Quantum Nature of Charge Transport in Inkjet-Printed Graphene Revealed in High Magnetic Fields up to 60T.

Inkjet-printing of graphene, iGr, provides an alternative route for the fabrication of highly conductive and flexible graphene films for use in devices. However, the contribution of quantum phenomena associated with 2D single layer graphene, SLG, to the charge transport in iGr is yet to be explored. Here, the first magneto-transport study of iGr in high magnetic fields up to 60 T is presented. The observed quantum phenomena, such as weak localization and negative magnetoresistance, are strongly affected by the thickness of the iGr film and can be explained by a combination of intra- and inter-flake classical and quantum charge transport. The quantum nature of carrier transport in iGr is revealed using temperature, electric field, and magnetic field dependences of the iGr conductivity. These results are relevant for the exploitation of inkjet deposition of graphene, which is of particular interest for additive manufacturing and 3D printing of flexible and wearable electronics. It is shown that printed nanostructures enable ensemble averaging of quantum interference phenomena within a single device, thereby facilitating comparison between experiment and underlying statistical models of electron transport.

A facile one step route that introduces functionality to polymer powders for laser sintering.

Laser Sintering (LS) is a type of Additive Manufacturing (AM) exploiting laser processing of polymeric particles to produce 3D objects. Because of its ease of processability and thermo-physical properties, polyamide-12 (PA-12) represents ~95% of the polymeric materials used in LS. This constrains the functionality of the items produced, including limited available colours. Moreover, PA-12 objects tend to biofoul in wet environments. Therefore, a key challenge is to develop an inexpensive route to introduce desirable functionality to PA-12. We report a facile, clean, and scalable approach to modification of PA-12, exploiting supercritical carbon dioxide (scCO2) and free radical polymerizations to yield functionalised PA-12 materials. These can be easily printed using commercial apparatus. We demonstrate the potential by creating coloured PA-12 materials and show that the same approach can be utilized to create anti-biofouling objects. Our approach to functionalise materials could open significant new applications for AM.

Photosensitisation of inkjet printed graphene with stable all-inorganic perovskite nanocrystals.

All-inorganic perovskite nanocrystals (NCs) with enhanced environmental stability are of particular interest for optoelectronic applications. Here we report on the formulation of CsPbX3 (X is Br or I) inks for inkjet deposition and utilise these NCs as photosensitive layers in graphene photodetectors, including those based on single layer graphene (SLG) as well as inkjet-printed graphene (iGr) devices. The performance of these photodetectors strongly depends on the device structure, geometry and the fabrication process. We achieve a high photoresponsivity, R > 106 A W-1 in the visible wavelength range and a spectral response controlled by the halide content of the perovskite NC ink. By utilising perovskite NCs, iGr and gold nanoparticle inks, we demonstrate a fully inkjet-printed photodetector with R ≈ 20 A W-1, which is the highest value reported to date for this type of device. The performance of the perovskite/graphene photodetectors is explained by transfer of photo-generated charge carriers from the perovskite NCs into graphene and charge transport through the iGr network. The perovskite ink developed here enabled realisation of stable and sensitive graphene-based photon detectors. Compatibility of inkjet deposition with conventional Si-technologies and with flexible substrates combined with high degree of design freedom provided by inkjet deposition offers opportunities for partially and fully printed optoelectronic devices for applications ranging from electronics to environmental sciences.

Ink-jet 3D printing as a strategy for developing bespoke non-eluting biofilm resistant medical devices.

Chronic infection as a result of bacterial biofilm formation on implanted medical devices is a major global healthcare problem requiring new biocompatible, biofilm-resistant materials. Here we demonstrate how bespoke devices can be manufactured through ink-jet-based 3D printing using bacterial biofilm inhibiting formulations without the need for eluting antibiotics or coatings. Candidate monomers were formulated and their processability and reliability demonstrated. Formulations for in vivo evaluation of the 3D printed structures were selected on the basis of their in vitro bacterial biofilm inhibitory properties and lack of mammalian cell cytotoxicity. In vivo in a mouse implant infection model, Pseudomonas aeruginosa biofilm formation on poly-TCDMDA was reduced by ∼99% when compared with medical grade silicone. Whole mouse bioluminescence imaging and tissue immunohistochemistry revealed the ability of the printed device to modulate host immune responses as well as preventing biofilm formation on the device and infection of the surrounding tissues. Since 3D printing can be used to manufacture devices for both prototyping and clinical use, the versatility of ink-jet based 3D-printing to create personalised functional medical devices is demonstrated by the biofilm resistance of both a finger joint prosthetic and a prostatic stent printed in poly-TCDMDA towards P. aeruginosa and Staphylococcus aureus.

Development of Conductive Gelatine-Methacrylate Inks for Two-Photon Polymerisation.

Conductive hydrogel-based materials are attracting considerable interest for bioelectronic applications due to their ability to act as more compatible soft interfaces between biological and electrical systems. Despite significant advances that are being achieved in the manufacture of hydrogels, precise control over the topographies and architectures remains challenging. In this work, we present for the first time a strategy to manufacture structures with resolutions in the micro-/nanoscale based on hydrogels with enhanced electrical properties. Gelatine methacrylate (GelMa)-based inks were formulated for two-photon polymerisation (2PP). The electrical properties of this material were improved, compared to pristine GelMa, by dispersion of multi-walled carbon nanotubes (MWCNTs) acting as conductive nanofillers, which was confirmed by electrochemical impedance spectroscopy and cyclic voltammetry. This material was also confirmed to support human induced pluripotent stem cell-derived cardiomyocyte (hPSC-CMs) viability and growth. Ultra-thin film structures of 10 µm thickness and scaffolds were manufactured by 2PP, demonstrating the potential of this method in areas spanning tissue engineering and bioelectronics. Though further developments in the instrumentation are required to manufacture more complex structures, this work presents an innovative approach to the manufacture of conductive hydrogels in extremely low resolution.

Exploiting Generative Design for 3D Printing of Bacterial Biofilm Resistant Composite Devices.

As the understanding of disease grows, so does the opportunity for personalization of therapies targeted to the needs of the individual. To bring about a step change in the personalization of medical devices it is shown that multi-material inkjet-based 3D printing can meet this demand by combining functional materials, voxelated manufacturing, and algorithmic design. In this paper composite structures designed with both controlled deformation and reduced biofilm formation are manufactured using two formulations that are deposited selectively and separately. The bacterial biofilm coverage of the resulting composites is reduced by up to 75% compared to commonly used silicone rubbers, without the need for incorporating bioactives. Meanwhile, the composites can be tuned to meet user defined mechanical performance with ±10% deviation. Device manufacture is coupled to finite element modelling and a genetic algorithm that takes the user-specified mechanical deformation and computes the distribution of materials needed to meet this under given load constraints through a generative design process. Manufactured products are assessed against the mechanical and bacterial cell-instructive specifications and illustrate how multifunctional personalization can be achieved using generative design driven multi-material inkjet based 3D printing.

The Effects of Feature Sizes in Selectively Laser Melted Ti-6Al-4V Parts on the Validity of Optimised Process Parameters.

Ti-6Al-4V is a popular alloy due to its high strength-to-weight ratio and excellent corrosion resistance. Many applications of additively manufactured Ti-6Al-4V using selective laser melting (SLM) have reached technology readiness. However, issues linked with metallurgical differences in parts manufactured by conventional processes and SLM persist. Very few studies have focused on relating the process parameters to the macroscopic and microscopic properties of parts with different size features. Therefore, the aim of this study was to investigate the effect of the size of features on the density, hardness, microstructural evolution, and mechanical properties of Ti-6Al-4V parts fabricated using a fixed set of parameters. It was found that there is an acceptable range of sizes that can be produced using a fixed set of parameters. Beyond a specific window, the relative density decreased. Upon decreasing the size of a cuboid from (5 × 5 × 5 mm) to (1 × 1 × 5 mm), porosity increased from 0.3% to 4.8%. Within a suitable size range, the microstructure was not significantly affected by size; however, a major change was observed outside the acceptable size window. The size of features played a significant role in the variation of mechanical properties. Under tensile loading, decreasing the gauge size, the ultimate and yield strengths deteriorated. This investigation, therefore, presents an understanding of the correlation between the feature size and process parameters in terms of the microscopic and macroscopic properties of Ti-6Al-4V parts manufactured using SLM. This study also highlights the fact that any set of optimized process parameters will only be valid within a specific size window.

Optimisation of Substrate Angles for Multi-material and Multi-functional Inkjet Printing.

Three dimensional inkjet printing of multiple materials for electronics applications are challenging due to the limited material availability, inconsistencies in layer thickness between dissimilar materials and the need to expose the printed tracks of metal nanoparticles to temperature above 100 °C for sintering. It is envisaged that instead of printing a dielectric and a conductive material on the same plane, by printing conductive tracks on an angled dielectric surface, the required number of silver layers and consequently, the exposure of the polymer to high temperature and the build time of the component can be significantly reduced. Conductive tracks printed with a fixed print height (FH) showed significantly better resolution for all angles than the fixed slope (FS) sample where the print height varied to maintain the slope length. The electrical resistance of the tracks remained under 10Ω up to 60° for FH; whereas for the FS samples, the resistance remained under 10Ω for samples up to 45°. Thus by fixing the print height to 4 mm, precise tracks with low resistance can be printed at substrate angles up to 60°. By adopting this approach, the build height "Z" can be quickly attained with less exposure of the polymer to high temperature.

A new photocrosslinkable polycaprolactone-based ink for three-dimensional inkjet printing.

A new type of photocrosslinkable polycaprolactone (PCL) based ink that is suitable for three-dimensional (3D) inkjet printing has been developed. Photocrosslinkable Polycaprolactone dimethylacrylate (PCLDMA) was synthesized and mixed with poly(ethylene glycol) diacrylate (PEGDA) to prepare an ink with a suitable viscosity for inkjet printing. The ink performance under different printing environments, initiator concentrations, and post processes was studied. This showed that a nitrogen atmosphere during printing was beneficial for curing and material property optimization, as well as improving the quality of structures produced. A simple structure, built in the z-direction, demonstrated the potential for this material for the production of 3D printed objects. Cell tests were carried out to investigate the biocompatibility of the developed ink. © 2016 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1645-1657, 2017.

Combined Inkjet Printing and Infrared Sintering of Silver Nanoparticles using a Swathe-by-Swathe and Layer-by-Layer Approach for 3-Dimensional Structures.

Despite the advancement of additive manufacturing (AM)/3-dimensional (3D) printing, single-step fabrication of multifunctional parts using AM is limited. With the view of enabling multifunctional AM (MFAM), in this study, sintering of metal nanoparticles was performed to obtain conductivity for continuous line inkjet printing of electronics. This was achieved using a bespoke three-dimensional (3D) inkjet-printing machine, JETx, capable of printing a range of materials and utilizing different post processing procedures to print multilayered 3D structures in a single manufacturing step. Multiple layers of silver were printed from an ink containing silver nanoparticles (AgNPs) and infrared sintered using a swathe-by-swathe (SS) and layer-by-layer sintering (LS) regime. The differences in the heat profile for the SS and LS was observed to influence the coalescence of the AgNPs. Void percentage of both SS and LS samples was higher toward the top layer than the bottom layer due to relatively less IR exposure in the top than the bottom. The results depicted a homogeneous microstructure for LS of AgNPs and showed less deformation compared to the SS. Electrical resistivity of the LS tracks (13.6 ± 1 µΩ cm) was lower than the SS tracks (22.5 ± 1 µΩ cm). This study recommends the use of LS method to sinter the AgNPs to obtain a conductive track in 25% less time than SS method for MFAM.