3D Bioplotter Research Papers
A dual-crosslinking electroactive hydrogel based on gelatin methacrylate and dibenzaldehyde-terminated telechelic polyethylene glycol for 3D bio-printing
Gelatin was widely used as scaffold materials in 3D bio-printing due to its excellent bioactivity and availability and especially that their arginine–glycine–aspartic acid (RGD) sequences could efficiently promote cell adhesion and proliferation. In this study, an electroactive and 3D bio-printable hydrogel was prepared through a two-step chemical cross-linking process. Specifically, residual free amino groups of methacrylated gelatin (GelMA) were cross-linked with the aldehyde groups of dibenzaldehyde-terminated telechelic polyethylene glycol (DF-PEG) via Schiff base bonds, forming a gel at 37 °C. During the subsequent 3D bio-printing process, GelMA underwent UV curing, forming a secondary cross-linked network to the mechanical strength and stability…
3D Printing-Electrospinning Hybrid Nanofibrous Scaffold as LEGO-Like Bricks for Modular Assembling Skeletal Muscle-on-a-Chip Functional Platform
Organ-on-a-chip stands as a pivotal platform for skeletal muscle research while constructing 3D skeletal muscle tissues that possess both macroscopic and microscopic structures remains a considerable challenge. This study draws inspiration from LEGO-like assembly, employing a modular approach to construct muscle tissue that integrates biomimetic macroscopic and microscopic structures. Modular LEGO-like hybrid nanofibrous scaffold bricks were fabricated by the combination of 3D printing and electrospinning techniques. Skeletal muscle cells cultured on these modular scaffold bricks exhibited a highly orientated nanofibrous structure. A variety of construction of skeletal muscle tissues further enabled development by various assembling processes. Moreover, skeletal muscle-on-a-chip (SMoC)…
Chemiresistive Sensor for Enhanced CO2 Gas Monitoring
Carbon dioxide (CO2) gas sensing and monitoring have gained prominence for applications such as smart food packaging, environmental monitoring of greenhouse gases, and medical diagnostic tests. Although CO2 sensors based on metal oxide semiconductors are readily available, they often suffer from limitations such as high operating temperatures (>250 °C), limited response at elevated humidity levels (>60% RH), bulkiness, and limited selectivity. In this study, we designed a chemiresistive sensor for CO2 detection to overcome these problems. The sensing material of this sensor consists of a CO2 switchable polymer based on N-3-(dimethylamino)propyl methacrylamide (DMAPMAm) and methoxyethyl methacrylate (MEMA) [P(D-co-M)], and diethylamine.…
Towards sustainable, direct printed, organic transistors with biocompatible copolymer gate dielectrics
We have investigated the potential of three dielectric materials to meet the future demands of green dielectrics: Polycaprolactone (PCL) thermoplastic, polyvinyl alcohol (PVA)-carrageenan (CAR) crosslinked biopolymer, and boron nitride nanotubes (BNNTs) as a nano additive in PVA. Metal–insulator–metal (MIM) capacitors and organic thin film transistors (OTFT) were built with bilayer dielectric stacks of PVA-CAR, PVA-PCL, and PVA-BNNT materials to examine their electrical properties. The PVA-CAR layer uses a cyclic freeze thaw process to crosslink PVA and CAR for superior mechanical and electrical properties to either material alone. The PVA-CAR MIM capacitors showed a dielectric constant of 23, which was found…
Tailoring fractal structure via 3D printing to achieve flexible stretchable electrodes based on Ecoflex/CNT/CF
Flexible electrodes are crucial for the widespread application of flexible electronics. Flexible stretchable electrodes are a research hotspot for finding a solution for the inability of flexible electrodes to withstand large deformations. In this study, the suitability of silicone rubber (Ecoflex), carbon nanotube (CNT), and carbon fiber (CF) composite materials for flexible devices and their ratios were evaluated for the first time. 3D-printed electrodes based on fractal structures with tensile insensitivity and high linearity were prepared to achieve integrated stretching of flexible devices. To demonstrate the benefits and impact of fractal structures on electrode performance, we fabricated flexible stretchable electrodes…
Direct Printed Flexible Organic Thin-Film Transistors With Cross-Linked PVA-Carrageenan Gate Dielectric
There is an urgent need to develop and implement green materials in electronic systems to minimize the negative environmental impact of traditional electronic materials. In this letter, low-temperature cross-linked polyvinyl alcohol (PVA)-carrageenan (CAR) layer is presented as a green electronic gate dielectric for high-performance organic thin-film transistors (OTFT). A metal-free, flexible OTFT, direct printed on polyaniline films using poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) gel-based gate–source–drain layers, PVA-CAR gate dielectric, and 6,13-bis(triisopropylsilylethynyl)pentacene semiconductor, is tested and characterized compared with a more conventional organic gate dielectric polymethylmethacrylate. PVA-CAR metal–dielectric–metal capacitors showed excellent dielectric properties with an average absolute dielectric constant value of 22.36 and an absolute…
System-on-Board Integrated Flexible OEGFET Aptasensor for Multianalyte Testing in Saliva
The need for oral health monitoring point-of-care (PoC) systems is ever growing. We have recently reported a novel, aptamer-based flexible biosensor for detection of a high impact hormone—cortisol—in saliva samples using organic electrolyte-gated FET (OEGFET) technology. In this work, we are reporting a system-on-board (SoB) level integration of an improved flexible OEGFET aptasensor, which was previously reliant on a bench-top measurement setup. The reported flexible OEGFET aptasensor has integrated soft microfluidics and a low-power (< 300 mW) customized printed circuit board. The interfacing of flexible aptasensor to the circuit board was achieved using a low-temperature extrusion printing technique. The system…
3D printing of architectured graphene-based aerogels by cross-linking GO inks with adjustable viscoelasticity for energy storage devices
Three-dimensional (3D) functional graphene-based architecture with superior electrical conductivity and good mechanical strength has promising applications in energy storage and electrics. Viscoelasticity-adjustable inks make it possible to achieve desired 3D architectures with interconnected and continuous interior networks by micro-extrusion printing. In this work, ultra-low-concentration graphene oxide (GO) inks of ~ 15 mg·ml−1 have been obtained and demonstrated in direct 3D printing with a facile cross-linking (direct ink writing). The rheological behavior of the GO strategy by cations, which is the lowest concentration to achieve direct ink writing inks, could be adjusted from 1×104 to 1×105 Pa·s−1 with different concentrations of cations due to strong…
Polysiloxane Inks for Multimaterial 3d Printing of High-Permittivity Dielectric Elastomers
Dielectric elastomer transducers (DET) are promising candidates for electrically-driven soft robotics. However, the high viscosity and low yield stress of DET formulations prohibit 3D printing, the most common manufacturing method for designer soft actuators. DET inks optimized for direct ink writing (DIW) produce elastomers with high stiffness and mechanical losses, diminishing the utility of DET actuators. To address the antagonistic nature of processing and performance constraints, principles of capillary suspensions are used to engineer DIW DET inks. By blending two immiscible polysiloxane liquids with a filler, a capillary ink suspension is obtained, in which the ink rheology can be tuned…
Multi-material 3D printing of piezoelectric and triboelectric integrated nanogenerators with voxel structure
Flexible and highly filled piezoelectric nanogenerators with excellent performance play an indispensable role in portable electronic devices, while the bottlenecks are hard to improve the polarization efficiency and prepare three-dimensional (3D) amplifying effect structure. Compared with other typical 3D printing technologies, direct ink writing multi-material printing (DIW-M3D), can extrude multiple viscoelastic ink materials with a wide selection of materials, which has the advantage of integrated multi-material processing. However, there are fewer reports on the use of DIW-M3D technology to print functional composite materials. Inspired from Lego block structures, we utilized DIW-M3D technology to prepare fabrications with alternating arrangements of piezoelectric…
A Percolation Model for Piezoresistivity in Conductor–Polymer Composites
Insulating polymer composites with conductive filler particles are attractive for sensor applications due to their large piezoresistive response. Composite samples composed of a polymer matrix filled with particles of doped semiconductor that gives a piezoresistive response that is 105 times larger than that of bulk semiconductor sensors are prepared here. The piezoresistance of such composite materials is typically described by using a tunneling mechanism. However, it is found that a percolation description not only fits prior data better but provides a much simpler physical mechanism for the more flexible and soft polymer composite prepared and tested in this study. A…
Advanced Printing Transfer of Assembled Silver Nanowire Network into Elastomer for Constructing Stretchable Conductors
Excellent electrical performance of assemblies of 1D silver nanowires (AgNWs) has been demonstrated in the past years. Up to now, however, there are limited approaches to realize simultaneously deterministic assembly with dense arrangement of AgNWs and desired functional layouts. Herein, an assembly strategy from compressed air-modulated alignment of AgNWs to heterogeneous integration of stretchable sensing devices through printing transfer is proposed. In this process, a convective flow induced by compressed air brings the AgNWs to the air–droplet interface, where the AgNWs are assembled with excellent alignment and packing due to the surface flow, van der Waals, and capillary interactions. Compared…
A Flexible and Polymer-Based Chemiresistive CO2 Gas Sensor at Room Temperature
CO2 sensing is important in many applications ranging from air-quality monitoring to food packaging. In this study, an amine-functionalized copolymer, poly(N-[3-(dimethylamino)propyl]-methacrylamide-co-2-N-morpholinoethyl methacrylate) (p(D-co-M)) is synthesized, offering moderate basicity suitable for a wide CO2 detection range. Taking advantage of this characteristic of p(D-co-M), this polymer is used for designing a chemiresistive, low-cost, flexible, and reversible CO2 sensor. The p(D-co-M)-based sensors show a noticeable decrease in their direct current resistance and alternating current impedance upon exposure to a wide range of CO2 concentration (1–100%) at room temperature with a response and a recovery time of 6 and 14 min, respectively. Additionally, the…
A Polymer-Based Chemiresistive Gas Sensor for Selective Detection of Ammonia Gas
Breath analysis is a non-invasive tool used in medical diagnosis. However, the current generation of breath analyzers is expensive, time-consuming, and requires sample gas separation. In this work, a simple, yet effective, low-cost ammonia gas sensor based on poly(2-acrylamido-2-methyl-1-propanesulfonic acid) is presented for non-invasive medical diagnosis. The designed sensor has a broad detection range to ammonia gas up to 1000 ppm with a limit of detection of 30 ppb. This is a robust sensor, which functions at high relative humidity (RH) (>90%) and exhibits consistent electrical responses under different test conditions. The result of a blind test validates the sensor’s…
Thermoelectric transport in bulk Ni fabricated via particle-based ink extrusion additive manufacturing
Bulk Ni samples were additively manufactured using particle-based ink extrusion. Three samples were characterized for thermoelectric transport properties including electrical resistivity, thermal conductivity, Seebeck coefficient, and thermoelectric figure of merit. Sample-to-sample deviations in transport were small but observable; these were attributed to stochastic porosity from the manufacturing method. Transport results were compared to previously published results in both porous and dense Ni, indicating that the salient features in the traditionally manufactured Ni samples are maintained in their additively manufactured counterparts. These results are offered as evidence of the feasibility of using particle-based ink extrusion additive manufacturing for thermoelectric applications.
Water-induced polymer swelling and its application in soft electronics
Polymer blend system has been commonly applied in a wide variety of applications. Herein, we propose to introduce sugar particles to polymer matrix, which results in a controllable polymer swelling under the action of osmotic pressure upon soaking in water. Taking advantage of this economic and environment-friendly, water-induced polymer swelling process, we have fabricated wrinkled conductive films and 3D structures by depositing conductive materials on the swollen polymer substrates for stretchable strain sensing devices. Several commercial silicone elastomers were utilized in the study. Key processing factors affecting the polymer swelling were investigated, including film thickness, sugar concentration, and temperature of…
Silver nanowire-based stretchable strain sensors with hierarchical wrinkled structures
As an engineering frontier, highly stretchable sensors are widely applied in many fields, such as human motion detection, personal healthcare monitoring, and human-machine interactions. In this study, novel silver nanowire (AgNW)-based stretchable sensors with hierarchical wrinkled structures were fabricated through a two-step process, namely water-induced swelling and AgNW deposition. As highly soluble additives, sodium chloride particles were incorporated into the elastomer matrix. Upon soaking in dopamine aqueous solution, significant swelling was introduced onto the elastomer substrate. The dopamine deposition is accompanied with the swelling process, which endows the sample surface with ultra-hydrophilicity. Additionally, the dopamine-modified swollen samples “capture” the nanowires…
Three-Dimensional Printed Bimodal Electronic Skin with High Resolution and Breathability for Hair Growth
People with neurological deficits face difficulties perceiving their surroundings, resulting in an urgent need for wearable electronic skin (e-skin) that can monitor external stimuli and temperature changes. However, the monolithic structure of e-skin is not conducive to breathability and hinders hair growth, limiting its wearing comfort. In this work, we prepared fully three-dimensional (3D) printed e-skin that allowed hair penetration and growth. This e-skin also achieved simultaneous pressure and temperature detection and a high tactile resolution of 100 cm–2, which is close to that of human fingertips. The temperature sensor maintained linear measurements within 10–60 °C. The pore microstructure prepared…
Electrical Response of Poly(N-[3-(dimethylamino)Propyl] Methacrylamide) to CO2 at a Long Exposure Period
Amine-functionalized polymers (AFPs) are able to react with carbon dioxide (CO2) and are therefore useful in CO2 capture and sensing. To develop AFP-based CO2 sensors, it is critical to examine their electrical responses to CO2 over long periods of time, so that the device can be used consistently for measuring CO2 concentration. To this end, we synthesized poly(N-[3-(dimethylamino)propyl] methacrylamide) (pDMAPMAm) by free radical polymerization and tested its ability to behave as a CO2-responsive polymer in a transducer. The electrical response of this polymer to CO2 upon long exposure times was measured in both the aqueous and solid phases. Direct current…
A 3D printable dynamic nanocellulose/nanochitin self-healing hydrogel and soft strain sensor
Presented here is the synthesis of a 3D printable nano-polysaccharide self-healing hydrogel for flexible strain sensors. Consisting of three distinct yet complementary dynamic bonds, the crosslinked network comprises imine, hydrogen, and catecholato-metal coordination bonds. Self-healing of the hydrogel is demonstrated by macroscopic observation, rheological recovery, and compression measurements. The hydrogel was produced via imine formation of carboxyl methyl chitosan, oxidized cellulose nanofibers, and chitin nanofibers followed by two subsequent crosslinking stages: immersion in tannic acid (TA) solution to create hydrogen bonds, followed by soaking in FeIII solution to form catecholato-metal coordination bonds between TA and FeIII. The metal coordination bonds…
Microstructure evolution during reduction and sintering of 3D-extrusion-printed Bi2O3+TeO2 inks to form Bi2Te3
As an alternative to beam-based additive manufacturing, 3D ink-extrusion additive manufacturing is studied here for thermoelectric Bi2Te3, starting from Bi2O3+TeO2 oxide precursor powders. In situ synchrotron XRD in flowing H2 at elevated temperatures reveals the complex phase evolution upon co-reduction leading to the formation of Bi2Te3, Bi2TeO5 and Bi2TeO2. Sintering trials performed using optimal temperatures identified by in situ XRD show that low heating rates and extensive holding times are required to achieve full co-reduction to pure Bi2Te3. The formation of liquid Bi at the temperatures required for oxide reduction leads to local transient-liquid-phase sintering, creating a coarse-grained porous structure.…
Thermoelectric Transport in Bulk Ni Fabricated via Particle-Based Ink Extrusion Additive Manufacturing
Additive manufacturing is becoming an increasingly attractive method for the fabrication of devices in both industry applications and materials science research. Comparatively, conventional synthesis methods are often more time-intensive and provide geometric constraints. This is true for the fabrication of thermoelectric devices, where additive manufacturing is being further explored to improve cost and design flexibility. Currently, little work has been conducted on the direct effects between additive manufacturing fabrication methods and if or how thermoelectric transport properties are altered from these methods. This work focuses on the process development of constructing bulk Ni samples via particle-based ink extrusion printing, where…
Versatile carbon-loaded shellac ink for disposable printed electronics
Emerging technologies such as smart packaging are shifting the requirements on electronic components, notably regarding service life, which counts in days instead of years. As a result, standard materials are often not adapted due to economic, environmental or manufacturing considerations. For instance, the use of metal conductive tracks in disposable electronics is a waste of valuable resources and their accumulation in landfills is an environmental concern. In this work, we report a conductive ink made of carbon particles dispersed in a solution of shellac. This natural and water-insoluble resin works as a binder, favourably replacing petroleum-derived polymers. The carbon particles…
3D Printable Conducting and Biocompatible PEDOT-graft-PLA Copolymers by Direct Ink Writing
Tailor-made polymers are needed to fully exploit the possibilities of additive manufacturing, constructing complex, and functional devices in areas such as bioelectronics. In this paper, the synthesis of a conducting and biocompatible graft copolymer which can be 3D printed using direct melting extrusion methods is shown. For this purpose, graft copolymers composed by conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and a biocompatible polymer polylactide (PLA) are designed. The PEDOT-g-PLA copolymers are synthesized by chemical oxidative polymerization between 3,4-ethylenedioxythiophene and PLA macromonomers. PEDOT-g-PLA copolymers with different compositions are obtained and fully characterized. The rheological characterization indicates that copolymers containing below 20 wt% of…
Fully 3D Printed and Disposable Paper Supercapacitors
With the development of the internet-of-things for applications such as wearables and packaging, a new class of electronics is emerging, characterized by the sheer number of forecast units and their short service-life. Projected to reach 27 billion units in 2021, connected devices are generating an exponentially increasing amount of electronic waste (e-waste). Fueled by the growing e-waste problem, the field of sustainable electronics is attracting significant interest. Today, standard energy-storage technologies such as lithium-ion or alkaline batteries still power most of smart devices. While they provide good performance, the nonrenewable and toxic materials require dedicated collection and recycling processes. Moreover,…
3D ink-printed, sintered porous silicon scaffolds for battery applications
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…
3D Printable and Biocompatible Iongels for Body Sensor Applications
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…
Recycled algae-based carbon materials as electroconductive 3D printed skeletal muscle tissue engineering scaffolds
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…
Additively manufactured BaTiO3 composite scaffolds: A novel strategy for load bearing bone tissue engineering applications
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 high thermal cycling stability created by Ag infiltration of 3D ink-extruded SnO2 microlattices
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…
Microfabricated and 3-D printed electroconductive hydrogels of PEDOT:PSS and their application in bioelectronics
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°,…
Highly Conductive Silicone Elastomers via Environment-Friendly Swelling and In Situ Synthesis of Silver Nanoparticles
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…
Paper-Based, Chemiresistive Sensor for Hydrogen Peroxide Detection
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…
Interfacial Piezoelectric Polarization Locking in Printable Ti3C2Tx MXene-Fluoropolymer Composites
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…
A 3D printed graphene electrode device for enhanced and scalable stem cell culture, osteoinduction and tissue building
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…
Double dynamic cellulose nanocomposite hydrogels with environmentally adaptive self-healing and pH-tuning properties
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…
Fabrication of a conductive composite structure with enhanced stretchability using direct-write 3D printing
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.
3D printing of free-standing and flexible nitrogen doped graphene/ polyaniline electrode for electrochemical energy storage
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).
Wet 3‐D printing of epoxy cross‐linked chitosan/carbon microtube composite
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…
A method to deliver patterned electrical impulses to Schwann cells cultured on an artificial axon
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…
3D extruded composite thermoelectric threads for flexible energy harvesting
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…
Defect-engineered reduced graphene oxide sheets with high electric conductivity and controlled thermal conductivity for soft and flexible wearable thermoelectric generators
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…
Voltaglue Bioadhesives Energized with Interdigitated 3D‐Graphene Electrodes
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…
Printed, Flexible pH Sensor Hydrogels for Wet Environments
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…
Conductive Composite Fibres from Reduced Graphene Oxide and Polypyrrole Nanoparticles
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…
Multi‐and mixed 3D‐printing of graphene‐hydroxyapatite hybrid materials for complex tissue engineering
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…
Three Dimensional Printing of High-Content Graphene Scaffolds for Electronic and Biomedical Applications
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…
Fabrication of Force Sensor Circuits on Wearable Conductive Textiles
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.
From nanoparticles to fibres: effect of dispersion composition on fibre properties
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…
A bio-friendly, green route to processable, biocompatible graphene/polymer composites
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…
Metallic Architectures from 3D‐Printed Powder‐Based Liquid Inks
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…
3D Micro‐Extrusion of Graphene‐based Active Electrodes: Towards High‐Rate AC Line Filtering Performance Electrochemical Capacitors
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…
Graphene oxide dispersions: tuning rheology to enable fabrication
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.
Biocompatibility analysis of an electrically-activated silver-based antibacterial surface system for medical device applications
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…
Emulsifier-Free Graphene Dispersions with High Graphene Content for Printed Electronics and Freestanding Graphene Films
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.…