This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce ∼4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applica...

Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications

We present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems, targeting an evolution in technology, that might lead to impacts and benefits reaching into most areas of society. This roadmap was developed within the framework of the European Graphene Flagship and outlines the main targets and research areas as best understood at the start of this ambitious project. We provide an overview of the key aspects of graphene and related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlighting the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries. We also define an extensive list of acronyms in an effort to standardize the nomenclature in this emerging field.

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Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems

Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting....

Polymers for 3D Printing and Customized Additive Manufacturing

The use of 3D printing for rapid tooling and manufacturing has promised to produce components with complex geometries according to computer designs. Due to the intrinsically limited mechanical properties and functionalities of printed pure polymer parts, there is a critical need to develop printable polymer composites with high performance. 3D printing offers many advantages in the fabrication of composites, including high precision, cost effective and customized geometry. This article gives an overview on 3D printing techniques of polymer composite materials and the properties and performance of 3D printed composite parts as well as their potential applications in the fields of biomedical, electronics and aerospace engineering. Common 3D printing techniques such as fused deposition modeling, selective laser sintering, inkjet 3D printing, stereolithography, and 3D plotting are introduced. The formation methodology and the performance of particle-, fiber- and nanomaterial-reinforced polymer composites are emphasized. Finally, important limitations are identified to motivate the future research of 3D printing.

3D printing of polymer matrix composites: A review and prospective

Shape-morphing systems can be found in many areas, including smart textiles, autonomous robotics, biomedical devices, drug delivery and tissue engineering. The natural analogues of such systems are exemplified by nastic plant motions, where a variety of organs such as tendrils, bracts, leaves and flowers respond to environmental stimuli (such as humidity, light or touch) by varying internal turgor, which leads to dynamic conformations governed by the tissue composition and microstructural anisotropy of cell walls. Inspired by these botanical systems, we printed composite hydrogel architectures that are encoded with localized, anisotropic swelling behaviour controlled by the alignment of cellulose fibrils along prescribed four-dimensional printing pathways. When combined with a minimal theoretical framework that allows us to solve the inverse problem of designing the alignment patterns for prescribed target shapes, we can programmably fabricate plant-inspired architectures that change shape on immersion in water, yielding complex three-dimensional morphologies.

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Biomimetic 4D printing

Pressurized blister tests show that the adhesion energies of graphene samples on silicon oxide are much higher than those measured in typical micromechanical structures.

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Ultrastrong adhesion of graphene membranes

Thermomechanics of shape memory polymers: Uniaxial experiments and constitutive modeling

We present a new 4D printing approach that can create high resolution (up to a few microns), multimaterial shape memory polymer (SMP) architectures. The approach is based on high resolution projection microstereolithography (PμSL) and uses a family of photo-curable methacrylate based copolymer networks. We designed the constituents and compositions to exhibit desired thermomechanical behavior (including rubbery modulus, glass transition temperature and failure strain which is more than 300% and larger than any existing printable materials) to enable controlled shape memory behavior. We used a high resolution, high contrast digital micro display to ensure high resolution of photo-curing methacrylate based SMPs that requires higher exposure energy than more common acrylate based polymers. An automated material exchange process enables the manufacture of 3D composite architectures from multiple photo-curable SMPs. In order to understand the behavior of the 3D composite microarchitectures, we carry out high fidelity computational simulations of their complex nonlinear, time-dependent behavior and study important design considerations including local deformation, shape fixity and free recovery rate. Simulations are in good agreement with experiments for a series of single and multimaterial components and can be used to facilitate the design of SMP 3D structures.

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Multimaterial 4D Printing with Tailorable Shape Memory Polymers

We advance a paradigm of printed active composite materials realized by directly printing glassy shape memory polymer fibers in an elastomeric matrix. We imbue the active composites with intelligence via a programmed lamina and laminate architecture and a subsequent thermomechanical training process. The initial configuration is created by three-dimension (3D) printing, and then the programmed action of the shape memory fibers creates time dependence of the configuration—the four-dimension (4D) aspect. We design and print laminates in thin plate form that can be thermomechanically programmed to assume complex three-dimensional configurations including bent, coiled, and twisted strips, folded shapes, and complex contoured shapes with nonuniform, spatially varying curvature. The original flat plate shape can be recovered by heating the material again. We also show how the printed active composites can be directly integrated with other printed functionalities to create devices; here we demonstrate this by creating a structure that can assemble itself.

Active materials by four-dimension printing

Recent advances in three dimensional (3D) printing technology that allow multiple materials to be printed within each layer enable the creation of materials and components with precisely controlled heterogeneous microstructures. In addition, active materials, such as shape memory polymers, can be printed to create an active microstructure within a solid. These active materials can subsequently be activated in a controlled manner to change the shape or configuration of the solid in response to an environmental stimulus. This has been termed 4D printing, with the 4th dimension being the time-dependent shape change after the printing. In this paper, we advance the 4D printing concept to the design and fabrication of active origami, where a flat sheet automatically folds into a complicated 3D component. Here we print active composites with shape memory polymer fibers precisely printed in an elastomeric matrix and use them as intelligent active hinges to enable origami folding patterns. We develop a theoretical model to provide guidance in selecting design parameters such as fiber dimensions, hinge length, and programming strains and temperature. Using the model, we design and fabricate several active origami components that assemble from flat polymer sheets, including a box, a pyramid, and two origami airplanes. In addition, we directly print a 3D box with active composite hinges and program it to assume a temporary flat shape that subsequently recovers to the 3D box shape on demand.

https://iopscience.iop.org/article/10.1088/0964-1726/23/9/094007/pdf

Martin L. Dunn

Papers

Ultrastrong adhesion of graphene membranes

Thermomechanics of shape memory polymers: Uniaxial experiments and constitutive modeling

Multimaterial 4D Printing with Tailorable Shape Memory Polymers

Active materials by four-dimension printing

Active origami by 4D printing