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This study aims to develop a comprehensive process to evaluate the leaching behavior of 3D-printed nanocomposite samples as candidate materials for potential use in wearable devices. The study involves the immersion of the 3D-printed test coupons, produced via Fused Filament Fabrication (FFF), into artificial sweat and deionized water in a controlled environment provided by a dissolution apparatus. Three distinct nanocomposite filaments were used, each consisting of different polymer matrices: thermoplastic polyurethane (TPU), copolyester (TX1501), and polyamide (PA12). The additives incorporated within these filaments encompassed silver nanoparticles (AgNPs), chopped carbon fibers (CCFs), and super paramagnetic iron oxide nanoparticles (SPIONs), respectively. The current study aims to identify potential risks associated with the release of nanomaterials and additives, through SEM/EDX analysis and in vitro measurements of proinflammatory cytokines. Furthermore, this research contributes to the advancement of safe and reliable 3D-printed materials for wearable technologies, fostering their widespread adoption in various applications.

Nanoparticles are being used in novel applications of the thermoplastics industry, including automotive parts, the sports industry and leisure and consumer goods, which can be produced nowadays through additive manufacturing. However, there is limited information on the health and safety aspects during the production of these new materials, mainly from recycled sources. This study covers the exposure assessment to nano- and micro-size particles emitted from the nanocomposites during the production of filaments for 3D printing through a compounding and extrusion pilot line using recycled (post-industrial) thermoplastic polyurethane (TPU) and recycled polyamide 12 (PA12), which have been also upcycled through reinforcement with iron oxide nanoparticles (Fe3O4 NPs), introducing matrix healing properties triggered by induction heating. The assessment protocol included near- and far-field measurements, considering the extruder as the primary emission source, and portable measuring devices for evaluating particulate emissions reaching the inhalable zone of the lab workers. A Failure Modes and Effects Analysis (FMEA) study for the extrusion process line was defined along with a Failure Tree Analysis (FTA) process in which the process deviations, their sources and the relations between them were documented. FTA allowed the identification of events that should take place in parallel (simultaneously) or in series for the failure modes to take place and the respective corrective actions to be proposed (additional to the existing control measures).

A continuous manufacturing platform was developed for the synthesis of aqueous colloidal 10–20 nm gold nanoparticles (Au NPs) in a flow reactor using chloroauric acid, sodium citrate and citric acid at 95 oC and 2.3 bar(a) pressure. The use of a two-phase flow system – using heptane as the continuous phase – prevented fouling on the reactor walls, while improving the residence time distribution. Continuous syntheses for up to 2 h demonstrated its potential application for continuous manufacturing, while live quality control was established using online UV-Vis photospectrometry that monitored the particle size and process yield. The synthesis was stable and reproducible over time for gold precursor concentration above 0.23 mM (after mixing), resulting in average particle size between 12 and 15 nm. A hydrophobic membrane separator provided successful separation of the aqueous and organic phases and collection of colloidal Au NPs in flow. Process yield increased at higher inlet flow rates (from 70 % to almost 100 %), due to lower residence time of the colloidal solution in the separator resulting in less fouling in the PTFE membrane. This study addresses the challenges for the translation of the synthesis from batch to flow and provides tools for the development of a continuous manufacturing platform for gold nanoparticles.Graphical abstract

Among the unconventional approaches of supporting catalyst nanoparticles, the layer-by-layer assembly of polyelectrolyte multilayers for nanoparticle adsorption represents an easy and convenient method. It enables the deposition of singularly adsorbed nanoparticles and prevents them from aggregating. In this work, polydopamine was grafted onto the internal surface of a Teflon AF-2400 tubular membrane, known for its excellent permeability to light gases and inertness to chemicals. Poly(acrylic acid) and poly(allylamine hydrochloride) were sequentially adsorbed onto the modified surface of the membrane. Ex situ synthesized spherical, cubical, truncated octahedral palladium or dendritic platinum-palladium nanoparticles were then incorporated. The catalytic membranes were assembled in a tube-in-tube configuration and tested over 6 h of continuous nitrobenzene hydrogenation with molecular hydrogen. Stable conversion was observed for the truncated octahedral and dendritic nanoparticles, while a progressive deactivation occurred for the other nanoparticles. Due to their small size, the 3.7 nm spherical nanoparticles exhibited the highest reaction rate, 629molreactant/(molcatalyst⋅h), while the cubical nanoparticles showed the highest turnover frequency, ∼3000 h−1. The reactor concept developed in this work demonstrates how such a design can serve as a platform for conducting continuous multiphase catalytic reactions in flow using singularly adsorbed and finely tuned nanoparticles. The small volume of pressurized gas present in the tube-in-tube reactor offers improved process safety compared to a batch process, while the Teflon AF-2400 membrane provides control over the gas permeation during reaction.

Despite the wide usage of magnetic nanoparticles, it remains challenging to synthesise particles with properties that exploit each application's full potential. Time consuming experimental procedures and particle analysis hinder process development, which is commonly constrained to a handful of experiments without considering particle formation kinetics, reproducibility and scalability. Flow reactors are known for their potential of large-scale production and high-throughput screening of process parameters. These advantages, however, have not been utilised for magnetic nanoparticle synthesis where particle characterisation is performed, with a few exceptions, post-synthesis. To overcome this bottleneck, we developed a highly sensitive magnetometer for flow reactors to characterise magnetic nanoparticles in solution in-line and in real-time using alternating current susceptometry. This flow magnetometer enriches the flow-chemistry toolbox by facilitating continuous quality control and high-throughput screening of magnetic nanoparticle syntheses. The sensitivity required to monitor magnetic nanoparticle syntheses at the typically low concentrations (

Fused Filament Fabrication (FFF) has been established as a widely practiced Additive Manufacturing technique, using various thermoplastic filaments. Carbon fibre (CF) additives enhance mechanical properties of the materials. The main operational hazard of the FFF technique explored in the literature is the emission of Ultrafine Particles and Volatile Organic Compounds. Exposure data regarding novel materials and larger scale operations is, however, still lacking. In this work, a thorough exposure assessment measurement campaign is presented for a workplace applying FFF 3D printing in various setups (four different commercial devices, including a modified commercial printer) and applying various materials (polylactic acid, thermoplastic polyurethane, copolyamide, polyethylene terephthalate glycol) and CF-reinforced thermoplastics (thermoplastic polyurethane, polylactic acid, polyamide). Portable exposure assessment instruments are employed, based on an established methodology, to study the airborne particle exposure potential of each process setup. The results revealed a distinct exposure profile for each process, necessitating a different safety approach per setup. Crucially, high potential for exposure is detected in processes with two printers working simultaneously. An updated engineering control scheme is applied to control exposures for the modified commercial printer. The establishment of a flexible safety system is vital for workplaces that apply FFF 3D printing.

The advancement of analytical methods for nanoparticle measurements is critical both for the growing industrial exploitation of engineered nanoparticles and for developing robust strategies to understand and control the concentration of nanomaterials in humans and the environment. For high value nanoparticles, the measurement of nanoparticle number concentration in a liquid directly impacts the ability to assess the scale and reproducibility of the production process, it allows optimisation of efficiency and supports regulatory compliance. This measurement is also useful to monitor and control the intentional or accidental release of engineered nanoparticles into the environment at the production plant, as well as by end-users., peer-reviewed

Three-dimensional (3D) printing has introduced a paradigm shift in the manufacturing world, and it is increasing in popularity. In cases of such rapid and widespread acceptance of novel technologies, material or process safety issues may be underestimated, due to safety research being outpaced by the breakthroughs of innovation. However, a definitive approach in studying the various occupational or environmental risks of new technologies is a vital part of their sustainable application. In fused filament fabrication (FFF) 3D printing, the practicality and simplicity of the method are juxtaposed by ultrafine particle (UFP) and volatile organic compound (VOC) emission hazards. In this work, the decision of selecting the optimal material for the mass production of a microfluidic device substrate via FFF 3D printing is supported by an emission/exposure assessment. Three candidate prototype materials are evaluated in terms of their comparative emission potential. The impact of nozzle temperature settings, as well as the microfluidic device’s structural characteristics regarding the magnitude of emissions, is evaluated. The projected exposure of the employees operating the 3D printer is determined. The concept behind this series of experiments is proposed as a methodology to generate an additional set of decision-support decision-making criteria for FFF 3D printing production cases.

The COVID-19 pandemic instigated massive production of critical medical supplies and personal protective equipment. Injection moulding (IM) is considered the most prominent thermoplastic part manufacturing technique, offering the use of a large variety of feedstocks and rapid production capacity. Within the context of the European Commission-funded imPURE project, the benefits of IM have been exploited in repurposed IM lines to accommodate the use of nanocomposites and introduce the unique properties of nanomaterials. However, these amendments in the manufacturing lines highlighted the need for targeted and thorough occupational risk analysis due to the potential exposure of workers to airborne nanomaterials and fumes, as well as the introduction of additional occupational hazards. In this work, a safety-oriented failure mode and effects analysis (FMEA) was implemented to evaluate the main hazards in repurposed IM lines using acrylonitrile butadiene styrene (ABS) matrix and silver nanoparticles (AgNPs) as additives. Twenty-eight failure modes were identified, with the upper quartile including the seven failure modes presenting the highest risk priority numbers (RPN), signifying a need for immediate control action. Additionally, a nanosafety control-banding tool allowed hazard classification and the identification of control actions required for mitigation of occupation risks due to the released airborne silver nanoparticles.

Seeded-growth synthetic protocols enable precise control of particle size and shape, crucial for many sensing applications. However, scaling-up these syntheses in a reproducible way is challenging, as minimal variation in process parameters such as seed size, concentration or reaction temperature can significantly alter the final product. Flow reactors enable tight control in the process parameters and high reproducibility of the synthesis, representing a potential technology to perform seeded-growth syntheses in large scale. This work reports the design of a flow platform for the controlled synthesis of spherical gold nanoparticles with size up to 150 n m through a seeded-growth approach, and their use in Surface Enhanced Raman Scattering (SERS) and Photoinduced Enhanced Raman Spectroscopy (PIERS). The particle growth kinetics were studied via in situ time-resolved UV–Vis spectroscopy. The spectroscopic data were fitted with a kinetic model, which was subsequently used for the design of the reactor. The kinetics-based design approach enabled fast translation of the growth synthesis in flow, eventually allowing the on demand flow synthesis of particles with controllable size, ranging from 50 to 150 n m , with high reproducibility and full precursor conversion. The particles were tested for SERS and PIERS for different substrates, including warfare agents and biomolecules, with enhancement factors between 10 3 and 10 8 depending on the analyte, demonstrating their potential for detection of various analytes.

Reproducibility in the synthesis of nanomaterials is a crucial aspect for their real-life applications. It is particularly pertinent in the context of gold nanoparticles, where a plethora of seeded-growth methods are being developed to control particle morphology and size. The translation of such methods to manufacturing can be hindered by poor reproducibility of the seed production step. This study focuses on the development of a highly reproducible platform for the synthesis of gold nanoparticles, as potential substrates for glucose sensing. A flow reactor was designed, starting from a detailed study of the synthesis in batch. The well-established Turkevich synthesis was investigated via in situ time-resolved UV-vis spectroscopy. In order to enhance the reproducibility of the synthesis the effect of passivating the gold precursor stock before its use in the synthesis was investigated. It is shown that starting from a pre-passivated precursor provided improved control over the initial reaction stage, at the expense of a small increase in the reaction time. At the optimal reaction conditions, the proposed modified Turkevich method allowed for the synthesis in batch of ∼12 nm monodisperse (RSD ∼10%) particles, with a variability from batch to batch of only ∼5%. The information gathered from the batch study, in particular the reaction time, was used to translate the synthesis from batch to flow. The system utilized for the flow synthesis consisted of a segmented flow reactor, where an organic stream was employed to segment the reactive aqueous stream to avoid reactor fouling and improve monodispersity. The use of segmented flow enables treating each droplet as a “travelling batch”, hence allowing the direct use of the kinetic data obtained in batch to design the flow reactor, leading to the rapid identification of the minimum residence time to allow for reaction completion. The flow reactor enabled the synthesis of ∼11 nm monodisperse (RSD ∼10%) particles, with full precursor conversion and reproducibility between reactor runs higher than that obtained in batch (variability of ∼2%). The flow-produced gold nanoparticles were tested for glucose sensing, exploiting their glucose oxidase-mimicking behaviour and demonstrated satisfactory glucose detection in the range of 1–10 mM.

Co-precipitation is by far the most common synthesis for magnetic iron oxide nanoparticles (IONPs), as cheap and environmentally friendly precursors and simple experimental procedures facilitate IONP production in many labs. Optimising co-precipitation syntheses remains challenging however, as particle formation mechanisms are not well understood. This is partly due to the rapid particle formation (within seconds) providing insufficient time to characterise initial precipitates. To overcome this limitation, a flow chemistry approach has been developed using steady-state operation to “freeze” transient reaction states locally. This allowed for the first time a comprehensive analysis of the early stages of co-precipitation syntheses via in-situ Small Angle X-ray Scattering and in-situ synchrotron X-Ray Diffraction. These studies revealed that after mixing the ferrous/ferric chloride precursor with the NaOH base solution, the most magnetic iron oxide phase forms within 5 s, the particle size changes only marginally afterwards, and co-precipitation and agglomeration occur simultaneously. As these agglomerates were too large to achieve colloidal stability via subsequent stabiliser addition, co-precipitated IONPs had to be de-agglomerated. This was achieved by adding the appropriate quantity of a citric acid solution which yielded within minutes colloidally stable IONP solutions around a neutral pH value. The new insights into the particle formation and the novel stabilisation procedure (not requiring any ultra-sonication or washing step) allowed to design a multistage flow reactor to synthesise and stabilise IONPs continuously with a residence time of less than 5 min. This reactor was robust against fouling and produced stable IONP solutions (of ~1.5 mg particles per ml) reproducibly via fast mixing ( 500 ml/h) for low materials cost.

Microwave technology is gaining popularity as a tool for chemical process intensification and an alternative to conventional heating. However, in flow systems non-uniform temperature profiles are commonly encountered and hence methods to characterise and improve them are required. In this work, we studied the effects of various operational parameters - microwave power, inlet flow rate, tube orientation and pressure - on the electric field and temperature profiles of water flowing in a PTFE tube (2.4 mm internal diameter), placed in a commercial single-mode microwave applicator. A finite element model was developed to estimate the longitudinal temperature profiles and the absorbed microwave power, while in situ temperature monitoring was performed by a fibre optic probe placed at multiple locations inside the tube. The water temperature inside the tube increased by increasing the microwave power input and temperature profiles stabilised beyond 20 W, while the percentage absorbed microwave power showed the inverse trend. When changing the tube orientation or decreasing the inlet flow rate, microwave absorption decreased significantly. When the pressure was increased to 2.3 bara, water temperature increased by ∼20 °C. Results from this study provide valuable insights on achievable temperature profiles and energy efficiency of microwave-assisted flow synthesis systems.