Human exposure to metals in consumer-focused fused filament fabrication (FFF)/ 3D printing processes.

Fused filament fabrication (FFF) or 3D printing is a growing technology used in industry, cottage industry and for consumer applications. Low-cost 3D printing devices have become increasingly popular among children and teens. Consequently, 3D printers are increasingly common in households, schools, and libraries. Because the operation of 3D printers is associated with the release of inhalable particles and volatile organic compounds (VOCs), there are concerns of possible health implications, particularly for use in schools and residential environments that may not have adequate ventilation such as classrooms bedrooms and garages, etc. Along with the growing consumer market for low-cost printers and printer pens, there is also an expanding market for a range of specialty filaments with additives such as inorganic colorants, metal particles and nanomaterials as well as metal-containing flame retardants, antioxidants, heat stabilizers and catalysts. Inhalation of particulate-associated metals may represent a health risk depending on both the metal and internal dose to the respiratory tract. Little has been reported, however, about the presence, speciation, and source of metals in the emissions; or likewise the effect of metals on emission processes and toxicological implications of these 3D printer generated emissions. This report evaluates various issues including the following: metals in feedstock with a focus on filament characteristics and function of metals; the effect of metals on the emissions and metals detected in emissions; printer emissions, particle formation, transport, and transformation; exposure and translation to internal dose; and potential toxicity on inhaled dose. Finally, data gaps and potential areas of future research are discussed within these contexts.

3D Printer Particle Emissions: Translation to Internal Dose in Adults and Children.

Desktop fused deposition modeling (FDM®) three-dimensional (3D) printers are becoming increasingly popular in schools, libraries, and among home hobbyists. FDM® 3D printers have been shown to release ultrafine airborne particles in large amounts, indicating the potential for inhalation exposure and consequent health risks among FDM® 3D printer users and other room occupants including children. These particles are generated from the heating of thermoplastic polymer feedstocks during the FDM® 3D printing process, with the most commonly used polymers being acrylonitrile butadiene styrene (ABS) and poly-lactic acid (PLA). Risk assessment of these exposures demands estimation of internal dose, especially to address intra-human variability across life stages. Dosimetry models have proven to effectively translate particle exposures to internal dose metrics relevant to evaluation of their effects in the respiratory tract. We used the open-access multiple path particle dosimetry (MPPD v3.04) model to estimate inhaled particle deposition in different regions of the respiratory tract for children of various age groups from three months to eighteen years old adults. Mass concentration data for input into the MPPD model were calculated using particle size distribution and density data from experimental FDM® 3D printer emissions tests using both ABS and PLA. The impact of changes in critical parameters that are principal determinants of inhaled dose, including: sex, age, and exposure duration, was examined using input parameter values available from the International Commission on Radiological Protection. Internal dose metrics used included regional mass deposition, mass deposition normalized by pulmonary surface area, surface area of deposited particles by pulmonary surface area, and retained regional mass. Total mass deposition was found to be highest in the 9-year-old to 18-year-old age groups with mass deposition by pulmonary surface area highest in 3-month-olds to 9-year-olds and surface area of deposited particles by pulmonary surface area to be highest in 9-year-olds. Clearance modeling revealed that frequent 3D printer users are at risk for an increased cumulative retained dose.

Particle and volatile organic compound emissions from a 3D printer filament extruder.

Fused Deposition Modeling (FDM®), also known as Fused Filament Fabrication (FFF), 3D printers have been shown in numerous studies to emit ultrafine particles and volatile organic compounds (VOCs). Filament extruders, designed to create feedstocks for 3D printers, have recently come onto the consumer market for at-home hobbyists as an alternative to buying 3D printer filaments. These instruments allow for the creation of 3D printer filaments from raw plastic pellets. Given the similarity in processes and materials used by 3D printers and filament extruders, we hypothesized that filament extruders may also release ultrafine particle emissions and VOCs. An off-the-shelf filament extruder was operated in a 2 m3 chamber using three separate feedstocks: acrylonitrile butadiene styrene (ABS) pellets, pulverized poly-lactic acid (PLA), and PLA pellets. Ultrafine particle emissions were measured in real-time using a scanning mobility particle sizer and thermal desorption tubes were used for both non-targeted and targeted analysis of VOCs present in emissions. Ultrafine particle number emission rates were comparable to those found in 3D printer studies with the greatest to least emission rates from ABS pellets, pulverized PLA, and PLA pellets, respectively. In addition, the majority of particles released were found to be ultrafine (1-100 nm), similar to 3D printer studies. A variety of VOCs were identified using the ABS feedstock, including styrene and ethylbenzene, and PLA feedstock. Styrene average mass concentration amounts were found to be near the EPA Integrated Risk Information System Reference Concentration for Inhalation Exposure for 3 min and 5 min samples. Further studies will be needed to determine the impact on emissions of environmental volume, air exchange rate, and extruder settings such as extrusion speed and temperature. The results support the hypothesis that use of a filament extruder may present an additional exposure risk to 3D printer hobbyists.

Photochemically Induced Phase Change in Monolayer Molybdenum Disulfide.

Monolayer transition metal dichalcogenide (TMDs) are promising candidates for two-dimensional (2D) ultrathin, flexible, low-power, and transparent electronics and optoelectronics. However, the performance of TMD-based devices is still limited by the relatively low carrier mobility and the large contact resistance between the semiconducting 2D channel material and the contact metal electrodes. Phase-engineering in monolayer TMDs showed great promise in enabling the fabrication of high-quality hetero-phase structures with controlled carrier mobilities and heterojunction materials with reduced contact resistance. However, to date, general methods to induce phase-change in monolayer TMDs either employ highly-hostile organometallic compounds, or have limited compatibility with large-scale, cost-effective device fabrication. In this paper, we report a new photochemical method to induce semiconductor to metallic phase transition in monolayer MoS2 in a benign chemical environment, through a bench-top, cost-effective solution phase process that is compatible with large-scale device fabrication. It was demonstrated that photoelectrons produced by the band-gap absorption of monolayer MoS2 have enough chemical potential to activate the phase transition in the presence of an electron-donating solvent. This novel photochemical phase-transition mechanism advances our fundamental understanding of the phase transformation in 2D transition metal dichalcogenides (TMDs), and will open new revenues in the fabrication of atomically-thick metal-semiconductor heterostructures for improved carrier mobility and reduced contact resistance in TMD-based electronic and optoelectronic devices.

Particle emissions from fused deposition modeling 3D printers: Evaluation and meta-analysis.

Fused deposition modeling (FDM) 3D printers, the most popular choice among home hobbyists, have been shown to release volatile organic chemicals (VOCs) and billions of airborne particles per minute, indicating the potential for consumer inhalation exposure and consequent health risks. Publications on FDM 3D printer emissions however, contain large heterogeneity of testing methods and analytical procedures making it difficult to reach overall conclusions for particle characteristics or particle number emission rates across the field. In this publication, data were collected over the printing time from 3D printer emission studies including particle count diameters (PCDs) (nanometers), particle number concentrations (PNCs) (particles/cm3), and particle number emission rates (PNERs) (particles min-1). Despite heterogeneity in methods, the majority of particles released were reported as ultrafine in size (i.e., <100 nm) indicating that using both acrylonitrile butadiene styrene (ABS) and poly-lactic acid (PLA) may present a risk of exposure to respirable particles. Mean PNC emitted in 3D printing tests ranged over several orders of magnitude across publications with overall means of 300,980 particles/cm3 for ABS and 65,482 particles/cm3 for PLA. Although mean PNC data were available from only 7 of the 16 papers reviewed, ABS resulted in greater particle numbers than PLA suggesting increased exposure to ultrafine particles. A linear mixed model was fitted for mean PNCs to further explore the impact of nozzle temperature and filament material. Finally, the PNER calculation method especially regarding losses, varied widely across studies, and directly impacted the PNERs reported. To strengthen direct comparability of results going forward, it is recommended that standard emissions testing protocols be developed for FDM 3D printers and particle influxes and losses be more uniformly calculated.

Sharp-Tip Silver Nanowires Mounted on Cantilevers for High-Aspect-Ratio High-Resolution Imaging.

Despite many efforts to fabricate high-aspect-ratio atomic force microscopy (HAR-AFM) probes for high-fidelity, high-resolution topographical imaging of three-dimensional (3D) nanostructured surfaces, current HAR probes still suffer from unsatisfactory performance, low wear-resistivity, and extravagant prices. The primary objective of this work is to demonstrate a novel design of a high-resolution (HR) HAR AFM probe, which is fabricated through a reliable, cost-efficient benchtop process to precisely implant a single ultrasharp metallic nanowire on a standard AFM cantilever probe. The force-displacement curve indicated that the HAR-HR probe is robust against buckling and bending up to 150 nN. The probes were tested on polymer trenches, showing a much better image fidelity when compared with standard silicon tips. The lateral resolution, when scanning a rough metal thin film and single-walled carbon nanotubes (SW-CNTs), was found to be better than 8 nm. Finally, stable imaging quality in tapping mode was demonstrated for at least 15 continuous scans indicating high resistance to wear. These results demonstrate a reliable benchtop fabrication technique toward metallic HAR-HR AFM probes with performance parallel or exceeding that of commercial HAR probes, yet at a fraction of their cost.