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Hypothesis\ud \ud Microscopic self-propelled motors (SPMs) are an area of active research, but very little investigation has been conducted on millimetre-scale or macroscopic SPMs and exploring their potential in biomedical research. In this study, we tested if 3D reactive inkjet (RIJ) printing could be used for precise fabrication of millimetre-scale self-propelled motors (SPMs) with well-defined shapes from regenerated silk fibroin (RSF) by converting water soluble RSF (silk I) to insoluble silk fibroin (silk II). Secondly, we compared the different propulsion behaviour of the SPMs to put forward the best geometry and propulsion mechanism for potential applications in enhancing the sensitivity of diffusion-rate limited biomedical assays by inducing fluid flow.\ud \ud \ud \ud Experiments\ud \ud SPMs with four different geometric shapes and propelled by two different mechanisms (catalysis and surface tension gradient) were fabricated by 3D RIJ printing and compared. For bubble propulsion, the structures were selectively doped in specific regions with the enzyme catalase in order to produce motion via bubble generation and detachment in hydrogen peroxide solutions. For surface tension propulsion, PEG400-doped structures were propelled through surface tension gradients caused by leaching of PEG400 surfactant in deionized water.\ud \ud \ud \ud Findings\ud \ud The results demonstrated the ability of 3D inkjet printing to fabricate SPMs with desired propulsion mechanism and fine-tune the propulsion by precisely fabricating the different geometric shapes. The resulting 3D structures were capable of generating motion without external actuation, thereby enabling applications in biomedicine such as micro-stirring small fluid volumes to enhance biological assay sensitivity. The surface tension gradient caused by the leaching of surfactant led to faster propulsion velocities with smooth deceleration, whereas, in comparison, catalysis-induced bubble propulsion tended to be jerky and uneven in deceleration, and therefore less suitable for aforementioned applications. Computational fluid dynamic simulations were used to compare the various experimental SPMs ability to enhance mixing when deployed within 96-well plate microwells, to reveal the effect of both SPM shape and motion character on performance, and show viability for small scale mixing applications.

Understanding the kinetics of the crystallization process for organometal halide perovskite formation is critical in determining the crystalline, nanoscale morphology and therefore the electronic properties of the films produced during thin film formation from solution. In this work, in situ grazing incidence small-angle X-ray scattering (GISAXS) and optical microscopy measurements are used to investigate the processes of nucleation and growth of pristine mixed halide perovskite (MAPbI3-x Cl x ) crystalline films deposited by bar coating at 60 °C, with and without additives in the solution. A small amount of 1,8-diiodooctane (DIO) and hydriodic acid (HI) added to MAPbI3-x Cl x is shown to increase the numbers of nucleation centers promoting heterogeneous nucleation and accelerate and modify the size of nuclei during nucleation and growth. A generalized formation mechanism is derived from the overlapping parameters obtained from real-time GISAXS and optical microscopy, which revealed that during nucleation, perovskite precursors cluster before becoming the nuclei that function as elemental units for subsequent formation of perovskite crystals. Additive-free MAPbI3-x Cl x follows reaction-controlled growth, in contrast with when DIO and HI are present, and it is highly possible that the growth then follows a hindered diffusion-controlled mechanism. These results provide important details of the crystallization mechanisms occurring and will help to develop greater control over perovskite films produced.

The ability to generate rotation in ellipsoidal catalytic micro swimming devices by catalyst deposition at glancing angles allows reliable access to circling trajectories. This behaviour could enable propulsive ellipsoids to gather cargo and enhance mixing at small scales. Catalytically propelled colloidal rotation has been previously achieved in spherical swimming devices by means of neighbour shadowing during catalyst deposition leading to non-symmetrical coatings. However in this work shadowing effects arise due to the ellipsoid's inherent anisotropy, removing the requirement for a closely packed colloidal crystal monolayer. We use geometric analysis of the catalyst deposition process, and mechanistic understanding to propose a link between the observed trajectories and the catalyst distribution and suggest further routes to improve control of rotation rates.

Dipeptide repeat proteins (DPRs) are aggregation-prone polypeptides encoded by the pathogenic G4C2 repeat expansion in the C9orf72 gene, the most common genetic cause of amyotrophic lateral sclerosis and frontotemporal dementia (ALS/FTD). In this study, we focus on the role of poly-GA DPRs in disease spread. We demonstrate that recombinant poly-GA oligomers can directly convert into solid-like aggregates and form characteristic &[beta]-sheet fibrils in vitro. To dissect the process of cell-to-cell DPR transmission, we closely follow the fate of poly-GA DPRs in either their oligomeric or fibrillized form after administration in the cell culture medium. We observe that poly-GA DPRs are taken up via dynamin-dependent and - independent endocytosis, eventually converging at the lysosomal compartment and leading to axonal swellings in neurons. We then use a co-culture system to demonstrate astrocyte-to- motor neuron DPR propagation, showing that astrocytes may internalise and release aberrant peptides in disease pathogenesis. Overall, our results shed light on the mechanisms of poly- GA cellular uptake and cell-to-cell propagation, suggesting lysosomal impairment as a possible feature underlying the cellular pathogenicity of these DPR species.

Dipeptide repeat (DPR) proteins are aggregation-prone polypeptides encoded by the pathogenic GGGGCC repeat expansion in the C9ORF72 gene, the most common genetic cause of amyotrophic lateral sclerosis and frontotemporal dementia. In this study, we focus on the role of poly-GA DPRs in disease spread. We demonstrate that recombinant poly-GA oligomers can directly convert into solid-like aggregates and form characteristic β-sheet fibrils in vitro. To dissect the process of cell-to-cell DPR transmission, we closely follow the fate of poly-GA DPRs in either their oligomeric or fibrillized form after administration in the cell culture medium. We observe that poly-GA DPRs are taken up via dynamin-dependent and -independent endocytosis, eventually converging at the lysosomal compartment and leading to axonal swellings in neurons. We then use a co-culture system to demonstrate astrocyte-to-motor neuron DPR propagation, showing that astrocytes may internalise and release aberrant peptides in disease pathogenesis. Overall, our results shed light on the mechanisms of poly-GA cellular uptake and propagation, suggesting lysosomal impairment as a possible feature underlying the cellular pathogenicity of these DPR species.

Catalytic Janus colloids produce rapid motion in fluids by decomposing dissolved fuel. There is great potential to exploit these "autonomous chemical swimmers" in applications currently performed by diffusion limited passive colloids. Key application areas for colloids include transporting active ingredients for drug delivery, gathering analytes for medical diagnostics, and self-assembling into regular structures used for photonic materials and lithographic templating. For drug delivery and medical diagnostics, controlling colloidal motion is key in order to target therapies, and transport analytes through lab-on-a-chip devices. Here, the autonomous motion of catalytic Janus colloids can remove the current requirements to induce and control colloid motion using external fields, thereby reducing the technological complexity required for medical therapies and diagnostics. For materials applications exploiting colloidal self-assembly, the additional interactions introduced by catalytic activity and rapid motion are predicted to allow access to new reconfigurable and responsive structures. In order to realize these goals, it is vital to develop methods to control both individual colloidal paths and collective behavior in motile catalytic colloidal systems. However, catalytic Janus colloids' trajectories are randomized by Brownian effects, and so require new strategies in order to be harnessed for transport. This is achievable using a variety of different approaches. For example, self-assembly and control of catalyst geometry can introduce controlled amounts of rotary motion, or "spin" into chemical swimmer trajectories. Furthermore, rotary motion combined with gravity, produces well-defined orientated helical trajectories. In addition, when catalytic colloids interact with topographical features, such as edges and trenches, they are steered. This gives rise to a new approach for autonomous colloidal microfluidic transport that could be deployed in future lab-on-a-chip devices. Chemical gradients can also influence the motion of catalytic Janus colloids, for example, to cause collective accumulations at specific locations. However, at present, the predicted theoretical degree of control over this phenomenon has not been fully verified in experimental systems. Collective behavior control for chemical swimmers is also possible by exploiting the potential for the complex interactions in these systems to allow access to self-assembled, dynamic and reconfigurable ordered structures. Again, current experiments have not yet accessed the breadth of possible behavior. Consequently, continued efforts are required to understand and control these interaction mechanisms in real world systems. Ultimately, this will help realize the use of catalytic Janus colloids for tasks that require well-controlled motion and structural organization, enabling functions such as analyte capture and concentration, or targeted drug delivery.

Although much attention has focused on self-motile asymmetrical catalytically active "Janus" colloids as a route to enable new fluidic transport applications, the motion of symmetrical catalytically active colloids is less investigated. This is despite isotropically active colloids being more accessible and commonly used as supports for heterogeneous catalysis. Here, we addressed this by systematically investigating the motion of platinum-coated colloids capable of isotropically decomposing hydrogen peroxide. We observed the onset of collective convective flow as the colloidal volume fraction increased above a threshold. The ballistic velocities induced by the collective flow were quantified by particle tracking and were found to increase with the volume fraction. We also determined the associated increase in the Péclet number as evidence of the potential to use convection as a simple method to enhance mass transport rates. By determining the persistence lengths, we were able to correlate the magnitude of convective flow with the overall catalytic activity per unit volume. This suggests that the mechanism for the collective flow is driven by chemical activity-induced local density differences. Finally, we discussed these results in the context of potential new fluidic applications and highlighted the role that activity-induced convection may play in experiments designed to investigate self-motile catalytic systems.

The phoretic mechanisms at stake in the propulsion of asymmetric colloids have been the subject of debates during the past years. In particular, the importance of electrokinetic effects on the motility of Pt-PS Janus sphere was recently discussed. Here, we probe the hydrodynamic flow field around a catalytically active colloid using particle tracking velocimetry both in the freely swimming state and when kept stationary with an external force. Our measurements provide information about the fluid velocity in the vicinity of the surface of the colloid, and confirm a mechanism for propulsion that was proposed recently. In addition to offering a unified understanding of the nonequilibrium interfacial transport processes at stake, our results open the way to a thorough description of the hydrodynamic interactions between such active particles and understanding their collective dynamics., In order to predict the behaviours of self-propelled particles it is important to understand the fluid disturbances they generate. Here the authors measure the flow-fields around active particles and show that they are in agreement with theoretical predictions which take into account electrokinetic effects.

Active colloids are small scale materials capable of producing enhanced motion within fluid environments. The field of active colloids has grown rapidly over the last ten years and is approaching maturity where viable applications are within reach. In this review, recent advances are surveyed with a strong emphasis on developments that can enable autonomous applications, where colloids execute useful tasks without external interventions. These applications are likely to prove transformative as the resulting technologies will be significantly less complex than current methods. A survey of the requirements to achieve autonomous applications is provided, considering guidance, solution compatibilities, manufacture and function; with reference to recent developments in these capacities. Following on from this, progress towards applications in environmental remediation, lab-on-a-chip microfluidics and in vivo drug delivery is highlighted.

The fabrication of multifunctional polymeric Janus colloids that display catalytically driven propulsion, change their size in response to local variations in pH, and vary cargo release rate is demonstrated. Systematic investigation of the colloidal trajectories reveals that in acidic environments the propulsion velocity reduces dramatically due to colloid swelling. This leads to a chemotaxis‐like accumulation for ensembles of these responsive particles in low‐pH regions. In synergy with this chemically defined accumulation, the colloids also show an enhancement in the release rate of an encapsulated cargo molecule. Together, these effects result in a strategy to harness catalytic propulsion for combined autonomous transport and cargo release directed by a chemical stimulus, displaying a greater than 30 times local cargo‐accumulation enhancement. Lactic acid can be used as the stimulus for this behavior, an acid produced by some tumors, suggesting possible eventual utility as a drug‐delivery method. Applications for microfluidic transport are also discussed.

The ability to control the degree of spin, or rotational velocity, for catalytic swimming devices opens up the potential to access well defined spiralling trajectories, enhance cargo binding rate, and realise theoretically proposed behaviour such as chiral diffusion. Here we assess the potential to impart a well-defined spin to individual catalytic Janus swimmers by using glancing angle metal evaporation onto a colloidal crystal to break the symmetry of the catalytic patch due to shadowing by neighbouring colloids. Using this approach we demonstrate a well-defined relationship between the glancing angle and the ratio of rotational to translational velocity. This allows batches of colloids with well-defined spin rates in the range 0.25 to 2.5 Hz to be produced. With reference to the shape and thickness variations across the catalytically active shapes, and their propulsion mechanism we discuss the factors that can lead to the observed variations in rotational propulsion.

The self-propulsion mechanism of active colloidal particles often generates not only translational but also rotational motion. For particles with an anisotropic mass density under gravity, the motion is usually influenced by a downwards oriented force and an aligning torque. Here we study the trajectories of self-propelled bottom-heavy Janus particles in three spatial dimensions both in experiments and by theory. For a sufficiently large mass anisotropy, the particles typically move along helical trajectories whose axis is oriented either parallel or antiparallel to the direction of gravity (i.e., they show gravitaxis). In contrast, if the mass anisotropy is small and rotational diffusion is dominant, gravitational alignment of the trajectories is not possible. Furthermore, the trajectories depend on the angular self-propulsion velocity of the particles. If this component of the active motion is strong and rotates the direction of translational self-propulsion of the particles, their trajectories have many loops, whereas elongated swimming paths occur if the angular self-propulsion is weak. We show that the observed gravitational alignment mechanism and the dependence of the trajectory shape on the angular self-propulsion can be used to separate active colloidal particles with respect to their mass anisotropy and angular self-propulsion, respectively., Comment: 12 pages, 6 figures, 2 tables

This chapter focuses on the use of reactive inkjet printing for generation of self-motile bubble-propelled silk micro-rockets. Initially some background information regarding self-motile swimming devices is given and how these can be used for future applications. The current issues revolving around many of the devices (as discussed in the relevant literature) are addressed, and why silk-based micro-rockets are a big step in the right direction regarding manufacture, biocompatibility, degradability and cost efficiency is discussed. After setting the scene we look into the challenges that have to be addressed when the researcher attempts to produce silk micro-rockets and look at how different types of inks and structures alter the bubble release of micro-rockets and thus change both their motion and directionality, control of which are key challenges for micromotor efficiency.

Stirring small volumes of solution can reduce immunoassay readout time, homogenize cell cultures, and increase enzyme reactivity in bioreactors. However, at present many small scale stirring methods require external actuation, which can be cumbersome. To address this, here, reactive inkjet printing is shown to be able to produce autonomously rotating biocompatible silk-based microstirrers that can enhance fluid mixing. Rotary motion is generated either by release of a surface active agent (small molecular polyethylene glycol) resulting in Marangoni effect, or by catalytically powered bubble propulsion. The Marangoni driven devices do not require any chemicals to be added to the fluid as the "fuel," while the catalytically powered devices are powered by decomposing substrate molecules in solution. A comparison of Marangoni effect and enzyme powered stirrers is made. Marangoni effect driven stirrers rotate up to 600 rpm, 75-100-fold faster than enzyme driven microstirrers, however enzyme powered stirrers show increased longevity. Further to stirring applications, the sensitivity of the motion generation mechanisms to fluid properties allows the rotating devices to also be exploited for sensing applications, for example, acting as motion sensors for water pollution.

We present results of the direct observation, in real-space, of the phase separation of high molecular weight polystyrene and poly(methyl methacrylate) from ortho-xylene using our newly developed technique of high speed stroboscopic interference microscopy. Taking a fixed concentration (3 wt % in o-xylene) at a fixed composition (1:4 by weight) and by varying the rotational rate during the spin-coating process, we are able to observe the formation of a range of phase separated bicontinuous morphologies of differing length-scales. Importantly, we are able to show that the mechanism by which the final phase separated structure is formed is through domain coarsening when rich in solvent, before vitrification occurs and fixes the phase separated structure. The ability to directly observe morphological development offers a route toward controlling the length-scale of the final morphology through process control and in situ feedback, from a single stock solution. © 2013 Wiley Periodicals, Inc.

We report a method to prepare catalytically active Janus colloids that "swim" in fluids and describe how to determine their 3D motion using\ud fluorescence microscopy. One commonly deployed method for catalytically active colloids to produce enhanced motion is via an asymmetrical\ud distribution of catalyst. Here this is achieved by spin coating a dispersed layer of fluorescent polymeric colloids onto a flat planar substrate,\ud and then using directional platinum vapor deposition to half coat the exposed colloid surface, making a two faced "Janus" structure. The Janus\ud colloids are then re-suspended from the planar substrate into an aqueous solution containing hydrogen peroxide. Hydrogen peroxide serves\ud as a fuel for the platinum catalyst, which is decomposed into water and oxygen, but only on one side of the colloid. The asymmetry results in\ud gradients that produce enhanced motion, or "swimming". A fluorescence microscope, together with a video camera is used to record the motion\ud of individual colloids. The center of the fluorescent emission is found using image analysis to provide an x and y coordinate for each frame of\ud the video. While keeping the microscope focal position fixed, the fluorescence emission from the colloid produces a characteristic concentric\ud ring pattern which is subject to image analysis to determine the particles relative z position. In this way 3D trajectories for the swimming colloid\ud are obtained, allowing swimming velocity to be accurately measured, and physical phenomena such as gravitaxis, which may bias the colloids\ud motion to be detected.\ud

Inkjet-printed enzyme-powered silk-based micro-rockets are able to undergo autonomous motion in a vast variety of fluidic environments including complex media such as human serum. By means of digital inkjet printing it is possible to alter the catalyst distribution simply and generate varying trajectory behavior of these micro-rockets. Made of silk scaffolds containing enzymes these micro-rockets are highly biocompatible and non-biofouling.

The advent of autonomous self-propulsion has instigated research towards making colloidal machines that can deliver mechanical work in the form of transport, and other functions such as sensing and cleaning. While much progress has been made in the last 10 years on various mechanisms to generate self-propulsion, the ability to steer self-propelled colloidal devices has so far been much more limited. A critical barrier in increasing the impact of such motors is in directing their motion against the Brownian rotation, which randomizes particle orientations. In this context, here we report directed motion of a specific class of catalytic motors when moving in close proximity to solid surfaces. This is achieved through active quenching of their Brownian rotation by constraining it in a rotational well, caused not by equilibrium, but by hydrodynamic effects. We demonstrate how combining these geometric constraints can be utilized to steer these active colloids along arbitrary trajectories., Self-propelled colloidal particles can be potentially used to transport cargoes at the microscale, but it is challenging to prevent randomization of their motion by Brownian rotations. Here, Das et al. quench these rotations by solid walls, which guide in-plane swimming without the need for external fields.

Nonconductive Janus particle swimmers made by coating fluorescent polymer beads with hemispheres of platinum have been fully characterized using video microscopy to reveal that they undergo propulsion in hydrogen peroxide fuel away from the catalytic platinum patch. The platinum coating shadows the fluorescence signal from half of each swimmer to allow the orientation to be observed directly and correlated quantitatively with the resulting swimming direction. The observed swimmer direction is consistent with both the bubble release and diffusiophoretic propulsion mechanisms.

Model poly(glycerol monomethacrylate)-based macromonomers have been used to prepare sterically stabilized polystyrene latexes by either aqueous emulsion or alcoholic dispersion polymerization, affording mean latex diameters of approximately 107 or 1188 nm respectively as judged by dynamic light scattering. Such PGMA50−PS latexes have appropriate surface wettability to stabilize 25−250 μm oil-in-water Pickering emulsions, depending on the latex concentration and oil type. Colloidosomes were formed by covalent cross-linking of the hydroxyl-functional stabilizer chains from within the oil droplets using a polymeric diisocyanate (tolylene 2,4-diisocyanate-terminated poly(propylene glycol) [PPG-TDI]. This oil-soluble cross-linker was confined within the oil droplets, allowing colloidosomes to be prepared at 50 vol % solids without any aggregation. The resulting microcapsules survive removal of the internal oil phase using excess alcohol, unlike the noncross-linked Pickering emulsion precursor. These observatio...

The ability of alkanethiol monolayers deposited on copper to prevent surface oxidation has suggested their application as preservatives for fluxless soldering. However, the utility of such coatings for this purpose will critically depend on their ability to continue to preserve the substrate during exposure to elevated temperatures throughout the electronics manufacturing process. Consequently, the aim of this paper is to systematically determine the effect of storage temperature and duration on the ability of alkanethiol coated copper samples to undergo fluxless soldering. Similarly, the effect of pre-heating copper immediately prior to soldering is also investigated. The effect of reducing atmospheric oxygen concentration during storage and soldering is also considered as a potential route to improve the thermal resilience of the coatings. Parallel to ascertaining these industrially relevant performance parameters, a quantitative correlation between surface chemistry and solder wetting is established, and the temperature dependence of the kinetics of surface oxidation through an alkanethiol barrier layer is discussed.

This study was conducted to accurately measure the dispersive surface free energy of lactose solids in ordered and disordered states.Atomic force microscopy (AFM) was used to determine the contact adhesion force between an AFM tip and lactose under low humidity (ca. 1% RH). The geometry of the tip contacting apex was characterized by scanning a porous aluminum film with ultrasharp spikes (radius 2-3 nm). A sphere vs. flat surface model was employed to relate the adhesion force determined to the surface energy based upon the Johnson-Kendal-Roberts theory. Spray-dried amorphous lactose in a compressed-disk form and single crystals of alpha-lactose monohydrate were prepared as model samples.The condition of the smooth sample surface and sphere-shaped tip used was shown to be appropriate to the application of the JKR model. The surface energy of crystalline [(0,-1,-1) face] and amorphous lactose was determined to be 23.3 +/- 2.3 and 57.4 +/- 7.9 mJ m(-2), respectively.We have demonstrated the capability of AFM to measure the dispersive surface free energy of pharmaceutical materials directly through a blank probe at the nanometer scale. These data, although consistent with results from more traditional methods, illustrate some unique attributes of this approach, namely, surface energies are directly derived from solid-solid interactions, measurements may be made on specific crystalline faces, and the potential exists to identify the submicron heterogeneity of organic solids in terms of their molecular energy states (such as ordered and disordered lactose).

Atomic force microscopy (AFM) provides three-dimensional images with resolution at or near the atomic level. Many researchers have addressed the metrological aspects of AFM imaging of physical samples, producing a range of recognized standards for calibrated spatial measurements. However, because of the complex interplay of forces between an AFM tip and biological samples, the dynamic environment in which such imaging takes place, and difficulties in immobilization, no satisfactory equivalents exist for the biological AFM community. Here an exploration of the effects of AFM imaging parameters on apparent biomolecular dimensions in aqueous environments is carried out for a three-component system comprising GroEL protein, plasmid DNA and gold nanoparticles. The biomolecules in this system have been chosen to present differing imaging challenges, while gold nanoparticles serve as an internal reference for tip performance. Concurrent immobilization of these entities requires optimization of sample preparation methodology, described here as it is hoped the system may act as a template for future bio-metrological standards. Investigation of differences in measured heights and lateral dimensions of DNA, GroEL and gold spheres under a range of imaging conditions and the implications of these results for accurate imaging of biological samples and as a potential bio-metrological standard are discussed.

The effectiveness of a packaging solution for the pharmaceutical and food industry is dependent on the integrity of the constituent layers and the interfaces formed between them. The deconvolution and analysis of the many intimate layers found in packaging is analytically challenging, requiring techniques capable of identifying sub-micron regions. Here we have characterized the chemical and physical nature of the layers in a multilayer packaging system along with the interfaces, using a combination of high-resolution atomic force microscopy (AFM), microthermal analysis using scanning thermal microscopy (SThM), and Fourier transform infrared (FT-IR) spectroscopy. In particular, localized thermal analysis is shown to reveal the thermal transitions of the individual layers, but it was found that care must be exercised when melting through one layer to the next, as this can result in overestimates of melting temperatures of the underlying layer due to excess power loss from the SThM probe to the already molten top layer surrounding the probe. Copyright © 2004 John Wiley & Sons, Ltd.

The surface enrichment of polyethylene−poly(dimethylsiloxane) (ABA) doped polyethylene films has been investigated by XPS, AFM, and contact angle measurements. The poly(dimethylsiloxane) copolymer is found to readily undergo surface segregation during annealing to produce a well-adhered polysiloxane-rich layer. Subsequent oxygen plasma exposure leads to conversion of the surface to SiOx with a concomitant increase in hydrophilicity. Pulsing the electrical discharge is found to significantly accentuate this behavior.

Spin-coating offers a facile fabrication route for the production of high quality colloidal crystals, which have potential as photonic band-gap materials. This paper presents the results of direct observations of the self-assembly of latex colloids during spin-coating through the use of stroboscopic microscopy. We have been able to identify several mechanisms by which self-assembly occurs, depending upon the dispersion properties, such as particle weight fraction, solvent volatility and viscosity. Through the use of stroboscopic microscopy we have directly observed ordering occurring due to high concentrations of colloid particles (where volatility is relatively low), resulting in the formation of regular close packed ordered particle arrays. Conversely when the system in spun-cast from a much more volatile solvent, highly disordered non-equilibrium arrangements of particles form. When spin-coating a low concentration, low volatility dispersion, ordering is dominated by the occurrence of capillary drying fronts, which drag the particles into ordered arrangements. At a volatility intermediate to that of water and ethanol, ordering occurring predominantly via shear forces. Finally when the volatility is increased beyond the shear ordering regime, excessive shear leads to the occurrence of drying fronts within the system and so again, capillary forces induce a large degree of order within the final film.

The surface segregation behavior of poly(dimethylsiloxane)/polyethylene (PDMS/PE) and poly(dimethylsiloxane)/polypropylene (PDMS/PP) blends has been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). It is shown that the overall concentration of silicon-containing species at the surface in these systems can be controlled by solvent washing, annealing, and plasma treatment. In the case of plasma oxidation, well-adhered SiOx coatings are produced.

The effect of added salt on the propulsion of Janus platinum-polystyrene colloids in hydrogen peroxide solution is studied experimentally. It is found that micromolar quantities of potassium and silver nitrate salts reduce the swimming velocity by similar amounts, while leading to significantly different effects on the overall rate of catalytic breakdown of hydrogen peroxide. It is argued that the seemingly paradoxical experimental observations could be theoretically explained by using a generalised reaction scheme that involves charged intermediates and has the topology of two nested loops., Two EPS Figures

In this work, we show that the asymmetrical distribution of mass at the surface of catalytic Janus swimmers results in the devices preferentially propelling themselves upward in a gravitational field. We demonstrate the existence of this gravitaxis phenomenon by observing the trajectories of fueled Janus swimmers, which generate thrust along a vector pointing away from their metallically coated half. We report that as the size of the spherical swimmer increases, the propulsive trajectories are no longer isotropic with respect to gravity, and they start to show a pronounced tendency to move in an upward direction. We suggest that this effect is due to the platinum caps asymmetric mass exerting an increasing influence on the azimuthal angle of the Janus sphere with size, biasing its orientation toward a configuration where the heavier propulsion generating surface faces down. This argument is supported by the good agreement we find between the experimentally observed azimuthal angle distribution for the Janus swimmers and predictions made by simple Boltzmann statistics. This gravitaxis phenomenon provides a mechanism to autonomously control and direct the motion of catalytic swimming devices and so enable a route to make autonomous transport devices and develop new separation, sensing, and controlled release applications.

In this paper we show that processes such as Brownian motion, convection, sedimentation, and bacterial contamination can cause small particles to move through liquids in a fashion which may be mistaken as nanopropulsion. It is shown that particle tracking and subsequent statistical analysis is essential to ascertain if small particles actually propel themselves, or if they are propelled by another process. Specifically we find that it is necessary to calculate the mean-squared displacement of particles at both short and long time intervals, to show that the direction of propulsion changes coincident with rotation of the particle by Brownian motion, as this allows nanopropulsion to be differentiated from Brownian motion, convection and sedimentation. We also find that bacteria can attach themselves to particles and cause them to be propelled. This leads to motion which appears very similar to nanopropulsion and cannot be differentiated using particle tracking and therefore find that carefully designed control experiments must be performed. Finally, we suggest an experimental protocol which can be used to investigate the motion of small objects and prove if they move due to nanopropulsion.

Isotropically conductive adhesives (ICAs) and inks are seen as suitable candidates for interconnecting components and for printed circuits. Silver (Ag) filled ICAs and inks are the most popular due to their high conductivity and good reliability. However, the price of Ag is a significant issue for the wider exploitation of these materials in low cost, high volume applications such as printed electronics. Copper (Cu) is considered as a more cost-effective filler with greater abundance. However, one of the major barriers to the implementation of Cu loaded ICAs is the poor oxidation resistance of Cu particles. The copper oxide is non-conducting and hence, the conductivity of untreated Cu loaded ICAs is limited. In this work, an efficient method for the removal of the copper oxide from copper powders and application of a protective organic coating to prevent re-oxidation was developed. The coating was found to be able to limit the re-oxidation of the copper before mixing and curing of the adhesive. The treated copper powder was combined with an adhesive resin and tracks were stencil printed onto glass substrates, and cured by heating under an inert atmosphere. The effect of different adhesive resins was investigated and the samples were characterised for electrical performance and microstructure. Tracks with electrical conductivity comparable to Ag filled adhesives were obtained. The cured materials showed good stability of resistivity during storage under ambient conditions, but when exposed to 85°C and 85% relative humidity, the resistivity of exposed tracks increased substantially after 12 hours storage and methods to reduce this were identified. Functional circuits were fabricated by printing a pattern of Cu paste, placing surface mount components into the wet paste and curing.

The propulsion velocity of active colloids that asymmetrically catalyze a chemical reaction is probed experimentally as a function of their sizes. It is found that over the experimentally accessible range, the velocity decays as a function of size, with a rate that is compatible with an inverse size dependence. A diffusion-reaction model for the concentrations of the fuel and waste molecules that takes into account a two-step process for the asymmetric catalytic activity on the surface of the colloid is shown to predict a similar behavior for colloids at the large size limit, with a saturation for smaller sizes. © 2012 American Physical Society.

Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications. Understanding the factors that determine the final phase-separated morphology in these systems is consequently an important goal. However, it has to date proved problematic to fully test theoretical models for phase separation during spin coating, due to the high spin speeds, which has limited the spatial resolution of experimental data obtained during the coating process. Without this fundamental understanding, production of optimized micro- and nanoscale structures is hampered. Here, we have employed synchronized stroboscopic illumination together with the high light gathering sensitivity of an electron-multiplying charge-coupled device camera to optically observe structure evolution in such blends during spin coating. Furthermore the use of monochromatic illumination has allowed interference reconstruction of three-dimensional topographies of the spin-coated film as it dries and phase separates with nanometer precision. We have used this new method to directly observe the phase separation process during spinning for a polymer blend (PS-PI) for the first time, providing new insights into the spin-coating process and opening up a route to understand and control phase separation structures.

A class of artificial microswimmers with combined translational and rotational self-propulsion is studied experimentally. The chemically fueled microswimmers are made of doublets of Janus colloidal beads with catalytic patches that are positioned at a fixed angle relative to one another. The mean-square displacement and the mean-square angular displacement of the active doublets are analyzed in the context of a simple Langevin description, using which the physical characteristics of the microswimmers such as the spontaneous translational and rotational velocities are extracted. Our work suggests strategies for designing microswimmers that could follow prescribed cycloidal trajectories.

The ability to produce conductive copper tracks using ink-jet printing to allow the routine digital manufacture of patterned electrical interconnects is a long standing industry aim. In this study an approach to achieve this goal is investigated that uses an ink-jet printed self-assembled monolayer (SAM) coating as a molecular etch resist. To date, ink-jet printed SAMs on copper have not had sufficient quality to allow them to act in this way. However, recently an improved etching solution that enables similar quality microcontact printed SAM layers to act as resists on copper has been reported. Here this new etch solution is used to attempt to "develop" ink-jet printed SAM patterns on thin copper laminates into conductive tracks. The success of this approach and quality of resulting tracks is tested using optical microscopy, scanning electron microscopy and atomic force microscopy. This allows an assessment of the performance of this novel approach to interconnection manufacture to be made.

Ink jet printing of self-assembled monolayers (SAMs) on copper provides a potential route to the digital manufacture of patterned tracks and micro-fabricated devices. However, forming a SAM layer using conventional solution methods is challenging due to the native oxide layer on copper, and this issue is magnified for ink-jet printing, where the oxide layer must be removed, without rendering the substrate unsuitable for high resolution printing. In this study, ink-jet patterning of SAMs on copper is reported. The correlation between oxide removal method and print resolution and SAM distribution within a deposited drop is investigated. In addition, the quality of the deposited layer is assessed using a variety of approaches including surface energy measurement.

Self-assembled monolayers of alkanethiols have been demonstrated to preserve copper surfaces for fluxless soldering. However, the performance of these coatings for electronics manufacturing will be strongly influenced by their thermal stability. For example, printed circuit boards (PCBs) may be subjected to several high temperature excursions including multiple reflows and adhesive cure. Consequently this study systematically investigates the fluxless solderability of alkanethiol coated copper after storage at a range of temperatures. It was found that while storage at elevated temperatures does reduce the coatings' preservative properties, this effect can be reduced by decreasing the oxygen content in the surrounding atmosphere. In addition, a quantitative relationship between loss of solderability and temperature was found to exist, providing evidence for the mechanism of the loss of coating preservative properties.

Self-assembled monolayers of alkanethiols have been demonstrated to preserve copper surfaces for fluxless soldering. However, the performance of these coatings for electronics manufacturing will be strongly influenced by their thermal stability. This study systematically investigates the effect of storage at a range of temperatures on the fluxless solderability of alkanethiol coated copper. In the past, experimental evidence has suggested that the key factor to allow good fluxless soldering is maintaining low levels of copper oxide. As a result, it is predicted that changes in the degree of solder wetting during storage will correlate with changes in the surface oxide level. X-ray Photoelectron Spectroscopy (XPS) is used here to investigate this relationship by providing detailed information about changes in surface chemistry. It is found that there is a well defined relationship between loss of solderability and storage temperature in air. This link is most apparent when solderability is measured using the maximum solder wetting force, but also applies to the rate of solder wetting. A correlation between surface oxide levels and wetting force is also shown, however the situation here is more complicated than expected and requires further investigation.

The aim of this study is to investigate the feasibility of depositing a self-assembled monolayer (SAM) coating using ink-jet printing, which can subsequently be used to pattern copper tracks on a printed circuit board (PCB). Such a technique could allow the rapid modification of interconnection layouts using computer aided design, and so aid prototype production and the manufacture of low-medium volume products. The study describes the adaptation of an existing solution based method for SAM formation on copper, to an ink-jet printing process. The challenges posed by the formulation of an ink possessing specific fluid properties, and the need to control the substrate wettability are discussed. Subsequently, using micro-liter scale droplet trials, the ability of deposited SAM layers to act as plating/etching resists is investigated. In addition, a novel patterning strategy is demonstrated, utilizing the ability of SAM modified regions to locally enhance solder wetting. Finally, the ink jet printing of an alkanethiol solution is demonstrated using a commercial print-head achieving 50 mum feature sizes.

This review describes recent developments in self-propelling nano- and micro-scale swimming devices. The ability of these devices to transport nano-scale components in a fluidic environment is demonstrated. Furthermore, the adaptations needed for these devices to meet biological transport challenges such as targeted drug delivery are highlighted. Particular emphasis is placed on describing autonomously powered devices driven by asymmetrical chemical reactions. Methods to control the speed and direction of such swimming devices using external fields are described, and contrasted to recent demonstrations of statistical autonomous migrations and organisations driven by chemical gradients, inter swimmer interactions and external photo-stimulus. Finally the challenges and advantages of converting other nature inspired swimming mechanisms into realistic artificial self-powered devices are considered.

This paper aims to use Atomic Force Microscopy (AFM) to characterise the interaction forces between micronized salbutamol particles, an active ingredient frequently used in metered dose inhalers, and also to glass, lactose and a fluoropolymer. The methodology used involves challenging a salbutamol functionalized AFM tip to the surfaces of interest and measuring the force experienced by the cantilever as a function of tip-sample separation. Analysis of this force-distance data allows quantification of the particle-substrate adhesion. This study yields a ranking of adhesion as glass>lactose>salbutamol>polytetrafluoroethylene (PTFE). An increase in the interaction force between the salbutamol particle and PTFE on repeated contact due to tribocharging is also observed.