arXiv subjects

Mary P. Ryan

Publications and source records attributed to Mary P. Ryan.

11 recordsLinked to original sources

arXiv2026

Revealing the Atomic-Scale Structure of the Copper Sulfuric Acid Interface

Corrosion originates from atomistic reactions occurring at dynamic solid liquid interfaces however, direct experimental observation of these reactions has remained elusive due to the inability to preserve transient interfacial states during characterization. To refine corrosion models, advanced techniques capable of analyzing corrosion interfaces at the atomic scale are essential. Recent advancements in cryogenic atom probe tomography (cryoAPT) enabled 3D nanoscale analysis of frozen liquid metal interfaces. However, challenges remain in sample preparation for cryoAPT on metals undergoing corrosion. This study introduces a microcorrosion cell fabricated using localized electrodeposition in liquid (LEL), enabling atomic scale capture of liquid metal reactions by integrating picoliterscale electrolytes encapsulated within sealed metallic microvessels, subsequently analyzed using cryoAPT.This approach enables 3D, nanoscale mapping of corrosion reactions with simultaneous spatial, chemical, and temporal resolution. As a model system, copper exposed to aerated dilute sulphuric acid reveals temperature and time dependent interfacial evolution, including nanoscale clustering of copper sulphate species, enhanced ion pairing at elevated temperature, and the emergence of transient carbon based interfacial complexes inaccessible to conventional characterization methods.Beyond copper corrosion, the presented microcorrosion cell architecture establishes a strategy for interrogating confined electrochemical and degradation processes across a wide range of material liquid systems, using a combination of microfabrication and cryoAPT.

cond-mat.mtrl-sci↗

arXiv2026

Atomic-scale Imaging of Iodide-Gold Interactions in Nanoconfined Liquid-Solid Interfaces

Functionalization of nanoporous metallic materials enables the tailoring of surface chemistry and morphology in nanostructured materials, optimising their performance for electrocatalytic and sensor applications. Liquid phase chemical functionalization is governed by liquid solid interfaces. Yet, these interfaces remain poorly understood due to the challenges of characterising the liquid phase at high spatial and chemical resolutions. To elucidate pathways for functionalizing nanoscale metals, it is crucial to measure the distribution of species, including light elements, across the liquid solid interface, capturing both reactants and products. Here, we employ cryogenic atom probe tomography to directly analyse frozen liquid solid reaction interfaces at near atomic resolution. Focusing on the interaction of iodide and sodium ions with nanoporous gold, we observe the formation of iodine containing complexes on gold nanoligament surfaces and subsurfaces. These findings reveal aspects of the gold iodide system that were previously hidden, including the reaction mechanism between iodide and gold atoms on the surface, and the multiple gold iodide complexes forming. Our work demonstrates that cryogenic atom probe tomography can provide unprecedented visualisation and characterisation of nanoscale interfaces during chemical and electrochemical reactions, with potential implications for modern manufacturing, energy technologies, and sustainable materials development.

cond-mat.mtrl-sci↗

arXiv2025

Quantifying Phase Transformations in Alloying Anodes via In-Situ Liquid Cell Hard X-ray Spectroscopy and Cryogenic Microscopy

Understanding electrochemical phenomena at complex liquid solid interfaces requires linking real time structural dynamics with atomic scale interfacial chemistry. Here, we integrate operando synchrotron X-ray fluorescence and diffraction with high resolution cryogenic electron and ion multi model microscopy to provide a mechanistic understanding of Pt based alloying anodes across length scales. We directly observe the initial lithiation driven formation of Li2Pt and its evolution to a stable LiPt intermetallic phase during extended cycling via a solid solution type reaction mechanism. Simultaneously, the solid electrolyte interphase transitions from an unstable carbonate rich to a stable LiF dominated composition, confirmed by cryogenic scanning transmission electron microscopy and electron energy loss spectroscopy. Crucially, cryogenic atom probe tomography reveals spatially distinct compositional regimes within the alloy anode, including lithium flux limited, heterogeneous interfacial zone and a diffusion controlled, homogeneous LiPt alloy bulk. This nanoscale compositional gradient rationalises the emergent solid solution reaction mechanism and highlights how kinetic limitations and interface dynamics govern alloy formation and electrochemical stability. Our findings demonstrate a broadly applicable correlative framework bridging operando structural dynamics with near atomic resolution interfacial chemistry, advancing the rational design of durable alloy electrodes for next generation energy storage.

cond-mat.mtrl-sci↗

arXiv2025

Degradation and SEI Evolution in Alloy Anodes Revealed by Correlative Liquid-Cell Electrochemistry and Cryogenic Microscopy

Understanding solid liquid interfaces at high spatial and chemical resolution is crucial for advancing electrochemical energy storage technologies, yet this remains a persistent challenge due to the lack of characterisation techniques that can capture dynamic processes and preserve fragile interfacial chemistries. In lithium ion batteries, interfacial phenomena such as lithium alloying, solid electrolyte interphase formation, and electrode degradation play a decisive role in capacity retention and failure mechanisms but are difficult to observe in their native state due to high mobility, reactivity, and low atomic number of lithium. Here, we use a recently introduced correlative operando characterisation approach that integrates electrochemical liquid cell transmission electron microscopy with cryogenic atom probe tomography to resolve the evolution of a platinum alloy anode at the solid liquid interface during electrochemical cycling. This correlative, cryo enabled workflow reveals spatially heterogeneous SEI formation, the presence of lithium carbonate rich inner SEI layers, and the retention of elemental lithium within the platinum electrode, most likely trapped along grain boundaries. Additionally, we observe the formation of mossy lithium structures and irreversible lithium loss through dead lithium accumulation. Our results provide direct mechanistic insight into lithium alloying and degradation pathways in alloy based anodes and establish a generalised platform for probing dynamic electrochemical interfaces with complementary structural and chemical sensitivity. The methodology is broadly applicable to next generation electrode materials and electrochemical devices where interfacial dynamics dictate performance and stability.

cond-mat.mtrl-sci↗

arXiv2025

Mechanistic Insights into Active Sites for Electrochemical CO2 and CO Reduction over the Strain-Engineered Dealloyed Cu

Nanoporous Cu produced by chemical dealloying is a promising catalyst for electrochemical CO2 reduction owing to its tunable chemistry, morphology, and surface defect sites. However, how dealloying controls the atomic-scale structure of Cu ligaments and how these features govern catalytic behavior remain unclear, particularly in nanostructured catalysts under realistic operating conditions. Here, we synthesize nanoporous Cu by dealloying Cu20Zn80 in H3PO4 at different temperatures, enabling control over ligament sizes from the nanoscale to the microscale. Nanoporous Cu outperforms polycrystalline Cu for CO reduction, with the sample dealloyed at 15 {\deg}C reaching 60% Faradaic efficiency at -0.65 V vs. RHE. Using in situ synchrotron X-ray diffraction and cryogenic atom probe tomography, we trace the structural and chemical evolution during dealloying, revealing, for the first time, the sequential phase transitions from epsilon brass to gamma brass to Cu and chemical segregation of Cu and Zn within nano-ligaments. We further establish a quantifiable strain metric linking surface defect density to ligament surface strain, quantified from the asymmetry of synchrotron XRD peaks. This approach reveals a direct correlation between catalytic activity and ligament surface strain, identifying surface strain as a practical descriptor for designing nanostructured Cu catalysts for CO2 reduction under realistic operating conditions.

cond-mat.mtrl-sci↗

arXiv2025

A Workflow for Correlative in-situ Nano-chip Liquid Cell Transmission Electron Microscopy and Atom Probe Tomography Enabled by Cryogenic Plasma Focused Ion Beam

Operando/in-situ liquid cell transmission electron microscopy (LCTEM) allows for real time imaging of dynamic nanoscale liquid-based processes. However, due to the thick liquid cell of traditional LCTEM holders and thus scattering of the electron beam passing through the cell, the achievable spatial and chemical resolution is limited. Cryogenic atom probe tomography (cryo-APT) overcomes these limitations by offering (near-)atomic scale compositional analysis of frozen liquid-solid interfaces. However, APT provides limited structural analysis and has no capacity for dynamic or operando liquid cell studies. This work presents a novel workflow for site-specific cryo-APT sample preparation of liquid-solid interfaces from in-situ electrochemical LCTEM Micro-Electro-Mechanical Systems (MEMS) chips. Using cryogenic inert gas transfer suitcase and a cryogenic plasma-focused ion beam (PFIB), a MEMs nanochip containing a Li electrolyte from an electrochemistry LCTEM holder was successfully frozen, transferred to the cryo stage of a PFIB and prepared into APT needle samples containing the electrolyte-electrode interface at cryogenic temperatures, followed by cryogenic transfer to an atom probe for nanoscale compositional analysis. This correlative approach provides dynamic nanoscale imaging and near atomic scale compositional analysis of liquid-solid interfaces. This method enables reliable and reproducible APT sample preparation of these frozen interfaces from MEMs based nanochips and can hence be used across materials systems and energy-conversion or storage devices.

cond-mat.mtrl-sci↗

arXiv2023

Determining the Fundamental Failure Modes in Ni-rich Lithium Ion Battery Cathodes

Challenges associated with in-service mechanical degradation of Li-ion battery cathodes has prompted a transition from polycrystalline to single crystal cathode materials. Whilst for single crystal materials, dislocation-assisted crack formation is assumed to be the dominating failure mechanism throughout battery life, there is little direct information about their mechanical behaviour, and mechanistic understanding remains elusive. Here, we demonstrated, using in situ micromechanical testing, direct measurement of local mechanical properties within LiNi0.8Mn0.1Co0.1O2 single crystalline domains. We elucidated the dislocation slip systems, their critical stresses, and how slip facilitate cracking. We then compared single crystal and polycrystal deformation behaviour. Our findings answer two fundamental questions critical to understanding cathode degradation: What dislocation slip systems operate in Ni-rich cathode materials? And how does slip cause fracture? This knowledge unlocks our ability to develop tools for lifetime prediction and failure risk assessment, as well as in designing novel cathode materials with increased toughness in-service.

cond-mat.mtrl-sci↗

arXiv2023

Fracture properties of La(Fe,Mn,Si)13 magnetocaloric materials

La(Fe,Mn,Si)13 alloys are a promising material family for magnetic refrigeration. Challenges associated with their structural integrity during device assembly and operation requires deep understanding of the mechanical properties. Here we developed a workflow to quantitatively study the fracture properties of La(Fe,Mn,Si)13 plates used in magnetic cooling devices. We employed microstructural characterisation, optical examination of defects, and four-point bending tests of samples with known defect sizes to evaluate their mechanical performance. We established the residual strength curve which directly links observed defects to mechanical strength. The estimated fracture toughness KC of hydrogenated La(Fe,Mn,Si)13 is approximately 4 MPa m^1/2 for the geometry employed. The established relationship between strength and crack length enables the prediction of mechanical performance through examination of defects via optical microscopy, therefore can be used industrially for directing plate selection to guarantee the mechanical stability of refrigeration devices.

cond-mat.mtrl-sci↗

arXiv2022

The effect of hydrogen on the multiscale mechanical behaviour of a La(Fe,Mn,Si)13-based magnetocaloric material

Magnetocaloric cooling offers the potential to improve the efficiency of refrigeration devices and hence cut the significant CO2 emissions associated with cooling processes. A critical issue in deployment of this technology is the mechanical degradation of the magnetocaloric material during processing and operation, leading to limited service-life. The mechanical properties of hydrogenated La(Fe,Mn,Si)13-based magnetocaloric material are studied using macroscale bending tests of polycrystalline specimens and in situ micropillar compression tests of single crystal specimens. The impact of hydrogenation on the mechanical properties are quantified. Understanding of the deformation/failure mechanisms is aided by characterization with transmission electron microscopy and atom probe tomography to reveal the arrangement of hydrogen atoms in the crystal lattice. Results indicate that the intrinsic strength of this material is ~3-6 GPa and is dependent on the crystal orientation. Single crystals under compressive load exhibit shearing along specific crystallographic planes. Hydrogen deteriorates the strength of La(Fe,Mn,Si)13 through promotion of transgranular fracture. The weakening effect of hydrogen on single crystals is anisotropic; it is significant upon shearing parallel to the {111} crystallographic planes but is negligible when the shear plane is {001}-oriented. APT analysis suggests that this is associated with the close arrangement of hydrogen atoms on {222} planes.

cond-mat.mtrl-sci↗

arXiv2021

Environment-assisted crack nucleation in La(Fe,Mn,Si)13-based magnetocaloric materials

Cracking in La(Fe,Si)13-based magnetocaloric materials has been observed to predominantly form around La-rich (La2O3) particles and pose a threat to their long-term structural integrity. To understand the formation of these cracks, FIB cross-sectional polishing followed by SEM characterisation was employed to study local microstructural evolution after air exposure. Results suggest that volume expansion and internal degradation associated with a chemical reaction between La2O3 particles and water/moisture can lead to crack nucleation in the 1:13 phase adjacent to La-rich particles. This observation indicates that the formation of La-rich phase should be suppressed, or their size minimised during material processing to ensure the long-term structural integrity of La(Fe,Mn,Si)13 magnetocaloric materials.

cond-mat.mtrl-sci↗

arXiv2010

Ultralong Copper Phthalocyanine Nanowires with New Crystal Structure and Broad Optical Absorption

The development of molecular nanostructures plays a major role in emerging organic electronic applications, as it leads to improved performance and is compatible with our increasing need for miniaturisation. In particular, nanowires have been obtained from solution or vapour phase and have displayed high conductivity, or large interfacial areas in solar cells. In all cases however, the crystal structure remains as in films or bulk, and the exploitation of wires requires extensive post-growth manipulation as their orientations are random. Here we report copper phthalocyanine (CuPc) nanowires with diameters of 10-100 nm, high directionality and unprecedented aspect ratios. We demonstrate that they adopt a new crystal phase, designated eta-CuPc, where the molecules stack along the long axis. The resulting high electronic overlap along the centimetre length stacks achieved in our wires mediates antiferromagnetic couplings and broadens the optical absorption spectrum. The ability to fabricate ultralong, flexible metal phthalocyanine nanowires opens new possibilities for applications of these simple molecules.

cond-mat.mes-hall↗