A comparison of two nano-sized particle air filtration tests in the diameter range of 10 to 400 nanometers

Two different air filter test methodologies are discussed and compared for challenges in the nano-sized particle range of 10–400 nm. Included in the discussion are test procedure development, factors affecting variability and comparisons between results from the tests. One test system which gives a discrete penetration for a given particle size is the TSI 8160 Automated Filter tester (updated and commercially available now as the TSI 3160) manufactured by the TSI, Inc., Shoreview, MN. Another filter test system was developed utilizing a Scanning Mobility Particle Sizer (SMPS) to sample the particle size distributions downstream and upstream of an air filter to obtain a continuous percent filter penetration versus particle size curve. Filtration test results are shown for fiberglass filter paper of intermediate filtration efficiency. Test variables affecting the results of the TSI 8160 for NaCl and dioctyl phthalate (DOP) particles are discussed, including condensation particle counter stability and the sizing of the selected particle challenges. Filter testing using a TSI 3936 SMPS sampling upstream and downstream of a filter is also shown with a discussion of test variables and the need for proper SMPS volume purging and filter penetration correction procedure. For both tests, the penetration versus particle size curves for the filter media studied follow the theoretical Brownian capture model of decreasing penetration with decreasing particle diameter down to 10 nm with no deviation. From these findings, the authors can say with reasonable confidence that there is no evidence of particle thermal rebound in the size range.     

Experimental study of nanoparticles penetration through commercial filter media

In this study, nanoparticle penetration was measured with a wide range of filter media using silver nanoparticles from 3 nm to 20 nm at three different face velocities in order to define nanoparticle filtration characteristics of commercial fibrous filter media. The silver particles were generated by heating a pure silver powder source via an electric furnace with a temperature of 870°C, which was found to be the optimal temperature for generating an adequate amount of silver nanoparticles for the size range specified above. After size classification using a nano-DMA, the particle counts were measured by an Ultrafine Condensation Particle Counter (UCPC) both upstream and downstream of the test filter to determine the nanoparticle penetration for each specific particle size. Particle sampling time continued long enough to detect more than 10⁵ counts at the upstream and 10 counts at the downstream sampling point so that 99.99% efficiency can be detected with the high efficiency filter. The results show a very high uniformity with small error bars for all filter media tested in this study. The particle penetration decreases continuously down to 3 nm as expected from the classical filtration theory, and together with a companion modeling paper by␣Wang et al. in this same issue, we found no significant evidence of nanoparticle thermal rebound down to 3 nm.     

Evaluation of environmental filtration control of engineered nanoparticles using the Harvard Versatile Engineered Nanomaterial Generation System (VENGES)

Applying engineering controls to airborne engineered nanoparticles (ENPs) is critical to prevent environmental releases and worker exposure. This study evaluated the effectiveness of two air sampling and six air cleaning fabric filters at collecting ENPs using industrially relevant flame-made engineered nanoparticles generated using a versatile engineered nanomaterial generation system (VENGES), recently designed and constructed at Harvard University. VENGES has the ability to generate metal and metal oxide exposure atmospheres while controlling important particle properties such as primary particle size, aerosol size distribution, and agglomeration state. For this study, amorphous SiO₂ ENPs with a 15.4 nm primary particle size were generated and diluted with HEPA-filtered air. The aerosol was passed through the filter samples at two different filtration face velocities (2.3 and 3.5 m/min). Particle concentrations as a function of particle size were measured upstream and downstream of the filters using a specially designed filter test system to evaluate filtration efficiency. Real time instruments (FMPS and APS) were used to measure particle concentration for diameters from 5 to 20,000 nm. Membrane-coated fabric filters were found to have enhanced nanoparticle collection efficiency by 20–46 % points compared to non-coated fabric and could provide collection efficiency above 95 %.     

Estimation of the upper limit of aerosol nanoparticles penetration through inhomogeneous fibrous filters

The fully segregated flow model (FSFM) was formulated to describe filtration of aerosol nanoparticles in polydisperse fibrous filters made of fibers with different diameters. The model is capable of predicting significantly higher penetration of nanoparticles through polydisperse filters than it may be expected from the classical theory applied to a mean fiber diameter. The model was solved numerically in the case of the log-normal fiber size distribution, and a simple correlation between the actual penetration through a polydisperse filter and the one calculated for the geometric mean fiber diameter was proposed. Equivalent fiber diameter for deposition due to Brownian diffusion was determined and it was found to be dependent on particle size and filter’s polydispersity degree, being significantly greater than any mean fiber diameter. It was noted that it is impossible to select any one universal mean fiber diameter to describe penetration of nanoparticles with different sizes. It was also shown that in the case of a polydisperse fibrous filter the apparent exponent of the Peclet number based on the mean fiber diameter is greater than the expected value of −2/3 for diffusional deposition in a monodisperse filter. This prediction is in agreement with the available experimental data. The FSFM is expected to give the estimation of the upper limit of nanoparticles penetration in polydisperse fibrous filters.     

Measurement of filtration efficiency of Nuclepore filters challenged with polystyrene latex nanoparticles: experiments and modeling

Membrane filtration has been demonstrated to be effective for the removal of liquid-borne nanoparticles (NPs). Such technique can be applied to purify and disinfect drinking water as well as remove NPs in highly pure chemicals used in the industries. This study aims to study the filtration process of a model membrane filter, the Nuclepore filter. Experiments were carried out using standard filtration tools and the nanoparticle tracking analysis (NTA) technique was used to measure particle (50–500 nm) concentration upstream and downstream of the filter to determine the filtration efficiency. The NTA technique has been calibrated using 150-nm polystyrene latex particles to determine its accuracy of particle concentration measurement. Measurements were found reliable within a certain concentration limit (about 10⁸–10¹⁰ particles/cm³), which is dependent on the camera settings during the measurement. Experimental results are comparable with previously published data obtained using the aerosolization method, validating the capability of the NTA technique. The capillary tube model modified from that developed for aerosol filtration was found to be useful to represent the experimental results, when a sticking coefficient of 0.15 is incorporated. This suggests that only 15% of the particle collisions with the filter results in successful attachment. The small sticking coefficient found can be explained by the unfavorable surface interactions between the particles and the filter medium.     

Metal-on-oxide nanoparticles produced using laser ablation of microparticle aerosols

A continuous aerosol process has been studied for producing nanoparticles of oxides that were decorated with smaller metallic nanoparticles and are free of organic stabilizers. To produce the oxide carrier nanoparticles, an aerosol of 3–6 μm oxide particles was ablated using a pulsed excimer laser. The resulting oxide nanoparticle aerosol was then mixed with 1.5–2.0 μm metallic particles and this mixed aerosol was exposed to the laser for a second time. The metallic micron-sized particles were ablated during this second exposure, and the resulting nanoparticles deposited on the surface of the oxide nanoparticles producing an aerosol of 10–60 nm oxide nanoparticles that were decorated with smaller 1–5 nm metallic nanoparticles. The metal and oxide nanoparticle sizes were varied by changing the laser fluence and gas type in the aerosol. The flexibility of this approach was demonstrated by producing metal-decorated oxide nanoparticles using two oxides, SiO₂ and TiO₂, and two metals, Au and Ag.     

In Situ Charge Characterization of TiO<Subscript>2</Subscript> and Cu–TiO<Subscript>2</Subscript> Nanoparticles in a Flame Aerosol Reactor

Charge distribution characteristics were investigated for nanoparticles synthesized in a diffusion flame aerosol reactor. The nanoparticles considered were pristine TiO₂ and Cu–TiO₂, with Cu dopant concentrations ranging from 1 to 5 wt% with particle size from 25 to 60 nm. In situ measurements were conducted by integrating a tandem differential mobility analyzer (TDMA) experimental setup with the flame aerosol reactor. A charging model was used to identify the important parameters that govern the two charging mechanisms (diffusion and thermo-ionization) in the flame and their relative importance at different operating parameters. The results indicate that TiO₂ and Cu–TiO₂ nanoparticles carry single as well as double unit charges. The charged fraction depends on particle size as well as on dopant concentration. The charged fraction increased with increasing particle size and decreased with copper dopant concentration. Measured charged fractions were similar for both the polarities at different mobility diameters. Based on the flame operating parameters, the calculations indicate that diffusion charging is dominant in the flame, which is consistent with the experimental results.     

Respiratory protection against airborne nanoparticles: a review

As a precautionary measure, it is often recommended that workers take steps to reduce their exposure to airborne nanoparticles through the use of respiratory protective devices. The purpose of this study was to provide a review and analysis of the research literature and current recommendations on respirators used for protection against nanoparticles. Key research findings were that studies with particles as small as 4 nm have shown that conventional single-fiber filtration theory can be used to describe the filtration performance of respirators and that the most penetrating particle size for respirators equipped with commonly used electrostatic filter media is in the range of 30–100 nm. Future research needs include human laboratory and workplace protection factor studies to measure the respirator total inward leakage of nanoparticles. Industrial hygienists and safety professionals should continue to use traditional respirator selection guidance for workers exposed to nanoparticles.     

Relativistic stellar models

We obtain a class of solutions to the Einstein–Maxwell equations describing charged static spheres. Upon specifying particular forms for one of the gravitational potentials and the electric field intensity, the condition for pressure isotropy is transformed into a hypergeometric equation with two free parameters. For particular parameter values we recover uncharged solutions corresponding to specific neutron star models. We find two charged solutions in terms of elementary functions for particular parameter values. The first charged model is physically reasonable and the metric functions and thermodynamic variables are well behaved. The second charged model admits a negative energy density and violates the energy conditions.     

The aerosol penetration through an electret fibrous filter

The aim of this paper is to present a theoretical study of the aerosol penetration through an electret fibrous filter, using a numerical approach. The aerosol sizes considered in this study were in the submicron range, and in the numerical model, the conventional mechanical mechanisms (impaction, interception, diffusion and gravitationally settling) were taken into consideration along with the electrostatic mechanisms, including the Coulombic and dielectrophoretic effects. The aerosol penetration through an electret fibrous filter is heavily dependent on the aerosol penetration of a single fibre. The aerosol penetration through a single electret fibre under various filtration conditions was calculated. The effects of aerosol diameter, aerosol and fibre charge state, face velocity, packing density and aerosol dielectric constant on the aerosol penetration were investigated.     

Measurement of multi-wall carbon nanotube penetration through a screen filter and single-fiber analysis

In this study, we carried out experiments to study penetration of airborne carbon nanotubes (CNTs) through a screen filter. An electrospray system was employed to aerosolize suspensions of multi-wall CNTs. The generated airborne CNTs were characterized by electron microscopy, and the length and diameter were measured. In the filtration experiments, the challenging CNTs are classified by a differential mobility analyzer. Monodisperse CNTs with the same electrical mobility were then employed to challenge the screen filter. Penetration was measured for CNTs in the range of 100–400 nm mobility diameters. The results showed that the CNT penetration was less than the penetration for a sphere with the same mobility diameter, which was mainly due to the larger interception length of the CNTs. We compared the modeling results using single-fiber filtration efficiency theories with the experimental data, and found that the effective interception length can be approximated by the CNT aerodynamic diameter multiplying a scaling factor. A hypothesis is proposed to understand the observation.     

Synthesis and characterization of Mg-doped ZnO hollow spheres

Mg-doped ZnO nanoparticles were synthesized by a simple chemical method at low temperature with Mg:Zn atomic ratio from 0 to 7%. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and magnesium acetate tetrahydrate were heated under refluxing at 65 °C using methanol as a solvent. X-ray diffraction analysis reveals that the Mg-doped ZnO crystallizes in a wurtzite structure with crystal size of 5–12 nm. These nanocrystals self-aggregated themselves into hollow spheres of size of 800–1100 nm. High resolution transmission electron microscopy images show that each sphere is made up of numerous nanoparticles of average diameter 5–11 nm. The XRD patterns, SEM and TEM micrographs of doping of Mg in ZnO confirmed the formation of hollow spheres indicating that the Mg²⁺ is successfully substituted into the ZnO host structure of the Zn²⁺ site. Furthermore, the UV–Vis spectra and photoluminescence (PL) spectra of the ZnO nanoparticles were also investigated. The band gap of the nanoparticles can be tuned in the range of 3.36–3.55 eV by the use of the dopants.     

A facile route to prepare hierarchical magnetic cobalt–silica hollow nanospheres with tunable shell thickness

Magnetic nanoshells composed of close-packed cobalt–silica nanoparticles have been successfully fabricated on silica spheres. The synthesis is facile and no high pressure, high temperature, or other severe reaction conditions were required. TEM images showed that two batches of the hollow-structured products have a good spherical morphology with an average diameter of 380 and 550 nm, respectively. The surface area and magnetic properties of cobalt–silica nanoshells are measured. By varying the times of the precipitation procedure, the shell thickness is successfully controlled within the 5–30 nm range and each time of procedure might increase the thickness about 5 nm. It is expected that the in situ reaction method can be extended to the synthesis of other hollow metal spheres. The prepared microcapsule with controllable shell thickness and interspaces has the potential to be used for controlled release applications.     

Fluorescence properties of biochemicals in dry NaCl composite aerosol particles and in solutions

Several fluorophores, such as tryptophan, NADH, NADPH, and riboflavin are found in airborne micro-organisms. In this work, the fluorescence properties of these biochemicals were studied both in dry NaCl composite aerosol particles and in saline solutions by means of laser-induced fluorescence. Fluorescence spectra were measured from individual, airborne aerosol particles and from solutions in cuvette. The excitation wavelength was varied in steps from 210 nm to 419 nm and the fluorescence was detected within a wavelength band of 310–670 nm. For each sample, the measured fluorescence emission spectra were combined into fluorescence maps. The fluorescence maximum of riboflavin in a dry NaCl composite particle is 20 nm red-shifted compared with the solution, whereas the maxima are blue-shifted by about 25 nm for tryptophan and 15 nm for NADH and NADPH. The molecular fluorescence cross sections have significant differences between the aerosol particles and the solutions, except for tryptophan. For NADH and NADPH the cross sections are over 20 times larger in the aerosol particles than in the solutions probably as a result of partial quenching of fluorescence in solution caused by the collision or stacking with the adenine moiety. The fluorescence cross section of riboflavin is almost 60 times larger in the solution than in the dry NaCl composite aerosol. This is probably caused by the different microenvironment around the fluorophore molecule and by the concentration quenching in the particles where the fluorescing molecules are relatively close to each other.     

Some exact solutions of F(R) gravity with charged (a)dS black hole interpretation

In this paper we obtain topological static solutions of some kind of pure F(R) gravity. The present solutions are two kind: first type is uncharged solution which corresponds with the topological (a)dS Schwarzschild solution and second type has electric charge and is equivalent to the Einstein-Λ-conformally invariant Maxwell solution. In other word, starting from pure gravity leads to (charged) Einstein-Λ solutions which we interpreted them as (charged) (a)dS black hole solutions of pure F(R) gravity. Calculating the Ricci and Kreschmann scalars show that there is a curvature singularity at r = 0. We should note that the Kreschmann scalar of charged solutions goes to infinity as r → 0, but with a rate slower than that of uncharged solutions.     

Three dimensional accurate morphology measurements of polystyrene standard particles on silicon substrate by electron tomography

Polystyrene latex (PSL) nanoparticle (NP) sample is one of the most widely used standard materials. It is used for calibration of particle counters and particle size measurement tools. It has been reported that the measured NP sizes by various methods, such as Differential Mobility Analysis, dynamic light scattering (DLS), optical microscopy (OM), scanning electron microscopy (SEM) and atomic force microscopy (AFM), differ from each other. Deformation of PSL NPs on mica substrate has been reported in AFM measurements: the lateral width of PSL NPs is smaller than their vertical height. To provide a reliable calibration standard, the deformation must be measured by a method that can reliably visualize the entire three dimensional (3D) shape of the PSL NPs. Here we present a method for detailed measurement of PSL NP 3D shape by means of electron tomography in a transmission electron microscope. The observed shape of the PSL NPs with 100 nm and 50 nm diameter were not spherical, but squished in direction perpendicular to the support substrate by about 7.4% and 12.1%, respectively. The high difference in surface energy of the PSL NPs and that of substrate together with their low Young modulus appear to explain the squishing of the NPs without presence of water film.     

Interlaboratory comparison for the measurement of particle size and zeta potential of silica nanoparticles in an aqueous suspension

The Institute for Reference Materials and Measurements has organised an interlaboratory comparison (ILC) to allow the participating laboratories to demonstrate their proficiency in particle size and zeta potential measurements on monomodal aqueous suspensions of silica nanoparticles in the 10–100 nm size range. The main goal of this ILC was to identify competent collaborators for the production of certified nanoparticle reference materials. 38 laboratories from four different continents participated in the ILC with different methods for particle sizing and determination of zeta potential. Most of the laboratories submitted particle size results obtained with centrifugal liquid sedimentation (CLS), dynamic light scattering (DLS) or electron microscopy (EM), or zeta potential values obtained via electrophoretic light scattering (ELS). The results of the laboratories were evaluated using method-specific z scores, calculated on the basis of consensus values from the ILC. For CLS (13 results) and EM (13 results), all reported values were within the ±2 |z| interval. For DLS, 25 of the 27 results reported were within the ±2 |z| interval, the two other results were within the ±3 |z| interval. The standard deviations of the corresponding laboratory mean values varied between 3.7 and 6.5%, which demonstrates satisfactory interlaboratory comparability of CLS, DLS and EM particle size values. From the received test reports, a large discrepancy was observed in terms of the laboratory’s quality assurance systems, which are equally important for the selection of collaborators in reference material certification projects. Only a minority of the participating laboratories is aware of all the items that are mandatory in test reports compliant to ISO/IEC 17025 (ISO General requirements for the competence of testing and calibration laboratories. International Organisation for Standardization, Geneva, 2005b). The absence of measurement uncertainty values in the reports, for example, hindered the calculation of zeta scores.     

Calibration and numerical simulation of Nanoparticle Surface Area Monitor (TSI Model 3550 NSAM)

TSI Nanoparticle Surface Area Monitor (NSAM) Model 3550 has been developed to measure the nanoparticle surface area deposited in different regions of the human lung. It makes use of an adjustable ion trap voltage to match the total surface area of particles, which are below 100 nm, deposited in tracheobronchial (TB) or alveolar (A) regions of the human lung. In this paper, calibration factors of NSAM were experimentally determined for particles of different materials. Tests were performed using monodisperse (Ag agglomerates and NaCl, 7–100 nm) and polydisperse particles (Ag agglomerates, number count mean diameter below 50 nm). Experimental data show that the currents in NSAM have a linear relation with a function of the total deposited nanoparticle surface area for the different compartments of the lung. No significant dependency of the calibration factors on particle materials and morphology was observed. Monodisperse nanoparticles in the size range where the response function is in the desirable range can be used for calibration. Calibration factors of monodisperse and polydisperse Ag particle agglomerates are in good agreement with each other, which indicates that polydisperse nanoparticles can be used to determine calibration factors. Using a CFD computer code (Fluent) numerical simulations of fluid flow and particle trajectories inside NSAM were performed to estimate response function of NSAM for different ion trap voltages. The numerical simulation results agreed well with experimental results.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

Predicting the Collection Efficiency of Agglomerates in Fibrous Filters

Particle collection in fibrous filters is a very complex problem in filtration theory, and therefore spherical particles are mainly considered. Nevertheless, real particles often have a complicated structure, which influences their deposition behavior. The equivalent diameter concept can be used to account for non-sphericity. We predict the penetration of carbon agglomerates through fibrous filters using a model for spheres and suitable equivalent diameters for the agglomerates. In addition, penetration measurements were performed through a glass fiber filter and a non-woven stainless-steel wire filter. The measured penetrations agreed well with the calculations.