Nucleation Rate Of Particles Research Articles

The Pivotal Role of Heavy Terpenes and Anthropogenic Interactions in New Particle Formation on the Southeastern Qinghai-Tibet Plateau.

Aerosol particles originating from the Qinghai-Tibet Plateau (QTP) readily reach the free troposphere, potentially affecting global radiation and climate. Although new particle formation (NPF) is frequently observed at such high altitudes, its precursors and their underlying chemistry remain poorly understood. This study presents direct observational evidence of anthropogenic influences on biogenic NPF on the southeastern QTP, near the Himalayas. The mean particle nucleation rate (J1.7) is 2.6 cm-3 s-1, exceeding the kinetic limit of sulfuric acid (SA) nucleation (mean SA: 2.4 × 105 cm-3). NPF is predominantly driven by highly oxygenated organic molecules (HOMs), possibly facilitated by low SA levels. We identified 1538 ultralow-volatility HOMs driving particle nucleation and 764 extremely low-volatility HOMs powering initial particle growth, with mean total concentrations of 1.5 × 106 and 3.7 × 106 cm-3, respectively. These HOMs are formed by atmospheric oxidation of biogenic precursors, unexpectedly including sesquiterpenes and diterpenes alongside the commonly recognized monoterpenes. Counterintuitively, over half of HOMs are organic nitrates, mainly produced by interacting with anthropogenic NOx via RO2+NO terminations or NO3-initiated oxidations. These findings advance our understanding of NPF mechanisms in this climate-sensitive region and underscore the importance of heavy terpene and NOx-influenced chemistry in assessing anthropogenic-biogenic interactions with climate feedbacks.

Rapid Nucleation and Growth of Indoor Atmospheric Nanocluster Aerosol during the Use of Scented Volatile Chemical Products in Residential Buildings.

Scented volatile chemical products (sVCPs) are frequently used indoors. We conducted field measurements in a residential building to investigate new particle formation (NPF) from sVCP emissions. State-of-the-art instrumentation was used for real-time monitoring of indoor atmospheric nanocluster aerosol (NCA; 1-3 nm particles) size distributions and terpene mixing ratios. We integrated our NCA measurements with a comprehensive material balance model to analyze sVCP-nucleated indoor NCA dynamics. Our results reveal that sVCPs significantly increase indoor terpene mixing ratios (10-1,000 ppb), exceeding those in outdoor forested environments. The emitted terpenes react with indoor atmospheric O3 and initiate indoor NPF, resulting in nucleation rates as high as ∼105 cm-3 s-1 and condensational growth rates up to 300 nm h-1; these are orders of magnitude higher than those reported during outdoor NPF events. Notably, high particle nucleation rates significantly increase indoor atmospheric NCA concentrations (105-108 cm-3), and high growth rates drive their survival and growth to sizes that efficiently reach the deepest regions of the human respiratory system. We found sVCP-nucleated NCA to cause respiratory exposures and dose rates comparable to or exceeding those from primary aerosol sources such as gas stoves and diesel engines, highlighting their significant impact on indoor atmospheric environments.

Effect of Dropping Speed of Reducing Agent on the Preparation of LA/Ag Phase-Change Nanocapsules

Lauric Acid (LA) phase-change nanocapsules prepared with silver as the shell exhibit excellent energy storage capacity and high thermal conductivity. Still, their functionality could be improved by ensuring uniform morphologies, even the size and thickness of silver particles. In this study, the LA/Ag nanocapsules were prepared under different reductant drop speeds. By adjusting the droplet speed of the reducing agent, the concentration of silver in the solution can be controlled, which affects the nucleation and growth rate of silver particles, thereby influencing the deposition of silver particles on the surface of the core material. The characterization results indicate the successful preparation of high sphericity and uniform-sized LA/Ag nanocapsules. The average diameter of capsules was 117–140 nm, the latent heat was 43.69–47.78 J/g, and the encapsulation efficiency was 80.69–82.53%. As the droplet speed increased, the thickness of the silver shell increased while the encapsulation efficiency decreased. The highest encapsulation efficiency was achieved when the reducing agent dropping speed was 0.03 mL/s.

Sulfuric Acid Nucleation Potential Model Applied to Complex Reacting Systems in the Atmosphere

AbstractAtmospheric aerosol particles impact Earth's radiation balance by acting as seeds for cloud droplet formation. Over half of global cloud seed particles are formed by nucleation, a process where gas‐phase compounds react to form stable particles. Reactions of sulfuric acid (SA) with a wide variety of atmospheric compounds have been previously shown to drive nucleation in the lower troposphere. However, global climate models poorly predict particle nucleation rates since current nucleation models do not describe nucleation for systems containing tens to hundreds of precursor compounds. The nucleation potential model (NPM) was recently developed to model SA nucleation of complex mixtures by measuring an effective base concentration using a 1‐nm condensation particle counter. This technique for estimating particle nucleation rates can be deployed at a much higher spatial and temporal resolution than current methods which require detailed knowledge of all nucleation reactions and measurements, typically using a mass spectrometer, of all nucleation precursor gases. This work expands NPM by showing that this model can capture enhancement and suppression of SA nucleation rates within a complex mixture of organic and inorganic acids, ambient air, and across a range of atmospherically relevant relative humidities. In addition, an expression for calculating atmospheric nucleation rates was also derived from the NPM. Ultimately, NPM provides a simple way to measure and model the extent compounds in a complex mixture enhance SA nucleation rates using a condensation particle counter.

Measurement Report: Wintertime new particle formation in the rural area of the North China Plain – influencing factors and possible formation mechanism

Abstract. The high concentration of fine particles and gaseous pollutants makes polluted areas, such as the urban setting of North China Plain (NCP) of China, a different environment for new particle formation (NPF) compared to many clean regions. Such conditions also hold for other polluted environments in this region (for instance, the rural area of NCP), yet the underlying mechanisms for NPF remain less understood, owing to the limited observations of particles in the sub−3 nm range. Comprehensive measurements, particularly covering the particle number size distribution down to 1.3 nm, were conducted at a rural background site of Gucheng (GC) in the North China Plain (NCP) from 12 November to 24 December 2018. In total, five NPF events during the 39 effective days of measurements for the campaign were identified, with the mean particle nucleation rate (J1.3) and growth rate (GR1.3–2.4) being 22.0 cm−3 s−1 and 3.9 nm h−1, respectively. During these 5 d, NPF concurrently occurred at an urban site in Beijing. Sharing similar sources and transport paths of air masses arriving at our site to that of urban Beijing, we hypothesize that NPF events during these days in this region might be a regional phenomenon. The simultaneous occurrence of NPF in both places implies that H2SO4-amine nucleation, concluded for urban Beijing there, could probably be the dominating mechanism for NPF at our rural site. The higher concentration of sulfuric acid during many non-event days compared to that of event days indicates that the content of sulfuric acid may not necessarily lead to NPF events under current atmosphere. Only when the condensation sink or coagulation sink was significantly lowered, atmospheric NPF occurred, implying that condensation sinks (CSs) and coagulation sinks (CoagSs) are the dominating factors controlling the occurrence of NPF for the present rural environment of the NCP, which is quite similar to the feature seen in urban Beijing.

Kinetically and thermodynamically controlled one-pot growth of gold nanoshells with NIR-II absorption for multimodal imaging-guided photothermal therapy

Since the successful clinical trial of AuroShell for photothermal therapy, there is currently intense interest in developing gold-based core-shell structures with near-infrared (NIR) absorption ranging from NIR-I (650–900 nm) to NIR-II (900–1700 nm). Here, we propose a seed-mediated successive growth approach to produce gold nanoshells on the surface of the nanoscale metal–organic framework (NMOF) of UiO-66-NH2 (UiO = the University of Oslo) in one pot. The key to this strategy is to modulate the proportion of the formaldehyde (reductant) and its regulator / oxidative product of formic acid to harness the particle nucleation and growth rate within the same system. The gold nanoshells propagate through a well-oriented and controllable diffusion growth pattern (points → facets → octahedron), which has not been identified. Most strikingly, the gold nanoshells prepared hereby exhibit an exceedingly broad and strong absorption in NIR-II with a peak beyond 1300 nm and outstanding photothermal conversion efficiency of 74.0%. Owing to such superior performance, these gold nanoshells show promising outcomes in photoacoustic (PA), computed tomography (CT), and photothermal imaging-guided photothermal therapy (PTT) for breast cancer, as demonstrated both in vitro and in vivo.

Role of Methanesulfonic Acid in Sulfuric Acid-Amine and Ammonia New Particle Formation.

Aerosol nucleation accounts for over half of all seed particles for cloud droplet formation. In the atmosphere, sulfuric acid (SA) nucleates with ammonia, amines, oxidized organics, and many more compounds to form particles. Studies have also shown that methanesulfonic acid (MSA) nucleates independently with amines and ammonia. MSA and SA are produced simultaneously via dimethyl sulfide oxidation in the marine atmosphere. However, limited knowledge exists on how MSA and SA nucleate together in the presence of various atmospherically relevant base compounds, which is critical to predicting marine nucleation rates accurately. This work provides experimental evidence that SA and MSA react to form particles with amines and that the SA-MSA-base nucleation has different reaction pathways than SA-base nucleation. Specifically, the formation of the SA-MSA heterodimer creates more energetically favorable pathways for SA-MSA-methylamine nucleation and an enhancement of nucleation rates. However, SA-trimethylamine nucleation is suppressed by MSA, likely due to the steric hindrance of the MSA and trimethylamine. These results display the importance of including nucleation reactions between SA, MSA, and various amines to predict particle nucleation rates in the marine atmosphere.

Effect of electropulsing treatment on the precipitation behavior of MnS in sulfur-containing microalloyed 49MnVS3 steel

An experimental investigation has been conducted with respect to the influence of electropulsing treatment (EPT) on the 2D and 3D morphologies, distribution, number and size of MnS precipitates in the high-sulfur micro-alloyed 49MnVS3 steel. After the application of electric current pulse with a peak pulsed voltage of 30 V, the microstructure was refined due to the increasing nucleation rate of particles in liquid steel. Moreover, compared with the untreated steel with spherical MnS randomly distributed in the matrix, the MnS precipitates moved directionally to aggregate on the bottom and top surfaces of the ingot in order to minimize the free energy of the system in case of EPT. For untreated steel samples, the number of MnS was 409 (bottom), 579 (middle) and 437 (top), while that of the treated samples were 226 (bottom), 38 (middle) and 224 (top) in the scanning area of 2.65 × 107 µm2 with ASPEX. The number of MnS with small size decreased while the large-size MnS increased with the application of EPT.

Hygroscopicity and CCN potential of DMS-derived aerosol particles

Abstract. Dimethyl sulfide (DMS) is emitted by phytoplankton species in the oceans and constitutes the largest source of naturally emitted sulfur to the atmosphere. The climate impact of secondary particles, formed through the oxidation of DMS by hydroxyl radicals, is still elusive. This study investigates the hygroscopicity and cloud condensation nuclei activity of such particles and discusses the results in relation to their chemical composition. We show that mean hygroscopicity parameters, κ, during an experiment for particles of 80 nm in diameter range from 0.46 to 0.52 or higher, as measured at both sub- and supersaturated water vapour conditions. Ageing of the particles leads to an increase in κ from, for example, 0.50 to 0.58 over the course of 3 h (Exp. 7). Aerosol mass spectrometer measurements from this study indicate that this change most probably stems from a change in chemical composition leading to slightly higher fractions of ammonium sulfate compared to methanesulfonic acid (MSA) within the particles with ageing time. Lowering the temperature to 258 K increases κ slightly, particularly for small particles. These κ values are well comparable to previously reported model values for MSA or mixtures between MSA and ammonium sulfate. Particle nucleation and growth rates suggest a clear temperature dependence, with slower rates at cold temperatures. Quantum chemical calculations show that gas-phase MSA clusters are predominantly not hydrated, even at high humidity conditions, indicating that their gas-phase chemistry should be independent of relative humidity.

Investigation of Operation Strategy Based on Solution pH for Improving the Crystal Quality Formed during Reactive Crystallization of l-Aspartic Acid.

The production of crystalline particles with a thick and low degree of agglomeration is required because the agglomerated crystals with thin primary particles, which are frequently formed during reactive crystallization, deteriorate the crystal size distribution (CSD) of the final product due to their fragile morphology. This study aimed to develop an operation strategy for improving the degree of agglomeration and thickness of crystalline particles in the reactive crystallization considering the effect of the solution pH using l-aspartic acid as an experimental system. The scanning electron microscopy observations showed that the thickness of primary particles which form agglomerated crystals could be increased by operating the crystallization under low solution pH conditions. In contrast, it was found that operating the crystallization under high solution pH led to a decrease in the nucleation rate of crystalline particles, which resulted in a decrease in the degree of agglomeration. Then, an operation method, that is, changing the addition method of feed solutions to overcome the trade-off between the thickness and degree of agglomeration, was proposed by considering the effect of solution pH. Consequently, crystalline particles with a narrow CSD could be successfully obtained using the proposed method due to the suppression of the agglomeration and increase of the thickness. Therefore, the development of the operation strategy based on the effect of the solution pH on the degree of agglomeration and thickness is important to produce crystalline particles with improved CSD in reactive crystallization.

Role of iodine oxoacids in atmospheric aerosol nucleation.

Iodic acid (HIO3) is known to form aerosol particles in coastal marine regions, but predicted nucleation and growth rates are lacking. Using the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber, we find that the nucleation rates of HIO3 particles are rapid, even exceeding sulfuric acid-ammonia rates under similar conditions. We also find that ion-induced nucleation involves IO3 - and the sequential addition of HIO3 and that it proceeds at the kinetic limit below +10°C. In contrast, neutral nucleation involves the repeated sequential addition of iodous acid (HIO2) followed by HIO3, showing that HIO2 plays a key stabilizing role. Freshly formed particles are composed almost entirely of HIO3, which drives rapid particle growth at the kinetic limit. Our measurements indicate that iodine oxoacid particle formation can compete with sulfuric acid in pristine regions of the atmosphere.

Ultrasonic-assisted production of precipitated calcium carbonate particles from desulfurization gypsum

This study aimed to investigate the effect of ultrasonic application on the production of precipitated calcium carbonate (PCC) particles from desulfurization gypsum via direct mineral carbonation method using conventional and venturi tube reactors in the presence of different alkali sources (NaOH, KOH and NH4OH). The venturi tube was designed to determine the effect of ultrasonication on PCC production. Ultrasonic application was performed three times (before, during, and after PCC production) to evaluate its exact effect on the properties of the PCC particles. Scanning electron microscope (SEM), X-ray diffraction (XRD), Atomic force microscope (AFM), specific surface area (SSA), Fourier transform infrared spectrometry (FTIR), and particle size analyses were performed. Results revealed the strong influence of the reactor types on the nucleation rate of PCC particles. The presence of Na+ or K+ ions in the production resulted in producing PCC particles containing only calcite crystals, while a mixture of vaterite and calcite crystals was observed if NH4+ ions were present. The use of ultrasonic power during PCC production resulted in producing cubic calcite rather than vaterite crystals in the presence of all ions. It was determined that ultrasonic power should be conducted in the venturi tube before PCC production to obtain PCC particles with superior properties (uniform particle size, nanosized crystals, and high SSA value). The resulting PCC particles in this study can be suitably used in paint, paper, and plastic industries according to the ASTM standards.

Ultrasonic refining mechanism of ternary phase in Al–Sc based alloys prepared through molten salt electrolysis

Aluminum alloys are widely used in cutting-edge technologies and emerging strategic industries, namely aerospace, high-speed rail transportation, electric vehicles, advanced functional materials, new energy storage, and conversion devices. The processability as well as the mechanical properties of aluminum alloys can be improved via the addition of trace scandium. The ultrasonically assisted molten salt electrolysis is a promising, short technical route for large-scale preparation of low-cost, Al–Sc-based alloys characterized by uniform and fine strengthening phases. At present, it is still unclear if that is the case for the ultrasonic refining mechanism of the Sc-bearing ternary phase. This study aims at clarifying the ultrasonic refining mechanism on the strengthening phase containing scandium. Two Al–Sc based alloys were prepared using ultrasonically assisted molten salt electrolysis while the effect of ultrasound on the morphology and size of the Sc-bearing ternary phase was studied using optical microscope, scanning electron microscope, and X-ray diffraction meter. The results show that the synergetic ultrasound facilitates the transformation of the ternary AlSiSc phase from the coarse rhombic tubes (~205 μm) to the short rod (40 μm). The cluster size of ternary AlCuSc phase is also greatly reduced from ~100 μm to ~30 μm. The ultrasonic refining mechanism is mainly related to the increase of the nucleation rate of the primary Al3Sc particles which are greatly refined and dispersed in the alloy melt before the solidification stage. The refinement of the Sc-bearing ternary phase is considered to be caused by the fine and disperse Al3Sc particles serving as nuclei. Furthermore, ultrasound can also aid the uniform distribution of solute field and prevent the precipitation of coarse Al3Sc phase. The effect of ultrasonic refinement of the ternary rhenium-containing phase is mainly present at the solidification stage after electrolysis.

LiYF4:Yb/LiYF4 and LiYF4:Yb,Er/LiYF4 core/shell nanocrystals with luminescence decay times similar to YLF laser crystals and the upconversion quantum yield of the Yb,Er doped nanocrystals

We developed a procedure to prepare luminescent LiYF4:Yb/LiYF4 and LiYF4:Yb,Er/LiYF4 core/shell nanocrystals with a size of approximately 40 nm revealing luminescence decay times of the dopant ions that approach those of high-quality laser crystals of LiYF4:Yb (Yb:YLF) and LiYF4:Yb,Er (Yb,Er:YLF) with identical doping concentrations. As the luminescence decay times of Yb3+ and Er3+ are known to be very sensitive to the presence of quenchers, the long decay times of the core/shell nanocrystals indicate a very low number of defects in the core particles and at the core/shell interfaces. This improvement in the performance was achieved by introducing two important modifications in the commonly used oleic acid based synthesis. First, the shell was prepared via a newly developed method characterized by a very low nucleation rate for particles of pure LiYF4 shell material. Second, anhydrous acetates were used as precursors and additional drying steps were applied to reduce the incorporation of OH− in the crystal lattice, known to quench the emission of Yb3+ ions. Excitation power density (P)-dependent absolute measurements of the upconversion luminescence quantum yield (ΦUC) of LiYF4:Yb,Er/LiYF4 core/shell particles reveal a maximum value of 1.25% at P of 180 Wcm−2. Although lower than the values reported for NaYF4:18%Yb,2%Er core/shell nanocrystals with comparable sizes, these ΦUC values are the highest reported so far for LiYF4:18%Yb,2%Er/LiYF4 nanocrystals without additional dopants. Further improvements may nevertheless be possible by optimizing the dopant concentrations in the LiYF4 nanocrystals.

Synthesis of composite powders composed of silver and carbon nanotubes by liquid-phase reduction method

A successful synthesis of composite powders composed of both silver (Ag) particles and multi walled carbon nanotubes (MWCNTs) by liquid-phase reduction methods is reported. Based on previous work on electroless deposition of Ag on MWCNTs and the mixing technique called “modified molecular level mixing”, the novel procedure strongly controls the amount of individualized MWCNTs in the Ag/MWCNTs composite powders with a mass fraction of MWCNTs between 0 and 0.6 wt%.The results show that temperature and the concentration of the reducing agent have a significant impact on the growth of the Ag particles while the MWCNTs concentration influences the nucleation rate of Ag particles during synthesis of Ag/MWCNTs composite powders. Thermogravimetric analysis of the powder synthesized also show a catalytic effect of Ag particles on the oxidation of MWCNTs.

CRI-HOM: A novel chemical mechanism for simulating highly oxygenated organic molecules (HOMs) in global chemistry–aerosol–climate models

Abstract. We present here results from a new mechanism, CRI-HOM, which we have developed to simulate the formation of highly oxygenated organic molecules (HOMs) from the gas-phase oxidation of α-pinene, one of the most widely emitted biogenic volatile organic compounds (BVOCs) by mass. This concise scheme adds 12 species and 66 reactions to the Common Representative Intermediates (CRI) mechanism v2.2 Reduction 5 and enables the representation of semi-explicit HOM treatment suitable for long-term global chemistry–aerosol–climate modelling, within a comprehensive tropospheric chemical mechanism. The key features of the new mechanism are (i) representation of the autoxidation of peroxy radicals from the hydroxyl radical and ozone initiated reactions of α-pinene, (ii) formation of multiple generations of peroxy radicals, (iii) formation of accretion products (dimers), and (iv) isoprene-driven suppression of accretion product formation, as observed in experiments. The mechanism has been constructed through optimisation against a series of flow tube laboratory experiments. The mechanism predicts a HOM yield of 2 %–4.5 % under conditions of low to moderate NOx, in line with experimental observations, and reproduces qualitatively the decline in HOM yield and concentration at higher NOx levels. The mechanism gives a HOM yield that also increases with temperature, in line with observations, and our mechanism compares favourably to some of the limited observations of [HOM] observed in the boreal forest in Finland and in the southeast USA. The reproduction of isoprene-driven suppression of HOMs is a key step forward as it enables global climate models to capture the interaction between the major BVOC species, along with the potential climatic feedbacks. This suppression is demonstrated when the mechanism is used to simulate atmospheric profiles over the boreal forest and rainforest; different isoprene concentrations result in different [HOM] distributions, illustrating the importance of BVOC interactions in atmospheric composition and climate. Finally particle nucleation rates calculated from [HOM] in present-day and pre-industrial atmospheres suggest that “sulfuric-acid-free” nucleation can compete effectively with other nucleation pathways in the boreal forest, particularly in the pre-industrial period, with important implications for the aerosol budget and radiative forcing.

Energy efficient and cost effective method for generation of in-situ silver nanofluids: Formation, morphology and thermal properties

In the present work, silver nanoparticles (AgNPs) are generated using the Micro-Electro Discharge Machining process (micro-EDM). Nanofluids are synthesised in dielectric fluids such as polar fluid like Deionized water (DI), Deionized water with 4 wt% of Poly-Vinyl Alcohol (DI + PVA), and non-polar fluids like Ethylene Glycol (EG) and Kerosene (KR). Low energy consumption, in-situ nanofluid synthesis, cleaner work environment, non-essential chemical post-processing during the synthesis using micro-EDM are the significant reasons creating broad scope for this process exploration. To understand the process, theoretical approach is explored to study the effect of dielectric fluids on particle formation mechanism, critical radius and nucleation rate of nanoparticles. In the experimental approach, silver nanoparticles are generated and characterized for the particle concentration, morphology and size distributions in all four dielectric fluids. High Resolution Scanning Electron Microscopy (HRSEM), Dynamic Light Scattering (DLS), and UV–Visible spectroscopy (UV–Vis) are used for the study. Nanofluid's decomposition temperatures and latent heat of vaporization are investigated using ThermoGravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC), respectively. Particles generated in DI + PVA fluid found to be smaller mean size of (30.06 ± 1.12) nm followed KR fluid of (40.32 ± 1.29) nm, EG fluid of (47.85 ± 1.24) nm, and in DI fluid of (149.04 ± 1.93) nm. Also polar liquids yielded wider and non-polar liquids yielded narrower particle distribution. KR nanofluid is thermally stable followed by DI + PVA, DI, and EG nanofluid. With the spark energy of 1.15 mJ, the in-house developed micro-EDM process yielded highest nanoparticles concentration of 2.68 g/L in KR fluid followed by DI + PVA fluid of 2.13 g/L, DI fluid of 2.09 g/L and least by EG fluid of 1.04 g/L.

Study into the effect of sodium lignosulfonate, anionic surfactants and their mixtures on the rate of copper ion cementation by zinc

The article focuses on the effect of sodium lignosulfonate (LS), anionic surfactants (sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate (SDBS)), and their mixtures on the rate of copper cementation by zinc. The results obtained demonstrate a decrease in copper cementation rate with the increasing LS and SDBS concentrations. There was also excessive zinc consumption for copper ion cementation noted due to LS and SDBS anion adsorption on positively charged zinc cathodic areas of the cementing agent and the precipitate. This led to a decrease in the rate of copper particle nucleation, energy consumption for forming new copper nucleation centers, and conditions for hydrogen overpotential reduction. In addition, rising temperature led to a decrease in zinc consumption in the presence of LS. Surfactants under investigation may be ranked by the negative impact on copper ion cementation in an ascending order as follows: SDS < SDBS < LS. LS + SDS mixture testing showed its irregular effect on copper cementation rate at test temperatures. Experiments with LS and SDBS mixtures demonstrated a linear decrease in copper ion cementation rate with increasing SDBS concentration and simultaneously rising zinc consumption. Due to the negative impact of investigated reagents discovered, we proposed a method for removing organic impurities from solutions using multilayered aluminosilicates modified by cationic surfactants. The results obtained indicate the high effectiveness of organic impurity removal from solutions providing for a 50 % increase in cementation rate in the presence of LS + SDBS mixture together with a decrease in zinc consumption.

Peering into the Formation of Cerium Oxide Colloidal Particles in Solution by In Situ Small-Angle X-ray Scattering.

The formation of CeO2 colloidal particles upon heating an aqueous solution of (NH4)2Ce(NO3)6 to 100 °C was investigated by time-resolved in situ SAXS analysis using synchrotron radiation, providing absolute intensity data. In particular, the experiments were performed by applying different temperatures between room temperature and 100 °C as well as under variation of the ionic strength and concentration. Using validated SAXS evaluation tools (SASfit and McSAS software), the analyses revealed the presence of two types of particle populations possessing average dimensions of ca. 2 nm and 5-15 nm, with the latter being agglomerates of the 2 nm particles rather than single crystallites. The analysis revealed not only the changes in the size, but also the relative volume fractions of these two CeO2 particle populations as a function of the aforementioned parameters. Increasing the temperature increases the number of the 5-15 nm agglomerates on one hand by the enhanced nucleation rate of the primary particles. On the other hand, especially at high temperatures (90 and 100 °C) the larger agglomerate particles precipitate, resulting in interesting trends in the fractions of the two populations as a function of time, temperature, ionic strength, and precursor concentration. The experimental studies are complemented by calculating colloidal interaction energies based on classical DLVO theory. Thereby, this study provides detailed insight into the nucleation, growth, and agglomeration of CeO2 nanoparticles. The primary objective of this study is to provide a better understanding of the nucleation and growth of particles by the hydrolysis of the tetravalent cerium ion in aqueous solutions.

Towards a controllability analysis of multiscale systems: Application of the set-theoretic approach to a semi-batch emulsion polymerization process

This work presents a framework to evaluating the controllability of multiscale systems based on a set-theoretic approach. Calculation of the Controllable Trajectories Set is the core of the set-theoretic approach. From a multi-scale perspective, such calculation is a computationally- intractable problem. Therefore, to overcome the intrinsic curse of dimensionality of the problem, Variance Algebra concepts and a statistical modeling approach are combined to obtain a closed-form allowing to perform an output-controllability analysis for a multiscale system. A semi-batch emulsion polymerization process is adopted as a case study. Results have shown that both, the final Particle Size Distribution (mesoscopic variable) and the secondary particle nucleation rate (microscopic variable) are output-controllable. Evaluating the controllability of lower-scale variables (i.e. below macroscopic) could mitigate the dependency of the current control strategies of on-line measurements at the lower scales as well as help to better understand the process capabilities of achieving the desired product quality specifications.