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. The range of polymers used in AM encompasses thermoplastics, thermosets, elastomers, hydrogels, functional polymers, polymer blends, composites, and biological systems. Aspects of polymer design, additives, and processing parameters as they relate to enhancing build speed and improving accuracy, functionality, surface finish, stability, mechanical properties, and porosity are addressed. Selected applications demonstrate how polymer-based AM is being exploited in lightweight engineering, architecture, food processing, optics, energy technology, dentistry, drug delivery, and personalized medicine. Unparalleled by metals and ceramics, polymer-based AM plays a key role in the emerging AM of advanced multifunctional and multimaterial systems including living biological systems as well as life-like synthetic systems.

Photo-curable resins based on multifunctional acrylate monomers are commonly applied as thin films (e.g. protective coatings, printing inks, etc.) and in recent years are also used for the fabrication of bulk objects such as dental fillings and 3D-printed parts. While rapid curing and good spatial resolution are advantages to these systems, brittleness and poor impact resistance due to inhomogeneous polymer architecture and high crosslink density are serious drawbacks. By comparison, epoxy thermoset resins suffered many years ago from similar problems, but since then are found in ever demanding applications thanks to a variety of approaches to increase polymer toughness. Based on these successes, researchers have tried to translate strategies for toughening epoxy resins to photopolymer networks. Therefore, this review surveys relevant scientific papers and patents on the development of crosslinked epoxy-based polymers and also photo-curable polymers based on multifunctional acrylates with improved toughness. Strategies developed to reduce brittleness include working with monomers, which intrinsically give tougher polymers, particulate additives, and alternate forms of polymerization and polymer architecture (e.g., dual-cure networks, interpenetrating networks, thiol–ene chemistry). All of these strategies have advantages and yet application specific rigours must also be considered before and during formulation development.

The natural extracellular matrix (ECM) represents a complex and dynamic environment. It provides numerous spatio‐temporal signals mediating many cellular functions including morphogenesis, adhesion, proliferation and differentiation. The cell–ECM interaction is bidirectional. Cells dynamically receive and process information from the ECM and remodel it at the same time. Theses complex interactions are still not fully understood. For better understanding, it is indispensable to deconstruct the ECM up to the point of investigating isolated characteristics and cell responses to physical, chemical and topographical cues. Two‐photon polymerization (2PP) allows the exact reconstruction of cell specific sites in 3D at micro‐ and nanometer precision. Processing biocompatible synthetic and naturally‐derived hydrogels, the microenvironment of cells can be designed to specifically investigate their behavior in respect to key chemical, mechanical and topographical attributes. Moreover, 3D manipulation can be performed in the presence of cells, guiding biological tissue formation in all stages of its development. Here, advances in 2PP microfabrication of synthetic and naturally based hydrogels are reviewed. Key components of photopolymerizable hydrogel precursors, their structure–property relationships and their polymerization mechanisms are presented. Furthermore, it is shown how biocompatible 2PP fabricated constructs can act as biologically relevant matrices to study cell functions and tissue development.

Stereolithography (SLA) is a widely used technique for the fabrication of prototypes and small series products. The main advantage of SLA and related solid freeform fabrication (SFF) techniques is their capability to fabricate parts with complex shapes with high resolution. Although the spectrum of available materials has been widened in recent years, there is still a lack of materials which can be processed with SLA on a routine basis. In this work, a micro-SLA (μSLA) system is presented which can shape a number of different photopolymers with resolutions down to 5 μ mi n thexy-plane and 10 μ mi n thez-direction. The system is capable of processing various specifically tailored photopolymers which are based on acrylate chemistry. The materials processed for this work range from hybrid sol-gel materials (ORMOCER) to photo-crosslinked elastomers and hydrogels. The elastic moduli of these materials can be tuned over several orders of magnitude and range from 0.1 MPa to 8000 MPa. The reactivity of these monomers is sufficient for achieving writing speeds up to 500 mm s−1 which is comparable to commercial SLA resins. Various test structures are presented which show the suitability of the process for fabricating parts required for applications in micro-mechanical systems as well as for applications in biomedical engineering. Using the presented system, internal channels with a diameter of 50 μm and a length of 1500 μm could be fabricated. It was also possible to manufacture a micro-mechanical system consisting of a fixed axe and a free spinning turbine wheel. (Some figures in this article are in colour only in the electronic version)