Mechanism Of Particle Formation Research Articles

Study on the mechanism of second phase formation in high-purity fused silica materials for semiconductor application

Gas bubble is a common defect in high-purity fused silica materials, but the formation of the second phase particles related to gas bubble and its mechanism remain unclear till now. In this work, we have presented a method for characterization of colored gas bubbles in high-purity fused silica crucibles for Czochralski silicon by the means of TEM and EDX. Based on it, the origin of the coloring of the gas bubbles is demonstrated to be induced by the gathering of Fe impurity and then, the formation of high-density second phase—ferric oxide (Fe2O3) crystals around the gas bubbles. Moreover, our results provide insight into the formation mechanism of second phase crystals which can be induced by stress field variations around gas bubbles during the cooling process that probably promoted by volume shrinkage effect and increasing solubility of gas from gas bubbles into fused silica substrate. The understanding of the second phase particle formation mechanism in high-purity fused silica materials is valuable for its further controlling.

Mechanism behind the Controlled Generation of Liquid Metal Nanoparticles by Mechanical Agitation.

The size-controlled synthesis of liquid metal nanoparticles is necessary in a variety of applications. Sonication is a common method for breaking down bulk liquid metals into small particles, yet the influence of critical factors such as liquid metal composition has remained elusive. Our study employs high-speed imaging to unravel the mechanism of liquid metal particle formation during mechanical agitation. Gallium-based liquid metals, with and without secondary metals of bismuth, indium, and tin, are analyzed to observe the effect of cavitation and surface eruption during sonication and particle release. The impact of the secondary metal inclusion is investigated on liquid metals' surface tension, solution turbidity, and size distribution of the generated particles. Our work evidences that there is an inverse relationship between the surface tension and the ability of liquid metals to be broken down by sonication. We show that even for 0.22 at. % of bismuth in gallium, the surface tension is significantly decreased from 558 to 417 mN/m (measured in Milli-Q water), resulting in an enhanced particle generation rate: 3.6 times increase in turbidity and ∼43% reduction in the size of particles for bismuth in gallium liquid alloy compared to liquid gallium for the same sonication duration. The effect of particles' size on the photocatalysis of the annealed particles is also presented to show the applicability of the process in a proof-of-concept demonstration. This work contributes to a broader understanding of the synthesis of nanoparticles, with controlled size and characteristics, via mechanical agitation of liquid metals for diverse applications.

Application of fluidized bed homogeneous crystallization for simultaneous recovery of Fe(II) and Cu(II) as particles from wastewater

The mixture of copper and iron often results in materials with favorable properties. The material production processes involving these metals including electroplating produce hazardous wastewater. In this study, the Fluidized Bed Homogeneous Crystallization (FBHC) process was applied to treat iron and copper-containing wastewater. The initial iron copper particles were successfully recovered from synthetic wastewater with [Fe]0:[Cu]0 of 2:1, the total metal concentration of 3 mM, at effluent pH = 7.75 ± 0.75, with the upflow velocity (U) of 1.76 m/h. The agglomerates hardening process is a crucial step for initial particle synthesis. The SEM analysis reveals the spherical particle's densified crust and porous core. The particle formation mechanism which includes the formation of the nucleus, attachment of precipitate flakes, and densification of particles was proposed after microscopic observation. The initial particles synthesized were used to initiate the treatment of synthetic wastewater at the operating condition pH = 7.75 ± 0.5, [Fe]0:[Cu]0 of 2:1, the total metal concentration of 3 mM, [CO32−]0:[M]0 = 1.2:1, and U of 28.66 m/h which results in the total metal removal of 99% and crystallization ratio of 90% and 88% for iron and copper respectively. The conditions were then applied to treat electroplating wastewater and resulted in the total metal removal of 99% for both iron and copper and a crystallization ratio of 83% and 79% for iron and copper, respectively. The treatment provided advantages in terms of treating larger amounts of sludge while eliminating the need to provide seed thus yielding a higher purity of product.

The Processing Space of the Spray-Dried Mannitol-Leucine System for Pulmonary Drug Delivery.

Designing spray-dried particles for inhalation aims at specific physicochemical properties including a respirable aerodynamic diameter and adequate powder dispersibility. Leucine, an amphiphilic amino acid, has been shown to aid in optimizing bulk powder properties. Mannitol, a model crystalline active and common bulking agent, was co-sprayed with leucine at several excipient ratios, ethanol/water ratios, and spray dryer outlet temperatures in order to experimentally probe the underlying particle formation mechanisms in this binary crystalline system. During the droplet drying of two crystallizing components, the material that nucleates first will preferentially enrich the surface. It is desired to have a completely crystalline leucine shell to improve powder properties, however, mannitol competes with leucine for the surface depending on excipient concentration and manufacturing parameters. The resulting particles were studied initially and at a two-month timepoint via solid state characterization, visual analysis, and particle size analysis in order to detect changes in bulk powder properties. It was determined that, similar to systems where only leucine can crystallize, initial leucine saturation in the formulation dictates powder characteristics.

Elucidating the mechanisms of atmospheric new particle formation in the highly polluted Po Valley, Italy

Abstract. New particle formation (NPF) is a major source of aerosol particles and cloud condensation nuclei in the troposphere, playing an important role in both air quality and climate. Frequent NPF events have been observed in heavily polluted urban environments, contributing to the aerosol number concentration by a significant amount. The Po Valley region in northern Italy has been characterized as a hotspot for high aerosol loadings and frequent NPF events in southern Europe. However, the mechanisms of NPF and growth in this region are not completely understood. In this study, we conducted a continuous 2-month measurement campaign with state-of-the-art instruments to elucidate the NPF and growth mechanisms in northern Italy. Our results demonstrate that frequent NPF events (66 % of all days during the measurement campaign) are primarily driven by abundant sulfuric acid (8.5×106 cm−3) and basic molecules in this area. In contrast, oxygenated organic molecules from the atmospheric oxidation of volatile organic compounds (VOCs) appear to play a minor role in the initial cluster formation but contribute significantly to the consecutive growth process. Regarding alkaline molecules, amines are insufficient to stabilize all sulfuric acid clusters in the Po Valley. Ion cluster measurements and kinetic models suggest that ammonia (10 ppb) must therefore also play a role in the nucleation process. Generally, the high formation rates of sub-2 nm particles (87 cm−3 s−1) and nucleation-mode growth rates (5.1 nm h−1) as well as the relatively low condensational sink (8.9×10-3 s−1) will result in a high survival probability for newly formed particles, making NPF crucial for the springtime aerosol number budget. Our results also indicate that reducing key pollutants, such as SO2, amine and NH3, could help to substantially decrease the particle number concentrations in the Po Valley region.

Spray freeze dried uniform mannitol microspheres

Spray freeze drying is an attractive technology for fabricating pharmaceutical powder, but it is still challenging to tailor the microparticle physical and chemical structure. Herein, a series of uniform mannitol microparticles with controllable morphology and crystal properties were successfully fabricated via a self-developed micro-fluidic jet spray freeze tower. The effects of feed solution composition and freezing temperature on microparticle size, morphology, surface architecture and crystal property were investigated to propose the particle formation mechanism. Freezing temperature showed more apparent effect on the microparticle characteristics with higher solid content (10 and 15 w/w%) in aqueous solution; Whereas the addition of ethanol as a co-solvent had a notable impact on microparticle morphology, concurrently perturbing the crystallization tendencies of mannitol. These results provide new insights for producing spray freeze dried pharmaceutical microparticles.

New Insights on the Formation of Nucleation Mode Particles in a Coastal City Based on a Machine Learning Approach.

Atmospheric particles have profound implications for the global climate and human health. Among them, ultrafine particles dominate in terms of the number concentration and exhibit enhanced toxic effects as a result of their large total surface area. Therefore, understanding the driving factors behind ultrafine particle behavior is crucial. Machine learning (ML) provides a promising approach for handling complex relationships. In this study, three ML models were constructed on the basis of field observations to simulate the particle number concentration of nucleation mode (PNCN). All three models exhibited robust PNCN reproduction (R2 > 0.80), with the random forest (RF) model excelling on the test data (R2 = 0.89). Multiple methods of feature importance analysis revealed that ultraviolet (UV), H2SO4, low-volatility oxygenated organic molecules (LOOMs), temperature, and O3 were the primary factors influencing PNCN. Bivariate partial dependency plots (PDPs) indicated that during nighttime and overcast conditions, the presence of H2SO4 and LOOMs may play a crucial role in influencing PNCN. Additionally, integrating additional detailed information related to emissions or meteorology would further enhance the model performance. This pilot study shows that ML can be a novel approach for simulating atmospheric pollutants and contributes to a better understanding of the formation and growth mechanisms of nucleation mode particles.

Root cause analysis of indentation mark defect on Zn coated steel sheet in continuous galvanizing line

The coated steel industry is growing as demand of corrosion resistant steels are ever increasing in automotive, construction, appliances, and general engineering segments. The surface requirement of the coated steel is becoming more stringent that demands coated surfaces within specified roughness, waviness, reflectance and free from surface defects. The continuous galvanising line number 2 of Tata Steel Limited, Jamshedpur suffers from a chronic surface defect that appears like a scratch mark in the coated steel. The present study deals with the root cause analysis of the defect focussing on the rolls within annealing furnace in CGL#2, Jamshedpur. The roll profile, roll and strip slippage, roll surface compositions (using profilometer, XRF) are studied in detail. Similarly, the steel strip collected from inside the furnace was also studied for the defect orientation, surface composition (using SEM & EDS), trapped particles etc. The mathematical calculation of slippage along with the characterization evidence confirm the formation of defect through a complex mechanism of particle formation due to non-uniform roll profile, followed by particle coagulation and finally formation of the defect on the strip under tension by those particles. Possible operational strategies to eliminate the defect is also outlined.

In situ Investigations of the Formation Mechanism of Metastable γ‐BiPd Nanoparticles in Polyol Reductions

AbstractSynthesizing intermetallic phases containing noble metals often poses a challenge as the melting points of noble metals often exceed the boiling point of bismuth (1560 °C). Reactions in the solid state generally circumvent this issue but are extremely time consuming. A convenient method to overcome these obstacles is the co‐reduction of metal salts in polyols, which can be performed within hours at moderate temperatures and even allows access to metastable phases. However, little attention has been paid to the formation mechanisms of intermetallic particles in polyol reductions. Identifying crucial reaction parameters and finding patterns are key factors to enable targeted syntheses and product design. Here, we chose metastable γ‐BiPd as an example to investigate the formation mechanism from mixtures of metal salts in ethylene glycol and to determine critical factors for phase formation. The reaction was also monitored by in situ X‐ray diffraction using synchrotron radiation. Products, intermediates and solutions were characterized by (in situ) X‐ray diffraction, electron microscopy, and UV‐Vis spectroscopy. In the first step of the reaction, elemental palladium precipitates. Increasing temperature induces the reduction of bismuth cations and the subsequent rapid incorporation of bismuth into the palladium cores, yielding the γ‐BiPd phase.

Particle Formation Mechanism of TiCl4 Hydrolysis to Prepare Nano TiO2

This study utilizes Aspen Plus chemical process simulation software (V11), applies uniform nucleation theory and growth kinetics equations, and explores the particle formation mechanism of TiCl4 hydrolysis to prepare nano TiO2. In the water/ethanol system, the effects of the reaction time, reaction temperature, water addition, pH value, and ethanol amount on the crystal nucleation rate and TiO2 particle distribution (PSD) were studied in detail by adding triethanolamine dropwise and using the Aspen Plus chemical process software simulation calculation method. The calculation results indicate that at room temperature, the formation of TiO2 crystal nuclei mainly occurs in the first 300 s and then enters the growth stage. The reaction was carried out under neutral conditions at room temperature for 4 h in 1 mL TiCl4, 6 mL C6H15NO3, 15 mL H2O, and 30 mL C2H5OH. The maximum number of particles reached 195 mesh per cubic micrometer, and the particle size after crystal nucleus growth was smaller, with a D50 of 6.15 nm. The distribution curve shows a normal distribution, which is basically consistent with the experimental results. When studying various factors, it was found that controlling the reaction time within 60 min and maintaining the reaction temperature at room temperature can reduce the particle size D50 to 2.44 nm. Continuing to adjust the amount of water added, it was found that at 1 mL, D50 decreased again to 0.19 nm. Adjusting the pH value found that maintaining the neutrality did not change the particle size. Continuing to adjust ethanol, it was found that adding an appropriate amount of ethanol promoted nucleation and growth. At 4 mL, the maximum number of particles reached 199 mesh per cubic micrometer, but D50 slightly increased to 0.24 nm.

Investigation of the Particle Formation Mechanism during Coprecipitation of Ni-Rich Hydroxide Precursor for Li-Ion Cathode Active Material

Industrial production of cathode active material (CAM) for lithium-ion batteries is conducted by coprecipitation of a hydroxide (NixCoyMnz(OH)2) precursor (referred to as pCAM) in a stirred tank reactor and subsequent high-temperature calcination of the pCAM with a lithium compound. The physical properties of the resulting CAM are significantly affected by the associated pCAM utilized for synthesis. For an economical manufacturing of pCAM and CAM, the pCAM particle size and sphericity during the coprecipitation reaction must be precisely controlled, requiring an in-depth understanding of the NixCoyMnz(OH)2 particle formation mechanism. Therefore, the development of the secondary particle size and morphology throughout the semi-batch coprecipitation of Ni0.8Co0.1Mn0.1(OH)2 at various stirring speeds was monitored by light scattering and SEM imaging, respectively. A two-stage particle formation mechanism was identified: In the initial seeding phase, irregular-shaped secondary particles agglomerates are formed, which in the subsequent growth phase linearly increase in size with the third root of time, governed by the growth of individual primary particles. Thereby, the degree of turbulence governs the initial agglomerate size and number formed during seeding, which dictates the growth rate and the secondary particle sphericity. Finally, the proposed particle formation mechanism is compared to mechanisms prevailing in the literature.

Understanding the Formation Mechanisms of Silicon Particles from the Thermal Disproportionation of Hydrogen Silsesquioxane.

Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route.

Iron isotopes reveal seasonal variations in the mechanisms for iron-bearing particle and colloid formation in the Lena River catchment, NE Siberia

Large Arctic rivers are an important source of iron (Fe) to the Arctic Ocean, though seasonal variations in the terrestrial source and supply of Fe to the ocean are unknown. To constrain the seasonal variability, we present Fe concentrations and isotopic compositions (δ56Fe) for particulate (>0.22 µm) and colloidal (<0.22 µm–1 kDa) Fe from the Lena River, NE Russia. Samples were collected every month during winter baseflow (September 2012–March 2013) and every 2–3 days before, during and after river ice break-up (May 2015).Iron in particles have isotope ratios lower than crustal values during winter (e.g., δ56FePart = −0.37 ± 0.16‰), and crustal-like values during river ice break-up and spring flood (e.g., δ56FePart = 0.07 ± 0.08‰), indicating a change in the source of particulate Fe between winter and spring flood. Low isotope values are indicative of mineral dissolution, transport of reduced Fe in sub-oxic, ice-covered sub-permafrost groundwaters and near-quantitative precipitation of Fe as particles. Crustal-like isotopic compositions result from the increased supply of detrital particles from riverbank and soil erosion during river ice break-up and flooding. Iron colloids (<0.22 μm) have δ56Fe values that are comparable to or lower than crustal values during winter (e.g., δ56FeCol = −0.08 ± 0.05‰) but similar to or higher than crustal values during spring flood (e.g., δ56FeCol = +0.24 ± 0.11‰). Low δ56Fe ratios for colloidal Fe during winter are consistent with precipitation from isotopically light Fe(II)aq transported in sub-permafrost groundwaters. Higher colloidal δ56Fe ratios during the spring flood indicate that these colloids are supplied from surface soils, where Fe is fractionated via oxidation or organic carbon complexation, similar to during summer. Approximately half of the annual colloidal Fe flux occurs during spring flood while most of the remaining colloidal Fe is supplied during summer months. The total amount of colloidal Fe transported during winter was relatively low. The seasonal variation in colloidal Fe isotope values may be a useful tool to trace the source of colloidal Fe to the Arctic Ocean and monitor future changes in the sources and supply of Fe from the permafrost landscape to the Lena River basin.

Nanosheet Particles with Defect-Free Block Copolymer Structures Driven by Emulsions Containing Crystallizable Surfactants.

Highly anisotropic-shaped particles with well-ordered internal nanostructures have received significant attention due to their unique shape-dependent photonic, rheological, and electronic properties and packing structures. In this work, nanosheet particles with cylindrical block copolymer (BCP) arrays are achieved by utilizing collapsed emulsions as a scaffold for BCP self-assembly. Highly elongated structures with large surface areas are formed by employing crystallizable surfactants that significantly reduce the interfacial tension of BCP emulsions. Subsequently, the stabilized elongated emulsion structures lead to the formation of BCP nanosheets. Specifically, when polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and 1-octadecanol (C18-OH) are co-assembled within an emulsion, C18-OH penetrates the surfactant layer at the emulsion interface, lowering the interfacial tension (i.e., below 1 mN m-1 ) and causing emulsion deformation. In addition, C18-OH crystallization allows for kinetic arrest of the collapsed emulsion shape during solvent evaporation. Consequently, PS-b-PDMS BCPs self-assemble into defect-free structures within nanosheet particles, exhibiting an exceptionally high aspect ratio of over 50. The particle formation mechanism is further investigated by controlling the alkyl chain length of the fatty alcohol. Finally, the coating behavior of nanosheet particles is investigated, revealing that the deposition pattern on a substrate is strongly influenced by the particle's shape anisotropy, thus highlighting their potential for advanced coating applications.

Self-stabilizing performance of γ-oryzanol in oil-in-water emulsions and solid dispersions

The surface activity of γ-oryzanol was evaluated by the pendant drop method (PDM), and its self-stabilizing properties were investigated by high-pressure homogenization (HPH) and solvent displacement method (SDM). Emulsions prepared by HPH were highly unstable due to the poor surface-active character of γ-oryzanol as identified by the PDM. In contrast, solid dispersions fabricated by SDM had comparable particle size to those prepared using Tween 80 (T80) as surfactant, and were stable up to 30 days of storage at 4 °C. The self-stabilizing properties of γ-oryzanol were attributed to the mechanism of spontaneous particle formation in SDM and to the ability of γ-oryzanol molecules to prevent particles aggregation by electrostatic repulsion. The outcome of this study indicates the potential of encapsulating selected bioactive compounds, such as γ-oryzanol, in stable colloidal systems by SDM without adding emulsifier(s), regardless of their surface-active character.

Alternative Local Melting‐Solidification of Suspended Nanoparticles for Heterostructure Formation Enabled by Pulsed Laser Irradiation

AbstractPhase formation by pulsed laser irradiation of suspended nanoparticles has recently been introduced as a promising synthesis technique for heterostructures. The main challenge still lingers regarding the exact mechanism of particle formation due to the non‐equilibrium kinetic by‐products resulting from the localized alternative, fast, high‐temperature nature of the process. Here, the authors analyze the bond breaking/formation of copper or copper (II) interfaces with ethanol during the absorption of pulses for Cu‐CuO‐Cu2O formation applicable as an electrocatalyst in ethanol oxidation fuel cells. This study includes but is not limited to, a comprehensive discussion of the interaction between nano‐laser pulses and suspension for practical control of the synthesis process. The observed exponential and logarithmic changes in the content of heterostructures for the CuO‐ethanol and Cu‐ethanol samples irradiated with different fluences are interpreted as the dominant role of physical and chemical reactions, respectively, during the pulsed laser irradiation of suspensions synthesis. It is also shown that the local interface between dissociated ethanol and the molten sphere is responsible for the oxidative/reductive interactions resulting in the formation of catalytic‐augmented Cu3+ by‐product, thanks to the reactive bond force field molecular dynamics studies confirmed by ab‐initio calculations and experimental observations.

Investigating the Particle Formation Mechanism during Precipitation of Ni-Rich Hydroxide Precursors for Cathode Active Materials for Lithium-Ion Batteries

The industrial production of lithium-nickel-cobalt-manganese-oxides (LiNi x Co y Mn z O2, with x+y+z = 1) as cathode active material (CAM) for lithium-ion batteries is conducted by precipitation of a mixed metal hydroxide (Ni x Co y Mn z (OH)2) precursor (referred to as pCAM) in a stirred tank reactor, followed by a calcination of the pCAM with a lithium compound at elevated temperatures in a roller hearth kiln.1 Thereby, the physical properties of the resulting CAM powders are significantly affected by those of the associated pCAM.2 Independent of the material composition, the fluidity and filterability of pCAM and CAM powders deteriorates drastically with decreasing particle size, with non-uniformity of the particle size distribution, and with a deviation from a spherical particle shape.3,4 However, a fluent form of the pCAM and CAM powders is imperative for their further processing in tonnage quantities during pCAM and CAM manufacturing to prevent clogging of the powders in the technical equipment. As frequent cleaning and/or pulverization of the materials between process steps is cost-intensive, an economical and efficient manufacturing of pCAM and CAM powders requires a precise control of particle size and sphericity, which in turn requires an in-depth knowledge of the pCAM particle formation mechanism during the precipitation reaction.To gain a fundamental mechanistic understanding about the pCAM particle formation mechanism, the development of the secondary particle size and morphology during the semi-batch precipitation of Ni0.8Co0.1Mn0.1(OH)2 at various stirring speeds (between 550 and 1350 rpm) was monitored by light scattering and SEM imaging. The evolution of the volume-based median particle size (d 50) over the course of the run time (t run) at the different stirring speeds is depicted in Figure 1a. The d 50 of initial particles generated after 5 minutes as well as the d 50 after 8.75 h depends inversely on the applied stirring speed. After an initial nucleation time, the analysis in Figure 1b shows that the size of the approximatively spherical particles at a given stirring speed (for constant feed flow rates) increases linearly with respect to the third square root of run time/run time to the power of one third (t run1/3 ). Thus, the course of particle growth in each experiment can be divided into two distinct regimes: i) for t run1/3 < 1.0 (stage I in Figure 1b), the particle size remains essentially constant; ii) after this initial phase, for t run1/3 ≥ 1.0 (stage II in Figure 1b), the d 50 increases perfectly linearly with. It is concluded that during stage I, the seeding phase, an increasing number of particles with a constant size are being generated, since the overall volume of formed solid is increasing. In contrast, in stage II, the growth phase, the continuing precipitation occurs via deposition on already existing particles without any further increase in particle number, reflected by the linear relationship between particle size and t run1/3 .In light of these results, it is further demonstrated by SEM imaging that, during the seeding phase (stage I), irregularly shaped secondary particle agglomerates are formed, which in the subsequent growth phase (stage II) increase in size by growth of individual plate-like shaped primary particles. Moreover, it is shown that, at constant process parameters, the degree of turbulence quantified by the average energy input and the Reynolds number, both depending on the stirring speed, governs the initial agglomerate size formed during seeding. This not only dictates the growth rate, thus the final particle size, but also the ability of particles to become spherical over t run. Finally, a particle formation mechanism is proposed and compared to mechanisms described in the literature. Figure 1

A Double-Emulsion Method for the Fabrication of PLA Single-Hole Hollow Particles

Background: Polymeric hollow particles with a single-hole structure have attracted broad interest due to their combined advantages of a hollow cavity and an opening hole in the shell. Aim: In the past decades, much progress has been made in the fabrication of such particles with various strategies. However, there is a lack of research on the easy fabrication of biodegradable polylactide (PLA) single hole particles (PLA SHHPs). Methods: In this work, we reported a simple double emulsion method for the fabrication of PLA SHHPs. The W/O/W double emulsion was formed by homogenizing PLA chloroform and brilliant blue G (BBG) solution. Scanning electron microscopy and confocal laser scanning microscopy were used for the characterization. It was found that the concentrations of PLA chloroform and BBG solution both had a significant influence on the emulsion structure. Result: PLA SHHPs with a percentage &gt;85% were obtained from the emulsion composed of PLA chloroform (10.0 w%) and BBG solution (4 mM). The particle formation mechanism was also proposed based on the result of the low interfacial tension between PLA chloroform/BBG solution. Conclusion: The results may inspire new development of PLA particles with unique structures, which are promising to be used in drug delivery, catalysis, microreaction and micromotors.

Interfacial Adsorption Controls Particle Formation in Antibody Formulations Subjected to Extensional Flows and Hydrodynamic Shear

During their manufacturing and delivery to patients, therapeutic proteins are commonly exposed to various interfaces and to hydrodynamic shear forces. Although adsorption of proteins to solid–liquid interfaces is known to foster formation of protein aggregates and particles, the impact of shear remains controversial, in part because of experimental challenges in separating the effects of shear from those caused by simultaneous exposure to interfaces. Extensional flows (occurring when solutions flow through sudden contractions) exert localized elongational forces that have been suspected to be damaging to proteins. In this work, we measured aggregation and particle formation in formulations of polyclonal and monoclonal antibodies subjected to extensional flow, high shear (105 s−1) and exposure to stainless-steel/water interfaces. Modification of the surface charge at the stainless steel/water interface changed protein adsorption characteristics without altering shear profiles, enabling shear and interfacial interactions to be separated. Even under conditions where antibodies were subjected to high hydrodynamic shear and extensional flow, production of subvisible particles could be inhibited by modifying the stainless-steel surface charge to minimize antibody adsorption. Digital images of particles recorded by flow imaging microscopy (FIM) and analyzed with machine learning algorithms were consistent with a particle formation mechanism by which antibodies adsorb and aggregate at the stainless-steel/water interface and subsequently form particles when shear displaces the interfacial aggregates, transporting them into the bulk solution. Topographical differences measured using atomic force microscopy (AFM) supported the proposed mechanism by showing reduced levels of protein adsorption on surface-charge-modified stainless-steel.

Cellulose nanocrystal/polymer nanocomposite latex via surfactant-free emulsion polymerization

Polar cellulose nanocrystals (CNCs) are difficult to disperse well in hydrophobic polymer matrices, and usually surfactants or expensive and time-consuming functionalization of the reinforcement or matrix have been attempted to improve dispersion. Here, we report a new, facile method to prepare CNC/polymer nanocomposite latices directly via surfactant-free emulsion polymerization of vinyl monomers and CNCs initiated by a cationic, water-soluble, free-radical initiator. The distribution of CNCs in the latex particles can be tailored through controlling the reaction procedures, namely, whether the monomers are added before or after preheating the CNCs with the initiator and has been confirmed by scanning electron microscopy (SEM) and scanning transmission X-ray microscopy (STXM) studies. CNCs distribute inside the latex particles if the monomers are added after the preheating step, and owing to the more even distribution of CNCs, such nanocomposite latices exhibit better mechanical properties than those prepared without preheating or via physically mixing CNCs with emulsions polymerized using conventional surfactant system. A latex particle formation mechanism is proposed based on these phenomena and polymerization kinetics studied in this work. Unlike typical CNC-based Pickering emulsion polymerization, our process can be operated without the need for intense mechanical shearing and provide an industrially scalable approach to prepare stable CNC/polymer nanocomposite latices that can be melt processed or used directly in a variety of applications, such as paints and coatings, adhesives, or cosmetics.