3D Bioplotter Research Papers

The fabrication of 3D ink-printed and sintered porous Si scaffolds as electrode material for lithium-ion batteries is explored. A hierarchically-porous architecture consisting of channels (~220 μm in diameter) between microporous Si struts is created to accommodate the large volume change from Si (de)lithiation during electrochemical (dis)charging. The influence of sintering parameters on Si strut porosity and the resulting mechanical and electrochemical properties of the scaffolds are studied experimentally and computationally. Varying sintering temperatures (1150–1300 °C) and sintering times (1–16 h) the open porosity within the Si filaments can be tailored between 46 and 60%. Pore size (3–6 μm) and wall…

Soft-ionic materials with biocompatibility and 3D printability are needed to develop next-generation devices to interface between electronic and biological signals. Herein, thermoreversible and biocompatible ionic liquid gels or iongels, which can be processed by direct ink writing are reported. The iongels are designed by taking advantage of polyvinyl alcohol/phenol interactions to gelify biocompatible cholinium carboxylate ionic liquids. The obtained iongels are stable, soft, and flexible materials (Young modulus between 14 and 70 kPa) with high ionic conductivity (1.8 × 10–2 S cm–1). Interestingly, they presented thermoreversible properties with gel–sol transitions ranging from 85 and 110 °C, which allows the iongel…

Skeletal muscle is an electrically and mechanically active tissue that contains highly oriented, densely packed myofibrils. The tissue has self-regeneration capacity upon injury, which is limited in the cases of volumetric muscle loss. Several regenerative therapies have been developed in order to enhance this capacity, as well as to structurally and mechanically support the defect site during regeneration. Among them, biomimetic approaches that recapitulate the native microenvironment of the tissue in terms of parallel-aligned structure and biophysical signals were shown to be effective. In this study, we have developed 3D printed aligned and electrically active scaffolds in which the electrical…

Piezoelectric ceramics, such as BaTiO3, have gained considerable attention in bone tissue engineering applications thanks to their biocompatibility, ability to sustain a charged surface as well as improve bone cells’ adhesion and proliferation. However, the poor processability and brittleness of these materials hinder the fabrication of three-dimensional scaffolds for load bearing tissue engineering applications. For the first time, this study focused on the fabrication and characterisation of BaTiO3 composite scaffolds by using a multi-material 3D printing technology. Polycaprolactone (PCL) was selected and used as dispersion phase for its low melting point, easy processability and wide adoption in bone tissue engineering….

SnO2-Ag composites with designed architectures with sub-millimeter feature sizes can provide enhanced functionality in electrical applications. SnO2-Ag composites consisting of a ceramic SnO2 micro-lattice filled with metallic Ag are created via a hybrid additive manufacturing method. The multistep process includes: (i) 3D extrusion printing of 0/90° cross-ply micro-lattices from SnO2-7%CuO nanoparticle-loaded ink; (ii) thermal treatment in air to burn the binders and sinter struts of the SnO2 micro-lattice to ~94% relative density; (iii) Ag melt infiltration of channels of sintered micro-lattices. Densification of the SnO2 struts during air-sintering is accelerated by CuO liquid phase forming at 1100°C. During the subsequent…

Biofabrication techniques such as microlithography and 3-D bioprinting have emerged in recent years as technologies capable of rendering complex, biocompatible constructs for biosensors, tissue and regenerative engineering and bioelectronics. While instruments and processes have been the subject of immense advancement, multifunctional bioinks have received less attention. A novel photocrosslinkable, hybrid bioactive and inherently conductive bioink formed from poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) nanomaterials within poly(2-hydroxyethyl methacrylate-co-polyethyleneglycol methacrylate) p(HEMA-co-EGMA) was used to render complex hydrogel constructs through microlithographic fabrication and 3-D printing. Constructs were directly compared through established metrics of acuity and fidelity, using side-by-side comparison of microarray grids, triangles incorporating angles 15–90°,…

Flexible and stretchable conductors are crucial components for next-generation flexible devices. Wrinkled structures often have been created on such conductors by depositing conductive materials on the pre-stretched or organic solvent swollen samples. Herein, water swelling is first proposed to generate the wrinkled structures on silicone elastomers. By immersing silicone/sugar hybrid in water, a significant amount of swelling occurs as a result of osmosis and capillary interactions with the sugar and silicone matrix. Considering the drastic swelling effect and controllable swelling ratio, water swelling is used to replace the conventional pre-stretching and organic solvent swelling to fabricate stretchable conductors. In situ…

Detecting hydrogen peroxide (H2O2) as the side product of enzymatic reactions is of great interest in food and medical applications. Despite the advances in this field, the majority of reported H2O2 sensors are bulky, expensive, limited to only one phase detection (either gas or liquid), and require multistep fabrications. This article aims to address some of these limitations by presenting a 3D printable paper-based sensor made from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) decorated with horseradish peroxidase, an enzyme able to interact with H2O2. Unlike most electrochemical PEDOT:PSS-based H2O2 sensors with voltametric or potentiometric mechanisms, the sensing mechanism in this technology is impedimetric, significantly…

Piezoelectric fluoropolymers convert mechanical energy to electricity and are ideal for sustainably providing power to electronic devices. To convert mechanical energy, a net polarization must be induced in the fluoropolymer, which is currently achieved via an energy intensive electrical poling process. Eliminating this process will enable the low-energy production of efficient energy harvesters. Here, by combining molecular dynamics simulations, piezoresponse force microscopy, and electrodynamic measurements, we reveal a hitherto unseen polarization locking phenomena of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) perpendicular to the basal plane of two-dimensional (2D) Ti3C2Tx MXene nanosheets. This polarization locking, driven by strong electrostatic interactions enabled exceptional energy harvesting…

Bone related diseases and disorders increasingly impact human health. Electrical stimulation (ES) has been shown to promote osteogenesis and healing of bone defects. Graphene, is an electrically conductive and biocompatible material with good mechanical properties (strength with flexibility), and therefore shows significant promise as a cell-compatible electrode for ES. Graphene-based scaffolds may therefore be used for 3D cell and tissue support, including 3D osteoinduction. We have fabricated 3D graphene electrode structures to provide ES to human adipose stem cells (ADSCs). The assemblies support ADSC growth and differentiation, with ES augmenting proliferation and osteogenesis. Our findings expand our previous work on…

Dynamic hydrogels are prepared by either dynamic covalent bonds or supramolecular chemistry. Herein, we develop a dynamic hydrogel by combining both dynamic covalent bonds and supramolecular chemistry that exhibits environmentally adaptive self-healing and pH-tuning properties. To do so, we prepared a gelatin–nanopolysaccharide mixed hydrogel containing pyrogallol/catechol groups and trivalent metal ions. The as-prepared hydrogels are able to heal damage inflicted on them under acidic (pH 3 and 6), neutral (pH 7), and basic (pH 9) environments. The mechanism of healing at acidic and neutral pHs is dominated by coordination bonds between pyrogallol/catechol groups of tannic acid and ferric ions, whilst…

High stretchability and mechanical stability are the key properties of a conductive polymer composite structure. In this work, an anisotropic composite is fabricated by wet 3D printing of epoxy crosslinked chitosan/carbon microtubes. The carbon microtubes were synthesized through a high temperature carbonization of chemically purified cellulose fibres. After the chemical treatment and high temperature carbonization, the removal amorphous substrates from the core of cotton fibres results in the formation of a tubular structure. Here, chitosan which is an abundant natural polymer was used as the composite matrix. It was found that the epoxy crosslinking increases the stretchability of composite filaments.

Flexible graphene film can be quickly realized by three-dimensional printing (3D printing), which has the potential in functional electronic devices. With a trace of cobalt ions as crosslinker, the graphene oxide sol can be converted into 3D printed ink, overcoming the disadvantage of insufficient viscosity of pure graphene oxide ink. The various graphene architectures were successfully obtained by 3D printing, moreover, graphene/polyaniline composites were obtained by electropolymerization. The specific capacitance of graphene/polyaniline electrode achieved up to 238 F/g at the current density of 0.5 A/g, which was much higher than that of graphene electrode (35 F/g).

Over the last decays, the use of conductive biopolymer composites has been growing in areas such as biosensors, soft robotics, and wound dressing applications. They are generally soft hydrophilic materials with good elastic recovery and compatible with biological environments. However, their application and removal from the host are still challenging mainly due to poor mechanical strength. This work displays a technique for the fabrication of complex‐shaped conductive structures with improved mechanical strength by wet three‐dimensional (3‐D) printing, which uses a coagulation bath to quickly solidify an epoxy cross‐linked chitosan/carbon microtube composite ink. The fabricated conductive structure demonstrated higher elongation strength…

Information from the brain travels back and forth along peripheral nerves in the form of electrical impulses generated by neurons and these impulses have repetitive patterns. Schwann cells in peripheral nerves receive molecular signals from axons to coordinate the process of myelination. There is evidence, however, that non-molecular signals play an important role in myelination in the form of patterned electrical impulses generated by neuronal activity. The role of patterned electrical impulses has been investigated in the literature using co-cultures of neurons and myelinating cells. The co-culturing method, however, prevents the uncoupling of the direct effect of patterned electrical impulses…

Whereas the rigid nature of standard thermoelectrics limits their use, flexible thermoelectric platforms can find much broader applications, for example, in low-power, wearable energy harvesting for internet-of-things applications. Here we realize continuous, flexible thermoelectric threads via a rapid extrusion of 3D-printable composite inks (Bi2Te3 n- or p-type micrograins within a non-conducting polymer as a binder) followed by compression through a roller-pair, and we demonstrate their applications in flexible, low-power energy harvesting. The thermoelectric power factors of these threads are enhanced up to 7 orders-of-magnitude after lateral compression, principally due to improved conductivity resulting from reduced void volume fraction and partial…

The direct use of graphene for potential thermoelectric material requires the opening of its bandgap without loss of its high electric conductivity. We herein demonstrate a synchronous reduction and assembly strategy to fabricate large-area reduced graphene oxide films with high electric conductivity and optimized low thermal conductivity assembly. The reduced graphene oxide films have a high electric conductivity and low thermal conductivity, which results from high longitudinal carrier mobility of the lattice domains as well as the enhanced scattering of phonons in the defects and their boundary that substantially reduces the mean phonon free path and the thermal conductivity. Flexible…

Soft tissue fixation of implant and bioelectrodes relies on mechanical means (e.g., sutures, staples, and screws), with associated complications of tissue perforation, scarring, and interfacial stress concentrations. Adhesive bioelectrodes address these shortcomings with voltage cured carbene‐based bioadhesives, locally energized through graphene interdigitated electrodes. Electrorheometry and adhesion structure activity relationships are explored with respect to voltage and electrolyte on bioelectrodes synthesized from graphene 3D‐printed onto resorbable polyester substrates. Adhesive leachates effects on in vitro metabolism and human‐derived platelet‐rich plasma response serves to qualitatively assess biological response. The voltage activated bioadhesives are found to have gelation times of 60 s or less…

Current sensors for monitoring environmental signals, such as pH, are often made from rigid materials that are incompatible with soft biological tissues. The high stiffness of such materials sets practical limitations on the in situ utilization of sensors under biological conditions. This article describes a soft yet robust hydrogel‐based pH sensor that can be 3D printed. The pH‐sensitive poly(3,4‐ethylenedioxythiophene) is combined with hydrophilic polyurethane to create novel printable inks with favorable biomechanical properties. These inks are employed to fabricate highly flexible pH sensors that linearly respond to pH in wet environments. The pH sensitive hydrogels can undergo extreme deformations including…

Continuous composite fibres composed of polypyrrole (PPy) nanoparticles and reduced graphene oxide (rGO) at different mass ratios were fabricated using a single step wet-spinning approach. The electrical conductivity of the composite fibres increased significantly with the addition of rGO. The mechanical properties of the composite fibres also improved by the addition of rGO sheets compared to fibres containing only PPy. The ultimate tensile strength of the fibres increased with the proportion of rGO mass present. The elongation at break was greatest for the composite fibre containing equal mass ratios of PPy nanoparticles and rGO sheets. L929 fibroblasts seeded onto fibres…

With the emergence of 3D-printing (3DP) as a vital tool in tissue engineering and medicine, there is an ever growing need to develop new biomaterials that can be 3D-printed and also emulate the compositional, structural, and functional complexities of human tissues and organs. In this work, we probe the 3D-printable biomaterials spectrum by combining two recently established functional 3D-printable particle-laden biomaterial inks: one that contains hydroxyapatite microspheres (Hyperelastic Bone, HB) and another that contains graphene nanoflakes (3D-Graphene, 3DG). We demonstrate that not only can these distinct, osteogenic and neurogenic inks be co-3D-printed to create complex, multi-material constructs, but that composite…

The exceptional properties of graphene enable applications in electronics, optoelectronics, energy storage, and structural composites. Here we demonstrate a 3D printable graphene (3DG) composite consisting of majority graphene and minority polylactide-co-glycolide, a biocompatible elastomer, 3D-printed from a liquid ink. This ink can be utilized under ambient conditions via extrusion-based 3D printing to create graphene structures with features as small as 100 μm composed of as few as two layers (10 cm thick object). The resulting 3DG material is mechanically robust and flexible while retaining electrical conductivities greater than 800 S/m, an order of magnitude increase over previously reported 3D-printed carbon…

This paper discusses design and fabrication processes in the development of a wearable and flexible conductive resistive sensor. The design and development of the sensor involve the use of Sn-Ag-Cu (SAC)plated Nylon fabric, precisionfused deposition modeling(FDM) using silicone and petrolatum for etch-resistant masks using the EnvisionTEC GmbH Bioplotter, and wet etching using Chromium, Ammonium Persulphate, and Salt-Vinegar etching solutions. Preliminary testing with other mask types, development processes, and sensor design approaches for various applications are discussed.

A polyvinyl alcohol (PVA)-stabilized polypyrrole nanodispersion has been optimised for conductivity and processability by decreasing the quantity of PVA before and after synthesis. A reduction of PVA before synthesis leads to the formation of particles with a slight increase in dry particle diameter (51 ± 6 to 63 ± 3 nm), and conversely a reduced hydrodynamic diameter. Conductivity of the dried nanoparticle films was not measureable after a reduction of PVA prior to synthesis. Using filtration of particles after synthesis, PVA content was sufficiently reduced to achieve dried thin film conductivity of 2 S cm−1, while the electroactivity of the…

Graphene-based polymer composites are a very promising class of compounds for tissue engineering scaffolds. However, in general the methods of synthesis are environmentally hazardous and residual toxic materials can affect the biocompatibility significantly. In this paper a simple, scalable, environmentally-friendly, microwave-assisted synthesis is described that results in conducting graphene/polycaprolactone composites that retain the processability and biocompatibility of the pristine polymer without introducing possibly hazardous reducing agents. Composites of polycaprolactone and graphene oxide were synthesised in a single step by the ring-opening polymerisation of ε-caprolactone in the presence of dispersed graphene oxide nanosheets under microwave irradiation. The graphene oxide provides a…

A new method for complex metallic architecture fabrication is presented, through synthesis and 3D-printing of a new class of 3D-inks into green-body structures followed by thermochemical transformation into sintered metallic counterparts. Small and large volumes of metal-oxide, metal, and metal compound 3D-printable inks are synthesized through simple mixing of solvent, powder, and the biomedical elastomer, polylactic-co-glycolic acid (PLGA). These inks can be 3D-printed under ambient conditions via simple extrusion at speeds upwards of 150 mm s–1 into millimeter- and centimeter-scale thin, thick, high aspect ratio, hollow and enclosed, and multi-material architectures. The resulting 3D-printed green-bodies can be handled immediately, are…

Here, we show that graphene oxide (GO) dispersions exhibit unique viscoelastic properties, making them a new class of soft materials. The fundamental insights accrued here provide the basis for the development of fabrication protocols for these two-dimensional soft materials, in a diverse array of processing techniques.

A facile one-step printing process by 3D micro-extrusion affording binder-free thermally reduced graphene oxide (TRGO) based electrochemical capacitors (ECs) that display high-rate performance is presented. Key intermediates are binder-free TRGO dispersion printing inks with concentrations up to 15 g L−1. This versatile printing technique enables easy fabrication of EC electrodes, useful in both aqueous and non-aqueous electrolyte systems. The as-prepared TRGO material with high specific surface area (SSA) of 593 m2 g−1 and good electrical conductivity of ≈16 S cm−1 exhibits impressive charge storage performances. At 100 and 120 Hz, ECs fabricated with TRGO show time constants of 2.5 ms…

The costs associated with the treatment of medical device and surgical site infections are a major cause of concern in the global healthcare system. To prevent transmission of such infections, a prophylactic surface system that provides protracted release of antibacterial silver ions using low intensity direct electric current (LIDC; 28 μA system current at 6 V) activation has been recently developed. To ensure the safety for future in vivo studies and potential clinical applications, this study assessed the biocompatibility of the LIDC-activated interdigitated silver electrodes-based surface system; in vitro toxicity to human epidermal keratinocytes, human dermal fibroblasts, and normal human…

A novel and highly versatile synthetic route for the production of functionalized graphene dispersions in water, acetone, and isopropanol (IPA), which exhibit long-term stability and are easy to scale up, is reported. Both graphene functionalization (wherein the oxygen content can be varied from 4 to 16 wt%) and dispersion are achieved by the thermal reduction of graphite oxide, followed by a high-pressure homogenization (HPH) process. For the first time, binders, dispersing agents, and reducing agents are not required to produce either dilute or highly concentrated dispersions of single graphene sheets with a graphene content of up to 15 g L−1….