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.     

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.     

Release of ultrafine particles from three simulated building processes

Building activities are recognised to produce coarse particulate matter but less is known about the release of airborne ultrafine particles (UFPs; those below 100 nm in diameter). For the first time, this study has investigated the release of particles in the 5–560 nm range from three simulated building activities: the crushing of concrete cubes, the demolition of old concrete slabs, and the recycling of concrete debris. A fast response differential mobility spectrometer (Cambustion DMS50) was used to measure particle number concentrations (PNC) and size distributions (PNDs) at a sampling frequency of 10 Hz in a confined laboratory room providing controlled environment and near–steady background PNCs. The sampling point was intentionally kept close to the test samples so that the release of new UFPs during these simulated processes can be quantified. Tri–modal particle size distributions were recorded for all cases, demonstrating different peak diameters in fresh nuclei (<10 nm), nucleation (10–30 nm) and accumulation (30–300 nm) modes for individual activities. The measured background size distributions showed modal peaks at about 13 and 49 nm with average background PNCs ~1.47 × 10⁴ cm⁻³. These background modal peaks shifted towards the larger sizes during the work periods (i.e. actual experiments) and the total PNCs increased between 2 and 17 times over the background PNCs for different activities. After adjusting for background concentrations, the net release of PNCs during cube crushing, slab demolition, and ‘dry’ and ‘wet’ recycling events were measured as ~0.77, 19.1, 22.7 and 1.76 (×10⁴) cm⁻³, respectively. The PNDs were converted into particle mass concentrations (PMCs). While majority of new PNC release was below 100 nm (i.e. UFPs), the bulk of new PMC emissions were constituted by the particles over 100 nm; ~95, 79, 73 and 90% of total PNCs, and ~71, 92, 93 and 91% of total PMCs, for cube crushing, slab demolition, dry recycling and wet recycling, respectively. The results of this study firmly elucidate the release of UFPs and raise a need for further detailed studies and designing health and safety related exposure guidelines for laboratory workplaces and operational building sites.     

Characteristic of nanoparticles generated from different nano-powders by using different dispersion methods

A standard rotating drum with a modified sampling train (RD), a vortex shaker (VS), and a SSPD (small-scale powder disperser) were used to investigate the emission characteristics of nano-powders, including nano-titanium dioxide (nano-TiO₂, primary diameter: 21 nm), nano-zinc oxide (nano-ZnO, primary diameter: 30–50 nm), and nano-silicon dioxide (nano-SiO₂, primary diameter: 10–30 nm). A TSI SMPS (scanning mobility particle sizer), a TSI APS (aerodynamic particle sizer), and a MSP MOUDI (micro-orifice uniform deposit impactor) were used to measure the number and mass distributions of generated particles. Significant differences in specific number and mass concentration or distributions were found among different methods and nano-powders with the most specific number and mass concentration and the smallest particles being generated by the most energetic SSPD, followed by VS and RD. Near uni-modal number or mass distributions were observed for the SSPD while bi-modal number or mass distributions existed for nano-powders except nano-SiO₂ which also exhibited bimodal mass distributions. The 30-min average results showed that the mass median aerodynamic diameter (MMAD) and number median diameter (NMD) of the SSPD ranged 1.1–2.1 μm and 166–261 nm, respectively, for all three nano-powders, which were smaller than those of the VS (MMAD: 3.3–6.0 μm and NMD: 156–462 nm), and the RD (MMAD: 5.2–11.2 μm and NMD: 198–479 nm). For nano-particles (electric mobility diameter < 100 nm), specific mass concentrations were nearly negligible for all three nano-powders and test methods. Specific number concentrations of nano-particles were low for the RD tester but were elevated when more energetic VS and SSPD testers were used. The quantitative size and concentration data obtained in this study is useful to elucidate the field emission and personal exposure data in the future provided that particle loss in the generation system is carefully assessed.     

Probing the effect of nitrogen gas on electrical conduction phenomena of ZnO and Cu-doped ZnO thin films prepared by spray pyrolysis

Zinc oxide (ZnO) and Cu-doped ZnO (CZO) thin films were prepared on borosilicate glass substrates by spray pyrolysis technique. The X-ray diffraction study revealed that Cu doping caused a reduction in crystallite size. AFM study showed an increase in roughness with doping. This is attributed to the aggregation of particles to form clusters. From transmission electron microscopy analysis, the particle size is measured to be in the range 30–65 nm (average particle size 48 nm) for undoped ZnO, whereas it is in the range 24–56 nm (average particle size 40 nm) for CZO film. The electrical resistivity of the thin films was investigated in the presence of air as well as N₂ mixed air at different temperatures in the range 30–270 °C. The change in resistivity properties was explained on the basis of conduction phenomena within the grain along with the grain boundaries as well as Cu- and N₂-induced defect states. The thermal activation energy of ZnO was found to be in the range 0.04–0.7 eV and dependent on Cu doping and N₂ level in air.     

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 %.     

Nanostructuring of thin Au films by means of short UV laser pulses

The particle size distribution, morphology and optical properties of the Au nanoparticle (NP) structures for surface enhanced Raman signal (SERS) application are investigated in dependence on their preparation conditions. The structures are produced from relatively thin Au films (10–20 nm) sputtered on fused silica glass substrate and irradiated with several pulses (6 ns) of laser radiation at 266 nm and at fluencies in the range of 160–412 mJ/cm². The SEM inspection reveals nearly homogeneously distributed, spherical gold particles. Their initial size distribution of the range of 20–60 nm broadens towards larger particle diameters with prolonged irradiation. This is accompanied by an increase in the uncovered surface of the glass substrate and no particle removal is observed. In the absorption profiles of the nanostructures, the broad peak centred at 546 nm is ascribed to resonant absorption of surface plasmons (SPR). The peak position, halfwidth and intensity depend on the shape, size and size distribution of the nanostructured particles in agreement with literature. From peak intensities of the Raman spectra recorded for Rhodamine 6G in the range of 300–1800 cm⁻¹, the relative signal enhancement by factor between 20 and 603 for individual peaks is estimated. The results confirm that the obtained structures can be applied for SERS measurements and sensing.     

From workplace air measurement results toward estimates of exposure? Development of a strategy to assess exposure to manufactured nano-objects

In the past few years, an increasing number of studies on workplace air measurements on manufactured nano-materials and -objects have been published. Most of the studies had a more explorative character, so a direct interpretation to workers” exposure for a given exposure situation, activity, or process is not a straight-forward process. In general, the studies use a quite similar package of devices for near real-time monitoring of particle number- and mass concentration in size ranges <100 nm up to 10 μm, and the collection of samples for off-line characterization of air samples. Various approaches for addressing background concentrations and its use to indicate the potential for exposure to nano-objects could be observed. Within the EU-sponsored NANOSH project, a harmonized approach for measurement strategy, data analysis and reporting was developed. In addition to time/activity–concentration profiles as reported by most studies, this approach enables a first step to estimate the potential for exposure to manufactured nano-objects, more quantitatively. The NANOSH data will be collated into a base, which may form the starting point for a harmonized database facilitating overall analysis in near future, to derive estimates for exposure for several exposure situations.     

One-pot synthesis of oleic acid-capped cadmium chalcogenides (CdE: E = Se,Te) nano-crystals

Surface-capped CdSe and CdTe nano-crystals (NCs) have been synthesized using cadmium acetate, oleic acid and respective tri-octylphosphine chalcogenide (TOPE; E = Se/Te) in diphenyl ether (DPE). Well-dispersed CdSe particles showed two absorption bands at the region of 431–34 and 458–60 nm in optical absorption study. A band-edge emission resulted at 515 nm with an excitation energy of 400 nm, in its photoluminescence (PL) spectrum. Similarly, UV–visible absorption study of CdTe revealed an absorption band at <700 nm. The broadened X-ray diffraction (XRD) pattern showed that at higher reaction temperature cubic CdSe but hexagonal CdTe can be obtained with crystallite size of <10 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that agglomerated particles are of spherical nature. The inter-planar spacing in CdTe was measured to be 0.406 nm, a characteristic of (100) lattice plane in hexagonal CdTe. X-ray photoelectron spectroscopy (XPS) showed that CdSe NCs have better air stability stable than CdTe. Presence of organic moiety around the semiconductor particles was confirmed by infra-red (IR) spectroscopy.     

High stability of the crystalline configuration of Au nanoparticles embedded in silica under ion and electron irradiation

Au nanoparticles (NPs) with a size in the 2–12 nm range have been grown in silica by 2 MeV Au-ion implantation and a subsequent thermal annealing in air. The as-prepared Au NPs were irradiated with 10 MeV Si ions elongating some of them. From transmission electron microscopy in Z-contrast mode, we observed a narrow size distribution of the minor axis of the deformed NPs, which presents its higher frequency around 6–7 nm and have a saturation about 9 nm. This final result agrees well with the diameter of the track formed by Si ions of 10 MeV in silica, supporting the thermal spike model, which would explain the deformation of the NPs. In this model, the NP melts and creeps along the ion track. Our results show that the NP crystallization is in the fcc structure. On the other hand, a 200 keV electron irradiation provoked roundness on the previously elongated nanoparticles. This effect was observed in situ by high-resolution transmission electron microscopy, showing additionally that, during the roundness process, the fcc structure, as well as its crystalline orientation, remain unchanged. Thus, this study shows how Au NPs embedded in silica, within this size distribution, keep the fcc bulk structure under both ion and electron irradiations.     

Aggregation modeling of calcium carbonate particles by Monte Carlo simulation

The mechanism on aggregation of spindle granular particles of calcite was investigated for the carbonation of calcium hydroxide in aqueous suspension for the purpose of controlling morphology of CaCO₃. The experimental carbonation process was carried out in a semi-batch bubble column reactor under different conditions. Although, fine rhombic nano-particles diameter ranged from 100 to 200 nm were obtained at 291 K, a higher temperature of 300 K provided spindle granular particles with a length of 1.0–1.5 μm and a width of 0.3–0.5 μm. The average crystallite size was 28 nm for the fine rhombic nano-particles and 43 nm for the spindle granules. Zeta potential measurement for the spindle granules indicated that the suspension tended to be aggregated during the carbonation process. The effect of the degree of particle aggregation on the shape of the obtained calcite particles was studied by Monte Carlo simulations. Our simulation results elucidated the dependence of aggregation on unit particles, i.e., primary particles, on the experiment carbonation condition where the spindle granules were formed out of the unit particles under the same condition as the experiments. In addition, the formation mechanism of the granules was investigated by applying classical nucleation theory to the present simulations.     

Measuring particle size-dependent physicochemical structure in airborne single walled carbon nanotube agglomerates

As-produced single-walled carbon nanotube (SWCNT) material is a complex matrix of carbon nanotubes, bundles of nanotubes (nanoropes), non-tubular carbon and metal catalyst nanoparticles. The pulmonary toxicity of material released during manufacture and handling will depend on the partitioning and arrangement of these components within airborne particles. To probe the physicochemical structure of airborne SWCNT aggregates, a new technique was developed and applied to aerosolized as-produced material. Differential Mobility Analysis-classified aggregates were analyzed using an Aerosol Particle Mass Monitor, and a structural parameter Γ (proportional to the square of particle mobility diameter, divided by APM voltage) derived. Using information on the constituent components of the SWCNT, modal values of Γ were estimated for specific particle compositions and structures, and compared against measured values. Measured modal values of Γ for 150 nm mobility diameter aggregates suggested they were primarily composed of non-tubular carbon from one batch of material, and thin nanoropes from a second batch of material – these findings were confirmed using Transmission Electron Microscopy. Measured modal values of Γ for 31 nm mobility diameter aggregates indicated that they were comprised predominantly of thin carbon nanoropes with associated nanometer-diameter metal catalyst particles; there was no indication that either catalyst particles or non-tubular carbon particles were being preferentially released into the air. These results indicate that the physicochemistry of aerosol particles released while handling as-produced SWCNT may vary significantly by particle size and production batch, and that evaluations of potential health hazards need to account for this. Disclaimer: The mention of any company or product does not constitute an endorsement by the Centers for Disease Control and Prevention. The findings and conclusions in this paper are those of the authors and do not necessarily represent the views of the National Institute for Occupational Safety and Health.     

Conceptual limitations and extensions of lung-deposited Nanoparticle Surface Area Monitor (NSAM)

Nanoparticle Surface Area Monitor (NSAM, TSI model 3550 and Aerotrak 9000) is an instrument designed to measure airborne surface area concentrations that would deposit in the alveolar or tracheobronchial region of the lung. It was found that the instrument can only be reliably used for the size range of nanoparticles between 20 and 100 nm. The upper size range can be extended to 400 nm, where the minimum in the deposition curves occurs. While the fraction below 20 nm usually contributes only negligibly to the total surface area and is therefore not critical, a preseparator is needed to remove all particles above 400 nm in cases where the size distribution extends into the larger size range. Besides limitations in the particle size range, potential implications of extreme concentrations up to the coagulation limit, particle material (density and composition) and particle morphology are discussed. While concentration does not seem to pose any major constraints, the effect of different agglomerate shapes still has to be further investigated. Particle material has a noticeable impact neither on particle charging in NSAM nor on the deposition curves within the aforementioned size range, but particle hygroscopicity can cause the lung deposition curves to change significantly which currently cannot be mimicked with the instrument. Besides limitations, possible extensions are also discussed. It was found that the tendencies of the particle deposition curves of a reference worker for alveolar, tracheobronchial, total and nasal depositions share the same tendencies in the 20–400 nm size range and that their ratios are almost constant. This also seems to be the case for different individuals and under different breathing conditions. By means of appropriate calibration factors NSAM can be used to deliver the lung deposited surface area concentrations in all these regions, based on a single measurement.     

Fabrication and characterization of Cu–CdSe–Cu nanowire heterojunctions

The Cu–CdSe–Cu nanowire heterojunctions were fabricated by sequential electrochemical deposition of layers of Cu metal and CdSe semiconductor within the nano-pores of anodic alumina membrane templates. X-ray diffraction reveals the cubic phase for Cu and hexagonal phase for CdSe in the electrodeposited Cu–CdSe–Cu nanowire heterojunctions. The composition of the nanowire heterojunction segments is characterized by energy dispersive X-ray spectroscopy. The morphological study of nanowire heterojunctions has been made using scanning electron microscope and high resolution transmission microscopy. The nanowire heterojunctions grown in 100 and 300 nm nano-pore size templates have been found to have optical band gaps of 1.92 and 1.75 eV, respectively. The absorption spectra of 100 nm nanowire heterojunctions show a blue shift of 0.18 eV. The collective nonlinear current–voltage (I–V) characteristics of the 300 and 100 nm nanowire heterojunctions show their rectifying and asymmetric behaviour, respectively.     

Use of nanomaterials in the European construction industry and some occupational health aspects thereof

In the European construction industry in 2009, the use of engineered nanoparticles appears to be confined to a limited number of products, predominantly coatings, cement and concrete. A survey among representatives of workers and employers from 14 EU countries suggests a high level of ignorance about the availability and use of nanomaterials for the construction industry and the safety aspects thereof. Barriers for a large-scale acceptance of products containing engineered nanoparticles (nanoproducts) are high costs, uncertainties about long-term technical material performance, as well as uncertainties about health risks of nanoproducts. Workplace measurements suggest a modest exposure of construction workers to nanoparticles (NPs) associated with the use of nanoproducts. The measured particles were within a size range of 20–300 nm, with the median diameter below 53 nm. Positive assignment of this exposure to the nanoproduct or to additional sources of ultrafine particles, like the electrical equipment used was not possible within the scope of this study and requires further research. Exposures were below the nano reference values proposed on the basis of a precautionary approach.     

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.     

Polypyrrole–silica core–shell nanocomposites: a new route towards active materials in dielectrophoretic displays

A direct route to polypyrrole–silica core–shell nanoparticles with diameters in the 150–300 nm range is described to design new nanocomposites, in which the conducting part is wrapped by an external silica shell in order to obtain finally neutral conductive nanoparticles. The nanocomposites are characterized by SEM, FTIR, electrochemistry and thermal gravimetric analysis, demonstrating that the external silica shell actually insulates the conjugated polymer from the outer medium. In a second step, the nanocomposites are coated with an additional PDMS layer. The electrorheological properties of the ink made by dispersion of these final nanoparticles in a low dielectric constant fluid are checked in a dielectrophoretic device, in which the motion of the particles induced by an external electric field can be used to monitor a switch of the light transmission properties with a low voltage threshold.     

Size dependence of complex refractive index function of growing nanoparticles

The evidence of the change of the complex refractive index function E(m) of carbon and iron nanoparticles as a function of their size was found from two-color time-resolved laser-induced incandescence (TiRe-LII) measurements. Growing carbon particles were observed from acetylene pyrolysis behind a shock wave and iron particles were synthesized by pulse Kr–F excimer laser photo-dissociation of Fe(CO)₅. The magnitudes of refractive index function were found through the fitting of two independently measured values of particle heat up temperature, determined by two-color pyrometry and from the known energy of the laser pulse and the E(m) variation. Small carbon particles of about 1–14 nm in diameter had a low value of E(m)∼0.05–0.07, which tends to increase up to a value of 0.2–0.25 during particle growth up to 20 nm. Similar behavior for iron particles resulted in E(m) rise from ∼0.1 for particles 1–3 nm in diameter up to ∼0.2 for particles >12 nm in diameter.     

Microbial synthesis of silver nanoparticles by Bacillus sp.

A silver resistant Bacillus sp. was isolated through exposure of an aqueous AgNO₃ solution to the atmosphere. Silver nanoparticles were synthesized using these airborne bacteria (Bacillus sp.). Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analyses confirmed that silver nanoparticles of 5–15 nm in size were deposited in the periplasmic space of the bacterial cells; a preferable cell surface location for the easy recovery of biogenic nanoparticles.     

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.