3D Bioplotter Research Papers

The fabrication of neural interfaces (NIs) typically relies nowadays on the implementation of complex, expensive, and time-consuming photolithographic processes. Metals and polymers are the materials currently used to fabricate NIs. Conductive polymers could be an alternative to metals to enhance the biocompatibility of the devices. Additive manufacturing techniques provide an easier and low-cost approach to process and finely tuning the geometrical and morphological features of polymers. Here, we propose a 3D printing strategy for the fabrication of completely polymeric neural interfaces, based on extrusion printing. The materials have been chosen to enhance the biocompatibility of the devices. PDMS has been…

Hypertrophic scars (HS) are considered to be the greatest unmet challenge in wound and burn rehabilitation. The most common treatment for HS is pressure therapy, but pressure garments may not be able to exert adequate pressure onto HS due to the complexity of the human body. However, the development of three-dimensional (3D) scanning and direct digital manufacturing technologies has facilitated the customized placement of additively manufactured silicone gel onto fabric as a component of the pressure therapy garment. This study provides an introduction on a novel and customized fabrication approach to treat HS and discusses the mechanical properties of 3D…

Currently, the commercial building sector accounts for 18% of total U.S. end-use energy consumption, of which almost a third was from on-site combustion of fossil fuels for space and water heating. Magnetic heat pumping (MHP) technology is an energy-efficient, sustainable, environmentally-friendly alternative to conventional vapor-compression cooling technology. Several MHP designs today are predicted to be highly energy efficient, on condition that suitable working materials can be developed. This materials challenge has proven to be daunting due to issues associated with intricate synthesis/post-processing protocols and complications related to shaping the mostly brittle magnetocaloric alloys into thin-walled channeled regenerator structures to facilitate…

An oxygen-resistant refractory high-entropy alloy is synthesized in microlattice or bulk form by 3D ink-extrusion printing, interdiffusion, and silicide coating. Additive manufacturing of equiatomic HfNbTaTiZr is implemented by extruding inks containing hydride powders, de-binding under H2, and sintering under vacuum. The sequential decomposition of hydride powders (HfH2+NbH+TaH0.5+TiH2+ZrH2) is followed by in situ X-ray diffraction. Upon sintering at 1400 °C for 18 h, a nearly fully densified, equiatomic HfNbTaTiZr alloy is synthesized; on slow cooling, both α-HCP and β-BCC phases are formed, but on quenching, a metastable single β-BCC phase is obtained. Printed and sintered HfNbTaTiZr alloys with ≈1 wt.% O shows excellent mechanical properties…

Single-crystal microstructure can bring high performance for many materials including piezoelectrics, semiconductors, and cuprate superconductors. Unlike single-crystal metals that can be machined into complex components, most single-crystal ceramics are limited to the shape of thin films or plates due to their brittleness. However, more designs of advanced devices need to break these geometric limitations. 3D-ink-printing can efficiently fabricate complex architectured ceramics, but the microstructure is polycrystals. Here, for the first time, we demonstrate a route to grow single-crystal on 3D printed ceramic-YBa2 Cu 3 O7-x (YBCO) superconductors that can simultaneously have complex architectures and high critical current density. An ink…

Liquid Crystal Elastomers (LCEs) are renowned for their reversible deformation capabilities. Yet, enhancing their mechanical strength while retaining such flexibility has posed a considerable challenge. To overcome this, we utilized 4D printing to develop an innovative composite of LCE with carbon fiber fabric (LCEC). This approach has notably increased the tensile strength of LCE by eightfold, all the while maintaining its exceptional capacity for reversible deformation. By adjusting the alignment angle between carbon fiber and the LCE printing direction from 0° to 90°, the LCEC demonstrates an array of new deformation patterns, including bending, twisting, wrapping, and S-shaped transformations, which…

Additive manufacturing (AM) is widely recognized as a versatile tool for achieving complex geometries and customized functionalities in designed materials. However, the challenge lies in selecting an appropriate AM method that simultaneously realizes desired microstructures and macroscopic geometrical designs in a single sample. This study presents a direct ink writing method for 3D printing intricate, high-fidelity macroscopic cellulose aerogel forms. The resulting aerogels exhibit tunable anisotropic mechanical and thermal characteristics by incorporating fibers of different length scales into the hydrogel inks. The alignment of nanofibers significantly enhances mechanical strength and thermal resistance, leading to higher thermal conductivities in the longitudinal…

Direct Ink Writing holds vast potential for additive manufacturing with broad material compatibility as long as appropriate rheological properties are exhibited by the material of choice. Additives are often included to attain the desired rheological properties for printing, but these same additives can yield products with undesirable mechanical properties. For example, silica fillers are used to create silicone inks appropriate for printing but yield cured structures that are too stiff. In this work, we investigate the applicability of PDMS microspheres as a rheological and thixotropic additive for PDMS based DIW inks. We utilize a facile oil-in-water emulsion method to reproducibly…

We present a new additive-reactive synthesis method where inks – cast into molds or 3D-additively extruded into architectured shapes – are reacted into intermetallic thermoelectric compounds. The new method, as demonstrated for equiatomic TiNiSn, combines: (i) extrusion printing (or casting) of inks containing Ni and Ti powders, (ii) debinding and reactive sintering to form a porous NiTi network, (iii) network infiltration with liquid Sn and subsequent reaction to synthesize the TiNiSn phase. Thin plates, created through this method, show high phase purity and low residual porosity. A thermoelectric figure of merit  = 0.47 ± 0.05 is achieved at 800 K, within the broad range…

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…

Solid-state electrolyte structures using sodium polyaluminate ceramics, have been fabricated for the first time using direct ink writing; a material extrusion-based additive manufacturing process. A series of test samples were prepared using a high solids loading (80 wt%; 51.2 vol%) ceramic paste formulations with suitable rheological characteristics for 3D printing. Following optimum densification via conventional sintering at 1600 °C for 30 min, the additively manufactured electrolyte test samples exhibited an ionic conductivity of σ = 0.14 ± 0.019 S·cm−1 at 300 °C and density of ρ = 3.1 ± 0.02 g·cm−3 (relative density of 95%). These results suggest that direct ink writing of sodium polyaluminates…

New material solutions are searched for the manufacturing and safety of current batteries. Herein, an extrusion printable polymer separator for lithium batteries based on single-ion polymer electrolytes is presented. The polymer electrolytes are based on methacrylic polymeric nanoparticles (NPs) functionalized with a lithium sulfonamide group combined with different organic plasticizers such as sulfolane and carbonates. The synthesis of the polymer NPs is carried out by emulsion copolymerization of methyl methacrylate and lithium sulfonamide methacrylate in the presence of a crosslinker, resulting in particle sizes of less than 30 nm, as shown by electron microscopy. Then polymer electrolytes are prepared by mixing…

Hydrogels and bioinks obtained from gelatin (Gel) generally present poor mechanical properties and require a series of time-consuming and stepwise chemical processes to exhibit improved elasticity and resistance to fatigue. Alkali lignin (AL) is an underutilized by-product of the paper and pulp industry. It is a widely available and inexpensive biomaterial that presents enormous potential for high-value applications owing to its ease of chemical modification and unique naturally occurring polyaromatic structure. This work aims to develop different GelAL hydrogel formulations with a single-step method that are innovative and sustainable. The results obtained from the mechanical, rheological, and degradation studies of…

Ni-Co-Fe-based high-entropy superalloys (HESAs) are fabricated into microlattices via a three-step process: (i) layer-by-layer extrusion of inks containing elemental powders (Ni, Co, Fe, Cr, Ti) and TiAl3 powders; (ii) sintering to densify and homogenize the struts; (iii) aging to achieve a γ/γ’ microstructure. The struts of the microlattices show a nearly pore-free and fully-homogenized microstructure. Increasing the Ti concentration from 4 at% (Al9Co26Cr7Fe16Ni38Ti4) to 9 at% (Al8Co25Cr7Fe15Ni36Ti9) leads to a significant increase in the volume fraction of strengthening γ’ precipitates, from 51 to 78 %. Furthermore, in the Ti-rich composition, the γ’ precipitates exhibit a sharp-edged cubic morphology with larger…

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…

The development of the effective 3D printing strategy for diverse functional monomers is still challenging. Moreover, the conventional 3D printing hydrogels are usually soft and fragile due to the lack of an energy dissipation mechanism. Herein, a microsphere mediating ink preparation strategy is developed to provide tailored rheological behavior for various monomer direct ink writings. The chitosan microspheres are used as an exemplary material due to their tunable swelling ratio under the acid-drived electrostatic repulsion of the protonated amino groups. The rheological behaviors of the swollen chitosan microsphere (SCM) are independent on the monomer types, and various functional secondary polymers…

Porcelain pastes (PlotPastes) were formulated to be used on an additive manufacturing (AM) process (material extrusion) process, primarily robocasting (R3D) technique. The material morphological and thermal characteristics were evaluated by scanning electron microscopy (SEM), differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The rheology and the electrical potential of the ceramic particles were also studied to select and adequate the porcelain paste properties to the R3D AM technique. It was found that shifting the pH values to acidic, the surface charge of the particles changes and increases the pastes viscosity due to agglomeration effects. This behaviour was exploited to optimize…

An enzyme-immobilized platform for biocatalysis was developed through 3D printing of a hydrogel ink comprising dimethacrylate-functionalized Pluronic F127 (F127-DMA) and sodium alginate (Alg) with laccase that can be done at ambient temperature, followed by UV-induced cross-linking. Laccase is an enzyme that can degrade azo dyes and various toxic organic pollutants. The fiber diameter, pore distance, and surface-to-volume ratio of the laccase-immobilized and 3D-printed hydrogel constructs were varied to determine their effects on the catalytic activity of the immobilized enzyme. Among the three geometrical designs investigated, the 3D-printed hydrogel constructs with flower-like geometry exhibited better catalytic performance than those with cubic…

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…

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 technical ceramics using direct ink writing (DIW) of multiphase colloidal inks has the unique ability to create structures with hierarchical features. To facilitate the application of 3D printed hierarchical porous ultra-high temperature ceramics (UHTCs), additional limiting factors such as strength and the effect of 3D printed internal lattice structure need to be better understood. This study reports on the strength dependence of common DIW print parameters including internal lattice structure shape, nozzle diameter and spacings between adjacent filaments. The present study applies Weibull statistics to the experimental array that considers macro features introduced through print parameters as…

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…

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…

Additive manufacturing of objects with complex geometries from refractory metals remains very challenging. Here, we demonstrate the fabrication of tungsten sheet-gyroids via 3D ink-extrusion of WO3 nano-powder followed by hydrogen reduction and activated sintering with NiO additions, as an alternative route to beam-based additive manufacturing of tungsten and other high melting metals and alloys. The microstructure and mechanical properties of the tungsten sheet-gyroids are measured for various wall architectures and processing conditions. The original gyroid architecture, separating two equally-sized volumes, is modified to achieve double-wall gyroids (with three separate volumes) with higher relative densities. The compressive properties of these single-…

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…

Aerogels were listed among the top ten emerging technologies in chemistry by IUPAC in 2022. Their record-breaking properties sparked the emergence of a thriving insulation market, but solutions are sought to promote additional applications. A 3D assembly process based on direct ink writing of “aerogel-in-aerogel” nanocomposites is presented. The printed polyimide-silica aerogels are non-brittle (E = 6.7 MPa) with a super-insulating thermal conductivity (20.3 mW m−1 K−1) and high thermal stability (T5wt% 447 °C). In addition, they display excellent low-loss dielectric properties and microwave transmission over all relevant communication bands and can be functionalized for electromagnetic interference (EMI) shielding. The high shape-fidelity printing, combined…

Hexagonal boron nitride (hBN) is a thermally conductive yet electrically insulating two-dimensional layered nanomaterial that has attracted significant attention as a dielectric for high-performance electronics in addition to playing a central role in thermal management applications. Here, we report a high-content hBN-polymer nanocomposite ink, which can be 3D printed to form mechanically robust, self-supporting constructs. In particular, hBN is dispersed in poly(lactic-co-glycolic acid) and 3D printed at room temperature through an extrusion process to form complex architectures. These constructs can be 3D printed with a composition of up to 60% vol hBN (solids content) while maintaining high mechanical flexibility and…

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…

Combined photothermal-hygroscopic effects enable novel materials actuation strategies based on renewable and sustainable energy sources such as sunlight. Plasmonic nanoparticles have gained considerable interest as photothermal agents, however, the employment in sunlight-driven photothermal-hygroscopic actuators is still bounded, mainly due to the limited absorbance once integrated into nanocomposite actuators and the restricted plasmonic peaks amplitude (compared to the solar spectrum). Herein, the design and fabrication of an AgNPs-based plasmonic photothermal-hygroscopic actuator integrated with printed cellulose tracks are reported (bioinspired to Geraniaceae seeds structures). The nanocomposite is actuated by sunlight power density (i.e., 1 Sun = 100 mW cm−2). The plasmonic AgNPs…

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…

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…

Distributed sensing of environmental parameters is going towards solutions that are more efficient by taking inspiration from flying plant seeds. Yet, present technologies mostly rely on electronics, and they are often heavy and not biodegradable. Here, we develop a biodegradable and porous material, based on cellulose acetate and lignin, and characterize its degree of porosity. We use this material to 3D print lightweight and porous artificial fliers inspired by Ailanthus altissima seeds. By 3D printing, we can tailor in a precise way the morphology of the artificial flier that strongly influences its aerodynamic behavior. We add a cellulose-based photonic crystal…

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.

Cellulose is a promising candidate for the fabrication of superinsulating materials, which would be of great interest for thermal management applications as well as for the scientific community. Until now, the production of strong cellulose-based aerogels has been dominated by traditional manufacturing processes, which have limited the possibilities to achieve the structural control and mechanical properties seen in natural materials such as wood. In this work, we show a simple but versatile method to fabricate cellulose aerogels in intricate geometries. We take advantage of the 3D printing technique direct ink writing to control both the shape and the thermal-mechanical properties…

Polarized THz time domain spectroscopy was used to study the anisotropic properties of wood-based materials for potential optical elements in the THz range, such as half-wave and quarter-wave plates. Wood samples of different species and sample thickness were studied experimentally showing high birefringence but rather high absorption. We elaborate on two approaches to optimize the optical properties for use as wave plates and assess them based on a figure of merit describing their efficiency as a function of birefringence and absorption. The first approach is to dry the wood samples, which significantly improves the efficiency of wave plates. The second…

Polyvinyl alcohol (PVA) is a biodegradable polymer having applications in several industries, such as textiles and paper manufacturing. Due to the water solubility, it is also a useful solvent in 3D dispensing to extrude printable solutions at a low temperature. However, its hydrophilicity is a drawback when considering the property of the end-use material if water contact is required. Using the water solubility of PVA as a benefit during 3D dispensing but avoiding the hydrophilicity in the printed material is tricky and unresolved. This study proposes a technique to achieve this phenomenon by taking advantage of the natural hydrophobicity of…

Damping mechanical resonances is a formidable challenge in an increasing number of applications. Many passive damping methods rely on using low stiffness, complex mechanical structures or electrical systems, which render them unfeasible in many of these applications. Herein, a new method for passive vibration damping, by allowing buckling of the primary load path in mechanical metamaterials and lattice structures, is introduced, which sets an upper limit for vibration transmission: the transmitted acceleration saturates at a maximum value in both tension and compression, no matter what the input acceleration is. This nonlinear mechanism leads to an extreme damping coefficient tanδ ≈ 0.23…

Geraniaceae seeds represent a role model in soft robotics thanks to their ability to move autonomously across and into the soil driven by humidity changes. The secret behind their mobility and adaptivity is embodied in the hierarchical structures and anatomical features of the biological hygroscopic tissues, geometrically designed to be selectively responsive to environmental humidity. Following a bioinspired approach, the internal structure and biomechanics of Pelargonium appendiculatum (L.f.) Willd seeds are investigated to develop a model for the design of a soft robot. The authors exploit the re-shaping ability of 4D printed materials to fabricate a seed-like soft robot, according…

With the increasing need for architectural sustainability, biodesign offers a new approach to incorporating living organisms in building materials. Bacteria hold a range of biological activities that impact their environment, and which could enable the solidification of inorganic materials; this has already been seen with microbially-induced carbonate precipitation that strengthens bonds between sand particles. This paper describes the novel development of an additive co-fabrication manufacturing process, demonstrating an interdisciplinary approach of architecture and microbiology. Specifically, the activity of a biological deposition (i.e., cyanobacterial calcium carbonate precipitation) and its integration with that of a robotic deposition (i.e., a sand-based biomixture) within…

Microlattices with orthogonal 0-90° architecture are 3D-extrusion printed from inks containing a blend of oxide powders (Co3O4, CuO, Fe2O3, and NiO) and metal powder (Cr). Equiatomic CoCrCuFeNi microlattices with ∼170 µm diameter struts are then synthesized by H2-reduction of the oxides followed by sintering and interdiffusion of the resulting metals. These process steps are studied by in-situ synchrotron X-ray diffraction on single extruded microfilaments (lattice struts) with ∼250 µm diameter. After reduction and partial interdiffusion at 600 ˚C for 1 h under H2, filaments consist of lightly-sintered metallic particles with some unreduced Cr2O3. A reduced, nearly fully densified (porosity: 1.6 ± 0.7%)…

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…

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…

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…

Using three-dimensional (3D) printing technology, a 3D calcium alginate/graphene oxide (3D CA/GO) adsorbent, with a hierarchical macroporous structure, was successfully constructed. Owing to the optimized construction process, the 3D CA/GO showed an enhanced adsorption capacity (490.2 mg/g at pH = 3.0) for lead (Pb(II)) in aqueous solution, which was two times higher than reported in the literature). Meanwhile, the selective adsorption ratio of 3D CA/GO for Pb(II) reached 99.8% when positive ions occurred. In addition, after eight adsorption–desorption cycles, the adsorption capacity did not experience a significant decrease and the structure remained stable. Meanwhile, the adsorbed Pb(II) could be eluted…

The membrane based on receptor functionalization provides a new paradigm for the development of mechanical biosensors. However, improvement of sensitivity and test accuracy is still a challenge for mechanical biosensors in practical application. Herein, a surface stress mechanical biosensor (MBioS) based on double-side-gold nanoparticale (AuNP)-coated grid-type polydimethylsiloxane (PDMS) membrane (D-G-MBioS) and 3D printing for human serum albumin (HSA) detection is developed. The surface stress is amplified by the grid coupling sandwich immune structure to improve the sensitivity of the MbioS, successfully reducing limite of detection (LOD) by two orders of magnitude. By self-assembly of AuNPs, the double-side-coated PDMS membrane is…

Magnetic refrigeration is an energy-efficient, sustainable, environmentally-friendly alternative to the conventional vapor-compression cooling technology. There are several magnetic refrigerator device designs in existence today that are predicted to be highly energy-efficient, on condition that suitable working materials can be developed. This challenge in manufacturing magnetocaloric devices is unresolved, mainly due to issues related to shaping the mostly brittle magnetocaloric alloys into thin-walled channeled regenerator structures to facilitate efficient heat transfer between the solid refrigerant and the heat exchange fluid in an active magnetic regenerator (AMR) cooling device. To address this challenge, a novel extrusion-based additive manufacturing (AM) method has been…

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…

Photoresponsive soft liquid crystalline elastomers (LCEs) transform light’s energy into dynamic shape changes and are considered promising candidates for production of soft robotic or muscle-like devices. 3D printing allows access to elaborated geometries as well as control of the photoactuated movements; however, this development is still in its infancy and only a limited choice of LCE is yet available. Herein, we propose to introduce biocompatible and sustainable cellulose nanocrystals (CNC) into an LCE in order to facilitate the printing process by direct ink writing (DIW) and to benefit from the anisotropic mechanical properties resulting from the extrusion-induced alignment of such…

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…

In this work, nanoparticles of a luminescent metal–organic framework were embedded in a photopolymerized methacrylated gelatin. Steady-state and time-resolved luminescence spectroscopy was used to explore the drying and the photopolymerization processes, as well as the effect the methacrylated gelatin had on the quantum yield and decay time of the nanoparticles. A drying time of 27.5 min was needed for a 20 µL droplet, and the proposed intensity ratio analysis resulted in a minimum irradiation time of 18.6 min, at a lamp intensity of 2.7 W/m2, for the photopolymerization process to end. The presence of the methacrylated gelatin decreased the quantum yield of the…

The cultured meat is the solution to reduce resources using in a traditional meat production. It helps produce meat without killing livestock and decrease residue products. The method could also integrate with scaffold’s material which does not derive from animal products. This study aims to investigate the effects of carboxymethyl cellulose (CMC) and apple powder on printability and cytotoxicity as additives in alginate/agarose-based hydrogel. 3D structures of them were printed to find a proper printing condition. From our experiments, the structure could maintain their shapes and uniform line sizes for carboxylmethyl cellulose, but not for apple powder at the 2%…

Cellulose nanocrystals (CNCs), a type of natural photonic crystal, have been used to develop various optical materials owing to their chiral nematic organization, renewability, sustainability, and abundance. However, scaling up the production of CNC-based photonic materials remains challenging because of their long self-assembly time, inevitable assembly defects, static optical properties, and brittle nature. To address these drawbacks, the current study introduces flexible photonic hydrogels with chromatic patterns that are 3D printed using CNC-based inks. These viscoelastic inks were composed of photopolymerizable monomers and CNCs that harbored high aspect ratios. The luminance and color difference of the patterns in the photonic…

Conventional manufacturing techniques allow the production of photoresponsive cellulose nanocrystals (CNC)-based composites that can reversibly modify their optical, mechanical, or chemical properties upon light irradiation. However, such materials are often limited to 2D films or simple shapes and do not benefit from spatial tailoring of mechanical properties resulting from CNC alignment. Herein, we propose the direct ink writing (DIW) of 3D complex structures that combine CNC reinforcement effects with photoinduced responses. After grafting azobenzene photochromes onto the CNC surfaces, up to 15 wt % of modified nanoparticles can be introduced into a polyurethane acrylate matrix. The influence of CNC on…

3D printed ceramics have received much attention of late due to the ability to manufacture complex near net shapes with a range of structures across multiple length scales. The introduction of hierarchical features offers a wider array of properties, yet with this comes additional unknowns as to their limits including the mechanisms behind failures. The present work applies in-situ Synchrotron micro X-ray computed tomography (μXCT) with 4-point flexural testing to study and further understand the failure pattern of 3D printed hierarchical porous ultra-high temperature ceramics. Samples were imaged at incremental load steps to observe the propagation of defects until final…

Fluoropolymers are amongst the most common polymers used for the fabrication of filtration membranes. Despite this, commercial production of these membranes remains dominated by simple casting and solvent phase separation. Herein, we show a rapid, simple approach to produce fluoropolymer membranes, with a porous patterned surface, via immersion precipitation printing (ipP). The patterns can act as a permeate spacer, which are traditionally added to a membrane separately to induce turbulent flow and subsequently decreasing membrane fouling. The direct phase inversion of the permeate spacer during membrane production induces a porous morphology. Further, intimate mechanical connection between the membrane surface and…

The generation of monoclonal antibodies using an in vitro immunization approach is a promising alternative to conventional hybridoma technology. As recently published, the in vitro approach enables an antigen-specific activation of B lymphocytes within 10–12 d followed by immortalization and subsequent selection of hybridomas. This in vitro process can be further improved by using a three-dimensional surrounding to stabilize the complex microenvironment required for a successful immune reaction. In this study, the suitability of Geltrex as a material for the generation of monoclonal antigen-specific antibodies by in vitro immunization was analyzed. We could show that dendritic cells, B cells, and…

Carbon-based materials are promising candidates for enhancing thermal properties of phase change materials (PCMs) without lowering its energy storage capacity. Nowadays, researchers are trying to find a proper porous structure as PCMs support for thermal energy storage applications. In this context, the main novelty of this paper consists in using a ZnO-CNT-based nanocomposite powder, prepared by an own hydrothermal method at high pressure, to obtain porous 3D printed support structures with embedding capacity of PCMs. The morphology of 3D structures, before and after impregnation with three PCMs inorganic salts (NaNO3, KNO3 and NaNO3:KNO3 mixture (1:1 vol% saturated solution) was investigated…

This study aimed to fabricate biodegradable substrate with colorimetric humidity indicator for detective moisture in food packaging. The poor properties of poly(lactic acid) (PLA) were enhanced by melt blending PLA with non-toxic poly(ethylene oxide) PEO at 180 °C. Specifically, three-dimensional (3D) substrates of PLA/PEO blends were fabricated by solvent-cast 3D printing. Furthermore, cobalt chloride (CoCl2) solution was printed onto the substrate with an inkjet printer to serve as a colorimetric humidity sensing indicator. It found that the flexibility and thermal stability of the PLA were improved and the hydrophilicity was increased with an increase in PEO content. Color changes and…

Liquid ink-printing followed by sintering is used to fabricate WC-Co microlattices and cutting tools. The microstructure of WC-xCo (x=0.5-20 wt.%) is studied for a range of carbide-to-binder ratios and for various sintering temperatures. For 0.5≤Co≤5 wt.%, struts in microlattices exhibit residual porosity due to incomplete densification, even at the highest sintering temperature of 1650 °C. With 10 wt.% Co, fully dense lattice struts are achieved after sintering at 1450 °C for 1 h. For 1450-1650 °C sintering temperatures, the hardness of WC-xCo struts initially increases (due to increasing densification with increased Co) and then gradually decreases (due to an increase…

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.…

Porous materials, including foams and lattice structures, are used in many applications such as biomedical implants, heat exchangers, catalysts, and batteries due to their light weight, high surface area and energy absorption properties. Lattice structures, specifically, are of great interest since their properties can be tailored by employing various design methodologies (e.g., topology optimization). On the other hand, Ni-based superalloys are used in many applications where high-temperature and oxidation/corrosion resistance are important such as in gas turbine components. The advantageous properties of these Ni-Cr-Al-based alloys with the geometry and tailored mechanical properties of lattice structures can be combined through a…

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…

Complex-shaped, finely-featured, ultra-high-melting ZrC/W composite structures were produced by coupling, for the first time, three-dimensional (3D) ink-extrusion printing with shape/size-preserving reactive melt infiltration (the Displacive Compensation of Porosity, DCP, process). Inks containing sub-micron WC powders were printed at ambient temperature into either fine-scale structures (sub-millimeter filaments) or into a larger-scale, finely-featured 3D structure (a centimeter-scale nozzle with a sub-millimeter-thick wall). After organic binder removal, the printed structures were sintered at 1650 °C for 1 h to achieve a porosity of 50%. The porous, rigid WC structures then underwent ambient pressure infiltration and reaction with Zr-Cu liquid at up to 1350…

The capacity for a soft material to combine remote sensing and remote actuation is highly desirable for many applications in soft robotics and wearable technologies. This work presents a silicone elastomer with a suspension of a small weight fraction of ferromagnetic nickel nanorods, which is capable of both sensing deformation and altering stiffness in the presence of an external magnetic field. Cylinders composed of silicone elastomer and 1% by weight nickel nanorods experience large increases in compressive modulus when exposed to an external magnetic field. Incremental compressions totaling 600 g of force applied to the same silicone–nanorod composites increase the…

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…

Polymeric systems displaying spontaneous formation of surface wrinkling patterns are useful for a wide range of applications, such as diffraction gratings, flexible electronics, smart adhesives, optical devices, and cell culture platforms. Conventional fabrication techniques for wrinkling patterns involves multitude of processing steps and impose significant limitations on fabrication of hierarchical patterns, creating wrinkles on 3D and nonplanar structures, the scalability of the manufacturing process, and the integration of wrinkle fabrication process into a continuous manufacturing process. In this work, 4D printing of surface morphing hydrogels enabling direct fabrication of wrinkling patterns on curved and/or 3D structures with user-defined and spatially…

The development of synthetic structures that mimic mechanical actuation in living matter such as autonomous translation and shape changes remains a grand challenge for materials science. In living systems the integration of supramolecular structures and covalent polymers contributes to the responsive behaviour of membranes, muscles and tendons, among others. Here we describe hybrid light-responsive soft materials composed of peptide amphiphile supramolecular polymers chemically bonded to spiropyran-based networks that expel water in response to visible light. The supramolecular polymers form a reversibly deformable and water-draining skeleton that mechanically reinforces the hybrid and can also be aligned by printing methods. The noncovalent…

Controlled release of drugs from medical implants is an effective approach to reducing foreign body reactions and infections. We report here on a one-step 3D printing strategy to create drug-eluting polymer devices with a drug-loaded bulk and a drug-free coating. The spontaneously formed drug-free coating dramatically reduces the surface roughness of the implantable devices and serves as a protective layer to suppress the burst release of drugs. A high viscosity liquid silicone that can be extruded based on its shear-thinning property and quickly vulcanize upon exposure to ambient moisture is used as the ink for 3D printing. S-Nitrosothiol type nitric…

Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric ceramics with porous structure of periodic distribution were fabricated successfully via Direct Ink Writing, a type of 3D printing technique. The effect of periodically distributed porous microstructure on the dielectric, ferroelectric, as well as hydrostatic-pressure-induced depolarization properties of PZT95/5 ferroelectric ceramics, was investigated. The printed porous ceramics exhibit relatively good viscoelasticity to retain the periodic structure during 3D printing and drying. In contrast with dense PZT95/5 ferroelectric ceramics prepared by conventional solid-state sintering, low bulk density of the periodically distributed porous PZT95/5 ceramics leads to a decreased remanent polarization of 22.9 µC/cm2 under 2 kV/mm. As the hydrostatic pressure…

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,…

Herein, we demonstrate 3D printing of an elastomeric imidazolium polyamide-ionene which exhibits intrinsic shape-memory (SM) and self-healing (SH) character, reporting optimized printing conditions and rheological properties. This study shows the suitability of this material for 3D-printing via fused deposition modeling. The 3D-printed objects retain elasticity and SM when external force is applied, and the elastomeric character is quantified via mechanical testing. This work highlights the benefits of SH behavior as a design feature combatting inherent material weaknesses or insufficient adhesion at seams and layer junctions. DFT calculations confirmed the importance of ionic interactions and H-bonding in the SH process.

The flow-induced supramolecular arrangement, or band texture, present in water-soluble anisotropic films prepared from blend solutions of hydroxypropyl cellulose and organosolv lignin is locked via esterification with bio-based polycarboxylic acids. Subsequent to shear casting of the blend solutions, the chemical cross-linking with citric acid-based cross-linkers and a dimerized fatty acid yields water-insoluble, anisotropic films prone to swelling in water. The liquid crystalline networks are analyzed by means of polarized optical microscopy, tensile testing, Fourier transform infrared, and swelling experiments. Depending on the cross-linker, the dry “banded” films reach up to 3.5 GPa in tensile modulus, 80 MPa in tensile strength…

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 ink-extrusion of powders followed by sintering is an emerging additive manufacturing method capable of creating metallic microlattices. Here, we study the creation of hierarchically porous Fe or Ni scaffolds by 3D extrusion of 0/90° lattices from inks consisting of fine oxide powders (Fe2O3 or NiO, < 3 µm), coarse space-holder particles (CuSO4, < 45 µm) and a polymer binder within a solvent. After space-holder leaching and debinding of the lattices, a sintering step densifies the metallic Fe or Ni powders created by oxide reduction with H2, while maintaining the larger pores templated by the space-holder particles within the printed…

Titanium metal matrix composite microlattices are fabricated using 3D ink extrusion printing and sintering. The inks consist of TiH2+TiB2 or TiH2+TiC powder blends to form (i) Ti-TiB composites by dehydrogenation and in situ reaction of Ti + TiB2 to form Ti + TiB and (ii) Ti-TiC composites, where TiC remains stable during the sintering process. Rapid densification of the printed powder blend is achieved during pressureless sintering in vacuum at 1200 °C between 1 and 4 h, due to the small Ti particle size available from dehydrogenation of micron-sized TiH2. Near-full density Ti-TiB and Ti-TiC is achieved within individual lattice…

Cobalt-based superalloy microlattices were created via (i) three-dimensional-extrusion printing of inks containing a suspension of Co-, Ni- and W-oxide particles, (ii) H2-reduction of the oxides and sintering to a homogenous Co-Ni-W alloy, (iii) Al pack-cementation to deposit Al on the microlattice struts, followed by Al-homogenization. The resulting Co-(18–20)Ni-(5–6)W-(10–13)Al (at.%) microlattices, with 27–30% relative density and 350 μm diameter struts, display a peak in yield strength at 750°C, consistent with their γ/γ′ aged microstructure. Oxidation resistance is strongly improved compared to Al-free printed Co-Ni-W lattices, via the formation of an Al2O3 surface layer. However, the resulting Al depletion within the struts…

Here, a hybrid process for the fabrication of dehydrofluorinated PVDF (dPVDF) microfiltration (MF) membranes is presented. dPVDF was fabricated through the bulk modification of PVDF using ethylenediamine. To produce inks for direct ink writing (DIW), the dPVDF was dissolved in N,N-dimethyacetamide along with a pore-forming agent, poly(vinyl pyrrolidone) (PVP) (5–30 wt%, relative to dPVDF concentration). Membranes were produced by direct ink writing of the inks into continuous films – followed by non-solvent induced phase separation (NIPS). Attenuated total reflectance – Fourier transform infrared (ATR-FTIR) and Raman spectroscopies confirmed alkene moieties within the dPVDF polymer, resulting from the dehydrofluorination process. The…

Cobalt-based superalloy microlattices with γ/γ′ microstructure are manufactured by combining two additive methods: ink-extrusion 3D-printing and pack-cementation surface alloying. First, a microlattice green structure is 3D-printed at ambient temperature from inks comprised of Co3O4, NiO, and WO3 powders, an elastomeric binder and solvents. Organic removal followed by oxide reduction under Ar-5% H2, sintering and homogenization at 1250 °C lead to a metallic microlattice with dense struts with uniform γ (fcc)-Co–22Ni–8W (at.%) composition. Second, aluminum is deposited on the strut surfaces via pack-cementation at 1000 °C, diffused at 1300 °C through the strut volume to achieve a uniform composition (Co–20Ni–6W–10Al or…

3D ink-extrusion of powders followed by sintering is an emerging alternative to beam-based additive manufacturing, capable of creating 3D metallic objects from 1D-extruded microfilaments. Here, in situ synchrotron X-ray diffraction and tomography are combined to study the phase evolution, alloy formation and sinter-densification of Fe-20Ni-5Mo (at.%) microfilaments. The filaments are

Using 3D printing to manufacture shape memory polymers (SMPs) becomes popular, since the technique endows SMPs the ability to shape into desired structures according to their applications. Among various types of SMPs, epoxy-based shape memory polymer and their composites are known for their high modulus and strength. However, limited by their rheological behavior, it is still hard to prepare high-quality printable epoxy materials. Here, by carefully tuning of rheological properties, we can prepare printable ink showing good shape retention, excellent mechanical performances below and above the glass transition temperature of epoxy, as well as good shape memory effect. The prepared…

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…

The effect of varying the solids volume fraction of an aqueous clay paste suspension on its printability via an Additive Manufacturing (AM) or 3D printing technique, Direct Ink Writing (DIW) or material extrusion, has been studied. DIW is a cost-effective and straightforward fabrication technology suitable for adoption at a larger scale by the traditional ceramics industry and the creative community. The pastes were prepared with volume fraction of solids ranging from 25–57 vol%. Their rheological properties (storage modulus and apparent yield stress) were measured by dynamic oscillatory rheometry. The relationships between solids content, rheological behaviour and print parameters were evaluated. An…

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…

3D printing technologies allow control over the alignment of building blocks in synthetic materials, but compositional changes often require complex multimaterial printing steps. Here, 3D printable materials showing locally tunable mechanical properties are produced in a single printing step of Direct Ink Writing. These new inks consist of a polymer matrix bearing biocompatible photoreactive cinnamate derivatives and up to 30 wt% of anisotropic cellulose nanocrystals. The printed materials are mechanically versatile and can undergo further crosslinking upon illumination. When illuminating the material and controlling the irradiation doses, the Young’s moduli can be adjusted between 15 and 75 MPa. Moreover, spatially…

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…

Following the recent demonstration of the potential to direct ink write lyotropic blends of organosolv lignin (OSL) and hydroxypropyl cellulose (HPC), this study aims to optimize the formulations and direct ink writing parameters for fully bio-based lignin/HPC inks. A prescreening identifies the theoretical window of printability for different compositions for formulations based on OSL solutions of 45, 47.5, and 50% solid contents and OSL/HPC wt %/wt % ratios of 30/70, 40/60, and 50/50. Measurements of shear–viscosity and recovery behavior evidence the shear-thinning contribution of HPC and the viscosity recovery contribution of lignin. Shape fidelity, morphology, and mechanical properties of printed…

Owing to their ultralow thermal conductivity and open pore structure, silica aerogels are widely used in thermal insulation, catalysis, physics, environmental remediation, optical devices and hypervelocity particle capture. Thermal insulation is by far the largest market for silica aerogels, which are ideal materials when space is limited. One drawback of silica aerogels is their brittleness. Fibre reinforcement and binders can be used to overcome this for large-volume applications in building and industrial insulation, but their poor machinability, combined with the difficulty of precisely casting small objects, limits the miniaturization potential of silica aerogels. Additive manufacturing provides an alternative route to…

Combining recycling of paper wastes (WPs) with extrusion‐based additive manufacturing represents a sustainable route to cellular cellulose composites tailored for lightweight construction. Particularly, shear mixing of shredded WPs with an aqueous solution of a polymer binder like polyvinyl alcohol (PVA) yields aqueous pastes suitable for 3D printing. As a shear thinning additive, both WP and microfibrillated cellulose account for enhanced shear thinning and dimensional stability. Opposite to the formation of dense WP/PVA composites by melt extrusion, 3D printing of aqueous pastes produces cellular cellulose/PVA composites exhibiting hierarchical pore architectures. In spite of low densities around 0.8 g cm−3, high Young’s…

Several problems in science and engineering are characterized by the interaction between fluid flows and deformable structures. Due to their complex and multidisciplinary nature, these problems cannot normally be solved analytically and experiments are frequently of limited scope, so that numerical simulations represent the main analysis tool. Key to the advancement of numerical methods is the availability of experimental test cases for validation. This paper presents results of an experiment specifically designed for the validation of numerical methods for aeroelasticity and fluid-structure interaction problems. Flexible filaments of rectangular cross-section and various lengths were exposed to air flow of moderate Reynolds…

Thermal management is of importance to microelectronic industry. Owing to both excellent thermal conduction and electrical insulation, hexagonal boron nitride (BN) platelets are the widely-used thermal conductive fillers in polymers. Adding high content of BN can endow polymers high thermal conductivity, but in most cases, destroy the flexibility, failure strength as well as processability of the polymers significantly. Here, we report a multi-material 3D printing technique to prepare high thermal conductive epoxy based composites, by which BN platelets were assembled together in heat-conducting phase to form the dense, continuous thermal pathway. The BN platelets show excellent alignment along printing direction…

Cellulose is an attractive material resource for the fabrication of sustainable functional products, but its processing into structures with complex architecture and high cellulose content remains challenging. Such limitation has prevented cellulose‐based synthetic materials from reaching the level of structural control and mechanical properties observed in their biological counterparts, such as wood and plant tissues. To address this issue, a simple approach is reported to manufacture complex‐shaped cellulose‐based composites, in which the shaping capabilities of 3D printing technologies are combined with a wet densification process that increases the concentration of cellulose in the final printed material. Densification is achieved by…

In order to compare the influence of the manufacturing methods on the property of silicone samples, the latticed structure of sample are designed, the silicone material is prepared and the silicone sample are produced by 3D printing and injection molding respectively. Four performance indexes of latticed silicone parts including the error of line width, the error of quality, tensile strength at break and elongation at break are proposed and measured. A fuzzy comprehensive evaluation system for evaluating the optimal forming method of the parts is provided. The performance indexes are used as evaluation factors, and the importance degree of the…

This paper describes experiments carried out in a wind tunnel with three flexible silicone filaments (length to diameter ratio L/D = 50, 100, 150) hanging in crossflow in the range of reduced velocities of 7 < U* < 150 and at various attachment angles (0 ≤ α ≤ 90°) with respect to the flow direction. At low reduced velocities, due to the negligible bending stiffness, the filaments were statically reconfigured but remained mostly rectilinear along their lengths, except for the relatively small bent portion of the filaments close to the upstream fixed end. As the reduced velocity was further increased the filaments started vibrating, but in…

Increasing demands for optical anticounterfeiting technology require the development of versatile luminescent materials with tunable photoluminescence properties. Herein, a number of fluorescent carbon‐ and oxygen‐doped hexagonal boron nitride (denoted as BCNO) phosphors are found to offer a such high‐tech anticounterfeiting solution. These multicolor BCNO powders, developed in a two‐step process with controlled annealing and oxidation, feature rod‐like particle shape, with varied luminescence properties. Studies of the optical properties of BCNO, along with other characterization, provide insight into this underexplored material. Anticounterfeiting applications are demonstrated with printed patterns which are indistinguishable to the naked eye under visible light but become highly…

Recent advances have demonstrated the ability to 3D-print, via extrusion, solvent-based liquid materials (previously named 3D-Paints) which solidify nearly instantaneously upon deposition and contain a majority by volume of solid particulate material. In prior work, the dissolved polymer binder which enables this process is a high molecular weight biocompatible elastomer, poly(lactic-co-glycolic) acid (PLGA). We demonstrate in this study an expansion of this solvent-based 3D-Paint system to two additional, less-expensive, and less-specialized polymers, polystyrene (PS) and polyethylene oxide (PEO). The polymer binder used within the 3D-Paint was shown to significantly affect the as-printed and thermal postprocessing behavior of printed structures. This…

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.

Soft biological tissues such as skeletal muscle and brain white matter can be inhomogeneous and anisotropic due to the presence of fibers. Unlike biological tissue, phantoms with known microstructure and defined mechanical properties enable a quantitative assessment and systematic investigation of the influence of inhomogeneities on the nature of shear wave propagation. This study introduces a mathematical measure for the wave shape, which the authors call as the 1-Norm, to determine the conditions under which homogenization may be a valid approach. This is achieved through experimentation using the Magnetic Resonance Elastography technique on 3D printed inhomogeneous fiber phantoms as well…

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).

Additive manufacturing of high-entropy alloys combines the mechanical properties of this novel family of alloys with the geometrical freedom and complexity required by modern designs. Here, a non-beam approach to additive manufacturing of high-entropy alloys is developed based on 3D extrusion of inks containing a blend of oxide nanopowders (Co3O4 + Cr2O3 + Fe2O3 + NiO), followed by co-reduction to metals, inter-diffusion and sintering to near-full density CoCrFeNi in H2. A complex phase evolution path is observed by in-situ X-ray diffraction in extruded filaments when the oxide phases undergo reduction and the resulting metals inter-diffuse, ultimately forming face-centered-cubic equiatomic CoCrFeNi alloy. Linked to the phase evolution…

The use of nanoparticles within living systems is a growing field, but the long‐term effects of introducing nanoparticles to a biological system are unknown. If nanoparticles remain localized after in vivo implantation unanticipated side effects due to unknown biodistribution can be avoided. Unfortunately, stabilization and retention of nanoparticles frequently alters their function.1 In this work multiple hydrogel platforms are developed to look at long‐term localization of nanoparticle sensors with the goal of developing a sensor platform that will stabilize and localize the nanoparticles without altering their function. Two different hydrogel platforms are presented, one with a liquid core of sensors…

There is a growing interest in 3D printing to fabricate culture substrates; however, the surface properties of the scaffold remain pertinent to elicit targeted and expected cell responses. Traditional 2D polystyrene (PS) culture systems typically require surface functionalization (oxidation) to facilitate and encourage cell adhesion. Determining the surface properties which enhance protein adhesion from media and cellular extracellular matrix (ECM) production remains the first step to translating 2D PS systems to a 3D culture surface. Here we show that the presence of carbonyl groups to PS surfaces correlated well with successful adhesion of ECM proteins and sustaining ECM production of…

Flexible piezoelectric generators (PEGs) present a unique opportunity for renewable and sustainable energy harvesting. Here, we present a low-temperature and low-energy deposition method using solvent evaporation-assisted three-dimensional printing to deposit electroactive poly(vinylidene fluoride) (PVDF)-trifluoroethylene (TrFE) up to 19 structured layers. Visible-wavelength transmittance was above 92%, while ATR-FTIR spectroscopy showed little change in the electroactive phase fraction between layer depositions. Electroactivity from the fabricated PVDF-TrFE PEGs showed that a single structured layer gave the greatest output at 289.3 mV peak-to-peak voltage. This was proposed to be due to shear-induced polarization affording the alignment of the fluoropolymer dipoles without an electric field…

Ni-29Mn-21.5Ga (at. %) wires are fabricated via a combination of (i) extrusion of liquid inks containing a binder, solvents, and elemental Ni, Mn, and Ga powders and (ii) heat treatments to remove the polymer binder and to interdiffuse and sinter the powders. To study the microstructural evolution, sintering mechanisms, and grain growth in these wires, both ex situ metallography and in situ X-Ray tomography were conducted while sintering at 800–1050 °C for up to 4 h. After debinding, Ga-rich regions melt and induce transient liquid phase sintering of the surrounding Ni and Mn powders, resulting in localized swelling of the wires and…

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…

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…

Experiments were carried out to study the dynamics of hanging cantilever flexible filaments in air cross-flow. Thirteen flexible filaments of 0.61 mm diameter and lengths from 20 mm to 60 mm were tested with wind speeds in the range of 1–15 m/s, corresponding to Reynolds numbers of 25 

Random poly (vinyl chloride-co-butyl acrylate) and poly (vinyl chloride-co-2-ethylhexyl acrylate copolymers obtained by single electron transfer-degenerative chain transfer living radical polymerization (SET- DTLRP) are investigated as potential candidates for 3D Printing. The analysis of the rheological implications of 3D Printing process allows establishing the basic viscoelastic conditions that the samples should fulfil to be printable, avoiding the ‘trial and error’ procedure. The effect of temperature and acrylates concentration on the rheological properties and 3D printing feasibility is contemplated. Eventually, thermal degradation is also considered. It is demonstrated that the copolymers which contain butyl acrylate comonomer, instead of 2-ethylhexyl acrylate, give…

We report a novel method for developing gelatin-based phantom materials for transmission x-ray imaging with high stability at room temperature and tunable x-ray attenuation properties. This is achieved by efficiently cross-linking gelatin in a glycerin solution with only 10% water by volume and systematically decreasing their x-ray attenuation coefficients by doping with microbubbles that are originally designed to be used as lightweight additives for paints and crack fillers. For demonstration, we mimic breast glandular and adipose tissues by using such gelatin materials and also study the feasibility of 3D printing them based on the extrusion-based technique. Results from x-ray spectroscopy…

Freedom of design, customisation, automation, waste minimisation, reduced labour and building complex structures with cheaper materials are the main initiatives for developing 3D printed structures. The fresh properties of concrete are the most important aspects of a successful 3D printing. Concrete requires high workability for extrusion, optimum open time and high early strength in order to support the subsequent layers for 3D printing. Therefore, a mixture design that can satisfy these requirements is needed. Geopolymer concrete is a sustainable solution to traditional Portland cement-based concrete that uses waste materials. In addition, the controlled alkali-activation of geopolymer precursors in order to…

The development of in situ fabrication methods for the infrastructure required to support human life on the Moon is necessary due to the prohibitive cost of transporting large quantities of materials from the Earth. Cellular structures, consisting of a regular network (truss) of micro-struts with ∼500 μm diameters, suitable for bricks, blocks, panels, and other load-bearing structural elements for habitats and other infrastructure are created by direct-extrusion 3D-printing of liquid inks containing JSC-1A lunar regolith simulant powders, followed by sintering. The effects of sintering time, temperature, and atmosphere (air or hydrogen) on the microstructures, mechanical properties, and magnetic properties of…

Reconfigured flexible filaments exposed to steady fluid load were investigated using a novel non-contact optical technique to measure the normal fluid force due to the fluid loading on inclined cylinders for Reynolds numbers from 25 to 460: a range not covered in previous studies that is of relevance in drag reduction and energy harvesting applications. The ranges of the buoyancy number and the Cauchy number covered in the tests were 3.6 × 10^4 ≤ B ≤ 2.1 × 10^6 and 7.6 × 10^4 ≤ Ca ≤ 1.4 × 10^7. These newly generated data were then used to assess and extend…

Using an innovative, tissue-independent approach to decellularized tissue processing and biomaterial fabrication, the development of a series of “tissue papers” derived from native porcine tissues/organs (heart, kidney, liver, muscle), native bovine tissue/organ (ovary and uterus), and purified bovine Achilles tendon collagen as a control from decellularized extracellular matrix particle ink suspensions cast into molds is described. Each tissue paper type has distinct microstructural characteristics as well as physical and mechanical properties, is capable of absorbing up to 300% of its own weight in liquid, and remains mechanically robust (E = 1–18 MPa) when hydrated; permitting it to be cut, rolled,…

In this work, we report the synthesis, characterization and three-dimensional (3D) printing of self-healing gels. The gels are prepared by cross-linking benzaldehyde-functionalized poly(2-hydroxyethyl methacrylate) (PHEMA) with ethylenediamine (EDA) to form dynamic imine bonds. An immediate gelation was observed within seconds, followed by a full maturation, enabling time independent and stable printing. The self-healing gels showed 98% recovery from mechanical damages. To establish a printable window for our well-defined system, and to allow robust printability, we examined a broad number of ink formulations. To tune the rheology towards the formation of soft and extrudable, yet stable and self-supporting materials, we examined…

Here, we present a comprehensive approach for creating robust, elastic, designer Lunar and Martian regolith simulant (LRS and MRS, respectively) architectures using ambient condition, extrusion-based 3D-printing of regolith simulant inks. The LRS and MRS powders are characterized by distinct, highly inhomogeneous morphologies and sizes, where LRS powder particles are highly irregular and jagged and MRS powder particles are rough, but primarily rounded. The inks are synthesized via simple mixing of evaporant, surfactant, and plasticizer solvents, polylactic-co-glycolic acid (30% by solids volume), and regolith simulant powders (70% by solids volume). Both LRS and MRS inks exhibit similar rheological and 3D-printing characteristics,…

The demand for rapid and accurate fabrication of light-weight, biocompatible, and soft actuators in soft robotics has perused researchers to design and fabricate such products by rapid manufacturing techniques. The self-folding origami structure is a type of soft actuator that has applications in micro electro mechanical systems, soft electronics, and biomedical devices. 3-dimentional (3D) printing is a current manufacturing process that can be used for fabrication of involute soft self-folding products by means of shape memory polymer materials. This paper presents, for the first time, a method for developing a photo thermal self-folding soft actuator using a 3D bioplotter. Easily…

In present work, we fabricate large area, all flexible and microwaveable PDMS microfluidic reactor that is printed via 3D bioplotter system. The sacrificial microchannels are printed on Polydimethoxylane (PDMS) substrates by direct ink writing method using water soluble Pluronic F-127 ink and encapsulated between PDMS layers. The structure of micrometer sized channels is analyzed by optical and electron microscopy techniques. The fabricated flexible microfluidic reactors are utilized for acetylation of different amines under microwave irradiation to get acetylamides in shorter reaction time and good yields in Microwave Assisted Flow Organic Synthesis (MAFOS).

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…

Animal experiments help to progress and ensure safety of an increasing number of novel therapies, drug development and chemicals. Unfortunately, these also lead to major ethical concerns, costs and limited experimental capacity. We foresee a coercion of all these issues by implantation of well systems directly into vertebrate animals. Here, we used rapid prototyping to create wells with biomaterials to create a three-dimensional (3D) well-system that can be used in vitro and in vivo. First, the well sizes and numbers were adjusted for 3D cell culture and in vitro screening of molecules. Then, the functionality of the wells was evaluated…