Mechanical Assembly of Thermo‐Responsive Polymer‐Based Untethered Shape‐Morphing Structures

Shape‐morphing robotic structures can provide innovative approaches for various applications ranging from soft robotics to flexible electronics. However, the programmed deformation of direct‐3D printed polymer‐based structures cannot be separated from their subsequent conventional shape‐programming process. This work aims to simplify the fabrication process and demonstrates a rapid and adaptable approach for building stimulus‐responsive polymer‐based shape‐morphing structures of any shape. This is accomplished through mechanically assembling a set of identical self‐bending units in different patterns to form morphing structures using auxiliary hard connectors. A self‐bending unit fabricated by a 3D printing method can be actuated upon heating without the need for tethered power sources and is able to transform from a flat shape to a bending shape. This enables the assembled morphing‐structure to achieve the programmed integral shape without the need for a shape‐programming process. Differently assembled morphing structures used as independent robotic mechanisms are sequentially demonstrated with applications in biomimetic morphing structures, grasping mechanisms, and responsive electrical devices. This proposed approach based on a mechanical assembling method paves the way for rapid and simple prototyping of stimulus‐responsive polymer‐based shape‐morphing structures with arbitrary architectures for a variety of applications in deployable structures, bionic mechanisms, robotics, and flexible electronics.     

Direct Printing of Thermal Management Device Using Low‐Cost Composite Ink

This work presents a new method for fabricating thermal devices, such as heat sinks, using a 3D printing technique and lightweight composite ink. The method focuses on formulating composite inks with desired properties and direct ink writing for manufacturing. The ink undergoes two phases: phase one uses low viscosity epoxy to provide viscoelastic properties and phase two provides the fillers consisting of carbon fiber and graphite nanoplatelets to provide high thermal conductivity and structural properties. By combining these functional materials, 3D structures with a high thermal conductivity (≈2 W m⁻¹ K⁻¹) are printed for thermal management applications with the storage modulus of 3000 MPa and a density only 1.24 g cm⁻³. The results show that by carefully tailoring functional properties of the ink, net‐shape multifunctional structures can be directly printed for thermal management device applications, such as heat sinks.     

3D printing dielectric elastomers for advanced functional structures: A mini-review

Three-dimensional (3D) printed bionic products play an important role in intelligent robotics, microelectronics, and polymers. The printing and manufacturing process of 3D printers is conducive to obtaining soft structures that meet specific requirements, and saves time and cost. Soft intelligent robotics, an emerging research field, has always been developed based on soft materials and actuators with their biological properties. This article reviews the current understanding of 3D bioprinting technologies for dielectric elastomers (DEs), DE actuators (DEAs) and soft robots, such as inkjet, extrusion, laser-induced and stereolithography bioprinting. 3D printers for fabricating soft materials are presented and classified. The approaches to exploit 3D bioprinters for DEs/DEAs are as follows: (1) 3D printing DEAs utilize ionic hydrogel–elastomer hybrids that are analogous to human muscles, and the DEAs usually have flexible structures and large deformations with multiple functionalities. (2) An electrohydrodynamic (EHD) 3D printer confers high printing resolution and high production efficiency, which offers advantages such as full automation and flexible design. The optimal printing conditions are mainly determined by the effects of printing voltages and ink properties, which are related to the formation of the liquid cone and the printed line width. Furthermore, the advantages of 3D bioprinting technologies have accelerated their development and applications.     

4D printing of polyurethane paint-based composites

ABSTRACT

In recent studies, polyurethane has shown multiple properties that make it an excellent candidate material in 4D printing. In this study, we present a simple and inexpensive additive method to print waterborne polyurethane paint-based composites by adding carboxymethyl cellulose (CMC) and silicon oxide (SiO₂) nanoparticles to the paint. The first function of CMC and SiO₂ is to improve rheological properties of the polyurethane paint for making a printable precursor, which improves the printing resolution and enhances additive manufacturability. Second, the composite precursors improve the curing rate of the polyurethane paint without changing its inherited shape memory properties. Third, the printed composite parts shown enhanced mechanical strength compared with that of the parts printed with pure polyurethane. Finally, the 3D printed polyurethane-CMC and SiO₂ parts exhibit time-resolved shape transformation upon heat stimulation. To the best of our knowledge, this is the first study of using the polyurethane paint as the precursor for 4D printing, which would open new possibilities in future applications in biomedical engineering, soft robotics and so on.     

Modified commercial UV curable elastomers for passive 4D printing

ABSTRACT

Conventional 4D printing technologies are realized by combining 3D printing with soft active materials such as shape memory polymers (SMPs) and hydrogels. However, the intrinsic material property limitations make the SMP or hydrogel-based 4D printing unsuitable to fabricate the actuators that need to exhibit fast-response, reversible actuations. Instead, pneumatic actuations have been widely adopted by the soft robotics community to achieve fast-response, reversible actuations, and many efforts have been made to apply the pneumatic actuation to 3D printed structures to realize passive 4D printing with fast-response, reversible actuation. However, the 3D printing of soft actuators/robots heavily relies on the commercially available UV curable elastomers the break strains of which are not suf?cient for certain applications which require larger elastic deformation. In this paper, we present two simple approaches to tune the mechanical properties such as stretchability, stiffness, and durability of the commercially available UV curable elastomers by adding: (i) mono-acrylate based linear chain builder; (ii) urethane diacrylate-based crosslinker. Material property characterizations have been performed to investigate the effects of adding the two additives on the stretchability, stiffness, mechanical repeatability as well as viscosity. Demonstrations of fully printed robotic finger, grippers, and highly deformable 3D lattice structure are also presented.     

Direct ink writing of chopped carbon fibers reinforced polymer-derived SiC composites with low shrinkage and high strength

The chopped carbon fiber reinforced SiC (C_f/SiC) composite has been regarded as one of the excellent high-temperature structural materials for applications in aerospace and military fields. This paper presented a novel printing strategy using direct ink writing (DIW) of chopped fibers reinforced polymer-derived ceramics (PDCs) with polymer infiltration and pyrolysis (PIP) process for the fabrication of C_f/SiC composites with high strength and low shrinkage. Five types of PDCs printing inks with different C_f contents were prepared, their rheological properties and alignment of carbon fiber in the printing filament were studied. The 3D scaffold structures and bending test samples of C_f/SiC composites were fabricated with different C_f contents. The results found that the C_f/SiC composite with 30 wt% C_f content has high bending strength (～ 7.09 MPa) and negligible linear shrinkage (～ 0.48%). After the PIP process, the defects on the C_f/SiC composite structures were sufficiently filled, and the bending strength of C_f/SiC composite can reach up to about 100 MPa, which was about 30 times greater than that of the pure SiC matrix without C_f. This work demonstrated that the printed C_f/SiC composites by using this method is beneficial to the development of the precision and complex high-temperature structural members.     

Printing conductive layers using waterless offset technology considering the influences of the low-viscosity polymer inks and the rubber blankets

This study describes the application of conductive polymer inks onto PET foils by the waterless offset printing technique. Commercially available conductive polymer inks were employed, which exhibit significantly lower viscosities than conventional offset printing inks. The main focus was put on the influence of the rubber blanket, which covers the blanket cylinder of the offset printing unit, on the morphology and electrical properties of the printed conductive polymer layers. Since film splitting occurs between substrate and rubber blanket, the latter affects the amount of ink which is transferred by the printing process. The wet film thickness of the printed material was determined for different rubber blanket specifications and inking rates. In addition, the resistivity of the printed conductive polymer layer was measured after flue-curing of the samples. Further, the electrical performance on corona-treated and untreated PET substrate foils was compared.     

Experimental study of polymeric stent fabrication using homemade 3D printing system

Biodegradable polymeric stents have received extensive attention due to the high efficiency in interventional therapy. Fabrication of well‐defined polymeric stents still poses a significant fabrication challenge. This study aims to investigate the feasibility of using a homemade three‐dimensional (3D) printing system to directly print customized polymeric stents. In the proposed system, a rotating shaft with controllable temperature and rotating speed has been integrated into a fused deposition modeling‐based 3D printing system to support the printed stents stably in situ. In addition, the effects of operating conditions including the rotating speed, printing temperature, printing speed, and step distance on the dimensions of the 3D printed stents have been investigated. Furthermore, orthogonal experiments have been designed and performed to comprehensively explore the significance of each processing parameter. Finally, based on the obtained knowledge, polymeric stents with various structures have been successfully 3D printed using the homemade 3D printing system with relatively high shape fidelity. POLYM. ENG. SCI., 59:1122–1131 2019. © 2019 Society of Plastics Engineers     

Selective Laser Sintering 3D Printing: A Way to Construct 3D Electrically Conductive Segregated Network in Polymer Matrix

Selective laser sintering (SLS), which can directly turn 3D models into real objects, is employed to prepare the flexible thermoplastic polyurethane (TPU) conductor using self‐made carbon nanotubes (CNTs) wrapped TPU powders. The SLS printing, as a shear‐free and free‐flowing processing without compacting, provides a unique approach to construct conductive segregated networks of CNTs in the polymer matrix. The electrical conductivity for the SLS processed TPU/CNTs composite has a lower percolation threshold of 0.2 wt% and reaches ≈10⁻¹ S m⁻¹ at 1 wt% CNTs content, which is seven orders of magnitude higher than that of conventional injection‐molded TPU/CNTs composites at the same CNTs content. The 3D printed TPU/CNTs specimen can maintain good flexibility and durability, even after repeated bending for 1000 cycles, the electrical resistance can keep at a nearly constant value. The flexible conductive TPU/CNTs composite with complicated structures and shapes like porous piezoresistors can be easily obtained by this approach.     

Tough thiourethane thermoplastics for fused filament fabrication

Fused filament fabrication (FFF) is the most common form of additive manufacturing. Most FFF materials are variants of commercially available engineering plastics. Their performance when printed can widely vary, thus there is an increasing volume of research on alternative materials with thermal and mechanical performance optimized for FFF. In this work, thiol–isocyanate polymerization is used for the development of a one‐pot synthesis for polythiourethane thermoplastics for tough three‐dimensional (3D) printing applications. The thiol–isocyanate reaction mechanism allows for rapid polymer synthesis with minimal byproduct formation and few limitations on reaction conditions. The resulting elastomer has high toughness and a low melting point, making it favorable for use as a 3D printing filament. The elastomer outperforms commercial filaments in tension when printed. Considering the rapid advancement of additive manufacturing and the limitations of many engineering polymers with the 3D printing process, these results are encouraging for the development of bespoke 3D printing thermoplastics. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45574.     

Preparation and mechanical performance of SiCw/geopolymer composites through direct ink writing

Traditional geopolymer structures benefit from the durability, irradiation resistance, and environmental friendliness, but their brittleness limits their applications where repeated, impactive strains are imparted. This situation may be alleviated if complex structures with tunable geometry can be fabricated, for example, through 3D printing based on direct ink writing (DIW). In this research, SiC whisker/geopolymer (SiC_w/GP) composites were fabricated by the DIW for the first time. The rheological behaviors of the SiC_w/GP inks and the fracture behaviors of the printed samples were explored. The modified printing inks exhibited non-Newtonian fluid behavior (shear-thinning). Subsequently, a series of lightweight architected structures were fabricated, and they revealed how reinforcement and architecture of the printed structures could influence both the strength and toughness of the SiC_w/GP composites.     

A review of 3D printed porous ceramics

Three-dimensional (3D) printing of ceramics has gained widespread attentions in recent years. Many excellent reviews have reported the printing of ceramics. However, most of them focus on printing of dense ceramics or general ceramic aspects, there is no systematical review about 3D printing of porous ceramics. In this review paper, the 3D printing technologies for fabricating of porous ceramic parts are introduced, including binder jetting, selective laser sintering, direct ink writing, stereolithography, laminated object manufacturing, and indirect 3D printing processes. The techniques to fabricate hierarchical porous ceramics by integrating 3D printing with one or more conventional porous ceramics fabrication approaches are reviewed. The main properties of porous ceramics such as pore size, porosity, and compressive strength are discussed. The emerging applications of 3D printed porous ceramics are presented with a focus on the booming application in bone tissue engineering. Finally, summary and a perspective on the future research directions for 3D printed porous ceramics are provided.     

Review on Three-Dimensionally Emulated Fiber-Embedded Lactic Acid Polymer Composites: Opportunities in Engineering Sector

The proficiency to three-dimensional (3D) interweaves engineering complex structures enables component engineering with heterogeneous geometries, attributing mechanically robust lightweight cellular structures. 3D printing proffers versatile contingencies toward the single-step engineering of near-net heterogeneous 3D structure for engineering application. For enhancing the current spectrum of 3D printing technologies and rising concern toward environmental issues, 3D printing of bioactive polylactic acid is extensively exploited owing to its biodegradability and renewable aspects. Synchronously, curiosity for 3D printed composites through fiber infusion has led to the configuration of high-performance composites with augmented mechanical, physical, and chemical attributes, paving its way for wide-array engineering applications.     

Direct ink writing of hierarchical porous ultra-high temperature ceramics (ZrB2)

An approach to producing hierarchical multi-scale porous ultra-high temperature ceramics (zirconium diboride, ZrB₂) using 3D printing has been developed. Porous ceramic filaments can be 3D printed via Direct Ink Writing (DIW) (paste extrusion). Millimeter scale porosity is created by the 3D printed scaffold filaments. We introduce 20-micron-scale porosity into the scaffold filaments with the addition of oil to produce capillary suspension paste inks. Micron-scale porosity is also developed by partial sintering of the ceramic. The rheological (flow) properties of the capillary suspension paste inks suitable for printing by extrusion through the needle of the 3D printer have been characterized. The samples are strengthened by partial sintering at high temperatures. Complex-shaped components can be printed and sintered into crack-free components, but distortion during drying and sintering lead to poor shape and tolerance control. X-ray tomography is used to characterize the internal structure of the printed components. Printed test bars measured in 4-point bend testing exhibit high strength to density ratio. Such materials potentially have applications as insulation near very high-temperature surfaces in aerospace applications.     

Suture Fiber Reinforcement of a 3D Printed Gelatin Scaffold for Its Potential Application in Soft Tissue Engineering

Gelatin has excellent biological properties, but its poor physical properties are a major obstacle to its use as a biomaterial ink. These disadvantages not only worsen the printability of gelatin biomaterial ink, but also reduce the dimensional stability of its 3D scaffolds and limit its application in the tissue engineering field. Herein, biodegradable suture fibers were added into a gelatin biomaterial ink to improve the printability, mechanical strength, and dimensional stability of the 3D printed scaffolds. The suture fiber reinforced gelatin 3D scaffolds were fabricated using the thermo-responsive properties of gelatin under optimized 3D printing conditions (−10 °C cryogenic plate, 40–80 kPa pneumatic pressure, and 9 mm/s printing speed), and were crosslinked using EDC/NHS to maintain their 3D structures. Scanning electron microscopy images revealed that the morphologies of the 3D printed scaffolds maintained their 3D structure after crosslinking. The addition of 0.5% (w/v) of suture fibers increased the printing accuracy of the 3D printed scaffolds to 97%. The suture fibers also increased the mechanical strength of the 3D printed scaffolds by up to 6-fold, and the degradation rate could be controlled by the suture fiber content. In in vitro cell studies, DNA assay results showed that human dermal fibroblasts’ proliferation rate of a 3D printed scaffold containing 0.5% suture fiber was 10% higher than that of a 3D printed scaffold without suture fibers after 14 days of culture. Interestingly, the supplement of suture fibers into gelatin biomaterial ink was able to minimize the cell-mediated contraction of the cell cultured 3D scaffolds over the cell culture period. These results show that advanced biomaterial inks can be developed by supplementing biodegradable fibers to improve the poor physical properties of natural polymer-based biomaterial inks.     

Inkjet printing of polyvinyl alcohol multilayers for additive manufacturing applications

Here we demonstrate that inkjet printing technology is capable of producing polyvinyl alcohol (PVOH) multilayer structures. PVOH water‐based inks were formulated with the addition of additives such as humectant and pigments. The intrinsic properties of the inks, such as surface tension, rheological behavior, pH, wetting, and time stability were investigated. The ink's surface tension was in the range 30–40 mN/m. All formulated inks displayed a pseudoplastic (non‐Newtonian shear thinning and thixotropic) behavior at low‐shear rates and a Newtonian behavior at high‐shear rates; were neutral solutions (pH7) and demonstrated a good time stability. A proprietary 3D inkjet printing system was utilized to print polymer multilayer structures. The morphology, surface profile, and the thickness uniformity of inkjet printed multilayers were evaluated by optical microscopy and FT‐IR microscopy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43572.     

Novel interconnected nanochannel hydroxyapatite ceramics: synthesis,microstructure, and permeability

Uniform interconnected micro/nanoporous ceramics with good mechanical properties hold universal applications in biomedical and engineering fields. Herein, using hydroxyapatite (HAP) microtubes as the raw material instead of traditional particles, a novel interconnected nanochannel hydroxyapatite ceramic was fabricated successfully through one-step microwave sintering method without the addition of pore generators. The tubular structure of the HAP microtubes remains even after microwave sintering, which endows the ceramic with uniform interconnected nanochannels and 3-D porous structure. The HAP microtube nanochannel ceramic has a narrow pore size distribution from 400 nm to 600 nm, and exhibits well permeability, high adsorption/desorption ability. The porosity is about 30%, the HAP microtube nanochannel ceramic can be totally dyed by methylene blue within several minutes, and the blue dye can be desorbed completely in 45 min by ultrasonic vibration. In addition, due to the one-dimensional structure of the HAP microtubes, the HAP microtube nanochannel ceramic has smaller shrinkage, bigger porosity, and better toughness than the control sample fabricated by nanoparticles. Base on the uniform interconnected nanochannel structure, well permeability, high adsorption/desorption ability, the HAP microtube nanochannel ceramic fabricated here may be a promising candidate for many applications in biomedical engineering, environmental engineering, and energy engineering.     

3D polymer composite filament development from post-consumer polypropylene and disposable chopstick fillers

This study focused on the development of three-dimensional (3D) polymer composite filament made of disposable chopstick (DC) and post-consumer polypropylene (PPP). The PPP/DC composite parts were printed via fused filament fabrication (FFF) process. The effect of the printing temperature and different DC fiber content on the properties of the 3D printed parts were investigated. The printing temperature of 200–220°C was suitable for these filaments because the printing temperature did not show any thermal degradation, as proven by thermogravimetric analysis. Furthermore, the thermal stability of the 3D filament increased with DC content. The chemical modification with sodium hydroxide (NaOH) was carried out on DC to remove the unwanted organic components by showing changes in peak intensity in the Fourier transform infrared analysis. Moreover, the melt flow index of the composite filaments decreased with increasing of the DC content and caused the composites' viscosity increased. The results show that the optimum printing temperature of 210°C would reduce the warping and gave better tensile properties to the 3D printed parts. Nevertheless, the tensile strength and elongation at break of the 3D printed PPP/DC parts reduced as the DC content increased because the presence of some air gap and fiber pull out on the fracture surface of 3D printed parts, which are in line with the results observed from scanning electron microscopy. However, the tensile strength and elongation at break percentage of all 3D printed PPP/DC composite parts were higher in comparison with the 3D parts printed by commercial wood plastic composite filament.     

Fabrication of ultra-fine nanostructures using edge transfer printing

The exploration of new methods and techniques for application in diverse fields, such as photonics, microfluidics, biotechnology and flexible electronics is of increasing scientific and technical interest for multiple uses over distance of 10-100 nm. This article discusses edge transfer printing--a series of unconventional methods derived from soft lithography for nanofabrication. It possesses the advantages of easy fabrication, low-cost and great serviceability. In this paper, we show how to produce exposed edges and use various materials for edge transfer printing, while nanoskiving, nanotransfer edge printing and tunable cracking for nanogaps are introduced. Besides this, different functional materials, such as metals, inorganic semiconductors and polymers, as well as localised heating and charge patterning, are described here as unconventional "inks" for printing. Edge transfer printing, which can effectively produce sub-100 nm scale ultra-fine structures, has broad applications, including metallic nanowires as nanoelectrodes, semiconductor nanowires for chemical sensors, heterostructures of organic semiconductors, plasmonic devices and so forth.     

Temperature-dependent Raman investigation of rolled up InGaAs/GaAs microtubes

Large arrays of multifunctional rolled-up semiconductors can be mass-produced with precisely controlled size and composition, making them of great technological interest for micro- and nano-scale device fabrication. The microtube behavior at different temperatures is a key factor towards further engineering their functionality, as well as for characterizing strain, defects, and temperature-dependent properties of the structures. For this purpose, we probe optical phonons of GaAs/InGaAs rolled-up microtubes using Raman spectroscopy on defect-rich (faulty) and defect-free microtubes. The microtubes are fabricated by selectively etching an AlAs sacrificial layer in order to release the strained InGaAs/GaAs bilayer, all grown by molecular beam epitaxy. Pristine microtubes show homogeneity of the GaAs and InGaAs peak positions and intensities along the tube, which indicates a defect-free rolling up process, while for a cone-like microtube, a downward shift of the GaAs LO phonon peak along the cone is observed. Formation of other type of defects, including partially unfolded microtubes, can also be related to a high Raman intensity of the TO phonon in GaAs. We argue that the appearance of the TO phonon mode is a consequence of further relaxation of the selection rules due to the defects on the tubes, which makes this phonon useful for failure detection/prediction in such rolled up systems. In order to systematically characterize the temperature stability of the rolled up microtubes, Raman spectra were acquired as a function of sample temperature up to 300°C. The reversibility of the changes in the Raman spectra of the tubes within this temperature range is demonstrated.