Nanopipettes are playing an increasingly prominent role in nanoscience, for sizing, sequencing, delivery, detection and mapping interfacial properties. Herein, the question of how to best resolve topography and surface charge effects when using a nanopipette as a probe for mapping in scanning ion conductance microscopy (SICM) is addressed. It is shown that using a bias modulated (BM) SICM scheme it is possible to map the topography faithfully, while also allowing surface charge to be estimated. This is achieved by applying zero net bias between the electrode in the SICM tip and the one in bulk solution for topographical mapping, with just a small harmonic perturbation of the potential to create an AC current for tip positioning.Then a net bias is applied, whereupon the ion conductance current becomes sensitive to surface charge. Practically this is optimally implemented in a hopping-cyclic voltammetry mode where the probe is approached at zero net bias at a series of pixels across the surface to reach a defined separation, and then a triangular potential waveform is applied and the current response is recorded. Underpinned with theoretical analysis, including finite element modeling of the DC and AC components of the ionic current flowing through the nanopipette tip, the powerful capabilities of this approach are demonstrated with the probing of interfacial acid-base equilibria and high resolution imaging of surface charge heterogeneities, simultaneously with topography, on modified substrates.

(2013) Fabrication and characterization of dual function nanoscale pH-scanning ion conductance microscopy (SICM) probes for high resolution pH mapping. Analytical Chemistry, Volume 85 (Number 17). pp. 8070-8074 Permanent WRAP url: http://wrap.warwick.ac.uk/57249 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work of researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-forprofit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Analytical Chemistry copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work http://dx.doi.org/10.1021/ac401883n The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. AbstractThe easy fabrication and use of nanoscale dual function pH-scanning ion conductance microscopy (SICM) probes is reported. These probes incorporate an iridium oxide coated carbon electrode for pH measurement and an SICM barrel for distance control, enabling simultaneous pH and topography mapping. These pH-SICM probes were fabricated rapidly from laser pulled theta quartz pipets, with the pH electrode prepared by in-situ carbon filling of one of the barrels by the pyrolytic decomposition of butane, followed by electrodeposition of a thin layer of hydrous iridium oxide. The other barrel was filled with an electrolyte solution and Ag/AgCl electrode as part of a conductance cell for SICM. The fabricated probes, with pH and SICM sensing elements typically on the 100 nm scale, were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy and various electrochemical measurements. They showed a linear super-Nernstian pH response over a range of pH (pH 2-10). The capability of the pH-SICM probe was demonstrated by detecting both pH and topographical changes during the dissolution of a calcite microcrystal in aqueous solution. This system illustrates the quantitative nature of pH-SICM imaging, because the dissolution process changes the crystal height and interfacial pH (compared to bulk) and each is sensitive to the rate. Both measurements reve...

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Remote laser welding (RLW) combines the positive features of tactile laser welding with additional benefits such as increased processing speed, reduced operational cost and service, and higher process flexibility. A leading challenge preventing the full uptake of RLW technology in industry is the lack of efficient closed loop in-process (CLIP) monitoring and weld quality control solutions. This underpins the need to fuse multiple sensor technologies and data analytics with predictive engineering simulations. Although the development and integration of a variety of sensors covers the radiation spectrum from ultraviolet to farinfrared, the flawless deployment of CLIP solutions is still challenged by the need for the following: signal denoising in the case of process instability; real-time data analytics; and adaptive control engineering architecture to cope with process variations induced by manufacturing tolerances. This paper focuses on the aspect of weld penetration depth control using optical coherence tomography (OCT) as a necessary step to enable adaptive penetration depth control during RLW of aluminum components in the fillet lap joint configuration with consideration to part-to-part gap variation. The approach entails decoupling the welding process parameters in two subsets: (1) in-plane control of the heat input on the upper part to facilitate the droplet formation; and (2) out-of-plane heat management to achieve the desired level of penetration control in the keyhole mode. This paper presents the results of finding the optimal placement of the OCT beam with variable part-to-part gap conditions. Results have shown that statistical signal processing of the raw OCT signal gives insight not only into the depth of the keyhole but can infer the shape of the keyhole itself. Current limitations and next phases of research and development are highlighted based on the experimental study.

Remote Laser Welding (RLW) has been successfully deployed for Steel products, particularly doors, closures and hang-on parts with overlap seam welding configurations. The growing demand for lightweight body structures has created interesting opportunities to apply RLW to fillet welding with application to Aluminium components. However, seamless migration from seam welding of Steel to fillet welding of Aluminium is limited by the following challenges: weld seam tracking capability to compensate trim edge variations; hot cracking resulting from the interaction between material chemistry and heat dissipation; form error variations leading to unwanted part-to-part gaps, which in absence of filling material must be bridged only by autogenous material. This paper focuses on the aspect of the part-to-part gap bridging and proposes a model to select and adjust welding process parameters to control the volume of molten pool, and achieve gap bridging. The proposed model is based on the observation that gap bridging is impaired by five distinct failure modes. Each mode is modelled by first-principle energy balance criteria. Selection of welding parameters is presented by a set of gap bridging capability charts which helps to prevent failure modes, and select feasible weld process parameters.