A novel electrochemical cell design in a vertically stacked configuration is presented. Through a layered structure using a top macroporous working electrode, a polyelectrolyte, and a bottom metallic ...conductor a standalone electrochemical cell with an internal reference electrode is built. This sensor allows monitoring an electrochemical property of an external solution with only one electrode in direct contact with the sample. Using paper-based platinum electrode for the porous top electrode and Nafion as polyelectrolyte material, the self-powered detection of hydrogen peroxide is performed. The system can be operated in multiple modes. In a capacitive way, the open circuit potential is measured. Alternatively, in a self-powered current mode, the system emulates a fuel cell. Additionally, a potential-current switched mode is also demonstrated. Because of this unique design and operational features this sensor is considered as an electrochemical pixel. To further demonstrate the advantages of this device, the detection of glucose is performed by building an array of sensors using a single back (reference) electrode and multiple working electrodes. These results lay the groundwork for the development of a new generation of simple and low cost biochemical sensors and electrochemical sensing arrays.
The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain ...entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80–0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 values of 59–110 nm. This HPL phase can be controllably induced into an order–order transition to a lamellar morphology upon further increase of ϕs to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕs does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.
The use of a Pt electrode coated with a layer of Nafion has been described in previous works as an attractive way to perform the potentiometric detection of hydrogen peroxide. Despite of the ...attractive features of this approach, the nature of the non-Nernstian response of this system was not properly addressed. In this work, using a mixed potential model, the open circuit potential of the Pt electrode is shown to be under kinetic control of the oxygen reduction reaction (ORR). It is proposed that hydrogen peroxide acts as an oxygenated species that blocks free sites on the Pt surface, interfering with the ORR. Therefore, the effect of the polyelectrolyte coating can be understood in terms of the modulation of the factors that affects the kinetics of the ORR, such as an increase of the H+ concentration, minimization of the effect of the spectator species, etc. Because of the complexity and the lack of models that accurately describe systems with practical applications, this work is not intended to provide a mechanistic but rather a phenomenological view on problem. A general framework to understand the factors that affect the potentiometric response is provided. Experimental evidence showing that the use of polyelectrolyte coatings are a powerful way to control the mixed potential open new ways for the development of robust and simple potentiometric sensors.
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•The open circuit potential of the Pt electrode is shown to be under kinetic control of the oxygen reduction reaction.•Surface charge and surface chemistry are key for the analytical application of mixed potential-based detection system.•Polyelectrolyte coatings are a powerful way to modulate the mixed potential of the Pt electrode.
Whilst titanium, stainless steel, and cobalt-chrome alloys are the most common materials for use in orthopaedic implant devices, there are significant advantages in moving to alternative non-metallic ...substrates. Substrates such as polymers may have advantageous mechanical biological properties whilst other substrates may bring unique capability. A key challenge in the use of non-metal products is producing substrates which can be modified to allow the formation of well-adhered hydroxyapatite films which promote osteointegration and have other beneficial properties. In this work, we aim to develop methodology for the growth of hydroxyapatite films on surfaces other than bulk metallic parts using a wet chemical coating process, and we provide a detailed characterisation of the coatings. In this study, hydroxyapatite is grown from saturated solutions onto thin titanium films and silicon substrates and compared to results from titanium alloy substrates. The coating process efficacy is shown to be dependent on substrate roughness, hydrophilicity, and activation. The mechanism of the hydroxyapatite growth is investigated in terms of initial attachment and morphological development using SEM and XPS analysis. XPS analysis reveals the exact chemical state of the hydroxyapatite compositional elements of Ca, P, and O. The characterisation of grown hydroxyapatite layers by XRD reveals that the hydroxyapatite forms from amorphous phases, displaying preferential crystal growth along the 002 direction, with TEM imagery confirming polycrystalline pockets amid an amorphous matrix. SEM-EDX and FTIR confirmed the presence of hydroxyapatite phases through elemental atomic weight percentages and bond assignment. All data are collated and reviewed for the different substrates. The results demonstrate that once hydroxyapatite seeds, it crystallises in the same manner as bulk titanium whether that be on a titanium or silicon substrate. These data suggest that a range of substrates may be coated using this facile hydroxyapatite deposition technique, just broadening the choice of substrate for a particular function.
This study introduces and explores the use of supersaturated solutions of calcium and phosphate ions to generate well-defined hydroxyapatite coatings for orthopaedic implants. The deposition of ...hydroxyapatite is conducted via several solutions of metastable precursors that precipitate insoluble hydroxyapatite minerals at a substrate–solution interface. Solutions of this nature are intrinsically unstable, but this paper outlines process windows in terms of time, temperature, concentration and pH in which coating deposition is controlled via the stop/go reaction. To understand the kinetics of the deposition process, comparisons based on ionic strength, particle size, electron imaging, elemental analyses and mass of the formed coating for various deposition solutions are carried out. This comprehensive dataset enables the measurement of deposition kinetics and identification of an optimum solution and its reaction mechanism. This study has established stable and reproducible process windows, which are precisely controlled, leading to the successful formation of desired hydroxyapatite films. The data demonstrate that this process is a promising and highly repeatable method for forming hydroxyapatites with desirable thickness, morphology and chemical composition at low temperatures and low capital cost compared to the existing techniques.
This study is the second part of a two-part study whereby supersaturated solutions of calcium and phosphate ions generate well-defined hydroxyapatite coatings for orthopaedic implants. An ‘ideal’ ...process solution is selected from Part 1, and the detailed characterisation of films produced from this solution is undertaken here in Part 2. Analysis is presented on the hydroxyapatite produced, in both powder form and as a film upon titanium substrates representative of orthopaedic implants. From thermal analysis data, it is shown that there is bound and interstitial water present in the hydroxyapatite. Nuclear magnetic resonance data allow for the distinction between an amorphous and a crystalline component of the material. As hydroxyapatite coatings are generated, their growth mechanism is tracked across repeated process runs. A clear understanding of the growth mechanism is achieved though crystallinity and electron imaging data. Transmission electron imaging data support the proposed crystal growth and deposition mechanism. All of the data conclude that this process has a clear propensity to grow the hydroxyapatite phase of octacalcium phosphate. The investigation of the hydroxyapatite coating and its growth mechanism establish that a stable and reproducible process window has been identified. Precise control is achieved, leading to the successful formation of the desired hydroxyapatite films.
A facile and versatile strategy was developed to produce highly ordered porous metal oxide structures via block copolymer (BCP) lithography. Phase separation of poly(2-vinylpyridine)-b-polystyrene ...(P2VP-b-PS) was induced by solvent vapor annealing in a nonselective solvent environment to fabricate cylindrical arrays. In this work, we thoroughly analyzed the effects of the film thickness, solvent annealing time, and temperature on the ordering of a P2VP-majority system for the first time, resulting in “inverse” structures. Reflectometry, atomic force microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy were used to characterize the formation of the highly ordered BCP morphology and the subsequently produced metal oxide film. At 40 min solvent annealing time, hexagonally close packed structures were produced with cylinder diameters ∼40 nm. Subsequently, the BCP films were infiltrated with different metal cations. Metal ions (Cr, Fe, Ni, and Ga) selectively infiltrated the P2VP domain, while the PS did not retain any detectable amount of metal precursor. This gave rise to a metal oxide porous structure after a UV/ozone (UVO) treatment. The results showed that the metal oxide structures demonstrated high fidelity compared to the BCP template and cylindrical domains presented a similar size to the previous PS structure. Moreover, XPS analyses revealed the complete elimination of the BCP template and confirmed the presence of the metal oxides. These metal oxides were used as hard masks for pattern transfer via dry etching as a further application. Silicon nanopores were fabricated mimicking the BCP template and demonstrated a pore depth of ∼50 nm. Ultimately, this strategy can be applied to create different inorganic nanostructures for a diverse range of applications, for example, solar cells, diodes, and integrated circuits. Furthermore, by optimizing the etching parameters, deeper structures can be obtained via ICP/RIE processes, leading to many potential applications.
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•Active block copolymer moiety is capable of selective infiltration.•Careful choice of solvent and metal salt leads to effective infiltration.•Block copolymer can act as template for ...metal oxide layers.•Metal chemistry directly affects the infiltration process.•Metal coordination is observed for metal-pyridinic N interactions.
This research studied the liquid-phase selective metal infiltration of a pyridine-containing block copolymer (BCP). The results demonstrated that the metal cations interact differently with the poly(2-vinylpyridine) in polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP); the oxidation state and type of cation play an important role in the infiltration process, which is also affected by the solvent. Silver (Ag+) did not present an effective infiltration, while nickel (Ni2+) and chromium (Cr3+) were able to reproduce the pattern of the BCP. These differences can be associated with the coordination of the pyridinic nitrogen and the metal, in parallel with π-interactions. Furthermore, in the case of chromium, the presence of oxyanions led to an improved infiltration and high fidelity on the formation of the ordered metal oxide layer.
The reliable and regular modification of the surface properties of substrates plays a crucial role in material research and the development of functional surfaces. A key aspect of this is the ...development of the surface pores and topographies. These can confer specific advantages such as high surface area as well as specific functions such as hydrophobic properties. Here, we introduce a combination of nanoscale self-assembled block-copolymer-based metal oxide masks with optimized deep reactive ion etching (DRIE) of silicon to permit the fabrication of porous topographies with aspect ratios of up to 50. Following the evaluation of our procedure and involved parameters using various techniques, such as AFM or SEM, the suitability of our features for applications relying on high light absorption as well as efficient thermal management is explored and discussed in further detail.
Bulk titanium and CoCr are the most common metals for use in orthopedic implants, but there are significant advantages in alternative substrates. Research in the last decade has focused on various ...alternatives; however, these materials are hindered by the adhesion of hydroxyapatite layers to non-bulk metal parts. Demonstrated in this work is the ability to grow hydroxyapatite on surfaces other than bulk metallic parts through the process and characterisation of coating properties. In this study, hydroxyapatite (HA) is grown from saturated solution onto thin titanium films and silicon substrates. Its efficacy is shown to be dependent on substrate roughness. The mechanism of the hydroxyapatite growth is investigated in terms of initial attachment and morphological development using SEM analysis. Characterisation of hydroxyapatite layers by XRD demonstrates how the hydroxyapatite forms from amorphous phases to preferential crystal growth along the 002 direction and TEM imagery confirms specific d-spacings. SEM-EDX and FTIR show adherence to known HA phases through elemental atomic weight percentages and bond assignment. All data are collated and reviewed through the lens of different substrates. The results suggest that once hydroxyapatite seeds, it grows identically regardless of substrate.
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