Dermal and oral exposure risks to heavy metals from 3D printing metal-fill thermoplastics.

Manufacturing advancements in polymer printing now allow for the addition of metal additives to thermoplastic feedstock up to 80-90 % by weight and subsequent printing on low-cost desktop 3D printers. Particles associated with metal additives are not chemically bound to the plastic polymer, meaning these particles can potentially migrate and become bioavailable. This study investigated the degree to which two human exposure pathways, oral (ingestion) and dermal (skin contact), are important exposure pathways for metals (copper, chromium, and tin) from metal-fill thermoplastics used in consumer fused filament fabrication (FFF). We found that dermal exposure to copper and bronze filaments presents the highest exposure risk due to chloride (Cl-) in synthetic sweat driving copper (Cu2+) release and dissolution. Chromium and tin were released as micron-sized particles < 24 µm in diameter with low bioaccessibility during simulated oral and dermal exposure scenarios, with potential to undergo dissolution in the gastrointestinal tract based on testing using synthetic stomach fluids. The rate of metal particle release increased by one to two orders of magnitude when thermoplastics were degraded under 1 year of simulated UV weathering. This calls into question the long-term suitability of biodegradable polymers such as PLA for use in metal-fill thermoplastics if they are designed not to be sintered. The greatest exposure risk appears to be from the raw filaments rather than the printed forms, with the former having higher metal release rates in water and synthetic body fluids for all but one filament type. For brittle feedstock that requires greater handling, as metal-fill thermoplastics can be, practices common in metal powder 3D printing such as wearing gloves and washing hands may adequately reduce metal exposure risks.

Metal compositions of particle emissions from material extrusion 3D printing: Emission sources and indoor exposure modeling.

Material extrusion 3D printing has been widely used in industrial, educational and residential environments, while its exposure health impacts have not been well understood. High levels of ultrafine particles are found being emitted from 3D printing and could pose a hazard when inhaled. However, metals that potentially transfer from filament additives to emitted particles could also add to the exposure hazard, which have not been well characterized for their emissions. This study analyzed metal (and metalloid) compositions of raw filaments and in the emitted particles during printing; studied filaments included pure polymer filaments with metal additives and composite filaments with and without metal powder. Our chamber study found that crustal metals tended to have higher partitioning factors from filaments to emitted particles; silicon was the most abundant element in emitted particles and had the highest yield per filament mass. However, bronze and stainless-steel powder added in composite filaments were less likely to transfer from filament to particle. For some cases, boron, arsenic, manganese, and lead were only detected in particles, which indicated external sources, such as the printers themselves. Heavy metals with health concerns were also detected in emitted particles, while their estimated exposure concentrations in indoor air were below air quality standards and occupational regulations. However, total particle exposure concentrations estimated for indoor environments could exceed ambient air fine particulate standards.

Spectroelectrochemical and Theoretical Study of [Si(ttpy)2](PF6)4: A Potential Polychromatic Electrochromic Dye.

Complexes consisting of earth-abundant main group metals such as silicon with polypyridine ligands are of interest for a variety of optical and electronic applications including as electrochromic colorants. Previous spectroelectrochemical studies with tris(2,2'-bipyridyl)silicon(IV) hexafluorophosphate, [Si(bpy)3](PF6)4, demonstrated an ability to control the color saturation of the potential electrochromic dye, with the intensity of the dye's green color increasing as the charge state sequentially reduces from 4+ to 1+. In this study, the synthesis of bis(4'-(4-tolyl)-2,2':6',2″-terpyridine)silicon(IV) hexafluorophosphate, [Si(ttpy)2](PF6)4, is reported along with electrochemical and spectroelectrochemical analyses. Computational modeling (density functional theory) is used to further elucidate the electrochromic properties of previously reported Si(bpy)3n+ species and the new Si(ttpy)2n+ species. While the homoleptic tris(bidentate)silicon(IV) complexes are attractive as electrochromic dyes for tunable color saturation, the bis(tridentate)silicon(IV) complexes are attractive as polychromatic electrochromic dyes.

Variability in the inorganic composition of colored acrylonitrile-butadiene-styrene and polylactic acid filaments used in 3D printing.

Fused filament fabrication is a 3D printing technique that has gained widespread use from homes to schools to workplaces. Thermoplastic filaments, such as acrylonitrile-butadiene-styrene (ABS) and polylactic acid (PLA), are extruded at temperatures near their respective glass transition temperature or melting point, respectively. Little has been reported on the inorganic elemental composition and concentrations present in these materials or the methods available for extracting that information. Because inorganic constituents may be included in the aerosolized particulates emitted during the printing process, identifying elements that could be present and at what specific concentrations is critical. The objective of the current research is to determine the range of metals present in thermoplastic filaments along with their relative abundance and chemical speciation as a function of polymer type, manufacturer, and color. A variety of filaments from select manufacturers were digested using a range of techniques to determine the optimal conditions for metal extraction from ABS and PLA polymers. The extraction potential for each method was quantified using by ICP-MS analysis. When possible, further characterization of the chemical composition of the filaments was investigated using X-ray Absorption spectroscopy to determine chemical speciation of the metal. Optimal digestion conditions were established using a high temperature, high pressure microwave-assisted acid digestion method to produce the most complete and repeatable extraction results. The composition and abundance of metals in the filaments varied greatly as a function of polymer, manufacturer, and color. Potential elements of concern present in the filaments at elevated concentration included that could pose a respiratory risk included Si, Al, Ti, Cu, Zn, and Sn. XAS analysis revealed a mixture of metal oxides, mineral, and organometallic compounds were present in the filaments that were being used to increase opaqueness impart color (dyes), polymeric catalysts, and flame retardants. This work shows that a variety of metals are present in the starting materials used for 3D printing and depending on their partitioning into 3D printed products and byproducts as well as the exposure route, may pose a health risk which merits further investigation.

Release and transformation of nanoparticle additives from surface coatings on pristine & weathered pressure treated lumber.

As the market for "nano-enabled" products (NEPs) continues to expand in commercial and industrial applications, there is a critical need to understand conditions that promote release of nanomaterials and their degradation products from NEPs. Moreover, these studies must aim to quantify both the abundance and form (aggregates, ions, hybrids, etc.) of material released from NEPs to produce reasonable estimates of human and environmental exposure. In this work ZnO nanoparticles (NPs), a common additive in NEP surface coatings, were dispersed in Milli-Q water and a commercially available wood stain before application to pristine and weathered (outdoor 1 year) micronized copper azole pressure treated lumber (MCA). Coated lumber surfaces were sampled consecutively eight times using a method developed by the Consumer Product Safety Commission (CPSC) to track potential human exposure to ZnO NPs and byproducts through simulated dermal contact. Surprisingly, the highest total release of Zn was observed from aged lumber coated with ZnO NPs dispersed in wood stain, releasing 233 ± 26 mg Zn/m2 over the course of all sampling events. Alternatively, separate leaching experiments using a synthetic precipitation solution to simulate environmental release found aged lumber released significantly less Zn than pristine lumber when using the same coating formulation. Zinc speciation analysis also demonstrates that transformation of crystalline ZnO to Zn-organic complexes shortly after application to aged lumber. Regardless of experimental treatment, the majority of applied zinc (>75%) remains on the MCA surface. Finally, this work highlights how the nature of the screening technique (dermal contact vs. leaching) may result in different interpretations of exposure and risk.

Multi-method assessment of PVP-coated silver nanoparticles and artificial sweat mixtures.

Research presented here utilizes silver nanoparticles (AgNPs) as a case study for how the immediate local environment alters the physical and chemical properties of nanomaterials. Dermal exposure is a primary route for exposure to many of the consumer products containing AgNPs. Interactions between AgNPs and human sweat/perspiration are critical for understanding how changes in Ag speciation will impact exposure. Previous studies have examined silver release from AgNP-containing products after exposure to artificial sweat (AS), however there is no basic assessment of how mixtures of AgNPs and AS alter the physical and chemical properties of AgNPs. The current research evaluated changes in size, aggregation, chemical composition, and silver speciation of four different sizes of AgNPs exposed to four different formulations of AS. The AS formulations were from standardized methods with different chemical compositions, ionic strengths, and pH. Samples were collected at four-time intervals for analysis using dynamic light scattering , UV-Vis spectroscopy, and single-particle inductively coupled plasma-mass spectrometry . Each mixture was also prepared for speciation analysis using X-ray absorption spectroscopy and scanning electron microscopy coupled to energy-dispersive X-ray analysis. The equivalent diameter measurements from the three techniques followed the order of DLS > UV-Vis > spICP-MS. Speciation analyses indicate significant changes for the smaller NPs, while the largest (100 nm) NPs had less measurable differences. This study shows the need to fully understand what specific information an analytical technique might provide and to use those techniques properly in tandem to give the fullest answer to a given research question.

Particle and organic vapor emissions from children's 3-D pen and 3-D printer toys.

Objective: Fused filament fabrication "3-dimensional (3-D)" printing has expanded beyond the workplace to 3-D printers and pens for use by children as toys to create objects.Materials and methods: Emissions from two brands of toy 3-D pens and one brand of toy 3-D printer were characterized in a 0.6 m3 chamber (particle number, size, elemental composition; concentrations of individual and total volatile organic compounds (TVOC)). The effects of print parameters on these emission metrics were evaluated using mixed-effects models. Emissions data were used to model particle lung deposition and TVOC exposure potential.Results: Geometric mean particle yields (106-1010 particles/g printed) and sizes (30-300 nm) and TVOC yields (

Spectroelectrochemistry of tris(bipyridyl)silicon(IV): ligand localized reductions with potential electrochromic applications.

Tris(bipyridyl)silicon(iv) was electrochemically reduced in acetonitrile to obtain the UV-vis spectra of its reduced species. Three stable, reversible reduced states (3+, 2+, and 1+) were observed with distinct isosbestic points for each of the redox reactions. The fully oxidized state (4+) is colorless, while the reduced states were green. The absorbance spectra for the three reduced states are consistent with ligand localized reductions. Potential advantages of using these complexes in electrochromic applications are discussed.