Three-dimensional printing (3DP) has attracted a considerable amount of attention during the past years, being globally recognized as one of the most promising and revolutionary manufacturing technologies. Although the field is rapidly evolving with significant technological advancements, materials research remains a spotlight of interest, essential for the future developments of 3DP. Smart polymers and nanocomposites, which respond to external stimuli by changing their properties and structure, represent an important group of materials that hold a great promise for the fabrication of sensors, actuators, robots, electronics, and medical devices. The interest in exploring functional materials and their 3DP is constantly growing in an attempt to meet the ever-increasing manufacturing demand of complex functional platforms in an efficient manner. In this review, we aim to outline the recent advances in the science and engineering of functional polymers and nanocomposites for 3DP technologies. The report covers temperature-responsive polymers, polymers and nanocomposites with electromagnetic, piezoresistive and piezoelectric behaviors, self-healing polymers, light- and pH-responsive materials, and mechanochromic polymers. The main objective is to link the performance and functionalities to the fundamental properties, chemistry, and physics of the materials, and to the process-driven characteristics, in an attempt to provide a multidisciplinary image and a deeper understanding of the topic. The challenges and opportunities for future research are also discussed.

2D & 3D-printing of self-healing gels enable selective deposition of protective coatings and advanced manufacturing of self-rolling, dynamic objects.

In this work we describe the synthesis, thermal and rheological characterization, hot-melt extrusion, and three-dimensional printing (3DP) of poly(2-vinylpyridine) (P2VP). We investigate the effect of thermal processing conditions on physical properties of produced filaments in order to achieve high quality, 3D-printable filaments for material extrusion 3DP (ME3DP). Mechanical properties and processing performances of P2VP were enhanced by addition of 12 wt % acrylonitrile-butadiene-styrene (ABS), which reinforced P2VP fibers. We 3D-print P2VP filaments using an affordable 3D printer. The pyridine moieties are cross-linked and quaternized postprinting to form 3D-printed pH-responsive hydrogels. The printed objects exhibited dynamic and reversible pH-dependent swelling. These hydrogels act as flow-regulating valves, controlling the flow rate with pH. Additionally, a macroporous P2VP membrane was 3D-printed and the coordinating ability of the pyridyl groups was employed to immobilize silver precursors on its surface. After the reduction of silver ions, the structure was used to catalyze the reduction of 4-nitrophenol to 4-aminophenol with a high efficiency. This is a facile technique to print recyclable catalytic objects.

Molecular weight and dispersity (Ð) influence physical and rheological properties of polymers, which are of significant importance in polymer processing technologies. However, these parameters provide only partial information about the precise composition of polymers, which is reflected by the shape and symmetry of molecular weight distribution (MWD). In this work, the effect of MWD symmetry on thermal and rheological properties of polymers with identical molecular weights and Ð is demonstrated. Remarkably, when the MWD is skewed to higher molecular weight, a higher glass transition temperature (T ), increased stiffness, increased thermal stability, and higher apparent viscosities are observed. These observed differences are attributed to the chain length composition of the polymers, easily controlled by the synthetic strategy. This work demonstrates a versatile approach to engineer the properties of polymers using controlled synthesis to skew the shape of MWD.

The dynamic covalent characteristics of oxime and boronate ester bonds have been explored. A small excess of a competing aldehyde under acidic conditions resulted in oxime polymer degradation from high molecular weights (30 kDa) to low molecular weight oligomers (2.2 kDa). The dynamic nature of oxime bonds imparts oxime cross-linked hydrogels with self-healing properties and the incorporation of phenyl boronic acid groups into the hydrogel network provides a platform for hydrogel functionalization. The addition of a polyphenol (tannic acid) proves a facile means to incorporate a second, dynamic covalent cross-linking network through boronate ester formation which, owing to the increase in the degree of cross-linking, is found to be nearly double the hydrogel strength (storage modulus increased from 4.6 to 8.5 kPa). Finally, the tannic acid cross-linking network is selectively degraded returning the hydrogel storage modulus to its initial value and providing a means for the synthesis of materials with tunable mechanical properties.

We report a novel synthetic and processing methodology for the preparation of doubly dynamic, selfhealing, 3D-printable macroporous gels. 3D-printable oxime hydrogels were prepared by cross-linking poly(n-hydroxyethyl acrylamide-co-methyl vinyl ketone) (PHEAA-co-PMVK) with a bifunctional hydroxylamine. 3D-printed oxime hydrogels were subjected to post-printing treatment by thermally induced phase separation (TIPS), which facilitated the formation of hydrogen bonding and oxime cross-links, and dramatically increased the mechanical strength of soft oxime objects in a well-controlled manner by up to ∼1900%. The mechanical properties of the cryogels were tuned by freezing conditions, which affected the microstructure of the cryogels. These doubly dynamic 3D-printed cryogels are macroporous, exhibit outstanding swelling performances, and can fully, rapidly and autonomously self-heal. † Electronic supplementary information (ESI) available. See