Direct Ink Research Articles

Direct ink writing of customized polymeric structures embedded in a nano-silicate based supporting matrix

The increase in use of intricate structures for engineering applications has encouraged researchers to find new fabrication techniques. This work presents an innovative approach of embedded 3D printing, which allows fabrication of freeform structures by directly 3D printing inside a supporting matrix. The polymer ink solution was prepared by blending polylactic acid (PLA) and polypropylene carbonate (PPC) in 1,4-dioxane. Laponite RD was used to prepare the aqueous nano-silicate suspension, which exhibited yield stress and thixotropic properties due to its house-of-cards arrangement. Solidification of the 3D printed polymer ink occurred due to the hydrogen bonding between the oxygen atoms of dioxane molecules and the protons of water molecules. Particle image velocimetry study showed that the increasing nano-silicate concentration caused a reduction in yield region as a result of increasing yield stress. Dimensionless parameters (Oldroyd number and ratio of yield stress to hydrostatic pressure) for nano-silicate concentrations with values less than 1 were found to facilitate the nozzle movement without crevice formation, while the values greater than 1 were found to be unsuitable for printing. Different intricate structures such as tubular structures with varying geometry that mimic the native trachea, and a bifurcated tube were 3D printed as a proof-of-concept study. The proposed method introduced a novel approach by utilizing the solvent-water interaction capability to fabricate objects with overhanging geometry. This approach allows 3D printing of a wide variety of polymers by leveraging the miscibility between its corresponding solvent and supporting matrix.

3D Printable κ‐Carrageenan‐Based Granular Hydrogels

Abstractκ‐carrageenan, an algae‐extracted polysaccharide known for its emulsifying properties, is widely used in food and beauty products. Because of its abundance in nature, similarity to natural glycosaminoglycans, and biocompatibility, it is a promising alternative to animal gelatin for tissue engineering. Key to the more widespread use of κ‐carrageenan for biomedical applications is its processability, which is hampered by its temperature‐dependent rheological properties. Here, a κ‐carrageenan‐based ink is introduced that can be 3D printed at room temperature through direct ink writing (DIW). This is achieved by formulating κ‐carrageenan as microgels that are covalently crosslinked through a second network, resulting in double network granular hydrogels (DNGHs). These DNGHs can be stiffened to reach stiffnesses up to 0.9 MPa under tension and 1.1 MPa under compression through the addition of metal ions and glucose. The metal/glucose reinforcement also increases the work of fracture up to 1.1 MJ m−3, exceeding that of unmodified κ‐carrageenan DNGHs 50‐fold. The potential of the ink by room temperature 3D printing cm‐sized free‐standing load‐bearing structures is demonstrated. This ink is envisaged to be a well‐suited algae‐derived alternative for the animal‐based gelatin for tissue engineering and in food applications for example as soft confectionery products.

Development of a processing route for the fabrication of thin hierarchically porous copper self-standing structure using direct ink writing and sintering for electrochemical energy storage application

Development of a processing route for the fabrication of thin hierarchically porous copper self-standing structure using direct ink writing and sintering for electrochemical energy storage application

Tailoring the Thermoelectric Properties of 3D-Printed n-Type Bi1.7Sb0.3Te3 with Incorporated Edge-Oxidized Graphene.

Using three-dimensional (3D) printing technology to fabricate Bi2Te3-based thermoelectric (TE) generators opens a potential way to create shape-conformable devices capable of recovering waste heat from thermal energy sources with diverse surface morphologies. However, pores formed in 3D-printed Bi2Te3-based materials by the removal of the organic ink binder result in unsatisfactory performance compared to the bulk materials, which has limited the widespread application of the ink-based 3D printing process. Furthermore, managing the volatile Se element in the n-type materials poses significant technological challenges compared to the p-type counterparts, resulting in a scarcity of research on 3D printing of n-type Bi2Te3. Here, we synthesized edge-oxidized graphene (EOG)-incorporated Se-free n-type Bi1.7Sb0.3Te3 (BST) using a direct ink writing (DIW) process with a binder-free novel ink. The incorporated EOG provides connectivity between small BST grains separated by pores and induces a bimodal-like grain structure during the DIW and sintering process. The optimal EOG content of 0.1 wt % in 3D-printed n-type BST simultaneously achieved both carrier transport control and active phonon scattering, due to its unique microstructure. A maximum ZT of 0.71 was obtained in the 0.1 wt % EOG/BST materials at 448 K, comparable to commercial bulk n-type Bi2Te3-based materials. Further, a single-element device composed of the EOG-BST material exhibited a 2-fold improvement in performance compared to pure-BST. These results open a technological route for the application of 3D printing technology for ink-based TE materials.

Recycling catfish bone for additive manufacturing of silicone composite structures

As a notable commercial aquaculture species, channel catfish ( Ictalurus punctatus) in US faces challenges including the global market competition and enhanced feed costs. Since fish bone waste is a major source of calcium and hydroxyapatite, re-utilization gives birth to several advanced products in the development of animal feed, fertilizers, and nutrition supplements. Recent research findings introduce fish bone powder (FBP) reinforcement in Fused Deposition Modeling (FDM) of plastic composites. However, FBP so far has not been widely utilized for Direct Ink Writing (DIW) 3D printing of silicone composite. In this paper, catfish bone waste has been recycled and processed with a thermal procedure. FBP reinforced silicone composite structures have been developed and manufactured using low-viscosity DIW 3D printing. Morphological and chemical structures of FBPs were analyzed and compared before and after calcination. The rheological and mechanical characterization have indicated the potential of calcinated FBP in advancing the silicone composites. With 0%–50% weight percentages of FBP, composite samples can be designed to get any specified mechanical response (0.5–1.4 MPa in 50% tension strain and 150–550 N in 30% compression strain). The shape holding, overhang, and dimensional accuracy of FBP reinforced silicone composites in single (DIW) and dual (FDM + DIW) 3D printing processes have been demonstrated and summarized. With appropriate adjustments, this FBP-based 3D printing technology can be applied to byproduct recycling of all the US food-fish species, poultry, and livestock.

Self-powered strain sensing devices with wireless transmission: DIW-printed conductive hydrogel electrodes featuring stretchable and self-healing properties

With rapid advancements in health and human–computer interaction, wearable electronic skins (e-skins) designed for application on the human body provide a platform for real-time detection of physiological signals. Wearable strain sensors, integral functional units within e-skins, can be integrated with Internet of Things (IoT) technology to broaden the applications for human body monitoring. A significant challenge lies in the reliance of most existing wearable strain sensors on rigid external power supplies, limiting their practical flexibility. In this study, we present an innovative strategy to fabricate glutaraldehyde (GA)-poly(vinyl alcohol) (PVA)/cellulose nanocrystals (CNC)/Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) conductive hydrogels through multiple hydrogen bonding systems. Combining the advantageous rheological properties of the precursor solution and the high specific surface area after freeze–thaw cycling, we have created a self-powered sensing system prepared by large-area printing using direct ink writing (DIW) printing. The resulting conductive hydrogel exhibits commendable mechanical properties (411 KPa), impressive stretchability (580 %), and robust self-healing capabilities (>98.3 %). The strain sensor, derived from the conductive hydrogel, demonstrates a gauge factor (GF) of 2.5 within a stretching range of 0–580 %. Additionally, the resultant supercapacitor displays a peak energy density of 0.131 mWh/cm3 at a power density of 3.6 mW/cm3. Benefiting from its elevated strain response and remarkable power density features, this self-powered strain sensing system enables the real-time monitoring of human joint motion. The incorporation of a 5G transmission module enhances its capabilities for remote data monitoring, thereby contributing to the progress of wireless tracking technologies for self-powered electronic skin.

Considerable enhancement of nanothermites propagation through worm-like expansion of expandable graphite

Metastable intermolecular composites (MICs) are known for their high energy density, high burn rate, and low diffusion distance, and they have various applications in military and civilian equipment and tasks. However, the introduction of binders, which facilitate shaping, during the processing of MICs for practical applications can lead to a decrease in the energy release rate and an increase in the required ignition energy. Herein, we incorporated graphene nanoplatelets (GNPs), multi-walled carbon nanotubes (MWCNTs), and expandable graphite (EG) into 90- wt% Al/CuO nanothermites stick using simple extrusion-based direct ink writing to improve their overall performance. The high-temperature expansion characteristics and unique structure after expansion caused EG to perform an important role during Al/CuO nanothermites system combustion, which effectively promotes heat transfer and considerably increases the burn rate (81.6%) and pressure rising rate (103.0%). This study demonstrated EG as a low-cost and efficient combustion catalyst for MICs and introduced a simple approach to modulate the energy release rate, combustion pressure and semiconductor bridge (SCB) ignition performance of MICs through incorporation of small amounts of carbon materials.

Direct Ink Write 3D Printing of Fully Dense and Functionally Graded Liquid Metal Elastomer Foams

AbstractLiquid metal (LM) elastomer composites offer promising potential in soft robotics, wearable electronics, and human‐machine interfaces. Direct ink write (DIW) 3D printing offers a versatile manufacturing technique capable of precise control over LM microstructures, yet challenges such as interfilament void formation in multilayer structures impact material performance. Here, a DIW strategy is introduced to control both LM microstructure and material architecture. Investigating three key process parameters–nozzle height, extrusion rate, and nondimensionalized nozzle velocity–it is found that nozzle height and velocity predominantly influence filament geometry. The nozzle height primarily dictates the aspect ratio of the filament and the formation of voids. A threshold print height based on filament geometry is identified; below the height, significant surface roughness occurs, and above the ink fractures, which facilitates the creation of porous structures with tunable stiffness and programmable LM microstructure. These porous architectures exhibit reduced density and enhanced thermal conductivity compared to cast samples. When used as a dielectric in a soft capacitive sensor, they display high sensitivity (gauge factor = 9.0), as permittivity increases with compressive strain. These results demonstrate the capability to simultaneously manipulate LM microstructure and geometric architecture in LM elastomer composites through precise control of print parameters, while maintaining geometric fidelity in the printed design.

Direct ink writing of WC-Co composite with flexible green bodies

Direct ink writing of 3D WC-Co with conformable green bodies was achieved benefiting from the highly flexible WC-Co paste with high solid loading. Rheology properties of the paste, microstructure of the 3D structure was investigated. Organic-based paste of WC-8Co with a high solid content of 91 wt% were prepared, which exhibited shear thinning behavior and had a high storage modulus, two key parameters for ensuring the smooth printing. After secondary molding, 3D WC-Co green bodies with overhanging structure and no cracks were confirmed through secondary treatment of twisting or bending. Sound 3D structures with uniform and dense microstructure were obtained after debinding and sintering in vacuum. This work showed a facile route for the fabrication of 3D bone cemented carbides by direct ink writing with flexible green bodies.

ADDITIVE MANUFACTURING OF SYNTHETIC RUBBER INK WITH HIGH SOLID CONTENT REINFORCED BY NETWORKED SILICA

ABSTRACT Silica is a reinforcing filler commonly used in the production of environmentally friendly tires, because tires reinforced with silica have lower rolling resistance that translates into reduced energy consumption and improved fuel economy. However, achieving the optimal dispersion of silica within the rubber matrix is crucial for maximizing its reinforcing effects. In this study, a three-dimensionally networked silica (NS) was introduced in various amounts to rubber inks to improve their tensile strength and increase miscibility to enable their use in additive manufacturing. The results show that synthetic rubber ink with a high content of SBR (90%) and reinforced by NS possesses adequate viscosity for use in the direct ink write (DIW) process. NS was confirmed to have an impact on the rheological properties and printability of the rubber ink as well as improve the tensile strength of the printed parts. Different formulations were tested to study and facilitate the vulcanization process and identify the optimal curing conditions as well as the print parameters to use in DIW printing. The successful printing and vulcanization of various printed structures demonstrate the potential for using the developed printable ink in additive manufacturing. This study opens up new possibilities for creating rubber products (such as tire treads) with adequate flexibility and high tensile strength.

Construction and combustion behavior of horizontal two-dimension combustion networks of boron-metal oxides

In order to break through the top-down combustion mode brought by the traditional pillars, it is explored to explore the exploration of delay composition array construction in two-dimensional dimensions. In this study, B-CuO, B-Bi2O3, B-Fe2O3 sticks and combustion networks with good forming properties were prepared with the help of a micro-pen direct ink writing device by dispersing the above materials in DMF with boron and metal oxides as the main body of the charge and F2602 as the binder. The sticks were thermally ignited using a nichrome wire, and the flame propagation behaviors of the sticks with different formulations, spacings and heights were tracked with a high-speed camera, and a series of combustion networks were designed on the premise of not leaping into flames. Results show that the B-CuO stick has the fastest ignition speed level (19.71–29.02 mm ·s−1) at equivalence ratios of 1.0–4.0, followed by B-Bi2O3 (5.99–16.01 mm ·s−1) and B-Fe2O3 is the slowest (1.91–4.94 mm ·s−1). The sticks burned best at an equivalence ratio of 1.0–1.5. A variety of combustion networks were constructed on 50 × 50 mm glass slides by selecting B-CuO, B-Bi2O3, and B-Fe2O3 at the equivalence ratios of 1.0, 1.5, and 1.5, respectively, among which B-CuO had the shortest combustion time (5.17 s), the shortest total combustion network length (252 mm), and 400 mm network could be realized for B-Bi2O3. Construction and 19.85 s, and B-Fe2O3 can realize 608 mm network length and 130.7 s combustion time. Through these studies, the two-dimensional combustion network construction of boron-metal oxides was realized, which provides a new idea for the delay action in small size.

In-situ chemically synthesized Fe3O4/K-geopolymer composite with microwave absorbency for additive manufacturing

In this work, we utilized an in-situ chemical synthesis method to fabricate a Fe3O4/K-geopolymer (KGP) composite to be applied in a microwave absorbent field. This material, as a type of ceramic precursor, is highly expected to be a 3D printing material to prepare microwave absorbing components with complex shapes. The investigation results demonstrate that the material possesses a large effective microwave absorbing bandwidth of 3.7 GHz with the minimum reflection loss reducing to −12.2 dB when the generated Fe3O4 percent reaches 12 wt% in the KGP composite. This microwave absorbent performance can be attributed to a synergistic effect between the eddy current loss caused by the improved electrical conductivity of magnetic nanoparticles and the interfacial polarization effect from the geopolymer matrix and magnetic medium interface. Also, we used direct ink writing technology to print two-dimensional components with desirable patterns. Thickness-dependent wave absorption evaluation results confirmed a maximum reflection loss of −25.9 dB at 15.2 Hz was obtained from the printed sample containing 9.0 wt% Fe3O4 for a layer thickness of 10 mm, indicating that wave consumption effectiveness was determined by porous microstructures, magnetic loss of Fe3O4 nanoparticles as well as suitable impedance matching. The preparation method and synthesized material pave the way for integrated manufacturing of 3D printing components with microwave absorbing performance.

Investigating the effect of polymer additives on the rheology of SiC/clay paste for use in Direct Ink Writing method

AbstractIn this study, we investigated the impact of polyethylene glycol, sodium carboxymethyl cellulose, and polyvinyl alcohol on the rheological behavior, printability, and mechanical/physical properties of 3D‐printed scaffolds for high‐temperature applications using SiC/clay ceramic paste. Employing the Direct Ink Writing method, varying concentrations of each polymer (PEG: 2.5%–10% weight, CMC: .6%–1.8% weight, PVA: .25%–1% weight) were incorporated into the composition. The resulting SiC/clay paste, with adjusted additive content, was used to 3D‐print scaffold structures through Direct Ink Writing. Sintering of clay‐bonded SiC samples were carried out at 1300°C for 1 h in an ambient atmosphere. The research revealed that altering the additive amounts significantly influenced the rheological behavior, mechanical properties, and physical characteristics of the printed specimens. Notably, the ideal properties with additive concentrations (10% wt PEG, 1% wt PVA, and .6% CMC) were identified, providing the best outcomes in terms of printability and firing results. High density samples with 2.09, 1.93, and 1.79 g/cm3, high compression strength of 20.82, 14.5 and 12.53 MPa with 32.26%, 42.5%, and 52.63% open porosity for samples containing PVA, CMC, and PEG modifiers were obtained, respectively. Additionally, the study led to the development of a high solid loading printable paste with an 80% weight.

Properties of SiO2-Al2O3 refractories based on silica glass binder suspension and investigation of their printability using the Direct Ink Writing method

The SiO2-Al2O3 refractories and corresponding inks for 3D printing were prepared from silica glass binder suspensions and fused alumina with grain sizes of 75 and 240 μm. Phase analysis (XRD) and morphological studies (SEM) were conducted to investigate the influence of sintering temperature and Al2O3 content on the strength, porosity, and density of the refractories. Rheological studies (rotational viscometry) were carried out determine the effect of polyethylene glycol (PEG) and hydroxypropyl methylcellulose (HPMC) content on the flow behavior of the inks. It was established that firing refractories based on fused silica and fused alumina at 1500 and 1600 °C led to the formation of mullite and aluminosilicate melt on the surface of Al2O3 grains, enhancing the strength of the synthesized materials. Addition of PEG and HPMC to the ink composition was found to improve their rheological properties by increasing yield strength and promoting plastic flow. The ink demonstrated high printability and they are suitable for producing refractories using the Direct Ink Writing method.

Inkjet Printing of a Gate Insulator: Towards Fully Printable Organic Field Effect Transistor

In this work, a gate insulator poly (4-vinylphenol) (PVP) of an organic field effect transistor (OFET) was deposited using an inkjet printing technique, realized via a high printing resolution. Various parameters, including the molecular weight of PVP, printing direction, printing voltage, and drop frequency, were investigated to optimize OFET performance. Consequently, PVP with a smaller molecular weight of 11 k and a printing direction parallel to the channel, a printing voltage of 18 V, and a drop frequency of 10 kHz showed the best OFET performance. With a direct ink writing-printed organic semiconductor, this work paves the way for fully inkjet-printed OFETs.

Thermal Weathering of 3D-Printed Lunar Regolith Simulant Composites.

The production of lunar regolith composites is a promising venture, especially when enabled by extrusion-based additive manufacturing techniques such as direct ink write. However, both three-dimensional (3D) printing production and usage of polymer composites containing regolish on the lunar surface are challenges due to harsh environmental conditions such as severe thermal cycling. While thermal degradation in polymer composites under thermal cycling has been studied, there is limited understanding of how polymer properties impact the mechanical performance of lunar regolith composites when both printing and usage are carried out under extreme thermal conditions. Here, we aim to bridge that gap through the creation of composites containing a lunar Highlands regolith simulant suspended in an ultraviolet (UV) curable binder, which were printed at -30 °C and thermally cycled between weekly lunar day (127 °C) and weekly night (-190 °C) temperatures. We validate that thermal stresses cause both physical and chemical degradation since the regolith simulant composites become stiffer, more porous, and show yellowing after exposure to thermal cycling. Moreover, we indicate that chemical degradation mechanisms seem to compete with residual polymerization in certain formulations. We attribute this phenomenon to partial crystallization of monomer species during printing at -30 °C, resulting in low vinyl bond conversion during initial curing. The results presented here shed light on the intricate interplay between thermal stresses, uncured polymer properties, and degradation mechanisms, which can help guide future use cases of regolith composites for lunar infrastructure needs.

Evaluating the Piezoelectric Energy Harvesting Potential of 3D-Printed Graphene Prepared Using Direct Ink Writing and Fused Deposition Modelling.

This research aims to use energy harvested from conductive materials to power microelectronic components. The proposed method involves using vibration-based energy harvesting to increase the natural vibration frequency, reduce the need for battery replacement, and minimise chemical waste. Piezoelectric transduction, known for its high-power density and ease of application, has garnered significant attention. Additionally, graphene, a non-piezoelectric material, exhibits good piezoelectric properties. The research explores a novel method of printing graphene material using 3D printing, specifically Direct Ink Writing (DIW) and fused deposition modelling (FDM). Both simulation and experimental techniques were used to analyse energy harvesting. The experimental technique involved using the cantilever beam-based vibration energy harvesting method. The results showed that the DIW-derived 3D-printed prototype achieved a peak power output of 12.2 µW, surpassing the 6.4 µW output of the FDM-derived 3D-printed prototype. Furthermore, the simulation using COMSOL Multiphysics yielded a harvested output of 0.69 µV.

Direct Ink Writing of Highly Conductive and Strongly Adhesive PEDOT:PSS-EP Coatings for Antistatic Applications

As the information age progresses, the electronics industry is evolving towards smaller and more sophisticated products. However, electrostatic potentials easily penetrate these components, causing damage. This underscores the urgent need for materials with superior antistatic properties to safeguard electronic devices from such damage. Antistatic coatings typically rely on polymers as the primary material, enhanced with conductive fillers and additives to improve performance. Despite significant progress, these coatings still face challenges related to advanced processing technologies and the integration of electrical and mechanical properties. Among various conductive fillers, the conducting polymer PEDOT:PSS stands out for its exceptional conductivity, environmental stability, and long cycle life. Additionally, epoxy resin (EP) is widely utilized in polymer coatings due to its strong adhesion to diverse substrates during curing. Here, we develop highly conductive and strongly adhesive PEDOT:PSS inks by combining PEDOT:PSS with EP using a composite engineering approach. These inks are used to fabricate PEDOT:PSS coatings by direct ink writing (DIW). We systematically evaluate the DIW of PEDOT:PSS-EP coatings, which show high electrical conductivity (ranging from 0.59 ± 0.07 to 41.50 ± 3.26 S cm−1), strong adhesion (ranging from 15.84 ± 2.18 to 99.3 ± 9.06 kPa), and robust mechanical strength (8 MPa). Additionally, we examine the surface morphology, wettability, and hardness of the coatings with varying PEDOT:PSS content. The resultant coatings demonstrate significant potential for applications in antistatic protection, electromagnetic shielding, and other flexible electronic technologies.

Printable, stretchable metal-vapor-desorption layers for high-fidelity patterning in soft, freeform electronics

High-fidelity patterning of thin metal films on arbitrary soft substrates promises integrated circuits and devices that can significantly augment the morphological functionalities of freeform electronics. However, existing patterning methods that decisively rely on prefabricated rigid masks are severely incompatible with myriad surfaces. Here, we report printable, stretchable metal-vapor-desorption layers (s-MVDLs) that can enable high-fidelity patterning of thin metal films on freeform polymeric surfaces. The printed rubbery matrix with highly mobile chains effectively repels various metal vapors from the surface and inhibits their condensation, thereby allowing selective metal deposition. The s-MVDLs are printed by direct ink writing techniques, enabling customizable and scalable thin metal patterns ranging from the micrometer to millimeter scale with high fidelity. Furthermore, the superior stretchability and mechanical robustness of the s-MVDLs allow highly compliant deformation along the substrates, enabling the construction of unconventional circuits and devices on multi-curvature, non-developable, and stretchable surfaces.

Pneumatic Bellow Actuator with Embedded Sensor Using Conductive Carbon Grease.

The present work demonstrates the manufacturing process of a pneumatic bellow actuator with an embedded sensor, utilizing a novel manufacturing approach through the complete use of additive manufacturing techniques, such as direct ink writing (DIW) and traditional fused deposition modeling (FDM) methods. This study is innovative in its integration of a dielectric electroactive polymer (DEAP) structure with sensing electrodes made of conductive carbon grease (CCG), showcasing a unique application of a 3D-printed DEAP with CCG electrodes for combined DEAP sensing and pneumatic actuation. Initial experiments, supported by computational simulations, evaluated the distinct functionality of the DEAP sensor by itself under various pressure conditions. The findings revealed a significant change in capacitance with applied pressure, validating the sensor's performance. After sensor validation, an additive manufacturing process for embedding the DEAP structure into a soft pneumatic actuator was created, exhibiting the system's capability for dual sensing and actuation, as the embedded sensor effectively responded to applied actuation pressure. This dual functionality represents an advancement in soft actuators, especially in applications that require integrated and responsive actuation and sensing capabilities. This work also represents a preliminary step in the development of a 3D-printed dual-modality actuator (pneumatic and electrically activated DEAP) with embedded sensing.