Three‐Dimensional Printing of Multifunctional Nanocomposites: Manufacturing Techniques and Applications

The integration of nanotechnology into three‐dimensional printing (3DP) offers huge potential and opportunities for the manufacturing of 3D engineered materials exhibiting optimized properties and multifunctionality. The literature relating to different 3DP techniques used to fabricate 3D structures at the macro‐ and microscale made of nanocomposite materials is reviewed here. The current state‐of‐the‐art fabrication methods, their main characteristics (e.g., resolutions, advantages, limitations), the process parameters, and materials requirements are discussed. A comprehensive review is carried out on the use of metal‐ and carbon‐based nanomaterials incorporated into polymers or hydrogels for the manufacturing of 3D structures, mostly at the microscale, using different 3D‐printing techniques. Several methods, including but not limited to micro‐stereolithography, extrusion‐based direct‐write technologies, inkjet‐printing techniques, and popular powder‐bed technology, are discussed. Various examples of 3D nanocomposite macro‐ and microstructures manufactured using different 3D‐printing technologies for a wide range of domains such as microelectromechanical systems (MEMS), lab‐on‐a‐chip, microfluidics, engineered materials and composites, microelectronics, tissue engineering, and biosystems are reviewed. Parallel advances on materials and techniques are still required in order to employ the full potential of 3D printing of multifunctional nanocomposites.     

Printing Polymer Nanocomposites and Composites in Three Dimensions

Recent advances in materials science and three‐dimensional (3D) printing hold great promises to conceive new classes of multifunctional materials and components for functional devices and products. Various functionalities (e.g., mechanical, electrical, and thermal properties, magnetism) can be offered by the nano‐ and micro‐reinforcements to the non‐functional pure printing materials for the realization of advanced materials and innovative systems. In addition, the ability to print 3D structures in a layer‐by‐layer manner enables manufacturing of highly‐customized complex features and allows an efficient control over the properties of fabricated structures. Here, the authors present a brief overview mainly over the latest progresses in 3D printing of multifunctional polymer nanocomposites and microfiber‐reinforced composites including the benefits, limitations, and potential applications. Only those 3D printing techniques that are compatible with polymer nanocomposites and composites, that is, materials that have already been used as printing materials, are introduced. The very hot topic of 3D printing of thermoplastic composites featuring continuous microfibers is also briefly introduced.     

高分子3D打印材料和打印工艺

3D打印技术亦称为增材制造,是基于三维数学模型数据,通过连续的物理层叠加,逐层增加材料来生成三维实体的技术。3D打印技术与传统材料加工技术相比有许多突出的优势,吸引了国内外工业界、投资界、学术界、新闻媒体和社会公众的热切关注。目前制约3D打印技术发展的因素主要有两个:打印工艺和打印材料。高分子聚合物在3D打印材料中占据主要地位。介绍了当前3D打印常用的高分子材料(热塑性高分子和光敏树脂)和与之相适应的打印工艺(FDM、SLS、SLA、Polyjet等),并对它们的特性和优缺点进行了评述,讨论了这些3D打印材料和工艺的开发面临的问题和挑战。     

3D printing of smart materials: A review on recent progresses in 4D printing

ABSTRACT

Additive manufacturing (AM), commonly known as three-dimensional (3D) printing or rapid prototyping, has been introduced since the late 1980s. Although a considerable amount of progress has been made in this field, there is still a lot of research work to be done in order to overcome the various challenges remained. Recently, one of the actively researched areas lies in the additive manufacturing of smart materials and structures. Smart materials are those materials that have the ability to change their shape or properties under the influence of external stimuli. With the introduction of smart materials, the AM-fabricated components are able to alter their shape or properties over time (the 4th dimension) as a response to the applied external stimuli. Hence, this gives rise to a new term called ‘4D printing’ to include the structural reconfiguration over time. In this paper, recent major progresses in 4D printing are reviewed, including 3D printing of enhanced smart nanocomposites, shape memory alloys, shape memory polymers, actuators for soft robotics, self-evolving structures, anti-counterfeiting system, active origami and controlled sequential folding, and some results from our ongoing research. In addition, some research activities on 4D bio-printing are included, followed by discussions on the challenges, applications, research directions and future trends of 4D printing.     

Development of Bioimplants with 2D, 3D,and 4D Additive Manufacturing Materials

Over the past 30 years, additive manufacturing (AM) has developed rapidly and has demonstrated great potential in biomedical applications. AM is a materials-oriented manufacturing technology, since the solidification mechanism, architecture resolution, post-treatment process, and functional application are based on the materials to be printed. However, 3D printable materials are still quite limited for the fabrication of bioimplants. In this work, 2D/3D AM materials for bioimplants are reviewed. Furthermore, inspired by Tai Chi, a simple yet novel soft/rigid hybrid 4D AM concept is advanced to develop complex and dynamic biological structures in the human body based on 4D printing hybrid ceramic precursor/ceramic materials that were previously developed by our group. With the development of multi-material printing technology, the development of bioimplants and soft/rigid hybrid biological structures with 2D/3D/4D AM materials can be anticipated.     

A New 3D Printing Strategy by Harnessing Deformation,Instability, and Fracture of Viscoelastic Inks

Direct ink writing (DIW) has demonstrated great potential as a multimaterial multifunctional fabrication method in areas as diverse as electronics, structural materials, tissue engineering, and soft robotics. During DIW, viscoelastic inks are extruded out of a 3D printer's nozzle as printed fibers, which are deposited into patterns when the nozzle moves. Hence, the resolution of printed fibers is commonly limited by the nozzle's diameter, and the printed pattern is limited by the motion paths. These limits have severely hampered innovations and applications of DIW 3D printing. Here, a new strategy to exceed the limits of DIW 3D printing by harnessing deformation, instability, and fracture of viscoelastic inks is reported. It is shown that a single nozzle can print fibers with resolution much finer than the nozzle diameter by stretching the extruded ink, and print various thickened or curved patterns with straight nozzle motions by accumulating the ink. A quantitative phase diagram is constructed to rationally select parameters for the new strategy. Further, applications including structures with tunable stiffening, 3D structures with gradient and programmable swelling properties, all printed with a single nozzle are demonstrated. The current work demonstrates that the mechanics of inks plays a critical role in developing 3D printing technology.     

3D Printing of Ultralight Biomimetic Hierarchical Graphene Materials with Exceptional Stiffness and Resilience

Biological materials with hierarchical architectures (e.g., a macroscopic hollow structure and a microscopic cellular structure) offer unique inspiration for designing and manufacturing advanced biomimetic materials with outstanding mechanical performance and low density. Most conventional biomimetic materials only benefit from bioinspired architecture at a single length scale (e.g., microscopic material structure), which largely limits the mechanical performance of the resulting materials. There exists great potential to maxime the mechanical performance of biomimetic materials by leveraging a bioinspired hierarchical structure. An ink‐based three‐dimensional (3D) printing strategy to manufacture an ultralight biomimetic hierarchical graphene material (BHGMs) with exceptionally high stiffness and resilience is demonstrated. By simultaneously engineering 3D‐printed macroscopic hollow structures and constructing an ice‐crystal‐induced cellular microstructure, BHGMs can achieve ultrahigh elasticity and stability at compressive strains up to 95%. Multiscale finite element analyses indicate that the hierarchical structures of BHGMs effectively reduce the macroscopic strain and transform the microscopic compressive deformation into the rotation and bending of the interconnected graphene flakes. This 3D printing strategy demonstrates the great potential that exists for the assembly of other functional materials into hierarchical cellular structures for various applications where high stiffness and resilience at low density are simultaneously required.     

Colloidal Nanosurfactants for 3D Conformal Printing of 2D van der Waals Materials

Printing techniques using nanomaterials have emerged as a versatile tool for fast prototyping and potentially large-scale manufacturing of functional devices. Surfactants play a significant role in many printing processes due to their ability to reduce interfacial tension between ink solvents and nanoparticles and thus improve ink colloidal stability. Here, a colloidal graphene quantum dot (GQD)-based nanosurfactant is reported to stabilize various types of 2D materials in aqueous inks. In particular, a graphene ink with superior colloidal stability is demonstrated by GQD nanosurfactants via the π–π stacking interaction, leading to the printing of multiple high-resolution patterns on various substrates using a single printing pass. It is found that nanosurfactants can significantly improve the mechanical stability of the printed graphene films compared with those of conventional molecular surfactant, as evidenced by 100 taping, 100 scratching, and 1000 bending cycles. Additionally, the printed composite film exhibits improved photoconductance using UV light with 400 nm wavelength, arising from excitation across the nanosurfactant bandgap. Taking advantage of the 3D conformal aerosol jet printing technique, a series of UV sensors of heterogeneous structures are directly printed on 2D flat and 3D spherical substrates, demonstrating the potential of manufacturing geometrically versatile devices based on nanosurfactant inks.     

Hybrid 3D Printing of Soft Electronics

Hybrid 3D printing is a new method for producing soft electronics that combines direct ink writing of conductive and dielectric elastomeric materials with automated pick‐and‐place of surface mount electronic components within an integrated additive manufacturing platform. Using this approach, insulating matrix and conductive electrode inks are directly printed in specific layouts. Passive and active electrical components are then integrated to produce the desired electronic circuitry by using an empty nozzle (in vacuum‐on mode) to pick up individual components, place them onto the substrate, and then deposit them (in vacuum‐off mode) in the desired location. The components are then interconnected via printed conductive traces to yield soft electronic devices that may find potential application in wearable electronics, soft robotics, and biomedical devices.     

人体植入医用材料的3D打印技术研究进展

3D打印技术是一种与传统制备方式完全不同的新兴技术,是基于三维数学模型,通过逐层增加材料来实现成型的技术。3D打印技术在个性化设计以及复杂结构产品制备方面具有独特的优势,在人体植入物的结构设计和制造领域具有巨大潜力和研究价值,吸引了国内外工业界、医学界和社会媒体的广泛关注。目前制约该技术发展的主要因素是可打印材料种类有限。综述了几种人体植入医用材料及其3D打印成型技术,如骨支架、心脏血管支架以及药物定向运输材料的3D打印制备技术,并分析了以上技术各自的特点。最后结合各种3D打印成型技术的特点以及几个应用案例,对3D打印在人体植入物医学领域的发展进行了展望。     

Progress in 3D Printing of Carbon Materials for Energy‐Related Applications

The additive‐manufacturing (AM) technique, known as three‐dimensional (3D) printing, has attracted much attention in industry and academia in recent years. 3D printing has been developed for a variety of applications. Printable inks are the most important component for 3D printing, and are related to the materials, the printing method, and the structures of the final 3D‐printed products. Carbon materials, due to their good chemical stability and versatile nanostructure, have been widely used in 3D printing for different applications. Good inks are mainly based on volatile solutions having carbon materials as fillers such as graphene oxide (GO), carbon nanotubes (CNT), carbon blacks, and solvent, as well as polymers and other additives. Studies of carbon materials in 3D printing, especially GO‐based materials, have been extensively reported for energy‐related applications. In these circumstances, understanding the very recent developments of 3D‐printed carbon materials and their extended applications to address energy‐related challenges and bring new concepts for material designs are becoming urgent and important. Here, recent developments in 3D printing of emerging devices for energy‐related applications are reviewed, including energy‐storage applications, electronic circuits, and thermal‐energy applications at high temperature. To close, a conclusion and outlook are provided, pointing out future designs and developments of 3D‐printing technology based on carbon materials for energy‐related applications and beyond.     

Patterning of Nanoparticle‐Based Aerogels and Xerogels by Inkjet Printing

Nanoparticle‐based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface‐to‐volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle‐based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle‐based aerogel‐ or xerogel‐coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle‐based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectro‐electrochemical measurements are recorded to investigate the charge–carrier mobility within these 3D semiconductor‐based xerogel networks.     

Rapid Open‐Air Digital Light 3D Printing of Thermoplastic Polymer

3D printing has witnessed a new era in which highly complexed customized products become reality. Realizing its ultimate potential requires simultaneous attainment of both printing speed and product versatility. Among various printing techniques, digital light processing (DLP) stands out in its high speed but is limited to intractable light curable thermosets. Thermoplastic polymers, despite their reprocessibility that allows more options for further manipulation, are restricted to intrinsically slow printing methods such as fused deposition modeling. Extending DLP to thermoplastics is highly desirable, but is challenging due to the need to reach rapid liquid–solid separation during the printing process. Here, a successful attempt at DLP printing of thermoplastic polymers is reported, realized by controlling two competing kinetic processes (polymerization and polymer dissolution) simultaneously occurring during printing. With a selected monomer, 4‐acryloylmorpholine (ACMO), printing of thermoplastic 3D scaffolds is demonstrated, which can be further converted into various materials/devices utilizing its unique water‐soluble characteristic. The ultralow viscosity of ACMO, along with surface oxygen inhibition, allows rapid liquid flow toward high‐speed open‐air printing. The process simplicity, enabling mechanism, and material versatility broaden the scope of 3D printing in constructing functional 3D devices including reconfigurable antenna, shape‐shifting structures, and microfluidics.     

3D printing technology and its impact on Chinese manufacturing

For both developed and developing countries, manufacturing plays a crucial role in international competition. There is a growing consensus that 3D printing (3DP) technologies will revolutionise the development of global manufacturing. Although considerable research has previously been conducted to define the technological and economic benefits of 3DP on global manufacturing, minimal research has linked 3DP with Chinese manufacturing (CM). Therefore, to address this research gap and to investigate 3DP’s potential impact on alleviating CM’s development issues, this paper explores the definition, characteristics and mainstream technologies of 3DP, presents the current situation and the main problems of CM, and analyses the potential impact of 3DP on the development of CM. Then, this study introduces the current 3DP promotion and industrialisation situation in China as well as the issues with promoting 3DP in CM.     

Electrohydrodynamic 3D Printing of Aqueous Solutions

Among the various electrohydrodynamic (EHD) processing techniques, electrowriting (EW) produces the most complex 3D structures. Aqueous solution EW similarly retains the potential for additive manufacturing well-resolved 3D structures, while providing new opportunities for processing biologically derived polymers and eschewing organic solvents. However, research on aqueous-based EHD processing is still limited. To summarize the field and advocate for increased use of aqueous bio-based materials, this review summarizes the most significant contributions of aqueous solution processing. Special emphasis has been placed on understanding the effects of different printing parameters, the prospects for 3D processing new materials, and future challenges.     

Associative Liquid-In-Liquid 3D Printing Techniques for Freeform Fabrication of Soft Matter

Shaping soft materials into prescribed 3D complex designs has been challenging yet feasible using various 3D printing technologies. For a broader range of soft matters to be printable, liquid-in-liquid 3D printing techniques have emerged in which an ink phase is printed into 3D constructs within a bath. Most of the attention in this field has been focused on using a support bath with favorable rheology (i.e., shear-thinning behavior) which limits the selection of materials, impeding the broad application of such techniques. However, a growing body of work has begun to leverage the interaction or association of the two involved phases (specifically at the liquid–liquid interface) to fabricate complex constructs from a myriad of soft materials with practical structural, mechanical, optical, magnetic, and communicative properties. This review article has provided an overview of the studies on such associative liquid-in-liquid 3D printing techniques along with their fundamentals, underlying mechanisms, various characterization techniques used for ensuring the structural stability, and practical properties of prints. Also, the future paths with the potential applications are discussed.     

Laws of 4D Printing

Three-dimensional (3D) printing is an additive manufacturing process. Accordingly, four-dimensional (4D) printing is a manufacturing process that involves multiple research fields. 4D printing conserves the general attributes of 3D printing (such as material waste reduction, and elimination of molds, dies, and machining) and further enables the fourth dimension of products to provide intelligent behavior over time. This intelligent behavior is encoded (usually by an inverse mathematical problem) into stimuli-responsive multi-materials during printing, and is enabled by stimuli after printing. The main difference between 3D- and 4D-printed structures is the presence of one additional dimension, which provides for smart evolution over time. However, currently there is no general formula for modeling and predicting this additional dimension. Herein, by starting from fundamentals, we derive and validate a general bi-exponential formula with a particular format that can model the time-dependent behavior of nearly all 4D (hydro-, photochemical-, photothermal-, solvent-, pH-, moisture-, electrochemical-, electrothermal-, ultrasound-, etc. responsive) structures. We show that two types of time constants are needed to capture the correct time-dependent behavior of 4D multi-materials. We introduce the concept of mismatch-driven stress at the interface of active and passive materials in 4D multi-material structures, leading to one of the two time constants. We develop and extract the other time constant from our unified model of time-dependent behavior of nearly all stimuli-responsive materials. Our results starting from the most fundamental concepts and ending with governing equations can serve as general design principles for future research in the field of 4D printing, where time-dependent behaviors should be properly understood, modeled, and predicted.     

Evolution of 3D Printing Methods and Materials for Electrochemical Energy Storage

Additive manufacturing has revolutionized the building of materials, and 3D-printing has become a useful tool for complex electrode assembly for batteries and supercapacitors. The field initially grew from extrusion-based methods and quickly evolved to photopolymerization printing, while supercapacitor technologies less sensitive to solvents more often involved material jetting processes. The need to develop higher-resolution multimaterial printers is borne out in the performance data of recent 3D printed electrochemical energy storage devices. Underpinning every part of a 3D-printable battery are the printing method and the feed material. These influence material purity, printing fidelity, accuracy, complexity, and the ability to form conductive, ceramic, or solvent-stable materials. The future of 3D-printable batteries and electrochemical energy storage devices is reliant on materials and printing methods that are co-operatively informed by device design. Herein, the material and method requirements in 3D-printable batteries and supercapacitors are addressed and requirements for the future of the field are outlined by linking existing performance limitations to requirements for printable energy-storage materials, casings, and direct printing of electrodes and electrolytes. A guide to materials and printing method choice best suited for alternative-form-factor energy-storage devices to be designed and integrated into the devices they power is thus provided.     

Recent Advances on 3D Printing Technique for Thermal‐Related Applications

Advances in ink formulation and printing techniques make producing material systems with new and versatile characteristics and functionalities possible. Additive manufacturing or 3D printing enables fabricating complex structures at a faster production rate using different types of materials for various applications. Recently, 3D printing methods are being studied for thermal‐related applications. In this paper, the authors review recent progress of materials and printing techniques for thermal application devices using composite materials.

     

Role of porosity defects in metal 3D printing: Formation mechanisms,impacts on properties and mitigation strategies

Metal 3D printing (3DP), a state-of-the-art manufacturing technology that brings the potential to fabricate complex structures at low cost and reduced energy consumption, has been extensively adopted in various industries. However, the porosity defects inherited from the printing process can significantly impede the mechanical properties and weaken the performance of as-printed components, potentially challenging this approach's reliability and reproducibility. The advancement of detection techniques currently opens up a more intuitive and deeper study of porosity defects. Given that, this review systematically states the 'restriction role' of porosity defects in metal 3DP by generalizing the detailed information on porosity defects, including their characterizations, formation and migration mechanisms, and their impacts on the performance of printed parts. Furthermore, feasible porosity mitigation measures are discussed to inspire more advanced methodologies for the next generation of metal 3DP.