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At least 37 records · Page 2

Improving Stability of an Optical Fiber pH Sensor with a Calcined Polyethylenimine-Coating at High Pressures and Temperatures

With an increased interest in subsurface gas storage technology for various energy applications, monitoring wellbore structural stability and subsurface geochemistry has become more pressing, and pH is a key parameter to measure. As high pressure and elevated temperatures in subsurface conditions are comparatively harsh relative to that expected for most standard pH sensor designs, any pH monitoring hardware must be designed for extended exposure to high pressures and temperatures. We previously reported that an optical fiber pH sensor functionalized with a calcined polyethylenimine coating had shown some promise as a high temperature and pressure pH sensor but with some drifting when operating for longer than 8 hours. In this paper, we investigated the coating composition and potential cause of the drifting and improved the stability of the prepared coating to minimize sensor drift under simulated wellbore conditions. Scanning electron microscopy (SEM) had previously shown moderate cracking at high pressures over short tests. By applying X-ray photoelectron spectroscopy (XPS) to characterize the sensor coating before and after one week of testing in an H2/CH4 gas blend at 80 °C and 900 psi, a compositional change in the coating was observable, which may indicate susceptibility to alteration by subsurface gas storage conditions. Non-reducing (CH4, N2) environments were also tested, and confirmed that both temperature and pressure were also contributing to the drift.

energy infrastructure

Probing the pH Effect on Boehmite Particles in Water Using Vacuum Ultraviolet Single-Photon Ionization Mass Spectrometry

Boehmite has been widely used in theoretical research and industry, especially for hazardous material processing. For the liquid-phase treating process, the interfacial properties of boehmite are believed to be affected by pH conditions, which change its physicochemical behavior. However, molecular-level detection on cluster ions is challenging when using bulk approaches. Herein we employ in situ vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with a vacuum-compatible microreactor system for analysis at the liquid–vacuum interface (SALVI) to investigate the solute molecular composition of boehmite under different pH conditions for the first time. The mass spectral results show that more complex clustering of solute molecules exists at the solid–liquid (s–l) interface than conventionally perceived in a “simple” aqueous solution. Besides solute ions, such as boehmite molecules and fragments, the composition and appearance energies of these newly discovered solvated cluster ions are determined by VUV SPI-MS in different pH solutions. We offer new results for the pH-dependent effect of boehmite and provide insights into a more detailed solvation mechanism at the s–l interface. By comparing the key products under different pH conditions, fundamental understanding of boehmite dissolution is revealed to assist the engineering design of waste processing and storage solutions.

SALVI

Improving Stability of an Optical Fiber pH Sensor with a Calcined Polyethylenimine-Coating at High Pressures and Temperatures

With an increased interest in subsurface gas storage technology for various energy applications, monitoring wellbore structural stability and subsurface geochemistry has become more pressing, and pH is a key parameter to measure. As high pressure and elevated temperatures in subsurface conditions are comparatively harsh relative to that expected for most standard pH sensor designs, any pH monitoring hardware must be designed for extended exposure to high pressures and temperatures. We previously reported that an optical fiber pH sensor functionalized with a calcined polyethylenimine coating had shown some promise as a high temperature and pressure pH sensor but with some drifting when operating for longer than 8 hours. In this paper, we investigated the coating composition and potential cause of the drifting and improved the stability of the prepared coating to minimize sensor drift under simulated wellbore conditions. Scanning electron microscopy (SEM) had previously shown moderate cracking at high pressures over short tests. By applying X-ray photoelectron spectroscopy (XPS) to characterize the sensor coating before and after one week of testing in an H2/CH4 gas blend at 80°C and 900 psi, a compositional change in the coating was observable, which may indicate susceptibility to alteration by subsurface gas storage conditions. Non-reducing (CH4, N2) environments were also tested, and confirmed that both temperature and pressure were also contributing to the drift.

energy infrastructure

The solubility of La hydroxide and stability of La 3+ and La hydroxyl complexes at acidic to mildly acidic pH from 25 to 250 °C

The mobility of rare earth elements (REE) in natural hydrothermal systems can be assessed using geochemical modeling, which requires reliable thermodynamic data of relevant aqueous species. In this study, we evaluate the controls of pH and temperature on La speciation and the role of hydroxyl complexes in REE transport at hydrothermal conditions. Batch-type hydrothermal solubility experiments were conducted using synthetic La hydroxide powders equilibrated in perchloric acid-based aqueous solutions at temperatures between 150 and 250 °C and starting pH of 2 to 5. The La hydroxide solubility is retrograde with temperature and displays a strong pH dependence with a decrease in La concentrations from acidic to mildly acidic pH spanning between 3 and 5 orders of magnitude (e.g. log La molality of –2.5 to –7.2 at 250 °C). Thermodynamic optimizations using GEMSFITS allow to retrieve the standard partial molal Gibbs energies for the La 3+ aqua ion and the formation constants for the La hydroxyl species (i.e., LaOH 2+ , La(OH) 2 + , La(OH) 3 0 ) between 25 and 250 °C. A comparison between the experimentally derived thermodynamic properties with the calculated values from the Helgeson-Kirkham-Flowers equation of state parameters indicates an increased divergence with temperature. Discrepancies in standard partial molal Gibbs energies range between ~ 1 – 12 kJ/mol and result in a predicted La hydroxide solubility differing by up to 3 orders of magnitude at 250 °C. Speciation calculations indicate a higher stability of La 3+ and LaOH 2+ over the other La hydroxyl species in the studied pH range of 3.4 to 6. Here, the optimized thermodynamic properties for La aqueous species have important implications for modeling the solubility of REE minerals such as monazite and the mobility of REE in hydrothermal systems.

58 GEOSCIENCES

Mapping Structure and Rheology of pH-Responsive Resins for Low-VOC Coatings

In recent years, the paint and coatings industry has shifted away from traditional resin formulations that require high concentrations of volatile organic compounds (VOCs) to achieve the desired rheological performance and sustainability targets. One approach to eliminate or reduce VOCs in paint and coating formulations while maintaining the final performance is to disperse stimuli-responsive polymer latex particles in water. The chemistry and architecture of these particles have been engineered such that the suspension rheology changes in response to the pH changes. The particles can also be swollen with organic solvents to illicit similar rheological changes. To understand how the particle microstructure influences the observed macroscopic properties, we use small-angle neutron scattering and dynamic light scattering to determine that these particles consist of a cross-linked core with long polymer tails that extend into the dispersing medium. Carboxylic acid groups present on the tails deprotonate with increasing pH, and the extension of the polymer chain due to charge repulsion increases the hydrodynamic drag on the particle. Here we find that adjusting the pH alone has a much more significant effect on the shear dependence of the viscosity of the studied resin than adding organic solvent alone. We also find that this resin architecture is more responsive per mole of pH-responsive group than other architectures of pH-responsive latex particles in the literature.

36 MATERIALS SCIENCE

Tracking Local pH Dynamics during Water Electrolysis via In-Line Continuous Flow Raman Spectroscopy

The performance of electrochemical devices, which play a critical role in decarbonization efforts, is often governed by proton-coupled electron transfer reactions at the electrode–electrolyte interface. These reactions are highly sensitive to the complex and dynamic microenvironment present at the electrode surface. However, characterizing this environment─particularly monitoring interfacial pH and its evolution under reaction conditions─remains challenging, necessitating the development of advanced analytical tools. Here, in this study, we introduce in-line continuous flow Raman spectroscopy (CFRS) as a spectroelectrochemical platform for quantifying interfacial pH swings generated during water-splitting. By monitoring phosphate ion speciation and controlling the hydrodynamics with a flow cell, we measure pH swings as a function of current density, flow rate, and distance from the electrode. Comparison with theoretical models reveals the impact of bulk pH, boundary layer thickness, and bubble dynamics at high current densities. Collectively, these findings establish CFRS as a platform for quantitatively investigating pH dynamics, offering critical insights for advancing electrochemical energy conversion technologies.

Marquez, Raul A. [Univ. of Texas, Austin, TX (Unit

Spectrophotometric determination of the stability of La hydroxyl complexes at near neutral to alkaline pH from 25 to 75 °C

The hydrolysis of rare earth elements (REE) potentially controls their mobility during fluid-rock interaction in a broad range of pH and temperature conditions. However, there is still a lack of thermodynamic data for modeling accurately the stability of REE hydroxyl complexes in hydrothermal aqueous fluids. Here, in this study, UV–Vis spectrophotometric experiments were conducted from 25 to 75 °C in near-neutral to alkaline NaOH-bearing aqueous solutions with varying lanthanum (La) concentrations (0 to ∼0.23 mmol/kg). The color indicator m-cresol purple was used to determine in situ pH and derive the average OH− ligand number ($\overrightarrow{n}$) and formation constants for the La hydroxyl complexes (LaOH 2+ , La(OH) 2 + , and La(OH) 3 0 ). From 25 to 50 °C, $\overrightarrow{n}$ ranges between ∼1 and 2 at pH from 7.0 to 9.3. At 75 °C, $\overrightarrow{n}$ ranges between ∼1.5 and 3 at pH from 6.3 to 8.8. These results suggest the predominance of LaOH 2+ and La(OH) 2 + complexes from 25 to 50 °C, and an increased predominance of La(OH) 3 0 at 75 °C. The cumulative formation constants (β n °, n = 1 to 3) are derived for the reaction La 3+ + nOH − = La(OH) n 3-n , and fitted between 25 and 250 °C by combining the UV–Vis and literature solubility data. The resulting logβ n ° are expressed as function of temperature (T in Kelvin): logβ 1 ° = −1.786 + 0.0133 T + 1.049·10 3 /T; logβ 2 ° = −5.797 + 0.0267 T + 2.713·10 3 /T; logβ 3 ° = 6.435 + 0.0223 T + 512.7/T. A comparison between these new fits and existing extrapolations using the Helgeson-Kirkham-Flowers equation of state indicates significant differences in the predicted hydrolysis of La. The latter extrapolations should therefore be updated for the hydrolysis of REE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Innovative use of CaO in combination with amino acid salt to convert CO 2 as CaCO 3 nanoparticles under mild pH and low temperature

The increasing demand for sustainable CO 2 management has driven the development of innovative methods that can convert point source CO 2 into value-added products. In this study, CaO in combination with amino acid salt was used to convert CO 2 into CaCO 3 nanoparticles. Different from the conventional method where CO 2 diffusion presents a major challenge in reacting with CaO to form CaCO 3 , amino acid salt solvent was applied to absorb CO 2 first and then rapidly reacted with CaO to form CaCO 3 nanoparticles (∼50 nm) at a low temperature (e.g., 60 °C). Our experiments showed that at a glycine (Gly)/NaOH ratio of 2:1 or 3:1, the solution pH values during the CO 2 absorption and conversion were about 8–9 at 60 °C, while at a ratio of 1:1, the solution pH values were about 9–11; without Gly, the solution pH values were about 12. Gly-optimized solvent substantially reduced corrosion risk to reactors. In addition, the use of amino acid (i.e., Gly) led to much smaller CaCO 3 particles, distinctly different chemical phases, and fundamentally different chemical reactions. Moreover, in the presence of Gly, the solution pH was completely reversed and the solution was regenerated for cyclic use when CaO was added. The solvent was recyclable and reusable, highlighting the cost-effectiveness and sustainability of this approach. The Gly-modulated CaCO 3 nanoparticles may have significant potential for industrial applications in the biomedicine, construction, plastics, and rubber industries.

36 MATERIALS SCIENCE

Measuring pH Changes Inside a Bipolar Membrane Junction

Here, the local pH environment within bipolar membrane (BPM) junctions is complex and not well understood, yet it is important to control for advancing the performance of BPM-based electrochemical systems. We report a voltammetric strategy using an ultrathin Ni mesh pH probe to spatially resolve pH changes in the BPM junction during model BPM electrolyzer operation. Under reverse bias, we observe depletion of OH – at the anion-exchange layer (AEL) interface, with a degree diminishing with increasing distance from the AEL. These gradients correlate with current-dependent water dissociation (WD) and are modulated by the electric field and the surface charge state of the catalyst. By correlating spatial pH profiles with the surface-charging behavior of WD catalysts, we explore a mechanism of catalyst-mediated H + and OH – transfer facilitated by hydrogen-bonding networks. These findings highlight the role of local chemistry and electrostatics in BPM performance and offer new methods to probe and engineer catalytic junctions in electrochemical energy devices.

Hou, Shujin [University of California, Berkeley, C

pH-dependent reactivity of water at MgO(100) and MgO(111) surfaces

Facet-dependent surface charging of metal oxides in water dominates the ion transport behavior across the interface, in turn impacting many natural and industrial processes such as adsorption, the formation and stabilization of nanoparticle suspensions, corrosion, and heterogeneous catalysis. Here we investigated the pH-dependent surface chemistry of two low-index MgO single crystal surfaces, namely MgO(100) and MgO(111), using vibrational sum frequency generation (vSFG) spectroscopy. This allowed us to evaluate facet-dependent pH effects on the hydration and hydroxylation at the solid/aqueous interface and point-of-zero charge (PZC) values. The MgO system is complicated by its thermodynamic instability with respect to Mg(OH) 2 in water at ambient conditions. Here, for both hydroxylated MgO(100) and MgO(111) surfaces, the PZC is found to be around pH ∼ 12, which compares well with reported values for MgO single crystal and nanoparticle surfaces. However, structure specific differences in the molecular water hydrogen bonding network near the surface are evident at mildly acidic pH. To our knowledge, this is the first account of the PZC values for the MgO(111) single-crystal surface, an electrostatically unstable MgO termination that is prone to reconstruction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Nannochloropsis oceanica IMET1 and its bacterial symbionts for carbon capture, utilization, and storage: biomass and calcium carbonate production under high pH and high alkalinity

ABSTRACT To combat the increasing levels of carbon dioxide (CO 2 ) released from the combustion of fossil fuels, microalgae have emerged as a promising strategy for biological carbon capture, utilization, and storage. This study used a marine microalgal strain, Nannochloropsis oceanica IMET1, which thrives in high CO 2 concentrations. A high-pH, high-alkalinity culture was designed for CO 2 capture through algal biomass production as well as permanent sequestration through calcium carbonate (CaCO 3 ) precipitation. This was accomplished by timed pH elevation and the addition of sodium bicarbonate to cultures of N. oceanica grown at lab scale (1 L) and pilot scale (500 L) with 10% and 5% CO 2 , respectively. Our data showed that 0.02 M NaHCO 3 promoted algal growth and that sparging cultures with ambient air after 12 days raised pH and created favorable CaCO 3 formation conditions. At the 1 L scale, we reached 1.52 g L −1 biomass after 12 days and an extra 9.3% CO 2 was captured in the form of CaCO 3 precipitates. At the 500 L pilot scale, an extra 60% CO 2 was captured (Day 40) with a maximum CO 2 capture rate of 63.2 g m −2 day −1 (Day 35). Bacterial communities associated with the microalgae were dominated by two novel Patescibacteria. Functional analysis revealed that genes for several plant growth-promotion traits (PGPTs) were enriched within this group. The microalgal-bacterial coculture system offers advantages for enhanced carbon mitigation through biomass production and simultaneous precipitation of recalcitrant CaCO 3 for long-term CO 2 storage. IMPORTANCE Capturing carbon dioxide (CO 2 ) released from fossil fuel combustion is of the utmost importance as the impacts of climate change continue to worsen. Microalgae can remove CO 2 through their natural photosynthetic pathways and are additionally able to convert CO 2 into a stable, recalcitrant form as calcium carbonate (CaCO 3 ). We demonstrate that microalgae-based carbon capture systems can be greatly improved with high pH and high alkalinity by providing optimal conditions for carbonate precipitation. Our results with the microalga, Nannochloropsis oceanica strain IMET1, show an extra 9.3% CO 2 captured as CaCO 3 at the 1 L scale and an extra 60% CO 2 captured at the 500 L (pilot) scale. Our optimized system provides a novel approach to capture CO 2 through two mechanisms: (i) as organic carbon within microalgal biomass and (ii) as inorganic carbon stored permanently in the form of CaCO 3.

20 FOSSIL-FUELED POWER PLANTS

Probing and Tuning Spatiotemporal pH Evolution in Aqueous Zinc Ion Batteries

Aqueous zinc-ion batteries (AZIBs) offer a combination of safety and low cost, but they suffer from dynamic pH fluctuations that drive parasitic reactions and capacity fading. In this review, we report the current mechanistic understanding of the dynamic pH evolution across the electrolyte-electrode interface and its role in triggering interphase instability. We summarize advanced strategies to regulate pH, including electrolyte engineering, electrode surface modification, and interphase construction. We further discuss current methods for probing pH dynamics and outline potential future approaches for gaining deeper mechanistic and design insights.

Zheng, Xueli [SLAC]

Ion Transport in Carbon Nanotube Porins with a pH-Switchable Entrance Gate

Molecular transport in nanofluidic channels often differs drastically from conventional bulk transport. Strong confinement in those channels amplifies the roles of surface transport, surface defects, and molecular gates. Here, in this study, we introduce a chemical functionality at the nanotube rim that acts as a pH-triggered molecular gate by forming a movable lid that blocks the pore entrance. We use ion and proton transport measurements to show that these sub-1 nm diameter fluorescent ultrashort carbon nanotube porins (FUNPs) modulate ion transport by switching between the “open” and “closed” conformations of this gate. Specifically, at neutral pH the channel lid is open, allowing unimpeded ion transport through the gate, whereas at acidic pH values the lid forms a “closed” conformation that blocks transport through the nanotube. We also report first-principles MD simulations that confirm this gating mechanism and reveal molecular details of the ion and proton transport processes in these functional nanopores.

Carbon nanotubes

Effect of deposition rate on microstructure and mechanical properties of 17-4 PH stainless steel fabricated by laser engineered net shaping

Laser engineered net shaping (LENS) is an additive manufacturing technique for fabricating and repairing metallic components. However, the relationships between its process parameters and the resulting mechanical properties of alloys such as 17-4 precipitation-hardening (PH) stainless steel require further investigation to enable reliable application. This study examines the specific effect of LENS deposition rate on the microstructure and mechanical properties of 17-4 PH stainless steel. Specimens were fabricated at two different deposition rates (8.47 and 9.31 mm s−1), subjected to subsequent solution and H900 aging treatment, and then evaluated via tensile testing, hardness measurements, and microscopy. A higher deposition rate results in a finer grain structure but increased porosity, leading to greater ultimate tensile strength (∼1294 MPa) yet lower ductility (strain at failure ∼5.8%) compared to the slower deposition rate (∼1266 MPa, ∼9.0% strain). Hardness follows the same trend as tensile strength. Tensile fracture surfaces for both conditions exhibited a mixed mode of ductile dimples and brittle quasi-cleavage regions, with chromium/silicon oxide particles identified within dimples. Complementary finite element modeling indicates that small void fractions primarily reduce ductility by enhancing localized plasticity, with only a marginal decrease in tensile strength. These integrated experimental and numerical results elucidate the mechanical properties linked to deposition rate, providing insight into tailoring LENS processes to achieve desired properties of 17-4 PH stainless steel.

17-4 PH stainlesssteel

Tailoring Thermal and Mechanical Performance Through Multimaterial Laser Powder Directed Energy Deposition of Copper and 17-4PH Stainless Steel

This study investigates the additive manufacturing (AM) processing, microstructural evolution, and resulting mechanical and thermal properties of multimaterial components combining 17-4PH stainless steel and pure copper (Cu) fabricated via laser powder directed energy deposition (LP-DED). Conventional tooling steels exhibit limited thermal conductivity, significantly constraining production throughput in high-volume processes. Incorporating Cu, with its superior thermal conductivity, could significantly enhance tool performance, though Cu and steel present metallurgical incompatibilities when processed via AM. A systematic investigation was conducted across compositions ranging from 0 to 100 wt% Cu, revealing critical thresholds influencing solidification behavior, defect formation, microstructure, hardness, and thermal transport. Optical microscopy, electron backscatter diffraction (EBSD), hardness testing, and thermal conductivity measurements provided comprehensive process–structure–property correlations. Severe hot cracking occurred at low-Cu contents (6–25 wt%), aligning generally well with crack susceptibility modeling, with an unexpected discrepancy at 25 wt%. Porosity remained low (≥99% dense) throughout the compositional spectrum. EBSD analysis revealed a transformation from columnar martensitic structures at low-Cu contents to equiaxed FCC Cu-dominated structures at higher Cu concentrations, highlighting the complex microstructural transitions driven by Cu-induced changes in solidification and phase stability. Hardness decreased from 330 HV (pure 17-4PH) to 62 HV (pure Cu), consistent with microstructural changes. Concurrently, thermal conductivity improved substantially from 13.5 W/m K to 367.9 W/m K, emphasizing Cu’s dominant role in thermal transport. The findings highlight the feasibility of leveraging compositional gradients between 17-4PH and Cu to achieve tailored tooling with optimized thermal and mechanical performance.

17-4PH

Mixed lipid bilayers enable enhanced stability and activity retention of Lipase A in low-pH environments

Lipase A (LipA) from Bacillus subtilis is a versatile and industrially relevant enzyme, but its activity is compromised under acidic conditions due to aggregation and deactivation. In this study, we investigated the use of mixed lipid bilayers to stabilize and improve activity retention of LipA at low pH. Attachment to lipid bilayers, particularly those containing cationic lipids, greatly enhanced the long-term stability of LipA in acidic conditions while also leading to improvements in activity. Tethering to cationic bilayers not only shifted the apparent pH activity profile toward more acidic conditions, but also significantly enhanced activity retention upon incubation at pH 6. Notably, this protective effect persisted even without direct tethering, indicating that reversible, non-covalent interactions with the bilayer surface are sufficient for long-term stability. Circular dichroism further revealed that the secondary structure of LipA was retained, while dynamic light scattering suggested that activity loss in solution was primarily due to aggregation of the native state. Together, these findings support a model in which lipid bilayers mitigate aggregation and stabilize LipA through transient interactions and electrostatic modulation of the local surface environment. Furthermore, this approach exemplifies a simple, tether-free strategy for enhancing enzyme performance in acidic or destabilizing conditions, with implications for biocatalysis, biosensing, and therapeutic delivery.

Biocatalysis

Revealing the coupled oxygen and hypochlorite chemistry in saltwater batteries through operando pH and oxygen monitoring

Saltwater batteries (SWBs) that utilize Na⁺ ions from seawater have emerged as promising candidates for low-cost and sustainable grid-scale energy storage. To date, the cathode reaction mechanism of SWBs has been predominantly described by oxygen evolution and reduction reactions (OER/ORR). However, this assumption is valid only under idealized ocean-like conditions with constant pH and continuous oxygen replenishment. In practical systems, SWBs operate in finite volumes of saltwater, where saltwater composition dynamically evolves during cycling. Here, in this work, we systematically investigate the cathode reaction mechanisms of SWBs under finite saltwater conditions using galvanostatic cycling combined with electrochemical diagnostics and operando monitoring of dissolved oxygen and pH. Our results reveal that the cathode chemistry during SWB operation is considerably more complex than previously assumed. In addition to OER and ORR, hypochlorite formation and consumption reactions, along with pH-dependent switching of dominant reaction pathways, play critical roles. We further identify the sequence and relative contributions of these reactions throughout charge–discharge cycling. These findings provide a comprehensive and mechanistically grounded understanding of SWB cathode processes under relatively realistic cell design and operation condition. The insights presented here establish a new framework for interpreting SWB electrochemistry and offer directions for future strategies aimed at improving performance, stability, and practical viability.

Hypochlorite redox reaction

Influence of americium complexation on the radiation-induced chemical reactivity of sulfophenyl bistriazinyl pyridine (SO 3 -Ph-BTP) towards the nitrate radical

Sulfophenyl bistriazinyl pyridine (SO 3 -Ph-BTP) is a hydrophilic organic ligand used to separate actinides and lanthanides. Dose accumulation and time-resolved studies have previously provided insight into the radiolytic stability and degradation pathways of SO 3 -Ph-BTP in reprocessing environments, but no study has yet addressed the impact of minor actinide complexation on the radiation chemistry of this ligand. To begin to fill this knowledge gap, a systematic, time-resolved study exploring the reactivity of the nitrate radical (NO 3 • ) with SO 3 -Ph-BTP in the presence of trivalent americium, Am(III), has been conducted, which demonstrates enhanced reactivity (an order of magnitude faster) upon metal complexation.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL