Stephanie S. Watson

Characterization of Metal Powders Used for Additive Manufacturing

Additive manufacturing (AM) techniques1 can produce complex, high-value metal parts, with potential applications as critical parts, such as those found in aerospace components. The production of AM parts with consistent and predictable properties requires input materials (e.g., metal powders) with known and repeatable characteristics, which in turn requires standardized measurement methods for powder properties. First, based on our previous work, we assess the applicability of current standardized methods for powder characterization for metal AM powders. Then we present the results of systematic studies carried out on two different powder materials used for additive manufacturing: stainless steel and cobalt-chrome. The characterization of these powders is important in NIST efforts to develop appropriate measurements and standards for additive materials and to document the property of powders used in a NIST-led additive manufacturing material round robin. An extensive array of characterization techniques was applied to these two powders, in both virgin and recycled states. The physical techniques included laser diffraction particle size analysis, X-ray computed tomography for size and shape analysis, and optical and scanning electron microscopy. Techniques sensitive to structure and chemistry, including X-ray diffraction, energy dispersive analytical X-ray analysis using the X-rays generated during scanning electron microscopy, and X-Ray photoelectron spectroscopy were also employed. The results of these analyses show how virgin powder changes after being exposed to and recycled from one or more Direct Metal Laser Sintering (DMLS) additive manufacturing build cycles. In addition, these findings can give insight into the actual additive manufacturing process.

NIST gold nanoparticle reference materials do not induce oxidative DNA damage

Abstract One primary challenge in nanotoxicology studies is the lack of well-characterised nanoparticle reference materials which could be used as positive or negative nanoparticle controls. The National Institute of Standards and Technology (NIST) has developed three gold nanoparticle (AuNP) reference materials (10, 30 and 60 nm). The genotoxicity of these nanoparticles was tested using HepG2 cells and calf-thymus DNA. DNA damage was assessed based on the specific and sensitive measurement of four oxidatively-modified DNA lesions (8-hydroxy-2´-deoxyguanosine, 8-hydroxy-2´-deoxyadenosine, (5´S)-8,5´-cyclo-2´-deoxyadenosine and (5´R)-8,5´-cyclo-2´-deoxyadenosine) using liquid chromatography/tandem mass spectrometry. Significantly elevated, dose-dependent DNA damage was not detected at concentrations up to 0.2 μg/ml, and free radicals were not detected using electron paramagnetic resonance spectroscopy. These data suggest that the NIST AuNPs could potentially serve as suitable negative-control nanoparticle reference materials for in vitro and in vivo genotoxicity studies. NIST AuNPs thus hold substantial promise for improving the reproducibility and reliability of nanoparticle genotoxicity studies.

DNA damaging potential of photoactivated p25 titanium dioxide nanoparticles.

Titanium dioxide nanoparticles (TiO2 NPs) are found in numerous commercial and personal care products. Thus, it is necessary to understand and characterize their potential environmental health and safety risks. It is well-known that photoactivated TiO2 NPs in aerated aqueous solutions can generate highly reactive hydroxyl radicals ((•)OH), which can damage DNA. Surprisingly, recent in vitro studies utilizing the comet assay have shown that nonphotoactivated TiO2 NPs kept in the dark can also induce DNA damage. In this work, we utilize stable isotope-dilution gas chromatography/tandem mass spectrometry to quantitatively characterize the levels and types of oxidatively generated base lesions in genomic DNA exposed to NIST Standard Reference Material TiO2 NPs (Degussa P25) under precisely controlled illumination conditions. We show that DNA samples incubated in the dark for 24 h with TiO2 NPs (0.5-50 μg/mL) do not lead to the formation of base lesions. However, when the same DNA is exposed to either visible light from 400 to 800 nm (energy dose of ∼14.5 kJ/m(2)) for 24 h or UVA light at 370 nm for 30 min (energy dose of ∼10 kJ/m(2)), there is a significant formation of lesions at the 50 μg/mL dose for the visible light exposure and a significant formation of lesions at the 5 and 50 μg/mL doses for the UVA light exposure. These findings suggest that commercial P25 TiO2 NPs do not have an inherent capacity to oxidatively damage DNA bases in the absence of sufficient photoactivation; however, TiO2 NPs exposed to electromagnetic radiation within the visible portion of the light spectrum can induce the formation of DNA lesions. On the basis of these findings, comet assay processing of cells exposed to TiO2 should be performed in the dark to minimize potential artifacts from laboratory light.

Critical role of particle/polymer interface in photostability of nano-filled polymeric coatings

Nanoparticle-filled polymeric coatings have attracted great interest in recent years because the incorporation of nanofillers can significantly enhance the mechanical, electrical, optical, thermal, and antimicrobial properties of coatings. Due to the small size of the fillers, the volume fraction of the nanoparticle/polymer interfacial area in nano-filled systems is drastically increased, and the interfacial region becomes important in the performance of the nano-filled system. However, techniques used for characterizing nanoparticle/polymer interfaces are limited, and thus, the mechanism by which interfacial properties affect the photostability and the long-term performance of nano-filled polymeric coatings is not well understood. In this study, the role of the nanoparticle/polymer interface on the ultraviolet (UV) stability of a nano-ZnO-filled polyurethane (PU) coating system was investigated. The effects of parameters influencing the particle/polymer interfacial properties, such as size, loading, surface modification of the nanoparticles, on photodegradation of ZnO/PU films were evaluated. The nature of the interfacial regions before and after UV exposures were characterized by atomic force microscopy (AFM)-based techniques. Results have shown that the interfacial properties strongly affect chemical, thermo-mechanical, and morphological properties of the UV-exposed ZnO/PU films. By combining tapping mode AFM and novel electric force microscopy (EFM), the particle/polymer interfacial regions have been successfully detected directly from the surface of the ZnO/PU films. Further, our results indicate that ZnO nanoparticles can function as a photocatalyst or a photostabilizer, depending on the UV exposure conditions. A hypothesis is proposed that the polymers in the vicinity of the ZnO/PU interface are preferentially degraded or protected, depending on whether ZnO nanoparticles act as a photocatalyst or a photostabilizer in the polymers. This study clearly demonstrates that the particle/polymer interface plays a critical role in the photostability of nano-filled polymeric coatings.

Biophysical characterization of functionalized titania nanoparticles and their application in dental adhesives

It is demonstrated that carboxylic acid-functionalized titanium dioxide (TiO2) NPs produce significantly higher levels of reactive oxygen species (ROS) after visible light irradiation (400-800nm, 1600mW/cm2) in comparison to nonfunctionalized TiO2 NPs. The level of ROS produced under these irradiation conditions was not capable of generating oxidatively induced DNA damage in a cell-free system for TiO2 concentrations of 0.5mg/L or 5mg/L. In addition, specific incorporation of the acrylic acid-functionalized TiO2 NPs into dental composites allowed us to utilize the generated ROS to enhance photopolymerization (curing and degree of vinyl conversion (DC)) of resin adhesives and create mechanically superior and biocompatible materials for dental applications. Incorporation of the TiO2 NPs into selected dental composites increased the mean DC values by ≈7%. The modified TiO2 materials and dental composite materials were extensively characterized using thermogravimetric analysis, electron microscopy, Fourier transform infrared spectroscopy, and electron paramagnetic resonance. Notably, dental adhesives incorporated with acrylic acid-functionalized TiO2 NPs produced stronger bonds to human teeth following visible light curing in comparison to traditional dental adhesives not containing NPs with an increase in the shear bond strength of ≈29%. In addition, no leaching of the incorporated NPs was detectable from the dental adhesives after 2500 thermal cycles using inductively coupled plasma-optical emission spectroscopy, indicating that biocompatibility of the adhesives was not compromised after extensive aging. These findings suggest that NP-induced ROS may be useful to produce enhanced nanocomposite materials for selected applications in the medical device field. STATEMENT OF SIGNIFICANCE Titanium dioxide nanoparticles (TiO2 NPs) have unique photocatalytic, antibacterial and UV-absorbing properties that make them beneficial additives in adhesives and composites. However, there is concern that the reactive oxygen species (ROS) produced by photoactivated TiO2 NPs might pose toxicological risks. We demonstrate that it is possible to incorporate acid-functionalized TiO2 NPs into dental resins which can be applied as dental adhesives to human teeth. The ROS generated by these NPs through visible-light irradiation may be utilized to increase the degree of vinyl conversion of resins, leading to adhesives that have an enhanced shear-bond strength to human teeth. Investigation into the potential genotoxicity of the NPs and their potential for release from dental composites indicated a low risk of genotoxic effects.

Tuning photo-catalytic activities of TiO2 nanoparticles using dimethacrylate resins.

OBJECTIVE The unique photo-catalytic activities (PCAs) of titanium dioxide nanoparticles (TiO2 NPs) made them attractive in many potential applications in medical devices. The objective of this study is to optimize the benefits of PCAs of TiO2 NPs through varying chemical structures of dimethacrylate resins. METHODS TiO2 NPs were functionalized to improve the PCAs and bonding to the resins. The PCAs of TiO2 NPs were evaluated using electron paramagnetic resonance (EPR) and UV-vis spectroscopy to determine the amount of the radicals generated and the energy required for their production, respectively. The beneficial effects of the radicals were assessed through: (1) the improvement of degree of vinyl conversion (DC) and (2) modification of resin hydrophilicity. One-way ANOVA with a 95% confidence interval was used to indicate the significant differences between the experimental groups. RESULTS EPR and UV-vis results clearly showed that the functionalization of TiO2 NPs enhanced PCAs in terms of generating radicals under visible light irradiation. The presence of hydroxyl and carboxylic acid functionalities played an important role in DC enhancement and hydrophilicity modification. The DC could be increased up to 22% by adding only 0.1wt% TiO2 NPs. Viscosity of the resins had minimal or no role in DC improvement through TiO2 NPs. In resins with abundant hydroxyl groups, radicals were more effective in making the resin more hydrophilic. SIGNIFICANCE Knowledge learned from this study will help formulating nano-composites with optimized use of TiO2 PCAs as co-initiators for photo-polymerization, additives for making super-hydrophilic materials and/or antibacterial agents.

Pigment and nanofiller photoreactivity database

The service life and durability of nanocomposites containing fillers are affected by photocatalytic properties of these fillers, particularly narrow band gap metal oxides (NBMOs) such as titanium dioxide (TiO2). When irradiated with ultraviolet flux, NBMOs produce electrons and other species that are capable of causing rapid degradation of organic materials with which they are in contact. Electrons and holes (positively charged species) migrate to the surface and react with species to generate various free radicals. Measurement science tools for characterizing TiO2 photoreactivity using electron paramagnetic resonance (EPR) methods have been developed by the Engineering Laboratory (EL) at the National Institute of Standards and Technology (NIST) and a linkage between EPR measurements and current industrial methods has been established. A database of TiO2 photoreactivity values and other data measured via the EPR methods and industrial assays has been compiled and will be accessed through a searchable software database in the NIST Standard Reference Database program—http://www.nist.gov/srd/index.cfm. The database provides fundamental photoreactivity data that can be used for product selection and development purposes to enable more reliable assessments of end-performance.

More durable or more vulnerable? – Effect of nanoparticles on long-term performance of polymeric nanocomposites during UV exposure

ZnO nanoparticle is being used as an inorganic UV absorber for polymers. However, the mechanism of how ZnO nanoparticles influence the photo degradation of polymersis is not well understood. This study has investigated the role of ZnO nanoparticles in the long-term performance of a polyurethane (PU) nanocomposite subject to UV radiation. PU samples containing different levels of ZnO nanoparticles were exposed to the NIST Simulated Photodegradation via High Energy Radiant Exposure (SPHERE) UV chamber under both dry (0% RH) and moist (75% RH) conditions at 45°C. Chemical and physical properties with exposure times were characterised using multiple spectroscopic and microscopic techniques. The results indicated that the studied ZnO nanoparticles acted as a catalyst and accelerated the photodegradation of PU. The photo-catalytic effect was dependent on ZnO concentration and RH. It is suggested that systematical long-term performance study under different exposure environments is important for correctly evaluating the role of nanoparticles on durability and sustainability of polymer nanocomposites.

Photofading in cotton fibers dyed using red, yellow, and blue direct dyes during examination with microspectrophotometry (MSP)

Microspectrophotometry (MSP) is a rapid, nondestructive technique for the analysis of color in textile fibers. This technique combines microscopy and ultraviolet (UV)/visible (Vis) spectroscopy, allowing for very small colored samples, like dyed textile fibers, to be analyzed directly and thereby eliminates the need for time consuming and destructive extractions. While MSP is generally accepted to be a nondestructive evaluation method, a loss of color during analysis, or photofading can occur. In this work, cotton fabric dyed with blue, yellow, and red direct dyes at different concentrations. Dye photofading during MSP examination was investigated by measuring the absorbance at a specific position on the fibers from these fabrics, periodically over the course of 30 minutes. Visible color loss and a reduction in absorbance was observed for all three colors, but was most pronounced for the fibers dyed red. A major goal of this study is to increase awareness of the photofading phenomenon when analyzing cotton fibers using MSP.

Chemical depth profiling of photovoltaic backsheets after accelerated laboratory weathering

Polymeric multilayer backsheets provide protection for the backside of photovoltaic (PV) module from the damage of moisture and ultraviolet (UV). Due to the nature of multilayer films, certain material property characterization of a backsheet could only be studied by examining its cross-section parallel to the thickness direction of the film. In this study, commercial PPE (polyethylene terephthalate (PET)/PET/ethylene vinyl acetate (EVA)) backsheet films were aged on the NIST (National Institute of Standards and Technology) SPHERE (Simulated Photodegradation via High Energy Radiant Exposure) with UV irradiance at 170 W/m2 (300 nm to 400 nm) under accelerated weathering conditions of 85°C and two relative humidity (R.H.) levels of 5% (low) and 60% (high). Cryo-microtomy was used to obtain cross-sectional PPE samples with a flat surface parallel to the thickness direction, and chemical depth profiling of multilayers was conducted by Raman microscopic mapping. Atomic force microscopy with peak force tapping mode was used complementarily for cross-sectional imaging. The results revealed that the PPE backsheet films were comprised of five main layers, including pigmented-PET, core PET, inner EVA, pigmented-EVA and outer EVA, along with their interfacial regions and two adhesive layers. UV and moisture degradation on the outer pigmented PET layer was clearly observed; while the damage on the core PET layer was less significance, indicating that the outer pigmented PET layer effectively reduced the damage from UV. In high R.H. exposure, both adhesive layers were severely deteriorated. It was found that the EVA layers were susceptible to moisture at elevated temperature, especially for the pigmented-EVA. Based on the results of accelerated weathering, this depth profiling study brings new understanding to the mechanisms of failure observed in polymeric multilayer backsheets during field exposure.