3D printing encouraging desired in-situ polypyrrole seed-polymerization for ultra-high energy density supercapacitors

The tireless pursuit of supercapacitors with high energy density entails the parallel advancement of wellsuited electrode materials and elaborately engineered architectures.Polypyrrole(PPy)emerges as an exceedingly conductive polymer and a prospective pseudocapacitive materials for supercapacitors,yet the inferior cyclic stability and unpredictable polymerization patterns severely impede its real-world applicability.Here,for the first time,an innovative seed-induced in-situ polymerization assisted 3D printing strategy is proposed to fabricate PPy-reduced graphene oxide/poly(vinylidene difluoride-cohexafluoropropylene)(PVDF-HFP)(PPy-rGO/PH)electrodes with controllable polymerization behavior and exceptional areal mass loading.The preferred active sites uniformly pre-planted on the 3D-printed graphene substrates serve as reliable seeds to induce efficient polypyrrole deposition,achieving an impressive mass loading of 185.6 mg cm^(-2)(particularly 79.2 mg cm^(-2)for polypyrrole)and a superior areal capacitance of 25.2 F cm^(-2)at 2 mA cm^(-2)for a 12-layer electrode.In agreement with theses appealing features,an unprecedented areal energy density of 1.47 mW h cm^(-2)for a symmetrical device is registered,a rarely achieved value for other PPy/rGO-based supercapacitors.This work highlights a promising route to preparing high energy density energy storage modules for real-world applications.

Light-based 3D printing of stimulus-responsive hydrogels forminiature devices:recent progress and perspective

Miniature devices comprising stimulus-responsive hydrogels with high environmental adaptability are now considered competitive candidates in the fields of biomedicine,precise sensors,and tunable optics.Reliable and advanced fabricationmethods are critical formaximizing the application capabilities ofminiature devices.Light-based three-dimensional(3D)printing technology offers the advantages of a wide range of applicable materials,high processing accuracy,and strong 3D fabrication capability,which is suitable for the development of miniature devices with various functions.This paper summarizes and highlights the recent advances in light-based 3D-printed miniaturized devices,with a focus on the latest breakthroughs in lightbased fabrication technologies,smart stimulus-responsive hydrogels,and tunable miniature devices for the fields of miniature cargo manipulation,targeted drug and cell delivery,active scaffolds,environmental sensing,and optical imaging.Finally,the challenges in the transition of tunable miniaturized devices from the laboratory to practical engineering applications are presented.Future opportunities that will promote the development of tunable microdevices are elaborated,contributing to their improved understanding of these miniature devices and further realizing their practical applications in various fields.

Biomimetic 3D printing of composite structures with decreased cracking

The development of tissue engineering and regeneration research has created new platforms for bone transplantation.However,the preparation of scaffolds with good fiber integrity is challenging,because scaffolds prepared by traditional printing methods are prone to fiber cracking during solvent evaporation.Human skin has an excellent natural heat-management system,which helps to maintain a constant body temperature through perspiration or blood-vessel constriction.In this work,an electrohydrodynamic-jet 3D-printing method inspired by the thermal-management system of skin was developed.In this system,the evaporation of solvent in the printed fibers can be adjusted using the temperature-change rate of the substrate to prepare 3D structures with good structural integrity.To investigate the solvent evaporation and the interlayer bonding of the fibers,finite-element analysis simulations of a three-layer microscale structure were carried out.The results show that the solvent-evaporation path is from bottom to top,and the strain in the printed structure becomes smaller with a smaller temperaturechange rate.Experimental results verified the accuracy of these simulation results,and a variety of complex 3D structures with high aspect ratios were printed.Microscale cracks were reduced to the nanoscale by adjusting the temperature-change rate from 2.5 to 0.5℃s-1.Optimized process parameters were selected to prepare a tissue engineering scaffold with high integrity.It was confirmed that this printed scaffold had good biocompatibility and could be used for bone-tissue regeneration.This simple and flexible 3D-printing method can also help with the preparation of a wide range of micro-and nanostructured sensors and actuators.

Investigation on mechanical properties regulation of rock-like specimens based on 3D printing and similarity quantification

3D printing is widely adopted to quickly produce rock mass models with complex structures in batches,improving the consistency and repeatability of physical modeling.It is necessary to regulate the mechanical properties of 3D-printed specimens to make them proportionally similar to natural rocks.This study investigates mechanical properties of 3D-printed rock analogues prepared by furan resin-bonded silica sand particles.The mechanical property regulation of 3D-printed specimens is realized through quantifying its similarity to sandstone,so that analogous deformation characteristics and failure mode are acquired.Considering similarity conversion,uniaxial compressive strength,cohesion and stress–strain relationship curve of 3D-printed specimen are similar to those of sandstone.In the study ranges,the strength of 3D-printed specimen is positively correlated with the additive content,negatively correlated with the sand particle size,and first increases then decreases with the increase of curing temperature.The regulation scheme with optimal similarity quantification index,that is the sand type of 70/140,additive content of 2.5‰and curing temperature of 81.6℃,is determined for preparing 3D-printed sandstone analogues and models.The effectiveness of mechanical property regulation is proved through uniaxial compression contrast tests.This study provides a reference for preparing rock-like specimens and engineering models using 3D printing technology.

Digital light processing based multimaterial 3D printing:challenges,solutions and perspectives

Multimaterial(MM)3D printing shows great potential for application in metamaterials,flexible electronics,biomedical devices and robots,since it can seamlessly integrate distinctive materials into one printed structure.Among numerous MM 3D printing technologies,digital light processing(DLP)MM 3D printing is compatible with a wide range of materials from hydrogels to ceramics,and can print MM 3D structures with high resolution,high complexity and fast speed.This paper introduces the fundamental mechanisms of DLP 3D printing,and reviews the recent advances of DLP MM 3D printing technologies with emphasis on material switching methods and material contamination issues.It also summarizes a number of typical examples of DLP MM 3D printing systems developed in the past decade,and introduces their system structures,working principles,material switching methods,residual resin removal methods,printing steps,as well as the representative structures and applications.Finally,we provide perspectives on the directions of the further development of DLP MM 3D printing technology.

Extrusion 3D printing of carbon nanotube-assembled carbon aerogel nanocomposites with high electrical conductivity

Carbon nanotubes(CNTs)with high aspect ratio and excellent electrical conduction offer huge functional improvements for current carbon aerogels.However,there remains a major challenge for achieving the on-demand shaping of carbon aerogels with tailored micro-nano structural textures and geometric features.Herein,a facile extrusion 3D printing strategy has been proposed for fabricating CNT-assembled carbon(CNT/C)aerogel nanocomposites through the extrusion printing of pseudoplastic carbomer-based inks,in which the stable dispersion of CNT nanofibers has been achieved relying on the high viscosity of carbomer microgels.After extrusion printing,the chemical solidification through polymerizing RF sols enables 3D-printed aerogel nanocomposites to display high shape fidelity in macroscopic geometries.Benefiting from the micro-nano scale assembly of CNT nanofiber networks and carbon nanoparticle networks in composite phases,3D-printed CNT/C aerogels exhibit enhanced mechanical strength(fracture strength,0.79 MPa)and typical porous structure characteristics,including low density(0.220 g cm^(-3)),high surface area(298.4 m^(2)g^(-1)),and concentrated pore diameter distribution(~32.8nm).More importantly,CNT nanofibers provide an efficient electron transport pathway,imparting 3D-printed CNT/C aerogel composites with a high electrical conductivity of 1.49 S cm^(-1).Our work would offer feasible guidelines for the design and fabrication of shape-dominated functional materials by additive manufacturing.

Polar-coordinate line-projection light-curing continuous 3D printing for tubular structures

3D printing techniques offer an effective method in fabricating complex radially multi-material structures.However,it is challenging for complex and delicate radially multi-material model geometries without supporting structures,such as tissue vessels and tubular graft,among others.In this work,we tackle these challenges by developing a polar digital light processing technique which uses a rod as the printing platform.The 3D model fabrication is accomplished through line projection.The rotation and translation of the rod are synchronized to project and illuminate the photosensitive material volume.By controlling the distance between the rod and the printing window,we achieved the printing of tubular structures with a minimum wall thickness as thin as 50 micrometers.By controlling the width of fine slits at the printing window,we achieved the printing of structures with a minimum feature size of 10 micrometers.Our process accomplished the fabrication of thin-walled tubular graft structure with a thickness of only 100 micrometers and lengths of several centimeters within a timeframe of just 100 s.Additionally,it enables the printing of axial multi-material structures,thereby achieving adjustable mechanical strength.This method is conducive to rapid customization of tubular grafts and the manufacturing of tubular components in fields such as dentistry,aerospace,and more.

3D printing in space:from mechanical structures to living tissues

3D printing stands at the forefront of transforming space exploration,offering unprecedented on-demand and rapid manufacturing capabilities.It adeptly addresses challenges such as mass reduction,intricate component fabrication,and resource constraints.Despite the obstacles posed by microgravity and extreme environments,continual advancements underscore the pivotal role of 3D printing in aerospace science.Beyond its primary function of producing space structures,3D printing contributes significantly to progress in electronics,biomedicine,and resource optimization.This perspective delves into the technological advantages,environmental challenges,development status,and opportunities of 3D printing in space.Envisioning its crucial impact,we anticipate that 3D printing will unlock innovative solutions,reshape manufacturing practices,and foster self-sufficiency in future space endeavors.

3D printing of poly(ethyleneimine)-functionalized Mg-Al mixed metal oxide monoliths for direct air capture of CO_(2)

Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.

Effect of fractures on mechanical behavior of sand powder 3D printing rock analogue under triaxial compression

In practical engineering applications,rock mass are often found to be subjected to a triaxial stress state.Concurrently,defects like joints and fractures have a notable impact on the mechanical behavior of rock mass.Such defects are identified as crucial contributors to the failure and instability of the surrounding rock,subsequently impacting the engineering stability.The study aimed to investigate the impact of fracture geometry and confining pressure on the deformation,failure characteristics,and strength of specimens using sand powder 3D printing technology and conventional triaxial compression tests.The results indicate that the number of fractures present considerably influences the peak strength,axial peak strain and elastic modulus of the specimens.Confining pressure is an important factor affecting the failure pattern of the specimen,under which the specimen is more prone to shear failure,but the initiation,expansion and penetration processes of secondary cracks in different fracture specimens are different.This study confirmed the feasibility of using sand powder 3D printing specimens as soft rock analogs for triaxial compression research.The insights from this research are deemed essential for a deeper understanding of the mechanical behavior of fractured surrounding rocks when under triaxial stress state.

3D Printing of Periodic Porous Metamaterials for Tunable Electromagnetic Shielding Across Broad Frequencies

The new-generation electronic components require a balance between electromagnetic interference shielding efficiency and open structure factors such as ventilation and heat dissipation.In addition,realizing the tunable shielding of porous shields over a wide range of wavelengths is even more challenging.In this study,the well-prepared thermoplastic polyurethane/carbon nanotubes composites were used to fabricate the novel periodic porous flexible metamaterials using fused deposition modeling 3D printing.Particularly,the investigation focuses on optimization of pore geometry,size,dislocation configuration and material thickness,thus establishing a clear correlation between structural parameters and shielding property.Both experimental and simulation results have validated the superior shielding performance of hexagon derived honeycomb structure over other designs,and proposed the failure shielding size(D_(f)≈λ/8-λ/5)and critical inclined angle(θf≈43°-48°),which could be used as new benchmarks for tunable electromagnetic shielding.In addition,the proper regulation of the material thickness could remarkably enhance the maximum shielding capability(85-95 dB)and absorption coefficient A(over 0.83).The final innovative design of the porous shielding box also exhibits good shielding effectiveness across a broad frequency range(over 2.4 GHz),opening up novel pathways for individualized and diversified shielding solutions.

Rapid fabrication of modular 3D paper-basedmicrofluidic chips using projection-based 3D printing

Paper-based microchips have different advantages,such as better biocompatibility,simple production,and easy handling,making them promising candidates for clinical diagnosis and other fields.This study describes amethod developed to fabricate modular three-dimensional(3D)paper-based microfluidic chips based on projection-based 3D printing(PBP)technology.A series of two-dimensional(2D)paper-based microfluidic modules was designed and fabricated.After evaluating the effect of exposure time on the accuracy of the flow channel,the resolution of this channel was experimentally analyzed.Furthermore,several 3D paper-based microfluidic chips were assembled based on the 2D ones using different methods,with good channel connectivity.Scaffold-based 2D and hydrogel-based 3D cell culture systems based on 3D paper-based microfluidic chips were verified to be feasible.Furthermore,by combining extrusion 3D bioprinting technology and the proposed 3D paper-based microfluidic chips,multiorgan microfluidic chips were established by directly printing 3D hydrogel structures on 3D paperbased microfluidic chips,confirming that the prepared modular 3D paper-based microfluidic chip is potentially applicable in various biomedical applications.

Method of fabricating artificial rock specimens based on extrusion free forming(EFF)3D printing

Three-dimensional(3D)printing technology has been widely used to create artificial rock samples in rock mechanics.While 3D printing can create complex fractures,the material still lacks sufficient similarity to natural rock.Extrusion free forming(EFF)is a 3D printing technique that uses clay as the printing material and cures the specimens through high-temperature sintering.In this study,we attempted to use the EFF technology to fabricate artificial rock specimens.The results show the physico-mechanical properties of the specimens are significantly affected by the sintering temperature,while the nozzle diameter and layer thickness also have a certain impact.The specimens are primarily composed of SiO_(2),with mineral compositions similar to that of natural rocks.The density,uniaxial compressive strength(UCS),elastic modulus,and tensile strength of the printed specimens fall in the range of 1.65–2.54 g/cm3,16.46–50.49 MPa,2.17–13.35 GPa,and 0.82–17.18 MPa,respectively.It is capable of simulating different types of rocks,especially mudstone,sandstone,limestone,and gneiss.However,the simulation of hard rocks with UCS exceeding 50 MPa still requires validation.

Cookie Baking Process Optimization and Quality Analysis Based on Food 3D Printing

In order to obtain better quality cookies, food 3D printing technology was employed to prepare cookies. The texture, color, deformation, moisture content, and temperature of the cookie as evaluation indicators, the influences of baking process parameters, such as baking time, surface heating temperature and bottom heating temperature, on the quality of the cookie were studied to optimize the baking process parameters. The results showed that the baking process parameters had obvious effects on the texture, color, deformation, moisture content, and temperature of the cookie. All of the roasting surface heating temperature, bottom heating temperature and baking time had positive influences on the hardness, crunchiness, crispiness, and the total color difference(ΔE) of the cookie. When the heating temperatures of the surfac and bottom increased, the diameter and thickness deformation rate of the cookie increased. However,with the extension of baking time, the diameter and thickness deformation rate of the cookie first increased and then decreased. With the surface heating temperature of 180 ℃, the bottom heating temperature of 150 ℃, and baking time of 15 min, the cookie was crisp and moderate with moderate deformation and uniform color. There was no burnt phenomenon with the desired quality. Research results provided a theoretical basis for cookie manufactory based on food 3D printing technology.

Prospects of 3D Printing Technology in Dental Medicine

With the continuous advancement of technology,the application of 3D printing technology in the field of dental medicine is becoming increasingly widespread.This article aims to explore the current applications and future potential of 3D printing technology in dental medicine and to analyze its benefits and challenges.It first introduces the current state of 3D printing technology in dental implants,crowns,bridges,orthodontics,and maxillofacial surgery.It then discusses the potential applications of 3D printing technology in oral tissue engineering,drug delivery systems,personalized dental prosthetics,and surgical planning.Finally,it analyzes the benefits of 3D printing technology in dental medicine,such as improving treatment accuracy and patient comfort,and shortening treatment times,while also highlighting the challenges faced,such as costs,material choices,and technical limitations.This article aims to provide a reference for professionals in the field of dental medicine and to promote the further application and development of 3D printing technology in this area.

3D‑Printed Carbon‑Based Conformal Electromagnetic Interference Shielding Module for Integrated Electronics

Electromagnetic interference shielding(EMI SE)modules are the core com-ponent of modern electronics.However,the tra-ditional metal-based SE modules always take up indispensable three-dimensional space inside electronics,posing a major obstacle to the integra-tion of electronics.The innovation of integrating 3D-printed conformal shielding(c-SE)modules with packaging materials onto core electronics offers infinite possibilities to satisfy ideal SE func-tion without occupying additional space.Herein,the 3D printable carbon-based inks with various proportions of graphene and carbon nanotube nanoparticles are well-formulated by manipulating their rheological peculiarity.Accordingly,the free-constructed architectures with arbitrarily-customized structure and multifunctionality are created via 3D printing.In particular,the SE performance of 3D-printed frame is up to 61.4 dB,simultaneously accompanied with an ultralight architecture of 0.076 g cm^(-3) and a superhigh specific shielding of 802.4 dB cm3 g^(-1).Moreover,as a proof-of-concept,the 3D-printed c-SE module is in situ integrated into core electronics,successfully replacing the traditional metal-based module to afford multiple functions for electromagnetic compatibility and thermal dissipa-tion.Thus,this scientific innovation completely makes up the blank for assembling carbon-based c-SE modules and sheds a brilliant light on developing the next generation of high-performance shielding materials with arbitrarily-customized structure for integrated electronics.

Challenges and Opportunities in Preserving Key Structural Features of 3D-Printed Metal/Covalent Organic Framework

Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.

Engineering Nano/Microscale Chiral Self‑Assembly in 3D Printed Constructs

Helical hierarchy found in biomolecules like cellulose,chitin,and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms.This study advances the integration of helical/chiral assembly and 3D printing technology,providing precise spatial control over chiral nano/microstructures of rod-shaped colloidal nanoparticles in intricate geometries.We designed reactive chiral inks based on cellulose nanocrystal(CNC)suspensions and acrylamide monomers,enabling the chiral assembly at nano/microscale,beyond the resolution seen in printed materials.We employed a range of complementary techniques including Orthogonal Superposition rheometry and in situ rheo-optic measurements under steady shear rate conditions.These techniques help us to understand the nature of the nonlinear flow behavior of the chiral inks,and directly probe the flow-induced microstructural dynamics and phase transitions at constant shear rates,as well as their post-flow relaxation.Furthermore,we analyzed the photo-curing process to identify key parameters affecting gelation kinetics and structural integrity of the printed object within the supporting bath.These insights into the interplay between the chiral inks self-assembly dynamics,3D printing flow kinematics and photopolymerization kinetics provide a roadmap to direct the out-of-equilibrium arrangement of CNC particles in the 3D printed filaments,ranging from uniform nematic to 3D concentric chiral structures with controlled pitch length,as well as random orientation of chiral domains.Our biomimetic approach can pave the way for the creation of materials with superior mechanical properties or programable photonic responses that arise from 3D nano/microstructure and can be translated into larger scale 3D printed designs.

Development and characterization of 3D-printed electroconductive pHEMA-co-MAA NP-laden hydrogels for tissue engineering

Tissue engineering(TE)continues to be widely explored as a potential solution to meet critical clinical needs for diseased tissue replacement and tissue regeneration.In this study,we developed a poly(2-hydroxyethyl methacrylate-co-methacrylic acid)(pHEMA-co-MAA)based hydrogel loaded with newly synthesized conductive poly(3,4-ethylene-dioxythiophene)(PEDOT)and polypyrrole(PPy)nanoparticles(NPs),and subsequently processed these hydrogels into tissue engineered constructs via three-dimensional(3D)printing.The presence of the NPs was critical as they altered the rheological properties during printing.However,all samples exhibited suitable shear thinning properties,allowing for the development of an optimized processing window for 3D printing.Samples were 3D printed into pre-determined disk-shaped configurations of 2 and 10 mm in height and diameter,respectively.We observed that the NPs disrupted the gel crosslinking efficiencies,leading to shorter degradation times and compressive mechanical properties ranging between 450 and 550 kPa.The conductivity of the printed hydrogels increased along with the NP concentration to(5.10±0.37)×10^(−7)S/cm.In vitro studies with cortical astrocyte cell cultures demonstrated that exposure to the pHEMA-co-MAA NP hydrogels yielded high cellular viability and proliferation rates.Finally,hydrogel antimicrobial studies with staphylococcus epidermidis bacteria revealed that the developed hydrogels affected bacterial growth.Taken together,these materials show promise for various TE strategies.

Process,Material,and Regulatory Considerations for 3D Printed Medical Devices and Tissue Constructs

Three-dimensional(3D)printing is a highly automated platform that facilitates material deposition in a layer-by-layer approach to fabricate pre-defined 3D complex structures on demand.It is a highly promising technique for the fabrication of personalized medical devices or even patient-specific tissue constructs.Each type of 3D printing technique has its unique advantages and limitations,and the selection of a suitable 3D printing technique is highly dependent on its intended application.In this review paper,we present and highlight some of the critical processes(printing parameters,build orientation,build location,and support structures),material(batch-to-batch consistency,recycling,protein adsorption,biocompatibility,and degradation properties),and regulatory considerations(sterility and mechanical properties)for 3D printing of personalized medical devices.The goal of this review paper is to provide the readers with a good understanding of the various key considerations(process,material,and regulatory)in 3D printing,which are critical for the fabrication of improved patient-specific 3D printed medical devices and tissue constructs.