Volatile organic compound and particulate emissions from the production and use of thermoplastic biocomposite 3D printing filaments.

Biocomposites (BCs) can be used as substitutes for unsustainable polymers in 3D printing, but their safety demands additional investigation as biological fillers may produce altered emissions during thermal processing. Commercial filament extruders can be used to produce custom feedstocks, but they are another source of airborne contaminants and demand further research. These knowledge gaps are targeted in this study. Volatile organic compound (VOC), carbonyl compound, ultrafine particle (UFP), and fine (PM2.5) and coarse (PM10) particle air concentrations were measured in this study as a filament extruder and a 3D printer were operated under an office environment using one PLA and four PLA-based BC feedstocks. Estimates of emission rates (ERs) for total VOCs (TVOC) and UFPs were also calculated. VOCs were analyzed with a GC-MS system, carbonyls were analyzed with an LC-MS/MS system, whereas real-time particle concentrations were monitored with continuously operating instruments. VOC concentrations were low throughout the experiment; TVOC ranged between 34-63 µg/m3 during filament extrusion and 41-56 µg/m3 during 3D printing, which represent calculated TVOC ERs of 2.6‒3.6 × 102 and 2.9‒3.6 × 102 µg/min. Corresponding cumulative carbonyls ranged between 60-91 and 190-253 µg/m3. Lactide and miscellaneous acids and alcohols were the dominant VOCs, while acetone, 2-butanone, and formaldehyde were the dominant carbonyls. Terpenes contributed for ca. 20-40% of TVOC during BC processing. The average UFP levels produced by the filament extruder were 0.85 × 102-1.05 × 103 #/cm3, while the 3D printer generated 6.05 × 102-2.09 × 103 #/cm3 particle levels. Corresponding particle ERs were 5.3 × 108-6.6 × 109 and 3.8 × 109-1.3 × 1010 #/min. PM2.5 and PM10 particles were produced in the following average quantities; PM2.5 levels ranged between 0.2-2.2 µg/m3, while PM10 levels were between 5-20 µg/m3 for all materials. The main difference between the pure PLA and BC feedstock emissions was terpenes, present during all BC extrusion processes. BCs are similar emission sources as pure plastics based on our findings, and a filament extruder produces contaminants at comparable or slightly lower levels in comparison to 3D printers.

Organic compound and particle emissions of additive manufacturing with photopolymer resins and chemical outgassing of manufactured resin products.

Photopolymer resins are applied at an increasing rate in additive manufacturing (AM) industry as vat photopolymerization (VP) and material jetting (MJ) methods gain more popularity. The aim of this study was to measure volatile organic compound (VOC), carbonyl compound, ultrafine particle (UFP), and particulate matter (PM10) air concentrations emitted in 3D printer operations. Individual chemicals were identified when multiple photopolymer resin feedstocks were used in various VP and MJ printers. The size distributions of UFPs, and indoor air parameters were also monitored. Finally, the VOC outgassing of the cured resin materials was determined over 84 days. The data demonstrated that 3D printer operators were exposed to low concentrations of airborne exposure agents as follows: average concentrations of VOCs were between 41 and 87 µg/m3, UFP number levels ranged between 0.19 and 3.62 × 103 number/cm3; however, no impact was detected on air parameters or PM10 concentrations. A majority of the UFPs existed in the 10-45 nm size range. The identified compounds included hazardous species included sensitizing acrylates and carcinogenic formaldehyde. The outgassed products included similar compounds that were encountered during the AM processes, and post-processing solvents. Products heated to 37°C emitted 1.4‒2.9-fold more VOCs than at room temperature. Total emissions were reduced by 84‒96% after 28 days roughly from 3000-14000 to 100-1000 µg/m2/hr. In conclusion, resin printer operators are exposed to low concentrations of hazardous emissions, which might result in adverse health outcomes during prolonged exposure. Manufactured resin products are suggested to be stored for 4 weeks after their production to reduce potential consumer VOC hazards.

Occupational exposure to gaseous and particulate contaminants originating from additive manufacturing of liquid, powdered, and filament plastic materials and related post-processes.

The aim of this study was to measure the concentrations of gaseous and particulate contaminants originated from additive manufacturing operations and post-processes in an occupational setting when plastics were used as feedstock materials. Secondary aims were to evaluate the concentration levels based on proposed exposure limits and target values and to propose means to reduce exposure to contaminants released in additive manufacturing processes. Volatile organic compounds were sampled with Tenax TA adsorption tubes and analyzed with a thermo desorption gas chromatography-mass spectrometry instrument. Carbonyl compounds were sampled with DNPH-Silica cartridges and analyzed with a high-performance liquid chromatography device. Particles were measured with P-Trak instrument and indoor air quality was sampled with IAQ-Calc instrument. Dust mass concentrations were measured simultaneously with a DustTrak DRX instrument and IOM-samplers. Particle concentrations were highest (2070-81 890 #/cm3 mean) during manufacturing with methods where plastics were thermally processed. Total volatile organic compounds concentrations, in contrast, were low (113-317 µg/m3 mean) during manufacturing with such methods, and vat photopolymerization. However, total volatile organic compounds concentrations of material jetting and multi jet fusion methods were higher (1,114-2,496 µg/m3 mean), perhaps because of material and binder spraying, where part of the spray can become aerosolized. Chemical treatment of manufactured objects was found to be a severe volatile organic compounds source as well. Formaldehyde was detected in low concentrations (3-40 µg/m3) in all methods except for material jetting method, in addition to several other carbonyl compounds. Notable dust concentrations (1.4-9.1 mg/m3) were detected only during post-processing of powder bed fusion and multi jet fusion manufactured objects. Indoor air quality parameters were not found to be notably impacted by manufacturing operations. Only low concentrations (below 2 ppm) of CO were detected during several manufacturing processes. All studied additive manufacturing operations emitted potentially harmful contaminants into their environments, which should be considered in occupational additive manufacturing and workplace design. According to the measured contaminant levels it is possible that adverse additive manufacturing related health effects may occur among exposed workers.