Airborne nanoparticle exposures associated with the manual handling of nanoalumina and nanosilver in fume hoods

Manual handling of nanoparticles is a fundamental task of most nanomaterial research; such handling may expose workers to ultrafine or nanoparticles. Recent studies confirm that exposures to ultrafine or nanoparticles produce adverse inflammatory responses in rodent lungs and such particles may translocate to other areas of the body, including the brain. An important method for protecting workers handling nanoparticles from exposure to airborne nanoparticles is the laboratory fume hood. Such hoods rely on the proper face velocity for optimum performance. In addition, several other hood design and operating factors can affect worker exposure. Handling experiments were performed to measure airborne particle concentration while handling nanoparticles in three fume hoods located in different buildings under a range of operating conditions. Nanoalumina and nanosilver were selected to perform handling experiments in the fume hoods. Air samples were also collected on polycarbonate membrane filters and particles were characterized by scanning electron microscopy. Handling tasks included transferring particles from beaker to beaker by spatula and by pouring. Measurement locations were the room background, the researcher’s breathing zone and upstream and downstream from the handling location. Variable factors studied included hood design, transfer method, face velocity/sash location and material types. Airborne particle concentrations measured at breathing zone locations were analyzed to characterize exposure level. Statistics were used to test the correlation between data. The test results found that the handling of dry powders consisting of nano-sized particles inside laboratory fume hoods can result in a significant release of airborne nanoparticles from the fume hood into the laboratory environment and the researcher’s breathing zone. Many variables were found to affect the extent of particle release including hood design, hood operation (sash height, face velocity), work practices, type and quantity of the material being handled, room conditions, and the adequacy of the room exhaust.

Particle release and control of worker exposure during laboratory-scale synthesis,handling and simulated spills of manufactured nanomaterials in fume hoods

Fume hoods are one of the most common types of equipment applied to reduce the potential of particle exposure in laboratory environments. A number of previous studies have shown particle release during work with nanomaterials under fume hoods. Here, we assessed laboratory workers’ inhalation exposure during synthesis and handling of CuO, TiO₂ and ZnO in a fume hood. In addition, we tested the capacity of a fume hood to prevent particle release to laboratory air during simulated spillage of different powders (silica fume, zirconia TZ-3Y and TiO₂). Airborne particle concentrations were measured in near field, far field, and in the breathing zone of the worker. Handling CuO nanoparticles increased the concentration of small particles (<?58 nm) inside the fume hood (up to 1?×?10⁵ cm^?3). Synthesis, handling and packaging of ZnO and TiO₂ nanoparticles did not result in detectable particle release to the laboratory air. Simulated powder spills showed a systematic increase in the particle concentrations inside the fume hood with increasing amount of material and drop height. Despite powder spills were sometimes observed to eject into the laboratory room, the spill events were rarely associated with notable release of particles from the fume hood. Overall, this study shows that a fume hood generally offers sufficient exposure control during synthesis and handling of nanomaterials. An appropriate fume hood with adequate sash height and face velocity prevents 98.3% of particles release into the surrounding environment. Care should still be made to consider spills and high cleanliness to prevent exposure via resuspension and inadvertent exposure by secondary routes.     

Exposure assessment of process by-product nanoparticles released during the preventive maintenance of semiconductor fabrication facilities

This study characterized the process by-product particles (mostly nanoparticles) released during the preventive maintenance of semiconductor fabrication facilities, such as chemical mechanical planarization (CMP), plasma-enhanced chemical vapor deposition (PECVD), and ion implantation. Manual sampling and real-time measurements with direct reading instruments were conducted to assess the exposure levels of nanoparticles and their physical and chemical properties. Significant amount of nanoparticles were observed in the breathing zone of the workers during the maintenance of the PECVD and ion implanters with the peak number concentrations as high as 6,470,000 and 65,444 #/cm³, respectively, indicating that the deposited residual chemicals in the reaction chambers were released as airborne nanoparticles by the maintenance activities. In contrast, nanoparticles released during the maintenance of the local scrubber, CMP, and replacing CMP slurry drums were insignificant. Causes of the particle release were discussed and suggestions were made to mitigate the nanoparticle release and reduce the exposure levels.     

Magnetic Field Mapping Around Individual Magnetic Nanoparticle Agglomerates Using Nitrogen-Vacancy Centers in Diamond

A modified diamond–photonics based metrology is proposed to explore the magnetic fields created by agglomerates of magnetic nanoparticles (MNPs). MNPs are promising for environmental and medical applications; those proposed for cancer magnetic hyperthermia treatments are small superparamagnetic <20 nm iron oxide particles. Inside cells, they assemble in larger MNP agglomerates, reaching cross-sections of several micrometers. Here, these conditions are reproduced and MNP agglomerates immobilized. Optically detected magnetic resonance (ODMR) signals recorded without a bias field in a confocal microscope and scanning across a homogenous shallow layer of fluorescent nitrogen-vacancy centers in a bulk diamond sample placed in direct contact with the MNP agglomerates are used to determine magnetic fields with a spatial resolution of 500 nm in a lateral direction. This spatial resolution allows determining magnetic field maps around individual MNP agglomerates, for which magnetic fields with strengths ranging from 0.03 mT to maximal 1.2 mT in the direct vicinity of the agglomerates and with detectable fields up to 5 µm away from the agglomerates, are determined. Based on the findings, a pathway to non-invasively study the micro/nano topology of MNP agglomerates is proposed.     

Generation of AuGe nanocomposites by co-sparking technique and their photoluminescence properties

Inhalation exposure to airborne nanoparticles (NPs) has been reported during manual activities using typical fume hoods. This research studied potential inhalation exposure associated with the manual handling of NPs using two new nanoparticle-handling enclosures and two biological safety cabinets, and discussed the ability to contain NPs in the hoods to reduce environmental release and exposure. Airborne concentrations of 5 nm to 20 μm diameter particles were measured while handling nanoalumina particles in various ventilated enclosures. Tests were conducted using two handling conditions and concentrations were measured using real-time particle counters, and particles were collected on transmission electron microscope grids to determine particle morphology and elemental composition. Airflow patterns were characterized visually using a laser-light sheet and fog. The average number concentration increase at breathing zone outside the enclosure was less than 1,400 particle/cm³ for each particle size at all tested conditions and the estimated overall mass concentration was about 83 μg/m³ which was less than the dosage of typical nanoparticle inhalation exposure studies. The typical front-to-back airflow was used in the studied hoods, which could potentially induce reverse turbulence in the wake region. However, containment of NPs using studied hoods was demonstrated with excellent performance. Smoke tests showed that worker’s hand motion could potentially cause nanoparticle escape. The challenge of front-to-back airflow can be partially overcome by gentle motion, low face velocity, and front exhaust to reduce nanoparticle escape.     

Workplace air measurements and likelihood of exposure to manufactured nano-objects,agglomerates, and aggregates

Workplace exposure to nanoparticles from gas metal arc welding (GMAW) process in an automobile manufacturing factory was investigated using a combination of multiple metrics and a comparison with background particles. The number concentration (NC), lung-deposited surface area concentration (SAC), estimated SAC and mass concentration (MC) of nanoparticles produced from the GMAW process were significantly higher than those of background particles before welding (P < 0.01). A bimodal size distribution by mass for welding particles with two peak values (i.e., 10,000–18,000 and 560–320 nm) and a unimodal size distribution by number with 190.7-nm mode size or 154.9-nm geometric size were observed. Nanoparticles by number comprised 60.7 % of particles, whereas nanoparticles by mass only accounted for 18.2 % of the total particles. The morphology of welding particles was dominated by the formation of chain-like agglomerates of primary particles. The metal composition of these welding particles consisted primarily of Fe, Mn, and Zn. The size distribution, morphology, and elemental compositions of welding particles were significantly different from background particles. Working activities, sampling distances from the source, air velocity, engineering control measures, and background particles in working places had significant influences on concentrations of airborne nanoparticle. In addition, SAC showed a high correlation with NC and a relatively low correlation with MC. These findings indicate that the GMAW process is able to generate significant levels of nanoparticles. It is recommended that a combination of multiple metrics is measured as part of a well-designed sampling strategy for airborne nanoparticles. Key exposure factors, such as particle agglomeration/aggregation, background particles, working activities, temporal and spatial distributions of the particles, air velocity, engineering control measures, should be investigated when measuring workplace exposure to nanoparticles.     

Comparison of nanoparticle measurement instruments for occupational health applications

Nanoparticles are used in many applications because of their novel properties compared to bulk material. A growing number of employees are working with nanomaterials and their exposure to nanoparticles trough inhalation must be evaluated and monitored continuously. However, there is an ongoing debate in the scientific literature about what are the relevant parameters to measure to evaluate exposure to level. In this study, three types of nanoparticles (ammonium sulphate, synthesised TiO₂ agglomerates and aerosolised TiO₂ powder, modes in a range of 30–140 nm mobility size) were measured with commonly used aerosol measurement instruments: scanning and fast mobility particle sizers (SMPS, FMPS), electrical low pressure impactor (ELPI), condensation particle counter (CPC) together with nanoparticle surface area monitor (NSAM) to achieve information about the interrelations of the outputs of the instruments. In addition, the ease of use of these instruments was evaluated. Differences between the results of different instruments can mainly be attributed to the nature of test particles. For spherical ammonium sulphate nanoparticles, the data from the instruments were in good agreement while larger differences were observed for particles with more complex morphology, the TiO₂ agglomerates and powder. For instance, the FMPS showed a smaller particle size, a higher number concentration and a narrower size distribution compared with the SMPS for TiO₂ particles. Thus, the type of the nanoparticle was observed to influence the data obtained from these different instruments. Therefore, care and expertise are essential when interpreting results from aerosol measurement instruments to estimate nanoparticle concentrations and properties.     

Dustiness test of nanopowders using a standard rotating drum with a modified sampling train

The standard rotating drum tester was used to determine the dustiness of two nanopowders, nano-TiO₂ and fine ZnO, in standard 1-min tests. Then, the sampling train was modified to determine the number and mass distributions of the generated particles in the respirable size range using a Scanning Mobility Particle Sizer (SMPS), an Aerodynamic Particle Sizer (APS) and a Multi-orifice Uniform Deposit Impactor (MOUDI) in the 30-min tests. It was found that very few particles below 100 nm were generated and the released rate of particles decreased with increasing rotation time for both nanopowders in the 30-min tests. Due to the fluffy structure of the released TiO₂ agglomerated particles, the mass distributions measured by the MOUDI showed large differences with those determined by the APS assuming the apparent bulk densities of the powders. The differences were small for the ZnO agglomerates, which were more compact than the TiO₂ agglomerates.     

Exposure to nanoscale particles and fibers during machining of hybrid advanced composites containing carbon nanotubes

This study investigated airborne exposures to nanoscale particles and fibers generated during dry and wet abrasive machining of two three-phase advanced composite systems containing carbon nanotubes (CNTs), micron-diameter continuous fibers (carbon or alumina), and thermoset polymer matrices. Exposures were evaluated with a suite of complementary instruments, including real-time particle number concentration and size distribution (0.005–20 μm), electron microscopy, and integrated sampling for fibers and respirable particulate at the source and breathing zone of the operator. Wet cutting, the usual procedure for such composites, did not produce exposures significantly different than background whereas dry cutting, without any emissions controls, provided a worst-case exposure and this article focuses here. Overall particle release levels, peaks in the size distribution of the particles, and surface area of released particles (including size distribution) were not significantly different for composites with and without CNTs. The majority of released particle surface area originated from the respirable (1–10 μm) fraction, whereas the nano fraction contributed ~10% of the surface area. CNTs, either individual or in bundles, were not observed in extensive electron microscopy of collected samples. The mean number concentration of peaks for dry cutting was composite dependent and varied over an order of magnitude with highest values for thicker laminates at the source being >1 × 10⁶ particles cm⁻³. Concentration of respirable fibers for dry cutting at the source ranged from 2 to 4 fibers cm⁻³ depending on the composite type. Further investigation is required and underway to determine the effects of various exposure determinants, such as specimen and tool geometry, on particle release and effectiveness of controls.

Investigation of airborne nanopowder agglomerate stability in an orifice under various differential pressure conditions

The stability of agglomerates is not only an important material parameter of powders but also of interest for estimating the particle size upon accidental release into the atmosphere. This is especially important when the size of primary particles is well below the agglomerate size, which is usually the case when the size of primary particles is below 100 nm. During production or airborne transportation in pipes, high particle concentrations lead to particle coagulation and the formation of agglomerates in a size range of up to some micrometers. Binding between the primary particles in the agglomerates is usually due to van der Waals forces. In the case of a leak in a pressurized vessel (e.g. reactor, transport pipe, etc.), these agglomerates can be emitted and shear forces within the leak can cause agglomerates to breakup. In order to simulate such shear forces and study their effect on agglomerate stability within the airborne state, a method was developed where agglomerate powders can be aerosolized and passed through an orifice under various differential pressure conditions. First results show that a higher differential pressure across the orifice causes a stronger fragmentation of the agglomerates, which furthermore seems to be material dependent.     

Release potential of single-wall carbon nanotubes produced by super-growth method during manufacturing and handling

We investigated the release potential of single-wall carbon nanotubes (CNTs) produced by the super-growth method during their manufacturing and handling processes at a research facility. We generally sampled air at points both outside and inside of protective enclosures such as a glove box and fume hood. Sampling the air outside of the enclosures was intended to evaluate the actual exposure of workers to CNTs, while sampling the air inside the enclosures was performed to quantify the release of CNTs to the air in order to estimate the potential exposure of workers without protection. The results revealed that airborne CNTs were generated when (1) CNTs were separated from the substrates using a spatula and placed in a container in a glove box; (2) an air gun was used to clean the air filters (containing dust that included CNTs) of a vacuum cleaner; (3) a vacuum cleaner was used to collect CNTs (emission with exhaust air from the cleaner); (4) the container of CNTs was opened; and (5) CNTs in the bin of the cleaner were transferred to a container. In these processes, airborne CNTs were only found inside the enclosures, except for a small amount of CNTs released from the glove box when it was opened. Electron microscopic observations of aerosol particles found CNT clusters, which were fragments of CNT forests, with sizes ranging from submicrometers to tens of micrometers.     

Experimental data and model predictions of aluminium agglomeration in ammonium perchlorate-based composite propellants including plateau-burning formulations

Sixteen propellant formulations based on ammonium perchlorate (AP), hydroxyl-terminated polybutadiene, and aluminium particles have been tested for size distribution of aluminium agglomerates emerging from their burning surface. The formulations are based on a bimodal size distribution of AP particles. Ten of the formulations exhibit one or two plateaus/mesa in their burning rate variation with pressure (zero/negative pressure exponent of burning rate). The relevant formulation variables, namely, coarse and fine AP sizes and coarse-to-fine ratio, aluminium size and content, and two different curing agents, have been varied. Tests are performed in the 1–10 MPa pressure range. A direct correlation between burning rate and agglomerate size exists for propellants with normal burning rate trends but a neutral or inverse correlation is observed for those exhibiting plateau burning behaviour. Larger the parent aluminium size, lesser the agglomeration, as expected; but the effect of aluminium content is non-monotonic. The coarse AP size influences the aluminium agglomerate size as expected from the pocket model regardless of plateau burning effects. The agglomerate size decreases with increase in fine AP size, however. A computer model developed earlier at this laboratory for prediction of aluminium agglomerates based on three-dimensional packing of particles and deduction of AP particles with attached leading edge diffusion flames is applied to the present formulations. The model under-predicts the agglomerate size, only marginally for propellants that do not exhibit plateau burning rate trends, but substantially, otherwise. This is because it does not take into account effects of binder melt flow and is independent of the curing agent of the binder.     

Study of the mobility,surface area,and sintering behavior of agglomerates in the transition regime by tandem differential mobility analysis

The surface area of nanosized agglomerates is of great importance as the reactivity and health effects of such particles are highly dependent on surface area. Changes in surface area through sintering during nanoparticle synthesis processes are also of interest for precision control of synthesised particles. Unfortunately, information on particle surface area and surface area dynamics is not readily obtainable through traditional particle mobility sizing techniques. In this study, we have experimentally determined the mobility diameter of transition regime agglomerates with 3, 4, and 5 primary particles. Agglomerates were produced by spray drying well-characterised polystyrene latex particles with diameters of 55, 67, 76, and 99 nm. Tandem differential mobility analysis was used to determine agglomerate mobility diameter by selecting monodisperse agglomerates with the same number of primary particles in the first DMA, and subsequently completely sintering the agglomerates in a furnace aerosol reactor. The size distribution of the completely sintered particles was measured by an SMPS system, which allowed for the determination of the number of primary particles in the agglomerates. A simple power law regression was used to express mobility diameter as a function of primary particle size and the number of primary particles, and had an excellent correlation (R² = 0.9971) with the experimental data. A scaling exponent was determined from the experimental data to relate measured mobility diameter to surface area for agglomerates. Using this relationship, the sintering characteristics of agglomerates were also examined for varying furnace temperatures and residence times. The sintering data agreed well with the geometric sintering model (GSM) model proposed by Cho & Biswas (2006a) as well as with the model proposed Koch & Friedlander (1990) for sintering by viscous flow.     

Size distributions of aerosols in an indoor environment with engineered nanoparticle synthesis reactors operating under different scenarios

Size distributions of nanoparticles in the vicinity of synthesis reactors will provide guidelines for safe operation and protection of workers. Nanoparticle concentrations and size distributions were measured in a research academic laboratory environment with two different types of gas-phase synthesis reactors under a variety of operating conditions. The variation of total particle number concentration and size distribution at different distances from the reactor, off-design state of the fume hood, powder handling during recovery, and maintenance of reactors are established. Significant increases in number concentration were observed at all the locations during off-design conditions (i.e., failure of the exhaust system). Clearance of nanoparticles from the work environment was longer under off-design conditions (20 min) compared to that under normal hood operating conditions (4–6 min). While lower particle number concentrations are observed during operation of furnace aerosol reactors in comparison to flame aerosol reactors, the handling, processing, and maintenance operations result in elevated concentrations in the work area.     

Monitor for detecting and assessing exposure to airborne nanoparticles

An important safety aspect of the workplace environment concerns the severity of its air pollution with nanoparticles (NP; <100 nm) and ultrafine particles (UFP; <300 nm). Depending on their size and chemical nature, exposure to these particles through inhalation can be hazardous because of their intrinsic ability to deposit in the deep lung regions and the possibility to subsequently pass into the blood stream. Recommended safety measures in the nanomaterials industry are pragmatic, aiming at exposure minimization in general, and advocating continuous control by monitoring both the workplace air pollution level and the personal exposure to airborne NPs. This article describes the design and operation of the Aerasense NP monitor that enables intelligence gathering in particular with respect to airborne particles in the 10–300 nm size range. The NP monitor provides real time information about their number concentration, average size, and surface areas per unit volume of inhaled air that deposit in the various compartments of the respiratory tract. The monitor’s functionality relies on electrical charging of airborne particles and subsequent measurements of the total particle charge concentration under various conditions. Information obtained with the NP monitor in a typical workplace environment has been compared with simultaneously recorded data from a Scanning Mobility Particle Sizer (SMPS) capable of measuring the particle size distribution in the 11–1086 nm size range. When the toxicological properties of the engineered and/or released particles in the workplace are known, personal exposure monitoring allows a risk assessment to be made for a worker during each workday, when the workplace-produced particles can be distinguished from other (ambient) particles.     

Emission measurement and safety assessment for the production process of silicon nanoparticles in a pilot-scale facility

Emission into the workplace was measured for the production process of silicon nanoparticles in a pilot-scale facility at the Institute of Energy and Environmental Technology e.V. (IUTA). The silicon nanoparticles were produced in a hot-wall reactor and consisted of primary particles around 60 nm in diameter. We employed real-time aerosol instruments to measure particle number and lung-deposited surface area concentrations and size distribution; airborne particles were also collected for off-line electron microscopic analysis. Emission of silicon nanoparticles was not detected during the processes of synthesis, collection, and bagging. This was attributed to the completely closed production system and other safety measures against particle release which will be discussed briefly. Emission of silicon nanoparticles significantly above the detection limit was only observed during the cleaning process when the production system was open and manually cleaned. The majority of the detected particles was in the size range of 100–400 nm and were silicon nanoparticle agglomerates first deposited in the tubing then re-suspended during the cleaning process. Appropriate personal protection equipment is recommended for safety protection of the workers during cleaning.     

Treatment of submicron particles using an electrostatic agglomerator in DC-negative voltage: Re-entrainment experimental study and modeling

The aim of this study is to highlight the re-entrainment phenomenon encountered with an electrostatic agglomerator having a fibrous collecting electrode and treating submicron particles. The idea is to propose a process to control the particle number emitted by automotive diesel engines. Rather than trying to directly measure agglomerates of diesel particles exiting the agglomerator, we propose working with a synthetic submicron aerosol dispersed in ambient filtered air as a representative exhaust gas. The study will contribute to build a numerical modeling of the behavior of particles in such a process. The particular point that will be treated here is the collected particle re-entrainment as micron-sized agglomerates. We propose a joint experimentation/modeling approach to approximate the re-entrained aerosol size distribution in controlled conditions. From the modeling point of view, a local approach which uses the method of the balance of moments on agglomerates provides the re-entrained particle size in the agglomerator, according to the filtration conditions. The experimental approach confirms the clearly micron-sized character of the re-entrained agglomerates. This is unambiguously shown by measuring a greater micron particle numerical concentration downstream from the agglomerator than upstream. We show that the fluorescein submicron particles use can greatly simplify the characterization of an electrostatic agglomerator by allowing the use of a commercial laser granulometer to measure the size and the number of the generated agglomerates.     

Characterization of palmitic and lauric acid aerosols from rapid expansion of supercritical CO2 solutions

Palmitic acid aerosols and lauric acid aerosols were generated by rapid expansion of supercritical CO₂ solutions. The particle properties were analysed by rapid-scan infrared spectroscopy in situ, by X-ray powder diffraction, with a scanning mobility particle sizer, and by scanning electron microscopy. Particles with irregular elongated shapes were found. Most particles and agglomerates have sizes between 250 and 750 nm. Fewer agglomerates with sizes up to several microns are observed. Our investigation reveals that strong agglomeration takes place at the Mach disc. Palmitic and lauric acid particles are both crystalline and most particles crystallize in the C-form.     

Nano particle fluidisation in model 2-D and 3-D beds using high speed X-ray imaging and microtomography

Nanoparticles and nanocomposites have become a major focus of interest in science and technology due to exceptional properties they provide. However, handling and processing of ultra-fine powders is very challenging because they are extremely cohesive. Fluidization is one of techniques available to process powders. It has become increasingly important to understand how these nanoparticles can be handled and processed to benefit from their favourable properties. A high spatial (down to 400 nm) and temporal resolution (down to 1 ms) X-ray imaging apparatus has been designed to study nanoparticles in fluidized beds under different gas flow velocities. The mean volume distribution of the nanoparticle agglomerates was determined with X-ray microtomography. The X-ray microtomography technique provides valuable in situ, non-destructive structural information on the morphological changes that take place during fluidisation of powder samples.     

Relationships Between Particle Properties and Bulk Behaviour for some industrial powders

A series of industrial powders, most of them organic, were characterized in terms of volumetric mean size, size distribution, density, particle shape, water rentention characteristics (under a series of controlled ambient relative humidities) and loosely packed and densely packed voidages (giving the compressibility). The behaviour of the powders in powder handling apparatus (a precision powder filler) was also determined. The minimum and maximum bulk densities of the powders were related to the properties of the individual particles by means of a semi-empirical equation. The filling capacity of the powder handling apparatus was found to be related to the maximum bulk density of the powder while the filling accuracy turned out to be related to the compressibility of the powder. Knowing these interrelations made it possible to predict the powder behaviour in the handling apparatus directly on basis of the particle properties.