Patrick J. Smith’s research while affiliated with The University of Sheffield and other places

Binders used in binder jetting often pose health and environmental risks during processing and post processing operations. The print-heads which are used to deposit binder selectively on the feedstock are prone to clogging, despite the trend of print-heads being highly customised to suit different kinds of binders. These factors often hide the advantages of binder jetting as an additive manufacturing process, especially its scalability and its faster printing rates in comparison to powder bed fusion methods. The work presented here takes a step back and focuses on the development of an aqueous, polyvinyl alcohol (PVA)-based liquid binder that is easy to manufacture and store, safe to handle, and can be reliably jetted to print parts. The feedstock considered was Inconel 718, a nickel-based super alloy which can be effectively processed by binder jetting without niobium segregation. PVA was added to the Inconel 718 powder in dry, granular form to manufacture a modified feedstock. The study also investigated the role of molecular weight of the PVA used, sintering environments and post-processing methods like hot isostatic pressing (HIP) on process responses like part densification, tensile strength, and hardness. Three different types of PVA were chosen which had molecular weights 10,000 g/mol (low molecular weight or LMW), 26,000 g/mol (medium molecular weight or MMW), and 84,000 g/mol (high molecular weight or HMW). The compatibility of the liquid, aqueous PVA-based binders with virgin Inconel 718 was examined by measuring the contact angle. The liquid, aqueous binder having MMW PVA reported better wetting with the Inconel 718 powder with a wetting angle of 26.6 which was lower than the wetting angle of 42.4°, seen in case of a commercial resin-based binder. The green strength reported by the MMW PVA liquid binder was 220 kPa which was higher than the other two PVA-based liquid binders. Green parts, upon successful printing, were sintered at 1260 °C. It was observed that a part printed using MMW PVA had a densification of 96.16% when sintered in 99.98% by volume argon gas, which increased to 98.96% after undergoing HIP. The same part reported a densification of 88.69% when sintered in a 95% by volume N2 and 5% by volume H2 gaseous environment, which was later attributed to the uptake of nitrogen by the chromium present in Inconel 718, which prevented necking between particles. Tensile specimens printed using MMW PVA, sintered in a 99.98% argon environment, showed the highest ultimate tensile strength of 220 MPa, which increased to 1010 MPa after the HIP process, which can be compared to commercially available Inconel 718.

Inkjet printing of magnetic materials has increased in recent years, as it has the potential to improve research in smart, functional materials. Magnetostriction is an inherent property of magnetic materials which allows strain or magnetic fields to be detected. This makes it very attractive for sensors in the area of structural health monitoring by detecting internal strains in carbon fibre-reinforced polymer (CFRP) composite. Inkjet printing offers design flexibility for these sensors to influence the magnetic response to the strain. This allows the sensor to be tailored to suit the location of defects in the CFRP. This research has looked into the viability of printable soft magnetic materials for structural health monitoring (SHM) of CFRP. Magnetite and nickel ink dispersions were selected to print using the JetLab 4 drop-on-demand technique. The printability of both inks was tested by selecting substrate, viscosity and solvent evaporation. Clogging was found to be an issue for both ink dispersions. Sonicating and adjusting the jetting parameters helped in distributing the nanoparticles. We found that magnetite nanoparticles were ideal as a sensor as there is more than double increase in saturation magnetisation by 49 Am2/kg and more than quadruple reduction of coercive field of 5.34 kA/m than nickel. The coil design was found to be the most sensitive to the field as a function of strain, where the gradient was around 80% higher than other sensor designs. Additive layering of 10, 20 and 30 layers of a magnetite square patch was investigated, and it was found that the 20-layered magnetite print had an improved field response to strain while maintaining excellent print resolution. SHM of CFRP was performed by inducing a strain via bending and it was found that the magnetite coil detected a change in field as the strain was applied.

This chapter asks the question “Can we reliably predict the printability of an ink?” The chapter is written from an experimentalist's point of view, with the aim of making the chapter more accessible. The chapter surveys the current academic literature on determining print stability for inkjet. The survey shows that the academic research has focused on simple solvents and single‐nozzle systems. The chapter concludes that more research is needed to produce a means of predicting ink jetting performance.

Additive manufacturing (AM) of carbon fibre reinforced thermoplastic composites can offer advantages over traditional carbon fibre manufacturing through improved design freedom and reduction in production time and cost. However, the carbon fibre composites produced using current state-of-the-art AM approaches generally possess high porosity (18-25%) compared to those produced by conventional manufacturing (1%). An approach known as composite fibre additive manufacturing (CFAM) is presented, involving selectively printing a binder and polymer powder onto discontinuous carbon fibre sheets, which are then compressed, heated and post-processed to form net shape components. The results demonstrate a correlation between compaction pressure applied and porosity/fibre volume fraction within components. Composite components were produced containing porosity of 1.5% and fibre volume content of 15% with 97 MPa tensile strength and 8.9 GPa elastic modulus, presenting a new approach for production of discontinuous carbon fibre reinforced polymer parts with mechanical properties exceeding those of state-of-the-art AM.

Inkjet-printing technology enables the contactless deposition of functional materials such as conductive inks on surfaces, hence reducing contamination and the risk of substrate damage. In printed electronics, inkjet technology offers the significant advantage of controlling the volume of material deposited, and therefore the fine-tuning of the printed geometry, which is crucial for the performance of the final printed electronics. Inkjet printing of functional inks can be used to produce sensors to detect failure of mechanical structures such as carbon fiber reinforced composite (CFRC) components, instead of using attached sensors, which are subject to delamination. Here, silver nanoparticle-based strain sensors were embedded directly in an insulated carbon-fiber laminate by using inkjet printing to achieve an optimized conductive and adhesive geometry, forming a piezoresistive strain sensor. Following the inkjet-printing optimization process, the sensor conductivity and adhesion performance were evaluated. Finally, the sensor was quantified by using a bending rig which applied a pre-determined strain, with the response indicating an accurate sensitivity as the resistance increased with an increased strain. The ability to embed the sensor directly on the CFRC prevents the use of interfacial adhesives which is the main source of failure due to delamination.

Structural health monitoring (SHM) represents the next generation of carbon fiber‐reinforced composite nondestructive testing. One challenge facing the application of magnetostrictive SHM is the lightweighting and ease of installation of actuators and sensors. Inkjet printing (IJP) technology is well suited to produce miniaturized electronic induction sensors that can be paired with magnetostrictive actuators to detect strain. These sensors have several advantages: their thicknesses can be minimized, the surface area can be maximized to increase sensitivity, and complex multifilar coil configurations can be fabricated. A parametric study of the efficacy of IJP induction coils with different parameters (number of coils, monofilar/bifilar, size) tested on a number of actuator‐functionalized composite coupons (FeSiB ribbon and impregnated epoxy sensors) is conducted. The samples are characterized by measuring their inductance response through induced strains. Increased sensitivity and accuracy of the 10‐turn monofilar IJP sensor are shown with respect to 1) 70‐turn hand‐wound coils, 2) a three‐axis AMR sensor, and 3) other IJP actuators with <10 turns. This is attributed to increased contact area to the composite surface and the requirement of minimum sensitivity (i.e., the number of turns and surface area) for strain detection.

High Speed Sintering (HSS) is a novel polymer additive manufacturing process which utilises inkjet printing of an infrared-absorbing pigment onto a heated polymer powder bed to create 2D cross-sections which can be selectively sintered using an infrared lamp. Understanding and improving the accuracy and repeatability of part manufacture by HSS are important, ongoing areas of research. In particular, the role of the ink is poorly understood; the inks typically used in HSS have not been optimised for it, and it is unknown whether they perform in a consistent manner in the process. Notably, the ambient temperature inside a HSS machine increases as a side effect of the sintering process, and the unintentional heating to which the ink is exposed is expected to cause changes in its fluid properties. However, neither the extent of ink heating during the HSS process nor the subsequent changes in its fluid properties have ever been investigated. Such investigation is important, since significant changes in ink properties at different temperatures would be expected to lead to inconsistent printing and subsequently variations in part accuracy and even the degree of sintering during a single build. For the first time, we have quantified the ink temperature rise caused by unintentional, ambient heating during the HSS process, and subsequently measured several of the ink’s fluid properties across the ink temperature range which is expected to be encountered in normal machine operation (25 to 45 ∘ C). We observed only small changes in the ink’s density and surface tension due to this heating, but a significant drop (36%) in its viscosity was seen. By inspection of the ink’s Z number throughout printing, it is concluded that these changes would not be expected to change the manner in which droplets are delivered to the powder bed surface. In contrast, the viscosity decrease during printing is such that it is expected that the printed droplet sizes do change in a single build, which may indeed be a cause for concern with regard to the accuracy and repeatability of the inkjet printing used in HSS, and subsequently to the properties of the polymer parts obtained from the process.

The pH dependent conductance of the Chitosan/Gelatin and Hydroxy-Ethyl Methacrylate (HEMA)/Gelatin hydrogel based systems was mapped out using a data acquisition system and several aspects of conductance characteristics namely accuracy, response time and sensitivity were compared and discussed. The material characteristics of these sensors were mapped out through FTIR. Specific accuracy tests were designed and conducted and both hydrogel based sensors have been found to give a reasonably predictable outcomes in the physiological pH range (4-10). Although Chitosan/Gelatin sensing systems have been explored with regards to conductivity, to the best of our knowledge, HEMA/Gelatin composite has not yet been explored in this respect. There are observable differences in the conductometric system analysis results of both hydrogels; it has been found that HEMA based hydrogels have a longer response time, but also offer a better sensitivity as compared to Chitosan based conductometric hydrogels. This difference in response may be attributed to the material based characteristics of the conductometric sensing system; the possible underlying mechanisms have also been discussed in this research. Our findings indicate that these conductometric composite hydrogels have the potential to be used in physiological applications; where varying response times are required, a hybrid sensor array comprising of both types of hydrogel sensors may be used; that can utilize the advantages of faster response time in case of Chitosan/Gelatin and better sensitivity in case of HEMA/Gelatin sensors.

Purpose The fabrication and characterization of a hydrogel-based conductometric sensor have been carried out. The purpose of this research is to fabricate a small robust hydrogel-based conductometric sensor for real-time monitoring of pH in the physiological range. Design/methodology/approach A pH-responsive Chitosan/Gelatin composite hydrogel has been used for this purpose. This study reports and analyzes the sensing response obtained from four hydrogel compositions with varying Chitosan/Gelatin ratios. The pH-responsive nature of the hydrogel has been mapped out through volumetric and conductometric tests. An attempt has been made to correlate these characteristics with the physico-chemical nature of the hydrogel through scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction techniques. Findings The four hydrogel compositions differed on the basis of gel composition ratios; the conductometric analysis results prove that the sensor with the hydrogel composition (Chitosan 2 per cent, Gelatin 7 per cent, ratio 1:2) produces the best pH resolution in the pH range of 4 to 9. The sensing mechanisms and the differences obtained between individual sensor outputs have been discussed in detail. On the basis of this extensive in vitro assessment, it has been concluded that while key pendant functional groups contribute to pH-responsive characteristics of the hydrogel, the overall sensitivity of the sensors gel component to surrounding pH is also determined by the crystalline to amorphous ratio of the hydrogel composite, its interpenetrating cross-linked structure and the relative ratio of the hydrophilic to the pH-sensitive components. Practical implications The conductometric sensor results prove that the fabricated sensor with the shortlisted hydrogel composition shows good sensitivity in the physiological pH range (4 to 9) and it has the potential for use in point of care medical devices for diagnostic purposes. Originality/value This is the first reported version of the fabrication and testing and analysis/comparison of a hydrogel-based conductometric sensor based on this composition. The work is original and has not been replicated anywhere.

Current commercially available barrier membranes for oral surgery have yet to achieve a perfect design. Existing materials used are either non-resorbable and require a second surgery for their extraction, or alternatively are resorbable but suffer from poor structural integrity or degrade into acidic by-products. Silk has the potential to overcome these issues and has yet to be made into a commercially available dental barrier membrane. Reactive inkjet printing (RIJ) has recently been demonstrated to be a suitable method for assembling silk in its regenerated silk fibroin (RSF) form into different constructs. This paper will establish the properties of RSF solutions for RIJ and the suitability of RIJ for the construction of RSF barrier membranes. Printed RSF films were characterised by their crystallinity and surface properties, which were shown to be controllable via RIJ. RSF films degraded in either phosphate buffered saline or protease XIV solutions had degradation rates related to RSF crystallinity. RSF films were also printed with the inclusion of nano-hydroxyapatite (nHA). As reactive inkjet printing could control RSF crystallinity and hence its degradation rate, as well as offering the ability to incorporate bioactive nHA inclusions, reactive inkjet printing is deemed a suitable alternative method for RSF processing and the production of dental barrier membranes.