Conductive Polylactic Acid Research Articles

Electrochemical Performance and Characterisation of Chemically Treated Conductive PLA Fused Deposition Modelling (FDM) Current Collectors within Additively Manufactured (3D-Printed) Symmetric Carbon Supercapacitors

Within the fields of materials science, producing reliable, long-lasting, and efficient energy storage devices to meet the world’s energy needs remains a foremost research goal. 3D-printing (also known as Additive Manufacturing) provides many benefits to this research [1-8], allowing for excellent customization and freedom of design, while eliminating waste material in the manufacturing process. Wearable electronics, medical implants, and the Internet of Things will doubtless benefit from the advantages provided by additive manufacturing.Our previous work compared the electrochemical performances of symmetric carbon-based supercapacitor devices made using two 3D-printing techniques, SLA (stereolithography) and FDM (fused deposition modelling). Though possessing excellent cycle life, the conductive polylactic acid (PLA) FDM printed current collectors suffered from relatively high resistance and poor cyclic voltammetry curves (far from the rectangular shape of ideal electronic double-layer capacitors). This study aims to improve the conductivity of the FDM current collectors via chemically induced surface modification [9]. Both dimethylformamide (DMF) and aqueous potassium hydroxide (KOH) treatments are used for this purpose. The untreated, DMF-treated, and KOH-treated FDM current collectors are loaded with 1:1 by mass single-walled carbon nanotubes and graphene nanoplatelets carbon slurry, placed within stereolithography (SLA) 3D-printed casings [10], and assembled as supercapacitor cells (separated by glass microfiber filter separators soaked in 6 M aqueous KOH electrolyte).This works shows how DMF treatment method results in little change in electrochemical performance compared to the untreated FDM current collector cells, but pre-treatment in a solution of KOH identical to the cell electrolyte markedly improves the current collector conductivity. The KOH treatment provides a tenfold decrease in the FDM current collector resistance, which correlates with the improved cyclic voltammetric response. Galvanostatic charge-discharge tests reveal the effect of these treatments on specific capacitance, charge-discharge response, efficiency, and rate capability for these printed cells. The pre-treatment confirms that the cell electrolyte does not limited long term performance by interacting with the PLA current collector in 3D printed supercapacitor cells and tests using other inorganic active materials will also be shown.

3D Printed Symmetric Carbon Supercapacitors: A Study Comparing Electrochemical Performance and Cycle Life Depending on 3D Printing Technique and Materials

With the ongoing global energy crisis, producing reliable and efficient methods of energy storage remains an integral part of cutting-edge materials research. Within this topic, 3D-printing (also known as additive manufacturing) is evolving from a niche hobby to a reliable scientific tool for materials science research [1-3]. 3D-printing energy storage materials provides unparalleled levels of customisation [4-9] and freedom of design, while also eliminating waste material during the manufacturing process.3D-printing energy storage materials has been widely covered, but usually just focuses on one method of 3D-printing. Directly comparing more than one 3D-printing method within a single energy storage study is far more seldom researched. This work directly compares the electrochemical performances of symmetric carbon-based supercapacitor devices made using two 3D-printing techniques, SLA (stereolithography) and FDM (fused deposition modelling). Two cell types are made in this study, one with gold-sputtered SLA-printed current collectors, the other with conductive PLA (polylactic acid) FDM-printed current collectors. Carbon-based electrode (various combinations of SWCNT, GNP, Super-P, PVDF) slurries and aqueous 6M KOH electrolyte are implemented in these cells. The benefits and limitations of these 3D-printing methods are directly compared, with the electrochemical performance of the supercapacitor cells being analysed using cyclic voltammetry and galvanostatic charge-discharge tests.The sputtered conductive SLA current collector cells display better conductivity and more ideal rectangular cyclic voltammetry curves for electronic double-layer capacitors (EDLCs) but suffer from poor cycle life in initial experiments (~5,000 charge-discharge cycles before losing all specific capacitance). The FDM current collector cells have poorer conductivity, less ideal cyclic voltammetry curves, and are less structurally sound (causing some electrolyte leakage over long term cycling) but offer extremely stable cycle life for supercapacitor cells, retaining most of their specific capacitance after 100,000 charge-discharge cycles. The cycle lives of the gold-sputtered SLA current collector cells are greatly improved after several changes made during the study, such as reducing the voltage window from 0.0-1.0 V to 0.2-0.7 V, and exploring additives for the carbon-based slurry electrodes, such as Super-P and PVDF (polyvinylidene fluoride).

A preliminary study on multi-material fused filament fabrication of an embedded strain gauge for low-cost real-time monitoring of part strain

Unlike other manufacturing techniques, additive manufacturing enables part consolidation through the production of multi-material parts with enhanced functionality. With reference to the functionality of monitoring the structural integrity of a product during its use, conductive filaments can be used in additive manufacturing. This work aims to investigate the applications of multi-material fused filament fabrication to produce embedded strain gauges for real-time monitoring of part deformations. In layer-by-layer fabrication, conductive filaments can be used to produce strain-sensitive elements inside products at a low cost. This preliminary study demonstrated the feasibility of the proposed approach using tensile samples fabricated through additive manufacturing. The samples were produced using a polyethylene terephthalate glycol filament and an acrylonitrile styrene acrylate filament, while electrically conductive polylactic acid was used for the strain gauge. The characterization and testing activities were conducted by comparing the results of the tensile testing with data acquired through an experimental system set up with an Arduino board, aligning with the resistance-based strain gauge theory. The findings show that the co-fabricated strain gauge successfully traces part deformation, enabling real-time monitoring of strain in the elastic field. Nevertheless, further optimization of the proposed approach is imperative to enhance the reliability and accuracy of the methodology.

3D printed honeycomb bilayer structures based on polylactic acid as lightweight microwave absorbing materials

Abstract3D printed honeycomb structures constituted by neat polylactic acid (PLA) and conductive PLA (PLAc) with different cell sizes and thicknesses were manufactured through 3D printing technology based on material extrusion (MEX). These structures were arranged into bi‐layer honeycomb structures (BHS) for evaluation of the microwave absorbing properties at the X‐band (8.2–12.4 GHz) and Ku‐band (12.4–18 GHz) frequency ranges. The effects of cell size, sample thickness, layer thickness ratio and the nature of the top layer on the electromagnetic attenuation performance of BHS samples were investigated in terms of reflection loss (RL). The components geometric characteristics and the arrangement of the layers exerted great influence on the RL values and effective absorption bandwidth (EAB). Overall the bilayer structures with 5 mm total thickness presented the best EM response in terms of EAB and minimum RL, where the component with the larger cell size (7.7 mm), PLAc (1 mm) as the top layer and PLA (4 mm) as the bottom layer exhibited the best results with RL values of −41 dB and EAB of 9.5 GHz. The BHS system with 7.7 mm cell size was more efficient in Ku band frequency range, whereas that with 3.5 mm cell size gave better response in the X‐band frequency range. Therefore, RL values and EAB can be adjustable by modifying the building strategy of the printed parts, such as thickness of the sample, cell size and thickness distribution of the conductive and non‐conductive layers. The findings in this work show the importance of the building strategy to fabricate components with controllable BHS and improved properties for microwave absorption application.

Electro-Mechanical Characterisation and Damage Monitoring by Acoustic Emission of 3D-Printed CB/PLA.

Even though the influence of the printing direction on the mechanical properties of 3D-printed samples by fused filament fabrication is established in the literature, very little is known about mechanical and electrical coupling. In this study, electrically conductive polylactic acid filled with carbon black particles undergoes monotonic and repeated progressive tensile loading to better understand the influence of the printing direction on the electro-mechanical properties of three-dimensional-printed samples. The objective is to analyse the electro-mechanical behaviour of this composite for its potential application as an actuator. The classical laminate theory is also applied to evaluate the relevance of this theory in predicting the mechanical characteristics of this material. In addition, a comprehensive damage analysis is performed using acoustic emission, infrared thermography, scanning electron microscopy, and X-ray microcomputed tomography imaging. Results show that the degradation of the mechanical and electrical properties is highly influenced by the printing direction. The appearance and development of crazes in 0° filaments are highlighted and quantified. The conclusions drawn by this study underline the interest in using longitudinal and unidirectional printing directions to improve the conductive path within the samples. Furthermore, the evolution of the resistance throughout the experiments emphasizes the need to control the implemented voltage in the design of future electro-thermally triggered actuators.

Joint angle prediction for a cable-driven gripper with variable joint stiffness through numerical modeling and machine learning

Soft grippers in automation, particularly those with variable joint stiffness, offer promising possibilities for precise manipulation tasks. However, accurately predicting finger joint bending angles in this field poses significant challenges due to the soft and complex nature of the grippers, making modeling and angle prediction difficult. This paper presents the development of a predictive model for precisely controlling bending angles in multi-material printed soft grippers with variable stiffness, which are pivotal for delicate manipulation tasks in automation. In particular, we explore a cable-driven gripper design made of thermoplastic polyurethane and conductive polylactic acid materials, featuring integrated resistive joints for stiffness modulation through controlled Joule heating. A data-driven modeling approach, combining numerical modeling of the gripper and machine learning techniques, was employed for the development of the predictive model. We performed static structural simulations using ANSYS Workbench to measure bending angles under various conditions for developing datasets for model training. In this work, we evaluated several machine learning models such as linear regression, decision tree, and K-nearest neighbor regression models to predict the correlation between temperature, pull distance, and bending angle. The K-nearest neighbor regression model demonstrated the highest accuracy, with a mean absolute error of approximately 11%. These findings underline the importance of precise angle prediction models in enhancing the functionality and reliability of soft grippers, paving the way for their broader application in automation and robotics.

ELECTRICAL STIMULATION COMBINED WITH ADDITIVE MANUFACTURED 3D CONDUCTIVE SCAFFOLDS TOWARDS IMPROVED BONE-TISSUE ENGINEERING STRATEGIES

The growing number of non-union fractures in an aging population has increased the clinical demand for tissue-engineered bone. Electrical stimulation (ES) has been described as a promising strategy for bone regeneration treatments in several clinical studies. However the underlying mechanism by which ES augments bone formation is still poorly understood and its use in bone tissue engineering (BTE) strategies is currently underexplored. Additive manufacturing (AM) technologies (Fused Deposition Modeling/3D Printing) have been widely used in BTE due to their ability to fabricate scaffolds with a high control over their structural and mechanical properties in a reproducible and scalable manner. Thus, in this work, we combined AM methods with conductive biomaterials and ES to enhance the osteogenic differentiation of human bone marrow-derived mesenchymal stem/stromal cells (hBMSCs) envisaging improved BTE strategies.First, we started by developing AM-based electro-bioreactor devices containing medical-grade electrodes (stainless steel and Ti6Al4V) to apply ES to monolayer 2D cultures and 3D cell-seeded scaffolds. Computer modeling(Finite Element Analysis-FEA) was employed to predict the magnitude/distribution of electrical fields within the ES devices and along the different conductive scaffolds. Prior to scaffold culture, 5 different ES protocols were tested in terms of their ability to promote hBMSCs proliferation and osteogenic differentiation in 2D cultures. The best performance ES protocol was then used in two different AM-based BTE strategies: 1) Two different conductive scaffolds (conductive poly lactic acid (PLA) and titanium) were seeded with hBMSCs and cultured for 21 days under osteogenic medium conditions with and without ES and their biological performance was evaluated in comparison to non-conductive standard PLA scaffolds; 2) Different PEDOT:PSS-based coating solutions were screened to obtain PEDOT:PSS/Gelatin-coated 3D polycaprolactone (PCL) scaffolds with a high(11 S.cm-1) and stable electroconductivity. When cultured under ES, PEDOT:PSS/Gelatin-PCL scaffolds enhanced significantly hBMSCs osteogenic differentiation and mineralization(calcium deposition), highlighting their potential for BTE applications.Acknowledgements: Funding received from FCT through projects InSilico4OCReg (PTDC/EME-SIS/0838/2021), OptiBioScaffold (PTDC/EME-SIS/4446/2020) and BioMaterARISES (EXPL/CTM-CTM/0995/2021), and to the institutions iBB (UIDB/04565/2020), CDRSP (UIDB/04044/2020) and Associate Laboratory i4HB (LA/P/0140/2020).

Recycled PETg embedded with graphene, multi-walled carbon nanotubes and carbon black for high-performance conductive additive manufacturing feedstock.

The first report of conductive recycled polyethylene terephthalate glycol (rPETg) for additive manufacturing and electrochemical applications is reported herein. Graphene nanoplatelets (GNP), multi-walled carbon nanotubes (MWCNT) and carbon black (CB) were embedded within a recycled feedstock to produce a filament with lower resistance than commercially available conductive polylactic acid (PLA). In addition to electrical conductivity, the rPETg was able to hold >10 wt% more conductive filler without the use of a plasticiser, showed enhanced temperature stability, had a higher modulus, improved chemical resistance, lowered levels of solution ingress, and could be sterilised in ethanol. Using a mix of carbon materials CB/MWCNT/GNP (25/2.5/2.5 wt%) the electrochemical performance of the rPETg filament was significantly enhanced, providing a heterogenous electrochemical rate constant, k0, equating to 0.88 (±0.01) × 10-3 cm s-1 compared to 0.46 (±0.02) × 10-3 cm s-1 for commercial conductive PLA. This work presents a paradigm shift within the use of additive manufacturing and electrochemistry, allowing the production of electrodes with enhanced electrical, chemical and mechanical properties, whilst improving the sustainability of the production through the use of recycled feedstock.

4D Printing of Commercial based Conductive Polylactic Acid: Strength and Resistance Properties

Four-dimensional (4D) printing technology is an innovative concept integrating conventional 3D printing additive manufacturing (AM) and smart materials programed to change properties or shape over time in response to environmental stimuli. This study aims to characterize the strength and electrical resistance of a commercial electrically conductive polylactic acid (PLA) with carbon black (CB) particles printed by fused filament fabrication (FFF) technique to evaluate the development feasibility of two sensor prototypes: (1) a load-cell sensor, and (2) a temperature sensor. Experiments were performed to study the orientation and raster angle–dependent mechanical and electrical performance of a PLA-CB conductive polymer manufactured by AM-FFF technology. A good agreement was observed between the data received from the manufacturer and the experimental density of the conductive AM-FFF PLA-CB three-point bending samples. The mechanical properties of 3D-printed PLA-CB were characterized based on three-point bending flexural test. Two build orientations (flat and upright) and three raster patterns (0°/90°, +45°/-45°, and concentric) were printed to check the optimal mechanical properties for electrical conductivity; six samples were printed for each one of the six configurations. The three-point bending flexural test results of the examined 36 specimens demonstrated that the samples printed in the concentric and +45°/-45° raster patterns exhibit the best mechanical properties, with the highest flexural strength and flexural modulus of elasticity in the flat orientation. Nevertheless, the concentric pattern has an advantage over the +45°/-45° pattern due to higher density and homogeneity. To examine the electrical resistance of the PLA-CB material another 12 specimens were printed and divided into four groups, each with different lengths. The electrical intrinsic resistivity was calculated from the geometry of the specimens and the measured resistance, with an average value of 13.2 [Ω·cm]. To check the production feasibility of a load-cell sensor prototype the effect of load on electrical conductivity was examined, however no effect of load on resistance was discovered. To prove the production feasibility of a sensor prototype for temperature measurements a preliminary device was designed and the effect of increasing and decreasing the temperature between 24 and 42°C on electrical resistance was examined. Based on the experimental results a calibration function was built linking between the temperature and the material’s resistance.

Integrating Fused Deposition Modeling and Melt Electrowriting for Engineering Branched Vasculature.

We demonstrate for the first time the combination of two additive manufacturing technologies used in tandem, fused deposition modelling (FDM) and melt electrowriting (MEW), to increase the range of possible MEW structures, with a focus on creating branched, hollow scaffolds for vascularization. First, computer-aided design (CAD) was used to design branched mold halves which were then used to FDM print conductive polylactic acid (cPLA) molds. Next, MEW was performed over the top of these FDM cPLA molds using polycaprolactone (PCL), an FDA-approved biomaterial. After the removal of the newly constructed MEW scaffolds from the FDM molds, complementary MEW scaffold halves were heat-melded together by placing the flat surfaces of each half onto a temperature-controlled platform, then pressing the heated halves together, and finally allowing them to cool to create branched, hollow constructs. This hybrid technique permitted the direct fabrication of hollow MEW structures that would otherwise not be possible to achieve using MEW alone. The scaffolds then underwent in vitro physical and biological testing. Specifically, dynamic mechanical analysis showed the scaffolds had an anisotropic stiffness of 1 MPa or 5 MPa, depending on the direction of the applied stress. After a month of incubation, normal human dermal fibroblasts (NHDFs) were seen growing on the scaffolds, which demonstrated that no deleterious effects were exerted by the MEW scaffolds constructed using FDM cPLA molds. The significant potential of our hybrid additive manufacturing approach to fabricate complex MEW scaffolds could be applied to a variety of tissue engineering applications, particularly in the field of vascularization.

A 3D Printing‐Enabled Artificially Innervated Smart Soft Gripper with Variable Joint Stiffness

AbstractThe manufacturing industry has witnessed advancements in soft robotics, specifically in robotic grippers for handling fragile or irregular objects. However, challenges remain in balancing shape compliance, structural rigidity, weight, and sensor integration. To address these limitations, a 3D‐printed multimaterial gripper design is proposed. This approach utilizes a single, nearly fully automated 3D printing process to create a universal gripper with almost no assembly work. By processing functional polymer, polymer nanocomposite, and metal wire simultaneously, this technique enables multifunctionality. The gripper achieves different gripping configurations by adjusting joint stiffness through Joule heating of conductive polylactic acid material, ensuring shape conformance. Embedded metal wires, created using an in‐house wire embedding technique, form reliable high‐current‐loading interconnections for the conductive joints acting as the heater. Additionally, an integrated soft sensor printed in thermoplastic polyurethane (TPU) and conductive TPU detects compression levels and discerns handled samples. This study showcases the potential of 3D multimaterial printing for on‐demand fabrication of a smart universal gripper with variable stiffness and integrated sensors, benefiting the automation industry. Overall, this work presents an effective strategy for designing and fabricating integrated multifunctional structures using soft, rigid, and conductive materials, such as polymer, polymer nanocomposite, and metal through multimaterial 3D printing.

Fabrication and Study of 3D Printed ABS-Carbon Composite Anodes for Single Chamber Microbial Fuel Cells

Microbial Fuel Cells (MFCs) are electrochemical devices that exploit microbes for wastewater treatment with simultaneous power production. Concerning reactor design, electrode materials and operation modes, great achievements have been reported with an emphasis on developing anode materials to improve overall MFC performance. Anode materials (carbon cloth, carbon veil, carbon sponges) and their properties such as biocompatibility, electrical conductivity, surface area and efficient transport of waste play a very important role in power generation in MFCs. Despite their low cost, they present structural-based disadvantages eg. Fragility, and low conductivity issues. Additive manufacturing of Fused Deposition Modelling (FDM) due to its tailoring properties, has employed various polymer-based materials such as Polylactic Acid (PLA) and Acrylonitrile Butadiene Styrene (ABS) for manufacturing applications. In addition, carbon-based composites and hybrid materials eg. electrically conductive PLA and ABS have already been fabricated and are commercially available to exploit good electrical conductivity and structural rigidness. In this research, FDM was used to fabricate custom-sized electrodes made of a laboratory-produced electrically conductive ABS filament. A parametric study of conductivity and biocompatibility properties of these electrodes in correlation to 3D printer parameters was investigated and reported. Furthermore, treatment with a combination of thermal, mechanical, and chemical procedures was performed to improve the crucial parameters of anodes for MFCs.

Dynamic Characterization of a Low-Cost Fully and Continuously 3D Printed Capacitive Pressure-Sensing System for Plantar Pressure Measurements.

In orthopedics, the evaluation of footbed pressure distribution maps is a valuable gait analysis technique that aids physicians in diagnosing musculoskeletal and gait disorders. Recently, the use of pressure-sensing insoles to collect pressure distributions has become more popular due to the passive collection of natural gait data during daily activities and the reduction in physical strain experienced by patients. However, current pressure-sensing insoles face the limitations of low customizability and high cost. Previous works have shown the ability to construct customizable pressure-sensing insoles with capacitive sensors using fused-deposition modeling (FDM) 3D printing. This work explores the feasibility of low-cost fully and continuously 3D printed pressure sensors for pressure-sensing insoles using three sensor designs, which use flexible thermoplastic polyurethane (TPU) as the dielectric layer and either conductive TPU or conductive polylactic acid (PLA) for the conductive plates. The sensors are paired with a commercial capacitance-to-voltage converter board to form the sensing system. Dynamic sensor performance is evaluated via sinusoidal compressive tests at frequencies of 1, 3, 5, and 7 Hz, with pressure levels varying from 14.33 to 23.88, 33.43, 52.54, and 71.65 N/cm2 at each frequency. Five sensors of each type are tested. Results show that all sensors display significant hysteresis and nonlinearity. The PLA-TPU sensor with 10% infill is the best-performing sensor with the highest average sensitivity and lowest average hysteresis and linearity errors. The range of average sensitivities, hysteresis, and linearity errors across the entire span of tested pressures and frequencies for the PLA-TPU sensor with 10% infill is 11.61-20.11·10-4 V/(N/cm2), 11.9-31.8%, and 9.0-22.3%, respectively. The significant hysteresis and linearity error are due to the viscoelastic properties of TPU, and some additional nonlinear effects may be due to buckling of the infill walls of the dielectric.

Performance evaluation of the novel 3D-printed aquatic plant-microbial fuel cell assembly with Eichhornia crassipes

Plant-Microbial Fuel Cells (PMFCs) are a sustainable derivative of fuel cells that capitalizes on plant rhizodeposition to generate bioelectricity. In this study, the performance of the novel 3D-printed aquatic PMFC assembly with Eichhornia crassipes as the model plant was investigated. The design made use of 1.75 mm Protopasta Conductive Polylactic Acid (PLA) for the electrodes and 1.75 mm CCTREE Polyethylene Terephthalate Glycol (PETG) filaments for the separator. Three systems were prepared with three replicates each: PMFCs with the original design dimensions (System A), PMFCs with cathode-limited surface area variations (System B), and PMFCs with anode-limited surface area variations (System C). The maximum power density obtained by design was 82.54 µW/m2, while the average for each system is 26.99 µW/m2, 36.24 µW/m2, and 6.81 µW/m2, respectively. The effect of variations on electrode surface area ratio was also examined, and the results suggest that the design benefits from increasing the cathode surface area up to a cathode-anode surface area ratio of 2:1. This suggests that the cathode is the crucial component for this design due to it facilitating the rate-limiting step. Plant health was also found to be a contributing factor to PMFC performance, thereby suggesting that PMFCs are an interplay of several factors not limited to electrode surface area alone. The performance of the novel PMFC did not achieve those obtained from existing studies. Nevertheless, the result of this study indicates that 3D-printing technology is a possible retrofit for PMFC technology and can be utilized for scale-up and power amplification.

Sensitivity enhancement through geometry modification of 3D printed conductive PLA-based strain sensors

PurposeThe purpose of this study is to increasing the gauge factor, reducing the hysteresis error and improving the stability over cyclic deformations of a conductive polylactic acid (CPLA)-based 3D-printed strain sensor by modifying the sensing element geometry.Design/methodology/approachFive different configurations, namely, linear, serpentine, square, triangular and trapezoidal, of CPLA sensing elements are printed on the thermoplastic polyurethane substrate material individually. The resistance change ratio of the printed sensors, when loaded to a predefined percentage of the maximum strain values over multiple cycles, is recorded. Finally, the thickness of substrate and CPLA and the included angle of the triangular strain sensor are evaluated for their influences on the sensitivity.FindingsThe triangular configuration yields the least hysteresis error with high accuracy over repeated loading conditions, because of its uniform stress distribution, whereas the conventional linear configuration produces the maximum sensitivity with low accuracy. The thickness of the substrate and sensing element has more influence over the included angle, in enhancing the sensitivity of the triangular configuration. The sensitivity of the triangular configuration exceeds the linear configuration when printed at ideal sensor dimensional values.Research limitations/implicationsThe 3D printing parameters are kept constant for all the configurations; rather it can be varied for improving the performance of the sensor. Furthermore, the influences of stretching rate and nozzle temperature of the sensing material are not considered in this work.Originality/valueThe sensitivity and accuracy of CPLA-based strain sensor are evaluated for modification in its geometry, and the performance metrics are enhanced using the regression modelling.

Thermo-electro-mechanical microstructural interdependences in conductive thermoplastics

Additive manufacturing has enabled the design of thermoplastic components that provide structural support, electrical conductivity and heat generation modulated by mechanical deformation. The mechanisms and interplays that govern the material response at the microstructural level remain, however, elusive. Here, we develop an experimental method to characterise conductive filaments from a combined mechanical, electrical and thermal perspective. This approach is used to unravel exciting material interplays of conductive polylactic acid. To overcome experimental limitations that prevent a complete microstructural analysis of the problem, we develop a full-field homogenisation framework and implement it for finite elements. The framework accounts for viscoplasticity, electrical and thermal conduction, convection and heat generation via Joule effect, as well as for the interdependences between them. After experimental validation, the framework is applied to virtually optimise fabrication requirements to obtain desired properties in final products, i.e., stiffer products, filaments with higher conductivities or with better sensing capabilities.

Thermo-electro-mechanical aging and degradation of conductive 3D printed PLA/CB composite

Conductive polymeric composites consist of a polymeric matrix filled with conductive particles, providing electrical properties to a naturally insulating material. Their use in material extrusion printers provides great flexibility to geometrical design functional components. However, the degradation of their mechanical behavior during and after the application of electric currents is still absent in the literature. The flow of electric currents induces material heating affecting the strength, and mechanical deformation alters the electric properties leading to bilateral dependences. These processes evolve during the application of electric fields and may degrade the material behavior permanently. In this work, we address these questions taking as baseline material a 3D printed conductive Polylactic Acid (PLA)/ Carbon Black (CB) composite. We performed multi-physical characterizations on samples with different printing orientations and lengths evaluating: i) electric behavior under direct current (DC) regime and a wideband analysis by a Frequency Response Analysis; ii) thermo-electrical behavior studying the temperature field evolution under applied electric fields; iii) thermo-mechanical behavior under uniaxial tension for different testing temperatures; iv) thermo-electrical aging/degradation effects on the mechanical behavior. The study considers a wide range of electric fields (from 180 V/m to 600 V/m) and temperatures (from 25° to 130 °C). The results show enhanced electrical conductivity and mechanical stiffness when using a printing orientation parallel to the electro-mechanical loading. This coupled response is highly influenced by thermal effects due to Joule heating, especially when surpassing the glass transition and cold crystallization temperatures of the composite. The occurrence of such phase transitions governs the material degradation by promoting the growth of mesostructural pores during heating cycles arising from the application of electric fields. The obtained results are essential to unravel changes in mechanical properties when standing for continuous electric conduction and provide an experimental background for the lifetime expectance for the devices and possible thermo-electro-mechanical failure.

Electrochemical enhancement of carbon black-infused poly(lactic acid) filament for additive manufactured electronic applications

Here we present an electrochemical method to enhance the electrical conductivity of commercially available, carbon-black infused polylactic acid (PLA) for use in material extrusion-based additive manufacturing (MEAM). After fabrication, the carbon-black infused PLA structure was processed in aqueous solutions consisting of either hydrochloric acid (HCl), nitric acid (HNO3), or sulfuric acid (H2SO4). This study examines the effects of acid concentration of the three types of acids, input waveform shape applied during the electrochemical process, waveform amplitude, and the frequency of the waveforms on the bonding of the negatively charged ions to the conductive PLA. We found that inputting a DC square pulse in a 7 M H2SO4 solution yielded a 51% reduction in electrical resistance. X-Ray diffraction (XRD) analysis shows that line width does shift to lower 2θ values without affecting the d-spacing and the 2θ peaks decay indicating that the ions introduced through the electrochemical doping process are being diffused into the conductive workpiece. Energy dispersive X-ray spectroscopy (EDS) showed the presence of sulfur ions located throughout the processed carbon-infused PLA, even at the core. Throughout this study, we found that this electrochemical process can create electrically in-active dead zones that occurs from higher current densities. XRD analysis reveals that peaks in these dead zones move to higher 2θ, rather than lower 2θ in the improved areas. This points to a shrinking of the lattice structure and verifies that structural changes are occurring. Electrically improved areas can be utilized in conjunction with electrically in-active dead zones to create conductive areas with insulating zones, mimicking copper traces on a PCB. This electrochemical process provides the opportunity for fused filament fabrication to be used in more electrical applications.

Ni-Pt coating on graphene based 3D printed electrodes for hydrogen evolution reactions in alkaline media

Additive manufacturing (AM), a three-dimensional (3D) printing method has attracted great attention in manufacturing technology because of the low cost of fabrication of medium to small sizes of products, fast prototyping, and high precision. The 3D printing method has emerged as an innovative interface in electrode applications due to the opportunity to use conductive Polylactic Acid (PLA) filaments. In this study, Nickel (Ni) and Platinum (Pt) with different metal ratios were deposited on 3D printed electrodes and prepared using conductive graphene-based PLA filament. Then, the NiPt coated 3D printed graphene-based electrodes were modified by different metal ratios of Ni/Pt: 1:1, 1:2, and 1:3, called NiPt1, NiPt2, and NiPt3, respectively. The physical properties of the NiPt coated 3D printed electrodes were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), FE-SEM/Energy Dispersive X-ray Spectroscopy (FE-SEM/EDX), FE-SEM mapping, X-ray Powder Diffraction (XRD), and X-ray Photoelectron Spectroscopy (XPS) techniques. Electrochemical measurements of the electrodes were examined by using Linear Sweep Voltammetry (LSV), Cyclic Voltammetry (CV), and Electrochemical Impedance Spectroscopy (EIS), Tafel polarization analysis and Chronoamperometry (CA) techniques. The results showed that on NiPt3 3D printed electrode surface, the current density was improved by 25% compared to the other electrode samples. Moreover, it was found that the NiPt3 coated 3D printed electrode had 1.5 times higher current density than the NiPt1 coated 3D printed electrode for HER.

Combining 3D-Printing and Electrospinning to Manufacture Biomimetic Heart Valve Leaflets.

Electrospinning has become a widely used technique in cardiovascular tissue engineering as it offers the possibility to create (micro-)fibrous scaffolds with adjustable properties. The aim of this study was to create multilayered scaffolds mimicking the architectural fiber characteristics of human heart valve leaflets using conductive 3D-printed collectors. Models of aortic valve cusps were created using commercial computer-aided design (CAD) software. Conductive polylactic acid was used to fabricate 3D-printed leaflet templates. These cusp negatives were integrated into a specifically designed, rotating electrospinning mandrel. Three layers of polyurethane were spun onto the collector, mimicking the fiber orientation of human heart valves. Surface and fiber structure was assessed with a scanning electron microscope (SEM). The application of fluorescent dye additionally permitted the microscopic visualization of the multilayered fiber structure. Tensile testing was performed to assess the biomechanical properties of the scaffolds. 3D-printing of essential parts for the electrospinning rig was possible in a short time for a low budget. The aortic valve cusps created following this protocol were three-layered, with a fiber diameter of 4.1 ± 1.6 µm. SEM imaging revealed an even distribution of fibers. Fluorescence microscopy revealed individual layers with differently aligned fibers, with each layer precisely reaching the desired fiber configuration. The produced scaffolds showed high tensile strength, especially along the direction of alignment. The printing files for the different collectors are available as Supplemental File 1, Supplemental File 2, Supplemental File 3, Supplemental File 4, and Supplemental File 5. With a highly specialized setup and workflow protocol, it is possible to mimic tissues with complex fiber structures over multiple layers. Spinning directly on 3D-printed collectors creates considerable flexibility in manufacturing 3D shapes at low production costs.