Challenges to Improve Extrusion-Based Additive Manufacturing Process of Thermoplastics toward Sustainable Development.

This review aims to present the different approaches to lessen the environmental impact of the extrusion-based additive manufacturing (MEX) process of thermoplastic-based resins and protect the ecosystem. The benefits and drawbacks of each alternative, including the use of biomaterials or recycled materials as feedstock, energy efficiency, and polluting emissions reduction, have been examined. First, the technological option of using a pellet-fed printer was compared to a filament-fed printer. Then, common biopolymers utilized in MEX applications are discussed, along with methods for improving the mechanical properties of associated printed products. The introduction of natural fillers in thermoplastic resins and the use of biocomposite filaments have been proposed to improve the specific performance of printed items, highlighting the numerous challenges related to their extrusion. Various polymers and fillers derived from recycling are presented as feeding raw materials for printers to reduce waste accumulation, showing the inferior qualities of the resulting goods when compared to printed products made from virgin materials. Finally, the energy consumption and emissions released into the atmosphere during the printing process are discussed, with the potential for both aspects to be controlled through material selection and operating conditions.

Pulmonary evaluation of whole-body inhalation exposure of polycarbonate (PC) filament 3D printer emissions in rats.

During fused filament fabrication (FFF) 3D printing with polycarbonate (PC) filament, a release of ultrafine particles (UFPs) and volatile organic compounds (VOCs) occurs. This study aimed to determine PC filament printing emission-induced toxicity in rats via whole-body inhalation exposure. Male Sprague Dawley rats were exposed to a single concentration (0.529 mg/m3, 40 nm mean diameter) of the 3D PC filament emissions in a time-course via whole body inhalation for 1, 4, 8, 15, and 30 days (4 hr/day, 4 days/week), and sacrificed 24 hr after the last exposure. Following exposures, rats were assessed for pulmonary and systemic responses. To determine pulmonary injury, total protein and lactate dehydrogenase (LDH) activity, surfactant proteins A and D, total as well as lavage fluid differential cells in bronchoalveolar lavage fluid (BALF) were examined, as well as histopathological analysis of lung and nasal passages was performed. To determine systemic injury, hematological differentials, and blood biomarkers of muscle, metabolic, renal, and hepatic functions were also measured. Results showed that inhalation exposure induced no marked pulmonary or systemic toxicity in rats. In conclusion, inhalation exposure of rats to a low concentration of PC filament emissions produced no significant pulmonary or systemic toxicity.

Temperature Dependence of Kinetic Friction: A Handle for Plastics Sortation?

Sortation is a crucial step in mechanical recycling of post-consumer plastics (PCR) whereby properties such as density or spectral signature are used to separate plastics. However it is difficult to sort polyolefin flakes at high throughput by these properties. We ask whether the frictional properties of plastics as a function of temperature may be used as an alternate sorting property. However, fundamental studies of friction at temperatures near their melting points are limited. Here we measure the temperature dependence of kinetic friction for three common polyolefins (high and low den- sity polyethylene and polypropylene) as well as polyethylene terephthalate (PET), focusing on the softening/melting regime. The results are augmented by differential scanning calorimetry and temperature dependence measurements of both dynamic modulus and and probe tack. For the polyolefins, we find strong increases in the coefficients of kinetic friction during temperature ramps in the melting/softening regime. For the PET, we report a notable peak in the kinetic friction which we associate with the glass transition and cold-crystallization. We discuss the enhanced friction in the context of rub- ber friction, which exhibits comparable coefficients of kinetic frictions.

Rapid integration of screen-printed electrodes into thermoplastic organ-on-a-chip devices for real-time monitoring of trans-endothelial electrical resistance.

Trans-endothelial electrical resistance (TEER) is one of the most widely used indicators to quantify the barrier integrity of endothelial layers. Over the last decade, the integration of TEER sensors into organ-on-a-chip (OOC) platforms has gained increasing interest for its efficient and effective measurement of TEER in OOCs. To date, microfabricated electrodes or direct insertion of wires has been used to integrate TEER sensors into OOCs, with each method having advantages and disadvantages. In this study, we developed a TEER-SPE chip consisting of carbon-based screen-printed electrodes (SPEs) embedded in a poly(methyl methacrylate) (PMMA)-based multi-layered microfluidic device with a porous poly(ethylene terephthalate) membrane in-between. As proof of concept, we demonstrated the successful cultures of hCMEC/D3 cells and the formation of confluent monolayers in the TEER-SPE chip and obtained TEER measurements for 4 days. Additionally, the TEER-SPE chip could detect changes in the barrier integrity due to shear stress or an inflammatory cytokine (i.e., tumor necrosis factor-α). The novel approach enables a low-cost and facile fabrication of carbon-based SPEs on PMMA substrates and the subsequent assembly of PMMA layers for rapid prototyping. Being cost-effective and cleanroom-free, our method lowers the existing logistical and technical barriers presenting itself as another step forward to the broader adoption of OOCs with TEER measurement capability.

Tough and Thermostable Polybutylene Terephthalate (PBT)/Vitrimer Blend with Enhanced Interfacial Compatibility.

Polymer blending is an efficient way to obtain extraordinary polymeric materials. However, once permanently cross-linked thermosets are involved in blending, there are challenges in designing and optimizing the structures and interfacial compatibility of blends. Vitrimer with dynamic covalent polymer networks provides an innovative opportunity for blending thermoplastics and thermosets. Herein, a reactive blending strategy is proposed to develop thermoplastic-thermoset blend with enhanced compatibility on the basis of dynamic covalent chemistry. Specifically, polybutylene terephthalate (PBT) and polymerized epoxy vitrimer can be directly melt blended to obtain tough and thermostable blends with desirable microstructures and interfacial interaction. Bond exchange facilitates the grafting of PBT and epoxy vitrimer chains, thus enhancing the interfacial compatibility and thermal stability of blends. The obtained blend balances the strength and stretchability of PBT and epoxy vitrimer, resulting in enhanced toughness. This work offers a new way of designing and fabricating new polymeric materials by blending thermoplastics and thermosets. It also suggests a facile direction towards upcycling thermoplastics and thermosets.

Evaluation of Pulmonary Effects of 3-D Printer Emissions From Acrylonitrile Butadiene Styrene Using an Air-Liquid Interface Model of Primary Normal Human-Derived Bronchial Epithelial Cells.

This study investigated the inhalation toxicity of the emissions from 3-D printing with acrylonitrile butadiene styrene (ABS) filament using an air-liquid interface (ALI) in vitro model. Primary normal human-derived bronchial epithelial cells (NHBEs) were exposed to ABS filament emissions in an ALI for 4 hours. The mean and mode diameters of ABS emitted particles in the medium were 175 ± 24 and 153 ± 15 nm, respectively. The average particle deposition per surface area of the epithelium was 2.29 × 107 ± 1.47 × 107 particle/cm2, equivalent to an estimated average particle mass of 0.144 ± 0.042 µg/cm2. Results showed exposure of NHBEs to ABS emissions did not significantly affect epithelium integrity, ciliation, mucus production, nor induce cytotoxicity. At 24 hours after the exposure, significant increases in the pro-inflammatory markers IL-12p70, IL-13, IL-15, IFN-γ, TNF-α, IL-17A, VEGF, MCP-1, and MIP-1α were noted in the basolateral cell culture medium of ABS-exposed cells compared to non-exposed chamber control cells. Results obtained from this study correspond with those from our previous in vivo studies, indicating that the increase in inflammatory mediators occur without associated membrane damage. The combination of the exposure chamber and the ALI-based model is promising for assessing 3-D printer emission-induced toxicity.

Effects of heating rate on thermal degradation behavior and kinetics of representative thermoplastic wastes.

Waste thermoplastics are the most common solid wastes, and thermal degradation has excellent advantages in the disposal of these wastes and obtaining valuable hydrocarbon fuels. As a significant factor, the heating rate is crucial to the thermal degradation process. Consequently, thermal degradation behavior and kinetics of representative thermoplastics under different heating rates were investigated by using thermogravimetric analysis and differential scanning calorimetry in the air. Kinetic parameters were estimated by using the Coats-Redfern method. Subsequently, the Shuffled Complex Evolution (SCE) method was used to optimize kinetic parameters, and the optimized results were compared with the calculated kinetics of distributed activation energy model (DAEM) method to find the effects of heating rate on kinetic parameters. The results showed that with the increase of heating rate, thermogravimetric curves moved to the right, which corresponded to a higher temperature range. The number of mass loss rate peaks and exothermic peaks decreased. Additionally, activation energy was the same at the determined minimum and maximum heating rates, and other heating rates had little effect on kinetic parameters. Moreover, the calculated activation energy of the DAEM method at the minimum heating rate of 5 K/min was closest to the optimized values of the SCE method, indicating that the lower the minimum heating rate was, the more accurate the activation energy was.

Emission Profiles of Volatiles during 3D Printing with ABS, ASA, Nylon, and PETG Polymer Filaments.

In this short communication we characterize the emission of volatile organic compounds (VOCs) from fused filament fabrication (FFF) 3D printing using four polymer materials, namely polyethylene terephthalate glycol-modified (PETG), acrylonitrile styrene acrylate (ASA), Nylon, and acrylonitrile butadiene styrene (ABS). Detailed emission profiles are obtained during thermal degradation of the polymers as a function of temperature and also in real-time during 3D printing. Direct quantitative measurement was performed using proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Qualitative determination of the volatiles emitted from the printed elements at various temperatures was accomplished using gas chromatography-mass spectrometry (GC-MS). The emission rates of VOCs differ significantly between the different polymer filaments, with the emission from Nylon and PETG more than an order of magnitude lower than that of ABS.

Functionalizable and Chemically Recyclable Thermoplastics from Chemoselective Ring-Opening Polymerization of Bio-renewable Bifunctional α-Methylene-δ-valerolactone.

It is a highly attractive strategy to develop chemically recyclable polymers to establish a circular plastic economy. Despite the recent advancements, chemically recyclable polymers still face challenges including high energy cost for polymer preparation or recycling, poor monomer recovery selectivity and efficiency as well as undesired material performance. In this contribution, we present the chemoselective controlled ring-opening polymerization of bio-renewable bifunctional α-methylene-δ-valerolactone (MVL) to produce exclusive functionalizable polyester using strong base/urea binary catalysts. The obtained polyester with high molar mass exhibits good tensile strength comparable to that of some commodity plastics. Remarkably, the obtained polyester can be depolymerized to recover pristine monomer with a 96 % yield by thermolysis, thus successfully establishing a closed-loop life cycle.

Role of Structural Morphology of Commodity Polymers in Microplastics and Nanoplastics Formation: Fragmentation, Effects and Associated Toxicity in the Aquatic Environment.

With the continued growth in plastic production, its ubiquitous use and insufficient waste management and disposal, the increased levels of plastics in the environment have led to growing ecological concerns. The breakdown of these plastic macromolecules to smaller micro and nanosized particles and their detection in the aerial, aquatic, marine and terrestrial environments has been reviewed extensively, especially for thermoplastics. However, the formation of micro and nanoplastics has typically been explained as a physical abrasion process, largely overlooking the underlying chemical structure-morphology correlations to the degradation mechanisms of the plastics. This is particularly true for the common commodity thermosets. This review focuses on the degradation pathways for the most widely produced commodity thermoplastics and thermosets into microplastics (MP)s and nanoplastics (NP)s, as well as their behaviour and associated toxicity. Special emphasis is placed on NPs, which are associated with greater risks for toxicity compared to MPs, due to their higher surface area to volume ratios. This review also assesses the current state of standardized detection and quantification methods as well as comprehensive regulations for these fragments in the aquatic environment.

Preparation and Characterization of Biobased Lignin-Co-Polyester/Amide Thermoplastics.

More than 23 million tonnes of lignin are produced annually in the US from wood pulping and 98% of this lignin is burnt. Therefore, creating products from lignin, such as plastics, offers an approach for obtaining sustainable materials in a circular economy. Lignin-based copolymers were synthesized using a single pot, solvent free, melt condensation reaction. The synthesis occurred in two stages. In the first stage, a biobased prepolymer consisting of butanediol (BD, 0.8-1 molar content) and a diacid (succinic (SA), adipic (AA) and suberic acids (SuA), with varying amounts of diaminobutane (DAB, 0-0.2 molar content) was heated under vacuum and monitored by Fourier transform infra-red (FTIR) spectroscopy and electrospray ionization-mass spectrometry (ESI-MS). In the second stage, prepolymer was mixed with a softwood kraft lignin (0-50 wt.%) and further reacted under vacuum at elevated temperature. Progression of the polymerization reaction was monitored using FTIR spectroscopy. The lignin-copolyester/amide properties were characterized using tensile testing, X-ray diffraction (XRD), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. Lignin co-polymer tensile (strength 0.1-2.1 MPa and modulus 2 to 338 MPa) properties were found to be influenced by the diacid chain length, lignin, and DAB contents. The lignin-copolymers were shown to be semi-crystalline polymer and have thermoplastic behavior. The SA based copolyesters/amides were relatively stiff and brittle materials while the AA based copolyesters/amides were flexible and the SuA based copolyesters/amides fell in-between. Additionally, > 30 wt.% lignin the lignin- copolyesters/amides did not exhibit melt behavior. Lignin-co-polyester/amides can be generated using green synthesis methods from biobased building blocks. The lignin- copolyesters/amides properties could be tuned based on the lignin content, DAB content and diacid chain length. This approach shows that undervalued lignin can be used in as a macromonomer in producing thermoplastic materials.

Open-tubular nanoelectrochromatography (OT-NEC): gel-free separation of single stranded DNAs (ssDNAs) in thermoplastic nanochannels.

Electrophoresis or electrochromatography carried out in nanometer columns (width and depth) offers some attractive benefits compared to microscale columns. These advantages include unique separation mechanisms that are scale dependent, fast separation times, and simpler workflow due to the lack of a need for column packing and/or wall coatings to create a stationary phase. We report the use of thermoplastics, in this case PMMA, as the substrate for separating single-stranded DNAs (ssDNAs). Electrophoresis nanochannels were created in PMMA using nanoimprint lithography (NIL), which can produce devices at lower cost and in a higher production mode compared to the fabrication techniques required for glass devices. The nanochannel column in PMMA was successful in separating ssDNAs in free solution that was not possible using microchip electrophoresis in PMMA. The separation could be performed in <1 s with resolution >1.5 when carried out using at an electric field strength of 280 V/cm and an effective column length of 60 µm (100 nm × 100 nm, depth and width). The ssDNAs transport through the PMMA column was driven electrokinetically under the influence of an EOF. The results indicated that the separation was dominated by chromatographic effects using an open tubular nano-electrochromatography (OT-NEC) mode of separation. Interesting to these separations was that no column packing was required nor a wall coating to create the stationary phase; the separation was affected using the native polymer that was UV/O3 activated and an aqueous buffer mobile phase.

Synthesis of Thermoplastic Poly(2-methoxyethyl acrylate)-Based Polyurethane by RAFT and Condensation Polymerization.

Thermoplastic solid poly(2-methoxyethyl acrylate) (PMEA)-based polyurethane (PU) is synthesized through the reversible addition-fragmentation chain transfer (RAFT) polymerization and the condensation polymerization, using hydroxyl-terminated RAFT reagents and diisocyanate, respectively. Neat PMEA is a promising antithrombogenic liquid used in the medical fields. The thermoplastic property of the solid PMEA-based PU due to hydrogen bonding is confirmed by the dynamic mechanical analysis (DMA) at temperature below 72 °C. The antithrombogenic property of PMEA-based PU is also analyzed by the platelet adhesion test. The number of platelets on PMEA-based PU is 17 cells per unit area, which is smaller than that on the fluorinated diamond-like carbon (F-DLC), a well-known highly antithrombogenic material. It is concluded that a newly synthesized PMEA-based PU exhibits thermoplastic characteristics with excellent antithrombogenicity.

Carbon nanotube filler enhances incinerated thermoplastics-induced cytotoxicity and metabolic disruption in vitro.

BACKGROUND: Engineered nanomaterials are increasingly being incorporated into synthetic materials as fillers and additives. The potential pathological effects of end-of-lifecycle recycling and disposal of virgin and nano-enabled composites have not been adequately addressed, particularly following incineration. The current investigation aims to characterize the cytotoxicity of incinerated virgin thermoplastics vs. incinerated nano-enabled thermoplastic composites on two in vitro pulmonary models. Ultrafine particles released from thermally decomposed virgin polycarbonate or polyurethane, and their carbon nanotube (CNT)-enabled composites were collected and used for acute in vitro exposure to primary human small airway epithelial cell (pSAEC) and human bronchial epithelial cell (Beas-2B) models. Post-exposure, both cell lines were assessed for cytotoxicity, proliferative capacity, intracellular ROS generation, genotoxicity, and mitochondrial membrane potential. RESULTS: The treated Beas-2B cells demonstrated significant dose-dependent cellular responses, as well as parent matrix-dependent and CNT-dependent sensitivity. Cytotoxicity, enhancement in reactive oxygen species, and dissipation of ΔΨm caused by incinerated polycarbonate were significantly more potent than polyurethane analogues, and CNT filler enhanced the cellular responses compared to the incinerated parent particles. Such effects observed in Beas-2B were generally higher in magnitude compared to pSAEC at treatments examined, which was likely attributable to differences in respective lung cell types. CONCLUSIONS: Whilst the effect of the treatments on the distal respiratory airway epithelia remains limited in interpretation, the current in vitro respiratory bronchial epithelia model demonstrated profound sensitivity to the test particles at depositional doses relevant for occupational cohorts.

Pulmonary and systemic toxicity in rats following inhalation exposure of 3-D printer emissions from acrylonitrile butadiene styrene (ABS) filament.

BACKGROUND: Fused filament fabrication 3-D printing with acrylonitrile butadiene styrene (ABS) filament emits ultrafine particulates (UFPs) and volatile organic compounds (VOCs). However, the toxicological implications of the emissions generated during 3-D printing have not been fully elucidated. AIM AND METHODS: The goal of this study was to investigate the in vivo toxicity of ABS-emissions from a commercial desktop 3-D printer. Male Sprague Dawley rats were exposed to a single concentration of ABS-emissions or air for 4 hours/day, 4 days/week for five exposure durations (1, 4, 8, 15, and 30 days). At 24 hours after the last exposure, rats were assessed for pulmonary injury, inflammation, and oxidative stress as well as systemic toxicity. RESULTS AND DISCUSSION: 3-D printing generated particulate with average particle mass concentration of 240 ± 90 µg/m³, with an average geometric mean particle mobility diameter of 85 nm (geometric standard deviation = 1.6). The number of macrophages increased significantly at day 15. In bronchoalveolar lavage, IFN-γ and IL-10 were significantly higher at days 1 and 4, with IL-10 levels reaching a peak at day 15 in ABS-exposed rats. Neither pulmonary oxidative stress responses nor histopathological changes of the lungs and nasal passages were found among the treatments. There was an increase in platelets and monocytes in the circulation at day 15. Several serum biomarkers of hepatic and kidney functions were significantly higher at day 1. CONCLUSIONS: At the current experimental conditions applied, it was concluded that the emissions from ABS filament caused minimal transient pulmonary and systemic toxicity.

A thermoplastic microfluidic microphysiological system to recapitulate hepatic function and multicellular interactions.

Hepatic in vitro platforms ranging from multi-well cultures to bioreactors and microscale systems have been developed as tools to recapitulate cellular function and responses to aid in drug screening and disease model development. Recent developments in microfabrication techniques and cellular materials enabled fabrication of next-generation, advanced microphysiological systems (MPSs) that aim to capture the cellular complexity and dynamic nature of the organ presenting highly controlled extracellular cues to cells in a physiologically relevant context. Historically, MPSs have heavily relied on elastomeric materials in their manufacture, with unfavorable material characteristics (such as lack of structural rigidity) limiting their use in high-throughput systems. Herein, we aim to create a microfluidic bilayer model (microfluidic MPS) using thermoplastic materials to allow hepatic cell stabilization and culture, retaining hepatic functional phenotype and capturing cellular interactions. The microfluidic MPS consists of two overlapping microfluidic channels separated by a porous tissue-culture membrane that acts as a surface for cellular attachment and nutrient exchange; and an oxygen permeable material to stabilize and sustain primary human hepatocyte (PHH) culture. Within the microfluidic MPS, PHHs are cultured in the top channel in a collagen sandwich gel format with media exchange accomplished through the bottom channel. We demonstrate PHH culture for 7 days, exhibiting measures of hepatocyte stabilization, secretory and metabolic functions. In addition, the microfluidic MPS dimensions provide a reduced media-to-cell ratio in comparison with multi-well tissue culture systems, minimizing dilution and enabling capture of cellular interactions and responses in a hepatocyte-Kupffer coculture model under an inflammatory stimulus. Utilization of thermoplastic materials in the model and ability to incorporate multiple hepatic cells within the system is our initial step towards the development of a thermoplastic-based high-throughput microfluidic MPS platform for hepatic culture. We envision the platform to find utility in development and interrogation of disease models of the liver, multi-cellular interactions and therapeutic responses.

Online Monitoring and Prediction of Thermo-Mechanics of AFP Based Thermoplastic Composites.

Precision sensing in the characterization of complex additive manufacturing processes such as the Automated Fibre Placement (AFP) technique is important since the process involves a significant level of uncertainty in terms of quality and integrity of the manufactured product. These uncertainties can be monitored by embedding optical fibre Bragg grating (FBGs) sensors which provide accurate and simultaneous measurement of strain and temperature during the AFP process. The embedded sensors have been shown to remain resilient in continuous health monitoring after manufacturing. The thermal history obtained from the FBG sensors demonstrates a reduction of temperature on the bottom ply by up to 25% when the plies are laid one above the other. A numerical tool is developed to identify the physical parameters which may be responsible for the rise/fall of the temperature during ply layup. The numerical findings agree well with the sensor data and is extended to capture a breadth of parametric studies through the layup simulation. The model provides a comprehensive insight to the characteristics of the laid and the laying ply from a thermo-mechanics perspective.

Ring-Opening Metathesis Polymerization of Biomass-Derived Levoglucosenol.

The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100 kg mol-1 and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 °C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.

Facile Thermally Impacted Water-Induced Phase Separation Approach for the Fabrication of Skin-Free Thermoplastic Polyurethane Foam and Its Recyclable Counterpart for Oil-Water Separation.

Developing a facile large-scale strategy to fabricate polymer foams with excellent wettability and recycling its counterpart for oil-water separation is in urgent demand. Here, a facile template-free thermally impacted water-induced phase separation approach for the fabrication of skin-free thermoplastic polyurethane foam with a water contact angle of 147°, porosity more than 90%, density less than 14 mg cm-3 , and excellent compressibility (>1000 cycles) is proposed. The foams show high efficiency of oil recovery (>98%) during the squeezing and pumping oil-water separation test. Moreover, the used foams could be recycled and reused to form refresh foams without sacrificing their high performance, which makes this method a promising prospect for environmental applications.

A Versatile Strategy to Synthesize Perfluoropolyether-Based Thermoplastic Fluoropolymers by Alkyne-Azide Step-Growth Polymerization.

Perfluoropolyether (PFPE)-based thermoplastic fluoropolymers are synthesized by A2 + B2 step-growth polymerization between PFPE-diyne and fluorinated diazides. This versatile method allows synthesizing PFPE-based materials with tunable physicochemical properties depending on the exact nature of the fluorinated segment of the diazide precursor. Semicrystalline or amorphous materials endowed with high thermostability (≈300 °C under air) and low glass transition temperature (≈-100 °C) are obtained, as confirmed by differential scanning calorimetry, thermogravimetry, and rheometry. Step-growth polymerizations can be copper-catalyzed but also thermally activated in some cases, thus avoiding the presence of copper residues in the final materials. This strategy opens up new opportunities to easily access PFPE-based materials on an industrial scale. Furthermore, a plethora of developments can be envisioned (e.g., by adding a third trifunctional component to the formulations for the synthesis of PFPE-based elastomers).