Everything falls apart: How solids degrade and release nanomaterials, composite fragments, and microplastics.

To ensure the safe use of materials, one must assess the identity and quantity of exposure. Solid materials, such as plastics, metals, coatings and cements, degrade to some extent during their life cycle, and releases can occur during manufacturing, use and end-of-life. Releases (e.g., what is released, how does release happen, and how much material is released) depend on the composition and internal (nano)structures of the material as well as the applied stresses during the lifecycle. We consider, in some depth, releases from mechanical, weathering and thermal stresses and specifically address the use cases of fused-filament 3D printing, dermal contact, food contact and textile washing. Solid materials can release embedded nanomaterials, composite fragments, or micro- and nanoplastics, as well as volatile organics, ions and dissolved organics. The identity of the release is often a heterogenous mixture and requires adapted strategies for sampling and analysis, with suitable quality control measures. Control materials enhance robustness by enabling comparative testing, but reference materials are not always available as yet. The quantity of releases is typically described by time-dependent rates that are modulated by the nature and intensity of the applied stress, the chemical identity of the polymer or other solid matrix, and the chemical identity and compatibility of embedded engineered nanomaterials (ENMs) or other additives. Standardization of methods and the documentation of metadata, including all the above descriptors of the tested material, applied stresses, sampling and analytics, are identified as important needs to advance the field and to generate robust, comparable assessments. In this regard, there are strong methodological synergies between the study of all solid materials, including the study of micro- and nanoplastics. From an outlook perspective, we review the hazard of the released entities, and show how this informs risk assessment. We also address the transfer of methods to related issues such as tyre wear, advanced materials and advanced manufacturing, biodegradable polymers, and non-solid matrices. As the consideration of released entities will become more routine in industry via lifecycle assessment in Safe-and-Sustainable-by-Design practices, release assessments will require careful design of the study with quality controls, the use of agreed-on test materials and standardized methods where these exist and the adoption of clearly defined data reporting practices that enable data reuse, meta-analyses, and comparative studies.

Quantifying Mechanical Abrasion of MWCNT Nanocomposites Used in 3D Printing: Influence of CNT Content on Abrasion Products and Rate of Microplastic Production.

Manufactured nanomaterials (MNMs) are incorporated as "nanofillers" into consumer products to enhance properties of interest. Multiwalled carbon nanotubes (MWCNTs) are known for their unique properties and have many applications in polymers. However, the release of MWCNTs during the nanoenabled product life cycle is concerning. During the use phase, mechanical stresses can produce fragmented materials containing MNMs. The degree of MNM release, the resulting exposure to these materials, and the potential impacts of their release are active research topics. In this study, we describe methodological improvements to study the abrasion of plastics containing MNMs (nanocomposites) and report on characteristics of abrasion products produced and rates of microplastic production. The abrasion device developed for this work allows for the measurement of power inputs to determine scaled release rates. Abrasion rates for plastics used in 3D printing were found to be 0.27 g/m2/s for the PETG polymer and 0.3 g/m2/s for the 2% MWCNT-PETG nanocomposite. Embedded and protuberant MWCNTs appeared to impact the particle size, shape, hydrophobicity, and surface charge of the microplastics, while the inclusion of MWCNTs had a small effect on microplastic production. Measurements of power input to the abrasion process provided a basis for estimating microplastic production rates for these nanocomposites.

Impacts of ingested MWCNT-Embedded nanocomposites in Japanese medaka (Oryzias latipes).

Polymer nanocomposites combine the versatile, lightweight characteristics of polymers with the properties of nanomaterials. Polyethylene terephthalate glycol (PETG) is commonly used in polymer additive manufacturing due to its controllable transparency, high modulus, and mechanical properties. Multi-walled carbon nanotubes (MWCNTs) add tensile strength, electrical conductivity, and thermal stability. The increased use of nanocomposites has led to concern over potential human health risks. We assessed morphologic alterations to determine impacts of ingested abraded nanocomposites compared to its component materials, pristine MWCNTs (1000 mg/L) and PETG. Adult transparent Japanese medaka (Oryzias latipes) were administered materials via oral gavage in 7 doses over 16 days. In vivo observations revealed altered livers and gallbladders following exposure to pristine MWCNTs and nanocomposites. Subsequent histologic sections showed fish exposed to pristine MWCNTs had highly altered biliary structures, and exposure to nanocomposites resulted in hepatocellular alteration. Thyroid follicle proliferation was also observed in fish exposed to materials containing MWCNTs. Transmission electron microscopy of livers showed that hepatocytes of fish exposed to MWCNTs had widespread swelling of rough endoplasmic reticulum, pronounced lysosomal activity, and swelling of intrahepatic biliary passageways. Fish exposed to nanocomposites had areas of degenerated hepatocytes with interspersed cellular debris. Each analysis showed that fish exposed to pristine PETG were most similar to controls. These results suggest that MWCNTs are the source of toxicity in abraded nanocomposite materials but that nanocomposites may also have some unique effects. The similarities of many teleost and mammalian tissues are such that these findings may indicate human health risks.

Effects of consumer use practices on nanosilver release from commercially available food contact materials.

Migration evaluation involving nano-enabled food contact materials (FCMs) mostly focuses on potential nanoparticle release from new unused products. This may not represent consumer use practices encountered by the FCMs in their lifecycle. In order to determine if product use impacts the release of nanoparticles or other FCM components, it is necessary to perform migration evaluations under typical consumer use scenarios. A quantitative assessment of nanoparticle release from a commercially available nanosilver-enabled cutting board was performed under five conditions intended to simulate consumer use. Knife motion, washing and scratching scenarios were simulated by linear abrasion using knife blades, scrubbing pads and tungsten carbide burr attachments, respectively. Migration was evaluated using water and 3% acetic acid as food simulants. Low concentrations of silver (Ag) were detected in water simulants, a small portion (<4 ng dm-2) in the form of silver nanoparticles (AgNPs) with particle number concentrations on the order of 106 particles dm-2. Median particle diameter was 40 nm. Nanoparticle release into water was observed under all five consumer use scenarios studied, however there was no correlation with the different levels of stress simulated.

Nondestructive shape process monitoring of three-dimensional high aspect ratio targets using through-focus scanning optical microscopy.

Low-cost, high-throughput and nondestructive metrology of truly three-dimensional (3-D) targets for process control/monitoring is a critically needed enabling technology for high-volume manufacturing (HVM) of nano/micro technologies in multi-disciplinary areas. In particular, a survey of the typically used metrology tools indicates the lack of a tool that truly satisfies the HVM metrology needs of 3-D targets, such as high aspect ratio (HAR) targets. Using HAR targets here we demonstrate that through-focus scanning optical microscopy (TSOM) is a strong contender to fill the gap for 3-D shape metrology. Differential TSOM (D-TSOM) images are extremely sensitive to small and/or dissimilar types of 3-D shape variations. Based on this here we propose a TSOM method that involves creating a database of cross-sectional profiles of the HAR targets along with their respective D-TSOM signals. Using the database, we present a simple-to-use, low-cost, high-throughput and nondestructive process-monitoring method suitable for HVM of truly 3-D targets, which also does not require optical simulations, making its use straightforward and automatable. Even though HAR targets are used for this demonstration, the similar process can be applied to any truly 3-D targets with dimensions ranging from micro-scale to nano-scale. The TSOM method couples the advantage of analyzing truly isolated targets with the ability to simultaneously analyze many targets present in the large field-of-view of a conventional optical microscope.

Separation, Sizing, and Quantitation of Engineered Nanoparticles in an Organism Model Using Inductively Coupled Plasma Mass Spectrometry and Image Analysis.

For environmental studies assessing uptake of orally ingested engineered nanoparticles (ENPs), a key step in ensuring accurate quantification of ingested ENPs is efficient separation of the organism from ENPs that are either nonspecifically adsorbed to the organism and/or suspended in the dispersion following exposure. Here, we measure the uptake of 30 and 60 nm gold nanoparticles (AuNPs) by the nematode, Caenorhabditis elegans, using a sucrose density gradient centrifugation protocol to remove noningested AuNPs. Both conventional inductively coupled plasma mass spectrometry (ICP-MS) and single particle (sp)ICP-MS are utilized to measure the total mass and size distribution, respectively, of ingested AuNPs. Scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) imaging confirmed that traditional nematode washing procedures were ineffective at removing excess suspended and/or adsorbed AuNPs after exposure. Water rinsing procedures had AuNP removal efficiencies ranging from 57 to 97% and 22 to 83%, while the sucrose density gradient procedure had removal efficiencies of 100 and 93 to 98%, respectively, for the 30 and 60 nm AuNP exposure conditions. Quantification of total Au uptake was performed following acidic digestion of nonexposed and Au-exposed nematodes, whereas an alkaline digestion procedure was optimized for the liberation of ingested AuNPs for spICP-MS characterization. Size distributions and particle number concentrations were determined for AuNPs ingested by nematodes with corresponding confirmation of nematode uptake via high-pressure freezing/freeze substitution resin preparation and large-area SEM imaging. Methods for the separation and in vivo quantification of ENPs in multicellular organisms will facilitate robust studies of ENP uptake, biotransformation, and hazard assessment in the environment.

Detecting Carbon in Carbon: Exploiting Differential Charging to Obtain Information on the Chemical Identity and Spatial Location of Carbon Nanotube Aggregates in Composites by Imaging X-ray Photoelectron Spectroscopy.

To better assess risks associated with nano-enabled products including multiwalled carbon nanotubes (MWCNT) within polymer matrices, it is important to understand how MWCNT are dispersed throughout the composite. The current study presents a method which employs imaging X-ray photoelectron spectroscopy (XPS) to chemically detect spatially segregated MWCNT rich regions at an epoxy composites surface by exploiting differential charging. MWCNT do not charge due to high conductivity and have previously been shown to energetically separate from their insulating surroundings when characterized by XPS. XPS in imaging mode revealed that these conductive regions were spatially separated due to micrometer-scale MWCNT aggregation and poor dispersion during the formation of the composite. Three MWCNT concentrations were studied; (1, 4 and 5) % by mass MWCNT within an epoxy matrix. Images acquired in periodic energy intervals were processed using custom algorithms designed to efficiently extract spectra from regions of interest. As a result, chemical and electrical information on aggregate and non-aggregate portions of the composite was extracted. Raman imaging and scanning electron microscopy were employed as orthogonal techniques for validating this XPS-based methodology. Results demonstrate that XPS imaging of differentially charging MWCNT composite samples is an effective means for assessing dispersion quality.

Giant Surface Conductivity Enhancement in a Carbon Nanotube Composite by Ultraviolet Light Exposure.

Carbon nanotube composites are lightweight, multifunctional materials with readily adjustable mechanical and electrical properties-relevant to the aerospace, automotive, and sporting goods industries as high-performance structural materials. Here, we combine well-established and newly developed characterization techniques to demonstrate that ultraviolet (UV) light exposure provides a controllable means to enhance the electrical conductivity of the surface of a commercial carbon nanotube-epoxy composite by over 5 orders of magnitude. Our observations, combined with theory and simulations, reveal that the increase in conductivity is due to the formation of a concentrated layer of nanotubes on the composite surface. Our model implies that contacts between nanotube-rich microdomains dominate the conductivity of this layer at low UV dose, while tube-tube transport dominates at high UV dose. Further, we use this model to predictably pattern conductive traces with a UV laser, providing a facile approach for direct integration of lightweight conductors on nanocomposite surfaces.

From Image Tiles to Web-Based Interactive Measurements in One Stop.

This article introduces readers to a web-based solution useful for interactive nanoscale measurements of centimeter-sized specimens. This solution is a client-server system that promotes collaborative measurements and discovery. The system consists of multiple computational modules that enable uploading microscopy images, extracting metadata, assembling many nanometer-resolution images into an image covering a centimeter-sized area, and interactive viewing and measuring of objects of interest at multiple length scales over terabyte-sized images. We illustrate the use of the system on images of aerosolized nanoparticles and dye particles on printing paper.

Effects of nanoparticle size and charge on interactions with self-assembled collagen.

HYPOTHESIS: Insights into bone formation have suggested that the critical first step in the biomineralization process is the integration of small (nanometer dimension) mineral clusters into collagen fibers. Not only is such behavior of interest for understanding biomineralization but also should be important to nanotoxicology because collagen is a major component of structural tissues in the human body and accounts for more than 25% of the whole body protein content. Here, utilizing the current insights from biomineralization, we hypothesize that the binding affinity of nanoparticles to self-assembled collagen fibers is size and surface charge dependent. EXPERIMENTS: We developed a self-assembled collagen substrate compatible with Quartz Crystal Microbalance with Dissipation monitoring (QCM-D), which is very sensitive to mechanical changes of the substrate as a consequence of nanoparticle binding. QCM-D experiments were conducted with both positively and negatively charged gold nanoparticles between 2 and 10 nm in size. Complementary ex situ imaging Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) were used to confirm the QCM-D results. FINDINGS: We find that both positively and negatively charged nanoparticles of all sizes exhibited binding affinity for self-assembled collagen fibers. Furthermore, the smallest particles (2 nm) mechanically integrated with collagen fibers.

Live, video-rate super-resolution microscopy using structured illumination and rapid GPU-based parallel processing.

Structured illumination fluorescence microscopy is a powerful super-resolution method that is capable of achieving a resolution below 100 nm. Each super-resolution image is computationally constructed from a set of differentially illuminated images. However, real-time application of structured illumination microscopy (SIM) has generally been limited due to the computational overhead needed to generate super-resolution images. Here, we have developed a real-time SIM system that incorporates graphic processing unit (GPU) based in-line parallel processing of raw/differentially illuminated images. By using GPU processing, the system has achieved a 90-fold increase in processing speed compared to performing equivalent operations on a multiprocessor computer--the total throughput of the system is limited by data acquisition speed, but not by image processing. Overall, more than 350 raw images (16-bit depth, 512 × 512 pixels) can be processed per second, resulting in a maximum frame rate of 39 super-resolution images per second. This ultrafast processing capability is used to provide immediate feedback of super-resolution images for real-time display. These developments are increasing the potential for sophisticated super-resolution imaging applications.

Characterization of SiGe films for use as a National Institute of Standards and Technology Microanalysis Reference Material (RM 8905).

Bulk silicon-germanium (SiGe) alloys and two SiGe thick films (4 and 5 microm) on Si wafers were tested with the electron probe microanalyzer (EPMA) using wavelength dispersive spectrometers (WDS) for heterogeneity and composition for use as reference materials needed by the microelectronics industry. One alloy with a nominal composition of Si0.86Ge0.14 and the two thick films with nominal compositions of Si0.90Ge0.10 and Si0.75Ge0.25 on Si, evaluated for micro- and macroheterogeneity, will make good microanalysis reference materials with an overall expanded heterogeneity uncertainty of 1.1% relative or less for Ge. The bulk Ge composition in the Si0.86Ge0.14 alloy was determined to be 30.228% mass fraction Ge with an expanded uncertainty of the mean of 0.195% mass fraction. The thick films were quantified with WDS-EPMA using both the Si0.86Ge0.14 alloy and element wafers as reference materials. The Ge concentration was determined to be 22.80% mass fraction with an expanded uncertainty of the mean of 0.12% mass fraction for the Si0.90Ge0.10 wafer and 43.66% mass fraction for the Si0.75Ge0.25 wafer with an expanded uncertainty of the mean of 0.25% mass fraction. The two thick SiGe films will be issued as National Institute of Standards and Technology Reference Materials (RM 8905).

3D imaging of diatoms with ion-abrasion scanning electron microscopy.

Ion-abrasion scanning electron microscopy (IASEM) takes advantage of focused ion beams to abrade thin sections from the surface of bulk specimens, coupled with SEM to image the surface of each section, enabling 3D reconstructions of subcellular architecture at approximately 30nm resolution. Here, we report the first application of IASEM for imaging a biomineralizing organism, the marine diatom Thalassiosira pseudonana. Diatoms have highly patterned silica-based cell wall structures that are unique models for the study and application of directed nanomaterials synthesis by biological systems. Our study provides new insights into the architecture and assembly principles of both the "hard" (siliceous) and "soft" (organic) components of the cell. From 3D reconstructions of developmentally synchronized diatoms captured at different stages, we show that both micro- and nanoscale siliceous structures can be visualized at specific stages in their formation. We show that not only are structures visualized in a whole-cell context, but demonstrate that fragile, early-stage structures are visible, and that this can be combined with elemental mapping in the exposed slice. We demonstrate that the 3D architectures of silica structures, and the cellular components that mediate their creation and positioning can be visualized simultaneously, providing new opportunities to study and manipulate mineral nanostructures in a genetically tractable system.