Comparison between Micro-Powder Injection Molding and Material Extrusion Additive Manufacturing of Metal Powders for the Fabrication of Sintered Components.

Original compositions based on iron micro-powders and an organic binder mixture were developed for the fabrication of sintered metallic elements with micro-powder injection molding (µPIM) and material extrusion additive manufacturing of metal powders (MEX). The binder formulation was thoroughly adjusted to exhibit rheological and thermal properties suitable for µPIM and MEX. The focus was set on adapting the proper binder composition to meet the requirements for injection/extrusion and, at the same time, to have comparable thermogravimetric characteristics for the thermal debinding and sintering process. A basic analysis of the forming process indicates that the pressure has a low influence on clogging, while the temperature of the material and mold/nozzle impacts the viscosity of the composition significantly. The influence of the Fe micro-powder content in the range of 45-60 vol.% was evaluated against the injection/extrusion process parameters and properties of sintered elements. Different debinding and sintering processes (chemical and thermal) were evaluated for the optimal properties of the final samples. The obtained sintered elements were of high quality and showed minor signs of binder-related flaws, with shrinkage in the range of 10-15% for both the injection-molded and 3D printed parts. These results suggest that, with minor modifications, compositions tailored for the PIM technique can be adapted for the additive manufacturing of metal parts, achieving comparable characteristics of the parts obtained for both forming methods.

3D printed electronics with nanomaterials.

A large variety of printing, deposition and writing techniques have been incorporated to fabricate electronic devices in the last decades. This approach, printed electronics, has gained great interest in research and practical applications and is successfully fuelling the growth in materials science and technology. On the other hand, a new player is emerging, additive manufacturing, called 3D printing, introducing a new capability to create geometrically complex constructs with low cost and minimal material waste. Having such tremendous technology in our hands, it was just a matter of time to combine advances of printed electronics technology for the fabrication of unique 3D structural electronics. Nanomaterial patterning with additive manufacturing techniques can enable harnessing their nanoscale properties and the fabrication of active structures with unique electrical, mechanical, optical, thermal, magnetic and biological properties. In this paper, we will briefly review the properties of selected nanomaterials suitable for electronic applications and look closer at the current achievements in the synergistic integration of nanomaterials with additive manufacturing technologies to fabricate 3D printed structural electronics. The focus is fixed strictly on techniques allowing as much as possible fabrication of spatial 3D objects, or at least conformal ones on 3D printed substrates, while only selected techniques are adaptable for 3D printing of electronics. Advances in the fabrication of conductive paths and circuits, passive components, antennas, active and photonic components, energy devices, microelectromechanical systems and sensors are presented. Finally, perspectives for development with new nanomaterials, multimaterial and hybrid techniques, bioelectronics, integration with discrete components and 4D-printing are briefly discussed.

Influence of Process Parameters on the Resistivity of 3D Printed Electrically Conductive Structures.

With recent developments in conductive composites, new possibilities emerged for 3D printed conductive structures. Complementary to a vast number of publications on materials properties, here we investigate the influence of printing parameters on the resistance of 3D printed structures. The influence of printing temperature on the resistance is significant, with too low value (210 °C) leading to nozzle clogging, while increasing the temperature by 20 °C above the recommended printing settings decreases resistivity by 15%, but causing degradation of the polymer matrix. The limitations of the FDM technique, related to the dimension accuracy emerging from the layer-by-layer printing approach, greatly influence the samples' cross-section, causing irregular resistivity values for different layer heights. For samples with layer thickness lower than 0.2 mm, regardless of the nozzle diameter (0.5-1 mm), high resistance is attributed to the quality of samples. But for a 1 mm nozzle, we observe stabilized values or resistance for 0.3 to 1 mm layer height. Comparing resistance values and layer height generated from the slicer software, we observe a direct correlation-for a larger height of the sample resistance value decrease. Presented modifications in printing parameters can affect the final resistance by 50%. Controlling several parameters simultaneously poses a great challenge for designing high-efficiency structural electronics.

Electromagnetic field controlled domain wall displacement for induced strain tailoring in BaTiO3-epoxy nanocomposite.

Failure in an epoxy polymer composite material is prone to initiate by the coalescence of microcracks in its polymer matrix. As such, matrix toughening via addition of a second phase as rigid or/and rubber nano/micro-particles is one of the most popular approaches to improve the fracture toughness across multiple scales in a polymer composite, which dissipates fracture energy via deformation mechanisms and microcracks arrest. Few studies have focused on tailorable and variable toughening, so-called 'active toughening', mainly suggesting thermally induced strains which offer slow and irreversible toughening due to polymer's poor thermal conductivity. The research presented in the current article has developed an instantaneous, reversible extrinsic strain field via remote electromagnetic radiation. Quantification of the extrinsic strain evolving in the composite with the microwave energy has been conducted using in-situ real-time fibre optic sensing. A theoretical constitutive equation correlating the exposure energy to micro-strains has been developed, with its solution validating the experimental data and describing their underlying physics. The research has utilised functionalised dielectric ferroelectric nanomaterials, barium titanate (BaTiO3), as a second phase dispersed in an epoxy matrix, able to introduce microscopic electro-strains to their surrounding rigid epoxy subjected to an external electric field (microwaves, herein), as result of their domain walls dipole displacements. Epoxy Araldite LY1564, a diglycidyl ether of bisphenol A associated with the curing agent Aradur 3487 were embedded with the BaTiO3 nanoparticles. The silane coupling agent for the nanoparticles' surface functionalisation was 3-glycidoxypropyl trimethoxysilane (3-GPS). Hydrogen peroxide (H2O2, 30%) and acetic acid (C2H4O2, 99.9%) used as functionalisation aids, and the ethanol (C2H6O, 99.9%) used for BaTiO3 dispersion. Firstly, the crystal microstructure of the functionalised nanoparticles and the thermal and dielectric properties of the achieved epoxy composite materials have been characterised. It has been observed that the addition of the dielectric nanoparticles has a slight impact on the curing extent of the epoxy. Secondly, the surface-bonded fibre Bragg grating (FBG) sensors have been employed to investigate the real-time variation of strain and temperature in the epoxy composites exposed to microwaves at 2.45 GHz and at different exposure energy. The strains developed due to the in-situ exposure at composite, adhesive and their holding fixture material were evaluated using the FBG. The domain wall induced extrinsic strains were distinguished from the thermally induced strains, and found that the increasing exposure energy has an instantaneously increasing effect on the development of such strains. Post-exposure Raman spectra showed no residual field in the composite indicating no remnant strain field examined under microwave powers < 1000 W, thus suggesting a reversible strain introduction mechanism, i.e. the composite retaining its nominal properties post exposure. The dielectric composite development and quantifications presented in this article proposes a novel active toughening technology for high-performance composite applications in numerous sectors.

Highly conductive electronics circuits from aerosol jet printed silver inks.

Recently, low-cost electronics printed on lightweight, flexible and 3D shaped substrates are gaining importance in the markets of wearables and smart packaging. However, printed electronics do not meet the electrical performance of subtractive techniques because the resistivity of metallic printed patterns is still much higher than that of bulk material. To fulfil this need, low-resistive and easy printable inks for high resolution printed electronics techniques are needed. In this work, parameters of silver nanoparticles ink for micro-scale printed electronics technique, Aerosol Jet Printing, are being enhanced. To increase electrical conductivity and enhance printability, surfactants and dispersing agents were used to increase ultrasonic atomisation efficiency, obtain a uniform structure of printed lines, and narrow the width of printed patterns. Electrical measurements show a decrease in resistivity value in samples enhanced by cationic and non-ionic surfactants, by 95%, compared to initially prepared inks. Surfactant additions to silver nanoparticles Aerosol Jet Printing ink show promising features for application in modern electronics.

Printed Flexible Thermoelectric Nanocomposites Based on Carbon Nanotubes and Polyaniline.

A new era of composite organic materials, nanomaterials, and printed electronics is emerging to the applications of thermoelectric generators (TEGs). Special attention is focused on carbon nanomaterials and conducting polymers, and the possibility to form pastes and inks for various low-cost deposition techniques. In this work, we present a novel approach to the processing of composite materials for screen-printing based on carbon nanotubes (CNTs) and polyaniline (PANI), supported with a dielectric polymer vehicle. Three different types of such tailor-made materials were prepared, with a functional phase consisted of carbon nanotubes and polyaniline composites fabricated with two methods: dry mixing of PANI CNT powders and in situ polymerisation of PANI with CNT. These materials were printed on flexible polymer substrates, exhibiting outstanding mechanical properties. The best parameters obtained for elaborated materials were σ=405.45 S·m-1, S=15.4 µV·K-1, and PF=85.2 nW·m-1K-2, respectively.

Printed Graphene, Nanotubes and Silver Electrodes Comparison for Textile and Structural Electronics Applications.

Due to the appearance of smart textiles and wearable electronics, the need for electro-conductive textiles and electro-conductive paths on textiles has become clear. In this article the results of a test of developed textile electro-conductive paths obtained by applying the method of screen printing pastes containing silver nanoparticles and carbon (graphene, nanotubes, graphite) are presented. Conducted research included analysis of the adhesion test, as well as evaluation of the surface resistance before and after the washing and bending cycles. Obtained results indicated that the samples with the content of carbon nanotubes 3% by weight in PMMA on substrate made of aramid fibers (surface mass of 260 g/m2) were characterized by the best adhesion and the best resistance to washing and bending cycles. Such electro-conductive paths have potential to be used in smart clothing applications.

Soldering of Electronics Components on 3D-Printed Conductive Substrates.

Rapid development of additive manufacturing and new composites materials with unique properties are promising tools for fabricating structural electronics. However, according to the typical maximum resolution of additive manufacturing methods, there is no possibility to fabricate all electrical components with these techniques. One way to produce complex structural electronic circuits is to merge 3D-printed elements with standard electronic components. Here, different soldering and surface preparation methods before soldering are tested to find the optimal method for soldering typical electronic components on conductive, 3D-printed, composite substrates. To determine the optimal soldering condition, the contact angles of solder joints fabricated in different conditions were measured. Additionally, the mechanical strength of the joints was measured using the shear force test. The research shows a possibility of fabricating strong, conductive solder joints on composites substrates prepared by additive manufacturing. The results show that mechanical cleaning and using additional flux on the composite substrates are necessary to obtain high-quality solder joints. The most repeatable joints with the highest shear strength values were obtained using reflow soldering together with low-temperature SnBiAg solder alloy. A fabricated demonstrator is a sample of the successful merging of 3D-printed structural electronics with standard electronic components.

Carbon nanotube embedded adhesives for real-time monitoring of adhesion failure in high performance adhesively bonded joints.

Carbon nanotubes (CNTs) embedded polymers are of increasing interest to scientific and industrial communities for multi-functional applications. In this article, CNTs have been introduced to high-strength epoxy adhesive for enabling in-situ strain sensing in adhesively bonded aluminium-to-aluminium single-lap joints to accurately indicate the onset and propagation of adhesion failure to the evolution of piezo-resistivity in varying mechanical loads. The CNT modified adhesive in bonded joints and the CNT modified adhesive alone have been tested under monothonic and cyclic tensile loads up to ultimate failure. The changes in the piezo-resistivity induced by the CNTs have been monitored in situ with respect to loading. A novel interpretation method has been developed for progressive, instantaneous adhesion failure estimation under cyclic tensile stresses from a resistivity baseline. The method indicates that the in-situ resistivity changes and the rate of the changes with strain, i.e. sensitivity, strongly correlate with the adhesion failure progression, irrespective of the CNT dispersion quality. Moreover, the effect of bond thickness on the evolution of piezo-resistivity and adhesion failure have been studied. It was observed that relatively thin adhesive bonds (0.18 mm thickness), possessing higher CNT contact points than thick bonds (0.43 mm thickness), provide 100 times higher sensitivity to varying cyclic loads.

Efficient Inkjet Printing of Graphene-Based Elements: Influence of Dispersing Agent on Ink Viscosity.

Inkjet printing is an excellent printing technique and an attractive alternative to conventional technologies for the production of flexible, low-cost microelectronic devices. Among many parameters that have a significant impact on the correctness of the printing process, the most important is ink viscosity. During the printing process, the ink is influenced by different strains and forces, which significantly change the printing results. The authors present a model and calculations referring to the shear rate of ink in an inkjet printer nozzle. Supporting experiments were conducted, proving the model assumptions for two different ink formulations: initial ink and with the addition of a dispersing agent. The most important findings are summarized by the process window regime of parameters, which is much broader for the inks with a dispersing agent. Such inks exhibit preferable viscosity, better print-ability, and higher path quality with lower resistivity. Presented results allow stating that proper, stable graphene inks adjusted for inkjet technique rheology must contain modifiers such as dispersing agents to be effectively printed.

Screen-printed resistive pressure sensors containing graphene nanoplatelets and carbon nanotubes.

Polymer composites with nanomaterials such as graphene nanoplatelets and carbon nanotubes are a new group of materials with high application possibilities in printed and flexible electronics. In this study such carbon nanomaterials were used as a conductive phase in polymer composites. Pastes with dispersed nanomaterials in PMMA and PVDF vehicles were screen printed on flexible substrates, and used as an active layer in pressure sensors, exploiting contact resistance phenomena. The relationship between resistance and pressure is nearly linear on a logarithmic scale for selected types of samples, and their response is several times higher than for similar sensors with graphite layers. The use of surfactants allowed us to fabricate evenly dispersed nanomaterials with different amount of nanoplatelets and nanotubes in the composites. The samples contained from 1.25 wt.% to 2 wt.% of graphene and 1 wt.% to 0.5 wt.% of nanotubes and exhibited diverse sheet resistivity. Experiments revealed the relationship between morphology and loading of functional phase in the polymer matrix and the sensors' sensitivity.

Flexible temperature sensors on fibers.

The aim of this paper is to present research dedicated to the elaboration of novel, miniaturized flexible temperature sensors for textronic applications. Examined sensors were manufactured on a single yarn, which ensures their high flexibility and good compatibility with textiles. Stable and linear characteristics were obtained by special technological process and applied temperature profiles. As a thermo-sensitive materials the innovative polymer compositions filled with multiwalled carbon nanotubes were used. Elaborated material was adapted to printing and dip-coating techniques to produce NTC composites. Nanotube sensors were free from tensometric effect typical for other carbon-polymer sensor, and demonstrated TCR of 0.13%/K. Obtained temperature sensors, compatible with textile structure, can be applied in rapidly developing smart textiles and be used for health and protections purposes.