampling techniques and setting thresholds. The cornerstone of any integrated insect management regime is accurately identifying pest insects (including assessing population density) and developing appropriate action thresholds. Various methods have evolved by which the populations of insects present in the turf environment may be determined relatively rapidly and efficiently. These methods have become standard techniques for reporting insect densities. The chapter differentiates between passive sampling techniques (use of traps) and active visual inspection techniques (actual quantification of insect populations). Thresholds in turf integrated pest management usually are more accurately considered tolerance levels, or action thresholds. The tolerance level, or action threshold, for turfgrass insects is site-specific and depends on many factors.

Root hairs are found on most terrestrial flowering plant species. They form from epidermal cells at a predetermined distance behind the growing root tip in three main patterns. Their presence, pattern, length, density and function are genetically controlled and numerous genes are expressed solely in root hairs. Their growth and proliferation are attenuated by the environment and root hairs growing in soil are generally shorter and less dense than those in laboratory studies. Root hairs have a number of functions including anchorage, root soil contact and bracing to enable roots to penetrate hard soils. However, their primary function is acquisition of nutrients and water, in particular phosphate. They are the site of transporters, exudation of active compounds and infection point of symbiotic microbial interactions. They have a profound effect on rhizosphere characteristics and are a potentially useful target for breeding crops for future agricultural sustainability.

A microarray works by exploiting the ability of a given mRNA molecule to bind specifically to the DNA template from which it originated under specific high stringency conditions. After this, the amount of mRNA bound to each DNA site on the array is determined, which represents the expression level of each gene. Qualification of the mRNA (probe) bound to each DNA spot (target) can help us to determine which genes are active or responsible for the current state of the cell. The probe target hybridization is usually detected and quantified using dyes/flurophore/chemiluminescence labels. The microarray data gives a single snapshot of the gene activity profile of a cell at any given time. Microarray data helps to elucidate the various genes involved in the disease and may also be used for diagnosis /prognosis. In spite of its huge potential, microarray data interpretation and use is limited by its error prone nature, the sheer size of the data and the subjectivity of the analysis. Initially, we describe the use of several techniques to develop a pre-processing methodology for denoising microarray data using signal process techniques. The noise free data thus obtained is more suitable for classification of the data as well as for mining useful information from the data. Discrete Fourier Transform (DFT) and Autocorrelation were explored for denoising the data. We also used microarray data to develop the use of microarray data as diagnostic tool in cancer using One Dimensional Fourier Transform followed by simple Euclidean Distance Calculations and Two Dimensional MUltiple SIgnal Classification (MUSIC). To improve the accuracy of the diagnostic tool, Volterra series were used to model the nonlinear behavior of the data. Thus, our efforts at denoising, representation, and classification of microarray data with signal processing techniques show that appreciable results could be attained even with the most basic techniques. To develop a method to search for a gene signature, we used a combination of PCA and density based clustering for inferring the gene signature of Parkinson’s disease. Using this technique in conjunction with gene ontology data, it was possible to obtain a signature comprising of 21 genes, which were then validated by their involvement in known Parkinson’s disease pathways. The methodology described can be further developed to yield future biomarkers for early Parkinson’s disease diagnosis, as well as for drug development.

It has been well established that the rate of heat transfer associated with boiling systems is strongly dependent on the nucleation site density. Over many years attempts have been made to predict nucleation site density in boiling systems using a variety of techniques. With the exception of specially prepared surfaces, these attempts have met with little success. This paper presents an experimental investigation of nucleation site density measured on roughly polished brass and stainless steel surfaces for gas nucleation and pool boiling over a large parameter space. The fluids used for this study, distilled water and ethanol, are moderately wetting and highly wetting, respectively. Using distilled water it has been observed that the trends of nucleation site density versus the inverse of the critical radius are similar for pool boiling and gas nucleation. The nucleation site density is higher for gas nucleation than for pool boiling. An unexpected result has been observed with ethanol as the heat transfer fluid, which casts doubt on the general validity of heterogeneous nucleation theory. Due to flooding, few sites are active on the brass surface and at most two are active on the stainless steel surface during gas nucleation experiments. However, nucleation sites readily form in large concentration on both the brass and stainless steel surfaces during pool boiling. The nucleation site densities for the rough and mirror polished brass surfaces are also compared. It shows that there is no large difference for the measured nucleation site density.

This research presents experimental approaches to accumulate the data for mechanistic model in subcooled flow boiling. A number of photographic studies have been provided to investigate phenomena of bubble nucleation and condensation process for accurate prediction of void fraction such as bubble detachment diameter, bubble detachment frequency and nucleation site density in a subcooled flow boiling. In this work, a transparent heated surface was used to obtain the data from back side of heated surface to avoid overlapping bubbles by using high speed video camera. It enabled to observe bubble nucleation process and active nucleation sites. The experiment was performed in a vertical rectangular channel at atmospheric pressure and the water was used as test fluid. In generally, the computational analysis for a subcooled flow boing deal with mean bubble size as the size of bubbles produced on heated surface. Although, it was found that mean bubble size can represent bubbles produced at same site because they are almost uniform size. Even though the size of bubbles at same site are almost uniform, the difference of the size of bubbles between other sites are considerable value. Therefore, mean bubble size on the surface should not represent bubbles for all site otherwise the serious error may be caused. It seems that bubble detachment diameter should not be given by correlations of mean bubble detachment diameter for accurate prediction of vaporization rate. Some researchers proposed that bubble size distribution should be considered by Gaussian distribution [1–3]. However, it found that bubble size distribution data accumulated in this work cannot be fitted by Gaussian distribution and there are probability that larger bubbles are neglected due to the configuration features of Gaussian distribution. So, Gamma distribution was used to predict the bubble size distribution and it was evaluated in terms of heat flux, wall superheat, mass flux and liquid subcooling. And then, by the experimental approaches, the important dimensionless parameters are identified such as Nusselt number, Jakob number, Reynolds number and dimensionless subcooling. Furthermore, vaporization rate was calculated by correlations of bubble detachment diameter, bubble detachment diameter and nucleation site density and compared with the data. Finally, the effect of using mean bubble size or bubble size distribution on vaporization rate was investigated.

An experimental study of nanostructure modified nucleation site density and contact angle that significantly enhances the Heat Transfer Coefficient (HTC) and the Critical Heat Flux (CHF) in pool boiling heat transfer of water on copper surfaces has been conducted. The nanostructures on copper surfaces have been created by an electrodeposition technique. It has been found that the nanostructured copper surfaces show an increase in CHF of up to 142% and an increase in HTC of 33% over that of a mirror-finished plain copper surface. Calculations for nucleation site density and active nucleation site diameter reveal a direct correlation between these factors and the HTC, as well as the CHF. More interestingly, a contact angle study on the tested surfaces shows that there is a connection between the contact angle reduction and CHF enhancement, which confirms the contact angle mechanism of CHF with experimental evidence.

The thermo-fluid properties of water change at high pressure. The performance of high pressure pool boiling greater than 50 Psi has not been studied widely. The aim of this paper is to analyze the experimental data to describe the effect of increasing pressure during pool boiling. Hsu’s correlation was used to predict the active nucleation sites. The maximum and minimum radii of the active nucleation sites were determined as a function of heat flux or degree of wall superheats over a wide range of pressures. The bubble dynamics are discussed using the predicted values of fundamental boiling quantities such as bubble departure diameter, active nucleation site density and bubble release frequency. The thickness of the boundary layer was assumed to be 30 microns. Rohsenow’s and Forster’s correlations were used to predict the pool boiling curve for different pressures. The comparison was made with the experimental data for water of a plain copper surface of increasing pressure. The parametric trend provides fundamental insight and explains how the system pressure can maximize the boiling efficiency of new generation boilers.

An experimental investigation is presented on flow boiling of de-ionized water in 227-μm hydraulic diameter microchannels with reentrant type cavities. Key features of nucleate boiling are discussed. Active nucleation site density, bubble frequency and departure diameter, and flow patterns over mass velocities ranging from 41 kg/m2-s to 302 kg/m2-s and heat fluxes ranging from 28 to 445 W/cm2 are studied. Similarities and differences with results obtained on large-scale systems and unenhanced microchannels are discussed.

Quantitative measurements are obtained from high-speed visualizations of pool boiling at atmospheric pressure from smooth and roughened surfaces, using a perfluorinated hydrocarbon (FC-77) as the working fluid. The boiling surfaces are fabricated from aluminum and prepared by mechanical polishing in the case of the smooth surface, and by electrical discharge machining (EDM) in the case of the roughened surface. The roughness values (Ra) are 0.03 and 5.89 micrometers for the polished and roughened surfaces, respectively. The bubble diameter at departure, bubble departure frequency, bubble terminal velocity, and active nucleation site density are measured from the monochrome movies, which are recorded at 8000 frames per second with a digital CCD camera and magnifying lens. Results are compared to predictions from existing models of bubble nucleation behavior in the literature. Wall superheat, heat flux, and heat transfer coefficient are also reported.

A method is developed to capture the distribution of surface temperature while simultaneously imaging the bubble motions in diabatic flow boiling in a horizontal minichannel. Liquid crystal thermography is used to obtain highly resolved surface temperature measurements on the uniformly heated upper surface of the channel. High-speed images of the flow field are acquired simultaneously and are overlaid with the thermal images. The local surface temperature and heat transfer coefficient can be analyzed with the knowledge of the nucleation site density and location, and bubble motion and size evolution. The horizontal channel is 1.2 mm high × 23 mm wide × 357 mm long, and the working fluids are Novec 649 and R-11. Optical access is through a machined glass plate which forms the bottom of the channel. The top surface is an electrically heated 76 μm-thick Hastelloy foil held in place by a water-cooled aluminum and glass frame. The heat loss resulting from this construction is computed using a conduction model in Fluent. The model is driven by temperature measurements on the foil, glass plate and aluminum frame. This model produces a corrected value for the local surface heat flux and enables the computation of the bulk fluid temperature and heat transfer coefficient along the channel. The streamwise evolution of the heat transfer coefficient for single-phase laminar flow is compared to theoretical values for a uniform-flux boundary condition. Examples of the use of the facility for visualizing subcooled two-phase flows are presented. These examples include measurements of the surface temperature distribution around active nucleation sites and the construction of boiling curves for locations along the test surface. Points on the curve can be associated with specific image sequences so that the role of mechanisms such as nucleation and the sliding of confined bubbles may be discerned.

This work aims to investigate pool boiling heat transfer enhancement by using nanostructured surfaces. Two types of nanostructured surfaces were employed, gold nanoparticle-coated surfaces and alumina nanoparticle-coated surfaces. The nanostructured surfaces were fabricated by an electrophoretic deposition technique, depositing nanoparticles in a nanofluid onto smooth copper surfaces under an electric field. N-pentane and acetone were tested as working fluids. Compared to the smooth surface, the pool boiling heat transfer coefficient has been increased by 80% for n-pentane and acetone. Possible mechanisms for the enhancement in heat transfer are qualitatively provided. The increase in active nucleation site density due to multiple micro/nanopores on nanoparticle-coated surfaces is likely the main contributor. The critical heat flux on nanostructured surfaces are approximately the same as that on the smooth surface because both smooth and modified surfaces show similar wickability for the two working fluids.

Abstract The present research is an experimental study of “double enhancement” behavior in pool boiling from heater surfaces simulating microelectronic devices immersed in saturated FC-72 at atmospheric pressure. The term “double enhancement” refers to the combination of two different enhancement techniques: a large-scale area enhancement (square pin fin array) and a small-scale surface enhancement (microporous coating). Fin lengths were varied from 0 (flat surface) to 8 mm. Effects of this double enhancement technique on critical heat flux (CHF) and nucleate boiling heat transfer in the horizontal orientation (fins are vertical) are investigated. Results showed significant increases in nucleate boiling heat transfer coefficients with the application of the microporous coating to the heater surfaces. CHF was found to be relatively insensitive to surface microstructure for the finned surfaces except in the case of the surface with 8 mm long fins. The nucleate boiling and CHF behavior has been found to be the result of multiple, counteracting mechanisms: surface area enhancement, fin efficiency, surface microstructure (active nucleation site density), vapor bubble departure resistance, and re-wetting liquid flow resistance.

Bubble departure frequency and active nucleation site density are two main factors that affect the nucleate boiling heat transfer. The potential enhancement of boiling heat transfer can be accomplished by surface modification. This treatment can be realized with changing parameters such as porosity, tilting angle and cavity radius. In this study, effects of different nanostructured Aluminum-Alloy (Al-Alloy) 2024 sheets on subcooled boiling heat transfer are investigated. A simple and environmentally friendly technique is used in order to produce these plates that are immersed into boiling deionized water for 20, 60 and 120 minutes. To examine boiling heat transfer characteristics, nanostructured plates are placed inside a rectangular channel. The channel is heated through four cartridge heaters connected to a DC power supply while deionized water is pumped inside using a micro gear pump at constant mass fluxes of 50 kg/m2s, 75 kg/m2s and 125 kg/m2s. It was found that an increase in nano-structure height leads to higher boiling heat transfer coefficients. Furthermore, a high speed camera system was used to investigate flow patterns in the microchannel. Visualization results indicated that bubbles movde faster the nano-structure height increased.

Review question / Objective: - Does the osseodensification drilling technique increase primary stability in low-density bone? - The aim of the present investigation was to evaluate primary stability in dental implants in people with low density bone using the osseodensification technique. Condition being studied: The replacement of missing teeth through dental implants is currently the most practiced in dental clinics. The main criterion for determining the success of an implant is osseointegration, which is a direct structural and functional connection between vital bone and the prosthetic load-bearing surface of an implant. In the same way, primary stability must be obtained for a good lasting clinical result of the implant and to achieve this purpose, the bone density must be evaluated where the dental implant is to be placed. Salah Huwais in 2013 introduced a new osteotomy procedure (Oseodensification) for site preparation without removal and bone preservation. The Osseodensification process produces an autograft layer around the implant with the osteotomy surface, the autologous bone comes into contact through an endosteal device that accelerates osseointegration due to the nucleation of osteoblasts in the instrumented bone adjacent to the implant and has a greater primary stability due to contact between the device and the bone.