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Zulassung von Schutzlagen
(1995)
Untersuchung der Wirksamkeit von Filtern zum Schutz vor Partikelemissionen aus Laserdrucksystemen
(2012)
Laserdrucksysteme (Laserdrucker, -kopierer, Multifunktionsgeräte) emittieren in sehr unterschiedlichen Mengen Partikel im Größenbereich zwischen 5 und 300 nm, die im Druckbetrieb überwiegend durch Kondensation aus der Gasphase entstehen. Eine präventive Minderung dieser Emissionen ist sinnvoll. Die Filtration der in Laserdruckern entstehenden Aerosole bietet eine Option für eine wirksame Emissionsminderung. Die untersuchten Filter mit verschiedenen Filterkonzepten zeigten in ihrer Wirkung deutliche Unterschiede. Die Ergebnisse unterstreichen die Notwendigkeit der gerätespezifischen Optimierung von Filtern für die Anwendung in Laserdrucksystemen.----------------------------------------------------------------------------------------------------------------------------------------------
Laser printing devices are sources of particle emission in different quantities in the size range between 5 and 300 nm. The particles are predominantly generated by re-condensation from the gas phase. Emission mitigation as a precautionary measure should be considered and exhaust air filtration is one technical option. Two particle filters with different filter concepts were compared and revealed different levels of performance. The result underpins the need for individual filter solutions for laser printing devices.
Partikelanalyse im Brandfall
(2013)
Geosynthetic clay liners (GCLs) often have a sandwich-like multilayer structure, e.g. bentonite encased between two geotextile layers connected by fibers or yarns, either by needle-punching or stitch-bonding. Therefore, the internal shear strength of the GCL depends on the strength of reinforcing fiber bundles or yarns and their anchoring strength in the cover and carrier geotextiles. When used on long and steep slopes and covered with thick soil layers, the GCL is permanently exposed to a combined action of compressive and shear stress. Such load conditions are characteristic for landfill covers and the slope stability of the overall cover system in the long run strongly depends on the long-term internal shear strength of the GCL. A new test method was developed to study this long-term shear behavior. The focus was not only on creep, as it is normally done, but on aging effects. The shear test devices allow the measurement of creep curves and times-to-failure at elevated temperatures in different media (tap water and de-ionized water). In this publication, the main findings of the experiments on needle-punched GCLs with and without thermal treatment are summarized. Tap water as a test medium was essential to ensure sodium to calcium ion exchange in the bentonite layer. Under this condition extremely long test durations without failure were achieved. Sliding failure occurred when de-ionized water was used. Two failure modes were observed: brittle failure of the GCLs with thermal treatment and slow disentanglement of fiber bundles for untreated GCLs. Short-term shear strength (e.g. peel strength) is unrelated to the actual long-term shear strength, i.e. to the times-to-failure achieved in long-term shear strength test. Hence, short-term shear strength alone will not provide reliable dimensioning data for product design and choice of resins. Therefore, the often suggested approach, namely, restriction to short-term tests only and application of factors of safety, is challenged by these results.
A screening test for potential emissions of volatile organic compounds (VOC) was run on different thermoplastic filaments used for 3D printing. The method of direct thermal desorption was used to simulate the high temperatures during the 3D printing process and to identify the main compounds emitted from the filaments. A )arge number of unexpected compounds were detected that might affect the user's health and have an impact on indoor air chemistry.
Measurements of aerosol particles are vital for enforcing EU air quality regulations to protect human health, and for research on climate change effects. Although metrics such as PM10 and PM2.5 are currently in use, the level of uncertainty of aerosol metrics is too high and the traceability is insufficient. The project AEROMET, which has been started in June 2017 aims at implementing improvements in a) the uncertainty of particle mass, size and number concentration measurements and b) in the characterization of regulated components in airborne particles. Both are demanded by existing networks within the EU as well as by global atmospheric research.
On-site measurement campaigns
One of the objects is the application of mobile x-ray spectroscopy techniques combined with aerosol sampling techniques for quantifying particle compositions in the field for real time analysis. During two in-field measurement campaigns in Budapest, Hungary in May 2018 and Cassino, Italy in September 2018 the size dependent mass concentrations of specific elements in ambient aerosols were monitored under dynamic conditions.
Typically, airborne particles are sampled on filter substrates. During this project new sampling methods with specially designed substrate holders for an in-situ TXRF analysis were developed and applied for the first time. This approach allows a direct time and size resolved analysis without laborious digestion steps and a reduced risk of contamination.
Aerosol particles were sampled in a 13-stage DLPI impactor - size range from 0,03 µm to 10 µm - which was equipped with special adapters for acrylic discs of 30 mm diameter, serving as substrates. TXRF analysis was performed on site with the transportable spectrometer S2 PICOFOX (Bruker Nano GmbH) equipped with a Mo X-ray tube and a 30 mm² Silicon Drift Detector (SDD). Excitation conditions were 50 kV, 600 µA, measurement time 1000 s. Quantification was based on internal standardization using 50 ng of Y in solution, which was pipetted into the centre of the discs prior to sampling.
At moderate air pollution levels, i.e. PM10 ~ 20 µg/m³, sampling times of less than 2 hours were enough for the detection of elements in different particle size bins. The in-situ approach and the high sensitivity of TXRF enables the observation of rather quick changes in the quantity and distribution of elements in an ambient aerosol on the day of sampling, as the below example from the Cassino field campaign on 11 Sept. 2018 shows: The analysis of the morning and afternoon sampling shifts reveals the occurrence of the elements Fe, Ca and Si in different size bins as well as their significant temporal change in respective mass concentrations over the day while the distributions of several other elements in the aerosol remain unchanged.
The validation of these results by backup measurements is planned.
A mobile Bruker S2 Picofox TXRF spectrometer has been used in two field campaigns within the EMPIR env07 AEROMET project for the on-site analysis of cascade impactor aerosol samples.The results show that even at moderate air pollution levels – i.e.PM10 fairly below 20 μg/m³ - element mass concentrations in air in the range of 100 pg/m³could be measured in up to 13 size bins after sampling times of less than only 0.5 days.
The physical and chemical analysis of aerosols using reliable and physically traceable methods is important for the thorough investigation of airborne particles to support a better understanding of their origin as well as their health and climate impacts. Within the European Metrology Research AeroMet project,the aim of hysikalisch–Technische Bundesanstalt’s (PTB) X-ray spectrometry group is to develop and establish traceable and reliable X-ray methods to measure the elemental mass deposition per unit area, the elemental composition,and the chemical binding state of particulate matter supported by a flat substrate. This approach can substantially contribute to support quantitative analytical methods during on-site measurement campaigns where portable Instrumentation is employed by qualifying suitable calibration samples for commercial analytical X-ray instruments and by investigating samples collected during the field campaign.
3D-printing or additive manufacturing has many promising and unique advantages. Especially low cost molten polymer Deposition Printers are increasingly populär in the private and educational sector.
Their environmental friendliness can be questioned due to recently reported ultrafine particle and suspected VOC emissions, To further investigate 3D-printing as a potential indoor air pollution source we characterized fine and ultrafine particle emissions from a molten polymer deposition printer producing a 3D object with ten marketable polymer filament materials under controlled conditions in a test chamber. VOC emissions from the filaments have also been compared. Using a straightforward emission model time dependent and averaged particle emission rates were determined. The results indicate that under comparable conditions some filament materials produce mainly ultrafine particles up to an average rate of 1013 per minute. This value is in the upper ränge of typical indoor ultrafine particle sources (e.g. Smoking, frying, candle light, laser printer). The observed material-specific rates differ by five Orders of magnitude. Filament-specific gaseous emissions of organic compounds such as bisphenol A, styrene and others were also detected.
Our results suggest a detailed evaluation of related risks and considering protective measures such as housing and filtering.
Es wurde untersucht, ob und unter welchen Bedingungen sich Kurzfasern aus Hanf heimischer Produktion für die Erzeugung einer Faser-Antifoulingbeschichtung auf Schiffsrümpfen sowie für die Beflockung anderer technischer Oberflächen verwenden lassen.
Das Grundprinzip der Beflockungstechnik besteht darin, Kurzfasern im Längenbereich zwischen 0.5 und 15 mm in einem elektrischen Feld auf eine frisch mit einem Lack oder Kleber beschichtete ebene oder profilierte bzw. gekrümmte Oberfläche aufzubringen und dort bevorzugt senkrecht zu verankern. Auf diese Weise entsteht ein dichter, die Oberfläche vollständig bedeckender Faserflor. Als Flockfasermaterial finden bisher vorwiegend Polyamid (Nylon, Perlon), Viskose, Polyester sowie Baumwolle als nachwachsende Faser Verwendung. Nach der Herstellung unterscheidet man Schnitt- und Mahlflockfasern. Beflockungsmaschinen größerer Leistungsfähigkeit sind in der Regel keine mobilen Aggregate, sondern stationäre, für einen bestimmten Anwendungszweck spezialisierte Aufbauten, auf denen z.B. Gehäuse, PKW-Innenausbauteile, Profile, Bezugsstoffe und andere Textilien beschichtet werden.
Die Besonderheit dieses Vorhabens liegt einerseits in der Verwendung einer neuen Faserart - Hanfkurzfasern - für Beflockungszwecke und andererseits in der Notwendigkeit ein eher mobiles Beflockungsaggregat zu entwickeln, um die Beflockung von Schiffsrümpfen und anderen größeren Objekten prinzipiell zu ermöglichen.
Mobility particle size spectrometers (MPSS) belong to the essential instruments in aerosol science that determine the particle number size distribution (PNSD)in the submicrometer size range. Following calibration procedures and target uncertainties against standards and reference instruments are suggested for a complete MPSS quality assurance program: a) calibration of the CPC counting efficiency curve (within 5% for the plateau counting efficiency; within 1 nm for the 50% detection efficiency diameter), b) sizing calibration of the MPSS, using a certified polystyrene latex (PSL) particle size standard at 203 nm (within 3%), c) intercomparison of the PNSD of the MPSS (within 10% and 20% of the dN/dlogDP concentration for the particle size range 20 – 200 nm and 200 to 800 nm, respectively), and d) intercomparison of the integral PNC of the MPSS (within 10%). Furthermore, following measurement uncertainties have been investigated: a) PSL particle size standards in the range from 100-500nm match within 1% after sizing calibration at 203 nm. b) Bipolar diffusion chargers based on the radioactive nuclides Kr85, Am241 and Ni63 and a new ionizer based on corona discharge follow the recommended bipolar charge distribution, while soft X-ray-based charges may alter faster than expected. c) The use of a positive high voltage supply show a 10% better performance than a negative one. d) The intercomparison of the integral PNC of an MPSS against the total number concentration is still within the target uncertainty at an ambient pressure of approximately 500 hPa.
Ultrafine particles emitted from laser printers are suspected to elicit adverse health effects. We performed 75-minute exposures to emissions of laser printing devices (LPDs) in a standardized, randomized, cross- over manner in 23 healthy subjects, 14 mild, stable asthmatics, and 15 persons reporting symptoms associated with LPD emissions. Low-level exposures (LLE) ranged at the particle background (3000 cm−3) and High-level exposures (HLE) at 100 000 cm−3. Examinations before and after exp sures included spirometry, body plethysmography, transfer factors for CO and NO (TLCO, TLNO), bronchial and alveolar NO, cytokines in serum and nasal secretions (IL-1β, IL-5, IL-6, IL-8, GM-CSF, IFNγ, TNFα), serum ECP, and IgE. Across all participants, no statistically significant changes occurred for lung mechanics and NO. There was a decrease in volume-related TLNO that was more pronounced in HLE, but the difference to LLE was not significant. ECP and IgE increased in the same way after exposures. Nasal IL-6 showed a higher increase after LLE. There was no coherent pattern regarding the responses in the participant subgroups or single sets of variables. In conclusion, the experimental acute responses to short but very high-level LPD exposures were small and did not indicate clinically relevant effects compared to low particle number concentrations.
Vor dem Hintergrund der anhaltenden öffentlichen Diskussion um mögliche gesundheitliche Risiken von Ultrafein- und Feinstaubemissionen aus Bürogeräten mit Laserdruckfunktion (LPD, Laser Printing Device) wurde vom Umweltbundesamt ein Forschungsvorhaben zur Entwicklung einer Prüfprozedur für die Quantifizierung der emittierten Partikel durch Zählung unter Standardbedingungen in Emissionsmesskammern, sowie zur physikalischen und chemischen Charakterisierung dieser Aerosole initiiert. Als Ergebnis konnte die Partikelzählung in den Entwurf des Prüfverfahrens für die Bestimmung von Emissionen (RAL-UZ-122, Anhang S-M) des Umweltzeichens "Blauer Engel" für Bürogeräte sowie in den Prüfstandards ECMA-328 und den Entwurf der ISO/IEC 28360 integriert werden. Die Methode wurde in einem internationalen Ringversuch erfolgreich getestet. Auf dieser Basis können Vergabekriterien und -werte für die Emission von Fein- und Ultrafeinpartikeln im Rahmen der Vergabe des Umweltzeichens Blauer Engel vereinbart und Produktprüfungen vorgenommen werden.
Der vorliegende Bericht ist der 2.Teil eines Gesamtberichtes und schildert ausführlich die im Kontext des BAM-Innovationsoffensive-Projektes „Chemische Brandspurenanalytik“ durchgeführten Untersuchungen und fasst die gewonnenen analytischen Erkenntnisse zusammen. Der gesamte Bericht gliedert sich in drei Teile. Der erste Teil beinhaltet den Aufbau, die Durchführung und die brandtechnologische Auswertung der durchgeführten Raumbrandversuche, während in dem hier vorliegenden Teil die analytischen Methoden zum Nachweis des Brandbeschleunigers in den Brandrückständen vorgestellt und ausgewertet werden. Die Beurteilung von Brandspuren und daraus abgeleitet die Rekonstruktion eines Brandverlaufes beruhen auch auf der präzisen chemischen Analyse der Brandprodukte. Im Rahmen dieses Projektes wurde eine innovative Methodik entwickelt, wie verfügbare Analysetechniken in geeigneter Weise kombiniert werden können, um aus festen, flüssigen und gasförmigen Brandrückständen Rückschlüsse auf den Brandverlauf ziehen zu können. Neben der Untersuchung von Proben von realen Brandorten wurden verschiedene wohnungstypische Materialien unter Laborbedingungen unterschiedlichen Brandszenarien unterworfen. Die dabei entstehenden Brandgase, Aerosole sowie der verbleibende Brandrückstand wurden durch geeignete analytische Verfahren analysiert, um mögliche Brandursachen beurteilen zu können. Der Schwerpunkt dieses Berichtes liegt in dem Nachweis von Brandbeschleunigern. Es zeigte sich, dass mittels der Kombination aus HS-SPME-GC-MS sowohl in den festen Brandrückständen, als auch in den Kondensaten Brandbeschleuniger eindeutig und verlässlich nachgewiesen werden können. Anhand von 5 verschiedenen Zimmerbrandversuchen wurde der Einfluss von Brandbeschleunigern auf den Brandverlauf experimentell untersucht. Es wurden verschiedene brandtechnologische Kennwerte, wie der Massenverlust des gesamten Brandraums, Brandraumtemperaturen, die Wärmefreisetzungen sowie die Rauchgasemissionen ermittelt und beurteilt. Die Rauchgasanalyse erfolgte im Schlot, im Brandraum sowie in der Brandraumöffnung mittels Fourier Transformierte Infrarot-FTIR-Spektroskopie. Neben diesen brandtechnologischen Untersuchungen, die im Bericht Teil 1 enthalten sind, erfolgten auch chemisch-analytische Untersuchungen nach dem Brand, mit dem Ziel, den eingesetzten Brandbeschleuniger nachzuweisen. Im Anschluss an die jeweiligen Zimmerbrandversuche wurden verschiedene Brandrückstandsproben aus dem Brandschutt, Wischproben von den Wänden und den übriggebliebenen Gegenständen genommen und mit Hilfe einer entwickelten HS-SPME-GC-MS-Methode (Headspace-Solid Phase Micro Extraction-Gas Chromatographie-Massenspekrometrie) in Hinblick eines möglichen Brandbeschleunigernachweis analysiert.
In einem von der Firma GSE Lining Technology GmbH geförderten F+E-Vorhaben wurde die Langzeitscherfestigkeit und die Oxidationsstabilität von deren strukturierten PE-HD- Dichtungsbahnen untersucht. Bei diesen strukturierten Dichtungsbahnen wird das Strukturmaterial in einem eigenen Arbeitsgang aufgebracht. Das PE-HD-Material der Grundbahn war in allen Fällen Vestolen A 3512 R. Für das Strukturmaterial wurden die PE- LLD-Werkstoffe Ladene 118 N mit zwei Rußbatches (Proben 229/1 und 229/2) und Dowlex 2045 E mit zwei Rußbatches (Proben 229/3 und 229/4) verwendet. Die Langzeitscherfestigkeit wurde in Zeitstand-Scherversuchen in Wasser bei 80 °C getestet und dabei auch die Veränderung der OIT Werte von Grundbahn und Strukturmaterial gemessen. Die Oxidationsstabilität des Strukturmaterials im Vergleich zur Grundbahn wurde in Autoklavenversuchen an Proben im Wasserbad unter einem Sauerstoffdruck von 20 bar und 80°C geprüft. Nach der Immersion wurde die Veränderung der Reibungsparameter in Scherkastenversuchen ermittelt.
The emission of ultrafine particles from small desktop Fused Filament Fabrication (FFF) 3D printers has been frequently investigated in the past years. However, the vast majority of FFF emission and exposure studies have not considered the possible occurrence of particles below the typical detection limit of Condensation Particle Counters and could have systematically underestimated the total particle emission as well as the related exposure risks. Therefore, we comparatively measured particle number concentrations and size distributions of sub-4 nm particles with two commercially available diethylene glycol-based instruments – the TSI 3757 Nano Enhancer and the Airmodus A10 Particle Size Magnifier. Both instruments were evaluated for their suitability of measuring FFF-3D printing emissions in the sub-4 nm size range while operated as a particle counter or as a particle size spectrometer. For particle counting, both instruments match best when the Airmodus system was adjusted to a cut-off of 1.5 nm. For size spectroscopy, both instruments show limitations due to either the fast dynamics or rather low levels of particle emissions from FFF-3D printing in this range. The effects are discussed in detail in this article. The findings could be used to implement sub-4 nm particle measurement in future emission or exposure studies, but also for the development of standard test protocols for FFF-3D printing emissions.
In this work, we characterise the performance of a Sharp optical aerosol sensor model GP2Y1010AU0F. The sensor was exposed to different environments: to a clean room, to a controlled atmosphere with known aerosol size distribution and to the ambient atmosphere on a busy city street. During the exposure, the output waveforms of the sensor pulses were digitised, saved and a following offline analysis enabled us to study the behaviour of the sensor pulse-by-pulse. A linear response of the sensor on number concentration of the monosized dispersed PSL particles was shown together with an almost linear dependence on particle diameters in the 0.4 to 4 micrometer range.
The gathered data about the sensor were used to predict its response to an ambient atmosphere, which was observed simultaneously with a calibrated optical particle counter.
Condensation particle counters (CPCs) are widely used for the measurement of aerosol particle number concentrations in the size range from approximately 3 nm to 3 μm. For an SI-traceable calibration of the size-dependent counting efficiency, which is advisable on a regular basis and required in several applications, Faraday cup aerosol electrometers (FCAEs) are considered to be a suitable SI-traceable reference.While the volumetric aerosol inlet flowrate and the electrical current measurement in FCAEs can be related to respective SI references, inter-comparison exercises for FCAEs are still performed on a regular basis to establish reliable uncertainty budgets and to further investigate the influences of designs and operational parameters on comparability. This is strongly demanded in the international community of metrological institutes and aerosol calibration facilities around the world, which provide CPC calibrations. In the present study, the performance of FCAEs was investigated,using Ag test aerosol particles with a 30 nm particle diameter by varying the inlet flowrates from 0.5 l min−1 to 4 l min−1. From our experimental results, significant deviations were observed in FCAE currents at sample flowrates smaller than 1.5 l min−1. It is recommended that these discrepancies should be quantified before an FCAE is used for CPC calibration at low sample flowrates and small particle sizes in the sub-30 nm size range.
Teil 1: In der Öffentlichkeit werden immer wieder mögliche gesundheitliche Auswirkungen von Laserdruckeremissionen diskutiert. Um diese möglichen Auswirkungen genauer zu analysieren, wurden die Effekte 75-minütiger Expositionen von sogenannten Low-Emittern (LE, Untergrund 2000-4000 UFP/cm3) gegenüber High-Emittern (HE, 100.000 UFP/cm3) untersucht.
Teil 2: Mögliche gesundheitliche Auswirkungen von Laserdruckeremissionen sind immer wieder Gegenstand öffentlicher Aufmerksamkeit. Die dabei auftretenden potenziellen psychologischen Aspekte, wurden in einem standardisierten Szenario mittels 75-minütiger Expositionen gegenüber Low-Emittern (LE, Untergrund 2000-4000 UFP/cm3) und High-Emittern (HE, 100.000 UFP/cm3) untersucht.
Two types of copper samples, compact certified copper reference materials and calibration samples prepared from liquid doped, pressed copper powders, were studied in terms of accuracy of obtained calibration functions originating from infrared spark ablation. Additionally, corresponding particle size distributions of the aerosols from infrared spark ablation were recorded. It is shown that the differences in quantification results, originating from the two sets of calibration functions, could not mainly be ascribed to different particle size distributions of the two copper sample types. Possible other causes, as different ablation rates, parts of melting and differences of the chemical constitutions of the two sample types were explored.
In this work, the elemental composition of fine and ultrafine particles emitted by ten different laser printing devices (LPD) is examined. The particle number concentration time series was measured as well as the particle size distributions. In parallel, emitted particles were size-selectively sampled with a cascade impactor and subsequently analyzed by the means of XRF. In order to identify potential sources for the aerosol's elemental composition, materials involved in the printing process such as toner, paper, and structural components of the printer were also analyzed. While the majority of particle emissions from laser printers are known to consist of recondensated semi volatile organic compounds, elemental analysis identifies Si, S, Cl, Ca, Ti, Cr, and Fe as well as traces of Ni and Zn in different size fractions of the aerosols. These elements can mainly be assigned to contributions from toner and paper. The detection of elements that are likely to be present in inorganic compounds is in good agreement with the measurement of nonvolatile particles. Quantitative measurements of solid particles at 400 °C resulted in residues of 1.6 × 109 and 1.5 × 1010 particles per print job, representing fractions of 0.2% and 1.9% of the total number of emitted particles at room temperature. In combination with the XRF results it is concluded that solid inorganic particles contribute to LPD emissions in measurable quantities. Furthermore, for the first time Br was detected in significant concentrations in the aerosol emitted from two LPD. The analysis of several possible sources identified the plastic housings of the fuser units as main sources due to substantial Br concentrations related to brominated flame retardants.
Quantitative characterization of nanoparticle emissions from office machines with printing function
(2007)
Development of wood-inorganic composites with enhanced properties and environmental stability
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This work presents results of investigations towards the emission of chemical reaction products and sound pressure during an outdoor and an indoor firework display. Potentially harmful and toxic gases, and aerosols, were measured as well as sound pressures. Aerosols were measured with a Differential Mobility Analyzer (DMA) as well as a Laser Particle Counter. The focus was on particles with diameters between 11 nm and 20 µm. A transportable Fourier Transform Infrared (FTIR) spectroscopy detector registered the concentrations of emitted reaction gases, simultaneously. During the outdoor firework display, peak particle concentrations of >550000 particles cm-3, equivalent to a mass concentration of approximately 3.95 mg m-3, were detected, revealing a concentration maximum at approximately 175 nm particle diameter. The time-averaged particle mass concentration did not exceed 1.58 mg m-3 over 15 minutes. Due to the large distances (110 m) to the firing points, no significant harmful or toxic gas concentrations were measured during the entire firework display. In contrast, concentrations of sulphur dioxide (SO2) rose after an indoor firework display in a large event hall. On two days, more than 23000 particles cm-3 (which equates to a mass concentration of approximately 0.41 mg m-3) were detected when the hall ventilation was turned off, and more than 11000 particles cm-3 (which equates to a mass concentration of approximately 1.18 mg m-3) when the hall ventilation was activated. Concentration maxima appeared at approximately 300 nm particle diameter. The time-averaged particle concentrations in this case did not exceed 0.56 mg m-3 (over 15 minutes).
Fused filament fabrication (FFF) is a material extrusion-based technique often used in desktop 3D printers. Polymeric filaments are melted and are extruded through a heated nozzle to form a 3D object in layers. The extruder temperature is therefore a key parameter for a successful print job but also one of the main emission driving factors as harmful pollutants (e.g., ultrafine particles) are formed by thermal polymer degradation. The awareness of potential health risks has increased the number of emission studies in the past years. However, studies usually refer their calculated emission data to the printer set extruder temperature for comparison purposes. In this study, we used a thermocouple and an infrared camera to measure the actual extruder temperature and found significant temperature deviations to the displayed set temperature among printer models. Our result shows that printing the same filament feedstocks with three different printer models and with identical printer set temperature resulted in a variation in particle emission of around two orders of magnitude. A temperature adjustment has reduced the variation to approx. one order of magnitude. Thus, it is necessary to refer the measured emission data to the actual extruder temperature as it poses a more accurate comparison parameter for evaluation of the indoor air quality in user scenarios or for health risk assessments.
11 laser printers from 5 manufacturers were purchased in 2017 and tested for their UFP emissions. Size resolved sampling of the emitted particles was done with a 13 stage (30 nm to 10 µm) low pressure cascade impactor. The sampled particles were analysed for their chemical composition by thermal extraction (vaporization at 290°C) followed by GC-MS analysis. High boiling cyclic siloxanes (D10 to D16) were detected as constituents of UFP from laser printers. In comparison to measurements in 2008, aliphatic long-chain alkanes (C22 to C34) were detected additionally as chemical constituents of UFP from most of the tested printers and their amounts were higher than for cyclic siloxanes. Printers of one manufacturer showed very low UPF emissions compared to the other manufacturers.
The diversity of fused filament fabrication (FFF) filaments continues to grow rapidly as the popularity of FFF-3D desktop printers for the use as home fabrication devices has been greatly increased in the past decade. Potential harmful emissions and associated health risks when operating indoors have induced many emission studies. However, the lack of standardization of measurements impeded an objectifiable comparison of research findings. Therefore, we designed a chamber-based standard method, i.e., the strand printing method (SPM), which provides a standardized printing procedure and quantifies systematically the particle emission released from individual FFF-3D filaments under controlled conditions. Forty-four marketable filament products were tested. The total number of emitted particles (TP) varied by approximately four orders of magnitude (1E9 ≤ TP ≤ 1E13), indicating that origin of polymers, manufacturer-specific additives, and undeclared impurities have a strong influence. Our results suggest that TP characterizes an individual filament product and particle emissions cannot be categorized by the polymer type (e.g., PLA or ABS) alone. The user's choice of a filament product is therefore decisive for the exposure to released particles during operation. Thus, choosing a filament product awarded for low emissions seems to be an easily achievable preemptive measure to prevent health hazards.
The development of traceable new methodologies to quantify elemental air pollutants in particulate matter (PM) supports modernization of methods used in air quality monitoring networks in Europe. In the framework of the EURAMET EMPIR AEROMET II project, the combination of cascade impactor aerosol sampling and total reflection X-ray fluorescence elemental spectroscopy (TXRF) was investigated. This technique requires a traceable calibration based on reference samples. This paper describes a new, simple and effective method to produce such reference samples using flexible, reusable, and low-cost parylene C shadow masks, fabricated by photolithographic steps. These shadow masks can be used to produce reference samples that mimic the Dekati cascade impactor’s deposition patterns by applying as-prepared micro stencils to 30 mm acrylic substrates and evaporating a reference material (Ti) in arrangements of thin circular dots. The highly flexible direct patterning of acrylic discs with reference material, otherwise impossible with conventional photolithography, allows multiple reusing of the same micro stencils. The aspect ratios of the dots could be repeated with an error less than 4 %. A first set of standard reference samples for the 13 stages of the Dekati cascade impactor was produced and preliminary TXRF measurements of the deposited Ti masses were performed. The centricity of the deposition patterns turned out to be an important parameter for the quality of the TXRF results. The parylene mask technology for the production of reference samples turns out to be a promising new approach for the traceable calibration of TXRF spectrometers for the quantification of element concentrations in environmental aerosol samples but, due to its great versatility, it could be used for several other micropatterning applications on conventional and unconventional substrates.
Previous studies have shown that desktop 3D printers (Fused Filament Fabrication) emit high numbers of particulate matter, mainly as ultrafine particles (UFP, particle diameter less than 100 nm). However, the chemical composition of emitted particles has been less extensively investigated. In this study, we therefore focused on the chemical composition of particles emitted from 3D printing. The measurements were conducted in a 1 m³ emission test chamber. Emitted particles were sampled by a 13-stage low-pressure cascade impactor onto aluminum foils and then analyzed by TD-GC/MS to identify their organic compounds. Nine commercial filaments made from basic polymers such as Acrylonitrile Butadiene Styrene (ABS), Acrylonitrile Styrene Acrylate (ASA), Polycarbonate (PC), Poly(methyl methacrylate) (PMMA), Nylon, High Performance Polystyrene (HIPS) and a copper-filled Polylactide (PLA) were investigated. The results show that the organic components of the particles are primarily plastic additives such as plasticizer, antioxidant agents, lubricants, UV-absorbers and UV-stabilizers from the filaments.
Quantitative chemical analysis of airborne particulate matter (PM) is vital for the understanding of health effects in indoor and outdoor environments, as well as for enforcing air quality regulations. Typically, airborne particles are sampled over long time periods on filters, followed by lab-based analysis, e.g., with inductively coupled plasma mass spectrometry (ICP-MS). Within the EURAMET EMPIR AEROMET project, cascade impactor aerosol sampling was combined for the first time with on-site total reflection X-ray fluorescence (TXRF) spectroscopy to develop a tool for quantifying particle element compositions within short time intervals and even on-site. This makes variations of aerosol chemistry observable with time resolution of only a few hours and with good size resolution in the PM10 range. A proof of principles of this methodological approach and the comparison to standard methods within the scope of a field campaign will be presented. Secondly, aerosol sampling and TXRF analysis seems suitable for the quantification of elements in indoor aerosols as well and may provide an important enhancement of existing methods for the analysis of organic species in aerosols (such as sampling and TD-GC/MS). As an example, the TXRF analysis of particles emitted from laser printers under controlled conditions in an environmental test chamber will be presented.