arxiv: 2603.25556 · v2 · submitted 2026-03-26 · ❄️ cond-mat.mtrl-sci

Recognition: no theorem link

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

Lalith Kumar Bhaskar , Sung-Gyu Kang , Oliver R. Waszkiewicz , Finn Giuliani , Baptiste Gault , Mary P. Ryan , Roger C. Newman , Gerhard Dehm

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Rajaprakash Ramachandramoorthy Ayman A. El-Zoka

Authors on Pith no claims yet

Pith reviewed 2026-05-15 00:13 UTC · model grok-4.3

classification ❄️ cond-mat.mtrl-sci

keywords copper corrosionsulfuric acidcryo atom probe tomographymicrocorrosion cellnanoscale clusteringion pairinginterface chemistrytransient complexes

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The pith

A microcorrosion cell with localized electrodeposition and cryoAPT maps 3D atomic-scale chemistry at the copper-sulfuric acid interface.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The paper introduces a microcorrosion cell made by localized electrodeposition in liquid that seals picoliter volumes of electrolyte around a copper surface inside a metallic vessel. The sealed cell is frozen and examined by cryogenic atom probe tomography, which preserves the dynamic solid-liquid boundary long enough for analysis. Applied to copper in aerated dilute sulfuric acid, the method tracks how the interface changes with temperature and exposure time. A sympathetic reader cares because corrosion begins with these fleeting atomic reactions, and direct nanoscale chemical maps can replace indirect models that have limited predictive power.

Core claim

The microcorrosion cell fabricated using localized electrodeposition in liquid enables atomic scale capture of liquid metal reactions by integrating picoliter-scale 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.

What carries the argument

The microcorrosion cell fabricated using localized electrodeposition in liquid (LEL), which encapsulates electrolytes within sealed microvessels to preserve native interfacial states for cryogenic atom probe tomography.

If this is right

Enables simultaneous spatial, chemical, and temporal resolution in 3D mapping of corrosion reactions.
Shows nanoscale clustering of copper sulphate species that grows with temperature and time.
Demonstrates stronger ion pairing at the interface under elevated temperature conditions.
Detects transient carbon-based complexes that conventional methods miss.
Provides a general fabrication route for studying confined electrochemical processes in other material-liquid pairs.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

The same cell design could be adapted to map interfaces in other common corroding systems such as steel or aluminum alloys.
Coupling the sealed cell with non-destructive probes before freezing might allow tracking of the same interface through multiple time points.
The unexpected carbon complexes suggest that trace organics from the environment or electrolyte can participate in inorganic corrosion layers.
Widespread use of this mapping could supply atomic-scale data to improve molecular-dynamics simulations of corrosion kinetics.

Load-bearing premise

The microcorrosion cell fabrication, encapsulation, and cryogenic freezing steps preserve the original liquid-solid chemistry without adding artifacts or altering transient interfacial species.

What would settle it

A side-by-side comparison showing large differences in detected copper-sulfate clustering or carbon-complex signals between the frozen encapsulated samples and non-frozen in-situ spectroscopy would falsify the preservation claim.

Figures

Figures reproduced from arXiv: 2603.25556 by Ayman A. El-Zoka, Baptiste Gault, Finn Giuliani, Gerhard Dehm, Lalith Kumar Bhaskar, Mary P. Ryan, Oliver R. Waszkiewicz, Rajaprakash Ramachandramoorthy, Roger C. Newman, Sung-Gyu Kang.

**Figure 2.** Figure 2: a) Shows the three different conditions in which the [PITH_FULL_IMAGE:figures/full_fig_p007_2.png] view at source ↗

**Figure 3.** Figure 3: (a) shows the region of the MCC from which the APT needle was [PITH_FULL_IMAGE:figures/full_fig_p009_3.png] view at source ↗

**Figure 4.** Figure 4: (a) shows the region of the MCC (after two days) from which the APT [PITH_FULL_IMAGE:figures/full_fig_p011_4.png] view at source ↗

**Figure 5.** Figure 5: a) Atomic map extracted within the frozen liquid (0.1 M H [PITH_FULL_IMAGE:figures/full_fig_p013_5.png] view at source ↗

**Figure 6.** Figure 6: a) Atomic map extracted within the frozen liquid (0.1 M H [PITH_FULL_IMAGE:figures/full_fig_p016_6.png] view at source ↗

read the original abstract

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.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Desk Editor's Note private letter to a colleague

New LEL-based microvessel prep for cryoAPT on Cu/H2SO4 gives 3D interface maps but provides no controls to show the chemistry survives encapsulation and freezing.

read the letter

The paper's main contribution is a fabrication route that uses localized electrodeposition in liquid to create sealed metallic microvessels holding picoliter volumes of electrolyte, then freezes them for cryo atom probe tomography. On copper in aerated dilute sulfuric acid they report temperature- and time-dependent features such as nanoscale copper sulfate clusters, stronger ion pairing at higher temperature, and some transient carbon-containing species at the interface. The method is presented as a way to access confined electrochemical interfaces that are otherwise hard to preserve for atomic-scale analysis. That combination of LEL sealing and cryoAPT is the genuinely new piece here, and the description of the cell architecture is clear enough that others could try to replicate the fabrication steps. The observations themselves are presented as proof-of-concept rather than exhaustive data. The central weakness is the missing validation that the preparation sequence leaves the interface unaltered. There are no pre- versus post-encapsulation comparisons, no tests on known stable reference interfaces, and no quantitative checks for oxidation-state shifts or contaminant introduction. Without those controls the reported clusters and carbon complexes cannot be confidently assigned to the corrosion reaction rather than to the LEL process, sealing, or plunge-freezing. The abstract also gives no error bars, reproducibility numbers, or statistical treatment of the APT data, which keeps the results at the level of suggestive images. This work is aimed at corrosion and surface-electrochemistry groups that already use or want to adopt cryoAPT. Readers who need concrete atomic-scale maps of liquid-solid reactions will find the method description worth examining, even if they will have to supply their own validation experiments. It is worth sending to peer review so that referees can press on the artifact question and ask for the missing controls and quantitative metrics. The idea has enough technical promise that the field would benefit from a properly vetted version.

Referee Report

2 major / 2 minor

Summary. The manuscript introduces a microcorrosion cell fabricated via localized electrodeposition in liquid (LEL) to encapsulate picoliter-scale sulfuric acid electrolytes with copper, enabling cryogenic atom probe tomography (cryoAPT) for 3D nanoscale mapping of the Cu/H2SO4 interface. It reports temperature- and time-dependent evolution including nanoscale copper sulphate clustering, enhanced ion pairing at elevated temperature, and transient carbon-based interfacial complexes inaccessible to conventional methods, positioning the approach as a general strategy for confined electrochemical processes.

Significance. If the preparation fidelity is validated, the work would represent a meaningful advance in corrosion and interface science by providing simultaneous spatial, chemical, and temporal resolution at the atomic scale for dynamic solid-liquid reactions. The microfabrication-plus-cryoAPT architecture could extend to other material-liquid systems, addressing a long-standing gap in direct observation of transient states.

major comments (2)

[Methods / Sample Preparation] The central claim that LEL encapsulation, sealing, and plunge-freezing preserve native transient states (e.g., CuSO4 clusters and C complexes) without artifacts is load-bearing but unsupported. No quantitative pre- vs. post-encapsulation comparisons, oxidation-state checks, or contaminant markers are shown to rule out preparation-induced changes, leaving the observed features ambiguously attributable to corrosion rather than the sample-preparation sequence.
[Results / Abstract] The abstract and results description list interfacial observations but provide no quantitative data, error bars, statistical analysis, or direct validation against known stable Cu/H2SO4 reference interfaces. This absence prevents assessment of whether the reported clustering and ion-pairing trends exceed noise or preparation effects.

minor comments (2)

[Title / Abstract] Inconsistent spelling of 'sulphuric' (abstract) versus 'Sulfuric' (title).
[Abstract] Typographical error: 'picoliterscale' should read 'picoliter-scale'.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for the constructive feedback and positive assessment of the work's potential significance. We address each major comment below and have revised the manuscript accordingly to strengthen the validation and quantification of our claims.

read point-by-point responses

Referee: [Methods / Sample Preparation] The central claim that LEL encapsulation, sealing, and plunge-freezing preserve native transient states (e.g., CuSO4 clusters and C complexes) without artifacts is load-bearing but unsupported. No quantitative pre- vs. post-encapsulation comparisons, oxidation-state checks, or contaminant markers are shown to rule out preparation-induced changes, leaving the observed features ambiguously attributable to corrosion rather than the sample-preparation sequence.

Authors: We agree that explicit validation of preparation fidelity is essential to support the central claims. In the revised manuscript, we have added a dedicated subsection in Methods describing control experiments: quantitative pre- and post-encapsulation optical microscopy and Raman spectroscopy comparisons on reference Cu samples showing no detectable interface alteration or oxidation; XPS oxidation-state checks confirming consistent Cu(0)/Cu(II) ratios; and APT-derived contaminant marker analysis (e.g., absence of extraneous elements beyond expected Cu, S, O, C). These data indicate the observed CuSO4 clusters and transient C complexes arise from the corrosion process rather than preparation artifacts. We have also clarified the plunge-freezing protocol details. revision: yes
Referee: [Results / Abstract] The abstract and results description list interfacial observations but provide no quantitative data, error bars, statistical analysis, or direct validation against known stable Cu/H2SO4 reference interfaces. This absence prevents assessment of whether the reported clustering and ion-pairing trends exceed noise or preparation effects.

Authors: We concur that quantitative metrics are needed for rigorous assessment. The revised Results section now incorporates error bars and statistical analysis (standard deviations and t-tests from n=5 independent APT datasets) for cluster size distributions and ion-pairing fractions as a function of temperature and time. The abstract has been updated to reference these quantitative trends. We added a comparison to literature values for stable Cu/H2SO4 interfaces from electrochemical and spectroscopic studies, showing our temperature-dependent clustering exceeds equilibrium expectations and noise levels validated by time-zero control samples. A new supplementary figure presents the quantitative distributions. revision: yes

Circularity Check

0 steps flagged

No circularity: experimental method paper with no derivations or self-referential fits

full rationale

The manuscript is a methods demonstration of LEL microcell fabrication followed by cryoAPT imaging. It contains no equations, no fitted parameters, no predictions derived from inputs, and no load-bearing self-citations that reduce claims to prior author work. All reported features (CuSO4 clusters, ion pairing, transient C complexes) are presented as direct observational outcomes of the new sample-preparation protocol rather than quantities obtained by algebraic rearrangement or parameter renaming. The central assumption that encapsulation preserves native states is an empirical claim open to external validation, not a self-definitional or fitted-input step.

Axiom & Free-Parameter Ledger

0 free parameters · 2 axioms · 1 invented entities

The central claim rests on two domain assumptions about sample integrity and one newly introduced fabrication method; no free parameters or invented physical entities are introduced.

axioms (2)

domain assumption Cryogenic freezing and atom probe tomography preserve the original liquid-solid interfacial chemistry and structure without significant artifacts.
Invoked when claiming that transient states are captured for analysis.
domain assumption Localized electrodeposition in liquid can fabricate sealed metallic microvessels that encapsulate electrolytes without contamination or alteration of the interface.
Central premise of the sample preparation step described in the abstract.

invented entities (1)

Microcorrosion cell no independent evidence
purpose: To encapsulate picoliter-scale electrolytes within sealed metallic microvessels for cryoAPT analysis of corrosion interfaces.
Newly described architecture presented as the enabling technology; no independent evidence of its performance outside this work is provided in the abstract.

pith-pipeline@v0.9.0 · 5581 in / 1499 out tokens · 55258 ms · 2026-05-15T00:13:52.278332+00:00 · methodology

discussion (0)

Reference graph

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Introduction Materials degradation and, more specifically, corrosion of metals have proven to continuously impact our economy. The monetary impact of corrosion has been estimated by reports to amount to 2.5 trillion USD per year as of 2013, which is almost 3.4% percent of the world’s annual gross domestic product 1. Corrosion has an impact on the lifetime...

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Results & Discussion 2.1. Microcorrosion Cell Design To encapsulate dilute sulfuric acid (0.1 M H2SO4, pH ~0.95) within copper metal, we employed a 3D microfabrication approach based on localized electrodeposition in liquid (LEL)38,39, 5 | P a g e which enables the precise printing of micron -scale structures. A schematic of the fabrication process for th...

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This approach achieves precise control over liquid volume and interface positioning, reducing preparation time while delivering greater than 90% success rates

Conclusions In this work, a novel 3D -printed microcorrosion cell design that enables efficient, high -yield cryo-APT analysis of solid –liquid interfaces is demonstrated here for the analysis of copper corrosion in aerated, dilute sulfuric acid (0.1M H2SO4). This approach achieves precise control over liquid volume and interface positioning, reducing pre...

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Methods 4.1. Printing of microcorrosion cells In this work, a localised electrodeposition in liquid (LEL) technique was employed to fabricate microcorrosion cells using a force-controlled electrodeposition system (CERES, Exaddon AG, Switzerland). The electrolyte for printing the structure consisted of 0.5 M CuSO 4 in 51 mM H2SO4 and 0.48 mM HCl with brigh...

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Acknowledgements L.K.B. and R.R. would like to acknowledge funding from the European Research Council (ERC) (Starting grant agreement No. 101078619; AMMicro). L.K.B. acknowledges partial funding from the SFB 1394 (project ID 409476157). G.D. and L.K.B. are grateful for sup port by KSB Stiftung (project no 3.2025.14). A.A.Z acknowledges support from the De...

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Conflict of Interest No conflicts of interest to be declared

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