Growth of Carbon Nanofibers and Carbon Nanotubes by Chemical Vapour Deposition on Half-Heusler Alloys: A Computationally Driven Experimental Investigation.

The possibility of directly growing carbon nanofibers (CNFs) and carbon nanotubes (CNTs) on half-Heusler alloys by Chemical Vapour Deposition (CVD) is investigated for the first time, without using additional catalysts, since the half-Heusler alloys per se may function as catalytic substrates, according to the findings of the current study. As a carbon source, acetylene is used in the temperature range of 700-750 °C. The n-type half-Heusler compound Zr0.4Ti0.60.33Ni0.33Sn0.98Sb0.020.33 is utilized as the catalytic substrate. At first, a computational model is developed for the CVD reactor, aiming to optimize the experimental process design and setup. The experimental process conditions are simulated to investigate the reactive species concentrations within the reactor chamber and the activation of certain reactions. SEM analysis confirms the growth of CNFs with diameters ranging from 450 nm to 1 µm. Raman spectroscopy implies that the formed carbon structures resemble CNFs rather than CNTs, and that amorphous carbon also co-exists in the deposited samples. From the characterization results, it may be concluded that a short reaction time and a low acetylene flow rate lead to the formation of a uniform CNF coating on the surface of half-Heusler alloys. The purpose of depositing carbon nanostructures onto half-Heusler alloys is to improve the current transfer, generated from these thermoelectric compounds, by forming a conductive coating on their surface.

Integrating Exposure Assessment and Process Hazard Analysis: The Nano-Enabled 3D Printing Filament Extrusion Case.

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).

Investigation of Carbon Fibres Reclamation by Pyrolysis Process for Their Reuse Potential.

During Carbon Fibre Reinforced Polymers (CFRPs) manufacturing, large quantities of scrap are being produced and usually disposed to landfill or incinerated, resulting in a high environmental impact. Furthermore, CFRP parts that have been damaged or reached their end-of-life, follow the same disposal route and because of this, not only the environment is affected, but also high added-value materials, such as carbon fibres (CFs) are lost without further valorisation. Several recycling technologies have been suggested, such as pyrolysis, to retrieve the CF reinforcement from the CFRPs. However, pyrolysis produces CFs that have residual resin and pyrolytic carbon at their surface. In order to retrieve clean long fibres, oxidation treatment in high temperatures is required. The oxidation treatment, however, has a high impact on the mechanical properties of the reclaimed CFs; therefore, an optimised pyrolysis procedure of CFRPs and post-pyrolysis treatment of reclaimed fibres (rCFs) is required. In this study, CFRPs have been subjected to pyrolysis to investigate the reclamation of CF fabrics in their primal form. The temperature of 550 °C was selected as the optimum processing temperature for the investigated composites. A parametric study on the post-pyrolysis treatment was performed in order to remove the residues from the fabrics and at the same time to investigate the CFs reusability, in terms of their mechanical and surface properties.

Pristine, carboxylated, and hybrid multi-walled carbon nanotubes exert potent antioxidant activities in in vitro-cell free systems.

Multi-walled carbon nanotubes (MWCNTs) are tubular-shaped carbon allotropes, composed of multiple concentric graphene cylinders. The extended systems of conjugated double bonds, that MWCNTs are constituted by, provide them with high electron affinities, enabling them to act as electron donors or acceptors. Consequently, their potential biomedical applications, as synthetic antioxidant agents, are of particular interest. Based on the above, the purpose of the present study was to evaluate the intrinsic antioxidant properties of pristine and carboxylated MWCNTs, as well as of novel hybrid nanocomposites of MWCNTs and inorganic nanoparticles. To this end, after the synthesis and characterization of MWCNTs, their antiradical, reducing, and antigenotoxic properties were assessed in cell-free assays, using a methodological approach that has been recently proposed by our research group. According to our results, most of the tested MWCNTs exhibited strong antioxidant activities. More elaborately, the hybrid material of MWCNTs and ferrous oxide nanoparticles, i.e., CNTs@Fe3O4, showed robust scavenging capacities in all free-radical scavenging assays examined. As regards reducing properties, the pristine MWCNTs, i.e., CNTs-Ref, exhibited the greater electron donating capacity. Finally, in terms of antigenotoxic properties, the hybrid material of MWCNTs and silicon carbide nanoparticles, i.e., CNTs@SiC, exhibited potent ability to inhibit the formation of peroxyl radicals, thus preventing from the oxidative DNA damage. Conclusively, our findings suggest that the MWCNTs of the study could be considered as promising broad-spectrum antioxidants, however, further investigations are required to evaluate their toxicological profile in cell-based and in vivo systems.

Occupational Safety Analysis for COVID-Instigated Repurposed Manufacturing Lines: Use of Nanomaterials in Injection Moulding.

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.

3D Printing Processability of a Thermally Conductive Compound Based on Carbon Nanofiller-Modified Thermoplastic Polyamide 12.

A polyamide (PA) 12-based thermoplastic composite was modified with carbon nanotubes (CNTs), CNTs grafted onto chopped carbon fibers (CFs), and graphene nanoplatelets (GNPs) with CNTs to improve its thermal conductivity for application as a heat sink in electronic components. The carbon-based nanofillers were examined by SEM and Raman. The laser flash method was used to measure the thermal diffusivity in order to calculate the thermal conductivity. Electrical conductivity measurements were made using a Keithley 6517B electrometer in the 2-point mode. The composite structure was examined by SEM and micro-CT. PA12 with 15 wt% of GNPs and 1 wt% CNTs demonstrated the highest thermal conductivity, and its processability was investigated, utilizing sequential interdependence tests to evaluate the composite material behavior during fused filament fabrication (FFF) 3D printing processing. Through this assessment, selected printing parameters were investigated to determine the optimum parametric combination and processability window for the composite material, revealing that the selected composition meets the necessary criteria to be processable with FFF.

Mechanical Properties, Surface Assessment, and Structural Analysis of Functionalized CFRPs after Accelerated Weathering.

The present study focuses on the effect of two novel carbon fibre surface treatments, electropolymerisation of methacrylic acid and air pressure plasma, on the mechanical properties and structural integrity of carbon-fibre-reinforced composites under operational conditions. Extensive mechanical testing was applied, both in nano- and macro-scale, to assess the performance of the composites and the interphase properties after ultraviolet/humidity weathering. The results of the mechanical assessment are supported by structure, surface, and chemistry examination in order to reveal the failure mechanism of the composites. Composites with the electropolymerisation treatment exhibited an increase of 11.8% in interlaminar shear strength, while APP treatment improved the property of 23.9%, rendering both surface treatments effective in increasing the fibre-matrix adhesion. Finally, it was proven that the developed composites can withstand operational conditions in the long term, rendering them suitable for a wide variety of structural and engineering applications.

The Impact of Carbon Nanofibres on the Interfacial Properties of CFRPs Produced with Sized Carbon Fibres.

In this work, different amounts of CNFs were added into a complex formulation to coat the CFs surfaces via sizing in order to enhance the bonding between the fibre and the resin in the CF-reinforced polymer composites. The sized CFs bundles were characterised by SEM and Raman. The nanomechanical properties of the composite materials produced were assessed by the nanoindentation test. The interfacial properties of the fibre and resin were evaluated by a push-out method developed on nanoindentation. The average interfacial shear strength of the fibre/matrix interface could be calculated by the critical load, sheet thickness and fibre diameter. The contact angle measurements and resin spreadability were performed prior to nanoindentation to investigate the wetting properties of the fibre. After the push-out tests, the characterisation via optical microscopy/SEM was carried out to ratify the results. It was found the CFs sizing with CNFs (1 to 10 wt%) could generally increase the interfacial shear strength but it was more cost-effective with a small amount of evenly distributed CNFs on CFs.

An integrated approach for assessing the in vitro and in vivo redox-related effects of nanomaterials.

Over the last few decades, nanotechnology has risen to the forefront of both the research and industrial interest, resulting in the manufacture and utilization of various nanomaterials, as well as in their integration into a wide range of fields. However, the consequent elevated exposure to such materials raises serious concerns regarding their effects on human health and safety. Existing scientific data indicate that the induction of oxidative stress, through the excessive generation of Reactive Oxygen Species (ROS), might be the principal mechanism of exerting their toxicity. Meanwhile, a number of nanomaterials exhibit antioxidant properties, either intrinsic or resulting from their functionalization with conventional antioxidants. Considering that their redox properties are implicated in the manifestation of their biological effects, we propose an integrated approach for the assessment of the redox-related activities of nanomaterials at three biological levels (in vitro-cell free systems, cell cultures, in vivo). Towards this direction, a battery of translational biomarkers is recommended, and a series of reliable protocols are presented in detail. The aim of the present approach is to acquire a better understanding with respect to the biological actions of nanomaterials in the interrelated fields of Redox Biology and Toxicology.

End-of-Life Recycling Options of (Nano)Enhanced CFRP Composite Prototypes Waste-A Life Cycle Perspective.

Life cycle assessment is a methodology to assess environmental impacts associated with a product or system/process by accounting resource requirements and emissions over its life cycle. The life cycle consists of four stages: material production, manufacturing, use, and end-of-life. This study highlights the need to conduct life cycle assessment (LCA) early in the new product development process, as a means to assess and evaluate the environmental impacts of (nano)enhanced carbon fibre-reinforced polymer (CFRP) prototypes over their entire life cycle. These prototypes, namely SleekFast sailing boat and handbrake lever, were manufactured by functionalized carbon fibre fabric and modified epoxy resin with multi-walled carbon nanotubes (MWCNTs). The environmental impacts of both have been assessed via LCA with a functional unit of '1 product piece'. Climate change has been selected as the key impact indicator for hotspot identification (kg CO2 eq). Significant focus has been given to the end-of-life phase by assessing different recycling scenarios. In addition, the respective life cycle inventories (LCIs) are provided, enabling the identification of resource hot spots and quantifying the environmental benefits of end-of-life options.

Comparative Physical-Mechanical Properties Assessment of Tailored Surface-Treated Carbon Fibres.

Carbon Fibres (CFs) are widely used in textile-reinforced composites for the construction of lightweight, durable structures. Since their inert surface does not allow effective bonding with the matrix material, the surface treatment of fibres is suggested to improve the adhesion between the two. In the present study, different surface modifications are compared in terms of the mechanical enhancement that they can offer to the fibres. Two main advanced technologies have been investigated; namely, plasma treatment and electrochemical treatment. Specifically, active screen plasma and low-pressure plasma were compared. Regarding the electrochemical modification, electrochemical oxidation and electropolymerisation of monomer solutions of acrylic and methacrylic acids, acrylonitrile and N-vinyl pyrrolidine were tested for HTA-40 CFs. In order to assess the effects of the surface treatments, the morphology, the physicochemical properties, as well as the mechanical integrity of the fibres were investigated. The CF surface and polymeric matrix interphase adhesion in composites were also analysed. The improvement of the carbon fibre's physical-mechanical properties was evident for the case of the active screen plasma treatment and the electrochemical oxidation.

Nano-Graphitic based Non-Volatile Memories Fabricated by the Dynamic Spray-Gun Deposition Method.

This paper deals with the fabrication of Resistive Random Access Memory (ReRAM) based on oxidized carbon nanofibers (CNFs). Stable suspensions of oxidized CNFs have been prepared in water and sprayed on an appropriate substrate, using the dynamic spray-gun deposition method, developed at Thales Research and Technology. This technique allows extremely uniform mats to be produced while heating the substrate at the boiling point of the solvent used for the suspensions. A thickness of around 150 nm of CNFs sandwiched between two metal layers (the metalized substrate and the top contacts) has been achieved, creating a Metal-Insulator-Metal (MIM) structure typical of ReRAM. After applying a bias, we were able to change the resistance of the oxidized layer between a low (LRS) and a high resistance state (HRS) in a completely reversible way. This is the first time that a scientific group has produced this kind of device using CNFs and these results pave the way for the further implementation of this kind of memory on flexible substrates.

Toxicity testing of MWCNTs to aquatic organisms.

The increase in global production of carbon nanotubes (CNTs), as well as their use in polymer nanocomposites has raised concerns as to their possible effects on the marine environment that could ultimately affect human populations. Specifically, CNTs have already been tested in antifouling formulations for the prevention of biofouling, mainly to protect ships' hulls, as well as in composite materials that come in contact with seawater. At this point, it seems crucial to assess the possible effects of CNTs on aquatic organisms and assess their toxicity. Thus, in this study, three different model organisms were selected for toxicity testing: Daphnia magna water flea, Artemia salina nauplii and Danio rerio zebrafish. The CNTs that were tested have been produced in house via the chemical vapour deposition method and were fully characterised in order to understand the effect of their properties on the aquatic organisms. In this study pristine multiwalled carbon nanotubes (MWCNTs) as well as functionalised with carboxyl groups were used. Dispersion issues were evident in all tests, both for the pristine and functionalised carbon nanotubes, thus their toxicity could not be determined in relation to their concentration. To overcome this issue, optical observation of the organisms took place. MWCNT black aggregates were clearly observed in the intestine of A. salina. Following an additional 24 h in seawater the intestine appeared clean and restored to its normal appearance. This observation leads to the conclusion that MWCNTs did not prove to be fatal to D. magna and A. salina despite their presence in the digestive track of both non-target organisms. These results show that MWCNTs do not affect the non-target organisms in the short term, thus their use in antifouling coatings and composite materials for maritime applications can be further investigated.

Toxicity determinants of multi-walled carbon nanotubes: The relationship between functionalization and agglomeration.

The elucidation of toxicity determinants of multi-walled carbon nanotubes (MWCNT) is still incomplete. Functionalization with carboxyl groups is, however, commonly used to mitigate MWCNT toxicity, although the rationale for the mitigating effect has not been fully clarified yet. In this work, two optimized chemical vapor deposition methods were employed to obtain MWCNT of comparable length but different diameter, which were subsequently functionalized. For MWCNT of diameter larger than 40 nm, no detrimental effects on cell viability of macrophages were observed, while mild cytotoxicity was recorded for diameters between 15 and 40 nm, with a mitigating effect of functionalization. To investigate the factors responsible for the mitigation, we used the thinnest MWCNT preparation on different cell models, evaluating several endpoints, such as viability, production of nitric oxide (NO), expression of pro-inflammatory markers, the Trans-Epithelial Electrical Resistance (TEER), and clonogenic activity. Substantial mitigation of the changes caused by pristine MWCNT was observed not only with carboxyl- but also with amino-functionalized MWCNT, suggesting that negative or positive surface charge was not the main factor responsible for the effect. Instead, either functionalized preparation exhibited a stronger tendency to agglomerate that was strictly dependent on the presence of proteins. Moreover, we found that either carboxyl- or amino-functionalized MWCNT adsorbed a larger amount of serum proteins than pristine counterparts, with a distinctive pattern for each type of MWCNT. We propose, therefore, that the formation of larger agglomerates, dependent upon different protein coronae, contributes to mitigate the biological effects of functionalized MWCNT in protein-rich biological media.