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Baltrus, John

Publications and source records attributed to Baltrus, John.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Luminescent Materials for the Detection of Economically Critical Metals in Harsh Environments

Renewable energy technologies used for electric vehicles and wind turbines are heavily reliant upon metals, such as rare earth elements, cobalt, lithium, and nickel. Indeed, there are 50 minerals that are currently considered “economically critical” by the 2022 United States Geological Survey. With anticipated global adoption of renewable energy technologies, producing sufficient metals to meet this demand presents a significant challenge, particularly due to the current monopolistic market for many of these metals. The production of metals from unconventional sources, such as coal utilization byproducts, is one of many promising strategies to boost domestic supply. However, sensitive, rapid, and inexpensive characterization technologies are needed to minimize production costs associated with metals prospecting and processing. Photoluminescence-based sensing techniques are particularly intriguing due to their potential for low cost and portability, coupled with high sensitivity and selectivity. This presentation focuses on the development of high-performance sensing materials for a range of critical metals, including metal-organic frameworks capable of sensitizing detection of parts-per-billion concentrations of six different rare earth elements, nanoparticles that can detect down to 600 parts-per-billion levels of cobalt, and thin films that sense aluminum down to 120 parts-per-billion. These materials are highly selective, capable of withstanding low pH conditions, and provide a response within minutes. Importantly, each sensing material is integrated with a custom-built, fully portable fiber-optic spectrometer for potential field deployment, providing significant cost savings over commercial instruments, along with potential advantages such as material regeneration for use across multiple sensing cycles and solvent removal for enhanced emission signal. These results highlight the exciting potential of luminescence platforms as cost-effective alternatives for metals characterization.

Crawford, Scott↗
DOE OSTI2024

Portable fiber optic sensor for rare earth elements and other critical metals using photoluminescence methods

Rare earth elements and other metals are vital to a range of technologies that are used in the energy and defense sectors. However, monopolistic market conditions have caused significant concern over the stability of the critical metal supply chain, and this has spurred extensive efforts in many nations to produce these metals domestically, both from conventional sources such as mining and well as from unconventional sources such as coal and its utilization byproducts. Slow and expensive characterization methods pose a significant barrier for both metals prospecting and process monitoring. A promising solution to this challenge is the development of highly sensitive luminescent sensors for metals, which can offer low costs, portability, and sensitivity. Anionic zinc adeninate metal-organic frameworks (BioMOFs) are known to distinguishing and detect part-per-billion levels of terbium, europium, samarium, and dysprosium in water by sensitizing the narrow, element-specific emission bands from these lanthanides. Here, a BioMOF material is immobilized onto a large diameter, solarization-resistant fiber optic tip integrated with a portable, low-cost spectrometer for rare earth element sensing. Immobilizing the sensing material on fiber instead of dispersing the sensing material in solution offers several advantages: it facilitates solvent removal, which enhances luminescent signal from the sensitized lanthanides, and it also allows the BioMOF to be recycled for multiple uses. The sensing system was deployed on a simulated process stream and exhibited qualitative agreement with inductively-coupled plasma mass spectrometry for terbium and europium detection, highlighting the potential for the sensing system to be deployed for real-world applications. By using different sensing materials, the same portable sensor may be deployed to detect other energy relevant metals such as cobalt, providing a cost-effective and sensitive platform for critical metal characterization.

Crawford, Scott↗
DOE OSTI2024

Fabrication of metal-organic framework thin films for luminescent sensing applications

Metal−organic frameworks (MOFs) have emerged as an exciting material class due to their nearly infinite design space: an inexhaustible combination of metal centers, organic linkers, and reaction conditions may be leveraged to obtained desired optical, physical, and chemical properties. This rich synthetic diversity enables properties such as pore dimensions and functionality to be rationally tailored for highly selective and sensitive detection of target analytes. Luminescent MOF-based sensors in particular offer advantages including low cost, portability, and ease-of-use. Often, performance is maximized by utilizing the luminescent MOF in thin film form, for example by integrating the film onto an optical fiber, yet the synthesis of high-quality MOF thin films often requires tedious, expensive, and/or slow approaches. Here, we demonstrate a rapid, simple strategy for growing copper MOFs using metal oxide templates; the concept is first demonstrated with a well-studied system, copper-1,3,5-benznetricarboxylate (Cu-BTC). Variables such as the choice of solvent, pH, and the choice of the copper salt anion all govern thin film quality. We then extend this method to synthesize a solvent and metal-responsive copper MOF that is particularly effective at detecting aluminum, an economically critical metal, at trace concentrations using a fully portable luminescence spectrometer. Taken together, this work demonstrates a convenient, versatile, and sustainable method for developing high quality MOF thin film-based optical sensors.

Crawford, Scott↗
DOE OSTI2024

Functionalization of nitrogen vacancy-containing nanodiamonds with a metal-organic framework for quantum sensing applications

Nitrogen vacancy (NV)-containing nanodiamonds (NDs) are an important material in applications such as biological imaging, catalysis, and, in particular, quantum sensing. Careful manipulation of the surface coating on NV NDs is essential for both enhancing quantum sensor performance and for tuning selectivity towards specific sensing targets. Here, we demonstrate a simple synthetic approach for functionalizing NV NDs with the zeolitic imidazole framework-8 (ZIF-8) metal–organic framework (MOF), providing a well-ordered, porous scaffold for immobilizing target analytes near the NV ND surface. The composites were structurally characterized by x-ray diffraction, electron microscopy, and X-ray photoelectron spectroscopy, and these results were all consistent with NV NDs fully encapsulated by ZIF-8. Critically, the luminescent properties of the NV NDs, which are vital for quantum sensing experiments such as optically detected magnetic resonance (ODMR), are unchanged by the MOF coating. Moreover, spin relaxometry experiments indicate that the ZIF-8 coating significantly enhances the NV ND spin longitudinal relaxation time T1, a critical quantum parameter for sensing applications. Given the tremendous structural diversity of MOFs, the NV ND@MOF composites are an exciting material class with exciting implications for the development of high-performance quantum sensors.

Crawford, Scott↗
DOE OSTI2024

Portable Luminescent Sensor Technologies for Economically Critical Metals

Presentation on the development of sensing materials and compact platforms for the photoluminescence-based detection of economically critical metals, including rare earth elements, cobalt, and aluminum. The important of detecting metals that interfere with critical metal processing, such as iron and aluminum, are also discussed. The presented results represent a significant step forward in reducing the economic and time costs associated with the characterization of metals during prospecting and downstream processing.

Crawford, Scott↗
DOE OSTI2024

Optimization of Conditions for Photoluminescence-Based Sensing of Critical Minerals: Strategies and Outlook

Economically critical minerals and metals are vital to America’s security, with application areas in energy, advanced technologies, and defense systems. The growing implementation of renewable energy sources such as electric vehicles is expected to significantly increase demand for these minerals, while the global supply is monopolistic, with most of the production occurring in a few countries outside of the US. To mitigate potential supply chain vulnerabilities, the domestic production of economically critical metals has become a bipartisan priority of the US government, and unconventional sources such as coal and its utilization byproducts such as fly ash and acid mine drainage are being actively explored as an alternative method for meeting domestic demand. Slow and expensive characterization methods for critical metals present a significant pain point for domestic production, which has led to the exploration of alternative low-cost, portable platforms capable of detecting target metals during resource prospecting and downstream process monitoring. The National Energy Technology Laboratory has developed a portable fiber optic-based luminescence spectrometer that utilizes a metal-organic framework (MOF) material to detect and distinguish parts-per-billion levels of the visible-emitting rare earth elements terbium, dysprosium, samarium, and europium, which are all economically critical metals. Although preliminary results with this system are promising, a crucial barrier to practical deployment is the ability to operate in low pH, high ionic strength environments, as acidic conditions and the presence of other metal ions can significantly reduce luminescence signal. Here, current strategies related to sample treatment, material design, and sensor configuration are discussed in the context of improving sensor performance in application-relevant conditions. Additionally, future opportunities, such as the optimization of the sensing binding environment through computational methods and specific metals to be removed for treatment will be discussed, presenting a forward-looking view for innovation in luminescent sensing of critical metals.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Materials for the Photoluminescence-Based Detection of Economically Critical Metals

Critical metals, such as rare earth elements (REEs), cobalt, lithium, aluminum, nickel, and others, are essential to advanced technologies and renewable energy in particular. Widespread global adoption of renewable energy technologies has spurred dramatic demand increases for these metals; however, the global supply of these metals is highly monopolistic and conventional mining poses economic and environmental challenges. As a result, there is increasing interest in domestic production from alternative resources such as coal and its utilization byproducts. Slow and expensive characterization costs remain a significant barrier for domestic production. Here, luminescent sensing materials and platforms are presented that provide an alternative to the current state-of-the-art characterization methods; highly sensitive and selective sensing materials for cobalt, aluminum, and rare earth elements are presented, as well as compact, inexpensive platforms capable of analyzing signal from these materials for rapid characterization of critical metal content.

Crawford, Scott↗
DOE OSTI2024

Materials for the Photoluminescence-Based Detection of Economically Critical Metals

Critical metals, such as rare earth elements (REEs), cobalt, lithium, aluminum, nickel, and others, are essential to advanced technologies and renewable energy in particular. Widespread global adoption of renewable energy technologies has spurred dramatic demand increases for these metals; however, the global supply of these metals is highly monopolistic and conventional mining poses economic and environmental challenges. As a result, there is increasing interest in domestic production from alternative resources such as coal and its utilization byproducts. Slow and expensive characterization costs remain a significant barrier for domestic production. Here, luminescent sensing materials and platforms are presented that provide an alternative to the current state-of-the-art characterization methods; highly sensitive and selective sensing materials for cobalt, aluminum, and rare earth elements are presented, as well as compact, inexpensive platforms capable of analyzing signal from these materials for rapid characterization of critical metal content.

Crawford, Scott↗
DOE OSTI2022

Surface analysis insight note: Differentiation methods applicable to noisy data for determination of sp2‐ versus sp3‐hybridization of carbon allotropes and AES signal strengths

The derivatives of the spectra are commonly used for quantification in Auger Electron Spectroscopy (AES) spectra, while the derivative of the KLL C Auger line has proven to be valuable in obtaining a measure of the relative proportions of sp 2 ‐ and sp 3 ‐hybridization using the D‐parameter in both AES and X‐ray Photoelectron Spectroscopy (XPS). Differentiation of X‐ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) spectra by numerical means is presented and illustrated for polymeric, such as PEEK and Nylon, as well as for graphitic materials including highly ordered pyrolytic graphite and graphene oxide. The most commonly available Savitzky–Golay method is explained mathematically and developed through the case of constructing a 5‐point quadratic polynomial convolution kernel suitable for differentiating spectra of adequate signal to noise. The concept of differentiation of spectra where signal to noise is less than adequate is also developed. Two alternative strategies to Savitzky–Golay differentiation are presented, which fit curves to data that allow derivatives to be obtained where Savitzky–Golay would otherwise fail. These alternative methods involve constructing a parametric curve that fits data over the entire energy interval of interest. Derivatives of spectra are then obtained by differentiating these parametric curves directly. A comparison of results for different materials for which specific sp 2 ‐ vs sp 3 ‐hybridized carbon proportions are of interest is used to emphasize the importance of characterizing methods used to differentiate spectra and understanding the characteristics of instrumentation used to measure spectra. The case for using Principal Component Analysis noise reduction with C KLL spectra is made for spectra collected from a heterogeneous graphene oxide sample.

Fairley, Neal↗