The modelling of the toughening of epoxy polymers via silica nanoparticles: The effects of volume fraction and particle size

Silica nanoparticles possessing three different diameters (23, 74 and 170 nm) were used to modify a piperidine-cured epoxy polymer. Fracture tests were performed and values of the toughness increased steadily as the concentration of silica nanoparticles was increased. However, no significant effects of particle size were found on the measured value of toughness. The toughening mechanisms were identified as (i) the formation of localised shear-band yielding in the epoxy matrix polymer which is initiated by the silica nanoparticles, and (ii) debonding of the silica nanoparticles followed by plastic void growth of the epoxy matrix polymer. These mechanisms, and hence the toughness of the epoxy polymers containing the silica nanoparticles, were modelled using the Hsieh et al. approach (Polymer 51, 2010, 6284–6294). However, it is noteworthy that previous modelling work has required the volume fraction of debonded silica particles to be measured from the fracture surfaces but in the present paper a new and more fundamental approach has been proposed. Here finite-element modelling has demonstrated that once one silica nanoparticle debonds then its nearest neighbours are shielded from the applied stress field, and hence may not debond. Statistical analysis showed that, for a good, i.e. random, dispersion of nanoparticles, each nanoparticle has six nearest neighbours, so only one in seven particles would be predicted to debond. This approach therefore predicts that only 14.3% of the nanoparticles present will debond, and this value is in excellent agreement with the value of 10–15% of those nanoparticles present debonding which was recorded via direct observations of the fracture surfaces. Further, this value of about 15% of silica nanoparticles particles present debonding has also been noted in other published studies, but has never been previously explained. The predictions from the modelling studies of the toughness of the various epoxy polymers containing the silica nanoparticles were compared with the measured fracture energies and the agreement was found to be good.     

Synthesis of ZrO2 nanoparticles and effect of surfactant on dispersion and stability

This work investigates the stability of dispersions of zirconium oxide nanoparticles, synthesized by the sol-gel method, with zirconium isopropoxide precursors. Nanofluids at concentrations of 0.1 wt% were prepared by dispersing the synthesized nanoparticles in deionized water. Anionic sodium dodecylbenzene sulfonate (SDBS), cationic cetyltrimethylammonium bromide (CTAB), and non-ionic polyvinyl pyrrolidone (PVP) at concentrations of 0.01 wt%, 0.03 wt%, and 0.05 wt% were used for nanoparticle dispersion. Stability was analyzed by means of dynamic light scattering (DLS), zeta potential, pH, visual inspection, and UV–vis. Transmission electron microcopy (TEM) images revealed particles with a size of 59.9 ± 13.5 nm, and x-ray diffraction (XRD) showed crystalline materials. The results of sedimentation, hydrodynamic radius, and absorbance indicate that the presence of surfactants reduces agglomeration and improves the stability of nanofluids over time. The non-ionic surfactant, PVP, produced a better effect on the hydrodynamic radius than its ionic counterparts (SDBS and CTAB). In addition, the type of surfactant was found to have a significant effect on the pH, zeta potential, and isoelectric point of the ZrO₂ nanoparticles. Finally, the stability analysis revealed that stable nanofluids with a final concentration of 0.01 wt% of particles can be obtained after 20 days, demonstrating the potential of such nanofluids for heat transfer applications.     

Modeling of ultrafine particle dispersion in indoor environments with an improved drift flux model

Ultrafine particle (sub-100 nm in diameter) can transport toxic chemicals into the human respiratory system, causing more damage to macrophage phagocytosis than micron particles do. Therefore, various computational fluid dynamics (CFD) models have been developed to help understand the transport and dispersion of these particles in indoor environments. This study is focused on an improved drift flux model that incorporates not only the effect of gravitational settling but also other mechanisms. After an experimental validation of the improved model, it was used to analyze the dispersion of different sizes of ultrafine particles in two typical types of indoor environments (mixing and displacement ventilation). It was found that mixing ventilation had higher concentrations of ultrafine particles than displacement ventilation in the zone below 1 meter, and this finding is different from micron range particles. In addition, both ventilation modes were insensitive to the particles in the range of 0.01–0.1 μm in diameter.     

Low-temperature synthesis of redispersible iron oxide nanoparticles under atmospheric pressure and ultradense reagent concentration

Highly dispersed α-Fe₂O₃ nanoparticles ca. 3 to 8 nm in diameter were prepared at atmospheric pressure, low temperature, and at an ultradense reagent concentration by titrating an aqueous ammonia solution into a dense iron oleate/toluene mixture. A transparent suspension was obtained by redispersing the prepared particles in nonpolar solvents since they were redispersible to primary particles without aggregate formations. The prepared particles were characterized by TEM, XRD, and FT-IR, and their dispersion stability in organic solvents was determined by dynamic light scattering (DLS) and viscosity measurements. In order to analyze the formation process of the highly dispersed α-Fe₂O₃ nanoparticles, time-course measurements of DLS and viscosity during the nanoparticle synthesis in toluene were carried out. A significant increase in the suspension viscosity and the formation of an aggregated structure were observed as soon as the titration of the aqueous ammonia solution. The suspension viscosity and aggregated particle size gradually reduced with continuous vigorous stirring; finally, α-Fe₂O₃ nanoparticles that were completely redispersible in nonpolar solvents were obtained after ca. 24 h. The particle size could be controlled by the synthesis temperature, and such redispersible α-Fe₂O₃ nanoparticles were obtained even when the reagent concentration was increased to 2.8 mol/L.     

Microgel/SiO2 hybrid colloids prepared using a water soluble silica precursor

In the present work we demonstrate that functional polymer microgels may act as smart self-catalyzing system inducing controlled formation of silica nanoparticles inside the polymer network and formation of hybrid colloids. We synthesized a water soluble silica precursor PEG-PEOS via post-modification of hyperbranched poly(ethoxysiloxane) (PEOS) with poly(ethylene glycol) monomethyl ether. We used poly(N-vinylcaprolactam)-based microgel functionalized with imidazole and β-diketone groups as a matrix for biomimetic deposition of silica. Composite microgel particles containing silica nanoparticles (up to 20 wt.-%) have been prepared by simultaneous PEG-PEOS conversion and silica deposition in the microgels. TEM studies indicate the infiltration of silica nanoparticles (～10 nm) inside the corona region of the microgels due to the strong acid–base interaction between the acidic silica and basic imidazole groups. The resulting composite particles were found to be colloidally stable and no aggregation was observed even after months of storage. The incorporation of silica nanoparticles increased the rigidity of the microgel particles and reduced their thermal sensitivity.     

Nanoparticle collection efficiency of capillary pore membrane filters

The surface and overall collection efficiencies of capillary pore membrane filters were measured for sub-micrometer particles. Collection efficiencies were derived from the surface loadings of particles on filters measured by scanning electron microscopy and from airborne particle concentrations measured with a scanning mobility particle sizer. Tests used filters with nominal pore diameters of 0.4 and 0.8 μm and face velocities of 3.7 and 18.4 cm/s. Surface collection efficiencies were below 100% for particles smaller than 316 nm and below 55% for particles smaller than 100 nm. Overall collection efficiencies reached as low as 45% for 70 nm particles. For nanoparticles, collection efficiencies overall were substantially higher than those to the filter surface, indicating that deposition occurs to a large extent inside the filter pores. These results underscore the need to account for surface collection efficiency when deriving airborne concentrations from microscopic analysis of nanoparticles on capillary pore membrane filters.     

Synthesis of dispersed CaCO3 nanoparticles by the ultrafine grinding

A one-step grinding process to obtain CaCO₃ nanoparticles from a micrometer-sized CaCO₃ was studied. A high-speed beads mill was employed to grind the particles, and poly(acrylic acid, sodium salt) was used to disperse the ground particles. The main parameters, which were investigated, were the slurry concentration, the rotor speed, the bead size, and the surfactant concentration. The larger bead size, higher slurry concentration, and faster rotor speed showed higher grinding efficiencies. However, there was severe agglomeration of the ground particles resulting in larger secondary particles as the grinding time increased after the certain point. The dispersion and enhanced grinding of particles were achieved by the surfactant. The particle size distribution of the ground particles had a narrow peak around 190 nm that was measured by the diffraction method. The primary particle size of the ground particles was around 40 nm.     

Mechanism of cellular uptake of genotoxic silica nanoparticles

ABSTRACT: Mechanisms for cellular uptake of nanoparticles have important implications for nanoparticulate drug delivery and toxicity. We have explored the mechanism of uptake of amorphous silica nanoparticles of 14 nm diameter, which agglomerate in culture medium to hydrodynamic diameters around 500 nm. In HT29, HaCat and A549 cells, cytotoxicity was observed at nanoparticle concentrations 1 mug/ml, but DNA damage was evident at 0.1 mug/ml and above. Transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy confirmed entry of the silica particles into A549 cells exposed to 10 mug/ml of nanoparticles. The particles were observed in the cytoplasm but not within membrane bound vesicles or in the nucleus. TEM of cells exposed to nanoparticles at 4 C for 30 minutes showed particles enter cells when activity is low, suggesting a passive mode of entry. Plasma lipid membrane models identified physical interactions between the membrane and the silica NPs. Quartz crystal microbalance experiments on tethered bilayer lipid membrane systems show that the nanoparticles strongly bind to lipid membranes, forming an adherent monolayer on the membrane. Leakage assays on large unilamellar vesicles (400 nm diameter) indicate that binding of the silica NPs transiently disrupts the vesicles which rapidly self-seal. We suggest that an adhesive interaction between silica nanoparticles and lipid membranes could cause passive cellular uptake of the particles.     

碳酸钙填充聚丙烯体系的流变行为研究

利用高压毛细管流变仪研究了纳米CaCO3和微米CaCO3分别单独填充和复配填充聚丙烯(PP)体系的流变行为。对纳米CaCO3填充PP体系,CaCO3的加入使体系的表观黏度(ηa)下降,但随着CaCO3的质量分数增加,ηa呈上升趋势。当CaCO3的质量分数为10%时,两种微米CaCO3(1.8μm和25μm)填充体系的ηa接近,但低于纳米CaCO3填充体系的;随着CaCO3的质量分数增加(如30%),三种体系的ηa接近。对纳米CaCO3和微米CaCO3复配填充PP体系,CaCO3的总质量分数为10%时,当微米CaCO3的质量低于CaCO3总质量的50%时,体系的ηa与纳米CaCO3单独填充体系相比呈显著下降;但随着CaCO3的总质量分数增加,ηa下降的幅度变小。     

In-situ, simultaneous milling and coating of particulates with nanoparticles

Fluid energy mill (FEM) was utilized to simultaneously realize several functions, namely: size reduction of coarse micron-sized pre-coated particles into smaller (ca. 1-10 μm) particles, as well as de-agglomeration and coating of nanoparticles onto the ground particles, all within the FEM chamber. Three types of coating nanoparticles - silica, alumina, and titania - were applied to study the effects of the nanoparticle type on the coating performance. It was found that material type and surface modification play a significant role in coating uniformity. The results show that the flowability of the ground KCl particulates can be improved significantly by the addition of nanoparticles. The flowability of the ground particulates is sensitive to the amount of the nanoparticles added. This study demonstrates that the novel process can be used to fluidize and coat highly cohesive particles.     

Viscoelastic properties and morphological characterization of silica/polystyrene nanocomposites synthesized by nitroxide-mediated polymerization

Polystyrene (PS) chains with molecular weights comprised between 15,000 and 60,000 g/mol and narrow polydispersities were successfully grown from the surface of silica nanoparticles by nitroxide-mediated polymerization (NMP). Small angle X-ray scattering was used to characterize the structure of the interface layer formed around the silica particles, and at a larger scale, dynamic light scattering was used to determine the hydrodynamic diameter of the functionalized silica suspension. In a second part, blends of PS-grafted silica particles and pure polystyrene were prepared to evaluate the influence of the length of the grafted PS segments on the viscoelastic behavior of the so-produced nanocomposites in the linear viscoelasticity domain.Combination of all these techniques shows that the morphology of the nanocomposite materials is controlled by grafting. The steric hindrance generated by the grafted polymer chains enables partial destruction of the agglomerates that compose the original silica particles when the latter are dispersed either in a solvent or in a polymeric matrix.     

Characterization of rheological properties of colloidal zirconia

Dynamic viscosity of aqueous suspensions of nanosized zirconia (ZrO₂) have been studied for the low volume fraction range. The specific surface area of dry powder was determined from the BET method. The zeta potential of zirconia particles as a function of pH was measured by the microelectrophoretic method. The isoelectric point found in this way was 4.7. The particle density in aqueous suspensions was found by the dilution method. The dynamic viscosity of suspensions was measured by using a capillary viscometer that eliminated the sedimentation effects. Experimental data showed that for dilute zirconia suspension, the relative viscosity increased more rapidly with the volume fraction than that the Einstein formula predicts. This allowed one to calculate the specific hydrodynamic volume of particles in the suspensions and their apparent density. It was found that particles forming zirconia suspensions were composed of aggregates having porosity of 40–50%. The size of the primary particles forming these aggregates was 0.2 μm that agrees well with the BET specific surface data. The influence of an anionic polyelectrolyte:polysodium 4-styrenesulfonate (PSS) on zirconia suspension viscosity also was studied. First the PSS viscosity alone was measured as a function of its volume fraction for various ionic strength of the solutions. The data were interpreted in terms of the flexible rod model of the polyelectrolyte. Then, the viscosity of ZrO₂ in PSS solutions of fixed concentration was measured as a function of the concentration of zirconia. It was revealed that the viscosity of the mixtures was proportional to the product of the zirconia and polyelectrolyte viscosities taken separately.     

In situ reduction of graphene oxide nanoplatelet during spark plasma sintering of a silica matrix composite

Well dispersed silica-graphene nanoplatelet (GNP) and silica-graphene oxide nanoplatelet (GONP) composites were fabricated by optimising their processing conditions. Different processing methods, including colloidal and powder processing, were investigated using different solvents. High temperature and inert environment during SPS resulted in the reduction of the GONP during sintering. The in situ reduction of GONP in the SPS was investigated for various sintering times and temperatures, and characterised using Raman spectroscopy and XRD analysis. The composite sintered at 1200 °C, 50 MPa pressure and 15 min dwell time confirmed the recovery of the crystalline graphitic phase of GNP after reduction without crystallising the silica matrix. GONP was found to inhibit the crystallisation of the silica matrix at higher sintering times and temperatures possibly due to increased viscosity and reduced mobility of the silica particles bound to GNP.     

Encapsulation of nanoparticles using CO2-expanded liquids

A new process for encapsulation based on the principle of precipitation of nanoparticles by pressure reduction of CO₂ gas-expanded liquids (PPRGEL) is presented here. Encapsulation has been studied for two types of core solid nanoparticles, namely suspended and in situ produced particles from solution. Mechanisms for both types of encapsulations have been proposed: for the former type deposition happens because of mass transfer from the bulk solution; for the latter type encapsulation happens if the supersaturation profiles of the core and coating solutes are staggered in time in order that the core solute precipitates first and the coating solute deposits on it by mass transfer. A model for the process that includes nucleation and growth has been developed to select systems and process conditions that favor encapsulation. The mechanisms have been experimentally verified at 52 bar and 303 K for (i) encapsulation of suspended nanoparticles of silica with ascorbylpalmitate (AP) dissolved acetone and (ii) encapsulation of in situ produced tartaric acid (TA) nanoparticles with AP, both initially dissolved in acetone. A uniform coating of about 10–20 nm of AP is formed on the 250 nm silica particles. For the two-solute system it is observed that AP deposits on TA resulting in encapsulated particles of an average size of about 520 nm.     

Effects of Silica and Titanium Oxide Particles on a Human Neural Stem Cell Line: Morphology,Mitochondrial Activity,and Gene Expression of Differentiation Markers

Several in vivo studies suggest that nanoparticles (smaller than 100 nm) have the ability to reach the brain tissue. Moreover, some nanoparticles can penetrate into the brains of murine fetuses through the placenta by intravenous administration to pregnant mice. However, it is not clear whether the penetrated nanoparticles affect neurogenesis or brain function. To evaluate its effects on neural stem cells, we assayed a human neural stem cell (hNSCs) line exposed in vitro to three types of silica particles (30 nm, 70 nm, and <44 μm) and two types of titanium oxide particles (80 nm and < 44 μm). Our results show that hNSCs aggregated and exhibited abnormal morphology when exposed to the particles at concentrations ≥ 0.1 mg/mL for 7 days. Moreover, all the particles affected the gene expression of Nestin (stem cell marker) and neurofilament heavy polypeptide (NF-H, neuron marker) at 0.1 mg/mL. In contrast, only 30-nm silica particles at 1.0 mg/mL significantly reduced mitochondrial activity. Notably, 30-nm silica particles exhibited acute membrane permeability at concentrations ≥62.5 μg/mL in 24 h. Although these concentrations are higher than the expected concentrations of nanoparticles in the brain from in vivo experiments in a short period, these thresholds may indicate the potential toxicity of accumulated particles for long-term usage or continuous exposure.     

Numerical simulation for the collision between a vortex ring and solid particles

This study is concerned with the numerical simulation for the collision between a vortex ring and an ensemble of small glass particles. The vortex ring, convecting with its self-induced velocity in a quiescent air, collides with the particles. The Reynolds number for the vortex ring is 2600, and the particle diameters are 50 and 200 μm. The Stokes number St for the 50 μm particle is 0.74, while the St for the 200 μm particle is 11.4. Immediately after the collision with the vortex ring, the 50 μm particles surround the vortex ring, forming a dome. It is parallel with the preferential distribution for the particle with St ? 1 around large-scale eddies, which has been measured experimentally and simulated numerically in various free turbulent flows. The 200 μm particles disperse more due to the collision with the vortex ring. This is attributable to the centrifugal effect of large-scale eddy, which has been reported by the numerical simulation for the motion of the particle with St = 10 in a wake flow. The collision between the vortex ring and the particles induces an organized three-dimensional vortical structure. It also reduces the strength and convective velocity of the vortex ring.     

Nano-mixing of dipyridamole drug and excipient nanoparticles by sonication in liquid CO2

Nanoparticles (about 200 nm thick and 600–12000 nm long flakes) of dipyridamole, a poorly water-soluble anti-thrombosis drug, are produced by supercritical antisolvent solvent with enhanced mass transfer method. Applicability of sonication in liquid CO₂ for mixing of drug and excipient nanoparticles is demonstrated for several binary mixtures of drug and excipient. The drug particles are mixed with three different excipients: silica nanoparticles, lactose microparticles, and polyvinylpyrrolidone nanoparticles. To intimately mix at nanoscale, macro mixtures of dipyridamole and excipient particles are sonicated in liquid carbon dioxide. The effects of ultrasonic energy, amplitude, and component weight ratio are studied for the binary mixtures. Characterization of mixing is done using several methods. Scanning electron microscopy is used as a primary method for microscopic analysis. Two macroscopic effects, drug dissolution and blend homogeneity (relative standard deviation), are used to characterize mixing quality of drug/lactose mixture. Results of drug dissolution and blend homogeneity show effectiveness of the proposed mixing method for fine size particles. Material handling properties of drug/silica and lactose/silica mixtures were examined. Upon mixing, the handling properties are significantly improved as measured by compressibility index and Hausner ratio. Liquid CO₂ offers an environmentally benign media for mixing. In addition, the mixture obtained does not contain any residual solvent as compared to the sonication in organic liquids. Upon depressurization, CO₂ is easily removed from the mixture providing a facile recovery of the product.     

Aqueous Gelcasting of Fused Silica Using Colloidal Silica Binder

An aqueous‐based gelcasting of fused silica ceramics by using colloidal silica binder was developed. Fused silica slurries having different volume percentage of solid loading from 63 to 74 vol% in colloidal silica were made and the rheological properties were evaluated. It was found that the slurry with 73 vol% of solid loading with viscosity 0.70 Pa.s is suitable for this gelcasting system. The influence of solid loading on physical and mechanical properties of gelcast green and sintered bodies has been studied. The fabricated green body by using colloidal silica binder exhibited a flexural strength of 9 MPa and 88% of theoretical density with 2.2% of drying shrinkage while the sintered sample exhibited flexural strength of 60 MPa and 95% of theoretical density with 4.3% of sintering shrinkage. It was observed that, the nano silica particles from the colloidal silica binder is filling the interstitial positions in the consolidated fused silica green body and enhancing physical and mechanical properties.     

Preparation of MEMO silane-coated SiO2 nanoparticles under high pressure of carbon dioxide and ethanol

The objective of this study is to investigate and compare methods of nanosilica coating with γ-methacryloxypropyltrimethoxy (MEMO) silane using supercritical carbon dioxide and carbon dioxide-ethanol mixture. Characterization of grafted silane coupling agent on the nanosilica surface was performed by the infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The d₅₀ value and particle size distribution were determined by laser particle size analyzer (PSA). The operating parameters of silanization process at 40 °C, such as the silica/silane weight ratio, the presence of ethanol, and the pressure, were found to be important for the successful coating of silica particles with minimum agglomeration. The results indicate that presence of ethanol in high-pressure carbon dioxide plays an important role in achieving successful deagglomeration of coated nanoparticles. Dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) revealed that dispersion of the silica particles in the PMMA matrix and interfacial adhesion between silica particles and polymer matrix were enhanced, when silica nanoparticles treated with silane under high pressure of carbon dioxide and ethanol were used for the nanocomposite preparation.     

Scouring-ball effect of microsized silica particles on operation stability of the membrane reactor for acetone ammoximation over TS-1

A ceramic membrane reactor system was developed for the continuous ammoximation of acetone to acetone oxime over titanium silicalites-1 (TS-1) catalysts. The effects of catalyst concentration and microsized silica particles on the performances of the membrane reactor system were examined in detail. For the membrane reactor system the optimal catalyst concentration is 17.0 g L^?1, obviously higher than the one obtained from the previous experiments in a batch glass reactor, because the strong adhesion of TS-1 catalyst particles on the surface of the pipeline, the tank and the membrane leads to the decrease of effective catalyst concentration. Adding the microsized silica particles can effectively inhibit the decrease of TS-1 catalysts concentration in reaction slurry and improve the operation stability of the membrane reactor system significantly, benefiting from the scouring effect and the attachment of TS-1 particles on the surfaces of larger silica particles. According to the estimation of hydrodynamic forces acting on particles, microsized silica particles are hard to deposit on the contact surfaces at the studied conditions and therefore a longer stable operation of the membrane reactor system has been achieved.